U.S. patent application number 09/535959 was filed with the patent office on 2003-02-13 for hetero-telechelic polymers and processes for making same.
Invention is credited to Kamienski, Conrad W., Letchford, Robert J., Quirk, Roderic P., Schwindeman, James A..
Application Number | 20030032745 09/535959 |
Document ID | / |
Family ID | 26669370 |
Filed Date | 2003-02-13 |
United States Patent
Application |
20030032745 |
Kind Code |
A1 |
Schwindeman, James A. ; et
al. |
February 13, 2003 |
Hetero-telechelic polymers and processes for making same
Abstract
Hetero-telechelic polymers having the formula:
FG--(Q).sub.d--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub.x (I) wherein
FG is a protected or non-protected functional group; Q is a
saturated or unsaturated hydrocarbyl group derived by incorporation
of a compound selected from the group consisting of conjugated
diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and
mixtures thereof; d is an integer from 10 to 200; Z is a branched
or straight chain hydrocarbon group which contains 3-25 carbon
atoms, optionally containing aryl or substituted aryl groups; J is
oxygen, sulfur, or nitrogen; [A(R.sup.1R.sup.2R.sup.3)].sub.x is a
protecting group, wherein A is an element selected from Group IVa
of the Periodic Table of Elements; R.sup.1, R.sup.2, and R.sup.3
are each independently selected from the group consisting of
hydrogen, alkyl, substituted alkyl groups containing lower alkyl,
lower alkylthio, and lower dialkylamino groups, aryl or substituted
aryl groups containing lower alkyl, lower alkylthio, and lower
dialkylamino groups, and cycloalkyl and substituted cycloalkyl
containing 5 to 12 carbon atoms; and x is dependent on the valence
of J and varies from one when J is oxygen or sulfur to two when J
is nitrogen, with the proviso J and FG are not the same, and
processes for making the same.
Inventors: |
Schwindeman, James A.;
(Lincolnton, NC) ; Letchford, Robert J.;
(Cherryville, NC) ; Kamienski, Conrad W.;
(Gastonia, NC) ; Quirk, Roderic P.; (Akron,
OH) |
Correspondence
Address: |
ALSTON & BIRD LLP
BANK OF AMERICA PLAZA
101 SOUTH TRYON STREET, SUITE 4000
CHARLOTTE
NC
28280-4000
US
|
Family ID: |
26669370 |
Appl. No.: |
09/535959 |
Filed: |
March 27, 2000 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09535959 |
Mar 27, 2000 |
|
|
|
08687111 |
Jul 18, 1996 |
|
|
|
6160054 |
|
|
|
|
60001693 |
Jul 31, 1995 |
|
|
|
Current U.S.
Class: |
526/176 ;
525/272; 526/177; 526/178; 526/180; 526/181 |
Current CPC
Class: |
C08F 2810/40 20130101;
C08F 4/48 20130101; C08F 36/04 20130101; C08F 36/04 20130101; C08F
4/72 20130101; C08F 36/04 20130101; C08F 112/08 20130101; C08F 4/72
20130101; C08F 4/46 20130101; C08F 8/34 20130101; C08F 4/46
20130101; C08F 12/04 20130101; C08F 4/46 20130101; C08F 4/48
20130101; C08F 12/04 20130101; C08F 36/04 20130101; C08F 8/34
20130101; C08C 19/44 20130101 |
Class at
Publication: |
526/176 ;
526/177; 526/178; 526/180; 526/181; 525/272 |
International
Class: |
C08F 004/44 |
Claims
That which is claimed is:
1. A hetero-telechelic polymer having the formula:
FG--(Q).sub.d--Z--J--[A- (R.sup.1R.sup.2R.sup.3)].sub.x (I)
wherein: FG is a protected or non-protected functional group; Q is
a saturated or unsaturated hydrocarbyl group derived by
incorporation of a compound selected from the group consisting of
conjugated diene hydrocarbons, alkenylsubstituted aromatic
hydrocarbons, and mixtures thereof; d is an integer from 10 to
2000; Z is a branched or straight chain hydrocarbon group which
contains 3-25 carbon atoms, optionally containing aryl or
substituted aryl groups; J is oxygen, sulfur, or nitrogen;
[A(R.sup.1R.sup.2R.sup.3)].sub.x is a protecting group, wherein A
is an element selected from Group IVa of the Periodic Table of
Elements; R.sup.1, R.sup.2, and R.sup.3 are each independently
selected from the group consisting of hydrogen, alkyl, substituted
alkyl groups containing lower alkyl, lower alkylthio, and lower
dialkylamino groups, aryl or substituted aryl groups containing
lower alkyl, lower alkylthio, and lower dialkylamino groups, and
cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon
atoms; and x is dependent on the valence of J and varies from one
when J is oxygen or sulfur to two when J is nitrogen, with the
proviso J and FG are not the same.
2. The polymer of claim 1, wherein said functional group is
selected from the group consisting of hydroxyl, thio, amino,
carboxyl, amide, silyl, acrylate, sulfonic acid, isocyanate, and
epoxide.
3. The polymer of claim 1, wherein: said conjugated diene
hydrocarbon is selected from the group consisting of 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,
2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,
1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,
3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,
3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,
4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,
2,3-di-n-propyl-1,3-butadiene, and
2-methyl-3-isopropyl-1,3-butadienes; and said alkenylsubstituted
aromatic hydrocarbon is selected from the group consisting of
styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine,
4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene,
1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphthalene,
1,2-diphenyl-4-methyl-1-hexene, and mixtures of these and alkyl,
cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in
which the total number of carbon atoms in the combined hydrocarbon
constituents is not greater than 18.
4. The polymer of claim 1, wherein A is carbon or silicon.
5. The polymer of claim 1, wherein at least a portion of aliphatic
unsaturation of said polymer has been saturated with hydrogen.
6. The polymer of claim 5, wherein at least about 90% of the
aliphatic unsaturation has been saturated with hydrogen.
7. The polymer of claim 5, wherein at least a portion of aliphatic
unsaturation of said polymer has been saturated with hydrogen prior
to deprotecting said polymer.
8. The polymer of claim 5, wherein at least a portion of aliphatic
unsaturation of said polymer has been saturated with hydrogen after
deprotecting said polymer.
9. The polymer of claim 1, wherein said protecting group
[A(R.sup.1R.sup.2R.sup.3)].sub.x has been removed.
10. The polymer of claim 1, wherein at least one of FG or J or both
is deprotected, and wherein said polymer of Formula (I) further
includes at least one di- or polyfunctional comonomer reacted with
at least one of said deprotected FG or J groups.
11. The polymer of claim 10, wherein said comonomer is selected
from the group consisting of diesters, polyesters, diisocyanates,
polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylic
acids, polycarboxylic acids, diols, polyols and mixtures
thereof.
12. A polymer having mixed functional ends produced by polymerizing
a monomer selected from conjugated diene hydrocarbons,
alkenylsubstituted aromatic hydrocarbons, and mixtures thereof,
with a protected functional organometallic initiator of the formula
M--Q.sub.n--Z--J--[A(R.sup.1R.sup- .2R.sup.3)].sub.x (II) wherein:
M is an alkali metal; Q is a saturated or unsaturated hydrocarbyl
group derived by incorporation of a compound selected from the
group consisting of conjugated diene hydrocarbons,
alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n
is an integer from 0 to 5; Z is a branched or straight chain
hydrocarbon group which contains 3-25 carbon atoms, optionally
containing aryl or substituted aryl groups; J is oxygen, sulfur, or
nitrogen; A is an element selected from Group IVa of the Periodic
Table of Elements; R.sub.1, R.sup.2, and R.sup.3 are independently
selected from hydrogen, alkyl, substituted alkyl groups containing
lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl
or substituted aryl groups containing lower alkyl, lower alkylthio,
and lower dialkylamino groups, and cycloalkyl and substituted
cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on
the valence of J and varies from one when J is oxygen or sulfur to
two when J is nitrogen, to form a mono-protected,
mono-functionalized living polymer, followed by functionalizing the
living polymer with a protected or non-protected functionalizing
compound capable of terminating or end-capping a living polymer to
provide a di-functional polymer, with the proviso that the
initiator and the functionalizing compound contain different
functional groups to provide a hetero-telechelic polymer.
13. The polymer of claim 12, wherein: said conjugated diene
hydrocarbon is selected from the group consisting of 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,
2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,
1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,
3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,
3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,
4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,
2,3-di-n-propyl-1,3-butadiene, and
2-methyl-3-isopropyl-1,3-butadienes; and said alkenylsubstituted
aromatic hydrocarbon is selected from the group consisting of
styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine,
4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene,
1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphthalene,
1,2-diphenyl-4-methyl-1-hexene, and mixtures of these and alkyl,
cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in
which the total number of carbon atoms in the combined hydrocarbon
constituents is not greater than 18.
14. The polymer of claim 12, wherein A is carbon or silicon.
15. The polymer of claim 12, wherein at least a portion of
aliphatic unsaturation of said polymer has been saturated with
hydrogen.
16. The polymer of claim 15, wherein at least about about 90% of
the aliphatic unsaturation has been saturated with hydrogen.
17. The polymer of claim 15, wherein at least a portion of
aliphatic unsaturation of said polymer has been saturated with
hydrogen prior to deprotecting said polymer.
18. The polymer of claim 15, wherein at least a portion of
aliphatic unsaturation of said polymer has been saturated with
hydrogen after deprotecting said polymer.
19. The polymer of claim 12, wherein
[A(R.sup.1R.sup.2R.sup.3)].sub.x has been removed.
20. The polymer of claim 12, wherein said functionalizing compound
is selected from the group consisting of ethylene oxide, propylene
oxide, styrene oxide, oxetane, oxygen, sulfur, carbon dioxide,
chlorine, bromine, iodine, chlorotrimethylsilane, styrenyldimethyl
chlorosilane, 1,3-propane sultone, caprolactam, N-benzylidene
trimethylsilylamide, dimethyl formamide, silicon acetals,
1,5-diazabicyclo[3.1.0]hexane, allyl bromide, allyl chloride,
methacryloyl chloride, 3-(dimethylamino)-propyl chloride,
N-(benzylidene)trimethylsilylamine, epichlorohydrin,
epibromohydrin, and epiiodohydrin.
21. The polymer of claim 12, wherein said organometallic initiator
is selected from the group consisting of
omega-(tert-alkoxy)-1-alkyllithiums- ,
omega-(tert-alkoxy)-1-alkyllithiums chain extended with conjugated
alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures
thereof, omega-(tert-alkylthio)-1-alkyllithiums,
omega-(tert-alkylthio)-1- -alkyllithiums chain extended with
conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons,
and mixtures thereof,
omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums,
omega-(tert-butyldimethylsilylthio)-1-alkyllithiums,
omega-(dialkylamino)-1-alkyllithiums,
omega-(dialkylamino)-1-alkyllithium- s chain-extended with
conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons,
and mixtures thereof, and omega-(bis-tert-alkylsilylamino)--
1-alkyllithiums.
