U.S. patent number RE38,116 [Application Number 10/035,497] was granted by the patent office on 2003-05-06 for method of making siloxane-based polymides.
This patent grant is currently assigned to Dow Corning Corporation. Invention is credited to Lenin James Petroff, Jay Brian Rose, Michael Ward Skinner.
United States Patent |
RE38,116 |
Petroff , et al. |
May 6, 2003 |
Method of making siloxane-based polymides
Abstract
A method of making siloxane-based polyamides which includes at
least one repeating unit represented by the formula ##STR1##
wherein X is a linear or branched C.sub.1 -C.sub.30 alkylene chain;
Y is a linear or branched C.sub.1 -C.sub.20 alkylene chain; DP is
an integer having a value of 10-500; n is an integer having a value
1-500. The method involves heating an intimate reaction mixture
containing an olefinic acid and an organic diamine at a temperature
greater than 100.degree. C. and forming an organic diamide; and
thereafter reacting the organic diamide with a hydride-terminated
polydimethylsiloxane in the presence of a hydrosilylation catalyst
to form the siloxane-based polyamide.
Inventors: |
Petroff; Lenin James (Bay City,
MI), Rose; Jay Brian (Midland, MI), Skinner; Michael
Ward (Midland, MI) |
Assignee: |
Dow Corning Corporation
(Midland, MI)
|
Family
ID: |
22354872 |
Appl.
No.: |
10/035,497 |
Filed: |
November 8, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
114381 |
Jul 13, 1998 |
05981680 |
Nov 9, 1999 |
|
|
Current U.S.
Class: |
528/26; 528/15;
528/31 |
Current CPC
Class: |
A61K
8/898 (20130101); A61Q 19/00 (20130101); C08G
69/42 (20130101); C08G 77/455 (20130101); A61Q
5/00 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/895 (20060101); A61Q
19/00 (20060101); C08G 69/00 (20060101); C08G
69/42 (20060101); C08G 77/00 (20060101); C08G
77/455 (20060101); C08G 077/26 () |
Field of
Search: |
;520/15,31,28,26 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Moore; Margaret G.
Attorney, Agent or Firm: Scaduto; Patricia M.
Claims
I claim:
1. A method of making a siloxane-based polyamide which includes at
least one repeating unit represented by the formula ##STR22##
wherein X is a linear or branched C.sub.3 to C.sub.10 alkylene
chain; Y is a linear or branched C.sub.1 -C.sub.20 alkylene chain;
R.sup.1 -R.sup.4 are independently methyl, ethyl, propyl,
isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3
members which are methyl or ethyl; DP is an integer having a value
of 10-500; and n is an integer having a value of 1-500; the method
comprising heating a reaction mixture containing an olefinic acid
and an organic diamine at a temperature greater than 100.degree. C.
and forming an organic diamide; and thereafter reacting the organic
diamide with a hydride-terminated polydimethylsiloxane in the
presence of a hydrosilylation catalyst to form the siloxane-based
polyamide.
2. A method according to claim 1 in which the organic diamine is a
compound selected from the group consisting of hexamethylene
diamine, ethylene diamine, and decamethylene diamine.
3. A method according to claim 1 in which the olefinic acid is a
compound selected from the group consisting of undecylenic acid,
acrylic acid, 3-butenoic acid, and 4-pentenoic acid.
4. A method according to claim 1 in which the siloxane-based
polyamide has a number average molecular weight of from 4,000 to
200,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard.
5. A method according to claim 4 in which the siloxane-based
polyamide has a number average molecular weight of from 5,000 to
65,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard.
6. A method according to claim 1 in which the repeating unit of the
siloxane-based polyamide is represented by the formula
##STR23##
wherein X is a linear or branched C.sub.3 to C.sub.10 alkylene
chain; Y, Y.sup.1, and Y.sup.2 are linear or branched C.sub.1
-C.sub.20 alkylene chains; DP1, DP2, and DP3 are integers each
having values of 10-500; n, m, and p are integers each having
values of 1-500; Z is represented by ##STR24##
wherein R', R", and R"' are linear or branched C.sub.1 -C.sub.10
alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl,
propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl
may optionally be substituted by 1-3 members which are methyl or
ethyl, or T is a trivalent atom such as N, P and Al; provided n is
not the same as m, or Y is not the same as Y.sub.1, or DP1 is not
the same as DP2.
