U.S. patent application number 14/376265 was filed with the patent office on 2015-01-01 for polymer, process and composition.
This patent application is currently assigned to DSM IP ASSETS B.V.. The applicant listed for this patent is DSM ASSETS B.V.. Invention is credited to Matthew Stewart Gebhard, Tijs Nabuurs, Gerardus Cornelis Overbeek, Jeffrey Stubbs.
Application Number | 20150005442 14/376265 |
Document ID | / |
Family ID | 47630390 |
Filed Date | 2015-01-01 |
United States Patent
Application |
20150005442 |
Kind Code |
A1 |
Nabuurs; Tijs ; et
al. |
January 1, 2015 |
POLYMER, PROCESS AND COMPOSITION
Abstract
There are described vinyl sequential copolymers (and processes
for making them) comprising (a) at least 8. 5 wt-% preferably
>=20 wt-% of a higher itaconate diester (preferably dibutyl
itaconate--DBI); (b) less than 23 wt-% acid monomer but also
sufficient to have an acid value less than 150 mg KOH/g of polymer,
(c) optionally with less than 50 wt-% of other itaconate monomers,
and (d) optionally less than 77 wt-% of other monomers not (a) to
(c). The DBI may be biorenewable. One embodiment is an aqueous
dispersion of the vinyl sequential polymer of two phases: A) 40 to
90 wt-% of a vinyl polymer A with Tg from -50 to 30.degree. C.; and
B) 10 to 60 wt-% of a vinyl polymer B with Tg from 50 to
130.degree. C.; where DBI is used to prepare A and/or B and polymer
A has from 0.1 to 10 wt-% of at least one acid-functional
olefinically unsaturated monomer.
Inventors: |
Nabuurs; Tijs; (Echt,
NL) ; Overbeek; Gerardus Cornelis; (Echt, NL)
; Stubbs; Jeffrey; (Echt, NL) ; Gebhard; Matthew
Stewart; (Echt, NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DSM ASSETS B.V. |
Heerlen |
|
NL |
|
|
Assignee: |
DSM IP ASSETS B.V.
Heerlen
NL
|
Family ID: |
47630390 |
Appl. No.: |
14/376265 |
Filed: |
February 4, 2013 |
PCT Filed: |
February 4, 2013 |
PCT NO: |
PCT/EP2013/052173 |
371 Date: |
August 1, 2014 |
Current U.S.
Class: |
524/548 ;
427/385.5; 524/559; 526/263; 526/304; 526/318.44; 526/318.45 |
Current CPC
Class: |
C08L 35/02 20130101;
Y10T 428/31938 20150401; B05D 3/0254 20130101; C08F 8/32 20130101;
C08F 8/32 20130101; C08F 22/38 20130101; C08F 220/14 20130101; C08F
220/1804 20200201; C08L 33/12 20130101; C09D 135/02 20130101; C08F
8/42 20130101; C08F 220/18 20130101; C08F 220/1804 20200201; C08F
222/04 20130101; C08F 222/14 20130101; C08L 67/08 20130101; C08F
26/06 20130101; C08L 75/04 20130101; C08L 2201/52 20130101; C09D
175/04 20130101; C08F 8/44 20130101; C08F 293/005 20130101; C08F
2810/20 20130101; C08F 8/32 20130101; C08F 220/14 20130101; C08F
220/1804 20200201; B05D 3/108 20130101; C08F 8/32 20130101; C08F
222/04 20130101; C08F 2438/03 20130101; C08L 33/10 20130101; C08F
8/42 20130101; C08F 220/06 20130101; C08F 2810/50 20130101; Y10T
428/31786 20150401; Y10T 428/31935 20150401; C08F 220/14 20130101;
C08F 220/14 20130101; C09D 133/08 20130101; C09D 133/12 20130101;
C08F 8/32 20130101; B05D 3/06 20130101; C09D 153/00 20130101; Y02P
20/582 20151101; C08F 2800/20 20130101; C08L 51/003 20130101; C09D
151/003 20130101; C08F 8/44 20130101; C08F 22/10 20130101; C08F
220/14 20130101; C09D 175/08 20130101; Y10T 428/31551 20150401;
C08F 8/44 20130101; C08F 220/1804 20200201; C09D 125/14 20130101;
C09D 133/10 20130101; C08F 8/42 20130101; C09D 133/02 20130101;
C08F 220/1804 20200201; C08F 301/00 20130101; C08F 8/44 20130101;
C08F 222/04 20130101; C08L 33/02 20130101; C08L 75/00 20130101;
C08F 8/44 20130101; C08F 220/14 20130101; C08F 220/1804 20200201;
C08F 8/42 20130101; C08F 8/44 20130101; C08F 8/44 20130101; C09D
133/14 20130101; C08F 8/42 20130101; C08F 8/44 20130101; C08F 26/08
20130101; C09D 167/08 20130101; C08F 8/44 20130101; C08F 220/1804
20200201; C08F 8/42 20130101; C08F 222/04 20130101; C08F 220/1804
20200201; C08F 220/1804 20200201; C08F 222/04 20130101; C08F 8/42
20130101; C08F 220/1804 20200201; C08F 8/32 20130101; C08F 220/1804
20200201; C08F 222/04 20130101; C08F 222/04 20130101; C08F 220/1804
20200201; C08F 220/1804 20200201; C08F 8/32 20130101; C08F 220/1804
20200201; C08F 220/1804 20200201; C08F 220/1804 20200201; C08F
222/04 20130101; C08F 222/04 20130101; C08F 8/32 20130101; C08F
220/1804 20200201; C08F 222/04 20130101; C08F 220/1804 20200201;
C08F 222/04 20130101; C08F 220/14 20130101; C08F 222/04 20130101;
C08F 220/1804 20200201; C08F 222/04 20130101; C08F 8/42 20130101;
C08F 220/14 20130101; C08F 8/42 20130101; C08F 220/14 20130101;
C08F 220/14 20130101; C08F 8/32 20130101; C08F 220/14 20130101;
C08F 222/04 20130101; C08F 222/04 20130101 |
Class at
Publication: |
524/548 ;
526/318.44; 526/304; 526/263; 526/318.45; 524/559; 427/385.5 |
International
Class: |
C08F 22/10 20060101
C08F022/10; C08F 26/06 20060101 C08F026/06; B05D 3/10 20060101
B05D003/10; C09D 133/12 20060101 C09D133/12; B05D 3/02 20060101
B05D003/02; B05D 3/06 20060101 B05D003/06; C08F 22/38 20060101
C08F022/38; C09D 133/14 20060101 C09D133/14 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 3, 2012 |
EP |
12153838.3 |
Feb 3, 2012 |
EP |
12153839.1 |
Feb 3, 2012 |
EP |
12153840.9 |
Feb 3, 2012 |
EP |
12153842.5 |
Jul 10, 2012 |
EP |
12175782.7 |
Jul 10, 2012 |
EP |
12175784.3 |
Jul 10, 2012 |
EP |
12175785.0 |
Jul 10, 2012 |
EP |
12175786.8 |
Jul 10, 2012 |
EP |
12175788.4 |
Claims
1. A vinyl sequential copolymer [optionally substantially free of
styrene (<1.5 wt-% of copolymer)] the copolymer composition
comprising: (a) at least 23% by weight of at least one monomer
represented by Formula 1 ##STR00009## where both R.sub.1 and
R.sub.2 independently represent an optionally substituted
hydrocarbo moiety having from 4 to 10 carbon atoms. (b) optionally
at least one hydrophilic monomer also in an amount sufficient that
the resultant polymer has an acid value less than 150 mg KOH per g
of polymer, (c) optionally of one or more monomers represented by
Formula 2 ##STR00010## where R.sub.3 and R.sub.4 independently
represent H or an optionally substituted hydrocarbo moiety having
from 1 to 20 carbon atoms X.sub.1 and X.sub.2 independently
represents O or NR.sub.5 where R.sub.5 denotes H or an optionally
substituted hydrocarbo moiety having from 1 to 20 carbon atoms with
the proviso that when X.sub.1 and/or X.sub.2 are 0 then the
respective R.sub.3 and/or R.sub.4 attached to the oxy group
independently represent an optionally substituted hydrocarbo having
from 1 to 3 carbon atoms (d) optionally less than 77% by weight of
monomers other than components (a), (b) or (c). where the
percentages or amounts of (a), (b) (c) (d) are by weight calculated
as a proportion of the total weight of (a)+(b)+(c)+(d) and thus
total 100%; where independently at least one of the components(a),
(b) (c) and/or (d) and/or the copolymer obtained from them are
biorenewable defined as comprising an amount of carbon-14
sufficient to produce a decay of at least about 1.5 dpm/gC
(disintegrations per minute per gram carbon).
2. A copolymer as claimed in claim 1, in which (a) component (a) is
from 24% to 70% by weight of one or more monomers represented by
Formula 1 (b) component (b) is one or more acid functional
monomer(s) in an amount from 0.5% to 15% by weight, in an amount
also sufficient that the resultant polymer has an acid value of
from 3 to 100 mg KOH per g of polymer, (c) component (c) is from
0.01% to 10% by weight of one or more monomers represented by
Formula 2 in which X.sub.1 and X.sub.2 are both O and R.sub.3
and/or R.sub.4 independently represent an optionally substituted
hydrocarbo having from 1 to 3 carbon atoms. (d) component (d) if
present is less than 75% wt-% by weight of monomer(s) other than
components (a), (b) or (c) and does not contain stryene. butyl
acrylate, 2-ethyl hexyl acrylate and/or mixtures thereof; where the
weight percentages or amounts of (a), (b) (c) (d) are calculated as
a proportion of the total amount of (a)+(b)+(c)+(d) which thus
totals 100%; with the provisos that where the copolymer is prepared
by an emulsion polymerisation a chaser monomer is not used; the
copolymer is not prepared in the presence of a seed polymer
comprising a poly(itaconate ester); the copolymer is not prepared
in the presence of an initiator system comprising an organoborane
amine complex.
3. A copolymer as claimed in claim 1, in which component (a)
comprises dibutyl itaconate;
4. A copolymer as claimed in claim 1, in which: (a) component (a)
is present in an amount of from 30 to 65 wt-% and is dibutyl
itaconate; (b) optional component (b) if present is present in an
amount of up to 10 wt-% and comprises an acid functional
ethylenically unsaturated monomer and/or anhydride thereof; (c)
optional component (c) if present is present in an amount of from 1
to 25 wt-% and is dimethyl itaconate and/or diethyl itaconate; (d)
optional component (d) if present is present in an amount such that
(a) and (d) [and (b) and (c) where present] total 100% by
weight.
5. A copolymer as claimed in claim 1 in which: component (d)
comprises at least one polymer precursor(s) of Formula 3
##STR00011## where Y denotes an electronegative group, R.sub.6 is
H, OH or an optionally hydroxy substituted C.sub.1-10hydrcarbo
R.sub.7 is H or a C.sub.1-10hydrocarbo; R.sub.8 is a
C.sub.1-10hydrocarbo group substituted by at least one activated
unsaturated moiety; and; either: A represents a divalent organo
moiety attached to both the --HN-- and --Y-- moieties so the --A--,
--NH--, --C(.dbd.O)-- and --Y-- moieties together represent a ring
of 4 to 8 ring atoms, and R.sub.7 and R.sub.8 are attached to any
suitable point on the ring; or A is not present (and Formula 3
represents a linear and/or branched moiety that does not comprise a
heterocyclic ring) in which case R.sub.7 and R.sub.8 are attached
to R.sub.6; and m is an integer from 1 to 4.
6. A process for preparing a copolymer as claimed in claim 1 and/or
the process comprising the step of polymerising polymer precursors
in a sequential polymerisation method the polymer precursors
comprising component (a), component (b) and optionally components
(c) and/or component (d) to obtain a sequential copolymer, where
optionally the polymerisation method is selected from aqueous
emulsion polymerisation and suspension polymerisation and where the
method does not comprise a chaser monomer step.
7. A copolymer obtained and/or obtainable by a process according to
claim 6.
8. A coating composition comprising a copolymer as claimed in claim
1.
9. A substrate and/or article having coated thereon an (optionally
cured) coating composition of claim 8.
10. A method of using a copolymer as claimed in claim 1 to prepare
a coating composition.
11. A method for preparing a coated substrate and/or article
comprising the steps of applying a coating composition of claim 8
to the substrate and/or article and optionally curing said
composition in situ to form a cured coating thereon.
Description
[0001] The present invention relates to polymers and polymeric
materials obtained and/or obtainable from certain
2-methylidenebutanedioate diester monomers (also referred to herein
as higher itaconate diesters) to a process for making such a
polymers and their use to prepare for example coatings, inks and/or
adhesives. It is preferred that polymers of the invention, and/or
the higher itaconate diesters, are obtained from bio-renewable
sources.
[0002] Many conventional polymers often suffer from undue
sensitivity to water. This is especially true for water based
polymer emulsions which can suffer from an increased water
sensitivity compared to their solvent borne counterparts. A common
way of countering this is to incorporate very hydrophobic monomers,
such as butyl acrylate (BA) or 2-ethylhexyl acrylate (EHA).
However, as homopolymers from these monomers have an extremely low
Tg, incorporation of large amounts of these monomers produces a
composition which is very often too soft (low Tg), yet is not
sufficient hydrophobic if the amount of these monomer is
sufficiently low to produce a satisfactory Tg. This might in turn
be mitigated by introduction of high Tg, hydrophobic monomer such
as styrene and the like. However polymer compositions comprising
stryenic monomers, suffer from reduced outdoor durability because
of the inherent UV sensitivity of styrene.
[0003] We have now surprisingly found that the dilemma described
above can be solved. Good water resistance and low water
sensitivity combined with high hardness and high elongation at
break may be achieved by introducing higher ester itaconates such
as dibutyl itaconate (DBI) as the hydrophobic monomer. Even though
these monomers are very hydrophobic, the applicant has unexpectedly
found that polymers made from higher itaconate esters do not suffer
the same reduction in hardness typically observed for copolymers
made from high concentrations of the typical hydrophobic monomers
such as butyl acryate (BA) and/or 2-ethyl hexyl acrylate (EHA).
[0004] Itaconate ester monomers have been described for very many
years. However they have not been widely used to make commercial
vinyl polymers because they are expensive and difficult to process.
Prior art documents describe the use of itaconate esters only in
general terms and typically describe or exemplify lower itaconate
diesters such as dimethyl itaconate (DMI). The few documents which
describe higher itaconate esters are described below.
[0005] U.S. Pat. No. 4,206,292 (Kureha Kagaku Kogyo Kabushiki
Kaisha) describes a vinyl chloride resin coating with a smooth
surface. The coating comprises: (1) 100 parts of vinyl chloride
polymer; and (2) 0.1 to 30 parts of a polymer processing aid
comprising: (A) 10 to 100 parts of a copolymer comprising 20 to 99%
of an alkyl methacrylate, 1 to 70% of a dialkyl itaconate, and 0 to
60% of a copolymerizable monomer; and (B) 0 to 90 parts of a
copolymer comprising 80 to 100% of an alkyl methacrylate, and 0 to
20% of a copolymerizable monomer. The vinyl chloride resins are not
prepared from bio-based or other environmentally benign sources.
The maximum amount of DBI that is used in the examples is 30% by
weight.
[0006] U.S. Pat. No. 4,547,428 (Monsanto) describes a terpolymer
comprising repeating units derived from an olefin, a diester of an
addition polymerizable unsaturated dicarboxylic acid, and a
solubilizing monomer which promotes compatibility between the
terpolymer and a vinyl halide polymer. A granular form of the
processing aid and a method for its preparation are also disclosed.
These polymers are not suitable for coating applications and the
highest concentration of DBI in the examples is 17% by weight.
[0007] U.S. Pat. No. 4,588,776 (Monsanto) describes a polymer
composition comprising a blend of a vinyl halide polymer and a
particulate terpolymer having a molecular weight of at least
100,000 and a glass transition temperature of at least 50.degree.
C. The terpolymer comprises repeating units derived from an olefin,
a diester of an addition polymerizable unsaturated dicarboxylic
acid, and a solubilizing monomer which promotes compatibility of
the terpolymer with the vinyl halide polymer. These polymers are
used to prepare shaped plastic articles and not for coating
applications. The maximum concentration of DBI used in the examples
is 17% by weight.
[0008] U.S. Pat. No. 6,951,909 (3M) describes a polymerizable
system comprises an organoborane, at least one polymerizable
monomer, and a work-life extending agent. These compositions are
not suitable for coating applications and the maximum concentration
of DBI used in the examples is 17% by weight.
[0009] WO11/073,417 (DSM) discloses an aqueous emulsion comprising
at least a vinyl polymer, said vinyl polymer comprising: a) 45 to
99 wt-% of itaconate ester monomers having formula (I), wherein R
and R' are independently an alkyl or an aryl group; b) 0.1 to 15
wt-% of ionic or potentially ionic unsaturated monomers; c) 0 to 54
wt-% of unsaturated monomers, different from a) and b); and 0.9 to
54.9 wt-% by weight of total monomers of a chaser monomer
composition added subsequently and polymerised after the
polymerisation of monomers a), b) and c); wherein a)+b)+c) and the
chaser monomer composition add up to 100 wt-%; and wherein the
aqueous emulsion contains less than 0.5 wt-% free itaconate ester
monomers of formula I based on the total weight of the aqueous
emulsion. Although it is a stated object of the invention to
provide a vinyl polymer with a high total concentration of
itaconate ester monomers (see page 2, lines 14 to 17) in practise
the larger proportion of such itaconate esters are lower itaconate
esters (i.e. esters of small alkyl groups such as DMI). This
document does not teach that it would be desirable to use a high
concentration of higher itaconate esters (i.e. esters of large
alkyl groups such as DBI). Indeed '417 states that itaonate esters
are difficult to process (see page 2, lines 23 to 25) which
combined with the teaching of the examples demotivates a reader to
incorporated large amounts of hydrophobic higher itaconate esters
like DBI in a copolymer.
[0010] The only examples in '417 that describe use of a DBI monomer
are Examples 2, 4, 5 and 6. The amounts of DBI and other monomers
used to prepare these Examples is given in Table A below. It can be
seen that DBI is used as co-monomer only at a low concentrations in
the final copolymer prepared in these Examples (at a maximum of
22.7 wt-%) which are each also prepared with significant amounts of
another hydrophobic monomer butyl acrylate (BA). A styrene chaser
monomer is always present in the final product (at least 1,5 wt-%).
These examples teach away from using DBI or other higher itaconate
esters to replace common hydrophobic monomers such as BA, EHA
and/or styrene. No significant improvement is seen in film
properties such as hardness and water sensitivity of the copolymers
prepared in this document.
[0011] GB1009486 (Borden) describes a latex of composite polymeric
particles where the core and shell may comprise a copolymer of a
vinylidene chloride and an ester of an alpha unsaturated aliphatic
acid (the amount of ester in the shell being greater than the
core). One example (Example 3) describes use of dibutyl itaconate
(DBI) as the ester in an total amount of 17% by weight of total
monomers (5% in the outer shell and 12% in an inner non core
layer). These composite multi-layer polymer particles address a
problem of providing a water vapour barrier coating for paper and
the like and they use much lower amounts of DBI than the present
invention.
TABLE-US-00001 TABLE A (prior art DBI examples from WO11/073417)
Monomers/wt-% (1 d.p.) Example Plex S Total of '417 Composition AA
BA MMA 652 DAAM MAA DMI DBI (chaser) Itaconate Ex 2 Initial feed
2.0 28.0 -- -- -- -- 45.0 25.0 -- 60.0 Single phase 1.8 25.2 -- --
-- -- 40.5 22.5 10.0 63.0 copolymer Ex 4 First feed 4.4 32.4 13.2
-- -- -- 20.0 30.0 -- 50.0 Second feed 5.0 11.0 34.0 -- -- -- 45.0
5.0 -- 50.0 Sequential copolymer 4.1 25.5 15.8 -- -- -- 22.7 22.7
9.1 45.4 Ex 5 First feed 4.2 30.0 9.5 8.4 -- -- 19.1 28.7 -- 47.8
Second feed 4.7 9.3 28.8 9.5 -- -- 42.9 4.7 -- 47.6 Sequential
copolymer 3.9 23.6 12.2 7.9 -- -- 21.8 21.8 8.7 43.6 Ex 6 Olg
initial feed 35.4 -- -- -- 8.0 5.0 51.6 -- -- 51.6 Olg-plr initial
feed -- 41.2 -- -- -- -- 17.6 41.2 -- 58.8 Polymer - oligomer 26.8
10.7 (inc 2.2 -- -- 6.1 3.8 42.7 8.5 1.5 51.2 BA chaser) In
Examples 2, 4 and 5 of WO11/073417-the chaser monomer was 100 wt-%
styrene, in Example 6 the chaser monomer composition was a mixture
of styrene (40 wt-%) and BA (60 wt %).