22. The polymer of claim 21, wherein said organometallic initiator
is selected from the group consisting of
3-(1,1-dimethylethoxy)-1-propyllith- ium,
3-(tert-butyldimethylsilyloxy)-1-propyllithium,
3-(1,1-dimethylethylthio)-1-propyllithium,
3-(dimethylamino)-1-propyllith- ium,
3-(di-tert-butyldimethylsilylamino)-1-propyllithium,
3-(1,1-dimethylethoxy)-1-propyllithium,
3-(1,1-dimethylethoxy)-2-methyl-1- -propyllithium,
3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium,
4-(1,1-dimethylethoxy)-1-butyllithium,
5-(1,1-dimethylethoxy)-1-pentyllit- hium,
6-(1,1-dimethylethoxy)-1-hexyllithium,
8-(1,1-dimethylethoxy)-1-octy- llithium,
3-(1,1-dimethylpropoxy)-1-propyllithium, 3-(1,1-dimethylpropoxy)-
-2-methyl-1-propyllithium,
3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propylli- thium,
4-(1,1-dimethylpropoxy)-1-butyllithium,
5-(1,1-dimethylpropoxy)-1-p- entyllithium,
6-(1,1-dimethylpropoxy)-1-hexyllithium,
8-(1,1-dimethylpropoxy)-1-octyllithium,
3-(t-butyldimethylsilyloxy)-1-pro- pyllithium,
3-(t-butyldimethylsilyloxy)-2-methyl--propyllithium,
3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyllithium,
4-(t-butyldimethylsilyloxy)-1-butyllithium,
5-(t-butyldimethylsilyloxy)-1- -pentyllithium,
6-(t-butyldimethylsilyloxy)-1-hexyllithium,
8-(t-butyldimethylsilyloxy)-1-octyllithium and
3-(trimethylsilyloxy)-2,2-- dimethyl-1-propyllithium,
3-(dimethylamino)-1-propyllithium,
3-(dimethylamino)-2-methyl-1-propyllithium,
3-(dimethylamino)-2,2-dimethy- l-1-propyllithium,
4-(dimethylamino)-1-butyllithium,
5-(dimethylamino)-1-pentyllithium,
6-(dimethylamino)-1-hexyllithium,
8-(dimethylamino)-1-propyllithium, 4-(ethoxy)-1-butyllithium,
4-(propyloxy)-1-butyllithium, 4-(1-methylethoxy)-1-butyllithium,
3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,
4-(triphenylmethoxy)-1-butyllithium,
3-[3-(dimethylamino)-1-propyloxy]-1-- propyllithium,
3-[2-(dimethylamino)-1-ethoxy]-1-propyllithium,
3-[2-(diethylamino)-1-ethoxy]-1-propyllithium,
3-[2-(diisopropyl)amino)-1- -ethoxy]-1-propyllithium,
3-[2-(1-piperidino)-1-ethoxy]-1-propyllithium,
3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyllithium,
4-[3-(dimethylamino)-1-pr- opyloxy]-1-butyllithium,
6-[2-(1-piperidino)-1-ethoxy]-1-hexyllithium,
3-[2-(methoxy)-1-ethoxy]-1-propyllithium,
3-[2-(ethoxy)-1-ethoxy]-1-propy- llithium,
4-[2-(methoxy)-1-ethoxy]-1-butyllithium, 5-[2-(ethoxy)-1-ethoxy]-
-1-pentyllithium, 3-[3-(methylthio)-1-propyloxy]-1-propyllithium,
3-[4-(methylthio)-1-butyloxy]-1-propyllithium,
3-(methylthiomethoxy)-1-pr- opyllithium,
6-[3-(methylthio)-1-propyloxy]-1-hexyllithium,
3-[4-(methoxy)-benzyloxy]-1-propyllithium,
3-[4-(1,1-dimethylethoxy)-benz- yloxy]-1-propyllithium,
3-[2,4-(dimethoxy)-benzyloxy]-1-propyllithium,
8-[4-(methoxy)-benzyloxy]-1-octyllithium,
4-[4-(methylthio)-benzyloxy]-1-- butyllithium,
3-[4-(dimethylamino)-benzyloxy]-1-propyllithium,
6-[4-(dimethylamino)-benzyloxy]-1-hexyllithium,
5-(triphenylmethoxy)-1-pe- ntyllithium,
6-(triphenylmethoxy)-1-hexyllithium, and
8-(triphenylmethoxy)-1-octyllithium,
3-(hexamethyleneimino)-1-propyllithi- um,
4-(hexamethyleneimino)-1-butyllithium,
5-(hexamethyleneimino)-1-pentyl- lithium,
6-(hexamethyleneimino)-1-hexyllithium, 8-(hexamethyleneimino)-1-o-
ctyllithium, 3-(t-butyldimethylsilylthio)-1-propyllithium,
3-(t-butyldimethylsilylthio)-2-methyl-1-propyllithium,
3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propyllithium,
4-(t-butyldimethylsilylthio)-1-butyllithium,
6-(t-butyldimethylsilylthio)- -1-hexyllithium,
3-(trimethylsilylthio)-2,2-dimethyl-1-propyllithium,
3-(1,1-dimethylethylthio)-1-propyllithium,
3-(1,1-dimethylethylthio)-2-me- thyl-1-propyllithium,
3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propyllithi- um,
4-(1,1-dimethylethylthio)-1-butyllithium,
5-(1,1-dimethylethylthio)-1-- pentyllithium,
6-(1,1-dimethylethylthio)-1-hexyllithium,
8-(1,1-dimethylethylthio)-1-octyllithium,
3-(1,1-dimethylpropylthio)-1-pr- opyllithium,
3-(1,1-dimethylpropylthio)-2-methyl-1-propyllithium,
3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propyllithium,
4-(1,1-dimethylpropylthio)-1-butyllithium,
5-(1,1-dimethylpropylthio)-1-p- entyllithium,
6-(1,1-dimethylpropylthio)-1-hexyllithium, and
8-(1,1-dimethylpropylthio)-1-octyllithium, hydrocarbon soluble
conjugated alkadiene, alkenylsubstituted aromatic hydrocarbons, and
mixtures thereof, chain extended oligomeric analogs thereof, and
mixtures thereof.
23. The polymer of claim 12, wherein said diene hydrocarbons and
said alkenylsubstituted aromatic hydrocarbons are reacted singly,
sequentially, or as mixtures thereof.
24. The polymer of claim 12, wherein at least one or both of said
functional groups is deprotected, and wherein said
hetero-telechelic polymer further includes at least one di- or
polyfunctional comonomer reacted with at least one of said
deprotected functional groups.
25. The polymer of claim 24, wherein said comonomer is selected
from the group consisting of diesters, polyesters, diisocyanates,
polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylic
acids, polycarboxylic acids, diols, polyols and mixtures
thereof.
26. The polymer of claim 25, wherein said polymer includes at least
one hydroxyl functional group, and wherein said at least one
hydroxyl functional group is reacted with diisocyanate and diol to
produce polyurethane blocks.
27. The polymer of claim 26, wherein said diol includes acid group
functionalities, and wherein said acid group functionalities are
neutralized with tertiary amines to provide dispersibility in
water.
28. The polymer of claim 25, wherein said polymer includes at least
one hydroxyl functional group, and wherein said at least one
hydroxyl functional group is reacted with diacid or anhydride and
diamine or lactam to produce polyamide blocks.
29. The polymer of claim 25, wherein said polymer includes at least
one hydroxyl functional group, and wherein said at least one
hydroxyl functional group is reacted with diacid or anhydride and
diol or polyol to produce polyester blocks.
30. The polymer of claim 29, wherein at least a portion of said
diacid or anhydride is substituted by an unsaturated acid or
anhydride to provide unsaturated polyester blocks capable of
crosslinking with unsaturated monomers by addition of free radical
initiators.
31. The polymer of claim 25, wherein said polymer includes at least
one hydroxyl functional group, and wherein said at least one
hydroxyl functional group is reacted with anhydride to form a
half-ester with free carboxyl functionality at the terminus
thereof.
32. The polymer of claim 31, wherein said carboxyl functional
terminal groups are further reacted with epoxy resins and amine
curing agents to form epoxy resin composites.
33. The polymer of claim 25, wherein said polymer includes at least
one hydroxyl functional group, and wherein said at least one
hydroxyl functional group is reacted with methacroyl chloride to
provide polymerizable alkenyl groups at the terminus thereof.
34. The polymer of claim 33, further comprising acrylic monomers
polymerized by use of free radical initiators onto said alkenyl
terminal groups.
35. The polymer of claim 34, wherein said acrylic acid monomers are
functional or amide functional acrylic monomers to provide polar
hydrophilic polymer segments.
36. The polymer of claim 33, wherein sulfonated styrene and/or
4-vinyl pyridine are polymerized by free radical initiators onto
said terminal alkenyl groups to provide functional polymer segments
capable of improving dispersability of the polymer.
37. The polymer of claim 25, wherein said polymer includes at least
one hydroxyl functional group, and wherein said at least one
hydroxyl functional group is reacted with sulfonyl chloride in the
presence of a tertiary amine catalyst to form sulfonate functional
groups at the terminus thereof.
38. The polymer of claim 37, wherein said sulfonate functional
groups are reacted with primary amines or ammonia, under heat and
pressure, to form polymers with amine functionality at the terminus
thereof.
39. The polymer of claim 31, wherein said carboxyl functional
groups are reacted with an epoxy resin and an excess of amine to
completely react all of the epoxy groups, the excess amine is
removed by distillation, and the resulting epoxy-amine adduct is
reacted with a water soluble organic or inorganic acid to form
water soluble quarternary ammonium containing polymers.
40. A process for preparing hetero-telechelic polymer having mixed
functional ends, comprising: polymerizing a monomer selected from
conjugated diene hydrocarbons, alkenylsubstituted aromatic
hydrocarbons, and mixtures thereof, with a protected functional
organometallic initiator of the formula
M--Q.sub.n--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub- .x (II) wherein:
M is an alkali metal; Q is a saturated or unsaturated hydrocarbyl
group derived by incorporation of a compound selected from the
group consisting of conjugated diene hydrocarbons,
alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n
is an integer from 0 to 5; Z is a branched or straight chain
hydrocarbon group which contains 3-25 carbon atoms, optionally
containing aryl or substituted aryl groups; J is oxygen, sulfur, or
nitrogen; A is an element selected from Group IVa of the Periodic
Table of Elements; R.sup.1, R.sup.2, and R.sup.3 are independently
selected from hydrogen, alkyl, substituted alkyl groups containing
lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl
or substituted aryl groups containing lower alkyl, lower alkylthio,
and lower dialkylamino groups, and cycloalkyl and substituted
cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on
the valence of J and varies from one when J is oxygen or sulfur to
two when J is nitrogen, to form a mono-protected,
mono-functionalized living polymer; and functionalizing said living
polymer with a functionalizing compound capable of terminating or
end-capping a living polymer to provide a di-functional polymer,
with the proviso that the initiator and the functionalizing
compound contain different functional groups to provide a
hetero-telechelic polymer.
41. The process of claim 40, wherein: said conjugated diene
hydrocarbon is selected from the group consisting of 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,
2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,
1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,
3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,
3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,
4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,
2,3-di-n-propyl-1,3-butadiene, and
2-methyl-3-isopropyl-1,3-butadienes; and said alkenylsubstituted
aromatic hydrocarbon is selected from the group consisting of
styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine,
4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene,
1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphthalene,
1,2-diphenyl-4-methyl-1-hexene, and mixtures of these and alkyl,
cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in
which the total number of carbon atoms in the combined hydrocarbon
constituents is not greater than 18.
42. The process of claim 40, wherein A is carbon or silicon.
43. The process of claim 40, further comprising saturating at least
a portion of aliphatic unsaturation of said hetero-telechelic
polymer with hydrogen after said polymerizing step.
44. The process of claim 43, wherein said saturating step comprises
saturating at least about 90% of the aliphatic unsaturation with
hydrogen.
45. The process of claim 43, wherein said saturating step comprises
saturating said polymer prior to deprotecting said polymer.
46. The process of claim 43, further comprising removing
deprotecting said polymer prior to said saturating step.
47. The process of claim 40, further comprising deprotecting at
least one of said functional ends of said hetero-telechelic
polymer.
48. The process of claim 40, wherein said functionalizing step
comprises functionalizing said living polymer with a
functionalizing compound selected from the group consisting of
ethylene oxide, propylene oxide, styrene oxide, oxetane, oxygen,
sulfur, carbon dioxide, chlorine, bromine, iodine,
chlorotrimethylsilane, styrenyldimethyl chlorosilane, 1,3-propane
sultone, caprolactam, N-benzylidene trimethylsilylamide, dimethyl
formamide, silicon acetals, 1,5-diazabicyclo[3.1.0]hexane, allyl
bromide, allyl chloride, methacryloyl chloride,
3-(dimethylamino)-propyl chloride,
N-(benzylidene)trimethylsilylamine, epichlorohydrin,
epibromohydrin, and epiiodohydrin.
49. The process of claim 40, wherein said organometallic initiator
is selected from the group consisting of
omega-(tert-alkoxy)-1-alkyllithiums- ,
omega-(tert-alkoxy)-1-alkyllithiums chain extended with conjugated
alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures
thereof, omega-(tert-alkylthio)-1-alkyllithiums,
omega-(tert-alkylthio)-1- -alkyllithiums chain extended with
conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons,
and mixtures thereof,
omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums,
omega-(tert-butyldimethylsilylthio)-1-alkyllithiums,
omega-(dialkylamino)-1-alkyllithiums,
omega-(dialkylamino)-1-alkyllithium- s chain-extended with
conjugated alkadienes, alkenylsubstituted aromatic hardrocarbons,
and mixtures thereof, and omega-(bis-tert-alkylsilylamino)-
-1-alkyllithiums.
