U.S. patent application number 15/956510 was filed with the patent office on 2018-08-23 for silicone polymer emulsions.
The applicant listed for this patent is Dow Silicones Corporation. Invention is credited to Kathleen BARNES, Jary David JENSEN, Walker L. ROCHLITZ, Andreas STAMMER.
Application Number | 20180237720 15/956510 |
Document ID | / |
Family ID | 38962825 |
Filed Date | 2018-08-23 |
United States Patent
Application |
20180237720 |
Kind Code |
A1 |
BARNES; Kathleen ; et
al. |
August 23, 2018 |
SILICONE POLYMER EMULSIONS
Abstract
Silicone oil-in-water emulsions containing a polysiloxane
containing polymer is prepared by first preparing a polysiloxane
containing polymer by the polymerisation of siloxane containing
monomers and/or oligomers in the presence of an inert organopoly
siloxane and/or an organic fluid, a suitable catalyst and
optionally an end-blocking agent; and quenching the reaction if
required. If required one or more surfactants may be introduced
into the polysiloxane containing polymer to form a homogenous oil
phase. Water is then added (in an amount of 0.1-10 percent by
weight based on total oil phase weight) to the homogenous oil phase
to form a water-in-oil emulsion. Shear is applied to the
water-in-oil emulsion to cause inversion of the water-in-oil
emulsion to an oil-in-water emulsion. Finally, if required the
oil-in-water emulsion can be diluted by adding more water.
Inventors: |
BARNES; Kathleen; (Midland,
MI) ; JENSEN; Jary David; (Beaverton, MI) ;
ROCHLITZ; Walker L.; (Midland, MI) ; STAMMER;
Andreas; (Pont-a Celles, BE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Silicones Corporation |
Midland |
MI |
US |
|
|
Family ID: |
38962825 |
Appl. No.: |
15/956510 |
Filed: |
April 18, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12445102 |
Dec 21, 2009 |
9976105 |
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PCT/US2007/021562 |
Oct 9, 2007 |
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15956510 |
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60828864 |
Oct 10, 2006 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2229/0415 20130101;
A61K 8/891 20130101; D06M 15/643 20130101; C10M 2229/0455 20130101;
A61Q 1/10 20130101; A61Q 5/02 20130101; C10M 2229/0435 20130101;
C10M 2229/0405 20130101; C10M 2229/045 20130101; C10M 173/02
20130101; C10M 155/02 20130101; C10M 2229/04 20130101; C11D 3/373
20130101; C08J 2383/04 20130101; A61Q 19/10 20130101; A61K 8/062
20130101; C10M 107/50 20130101; A61Q 5/12 20130101; C10M 2229/043
20130101; C08J 3/03 20130101; A61Q 19/00 20130101; C10M 2229/041
20130101; A61K 8/068 20130101 |
International
Class: |
C10M 155/02 20060101
C10M155/02; D06M 15/643 20060101 D06M015/643; A61K 8/06 20060101
A61K008/06; C11D 3/37 20060101 C11D003/37; A61K 8/891 20060101
A61K008/891; A61Q 19/00 20060101 A61Q019/00; C08J 3/03 20060101
C08J003/03; C10M 107/50 20060101 C10M107/50; C10M 173/02 20060101
C10M173/02 |
Claims
1-15. (canceled)
16. A silicone oil-in-water emulsion comprising: an inert
organopolysiloxane and/or an organic fluid; and a polysiloxane
containing polymer comprising the reaction product of siloxane
containing monomers and/or oligomers in the presence of a catalyst
and the inert fluid; wherein the polysiloxane containing polymer is
of the following general formula
R.sub.(3-a)R.sup.1.sub.aSiO[(R.sub.2SiO).sub.b(RR.sup.1SiO).sub.-
c]SiR.sub.(3-a)R.sup.1.sub.a (1) wherein each R is the same or
different and is an alkyl group containing 1 to 8 carbon atoms, a
substituted alkyl group containing 1 to 6 carbon atoms, or a phenyl
group; R.sup.1 is a hydroxy group, a hydrolysable group, or an
unsaturated organic group; a is zero or 1; b is an integer; c is
zero or an integer; and the sum of b+c is equal to a value of at
least 200.
17. The emulsion according to claim 16, wherein the sum of b+c is
equal to a value of at least 500, optionally is equal to a value of
at least 1500.
18. The emulsion according to claim 16, wherein the inert fluid is
retained within the polysiloxane containing polymer in an amount of
not more than 70% w/w.
19. The emulsion according to claim 18, wherein the inert fluid is
retained within the polysiloxane containing polymer in an amount of
from 5 to 70% w/w.
20. The emulsion according to claim 16, wherein the polysiloxane
containing polymer comprises a degree of branching of less than
10%, optionally a degree of branching of less than 2%.
21. The emulsion according to claim 16, wherein the inert fluid is
selected from the group of an organic extender, a plasticizer, a
natural oil, and combinations thereof.
22. The emulsion according to claim 16, wherein the inert fluid is
a cyclic siloxane comprising between 3 to 20 silicon atoms.
23. The emulsion according to claim 22, wherein the polysiloxane
containing polymer is a polydimethyl gum.
24. The emulsion according to claim 16, wherein the inert fluid is
a trialkylsilyl terminated polydialkylsiloxane or a derivative
thereof, and optionally has a viscosity of from 0.65 to 10000 mPas
at 25.degree. C.
25. The emulsion according to claim 16, wherein the polysiloxane
containing polymer is prepared via a reaction process selected from
the group of polycondensation, chain extension, polyaddition, and
ring opening.
26. The emulsion according to claim 16, further comprising a
surfactant, and optionally wherein the catalyst is part of the
surfactant.
27. The emulsion according to claim 26, wherein the polysiloxane
containing polymer is prepared via a polycondensation reaction and
the catalyst is dodecylbenzenesulphonic acid.
28. The emulsion according to claim 16, wherein a homogenous oil
phase is from 1000 to 100000 mPas at 25.degree. C.
29. The emulsion according to claim 16, prepared by a method
comprising the steps of: (i) preparing the polysiloxane containing
polymer by the polymerization of siloxane containing monomers
and/or oligomers in the presence of the inert fluid and catalyst
and optionally an end-blocking agent; (ii) optionally quenching the
polymerization process; wherein the inert fluid is retained within
the resulting polysiloxane containing polymer; (iii) optionally
introducing one or more surfactants into the polysiloxane
containing polymer to form a homogenous oil phase; (iv) adding
water to the homogenous oil phase to form a water-in-oil emulsion,
the water being added in an amount of 0.1 to 10 percent by weight
based on the total oil phase weight; (v) applying shear to the
water-in-oil emulsion to cause inversion of the water-in-oil
emulsion to an oil-in-water emulsion; and (vi) optionally diluting
the oil-in-water emulsion by adding more water.
30. The emulsion according to claim 29, wherein the sum of b+c is
equal to a value of at least 500, optionally at least 1500.
31. The emulsion of claim 29, wherein the inert fluid is retained
within the polysiloxane containing polymer in an amount of not more
than 70% w/w, optionally in an amount of from 5 to 70% w/w.
32. The emulsion according to claim 29, wherein the inert fluid has
a viscosity of from 0.65 mPas to 10000 mPas at 25.degree. C. and is
selected from an organopolysiloxane extender or plasticizer, an
organic extender or plasticizer, or a cyclic siloxane comprising
between 3 and 20 silicon atoms.
33. The emulsion according to claim 29, wherein the siloxane
containing monomers and/or oligomers comprise hydroxyl-terminated
organopolysiloxanes.
34. A personal care product comprising the emulsion according to
claim 16.
35. The emulsion according to claim 16 in paints, construction
applications, textile fibre treatments, leather lubrication, fabric
softening, fabric care for laundry applications, healthcare,
homecare, personal care, release agents, water based coatings, oil
drag reduction, lubrication, and facilitation of cutting cellulose
materials.
Description
[0001] This invention relates to silicone in water emulsions,
methods of making said emulsions and their uses.
[0002] Silicone emulsions are well known in the art. Such silicone
emulsions can be made by processes such as (i) mechanical
emulsification, (ii) mechanical emulsification by inversion, or by
(iii) emulsion polymerization. However, because of the high
viscosity of some silicones such as silicone gums, their
emulsification has for all practical purposes been limited to
emulsion polymerization. In contrast, silicones with a low
viscosity and hence a low molecular weight can easily be obtained
mechanically.
[0003] Attempts to use mechanical methods for emulsifying high
molecular weight and viscosity organopolysiloxane polymers, often
referred to as silicone gums, have largely been unsuccessful,
because it is difficult to incorporate a surfactant or a mixture of
surfactants into the polymer because of the viscosity of the
polymer. It is also difficult to incorporate water into mixtures
containing high viscosity silicones, a surfactant, or a mixture of
surfactants, and at the same time impart sufficient shear to cause
inversion. In addition, the control of particle size has been
limited to processes involving batch-wise mechanical emulsification
in the presence of a volatile solvent which is substantially
removed during the polymerisation process.
[0004] In contrast to the above, the present invention provides an
inexpensive technique for producing stable emulsions comprising
silicone polymers including polymers which if traditionally
prepared would have the viscosity of a silicone gum or like high
viscosity polymers.
[0005] Whilst the present application relates to organopolysiloxane
polymers having a viscosity when prepared traditionally of greater
than 50 000 mPas at 25.degree. C. being used to prepare emulsions
it is considered particularly pertinent to organopolysiloxane
polymers of very high viscosity, known in the industry as Silicone
gums (e.g. viscosity of about 1 000 000 mPas at 25.degree. C. or
greater). Silicone gums are high molecular weight generally linear
or branched polydiorganosiloxanes that can be converted from their
highly viscous plastic state into a predominately elastic state by
crosslinking. Silicone gums are often used as one of the main
components in the preparation of silicone elastomers and silicone
rubbers.
[0006] For purposes of this invention therefore, silicone gum can
be considered to describe stiff gum-like organosiloxane polymer
having a degree of polymerisation equal to or greater than 1500.
These polymers are preferably substantially linear, most preferably
completely linear and have a viscosity which is sufficiently high
to render direct viscosity very difficult and as such are often
referred to in terms of their Williams plasticity number. Gums
typically have a Williams plasticity number (ASTM D926) in the
range of from about 30 to 250 (the thickness in
millimetres.times.100 of a cylindrical test specimen 2 cubic cm in
volume and approximately 10 mm in height after the specimen has
been subjected to a compressive load of 49 Newtons for three
minutes at 25.degree. C.
[0007] The two main routes to emulsifying high molecular weight
silicones are emulsion polymerisation or the dilution of pre-formed
high molecular weight polymers with low molecular weight silicone
fluids such as cyclic siloxanes comprising between 2 and 20 silicon
atoms. Proceeding down either of these routes can lead to a number
of processing problems which are extremely difficult to overcome.
In the case of emulsion polymerisation it is exceptionally
difficult to control the molecular weight of the end product and
indeed viscosities resulting from such processes are so high that
there is typically no absolute means of measuring the viscosity of
the product manufactured via this route. It is also difficult to
achieve a truly continuous process. Pre-formed siloxane polymers
having very high viscosities (viscosity greater than 1 000 000 mPas
at 25.degree. C.) are very difficult to dilute because it is very
difficult to get lower weight compounds to blend in to the high
molecular weight polymer.
[0008] U.S. Pat. No. 5,973,068 discusses the emulsion
polymerisation of a silanol-terminated resin and a vinyl monomer.
Polymerization in the emulsion polymerization process occurs at the
silicone water interface so that the rate of polymerization is
faster with smaller particles because of the larger surface area.
Thus, it is impossible to produce large particle size, high
molecular weight silicone gum in water emulsions by emulsion
polymerisation.
[0009] EP1646696 describes a method of making a silicone
oil-in-water emulsion comprising the steps of forming a homogeneous
oil phase containing a silicone gum, or the like in the homogenous
oil phase mixing one or more surfactants with the homogenous oil
phase; adding water to the homogenous oil phase to form a
water-in-oil emulsion containing a continuous phase and a dispersed
phase, the water being added in an amount of about 0.5-10 percent
by weight based on the weight of the silicone in the homogenous oil
phase; applying high shear to the water-in-oil emulsion in a
twin-screw extruder having a length to diameter L/D ratio of at
least 15, to cause inversion of the water-in-oil emulsion to an
oil-in-water emulsion; and diluting the oil-in-water emulsion by
the addition of water.
[0010] EP1447423 describes a process for the production of a
silicone in water emulsion in which a polysiloxane fluid, at least
one surfactant and water are continuously fed to a high shear mixer
in such proportions as to form a viscous oil in water emulsion
which is continuously withdrawn from the mixer. The polysiloxane
fluid may be a non-reactive fluid or may have reactive groups
capable of taking part in a chain extension reaction.
