U.S. patent application number 16/635155 was filed with the patent office on 2021-03-25 for moisture curable compositions.
The applicant listed for this patent is DOW SILICONES CORPORATION. Invention is credited to Xu CHEN, Yi GUO, Yanxia HUANG.
Application Number | 20210087398 16/635155 |
Document ID | / |
Family ID | 1000005301526 |
Filed Date | 2021-03-25 |
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United States Patent
Application |
20210087398 |
Kind Code |
A1 |
HUANG; Yanxia ; et
al. |
March 25, 2021 |
MOISTURE CURABLE COMPOSITIONS
Abstract
Disclosed is a two-component silicone composition, which can
cure via two part moisture cure organosiloxanc composition. The
composition generally has which could improved cure speed while
whilst maintaining good storage stability.
Inventors: |
HUANG; Yanxia; (Shanghai,
CN) ; GUO; Yi; (Shanghai, CN) ; CHEN; Xu;
(Shanghai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW SILICONES CORPORATION |
Midland |
MI |
US |
|
|
Family ID: |
1000005301526 |
Appl. No.: |
16/635155 |
Filed: |
July 30, 2018 |
PCT Filed: |
July 30, 2018 |
PCT NO: |
PCT/CN2018/000275 |
371 Date: |
January 29, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 83/06 20130101 |
International
Class: |
C08L 83/06 20060101
C08L083/06 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 31, 2017 |
CN |
PCT/CN2017/095155 |
Claims
1. A two-component moisture curing silicone composition having a
base component and catalyst package component wherein the catalyst
package component comprises: (i) an
(R.sup.4O).sub.m(Y.sup.1).sub.3-mSi-terminated organic polymer,
where R.sup.4 is a C.sub.1-10-alkyl group, Y.sup.1 is a
C.sub.1-8-alkyl group, and m is 1, 2 or 3, and where the organic
polymer is selected from the group consisting of polyethers,
hydrocarbon polymers, acrylate polymers, polyurethanes, and
polyureas; (ii) at least one dipodal silane with the general
formula:
(R.sup.4O).sub.m(Y.sup.1).sub.3-mSi--(CH.sub.2).sub.x--(NHCH.sub.2CH.sub.-
2).sub.t-Q(CH.sub.2).sub.x--Si(OR.sup.4).sub.m(Y.sup.1).sub.3-m,
where each --R.sup.4 is independently a C.sub.1-10-alkyl group,
each Y.sup.1 is independently a C.sub.1-8 alkyl group, Q is a
heteroatom containing moiety with a lone pair of electrons, each x
is independently an integer of from 1 to 6, t is 0 or 1, and each m
is independently 1, 2 or 3; (iii) a non-dipodal adhesion promoter;
(iv) a tin based catalyst; and optionally (v) a cross-linker.
2. The two component moisture curing silicone composition in
accordance with claim 1, wherein the base component comprises: (a)
a siloxane polymer having at least two terminal hydroxyl or
hydrolysable groups and a viscosity of from 1000 to 200,000 mPas at
25.degree. C.; (b) at least one reinforcing fillers; and optionally
(c) at least one non-reinforcing fillers.
3. (canceled)
4. The two part moisture curing composition in accordance with
claim 1, wherein the dipodal silanes (ii) are is selected from the
group consisting of bis (trialkoxysilylalkyl) amines, bis
(dialkoxyalkylsilylalkyl) amines, bis (trialkoxysilylalkyl)
N-alkylamines, bis (dialkoxyalkylsilylalkyl) N-alkylamine, and bis
(trialkoxysilylalkyl) ureas, bis (dialkoxyalkylsilylalkyl) ureas,
and combinations thereof.
5. The two part moisture curing composition in accordance with
claim 1, wherein the dipodal silanes (ii) is selected from the
group consisting of bis (3-trimethoxysilylpropyl) amine, bis
(3-triethoxysilylpropyl) amine, bis (4-trimethoxysilylbutyl) amine,
bis (4-triethoxysilylbutyl) amine, bis (3-trimethoxysilylpropyl)
N-methylamine, bis (3-triethoxysilylpropyl) N-methylamine, bis
(4-trimethoxysilylbutyl) N-methylamine, bis (4-triethoxysilylbutyl)
N-methylamine, bis (3-trimethoxysilylpropyl) urea, bis
(3-triethoxysilylpropyl) urea, bis (4-trimethoxysilylbutyl) urea,
bis (4-triethoxysilylbutyl) urea, bis
(3-dimethoxymethylsilylpropyl) amine, bis (3-diethoxymethyl
silylpropyl) amine, bis (4-dimethoxymethylsilylbutyl) amine, bis
(4-diethoxymethyl silylbutyl) amine, bis
(3-dimethoxymethylsilylpropyl) N-methylamine, bis (3-diethoxymethyl
silylpropyl) N-methylamine, bis (4-dimethoxymethylsilylbutyl)
N-methylamine, bis (4-diethoxymethyl silylbutyl) N-methylamine, bis
(3-dimethoxymethylsilylpropyl) urea, bis (3-diethoxymethyl
silylpropyl) urea, bis (4-dimethoxymethylsilylbutyl) urea, bis
(4-diethoxymethyl silylbutyl) urea, bis
(3-dimethoxyethylsilylpropyl) amine, bis (3-diethoxyethyl
silylpropyl) amine, bis (4-dimethoxyethylsilylbutyl) amine, bis
(4-diethoxyethyl silylbutyl) amine, bis
(3-dimethoxyethylsilylpropyl) N-methylamine, bis (3-diethoxyethyl
silylpropyl) N-methylamine, bis (4-dimethoxyethylsilylbutyl)
N-methylamine, bis (4-diethoxyethyl silylbutyl) N-methylamine, bis
(3-dimethoxyethylsilylpropyl) urea bis (3-diethoxyethyl
silylpropyl) urea, bis (4-dimethoxyethylsilylbutyl) urea, bis
(4-diethoxyethyl silylbutyl) urea, and combinations thereof.
6. The two part moisture curing composition in accordance with
claim 1, wherein the dipodal silanes (ii) has the general formula:
(R.sup.4O).sub.3Si--(CH.sub.2).sub.x--(NHCH.sub.2CH.sub.2).sub.t--NH(CH.s-
ub.2).sub.x--Si(OR.sup.4).sub.3, where each of R.sup.4, x, and t is
as defined above.
7. The two part moisture curing composition in accordance with
claim 1, wherein the dipodal silanes (ii) is selected from the
group consisting of bis (3-tripropyloxysilypropyl) amine, bis
(3-methyldiethoxysilypropyl) amine, bis
(3-methyldimethoxysilypropyl) amine, bis (3-triethoxysilylpropyl)
amine, bis (3-trimethoxysilylpropyl) amine N,N'-bis
[3-trimethoxysilyl) propyl] ethylenediamine and combinations
thereof.
8. The two part moisture curing composition in accordance with
claim 2, wherein the siloxane polymer (a) is present in the
composition in an amount of from 10 to 90 weight % based on the
total weight of the base component.
9. The two part moisture curing composition in accordance with
claim 2 wherein the reinforcing filler (b) is selected from the
group consisting of fumed silicas, precipitated silicas,
precipitated calcium carbonate, and combinations thereof.
10. The two part moisture curing composition in accordance with
claim 1, wherein the weight ratio of the base component to the
catalyst package component, when mixed, is between 15:1 and
1:1.
11. A one-part moisture curing composition comprising a mixture of
the base component and the catalyst package component in accordance
with the two-part moisture curing composition of claim 1.
12. The two part moisture curing composition in accordance with
claim 2, wherein the base component comprises: 10 to 90 weight % of
the siloxane polymer (a); 10 to 80 weight % of the reinforcing
fillers (b); and 0 to 20 weight % of the non-reinforcing fillers
(c); with the total weight % of the base component being 100 weight
%.