50. The process of claim 49, wherein said organometallic initiator
is selected from the group consisting of
3-(1,1-dimethylethoxy)-1-propyllith- ium,
3-(tert-butyldimethylsilyloxy)-1-propyllithium,
3-(1,1-dimethylethylthio)-1-propyllithium,
3-(dimethylamino)-1-propyllith- ium,
3-(di-tert-butyldimethylsilylamino)-1-propyllithium,
3-(1,1-dimethylethoxy)-1-propyllithium,
3-(1,1-dimethylethoxy)-2-methyl-1- -propyllithium,
3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium,
4-(1,1-dimethylethoxy)-1-butyllithium,
5-(1,1-dimethylethoxy)-1-pentyllit- hium,
6-(1,1-dimethylethoxy)-1-hexyllithium,
8-(1,1-dimethylethoxy)-1-octy- llithium,
3-(1,1-dimethylpropoxy)-1-propyllithium, 3-(1,1-dimethylpropoxy)-
-2-methyl-1-propyllithium,
3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propylli- thium,
4-(1,1-dimethylpropoxy)-1-butyllithium,
5-(1,1-dimethylpropoxy)-1-p- entyllithium,
6-(1,1-dimethylpropoxy)-1-hexyllithium,
8-(1,1-dimethylpropoxy)-1-octyllithium,
3-(t-butyldimethylsilyloxy)-1-pro- pyllithium,
3-(t-butyldimethylsilyloxy)-2-methyl-1-propyllithium,
3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyllithium,
4-(t-butyldimethylsilyloxy)-1-butyllithium,
5-(t-butyldimethylsilyloxy)-1- -pentyllithium,
6-(t-butyldimethylsilyloxy)-1-hexyllithium,
8-(t-butyldimethylsilyloxy)-1-octyllithium and
3-(trimethylsilyloxy)-2,2-- dimethyl-1-propyllithium,
3-(dimethylamino)-1-propyllithium,
3-(dimethylamino)-2-methyl-1-propyllithium,
3-(dimethylamino)-2,2-dimethy- l-1-propyllithium,
4-(dimethylamino)-1-butyllithium,
5-(dimethylamino)-1-pentyllithium,
6-(dimethylamino)-1-hexyllithium,
8-(dimethylamino)-1-propyllithium, 4-(ethoxy)-1-butyllithium,
4-(propyloxy)-1-butyllithium, 4-(1-methylethoxy)-1-butyllithium,
3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,
4-(triphenylmethoxy)-1-butyllithium,
3-[3-(dimethylamino)-1-propyloxy]-1-- propyllithium, 3-
[2-(dimethylamino)-1-ethoxy]-1-propyllithium,
3-[2-(diethylamino)-1-ethoxy]-1-propyllithium,
3-[2-(diisopropyl)amino)-1- -ethoxy]-1-propyllithium,
3-[2-(1-piperidino)-1-ethoxy]-1-propyllithium,
3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyllithium,
4-[3-(dimethylamino)-1-pr- opyloxy]-1-butyllithium,
6-[2-(1-piperidino)-1-ethoxy]-1-hexyllithium,
3-[2-(methoxy)-1-ethoxy]-1-propyllithium,
3-[2-(ethoxy)-1-ethoxy]-1-propy- llithium,
4-[2-(methoxy)-1-ethoxy]-1-butyllithium, 5-[2-(ethoxy)-1-ethoxy]-
-1-pentyllithium, 3-[3-(methylthio)-1-propyloxy]-1-propyllithium,
3-[4-(methylthio)-1-butyloxy]-1-propyllithium,
3-(methylthiomethoxy)-1-pr- opyllithium,
6-[3-(methylthio)-1-propyloxy]-1-hexyllithium,
3-[4-(methoxy)-benzyloxy]-1-propyllithium,
3-[4-(1,1-dimethylethoxy)-benz- yloxy]-1-propyllithium,
3-[2,4-(dimethoxy)-benzyloxy]-1-propyllithium,
8-[4-(methoxy)-benzyloxy]-1-octyllithium,
4-[4-(methylthio)-benzyloxy]-1-- butyllithium,
3-[4-(dimethylamino)-benzyloxy]-1-propyllithium,
6-[4-(dimethylamino)-benzyloxy]-1-hexyllithium,
5-(triphenylmethoxy)-1-pe- ntyllithium,
6-(triphenylmethoxy)-1-hexyllithium, and
8-(triphenylmethoxy)-1-octyllithium;
3-(hexamethyleneimino)-1-propyllithi- um,
4-(hexamethyleneimino)-1-butyllithium,
5-(hexamethyleneimino)-1-pentyl- lithium,
6-(hexamethyleneimino)-1-hexyllithium, 8-(hexamethyleneimino)-1-o-
ctyllithium, 3-(t-butyldimethylsilylthio)-1-propyllithium,
3-(t-butyldimethylsilylthio)-2-methyl-1-propyllithium,
3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propyllithium,
4-(t-butyldimethylsilylthio)-1-butyllithium,
6-(t-butyldimethylsilylthio)- -1-hexyllithium,
3-(trimethylsilylthio)-2,2-dimethyl-1-propyllithium,
3-(1,1-dimethylethylthio)-1-propyllithium,
3-(1,1-dimethylethylthio)-2-me- thyl-1-propyllithium,
3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propyllithi- um,
4-(1,1-dimethylethylthio)-1-butyllithium,
5-(1,1-dimethylethylthio)-1-- pentyllithium,
6-(1,1-dimethylethylthio)-1-hexyllithium, 8-
(1,1-dimethylethylthio)-1-octyllithium,
3-(1,1-dimethylpropylthio)-1-prop- yllithium,
3-(1,1-dimethylpropylthio)-2-methyl-1-propyllithium,
3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propyllithium,
4-(1,1-dimethylpropylthio)-1-butyllithium,
5-(1,1-dimethylpropylthio)-1-p- entyllithium,
6-(1,1-dimethylpropylthio)-1-hexyllithium, and
8-(1,1-dimethylpropylthio)-1-octyllithium, hydrocarbon soluble
conjugated alkadiene, alkenylsubstituted aromatic hydrocarbons, and
mixtures thereof, chain extended oligomeric analogs thereof, and
mixtures thereof.
51. The process of claim 40, wherein said polymerizing step
comprises polymerizing said diene hydrocarbons or said
alkenylsubstituted aromatic hydrocarbons singly, sequentially, or
as mixtures thereof.
52. The process of claim 40, further comprising copolymerizing at
least one of said functional groups of said hetero-telechelic
polymer with at least one di- or polyfunctional comonomer after
said functionalizing step to form a copolymer.
53. The process of claim 52, wherein said comonomer is selected
from the group consisting of diesters, polyesters, diisocyanates,
polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylic
acids, polycarboxylic acids, diols, polyols and mixtures
thereof.
54. The process of claim 52, wherein said copolymerizing step
comprises reacting said polymer with one or more comonomers under
conditions sufficient to deprotect said polymer and to polymerize
said one or more comonomers at both functional ends of said
deprotected polymer.
55. The process of claim 54, wherein said reacting step comprises
reacting said polymer and said one or more comonomers in the
presence of a strong acid catalyst.
56. The process of claim 52, wherein said copolymerizing step
comprises reacting said polymer with one or more comonomers under
conditions sufficient to maintain the integrity of at least one
protective group of said polymer to provide at least one
deprotected functional end and to polymerize said one or more
comonomers at said at least one deprotected functional end of said
polymer.
57. The process of claim 56, further comprising deprotecting said
protected functional end.
58. The process of claim 56, further comprising reacting said
copolymer with a comonomer.
59. A process for modifying the surface adhesion properties of
polyolefins, comprising melt mixing the functional polymer of claim
1 or 12 with a polyolefin in an amount of 1 to 25% by weight based
on the polyolefin.
60. The process of claim 59, wherein the polyolefin is selected
from the group consisting of low density polyethylene, linear low
density polyethylene, high density polyethylene, propylene,
polyisobutylene and copolymers and blends thereof.
Description
Cross-Reference to Related Applications
[0001] This application is related to commonly owned copending
Provisional Application Ser. No. 60/001,693, filed Jul. 31, 1995,
and claims the benefit of its earlier filing date under 35 U.S.C.
119(e).
FIELD OF THE INVENTION
[0002] This invention relates to novel polymers and processes for
producing the same. More particularly, the invention relates novel
hetero-telechelic polymers, and to processes for the anionic
polymerization of olefinic-containing monomers to produce the
same.
BACKGROUND OF THE INVENTION
[0003] Telechelic polymers are polymers that contain two functional
groups per molecule at the termini of the polymer. Such polymers
have found wide utility in many applications. For instance,
telechelic polymers have been employed as rocket fuel binders, in
coatings and sealants and in adhesives. In addition, polymers that
contain two hydroxyl groups per molecule can be co-polymerized with
appropriate materials to form polyesters, polycarbonates, and
polyamides (see U.S. Pat. No. 4,994,526).
[0004] A variety of polymerization techniques, such as cationic and
free radical polymerizations, have been employed to prepare
telechelic polymers. However, functionality can be best controlled
with anionic polymerization. An early approach to the preparation
of telechelic polymers is described in D. N. Schulz, et al, J.
Polym. Sci., Polym. Chem.Ed. 12, 153 (1974), which describes the
reaction of a protected hydroxy initiator with butadiene. The
resultant living anion was quenched with ethylene oxide to afford
mono-protected di-hydroxy polybutadiene. While excellent
functionality (f=1.87-2.02) was achieved by this process, the
protected initiator was insoluble in hydrocarbon solution.
Therefore, the reaction was conducted in diethyl ether, and as a
result, relatively high 1,2 microstructure (31-54%) was
obtained.
[0005] Another approach that has been employed to prepare
telechelic polymers is the generation and subsequent
functionalization of a "dilithium initiator". A dilithium initiator
is prepared by the addition of two equivalents of secondary
butyllithium to meta-diisopropenylbenzene- . The dilithium
initiator is then reacted with a conjugated diene, such as
butadiene or isoprene, to form a polymer chain with two anionic
sites. The resultant polymer chain is then reacted with two
equivalents of a functionalizing agent, such as ethylene oxide.
While useful, gelation is frequently observed during the
functionalization step. This leads to lower capping efficiency
(see, for example, U.S. Pat. No. 5,393,843, Example 1, wherein the
capping efficiency was only 82%). Additional details of this
gelation phenomenon are described in U.S. Pat. No. 5,478,899.
Further, this dilithium approach can only afford telechelic
polymers with the same functional group on each end of the polymer
chain.
[0006] Great Britain published patent application 2,241,239,
published Aug. 28, 1991, describes a novel approach for producing
telechelic polymers in hydrocarbon solution. Telechelic polymers
were prepared using monofunctional silyl ether initiators
containing alkali metal end groups that were soluble in hydrocarbon
solutions. These monofunctional silyl ether initiators were
demonstrated to be useful in producing dihydroxy (telechelic)
polybutadienes having desirable characteristics, such as a
molecular weight of typically 1,000 to 10,000, a 1,4 microstructure
content of typically 90%, and the like.
SUMMARY OF THE INVENTION
[0007] The present invention provides novel hetero-telechelic
polymers and processes for preparing the same. The novel
hetero-telechelic polymers of the invention can be generally
described as having different functionalities at opposite ends of
the polymer chain. The presence of different functionalities can
provide unique properties to the polymers. Further, the
hetero-telechelic polymers of the invention can be copolymerized
with other monomers to provide novel copolymers possessing a wide
range of useful physical properties.
[0008] Preferred hetero-telechelic polymers have the formula:
FG--(Q).sub.d--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub.x (I)
[0009] wherein FG is a protected or non-protected functional group;
Q is a saturated or unsaturated hydrocarbyl group derived by
incorporation of a compound selected from the group consisting of
conjugated diene hydrocarbons, alkenylsubstituted aromatic
hydrocarbons, and mixtures thereof; d is an integer from 10 to 200;
Z is a branched or straight chain hydrocarbon group which contains
3-25 carbon atoms, optionally containing aryl or substituted aryl
groups; J is oxygen, sulfur, or nitrogen;
[A(R.sup.1R.sup.2R.sup.3)].sub.x is a protecting group, in which A
is an element selected from Group IVa of the Periodic Table of
Elements; R.sup.1, R.sup.2, and R.sup.3 are each independently
selected from the group consisting of hydrogen, alkyl, substituted
alkyl groups containing lower alkyl, lower alkylthio, and lower
dialkylamino groups, aryl or substituted aryl groups containing
lower alkyl, lower alkylthio, and lower dialkylamino groups, and
cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon
atoms; and x is dependent on the valence of J and varies from one
when J is oxygen or sulfur to two when J is nitrogen, with the
proviso J and FG are not the same.
[0010] The present invention also provides for the preparation of
the novel hetero-telechelic polymers described above. The process
of the invention includes polymerizing a monomer, including
conjugated diene hydrocarbons, alkenylsubstituted aromatic
hydrocarbons, and mixtures thereof, with a protected functional
organometallic initiator of the formula
M--Q.sub.n--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub.x (II)
[0011] wherein M is an alkali metal, preferably lithium, n is an
integer from 0 to 5, and Q, Z, J, A, R.sup.1, R.sup.2, R.sup.3 and
x are the same as defined above, to form a mono-protected,
mono-functionalized living polymer. The resultant living polymer is
then functionalized by reaction with a reactive or functionalizing
group capable of terminating or end-capping a living polymer to
provide a mono-protected or di-protected, di-functional polymer,
with the proviso that the initiator and the reactive group contain
different functional groups. The resultant hetero-telechelic
polymer can be further reacted with other comonomers.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The novel hetero-telechelic polymers of the invention can be
generally described as having different functionalities at opposite
ends of the polymer chain. This is represented schematically by the
formula A--B, wherein A and B are different functional groups.
[0013] Preferred hetero-telechelic polymers of the present
invention have the following formula:
FG--(Q).sub.d--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub.x (I)
[0014] wherein FG is a protected or non-protected functional group;
Q is a saturated or unsaturated hydrocarbyl group derived by
incorporation of a compound selected from the group consisting of
conjugated diene hydrocarbons, alkenylsubstituted aromatic
hydrocarbons, and mixtures thereof; d is an integer from 10 to 200;
Z is a branched or straight chain hydrocarbon group which contains
3-25 carbon atoms, optionally containing aryl or substituted aryl
groups; J is oxygen, sulfur, or nitrogen;
[A(R.sup.1R.sup.2R.sup.3)].sub.x is a protecting group, in which A
is an element selected from Group IVa of the Periodic Table of
Elements; R.sup.1, R.sup.2, and R.sup.3 are each independently
selected from the group consisting of hydrogen, alkyl, substituted
alkyl groups containing lower alkyl, lower alkylthio, and lower
dialkylamino groups, aryl or substituted aryl groups containing
lower alkyl, lower alkylthio, and lower dialkylamino groups, and
cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon
atoms; and x is dependent on the valence of J and varies from one
when J is oxygen or sulfur to two when J is nitrogen, with the
proviso J and FG are not the same.
[0015] Removal of the protecting group (deprotection) produces
polymers with oxygen, sulfur or nitrogen functional groups on the
ends of the polymers. The residual aliphatic unsaturation can be
optionally removed by hydrogenation before or after removal of the
protecting groups. These functional groups can then participate in
various copolymerization reactions by reaction of the functional
groups on the ends of the polymer with selected difunctional or
polyfunctional comonomers, as described in more detail below.