[0011] The invention is directed to a method of making silicone
oil-in-water emulsions containing a polysiloxane containing polymer
comprising the steps of [0012] i) Preparing a polysiloxane
containing polymer by the polymerisation of siloxane containing
monomers and/or oligomers in the presence of an inert
organopolysiloxane and/or an organic fluid, a suitable catalyst and
optionally an end-blocking agent; and [0013] ii) Where required
quenching the polymerisation process; wherein the inert fluid is
substantially retained within the resulting diluted polysiloxane
containing polymer [0014] (iii) if required, introducing one or
more surfactants into the polysiloxane containing polymer to form a
homogenous oil phase; [0015] (iv) adding water to the homogenous
oil phase to form a water-in-oil emulsion containing a continuous
phase and a dispersed phase, [0016] (v) applying shear to the
water-in-oil emulsion to cause inversion of the water-in-oil
emulsion to an oil-in-water emulsion; and optionally [0017] (vi)
diluting the oil-in-water emulsion by adding more water.
[0018] The concept of "comprising" where used herein is used in its
widest sense to mean and to encompass the notions of "include" and
"consist of". All viscosity measurements referred to herein were
measured at 25.degree. C. unless otherwise indicated.
[0019] For the sake of this application an inert fluid a
substantially non-volatile fluid which is intended to be unreactive
towards any other constituent i.e. it does not chemically
participate in the polymerisation reaction of step (i) or
chemically interact with the additives introduced in any of steps
(i) through to (vi). The inert fluid is not removed prior to
emulsification. Hence the inert fluid is substantially present in
the emulsion.
[0020] A polysiloxane containing polymer is intended to mean a
polymer comprising multiple organosiloxane or polyorganosiloxane
groups per molecule and is intended to include a polymer
substantially containing only organosiloxane or polyorganosiloxane
groups in the polymer chain and polymers where the backbone
contains both organosiloxane and/or polyorganosiloxane groups and
e.g. organic polymeric groups in the polymeric chain. Such polymers
can be homopolymers or co-polymers, including, but not limited to,
block co-polymers and random co-polymers.
[0021] In accordance with the present invention a polysiloxane
containing polymer is polymerised in the presence of an inert fluid
preferably has the general formula:
R.sub.(3-a)R.sup.1.sub.aSiO[(R.sub.2SiO).sub.b(RR.sup.1SiO).sub.c]SiR.su-
b.(3-a)R.sup.1.sub.a (1)
wherein each R is the same or different and is an alkyl group
containing 1-8 carbon atoms, a substituted alkyl group containing 1
to 6 carbon atoms or an optionally substituted phenyl group;
R.sup.1 is hydrogen, a hydroxy group, a hydrolysable group, an
unsaturated organic group; a is zero or 1, b is an integer and c is
zero or an integer and the sum of b+c is equal to a value of at
least 200 preferably at least 500, more preferably at least 1500.
Such a polymer may comprise a degree of branching (preferably less
than 10%, more preferably less that 2%).
[0022] For the purpose of this application "Substituted", when used
in relation to hydrocarbon groups, means one or more hydrogen atoms
in the hydrocarbon group has been replaced with another
substituent. Examples of such substituents include, but are not
limited to, halogen atoms such as chlorine, fluorine, bromine, and
iodine; halogen atom containing groups such as chloromethyl,
perfluorobutyl, trifluoroethyl, and nonafluorohexyl; oxygen atoms;
oxygen atom containing groups such as (meth)acrylic and carboxyl;
nitrogen atoms; nitrogen atom containing groups such as amines,
amino-functional groups, amido-functional groups, and
cyano-functional groups; sulphur atoms; and sulphur atom containing
groups such as mercapto groups.
[0023] The polymeric chain may comprise blocks made from chains of
units depicted in Formula (1) above where the two R groups or R and
R.sup.1 groups are:-- [0024] both alkyl groups (preferably both
methyl or ethyl), or [0025] alkyl and phenyl groups, or [0026]
alkyl and fluoropropyl, or [0027] alkyl and vinyl or [0028] alkyl
and hydrogen groups. Typically at least one block will comprise
siloxane units in which both R groups are alkyl groups.
[0029] Whilst preferably the polysiloxane containing polymer has a
substantially organopolysiloxane molecular chain, the polysiloxane
containing polymer may alternatively contain a block copolymeric
backbone comprising at least one block of siloxane groups and an
organic component comprising any suitable organic based polymer
backbone for example the organic polymer backbone may comprise, for
example, polystyrene and/or substituted polystyrenes such as
poly(.alpha.-methylstyrene), poly(vinylmethylstyrene), dienes,
poly(p-trimethylsilylstyrene) and
poly(p-trimethylsilyl-.alpha.-methylstyrene). Other organic
components which may be incorporated in the polymeric backbone may
include acetylene terminated oligophenylenes, vinylbenzyl
terminated aromatic polysulphones oligomers, aromatic polyesters;
aromatic polyester based monomers, polyalkylenes, polyurethanes,
aliphatic polyesters, aliphatic polyamides and aromatic polyamides
and the like.
[0030] However perhaps the most preferred organic based polymeric
blocks in polysiloxane containing polymer are polyoxyalkylene based
blocks. The oxyalkylene units are not necessarily identical
throughout the polyoxyalkylene monomer, but can differ from unit to
unit. A polyoxyalkylene block, for example, can be comprised of
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 and/or oxypropylene units.
[0031] Other polyoxyalkylene blocks in the polysiloxane containing
polymer may include for example units of the structure--
-[--R.sup.2--O--(--R.sup.3--O--).sub.d--Pn--C(R.sup.4).sub.2--Pn--O--(---
R.sup.3--O--).sub.e--R.sup.2]--
in which Pn is a 1,4-phenylene group, each R.sup.2 is the same or
different and is a divalent hydrocarbon group having 2 to 8 carbon
atoms, each R.sup.3 is the same or different and, is, an ethylene
group propylene group or isopropylene group, each R.sup.4 is the
same or different and is a hydrogen atom or methyl group and each
of the subscripts d and e is a positive integer in the range from 3
to 30.
[0032] Preferably the inert fluid is selected from an
organopolysiloxane extender and/or plasticiser and/or an organic
extender or plasticiser or a cyclic siloxane comprising between 3
and 20 silicon atoms. Preferably the inert fluid has a viscosity of
from 0.65 mPas at 25.degree. C.--10000 mPas at 25.degree. C.
[0033] For the sake of this application an extender (sometimes also
referred to as a process aid or secondary plasticiser) is a
compound typically used to dilute e.g. silicone based product to
make the product more economically competitive without
substantially negatively affecting the properties of the sealant
formulation.
[0034] A plasticiser (otherwise referred to as a primary
plasticiser) is added to silicone based compositions to provide
properties within the final polymer based product to increase the
flexibility and toughness of cured elastomers. This is generally
achieved by reduction of the glass transition temperature (T.sub.g)
of the cured polymer composition thereby e.g. enhancing the
elasticity of the elastomer (e.g. a sealant). Plasticisers tend to
be generally less volatile than extenders.
[0035] Suitable inert liquids include trialkylsilyl terminated
polydialkylsiloxanes and derivatives thereof which may comprise a
degree of substitution, with the provision that any substituted
groups in the inert fluid do not participate in the polymerisation
reaction. The substituted groups on the inert fluid are preferably
the same as those identified in the previous definition of
substituted groups with respect to hydrocarbon groups. Preferably
each alkyl group may be the same or different and comprises from 1
to 8 carbon atoms but is preferably a methyl or ethyl group,
preferably with a viscosity of from 0.65 to 100 000 mPas at
25.degree. C. and most preferably from 10 to 1000 mPas at
25.degree. C.
[0036] The inert fluid may comprise any suitable organic
extender/organic plasticiser. Mineral oil extenders and
plasticisers are however particularly preferred. Examples include
linear or branched mono unsaturated hydrocarbons such as linear or
branched alkenes or mixtures thereof containing at least 12, e.g.
from 12 to 25 carbon atoms; and/or mineral oil fractions comprising
linear (e.g. n-paraffinic) mineral oils, branched (iso-paraffinic)
mineral oils, cyclic (referred in some prior art as naphthenic)
mineral oils and mixtures thereof. Preferably the hydrocarbons
utilised comprise at least 10, preferably at least 12 and most
preferably greater than 20 carbon atoms per molecule.
[0037] Other preferred mineral oil extenders include
alkylcycloaliphatic compounds, low molecular weight
polyisobutylenes, Phosphate esters, alkybenzenes including
polyalkylbenzenes which are unreactive with the polymer.
[0038] Any suitable mixture of mineral oil fractions may be
utilised as the extender in the present invention but high
molecular weight extenders (e.g. >220) are particularly
preferred. Examples include:--
alkylcyclohexanes (molecular weight >220); paraffinic
hydrocarbons and mixtures thereof containing from 1 to 99%,
preferably from 15 to 80% n-paraffinic and/or isoparaffinic
hydrocarbons (linear branched paraffinic) and 1 to 99%, preferably
85 to 20% cyclic hydrocarbons (naphthenic) and a maximum of 3%,
preferably a maximum of 1% aromatic carbon atoms. The cyclic
paraffinic hydrocarbons (naphthenics) may contain cyclic and/or
polycyclic hydrocarbons. Any suitable mixture of mineral oil
fractions may be used, e.g. mixtures containing [0039] (i) 60 to
80% paraffinic and 20 to 40% naphthenic and a maximum of 1%
aromatic carbon atoms; [0040] (ii) 30-50%, preferably 35 to 45%
naphthenic and 70 to 50% paraffinic and or isoparaffinic oils;
[0041] (iii) hydrocarbon fluids containing more than 60 wt. %
naphthenics, at least 20 wt. % polycyclic naphthenics and an ASTM
D-86 boiling point of greater than 235.degree. C.; [0042] (iv)
hydrocarbon fluid having greater than 40 parts by weight naphthenic
hydrocarbons and less than 60 parts by weight paraffinic and/or
isoparaffinic hydrocarbons based on 100 parts by weight of
hydrocarbons.
[0043] Preferably the mineral oil based extender or mixture thereof
comprises at least one of the following parameters:-- [0044] (i) a
molecular weight of greater than 150, most preferably greater than
200; [0045] (ii) an initial boiling point equal to or greater than
230.degree. C. (according to ASTM D 86). [0046] (iii) a viscosity
density constant value of less than or equal to 0.9; (according to
ASTM 2501) [0047] (iv) an average of at least 12 carbon atoms per
molecule, most preferably 12 to 30 carbon atoms per molecule;
[0048] (v) an aniline point equal to or greater than 70.degree. C.,
most preferably the aniline point is from 80 to 110.degree. C.
(according to ASTM D 611); [0049] (vi) a naphthenic content of from
20 to 70% by weight of the extender and a mineral oil based
extender has a paraffinic content of from 30 to 80% by weight of
the extender according to ASTM D 3238); [0050] (vii) a pour point
of from -50 to 60.degree. C. (according to ASTM D 97); [0051]
(viii) a kinematic viscosity of from 1 to 20 cSt at 40.degree. C.
(according to ASTM D 445) [0052] (ix) a specific gravity of from
0.7 to 1.1 (according to ASTM D1298); [0053] (x) a refractive index
of from 1.1 to 1.8 at 20.degree. C. (according to ASTM D 1218)
[0054] (xi) a density at 15.degree. C. of greater than 700
kg/m.sup.3 (according to ASTM D4052) and/or [0055] (xii) a flash
point of greater than 100.degree. C., more preferably greater than
110.degree. C. (according to ASTM D 93) [0056] (xiii) a saybolt
colour of at least +30 (according to ASTM D 156) [0057] (xiv) a
water content of less than or equal to 250 ppm [0058] (xv) a
Sulphur content of less than 2.5 ppm (according to ASTM D 4927)
[0059] Other organic extenders may include for the sake of example,
fatty acids and fatty acid esters, alkylbenzene compounds suitable
for use include heavy alkylate alkylbenzene or an
alkylcycloaliphatic compound. Examples of alkyl substituted aryl
compounds useful as extenders and/or plasticisers are compounds
which have aryl groups, especially benzene substituted by alkyl and
possibly other substituents, and a molecular weight of at least
200.
[0060] The alkylbenzene compounds suitable for use include heavy
alkylate alkylbenzene or an alkylcycloaliphatic compound. Examples
of alkyl substituted aryl compounds useful as extenders and/or
plasticisers are compounds which have aryl groups, especially
benzene substituted by alkyl and possibly other substituents, and a
molecular weight of at least 200. Examples of such extenders are
described in U.S. Pat. No. 4,312,801, the content of which is
incorporated herein by reference. These compounds can be
represented by general formula (2), (3), (4) and (5):--
##STR00001##
where R.sup.6 is an alkyl chain of from 1 to 30 carbon atoms, each
of R.sup.7 through to R.sup.16 is independently selected from
hydrogen, alkyl, alkenyl, alkynyl, halogen, haloalkyl, nitrile,
amine, amide, an ether such as an alkyl ether or an ester such as
an alkyl ester group, and n is an integer of from 1 to 25.