13. The two part moisture curing composition in accordance with
claim 1, wherein the catalyst package component comprises: 30 to 80
weight % of the terminated organic polymer (i); 5 to 50 weight % of
the dipodal silanes (ii); 5 to 25 weight % of the non-dipodal
adhesion promoter (iii); 0.01 to 3 weight % of the tin based
catalyst (iv); and 0 to 25 weight % of the cross-linker (v); with
the total weight % of the catalyst package component being 100
weight %.
14. An article comprising a composition or a reaction product
thereof, wherein the composition is the two-part moisture curing
composition in accordance with claim 1.
15. The article in accordance with claim 14, wherein the
composition or reaction product thereof is further defined as a
material selected from the group consisting of coating materials,
caulking materials, mold making materials, encapsulating materials,
and combinations thereof.
Description
[0001] This concerns a two part moisture cure organosiloxane
composition designed to improve cure speed whilst maintaining
storage stability.
[0002] Condensation curable organosiloxane compositions, which cure
to elastomeric solids, are well known. Typically, such compositions
are obtained by mixing a polydiorganosiloxane having reactive
terminal groups, e.g. hydroxy groups or hydrolysable groups, with
e.g. a silane cross-linking agent which is reactive with the
polydiorganosiloxane, for example an acetoxy silane, an
oximosilane, an aminosilane or an alkoxysilane in the presence of a
suitable catalyst. The resulting compositions are curable upon
exposure to atmospheric moisture at room temperature and may be
used as structural sealants/adhesives.
[0003] In use as sealants and adhesives, it is important that a
composition is capable of curing in comparatively thick layers to
provide an elastomeric body. It is frequently desirable that the
organopolysiloxane composition cures quickly enough to provide a
sound seal within several hours but not so quickly that the surface
cannot be tooled to desired configuration shortly after
application. Dependent on the means of cure (e.g. cross-linker and
catalyst) such compositions may be provided to the user in a one
part curable product, which can be applied onto a substrate
directly or alternatively in a multi-part, typically two part,
combination requiring the multiple parts to be mixed together
immediately before use.
[0004] The properties of Individual parts of said multi-part
compositions are generally not affected by atmospheric moisture,
but once mixed together the resulting mixture possess excellent
deep curability and enables substantially uniform curing throughout
the entire body of the sealing material, i.e., from the surface to
the inner part. Typically such two part compositions comprise a
first component (base) that contains silanol-terminated
diorganopolysiloxane and calcium carbonate filler and a second
component (catalyst or cure package) containing an alkyl-terminated
diorganopolysiloxane, tin based catalyst, cross-linker and adhesion
promoter, e.g. a primary aminosilane.
[0005] Adhesives for LED lighting often utilise silicone adhesives
reliant on hydrosilylation cure because they require high
throughput, fast cure and good adhesion to the substrates being
adhered together. Such adhesives use platinum catalysts which can
be poisoned if they come into contact with other chemicals
containing some forms of sulphur, nitrogen and phosphorus. Hence
for some LED/electronics applications it would be advantageous to
use condensation cure adhesives instead of hydrosilylation cure
systems to avoid catalyst poisoning providing cure takes place with
sufficient speed.
[0006] It is generally acknowledged that the cure speed of two
component silicone adhesive/sealant compositions as described above
can provide excellent deep curability and enables substantially
uniform curing throughout the entire body of the sealing material
in quick time compared to most 1 part sealant compositions. It is
also appreciated that cure can be accelerated by increasing either
or both of the tin catalyst level and the adhesion promoter level.
However, with the increase of adhesion promoter, especially in the
case of primary amino silanes, the trialkyl-terminated
diorganopolysiloxane, used as a carrier in the catalyst package,
undergoes random chain scission which causes viscosity to decrease
and making the mixture unstable. Also, the ingredients in the
catalyst package are not always miscible. This immiscibility may
cause the alkyl-terminated diorganopolysiloxane to phase separate
by rising to the top of the container, and as a result the silanes
and filler in the catalyst package settle to the bottom of the
mixture. As a result of the above phase separation, storage
stability of the catalyst package may be dramatically impacted.
Phase separation is a significant issue for end users. It is
extremely messy and time consuming to remix the catalyst package of
such two part compositions before use, after a storage period,
especially on a large scale as some of the catalysts used can be
inflammable thereby causing a potential safety hazard. Furthermore,
there is a tendency for carrier fluid e.g. unreactive silicones to
accumulate in an upper phase at the top of the material, whilst
filler is likely to settle in a silane rich lower phase, rendering
re-mixing on a large scale, at least problematic but in extreme
cases particularly on an industrial scale, when significant phase
separation is evident, can lead to the catalyst package having to
be replaced.
[0007] Hence, there is a need to provide two part condensation cure
adhesives/sealants in which the catalyst package is designed to
improve cure speed whilst maintaining storage stability.
[0008] There is provided herein a two component moisture curing
silicone composition having a base component and catalyst package
component in which, the catalyst package comprises: [0009] (i) An
(R.sup.4O).sub.m(Y.sup.1).sub.3-m--Si terminated organic polymer,
where R.sup.4 is a C.sub.1-10 alkyl group, Y.sup.1 is an alkyl
groups containing from 1 to 8 carbons and m is 1, 2 or 3, which
organic polymer is selected from polyethers, hydrocarbon polymers,
acrylate polymers, polyurethanes and polyureas; [0010] (ii) One or
more dipodal silanes in accordance with the formula:
[0010] (R.sup.4O).sub.m(Y.sup.1).sub.3-m--Si
(CH.sub.2).sub.x--((NHCH.sub.2CH.sub.2).sub.t-Q(CH.sub.2).sub.x).sub.n--S-
i(OR.sup.4).sub.m(Y.sup.1).sub.3-m [0011] where R.sup.4 is a
C.sub.1-10 alkyl group, Y.sup.1 is an alkyl groups containing from
1 to 8 carbons, Q is a chemical group containing a heteroatom with
a lone pair of electrons; each x is an integer of from 1 to 6,t is
0 or 1; each m is independently 1, 2 or 3 and n is 0 or 1; and
[0012] (iii) a non-dipodal adhesion promoter; [0013] (iv) a tin
based catalyst and optionally [0014] (v) a cross-linker.
Base Component
[0015] Any suitable base component may be utilised. For example the
base component may comprise: [0016] (a) A siloxane polymer having
at least two terminal hydroxyl or hydrolysable groups having a
viscosity of from 1000 to 200,000mPas at 25.degree. C.; [0017] (b)
One or more reinforcing fillers; and optionally [0018] (c) One or
more non-reinforcing fillers
[0019] Alternatively, there is provided herein a two part moisture
curing composition having a base component and catalyst package in
which, the base component comprises: [0020] (a) A siloxane polymer
having at least two terminal hydroxyl or hydrolysable groups having
a viscosity of from 1000 to 200,000, alternatively 2000 to
150000mPas at 25.degree. C.; [0021] (b) One or more reinforcing
fillers; and optionally [0022] (c) One or more non-reinforcing
fillers [0023] and [0024] the catalyst package comprises [0025] (i)
An (R.sup.4O).sub.m(Y.sup.1).sub.3-m--Si terminated organic
polymer, where R.sup.4 is a C.sub.1-10 alkyl group, Y.sup.1 is an
alkyl groups containing from 1 to 8 carbons and m is 1, 2 or 3,
which organic polymer is selected from polyethers, hydrocarbon
polymers, acrylate polymers, polyurethanes and polyureas; [0026]
(ii) One or more dipodal silanes in accordance with the formula:
(R.sup.4O).sub.m(Y.sup.1).sub.3-m--Si
(CH.sub.2).sub.x--(NHCH.sub.2CH.sub.2).sub.t-Q(CH.sub.2).sub.x--Si(OR.sup-
.4).sub.m(Y.sup.1).sub.3-m, where R.sup.4 is a C.sub.1-10 alkyl
group, Y.sup.1 is an alkyl groups containing from 1 to 8 carbons, Q
is a chemical group containing a heteroatom with a lone pair of
electrons; each x is an integer of from 1 to 6,t is 0 or 1 and each
m is independently 1, 2 or 3; [0027] and [0028] (iii) a non-dipodal
adhesion promoter; [0029] (iv) a tin based catalyst and optionally
[0030] (v) a cross-linker.
