U.S. patent application number 09/974102 was filed with the patent office on 2002-03-28 for functionalized ethylene/vinyl or vinylidene aromatic interpolymers.
Invention is credited to Burdett, Kenneth A., Drumright, Ray E., Hahn, Stephen F., Terbrueggen, Robert H., Timmers, Francis J..
Application Number | 20020037988 09/974102 |
Document ID | / |
Family ID | 22924629 |
Filed Date | 2002-03-28 |
United States Patent
Application |
20020037988 |
Kind Code |
A1 |
Drumright, Ray E. ; et
al. |
March 28, 2002 |
Functionalized ethylene/vinyl or vinylidene aromatic
interpolymers
Abstract
Novel substantially random functionalized interpolymers and
processes for making them are disclosed. The novel interpolymers
include those prepared from ethylene and vinyl aromatic monomers
such as ethylene-styrene interpolymers which are then
functionalized with a variety of electrophilic and nucleophilic
reagents.
Inventors: |
Drumright, Ray E.; (Midland,
MI) ; Terbrueggen, Robert H.; (Pasadena, CA) ;
Burdett, Kenneth A.; (Midland, MI) ; Timmers, Francis
J.; (Midland, MI) ; Hahn, Stephen F.;
(Midland, MI) |
Correspondence
Address: |
THE DOW CHEMICAL COMPANY
INTELLECTUAL PROPERTY SECTION
2301 N BRAZOSPORT BLVD
FREEPORT
TX
77541-3257
US
|
Family ID: |
22924629 |
Appl. No.: |
09/974102 |
Filed: |
October 10, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09974102 |
Oct 10, 2001 |
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09244921 |
Feb 4, 1999 |
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6313252 |
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Current U.S.
Class: |
526/347 ;
525/268; 525/279; 525/309; 525/311; 525/333.3; 525/333.4;
525/333.5; 525/333.6; 525/343; 525/379; 525/383; 526/282;
526/307.4; 526/308; 526/314; 526/318.1; 526/324; 526/325 |
Current CPC
Class: |
C08F 8/44 20130101; C08F
8/04 20130101; C08F 8/10 20130101; C08F 210/02 20130101; C08F 8/10
20130101; C08F 8/24 20130101; C08F 210/02 20130101; C08F 8/24
20130101; C08F 8/24 20130101; C08F 210/02 20130101; C08F 210/02
20130101; C08F 210/02 20130101; C08F 210/02 20130101; C08F 210/02
20130101; C08F 8/32 20130101; C08F 210/02 20130101; C08F 210/02
20130101; C08F 210/02 20130101; C08F 210/02 20130101; C08F 210/02
20130101; C08F 8/24 20130101; C08F 8/24 20130101; C08F 210/02
20130101; C08F 8/30 20130101; C08F 8/30 20130101; C08F 8/22
20130101; C08F 8/10 20130101; C08F 8/30 20130101; C08F 8/42
20130101; C08F 2800/10 20130101; C08F 2810/30 20130101; C08F 8/24
20130101; C08F 2810/50 20130101; C08F 8/30 20130101; C08F 8/34
20130101; C08F 8/24 20130101; C08F 8/06 20130101; C08F 8/40
20130101; C08F 2800/20 20130101; C08F 8/04 20130101; C08F 8/00
20130101 |
Class at
Publication: |
526/347 ;
526/308; 526/314; 526/318.1; 526/324; 526/325; 526/307.4; 526/282;
525/333.3; 525/333.4; 525/333.5; 525/333.6; 525/379; 525/383;
525/343; 525/279; 525/268; 525/309; 525/311 |
International
Class: |
C08F 212/08 |
Claims
What is claimed is:
1. A substantially random interpolymer comprising; (a) from 0 to
about 64.95 mole percent of repeating units represented by the
following formula (I): 13 wherein Y is independently selected from
the group consisting of hydrogen, substituted and unsubstituted
alkyl radicals, benzyl radicals, aryl radicals, and aralkyl
radicals containing up to 18 carbon atoms, --Br, --CH.sub.2X,
--C(O)R.sup.6, --(Z)--CO.sub.2H, --(Z)--SO.sub.3H, --NO.sub.2,
--C(O)OR.sup.6, --(Z)--OR.sup.6, --N(R.sup.6).sub.2,
--(Z)--N(R.sup.6).sub.2, --P(OR.sup.6).sub.2,
--(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof; R.sup.1 is selected from the group of radicals
consisting of hydrogen and alkyl radicals containing from 1 to 4
carbon atoms; R.sup.2 is independently selected from the group of
radicals consisting of hydrogen and alkyl radicals containing from