[0061] Of these formula (2) where each of R.sup.7, R.sup.8,
R.sup.9, R.sup.10 and R.sup.11 is hydrogen and R.sup.6 is a
C.sub.10-C.sub.13 alkyl group. A particularly useful source of such
compounds are the so-called "heavy alkylates", which are
recoverable from oil refineries after oil distillation. Generally
distillation takes place at temperatures in the range of from 230
to 330.degree. C., and the heavy alkylates are present in the
fraction remaining after the lighter fractions have been distilled
off.
[0062] Examples of alkylcycloaliphatic compounds are substituted
cyclohexanes with a molecular weight in excess of 220. Examples of
such compounds are described in EP 0842974, the content of which is
incorporated herein by reference. Such compounds may be represented
by general formula (6).
##STR00002##
where R.sup.17 is a straight or branched alkyl group of from 1 to
25 carbon atoms, and R.sup.18 and R.sup.19 are independently
selected from hydrogen or a C.sub.1-25 straight or branched chain
alkyl group.
[0063] Alternatively the inert fluid may comprise may comprise a
suitable non-mineral based natural oil or a mixture thereof, i.e.
those derived from animals, seeds and nuts and not from mineral
oils (i.e. not from petroleum or petroleum based oils) such as for
example almond oil, avocado oil, beef tallow, borrage oil,
butterfat, canola oil, cardanol, cashew nut oil, cashew nutshell
liquid, castor oil, citrus seed oil, cocoa butter, coconut oil, cod
liver oil, corn oil, cottonseed oil, cuphea oil, evening primrose
oil, hemp oil, jojoba oil, lard, linseed oil, macadamia oil,
menhaden oil, oat oil, olive oil, palm kernel oil, palm oil peanut
oil, poppy seed oil, rapeseed oil, rice bran oil, safflower oil,
safflower oil (high oleic), sesame oil, soybean oil, sunflower oil,
sunflower oil (high oleic), tall oil, tea tree oil, turkey red oil,
walnut oil perilla oil, dehydrated castor oils, apricot oil, pine
nut oil, kukui nut oil, amazon nut oil almond oil, babasu oil,
argan oil, black cumin oil, bearberry oil, calophyllum oil,
camelina oil, carrot oil, carthamus oil, cucurbita oil, daisy oil,
grape seed oil, foraha oil, jojoba oil, queensland oil, onoethera
oil, ricinus oil, tamanu oil, tucuma oil, fish oils such as
pilchard, sardine and herring oils. The extender may alternatively
comprise mixtures of the above and/or derivatives of one or more of
the above.
[0064] A wide variety of natural oil derivates are available. These
include transesterified natural vegetable oils, boiled natural oils
such as boiled linseed oil, blown natural oils and stand natural
oils. An example of a suitable transesterified natural vegetable
oil is known as biodiesel oil, the transesterification product
produced by reacting mechanically extracted natural vegetable oils
from seeds, such as rape, with methanol in the presence of a sodium
hydroxide or potassium hydroxide catalyst to produce a range of
esters dependent on the feed utilised. Examples might include for
example methyloleate
(CH.sub.3(CH.sub.2).sub.7CH.dbd.CH(CH.sub.2).sub.7CO.sub.2CH.sub.3).
[0065] Stand natural oils which are also known as thermally
polymerised or heat polymerised oils and are produced at elevated
temperatures in the absence of air. The oil polymerises by
cross-linking across the double bonds which are naturally present
in the oil. The bonds are of the carbon-carbon type. Stand oils are
pale coloured and low in acidity. They can be produced with a wider
range of viscosities than blown oils and are more stable in
viscosity. In general, stand oils are produced from linseed oil and
soya bean oil but can also be manufactured based on other oils.
Stand oils are widely used in the surface coatings industry.
[0066] Blown oils which are also known as oxidised, thickened and
oxidatively polymerised oils and are produced at elevated
temperatures by blowing air through the oil. Again the oil
polymerises by cross-linking across the double bonds but in this
case there are oxygen molecules incorporated into the cross-linking
bond. Peroxide, hydroperoxide and hydroxyl groups are also present.
Blown oils may be produced from a wider range of oils than stand
oils. In general, blown oils are darker in colour and have a higher
acidity when compared to stand oils. Because of the wide range of
raw materials used, blown oils find uses in many diverse
industries, for example blown linseed oils are used in the surface
coatings industry and blown rapeseed oils are often used in
lubricants.
[0067] The amount of inert fluid which may be included in the
composition will depend upon factors such as the purpose to which
the composition is to be put, the molecular weight of the inert
fluid(s) concerned etc. In general however, the higher the
molecular weight of the inert fluids(s), the less will be tolerated
in the composition but such high molecular weight inert fluids have
the added advantage of lower volatility. Typical compositions will
contain up to 70% w/w inert fluids(s). More suitable polymer
products comprise from 5-60% w/w of inert fluid(s).
[0068] Such polysiloxane containing polymers as prepared in step
(i) of the process in accordance with the present invention may be
made by a variety of routes with the polymers produced being
end-capped with compounds which will provide the required terminal
groupings on the polymer and provided the polymer or its precursors
and/or intermediates is/are diluted in the inert fluid described
above during the polymerisation process. Preferred routes to the
preparation of said polymers include
(i) polycondensation (ii) ring opening/equilibrium (iii)
polyaddition (iv) chain extension
[0069] (i) Polycondensation (i.e. the polymerisation of multiple
monomers and/or oligomers with the elimination of low molecular
weight by-product(s) such as water, ammonia or methanol etc.). Any
suitable polycondensation reaction pathway may be utilised.
[0070] The sort of reaction envisaged between the condensable end
groups of the starting materials are most preferably generally
linked to the interaction of compounds having hydroxyl and/or
hydrolysable end groups which can interact with the release of e.g.
water or methanol or the like. However, the following list
indicates other interactions which might be considered for the cure
process of the composition in accordance with the present
invention:-- [0071] 1) the condensation of organohalosilyl groups
with an organoalkoxysilyl groups, [0072] 2) the condensation of
organohalosilyl groups with organoacyloxysilyl groups, [0073] 3)
the condensation of organohalosilyl groups with organosilanols,
[0074] 4) the condensation of organohalosilyl groups with
silanolates, [0075] 5) the condensation of organo-hydrosilyl groups
with organosilanol groups [0076] 6) the condensation of
organoalkoxysilyl groups with organoacyloxysilyl groups [0077] 7)
the condensation of organoalkoxysilyl groups with organosilanol
groups, [0078] 8) the condensation of organoaminosilyl groups with
organosilanols, [0079] 9) the condensation of organoacyloxysilyl
groups silanolate groups [0080] 10) the condensation of
organoacyloxysilyl groups with organosilanols, [0081] 11) the
condensation of organooximosilyl groups with organosilanol groups
[0082] 12) the condensation of organoenoxysilyl groups with
organosilanols, [0083] 13) The condensation of a siloxane compound
comprising one or more hydrosilane functional groups with a
siloxane compounds containing at least one alkoxysilane functional
group, generating hydrocarbon by-products.
[0084] Most preferably the condensation reaction which occurs
between monomers/oligomers and intermediates with hydroxyl and/or
alkoxy end-groups thereby producing water or alcohols as a
by-product.
[0085] A preferred method for the polymerisation process is the
polymerisation of straight chain precursors and/or branched
organopolysiloxanes of formula (1) including for example
R.sub.(3-f)R.sup.5.sub.fSiO(R.sub.2SiO).sub.gSiR.sub.(3-f)R.sup.5.sub.f
R.sub.(3-f)R.sup.5.sub.fSiO(RR.sub.1SiO).sub.hSiR.sub.(3-f)R.sup.5.sub.f
R.sub.(3-f)R.sup.5.sub.fSiO[(R.sub.2SiO).sub.j(RR.sup.5SiO).sub.k]SiR.su-
b.(3-f)R.sup.5.sub.f
Where R is as previously defined, R.sup.5 is --OH or an alkoxy
group having from 1 to 6 carbon atoms, preferably a methoxy or
ethoxy group, f is 0 or 1, preferably 1, g is an integer from 2 to
100, his from 2 to 100, j is an integer from 1 to 100 and k is an
integer between 1 to 100. Some branching may occur with the
presence of other groups in the polymeric chain but preferably this
is kept to a minimum.
[0086] The above starting materials preferably have a viscosity of
between 10 mPas and 5000 mPas at 25.degree. C.
[0087] Many of the above processes require the presence of
catalyst. Any suitable polycondensation catalyst may be utilised
including tin, lead, antimony, iron, cadmium, barium, manganese,
zinc, chromium, cobalt, nickel, titanium, aluminium, gallium or
germanium and zirconium based catalysts such as organic tin metal
catalysts and 2-ethylhexoates of iron, cobalt, manganese, lead and
zinc may alternatively be used.
[0088] Tin catalysts may include 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 dineodeconoate, dibutyltin dioctoate.
Dibutyltin dilaurate, dibutyltin diacetate are particularly
preferred.
[0089] Titanate catalysts may comprise a compound according to the
general formula Ti[OR.sup.20].sub.4 and Zr[OR.sup.20].sub.4
respectively where each R.sup.20 may be the same or different and
represents a monovalent, primary, secondary or tertiary aliphatic
hydrocarbon group which may be linear or branched containing from 1
to 10 carbon atoms. Optionally the titanate may contain partially
unsaturated groups. However, preferred examples of R.sup.20 include
but are not restricted to methyl, ethyl, propyl, isopropyl, butyl,
tertiary butyl and a branched secondary alkyl group such as
2,4-dimethyl-3-pentyl. Preferably, when each R.sup.20 is the same,
R.sup.20 is an isopropyl, branched secondary alkyl group or a
tertiary alkyl group, in particular, tertiary butyl. Examples
include tetrabutyltitanate, tetraisopropyltitanate, or chelated
titanates or zirconates such as for example diisopropyl
bis(acetylacetonyl)titanate, diisopropyl
bis(ethylacetoacetonyl)titanate, diisopropoxytitanium
Bis(Ethylacetoacetate) and the like. Further examples of suitable
catalysts are described in EP1254192 and/or WO200149774 the
contents of which are incorporated herein by reference. The amount
of catalyst used depends on the cure system being used but
typically is from 0.01 to 3% by weight of the total
composition.
[0090] Other condensation catalysts which may be used, protic
acids, Lewis acids, organic and inorganic bases, metal salts and
organometallic complexes. Lewis acid catalysts. (a "Lewis acid" is
any substance that will take up an electron pair to form a covalent
bond) suitable for the polymerisation in the present invention
include, for example, boron trifluoride FeCl.sub.3, AlCl.sub.3,
ZnCl.sub.2, and ZnBr.sub.2.
[0091] More preferred are condensation specific catalysts such as
acidic condensation catalysts of the formula R.sup.21SO.sub.3H in
which R.sup.21 represents an alkyl group preferably having from 6
to 18 carbon atoms such as for example a hexyl or dodecyl group, an
aryl group such as a phenyl group or an alkaryl group such as
dinonyl- or didoecyl-naphthyl. Water may optionally be added.
Preferably R.sup.21 is an alkaryl group having an alkyl group
having from 6 to 18 carbon atoms such as dodecylbenzenesulphonic
acid (DBSA). Other condensation specific catalysts include
n-hexylamine, tetramethylguanidine, carboxylates of rubidium or
caesium, hydroxides of magnesium, calcium or strontium and other
catalysts as are mentioned in the art, e.g. in GB895091, GB918823
and EP 0382365. Also preferred are catalysts based on
phosphonitrile chloride, for example those prepared according to
U.S. Pat. No. 3,839,388, U.S. Pat. No. 4,564,693 or EP215 470 and
phosphonitrile halide ion based catalysts, as described in
GB2252975, having the general formula
[X(PX.sub.2.dbd.N).sub.pPX.sub.3].sup.+[M.sup.2.sub.(m-n+1)R.sup.-
III.sub.m].sup.-, wherein X denotes a halogen atom, M.sup.2 is an
element having an electronegativity of from 1.0 to 2.0 according to
Pauling's scale, R.sup.III is an alkyl group having up to 12 carbon
atoms, p has a value of from 1 to 6, m is the valence or oxidation
state of M.sup.2 and n has a value of from 0 to m-1.
[0092] Alternatively the catalyst may comprise an oxygen-containing
chlorophosphazene containing organosilicon radicals having the
following general formula:--
Z.sup.1--PCl.sub.2.dbd.N(--PCl.sub.2.dbd.N).sub.q--PCl.sub.2--O
in which Z.sup.1 represents an organosilicon radical bonded to
phosphorus via oxygen, a chlorine atom of the hydroxyl group and q
represents 0 or an integer from 1 to 8. The catalyst may also
comprise condensation products of the above and/or tautomers
thereof (the catalyst exists in a tautomeric form when Z.sup.1 is a
hydroxyl group).