7. A method of making a siloxane-based polyamide which includes at
least one repeating unit represented by the formula ##STR25##
wherein X is a linear or branched C.sub.3 to C.sub.10 alkylene
chain; Y is a linear or branched C.sub.1 -C.sub.20 alkylene chain;
R.sup.1 -R.sup.4 are independently methyl, ethyl, propyl,
isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3
members which are methyl or ethyl; DP is an integer having a value
of 10-500; and n is an integer having a value of 1-500; the method
comprising reacting an organic diamide with a hydride-terminated
polydimethylsiloxane in the presence of a hydrosilylation catalyst
to form the siloxane-based polyamide.
8. A method according to claim 7 in which the siloxane-based
polyamide has a number average molecular weight of from 4,000 to
200,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard.
9. A method according to claim 8 in which the siloxane-based
polyamide has a number average molecular weight of from 5,000 to
65,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard.
10. A method according to claim 7 in which the repeating unit of
the siloxane-based polyamide is represented by the formula
##STR26## ##STR27##
wherein X is a linear or branched C.sub.3 to C.sub.10 alkylene
chain; Y, Y.sup.1, and Y.sup.2 are linear or branched C.sub.1
-C.sub.20 alkylene chains; DP1, DP2, and DP3 are integers each
having values of 10-500; n, m, and p are integers each having
values of 1-500; Z is represented by ##STR28##
wherein R', R", and R'" are linear or branched C.sub.1 -C.sub.10
alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl,
propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl
may optionally be substituted by 1-3 members which are methyl or
ethyl, or T is a trivalent atom such as N, P and Al; provided n is
not the same as m, or Y is not the same as Y.sup.1, or DP1 is not
the same as DP2..Iadd.
11. A method of making a siloxane-based polyamide which includes at
least one repeating unit represented by the formula ##STR29##
wherein X is a linear or branched C.sub.3 -C.sub.10 alkylene chain;
Y is a linear or branched C.sub.1 -C.sub.20 alkylene chain; R.sup.1
-R.sup.4 are independently methyl, ethyl, propyl, isopropyl, a
siloxane chain, phenyl, or phenyl substituted by 1-3 members which
are methyl or ethyl; DP is an integer having a value of 10-500; and
n is an integer having a value of 1-500; the method comprising
heating a reaction mixture containing an olefinic acid and an
organic diamine at a temperature greater than 100.degree. C. and
forming an organic diamide; and thereafter reacting the organic
diamide with an .ident.SiH containing polysiloxane in the presence
of a hydrosilylation catalyst to form the siloxane-based
polyamide..Iaddend..Iadd.
12. A method according to claim 11 in which the organic diamine is
a compound selected from the group consisting of hexamethylene
diamine, ethylene diamine, and decamethylene
diamine..Iaddend..Iadd.
13. A method according to claim 11 in which the olefinic acid is a
compound selected from the group consisting of undecylenic acid,
acrylic acid, 3-butenoic acid, and 4-pentenoic
acid..Iaddend..Iadd.
14. A method according to claim 11 in which the siloxane-based
polyamide has a number average molecular weight of from 4,000 to
200,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard..Iaddend..Iadd.
15. A method according to claim 14 in which the siloxane-based
polyamide has a number average molecular weight of from 5,000 to
65,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard..Iaddend..Iadd.
16. A method according to claim 11 in which the repeating unit of
the siloxane-based polyamide is represented by the formula
##STR30##
or the formula ##STR31##
wherein X is a linear or branched C.sub.3 -C.sub.10 alkylene chain;
Y, Y.sup.1, and Y.sup.2 are linear or branched C.sub.1 -C.sub.20
alkylene chains; DP1, DP2, and DP3 are integers each having values
of 10-500; n, m, and p are integers each having values of 1-500; Z
is represented by ##STR32##
wherein R', R", and R'" are linear or branched C.sub.1 -C.sub.10
alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl,
propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl
may optionally be substituted by 1-3 members which are methyl or
ethyl, or T is a trivalent atom such as N, P and Al; provided n is
not the same as m, or Y is not the same as Y.sup.1, or DP1 is not
the same as DP2..Iaddend..Iadd.