[0012] U.S. Pat. No. 3,766,112 describes a high gloss latex for
floor polish comprising a chlorinated paraffin wax with a polyvinyl
pyrrolidone protective colloid. Four monomer components used to
prepare the colloid: styrene (70 to 85%), 2-ethylhexyl acrylate
(EHA) (5 to 15%) (meth)acrylic acid (3 to 10%) and a fourth monomer
(1 to 5%) all percentages by weight of total monomers of the
polyvinyl pyrrolidone. One of the seven monomers suggested as the
fourth monomer is DBI. These polymers address the problem of
providing high gloss floor coatings and DBI is used in much lower
amounts than in the present invention.
[0013] US2011-144265 (Durant Yvon) describes polymer particles
prepared by polymerising esters of itaconic acid in the presence of
seed particles to control particle size.
[0014] WO2002-068479 (3M) describes polymerisation of (meth)acrylic
monomers using a two part initator system of organoborane amine
complex and an activator. One of the many different examples
(Example 6) is prepared from a low amount of DBI (20% by weight)
and this example does not use any other itaconate diester
monomer.
[0015] WO 2007-026949 (Nippon Cat.) describes emulsion resin
compositions that have a minimum film forming temperature (MFT) of
.ltoreq.0.degree. C. and are free of volatile organic compounds
(VOC). These compositions are obtained by mixing a polymer with a
high glass transition temperature (high Tg) with a polymer with low
Tg. These polymers may be water dispersible and a wide variety of
carboxy acid fucnctional acid monomers are suggested to impart such
water solubility including itaconic acid, mono-methyl itaconate
ester and mono butyl itaconate ester (see page 12 lines 12 to 14).
No other itaconic acid derived monomers are described and a reader
of this document would have no reason to incorporate (non
carboxy-acid functional) itaconate diester monomers.
[0016] The esters (including both mono and di-esters) of
2-methylidenebutanedioate (also referred to herein generically as
itaconate esters) may be represented by Formula A:
##STR00001##
where Ra and Rb can independently be H or any optionally
substituted hydrocarbo moiety (such as any aliphatic,
cycloaliphatic or aromatic moieties) provided that Ra and Rb are
other than H (which is not an ester but itaconic acid).
[0017] It has been found that certain hydrophobic itaconate
diesters (e.g. di esters of large alkyl groups) are difficult to
use in conventional polymerisation processes (especially in aqueous
emulsion polymerisation) and are also expensive. Therefore there
has been a reluctance to use such hydrophobic higher itaconate
esters at high concentrations in such processes.
[0018] It is an object of the present invention to solve some or
all of the problems identified herein for example by providing
polymeric materials made from larger amounts of higher itaconate
esters (such as DBI) optionally together with other olefinically
unsaturated monomers (also optionally from a biorenewable source).
The resultant polymers may have various additional advantages as
well as those already described herein such as good film forming at
room temperature with the films having high flexibility
(elasticity) and good resistance to blocking.
[0019] A second aspect of the present invention addresses the
following problems in addition to or as well as those described
herein. Traditional coatings may be unsatisfactory because the
conventional coating films made from hard polymers possess little
flexibility and when coated on substrates which are not
dimensionally stable (such as wood) the coating can tear and chip
off. To improve the processing of dispersions of hard polymers
large amounts of ingredients are added to assist film forming. When
used in high concentrations these film formers are still present in
the binder film in the coating and are released only gradually by
conventional polymers at room temperature. This creates a high
initial block resistance, which is the tendency of freshly applied
coatings to block if they have dried for only a short time. High
initial block resistance makes it virtually impossible to stack
freshly coated substrates rapidly as when dried at room temperature
their final block resistance is usually reached only after several
days.
[0020] EP 387664 discloses an aqueous synthetic resin dispersion
having a minimum film forming temperature below 50.degree. C.
containing an emulsion polymer with a core/shell structure
consisting of A) 65-90% by weight of a weakly crosslinked core
polymer having a glass transition temperature below 0.degree. C.
and an extension at break of at least 150% and B) 10-35% by weight
of an essentially non-crosslinked shell polymer having a glass
transition temperature below 60.degree. C., the glass transition
temperature of said core polymer being at least 10.degree. C. below
that of said shell polymer.
[0021] U.S. Pat. No. 5,021,469 discloses a binder, for water based
gloss paints contains, dispersed in a aqueous phase, particles of a
multiphase emulsion polymer made up of (a) core material having a
glass transition temperature exceeding 40.degree. C. and (b) a
shell material having a glass transition temperature of less than
70.degree. C.
[0022] U.S. Pat. No. 4,654,397 discloses a process for the
preparation of aqueous polymer dispersions which have a low
film-forming temperature but still give films having a high block
resistance, and the use of these polymer dispersions as binders for
coating materials.
[0023] None of the above documents describe dispersions having the
selected combination of features and integers as defined herein to
produce the advantageous combination of properties as discussed
herein.
[0024] This second aspect of the invention has as its preferred
object to provide a physically-drying binder in the form of an
aqueous synthetic resin dispersion which physically dries at low
temperatures to give highly elastic films which are more or less
non-tacky from the beginning. The emulsion polymers according to
this second aspect of the invention address some or all of the
problems described herein.
[0025] Therefore broadly in accordance with the present invention
there is provided a copolymer (optionally a sequential copolymer)
composition comprising (preferably consisting essentially of):
[0026] (a) greater than 8.5 wt-%, usefully .gtoreq.15 wt-%,
preferably at least 20 wt-%, more preferably at least 24 wt-%, more
preferably at least 30 wt-% for example at least 45 wt-% of at
least one monomer represented by Formula 1
[0026] ##STR00002## [0027] where both R.sub.1 and R.sub.2
independently represent an optionally substituted hydrocarbo moiety
having from 4 to 10 carbon atoms. [0028] (b) optionally at least
one hydrophilic monomer preferably in an amount less than 23 wt-%,
more preferably 0.5 to 15 wt-%, and also in an amount sufficient
that the resultant polymer has an acid value of from 0 to 150 mg
KOH/g, preferably less than 150 mg KOH/g, more preferably from 3 to
100 mg KOH per g of polymer, [0029] (c) optionally less than 50
wt-%, for example from 0.01 to 10 wt-% and/or one or more monomers
represented by Formula 2
[0029] ##STR00003## [0030] (Formula 2 including itaconate diester
monomers being other than those represented by Formula 1) [0031]
where R.sub.3 and R.sub.4 independently represent H or an
optionally substituted hydrocarbo moiety having from 1 to 20 carbon
atoms [0032] X.sub.1 and X.sub.2 independently represents O or
NR.sub.5 where R.sub.5 denotes H or an optionally substituted
hydrocarbo moiety having from 1 to 20 carbon atoms with the proviso
that when X.sub.1 and/or X.sub.2 are 0 then the respective R.sub.3
and/or R.sub.4 attached to the oxy group independently represent an
optionally substituted hydrocarbo having from 1 to 3 carbon atoms
[0033] (d) optionally less than 80 wt-%, usefully less than 77
wt-%, preferably less than 75 wt-%, more preferably <70 wt-%,
most preferably <65% wt-% of monomers other than components (a),
(b) or (c). [0034] where the weight percentages (also denoted
herein as "% by weight" and/or "wt-%") of amounts of (a), (b) (c)
(d) are calculated as a proportion of the total (weight) amount of
(a)+(b)+(c)+(d) which thus totals 100%.
[0035] Copolymers of the invention may also be limited by one or
more of the following optional provisos: [0036] (I) when component
(a) consists of DBI in an amount of less than 30% by weight of the
total monomers then the copolymer is substantially free of any
chloro groups; and [0037] (II) when component (a) consists of DBI
in an amount of less than 23% by weight of the total monomers then
the copolymer is prepared by other than an emulsion polymerisation
method in which a chaser monomer is used; and [0038] (III) when
component (a) consists of DBI in an amount of less than 23% by
weight of the total monomers then if component (d) is present,
component (d) is other than styrene or a mixture consisting of
butyl acrylate (60 wt-% of mixture) and styrene (40 wt-% of
mixture) [0039] (IV) the copolymer is substantially free of styrene
(preferably styrene free), more preferably component (d) if present
is other than styrene or a mixture consisting of butyl acrylate (60
wt-% of mixture) and styrene (40 wt-% of mixture), more preferably
component (d) if present is other than styrene (S), butyl acrylate
(BA), 2-ethyl hexyl; acrylate (EHA) or mixtures thereof. [0040] (V)
is prepared by other than an emulsion polymerisation method in
which a chaser monomer is used; and [0041] (VI) the copolymer is
prepared by other than an emulsion polymerisation method in which a
chaser monomer is used optionally this proviso applying only when
component (a) consists of DBI preferably in an amount of from 8.5
to 15% by weight of the total monomers (a)+(b)+(c)+(d). [0042]
(VII) when component (a) consists of DBI then component (a) is
present in an amount other than 8.5 wt-%, 21.8 wt-%, 22.5 wt-% or
22.7 wt % of the total monomer composition, preferably other than
from 8 wt-% to 23 wt %, [0043] (VIII) when component (a) consists
of DBI then component (a) is present in an amount other than 4.7
wt-%, 5.0 wt-%, 8.5 wt-%, 21.8 wt-%, 22.5 wt-%, 22.7 wt %, 25.0
wt-%, 28.7 wt-%, 30.0 wt-% or 41.2 wt-% of the total monomer
composition, preferably other than from 4 wt-% to 42 wt %, [0044]
(IX) the copolymer is obtained other than from a polymerisation of
a dimethyl itaconate (DMI) and dibutyl itaconate (DBI) in the
respective weight ratio of 15 to 85 in the presence of poly diethyl
itaconate seed polymer; more preferably the copolymer is obtained
other than from polymerisation of dialkyl itaconate(s) in the
presence of a poly diethyl itaconate seed polymer; most preferably
the copolymer is obtained other than from polymerisation in the
presence of a poly dialkyl itaconate seed polymer; [0045] (X) if
polymerisation of the copolymer occurs in the presence of an
initator system comprising organoborane amine complex and an
activator then component (a) is present in an amount greater than
20 wt-%, preferably at least 24 wt-% of total monomers
(a)+(b)+(c)+(d).
[0046] Preferably the copolymer of the invention is a sequential
copolymer. As used herein the term sequential copolymer denotes a
polymer obtained and/or obtainable by polymerisation of different
polymer precursors (e.g. monomers) in sequence, for example in a
living anionic polymerisation and/or emulsion polymerisation. A
sequential polymer may be prepared in separate steps and/or in a
single step for example by an all in one polymerisation where all
the required ingredients are already present in the same vessel.
Sequential copolymers of the invention may have any suitable
distribution of monomers within the copolymer, for example be
statistic, random, gradient, alternating, periodic and/or block
copolymers.
[0047] Preferably the sequential copolymer composition is an
emulsion copolymer (usefully an emulsion polymer prepared where no
chaser monomer has been used), more preferably an aqueous emulsion
copolymer, most preferably an aqueous coating composition.
[0048] Conveniently the composition is substantially free of
polyvinyl chloride polymer and/or chlorinated paraffin wax, more
preferably is substantially free of any monomer comprising chloro
groups, most preferably is substantially free of any species
comprising Cl whether as a substituent, atom, di-molecule, ion or
otherwise
[0049] Broadly there is provided in a yet further aspect of the
present invention a process for preparing a copolymer comprising
the step of polymerising polymer precursors in a polymerisation
method the polymer precursors comprising component (a), component
(b) and optionally component (c) and/or component (d) as described
above.
[0050] Preferably the polymerisation method is selected from an
emulsion and/or suspension polymerisation. More preferably the
copolymer is an emulsion copolymer.
[0051] Another aspect of the invention broadly provides for an
optionally copolymer obtained and/or obtainable by a process of the
present invention.
Hydrophobic Component (a) (Higher Itaconate Esters)
[0052] The present invention is particularly concerned with
polymers obtained and/or obtainable from a narrow class of
itaconate diester monomers selected from the broad disclosure of
general itaconate esters of Formula A. Thus the hydrophobic
component (a) comprises itaconate diester(s) of Formula 1:
##STR00004##
where both R.sub.1 and R.sub.2 independently represent an
optionally substituted hydrocarbo moiety having from 4 to 10,
preferably from 4 to 8, more preferably from 4 to 6, most
preferably 4 carbon atoms.
[0053] The diesters of Formula 1 are also referred to herein as
higher itaconate diesters.
[0054] Usefully R.sub.1 and R.sub.2 may independently represent
optionally substituted C.sub.4-10alkyl and/or C.sub.4-10aryl, more
usefully C.sub.4-8alkyl and/or C.sub.4-8aryl and most usefully
C.sub.4-6alkyl, even more usefully butyl (n-butyl being especially
useful).
[0055] Whilst R.sub.1 and R.sub.2 may be different, more
conveniently they represent identical moieties. Especially
preferred examples of Formula 1 include those where R.sub.1 and
R.sub.2 are identical, such di(benzyl)itaconate,
di(phenyl)itaconate, di-n-butyl itaconate, di-i-butyl itaconate,
and/or di-2-ethyl hexyl itaconate. Where R.sub.1 and R.sub.2 both
represent n-butyl Formula 1 represents dibutyl
2-methylidenebutanedioate (also referred to herein as
di(n-butyl)itaconate or DBI) which has the following structure:
##STR00005##
[0056] DBI is the most preferred monomer for use as component (a)
in the present invention.
[0057] Preferably component (a) is used in a total amount of at
least 40%, and more preferably at least 50% by weight of the total
monomers.
[0058] The itaconate functional component (a) is present in the
compositions and/or copolymers of the invention in an amount of
greater than 8.5% wt-%, usefully 15 wt-%, preferably at least 20
wt-%, usefully at least 24 wt-%, more usefully at least 30 wt-%,
even more usefully at least 35 wt-% and most usefully at least 40
wt-%, for example at least 50% based on the total weight of
monomers (a), (b), (c) and (d) used to prepare the copolymer being
100%.
[0059] Conveniently the itaconate functional component (a) may be
present in the compositions and/or copolymers of the invention in
an amount of less than 80 wt-%, more conveniently less than 70
wt-%, even more conveniently less than 65 wt-%, most conveniently
less than 58 wt-%, and for example less than 55 wt-%; based on the
total weight of monomers (a), (b), (c) and (d) used to prepare the
copolymer being 100%.
[0060] Preferably the itaconate functional component (a) may be
present in the compositions and/or copolymers of the invention in
an amount of from 20 to 80 wt-%, more preferably from 24 to 70
wt-%, even more preferably from 30 to 65 wt-%, most preferably from
35 to 65 wt-%, for example from 40 to 55 wt-% based on the total
weight of monomers (a), (b), (c) and (d) used to prepare the
copolymer being 100%.
Hydrophilic Component (b) (Acid Functional Monomers)
[0061] Suitable hydrophilic monomers of component (b) are those
that are co-polymerisible with the hydrophobic monomer(s) of
component (a) and are water soluble. Conveniently the at least one
hydrophilic monomer of component (b) may comprise at least one
activated unsaturated moiety as defined herein.
[0062] Usefully the hydrophilic monomer of component (b) is an acid
functional ethylenically unsaturated monomer for example an acid
functional acrylic monomer.
[0063] It will be understood that when referring to acid functional
and/or acidic components herein this may relate to acidic moieties
and/or potential acidic moieties which under the conditions of use
may form acidic groups (e.g. anhydrides). An acid bearing monomer
could be polymerised as the free acid or as a salt, e.g. the
ammonium and/or alkali metal salt thereof. References herein to
acids should therefore also be understood to include suitable salts
and/or derivates thereof (such as anhydrides and/or acid chlorides
thereof).
[0064] Preferred hydrophilic monomers comprise, advantageously
consist essentially of, at least one ethylenically unsaturated
carboxylic acid although other acid groups such as optionally
substituted organo phosphoric and/or sulphonic acids may also be
used.
[0065] Examples include phosphated alkyl (meth)acrylates, sulphonic
acids (and derivatives thereof) of arylalkylenes, sulphonic acids
(and derivatives thereof) of alkyl (meth)acrylates and/or other
organo substituted sulphonic acids (such as acrylamidoalkyl
sulfonic acids).
[0066] Preferred arylalkylene sulphonic acids are those where the
arylalkylene moiety comprises optionally hydrocarbo substituted
styrene, conveniently optionally C.sub.1-10hydrocarbyl substituted
styrene more conveniently optionally C.sub.1-4alkyl substituted
styrene. Useful acids are sulphonic acid substituted derivatives of
stryenic compounds selected from the group consisting of styrene,
.alpha.-methyl styrene, vinyl toluene, t-butyl styrene, di-methyl
styrene and/or mixtures thereof. Especially preferred is styrene
p-sulphonic acid and its corresponding acid chloride styrene
p-sulphonyl chloride.
[0067] Preferred phosphated organo acids comprise phosphated (meth)
acrylates optionally substituted for example with one or more
hydroxyl groups, for example phosphated hydroxy(meth)acrylates and
C.sub.1-4alkyl esters thereof.
[0068] Other preferred hydrophilic monomers of component (b)
comprises partial acids of multivalent esters, more preferably.
half esters of diesters, most preferably mono acid half itaconate
esters (i.e. those esters of Formula A where either R.sub.a or
R.sub.b is H). Itaconic acid is also another example of a (di)acid
functional monomer which is also suitable as component (b).
[0069] More preferred acids have one ethylenic group and one or two
carboxy groups. Most preferably the acid(s) (and/or suitable acid
derivative(s) thereof) are selected from the group consisting of:
acrylic acid (and copolymerisable oligomers thereof), beta carboxy
ethyl acrylate, citraconic acid, mesaconic acid, crotonic acid,
fumaric acid, itaconic acid, maleic acid, methacrylic acid,
methylene malonic acid, anhydrides thereof, salts thereof, acid
chlorides thereof, combinations thereof in the same species and/or
mixtures thereof.
[0070] Especially preferred monomers that may comprise component
(b) are selected from:
[0071] acrylic acid, methacrylic acid, beta carboxy ethyl acrylate,
methylene malonic acid, maleic anhydride, itaconic acid, itaconic
anhydride, phosphated hydroxyl ethyl methacrylate (phosphated
HEMA), phosphated hydroxylethyl acrylate (phosphated HEA),
phosphated hydroxylpropyl methacrylate (phosphated HPMA),
phosphated hydroxylpropyl acrylate (phosphated HPA), sulphonated
styrene (and its chloride), 2-acrylamido-2-methylpropane sulfonic
acid (AMPS) and ethylmethacrylate-2-sulphonic acid.
[0072] Particularly preferred acid monomers are acrylic acid,
methacrylic acid, beta carboxy ethyl acrylate, itaconic acid,
and/or itaconic anhydride.
[0073] For emulsion polymerization acrylic acid, methacrylic acid,
beta carboxy ethyl acrylate, and/or itaconic acid may be
convenient. For SAD copolymerization, acrylic acid, methacrylic
acid, and/or itaconic anhydride are preferred.
[0074] The hydrophillic monomer component (b) may optionally be
absent from the compositions and/or copolymers of the invention but
if present is present in an amount of more than a trace amount
usefully greater than or equal to 0.1 wt-%, conveniently greater
than or equal to 0.5 wt-%, for example greater than 0.8 wt-% based
on the total weight of monomers (a), (b), (c) and (d) used to
prepare the copolymer being 100%.
[0075] Conveniently component (b) if present is present in the
compositions and/or copolymers of the invention in an amount of
less than 23 wt-%, more conveniently less than or equal to 20 wt-%,
even more conveniently less than or equal to 10 wt-%, most
conveniently .ltoreq.5 wt-%, such as .ltoreq.3 wt-%; for example 51
wt % based on the total weight of monomers (a), (b), (c) and (d)
used to prepare the copolymer being 100%.
[0076] Preferably, component (b) may be used in a total amount from
0 to 10 wt-%, more preferably from about 0.1 to about 5 wt-%, even
more preferably from about 0.1 to about 3 wt-%, most preferably
from about 0.5 to about 1% by weight based on the total weight of
monomers (a), (b), (c) and (d) used to prepare the copolymer being
100%.
[0077] Conveniently component (b) may be used in a total amount
sufficient that the resultant polymer has an acid value (AV) of
between 3 and 100 mg KOH per g of solid polymer, preferably from 8
to 80 mg KOH per g, more preferably from 15 to 65 mg KOH per g, and
most preferably from 15 to 45 mg KOH per g.
[0078] Usefully component (b) satisfies both the acid value (AV)
and weight limits herein, but it will be appreciated that depending
on the monomer used the AV specified herein may be achieved using
weight percentages outside those preferred wt-% values given
herein. Where there is an apparent inconsistency herein between any
weight % of monomer or other component and the acid values
specified it will be appreciated that satisfying the AV is
generally the more desirable objective. If necessary the values for
weight % of the relevant ingredients can be modified appropriately
in a manner well known to a skilled person.