[0093] A further alternative catalyst which might be used as the
catalyst in the present invention is any suitable compound
providing a source of anions comprising at least one
quadri-substituted boron atom and protons capable of interaction
with at least one silanol group as defined in WO 01/79330.
[0094] The activity of the catalyst is preferably quenched by using
a neutralizing agent which reacts with the catalyst to render it
non-active. Typically in the case of the acid type condensation
catalysts the neutralising agent is a suitable base such as an
amine such as a mono/di and trialkanolamines for example
monoethanolamine (MEA) and triethanolamine (TEA). In the case of
systems using a DBSA catalyst alternative quenching means include
aluminasilicate zeolite materials that were found to absorb DBSA
and leave a stable polymer. In most cases catalyst residues remain
in the polymer product or where appropriate may be removed by
filtration or alternative methods. In the case of phosphazene based
catalysts when the desired viscosity has been reached, the
viscosity of the organosilicon compound obtained in the process can
be kept constant by a procedure in which the catalyst used, or a
reaction product which has been formed from this catalyst by
reaction with organosilicon compound to be subjected to
condensation and/or equilibration and likewise promotes the
condensation and/or equilibration of organosilicon compounds, is
inhibited or deactivated by addition of inhibitors or deactivators
which have been employed to date in connection with phosphazenes,
for example, triisononylamine, n-butyllithium, lithium
siloxanolate, hexamethylcyclotrisilazane, hexamethyldisilazane and
magnesium oxide.
[0095] Where appropriate any suitable end-blocking agent, which
halts the polymerization reaction and thereby limits the average
molecular weight, may be used to introduce the appropriate
end-groups in polymer (a).
(II) Equilibration/Ring Opening
[0096] The starting material for equilibration polymerisation
processes such as ring-opening polymerisation is a cyclosiloxane
(also known as a cyclic siloxane). Cyclic siloxanes which are
useful are well known and commercially available materials. They
have the general formula (R.sup.22SiO).sub.r, wherein each R.sup.22
is selected from an alkyl group, an alkenyl group, an aryl group or
an aralkyl group and r denotes an integer with a value of from 3 to
12. R.sup.22 can contain substitution, e.g. by halogen such as
fluorine or chlorine. The alkyl group can be, for example, methyl,
ethyl, n-propyl, trifluoropropyl, n-butyl, sec-butyl, and
tert-butyl. The alkenyl group can be, for example, vinyl, allyl,
propenyl, and butenyl. The aryl and aralkyl groups can be, for
example, phenyl, tolyl, and benzoyl. The preferred groups are
methyl, ethyl, phenyl, vinyl, and trifluoropropyl. Preferably at
least 80% of all R.sup.22 groups are methyl or phenyl groups, most
preferably methyl. Preferably the average value of r is from 3 to
6. Examples of suitable cyclic siloxanes are
octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane,
decamethylcyclopentasiloxane, cyclopenta(methylvinyl)siloxane,
cyclotetra(phenylmethyl)siloxane, cyclopentamethylhydrosiloxane and
mixtures thereof. One particularly suitable commercially available
material is a mixture of comprising octamethylcyclotetrasiloxane
and decamethylcyclopentasiloxane. Typically moisture is present in
the monomers. The water present acts as an end-blocker by forming
OH end groups on the polymers thereby preventing further
polymerisation.
[0097] Any suitable catalyst may be used. These include alkali
metal hydroxides such as lithium hydroxide, sodium hydroxide,
potassium hydroxide or caesium hydroxide, alkali metal alkoxides or
complexes of alkali metal hydroxides and an alcohol, alkali metal
silanolates such as potassium silanolate caesium silanolate, sodium
silanolate and lithium silanolate or trimethylpotassium silanolate.
Other catalysts which might be utilised include the catalyst
derived by the reaction of a tetra-alkyl ammonium hydroxide and a
siloxane tetramer and the boron based catalysts as hereinbefore
described.
[0098] Catalysts which are most preferred for equilibrium type
reactions however are phosphonitrile halides, phosphazene acids and
phosphazene bases as hereinbefore described.
[0099] Where required the polymer obtained may be end-blocked as a
means of regulating the molecular weight of the polymer and/or to
add functionality. Whilst this end-blocking function can be
achieved by water as discussed above, other suitable end-blocking
agents include silanes having one group capable of reacting with
the terminal groups of the resulting polymeric constituent prepared
in the diluted polymer to produce the required end-groups for
polymer (a).
(III) Polyaddition
[0100] For the sake of this specification a "polyaddition" or
"addition polymerisation" process is a polymerisation process
whereby unlike in a condensation reaction no by-products such as
water or alcohols are generated from the monomeric and oligomeric
co-reactants during polymerisation. A preferred addition
polymerisation route is a hydrosilylation reaction between an
unsaturated organic group e.g. an alkenyl or alkynyl group and an
Si--H group in the presence of a suitable catalyst. In this route
suitable silanes may be utilised as well as siloxane containing
monomers and/or oligomers.
[0101] Typically the polyaddition route is utilised to form block
copolymers by reacting [0102] a) (i) an organopolysiloxane or (ii)
a silane with:-- [0103] b) one or more organopolysiloxane
polymer(s) via an addition reaction pathway in the presence of the
extender and/or plasticiser, and a suitable catalyst and optionally
an end-blocking agent; and where required quenching the
polymerisation process.
[0104] The organopolysiloxane or silane (a) is selected from a
silane (a) (ii) containing at least one group capable of undergoing
addition type reactions and an organopolysiloxane monomer (a) (i)
containing groups capable of undergoing addition type reactions.
The organopolysiloxane or silane (a) must contain substituents such
that it is capable of undergoing an appropriate addition reaction
with polymer (b). The preferred addition reaction is a
hydrosilylation reaction between an unsaturated group and an Si--H
group.
[0105] Preferably silane (a) (ii) has at least 1 and preferably 2
groups capable of undergoing addition type reactions with (b). When
the addition reaction is a hydrosilylation reaction the silane may
contain an unsaturated constituent but preferably contains at least
one Si--H group. Most preferably each silane contains one or more
Si--H groups. In addition to the one or more Si--H groups,
preferred silanes may include for example an alkyl group, an alkoxy
group, an acyloxy group, a ketoximato group, an amino group, an
amido group, an acid amido group, an aminoxy group, a mercapto
group, an alkenyloxy group and the like. Among these, alkoxy,
acyloxy, ketoximato, amino, amido, aminoxy, mercapto and alkenyloxy
groups are preferred. Practical examples of the silicon hydride are
halosilane tri-chlorosilane, methyl dichlorosilane, dimethyl
chlorosilane, and phenyl dichlorosilane; alkoxy silanes, such as
tri-methyoxy silane, tri-ethoxy silane, methyl di-ethoxy silane,
methyl di-methoxy silane and phenyl-di-methoxy silane; acyloxy
silanes, such as methyl di-acetoxy silane and phenyl diacetoxy
silane; and ketoximato silanes, such as
bis-(dimethyl-ketoximate)-methyl silane and bis-(cyclohexyl
ketoximate)methyl silane. Among them, halosilanes and alkoxyl
silanes are preferred. Particularly preferred silanes include for
example methyl dimethoxy silane (H--Si(--CH.sub.3)
(--OCH.sub.3).sub.2).
[0106] It will be appreciated that the addition reaction between
silane (a) (ii) and (b) results in a polymer chain extension
process or as a means of end-blocking a polymer with pre-required
end groups, in which case the extender may be added in combination
with silane (a) (ii), i.e. immediately prior to the addition
reaction or may be present during the polymerisation of polymer (b)
and as such silane (a) (ii) is added to an extended polymer (b)
which has been polymerised in the presence of the extender.
[0107] Organopolysiloxane monomer (a) (i) is preferably in the form
of a straight chain and/or branched organopolysiloxane comprising
units of formula (1a)
R'.sub.a--SiO.sub.4-a'/2 (1a)
wherein each R' may be the same or different and denotes a
hydrocarbon group having from 1 to 18 carbon atoms, a substituted
hydrocarbon group having from 1 to 18 carbon atoms or a
hydrocarbonoxy group having up to 18 carbon atoms and a' has, on
average, a value of froth 1 to 3, preferably 1.8 to 2.2. Preferably
each R' is the same or different and is exemplified by, but not
limited to hydrogen, alkyl groups such as methyl, ethyl, propyl,
butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl;
cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl,
benzyl, and 2-phenylethyl; and halogenated hydrocarbon groups such
as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl. Some
R' groups may be hydrogen groups. Preferably the
polydiorganosiloxanes are polydialkylsiloxanes, most preferably
polydimethylsiloxanes. When (a) is an organopolysiloxane monomer,
said organopolysiloxane monomer must have at least one group which
is reactable with at least two groups, typically the terminal
groups, of (b) via an addition reaction process. Preferably
organopolysiloxane (a) (i) comprises at least one Si--H per
molecule, preferably at least two Si--H groups per molecule.
Preferably organopolysiloxane (a) (i) is end-blocked with a
siloxane group of the formula H(R'').sub.2SiO.sub.1/2, wherein each
R'' is a hydrocarbon or substituted hydrocarbon group, most
preferably an alkyl group. Preferably organopolysiloxane (a) (i)
has a viscosity of between 10 mPas and 5000 mPas at 25.degree.
C.
[0108] Organopolysiloxane polymer (b) is preferably a straight
chain and/or branched organopolysiloxane comprising units of
formula (1b)
R'''.sub.a'SiO.sub.4-a'/2 (1b)
wherein each R''' may be the same or different and denotes a
hydrocarbon group having from 1 to 18 carbon atoms, a substituted
hydrocarbon group having from 1 to 18 carbon atoms or a
hydrocarbonoxy group having up to 18 carbon atoms and a' is as
previously described. Preferably no R''' groups may be hydrogen
groups. Preferably each R''' is the same or different and are
exemplified by, but not limited to alkyl groups such as methyl,
ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and
octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl,
tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated
hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl,
and dichlorophenyl.
[0109] Organopolysiloxane polymer (b) may comprise any suitable
organopolysiloxane polymeric backbone but is preferably linear or
branched, and comprises at least one, preferably at least two
substituent groups which will react with the aforementioned groups
in the organopolysiloxane or silane (a) via an addition reaction
pathway. Preferably the or each addition reactive substituent group
of polymer (b) is a terminal group. When the organopolysiloxane or
silane (a) comprises at least one Si--H group, the preferred
substituent groups on organopolysiloxane polymer (b), which are
designed to interact with the Si--H groups, are preferably
unsaturated groups (e.g. alkenyl terminated e.g. ethenyl
terminated, propenyl terminated, allyl terminated
(CH.sub.2.dbd.CHCH.sub.2--)) or terminated with acrylic or
alkylacrylic such as CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2-- groups
Representative, non-limiting examples of the alkenyl groups are
shown by the following structures; H.sub.2C.dbd.CH--,
H.sub.2C.dbd.CHCH.sub.2--, H.sub.2C.dbd.C(CH.sub.3)CH.sub.2--,
H.sub.2C.dbd.CHCH.sub.2CH.sub.2--,
H.sub.2C.dbd.CHCH.sub.2CH.sub.2CH.sub.2--, and
H.sub.2C.dbd.CHCH.sub.2CH.sub.2CH.sub.2CH.sub.2--. Representative,
non-limiting examples of alkynyl groups are shown by the following
structures; HC.ident.C--, HC.ident.CCH.sub.2--,
HC.ident.CC(CH.sub.3)--, HC.ident.CC(CH.sub.3).sub.2--,
HC.ident.CC(CH.sub.3).sub.2CH.sub.2-- Alternatively, the
unsaturated organic group can be an organofunctional hydrocarbon
such as an acrylate, methacrylate and the like such as alkenyl
an/or alkynyl groups. Alkenyl groups are particularly
preferred.
[0110] In cases where the organopolysiloxane or silane (a)
comprises only one addition reactable group and (b) comprises two
addition reactable groups which will react with the
organopolysiloxane or silane (a), the resulting product will be an
"ABA" type polymeric product. Whereas when both the
organopolysiloxane or silane (a) comprises two addition reactable
groups and (b) comprises two addition reactable groups which will
react with the organopolysiloxane or silane (a) interaction between
the two components would lead to (AB)n block copolymers in which
the length of the polymer is largely determined by the relative
amounts of the two constituents.
[0111] It will also be appreciated that this hydrosilylation route
may be utilised to prepare silicone-organic copolymers by using an
organopolysiloxane polymer which contains organic groups in the
polymer backbone or by replacing organopolysiloxane polymer (b)
with, for example alkenyl terminated polyethers Hence linear
non-hydrolysable (AB)n block copolymers in accordance with the
present invention of this invention can be prepared by catalyzed
hydrosilylation of alkenyl terminated polyethers with
SiH-terminated dialkylsiloxane fluids. The resulting copolymer
being a combination of polyoxyalkylene blocks linked through
silicon to carbon to oxygen linkages (i.e. a propyleneoxy group)
and the endblocking groups being selected from the group consisting
of allyl, propenyl and/or hydrogen (dialkyl) siloxy groups
(dependent on the relative amounts of the constituents which are
present).