17. A method of making a siloxane-based polyamide which includes at
least one repeating unit represented by the formula ##STR33##
wherein X is a linear or branched C.sub.3 -C.sub.10 alkylene chain;
Y is a linear or branched C.sub.1 -C.sub.20 alkylene chain; R.sup.1
-R.sup.4 are independently methyl, ethyl, propyl, isopropyl, a
siloxane chain, phenyl, or phenyl substituted by 1-3 members which
are methyl or ethyl; DP is an integer having a value of 10-500; and
n is an integer having a value of 1-500; the method comprising
reacting an organic diamide with an .ident.SiH containing
polysiloxane in the presence of a hydrosilylation catalyst to form
the siloxane-based polyamide..Iaddend..Iadd.
18. A method according to claim 17 in which the siloxane-based
polyamide has a number average molecular weight of from 4,000 to
200,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard..Iaddend..Iadd.
19. A method according to claim 18 in which the siloxane-based
polyamide has a number average molecular weight of from 5,000 to
65,000 daltons, as determined by gel permeation chromatography
using polydimethylsiloxane as a standard..Iaddend..Iadd.
20. A method according to claim 17 in which the repeating time of
the siloxane-based polyamide is represented by the formula
##STR34##
or the formula ##STR35##
wherein X is a linear or branched C.sub.3 -C.sub.10 alkylene chain;
Y, Y.sup.1, and Y.sup.2 are linear or branched C.sub.1 -C.sub.20
alkylene chains; DP1, DP2, and DP3 are integers each having values
of 10-500; n, m, and p are integers each having values of 1-500; Z
is represented by ##STR36##
wherein R', R", and R'" are linear or branched C.sub.1 -C.sub.10
alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl,
propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl
may optionally be substituted by 1-3 members which are methyl or
ethyl, or T is a trivalent atom such as N, P and Al; provided n is
not the same as m, or Y is not the same as Y.sup.1, or DP1 is not
the same as DP2..Iaddend.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
REFERENCE TO A MICROFICHE APPENDIX
Not applicable.
FIELD OF THE INVENTION
This invention is directed to an improvement in the method of
making siloxane-based polyamides described in a prior copending
application, U.S. Ser. No. 08/904,709, filed Aug. 1, 1997, and
entitled "Cosmetic Composition Containing Siloxane-Based Polyamides
as Thickening Agents", hereafter referred to as the '709
application.
BACKGROUND OF THE INVENTION
The present invention relates to a novel method of making
siloxane-based polyamides.
There is a growing demand in the personal care arena for polymeric
materials capable of thickening dimethylcyclosiloxanes in order to
modify product viscosity in various market niche hair, skin,
cosmetic, and underarm, applications.
The '709 application is directed to one type of a process for
preparing siloxane-based polyamides. The process according to the
'709 application involves many steps, and this results in cost
prohibitive products which are difficult to produce in commercial
quantity.
For example, in the '709 application process, a dimethyl hydride
endblocked polydimethylsiloxane is first prepared containing the
appropriate number of siloxane units to achieve a desired value of
DP. The carboxylic acid group of undecylenic acid is then protected
through reaction with hexamethyldisilazane. The dimethyl hydride
endblocked polydimethylsiloxane and the protected undecylenic acid
are reacted to produce a siloxane diacid, i.e., a carboxydecyl
terminated polydimethylsiloxane. This reaction is accomplished in
the presence of a platinum catalyst, and the product is washed with
methanol to remove the trimethylsilyl protecting group from the
protected siloxane diacid. The siloxane diacid is then reacted with
an organic diamine to produce a siloxane-based polyamide.
Accordingly, a new process has been discovered herein that
eliminates many of the otherwise costly steps involved in the
process according to the '709 application.
The new process basically involves the addition of an olefinic acid
with an organic diamine to produce an organic diamide. One the
olefinic acid and the organic diamine are fully reacted, an
.ident.SiH endblocked polysiloxane is added in the presence of a
platinum catalyst, to produce a siloxane-based polyamide via
hydrosilylation. The resulting polymeric product is in the form of
a high molecular weight thermoplastic polymer. The benefits of this
process is that it allows for the production of a cost effective
manufactured product in commercial quantity.