[0031] Unless otherwise indicated all viscosity measurements were
determined by using a Brookfield.RTM. cone plate viscometer (RV
DIII) using cone plate CP-52 for viscosities of 40, 000mPas and
below and cone plate CP-41 for materials having viscosities greater
than 40, 000mPas adapting the speed according to the polymer
viscosity and all viscosity measurements were taken at 25.degree.
C. unless otherwise indicated.
[0032] The base component comprises may comprise (a) a siloxane
polymer having at least two i.e. having 2 or more terminal hydroxyl
or hydrolysable groups having a viscosity of from 1000 to 200,000
mPas at 25.degree. C., alternatively 2000 to 150000 mPas at
25.degree. C. The siloxane polymer (a) may be described by the
following molecular Formula (1)
X.sub.3-aR.sub.aSi--Z.sub.b--O--(R.sup.1.sub.ySiO.sub.(4-y)/2).sub.z--Z.-
sub.b--Si--R.sub.aX.sub.3-a tm (1)
where [0033] a is 0, 1, 2 or 3, [0034] b is 0 or 1, [0035] z is an
integer from 300 to 5000 inclusive, [0036] y is 0, 1 or 2
preferably 2.
[0037] At least 97% (i.e. from 97% to 100%) of
theR.sup.1.sub.ySiO.sub.(4-y)/2 are characterized with y=2. [0038]
X is a hydroxyl group or any condensable or any hydrolyzable
group,
[0039] Each R is individually selected from aliphatic organic
groups selected from alkyl, aminoalkyl, polyaminoalkyl, epoxyalkyl
or alkenyl alternatively alkyl, aminoalkyl, polyaminoalkyl,
epoxyalkyl groups having, in each case, from 1 to 10 carbon atoms
per group or alkenyl groups having in each case from 2 to 10 carbon
atoms per group or is an aromatic aryl group, alternatively an
aromatic aryl group having from 6 to 20 carbon atoms and Most
preferred are the methyl, ethyl, octyl, vinyl, allyl and phenyl
groups.
[0040] Each R.sup.1 is individually selected from the group
consisting of X, alkyl groups, alternatively alkyl groups having
from 1 to 10 carbon atoms, alkenyl groups alternatively alkenyl
groups having from 2 to 10 carbon atoms and aromatic groups,
alternatively aromatic groups having from 6 to 20 carbon atoms.
Most preferred are methyl, ethyl, octyl, trifluoropropyl, vinyl and
phenyl groups. It is possible that some R' groups may be siloxane
branches off the polymer backbone which may have terminal groups as
hereinbefore described.
[0041] Most preferred R.sup.1 is methyl.
[0042] Each X group of siloxane polymer (a) may be the same or
different and can be a hydroxyl group or a condensable or
hydrolyzable group. The term "hydrolyzable group" means any group
attached to the silicon which is hydrolyzed by water at room
temperature. The hydrolyzable group X includes groups of the
Formula --OT, where T is an alkyl group such as methyl, ethyl,
isopropyl, octadecyl, an alkenyl group such as allyl, hexenyl,
cyclic groups such as cyclohexyl, phenyl, benzyl, beta-phenylethyl;
hydrocarbon ether groups, such as 2-methoxyethyl,
2-ethoxyisopropyl, 2-butoxyisobutyl, p-methoxyphenyl or
--(CH.sub.2CH.sub.2O).sub.2CH.sub.3; or any N,N-amino radical, such
as dimethylamino, diethylamino, ethylmethylamino, diphenylamino or
dicyclohexylamino.
[0043] The most preferred X groups are hydroxyl groups or alkoxy
groups. Illustrative alkoxy groups are methoxy, ethoxy, propoxy,
isopropoxy, butoxy, isobutoxy, pentoxy, hexoxy octadecyloxy and
2-ethylhexoxy; dialkoxy radicals, such as methoxymethoxy or
ethoxymethoxy and alkoxyaryloxy, such as ethoxyphenoxy. The most
preferred alkoxy groups are methoxy or ethoxy.
[0044] Each Z is independently selected from an alkylene group
having from 1 to 10 carbon atoms. In one alternative each Z is
independently selected from an alkylene group having from 2 to 6
carbon atoms; in a further alternative each Z is independently
selected from an alkylene group having from 2 to 4 carbon
atoms.
[0045] Siloxane polymer (a) of the base component can be a single
siloxane represented by Formula (1) or it can be mixtures of
siloxanes represented by the aforesaid formula. The term "siloxane
polymer mixture" in respect to component (a) of the base component
is meant to include any individual siloxane polymer (a) or mixtures
of siloxane polymers (a). As used herein, the term "silicone
content" means the total amount of silicone used in the base
component and the catalyst package, irrespective of the source,
including, but not limited to the siloxane polymer (a), polymer
mixtures, and/or resins.
[0046] The Degree of Polymerization (DP), (i.e. in the above
formula substantially z), is usually defined as the number of
monomeric units in a macromolecule or polymer or oligomer molecule
of silicone. Synthetic polymers invariably consist of a mixture of
macromolecular species with different degrees of polymerization and
therefore of different molecular weights. There are different types
of average polymer molecular weight, which can be measured in
different experiments. The two most important are the number
average molecular weight (Mn) and the weight average molecular
weight (Mw). The Mn and Mw of a silicone polymer can be determined
by Gel permeation chromatography (GPC) with precision of about
10-15%. This technique is standard and yields Mw, Mn and
polydispersity index (PI). The degree of polymerisation (DP)=Mn/Mu
where Mn is the number-average molecular weight coming from the GPC
measurement and Mu is the molecular weight of a monomer unit.
PI=Mw/Mn. The DP is linked to the viscosity of the polymer via Mw,
the higher the DP, the higher the viscosity. Siloxane polymer (a)
is going to be present in an amount of from 20 to 90%,
alternatively 20 to 80% by weight of the base composition,
alternatively from 35 to 65% by weight of the base composition.
[0047] The reinforcing filler (b) of the base component may contain
one or more finely divided, reinforcing fillers such as calcium
carbonate, high surface area fumed silica and/or precipitated
silica including, for example, rice hull ash. Typically, the
surface area of the reinforcing filler (b) is at least 50
m.sup.2/g. In the case of high surface area fumed silica and/or
high surface area precipitated silica, these may have surface areas
of, for example, from 100 to 400 m.sup.2/g measured in accordance
with the BET method, alternatively of from 100 to 300 m.sup.2/g in
accordance with the BET method. Typically the reinforcing fillers
are present in the base composition in an amount of from 10 to 80
wt. % of the base composition, alternatively 20 to 70 wt. %,
alternatively from 35 to 65% wt. %.
[0048] The optional non-reinforcing filler (c) of the base
component may comprise non-reinforcing fillers such as crushed
quartz, diatomaceous earths, barium sulphate, iron oxide, titanium
dioxide and carbon black, talc, wollastonite. Other fillers which
might be used alone or in addition to the above include aluminite,
calcium sulphate (anhydrite), gypsum, calcium sulphate, magnesium
carbonate, clays such as kaolin, aluminium trihydroxide, magnesium
hydroxide (brucite), graphite, copper carbonate, e.g. malachite,
nickel carbonate, e.g. zarachite, barium carbonate, e.g. witherite
and/or strontium carbonate e.g. stronti anite.