[0112] When the addition reaction chosen is a hydrosilylation
reaction, any suitable hydrosilylation catalyst may be utilised.
Such hydrosilylation catalysts are illustrated by any
metal-containing catalyst which facilitates the reaction of
silicon-bonded hydrogen atoms of the SiH terminated
organopolysiloxane with the unsaturated hydrocarbon group on the
polyoxyethylene. The metals are illustrated by ruthenium, rhodium,
palladium, osmium, iridium, or platinum.
[0113] Hydrosilylation catalysts are illustrated by the following;
chloroplatinic acid, alcohol modified chloroplatinic acids, olefin
complexes of chloroplatinic acid, complexes of chloroplatinic acid
and divinyltetramethyldisiloxane, fine platinum particles adsorbed
on carbon carriers, platinum supported on metal oxide carriers such
as Pt(Al.sub.2O.sub.3), platinum black, platinum acetylacetonate,
platinum(divinyltetramethyldisiloxane), platinous halides
exemplified by PtCl.sub.2, PtCl.sub.4, Pt(CN).sub.2, complexes of
platinous halides with unsaturated compounds exemplified by
ethylene, propylene, and organovinylsiloxanes, styrene
hexamethyldiplatinum, Such noble metal catalysts are described in
U.S. Pat. No. 3,923,705, incorporated herein by reference to show
platinum catalysts. One preferred platinum catalyst is Karstedt's
catalyst, which is described in Karstedt's U.S. Pat. Nos. 3,715,334
and 3,814,730, incorporated herein by reference. Karstedt's
catalyst is a platinum divinyl tetramethyl disiloxane complex
typically containing one weight percent of platinum in a solvent
such as toluene. Another preferred platinum catalyst is a reaction
product of chloroplatinic acid and an organosilicon compound
containing terminal aliphatic unsaturation. It is described in U.S.
Pat. No. 3,419,593, incorporated herein by reference. Most
preferred as the catalyst is a neutralized complex of platinous
chloride and divinyl tetramethyl disiloxane, for example as
described in U.S. Pat. No. 5,175,325.
[0114] Ruthenium catalysts such as RhCl.sub.3(Bu.sub.2S).sub.3 and
ruthenium carbonyl compounds such as ruthenium
1,1,1-trifluoroacetylacetonate, ruthenium acetylacetonate and
triruthinium dodecacarbonyl or a ruthenium 1,3-ketoenolate may
alternatively be used.
[0115] Other hydrosilylation catalysts suitable for use in the
present invention include for example rhodium catalysts such as
[Rh(O.sub.2CCH.sub.3).sub.2]2, Rh(O.sub.2CCH.sub.3).sub.3,
Rh.sub.2(C.sub.8H.sub.15O.sub.2).sub.4,
Rh(C.sub.5H.sub.7O.sub.2).sub.3,
Rh(C.sub.5H.sub.7O.sub.2)(CO).sub.2,
Rh(CO)[Ph.sub.3P](C.sub.5H.sub.17O.sub.2),
RhX.sup.4.sub.3[(R.sup.3).sub.2S].sub.3,
(R.sup.2.sub.3P).sub.2Rh(CO)X.sup.4, (R.sup.2.sub.3P).sub.2Rh(CO)H,
Rh.sub.2X.sup.4.sub.2Y.sup.4.sub.4,
H.sup.aRh.sup.bolefin.sup.cCl.sup.d,
Rh(O(CO)R.sup.3).sub.3-n(OH).sub.n where X.sup.4 is hydrogen,
chlorine, bromine or iodine, Y.sup.4 is an alkyl group, such as
methyl or ethyl, CO, C.sub.8H.sub.14 or 0.5 C.sub.8H.sub.12,
R.sup.3 is an alkyl radical, cycloalkyl radical or aryl radical and
R.sup.2 is an alkyl radical an aryl radical or an oxygen
substituted radical, a is 0 or 1, b is 1 or 2, c is a whole number
from 1 to 4 inclusive and d is 2, 3 or 4, n is 0 or 1. Any suitable
iridium catalysts such as Ir(OOCCH.sub.3).sub.3,
Ir(C.sub.5H.sub.7O.sub.2).sub.3, [Ir(Z.sup.2)(En).sub.2].sub.2, or
(Ir(Z.sup.2)(Dien)].sub.2, where Z.sup.2 is chlorine, bromine,
iodine, or alkoxy, En is an olefin and Dien is cyclooctadiene may
also be used.
[0116] The hydrosilylation catalyst may be added to the present
composition in an amount equivalent to as little as 0.001 part by
weight of elemental platinum group metal, per one million parts
(ppm) of the composition. Preferably, the concentration of the
hydrosilylation catalyst in the composition is that capable of
providing the equivalent of at least 1 part per million of
elemental platinum group metal. A catalyst concentration providing
the equivalent of about 3-50 parts per million of elemental
platinum group metal is generally the amount preferred.
[0117] Typically when (a) has at least two Si--H groups, typically,
the process is carried out using approximately a 1:1 molar ratio of
(a) to (b). However, useful materials may also be prepared by
carrying out the process with an excess of either (a) or (b) but
this would be considered a less efficient use of the materials.
Typically, the material containing the unsaturation (b) is used in
slight excess to ensure all the Si--H is consumed in the reaction.
As polymer (b) used in the present invention is preferably
terminated with unsaturated end-groups, end-blocking agents are not
typically required when making the polymer via this route. However,
they may be utilised if required.
[0118] Optionally when a hydrosilylation route is utilised for
polymerisation a suitable hydrosilylation catalyst inhibitor may be
required. Any suitable platinum group type inhibitor may be used.
One useful type of platinum catalyst inhibitor is described in U.S.
Pat. No. 3,445,420, which is hereby incorporated by reference to
show certain acetylenic inhibitors and their use. A preferred class
of acetylenic inhibitors are the acetylenic alcohols; especially
2-methyl-3-butyn-2-ol and/or 1-ethynyl-2-cyclohexanol which
suppress the activity of a platinum-based catalyst at 25.degree. C.
A second type of platinum catalyst inhibitor is described in U.S.
Pat. No. 3,989,667, which is hereby incorporated by reference to
show certain olefinic siloxanes, their preparation and their use as
platinum catalyst inhibitors. A third type of platinum catalyst
inhibitor includes polymethylvinylcyclosiloxanes having three to
six methylvinylsiloxane units per molecule.
[0119] Compositions containing these hydrosilylation catalysts
typically require heating at temperatures of 70.degree. C. or above
to cure at a practical rate, particularly if an inhibitor is used.
Room temperature cure is typically accomplished with such systems
by use of a two-part system in which the cross-linker and inhibitor
are in one of the two parts and the platinum is in the other part.
The amount of platinum is increased to allow for curing at room
temperature. The optimum concentration of platinum catalyst
inhibitor is that which will provide the desired storage stability
or pot life at ambient temperature without excessively prolonging
the time interval required to cure the present compositions at
elevated temperatures. This amount will vary widely and will depend
upon the particular inhibitor that is used. Inhibitor
concentrations as low as one mole of inhibitor per mole of platinum
will in some instances yield a desirable level of storage stability
and a sufficiently short curing period at temperatures above about
70.degree. C. In other cases, inhibitor concentrations of up to 10,
50, 100, 500 or more moles per mole of platinum may be needed. The
optimum concentration for a particular inhibitor in a given
composition can be determined by routine experimentation.
[0120] Additional components can be added to the hydrosilylation
reaction which are known to enhance such reactions. These
components include salts such as sodium acetate which have a
buffering effect in combination with platinum based catalysts.
[0121] For this type of polymerisation the amount of
hydrosilylation catalyst used is not narrowly limited as long as
there is a sufficient amount to accelerate a reaction between
[0122] (a) (i) an organopolysiloxane or (ii) a silane the chosen of
which must contain at least one and preferably at least two Si--H
groups with [0123] (b) one or more organopolysiloxane polymer(s) or
an alternative therefore such as a polyoxyethylene having an
unsaturated hydrocarbon group at each molecular terminal at room
temperature or at temperatures above room temperature. The actual
amount of this catalyst will depend on the particular catalyst
utilized and is not easily predictable. However, for
platinum-containing catalysts the amount can be as low as one
weight part of platinum for every one million weight parts of
components (a) and (b). The catalyst can be added at an amount 10
to 120 weight parts per one million parts of components (a) and
(b), but is typically added in an amount from 10 to 60 weight parts
per one million parts of (a) and (b).
[0124] Where appropriate, polymers obtained via a hydrosilylation
route can also be cured and/or crosslinked by a hydrosilylation
reaction catalyst in combination with an organohydrogensiloxane as
the curing agent providing each polymer molecule produced contains
at least two unsaturated groups suitable for cross-linking with the
organohydrogensiloxane. To effect curing of the present
composition, the organohydrogensiloxane must contain more than two
silicon bonded hydrogen atoms per molecule. The
organohydrogensiloxane can contain, for example, from about 4-20
silicon atoms per molecule, and have a viscosity of up to about 10
Pa-s at 25.degree. C. The silicon-bonded organic groups present in
the organohydrogensiloxane can include substituted and
unsubstituted alkyl groups of 1-4 carbon atoms that are otherwise
free of ethylenic or acetylenic unsaturation.
(IV) Chain Extension
[0125] In this case rather than adding chain extender into a final
pre-prepared polymer composition the extender is mixed into the
polymer during a chain extension polymerisation step. Typically the
polymeric starting material is an organopolysiloxane having end
groups suitable for interaction with the chosen chain extending
materials. Typically the polymer end groups are either hydrolysable
or suitable for addition reaction (typically hydrosilylation) and
the chain extending material is chosen on the basis of having
suitable reactive groups which will chain extend the polymer.
Preferred chain extending materials for chain extending polymers
having hydroxyl and/or hydrolysable end groups are as hereinbefore
described.
[0126] For pre-formed polymers with alkenyl or Si--H groups
(typically end groups) suitable for addition reactions via a
hydrosilylation route the chain extender will contain two group
which will undergo an addition reaction with the respective
addition reactive groups on the chosen polymer. Such chain
extenders may include for example:--
A silane comprising two alkenyl groups, a dihydrosilane, a
polydialkylsiloxane having a degree of polymerisation of from 2 to
25 and at least one Si-alkenyl bond per terminal group, A
polydialkylsiloxane having a degree of polymerisation of from 2 to
25 and at least one Si--H bond per terminal group and wherein each
alkyl group independently comprises from 1 to 6 carbon atoms;
organosilicon compounds with the general formula
##STR00003##
in which R is as hereinbefore described, j is 1, 2, or 3, k is 0 or
1, and j+k is 2 or 3. exemplified by compounds with the following
formulas, (ViMe.sub.2SiO).sub.2SiVi(OMe).sub.1
(ViMe.sub.2SiO).sub.1SiVi(OMe).sub.2,
(ViMe.sub.2SiO).sub.2SiVi(OEt).sub.1,
(ViMe.sub.2SiO).sub.2SiVi(OEt).sub.2,
(ViMe.sub.2SiO).sub.3Si(OMe).sub.1,
(ViMe.sub.2SiO).sub.2Si(OMe).sub.2,
(ViMe.sub.2SiO).sub.3Si(OEt).sub.1 and
(ViMe.sub.2SiO).sub.2Si(OEt).sub.2 As used herein, Vi represents a
vinyl group, Me represents a methyl group, and Et represents an
ethyl group.
[0127] The catalyst used to catalyse the chain extension reaction
is determined by the reaction to take place. When the reaction
occurring is a condensation reaction any suitable condensation
catalyst as hereinbefore described may be utilised. When the
reaction occurring is a hydrosilylation reaction any suitable
hydrosilylation catalyst as hereinbefore described may be
utilised.
[0128] Where required the polymer contains hydrolysable terminal
groups, end-blocking agents as described above in relation to
condensation may be utilised to obtain appropriate terminal groups.
Where required the polymer contains addition reactable terminal
groups, end-blocking agents as described above in relation to
polyaddition may be utilised to obtain appropriate terminal
groups.
[0129] The process can be carried out either batchwise or
continuously on any suitable mixers. In case of a polycondensation,
generated water can either be removed by chemical drying using e.g.
hydrolysable silanes like methyltrimethoxysilane or by physical
separation using evaporation, coalescing or centrifuging
techniques.
[0130] Chain extension may take place at any suitable temperature
and pressure for the process concerned in batch or continuous modes
of operation as preferred. Hence in the case of the phosphazene
catalysed methods polymerisation may occur at temperatures of
between 50.degree. C. to 200.degree. C., more preferably 80.degree.