BRIEF SUMMARY OF THE INVENTION
This invention relates to a method of forming a siloxane-based
polyamides which are useful as thickening agents to formulate a
wide variety of cosmetic compositions. The polyamides of this
invention are multiples of a unit represented by the following
Formula A: ##STR2##
where: (1) The degree of polymerization (DP) is 1-700, preferably
10-500, and more preferably 15-45. DP represents an average value
for degree of polymerization of the siloxane units in the polymer
with greater or lesser DP values centered around the indicated DP
value. (2) n is 1-500, particularly 1-100, and more particularly
4-25. (3) X is a linear or branched chain alkylene having 1-30
carbons, particularly 3-10 carbons, and more particularly 10
carbons. (4) Y is a linear or branched chain alkylene having 1-40
carbons, particularly 1-20 carbons, more particularly 2-6 carbons,
and especially 6 carbons wherein (a) The alkylene group may
optionally and additionally contain in the alkylene portion at
least one of (i) 1-3 amide linkages; (ii) a C5 or C6 cycloalkane;
or (iii) phenylene, optionally substituted by 1-3 members which are
independently C1-C3 alkyls; and (b) the alkylene group itself may
optionally be substituted by at least one of (i) hydroxy; (ii) a
C3-C8 cycloalkane; (iii) 1-3 members which are independently C1-C3
alkyls; phenyl, optionally substituted by 1-3 members which are
independently C1-C3 alkyls; (iv) a C1-C3 alkyl hydroxy; or (v) a
C1-C6 alkyl amine; and (c) Y can be Z where Z is
T(R.sup.20)(R.sup.21)(R.sup.22) where R.sup.20, R.sup.21 and
R.sup.22 are each independently linear or branched C1-C 10
alkylenes; and T is CR in which R is hydrogen, the group defined
for R.sup.1 -R.sup.4, or a trivalent atom such as N, P and Al. (5)
Each of R.sup.1 -R.sup.4 (collectively "R") is independently
methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl,
wherein the phenyl may optionally be substituted by 1-3 members
which are methyl or ethyl. More particularly, R.sup.1 -R.sup.4 are
methyl or ethyl, especially methyl. (6) X, Y, DP, and R.sup.1
-R.sup.4 may be the same or different for each polyamide unit.
By "siloxane chain" is meant a group of units such as: ##STR3##
where R.sup.30 and R.sup.31 are each independently organic
moieties; and each R.sup.30 and R.sup.31 are connected to silicon
by a carbon-silicon bond.
The carbon numbers in the alkylene chain do not include the carbons
in the extra segments or substitutions. Also, the polyamides must
have a siloxane portion in the backbone and optionally may have a
siloxane portion in a pendant or branched portion.
If repeated with no variations in the defined variables, Formula A
is representative of a linear homopolymer. Variations of the
invention include: (1) polyamides in which multiple values of DP,
and of units X, Y, and R.sup.1 -R.sup.4 occur in one polymeric
molecule, and wherein the sequencing of these units may be
alternating, random or block; (2) polyamides in which an organic
triamine or higher amine such as tris(2-aminoethyl)amine replaces
the organic diamine in part, to produce a branched or crosslinked
molecule; and (3) physical blends of any of (1) and (2) and/or
linear homopolymers.
These and other features of the invention will become apparent from
a consideration of the detailed description.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
Not applicable.
DETAILED DESCRIPTION OF THE INVENTION
This invention is directed to a new and novel process for making
siloxane-based polyamides. As it relates to the '709 application,
the process eliminates costly steps and produces a polymer with
higher molecular weights than achieved with the previous process in
the '709 application. For example, average molecular weights as
measured by gel permeation chromatography (GPC), using the process
according to the '709 application were determined to be
approximately 50,000. The new process according to the present
invention produces average molecular weights of approximately
65,000.
In addition, the process according to this invention is much faster
than the particular process of the '709 application as well as
other traditional processes for making siloxane-based polyamides.
The '709 application process takes approximately four days to make
a finished siloxane-based polyamide polymer, while the new route
according to the present invention takes approximately one day. The
thermoplastic polymer produced as a result of the instant process
is ideal for the thickening of dimethylcyclosiloxanes, which
renders it of benefit in a large number of personal care product
applications.
Basically the new, process involves the addition of an olefinic
acid such as undecylenic acid H.sub.2 C.dbd.CH(CH.sub.2).sub.8 COOH
to an organic diamine such as hexamethylene diamine H.sub.2
N(CH.sub.2).sub.6 NH.sub.2, to produce an organic diamide. This
organic diamide product is then reacted with an .ident.SiH
endblocked polysiloxane in the presence of a platinum catalyst to
produce the siloxane-based polyamide. Analysis using GPC confirm
and indicate the achievement of high molecular weight growth using
the process according to the present invention.