[0016] The olefinic monomer to be anionically polymerized is
preferably an alkenylsubstituted aromatic hydrocarbon or a
1,3-diene. The alkenylsubstituted aromatic hydrocarbon or 1,3-diene
can be chosen from the group of unsaturated organic compounds that
can be polymerized anionically (i.e. in a reaction initiated by an
organo-alkali metal). Examples of suitable conjugated diene
hydrocarbons include, but are not limited to, 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,
2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,
1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,
3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,
3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,
4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,
2,3-di-n-propyl-1,3-butadiene, and
2-methyl-3-isopropyl-1,3-butadiene. Examples of polymerizable
alkenylsubstituted aromatic hydrocarbons include, but are not
limited to, styrene, alpha-methylstyrene, vinyltoluene,
2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,
2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,
2-alpha-methylvinylnaphthalene, 1,2-diphenyl-4-methyl-1-hexene and
mixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl
and arylalkyl derivatives thereof in which the total number of
carbon atoms in the combined hydrocarbon constituents is generally
not greater than 18. Examples of these latter compounds include
3-methylstyrene, 3,5-diethylstyrene, 4-tert-butylstyrene,
2-ethyl-4-benzylstyrene, 4-phenylstyrene, 4-p-tolylstyrene,
2,4-divinyltoluene and 4,5-dimethyl-1-vinylnaphthalene. U.S. Pat.
No. 3,377,404, incorporated herein by reference in its entirety,
discloses suitable additional alkenylsubstituted aromatic
hydrocarbons.
[0017] The dienes or alkenylsubstituted aromatic hydrocarbons may
be polymerized singly, or in admixture with each other or with
other dienes or alkenylsubstituted aromatic hydrocarbons to form
random or tapered copolymers, or by charging the compounds to the
reaction mixture sequentially, either with each other or with other
dienes or alkenylsubstituted aromatic hydrocarbons, to form block
copolymers.
[0018] The hetero-telechelic polymers of the present invention are
prepared by the reaction of protected functional organolithium
initiators with conjugated alkadienes or alkenylsubstituted
aromatic hydrocarbons, as described above, either singly,
sequentially, or as mixtures thereof, to form a mono-protected
mono-functional living polymer. This reaction can be in a
hydrocarbon or mixed hydrocarbon-polar solvent medium, preferably
at a temperature of -30.degree. C. to 150.degree. C.
[0019] Polymerization is followed by functionalization of the
resultant living polymer with a suitable functionalizing compound
or electrophile or other material as known in the art to be useful
for terminating or end capping living polymers to provide a
mono-protected, or di-protected, di-functional polymer. The
mono-protected, or di-protected, di-functional polymer is then
recovered by standard techniques. Optionally the protecting group
or groups are removed to provide a di-functional polymer. The
polymer is optionally hydrogenated, either before or after removing
the protecting group, or before or after functionalization.
[0020] Exemplary organolithium initiators useful in the present
invention include initiators selected from the group consisting of
omega-(tert-alkoxy)-1-alkyllithiums,
omega-(tert-alkoxy)-1-alkyllithiums chain extended with conjugated
alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures
thereof, omega-(tert-alkylthio)-1-alkyllithium- s,
omega-(tert-alkylthio)-1-alkyllithiums chain extended with
conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons,
and mixtures thereof,
omega-(tert-butyldimethylsilyloxy)-1-alkyllithiums,
omega-(tert-butyldimethylsilylthio)-1-alkyllithiums,
omega-(dialkylamino)-1-alkyllithiums,
omega-(dialkylamino)-1-alkyllithium- s chain-extended with
conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons,
and mixtures thereof, and omega-(bis-tert-alkylsilylamino)--
1-alkyllithiums.
[0021] Initiators useful in the preparation of telechelic polymers
of the present invention are also represented by the following
formula:
M--Q.sub.n--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub.x (II)
[0022] wherein M is an alkali metal; Q is a saturated or
unsaturated hydrocarbyl group derived by incorporation of a
compound selected from the group consisting of conjugated diene
hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and
mixtures thereof; n is an integer from 0 to 5; Z is a branched or
straight chain hydrocarbon group which contains 3-25 carbon atoms,
optionally containing aryl or substituted aryl groups; J is a
hetero atom, e.g., oxygen, sulfur, or nitrogen; A is an element
selected from Group IVa of the Periodic Table of Elements; R.sup.1,
R.sup.2, and R.sup.3 are independently selected from hydrogen,
alkyl, substituted alkyl groups containing lower alkyl, lower
alkylthio, and lower dialkylamino groups, aryl or substituted aryl
groups containing lower alkyl, lower alkylthio, and lower
dialkylamino groups, and cycloalkyl and substituted cycloalkyl
containing 5 to 12 carbon atoms; and x is dependent on the valence
of J and varies from one when J is oxygen or sulfur to two when J
is nitrogen.
[0023] These initiators (II) can be prepared by reaction of
protected organolithium compounds of the following formula:
M--Z--J--[A(R.sup.1R.sup.2R.sup.3)].sub.x (III)
[0024] wherein each of M, Z, J, A, R.sup.1, R.sup.2, R.sup.3, and x
are the same as defined above, with conjugated alkadienes (such as
butadiene or isoprene), alkenylsubstituted aromatic hydrocarbons
(such as styrene or alpha-methylstyrene), and mixtures thereof, to
form an extended hydrocarbon chain between M and Z in Formula
(III), which extended chain is denoted as Q.sub.n in Formula
(II).
[0025] The compounds of Formula (III) are prepared by first
reacting in an inert solvent a selected tertiary
amino-1-haloalkane, omega-hydroxy-protected-1-haloalkane or
omega-thio-protected-1-haloalkane- , depending on whether J is to
be N, O or S, (the alkyl portions of the haloalkyl groups contain 3
to 25 carbon atoms) with an alkali metal, preferably lithium, at a
temperature between about 35.degree. C. and about 130.degree. C.,
preferably at the solvent reflux temperature, to form a protected
monofunctional lithium initiator (of Formula III), which is then
optionally reacted with a one or more conjugated diene
hydrocarbons, one or more alkenylsubstituted aromatic hydrocarbons,
or mixtures of one or more dienes with one or more
alkenylsubstituted aromatic hydrocarbons, in a predominantly
alkane, cycloalkane, or aromatic reaction solvent, which solvent
contains 5 to 10 carbon atoms, and mixtures of such solvents to
produce a monofunctional initiator with an extended chain or tether
between the metal atom (M) and element (J) in Formula (II) above
and mixtures thereof with compounds of Formula (III). Q in Formula
(II) is preferably derived from conjugated 1,3-dienes. While A in
the protecting group [A(R.sup.1R.sup.2R.sup.3)] of the formulae
above can be any of the elements in Group IVa of the Periodic Table
of the Elements, carbon and silicon currently appear the most
useful, especially when polymerizing conjugated dienes.
[0026] Incorporation of Q groups into the M--Z linkage to form the
compounds of Formula (II) above involves addition of compounds of
the Formula
M--Z--J--[A--(R.sup.1R.sup.2R.sup.3)].sub.x
[0027] where the symbols have the meanings ascribed above, across
the carbon to carbon double bonds in compounds selected from the
consisting of one or more conjugated diene hydrocarbons, one or
more alkenylsubstituted aromatic hydrocarbons, or mixtures of one
or more dienes with one or more alkenylsubstituted aromatic
hydrocarbons, to produce new carbon-lithium bonds of an allylic or
benzylic nature, much like those found in a propagating
polyalkadiene or polyarylethylene polymer chain derived by anionic
initiation of the polymerization of conjugated dienes or
arylethylenes. These new carbon-lithium bonds are now activated
toward polymerization and so are much more efficient in promoting
polymerization than the precursor M--Z (M.dbd.Li) bonds,
themselves.
[0028] The tertiary amino-1-haloalkanes useful in practicing this
invention include compounds of the following general
structures:
X--Z--N[A(R.sup.1R.sup.2R.sup.3)].sub.2
[0029] and 1
[0030] wherein X is halogen, preferably chlorine or bromine; Z is a
branched or straight chain hydrocarbon tether or connecting group
which contains 3-25 carbon atoms, which tether may also contain
aryl or substituted aryl groups; A is an element selected from
Group IVa of the Periodic Table of the Elements; R.sup.1, R.sup.2,
and R.sup.3 are independently defined as hydrogen, alkyl,
substituted alkyl groups containing lower alkyl, lower alkylthio,
and lower dialkylamino groups, aryl or substituted aryl groups
containing lower alkyl, lower alkylthio, and lower dialkylamino
groups, or cycloalkyl and substituted cycloalkyl groups containing
5 to 12 carbon atoms; and m is an integer from 1 to 7, and their
employment as initiators in the anionic polymerization of olefin
containing monomers in an inert, hydrocarbon solvent optionally
containing a Lewis base. The process reacts selected tertiary
amino-1-haloalkanes whose alkyl groups contain 3 to 25 carbon
atoms, with alkali metal, preferably lithium, at a temperature
between about 35.degree. C. and about 130.degree. C., preferably at
the reflux temperature of an alkane, cycloalkane or aromatic
reaction solvent containing 5 to 10 carbon atoms and mixtures of
such solvents.
[0031] Anionic polymerizations employing the tertiary amine
initiators can be conducted in an inert solvent, preferably a
non-polar solvent, optionally containing an ethereal modifier,
using an olefinic monomer which is an alkenylsubstituted aromatic
hydrocarbon or a 1,3-diene at a temperature of about -30.degree. C.
to about 150.degree. C. The polymerization reaction proceeds from
initiation to propagation and is finally terminated with
appropriate reagents so that the polymer is mono-functionally or
di-functionally terminated. The polymers may have a molecular
weight range of about 1000 to 10,000 but the molecular weight can
be higher. Typically 5 to 50 milli-moles of initiator is used per
mole of monomer.
[0032] Tertiary amino-1-haloalkanes useful in the practice of this
invention include, but are not limited to,
3-(N,N-dimethylamino)-1-propyl halide,
3-(N,N-dimethylamino)-2-methyl-1-propyl halide,
3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl halide,
4-(N,N-dimethylamino)-1-butyl halide,
5-(N,N-dimethylamino)-1-pentyl halide,
6-(N,N-dimethylamino)-1-hexyl halide, 3-(N,N-diethylamino)-1-prop-
yl halide, 3-(N,N-diethylamino-2-methyl-1-propyl halide,
3-(N,N-diethylamino)-2,2-dimethyl-1-propyl halide,
4-(N,N-diethylamino)-1-butyl halide, 5-(N,N-diethylamino)-1-pentyl
halide, 6-(N,N-diethylamino)-1-hexyl halide,
3-(N-ethyl-N-methylamino)-1-- propyl halide,
3-(N-ethyl-N-methylamino)-2-methyl-1-propyl halide,
3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl halide,
4-(N-ethyl-N-methylamino)-1-butyl halide,
5-(N-ethyl-N-methylamino)-1-pen- tyl halide,
6-(N-ethyl-N-methylamino)-1-hexyl halide, 3-(piperidino)-1-propyl
halide, 3-(piperidino)-2-methyl-1-propyl halide,
3-(piperidino)-2,2-dimethyl-1-propyl halide, 4-(piperidino)-1-butyl
halide, 5-(piperidino)-1-pentyl halide, 6-(piperidino)-1-hexyl
halide, 3-(pyrrolidino)-1-propyl halide,
3-(pyrrolidino)-2-methyl-1-propyl halide,
3-(pyrrolidino)-2,2-dimethyl-1-propyl halide,
4-(pyrrolidino)-1-butyl halide, 5-(pyrrolidino)-1-pentyl halide,
6-(pyrrolidino)-1-hexyl halide, 3-(hexamethyleneimino)-1-propyl
halide, 3-(hexamethyleneimino)-2-methyl-1-propyl halide,
3-(hexamethyleneimino)-2- ,2-dimethyl-1-propyl halide,
4-(hexamethyleneimino)-1-butyl halide,
5-(hexamethyleneimino)-1-pentyl halide,
6-(hexamethyleneimino)-1-hexyl halide,
3-(N-isopropyl-N-methyl)-1-propyl halide, 2-(N-isopropyl-N-methyl-
)-2-methyl-1-propyl halide,
3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl halide, and
4-(N-isopropyl-N-methyl)-1-butyl halide. The halo- or halide group
is preferably selected from chlorine and bromine.
[0033] Omega-hydroxy-protected-1-haloalkanes useful in producing
monofunctional ether initiators useful in practicing this invention
can have the following general structure:
X--Z--O--[C(R.sup.1R.sup.2R.sup.3)]
[0034] wherein X is halogen, preferably chlorine or bromine; Z is a
branched or straight chain hydrocarbon group which contains 3-25
carbon atoms, optionally containing aryl or substituted aryl
groups; and R.sup.1, R.sup.2, and R.sup.3 are independently defined
as hydrogen, alkyl, substituted alkyl groups containing lower
alkyl, lower alkylthio, and lower dialkylamino groups, aryl or
substituted aryl groups containing lower alkyl, lower alkylthio,
and lower dialkylamino groups, or cycloalkyl and substituted
cycloalkyl groups containing 5 to 12 carbon atoms, and their
employment as initiators in the anionic polymerization of olefin
containing monomers in an inert, hydrocarbon solvent optionally
containing a Lewis base. The process reacts selected
omega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3
to 25 carbon atoms, with lithium metal at a temperature between
about 35.degree. C. and about 130.degree. C., preferably at the
reflux temperature of an alkane, cycloalkane or aromatic reaction
solvent containing 5 to 10 carbon atoms and mixtures of such
solvents.