C. to 160.degree. C. Furthermore, in order to facilitate removal of
the by-products formed during the condensation, for example, water,
HCl or alcohol, the condensation and/or equilibration of the
organosilicon compounds may be carried out at a pressure below 80
kPa. Alternative methods for the removal of condensation
by-products include removal by chemical drying using e.g.
hydrolysable silanes like methyltrimethoxysilane (where
appropriate) or by physical separation using evaporation,
coalescing or centrifuging techniques.
[0131] The process can be carried out either batchwise or
continuously on any suitable mixers. In case of a polycondensation,
generated water can either be removed by chemical drying using e.g.
hydrolysable silanes like methyltrimethoxysilane or by physical
separation using evaporation, coalescing or centrifuging
techniques.
[0132] Preferably the viscosity of the mixture of the polymer and
inert fluid prior to emulsifying is in the range of viscosity of
1000-100000 mPas at 25.degree. C. and preferably the viscosity of
the polymer in the emulsion is greater than 1 000 000 mPas at
25.degree. C.
[0133] Any suitable surfactant or combination of surfactants may be
utilised. The surfactant can in general be a non-ionic surfactant,
a cationic surfactant, an anionic surfactant, or an amphoteric
surfactant, although not all procedures for carrying out the
process of the invention can be used with all surfactants. The
amount of surfactant used will vary depending on the surfactant,
but generally is up to about 30 wt. % based on the
polydiorganosiloxane.
[0134] Examples of nonionic surfactants include condensates of
ethylene oxide with long chain fatty alcohols or fatty acids such
as a C.sub.12-16 alcohol, condensates of ethylene oxide with an
amine or an amide, condensation products of ethylene and propylene
oxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylol
amides, sucrose esters, fluoro-surfactants, fatty amine oxides,
polyoxyalkylene alkyl ethers such as polyethylene glycol long chain
(12-14C) alkyl ether, polyoxyalkylene sorbitan ethers,
polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol
ethers, ethylene glycol propylene glycol copolymers and
alkylpolysaccharides, for example materials of the structure
R.sup.24--O--(R.sup.25O).sub.s-(G).sub.t wherein R.sup.24
represents a linear or branched alkyl group, a linear or branched
alkenyl group or an alkylphenyl group, R.sup.25 represent an
alkylene group, G represents a reduced sugar, s denotes 0 or a
positive integer and t represent a positive integer as described in
U.S. Pat. No. 5,035,832. non ionic surfactants additionally include
polymeric surfactants such as polyvinyl alcohol (PVA) and
polyvinylmethylether.
[0135] Representative examples of suitable commercially available
nonionic surfactants include polyoxyethylene fatty alcohols sold
under the tradename BRIJ.RTM. by Uniqema (ICI Surfactants),
Wilmington, Del. Some examples are BRIJ.RTM. 35 Liquid, an
ethoxylated alcohol known as polyoxyethylene (23) lauryl ether, and
BRIJ.RTM. 30, another ethoxylated alcohol known as polyoxyethylene
(4) lauryl ether. Some additional nonionic surfactants include
ethoxylated alcohols sold under the trademark TERGITOL.RTM. by The
Dow Chemical Company, Midland, Mich. Some example are TERGITOL.RTM.
TMN-6, an ethoxylated alcohol known as ethoxylated
trimethylnonanol; and various of the ethoxylated alcohols, i.e.,
C.sub.12-C.sub.14 secondary alcohol ethoxylates, sold under the
trademarks TERGITOL.RTM. 15-S-5; TERGITOL.RTM. 15-S-12,
TERGITOL.RTM. 15-S-15, and TERGITOL.RTM. 15-S-40. Surfactants
containing silicon atoms can also be used.
[0136] Examples of suitable amphoteric surfactants include
imidazoline compounds, alkylaminoacid salts, and betaines. Specific
examples include cocamidopropyl betaine; cocamidopropyl
hydroxysulfate, cocobetaine, sodium cocoamidoacetate, cocodimethyl
betaine, N-coco-3-aminobutyric acid and imidazolinium carboxyl
compounds. Representative examples of suitable amphoteric
surfactants include imidazoline compounds, alkylaminoacid salts,
and betaines.
[0137] Examples of cationic surfactants include quaternary ammonium
hydroxides such as octyl trimethyl ammonium hydroxide, dodecyl
trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium
hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl
benzyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide,
dioctadecyl dimethyl ammonium hydroxide, tallow trimethyl ammonium
hydroxide and coco trimethyl ammonium hydroxide as well as
corresponding salts of these materials, fatty amines and fatty acid
amides and their derivatives, basic pyridinium compounds,
quaternary ammonium bases of benzimidazolines and
polypropanolpolyethanol amines. Other representative examples of
suitable cationic surfactants include alkylamine salts, sulphonium
salts, and phosphonium salts.
[0138] Examples of suitable anionic surfactants include alkyl
sulphates such as lauryl sulphate, polymers such as
acrylates/C.sub.10-30 alkyl acrylate crosspolymer
alkylbenzenesulfonic acids and salts such as hexylbenzenesulfonic
acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid,
dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid and
myristylbenzenesulfonic acid; the sulphate esters of monoalkyl
polyoxyethylene ethers; alkylnapthylsulfonic acid; alkali metal
sulforecinates, sulfonated glyceryl esters of fatty acids such as
sulfonated monoglycerides of coconut oil acids, salts of sulfonated
monovalent alcohol esters, amides of amino sulfonic acids,
sulfonated products of fatty acid nitriles, sulfonated aromatic
hydrocarbons, condensation products of naphthalene sulfonic acids
with formaldehyde, sodium octahydroanthracene sulfonate, alkali
metal alkyl sulphates, ester sulphates, and alkarylsulfonates.
Anionic surfactants include alkali metal soaps of higher fatty
acids, alkylaryl sulphonates such as sodium dodecyl benzene
sulphonate, long chain fatty alcohol sulphates, olefin sulphates
and olefin sulphonates, sulphated monoglycerides, sulphated esters,
sulphonated ethoxylated alcohols, sulphosuccinates, alkane
sulphonates, phosphate esters, alkyl isethionates, alkyl taurates,
and alkyl sarcosinates. One example of a preferred anionic
surfactant is sold commercially under the name Bio-Soft N-300. It
is a triethanolamine linear alkylate sulphonate composition
marketed by the Stephan Company, Northfield, Ill.
[0139] The above surfactants may be used individually or in
combination.
[0140] In a preferred embodiment of the present invention the
polymerisation catalyst is selected with a view to additionally
being the or one of the surfactants involved in the emulsification
process. A particularly preferred family of catalysts which can act
as surfactants are acidic condensation catalysts such as for
example DBSA.
[0141] Phase inversions generally occurs when the continuous phase
of a dispersion becomes the dispersed phase, or vice versa. Phase
inversions in liquid/liquid dispersions generally are known in the
art to be effected by one of two methods. An inversion may be
caused by changing the phase ratio until there is a high enough
ratio of the dispersed phase that it becomes the continuous phase.
Alternatively, a transitional inversions may occur when the
affinity of the surfactant for the two phases is altered in order
to cause the inversion. Typically, the inversions occurring in this
invention occur due to a change in the phase ratio.
[0142] Thus, the inversion method used to make emulsions, according
to the invention, is carried out by forming an oil phase containing
the diluted polysiloxane containing polymer and mixing and
agitating the oil phase. A limited and very small amount of water
is added to the oil phase in a stepwise fashion, such that an
inversion occurs, and an oil-in-water emulsion is formed.
Generally, the amount of water required is about 0.5-10 percent by
weight based on the cumulative weight of polysiloxane containing
polymer present in the oil phase. Preferably, the amount of water
will be about 1-5 percent by weight based on the weight of the
polysiloxane containing polymer present in the oil phase. While the
water can be added in 2-4 portions, addition of water in a single
portion is preferred. The initial addition of water can include the
surfactant. After the desired particle size has been reached, the
emulsion is diluted with the balance of water to achieve the
preferred solids content.
[0143] The emulsions produced by the process of this invention can
have a wide variety of polysiloxane containing polymer
concentrations, particle sizes and molecular weights, including
novel materials having high concentrations of large particle
polysiloxane containing polymer of high molecular weight. The
particle size can for example be chosen within the range 0.1 to
1000 micrometres.
[0144] The quantity of water and/or surfactant used in the initial
phase inversion process may have an impact on the particle size of
the final emulsion. For instance, if an emulsion is formed with the
same quantity of water in two instances but in the first a large
quantity of water is mixed before the phase inversion step and in
the second a small quantity of water is mixed before the phase
inversion step followed by mixing the remaining additional water
after the phase inversion step, the first emulsion will generally
have a larger particle size than the second. No matter how the
water is added, the total amount of water used is generally between
about 1 and 99 wt. %, preferably between about 6 and about 99 wt.
%, based on the weight of the emulsion.
[0145] If desired, other materials can be added to either phase of
the emulsions, for example perfumes, fillers, relaxers, colorants,
thickeners, preservatives, or active ingredients such as
pharmaceuticals antifoams, freeze thaw stabilizers, inorganic salts
to buffer pH, and thickeners
[0146] The emulsions of the present invention can generally have a
silicone loading in the range of about 1 to about 94 wt. %.
[0147] The emulsions of the invention are useful in most known
applications for silicone emulsions, for example in personal care
applications such as on hair, skin, mucous membrane or teeth. In
these applications, the silicone is lubricious and will improve the
properties of skin creams, skin care lotions, moisturisers, facial
treatments such as acne or wrinkle removers, personal and facial
cleansers such as shower gels, liquid soap, bar soaps hand
sanitizers and wipes, bath oils, perfumes, fragrances, colognes,
sachets, deodorants, sun protection creams, lotions, spray, stick
and wipes, Self tanning creams, lotions, spray and wipes, pre-shave
and after shave lotions, after sun lotion and creams,
anti-perspirant sticks, soft solid and roll ons, hand sanitizers,
shaving soaps and shaving lathers. It can likewise be use in hair
shampoos, rinse-off and leave-on hair conditioners, hair styling
aids, such as sprays, mousses and gels, hair colorants, hair
relaxers, permanents, depilatories, and cuticle coats, for example
to provide styling and conditioning benefits. In cosmetics, it
function as a levelling and spreading agent for pigment in
make-ups, colour cosmetics, compact gel, cream and liquid
foundations (w/o and o/w emulsions, anhydrous), blushes, lipsticks,
lip gloss, eye liners, eye shadows, mascaras, make up removers,
colour cosmetic removers and powders. It is likewise useful as a
delivery system for oil and water soluble substances such as
vitamins, fragrances, emollients, colorants, organic sunscreens,
ceramides, pharmaceuticals and the like. When compounded into
sticks, anhydrous and aqueous gels, o/w and w/o creams and lotions,
aerosols and roll-ons, the emulsions of this invention impart a dry
silky-smooth payout.
[0148] When used in personal care products, they are generally
incorporated in amounts of about 0.01 to about 50 weight percent,
preferably 0.1 to 25 wt. percent, of the personal care product.
They are added to conventional ingredients for the personal care
product chosen. Thus, they can be mixed with deposition polymers,
surfactants, detergents, antibacterials, anti-dandruffs, foam
boosters, proteins, moisturising agents, suspending agents,
pacifiers, perfumes, colouring agents, plant extracts, polymers,
and other conventional care ingredients.
[0149] Beyond personal care, the emulsion of the invention are
useful for numerous other applications such as paints, construction
applications, textile fibre treatment, leather lubrication, fabric
softening, fabric care in laundry applications, healthcare,
homecare, release agents, water based coatings, oil drag reduction,
particularly in crude oil pipelines, lubrication, facilitation of
cutting cellulose materials, and in many other areas where
silicones are conventionally used. The silicone organic copolymers
have particular advantages in oil drag reduction resulting from
increased compatibility with hydrocarbon fluids.
EXAMPLES
[0150] The following Examples are provided so that one skilled in
the art will more readily understand the invention. Unless
otherwise indicated, all parts and percents are by weight and all
viscosities are at 25.degree. C. Viscosity measurements of the
polymer products were carried out using a Brookfield Viscometer,
spindle 6, 10 rpm. All Particle size values were determined using a
Malvern Mastersizer 2000.
Example 1
[0151] A polymer was prepared by polymerising 80 g of dimethyl
hydroxyl terminated polydimethylsiloxane having 71 mPas at
25.degree. C. in 80 g of trimethylsilyl terminated
polydimethylsiloxane (PDMS) having a viscosity of 100 mPas at
25.degree. C. using 2.4 g of dodecylbenzenesulphonic acid (DBSA) as
catalyst for the condensation reaction. The polymerisation was
stopped once a viscosity of 10500 mPas at 25.degree. C. was reached
by the addition of 1.12 g of Triethanolamine (TEA).
[0152] To 36 g of the above polymer the following surfactants were
added, 1.1 g Brij.RTM. 30 and 1.9 g Brij.RTM. 35 L. These were
added and mixed for 30 s at 3000 rpm in Hausschild dental mixer.