1 to 4 carbon atoms; R.sup.6 is independently selected from the
group of radicals consisting of hydrogen, substituted or
unsubstituted alkyl radicals containing from 1 to 18 carbon atoms,
and substituted or unsubstituted aryl radicals; X is a halogen; and
Z is alkylene or arylene; and n has a value from zero to 4; (b)
from about 0.05 to about 65 mole percent of repeating units
represented by the following formula (II) 14 wherein Y, R.sup.1,
R.sup.2, n, and X are as described for I with the proviso that at
least one Y is not hydrogen or a substituted or unsubstituted alkyl
radical; (c) from 0 to about 25 mole percent of repeating units
represented by the following formula (III): 15 wherein R.sup.1 and
R.sup.2 are as described for I and A.sup.1 is a sterically bulky,
aliphatic or cycloaliphatic substituent of up to 20 carbons or
R.sup.2 and A.sup.1 together form a ring system wherein the ring
system formed by A.sup.1 and R.sup.2 is optionally substituted with
one or more substituents selected from substituted and
unsubstituted alkyl radicals, benzyl radicals, aryl radicals, and
aralkyl radicals containing up to 18 carbon atoms, --Br,
--CH.sub.2X, --C(O)R.sup.6, --(Z)--CO.sub.2H, --(Z)--SO.sub.3H,
--NO.sub.2, --C(O)OR.sup.6, --(Z)--OR.sup.6, --N(R.sup.6).sub.2,
--(Z)--N(R.sup.6).sub.2, --P(OR.sup.6).sub.2,
--(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof, wherein R.sup.6, X, and Z are as defined above
for 1; and (d) from 35 to 99.95 mole percent of repeating units
represented by the following formula (IV); 16 wherein R.sup.3 and
R.sup.4 are selected from the group consisting of hydrogen and
alkyl radicals having from 1 to 18 carbon atoms, with the proviso
that R.sup.3 and R.sup.4 are different alkyl radicals.
2. The substantially random interpolymer of claim 1 comprising from
0 to about 50 mole percent of repeating units of formula I; from
about 0.5 to about 50 mole percent of repeating units of formula
II; from 0 to about 5 mole percent of repeating units of formula
III; and from about 50 to about 99.5 mole percent of repeating
units of formula IV.
3. The substantially random interpolymer of claim 2 wherein Z is
alkylene having from 1 to 4 carbon atoms or phenylene.
4. The substantially random interpolymer of claim 1 comprising from
0.5 to 50 mole percent of repeating units of formula II and from
about 50 to about 99.5 mole percent of repeating units of Formula
IV.
5. The substantially random interpolymer of claim 4 wherein the Y
group which is not hydrogen or a substituted or unsubstituted alkyl
radical is substituted at the para position.
6. The substantially random interpolymer of claim 5 wherein the Y
group is selected from the group consisting of --Br, --CH.sub.2X,
--C(O)R.sup.6, --(Z)--CO.sub.2H, --(Z)--SO.sub.3H, --NO.sub.2.
7. The substantially random interpolymer of claim 5 wherein Y is
independently selected from the group consisting of unsubstituted
or substituted alkylcarbonyl, arylcarbonyl, and aralkyl groups;
alkyl groups substituted with carboxylic acid or sulfonic acid
groups; NO.sub.2; NH.sub.2, acyl, substituted or unsubstituted
phenylcarbonyl and carboxyalkylcarbonyl; substituted or
unsubstituted carboxybenzyl; --C(O)Me, --CO.sub.2H,
--C(O)--pC.sub.6H.sub.4--Me, --CH(OH)--pC.sub.6H.sub.4--Me,
--CH(R.sup.5)CH.sub.2CH.sub.2CO.sub.2H,
--CH(R.sup.5)CH.sub.2CH.sub.2SO.sub.3H,
--CH(R.sup.5)--pC.sub.6H.sub.4--C- O.sub.2H,
C(O)CH.sub.2CH.sub.2CO.sub.2H; ionomeric salts of --CO.sub.2.sup.-,
--(Z)--CO.sub.2.sup.-, --(Z)--SO.sub.3.sup.-,
--N.sup.+(R.sup.6).sub.3, --(Z)--N.sup.+(R.sup.6).sub.3,
--P.sup.+(R.sup.6).sub.3, --(Z)--P.sup.+(R.sup.6).sub.3,
--(Z)--S.sup.+(R.sup.6).sub.2, and mixtures thereof and mixtures
thereof, and wherein R.sup.5 is hydrogen or an alkyl group.