[0049] Aluminium oxide, silicates from the group consisting of
olivine group; garnet group; aluminosilicates; ring silicates;
chain silicates; and sheet silicates. The olivine group comprises
silicate minerals, such as but not limited to, forsterite and
Mg.sub.2SiO.sub.4. The garnet group comprises ground silicate
minerals, such as but not limited to, pyrope;
Mg.sub.3Al.sub.2Si.sub.3O.sub.12; grossular; and
Ca.sub.2Al.sub.2Si.sub.3O.sub.12. Aluninosilicates comprise ground
silicate minerals, such as but not limited to, sillimanite;
Al.sub.2SiO.sub.5 ; mullite; 3Al.sub.2O.sub.3.2SiO.sub.2; kyanite;
and Al.sub.2SiO.sub.5
[0050] The ring silicates group comprises silicate minerals, such
as but not limited to, cordierite and
Al.sub.3(Mg,Fe).sub.2[Si.sub.4AlO.sub.18]. The chain silicates
group comprises ground silicate minerals, such as but not limited
to, wollastonite and Ca[SiO.sub.3].
[0051] The sheet silicates group comprises silicate minerals, such
as but not limited to, mica;
K.sub.2AI.sub.14[Si.sub.6Al.sub.2O.sub.20](OH).sub.4; pyrophyllite;
Al.sub.4[Si.sub.8O.sub.20](OH).sub.4; talc;
Mg.sub.6[Si.sub.8O.sub.20](OH).sub.4; serpentine for example,
asbestos; Kaolinite; Al.sub.4[Si.sub.4O.sub.10](OH).sub.8; and
vermiculite. The optional non-reinforcing filler, when present, is
present in an amount up to 20% by weight of the base.
[0052] In addition, a surface treatment of the reinforcing filler
(b) of the base component and optional non-reinforcing filler (c)
of the base component may be performed, for example with a fatty
acid or a fatty acid ester such as a stearate, or with
organosilanes, organosiloxanes, or organosilazanes hexaalkyl
disilazane or short chain siloxane diols to render the filler(s)
hydrophobic and therefore easier to handle and obtain a homogeneous
mixture with the other sealant components The surface treatment of
the fillers makes them easily wetted by siloxane polymer (a) of the
base component. These surface modified fillers do not clump, and
can be homogeneously incorporated into the silicone polymer (i) of
the base component. This results in improved room temperature
mechanical properties of the uncured compositions.
[0053] The proportion of such fillers when employed will depend on
the properties desired in the elastomer-forming composition and the
cured elastomer. Filler (b) is going to be present in an amount of
from 10 to 80% by weight of the base composition.
Catalyst Package
[0054] It was found that increasing cure speed by introducing
additional primary amine based adhesion promoters and or tin
catalyst did indeed lead to unreactive siloxane carrier in the
catalyst package becoming unstable and being degrading causing
reductions in the viscosity of the catalyst package and storage
instability. However, the catalyst package described herein was
developed and provided the required cure speed improvements while
not degrading.
[0055] As hereinbefore described the catalyst package of the two
component composition comprises an alkoxy silyl terminated organic
polymer (i), which organic polymer is selected from polyethers,
hydrocarbon polymers, acrylate polymers, polyurethanes and
polyureas. The alkoxy silyl terminated organic polymer the polymer
has an organic backbone having terminal curable silyl groups. The
silyl groups may be selected from alkoxydialkylsilyl,
dialkoxyalkylsilyl or trialkoxysilyl terminal groups as indicated
above. In one alternative the alkoxy groups are methoxy or ethoxy
groups and the alkyl, groups are C.sub.1-C.sub.6 alkyl groups,
alternatively methyl or ethyl groups.
[0056] One preferred type of polymer backbone is an acrylate
polymer backbone. The acrylate polymer is an addition polymerised
polymer of acrylate and/or methacrylate ester monomers, which
comprise at least 50%, (i.e. from 50% to 100%) by weight of the
monomer units in the acrylate polymer. Examples of acrylate ester
monomers are n-butyl, isobutyl, n-propyl, ethyl, methyl, n-hexyl,
n-octyl and 2-ethylhexyl acrylates. Examples of methacrylate ester
monomers are n-butyl, isobutyl, methyl, n-hexyl, n-octyl,
2-ethylhexyl and lauryl methacrylates. The acrylate polymer
preferably has a glass transition temperature (Tg) below ambient
temperature; acrylate polymers are generally preferred over
methacrylates since they form lower Tg polymers. Polybutyl acrylate
is particularly preferred. The acrylate polymer can contain lesser
amounts of other monomers such as styrene, acrylonitrile or
acrylamide. The acrylate(s) can be polymerized by various methods
such as conventional radical polymerization, or living radical
polymerization such as atom transfer radical polymerization,
reversible addition--fragmentation chain transfer polymerization,
or anionic polymerization including living anionic
polymerisation.
[0057] Other suitable types of organic polymer having hydrolysable
silyl groups include silyl modified polyisobutylene.
[0058] In one alternative the alkoxy silyl terminated organic
polymer is a polyether. Such polyethers may comprise recurring
oxyalkylene units, illustrated by the average formula
(--C.sub.nH.sub.2n--O--).sub.y wherein n is an integer from 2 to 4
inclusive and y is an integer .gtoreq.4 i.e. of at least four. The
number average molecular weight of each polyether may range from
about 300 to about 10,000. Moreover, the oxyalkylene units are not
necessarily identical throughout the polyoxyalkylene, but can
differ from unit to unit. A polyoxyalkylene, for example, can
comprise oxyethylene units (--C.sub.2H.sub.4--O--), oxypropylene
units (--C.sub.3H.sub.6--O--) or oxybutylene units
(--C.sub.4H.sub.8--O--), or mixtures thereof. Preferably the
polyoxyalkylene polymeric backbone consists essentially of
oxyethylene units or oxypropylene units. Other polyoxyalkylenes may
include for example: units of the structure:
--[--R.sup.e--O--(--R.sup.f--O--).sub.h-Pn-CR.sup.g.sub.2-PnO--(--R.sup.-
f--O--).sub.q1--R.sup.e]--
in which Pn is a 1,4-phenylene group, each Re is the same or
different and is a divalent hydrocarbon group having 2 to 8 carbon
atoms, each R.sup.f is the same or different and is an ethylene
group or propylene group, each R.sup.g is the same or different and
is a hydrogen atom or methyl group and each of the subscripts h and
q1 is a positive integer in the range from 3 to 30.
[0059] One preferred type of polyether is a polyoxyalkylene polymer
comprising recurring oxyalkylene units of the formula
(--C.sub.nH.sub.2n--O--) wherein n is an integer from 2 to 4
inclusive, as described above in connection with siloxane
polyoxyalkylene block copolymers. Polyoxyalkylenes usually have
terminal hydroxyl groups and can readily be terminated with
moisture curable silyl groups, for example by reaction with an
excess of an alkyltrialkoxysilane to introduce terminal
alkyldialkoxysilyl groups. Alternatively polymerization may occur
via a hydrosilylation type process. Polyoxyalkylenes consisting
wholly or mainly of oxypropylene units have properties suitable for
many sealant uses.
[0060] Examples of silyl modified hydrocarbon polymers include
silyl modified polyisobutylene. Silyl modified polyisobutylene can
for example contain curable silyl groups derived from a
silyl-substituted alkyl acrylate or methacrylate monomer such as
alkoxydialkylsilylpropyl methacrylate, dialkoxyalkylsilylpropyl
methacrylate or trialkoxysilylpropyl methacrylate, which can be
reacted with a polyisobutylene.
[0061] Basically, the cure speed of this type of two component
silicone sealants can be accelerated with increased tin catalyst
level and amino silane level in catalyst package composition.
However, with the increase of amino silane level in catalyst
package, the PDMS in catalyst package matrix tends to degrade with
time past and then cause significant viscosity decrease. Also, with
high level of amino silane in the catalyst package formulation, the
matrix is easy to be separated due to poor compatibility of the
silane and PDMS. As a results of the above phenomena, the storage
stability of the catalyst package material will be dramatically
impacted. With the solution from our study, we could solve the
storage stability issue, but still achieving the fast cure
performance. In our finding, we used different types of amino
silanes at high level to speed up the curing speed and alkoxyl
silane terminated polyether to stabilize the product shelf-life.