[0035] Anionic polymerizations employing the monofunctional ether
initiators can be conducted in an inert solvent, preferably a
non-polar solvent, optionally containing an ethereal modifier,
using an olefinic monomer which is an alkenylsubstituted aromatic
hydrocarbon cor a 1,3-diene at a temperature of about -30.degree.
C. to about 150.degree. C. The polymerization reaction proceeds
from initiation to propagation and is finally terminated with
appropriate reagents so that the polymer is mono-functionally or
di-functionally terminated. The polymers may have a molecular
weight range of about 1000 to 10,000 but the molecular weight can
be higher. Typically 5 to 50 milli-moles of initiator is used per
mole of monomer.
[0036] The precursor omega-protected-1-haloalkanes (halides) can be
prepared from the corresponding haloalcohol by standard literature
methods. For example, 3-(1,1-dimethylethoxy)-1-chloropropane can be
synthesized by the reaction of 3-chloro-1-propanol with
2-methylpropene according to the method of A. Alexakis, M.
Gardette, and S. Colin, Tetrahedron Letters, 29, 1988, 2951. The
method of B. Figadere, X. Franck and A. Cave, Tetrahedron Letters,
34, 1993, 5893, which involves the reaction of the appropriate
alcohol with 2-methyl-2-butene catalyzed by boron trifluoride
etherate, can be employed for the preparation of the t-amyl ethers.
The alkoxy, alkylthio or dialkylamino substituted ethers, for
example 6-[3-(methylthio)-1-propyloxy]-1-chlorohexane, can be
synthesized by reaction of the corresponding substituted alcohol,
for instance 3-methylthio-1-propanol, with an
alpha-bromo-omega-chloroalkane, for instance 1-bromo-6-hexane,
according to the method of J. Almena, F. Foubelo and M. Yus,
Tetrahedron, 51, 1995, 11883. The compound
4-(methoxy)-1-chlorobutane, and the higher analogs, can be
synthesized by the ring opening reaction of tetrahydrofuran with
thionyl chloride and methanol, according to the procedure of T.
Ferrari and P. Vogel, SYNLETT, 1991, 233. The triphenylmethyl
protected compounds, for example
3-(triphenylmethoxy)-1-chloropropane, can be prepared by the
reaction of the haloalcohol with triphenylmethylchloride, according
to the method of S. K. Chaudhary and O. Hernandez, Tetrahedron
Letters, 1979, 95.
[0037] Omega-hydroxy-protected-1-haloalkanes prepared in accordance
with this earlier process useful in practicing this invention
include, but are not limited to, 3-(1,1-dimethylethoxy)-1-propyl
halide, 3-(1,1-dimethylethoxy)-2-methyl-1-propyl halide,
3-(1,1-dimethylethoxy)-2- ,2-dimethyl-1-propyl halide,
4-(1,1-dimethylethoxy)-1-butyl halide,
5-(1,1-dimethylethoxy)-1-pentyl halide,
6-(1,1-dimethylethoxy)-1-hexyl halide,
8-(1,1-dimethylethoxy)-1-octyl halide, 3-(1,1-dimethylpropoxy)-1--
propyl halide, 3-(1,1-dimethylpropoxy)-2-methyl-1-propyl halide,
3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propyl halide,
4-(1,1-dimethylpropoxy)-1-butyl halide,
5-(1,1-dimethylpropoxy)-1-pentyl halide,
6-(1,1-dimethylpropoxy)-1-hexyl halide, 8-(1,1-dimethylpropoxy)-1-
-octyl halide, 4-(methoxy)-1-butyl halide, 4-(ethoxy)-1-butyl
halide, 4-(propyloxy)-1-butyl halide, 4-(1-methylethoxy)-1-butyl
halide, 3-(triphenylmethoxy)-2,2-dimethyl-1-propyl halide,
4-(triphenylmethoxy)-1-butyl halide,
3-[3-(dimethylamino)-1-propyloxy]-1-- propyl halide,
3-[2-(dimethylamino)-1-ethoxy]-1-propyl halide,
3-[2-(diethylamino)-1-ethoxy]-1-propyl halide,
3-[2-(diisopropyl)amino)-1- -ethoxy]-1-propyl halide,
3-[2-(1-piperidino)-1-ethoxy]-1-propyl halide,
3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyl halide,
4-[3-(dimethylamino)-1-pr- opyloxy]-1-butyl halide,
6-[2-(1-piperidino)-1-ethoxy]-1-hexyl halide,
3-[2-(methoxy)-1-ethoxy]-1-propyl halide,
3-[2-(ethoxy)-1-ethoxy]-1-propy- l halide,
4-[2-(methoxy)-1-ethoxy]-1-butyl halide, 5-[2-(ethoxy)-1-ethoxy]-
-1-pentyl halide, 3-[3-(methylthio)-1-propyloxy]-1-propyl halide,
3-[4-(methylthio)-1-butyloxy]-1-propyl halide,
3-(methylthiomethoxy)-1-pr- opyl halide,
6-[3-(methylthio)-1-propyloxy]-1-hexyl halide,
3-[4-(methoxy)-benzyloxy]-1-propyl halide,
3-[4-(1,1-dimethylethoxy)-benz- yloxy]-1-propyl halide,
3-[2,4-(dimethoxy)-benzyloxy]-1-propyl halide,
8-[4-(methoxy)-benzyloxy]-1-octyl halide,
4-[4-(methylthio)-benzyloxy]-1-- butyl halide,
3-[4-(dimethylamino)-benzyloxy]-1-propyl halide,
6-[4-(dimethylamino)-benzyloxy]-1-hexyl halide,
5-(triphenylmethoxy)-1-pe- ntyl halide,
6-(triphenylmethoxy)-1-hexyl halide, and
8-(triphenylmethoxy)-1-octyl halide. The halo- or halide group is
preferably selected from chlorine and bromine.
[0038] U.S. Pat. No. 5,362,699 discloses a process for the
preparation of hydrocarbon solutions of monofunctional ether
initiators derived from omega-hydroxy-silyl-protected-1-haloalkanes
of the following general structure:
X--Z--O--[Si(R.sup.1R.sup.2R.sup.3)]
[0039] wherein X is halogen, preferably chlorine or bromine; Z is a
branched or straight chain hydrocarbon group which contains 3-25
carbon atoms, optionally containing aryl or substituted aryl
groups; and R.sup.1, R.sup.2, and R.sup.3 are independently defined
as saturated and unsaturated aliphatic and aromatic radicals, and
their employment as initiators in the anionic polymerization of
olefin containing monomers in an inert, hydrocarbon solvent
optionally containing a Lewis base. The process reacts selected
omega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3
to 25 carbon atoms, with lithium metal at a temperature between
about 25.degree. C. and about 40.degree. C., in an alkane or
cycloalkane reaction solvent containing 5 to 10 carbon atoms and
mixtures of such solvents.
[0040] Anionic polymerizations employing the monofunctional siloxy
ether initiators can be conducted in an inert solvent, preferably a
non-polar solvent, optionally containing an ethereal modifier,
using an olefinic monomer which is an alkenylsubstituted aromatic
hydrocarbon or a 1,3-diene at a temperature of about -30.degree. C.
to about 150.degree. C. The polymerization reaction proceeds from
initiation to propagation and is finally terminated with
appropriate reagents so that the polymer is mono-functionally or
di-functionally terminated. The polymers may have a molecular
weight range of about 1000 to 10,000 but the molecular weight can
be higher. Typically 5 to 50 milli-moles of initiator is used per
mole of monomer.
[0041] Omega-silyl-protected-1-haloalkanes prepared in accordance
with this earlier process useful in practicing this invention
include, but are not limited to,
3-(t-butyldimethylsilyloxy)-1-propyl halide,
3-(t-butyldimethyl-silyloxy)-2-methyl-1-propyl halide,
3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl halide,
4-(t-butyldimethylsilyloxy)-1-butyl halide,
5-(t-butyldimethyl-silyloxy-1- -pentyl halide,
6-(t-butyldimethylsilyloxy)-1-hexyl halide,
8-(t-butyldimethylsilyloxy)-1-octyl halide,
3-(t-butyldiphenylylsilyloxy)- -1-propyl halide,
3-(t-butyldiphenylylsilyloxy)-2-methyl-1-propyl halide,
3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-propyl halide,
4-(t-butyldiphenylylsilyloxy)-1-butyl halide,
6-(t-butyldiphenylsilyloxy)- -1-hexyl halide and
3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl halide. The halo- or
halide group is preferably selected from chlorine and bromine.
[0042] Monofunctional thioether initiators useful in the practice
of this invention can be derived from
omega-thio-protected-1-haloalkanes of the following general
structure:
X--Z--S--[A(R.sup.1R.sup.2R.sup.3)]
[0043] wherein X is halogen, preferably chlorine or bromine; Z is a
branched or straight chain hydrocarbon group which contains 3-25
carbon atoms, optionally containing aryl or substituted aryl
groups; [A(R.sup.1R.sup.2R.sup.3)] is a protecting group in which A
is an element selected from Group IVa of the Periodic Table of the
Elements, and R.sup.1, R.sup.2, and R.sup.3 are independently
defined as hydrogen, alkyl, substituted alkyl groups containing
lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl
or substituted aryl groups containing lower alkyl, lower alkylthio,
and lower dialkylamino groups, or cycloalkyl and substituted
cycloalkyl groups containing 5 to 12 carbon atoms, and their
employment as initiators in the anionic polymerization of olefin
containing monomers in an inert, hydrocarbon solvent optionally
containing a Lewis base. The process reacts selected
omega-thioprotected-1-haloalkyls whose alkyl groups contain 3 to 25
carbon atoms, with alkali metal, preferably lithium, at a
temperature between about 35.degree. C. and about 130.degree. C.,
preferably at the reflux temperature of an alkane, cycloalkane or
aromatic reaction solvent containing 5 to 10 carbon atoms and
mixtures of such solvents.
[0044] Anionic polymerizations employing the monofunctional
thioether initiators can be conducted in an inert solvent,
preferably a non-polar solvent, optionally containing an ethereal
modifier, using an olefinic monomer which is an alkenylsubstituted
aromatic hydrocarbon or a 1,3-diene at a temperature of about
-30.degree. C. to about 150.degree. C. The polymerization reaction
proceeds from initiation to propagation and is finally terminated
with appropriate reagents so that the polymer is mono-functionally
or di-functionally terminated. The polymers may have a molecular
weight range of about 1000 to 10,000 but the molecular weight can
be higher. Typically 5 to 50 milli-moles of initiator is used per
mole of monomer.
[0045] The initiator precursor, omega-thio-protected-1-haloalkanes
(halides), can be prepared from the corresponding halothiol by
standard literature methods. For example,
3-(1,1-dimethylethylthio)-1-propylchlori- de can be synthesized by
the reaction of 3-chloro-1-propanthiol with 2-methylpropene
according to the method of A. Alexakis, M. Gardette, and S. Colin,
Tetrahedron Letters, 29, 1988, 2951. Alternatively, reaction of
1,1-dimethylethylthiol with 1-bromo-3-chloropropane and a base
affords 3-(1,1-dimethylethylthio)-1-propylchloride. The method of
B. Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993,
5893, which involves the reaction of the appropriate thiol with
2-methyl-2-butene catalyzed by boron trifluoride etherate, can be
employed for the preparation of the t-amyl ethers. Additionally,
5-(cyclohexylthio)-1-pentylhalide and the like, can be prepared by
the method of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51,
1995, 11883. This synthesis involves the reaction of the
appropriate thiol with an alkyllithium, then reaction of the
lithium salt with the corresponding alpha, omega dihalide.
3-(Methylthio)-1-propylchlo- ride can be prepared by chlorination
of the corresponding alcohol with thionyl chloride, as taught by D.
F. Taber and Y. Wang, J. Org, Chem., 58, 1993, 6470.
Methoxymethylthio compounds, such as
6-(methoxymethylthio)-1-hexylchloride, can be prepared by the
reaction of the omega-chloro-thiol with bromochloromethane,
methanol, and potassium hydroxide, by the method of F. D. Toste and
I. W. J. Still, Synlett, 1995, 159. T-Butyldimethylsilyl protected
compounds, for example 4-(t-butyldimethylsilylthio)-1-butylhalide,
can be prepared from t-butyldimethylchlorosilane, and the
corresponding thiol, according to the method described in U.S. Pat.
No. 5,493,044.