1.2 g water was added and mixing was repeated for 30 s at 3000 rpm.
Another 0.4 g water was added and the mixing was repeated again
under the same conditions. After the second water addition the
mixture had phase inverted and was diluted to a polymer content of
60%. The so obtained emulsion has a particle size of D(v, 0.5)
.mu.m=0.81 and D(v, 0.9) .mu.m=1.14. The emulsion remained intact
for a period of at least 6 months.
[0153] Brij.RTM. 30/Brij.RTM. 35 L are non-ionic polyoxyethylene
fatty ether (POE) surfactants. Brij.RTM. 30 is POE(4) lauryl ether
with a hydrophile-lipophile balance (HLB) of 9.7. Brij.RTM. 35 L is
a POE (23) lauryl ether with an HLB of 16.9.
Example 2
[0154] A polymer was prepared polymerising 128 g of dimethyl
hydroxyl terminated polydimethylsiloxane having a viscosity of 71
mPas at 25.degree. C. in 32 g of PDMS having a viscosity of 100
mPas at 25.degree. C. using 5.12 g of DBSA as the condensation
catalyst. The polymerisation was stopped, once a viscosity of
171000 mPas at 25.degree. C. was reached, by the addition of 2.39 g
of TEA.
[0155] To 36 g of the above polymer the following surfactants were
added, 1.1 g Brij.RTM. 30 and 1.9 g Brij.RTM. 35 L. These were
added and mixed for 30 s at 3000 rpm in Hausschild dental mixer.
0.5 g water was added mixing was repeated for 30 s at 3000 rpm.
After mixing the mixture had phase inverted and was diluted to a
polymer content of 60%. The so obtained emulsion has a particle
size of D(v, 0.5) .mu.m=1.77 and D(v, 0.9) .mu.m=4.28. The emulsion
remained intact for a period of at least 6 months.
Example 3
[0156] A polymer was prepared polymerising 128 g of dimethyl
hydroxyl terminated polydimethylsiloxane polydimethylsiloxane
having a viscosity of 71 mPas at 25.degree. C. in 32 g of PDMS 100
mPas at 25.degree. C. using 4.48 g of DBSA. The polymerisation was
stopped once a viscosity of 171000 mPas at 25.degree. C. was
reached by the addition of 2.09 g of TEA.
[0157] To 36 g of the above polymer the following two surfactants
were added: 1.3 g Brij.RTM. 30 and 2.4 g Brij.RTM. 35 L. The
surfactants and polymer were mixed for 30 s at 3000 rpm in
Hausschild dental mixer. After mixing the mixture had phase
inverted and was diluted to a polymer content of 60%. The so
obtained emulsion has a particle size of D(v, 0.5) .mu.m=2.07 and
D(v, 0.9) .mu.m=2.58. The emulsion remained intact for a period of
at least 6 months.
Example 4
[0158] To 36 g of the polymer prepared in example 3, were added the
following surfactants, 2.25 g of Arquad 16-29 Arquad.RTM. 16-29
(Akzo Nobel) and 2.25 g Tergitol.RTM.TMN-6 (Dow Chemical). No
additional water was introduced as Arquad.RTM. 16-29 contains 70%
by weight of water and 2.25 g TMN-6 contains 10% by weight of
water. These were added and mixed for 30 s at 3000 rpm in
Hausschild dental mixer. After mixing the mixture had phase
inverted and was diluted to a polymer content of 60%. The so
obtained emulsion has a particle size of D(v, 0.5) .mu.m=1.23 and
D(v, 0.9) .mu.m=1.7. The emulsion remained intact for a period of
at least 6 months.
Example 5
[0159] To 36 g of the polymer prepared in example 3 the following
surfactants were added, 2.25 g Arquad 16-29 and 2.25 g TMN-6
together with 0.5 g water. These were mixed for 30 s at 3000 rpm in
Hausschild dental mixer. After mixing the mixture had phase
inverted and was diluted to a polymer content of 60%. The so
obtained emulsion has a particle size of D(v, 0.5) .mu.m=1.28 and
D(v, 0.9) .mu.m=1.96.
[0160] Arquad 16-29 is a cationic quaternary surfactant. TMN-6 is a
non-ionic ethoxylated alcohol with an HLB=13.1
Example 6
[0161] To 36 g of the polymer prepared in example 3 the following
surfactants were added, 1 g Biosoft N300 and 2 g Brij 30 (No
additional water added). The surfactants were mixed with the
polymer for 30 s at 3000 rpm in Hausschild dental mixer. After
mixing the mixture had phase inverted and was diluted to a polymer
content of 60%. The so obtained emulsion has a particle size of
D(v, 0.5) .mu.m=2.14 and D(v, 0.9) .mu.m=3.14
Example 7
[0162] A polymer was prepared polymerising a 1 to 1 mixture of
dimethyl hydroxyl terminated polydimethylsiloxane having a
viscosity of 70 mPas at 25.degree. C. and of an organic extender
(Hydroseal G 250H (sold by Total) using 2.4% of DBSA as a catalyst.
The polymerisation was stopped, by the addition of 1.54% of TEA,
once a viscosity of 40000 mPas at 25.degree. C. was reached.
[0163] To 40 g of the above polymer 1 g water was added and mixed
for 30 s at 3000 rpm in a Hausschild dental mixer. After mixing the
mixture had phase inverted. Additional 9 g water were added and
mixing repeated under the same conditions. The mixture was then
diluted to a polymer content of 40%. The so obtained emulsion has a
particle size of D(v, 0.5) .mu.m=1.46 and D(v, 0.9) .mu.m=2.22
[0164] In this example no additional surfactant was required
because the condensation catalyst DBSA used in the preparation of
the polymer functioned as the required surfactant.
Example 8
[0165] 40 g of the polymer prepared in example 7 and 1 g water
where mixed for 30 s at 3000 rpm in Hausschild dental mixer. After
mixing the mixture had phase inverted. An additional 1 g water was
then added and mixing repeated under the same conditions. The
mixture was then diluted to a polymer content of 50%. The so
obtained emulsion has a particle size of D(v, 0.5) .mu.m=1.75 and
D(v, 0.9) .mu.m=2.76
[0166] In this example no additional surfactant was required
because the condensation catalyst DBSA used in the preparation of
the polymer functioned as the required surfactant.
Example 9
[0167] A polymer was prepared by polymerising a 1:1 mixture of
dimethyl hydroxyl terminated polydimethylsiloxane having a
viscosity of 70 mPas at 25.degree. C. and of
decamethylcyclopentasiloxane which has a viscosity of 3.8 mPas at
25.degree. C. using 2.4% of DBSA as a catalyst. The polymerisation
was stopped once a viscosity of 27000 mPas at 25.degree. C. was
reached by the addition of 1.54% of TEA. In this case the DBSA
catalyst used in the polymerisation step above additionally
functioned as the surfactant in the preparation of emulsions as
described below.
[0168] 0.3 g water was added to 36 g of the above polymer and mixed
for 30 s at 3000 rpm in a Hausschild dental mixer. Another 0.9 g
water were subsequently added and mixed under the same conditions.
After mixing the mixture had phase inverted. A further 1.9 g of
water was then added and mixing repeated under the same conditions.
The resulting mixture was then diluted to a polymer content of 50%.
The resulting emulsion has a particle size of D(v, 0.5) .mu.m=1.46
and D(v, 0.9) .mu.m=2.34.
Example 10
[0169] A polymer was prepared by polymerising a 4:1 mixture of
dimethyl hydroxyl terminated polydimethylsiloxane having a
viscosity of 70 mPas at 25.degree. C. in an organic extender
(Hydroseal G 250H) using 2.4% g of DBSA as a catalyst. The
polymerisation was stopped once a viscosity of 40000 mPas at
25.degree. C. was reached by the addition of 1.54% g of TEA.
[0170] 1 g water was added to 40.2 g of the above polymer and mixed
for 30 s at 3000 rpm in a Hausschild dental mixer. After mixing the
mixture had phase inverted. An additional 1.1 g of water was added
and mixing repeated under the same conditions. The resulting
mixture was then diluted to a polymer content of 50%. The so
obtained emulsion has a particle size of D(v, 0.5) .mu.m=1.46 and
D(v, 0.9) .mu.m=2.26.
Example 11
[0171] 1.1 g water was added and mixed with 40.2 g of the polymer
prepared in Example 10 for 30 s at 3000 rpm in a Hausschild dental
mixer. After mixing the resulting mixture had phase inverted. An
additional 1.4 g of water was added and mixing repeated under the
same conditions. A still further 2.5 g of water was subsequently
added and mixing repeated under the same conditions. The resulting
mixture was then diluted to a polymer content of 80%. The resulting
viscous cream (emulsion) had a particle size of D(v, 0.5)
.mu.m=1.26 and D(v, 0.9) .mu.m=1.84.
Example 12
[0172] A polymer was prepared by polymerising a 1:1 mixture of
dimethyl hydroxyl terminated polydimethylsiloxane having a
viscosity of 70 mPas at 25.degree. C. in cosmetic grade organic
fluid (Isopar.RTM. M, sold by Exxon) using 20 parts per million
(ppm) of a phosphonitrile catalyst. The polymerisation was stopped
once a viscosity of 51000 mPas at 25.degree. C. was reached by the
addition of trihexylamine. The polymer had a number average
molecular weight of 198000 g/mol and a polydispersity index of
1.54.
[0173] 1.1 g Volpo.RTM. L3, 1.6 g Volpo.RTM. L23 and 1.1 g water
was added to 50.2 g of the polymer prepared as described above and
the resulting mixture was mixed for 60 s at 3000 rpm in a
Hausschild dental mixer. An additional 1.0 g of water was added and
mixing repeated under the same conditions. A still further 1.0 g of
water was added and the same mixing process was repeated again.
After mixing the resulting mixture had phase inverted. Further 2.2
g of water was subsequently added and mixing repeated under the
same conditions. The resulting mixture was then diluted to a
polymer/fluid content of 50%. The resulting emulsion had a particle
size of D(v, 0.1) .mu.m=1.23, D(v, 0.5) .mu.m=2.67 and D(v, 0.9)
.mu.m=5.01 and henceforth is referred to as sample 12.1
emulsion.
[0174] The resulting emulsion was introduced into a selection of
personal care formulations, including fruity gel blushers, eye
shadow, water in oil skin creams, hair care conditioners, leave-on
and the following:--
Cold Mix Lotion
[0175] This lotion was prepared with the ingredients depicted in
Table 12(a) below by initially mixing the phase B ingredients
together and then introducing phase A into the phase B and then
mixing the resulting product until it is homogeneous.
TABLE-US-00001 TABLE 12(A) Ingredients INCI Name % Phase A Sample
12.1 emulsion 20 Phase B Water 78 Phenochem Phenoxyethanol (and)
Methylparaben (and) 1 Butylparaben (and) Ethylparaben (and)
Propylparaben (and) Isobutylparaben Keltrol Xanthan Gum 1
It was found that the sample 12.1 emulsion could be easily
incorporated in a lotion type product and the resulting lotion was
found to have a significant impact on sensory profile, in upon
testing using 18 panelists. Significant differences in >95% of
results was found for speed of absorption, gloss, film residue,
greasiness. This indicates that sample 12.1 emulsion could
significantly impact the sensory of lotion prepared as described
herein, making it richer and more nourishing.
Water in Silicone Skin Cream
[0176] The above was prepared using the ingredients identified in
Table 12(b) below:--
TABLE-US-00002 TABLE 12(B) Ingredients INCI Name % Phase A Dow
Corning .RTM.5225C Cyclopentasiloxane (and) 10 Formulation Aid
PEG/PPG-18/18 Dimethicone Dow Corning .RTM.245 Cyclopentasiloxane
18.6 Fluid Phase B Sample 12.1 emulsion 2.3 Sodium Chloride 2 Water
67.1 Viscosity: Spindle 7, 20 rpm 11800 mPa s
[0177] The ingredients of phase A were mixed together. The
ingredients of phase B were mixed together. Phase B was then
introduced dropwise into the phase A mixture whilst continuously
agitation the resulting mixture and finally the resulting mixture
was homogenized using a high shear mixer.
[0178] Sensory tests were carried out using 18 panelists to
determine the performance of the resulting cream as described
above, containing 2.3% by weight of Sample 12.1 emulsion in
comparison to an identical cream in the absence of the sample 12.1
emulsion. Significant differences >95% were identified with
respect to speed of absorption, gloss, film residue and greasiness
demonstrating that the presence of Sample 12.1 emulsion at levels
as low as 2.3% impact significantly the sensory of the cream making
it richer and more nourishing.