8. A substantially random interpolymer comprising repeating units
derived from (1) monomer units derived from (i) at least one vinyl
or vinylidene aromatic monomer, or (ii) at least one sterically
hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer;
(iii) a combination of at least one vinyl or vinylidene aromatic
monomer and at least one sterically hindered aliphatic or
cycloaliphatic vinyl or vinylidene monomer; and (2) monomer units
derived from (i) ethylene, or (ii) C.sub.3-20 .alpha.-olefin; (iii)
or a combination (i) and (ii) wherein the aromatic group of one or
more of said vinyl or vinylidene aromatic monomers is
functionalized subsequent to interpolymer formation with one or
more substituents selected from the group consisting of benzyl
radicals, aryl radicals, and aralkyl radicals containing up to 18
carbon atoms, --Br, --CH.sub.2X, --C(O)R.sup.6, --(Z)--CO.sub.2H,
--(Z)--SO.sub.3H, --NO.sub.2, --C(O)OR.sup.6, --(Z)--OR.sup.6,
--N(R.sup.6).sub.2, --(Z)--N(R.sup.6).sub.2, --P(OR.sup.6).sub.2,
--(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.-(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof; R.sup.1 is selected from the group of radicals
consisting of hydrogen and alkyl radicals containing from 1 to 4
carbon atoms; R.sup.2 is independently selected from the group of
radicals consisting of hydrogen and alkyl radicals containing from
1 to 4 carbon atoms; R.sup.6 is independently selected from the
group of radicals consisting of hydrogen, substituted or
unsubstituted alkyl radicals containing from 1 to 18 carbon atoms,
and substituted or unsubstituted aryl radicals; X is a halogen; and
Z is alkylene or arylene; and n has a value from zero to 4.
9. The substantially random interpolymer of claim 8 which further
comprises monomer units derived from one or more ethylenically
unsaturated polymerizable monomers other than (1) or (2).
10. The substantially random interpolymer of claim 9 wherein the
monomers other than (1) or (2) are norbornene and C.sub.1-10 alkyl
or C.sub.6-10 aryl substituted norbornenes.
11. The substantially random interpolymer of claim 8 which
comprises from 5 to 65 mole percent of monomer units derived from
said vinyl or vinylidene aromatic monomer and wherein 1 to 100
percent of said monomer units derived from said vinyl or vinylidene
aromatic monomer are substituted with one or more of said
substituents.
12. The substantially random interpolymer of claim 8 wherein said
vinyl or vinylidene aromatic monomer is styrene and X is
chlorine.
13. The substantially random interpolymer of claim 8 wherein
Component (1) is styrene and Component (2) is ethylene.
14. The substantially random interpolymer of claim 13 wherein said
substituent is --CH.sub.2X.
15. A method for functionalizing a substantially random
interpolymer comprising (1) monomer units derived from (i) at least
one vinyl or vinylidene aromatic monomer, or (ii) a combination of
at least one vinyl or vinylidene aromatic monomer and at least one
sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene
monomer; and (2) monomer units derived from (i) ethylene, or (ii)
C.sub.3-20 .alpha.-olefin; (iii) or a combination (i) and (ii) said
method comprising; reacting halomethyl ether and said interpolymer
under conditions sufficient to produce a substantially random,
halomethylated interpolymer, and transforming the halomethyl groups
on the halomethylated interpolymer to functional groups selected
from the group consisting of phosphonium, ammonium, ester, ether,
cyano, hydroxyl, and mixtures thereof.
16. The method of claim 15 wherein the halomethyl ether is a
halomethyl alkyl ether.
17. The method of claim 15 wherein the halomethyl ether is a
chloromethyl alkyl ether selected from the group consisting of
chloromethyl methyl ether and chloromethyl ethyl ether and wherein
the halomethyl ether and the interpolymer are reacted in the
presence of a Lewis acid catalyst and a solvent wherein said
catalyst is selected from the group consisting of tin
tetrachloride, zinc chloride, and mixtures thereof and said solvent
is selected from the group consisting of 1,2-dichloroethane,
trichloromethane, methylene chloride, and mixtures thereof.
18. The method of claim 17 wherein the ratio of halomethyl ether to
catalyst is such that halomethylation is maximized and gellation is
minimized.
19. The method of claim 15 wherein the interpolymer further
comprises monomer units derived from one or more ethylenically
unsaturated polymerizable monomers other than (1) or (2) wherein
said monomers are selected from the group consisting of propylene,
1-hexene, 1-octene, 1-butene, 4-methyl-1-pentene, vinyl toluene,
alpha-methyl-styrene, or t-butyl styrene.
20. A method for functionalizing a substantially random
interpolymer comprising (1) monomer units derived from (i) at least
one vinyl or vinylidene aromatic monomer, or (ii) a combination of
at least one vinyl or vinylidene aromatic monomer and at least one
sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene
monomer; and (2) monomer units derived from (i) ethylene, or (ii)
C.sub.3-20 .alpha.-olefin; (iii) or a combination (i) and (ii) said
method comprising reacting the substantially random interpolymer
with an electrophile under conditions sufficient to produce an
interpolymer having one or more functional groups substituted on
the aromatic group wherein such functional groups are selected from
the group consisting of substituted or unsubstituted aryl,
substituted or unsubstituted alkylcarbonyl, and substituted or
unsubstituted arylcarbonyl.
21. A method for functionalizing a substantially random
interpolymer comprising (1) monomer units derived from (i) at least
one vinyl or vinylidene aromatic monomer, or (ii) a combination of
at least one vinyl or vinylidene aromatic monomer and at least one
sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene
monomer; and (2) monomer units derived from (i) ethylene, or (ii)
C.sub.3-20 .alpha.-olefin; (iii) or a combination (i) and (ii) said
method which comprises: reacting a nitrating agent and said
interpolymer under conditions sufficient to produce a substantially
random, nitrated interpolymer, and transforming the nitro groups on
the nitrated interpolymer to amino groups.