[0046] Omega-thio-protected 1-haloalkanes prepared in accordance
with this earlier process useful in practicing this invention
include, but are not limited to, 3-(methylthio)-1-propylhalide,
3-(methylthio)-2-methyl-1-prop- ylhalide,
3-(methylthio)-2,2-dimethyl-1-propylhalide,
4-(methylthio)-1-butylhalide, 5-(methylthio)-1-pentylhalide,
6-(methylthio)-1-hexylhalide, 8-(methylthio)-1-octylhalide,
3-(methoxymethylthio)-1-propylhalide,
3-(methoxymethylthio)-2-methyl-1-pr- opylhalide,
3-(methoxymethylthio)-2,2-dimethyl-1-propylhalide,
4-(methoxymethylthio)-1-butylhalide,
5-(methoxymethylthio)-1-pentylhalide- ,
6-(methoxymethylthio)-1-hexylhalide,
8-(methoxymethylthio)-1-octylhalide- ,
3-(1,1-dimethylethylthio)-1-propylhalide,
3-(1,1-dimethylethylthio)-2-me- thyl-1-propylhalide,
3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propylhalide- ,
4-(1,1-dimethylethylthio)-1-butylhalide,
5-(1,1-dimethylethylthio)-1-pen- tylhalide,
6-(1,1-dimethylethylthio)-1-hexylhalide,
8-(1,1-dimethylethylthio)-1-octylhalide,
3-(1,1-dimethylpropylthio)-1-pro- pylhalide, 3-
(1,1-dimethylpropylthio)-2-methyl-1-propylhalide,
3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propylhalide,
4-(1,1-dimethylpropylthio)-1-butylhalide,
5-(1,1-dimethylpropylthio)-1-pe- ntylhalide,
6-(1,1-dimethylpropylthio)-1-hexylhalide,
8-(1,1-dimethylpropylthio)-1-octylhalide,
3-(cyclopentylthio)-1-propylhal- ide,
3-(cyclopentylthio)-2-methyl-1-propylhalide,
3-(cyclopentylthio)-2,2-- dimethyl-1-propylhalide,
4-(cyclopentylthio)-1-butylhalide,
5-(cyclopentylthio)-1-pentylhalide,
6-(cyclopentylthio)-1-hexylhalide,
8-(cyclopentylthio)-1-octylhalide,
3-(cyclohexylthio)-1-propylhalide,
3-(cyclohexylthio)-2-methyl-1-propylhalide,
3-(cyclohexylthio)-2,2-dimeth- yl-1-propylhalide,
4-(cyclohexylthio)-1-butylhalide,
5-(cyclohexylthio)-1-pentylhalide,
6-(cyclohexylthio)-1-hexylhalide, 8-(cyclohexylthio)-1-octylhalide,
3-(t-butyldimethylsilylthio)-1-propyhal- ide,
3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,
3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propylhalide,
3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,
4-(t-butyldimethylsilylthio)-1-butylhalide,
6-(t-butyldimethylsilylthio)-- 1-hexylhalide and
3-(trimethylsilylthio)-2,2-dimethyl-1-propylhalide. The halo- or
halide group is preferably selected from chlorine and bromine.
[0047] Examples of functionalized organolithium initiators (II)
include, but are not limited to, tert-alkoxy-alkyllithiums such as
3-(1,1-dimethylethoxy)-1-propyllithium and its more
hydrocarbon-soluble isoprene chain-extended oligomeric analog
(n=2), 3-(tert-butyldimethylsil- yloxy)-1-propyllithium (n=0),
tert-alkylthio-alkyllithiums such as
3-(1,1-dimethylethylthio)-1-propyllithium and its more
hydrocarbon-soluble isoprene chain-extended oligomeric analog
(n=2), 3-(dimethylamino)-1-propyllithium and its more
hydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2)
and 3-(di-tert-butyldimethylsilylamino)-1-propyllithium, and
mixtures thereof. Further examples of protected functionalized
initiators that may be employed in this invention include, but are
not limited to, 3-(1,1-dimethylethoxy)-1-propyllithium,
3-(1,1-dimethylethoxy)-2-methyl-1- -propyllithium,
3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium,
4-(1,1-dimethylethoxy)-1-butyllithium,
5-(1,1-dimethylethoxy)-1-pentyllit- hium,
6-(1,1-dimethylethoxy)-1-hexyllithium,
8-(1,1-dimethylethoxy)-1-octy- llithium,
3-(1,1-dimethylpropoxy)-1-propyllithium, 3-(1,1-dimethylpropoxy)-
-2-methyl-1-propyllithium,
3-(1,1-dimethylpropoxy)-2,2-dimethyl-1-propylli- thium,
4-(1,1-dimethylpropoxy)-1-butyllithium,
5-(1,1-dimethylpropoxy)-1-p- entyllithium,
6-(1,1-dimethylpropoxy)-1-hexyllithium,
8-(1,1-dimethylpropoxy)-1-octyllithium,
3-(t-butyldimethylsilyloxy)-1-pro- pyllithium,
3-(t-butyldimethylsilyloxy)-2-methyl-1-propyllithium, 3-
(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyllithium,
4-(t-butyldimethylsilyloxy)-1-butyllithium,
5-(t-butyldimethylsilyloxy)-1- -pentyllithium,
6-(t-butyldimethylsilyloxy)-1-hexyllithium,
8-(t-butyldimethylsilyloxy)-1-octyllithium and
3-(trimethylsilyloxy)-2,2-- dimethyl-1-propyllithium,
3-(dimethylamino)-1-propyllithium,
3-(dimethylamino)-2-methyl-1-propyllithium, 3- (dimethylamino)
-2,2-dimethyl-1-propyllithium, 4- (dimethylamino) -1-butyllithium,
5-(dimethylamino)-1-pentyllithium,
6-(dimethylamino)-1-hexyllithium,
8-(dimethylamino)-1-propyllithium, 4-(ethoxy)-1-butyllithium,
4-(propyloxy) 1-butyllithium, 4-(1-methylethoxy)-1-butyllithium,
3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,
4-(triphenylmethoxy)-1-butyllithium,
3-[3-(dimethylamino)-1-propyloxy]-1-- propyllithium,
3-[2-(dimethylamino)-1-ethoxy]-1-propyllithium,
3-[2-(diethylamino)-1-ethoxy]-1-propyllithium,
3-[2-(diisopropyl)amino)-1- -ethoxy]-1-propyllithium,
3-[2-(1-piperidino)-1-ethoxy]-1-propyllithium,
3-[2-(1-pyrrolidino)-1-ethoxy]-1-propyllithium,
4-[3-(dimethylamino)-1-pr- opyloxy]-1-butyllithium,
6-[2-(1-piperidino)-1-ethoxy]-1-hexyllithium,
3-[2-(methoxy)-1-ethoxy]-1-propyllithium,
3-[2-(ethoxy)-1-ethoxy]-1-propy- llithium,
4-[2-(methoxy)-1-ethoxy]-1-butyllithium, 5-[2-(ethoxy)-1-ethoxy]-
-1-pentyllithium, 3-[3-(methylthio)-1-propyloxy]-1-propyllithium,
3-[4-(methylthio)-1-butyloxy]-1-propyllithium,
3-(methylthiomethoxy)-1-pr- opyllithium,
6-[3-(methylthio)-1-propyloxy]-1-hexyllithium,
3-[4-(methoxy)-benzyloxy]-1-propyllithium,
3-[4-(1,1-dimethylethoxy)-benz- yloxy]-1-propyllithium,
3-[2,4-(dimethoxy)-benzyloxy]-1-propyllithium,
8-[4-(methoxy)-benzyloxy]-1-octyllithium,
4-[4-(methylthio)-benzyloxy]-1-- butyllithium, 3-[4-
(diethylamino)-benzyloxy]-1-propyllithium,
6-[4-(dimethylamino)-benzyloxy]-1-hexyllithium,
5-(triphenylmethoxy)-1-pe- ntyllithium,
6-(triphenylmethoxy)-1-hexyllithium, and
8-(triphenylmethoxy)-1-octyllithium,
3-(hexamethyleneimino)-1-propyllithi- um,
4-(hexamethyleneimino)-1-butyllithium,
5-(hexamethyleneimino)-1-pentyl- lithium,
6-(hexamethyleneimino)-1-hexyllithium, 8-(hexamethyleneimino)-1-o-
ctyllithium, 3-(t-butyldimethylsilylthio)-1-propyllithium,
3-(t-butyldimethylsilylthio)-2-methyl-1-propyllithium,
3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propyllithium,
4-(t-butyldimethylsilylthio)-1-butyllithium,
6-(t-butyldimethylsilylthio)- -1-hexyllithium,
3-(trimethylsilylthio)-2,2-dimethyl-1-propyllithium,
3-(1,1-dimethylethylthio)-1-propyllithium,
3-(1,1-dimethylethylthio)-2-me- thyl-1-propyllithium,
3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propyllithi- um,
4-(1,1-dimethylethylthio)-1-butyllithium,
5-(1,1-dimethylethylthio)-1-- pentyllithium,
6-(1,1-dimethylethylthio)-1-hexyllithium,
8-(1,1-dimethylethylthio)-1-octyllithium,
3-(1,1-dimethylpropylthio)-1-pr- opyllithium,
3-(1,1-dimethylpropylthio)-2-methyl-1-propyllithium,
3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propyllithium,
4-(1,1-dimethylpropylthio)-1-butyllithium,
5-(1,1-dimethylpropylthio)-1-p- entyllithium,
6-(1,1-dimethylpropylthio)-1-hexyllithium, and
8-(1,1-dimethylpropylthio)-1-octyllithium and their more
hydrocarbon soluble conjugated alkadiene, alkenylsubstituted
aromatic hydrocarbon, and mixtures thereof, chain extended
oligomeric analogs (n=1-5).
[0048] The resultant polymer has one or more terminal functional
groups having the Formula (I) described above, wherein FG is a
functional group derived from reaction of the intermediate polymer
with one of the functionalizing compounds described below, and d is
the number of units of conjugated diene, alkenylsubstituted
aromatic hydrocarbon, and mixtures thereof (including that employed
originally to solubilize the initiator) and may vary from 10 to
200.
[0049] The functional polymer of Formula (I) can be further reacted
with other comonomers such as di- or polyesters, di- or
polyiisocyanates, di-, poly-, or cyclic amides, di- or
polycarboxylic acids, and di- and polyols in the presence of a
strong acid catalyst to simultaneously deprotect the functional
polymer and polymerize both functional ends thereof to produce
novel segmented block polymers. Alternatively, the functional
polymer of Formula (I) can be reacted with other comonomers in the
absence of a strong acid catalyst to yield block copolymers, while
maintaining the integrity of the protective group to provide a
functional block copolymer. Still another alternative is to remove
the protective group of the functional polymer of Formula (I) and
to polymerize a functional block copolymer of the preceding
sentence with the same or other comonomers to produce novel
segmented block polymers.
[0050] The inert solvent is preferably a non-polar solvent such as
a hydrocarbon, since anionic polymerization in the presence of such
non-polar solvents is known to produce polyenes with high
1,4-contents from 1,3-dienes. Solvents useful in practicing this
invention include, but are not limited to, inert liquid alkanes,
cycloalkanes and aromatic solvents such as alkanes and cycloalkanes
containing five to ten carbon atoms, such as pentane, hexane,
cyclohexane, methylcyclohexane, heptane, methylcycloheptane,
octane, decane and the like, and aromatic solvents containing six
to ten carbon atoms such as toluene, ethylbenzene, p-xylene,
m-xylene, o-xylene, n-propylbenzene, isopropylbenzene,
n-butylbenzene, t-butylbenzene, and the like.
[0051] Polar solvents (modifiers) can be added to the
polymerization reaction to alter the microstructure of the
resulting polymer, i.e., increase the proportion of 1,2 (vinyl)
microstructure or to promote functionalization or randomization.
Examples of polar modifiers include, but are not limited to,
diethyl ether, dibutyl ether, tetrahydrofuran,
2-methyltetrahydrofuran, methyl tert-butyl ether,
diazabicyclo[2.2.2]octa- ne, triethylamine, tributylamine,
N,N,N',N'-tetramethylethylene diamine (TMEDA), 1,2-dimethoxyethane
(glyme), alkali metal alkoxides, and amino-substituted alkali metal
alkoxides. The amount of the polar modifier added depends on the
vinyl content desired, the nature of the monomer, the temperature
of the polymerization, and the identity of the polar modifier.
[0052] Electrophiles that are useful in functionalizing the
polymeric living anion include, but are not limited to, alkylene
oxides, such as ethylene oxide, propylene oxide, styrene oxide, and
oxetane; oxygen; sulfur; carbon dioxide; halogens such as chlorine,
bromine and iodine; haloalkyltrialkoxysilanes, alkenylhalosilanes
and omega-alkenylarylhalosi- lanes, such as chlorotrimethylsilane
and styrenyldimethyl chlorosilane; sulfonated compounds, such as
1,3-propane sultone; amides, including cyclic amides, such as
caprolactam, N-benzylidene trimethylsilylamide, and dimethyl
formamide; silicon acetals; 1,5-diazabicyclo[3.1.0]hexane; allyl
halides, such as allyl bromide and allyl chloride; methacryloyl
chloride; amines, including primary, secondary, tertiary and cyclic
amines, such as 3-(dimethylamino)-propyl chloride and
N-(benzylidene)trimethylsilylamine; epihalohydrins, such as
epichlorohydrin, epibromohydrin, and epiiodohydrin, and other
materials as known in the art to be useful for terminating or end
capping polymers. These and other useful functionalizing agents are
described, for example, in U.S. Pat. Nos. 3,786,116 and 4,409,357,
the entire disclosure of each of which is incorporated herein by
reference. The only proviso is that the initiator and the
electrophile contain different functional groups, thus leading to
hetero-telechelic polymers.