Component (c) (Lower Itaconate Esters and Itaconate Amides)
[0079] Component (c) comprises one or more other diester itaconate
monomers other than those of Formula 1, preferably a monomer of
Formula A where neither Ra nor Rb are H or an optionally
substituted C.sub.4-10hydrocarbo. More preferably component (c)
comprises a lower itaconate diester. As used herein the term lower
itaconate diester denotes diesters of Formula A where Ra and Rb are
independently optionally substituted C.sub.1-3hydrocarbo groups,
such as C.sub.1-3alkyl, an example of which is dimethyl itaconate
(DMI).
[0080] Usefully component (c) may comprise lower itaconate diesters
(i.e. diesters other than those of Formula 1), and/or higher or
lower itaconate amides and thus component (c) may be represented by
Formula 2
##STR00006##
where R.sub.3 and R.sub.4 independently represent H or an
optionally substituted hydrocarbo moiety having from 1 to 20 carbon
atoms (e.g. from 1 to 6 carbon atoms); preferably C.sub.1-20alkyl,
preferably C.sub.1-6alkyl, more preferably C.sub.1-4alkyl, most
preferably C.sub.1-3alkyl; X.sub.1 and X.sub.2 independently
represents O or NR.sub.5 where R.sub.5 denotes H or an optionally
substituted hydrocarbo moiety having from 1 to 20 carbon atoms
(e.g. from 1 to 6 carbon atoms); preferably C.sub.1-20alkyl, more
preferably C.sub.1-6alkyl; even more preferably C.sub.1-4alkyl; for
example C.sub.1-3alkyl; with the proviso that when X.sub.1 and/or
X.sub.2 are 0 then the respective R.sub.3 and/or R.sub.4 attached
to the oxy group independently represent an optionally substituted
hydrocarbo having from 1 to 3 carbon atoms, preferably
C.sub.1-3alkyl.
[0081] Components (a), (b), (c) and (d) are mutually exclusive.
Thus compounds of Formula 2 are different from those of Formula 1
and the mono acid half itaconate esters are also excluded from
Formulae 1 and 2, optionally comprising part of hydrophilic
component (b).
[0082] Thus in one preferred embodiment of the invention
components(a) and (b) (and optionally (c) where present) are each
derived from itaconates and/or acids and/or derivatives thereof,
more preferably from a biorenewable source. Thus for example
component (a) may be a di(C.sub.4-6dialkyl)itaconate, (e.g. DBI),
component (b) may be itaconic anhydride itaconic acid, and/or
C.sub.1-4alkyl monoester of itaconic acid and component (c) where
present may be a di(C.sub.1-3dialkyl)itaconate (e.g. DMI). In such
an embodiment optionally there is no component (d) so the copolymer
may advantageously be obtained from monomers from the same
itaconate source.
[0083] Whilst R.sub.3 and R.sub.4 may be different, more
conveniently they represent identical moieties.
[0084] Whilst X.sub.1 and X.sub.2 may be different, more
conveniently they represent identical moieties.
[0085] Preferably component (c) may be used in a total amount of
less than 35%, more preferably from 0 to 25% by weight.
[0086] The component (c) if present may optionally be present in an
amount usefully greater than or equal to 0.1 wt-%, conveniently
greater than or equal to 0.5 wt-%, for example greater than 1.0
wt-% based on the total weight of monomers (a), (b), (c) and (d)
used to prepare the copolymer being 100%.
[0087] Conveniently component (c) is present in the compositions
and/or copolymers of the invention in an amount of less than 40
wt-%, more conveniently less than or equal to 35 wt-%, even more
conveniently less than or equal to 25 wt-%, most conveniently
.gtoreq.20 wt-%, for example .gtoreq.15 wt % based on the total
weight of monomers (a), (b), (c) and (d) used to prepare the
copolymer being 100%.
[0088] Component (c) may be used in a total amount from 0 to 10
wt-%, preferably from 0.01 to 10 wt-%, more preferably from 0.1 to
40 wt-%, even more preferably from 0.5 to 35 wt-%, most preferably
from 1.0 to 30 wt-%, for example from 1.0 to 25 wt-% by weight
based on the total weight of monomers (a), (b), (c) and (d) used to
prepare the copolymer being 100%.
Component (d) (Other Copolymerisable Monomers)
[0089] Preferably component (d) comprises monomers not part of
components (a), (b) or (c), more preferably that are
copolymerisable with them in any suitable technique such as any of
those described herein (for example in a SAD and/or an emulsion
polymerisation).
[0090] Component (d) may comprise a suitable activated unsaturated
moiety (such as ethylenic unsaturation) where the structure(s) of
component (d) do not overlap with any of components (a), (b) or
(c).
[0091] Preferably component (d) is used in an amount of less than
50% and more preferably less than 40% by weight.
[0092] Component (d) may comprise monomers that can undergo
crosslinking, that can improve adhesion of the coating to various
substrates, that can enhance the colloidal stability of the polymer
emulsion, or that can be used to affect Tg, or polymer
polarity.
[0093] Conveniently component (d) may comprise (meth)acrylate
monomers having alkyl moieties comprising between 1 and 20 carbon
atoms, styrene, alpha-methyl styrene, (meth)acrylonitrile,
(meth)acryl amide or alkylated (meth)acryl amides, diacetone acryl
amide, acetoacetoxyethyl methacrylate, hydroxyethyl (meth)acrylate,
hydroxypropyl (meth)acrylate, silane functional monomers, such as
3-methacryloxypropyl trimethoxysilane (Geniosil GF31, ex Wacker),
ureido functional monomers, such as Plex 6852-O (ex. Evonik),
i-bornyl (meth)acrylate, polyethylene (meth)acrylate, polypropylene
(meth)acrylate.
[0094] Component (d) may also comprise crosslinking monomers that
can induce crosslinking of the copolymer composition. Crosslinking
can occur at ambient temperatures (using for instance diacetone
acryl amide combined with adipic dihydrazide), at elevated
temperatures (stoving conditions in which for instance
copolymerized hydroxyethyl (meth)acrylate reacts with hexamethoxy
methyl melamines), as 2C composition (copolymerized hydroxyethyl
(meth)acrylate reacting with polyisocyanates, such as Bayhydur
3100), or as UV coating (when polymers or oligomers having multiple
unsaturated groups are admixed. Typical examples include di- or
tri-functional multifunctional acrylates such as trimethylol
propane triacrylate or ethoxylated or propoxylated versions
thereof).
[0095] Optionally component (d) may also comprise least one polymer
precursor(s) of Formula 3
##STR00007##
where Y denotes an electronegative group, R.sub.6 is H, OH or an
optionally hydroxy substituted C.sub.1-10hydrcarbo R.sub.7 is H or
a C.sub.1-10hydrocarbo; R.sub.8 is a C.sub.1-10hydrocarbo group
substituted by at least one activated unsaturated moiety; and;
either: A represents a divalent organo moiety attached to both the
--HN-- and --Y-- moieties so the -A-, --NH--, --C(.dbd.O)-- and
--Y-- moieties together represent a ring of 4 to 8 ring atoms, and
R.sub.7 and R.sub.8 are attached to any suitable point on the ring;
or A is not present (and Formula 3 represents a linear and/or
branched moiety that does not comprise a heterocyclic ring) in
which case R.sub.7 and R.sub.8 are attached to R.sub.6; and m is an
integer from 1 to 4.
[0096] The ring moiet(ies) of Formula 3 are each attached to
R.sub.8 and in Formula 3 when m is 2, 3 or 4 then R.sub.8 is
multi-valent (depending on the value of m). If m is not 1 R.sub.7
and --Y-- may respectively denote the same or different moieties in
each ring, preferably the same respective moieties in each ring.
R.sub.7 and R.sub.9 may be attached at any suitable position on the
ring.
[0097] Preferred monomers of Formula 3 comprise, conveniently
consist essentially of, those where: A represents a optional
substituted divalent C.sub.1-5hydrocarbylene; and
--Y-- is divalent --NR.sub.9-- (where R.sub.9 is H, OH, optionally
hydroxy substituted C.sub.1-10hydrocarbo or R.sub.8) or divalent
O,
[0098] More preferred monomers of Formula 3 comprise those where: m
is 1 or 2
--Y-- is --NR.sub.8-- (i.e. where Formula 2 is attached to R.sub.9
via a ring nitrogen), A represents a divalent
C.sub.1-3hydrocarbylene; R.sub.6 is H, R.sub.7 is a
C.sub.1-10hydrocarbo; and R.sub.8 comprises a
(meth)acryloxyhydrocarbo group or derivative thereof (e.g. maleic
anhydride).
[0099] Monomers represented by Formula 3 include some monomers
informally referred to as ureido monomers. Further suitable ureido
monomers of Formula 3 are described in "Novel wet adhesion monomers
for use in latex paints" Singh et al, Progress in Organic Coatings,
34 (1998), 214-219, (see especially sections 2.2 & 2.3) and EP
0629672 (National Starch) both of which are hereby incorporated by
reference. Conveniently the monomers of Formula 3 may be used as a
substantially pure compound (or mixture of compounds) or may be
dissolved in a suitable solvent such as a suitable (meth)acrylate
or acrylic derivative for example methyl methacrylate.
[0100] Other and/or additional component (d) may be used in those
cases where higher molecular weights are desired, such as suitable
multi functional (meth)acrylates or divinyl aromatics. Typical
examples include di-, tri-, or tetra-functional (meth)acrylates,
especially difunctional (meth)acrylates and divinyl benzene.
Typical concentrations are less than 10%, more preferred less than
5%, even more preferred between 0.05 and 4%, most preferred between
0.1 and 2.5%, and even most preferred between 0.15 and 1.5% by
weight based on total monomers.
[0101] The component (d) may optionally be present in an amount
usefully greater than or equal to 0.1 wt-%, conveniently greater
than or equal to 0.5 wt-%, for example greater than 1.0 wt-% based
on the total weight of monomers (a), (b), (c) and (d) used to
prepare the copolymer being 100%.
[0102] Conveniently component (d) is present in the compositions
and/or copolymers of the invention in an amount of less than 77
wt-%, more conveniently less than or equal to 50 wt-%, even more
conveniently less than or equal to 40 wt-%, most conveniently
.ltoreq.30 wt-%, for example .ltoreq.25 wt % based on the total
weight of monomers (a), (b), (c) and (d) used to prepare the
copolymer being 100%.
[0103] Preferably, component (d) may be used in a total amount from
0 to 77 wt-%, more preferably from about 0.1% to about 50 wt-%,
even more preferably from about 0.5% to about 40 wt-%, most
preferably from about 1.0% to about 30% by weight based on the
total weight of monomers (a), (b), (c) and (d) used to prepare the
copolymer being 100%.
[0104] One aspect of the invention relates to an aqueous sequential
vinyl polymer dispersion comprising 30% by weight (preferably at
least 40%) of polymer obtained or obtainable from one or more
higher itaconate diester(s).
[0105] Other examples of suitable monomers that may comprises all
or part of components (a), (b), (c), or (d) may be described in the
various further aspects of the invention later in this application.
It will be understood that where suitable such monomers where not
already mentioned above may also be used as components in the above
aspect of the invention.
Polymerisation Processes
[0106] Copolymers (optionally sequential copolymers) of the
invention may be formed using a number of processes. These include
emulsion polymerisation, suspension polymerisation, bulk
polymerisation and solution polymerisation. Such processes are
extremely well known and need not be described in great detail.
[0107] In one embodiment emulsion polymerisation is used to form
copolymers of the invention.
[0108] A conventional emulsion process involves dispersing the
monomers in an aqueous medium and conducting polymerisation using a
free-radical initiator (normally water soluble) and appropriate
heating (e.g. 30 to 120.degree. C.) and agitation.
[0109] The aqueous emulsion polymerisation can be effected with
conventional emulsifying agents (surfactants) being used such as
anionic and/or non-ionic emulsifiers. The amount used is preferably
low, preferably 0.3 to 2% by weight, more usually 0.3 to 1% by
weight based on the weight of total monomers charged.
[0110] The aqueous emulsion polymerisation can employ conventional
free radical initiators such as peroxides, persulphates and redox
systems as are well known in the art. The amount of initiator used
is generally 0.05 to 3% based on the weight of total monomers
charged.
[0111] The aqueous emulsion polymerisation process may be carried
out using an "all-in-one" batch process (i.e. a process in which
all the components to be employed are present in the polymerisation
medium at the start of polymerisation) or a semi-batch process in
which one or more of the components employed (usually at least one
of the monomers), is wholly or partially fed to the polymerisation
medium during the polymerisation. Although not preferred, fully
continuous processes could also be used in principle. Preferably a
semi-batch process is employed for example power feed
polymerization which is a semi-continuous emulsion copolymerization
in which the instantaneous composition of the formed copolymer is
the same as that of the added monomer mixture(s). Power feed
polymerisation is typically used to make gradient polymers.
Sequential copolymers of the invention may also be prepared from a
dispersion of a first (co)polymer that is mixed with further
unpolymerised polymer precursor or monomer which is then
polymerised in the present of the first polymer.
[0112] The polymerisation technique employed may be such that a low
molecular weight polymer is formed, e.g. by employing a chain
transfer agent such as one selected from mercaptans (thiols),
certain halohydrocarbons and alpha-methyl styrene; or catalytic
chain transfer polymerisation using for example cobalt chelate
complexes as is quite conventional. Alternatively a controlled
radical polymerisation process can be used, for instance by making
use of an appropriate nitroxide or a thiocarbonylthio compounds
such as dithioesters, dithiocarbamates, trithiocarbonates, and
xanthates in order to mediate the polymerization via for example a
nitrox mediated polymerisation (NMP), a reversible addition
fragmentation chain-transfer process (RAFT) or atom transfer
radical polymerization (ATRP).
[0113] When the copolymer of the invention is an emulsion polymer
it may be mixed with a variety of other polymer emulsions such as
those that do not comprise DBI (or higher itaconate esters).
Examples of such second polymer emulsions can be polyurethane
emulsions, polyurethane-poly(meth)acrylate emulsions, alkyd
emulsions, polyester emulsions and/or polyvinyl emulsions. This
latter group of copolymer emulsions may comprise oligomer-polymer
emulsions, gradient morphology emulsions, sequentially polymerized
emulsions, or single phase copolymer emulsions.
[0114] The emulsions according to the description above can be
produced via emulsion polymerization or via a process called
solvent assisted dispersion (SAD) polymerization.
[0115] When the copolymer emulsion is produced via emulsion
polymerization this can be according to a single feed process, a
sequentially fed multi-phase copolymerization process, an oligomer
supported emulsion polymerization process or a power feed process,
resulting in a gradient particle morphology.
[0116] In the case of solvent assisted dispersion polymerization
process, or SAD polymerization, the polymerization is performed in
organic solvents. Next, base and/or surfactant are added and the
polymer solution is emulsified. Preferably, the solvent is removed
via evaporation at the end of the complete process.
[0117] SAD polymer emulsions can be produced via as single feed
solution polymerization or by a sequentially fed multi-phase
polymerization. It is also envisaged that an SAD polymer emulsion,
prior or after the optional removal of the solvent, is used as a
seed for an emulsion polymerization stage. In this case, the
polymer emulsion prepared according to the SAD process is used as
seed in a batch or semi-batch polymerization process.
[0118] The preferred polymerization process is emulsion
polymerization.
[0119] Preferably, the weight average molecular weight (M.sub.w)
(as determined with GPC as described herein) of the DBI containing
copolymers is more than 2000 g/mol, more preferably more than
10,000 g/mol, even more preferably more than 25,000 g/mol, most
preferably more than 40,000 g/mol, and even most preferably more
than 100,000 g/mol.
[0120] In the case of oligomer-polymer emulsions prepared via
emulsion polymerization lower molecular weights may be desired. In
those cases chain transfer agents may be employed. Typical chain
transfer agents can be mercaptans, such as lauryl mercaptan,
i-octyl thioglycolate, or 3-mercapto propionic acid, or
halogenides, such as bromomethane, bromoethane. Typical chain
transfer concentrations in these cases are enough to reduce the
weight average molecular weight of the oligomer phase to between
500 and 100,000 g/mol, more preferred between 1,000 and 60,000
g/mol, even more preferred between 2,500 and 50,000 g/mol, and most
preferred between 5,000 and 25,000. Typical chain transfer agent
concentrations are below 5%, more preferably below 2.5%, and most
preferably between 0.5 and 2.5% by weight of total monomer. In the
case that the oligomer is combined with a high molecular weight
polymer, the preferred molecular weights for the high molecular
weight fraction will be as described earlier.
[0121] In those cases where the copolymer emulsion comprises
multiple phases or is made up from multiple monomer feeds
(sequential, oligomer-polymer or power feed) one of the copolymer
phases preferably comprises between 10 and 80%, more preferably
between 15 and 50%, and most preferably between 20 and 40% by
weight of the total monomers used to prepare the sequential, power
feed, and/or oligomer-polymer composition. This particular
copolymer phase has a Tg, as calculated using the Fox equation, of
higher than 40.degree. C., more preferably higher than 60.degree.
C., and most preferably higher than 80.degree. C. The other
copolymer phase(s) may then comprise between 20 and 90% of the
total monomers more preferably between 50 and 85%, and most
preferably between 60 and 80% by weight of the total monomers used
to prepare the sequential, power feed, and/or oligomer-polymer
composition. These particular copolymer phase(s) have a Tg, as
calculated using the Fox equation, of less than 40.degree. C., more
preferably of less than 20.degree. C., and most preferably of less
than 0.degree. C.
[0122] The difference in Tg in such emulsions between that of the
high Tg phase(s) and that of the low Tg phase(s) is preferably at
least 20.degree. C., more preferably at least 30.degree. C., and
most preferably at least 40.degree. C.
[0123] In a special case it is envisaged that the itaconic
anhydride which is copolymerized in an SAD copolymerization process
can be post modified using chemicals having anhydride reactive
groups. The objective in these cases is to introduce special
functionalities, such as crosslinking or adhesion promoting groups,
while maintaining an acid group that can be used for colloidal
stabilization.
[0124] Modification of the anhydride groups can occur with any
nucleophilic functionality. Preferred functionalities include
hydroxyl groups, hydrazide groups, hydrazine groups, semi-carbazide
groups and amine groups. In all cases, modification will result in
the introduction of the moiety attached to the hydroxyl, hydrazide,
hydrazine, semi-carbazide or amine group and, simultaneously, of an
acid group. The acid group can subsequently be used for emulsifying
the copolymer.
[0125] The modification can be done with monofunctional hydroxyl
groups, hydrazide, or hydrazine, or primary, or secondary amines,
but also with di-functional or higher functional hydroxyl,
hydrazine, hydrazide, semi-carbazide, or primary or secondary
amines. Potential hydroxyl functionalities can include
C.sub.1-C.sub.20 aliphatic, aromatic, or cycloaliphatic mono-, di-,
or high functional alcohols. The aliphatic, aromatic, or
cycloaliphatic groups can include other functionalities that can,
for instance, be used for improved adhesion, crosslinking or other
purposes. Typical examples of such functionalities can include
phosphate, phosphonate, sulphate, sulphonate, ketone, silane,
(cyclic) ureido, (cyclic) carbonate, hydrazide, hydrazine,
semi-carbazide, urethane, urea, carbamate, and melamine
[0126] The preferred (poly)amines, (poly)hydrazines, or
(poly)hydrazides can be characterized by the same description.
[0127] In the case where the copolymer composition is prepared via
emulsion polymerization, the pH of the emulsion can preferably be
increased using organic or inorganic bases. Typical examples
include ammonia, primary and secondary organic amines, lithium
hydroxide, sodium hydroxide or potassium hydroxide, sodium
carbonate or sodium bicarbonate. Typically, the pH is increased
only at the end of the manufacturing process, although it can be
envisaged that either at the start of the polymerization the pH of
the aqueous phase is already increased (buffered) or that the pH of
a polymerizing mixture is increased for instance between sequential
monomer feeds. In the case of copolymers prepared via emulsion
polymerization the pH is preferably increased at the end of the
manufacturing process, preferably using ammonia or lithium
hydroxide.
[0128] Typically, the pH is raised to values above 5, more
preferred above 6, and most preferred to values of between 6 and
9.
[0129] When the copolymer emulsion is prepared via the SAD
polymerization process, emulsification can be done by addition of
surfactants, but is preferably done by first neutralizing the
polymer acid groups. This can be done by addition of base to the
solution polymerized polymer followed by the addition of water or
by addition of base to an aqueous phase followed by the addition of
the polymer solution. In both cases, suitable bases are the same as
above. Preferred bases are ammonia, lithium hydroxide or dimethyl
ethanol amine, diethanol methyl amine, diethanol ethyl amine,
diethyl ethanol amine and the like. Typically, the molar ratio of
base to acid groups is between 0.5 and 1.3, more preferred between
0.6 and 1.2, most preferred between 0.6 and 1.
[0130] The concentration of volatile organic compounds (VOC) in the
aqueous copolymer emulsions is preferably low. In a preferred case,
the VOC level is below 20 wt-%, more preferred below 10 wt-%, even
more preferred below 5 wt-%, most preferred below 1 wt-%, and even
most preferred below 0.5 wt-%. Intentionally, the VOC level of the
copolymer emulsions, prior to formulating them into paints, is
close to 0 wt-%, typically below 0.1 wt-%.