Typically the alkoxy silyl terminated organic polymer (i),is
present in the catalyst package as a carrier and is present in the
catalyst package in an amount of from 30 to 80% weight,
alternatively 40 to 65 weight % of the total weight of the catalyst
package.
[0062] The catalyst package of the two component composition also
contains one or more dipodal silanes (ii). The dipodal silanes of
the catalyst package can be defined by the following formula:
(R.sup.4O).sub.m(Y.sup.1).sub.3-m--Si
(CH.sub.2).sub.x--(NHCH.sub.2CH.sub.2).sub.t-Q(CH.sub.2).sub.x--Si(OR.sup-
.4).sub.m(Y.sup.1).sub.3-m
where R.sup.4 is a C.sub.1-10 alkyl group, Y.sup.1 is an alkyl
groups containing from 1 to 8 carbons, Q is a chemical group
containing a heteroatom with a lone pair of electrons,
alternatively an amine or a urea; each x is an integer of from 1 to
6, t is 0 or 1; each m is independently 1, 2 or 3, alternatively 2
or 3, in a further alternative m=3.
[0063] In one alternative Q is a secondary amine and each x is from
2 to 4.
[0064] Examples of dipodal Silane (ii) include: bis
(trialkoxysilylalkyl)amines, bis (dialkoxyalkylsilylalkyl)amine,
bis (trialkoxysilylalkyl) N-alkylamine, bis
(dialkoxyalkylsilylalkyl) N-alkylamine and bis
(trialkoxysilylalkyl)urea and bis (dialkoxyalkylsilylalkyl)
urea.
[0065] Specific suitable examples include example bis
(3-trimethoxysilylpropyl)amine, bis (3-triethoxysilylpropyl)amine,
bis (4-trimethoxysilylbutyl)amine, bis
(4-triethoxysilylbutyl)amine, bis
(3-trimethoxysilylpropyl)N-methylamine, bis
(3-triethoxysilylpropyl) N-methylamine, bis
(4-trimethoxysilylbutyl) N-methylamine, bis (4-triethoxysilylbutyl)
N-methylamine, bis (3-trimethoxysilylpropyl)urea, bis
(3-triethoxysilylpropyl)urea, bis (4-trimethoxysilylbutyl)urea, bis
(4-triethoxysilylbutyl)urea, bis
(3-dimethoxymethylsilylpropyl)amine, bis (3-diethoxymethyl
silylpropyl)amine, bis (4-dimethoxymethylsilylbutyl)amine, bis
(4-diethoxymethyl silylbutyl)amine, bis
(3-dimethoxymethylsilylpropyl) N-methylamine, bis (3-diethoxymethyl
silylpropyl) N-methylamine, bis (4-dimethoxymethylsilylbutyl)
N-methylamine, bis (4-diethoxymethyl silylbutyl) N-methylamine, bis
(3-dimethoxymethylsilylpropyl)urea, bis (3-diethoxymethyl
silylpropyl)urea, bis (4-dimethoxymethylsilylbutyl)urea, bis
(4-diethoxymethyl silylbutyl)urea, bis
(3-dimethoxyethylsilylpropyl)amine, bis (3-diethoxyethyl
silylpropyl)amine, bis (4-dimethoxyethylsilylbutyl)amine, bis
(4-diethoxyethyl silylbutyl)amine, bis
(3-dimethoxyethylsilylpropyl) N-methylamine, bis (3-diethoxyethyl
silylpropyl) N-methylamine, bis (4-dimethoxyethylsilylbutyl)
N-methylamine, bis (4-diethoxyethyl silylbutyl) N-methylamine, bis
(3-dimethoxyethylsilylpropyl)urea bis (3-diethoxyethyl
silylpropyl)urea, bis (4-dimethoxyethylsilylbutyl)urea and/or bis
(4-diethoxyethyl silylbutyl)urea.
[0066] In a still further alternative the dipodal silanes are of
the formula:
(R.sup.4O).sub.3--Si
(CH.sub.2).sub.x--(NHCH.sub.2CH.sub.2).sub.t--NH(CH.sub.2).sub.x--Si(OR.s-
up.4).sub.3,
[0067] In which case the dipodal silane may be selected from a bis
(trialkoxysilylalkyl) amine such as bis
(3-tripropyloxysilypropyl)amine, bis
(3-methyldiethoxysilypropyl)amine, bis
(3-methyldimethoxysilypropyl)amine, as well as bis
(3-triethoxysilylpropyl)amine
##STR00001##
or bis (3-trimethoxysilylpropyl)amine
##STR00002##
[0068] Alternatively the dipodal silane may be a bis
(trialkoxysilylalkyl) alkylenediamine such as N,N'-bis
((3-trimethoxysilyl)propyl]ethylenediamine
##STR00003##
[0069] The dipodal silane (ii) is compatible with the
polydialkylsiloxane (i) in the catalyst package.
[0070] Two part compositions of the type herein provide a fast deep
cure and as such adhesion promoters are an essential ingredient in
such compositions to ensure speed of cure and, of course, adhesion
to the substrate surface to which the composition is to be
applied
[0071] The dipodal silanes (ii) may be present in the catalyst
package in an amount of from 5 to 50 weight %, alternatively 10 to
30 weight %. Dipodal silane (ii) may function as a cross-linker as
well as the adhesion promoter and as such no additional
cross-linker is provided as an essential ingredient. However,
additional cross-linkers may be provided where deemed
appropriate.
Non-Dipodal Adhesion Promoters (iii)
[0072] Examples of non-dipodal adhesion promoters (v) which may
optionally be incorporated in the catalyst package for the two
component moisture curing silicone compositions described herein
include alkoxysilanes such as (ethylenediaminepropyl)trimethoxy
silane, aminoalkylalkoxysilanes, for example
gamma-aminopropyltriethoxysilane or
gamma-aminopropyltrimethoxysilane, epoxyalkylalkoxysilanes, for
example, 3-glycidoxypropyltrimethoxysilane and ,
glycidoxypropyltriethoxysilane, mercapto-alkylalkoxysilanes, and
reaction products of ethylenediamine with silylacrylates.
Isocyanurates containing silicon groups such as
1,3,5-tris(trialkoxysilylalkyl) isocyanurates may additionally be
used. Further suitable adhesion promoters (v) are reaction products
of epoxyalkylalkoxysilanes such as
3-glycidoxypropyltrimethoxysilane with amino-substituted
alkoxysilanes such as 3-aminopropyltrimethoxysilane and optionally
with alkylalkoxysilanes such as methyltrimethoxysilane. Typically
these are present in a range of from 1 to 25 weight % of
non-dipodal adhesion promoter (iii), alternatively 2 to 20 weight %
of the catalyst package to enhance adhesion in combination with the
dipodal silanes (ii).
Catalyst (iv)
[0073] The fourth essential ingredient in the catalyst package is a
suitable tin based condensation catalyst (iv) which is for use as
the catalyst for the cure reaction subsequent to mixing the base
component and catalyst package component together. Examples include
tin triflates, organic tin metal catalysts such as triethyltin
tartrate, tin octoate, tin oleate, tin naphthate,
butyltintri-2-ethylhexoate, tinbutyrate, carbomethoxyphenyl tin
trisuberate, isobutyltintriceroate, and diorganotin salts
especially diorganotin dicarboxylate compounds such as dibutyltin
dilaurate, dimethyltin dibutyrate, dibutyltin dimethoxide,
dibutyltin diacetate, dimethyltin bisneodecanoate, dibutyltin
dibenzoate, stannous octoate, dimethyltin dineodecanoate (DMTDN)
and dibutyltin dioctoate. The tin catalyst may be present in an
amount of from 0.01 to 3 weight %; alternatively 0.1 to 0.5 weight
% of the catalyst package.