[0053] If desired, the protecting groups can be removed from the
polymer. This deprotection can be performed either prior to or
after the optional hydrogenation of the residual aliphatic
unsaturation. For example, to remove tert-alkyl-protected groups,
the protected polymer can be mixed with Amberlyst.RTM. 15 ion
exchange resin and heated at an elevated temperature, for example
150.degree. C., until deprotection is complete.
Tert-alkyl-protected groups can also be removed by reaction of the
polymer with para-toluenesulfonic acid, trifluoroacetic acid, or
trimethylsilyliodide. Additional methods of deprotection of the
tert-alkyl protecting groups can be found in T. W. Greene and P. G.
M. Wuts, Protective Groups in Organic Synthesis, Second Edition,
Wiley, New York, 1991, page 41.
[0054] Tert-butyldimethylsilyl protecting groups can be removed by
treatment of the polymer with acid, such as hydrochloric acid,
acetic acid, para-toluensulfonic acid, or Dowex.RTM. 50W-X8.
Alternatively, a source of fluoride ions, for instance,
tetra-n-butylammonium fluoride, potassium fluoride and 18-crown-6,
or pyridine-hydrofluoric acid complex, can be employed for
deprotection of the tert-butyldimethylsilyl protecting groups.
Additional methods of deprotection of the tert-butyldimethylsilyl
protecting groups can be found in T. W. Greene and P. G. M. Wuts,
Protective Groups in Organic Synthesis, Second Edition, Wiley, New
York, 1991, pages 80-83.
[0055] In addition, protecting groups can be selectively removed
from the polymers, i.e., deprotecting conditions can be selected so
as to remove at least one protecting group without removing other
dissimilar protecting groups by proper selection of deprotecting
reagents and conditions.
[0056] The following table details representative experimental
conditions capable of selectively removing protecting groups (more
labile) while maintaining the integrity of other different
protecting groups (more stable).
1 Labile Stable Conditions t-butyldimethylsilyl t-butyl
tetrabutylammonium fluoride t-butyldimethylsilyl t-butyl 1 N HCL
t-butyldimethylsilyl dialkylamino tetrabutylammonium fluoride
t-butyldimethylsilyl dialkylamino 1 N HCL t-butyl dialkylamino
Amberlyst .RTM. resin t-amyl dialkylamino Amberlyst .RTM. resin
trimethylsilyl t-butyl tetrabutylammonium fluoride trimethylsilyl
t-butyl 1 N HCl trimethylsilyl dialkylamino tetrabutylammonium
fluoride trimethylsilyl dialkylamino 1 N HCl
[0057] The progress of the deprotection reactions can be monitored
by conventional analytical techniques, such as Thin Layer
Chromatography (TLC), Nuclear Magnetic Resonance (NMR), or InfraRed
(IR) spectroscopy.
[0058] Examples of methods to hydrogenate the polymers of this
invention are described in U.S. Pat. Nos. 4,970,254, 5,166,277,
5,393,843 and 5,496,898, the entire disclosure of each of which is
incorporated by reference. The hydrogenation of the functionalized
polymer is conducted in situ, or in a suitable solvent, such as
hexane, cyclohexane or heptane. This solution is contacted with
hydrogen gas in the presence of a catalyst, such as a nickel
catalyst. The hydrogenation is typically performed at temperatures
from 25.degree. C. to 150.degree. C., with a archetypal hydrogen
pressure of 15 psig to 1000 psig. The progress of this
hydrogenation can be monitored by InfraRed (IR) spectroscopy or
Nuclear Magnetic Resonance (NMR) spectroscopy. The hydrogenation
reaction is conducted until at least 90% of the aliphatic
unsaturation has been saturated. The hydrogenated functional
polymer is then recovered by conventional procedures, such as
removal of the catalyst with aqueous acid wash, followed by solvent
removal or precipitation of the polymer.
[0059] For example, a protected functional living polymer of this
invention can be generated by polymerizing 1,3-butadiene with an
initiator of Formula (II) above, wherein M is lithium, Z is a
trimethylene connecting group, Q is isoprene, J is sulfur, A is
carbon, n is 3, and R.sup.1, R.sup.2, and R.sup.3 are methyl
groups. A living polymer is produced having the formula
Li--(B).sub.m--(Ip).sub.3(CH2).sub.3--S--C(CH.sub.3).sub.3 (IV)
[0060] where B is a unit derived by polymerizing butadiene, m is an
integer from about 10 to 200, and Ip is a unit derived by
polymerization of isoprene. The living polymer (IV) may be reacted,
for example, with ethylene oxide to yield, after hydrolysis, a
hetero-telechelic compound of the formula
HOCH.sub.2CH.sub.2--(B).sub.m(Ip).sub.3--(CH.sub.2).sub.3--S--C(CH.sub.3).-
sub.3 (V)
[0061] which may optionally be hydrogenated to the corresponding
asymmetric polymer. Deprotection of polymer (V), for example with
trifluoroacetic acid or para-toluenesulfonic acid, would generate
the polymer (VI)
HOCH.sub.2CH.sub.2--(B).sub.m(Ip).sub.3--(CH.sub.2).sub.3--SH
(VI)
[0062] which contains two different functional groups on the
termini of the polymer.
[0063] Additionally, a wide variety of asymmetrically
monofunctional polymers may be produced by reacting the living
polymer (IV) above with various functionalizing agents. For
example, addition of carbon dioxide (see J.Polym.Sci., Polym.Chem.
30, 2349 (1992)) to polymer (IV) would produce a polymer with one
protected thiol and one carboxyl group, or the living polymer (IV)
may be reacted with 1,5 diazabicyclo-(3.1.0) hexane as described in
U.S. Pat. No. 4,753,991 to produce a polymer with one protected
thiol and one amino group. A polymer with one protected thiol group
and one protected amino group can be prepared by reaction of the
living anion (IV) with a protected amino propyl bromide, see
Macromolecules, 23, 939 (1990). Reaction of the living polymer
anion (IV) with oxetane or substituted oxetanes (see U.S. Pat. No.
5,391,637) would afford a polymer which contained one protected
thiol and a hydroxyl group. A polymer with a protected thiol and a
protected hydroxy group can be prepared by reaction of the living
anion (IV) with a silicon derived acetal, see U.S. Pat. No.
5,478,899.
[0064] Other asymmetrically substituted monofunctional polymers may
be produced having epoxy or isocyanate groups at one end, for
example, by reacting the lithium salt of (V) above (before
hydrolysis), with epichlorohydrin or, by reacting (V) itself with
an equivalent of a diisocyanate, such as methylene 4,4-diphenyl
diisocyanate (2/1 NCO/OH). These unsymmetrically substituted
monofunctional polymers could then be further reacted with other
comonomers either with or without simultaneous deprotection as
described below.
[0065] The protected monohydroxy polymers (V) alone and in their
hydrogenated forms could be used as base materials to lend
flexibility and higher impact strength in a number of formulas to
produce coatings, sealants, binders and block copolymers with
polyesters, polyamides and polycarbonates as described in UK Patent
Application GB 2270317A and in "Polytail" data sheets and brochures
(Mitsubishi Kasei America).
[0066] In the presence of acidic catalysts used to promote the
formation of many of these block copolymer resins, the protective
group of the hydrogenated polymer is removed as well, allowing the
exposed hydroxyl grouping in the base polymer molecule to
simultaneously participate in the block copolymer reaction.
[0067] For example, hydrogenated polymers (VI) may be reacted with
bisphenol A and phosgene in the presence of appropriate catalysts
to yield a polycarbonate alternating block copolymer. The resulting
products are useful as molding resins, for example, to prepare
interior components for automobiles.
[0068] A segmented polyamide-hydrogenated block copolymer is also
useful as a molding composition to prepare exterior automotive
components and can be prepared, for example, by reacting
hydrogenated (VI) polymer with caprolactam or adipic acid and a
diamine in the presence of a suitable catalyst.
[0069] A segmented polyester-hydrogenated block copolymer is
produced by reaction of hydrogenated (VI) polymer with dimethyl
terephthalate and a diol and a suitable acidic catalyst. Again, the
products are useful as molding compounds for exterior automotive
components.
[0070] Isocyanate-terminated prepolymers can be produced from
hydrogenated (VI) polymers by reaction with suitable diisocyanates
(2/1 NCO/OH) as above and which can be further reacted with diols
and additional diisocyanates to form segmented polyurethanes useful
for water based, low VOC coatings. Inclusion of acid functional
diols, such as dimethylolpropionic acid, in the polyurethane
introduces pendant carboxyl groups which can be neutralized with
tertiary amines to afford water dispersable polyolefin/polyurethane
segmented polymers, useful for water based coatings. This same
principle could be applied to acrylic polymers made with tertiary
amine functional monomers included, which could be made by free
radical polymerization following reacting the hydroxyl groups at
the terminal ends of the polymer with acryloyl chloride or
methacryloyl chloride. Segmented polyurethane prepolymers may be
mixed with tackifying resins and used as a moisture-curable
sealant, caulk or coating.
[0071] Another possible application in coatings would be the use of
new dendrimers, based on the use of the polymer with hydroxyl
functionality at the termini thereof to form the core for dendritic
hybrid macromolecules based on condensation or addition
polymerizations, utilizing the hydroxyl functionality as the
initiating site (see, for example Gitsov and Frechet, American
Chemical Society PMSE Preprints, Volume 73, August 1995.
[0072] Yet another application includes use as toughening polymers
for epoxy composites, utilizing the polymer core with the hydroxyl
groups converted to half esters by reaction with anhydrides. These
epoxy reactive polymers can then be utilized as reactants with
epoxy resins and amines in composite systems. Reacting the hydroxyl
functional polymers into unsaturated polyesters provides a new
polymer toughening system for polyester molding compounds for
automotive and other uses. For a review of the use of linear
polymers for toughening of epoxies and polyesters, see
"Rubber-Toughened Plastics", Edited By C.Keith Riew, ACS Advances
in Chemistry Series, #222.
[0073] Cathodic electrodepositable coatings may be prepared from
epoxy functional polymers described above by reacting with epoxy
resins in the presence of excess amine or polyamine, to completely
react all the epoxy groups, distilling off excess amine, and
neutralizing the resulting epoxy-amine adduct with water soluble
organic or inorganic acids to form water soluble, quarternary
ammonium containing polymer salts (see for reference, U.S. Pat.
Nos. 3,617,458, 3,619,398, 3,682,814, 3,891,527, 3,947,348, and
4,093,594). Alternatively, the above epoxy-amine polymer adducts
may be converted to quarternary phosphonium or sulfonium ion
containing polymers, as described in U.S. Pat. No. 3,935,087.
[0074] An acrylate-terminated prepolymer curable by free-radical
processes can be prepared from the hydrogenated (VI) polymer by
reaction with a diisocyanate (2 NCO/OH) followed by further
reaction with hydroxyethyl acrylate in the presence of a basic
reagent.
[0075] Another likely application for hetero-telechelic terminated
polymers include use as viscosity index (I.V.) improvers. Using
carboxyl functional monomers, such as acrylic acid and methacrylic
acid, and/or amine functional monomers such as acrylamide, along
with free radical initiators in further polymerizations, can result
in the formation of polymer segments at the periphery of each
termini with amine or other functionalities which, in addition to
the advantageous properties of the polymers as V.I. improvers,
combines the ability to add functionality to the polymers for
dispersant properties (see, for example, U.S. Pat. Nos. 5,496,898,
4,575,530, 4,486,573, 5,290,874, 5,290,868, 4,246,374 and
5,272,211).
[0076] The versatility of the hydroxyl functional polymers of this
invention, and the wide range of different segmented polymers
(polyethers, polyesters, polyamides, polycarbonates, polyurethanes,
etc.) which can be initiated at the hydroxyl groups, leads to
numerous possible applications as compatibilizers for polymer
blends and alloys. In addition to the use of such blends for new
applications, much recent interest is generated in the use of
compatibilizers to facilitate polymer waste recycling.
[0077] The polar functional groups of the polymer chain ends allow
the polymers of this invention to alter the surface properties of
polymers like polyethylene (including high density polyethylene,
low density polyethylene and linear low density polyethylene),
polypropylene, polyisobutylene and copolymers and blends thereof.
When the polymers of this invention are blended with non-polar
polyolefins, the polar functional groups on the chain ends, being
incompatible with the non-polar polyolefin, will phase separate and
migrate to the surface of the polyolefin. The functional polymers
of the invention can be added in amounts ranging from 1 to 25% by
weight based on the weight of the polyolefin. Properties such as
surface adhesion are thus greatly enhanced, leading to improved
adhesion of pigments in printing inks for labels, composite
layering, and other adhesive applications. An alternative approach
to modification of polymer surfaces to alter properties by
introduction of functional groups has been the use of chemical
reagents such as alkyllithiums (see, for example, A. J. Dias, K- W
Lee, and T. J. McCarthy, Rubber & Plastics News, 18-20, Oct.
31, 1988, and A. J. Dias and T. J. McCarthy, Macromolecules, 20,
1437 (1987).
[0078] Alternatively, protecting groups may be removed, either
before or after optional hydrogenation of the aliphatic
unsaturation, then the hydroxy terminated polymer may be reacted
with functional comonomers to produce novel copolymers using these
and other processes. Thus, for example, a hydroxy terminated
polymer may be hydrogenated, and then reacted with ethylene oxide
in the presence of potassium tert-butoxide to produce a
poly(ethylene oxide)-hydrogenated block copolymer. This reaction
sequence affords a hydrogel.