[0131] When the copolymer composition is prepared via SAD
polymerization, solvents are required for the solution
polymerization process. Typical solvents include organic solvents
that are well known to those experienced in the field, such as
acetone, methyl ethylketone, ethanol, methanol, i-propanol, i-octyl
alcohol, xylene, glycol ethers, glycol esters. Preferably solvents
are used that--following polymerization at elevated pressure--can
be removed from the emulsion by evaporation. Preferred solvents in
this respect are acetone and methyl ethylketone.
[0132] Initiators are required to start the radical polymerization.
These, too, are well known to those experienced in the field. The
aqueous emulsion polymerisation can employ conventional free
radical initiators such as peroxides, persulphates and redox
systems. Useful examples include inorganic peroxides, such as
ammonium persulphate, sodium persulphate, potassium persulphate,
AZO initiator, such as azobisisobutyronitrile (AIBN),
2,2'-azodi(2-methylbutyronitrile) (AMBN), and organic peroxide and
hydroperoxides. (Hydro)peroxide can readily be used in combination
with suitable reducing agents. Preferably, initiators are used in
an amount of between 0.05 and 6%, more preferably between 0.5 and
4%, most preferably from 0.5 to 3% by weight of the total
monomers.
[0133] Surfactants are used in emulsion polymerization as known to
those skilled in the art. Typical surfactants have been extensively
described in all kinds of patent applications. The choice and
concentration of surfactants are not deemed to be critical for this
invention. The aqueous emulsion polymerisation can be effected with
conventional emulsifying agents (surfactants) being used such as
anionic and/or non-ionic emulsifiers. The amount used is preferably
low, preferably 0.3 to 2% by weight, more usually 0.3 to 1% by
weight based on the weight of total monomers charged to make the
polymer.
[0134] In the case of SAD copolymer emulsions, emulsification can
be aided by selecting the right anionic, nonionic and mixed
anionic/nonionic surfactant(s). Typically, surfactant is used in an
amount of less than 5% more preferably less than 3%, and most
preferably between 0.2 and 2.5% by weight of the total
monomers.
[0135] Preferably (and subject to the provisos herein) in one
embodiment of the invention the process of making a copolymer
emulsion of the invention comprises using a chaser monomer
composition as described in WO2011073417. In another embodiment a
chaser monomer may optionally not be used.
[0136] In a preferred case the residual monomer content of the
copolymer emulsion is below 2000 mg/L, more preferred below 1500
mg/L, most preferred below 1000 mg/L, and especially preferred
below 550 mg/L.
[0137] The aqueous coating composition yields coatings with typical
Konig hardness values of at least 30 s, more preferred at least 40
s, even more preferred at least 50 s, and most preferred at least
60 s.
[0138] In another embodiment the polymer of the invention may be
made using a bulk polymerisation process. Bulk polymerisation of
olefinically unsaturated monomers is described in detail in EP
0156170, WO82/02387, and U.S. Pat. No. 4,414,370 the contents of
which are hereby incorporated by reference.
[0139] In general in a bulk polymerisation process a mixture of two
or more monomers are charged continuously into a reactor zone
containing molten vinyl polymer having the same ratio of vinyl
monomers as the monomer mixture. The molten mixture is maintained
at a preset temperature to provide a vinyl polymer of the desired
molecular weight. The product is pumped out of the reaction zone at
the same rates as the monomers are charged to the reaction zone to
provide a fixed level of vinyl monomer and vinyl polymer in the
system. The particular flow rate selected will depend upon the
reaction temperature, vinyl monomers, desired molecular weight and
desired polydispersity.
[0140] For polymers of the invention especially those to be used in
coating compositions, providing amino functional groups thereon may
also be useful as such groups provide enhanced adhesion to certain
substrates, such as wood and alkyd resins. Amino groups may be
incorporated into a polymer by using a carboxyl functional
precursor for example prepared by employing ethylenically
unsaturated acid functional monomer(s) such as acrylic acid or
methacrylic acid. At least some of the carboxy-functional groups
may be converted to amino groups (as part of amino ester groups) by
reaction with alkylene imines such as ethylene imine, propylene
imine or butylene imine. Such a reaction is well established in the
art, being known as an imination reaction and the details of this
are for example taught in U.S. Pat. No. 7,049,352 the contents of
which are hereby incorporated herein by reference. Therefore a
further aspect of the invention comprises iminated versions of the
all the copolymers of the present invention as described
herein.
[0141] If it is desired to crosslink polymers (for example in a
polymer dispersion), the relevant polymers can carry functional
groups such as hydroxyl groups and the dispersion subsequently
formulated with a crosslinking agent such as a polyisocyanate,
melamine, or glycoluril; or the functional groups on one or both
polymers could include keto or aldehyde carbonyl groups and the
subsequently formulated crosslinker in step c) could be a polyamine
or polyhydrazide such as adipic acid dihydrazide, oxalic acid
dihydrazide, phthalic acid dihydrazide, terephthalic acid
dihydrazide, isophorone diamine and 4,7-dioxadecane-1,10 diamine.
It will be noted that such crosslinking agents will effect
crosslinking by virtue of forming covalent bonds.
[0142] The designation of the polymer phase involved as a first
phase or core material and second phase or shell material does not
mean that the invention should be bound by any particular
morphology of the latex particles. The term polymer phase is to be
understood as meaning a portion of the emulsion polymer which is
prepared during a temporally-limited segment of the emulsion
polymerization and the dispersion of which differs from that of the
foregoing or following phase. This is also known as a multi-stage
polymerization.
[0143] The two-phase structure of the dispersions of the invention
influences the properties of the film formed when the dispersion
dries after coating a substrate.
[0144] This aspect of the invention provides an aqueous vinyl
polymer dispersion with an advantageous combination of MFFT and
anti-blocking properties which can be prepared at least in part
from bio-renewable monomers (such as biorenewable DBI).
[0145] According to this aspect of the present invention there is
provided an aqueous polymer dispersion having a minimum film
forming temperature below 50.degree. C., more preferably below
30.degree. C. comprising a vinyl polymer derived from olefinically
unsaturated monomers, with at least two phases comprising: [0146]
A) 40 to 90 wt-%, more preferably 50 to 85 wt-% and especially 60
to 80 wt-% of a vinyl polymer A having a glass transition
temperature in the range of from -(minus)50 to 30.degree. C.; and
[0147] B) 10 to 60 wt-%, more preferably 15 to 50 wt-% and
especially 20 to 40 wt-% of a vinyl polymer B having a glass
transition temperature the range of from 50 to 130.degree. C.;
where [0148] (i) at least one of the monomers used to prepare vinyl
polymer A and/or vinyl polymer B is represented by Formula 1 as
described herein (usefully a higher itaconate ester such as DBI)
preferably in an amount from 20 to 80 wt-%, more preferably from 20
to 65 wt-%, most preferably 30 to 55 wt-% of the total monomers
[0149] (ii) optionally 10% by weight (preferably at least 20 wt-%)
of the total amount of monomer used to form vinyl polymer A and
vinyl polymer B is derived from at least one bio-renewable
olefinically unsaturated monomer; [0150] where the weight
percentage of monomers in A and B are calculated in (i) and (ii)
based on the total amount of olefinically unsaturated monomers used
to prepare polymer A and polymer B being 100%; [0151] (iii) vinyl
polymer A comprises 0.1 to 10 wt-% of at least one acid-functional
olefinically unsaturated monomer where the weight percentage of
acid functional monomer is calculated based on the total amount of
olefinically unsaturated monomer used to prepare polymer A being
100%.
[0152] In this aspect of the invention features (i) and (iii)
correspond respectively to components (a) and (b) of the present
invention and the other monomers used to prepare polymers A and B
corresponding to optional components (c) and/or (d) as
appropriate.
[0153] Other preferred features of this aspect of the present
invention are given below and/or in the claims.
[0154] The acid-functional olefinically unsaturated monomer may be
selected from the group consisting of acrylic acid, methacrylic
acid, itaconic anhydride, maleic anhydride methylene malonic acid,
itaconic acid, crotonic acid and fumaric acid.
[0155] Vinyl polymer A may comprise 0.1 to 20 wt-% of at least one
crosslinking olefinically unsaturated monomer, preferably 0.4 to 6
wt-% of at least one olefinically unsaturated monomer with a
wet-adhesion promoting functionality.
[0156] The crosslinking monomer(s) and wet adhesion promoting
monomer(s) can be used together in the same polymer composition. It
is, however, often desired to use either crosslinking monomer(s) or
wet adhesion promoting monomer(s) in any phase. This means that
vinyl polymer A can comprise crosslinking monomer(s) or wet
adhesion promoting monomer(s), while vinyl polymer contains wet
adhesion promoting monomer(s) or crosslinking monomer(s). In
addition to this it is also possible to use wet adhesion promoting
monomer(s) in either vinyl polymer A and/or vinyl polymer B or in
both and no crosslinking monomer(s) or to use crosslinking
monomer(s) in vinyl polymer A and/or vinyl polymer B and no wet
adhesion promoting monomer(s).
[0157] Olefinically unsaturated monomer with a wet-adhesion
promoting functionality contain wet-adhesion promoting functional
groups such as acetoacetoxy groups and optionally substituted amine
or urea groups, for example cyclic ureido groups, imidazole groups,
pyridine groups, hydrazine or semicarbazide groups.
[0158] The bio-renewable olefinically unsaturated monomers may
comprise bio-renewable (meth)acrylic acid and or bio-renewable
alkyl (meth)methacrylate.
[0159] The bio-renewable olefinically unsaturated monomers may also
comprise bio-renewable: .alpha.-methylene butyrolactone,
.alpha.-methylene valerolactone, .alpha.-methylene .gamma.-R.sup.1
butyrolactone (R.sup.1 can be an optionally substituted alkyl or
optionally substituted aryl); itaconates such as dialkyl itaconates
and monoalkyl itaconates, itaconic acid, itaconic anhydride,
crotonic acid and alkyl esters thereof, citraconic acid and alkyl
esters thereof, methylene malonic acid and its mono and dialkyl
esters, citraconic anhydride, mesaconic acid and alkyl esters
thereof.
[0160] The bio-renewable monomers may also comprise bio-renewable:
N--R.sup.2, .alpha.-methylene butyrolactam (R.sup.2 can be an
optionally substituted alkyl or optionally substituted aryl);
N--R.sup.2, .alpha.-methylene .gamma.-R.sup.1 butyrolactam; N-alkyl
itaconimids; itaconmonoamids; itacondiamids; dialkyl itaconamides,
mono alkyl itaconamides; furfuryl (meth)acrylate; and fatty acid
functional (meth)acrylates.
[0161] Vinyl polymer A and vinyl polymer B may comprise at least
about 1.5 dpm/gC of carbon-14.
[0162] In a further aspect of the present invention provides a
process for preparing the aqueous polymer dispersion (or polymer A
and polymer B as described above)
which process comprises steps: [0163] a) a first polymerization
step, to form a first phase vinyl polymer; [0164] b) a second
polymerization step in the presence of the resulting first phase
vinyl polymer from step a) to form a second phase vinyl
polymer.
[0165] Vinyl polymer A may be the first phase in which case vinyl
polymer B is the second phase. Alternatively vinyl polymer B may be
the first phase in which case vinyl polymer A is the second phase.
Preferably vinyl polymer A is the first phase. Preferably the
second phase vinyl polymer is prepared in the presence of the first
phase vinyl polymer.
[0166] Optionally the process includes c) a neutralisation step
before/after or during step c) to solubilise the first polymer
phase.
[0167] Optionally the process includes d) the addition of a
crosslinking agent after the polymerization step a) and/or step b),
said crosslinking agent being reactable with any crosslinking
functional groups of vinyl polymer A and for vinyl polymer B on
subsequent drying of the coating dispersion to effect covalent bond
crosslinking.
[0168] Optionally the process includes a post treatment imination
step e) with alkylene imines like for instance propylene imine)
which can greatly improve wet adhesion.
[0169] A film, polish, varnish, lacquer, paint, ink and/or adhesive
may comprise the aqueous polymer dispersion comprising polymer A
and polymer B described above and these aqueous polymer dispersions
may also be used protective coatings on wood, plastic, paper and/or
metal substrates.
[0170] An embodiment of the invention provides an aqueous polymer
dispersion where vinyl polymers A and B comprise individually at
least 30 wt-%, more preferably at least 40 wt-%, most preferably at
least 60 wt-%, and especially preferably at least 70 wt-% of
compounds of Formula 1 such as higher itaconate diesters for
example DBI. Although the concentration of itaconate monomers in
polymers A and B can be similar, it is preferred that the
concentrations are different. In each of the preferred cases
described above, it is envisaged that the concentration of
itaconate monomers in the other phase can always be below 20 wt-%
or even be 0 wt-%.
[0171] Preferably the concentration of itaconate esters according
to the invention in the low Tg phase is at least 10 wt-% higher
than that in the high Tg phase, more preferably at least 20
wt-%.
[0172] In yet another preferred embodiment of the invention there
is provided an aqueous polymer emulsion according to the invention
where the monomer feed making up polymer A or the feed making up
polymer B comprise up to 20 wt-% of organic solvent, more
preferably less than 10 wt-%, even more preferably less than 5
wt-%, and most preferably between 0.1 and 2.5 wt-%.
[0173] Improved properties of the copolymers of the this aspect of
the invention may include heat resistance, colloidal stability,
pigment compatibility, surface activity, blocking resistance and
reduced MFFT depending on the monomers used.
[0174] The monomer system used for the preparation of vinyl polymer
A and vinyl polymer B is any suitable combination of olefinically
unsaturated monomers which is amenable to copolymerisation
(including bio-renewable monomers described herein which may of
course also be acid-functional, crosslinkable etc at described
below).
[0175] Preferably vinyl polymer A comprises 0.5 to 9 wt-%, more
preferably 1 to 8 wt-% and especially 1.5 to 5 wt-% of at least one
acid-functional olefinically unsaturated monomer.
[0176] Preferably vinyl polymer B comprises less than 5 w % of any
acid functional monomers and preferably less than 2 w %, and in
some preferred embodiments none at all.
[0177] Other, non-acid functional, non-crosslinking monomers which
may be copolymerized with the acid monomers include acrylate and
methacrylate esters and styrenes; also dienes such as 1,3-butadiene
and isoprene, vinyl esters such as vinyl acetate, and vinyl
alkanoates. Methacrylates include normal or branched alkyl esters
of C1 to C12 alcohols and methacrylic acid, such as methyl
methacrylate, ethyl methacrylate, and n-butyl methacrylate, and
(usually C5 to C12) cycloalkyl methacrylates acid such as isobornyl
methacrylate and cyclohexyl methacrylate. Acrylates include normal
and branched alkyl esters of C1 to C12 alcohols and acrylic acid,
such as methyl acrylate, ethyl acrylate, n-butyl acrylate, and
2-ethylhexyl acrylate, and (usually C5-C12) cycloalkyl acrylates
such as isobornyl acrylate and cyclohexylacrylate. Also included
are (meth)acrylamide, and mono- or di-alkyl amides of (meth)acrylic
acid. Styrenes include styrene itself and the various substituted
styrenes, such as .alpha.-methyl styrene and t-butyl styrene.
Nitriles such as acrylonitrile and methacrylonitrile may also be
polymerised, as well as olefinically unsaturated halides such as
vinyl chloride, vinylidene chloride and vinyl fluoride.
[0178] Functional monomers which impart crosslinkability
(crosslinking monomers for short) include epoxy (usually glycidyl)
and hydroxyalkyl (usually C.sub.1-C12, e.g.
hydroxyethyl)methacrylates and acrylates, as well as keto or
aldehyde functional monomers such as acrolein, methacrolein and
vinyl methyl ketone, the acetoacetoxy esters of hydroxyalkyl
(usually C.sub.1-C.sub.12) acrylates and methacrylates such as
acetoacetoxyethyl methacrylate and acrylate, and also
keto-containing amides such as diacetone acrylamide. The purpose of
using such functional monomer is to provide subsequent
crosslinkability in the resulting polymer system as discussed. In
principle the functional monomer used for imparting
crosslinkability could be acid-bearing monomer, but this is not
usual.
[0179] Preferably vinyl polymer A comprises 0.1 to 3 wt-% of at
least one crosslinking monomer containing at least two olefinically
unsaturated groups.
[0180] Preferably vinyl polymer A comprises 0.1 to 20 w %,
preferably 1 to 15 w %, and particularly 1 to 10 w % of
crosslinking monomers.
[0181] Adhesion promoting monomers include amino, urea, or
N-heterocyclic groups. As known to those skilled in the art this
property can also be achieved by imination i.e. reaction of the
acid groups with propylene imine.
[0182] Preferably vinyl polymer A comprises 0.4 to 6 wt-% of at
least one olefinically unsaturated monomer with a wet-adhesion
promoting functionality, more preferably between 0.5 and 4
wt-%.
[0183] Vinyl polymer A preferably has a weight average molecular
weight (M.sub.w) as determined with GPC of from 20,000 to 6,000,000
g/mol, preferably more than 80,000 g/mol and most preferably more
than 100,000 g/mol. More preferably the upper limit does not exceed
4,000,000 g/mol.
[0184] Vinyl polymer B preferably has a weight average molecular
weight (M.sub.w) as determined with GPC of from 20,000 to 6,000,000
g/mol, preferably more than 80,000 g/mol and most preferably more
than 100,000 g/mol. More preferably the upper limit does not exceed
4,000,000 g/mol.
[0185] Preferably vinyl polymer A has a glass transition
temperature in the range of from -(minus)20 to 20.degree. C.
[0186] Preferably vinyl polymer B has a glass transition
temperature in the range of from 65 to 110.degree. C.
[0187] Preferably the polymer dispersion contains latex particles
having a diameter from 30 to 900 nanometres (nm), particularly 60
to 300 nm. The particle size distribution can be unimodal, bimodal,
or polymodal. Dispersions having bi- or poly-modal particle size
distributions can be made according to the method described in
DE3147 008 or U.S. Pat. No. 4,456,726.
[0188] In a preferred embodiment there is provided an aqueous
polymer dispersion having a minimum film forming temperature of
below 30.degree. C. comprising a vinyl polymer derived from
olefinically unsaturated monomers, with at least two phases
comprising: [0189] A) 60 to 80 wt-% of a vinyl polymer A having a
glass transition temperature in the range of from -20 to 20.degree.
C.; and [0190] B) 20 to 40 wt-% of a vinyl polymer B having a glass
transition temperature the range of from 65 to 110.degree. C.;
wherein vinyl polymer A comprises 2 to 5 wt-% of at least one
acid-functional olefinically unsaturated monomer, and wherein at
least 50 wt-% of the monomer composition used to form vinyl polymer
A and vinyl polymer B comprises itaconate diesters of Formula 1,
preferably from a biorenewable source.
[0191] If vinyl polymer A is made in the second phase then
preferably vinyl polymer A has at least 80%, more preferably at
least 100% and most preferably 110% of the acid value of vinyl
polymer B being made in the first phase and this helps to affect
the morphology of the particles to get good film formation.
[0192] According to an embodiment of the invention there is also
provided a process to obtain an aqueous polymer dispersion as
defined herein which process comprises steps: [0193] a) a first
polymerization step, to form a first phase vinyl polymer; [0194] b)
a second polymerization step in the presence of the resulting first
phase vinyl polymer from step a) to form a second phase vinyl
polymer.
[0195] The first phase vinyl polymer may be formed using emulsion
polymerisation. Such processes are extremely well known, are
described elsewhere in this specification and need not be described
further great detail.
[0196] If desired the pH of the polymer emulsion can be adjusted to
higher values using suitable bases. Examples of which include
organic amines such as trialkylamines (e.g. triethylamine,
tributylamine), morpholine and alkanolamines, and inorganic bases
such as ammonia, NaOH, KOH, and LiOH.
[0197] In an embodiment of the invention it is also possible to use
a gradient polymerisation process as described in for example
EP1434803 to make at least part of the first and second phase. The
second phase monomer feed preferably starts after 20 to 80%
completion of the first phase monomer feed.
[0198] In a preferred embodiment when >30 wt-% of monomers of
Formula 1 (such as DBI) are used the monomers are preferably fed
into the reactor during polymerisation, with a preferred feed time
>60 minutes, more preferably >120 minutes and most preferred
>150 minutes.
[0199] Preferably, the concentration of unreacted monomer according
to Formula 1 during the polymerisation is less than 5 wt-% on total
weight of the emulsion, more preferably less than 3 wt-%, most
preferably less than 1 wt-%, and typically less than 0.5 wt-% on
total weight of the emulsion. The concentration of unreacted
monomer(s) other than according to Formula 1 during the
polymerisation is less than 5 wt-%, more preferred less than 2.5
wt-%, most preferably less than 1 wt-%, and typically less than 0.3
wt-% on total weight of the emulsion.