[0074] The catalyst package may also include one or more of
cross-linkers (v), pigments (vi) and fillers (vii).
Cross-Linker (v)
[0075] Any suitable cross-linker may be used as cross-linker (v),
if required. When present the crosslinker (v) in the curable
composition as hereinbefore described may be one or more silanes or
siloxanes which contain silicon bonded hydrolysable groups such as
acyloxy groups (for example, acetoxy, octanoyloxy, and benzoyloxy
groups); ketoximino groups (for example dimethyl ketoximo, and
isobutylketoximino); alkoxy groups (for example methoxy, ethoxy,
iso-butoxy and propoxy) and alkenyloxy groups (for example
isopropenyloxy and 1-ethyl-2-methylvinyloxy).
[0076] In the case of siloxane based cross-linkers (v), when
present, in the catalyst package the molecular structure can be
straight chained, branched, or cyclic.
[0077] When present, the crosslinker (v) of the catalyst package
preferably has at least three or four silicon-bonded condensable
(preferably hydroxyl and/or hydrolysable) groups per molecule which
are reactive with the condensable groups of siloxane polymer (a) in
the base component. When crosslinker (v) of the catalyst package is
a silane and when the silane has three silicon-bonded hydrolysable
groups per molecule, the fourth group is suitably a
non-hydrolysable silicon-bonded organic group. These silicon-bonded
organic groups are suitably hydrocarbyl groups which are optionally
substituted by halogen such as fluorine and chlorine. Examples of
such fourth groups include alkyl groups (for example methyl, ethyl,
propyl, and butyl); cycloalkyl groups (for example cyclopentyl and
cyclohexyl); alkenyl groups (for example vinyl and allyl); aryl
groups (for example phenyl, and tolyl); aralkyl groups (for example
2-phenylethyl) and groups obtained by replacing all or part of the
hydrogen in the preceding organic groups with halogen. Preferably
however, the fourth silicon-bonded organic groups is methyl.
[0078] Silanes and siloxanes which can be used as crosslinkers
include bis (trimethoxysilyl)hexane, 1,2-bis
(triethoxysilyl)ethane, alkyltrialkoxysilanes such as
methyltrimethoxysilane (MTM) and methyltriethoxysilane,
alkenyltrialkoxy silanes such as vinyltrimethoxysilane and
vinyltriethoxysilane, isobutyltrimethoxysilane (iBTM). Other
suitable silanes include ethyltrimethoxysilane,
vinyltriethoxysilane, phenyltrimethoxysilane, alkoxytrioximosilane,
alkenyltrioximosilane, 3,3,3-trifluoropropyltrimethoxysilane,
methyltriacetoxysilane, vinyltriacetoxysilane, ethyl
triacetoxysilane, di-butoxy diacetoxysilane,
phenyl-tripropionoxysilane, methyltris(methylethylketoximo)silane,
vinyl-tris-methylethylketoximo)silane,
methyltris(methylethylketoximino)silane,
methyltris(isopropenoxy)silane, vinyltris(isopropenoxy)silane,
ethylpolysilicate, n-propylorthosilicate, ethylorthosilicate,
dimethyltetraacetoxydisiloxane.The cross-linker used may also
comprise any combination of two or more of the above. For example
the catalyst package may comprise from 1 to 30 weight % of
cross-linker (iii), alternatively 5 to 25 weight %.
Pigments (vi)
[0079] Pigments are utilised to colour the composition as required.
Any suitable pigment may be utilised providing it is compatible
with the composition. In two part compositions pigments and/or
coloured (non-white) fillers e.g. carbon black may be utilised in
the catalyst package to colour the end sealant product. When
present carbon black will function as both filler and colorant.
Fillers (vii)
[0080] One of the fillers used in the base component may also be
used in the catalyst package if/when deemed appropriate. Silica,
e.g. fumed silica and/or calcium carbonate being preferred. Fillers
(vii) may be present in the catalyst package in an amount of from 0
to 50 weight % depending on the mixing ratio of the two parts of
the composition.
[0081] Other additives may be used if necessary. These may include
heat stabilizers, flame retardants, UV stabilizers, cure modifiers,
electrically conductive fillers, heat conductive fillers, and
fungicides and/or biocides and the like.
Biocides
[0082] Biocides may additionally be utilized in the composition if
required. It is intended that the term "biocides" includes
bactericides, fungicides and algicides, and the like. Suitable
examples of useful biocides which may be utilised in compositions
as described herein include, for the sake of example:
[0083] Carbamates such as methyl-N-benzimidazol-2-ylcarbamate
(carbendazim) and other suitable carbamates,
10,10'-oxybisphenoxarsine, 2-(4-thiazolyl)-benzimidazole,
N-(fluorodichloromethylthio)phthalimide, diiodomethyl p-tolyl
sulfone, if appropriate in combination with a UV stabilizer, such
as 2,6-di(tert-butyl)-p-cresol, 3-iodo-2-propinyl butylcarbamate
(IPBC), zinc 2-pyridinethiol 1-oxide, triazolyl compounds
andisothiazolinones, such as
4,5-dichloro-2-(n-octyl)-4-isothiazolin-3-one (DCOIT),
2-(n-octyl)-4-isothiazolin-3-one (OTT) and
n-butyl-1,2-benzisothiazolin-3-one (BBIT). Other biocides might
include for example Zinc Pyridinethione,
1-(4-Chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-ylmethyl)pentan-3-ol
and/or 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]
methyl]-1H-1,2,4-triazole.
[0084] The fungicide and/or biocide may suitably be present in an
amount of from 0 to 0.3% by weight of the composition and may be
present in an encapsulated form where required such as described in
EP2106418.
[0085] In the case of 2 part compositions the base component
comprises: [0086] 10 to 90% weight of siloxane polymer (a); [0087]
10 to 80 weight % reinforcing fillers (b); [0088] 0 to 20 Weight %
of non-reinforcing fillers (c); with the total weight % of the base
component being 100 weight % and in the catalyst package: [0089] 30
to 80% weight of alkoxy silyl terminated organic polymer (i),is
present in the catalyst package as a carrier and is present in the
catalyst package in an amount of from 30 to 80% weight,
alternatively 40 to 65 weight % of the total weight of the catalyst
package; 5 to 50 weight % of dipodal silanes (ii), alternatively 10
to 30 weight % of dipodal silanes (ii), [0090] 5 to 25 weight % of
non-dipodal adhesion promoter (iii), alternatively 2 to 20 weight %
[0091] to 3 weight % of tin based catalyst; alternatively 0.1 to
0.5 weight % of tin based catalyst (iv); [0092] 0 to 25 weight % of
cross-linker (v), alternatively 2 to 20 weight %; with the total
weight % of the catalyst package being 100 weight %.
[0093] In the case of 2 part sealant compositions, the components
of each part are mixed together in amounts within the ranges given
above and then the base component composition and the catalyst
package composition are inter-mixed in a predetermined ratio e.g.
from 15:1 to 1:1, alternatively from 14:1 to 5:1 alternatively from
14:1 to 7:1. If the intended mixing ratio of the base component:
catalyst package is 15:1 or greater then no filler will be
generally utilized in the catalyst package. However if the intended
mixing ratio of the base component: catalyst package is less than
15:1 an increasing amount filler will be utilized in the catalyst
package up to the maximum of 50% weight of the catalyst package, if
the intended ratio is 1:1. The moisture curable compositions can be
prepared by mixing the ingredients employing any suitable mixing
equipment.
[0094] Resulting compositions may be employed in a variety of
applications, for example as an adhesive for electronic
applications e.g. for LED lamps, general bonding and as a pottant
and the like. Other applications include uses involving coating,
caulking, mold making and encapsulating materials. For example, as
a sealant for structural glazing, insulating glazing, solar
applications, in industrial assembly and/or as an insulating glass
sealant. It may also be used for weather proofing.