Some examples of compounds of Formula A include: 1) Polyamides of
Formula I: ##STR4## where X, Y, n, R.sup.1 -R.sup.4, and DP are as
defined for Formula A, A particular subgroup of Formula I are
compounds where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each
methyl.
Preferred polyamides of Formula I are: ##STR5##
where DP is 10-500, particularly 15-45, and more particularly 29.
Another particular group contains polyamides of Formula I where X,
Y, DP and R.sup.1 -R.sup.4 are the same in each unit of the
polymer. 2) Polyamides containing multiple siloxane block lengths
as shown in Formula II: ##STR6## where X, Y, n, and R.sup.1
-R.sup.4 have the meanings described above for Formula A; m is the
same as the value defined for n; and n and m denote the total
number of units enclosed within the brackets; with the individual
units arranged with regular, alternating, block, or random
sequencing.
R.sup.5 -R.sup.8 is the same group as defined for R.sup.1 -R.sup.4
; DP1 and DP2 may be the same or different, and each can be
independently the same as defined for DP. The units denominated by
n and m may be structured to form either block (regularly
sequenced) or random copolymers.
A particular subgroup for compounds of Formula II may have methyl
for all R groups. Another particular subgroup of compounds of
Formula II may have DP1 equal to DP2. A third particular subgroup
may have methyl for all R groups, and DP1 equal to DP2. 3)
Polyamides synthesized from multiple diamines as shown in Formula
III: ##STR7## where X, Y, m, n, R.sup.1 -R.sup.8, DP1, DP2 have the
same meanings as described above for Formula A and Formula II;
Y.sup.1 is independently selected from the same group as defined
for Y; and the units denominated by n and m may be structured to
form either block (regularly sequenced) or random copolymers.
A particular subgroup of compounds of Formula III may have DP1
equal to DP2. Another particular subgroup of compounds of Formula
III may have methyl for all R groups. A third particular subgroup
may have methyl for all R groups, and DP1 equal to DP2. 4)
Polyamides synthesized with a trifunctional amine as shown in
Formula IV: ##STR8## where X, Y, Y.sup.1, R.sup.1 -R.sup.8, m, n,
DP1, and DP2, are the same as defined above; R.sup.9 -R.sup.12 are
the same as defined for R.sup.1 -R.sup.8 ; DP3 is the same as
defined for DP; p is the same as defined for m and n; Z is
T(R.sup.20)(R.sup.21)(R.sup.22) where R.sup.20, R.sup.21 and
R.sup.22 are each independently linear or branched C1-C10
alkylenes; and T is CR where R is hydrogen, the same as defined for
R.sup.1 -R.sup.4, or a trivalent atom such as N, P and Al.
Preferred values for p are 1-25, with more preferred values being
1-7. Preferred units for R.sup.1 -R.sup.12 are methyl. T is
preferably N. Particular values for DP1 to DP3 are 10-500, and more
particularly 15-45. R.sup.20, R.sup.21, and R.sup.22 are preferably
ethylene. A preferred group representative of Z is (--CH.sub.2
CH.sub.2).sub.3 N.
One particular group of compounds of Formula IV is represented by
the formula ##STR9##
where X is --(CH.sub.2).sub.10 --, Y is --(CH.sub.2)--; DP is
15-45; m is 5-20% of n+p; and Z is (--CH.sub.2 CH.sub.2).sub.3
N.
Siloxane-based polyamides according to this invention (1) contain
both siloxane groups and amide groups which facilitate the
thickening of compositions containing volatile silicone fluids and
non-volatile silicone fluids; (2) are non-flowable solids at room
temperature; and (3) dissolve in a fluid which contains silicone at
a temperature of 25-160.degree. C., to form translucent or clear
solutions at a temperature in this range.
With regard to the siloxane units in the siloxane-based polyamides,
the siloxane units must be in the main or backbone chain but can
also optionally be present in branched or pendent chains. In the
main chain the siloxane units occur in segments as described above.
In the branched or pendent chains the siloxane units can occur
individually or in segments.