[0200] Preferably the dispersions of the invention have VOC levels
of less than 100 g/L and more preferably less than 80 g/L, most
preferably less than 50 g/L and especially less than 20 g/L of
volatile organic components (VOC) such as coalescing solvents.
[0201] If crosslinking monomers are present then preferably the
amount of crosslinking agent that is employed is such that the
ratio of the number of crosslinker groups present in the first
phase vinyl polymer and (if employed) in the second phase vinyl
polymer to the number of reactive groups (for crosslinking
purposes) in the crosslinking agent is within the range of from
10/1 to 1/3, preferably 2/1 to 1/1.5.
[0202] A crosslinker reactive with a copolymerised crosslinking
monomer, if present, is usually combined with the aqueous
dispersion by adding it thereto after the preparation of the second
phase vinyl polymer (and sometimes just before use of the
dispersion), although it may in principle also be combined by
performing the polymerisation of the second phase vinyl polymer in
the presence of the crosslinking agent. A combination of both
incorporation expedients may also in principle be used.
[0203] It will be appreciated that vinyl polymer A and optionally
vinyl polymer B possess functional groups for imparting latent
crosslinkability to the dispersion (i.e. so that crosslinking takes
place e.g. after the formation of a coating therefrom) when
combined with the crosslinking agent. For example, one or both
polymers could carry functional groups such as hydroxyl groups and
the dispersion subsequently formulated with a crosslinking agent
such as a polyisocyanate, melamine, or glycoluril; or the
functional groups on one or both polymers could include keto or
aldehyde carbonyl groups and the subsequently formulated
crosslinker in step c) could be a polyamine or polyhydrazide such
as adipic acid dihydrazide, oxalic acid dihydrazide, phthalic acid
dihydrazide, terephthalic acid dihydrazide, isophorone diamine and
4,7-dioxadecane-1,10 diamine. It will be noted that such
crosslinking agents will effect crosslinking by virtue of forming
covalent bonds.
[0204] According to an embodiment of the invention there is
provided a process for the production of the aqueous polymer
coating dispersion, which process comprises steps: a') a first
polymerization step, to form a first phase vinyl polymer; b') a
second polymerization step in the presence of the resulting first
phase vinyl polymer from step a') to form a second phase vinyl
polymer. Optionally the process includes c') a neutralisation step
before/after or during step b'). Optionally the process includes a
post treatment imination step d') with alkylene imines like for
instance propylene imine) which can greatly improve wet adhesion.
Optionally the process includes e') the addition of a crosslinking
agent after the polymerization step a') and/or step b'), and
preferably after the optional imination step d'), said crosslinking
agent being reactable with any crosslinking functional groups of
vinyl polymer A and/or vinyl polymer B on subsequent drying of the
coating dispersion to effect covalent bond crosslinking (as
described herein).
[0205] The term "activated unsaturated moiety", is used herein to
denote a species comprising at least one unsaturated carbon to
carbon double bond in chemical proximity to at least one activating
moiety. Preferably the activating moiety comprises any group which
activates an ethylenically unsaturated double bond for addition
thereon by a suitable electrophillic group. Conveniently the
activating moiety comprises oxy, thio, (optionally organo
substituted)amino, thiocarbonyl and/or carbonyl groups (the latter
two groups optionally substituted by thio, oxy or (optionally
organo substituted) amino). More convenient activating moieties are
(thio)ether, (thio)ester and/or (thio)amide moiet(ies). Most
convenient "activated unsaturated moieties" comprise an
"unsaturated ester moiety" which denotes an organo species
comprising one or more "hydrocarbylidenyl(thio)carbonyl(thio)oxy"
and/or one or more "hydrocarbylidenyl(thio)-carbonyl(organo)amino"
groups and/or analogous and/or derived moieties for example
moieties comprising (meth)acrylate functionalities and/or
derivatives thereof. "Unsaturated ester moieties" may optionally
comprise optionally substituted generic .alpha.,.beta.-unsaturated
acids, esters and/or other derivatives thereof including thio
derivatives and analogs thereof.
[0206] Preferred activated unsaturated moieties are those
represented by a radical of Formula 4.
##STR00008##
where n' is 0 or 1, X.sup.6 is oxy or, thio; X.sup.7 is oxy, thio
or NR.sup.17 (where R.sup.17 represents H or optionally substituted
organo), R.sup.13, R.sup.14, R.sup.15 and R.sup.16 each
independently represent a bond to another moiety in Formula 1, H,
optional substituent and/or optionally substituted organo groups,
where optionally any of R.sup.13, R.sup.14, R.sup.15 and R.sup.16
may be linked to form a ring; where at least one of R.sup.13,
R.sup.14R.sup.15 and R.sup.16 is a bond; and all suitable isomers
thereof, combinations thereof on the same species and/or mixtures
thereof.
[0207] The terms "activated unsaturated moiety"; "unsaturated ester
moiety" and/or Formula 4 herein represents part of a formula herein
and as used herein these terms denote a radical moiety which
depending where the moiety is located in the formula may be
monovalent or multivalent (e.g. divalent).
[0208] More preferred moieties of Formula 4 (including isomers and
mixtures thereof) are those where n' is 1; X.sup.6 is O; X.sup.7 is
O, S or NR.sup.7.
[0209] R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are independently
selected from: a bond, H, optional substituents and optionally
substituted C.sub.1-10hydrocarbo, optionally R.sup.15 and R.sup.16
may be linked to form (together with the moieties to which they are
attached) a ring; and where present R.sup.17 is selected from H and
optionally substituted C.sub.1-10hydrocarbo.
[0210] Most preferably n' is 1, X.sup.6 is O; X.sup.7 is O or S and
R.sup.13R.sup.14, R.sup.15 and R.sup.16 are independently a bond,
H, hydroxy and/or optionally substituted C.sub.1-10hydrocarbyl.
[0211] For example n' is 1, X.sup.6 and X.sup.7 are both O; and
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are independently a bond, H,
OH, and/or C.sub.1-4alkyl; or optionally R.sup.5 and R.sup.6 may
together form a divalent C.sub.0-4alkylenecarbonylC.sub.0-4alkylene
moiety so Formula 4 represents a cyclic anhydride (e.g. when
R.sup.15 and R.sup.16 together are carbonyl then Formula 4
represents a maleic anhydride or derivative thereof).
[0212] For moieties of Formula 4 where n' is 1 and X.sup.6 and
X.sup.7 are both O then when one of (R.sup.13 and R.sup.14) is H
and also R.sup.13 is H, Formula 4 represents an acrylate moiety,
which includes acrylates (when both R.sup.13 and R.sup.14 are H)
and derivatives thereof (when either R.sup.13 and R.sup.14 is not
H). Similarly when one of (R.sup.13 and R.sup.14) is H and also
R.sup.15 is CH.sub.3, Formula 4 represents an methacrylate moiety,
which includes methacrylates (when both R.sup.13 and R.sup.14 are
H) and derivatives thereof (when either R.sup.13 and R.sup.14 is
not H). Acrylate and/or methacrylate moieties of Formula 5 are
particularly preferred.
[0213] Conveniently moieties of Formula 4 are those where n' is 1;
X.sup.6 and X.sup.7 are both O; R.sup.13 and R.sup.14 are
independently a bond, H, CH.sub.3 or OH, and R.sup.15 is H or
CH.sub.3; R.sup.16 is H or R.sup.15 and R.sup.16 together are a
divalent C.dbd.O group.
[0214] More conveniently moieties of Formula 4 are those where n'
is 1; X.sup.6 and X.sup.7 are both O; R.sup.13 is OH, R.sup.4 is
CH.sub.3, and R.sup.15 is H and R.sup.6 is a bond and/or
tautomer(s) thereof (for example of an acetoacetoxy functional
species).
[0215] Most convenient unsaturated ester moieties are selected
from: --OCO--CH.dbd.CH.sub.2; --OCO--C(CH.sub.3).dbd.CH.sub.2;
acetoacetoxy, --OCOCH.dbd.C(CH.sub.3)(OH) and all suitable
tautomer(s) thereof.
[0216] It will be appreciated that any suitable moieties
represented by Formula 4 could be used in the context of this
invention such as other reactive moieties.
[0217] Whilst the term vinyl polymer is commonly used to refer to
thermoplastic polymers derived by polymerization from compounds
containing the vinyl group (CH.sub.2.dbd.CH--), the term "vinyl
polymer" is used herein more broadly to denote any polymer (whether
thermoplastic or not) that comprises (e.g. as repeat units therein)
and/or is derived from monomers and/or polymer precursors
comprising one or more of the following moieties: activated
unsaturated moieties (such as acrylates and/or methacrylates); any
olefinically unsaturated moieties (such as vinyl moieties);
mixtures thereof; and/or combinations thereof within the same
moiety.
[0218] There is an increasing demand to use bio-renewable monomers
in order to improve the sustainability of the polymers used in for
example coating applications. In view of concerns about depletion
of fossil fuel resources or an increase in carbon dioxide in the
air that poses a global-scale environmental problem in recent
years, methods for producing raw materials of these polymers from
biomass resources have attracted al lot of attention. Since these
resources are renewable and therefore have a carbon-neutral
biomass, such methods are expected to gain in particular importance
in future. It is therefore a preferred feature of the present
invention and the aspects described herein that where possible the
monomers (especially the higher itaconate diesters such as DBI) as
far as possible are biorenewable.
[0219] Preferably at least 30 wt-%, more preferably at least 50
wt-%, and especially 70 wt-% of the olefinically unsaturated
monomers used to form the polymers of the invention are derived
from at least one bio-renewable olefinically unsaturated monomer.
Bio-renewable monomers may be obtained fully or in part from
bio-renewable sources. Thus it is preferred to also measure the
carbon-14 content to determine the biorenewability.
[0220] The content of carbon-14 (C-14) is indicative of the age of
a bio-based material. It is known in the art that C-14, which has a
half life of about 5,700 years, is found in bio-renewable materials
but not in fossil fuels. Thus, "bio-renewable materials" refer to
organic materials in which the carbon comes from non-fossil
biological sources. Examples of bio-renewable materials include,
but are not limited to, sugars, starches, corns, natural fibres,
sugarcanes, beets, citrus fruits, woody plants, cellulosics,
lignocelluosics, hemicelluloses, potatoes, plant oils, other
polysaccharides such as pectin, chitin, levan, and pullulan, and a
combination thereof.
[0221] C-14 levels can be determined by measuring its decay process
(disintegrations per minute per gram carbon or dpm/gC) through
liquid scintillation counting. In one embodiment of the present
invention, polymer A, polymer B and/or the olefinically unsaturated
monomer(s) that are used to obtain polymer A and/or polymer B may
considered sufficiently biorenewable for the purposes of this
embodiment of the invention when the respective polymer A, polymer
B and/or olefinically unsaturated monomer comprise an amount of
carbon-14 to produce a decay of at least about 1.5 dpm/gC
(disintegrations per minute per gram carbon), more preferably at
least 2 dpm/gC, most preferably at least 2.5 dpm/gC, and especially
at least 4 dpm/gC.
[0222] It is preferred that the higher itaconate diesters such as
DBI are biorenewable, however other monomers used in the present
invention may also be biorenewable. Examples of bio-renewable
monomers include but are not limited to bio-based acrylics obtained
by for example using bio-derived alcohols such as bio-butanol and
include (meth)acrylic acid and alkyl (meth)acrylate, where alkyl is
preferably selected from methyl, ethyl, butyl or 2-ethylhexyl.
[0223] Acrylic acid can be made from glycerol, as is disclosed by
Arkema, or from lactic acid as described by US7687661. Methacrylic
acid can be prepared from ethene, methanol and carbon monoxide (all
bio-renewable), as disclosed by Lucite International Ltd.
[0224] Olefinically unsaturated bio-renewable monomers which may
additionally provide a contribution to improved coating properties
include .alpha.-methylene butyrolactone, .alpha.-methylene
valerolactone, .alpha.-methylene .gamma.-R.sup.3 butyrolactone
(R.sup.3 can be an optionally substituted alkyl or optionally
substituted aryl); itaconates such as dialkyl itaconates (including
DBI) and monoalkyl itaconates, itaconic acid, itaconic anhydride,
crotonic acid and alkyl esters thereof, citraconic acid and alkyl
esters thereof, methylene malonic acid and its mono and dialkyl
esters, citraconic anhydride, mesaconic acid and alkyl esters
thereof.
[0225] Other non-acid functional, non-crosslinking monomers include
diesters of itaconic acid. Preferred examples of such monomers
include dimethyl itaconate, diethyl itaconate, di-n-propyl
itaconate, di-1-propyl itaconate, di-n-butyl itaconate, di-1-butyl
itaconate, and di-2-ethyl hexyl itaconate.
[0226] Another useful set of useful bio-renewable monomers include
N--R.sup.2, .alpha.-methylene butyrolactam (R.sup.2 can be an
optionally substituted alkyl or optionally substituted aryl);
N--R.sup.2, .alpha.-methylene .gamma.-R.sup.1 butyrolactam; N-alkyl
itaconimids; itaconmonoamids; itacondiamids; ialkyl itaconamides,
mono alkyl itaconamides; furfuryl (meth)acrylate; fatty acid
functional (meth)acrylates such as DAPRO FX-522 from Elementis and
Visiomer.RTM. MUMA from Evonik.
[0227] It is appreciated that certain features of the invention,
which are for clarity described in the context of separate
embodiments may also be provided in combination in a single
embodiment. Conversely various features of the invention, which are
for brevity, described in the context of a single embodiment, may
also be provided separately or in any suitable sub-combination.
[0228] The object of the present invention is to solve some or all
of the problems or disadvantages (such as identified throughout the
application herein) with the prior art.
[0229] Unless the context clearly indicates otherwise, as used
herein plural forms of the terms herein are to be construed as
including the singular form and vice versa.
[0230] The term "comprising" as used herein will be understood to
mean that the list following is non exhaustive and may or may not
include any other additional suitable items, for example one or
more further feature(s), component(s), ingredient(s) and/or
substituent(s) as appropriate.
[0231] The terms `effective`, `acceptable`, `active` and/or
`suitable` (for example with reference to any process, use, method,
application, preparation, product, material, formulation, compound,
monomer, oligomer, polymer precursor, and/or polymers described
herein as appropriate) will be understood to refer to those
features of the invention which if used in the correct manner
provide the required properties to that which they are added and/or
incorporated to be of utility as described herein. Such utility may
be direct for example where a material has the required properties
for the aforementioned uses and/or indirect for example where a
material has use as a synthetic intermediate and/or diagnostic tool
in preparing other materials of direct utility. As used herein
these terms also denote that a functional group is compatible with
producing effective, acceptable, active and/or suitable end
products.
[0232] Preferred utility of the present invention comprises as a
coating composition.
[0233] In the discussion of the invention herein, unless stated to
the contrary, the disclosure of alternative values for the upper
and lower limit of the permitted range of a parameter coupled with
an indicated that one of said values is more preferred than the
other, is to be construed as an implied statement that each
intermediate value of said parameter, lying between the more
preferred and less preferred of said alternatives is itself
preferred to said less preferred value and also to each less
preferred value and said intermediate value.
[0234] For all upper and/or lower boundaries of any parameters
given herein, the boundary value is included in the value for each
parameter. It will also be understood that all combinations of
preferred and/or intermediate minimum and maximum boundary values
of the parameters described herein in various embodiments of the
invention may also be used to define alternative ranges for each
parameter for various other embodiments and/or preferences of the
invention whether or not the combination of such values has been
specifically disclosed herein. Thus for example a substance stated
as present herein in an amount from 0 to "x" (e.g. in units of mass
and/or weight %) is meant (unless the context clearly indicates
otherwise) to encompass both of two alternatives, firstly a broader
alternative that the substance may optionally not be present (when
the amount is zero) or present only in an de-minimus amount below
that can be detected. A second preferred alternative (denoted by a
lower amount of zero in a range for amount of substance) indicates
that the substance is present, and zero indicates that the lower
amount is a very small trace amount for example any amount
sufficient to be detected by suitable conventional analytical
techniques and more preferably zero denotes that the lower limit of
amount of substance is greater than or equal to 0.001 by weight %
(calculated as described herein).
[0235] It will be understood that the total sum of any quantities
expressed herein as percentages cannot (allowing for rounding
errors) exceed 100%. For example the sum of all components of which
the composition of the invention (or part(s) thereof) comprises
may, when expressed as a weight (or other) percentage of the
composition (or the same part(s) thereof), total 100% allowing for
rounding errors.
[0236] However where a list of components is non exhaustive the sum
of the percentage for each of such components may be less than 100%
to allow a certain percentage for additional amount(s) of any
additional component(s) that may not be explicitly described
herein.
[0237] In the present invention, unless the context clearly
indicates otherwise, an amount of an ingredient stated to be
present in the composition of the invention when expressed as a
weight percentage, is calculated based on the total amount of
monomers in the composition being equivalent to 100% (thus for
example components (a)+(b)+(c)+(d) total 100%). For convenience
certain non monomer ingredients (such as for example chain transfer
agents (CTA)) which fall outside the definitions of any of
components (a) to (d) may also be calculated as weight percentages
based on total monomer (i.e. where the weight of total monomers
alone is set at 100%). As the weight % of monomers (for example for
components (a) to (d)) by definition total 100% it will be seen
that using monomer based weight % values for the non-monomer
ingredients (i.e. those components outside (a) to (d)) will mean
the total percentages will exceed 100%. Thus amounts of non-monomer
ingredients expressed as monomer based weight percentages can be
considered as providing a ratio for the weight amounts for these
ingredients with respect to the total weight of monomers which is
used only as a reference for calculation rather than as a strict
percentage. Further ingredients are not excluded from the
composition when (a)+(b)+(c)+(d) total 100% and weight percentages
based on total monomers should not be confused with weight
percentages of the total composition.
[0238] The term "substantially" as used herein may refer to a
quantity or entity to imply a large amount or proportion thereof.
Where it is relevant in the context in which it is used
"substantially" can be understood to mean quantitatively (in
relation to whatever quantity or entity to which it refers in the
context of the description) there comprises an proportion of at
least 80%, preferably at least 85%, more preferably at least 90%,
most preferably at least 95%, especially at least 98%, for example
about 100% of the relevant whole. By analogy the term
"substantially-free" may similarly denote that quantity or entity
to which it refers comprises no more than 20%, preferably no more
than 15%, more preferably no more than 10%, even more preferably no
more than 5%, most preferably no more than 2%, especially no more
than 1.5%, for example about 0% (e.g. completely absent or if
present only in an undetectable amount) of the relevant whole.
[0239] The terms `optional substituent` and/or `optionally
substituted` as used herein (unless followed by a list of other
substituents) signifies the one or more of following groups (or
substitution by these groups): carboxy, sulpho, formyl, hydroxy,
amino, imino, nitrilo, mercapto, cyano, nitro, methyl, methoxy
and/or combinations thereof. These optional groups include all
chemically possible combinations in the same moiety of a plurality
(preferably two) of the aforementioned groups (e.g. amino and
sulphonyl if directly attached to each other represent a sulphamoyl
group). Preferred optional substituents comprise: carboxy, sulpho,
hydroxy, amino, mercapto, cyano, methyl, halo, trihalomethyl and/or
methoxy.
[0240] The synonymous terms `organic substituent` and "organic
group" as used herein (also abbreviated herein to "organo") denote
any univalent or multivalent moiety (optionally attached to one or
more other moieties) which comprises one or more carbon atoms and
optionally one or more other heteroatoms. Organic groups may
comprise organoheteryl groups (also known as organoelement groups)
which comprise univalent groups containing carbon, which are thus
organic, but which have their free valence at an atom other than
carbon (for example organothio groups). Organic groups may
alternatively or additionally comprise organyl groups which
comprise any organic substituent group, regardless of functional
type, having one free valence at a carbon atom. Organic groups may
also comprise heterocyclyl groups which comprise univalent groups
formed by removing a hydrogen atom from any ring atom of a
heterocyclic compound: (a cyclic compound having as ring members
atoms of at least two different elements, in this case one being
carbon). Preferably the non carbon atoms in an organic group may be
selected from: hydrogen, halo, phosphorus, nitrogen, oxygen,
silicon and/or sulphur, more preferably from hydrogen, nitrogen,
oxygen, phosphorus and/or sulphur.
[0241] Most preferred organic groups comprise one or more of the
following carbon containing moieties: alkyl, alkoxy, alkanoyl,
carboxy, carbonyl, formyl and/or combinations thereof; optionally
in combination with one or more of the following heteroatom
containing moieties: oxy, thio, sulphinyl, sulphonyl, amino, imino,
nitrilo and/or combinations thereof. Organic groups include all
chemically possible combinations in the same moiety of a plurality
(preferably two) of the aforementioned carbon containing and/or
heteroatom moieties (e.g. alkoxy and carbonyl if directly attached
to each other represent an alkoxycarbonyl group).