Description
FIELD OF THE INVENTION
[0001] The present invention pertains to functionalized
interpolymers of ethylene or one or more .alpha.-olefin monomers,
or combinations thereof, with one or more vinyl or vinylidene
aromatic monomers or one or more sterically hindered aliphatic or
cycloaliphatic vinyl or vinylidene monomers, or combination
thereof, and methods of preparing the interpolymers.
BACKGROUND OF THE INVENTION
[0002] The generic class of materials of .alpha.-olefin/vinyl or
vinylidene monomer substantially random interpolymers, including
materials such as substantially random .alpha.-olefin/vinyl
aromatic monomer interpolymers, and their preparation, are known in
the art, such as described in U.S. Pat. No. 5,703,187 (EP 416 815
A2), the contents of which are herein incorporated by
reference.
[0003] These materials offer a wide range of material structures
and properties which makes them useful for varied applications,
such as, for example, asphalt modifiers or as compatibilizers for
blends of polyethylene and polystyrene, as described in U.S. Pat.
No. 5,460,818 the contents of which are herein incorporated by
reference.
[0004] The structure, thermal transitions and mechanical properties
of substantially random interpolymers of ethylene and styrene
containing up to about 50 mole percent styrene have been described
(see Y. W. Cheung, M. J. Guest; Proc. Antec '96 pp. 1634-1637) the
contents of which are herein incorporated by reference. These
polymers are found to have glass transitions in the range of
-20.degree. C. to +35.degree. C., and show no measurable
crystallinity above about 25 mole percent styrene incorporation,
that is they are essentially amorphous.
[0005] Although of utility in their own right, industry is
constantly seeking to improve the applicability of the
substantially random interpolymers. To perform well in certain
applications, it may be desirable to modify the properties of these
interpolymers. One method of modifying the properties of the
substantially random interpolymers is to functionalize the vinyl or
vinylidene group subsequent to interpolymer formation. WO 97/05175
describes functionalized styrene polymers and copolymers and WO
96/16096 describes alpha olefin/para-alkyl styrene copolymers and
functionalized copolymers thereof, the contents of both of which
are herein incorporated by reference.
[0006] Thus, it would be advantageous to discover a method of
modifying the conventional substantially random interpolymers.
Further, it would be advantageous if such a method could be applied
to a variety of interpolymers to form a variety of new, modified
interpolymers.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention relates to a functionalized
substantially random interpolymer comprising;
[0008] (a) from 0 to about 64.95 mole percent of repeating units
represented by the following formula (I); 1
[0009] wherein Y is independently selected from the group
consisting of hydrogen, substituted and unsubstituted alkyl
radicals, benzyl radicals, aryl radicals, and aralkyl radicals
containing up to 18 carbon atoms, --X, --CH.sub.2X, --C(O)R.sup.6,
--(Z)--CO.sub.2H, --(Z)--SO.sub.3H, --NO.sub.2, --C(O)OR.sup.6,
--(Z)--OR.sup.6, --N(R.sup.6).sub.2, --(Z)--N(R.sup.6).sub.2,
--P(OR.sup.6).sub.2, --(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).- sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, , or
combinations thereof, R.sup.1 is selected from the group of
radicals consisting of hydrogen and alkyl radicals containing from
about 1 to about 4 carbon atoms; R.sup.2 is independently selected
from the group of radicals consisting of hydrogen and alkyl
radicals containing from about 1 to about 4 carbon atoms; R.sup.6
is independently selected from the group of radicals consisting of
hydrogen, substituted or unsubstituted alkyl radicals containing
from about 1 to about 18 carbon atoms, and substituted or
unsubstituted aryl radicals; X is a halogen; and Z is alkylene or
arylene; and n has a value from zero to about 4;
[0010] (b) from about 0.05 to about 65 mole percent of repeating
units represented by the following formula (II); 2
[0011] wherein Y, R.sup.1, R.sup.2, n, and X are as described for I
with the proviso that at least one Y is not hydrogen or a
substituted or unsubstituted alkyl radical;
[0012] (c) from 0 to about 25 mole percent of repeating units
represented by the following formula (III); 3
[0013] wherein R.sup.1 and R.sup.2 are as described for I and
A.sup.1 is a sterically bulky, aliphatic or cycloaliphatic
substituent of up to about 20 carbons or R.sup.2 and A.sup.1
together form a ring system wherein the ring system formed by
A.sup.1 and R.sup.2 is optionally substituted with one or more
substituents selected from alkyl radicals having from 1 to 18
carbon atoms, --X, --CH.sub.2X, --C(O)R.sup.6, --(Z)--CO.sub.2H,
--(Z)--SO.sub.3H, --NO.sub.2, --C(O)OR.sup.6, --(Z)--OR.sup.6,
--N(R.sup.6).sub.2, --(Z)--N(R.sup.6).sub.2, --P(OR.sup.6).sub.2,
--(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.- 2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof wherein R.sup.6, X, and Z are as defined above for
I; and
[0014] (d) from 35 to 99.95 mole percent of repeating units
represented by the following formula (IV); 4
[0015] wherein R.sup.3 and R.sup.4 are selected from the group
consisting of hydrogen and alkyl radicals having from 1 to 18
carbon atoms, with the proviso that R.sup.3 and R.sup.4 are
different alkyl radicals.