Opaque Shampoo
[0179] The above was prepared using the ingredients identified in
Table 12(c) below:--
TABLE-US-00003 TABLE 12(C) Ingredients INCI Name % Phase A Water
60.5 Crothix liquid PEG-150 Pentaerythrityl 1.5 Tetrastearate and
PEG-6 Caprylic/Capric Glycerides and Water Empicol ESB-3 Sodium
Laureth Sulfate 12 Texapon A 400 Ammonium Lauryl Sulfate 10 Amonyl
380BA Cocamidopropyl Betaine 8 Comperlan KD Cocamide DEA 4 Phase B
Sample 12.1 emulsion 4 Phase C Citric Acid q.s Nipaguard DMDMH DMDM
Hydantoin q.s Viscosity: Spindle 7, 20 rpm 41600 mPa s
[0180] Water was heated to 70.degree. C. The ingredients of phase A
were mixed together. Phase B was inter-mixed with phase A with
gentle mixing and then phase C was introduced and the resulting
composition was allowed to cool.
[0181] Several panelists were asked to comb slightly bleached hair
tresses washed with the resulting shampoo. The time to wet detangle
the hair tresses was measured. As a direct comparison the panelists
also undertook the same process with slightly bleached hair tresses
using the same shampoo formulation without any emulsion. The
results indicate a slight decrease in the detangling time with the
shampoo containing the sample 12.1 emulsion. This indicates an
improvement in the conditioning effect in the shampoo when the
emulsions in accordance with the present invention were
present.
Example 13
[0182] A range of polymers Examples 13(a) to 13(i) were prepared by
polymerising mixtures of dimethyl hydroxyl terminated
polydimethylsiloxane having a viscosity of 70 mPas at 25.degree. C.
and sunflower seed oil using DBSA as a catalyst (as indicated in
Table 13(a). All ingredients were mixed at 1500 rpm for 30 s
(Hausschild dental mixer). The polymerisation was stopped after
different times by adding TEA and mixing again under the same
conditions.
TABLE-US-00004 TABLE 13A Example a b c d e f g h I Silox- 45 45 45
40 40 40 35 35 35 ane (g) Sun- 5 5 5 10 10 10 15 15 15 flower Oil
(g) DBSA 1.5 2 2.5 1.5 2 2.5 1.5 2 2.5 (g) TEA (g) 0.94 1.25 1.56
0.94 1.25 1.56 0.94 1.25 1.56 Re- 35 31 20 34 29 21 33 29 21 action
time (min)
[0183] Subsequent to completion of polymerisation, emulsions were
prepared using the following process:--
Firstly 1 g water was directly added to the polymerisation product
and the resulting mixture was mixed at 3000 rpm for 60 s. The water
addition step was repeated was repeated with 1 g water added and
mixed at 3000 rpm for 60 s, then, a further 8 g of water was added
and mixed at 3000 rpm for 60 s and finally 40 g of water was added
and mixed at 1500 .mu.m for 30 s.
[0184] The resulting emulsions were analysed for Molecular weight
(obtained by GPC) and cyclic siloxane content (D.sub.4-D.sub.12) by
gas chromatography. The results are provided in Table 13(b)
below
TABLE-US-00005 TABLE 13(B) Example a b c d e f g h i D(v, 0.1) 0.5
0.33 0.6 0.53 0.36 0.26 0.21 0.22 0.23 Mm D(v, 0.5) 0.77 2.49 0.99
0.94 1.14 1.7 0.77 1.09 1.67 Mm D(v, 0.9) 1.05 6.11 1.61 1.48 1.91
3.8 1.91 2.39 4.01 Mm Mn 82 158 229 98 162 211 129 174 205 kg/mol
Mw 112 220 312 142 229 296 183 252 300 kg/mol D.sub.4 (%) 0.06 0.09
0.09 0.07 0.07 0.07 0.05 0.06 0.06 D.sub.5 (%) 0.04 0.06 0.06 0.05
0.05 0.05 0.04 0.04 0.04 D.sub.6 (%) 0.05 0.07 0.06 0.06 0.06 0.05
0.05 0.05 0.05 D.sub.7 (%) 0.06 0.07 0.06 0.07 0.07 0.06 0.06 0.06
0.05 D.sub.8 (%) 0.05 0.07 0.05 0.06 0.06 0.05 0.05 0.05 0.04
D.sub.9 (%) 0.05 0.06 0.05 0.06 0.05 0.05 0.05 0.05 0.04 D.sub.10
(%) 0.04 0.05 0.04 0.05 0.05 0.04 0.05 0.05 0.04 D.sub.11 (%) 0.04
0.05 0.03 0.04 0.04 0.04 0.04 0.04 0.03 D.sub.12 (%) 0.04 0.05 0.04
0.04 0.04 0.04 0.04 0.04 0.04
[0185] The resulting emulsions prepared in accordance with the
above and identified as Example 13b, Example 13e and Example 13h
were introduced into a selection of personal care formulations,
including fruity gel blushers, water in oil and water in silicone
skin creams, hair care shampoo, leave-on, and the following:--
Ethnic Hair Care: Conditioner
[0186] The above was prepared using the ingredients identified in
Table 13(c) below:--
TABLE-US-00006 TABLE 13(C) Ingredients INCI Name % Phase A Water
79.47 Natrosol 250 HHR Hydroxyethylcellulose 1.5 Arquad 16-29
Cetrimonium Chloride 0.7 Phase B Lanette Wax O Cetearyl Alcohol 4
Arlacel 165 Glyceryl Stearate and PEG-100 1 Stearate Phase C
Propylene Glycol 4 Glycerin 4 Phase D Gluadin W20 Hydrolyzed Wheat
Protein 1 Germaben II Propylene Glycol and 1 Diazolidinyl Urea and
Methylparaben and Propylparaben Phase E Example 13e Emulsion 3.33
Viscosity: Spindle 7, 20 rpm 45200 mPa s
[0187] The ingredients of phase A were mixed together and then
heated to 75.degree. C. Phase B was then added whilst mixing and
the mixture was allowed to commence cooling. Phase C was then
introduced and the resulting mixture was allowed to cool to
50.degree. C. Phase D was then added and the mixture was cooled to
room temperature. Phase E was then added and finally water was
introduced to compensate for water loss during heating phase.
[0188] Several panelists were asked to comb slightly bleached hair
tresses washed with the resulting conditioner to determine the time
taken to detangle the wet hair. In comparison the participants had
to comb slightly bleached hair tresses which had been washed with
the same conditioner formulation without any emulsion. The results
indicate a significant decrease (>99%) into the detangling time
when using the conditioner containing example 13e emulsion
indicating a positive impact on hair conditioning.
Shower Gel
[0189] The above was prepared using the ingredients identified in
Table 13(d) below:--
TABLE-US-00007 TABLE 13(D) Ingredients INCI Name % Phase A Empicol
ESB-3 Sodium Laureth Sulfate 30 Oramix NS10 Decyl Glucoside 5
Amonyl 380BA Cocamidopropyl Betaine 10 Brij 30 Laureth-4 2 Sepigel
305 Polyacrylamide and C13-14 2 Isoparaffin and Laureth-7 Water
42.7 Phase B Example 13e Emulsion 8.3 Phase C Sodium Chloride q.s
Viscosity: Spindle 5, 100 rpm 4000 mPa s
[0190] The ingredients of phase A were initially mixed until
homogeneous, after which phase B was introduced whilst mixing was
continued. Phase C was then introduced to adjust the viscosity of
the final mixture to the required value. It was found that
emulsions in accordance with the present invention, such as example
13e emulsion, can be easily added to shower gel formulations and
provide stable formulations.
Smooth Stay Shadow (Eye Make-Up)
[0191] The above was prepared using the ingredients identified in
Table 13(e) below:--
TABLE-US-00008 TABLE 13(E) Ingredients INCI Name % Phase A Glycerin
8 Propylene Glycol 8 Phase B Covacryl RH Sodium Polyacrylate 0.7
Phase C Water 42 Nipaguard DMDMH DMDM Hydantoin 0.3 Phase D Example
13b Emulsion 6 Covacryl E14 Acrylates Copolymer 20 Phase E
Covapearl light brown 830 AS Mica and CI 77491 and 4
Triethoxycaprylysilane Covapearl satin 931 AS Mica and CI 77891 and
11 Triethoxycaprylysilane
[0192] Phase B was first dispersed in phase A. The resulting
mixture of Phases A and B were then mixed into phase C under
agitation. Phase D was then added to the mixture and was mixed
until homogeneous. Finally phase E was added and the final
formulation was mixed until homogeneous.
[0193] It was found that that emulsions such as Example 13b
emulsion as hereinbefore described can be easily incorporated into
a eye shadow formulations with high pigment levels. 18 panelists
compared the eye shadow formulation with example 13b emulsion in
comparison with the same formulation in the absence of said
emulsion. It was identified that the formulation containing Example
13b emulsion increased the tackiness of the formulation without
significantly impacting the gloss and spreadability of the
formulation thereby improving adhesion and retention of the
formulation on the skin.
Skinshield--Water in Oil Skin Cream
[0194] The above was prepared using the ingredients identified in
Table 13(f) below:--
TABLE-US-00009 TABLE 13(F) Ingredients INCI Name % Phase A Dow
Corning .RTM.5200 Formulation Lauryl PEG/PPG-18/18 Methicone 2 Aid
Mineral Oil 8 Dow Corning .RTM.2-1184 Fluid Trisiloxane and
Dimethicone 4.5 Dow Corning .RTM.9040 Silicone Cyclopentasiloxane
and Dimethicone 5 Elastomemr Blend Crosspolymer Escalol 557
Ethylhexyl Methoxycinnamate 2 Dekaben (as sold by Jan Dekker
Phenoxyethanol and Methylparaben and 0.5 company) Ethylparaben and
Propylparaben and Butylparaben Phase B Water 61.94 Sodium Chloride
1 Propylene Glycol 5 Glycofilm Biosaccharide Gum-4 5 Example 13h
Emulsion 5 Phase C D&C Red 28 (0.5% in water) D&C red
28/LCW 0.06 Viscosity: Spindle 7, 20 rpm 27400 mPa s
[0195] The ingredients of phase A were mixed until homogeneous. The
phase B ingredients were then mixed together with sufficient
agitation to obtain a homogeneous mixture. Phase C was then
introduced into phase B whilst mixing was continued and then the
phases B and C mixture was introduced into phase A whilst mixing.
After the complete addition mixing was continued for a further 15
minutes
Cold Mix Lotion
[0196] The above was prepared using the ingredients identified in
Table 13(g) below:--
TABLE-US-00010 TABLE 13(G) Ingredients INCI Name % % Phase A
Example 13h Emulsion -- 20 Phase B Water 78 78 Phenochem
Phenoxyethanol (and) Methylparaben 1 1 (and) Butylparaben (and)
Ethylparaben (and) Propylparaben (and) Isobutylparaben Keltrol
Xanthan Gum 1 1
[0197] The ingredients of phase B were initially mixed together and
then the resulting mixture was introduced into phase A and was
mixed until homogeneous.
Example 14
[0198] A polymer was prepared by polymerising a 1:1 mixture of
dimethyl hydroxyl terminated polydimethylsiloxane having a
viscosity of 70 mPas at 25.degree. C. and an organic extender
(Hydroseal G 250H) using 20 ppm of a phosphonitrile catalyst. The
polymerisation was stopped once a viscosity of 100000 mPas at
25.degree. C. was reached by the addition of trihexylamine. The
polymer had a number average molecular weight of 235000 g/mol and a
polydispersity index of 1.48.
[0199] 1.75 g Volpo.RTM. L4, 1.25 g and Volpo.RTM. L23 was added to
30 g of the polymer/extender blend described above and mixed for 20
s at 3000 rpm in a Hausschild dental mixer. An additional 2.0 g of
water was added and mixing repeated under the same conditions.
Further additions of 2.0 g of water were repeated four more times.
The resulting mixture was then diluted with additional 30 g of
water.
[0200] The above emulsion was evaluated in a fabric softener
consisting of: [0201] 55.6 g Tetranyl L1/90 standard [0202] 8 g
MgCl.sub.2.6H.sub.2O solution @ 20% [0203] 936.4 g of water [0204]
Total=1000 g.fwdarw.5% active Quat
[0205] The Tetranyl L1/90 standard was first melted at 55.degree.
C. The resulting liquid was then poured whilst being continuously
stirred into in hot water and the resulting mixture was allowed to
cool with continued stirring. During the cooling period, again with
continuous stirring the magnesium chloride salt and the emulsion
prepared in accordance with the invention were introduced.
[0206] The fabric (cotton towels) was treated by adding the
softener using a Miele washing machine and a washing it with
commercial detergent powder (DASH). Softness of towels was
determined in a panel test and rated from 1-10 (10=softest). While
the fabric softener described above was rated at 5.0, the fabric
softener containing the emulsion in accordance with the present
invention was rated at 5.5.
[0207] The water absorbency of the treated fabric was tested by
dropping a 2 cm*2 cm sample into 250 ml water. The time until the
fabric is sinking is recorded. The result was 9 s for the sample
treated with softener containing the emulsion as described above
and 128 s for a sample treated with a softener only, showing
therefore improved water absorbency
* * * * *