[0242] The term `hydrocarbo group` as used herein is a sub-set of a
organic group and denotes any univalent or multivalent moiety
(optionally attached to one or more other moieties) which consists
of one or more hydrogen atoms and one or more carbon atoms and may
comprise one or more saturated, unsaturated and/or aromatic
moieties. Hydrocarbo groups may comprise one or more of the
following groups. Hydrocarbyl groups comprise univalent groups
formed by removing a hydrogen atom from a hydrocarbon (for example
alkyl). Hydrocarbylene groups comprise divalent groups formed by
removing two hydrogen atoms from a hydrocarbon, the free valences
of which are not engaged in a double bond (for example alkylene).
Hydrocarbylidene groups comprise divalent groups (which may be
represented by "R.sub.2C.dbd.") formed by removing two hydrogen
atoms from the same carbon atom of a hydrocarbon, the free valences
of which are engaged in a double bond (for example alkylidene).
Hydrocarbylidyne groups comprise trivalent groups (which may be
represented by "RC.ident."), formed by removing three hydrogen
atoms from the same carbon atom of a hydrocarbon the free valences
of which are engaged in a triple bond (for example alkylidyne).
Hydrocarbo groups may also comprise saturated carbon to carbon
single bonds (e.g. in alkyl groups); unsaturated double and/or
triple carbon to carbon bonds (e.g. in respectively alkenyl and
alkynyl groups); aromatic groups (e.g. in aryl groups) and/or
combinations thereof within the same moiety and where indicated may
be substituted with other functional groups
[0243] The term `alkyl` or its equivalent (e.g. `alk`) as used
herein may be readily replaced, where appropriate and unless the
context clearly indicates otherwise, by terms encompassing any
other hydrocarbo group such as those described herein (e.g.
comprising double bonds, triple bonds, aromatic moieties (such as
respectively alkenyl, alkynyl and/or aryl) and/or combinations
thereof (e.g. aralkyl) as well as any multivalent hydrocarbo
species linking two or more moieties (such as bivalent
hydrocarbylene radicals e.g. alkylene).
[0244] Any radical group or moiety mentioned herein (e.g. as a
substituent) may be a multivalent or a monovalent radical unless
otherwise stated or the context clearly indicates otherwise (e.g. a
bivalent hydrocarbylene moiety linking two other moieties). However
where indicated herein such monovalent or multivalent groups may
still also comprise optional substituents. A group which comprises
a chain of three or more atoms signifies a group in which the chain
wholly or in part may be linear, branched and/or form a ring
(including spiro and/or fused rings). The total number of certain
atoms is specified for certain substituents for example
C.sub.1-Norgano, signifies a organo moiety comprising from 1 to N
carbon atoms. In any of the formulae herein if one or more
substituents are not indicated as attached to any particular atom
in a moiety (e.g. on a particular position along a chain and/or
ring) the substituent may replace any H and/or may be located at
any available position on the moiety which is chemically suitable
and/or effective.
[0245] Preferably any of the organo groups listed herein comprise
from 1 to 36 carbon atoms, more preferably from 1 to 18. It is
particularly preferred that the number of carbon atoms in an organo
group is from 1 to 12, especially from 1 to 10 inclusive, for
example from 1 to 4 carbon atoms.
[0246] As used herein chemical terms (other than IUAPC names for
specifically identified compounds) which comprise features which
are given in parentheses--such as (alkyl)acrylate, (meth)acrylate
and/or (co)polymer--denote that that part in parentheses is
optional as the context dictates, so for example the term
(meth)acrylate denotes both methacrylate and acrylate.
[0247] Certain moieties, species, groups, repeat units, compounds,
oligomers, polymers, materials, mixtures, compositions and/or
formulations which comprise and/or are used in some or all of the
invention as described herein may exist as one or more different
forms such as any of those in the following non exhaustive list:
stereoisomers (such as enantiomers (e.g. E and/or Z forms),
diastereoisomers and/or geometric isomers); tautomers (e.g. keto
and/or enol forms), conformers, salts, zwitterions, complexes (such
as chelates, clathrates, crown compounds, cyptands/cryptades,
inclusion compounds, intercalation compounds, interstitial
compounds, ligand complexes, organometallic complexes,
non-stoichiometric complexes, .pi.-adducts, solvates and/or
hydrates); isotopically substituted forms, polymeric configurations
[such as homo or copolymers, random, graft, comb and/or block
polymers, linear and/or branched polymers (e.g. hyperbranched, star
and/or side branched), cross-linked and/or networked polymers,
polymers obtainable from di and/or tri-valent repeat units,
dendrimers, polymers of different tacticity (e.g. isotactic,
syndiotactic or atactic polymers)]; polymorphs (such as
interstitial forms, crystalline forms and/or amorphous forms),
different phases, solid solutions; and/or combinations thereof
and/or mixtures thereof where possible. The present invention
comprises and/or uses all such forms which are effective as defined
herein.
[0248] Polymers of the present invention may be prepared by one or
more suitable polymer precursor(s) which may be organic and/or
inorganic and comprise any suitable (co)monomer(s), (co)polymer(s)
[including homopolymer(s)] and mixtures thereof which comprise
moieties which are capable of forming a bond with the or each
polymer precursor(s) to provide chain extension and/or
cross-linking with another of the or each polymer precursor(s) via
direct bond(s) as indicated herein.
[0249] Polymer precursors of the invention may comprise one or more
monomer(s), oligomer(s), polymer(s); mixtures thereof and/or
combinations thereof which have suitable polymerisable
functionality. It will be understood that unless the context
dictates otherwise term monomer as used herein encompasses the term
polymer precursor and does not necessarily exclude monomers that
may themselves be polymeric and/or oligomeric in character.
[0250] A monomer is a substantially monodisperse compound of a low
molecular weight (for example less than one thousand daltons) which
is capable of being polymerised.
[0251] A polymer is a polydisperse mixture of macromolecules of
large molecular weight (for example many thousands of daltons)
prepared by a polymerisation method, where the macromolecules
comprises the multiple repetition of smaller units (which may
themselves be monomers, oligomers and/or polymers) and where
(unless properties are critically dependent on fine details of the
molecular structure) the addition or removal one or a few of the
units has a negligible effect on the properties of the
macromolecule.
[0252] A oligomer is a polydisperse mixture of molecules having an
intermediate molecular weight between a monomer and polymer, the
molecules comprising a small plurality of monomer units the removal
of one or a few of which would significantly vary the properties of
the molecule.
[0253] Depending on the context the term polymer may or may not
encompass oligomer.
[0254] The polymer precursor of and/or used in the invention may be
prepared by direct synthesis or (if the polymeric precursor is
itself polymeric) by polymerisation. If a polymerisable polymer is
itself used as a polymer precursor of and/or used in the invention
it is preferred that such a polymer precursor has a low
polydispersity, more preferably is substantially monodisperse, to
minimise the side reactions, number of by-products and/or
polydispersity in any polymeric material formed from this polymer
precursor. The polymer precursor(s) may be substantially
un-reactive at normal temperatures and pressures.
[0255] Except where indicated herein polymers and/or polymeric
polymer precursors of and/or used in the invention can be
(co)polymerised by any suitable means of polymerisation well known
to those skilled in the art. Examples of suitable methods comprise:
thermal initiation; chemical initiation by adding suitable agents;
catalysis; and/or initiation using an optional initiator followed
by irradiation, for example with electromagnetic radiation
(photo-chemical initiation) at a suitable wavelength such as UV;
and/or with other types of radiation such as electron beams, alpha
particles, neutrons and/or other particles.
[0256] The substituents on the repeating unit of a polymer and/or
oligomer may be selected to improve the compatibility of the
materials with the polymers and/or resins in which they may be
formulated and/or incorporated for the uses described herein. Thus
the size and length of the substituents may be selected to optimise
the physical entanglement or interlocation with the resin or they
may or may not comprise other reactive entities capable of
chemically reacting and/or cross linking with such other resins as
appropriate.
[0257] Another aspect of the invention broadly provides a coating
composition comprising the polymers and/or beads of the present
invention and/or as described herein.
[0258] A further aspect of the invention provides a coating
obtained or obtainable from a coating composition of the present
invention.
[0259] A yet other aspect of the invention broadly provides a
substrate and/or article having coated thereon an (optionally
cured) coating composition of the present invention.
[0260] A yet further aspect of the invention broadly provides a
method of using polymers of the present invention and/or as
described herein to prepare a coating composition.
[0261] A still further aspect of the invention broadly provides a
method for preparing a coated substrate and/or article comprising
the steps of applying a coating composition of the present
invention to the substrate and/or article and optionally curing
said composition in situ to form a cured coating thereon. The
curing may be by any suitable means, such as thermally, by
radiation and/or by use of a cross-linker.
[0262] Preferred coating compositions are solvent coating
compositions or aqueous coating compositions, more preferably are
aqueous coating compositions.
[0263] Optionally aqueous coating compositions may also comprise a
co-solvent. A co-solvent, as is well known in the coating art, is
an organic solvent employed in an aqueous composition to ameliorate
the drying characteristics thereof, and in particular to lower its
minimum film forming temperature. The co-solvent may be solvent
incorporated or used during preparation of polymers of the
invention or may have been added during formulation of the aqueous
composition.
[0264] The compositions of the invention are particularly useful as
or for providing the principle component of coating formulations
(i.e. composition intended for application to a substrate without
further treatment or additions thereto) such as protective or
decorative coating compositions (for example paint, lacquer or
varnish) wherein an initially prepared composition optionally may
be further diluted with water and/or organic solvents, and/or
combined with further ingredients or may be in more concentrated
form by optional evaporation of water and/or organic components of
the liquid medium of an initially prepared composition.
[0265] The compositions of the invention may be used in various
applications and for such purposes may be optionally further
combined or formulated with other additives and/or components, such
as defoamers, rheology control agents, thickeners, dispersing
and/or stabilizing agents (usually surfactants and/or emulsifiers),
wetting agents, fillers, extenders, fungicides, bacteriocides,
coalescing and wetting solvents or co-solvents (although solvents
are not normally required), plasticisers, anti-freeze agents,
waxes, colorants, pigments, dyes, heat stabilisers, levelling
agents, anti-cratering agents, fillers, sedimentation inhibitors,
UV absorbers, antioxidants, reactive diluents, neutralising agents,
adhesion promoters and/or any suitable mixtures thereof.
[0266] The aforementioned additives and/or components and the like
may be introduced at any stage of the production process or
subsequently. It is possible to include fire retardants (such as
antimony oxide) to enhance fire retardant properties.
[0267] The compositions of the invention may also be blended with
other polymers such as vinyl polymers, alkyds (saturated or
unsaturated), polyesters and or polyurethanes.
[0268] The coating composition of the invention may be applied to a
variety of substrates including wood, board, metals, stone,
concrete, glass, cloth, leather, paper, plastics, foam and the
like, by any conventional method including brushing, dipping, flow
coating, spraying, and the like. The coating composition of the
invention may also be used to coat the interior and/or exterior
surfaces of three-dimensional articles. The coating compositions of
the invention may also be used, appropriately formulated if
necessary, for the provision of films, polishes, varnishes,
lacquers, paints, inks and adhesives. However, they are
particularly useful and suitable for providing the basis of
protective coatings for substrates that comprise wood (e.g. wooden
floors), plastics, polymeric materials, paper and/or metal.
[0269] The carrier medium may be removed from the compositions of
the invention once they have been applied to a substrate by being
allowed to dry naturally at ambient temperature, or the drying
process may be accelerated by heat. Crosslinking can be developed
by allowing to stand for a prolonged period at ambient temperature
(several days) or by heating at an elevated temperature (e.g.
50.degree. C.) for a much shorter period of time.
[0270] Many other variations embodiments of the invention will be
apparent to those skilled in the art and such variations are
contemplated within the broad scope of the present invention.
[0271] Further aspects of the invention and preferred features
thereof are given in the claims herein.
Tests
Minimum Film Forming Temperature
[0272] The minimum film forming temperature (MFFT) of a dispersion
as used herein is the temperature where the dispersion forms a
smooth and crack free coating or film using DIN 53787 and when
applied using a Sheen MFFT bar SS3000.
Spot Tests
[0273] Coating films formed by blends of the invention can be
tested in well known conventional spot tests (such as ASTM
D1308-02e1) to determine the resistance of the film to various
liquid reagents such as water, ethanol, detergent (e.g. that
available commercially from Unilever under the trade mark Andy) and
coffee. In one such test a standard volume (e.g. 0.5 ml) of the
liquid reagent may be applied to the film to form a spot thereon
(e.g. by pipette) which is then covered with a watch glass. After
the time specified (e.g. in the tables herein) the film can be
assessed and rated visually on a scale of 1 to 5 as described
below.
Koening Hardness
[0274] Koening hardness as used herein is a standard measure of
hardness, being a determination of how the viscoelastic properties
of a film formed from the dispersion slows down a swinging motion
deforming the surface of the film, and is measured according to DIN
53157 NEN5319.
Glass Transition Temperature (Tg)
[0275] As is well known, the glass transition temperature of a
polymer is the temperature at which it changes from a glassy,
brittle state to a plastic, rubbery state. The glass transition
temperatures may be determined experimentally using Differential
Scanning calorimetry (DSC), taking the peak of the derivative curve
as Tg, or calculated from the Fox equation. Thus the Tg, in degrees
Kelvin, of a copolymer having "n" copolymerised comonomers is given
by the weight fractions W of each comonomer type and the Tgs of the
homopolymers (in degrees Kelvin) derived from each comonomer
according to the equation:
1 Tg = W 1 Tg 1 + W 2 Tg 2 + W n Tg n ##EQU00001##
[0276] The calculated Tg in degrees Kelvin may be readily converted
to .degree. C.
Solids Content
[0277] The solids content of an aqueous dispersion of the invention
is usually within the range of from about 20 to 65 wt-% on a total
weight basis, more usually 30 to 55 wt-%. Solids content can, if
desired, be adjusted by adding water or removing water (e.g. by
distillation or ultrafiltration).
pH Value
[0278] The pH value of the dispersion of the invention can be from
2 to 10 and mostly is from 6 to 9.5.
Blocking
Block Resistance Measurement [Includes Blocking and Early
Blocking]:
Step 1: Blocking:
[0279] A 100 micron wet film of the aqueous emulsion of the
invention to which 10% butyldiglycol is added is cast on to a paper
substrate and dried for 16 hours at 52.degree. C.
Step 1: Early Blocking:
[0280] A 250 micron wet film of the aqueous emulsion of the
invention to which 10% butyldiglycol was added, is cast on to a
paper substrate and dried for 24 hours at room temperature.
Step 2: Blocking and Early Blocking:
[0281] After cooling down to room temperature two pieces of coated
film are placed with the coated side against each other under a
load of 1 Kg/cm.sup.2 for 4 hours at 52.degree. C. After this time
interval the load on the samples is removed and the samples are
left to cool down to room temperature (22+-2.degree. C.). When the
two coatings can be removed from each other without any damage to
the film (do not stick) the block resistance is very good and
assessed as a 5. When they however completely stick together, block
resistance is very bad and assessed as a 0.
Gas Chromatography Mass Spectrometry (GCMS)
[0282] to confirm polymerisation is substantially complete the
content of free itaconate ester monomers content can be determined
by GCMS. The GCMS analyses were performed on a Trace GC-DSQ MS
(Interscience, Breda, the Netherlands) equipped with a CTC combi
Pal robotic autosampler for head space has been used. The carrier
gas was Helium and a CP Sil 5 low bleed/MS, 25 m.times.0.25 mm
i.d., 1.0 .mu.m (CP nr. 7862) column has been used.
[0283] The GC-oven was programmed from 50.degree. C. (5 min)
followed by different sequential temperature ramps of 5.degree.
C./min to 70.degree. C. (0 min), 15.degree. C./min to 220.degree.
C. (0 min), and ending with 25.degree. C./min to 280.degree. C. (10
min). A continuous Helium flow of 1.2 ml/min was used. A hot split
injection at 300.degree. C. was performed on a programmed
temperature vaporizer (PTV). The injection volume was 1 .mu.l. The
MS transfer line and ion source were both kept at 250.degree. C.
The samples were measured with single ion monitoring (SIM). For the
specific case of dibutyl itaconate (DBI) the masses 127.0 and 59.0
Da were used, for the internal standard (iso butyl acrylate) the
masses 55.0 and 73.0 were applied. The sample solutions were
approximately 500 mg in 3 ml of internal standard solution (iso
butyl acrylate in acetone). The calibration was performed with 5
different concentration levels from 0 to 500 ppm. The calculation
was performed using Microsoft Excel with a linear calibration
curve.
Molecular Weight
[0284] Unless the context clearly dictates otherwise the term
molecular weight of a polymer or oligomer as used herein denotes
weight average molecular weight (also denoted as M.sub.w). M.sub.w
may be measured by any suitable conventional method for example by
Gas Phase Chromatography (GPC--performed similarly to the GCMS
method described above) and/or by the SEC method described below.
GPC method is preferred
Determination of Molecular Weight of a Polymer Using SEC
[0285] The molecular weight of a polymer may also be determined
using Size Exclusion Chromatography (SEC) with tetrahydrofuran as
the eluent or with 1,1,1,3,3,3 hexafluoro isopropanol as the
eluent.
1) Tetrahydrofuran
[0286] The SEC analyses were performed on an Alliance Separation
Module (Waters 2690), including a pump, auto injector, degasser,
and column oven. The eluent was tetrahydrofuran (THF) with the
addition of 1.0 vol % acetic acid. The injection volume was 150
.mu.l. The flow was established at 1.0 ml/min. Three PL MixedB
(Polymer Laboratories) with a guard column (3 .mu.m PL) were
applied at a temperature of 40.degree. C. The detection was
performed with a differential refractive index detector (Waters
410). The sample solutions were prepared with a concentration of 20
mg solids in 8 ml THF (+1 vol % acetic acid), and the samples were
dissolved for a period of 24 hours. Calibration is performed with
eight polystyrene standards (polymer standard services), ranging
from 500 to 4,000,000 g/mol. The calculation was performed with
Millennium 32 software (Waters) with a third order calibration
curve. The obtained molar masses are polystyrene equivalent molar
masses (g/mol).
2) 1,1,1,3,3,3 Hexafluoro Isopropanol
[0287] The SEC analyses were performed on a Waters Alliance 2695
(pump, degasser and autosampler) with a Shodex RI-101 differential
refractive index detector and Shimadzu CTO-20AC column oven. The
eluent was 1,1,1,3,3,3 hexafluoro isopropanol (HFIP) with the
addition of 0.2M potassium trifluoro acetate (KTFA). The injection
volume was 50 .mu.l. The flow was established at 0.8 ml/min. Two
PSS PFG Linear XL columns (Polymer Standards Service) with a guard
column (PFG PSS) were applied at a temperature of 40.degree. C. The
detection was performed with a differential refractive index
detector. The sample solutions were prepared with a concentration
of 5 mg solids in 2 ml HFIP (+0.2M KTFA), and the samples were
dissolved for a period of 24 hours. Calibration is performed with
eleven polymethyl methacrylate standards (polymer standard
services), ranging from 500 to 2,000,000 g/mol. The calculation was
performed with Empower Pro software (Waters) with a third order
calibration curve. The molar mass distribution is obtained via
conventional calibration and the molar masses are polymethyl
methacrylate equivalent molar masses (g/mol).
Standard Conditions
[0288] As used herein, unless the context indicates otherwise,
standard conditions (e.g. for drying a film) means a relative
humidity of 50%.+-.5%, ambient temperature (which denotes herein a
temperature of 23.degree. C..+-.2.degree.) and an air flow of
.ltoreq. (less than or equal to) 0.1 m/s.
[0289] The following examples are provided to further illustrate
the processes and compositions of the present invention. These
examples are illustrative only and are not intended to limit the
scope of the invention in any way. Unless otherwise specified all
parts, percentages, and ratios are on a weight basis. The prefix C
before an example indicates that it is comparative.
[0290] Various registered trademarks, other designations and/or
abbreviations are used herein to denote some of ingredients used to
prepare polymers and compositions of the invention. These are
identified below by chemical name and/or trade-name and optionally
their manufacturer or supplier from whom they are available
commercially. However where a chemical name and/or supplier of a
material described herein is not given it may easily be found for
example in reference literature well known to those skilled in the
art: such as: `McCutcheon's Emulsifiers and Detergents`, Rock Road,
Glen Rock, N.J. 07452-1700, USA, 1997 and/or Hawley's Condensed
Chemical Dictionary (14th Edition) by Lewis, Richard J., Sr.; John
Wiley & Sons.