[0016] The invention also relates to processes of making the
functionalized polymers described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The following definitions are used throughout the
disclosure. The term "interpolymer" is used herein to indicate a
polymer wherein at least two different monomers are polymerized to
make the interpolymer. This includes copolymers, terpolymers,
etc.
[0018] The term "repeating unit" as employed herein means a
combination of atoms which may be represented by a formula wherein
the formula occurs more than once in a given interpolymer
chain.
[0019] The term "ionomer" or "ionomeric salt" as employed herein
means a polymer containing interchain ionic bonding. Ionomeric
salts are ionically crosslinked thermoplastics generally obtained
by neutralizing a copolymer containing pendant acid groups, for
example, carboxylic acid groups, with an ionizable compound, for
example, a compound of the monovalent, divalent and/or trivalent
metals of Group I, II, IV-A and VIIIB of the periodic table of the
elements. Preferred ionomeric salts are obtained by reacting the
functionalized interpolymers with a sufficient amount of base as to
neutralize at least some portion of the acid groups, preferably at
least 5 percent by weight and preferably from 20 to 100 percent by
weight, of the acid groups present. Suitable bases include amines,
salts of substituted and unsubstituted ammonium and phosphonium
ions and salts of metal ions including Na.sup.+, K.sup.+, Li.sup.+,
Cs.sup.+, Rb.sup.+, Hg.sup.+, Cu.sup.+, Be.sup.+2, Mg.sup.+2,
Ca.sup.+2, Sr.sup.+2, Cu.sup.+2, Cd.sup.+2, Hg.sup.+2, Sn.sup.+2,
Pb.sup.+2, Fe.sup.+2, Co.sup.+2, Ni.sup.+2, Zn.sup.+2, Al.sup.+3,
Sc.sup.+3 and Y.sup.+3. Basic salts of preferred metals suitable
for neutralizing the copolymers used herein are the alkali metals,
particularly, cations such as sodium, lithium and potassium and
alkaline earth metals, in particular, cations such as sodium,
calcium, magnesium and zinc. However also contemplated in the
present invention are ionomeric salts in which the polymer bears a
positive charge and the counterion bears the negative charge. Both
organic and inorganic anions are included in the possible ionomeric
salts where the polymer bears a positive charge, said anions
including, but not limited to carboxylate, alkoxide, halide,
borate, phenate, carbonate, bicarbonate, sulfate, nitrate, and
bisulfate.
[0020] The term "substantially random" (in the substantially random
interpolymer comprising monomer units derived from ethylene and/or
one or more .alpha.-olefin monomers with one or more vinyl or
vinylidene aromatic monomers and/or one or more sterically hindered
aliphatic or cycloaliphatic vinyl or vinylidene monomers) or the
functionalized derivatives thereof, as used herein means that the
distribution of the monomers of said interpolymer can generally be
described by the Bernoulli statistical model or by a first or
second order Markovian statistical model, as described by J. C.
Randall in Polymer Sequence Determination, Carbon-13 NMR Method,
Academic Press, New York, 1977, pp. 71-78. Preferably,
substantially random interpolymers do not contain more than 15
percent of the total amount of vinyl aromatic monomer in blocks of
vinyl aromatic monomer of more than 3 units. More preferably, the
interpolymer is not characterized by a high degree of either
isotacticity or syndiotacticity. This means that in the carbon-13
NMR spectrum of the substantially random interpolymer the peak
areas corresponding to the main chain methylene and methine carbons
representing either meso diad sequences or racemic diad sequences
should not exceed 75 percent of the total peak area of the main
chain methylene and methine carbons.
[0021] Any numerical values recited herein include all values from
the lower value to the upper value in increments of one unit
provided that there is a separation of at least 2 units between any
lower value and any higher value. As an example, if it is stated
that the amount of a component or a value of a process variable
such as, for example, temperature, pressure, time is, for example,
from 1 to 90, preferably from 20 to 80, more preferably from 30 to
70, it is intended that values such as 15 to 85, 22 to 68, 43 to
51, 30 to 32, etc. are expressly enumerated in this specification.
For values which are less than one, one unit is considered to be
0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples
of what is specifically intended and all possible combinations of
numerical values between the lowest value and the highest value
enumerated are to be considered to be expressly stated in this
application in a similar manner.
[0022] The interpolymers suitable for functionalization according
to the present invention include, but are not limited to
interpolymers prepared by polymerizing ethylene and/or one or more
.alpha.-olefins with one or more vinyl or vinylidene aromatic
monomers and/or one or more sterically hindered aliphatic or
cycloaliphatic vinyl or vinylidene monomers.