Particular groups of siloxane-based polyamides include: (a)
polyamides of Formula I where the DP is 15-50; (b) physical blends
of two or more polyamides wherein at least one polyamide has a
value for DP in the range of 15-50, and at least one polyamide has
a value for DP in the range of 30-500; (c) compounds of Formula II
where (1) the value for DP1 is 15-50, and the value for DP2 is
30-500; and (2) the portion of the polyamide having DP1 is about
1-99 weight % based on the weight of the total polyamide content,
and the portion of the polyamide having DP2 is about 1-99 weight %;
(d) physical blends of polyamides of Formula I made by combining
(1) 80-99 weight % of a polyamide where n is 2-10, and especially
where n is 3-6; and (2) 1-20 weight % of a polyamide where n is
5-500, especially where n is 6-100; (e) polyamides of Formula III
where at least one Y or Y.sup.1 contains at least one hydroxyl
substitution; (f) polyamides of Formula A synthesized with at least
a portion of an activated diacid, such as a diacid chloride,
dianhydride, or diester, instead of the diacid; (g) polyamides of
Formula A where X is --(CH.sub.2).sub.3 --; and (h) polyamides of
Formula A where X is --(CH.sub.2).sub.10 --.
THE PROCESS ACCORDING TO THE '709 APPLICATION
A reaction scheme for making polyamides of Formula I according to
the '709 application involves the condensation of a siloxane diacid
with an organic diamine as shown below. (1) A dimethyl hydride
endblocked polydimethylsiloxane, such as one of the type shown
below, is prepared containing the appropriate number of siloxane
units "n" to achieve the desired value of DP. ##STR10## (2) The
carboxylic acid group of undecylenic acid is protected through
reaction with hexamethyldisilazane (CH.sub.3).sub.3
--Si--NH--Si--(CH.sub.3).sub.3. This step is shown below. ##STR11##
(3) The dimethyl hydride endblocked polydimethylsiloxane and the
protected undecylenic acid (the products of Steps (1) and (2)) are
reacted to produce a siloxane diacid )carboxydecyl terminated
polydimethylsiloxane). This reaction is accomplished in the
presence of a platinum catalyst such as chloroplatinic acid, and
the product is washed with methanol to remove the trimethylsilyl
protecting group from the protected siloxane diacid shown below.
##STR12##
where Q is ##STR13## (4) The siloxane diacid (product of Step (3))
is reacted with an organic diamine to produce a siloxane-based
polyamide. The siloxane diacid is shown below. This reaction may
involve the use of a reaction solvent such as toluene or xylene.
##STR14## ##STR15##
THE PROCESS ACCORDING TO THE PRESENT INVENTION
The simplified process of the present invention can be illustrated
schematically with reference to the following reaction scenario in
which an olefinic acid is reacted with an organic diamine to
produce an organic diamide. ##STR16##
The organic diamide is then in turn reacted with a
hydride-terminated polydimethylsiloxane of the structure such as
the one depicted below: ##STR17##
in the presence of a hydrosilylation catalyst to form a
siloxane-based polyamide which includes at least one repeating unit
represented by the formula ##STR18##
wherein X is a linear or branched C.sub.1 -C.sub.30 alkylene chain;
Y is a linear or branched C.sub.1 -C.sub.20 alkylene chain; DP is
an integer having a value of 10-500; n is an integer having a value
of 1-500.
Suitable olefinic acids which can be used include undecylenic acid
H.sub.2 C.dbd.CH(CH.sub.2).sub.8 COOH, acrylic acid H.sub.2
C.dbd.CHCOOH, 3-butenoic acid (vinylacetic acid) H.sub.2
C.dbd.CHCH.sub.2 COOH, 4-pentenoic acid H.sub.2 C.dbd.CHCH.sub.2
COOH, and other olefinic acids with carbon chains of varying
length.
Organic amines which can be used herein preferably include linear
alkyl diamines such as hexamethylene diamine, ethylene diamine, and
mixtures of linear alkyl diamines, as well as other amines such as
decamethylene diamine.
A platinum catalyzed hydrosilylation reaction is employed according
to this invention. Generally, hydrosilylation involves the reaction
between a polysiloxane containing .ident.Si--H groups, and a
material containing unsaturation, e.g., vinyl groups. Some
attractive features of this mechanism are that no by-products are
formed, and hydrosilylation will proceed even at room temperature.