[0291] In the examples the following abbreviations/monomers may be
used:
BA=n-butyl acrylate (may be biorenewable) BMA=n-butyl methacrylate
(may be prepared using bio-renewable alkanols) DBI denotes
di(n-butyl) itaconate (also known as dibutyl
2-methylidenebutanedioate) (may be bio-renewable) DDM denotes
n-dodecyl mercaptane DMI=dimethyl itaconate (may be bio-renewable)
DMW denotes dematerialized water EDTA=ethylene diamine tetraacetic
acid HFIP denotes hexafluoro isopropanol KTFA denotes potassium
trifluoro actetate MMA=methyl methacrylate (may be prepared using
bio-renewable alkanols) MAA=methacrylic acid (may be biorenewable)
NS denotes sodium sulfate PAA denotes polyacrylic acid STY denotes
styrene; D(iB)I denotes di(iso-butyl) itaconate (also known as
di(tert-butyl)itaconate) DPI denotes di(pentyl) itaconate DHI
denotes di(hexyl) itaconate DHpI denotes di(heptyl) itaconate DOI
denotes di(n-octyl) itaconate D(EH)I denotes di(2-ethylhexyl)
itaconate DDI denotes di(decyl) itaconate DBzI denotes di(benzyl)
itaconate DPhI denotes di(phenyl) itaconate BPI denotes butyl
pentyl itaconate BHI denotes butyl hexyl itaconate HOI denotes
hexyl n-octyl itaconate IA denotes itaconic acid MSA denotes the
sulphonic acid of .alpha.-methyl styrene DPrI denotes di(propyl)
itaconate CEA denotes beta carboxy ethyl acrylate PA denotes propyl
acrylate OA denotes n-ocyl acrylate MBI denotes the mono acid butyl
itaconate (i.e. half ester) IAn denotes itaconic anhydride MMalA
denotes methylene malonic acid, MalAn denotes maleic anhydride, i
PHEMA denotes phosphated hydroxylethyl methacrylate AMPS denotes
2-acrylamido-2-methylpropane sulfonic acid URED denotes the monomer
N-[2-(2-Oxo-1-imidazolidinyl)ethyl]methacrylate MSTY denotes alpha
methyl styrene.
EXAMPLES 1 TO 3
Sequential Vinyl Polymers
Example 1
[0292] To a round-bottomed flask equipped with a condenser,
thermometer and mechanical stirrer 84.853 parts of water, 0.253
parts of sodium bicarbonate, and 1.786 parts of a 30 wt-% solution
of sodium lauryl sulphate in water are added and this mixture is
heated to 50.degree. C. At 50.degree. C., 10% of a first monomer
feed consisting of 20.93 parts of water, 4.285 of a 30 wt-%
solution of sodium lauryl sulphate in water, 0.726 parts of sodium
bicarbonate, 0.246 parts of ammonium persulphate, 1.340 parts of
methacrylic acid, 26.811 parts of dibutyl itaconate, and 25.456
parts of methyl methacrylate is added and the reactor contents are
heated to 90.degree. C. After the reaction temperature has been
reached, the reactor contents are stirred for 15 minutes.
[0293] Next, the remainder of the first monomer feed is added over
a period of 210 minutes. When the feed is completed, the feed tank
is rinsed with 1.885 parts of water.
[0294] The batch is kept at 90.degree. C. for 30 minutes and cooled
the batch to 70.degree. C. Next, a slurry comprising 0.289 parts of
a 70 wt-% solution of t-butyl hydroperoxide in water and 1.228
parts of water is added and the batch is stirred for 5 minutes.
Next, a second monomer feed, comprising 2.681 parts of methacrylic
acid, 4.932 parts of methyl methacrylate, 15.117 parts of butyl
acrylate, and 30.877 parts of butyl methacrylate is added over a
period of 240 minutes. Simultaneously, a catalyst feed comprising
11.943 parts of water, 0.120 parts of i-ascorbic acid, and 1.071
parts of a 30 wt-% solution of sodium lauryl sulphate, is fed over
the same period. After the second monomer feed is finished, the
feed tank is rinsed with 1.885 parts of water.
[0295] The reactor contents are stirred at 70.degree. C. for
another 30 minutes, after which the batch is cooled to 30.degree.
C. The pH of the emulsion is adjusted to 7 using 0.6 parts of a 25%
solution of ammonia in water or part of it. Simultaneously, 0.623
parts of water are added. The solids content of the emulsion is
adjusted to 45% using water.
[0296] The resulting emulsion has a solids content of 45%, and a pH
of 7.0.
Example 2
[0297] To a round-bottomed flask equipped with a condenser,
thermometer and mechanical stirrer 84.853 parts of water, 0.253
parts of sodium bicarbonate, and 1.786 parts of a 30 wt-% solution
of sodium lauryl sulphate in water are added and this mixture is
heated to 50.degree. C. At 50.degree. C., 10% of a first monomer
feed consisting of 20.93 parts of water, 4.285 of a 30 wt-%
solution of sodium lauryl sulphate in water, 0.726 parts of sodium
bicarbonate, 0.246 parts of ammonium persulphate, 1.340 parts of
methacrylic acid, 14.044 parts of butyl methacrylate, 24.123 parts
of dimethyl itaconate, and 14.100 parts of methyl methacrylate is
added and the reactor contents are heated to 90.degree. C. After
the reaction temperature has been reached, the reactor contents are
stirred for 15 minutes.
[0298] Next, the remainder of the first monomer feed is added over
a period of 210 minutes. When the feed is completed, the feed tank
is rinsed with 1.885 parts of water.
[0299] The batch is kept at 90.degree. C. for 30 minutes and cooled
the batch to 70.degree. C. Next, a slurry comprising 0.289 parts of
a 70 wt-% solution of t-butyl hydroperoxide in water and 1.228
parts of water is added and the batch is stirred for 5 minutes.
Next, a second monomer feed, comprising 2.681 parts of methacrylic
acid, 4.932 parts of methyl methacrylate, 15.117 parts of butyl
acrylate, 18.762 parts of dibutyl itaconate, and 12.115 parts of
butyl methacrylate is added over a period of 240 minutes.
Simultaneously, a catalyst feed comprising 11.943 parts of water,
0.120 parts of i-ascorbic acid, and 1.071 parts of a 30 wt-%
solution of sodium lauryl sulphate, is fed over the same period.
After the second monomer feed is finished, the feed tank is rinsed
with 1.885 parts of water.
[0300] The reactor contents are stirred at 70.degree. C. for
another 30 minutes, after which the batch is cooled to 30.degree.
C. The pH of the emulsion is adjusted to 7 using 0.6 parts of a 25%
solution of ammonia in water or part of it. Simultaneously, 0.623
parts of water are added. The solids content of the emulsion is
adjusted to 45% using water.
[0301] The resulting emulsion has a solids content of 45%, and a pH
of 7.0.
Example 3
[0302] To a round-bottomed flask equipped with a condenser,
thermometer and mechanical stirrer 84.853 parts of water, 0.253
parts of sodium bicarbonate, and 1.786 parts of a 30 wt-% solution
of sodium lauryl sulphate in water are added and this mixture is
heated to 50.degree. C. At 50.degree. C., 10% of a first monomer
feed consisting of 20.93 parts of water, 4.285 of a 30 wt-%
solution of sodium lauryl sulphate in water, 0.726 parts of sodium
bicarbonate, 0.246 parts of ammonium persulphate, 1.340 parts of
methacrylic acid, 14.044 parts of butyl methacrylate, and 38.223
parts of methyl methacrylate is added and the reactor contents are
heated to 90.degree. C. After the reaction temperature has been
reached, the reactor contents are stirred for 15 minutes.
[0303] Next, the remainder of the first monomer feed is added over
a period of 210 minutes. When the feed is completed, the feed tank
is rinsed with 1.885 parts of water.
[0304] The batch is kept at 90.degree. C. for 30 minutes and cooled
the batch to 70.degree. C. Next, a slurry comprising 0.289 parts of
a 70 wt-% solution of t-butyl hydroperoxide in water and 1.228
parts of water is added and the batch is stirred for 5 minutes.
Next, a second monomer feed, comprising 2.681 parts of methacrylic
acid, 4.932 parts of methyl methacrylate, 2.673 parts of diacetone
acrylamide, 12.444 parts of butyl acrylate, 26.803 parts of dibutyl
itaconate, and 4.074 parts of butyl methacrylate is added over a
period of 240 minutes. Simultaneously, a catalyst feed comprising
11.943 parts of water, 0.120 parts of i-ascorbic acid, and 1.071
parts of a 30 wt-% solution of sodium lauryl sulphate, is fed over
the same period. After the second monomer feed is finished, the
feed tank is rinsed with 1.885 parts of water.
[0305] The reactor contents are stirred at 70.degree. C. for
another 30 minutes, after which the batch is cooled to 30.degree.
C. The pH of the emulsion is adjusted to 7 using 0.6 parts of a 25%
solution of ammonia in water or part of it. Simultaneously, 0.623
parts of water are added. The solids content of the emulsion is
adjusted to 45% using water.
[0306] The resulting emulsion has a solids content of 45%, and a pH
of 7.0.
FURTHER EXAMPLES
Examples 4 to 13
[0307] Further examples for the various embodiments can be prepared
according the Common method E below and with reference to the Table
1 below. The percentages in the tables are mostly quoted to the
nearest percentage and/or to 2 significant figures and thus may not
total 100% due to rounding errors.
Common Method E (for Sequential Vinyl Polymers)
[0308] The total weight of monomer used in Examples below can be
the same as the total amount used to prepare Example 1 and so for
convenience the amount of monomers used in these examples can be
expressed as a weight percent of the total monomers used in both
the first and second monomer feeds. The first monomer feed (used to
prepare the low Tg part of the polymer) consists of the same
ingredients described in Example 1 (or with consequent
modification), other than the monomers which can be:z1% of Monomer
Z1, y1% of Monomer Y1, x1% of Monomer X1 and/or w1% of Monomer W1.
To the equipment described in Example 1 and the pre-feed described
therein the same initial amount of the first monomer feed can be
added under the conditions described therein and then the remainder
of the first monomer feed can be added and the reaction continued
as described in Example 1 (or with consequent modification) until
the second monomer feed can be added. The second monomer feed (used
to prepare the high Tg part of the polymer) consists of the same
ingredients described in Example 1 (or with consequent
modification), other than the monomers which can be:z2% of Monomer
Z2, y2% of Monomer Y2, x2% of Monomer X2 and/or w2% of Monomer
W2.
[0309] The rest of the process can be followed as described in
Example 1 (or with consequent modification) with reference to Table
1 to obtain vinyl sequential polymers analogous to that described
in Example 1. The relative weight ratio (R) of the respective total
amount of low Tg polymer A to the total amount of high Tg polymer B
is also given in Table 2 and if necessary the method described in
Example 1 can be modified according by adjusting the weight of the
total amount of monomers used to prepare polymer B relative to the
weight of the total amount of monomers used to prepare polymer
A.
[0310] The total amount of monomer of Formula 1 (as a percentage T
of the total amount of monomers A+B is also given in Table 1)
TABLE-US-00002 TABLE 1 Examples 4 to 13 - sequential polymers (see
method E) T % Low Tg polymer A (% of A) High Tg polymer B (% of B)
R (of Ex z1% Z1 y1% Y1 x1% X1 W1% W1 z2% Z2 y2 % Y2 x2% X2 w2% W2
(A to B) A + B) 4 10 MAA 40 MMA 50 DPI -- -- 5 MAA 10 MMA 30 DMI 55
BMA 40/60 20 5 0.1 AA 39.9 MA 60 DHI -- -- 10 MAA 10 MMA 20 DEI 60
BMA 45/55 27 6 0.5 MSA 20 EA 65 DOI 14.5 BA 15 MA 5 EMA 50 DPrI 30
OA 50/50 23.5 7 1 CEA 36 PA 30 DBI 33 MA 60 DBzI 30 BA 10 DEI -- --
55/45 43.5 8 2 MBI 80 MMA 18 EMA -- -- 85 DPhI 10 EMA 5 DMI -- --
60/40 34 9 4 IA 22 BA 74 DBI -- -- 90 DHI 10 URED -- -- -- -- 65/35
79.6 10 6 IAn 20 MMA 64 DBI 10 EA 5 MAA 10 BA 65 DMI 20 BA 70/30
44.8 11 7.5 MMaIA 40 EMA 52.5 BPI -- -- 10 AA 40 EHA 10 DEI 40 BMA
75/25 39.4 12 8 PHEMA 30 MMA 42 BHI 20 EA 1 MMA 49 OA 50 DMI 80/20
33.6 13 3 AMPS 35 PA 62 HOI -- -- 2 MSA 30 DBI 30 DEI 38 EA 90/10
58.8
Examples 14 to 18 and Comparative Examples Comp I to V
Example 14
DBI Polymer Containing Wet-Adhesion Promoting Monomer
[0311] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 559.2 parts of
demineralized water, 5.5 parts of sodium bicarbonate, 29.4 parts of
a 30 wt-% solution of sodium lauryl sulphate in water, and 1.1
parts of sodium persulphate. The reactor contents were heated to
70.degree. C. At 50.degree. C., 10% of a monomer feed consisting of
510.3 parts of demineralized water, 12.5 parts of a 30 wt-%
solution of sodium lauryl sulphate in water, 516.7 parts of butyl
acrylate, 33.0 parts of methacrylic acid, 494.7 parts of dibutyl
itaconate, and 110.0 parts of a 50 wt-% solution of
N-(2-methacryloyloxyethyl)ethylene urea in water (Plex 6852-0, ex.
Evonik), was added. Due to the exothermic nature of the
polymerizing monomers, the temperature increased to 85.degree. C.
(if the exotherm would be insufficient the mixture could be heated
slightly to reach a temperature of 85.degree. C.). At 85.degree.
C., the monomer feed, comprising the remaining 90% of the original
feed, and the initiator feed, consisting of 124.5 parts of
demineralized water, 4.4 parts of sodium persulphate, and 2.2 parts
of a 30 wt-% solution of sodium lauryl sulphate in water, were
started. Both feeds were added over a period of 120 minutes. At the
end of the monomer feed, the feed tank was rinsed with 19.7 parts
of demineralized water and the mixture was stirred at 85.degree. C.
for another 35 minutes.
[0312] Next, the emulsion was cooled to 45.degree. C., and a
solution of 0.7 parts of iso-ascorbic acid in 12.5 parts of
demineralized water was added, followed by 1.0 part of a 70 wt-%
solution of t-butyl hydroperoxide in water, 1.5 parts of
demineralized water, and 0.3 parts of a 30 wt-% solution of sodium
lauryl sulphate in water. The entire reactor contents were stirred
for 30 minutes at 45.degree. C.
[0313] The emulsion was cooled to room temperature, and 55.0 parts
of an equal mixture of a 25% solution of ammonia in water and
demineralized water were added. The solids content of the emulsion
was adjusted to 45% using demineralized water.
Example 15
DBI and Styrene Containing Polymer
[0314] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 644.0 parts of
demineralized water, 0.5 parts of sodium bicarbonate, 13.3 parts of
a 30 wt-% solution of sodium lauryl sulphate in water, and 0.8
parts of sodium persulphate. The reactor contents were heated to
80.degree. C. and stirred for 5 minutes at 80.degree. C. Next, 10%
of a monomer feed, consisting of 132.9 parts of demineralized
water, 13.0 parts of a 30 wt-% solution of sodium lauryl sulphate
in water, 23.3 parts of methacrylic acid, 280.1 parts of dibutyl
itaconate, and 280.1 parts of styrene, was added, after the
temperature rose to approximately 90.degree. C. due to the
exothermic nature of the polymerization. As soon as the temperature
of 90.degree. C. was reached, the remaining monomer feed and the
initiator feed, consisting of 58.7 parts of demineralized water,
2.5 parts of sodium persulphate, and 3.7 parts of a 30 wt-%
solution of sodium lauryl sulphate in water, were started. Both
feeds were added over a period of 2 hours. At the end of the
monomer feed the feed tank was rinsed with 10.4 parts of
demineralized water. The temperature of the reactor contents were
cooled to 80.degree. C., after which a solution of 1.8 parts of
iso-ascorbic acid dissolved in 26.5 parts of demineralized water
(which was brought to a pH of 8.5 using an ammonia solution) was
fed over a period of 30 minutes, during which a mixture of 2.8
parts of t-butyl hydroperoxide and 5.6 parts of demineralized water
was added in two shots; one at the start of the iso-ascorbic acid
feed and 15 minutes later.
[0315] At the end of the feed, the mixture was stirred at
80.degree. C. for 30 minutes, and the pH was raised to 7.2 using a
25 wt-% solution of ammonia in water. After stirring for another 30
minutes, the batch was cooled to room temperature. The solids
content was adjusted to 40% using demineralized water.
Comparative Example Comp I
BA and Styrene Containing Polymer
[0316] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 639.5 parts of
demineralized water, 0.5 parts of sodium bicarbonate, and 13.3
parts of a 30 wt-% solution of sodium lauryl sulphate in water. The
reactor contents were heated to 80.degree. C., after which a
solution of 0.8 parts of sodium persulphate in 4.5 parts of
demineralized water were added and stirred for 5 minutes at
80.degree. C. Next, 10% of a monomer feed, consisting of 132.9
parts of demineralized water, 13.0 parts of a 30 wt-% solution of
sodium lauryl sulphate in water, 23.3 parts of methacrylic acid,
280.1 parts of butyl acrylate, and 280.1 parts of styrene, was
added, after the temperature rose to approximately 90.degree. C.
due to the exothermic nature of the polymerization. As soon as the
temperature of 90.degree. C. was reached, the remaining monomer
feed and the initiator feed, consisting of 58.7 parts of
demineralized water, 2.5 parts of sodium persulphate, and 3.7 parts
of a 30 wt-% solution of sodium lauryl sulphate in water, were
started. Both feeds were added over a period of 2 hours. At the end
of the monomer feed the feed tank was rinsed with 10.4 parts of
demineralized water. The temperature of the reactor contents were
cooled to 80.degree. C., after which a solution of 1.8 parts of
iso-ascorbic acid dissolved in 26.5 parts of demineralized water
(which was brought to a pH of 8.5 using an ammonia solution) was
fed over a period of 30 minutes, during which a mixture of 2.8
parts of t-butyl hydroperoxide and 5.6 parts of demineralized water
was added in two shots; one at the start of the iso-ascorbic acid
feed and 15 minutes later.
[0317] At the end of the feed, the mixture was stirred at
80.degree. C. for 30 minutes, and the pH was raised to 7.2 using a
25 wt-% solution of ammonia in water. After stirring for another 30
minutes, the batch was cooled to room temperature. The solids
content was adjusted to 40% using demineralized water.
Example 16
DBI and MMA Containing Polymer
[0318] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 639.5 parts of
demineralized water, 0.5 parts of sodium bicarbonate, and 13.3
parts of a 30 wt-% solution of sodium lauryl sulphate in water. The
reactor contents were heated to 80.degree. C., after which a
solution of 0.8 parts of sodium persulphate in 4.5 parts of
demineralized water were added and stirred for 5 minutes at
80.degree. C. Next, 10% of a monomer feed, consisting of 132.9
parts of demineralized water, 13.0 parts of a 30 wt-% solution of
sodium lauryl sulphate in water, 23.3 parts of methacrylic acid,
280.1 parts of dibutyl itaconate, and 280.1 parts of methyl
methacrylate, was added, after the temperature rose to
approximately 90.degree. C. due to the exothermic nature of the
polymerization. As soon as the temperature of 90.degree. C. was
reached, the remaining monomer feed and the initiator feed,
consisting of 58.7 parts of demineralized water, 2.5 parts of
sodium persulphate, and 3.7 parts of a 30 wt-% solution of sodium
lauryl sulphate in water, were started. Both feeds were added over
a period of 2 hours. At the end of the monomer feed the feed tank
was rinsed with 10.4 parts of demineralized water. The temperature
of the reactor contents were cooled to 80.degree. C., after which a
solution of 1.8 parts of iso-ascorbic acid dissolved in 26.5 parts
of demineralized water (which was brought to a pH of 8.5 using an
ammonia solution) was fed over a period of 30 minutes, during which
a mixture of 2.8 parts of t-butyl hydroperoxide and 5.6 parts of
demineralized water was added in two shots; one at the start of the
iso-ascorbic acid feed and 15 minutes later.
[0319] At the end of the feed, the mixture was stirred at
80.degree. C. for 30 minutes, and the pH was raised to 7.2 using a
25 wt-% solution of ammonia in water. After stirring for another 30
minutes, the batch was cooled to room temperature. The solids
content was adjusted to 40% using demineralized water.
Comparative Example Comp II
BA and MMA Containing Polymer
[0320] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 639.5 parts of
demineralized water, 0.5 parts of sodium bicarbonate, and 13.3
parts of a 30 wt-% solution of sodium lauryl sulphate in water. The
reactor contents were heated to 80.degree. C., after which a
solution of 0.8 parts of sodium persulphate in 4.5 parts of
demineralized water were added and stirred for 5 minutes at
80.degree. C. Next, 10% of a monomer feed, consisting of 132.9
parts of demineralized water, 13.0 parts of a 30 wt-% solution of
sodium lauryl sulphate in water, 23.3 parts of methacrylic acid,
280.1 parts of butyl acrylate, and 280.1 parts of methyl
methacrylate, was added, after the temperature rose to
approximately 90.degree. C. due to the exothermic nature of the
polymerization. As soon as the temperature of 90.degree. C. was
reached, the remaining monomer feed and the initiator feed,
consisting of 58.7 parts of demineralized water, 2.5 parts of
sodium persulphate, and 3.7 parts of a 30 wt-% solution of sodium
lauryl sulphate in water, were started. Both feeds were added over
a period of 2 hours. At the end of the monomer feed the feed tank
was rinsed with 10.4 parts of demineralized water. The temperature
of the reactor contents were cooled to 80.degree. C., after which a
solution of 1.8 parts of iso-ascorbic acid dissolved in 26.5 parts
of demineralized water (which was brought to a pH of 8.5 using an
ammonia solution) was fed over a period of 30 minutes, during which
a mixture of 2.8 parts of t-butyl hydroperoxide and 5.6 parts of
demineralized water was added in two shots; one at the start of the
iso-ascorbic acid feed and 15 minutes later.