[0023] Suitable .alpha.-olefins include for example,
.alpha.-olefins containing from about 3 to about 20, preferably
from about 3 to about 12, more preferably from about 3 to about 8
carbon atoms. Particularly suitable are propylene,
butene-1,4-methyl-1-pentene, hexene-1 and octene-1. Suitable
.alpha.-olefins typically do not contain an aromatic moiety.
[0024] Suitable vinyl or vinylidene aromatic monomers which can be
employed to prepare the interpolymers include, for example, those
represented by the following formula: 5
[0025] wherein R.sup.1 is selected from the group of radicals
consisting of hydrogen and alkyl radicals containing from about 1
to about 4 carbon atoms, preferably hydrogen or methyl; each
R.sup.2 is independently selected from the group of radicals
consisting of hydrogen and alkyl radicals containing from about 1
to about 4 carbon atoms, preferably hydrogen or methyl; Ar is a
phenyl group or a phenyl group substituted with from about 1 to
about 5 substituents selected from the group consisting of halo,
C.sub.1-4-alkyl, and C.sub.1-4-haloalkyl; and n has a value from
zero to about 4, preferably from zero to about 2, most preferably
zero. Exemplary vinyl aromatic monomers include styrene, vinyl
toluene, .alpha.-methylstyrene, t-butyl styrene, chlorostyrene,
including all isomers of these compounds,. Particularly suitable
such monomers include styrene and lower alkyl- or
halogen-substituted derivatives thereof. Preferred monomers include
styrene, .alpha.-methyl styrene, the lower alkyl-(C.sub.1-C.sub.4)
or phenyl-ring substituted derivatives of styrene, such as for
example, ortho-, meta-, and para-methylstyrene, the ring
halogenated styrenes, para-vinyl toluene or mixtures thereof. A
more preferred aromatic vinyl monomer is styrene.
[0026] By the term "sterically hindered aliphatic or cycloaliphatic
vinyl or vinylidene compounds," it is meant addition polymerizable
vinyl or vinylidene monomers such as those corresponding to the
formula: 6
[0027] wherein A.sup.1 is a sterically bulky, aliphatic or
cycloaliphatic substituent of up to about 20 carbons, R.sup.1 is
selected from the group of radicals consisting of hydrogen and
alkyl radicals containing from about 1 to about 4 carbon atoms,
preferably hydrogen or methyl; each R.sup.2 is independently
selected from the group of radicals consisting of hydrogen and
alkyl radicals containing from about 1 to about 4 carbon atoms,
preferably hydrogen or methyl; or alternatively R.sup.1 and A.sup.1
together form a ring system. By the term "sterically bulky" is
meant that the monomer bearing this substituent is normally
incapable of addition polymerization by standard Ziegler-Natta
polymerization catalysts at a rate comparable with ethylene
polymerizations. Preferred hindered aliphatic or cycloaliphatic
vinyl or vinylidene compounds are monomers in which one of the
carbon atoms bearing ethylenic unsaturation is tertiary or
quaternary substituted. Examples of such substituents include
cyclic aliphatic groups such as cyclohexyl, cyclohexenyl,
cyclooctenyl, or ring alkyl or aryl substituted derivatives
thereof, tert-butyl, norbornyl,. Most preferred hindered aliphatic
or cycloaliphatic vinyl or vinylidene compounds are the various
isomeric vinyl-ring substituted derivatives of cyclohexene and
substituted cyclohexenes, and 5-ethylidene-2-norbornene. Especially
suitable are vinylcyclohexane, and 1-, 3-, and 4-vinylcyclohexene.
Olefin monomers containing from about 3 to about 20 carbon atoms
and having a linear non-branched aliphatic structure such as
propylene, butene-1,hexene-1and octene-1 are not considered as
hindered aliphatic monomers.
[0028] Other optional polymerizable ethylenically unsaturated
monomer(s) include norbornene and C.sub.1-10 alkyl or C.sub.6-10
aryl substituted norbornenes, with an exemplary interpolymer being
ethylene/styrene/norbor- nene.
[0029] The interpolymers of ethylene and/or one or more
.alpha.-olefins and one or more vinyl or vinylidene aromatic
monomers and/or one or more sterically hindered aliphatic or
cycloaliphatic vinyl or vinylidene monomers employed in the present
invention are substantially random polymers. These interpolymers
usually contain from about 5 to about 65, preferably from about 5
to about 50, more preferably from about 10 to about 50 mole percent
of one or more vinyl or vinylidene aromatic monomers and/or one or
more hindered aliphatic or cycloaliphatic vinyl or vinylidene
monomers and from about 35 to about 95, preferably from about 50 to
about 95, more preferably from about 50 to about 90 mole percent of
ethylene and/or at least one aliphatic .alpha.-olefin having from
about 3 to about 20 carbon atoms.