In the mechanism, crosslinking involves addition of .ident.SiH
across double bonds, i.e.,
The process requires a catalyst to effect the reaction between the
.ident.SiH containing polysiloxane and the material containing
unsaturation, i.e., the organic diamide in the case of the present
invention. Suitable catalysts are Group VIII transition metals,
i.e., the noble metals. 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 about 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.
The noble metal catalyst can be used in an amount of from
0.00001-0.5 parts per 100 weight parts of the .ident.SiH containing
polysiloxane. Preferably, the catalyst should be used in an amount
sufficient to provide 5-15 parts per million (ppm) Pt metal per
total composition.
Carrying out of the process is simply a matter of combining the
.ident.SiH containing polysiloxane(s), the material containing
unsaturation, i.e., the organic diamide, and the catalyst; and
mixing these ingredients. The reaction temperature can vary over a
wide range, and the optimum temperature is dependent upon the
concentration of the catalyst and the nature of the reactants.
Ordinarily, it is best to keep the reaction temperature below about
300.degree. C. Best results with most reactants can be obtained by
initiating the reaction at about 80.degree. C. to 180.degree. C.,
and maintaining the reaction within reasonable limits of this
range.
Typically, the process is carried out using approximately a 1:1
molar ratio of .ident.Si--H containing polysiloxane and the
material containing unsaturation. It is expected that useful
materials may also be prepared by carrying out the process with an
excess of either the .ident.Si--H containing polysiloxane or the
material containing unsaturation, but this would be considered a
less efficient use of the materials.
The process can also be used to make other types of siloxane-based
polyamides in which the repeating unit of the siloxane-based
polyamide is represented by the formula ##STR19##
or by the formula ##STR20##
wherein X is a linear or branched C.sub.1 -C.sub.30 alkylene chain;
Y, Y.sup.1, and Y.sup.2 are linear or branched C.sub.1 -C.sub.20
alkylene chains; DP1, DP2, and DP3 are integers each having values
of 10-500; n, m, and p are integers each having values of 1-500; Z
is represented by ##STR21##
wherein R', R", and R"' are linear or branched C.sub.1 -C.sub.10
alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl,
propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl
may optionally be substituted by 1-3 members which are methyl or
ethyl, or T is a trivalent atom such as N, P and Al; provided n is
not the same as m, or Y is not the same as Y.sup.1, or DP1 is not
the same as DP2.
EXAMPLES
Following are specific synthesis examples for forming
siloxane-based polyamides according to the method of this
invention. Unless otherwise indicated, the vacuums described in
Examples 1-4 are in the range of 5-20 millimeters of mercury. While
particular siloxane-based polyamides are disclosed or used in the
following Examples, it is to be understood that other
siloxane-based polyamides, for example, those made with a purified
siloxane diacid, dianhydride, diester, or diacid chloride, may also
be used.
Example 1
30 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical
stirrer, nitrogen sweep, and a condenser, was charged with 50.12 g
of undecylenic acid, and 22.58 g of a 70% hexamethylene diamine
mixture in water. The flask was immediately heated to 225 degrees
C. and kept at this temperature for 2 hours. After 2 hours, a
vacuum was applied to the system for 2 hours to remove any
unreacted materials. Upon completion of vacuum stripping, the flask
was reweighed to obtain the product weight. The temperature was
increased to 120 degrees C., and 65 g of toluene, complex of
platinous chloride and divinyl tetramethyl disiloxane, were added
to the flask. The temperature was increased to 185 degrees C., and
279.2 g of a 30 DP dimethylhydrogen endblocked polydimethylsiloxane
was added to the flask over a 30 minute period. After complete
addition, a dean stark trap was used to replace the addition funnel
on the flask, and the toluene was removed from the flask. After
removal of the toluene, the materials were allowed to react for an
additional period of one hour. Vacuum stripping was applied to the
flask for 1 hour to ensure complete removal of any residual
solvent. The temperature of the final siloxane-based polyamide was
cooled to 150.degree. C. and poured off while still in the melt
form.