[0321] At the end of the feed, the mixture was stirred at
80.degree. C. for 30 minutes, and the pH was raised to 7.2 using a
25 wt-% solution of ammonia in water. After stirring for another 30
minutes, the batch was cooled to room temperature. The solids
content was adjusted to 40% using demineralized water.
Comparative Example Comp III
DMI Containing Copolymer
[0322] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 639.5 parts of
demineralized water, 0.5 parts of sodium bicarbonate, and 13.3
parts of a 30 wt-% solution of sodium lauryl sulphate in water. The
reactor contents were heated to 80.degree. C., after which a
solution of 0.8 parts of sodium persulphate in 4.5 parts of
demineralized water were added and stirred for 5 minutes at
80.degree. C. Next, 10% of a monomer feed, consisting of 132.9
parts of demineralized water, 13.0 parts of a 30 wt-% solution of
sodium lauryl sulphate in water, 23.3 parts of methacrylic acid,
414.3 parts of dimethyl itaconate, and 145.9 parts of ethyl
acrylate, was added, after the temperature rose to approximately
90.degree. C. due to the exothermic nature of the polymerization.
As soon as the temperature of 90.degree. C. was reached, the
remaining monomer feed and the initiator feed, consisting of 58.7
parts of demineralized water, 2.5 parts of sodium persulphate, and
3.7 parts of a 30 wt-% solution of sodium lauryl sulphate in water,
were started. Both feeds should be added over a period of 2
hours.
[0323] After 110 minutes of the monomer feed, the emulsion gelled,
showing that higher itaconates, such as DBI, yield superior
properties over lower itaconates, such as DMI.
Example 17
DBI Containing h/s Sequential Copolymer
[0324] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 426.6 parts of
demineralized water, 0.4 parts of sodium bicarbonate, 31.3 parts of
a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), and 0.4 parts of a 25 wt-% ammonia
solution. The reactor contents were heated to 80.degree. C., after
which a solution of 0.4 parts of sodium persulphate in 7.9 parts of
demineralized water were added, followed by 10% of a first monomer
feed consisting of 115.1 parts of demineralized water, 35.9 parts
of a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 15.7
parts of acrylic acid, 90.1 parts of dibutyl itaconate, and 286.0
parts of methyl methacrylate. Due to the heat formed as a result of
the polymerizing monomers, the temperature rose to 90.degree. C.,
after which adding the remainder of the first monomer feed was
started. The first monomer feed was added over a period of 45
minutes. Simultaneously, 60% of an initiator feed, consisting of
36.3 parts of demineralized water, 0.2 parts of sodium bicarbonate,
and 2.0 parts of sodium persulphate, was fed over a period of 45
minutes. At the end of the monomer feed, the feed tank was rinsed
with 7.6 parts of demineralized water.
[0325] Next, a mixture of 0.9 parts of a 25 wt-% ammonia solution
and 1.2 parts of demineralized water was fed over a period of 15
minutes. 45 minutes after the end of the first monomer feed, a
second monomer feed, consisting of 76.7 parts of demineralized
water, 23.9 parts of a 20 wt-% aqueous solution of a phosphate
functional surfactant (Fosfodet FAZ109V, ex. KAO), 0.4 parts of
sodium bicarbonate, 10.5 parts of acrylic acid, 198.5 parts of
dibutyl itaconate, and 52.2 parts of butyl acrylate, was started.
This feed, and the remainder of the initiator feed that was fed
simultaneously, were added over a period of 30 minutes. After
completion of the second monomer feed, the feed tank was rinsed
with 15.3 parts of demineralized water and the mixture was allowed
to stir at 90.degree. C. for another 30 minutes.
[0326] Finally, the emulsion was cooled to room temperature, the
solids content was corrected to 45% using demineralized water, and
the pH was corrected to 7.5 using a 25 wt-% ammonia solution.
Comparative Example Comp IV
DBI Free h/s Sequential Copolymer
[0327] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 426.6 parts of
demineralized water, 0.4 parts of sodium bicarbonate, 31.3 parts of
a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), and 0.4 parts of a 25 wt-% ammonia
solution. The reactor contents were heated to 80.degree. C., after
which a solution of 0.4 parts of sodium persulphate in 7.9 parts of
demineralized water were added, followed by 10% of a first monomer
feed consisting of 115.1 parts of demineralized water, 35.9 parts
of a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 15.7
parts of acrylic acid, 90.1 parts of butyl acrylate, and 286.0
parts of methyl methacrylate. Due to the heat formed as a result of
the polymerizing monomers, the temperature rose to 90.degree. C.,
after which adding the remainder of the first monomer feed was
started. The first monomer feed was added over a period of 45
minutes. Simultaneously, 60% of an initiator feed, consisting of
36.3 parts of demineralized water, 0.2 parts of sodium bicarbonate,
and 2.0 parts of sodium persulphate, was fed over a period of 45
minutes. At the end of the monomer feed, the feed tank was rinsed
with 7.6 parts of demineralized water.
[0328] Next, a mixture of 0.9 parts of a 25 wt-% ammonia solution
and 1.2 parts of demineralized water was fed over a period of 15
minutes. 45 minutes after the end of the first monomer feed, a
second monomer feed, consisting of 76.7 parts of demineralized
water, 23.9 parts of a 20 wt-% aqueous solution of a phosphate
functional surfactant (Fosfodet FAZ109V, ex. KAO), 0.4 parts of
sodium bicarbonate, 10.5 parts of acrylic acid, and 250.7 parts of
butyl acrylate, was started. This feed, and the remainder of the
initiator feed that was fed simultaneously, were added over a
period of 30 minutes. After completion of the second monomer feed,
the feed tank was rinsed with 15.3 parts of demineralized water and
the mixture was allowed to stir at 90.degree. C. for another 30
minutes.
[0329] Finally, the emulsion was cooled to room temperature, the
solids content was corrected to 45% using demineralized water, and
the pH was corrected to 7.5 using a 25 wt-% ammonia solution.
Example 18
DBI Containing s/h Sequential
[0330] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 426.6 parts of
demineralized water, 0.4 parts of sodium bicarbonate, 31.3 parts of
a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), and 0.4 parts of a 25 wt-% ammonia
solution. The reactor contents were heated to 80.degree. C., after
which a solution of 0.4 parts of sodium persulphate in 7.9 parts of
demineralized water were added, followed by 10% of a first monomer
feed consisting of 114.3 parts of demineralized water, 37.9 parts
of a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 18.3
parts of acrylic acid, 420.6 parts of dibutyl itaconate, 18.3 parts
of a 50 wt-% solution of N-(2-methacryloyloxyethyl)ethylene urea in
water (Plex 6852-0 ex. Evonik), and 9.1 parts of methyl
methacrylate. Due to the heat formed as a result of the
polymerizing monomers, the temperature rose to 90.degree. C., after
which adding the remainder of the first monomer feed was started.
The first monomer feed was added over a period of 45 minutes.
Simultaneously, 60% of an initiator feed, consisting of 36.3 parts
of demineralized water, 0.2 parts of sodium bicarbonate, and 2.0
parts of sodium persulphate, was fed over a period of 45 minutes.
At the end of the monomer feed, the feed tank was rinsed with 7.6
parts of demineralized water.
[0331] Next, a mixture of 0.9 parts of a 25 wt-% ammonia solution
and 1.2 parts of demineralized water was fed over a period of 15
minutes. 45 minutes after the end of the first monomer feed, a
second monomer feed, consisting of 77.5 parts of demineralized
water, 21.9 parts of a 20 wt-% aqueous solution of a phosphate
functional surfactant (Fosfodet FAZ109V, ex. KAO), 0.4 parts of
sodium bicarbonate, 7.8 parts of acrylic acid, 45.0 parts of
dibutyl itaconate, and 143.0 parts of methyl methacrylate, was
started. This feed, and the remainder of the initiator feed that
was fed simultaneously, were added over a period of 30 minutes.
After completion of the second monomer feed, the feed tank was
rinsed with 15.3 parts of demineralized water and the mixture was
allowed to stir at 90.degree. C. for another 30 minutes.
[0332] Finally, the emulsion was cooled to room temperature, the
solids content was corrected to 45% using demineralized water, and
the pH was corrected to 7.5 using a 25 wt-% ammonia solution.
Comparative Example Comp V
DBI Free s/h Sequential
[0333] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer were charged 426.6 parts of
demineralized water, 0.4 parts of sodium bicarbonate, 31.3 parts of
a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), and 0.4 parts of a 25 wt-% ammonia
solution. The reactor contents were heated to 80.degree. C., after
which a solution of 0.4 parts of sodium persulphate in 7.9 parts of
demineralized water were added, followed by 10% of a first monomer
feed consisting of 114.3 parts of demineralized water, 37.9 parts
of a 20 wt-% aqueous solution of a phosphate functional surfactant
(Fosfodet FAZ109V, ex. KAO), 0.6 parts of sodium bicarbonate, 18.3
parts of acrylic acid, 420.6 parts of butyl acrylate, 18.3 parts of
a 50 wt-% solution of N-(2-methacryloyloxyethyl)ethylene urea in
water (Plex 6852-0 ex. Evonik), and 9.1 parts of methyl
methacrylate. Due to the heat formed as a result of the
polymerizing monomers, the temperature rose to 90.degree. C., after
which adding the remainder of the first monomer feed was started.
The first monomer feed was added over a period of 45 minutes.
Simultaneously, 60% of an initiator feed, consisting of 36.3 parts
of demineralized water, 0.2 parts of sodium bicarbonate, and 2.0
parts of sodium persulphate, was fed over a period of 45 minutes.
At the end of the monomer feed, the feed tank was rinsed with 7.6
parts of demineralized water. Next, a mixture of 0.9 parts of a 25
wt-% ammonia solution and 1.2 parts of demineralized water was fed
over a period of 15 minutes.
[0334] 45 minutes after the end of the first monomer feed, a second
monomer feed, consisting of 77.5 parts of demineralized water, 21.9
parts of a 20 wt-% aqueous solution of a phosphate functional
surfactant (Fosfodet FAZ109V, ex. KAO), 0.4 parts of sodium
bicarbonate, 7.8 parts of acrylic acid, 45.0 parts of butyl
acrylate, and 143.0 parts of methyl methacrylate, was started. This
feed, and the remainder of the initiator feed that was fed
simultaneously, were added over a period of 30 minutes. After
completion of the second monomer feed, the feed tank was rinsed
with 15.3 parts of demineralized water and the mixture was allowed
to stir at 90.degree. C. for another 30 minutes.
[0335] Finally, the emulsion was cooled to room temperature, the
solids content was corrected to 45% using demineralized water, and
the pH was corrected to 7.5 using a 25 wt-% ammonia solution.
[0336] To illustrate the invention, film properties were determined
for a selection of the polymer emulsions described above. The
polymer emulsions were formulated with 8% of butyl diglycol to make
them film forming. The films were cast, dried at ambient
temperature for 4 hours, and next dried for 34 hours at 50.degree.
C. The results are shown below in Table 4.
TABLE-US-00003 TABLE 4 Film properties; "5" means excellent
resistance properties, no damage to the film, "1" indicated
completely destroyed film Water spot test Stain resistance Konig 16
Blocking (16 hrs)* hardness 1 hr hrs resistance EtOH Andy Coffee
(s) Ex 15 5 5 3 5 4 5 201 Comp I 5 4 1 4 2 5 110 Ex 16 5 5 5 4 4 5
173 Comp II 5 3 3 3 2 4 115 Comp III Could not be prepared due to
instable processing. Ex 17 5 5 5 3 4 5 70 Comp IV 5 5 3 3 2 4 60 Ex
18 5 5 4 3 3 5 115 Comp V 5 5 0 3 2 4 8 *Determined as spot
test.
[0337] In all cases (except Comp III), the water spot was good.
Blocking resistance and Konig hardness were in all cases better for
the polymers according to the invention compared to their most
similar comparative examples. While resistance to coffee and
ethanol were comparable between polymers according to the invention
and the comparatives, the resistance to soap (Andy) was clearly
better for the polymers according to the invention.
Example 19
MMA/DMI/AA
[0338] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer are charged 394.0 parts of 2-butanone.
The reactor contents are heated to 80.degree. C. As soon as the
polymerization temperature is reached, 13.3 parts of
azobis(2-methyl butyronitrile) are added and the monomer feed and
catalyst feed are started. The monomer feed consists of 244.4 parts
of methyl methacrylate, 244.4 parts of dimethyl itaconate, and
244.4 parts of acrylic acid. The catalyst feed consists of 31.1
parts of azobis(2-methyl butyronitrile) dissolved in 125.9 parts of
2-butanone. Both feeds are added over a period of 180 minutes.
[0339] At the end of the feeds 2.5 parts of azobis(2-methyl
butyronitrile) are added and the mixture is stirred at 80.degree.
C. for another 150 minutes. The mixture is cooled to room
temperature.
[0340] To 615.8 parts of the polymer solution is added a mixture of
99.6 parts of a 25 wt-% of ammonia in water, and 1080.5 parts of
water. Next, the 2-butanone is removed at 50.degree. C. under
reduced pressure. The solids content is corrected to 22.5% using
demineralized water and the pH is corrected to 8.6-8.8 using a 25
wt-% solution of ammonia in water.
[0341] The final polymer solution has a solids content of 22.5% and
a pH of 8.7.
Example 20
S/DMI/AA
[0342] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer are charged 394.0 parts of 2-butanone.
The reactor contents are heated to 80.degree. C. As soon as the
polymerization temperature is reached, 13.3 parts of
azobis(2-methyl butyronitrile) are added and the monomer feed and
catalyst feed are started. The monomer feed consists of 244.4 parts
of styrene, 244.4 parts of dimethyl itaconate, and 244.4 parts of
acrylic acid. The catalyst feed consists of 31.1 parts of
azobis(2-methyl butyronitrile) dissolved in 125.9 parts of
2-butanone. Both feeds are added over a period of 180 minutes.
[0343] At the end of the feeds 2.5 parts of azobis(2-methyl
butyronitrile) are added and the mixture is stirred at 80.degree.
C. for another 150 minutes. The mixture is cooled to room
temperature.
[0344] To 546.1 parts of polymer solution is added a mixture of
105.4 parts of a 25 wt-% of ammonia in water, and 1144.1 parts of
water. Next, the 2-butanone is removed at 50.degree. C. under
reduced pressure. The solids content is corrected to 22.5% using
demineralized water and the pH is corrected to 8.6-8.8 using a 25
wt-% solution of ammonia in water.
[0345] The final polymer solution has a solids content of 22.4% and
a pH of 8.6.
Example 21
MMA/DMI/AA
[0346] To a high pressure reactor equipped with a thermometer, and
a stirrer are charged 500.0 parts of 2-butanone. The reactor
contents are heated to 140.degree. C. As soon as the polymerization
temperature is reached, 2.9 parts of di-t-butyl peroxide and 40
parts of 2-butanone are added. 5 minutes later the monomer feed is
started. The monomer feed consists of 331.8 parts of methyl
methacrylate, 331.8 parts of dimethyl itaconate, 331.8 parts of
acrylic acid, 5.7 parts of di-t-butyl peroxide, and 6.6 parts of
t-butyl perbenzoate, and is added over a period of 180 minutes at
140.degree. C.
[0347] At the end of the feed the feed tank is rinsed with 90.9
parts of 2-butanone. 45 minutes after completion of the monomer
feed 2.5 parts of t-butyl perbenzoate dissolved in 40 parts of
2-butanone are added and the mixture is stirred at 140.degree. C.
for another 45 minutes. Next, 2.5 parts of t-butyl perbenzoate
dissolved in 40 parts of 2-butanone are added and the mixture is
stirred for another 135 minutes at 140.degree. C.
[0348] The mixture is cooled to room temperature.
[0349] To 619.3 parts of the polymer solution is added a mixture of
99.3 parts of a 25 wt-% of ammonia in water, and 1077.3 parts of
water. Next, the 2-butanone is removed at 50.degree. C. under
reduced pressure. The solids content is corrected to 22.5% using
demineralized water and the pH is corrected to 8.6-8.8 using a 25
wt-% solution of ammonia in water.
[0350] The final polymer solution has a solids content of 22.5% and
a pH of 8.6.
Example 22
S/DMI/AA
[0351] To a high pressure reactor equipped with a thermometer, and
a stirrer are charged 500.0 parts of 2-butanone. The reactor
contents are heated to 140.degree. C. As soon as the polymerization
temperature is reached, 4.4 parts of di-t-butyl peroxide and 40
parts of 2-butanone are added. 5 minutes later the monomer feed is
started. The monomer feed consists of 331.8 parts of styrene, 331.8
parts of dimethyl itaconate, 331.8 parts of acrylic acid, 8.6 parts
of di-t-butyl peroxide, and 10.0 parts of t-butyl perbenzoate, and
is added over a period of 180 minutes at 140.degree. C.
[0352] At the end of the feed the feed tank is rinsed with 90.9
parts of 2-butanone. 45 minutes after completion of the monomer
feed 2.5 parts of t-butyl perbenzoate dissolved in 40 parts of
2-butanone are added and the mixture is stirred at 140.degree. C.
for another 45 minutes. Next, 2.5 parts of t-butyl perbenzoate
dissolved in 40 parts of 2-butanone are added and the mixture is
stirred for another 135 minutes at 140.degree. C.
[0353] The mixture is cooled to room temperature.
[0354] To 617.8 parts of the polymer solution is added a mixture of
99.4 parts of a 25 wt-% of ammonia in water, and 1078.6 parts of
water. Next, the 2-butanone is removed at 50.degree. C. under
reduced pressure. The solids content is corrected to 22.5% using
demineralized water and the pH is corrected to 8.6-8.8 using a 25
wt-% solution of ammonia in water.
[0355] The final polymer solution has a solids content of 22.5% and
a pH of 8.7.
Example 23
Sequential Polymerization Using the Polymer from Example 44
[0356] To a round-bottomed flask equipped with a condenser,
thermometer, and a stirrer are charged 128.9 parts of the alkaline
solution obtained from Example 44. The mixture is heated to
80.degree. C..+-.2.degree. C.
[0357] As soon as the reaction temperature is reached, a mixture of
0.2 parts of sodium persulphate and 0.4 parts of demineralized
water is added. After 5 minutes, the monomer feed, consisting of
43.8 parts of methyl methacrylate and 43.8 parts of butyl acrylate,
and the initiator feed, consisting of 10.8 parts of demineralized
water and 0.4 parts of sodium persulphate (corrected to a pH of 8
using a 25 wt-% ammonia solution) are started. Both feeds should
take 120 minutes. At the end of the monomer feed, the feed tank is
rinsed with 1.2 parts of water. After both feeds are completed, the
batch is stirred at 80.degree. C. for another 30 minutes, after
which it is cooled to 50.degree. C.
[0358] At 50.degree. C., one third of a mixture consisting of 0.1
part of a 70 wt-% solution of t-butyl hydroperoxide is added
followed by one third of a solution of 0.1 part of iso-ascorbic
acid in 2.9 parts of water. 15 minutes later and 30 minutes later
similar portions are added and the batch is stirred at 50.degree.
C. for another 15 minutes.
[0359] The pH is checked and, if necessary, adjusted to 8.4.+-.0.1
using a 25 wt-% solution of ammonia in water. The batch is cooled
to room temperature, after which the solids content is adjusted to
48.5%.+-.1% using demineralized water.
Example 24
Sequential Polymerization Using the Polymer from Example 20
[0360] Example 24 was prepared analogously to the method described
in Example 23, replacing Example 19 with the alkaline solution
obtained from Example 20. The final emulsion obtained was highly
viscous, requiring a dilution to a solids content of 35%.
Example 25
Sequential Polymerization Using the Polymer from Example 21
[0361] Example 25 was prepared analogously to the method described
in Example 23, replacing Example 19 with the alkaline solution
obtained from Example 21.
Example 26
Sequential Polymerization Using the Polymer from Example 22
[0362] Example 26 was prepared analogously to the method described
in Example 23, replacing Example 19 with the alkaline solution
obtained from Example 22.
TABLE-US-00004 TABLE 5 Results SC (%) Viscosity (mPa s) pH Example
23 47.6 208 8.4 Example 24 34.8 1006 8.4 Example 25 48.1 35 8.5
Example 26 48.1 201 8.4
* * * * *