[0030] While preparing the substantially random interpolymer, an
amount of atactic vinyl or vinylidene aromatic homopolymer may be
formed due to homopolymerization of the vinyl or vinylidene
aromatic monomer at elevated temperatures. The presence of the
vinyl or vinylidene aromatic homopolymer is in general not
detrimental for the purposes of the present invention. The vinyl or
vinylidene aromatic homopolymer may be separated from the
interpolymer, if desired, by extraction techniques such as
selective precipitation from solution with a non solvent for either
the interpolymer or the vinylidene aromatic homopolymer. For the
purpose of the present invention it is preferred that no more than
about 20 weight percent, preferably less than about 15 weight
percent based on the total weight of the interpolymers of vinyl or
vinylidene aromatic homopolymer be present.
[0031] One method of preparation of the substantially random
interpolymers includes polymerizing a mixture of polymerizable
monomers in the presence of one or more metallocene or constrained
geometry catalysts in combination with various cocatalysts, as
described in EP-A-0,416,815 by James C. Stevens et al. and U.S.
Pat. No. 5,703,187 by Francis J. Timmer, the contents of which are
herein incorporated by reference.
[0032] Preferred operating conditions for such polymerization
reactions are pressures from atmospheric up to about 3000
atmospheres and temperatures from about -30.degree. C. to about
200.degree. C. Polymerizations and unreacted monomer removal at
temperatures above the autopolymerization temperature of the
respective monomers may result in formation of some amounts of
homopolymer polymerization products resulting from free radical
polymerization.
[0033] Examples of suitable catalysts and methods for preparing the
substantially random interpolymers are disclosed in U.S. patent
application Ser. No. 702,475, filed May 20, 1991 (EP-A-514,828); as
well as U.S. Pat. Nos.: 5,055,438; 5,057,475; 5,096,867; 5,064,802;
5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696;
5,399,635; 5,470,993; 5,703,187; and 5,721,185 the entire contents
of all of which are herein incorporated by reference.
[0034] The substantially random .alpha.-olefin/vinyl or vinylidene
aromatic interpolymers can also be prepared by the methods
described by John G. Bradfute et al. (W. R. Grace & Co.) in WO
95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO
94/00500; and in Plastics Technology, p. 25, September, 1992, the
contents of which are herein incorporated by reference.
[0035] Also suitable are the substantially random interpolymers
which comprise at least one .alpha.-olefin/vinyl aromatic/vinyl
aromatic/.alpha.-olefin tetrad disclosed in WO 98/09999, by Francis
J. Timmers et al., the contents of which are herein incorporated by
reference.
[0036] These interpolymers contain additional signals with
intensities greater than three times the peak to peak noise. These
signals appear in the chemical shift range 43.70-44.25 ppm and
38.0-38.5 ppm. Specifically, major peaks are observed at 44.1,
43.9, and 38.2 ppm. A proton test NMR experiment indicates that the
signals in the chemical shift region 43.70-44.25 ppm are methine
carbons and the signals in the region 38.0-38.5 ppm are methylene
carbons.
[0037] In order to determine the carbon-13 NMR chemical shifts of
the interpolymers described, the following procedures and
conditions are employed. A five to ten weight percent polymer
solution is prepared in a mixture consisting of 50 volume percent
1,1,2,2-tetrachloroethane-d.sub.2 and 50 volume percent 0.10 molar
chromium tris-(acetylacetonate) in 1,2,4-trichlorobenzene. NMR
spectra are acquired at 130.degree. C. using an inverse gated
decoupling sequence, a 90.degree. pulse width and a pulse delay of
five seconds or more. The spectra are referenced to the isolated
methylene signal of the polymer assigned at 30.000 ppm.
[0038] It is believed that these new signals are due to sequences
involving two head-to-tail vinyl aromatic monomer insertions
preceded and followed by at least one .alpha.-olefin insertion, for
example an ethylene/styrene/styrene/ethylene tetrad wherein the
styrene monomer insertions of said tetrads occur exclusively in a
1,2 (head to tail) manner. It is understood by one skilled in the
art that for such tetrads involving a vinyl aromatic monomer other
than styrene and an .alpha.-olefin other than ethylene that the
ethylene/vinyl aromatic monomer/vinyl aromatic monomer/ethylene
tetrad will give rise to similar carbon-13 NMR peaks but with
slightly different chemical shifts.