[0079] Alternatively, the protected monohydroxy terminated polymer
(V) may be reacted with functional comonomers, without
simultaneously removing the protective group. These copolymers then
may be deprotected and then further reacted with the same or
different comonomers to form yet other novel copolymers. Thus, for
example, the hydroxyterminated polymer of Formula (V) may be
hydrogenated, and then reacted with ethylene oxide in the presence
of potassium tert-butoxide to produce a poly(ethylene
oxide)-hydrogenated polybutadiene copolymer with one protected
thiol group on the polybutadiene segment. This thiol can then be
deprotected and a poly(ethylene oxide) polymer having different
chain lengths grown onto both ends of the polybutadiene
segment.
[0080] In another possible application, the living polymer (IV) may
be reacted with an alkenylarylhalosilane, such as
styrenyldimethylchlorosila- ne, to yield the corresponding
omega-styrenyl terminated macromonomer according to the teachings
of U.S. Pat. No. 5,278,244, which may then be further polymerized
by a variety of techniques to yield "comb" polymers which, on
deprotection and hydrogenation yield branched polymers with
hydroxyfunctionality on the branch-ends. Such multi-functionality
can be utilized to graft a water-soluble polymer such as
polyethylene oxide onto a hydrophobic polyolefinic core to produce
hydrogels.
[0081] In still another possible application, hydrogenated
hydroxyterminated branches of the polymers may be further reacted
with acryloyl chloride or methacryloyl chloride, and the resultant
acrylate or methacrylate-terminated polymer further polymerized
with monomers selected from the group of alkyl acrylates, alkyl
methacrylates, and dialkylacrylamides to produce hydrogels.
Further, acrylate or methacrylate-terminated polymers may be
polymerized by free-radical processes.
[0082] The following examples further illustrate the invention.
PREPARATION OF THE INITIATORS
EXAMPLE A
Preparation of 3-(t-Butyldimethylsilyloxy) -1-Propyllithium Chain
Extended with 2 Moles of Isoprene
[0083] A 500 ml, three-necked Morton flask was equipped with a
mechanical stirrer, a 125 ml pressure-equalizing addition funnel,
and a Claisen adapter fitted with a thermocouple, a reflux
condenser, and an argon inlet. This apparatus was dried in an oven
overnight at 125.degree. C., assembled hot, and allowed to cool to
room temperature in a stream of argon. Lithium dispersion was
washed free of mineral oil with hexane (2.times.70 ml), and pentane
(1.times.70 ml), then dried in a stream of argon. The dry
dispersion, 5.20 grams (0.749 mole, 2.80 equivalents) was
transferred to the flask with 260 ml cyclohexane. This suspension
was stirred at 450 RPMs, and heated to 65.degree. C. with a heating
mantle. The heat source was removed.
1-(t-Butyldimethylsilyloxy)-3-chloro-propane- , 58.82 grams (0.268
mole, 1.00 equivalent) was added dropwise. An exotherm was detected
after 31.8% of the feed had been added. A dry ice/hexane cooling
bath was applied to maintain the reaction temperature at
60-65.degree. C. The total feed time was one hundred five minutes.
An exotherm was noted until the last drop of feed was added, then
the temperature fell off rapidly to room temperature. The reaction
mixture was stirred at room temperature for forty five minutes,
then heated to 65.degree. C. with a heating mantle. The heat source
was removed. Isoprene, 36.45 grams (0.535 mole, 2.00 equivalents)
was then added dropwise. An exotherm was noted after 24.6% of the
feed had been added. Hexane cooling was applied to maintain the
reaction temperature at 60-65.degree. C. The total isoprene feed
time was thirty eight minutes. The reaction mixture was allowed to
stir at room temperature for one hour, then transferred to a small
pressure filter with argon pressure. Very rapid filtration was
observed with 2 psi argon. The muds were reslurried with
cyclohexane (2.times.50 ml). This afforded an orange solution,
yield=530 ml, 425.34 grams. Total base=17.1 wt. %; Active
C--Li=15.9 wt %; Yield (based on active C--Li)=80.8%.
EXAMPLE B
Preparation of 3-(t-Butyldimethylsilylthio)-1-Propyllithium Chain
Extended with 2 Moles of Isoprene
[0084] A 500 ml, three-necked Morton flask is equipped with a
mechanical stirrer, a 125 ml pressure-equalizing addition funnel,
and a Claisen adapter fitted with a thermocouple, a reflux
condenser, and an argon inlet. This apparatus is dried in an oven
overnight at 125.degree. C., assembled hot, and allowed to cool to
room temperature in a stream of argon. Lithium dispersion is washed
free of mineral oil with hexane (2 .times.70 ml), and pentane
(1.times.70 ml), then dried in a stream of argon. The dry
dispersion, 5.20 grams (0.749 mole, 2.80 equivalents) is
transferred to the flask with 260 ml cyclohexane. This suspension
is stirred at 450 RPMs, and heated to 65.degree. C. with a heating
mantle. The heat source is removed.
1-(t-Butyldimethylsilylthio)-3-chloro-propane- , 60.22 grams (0.268
mole, 1.00 equivalent) is added dropwise. An exotherm is detected
after 21.8% of the feed has been added. A dry ice/hexane cooling
bath is applied to maintain the reaction temperature at
60-65.degree. C. The total feed time is one hundred minutes. An
exotherm is noted until the last drop of feed is added, then the
temperature falls off rapidly to room temperature. The reaction
mixture is stirred at room temperature for forty five minutes, then
heated to 65.degree. C. with a heating mantle. The heat source is
removed. Isoprene, 36.45 grams (0.535 mole, 2.00 equivalents) is
then added dropwise. An exotherm is noted after 24.6% of the feed
has been added. Hexane cooling is applied to maintain the reaction
temperature at 60-65.degree. C. The total isoprene feed time is
thirty eight minutes. The reaction mixture is allowed to stir at
room temperature for one hour, then transferred to a small pressure
filter with argon pressure. Very rapid filtration is achieved with
2 psi argon. The muds are reslurried with cyclohexane (2.times.50
ml). This affords an orange solution; yield=530 ml, 435.21 grams.
Total base=17.7 wt. %; Active C--Li=16.9 wt t; Yield (based on
active C--Li)=82.4%.
EXAMPLE C
Preparation of 3-(N,N-Dimethylamino)-1-propyllithium Chain Extended
with 2 Moles of Isoprene
[0085] A 500 ml, three-necked Morton flask was equipped with a
mechanical stirrer, a 125 ml pressure-equalizing addition funnel,
and a Claisen adapter fitted with a thermocouple, a reflux
condenser, and an argon inlet. This apparatus was dried in an oven
overnight at 125.degree. C., assembled hot, and allowed to cool to
room temperature in a stream of argon. Lithium dispersion was
washed free of mineral oil with hexane (2.times.70 ml), and pentane
(1.times.70 ml), then dried in a stream of argon. The dry
dispersion, 10.57 grams (1.520 moles) was transferred to the flask
with 250 ml cyclohexane. Coarse sand, 45.3 grams, was added to the
reaction mixture. This suspension was stirred at 600-675 RPMs, and
heated to 37.degree. C. with a heating mantle. The heat source was
removed. 1-Chloro-3-(N,N-dimethylamino)propane, 19.64 grams (0.1615
mole) dissolved in 120 ml. Cyclohexane was added dropwise. An
exotherm (up to 52.degree. C.) was detected after 7% of the feed
had been added. A dry ice/hexane cooling bath was applied to
maintain the reaction temperature at 41-44.degree. C. The total
feed time was thirty-two minutes. An exotherm was noted until the
last drop of feed was added, then the temperature was maintained at
36-40.degree. C. for an additional thirty minutes. The reaction
mixture was then transferred to a sintered glass filter while still
warm. The filtration was complete in three minutes with three psi
argon pressure. This afforded a hazy suspension. Yield=400 ml,
298.2 grams. Active C--Li=0.361 M (0.469 m/kg) at 40.degree. C.
Yield (based on active C--Li=87%.
[0086] The product crystallized from solution upon standing at room
temperature. The concentration of the clear supernatant solution
was about 0.3 M.
[0087] A dry 500 ml round bottom flask was fitted with a magnetic
stir bar, and an argon inlet. This apparatus was purged with argon,
then 154.77 grams (0.0726 mole) of the suspension prepared above
was added to the flask. Isoprene, 9.4 grams (0.138 mole, 1.90
equivalents) was then added all at once. The reaction mixture was
then heated to 48-49.degree. C. for forty minutes. This afforded a
slightly hazy golden solution, which was partially vacuum-stripped
on the rotary evaporator to afford the product solution.
Yield=43.32 grams. Active C--Li=1.36 M (1.65 m/kg). Recovered yield
(based on active C--Li)=98.5%.
EXAMPLES OF THE INVENTION--PREPARATION OF POLYMERS
EXAMPLE 1
Hetero-telechelic Polyisoprene with Tertiary Amine Functional Group
at the .omega.-Chain End
[0088] Isoprene and cyclohexane were purified according to the
conventional methods for anionic polymerization. Solutions of
3-(1,1-dimethyl ethoxy)-1-propyllithium, chain extended with two
moles of isoprene, which has t-butoxy group at the chain end, was
injected into the reactor in the amount of 25.8 ml
(7.74.times.10.sup.-3 M). Purified 450 ml of cyclohexane was
distilled into the reactor and then reactor was flame sealed off.
After the adding the monomer into the reactor by breaking the
break-seal for the ampoule containing 38 ml of purified isoprene,
the reaction proceeded for eight hours at room temperature. An
ampoule of 260 ml of living poly(isoprenyl)lithium was sealed off
for further functionalization reaction and the small amount of
residual polymer solution was terminated by degassed methanol for
the determination of molecular weight. This 260 ml of
polyisoprenyllithium solution which has 4.47.times.10.sup.-3 M of
living chain ends was deactivated by 1.5-molar excess
(6.71.times.10.sup.-3M) of 3-(dimethylamino)propyl chloride(DMAPC)
which was prepared by the neutralization of DMAPC.HCl by sodium
hydroxide in water. DMAPC was stirred over calcium hydride for
several hours before distillation into the ampoule. After
termination with degassed methanol, polyisoprene was isolated into
a large amount of methanol. Molecular weight and polydispersity
were determined by SEC as M.sub.n=3150 g/mol and
M.sub.w/M.sub.n=1.06. By TLC analysis using toluene as an eluent,
small amount of unfunctionalized polymer was detected and separated
by silica gel column chromatography. It was characterized by
titration and .sup.1H--NMR (.delta.=2.20 ppm) and the pure
dimethylamino-functionalized polyisoprene was isolated in 85% yield
by silica gel column chromatography.
EXAMPLE 2
Hetero-telechelic Polystyrene with Sulfonated Functional Group at
the .omega.-Chain End
[0089] Styrene and benzene were purified as described previously.
16.7 ml solution of 3-(tert-amyloxy)-1-propyllithium, chain
extended with two moles of isoprene, which has t-amyloxy group at
the chain end in cyclohexane (5.0.times.10.sup.-3 M) was injected
into the reactor. After distillating 200 ml of benzene into the
reactor, the purified styrene monomer was added to solution by
breaking the breakseal. Living polystytryllithum was end-capped
with 1.5 molar excess (4.0 mmol) of 1,1-diphenylethylene and the
crossover reaction, monitored by UV/Vis spectroscopy, was complete
in an hour. A 1:6 (v/v) ratio of THF/benzene solution of a 1.5
molar excess (4.0 mmol) of 1,3-propane sultone was added to the
living polystyryllithium which was end-capped with
1,1-diphenylethylene. The molecular weight of the base polymer
which was obtained by termination with degassed methanol before the
functionalization was 3,100 g/mol from the SEC with 1.18 of
polydispersity. After the silica gel column chromatography
separation, the functionality of the .omega.-sulfonated polystyrene
obtained was over 90%.
[0090] Table 1 below sets forth information relating to the
polymers prepared as described above in Examples 1 and 2, as well
as additional information relating to other proposed polymers in
accordance with the invention.
2TABLE 1 Initiator Terminating Polymer Molecular Polydispersity
Functionality Polymer Functionality Agent Functionality Weight
(M.sub.n) (M.sub.w/M.sub.n) (%) PS.sup.1 X-SH.sup.2 ethylene HS--OH
4,100 1.17 >90 oxide PI.sup.3 X'-SH.sup.4 ethylene HS--OH 6,910
1.08 >90 oxide PI X-SH CO.sub.2 HS--COOH 7,420 1.07 >90 PI
X-OH DMAPC.sup.5 HO--N(CH.sub.3).sub.2 3,150 1.06 85 PI X'-OH 1,3-
HO--SO.sub.3H 2,200 1.06 93 propane sultone PS X'-OH NBTSA.sup.6
HO--NH.sub.2 3,100 1.18 >90 PS X-OH CO.sub.2 HO--COOH 2,000
<1.1 >90 PI X-OH CO.sub.2 HO--COOH 2,000 <1.1 >90
Notes: .sup.1PS is polystyrene. .sup.2X represents t-butyl group
from initiator. .sup.3PI is polyisoprene. .sup.4X' represents
t-amyl group from initiator. .sup.5DMAPC is 3-(dimethylamino)
propyl chloride. .sup.6NBTSA is N-(benzylidene)
trimethylsilylamine.
[0091] The foregoing examples are illustrative of the present
invention and are not to be construed as limiting thereof. The
invention is defined by the following claims, with equivalents of
the claims to be included therein.
* * * * *