[0095] There is also provided herein an insulating glass unit
and/or building facade element e.g. a shadow box and/or structural
glazing unit and/or a gas filled insulation construction panel
which in each case is sealed with a sealant cured from the silicone
sealant composition as hereinbefore described.
[0096] Use of the sealant composition as described above as an
insulating glass sealant e.g. for structural glazing, as a sealant
for LED lighting and other electrical applications and/or as a
sealant in an oven and/or as a structural coating on a
substrate.
EXAMPLES
Example 1
[0097] The intention herein was to provide a condensation cure
adhesive/sealant for LED lamp substrates as an alternative to
hydrosilylation cured materials to improve the strength of adhesion
between substrates. Two part condensation cure adhesives/sealants
provide fast deep section cure (over 90% of strength over 24 hours)
and have a typical snap time of between 20-120 min), good adhesion
to most substrates. They have the added advantage that the tin
catalysts used to cure such compositions are not inactivated by
other chemicals containing e.g. sulphur, and phosphorus. In order
to be suitable for LED lighting applications it was needed to
significantly reduce the snap time to between 3-6 min, and adhesion
and strength build up need to be quick enough within 30 min.
[0098] The catalyst package composition is provided in Table 1a.
Two base compositions were utilised for the present examples,
identified as base (1) and Base (2) in Table 1b. In respect to this
example base (1) was utilised.
TABLE-US-00001 TABLE 1a Catalyst Package Comp. 1 (wt. %)
Trimethoxysilylethylene terminated 52.5 polydimethylsiloxane,
viscosity = 30,000 mPa s @ 25.degree. C.
2,2,4,4,6,6-Hexamethylcyclotrisilazane 0.5 Treated Fumed silica
3.50 1,6-Bis (trimethoxysilyl)hexane 20 aminopropyltriethoxysilane
16 bis (3-trimethoxysilypropyl)amine 7 Dimethyl TIN Dineodecanoate
0.275
TABLE-US-00002 TABLE 1b Base 1 Base 2 Base Component (wt. %) (wt.
%) Treated precipitated calcium 49.5 50 carbonate Hydroxydimethyl
terminated 50.5 50 polydimethylsiloxane viscosity of 4000 mPa s @
25.degree. C.
[0099] The viscosity over time of the catalyst package was
determined using a Brookfield.RTM. cone plate viscometer (RV DM)
using cone plate CP-41 at 1 rpm and 5 rpm. Measurements were taken
at 25.degree. C. unless otherwise indicated. Results noted over
time for samples aged at room temperature are provided in Table 1c
and results noted over time after aging at a temperature of
50.degree. C. are provided in Table 1d.
TABLE-US-00003 TABLE 1c 3 Month 5 Month aging at aging at Fresh
Room temp. Room temp. Appearance OK OK Begin to crack after 4 Month
storage viscosity (mPa s) 14150 6779 4617 using cone plate CP-41 at
1 rpm for 3 minutes viscosity (mPa s) 8802 3390 1611 using cone
plate CP-41 at 1 rpm for 3 minutes
TABLE-US-00004 TABLE 1d 2 weeks 4 weeks 6 weeks 8 weeks aging at
aging at aging at aging at Fresh 50.degree. C. 50.degree. C.
50.degree. C. 50.degree. C. Viscosity 14150 8449 5796 4814 5207
(mPa s) using cone plate CP-41 at 1 rpm for 3 minutes Viscosity
8802 3910 2299 1709 1709 (mPa s) using cone plate CP-41 at 1 rpm
for 3 minutes
Snap time
[0100] After each time period identified in Table 1d the catalyst
package analysed was mixed with the base (1) of Table 1b above and
the snap time was determined and values are provided in Table 1e
below.
[0101] Snap time is measured by gently touching at regular time
intervals (typically 2-3 min) a spatula on the surface of the
curing composition. As the cure progresses, the coating gains
viscosity and elasticity. When these two are sufficiently high, the
coating "snaps off" the spatula. The time elapsed between the
casting of the coating and the first observation of the snap-off
effect is recorded as snap time. This value has practical
importance, because it provides an indication about the working
time of the coating. The working time is defined as the time which
the applicator is able to work with the material before the latter
reaches a state of sufficiently high viscosity which prevents it
from being properly handled and tooled. Snap time is used as a
rough estimation of the working time. In this case base 2 was mixed
with the catalyst package for the measurement of snap time.
TABLE-US-00005 TABLE 1e 2 weeks 4 weeks 6 weeks 8 weeks aging at
aging at aging at aging at Fresh 50.degree. C. 50.degree. C.
50.degree. C. 50.degree. C. snap time 5.5' 7.08 7.17 6.83 6.5
(min)
[0102] It was identified in Example 1 that whilst the addition of
higher levels of primary amino silane and bis
(3-trimethoxysilylpropyl)amine adhesion promoters certainly
enhanced snap times, they met other complications in that the high
levels of adhesion promoter used lead to destabilizing of the
siloxane polymer carrier in the catalyst package leading to a
significant reduction of viscosity of the catalyst package, i.e.
poor storage stability.
Example 2
[0103] In this example the stability of two catalyst packages Ex.1
and Ex.2 as hereinbefore described are compared with those of a
prior art unreactive silicone carrier material accordance with the
invention. The composition of the catalyst packages used are
provided in Table 2a. Polyether (1) was a
trimethoxysilyl-terminated polyether having a viscosity of between
32000 and 45000 mPas at 25.degree. C. and polyether (2) was
trimethoxysilyl-terminated polyether having a viscosity of
approximately 120,000 mPas at 25.degree. C.
TABLE-US-00006 TABLE 2a Ex. 1 Ex. 2 Comp. 2 (wt. %) (wt. %) (wt. %)
Polyether (1) 60.70 Polyether (2) 60.7 Trimethyl terminated
polydimethyl- 60.70 siloxane 60,000 mPa s @ 25.degree. C.
2,2,4,4,6,6-Hexamethylcyclotrisilazane 0.5 0.5 0.50 Treated Fumed
silica 3.5 3.5 3.50 1,6-Bis (trimethoxysilyl)hexane 14 14 14.00
aminopropyltriethoxysilane 16 16 16.00 bis
(3-trimethoxysilypropyl)amine 5 5 5.00 Dimethyl TIN Dineodecanoate
0.3 0.3 0.30 100.00 100.00 100.00
[0104] The viscosity over time of the catalyst package was
determined, unless otherwise indicated) using a Brookfield.RTM.
cone plate viscometer (RV Dill) using cone plate CP-41 at 5 rpm.
Measurements were taken at 25.degree. C. unless otherwise
indicated. Results noted over time for samples aged at room
temperature and results noted over time after aging at a
temperature of 50.degree. C. are provided in Table 2b.
TABLE-US-00007 TABLE 2b Viscosity Viscosity Viscosity Ex. 1 Ex. 2
Comp. 3 (mPa s) (mPa s) (mPa s) Fresh at Room 6838 4853 36742
temperature (RT) (measured at 1 rpm as the viscosity will be out of
the measurement range if measure at 5 rpm) Aging for 1 6857 4460
17349 week at RT Aging for 1 7132 4696 11258 month at RT Aging for
1 6562 4558 6464 week at 50.degree. C. Aging for 2 6091 4774 6307
weeks at 50.degree. C. Aging for 4 6012 4657 2731 weeks at
50.degree. C.
[0105] It will be appreciated that the compositions using
polyethers (1) and (2) carrier material in the catalyst package
retained a reasonably constant measurements for viscosity over time
after both room temperature and high temperature aging. Given these
results weight average molecular weight values were determined for
the polyethers and siloxane in the compositions as different
polymer carriers using gel permeation chromatography. The results
are depicted in Table 2c
TABLE-US-00008 TABLE 2c Ex. 1 Ex. 2 Comp. 3 Mw Mw Mw Fresh 35093
26292 107164 Aging for 1 29980 23548 82176 month at RT Aging for 1
33967 26660 67179 week at 50.degree. C. Aging for 2 26918 21606
47704 weeks at 50.degree. C. Aging for 4 27390 23239 36546 weeks at
50.degree. C.