Example 2
20 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical
stirrer, nitrogen sweep, and a condenser, was charged with 55.0 g
of undecylenic acid, and 24.77 g of a 70% hexamethylene diamine
mixture in water. The flask was immediately heated to 225 degrees
C., and kept at this temperature for 2 hours. After 2 hours, a
vacuum was applied to the system for 2 hour to remove any unreacted
materials. Upon completion of vacuum stripping, the flask was
reweighed to obtain the product weight. The temperature controller
was increased to 120 degrees C., and 65 g of toluene, and 0.5 g of
a solution containing platinum in the form of a complex of
platinous chloride and divinyl tetramethyl disiloxane, were added
to the flask. The temperature was then increased to 185 degrees C.,
and 222.0 g of a 20 DP dimethylhydrogen endblocked
polydimethylsiloxane was added to the flask over a 30 minute
period. After complete addition, a dean stark trap was used to
replace the addition funnel on the flask, and the toluene was
removed from the flask. After removal of the toluene, the materials
were allowed to react for an additional period of one hour. Vacuum
stripping was applied to the flask for 1 hour to ensure complete
removal of any residual solvent. The temperature of the final
siloxane-based polyamide was cooled to 150.degree. C. and poured
off while still in the melt form.
Example 3
15 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical
stirrer, nitrogen sweep, and a condenser, was charged with 57.75 g
of undecylenic acid, and 24.77 g of a 70% hexamethylene diamine
mixture in water. The flask was immediately heated to 225 degrees
C., and kept at this temperature for 2 hours. After 2 hours, a
vacuum was applied to the system for 2 hours to remove any
unreacted materials. Upon completion of vacuum stripping, the flask
was reweighed to obtain the product weight. The temperature was
increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a
solution containing platinum in the form of a complex of platinous
chloride and divinyl tetramethyl disiloxane were added to the
flask. The temperature was then increased to 185 degrees C., and
168.72 g of a 15 DP dimethylhydrogen endblocked
polydimethylsiloxane was added to the flask over a 30 minute
period. After complete addition, a dean stark trap was used to
replace the addition funnel on the flask, and the toluene was
removed from the flask. After removal of the toluene, the materials
were allowed to react for an additional period of one hour. Vacuum
stripping was applied to the flask for 1 hour to ensure complete
removal of any residual solvent. The temperature of the final
siloxane-based polyamide was cooled to 150.degree. C. and poured
off while still in the melt form.
Example 4
10 DP Polymer
A 500 ml three neck flask equipped with a thermometer, electrical
stirrer, nitrogen sweep, and a condenser, was charged with 67.0 g
of undecylenic acid, and 29.82 g of a 70% hexamethylene diamine
mixture in water. The flask was immediately heated to 225 degrees
C., and kept at this temperature for 2 hours. After 2 hours, a
vacuum was applied to the system for 2 hours to remove any
unreacted materials. Upon completion of vacuum stripping, the flask
was reweighed to obtain the product weight. The temperature was
increased to 120 degrees C., and 65 g of toluene, and 0.5 g of a
solution containing platinum in the form of a complex of platinous
chloride and divinyl tetramethyl disiloxane, were added to the
flask. The temperature was then increased to 185 degrees C., and
150.97 g of a 10 DP dimethylhydrogen endblocked
polydimethylsiloxane was added to the flask over a 30 minute
period. After complete addition, a dean stark trap was used to
replace the addition funnel on the flask, and the toluene was
removed from the flask. After removal of the toluene, the materials
were allowed to react for an additional period of one hour. Vacuum
stripping was applied to the flask for 1 hour to ensure complete
removal of any residual solvent. The temperature of the final
siloxane-based polyamide was cooled to 150.degree. C. and poured
off while still in the melt form.
Although undecylenic acid, acrylic acid, 3-butenoic acid
(vinylacetic acid), and 4-pentenoic acid, have been set forth as
being representative examples of some suitable olefinic acids, it
should be understood that other branched or straight-chain alkenoic
acids C.sub.n H.sub.2n-2)O.sub.2 O.sub.2 can be employed in
accordance with the method of the present invention.
The siloxane-based polyamides according to this present invention
can be used as thickening agents in hair, skin, underarm, and
cosmetic, product applications. The siloxane units provide
compatibility with silicone fluids such as cyclomethicones, while
the amide linkages and the spacing and selection of the locations
of the amide linkages, facilitate thickening and formation of such
products.
Other variations may be made in compounds, compositions, and
methods described herein without departing from the essential
features of the invention. The embodiments of the invention
specifically illustrated herein are exemplary only and not intended
as limitations on their scope except as defined in the appended
claims.
* * * * *