[0106] These results supported the results in Table 2b, i.e. that
whilst the polyether based polymers were retaining their weight
average Molecular weight during aging the siloxane was degrading
resulting in a significant decrease in viscosity which showed a
lack of stability of the catalyst package.
Example 3
[0107] In this study it is intended to determine the effect of high
levels of catalyst in the absence of the dipodal silane (ii) and
also the presence of the dipodal silane (ii) had an effect on snap
time. The compositions used for the assessment are provided in
Table 3a and the results attained are provided in Table 3b.
TABLE-US-00009 TABLE 3a Comp. 4 Ex. 3 Comp. 5 Comp. 6 Polyether (1)
66.7 59.7 64 54 Treated fumed silica 3 3 3 3 Bis 14 14 14 14
(trimethoxysilyl)hexane aminopropyl- 16 16 16 16 triethoxysilane
Bis (3-trimethoxy- 0 7 0 0 silylpropyl)amine Dimethyl tin 0.3 0.3 3
13 dineodecanoate Total 100.00 100.00 100.00 100.00
[0108] In the following Table the adhesion to substrate surfaces
was assessed by determining the lap shear tensile strength and the
failure type (Adhesive/cohesive) as discussed below.
[0109] Lap shear Tensile Strength The base component and catalyst
package were mixed and Samples of a pre-determined amount of the
composition were applied onto a pre-cleaned first substrate surface
in a laminating apparatus. A second substrate was the placed on top
of the composition applied to the first substrate to give a
pre-sized lap. The two substrates were compressed and excess
composition was removed. The samples were cured at a temperature of
80.degree. C. for a period of 30 minutes after which the lap shear
tensile strength was determined by pulling apart by shear rather
than peel (180.degree. pull) at a rate of 5.1 cm/min.
Adhesive/Cohesive Failure
[0110] Adhesive failure (AF) refers to the situation when a sample
detaches cleanly (peels off) from a substrate surface. Cohesive
failure (CF) is observed when the coating itself breaks without
detaching form the substrate surface. In most cases cohesive
failure was observed on the previously pulled apart laminates. In
some cases a mixed failure mode has been observed: i.e. some areas
peel-off (i.e. AF) while some remain covered with coating (i.e.
CF). In such instances the portion displaying CF (%C F) is recorded
(bearing in mind % CF+% AF=100%). In this example the catalyst
package was mixed with base 1.
TABLE-US-00010 TABLE 3b Comp. 4 Ex. 3 Comp. 5 Comp. 6 Snap time
(min) 23.5 3.75 7.00 5.00 Viscosity Fresh 14481 8115 17899 10060
Viscosity, after 2 weeks 11455 5934 9156 6661 aging at 50.degree.
C. Lap shear tensile 887 907 1147 1103 strength (Adhesion build-up
at Glass/Glass, interface) (kPa) Cohesive Failure on 100 100 100
100 glass (%) Lap shear Tensile 730 747 860 1215 Strength (Adhesion
build- up at Glass/PBT interface) (KPa) Cohesive Failure on 95 100
100 100 glass (%) Cohesive Failure on 95 75 60 100 PBT (%) Lap
Shear Tensile 975 1183 1265 1360 Strength (Adhesion build-up at
Glass/ Aluminium interface), (KPa) Cohesive Failure on 100 100 100
100 glass (%) Cohesive Failure on 100 100 100 100 aluminium (%)
[0111] For the avoidance of doubt PBT is polybutylene
terephthalate. The adhesion test with PBT gave apparently low
results but these are standard for untreated PBT and the experiment
was not repeated on activated PBT.
[0112] It was seen that in the absence of dipodal silane (ii) the
snap time was significantly slower than required. It was also to be
noted that compositions containing high levels of catalyst cause a
significant reduction in polymer viscosity i.e. catalyst package
stability.
Example 4
[0113] This example sought to determine whether or not the
compositions would cure without the tin based catalyst (iii). The
compositions used is depicted in Table 4a.
TABLE-US-00011 TABLE 4a Comp. 7 Comp. 8 Comp. 9 Comp. 10 polyether
(1) 64 60 57 52 Treated fumed silica 3 3 3 3 Bis 14 14 14 14
(trimethoxysilyl)hexane aminopropyltriethoxy- 16 16 16 16 silane
Bis (3-trimethoxy- 3 7 10 15 silylpropyl)amine Dimethyl tin 0 0 0 0
dineodecanoate Total 100.00 100.00 100.00 100.00
[0114] To generate snap time results etc., the catalyst package was
mixed with base 1.
TABLE-US-00012 TABLE 4b Comp. 7 Comp. 8 Comp. 9 Comp. 10 Snap time
(hours) >3.5 >3.5 >3.5 3 Viscosity Fresh 10394 7388 5423
3537 (mPa s) Viscosity, after 2 9274 6798 5108 3136 weeks aging at
50.degree. C. (mPa s) Lap shear Tensile 30 26 25 20 Strength
(Adhesion build-up at Glass/Glass interface) (KPa) Cohesive Failure
on Did not Did not Did not Did not glass (%) Cure Cure Cure
Cure
[0115] It was identified that the tin catalyst, (iii) was clearly
an essential ingredient of the composition.
Example 5
[0116] Catalyst packages were prepared using a selection of
alternative alkoxy silyl terminated organic polymers (i) with the
compositions of the catalyst package being provided in Table 5a
below wherein the alkoxy silyl terminated organic polymers (i) were
as follows:
[0117] The acrylate polymer was a trimethoxysilyl-terminated
polyacrylate having a viscosity of between about 70 Pas at
25.degree. C. (E-type viscometer) and a glass temperature of about
-50.degree. C.;
[0118] Aliphatic polymer (1) was an alkoxysilyl terminated
aliphatic prepolymer with a viscosity of approximately 20,000 mPas
at 23.degree. C. (method M014-ISO 3219/A.3).
[0119] liphatic polymer (2) was an alkoxysilyl terminated aliphatic
prepolymer with a viscosity of approximately 30,000-50,000 mPas at
23.degree. C. (method M014-ISO 3219/A.3).
[0120] In this case base 1 was mixed with the catalyst package.
TABLE-US-00013 TABLE 5a Ex. 4 Ex. 5 Ex 6 Ex. 7 Polyether (1) 59.65
Acrylate polymer 52.7 Aliphatic Polymer (1) 56.7 Aliphatic Polymer
(2) 56.7 Treated fumed silica 3 10 6 6 Bis (trimethoxysilyl)hexane
14 14 14 14 aminopropyltriethoxy silane 16 16 16 16 Bis (3- 7 7 7 7
trimethoxysilylpropyl)amine Dimethyl tin dineodecanoate 0.35 0.3
0.3 0.30 Total 100.00 100.00 100.0 100.00
TABLE-US-00014 TABLE 5b Ex. 4 Ex. 5 Ex 6 Ex. 7 Snap time (min) 5.5
4.58 4.67 5.58 Compatibility good good, good good yellowing Lap
Shear Tensile 953 760 600 810 Strength (Adhesion build-up at
Glass/Glass interface) (KPa) Cohesive Failure on 100 100 100 100
glass (%)
TABLE-US-00015 TABLE 5c Viscosity Viscosity Viscosity Viscosity Ex.
4 Ex. 5 Ex. 6 Ex. 7 (mPa s) (mPa s) (mPa s) (mPa s) Fresh at Room
6798 33107 57372 50102 temperature (RT) Aging for 2 5894 43226
28883 25444 weeks at 50.degree. C. Aging for 4 5875 32419 43520
28490 weeks at 50.degree. C.
* * * * *