[0039] These interpolymers are prepared by conducting the
polymerization at temperatures of from about -30.degree. C. to
about 250.degree. C. in the presence of such catalysts as those
represented by the formula 7
[0040] wherein: each Cp is independently, each occurrence, a
substituted cyclopentadienyl group .pi.-bound to M; E is C or Si; M
is a group IV metal, preferably Zr or Hf, most preferably Zr; each
R" is independently, each occurrence, H, hydrocarbyl,
silahydrocarbyl, or hydrocarbylsilyl, containing up to 30
preferably from 1 to 20 more preferably from 1 to 10 carbon or
silicon atoms; each R' is independently, each occurrence, H, halo,
hydrocarbyl, hyrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl
containing up to 30 preferably from 1 to 20 more preferably from 1
to 10 carbon or silicon atoms or two R' groups together can be a
C.sub.1-20 hydrocarbyl mono- or poly-substituted 1,3-diene; m is 1
or 2; and optionally, but preferably in the presence of an
activating cocatalyst. Particularly suitable substituted
cyclopentadienyl groups include those illustrated by the formula:
8
[0041] wherein each R in the formula is independently, each
occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl,
containing up to 30 preferably from 1 to 20 more preferably from 1
to 10 carbon or silicon atoms or two R groups together form a
divalent derivative of such group. Preferably, R independently each
occurrence is (including where appropriate all isomers) hydrogen,
methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or
silyl or (where appropriate) two such R groups are linked together
forming a fused ring system such as indenyl, fluorenyl,
tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
[0042] Particularly preferred catalysts include, for example,
racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)
zirconium dichloride,
racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zi-
rconium 1,4-diphenyl-1,3-butadiene, racemic
(dimethylsilanediyl)-bis-(2-me- thyl-4-phenylindenyl) zirconium
di-C.sub.1-4 alkyl,
racemic(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)
zirconium di-C.sub.1-4 alkoxide, or any combination thereof.
[0043] It is also possible to use the following titanium-based
constrained geometry catalysts,
[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-.et-
a.)-1,5,6,7-tetrahydro-s-indacen-1-yl]silanaminato(2-)-N]titanium
dimethyl; (1-indenyl)(tert-butylamido)dimethyl-silane titanium
dimethyl;
((3-tert-butyl)(1,2,3,4,5-.eta.)-1-indenyl)(tert-butylamido)
dimethylsilane titanium dimethyl; and
((3-iso-propyl)(1,2,3,4,5-.eta.)-1-- indenyl)(tert-butyl
amido)dimethylsilane titanium dimethyl, or any suitable combination
thereof.
[0044] Further preparative methods for the interpolymer have been
described in the literature. Longo and Grassi (Makromol. Chem.,
191:2387-2396, 1990), and D'Anniello et al. (Journal of Applied
Polymer Science, 58:1701-1706, 1995) reported the use of a
catalytic system based on methylalumoxane (MAO) and
cyclopentadienyltitanium trichloride (CpTiCl.sub.3) to prepare an
ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am.
Chem. Soc., Div. Polym. Chem.), Vol. 35, pp. 686, 687, 1994, have
reported copolymerization using a MgCl.sub.2/TiCl.sub.4/N-
dCl.sub.3/Al(iBu).sub.3 catalyst to give random copolymers of
styrene and propylene. Lu et al. (Journal of Applied Polymer
Science, 53:1453-1460, 1994, have described the copolymerization of
ethylene and styrene using a TiCl.sub.4/NdCl.sub.3/ MgCl.sub.2
/Al(Et).sub.3 catalyst. The manufacture of .alpha.-olefin/vinyl
aromatic monomer interpolymers such as propylene/styrene and
butene/styrene are described in U.S. Pat. No. 5,244,996, issued to
Mitsui Petrochemical Industries Ltd or U.S. Pat. No. 5,652,315 also
issued to Mitsui Petrochemical Industries Ltd or as disclosed in DE
197 11 339 A1 to Denki Kagaku Kogyo KK, the contents of all of
which are herein incorporated by reference.
[0045] The random copolymers of ethylene and styrene as disclosed
in Polymer Preprints Vol 39, No. 1, March 1998 by Toru Aria et al.
may also be employed as starting materials for the functionalized
interpolymers of the present invention.
[0046] Once the .alpha.-olefin/vinyl aromatic monomer interpolymer
has been prepared, the present invention involves functionalizing
the interpolymer to prepare a substantially random interpolymer of
the following repeating units in the indicated mole percent (%)
quantities, (wherein the sum of a, b, c, and d is not greater than
100 mole percent); comprising
[0047] (a) from 0 to about 64.95, preferably from 0 to about 55,
more preferably from 0 to about 50 mole percent of repeating units
represented by the following formula (I): 9
[0048] wherein Y is independently selected from the group
consisting of hydrogen, substituted and unsubstituted alkyl
radicals, benzyl radicals, aryl radicals, and aralkyl radicals
containing up to 18 carbon atoms, --X, --CH.sub.2X, --C(O)R.sup.6,
--(Z)--CO.sub.2H, --(Z)--SO.sub.3H, --NO.sub.2, --C(O)OR.sup.6,
--(Z)--OR.sup.6, --N(R.sup.6).sub.2, --(Z)--N(R.sup.6).sub.2,
--P(OR.sup.6).sub.2, --(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(.sup.6).sub.2, --(Z)--C(O)N(.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof; R.sup.1 is selected from the group of radicals
consisting of hydrogen and alkyl radicals containing from about 1
to about 4 carbon atoms; R.sup.2 is independently selected from the
group of radicals consisting of hydrogen and alkyl radicals
containing from about 1 to about 4 carbon atoms; R.sup.6 is
independently selected from the group of radicals consisting of
hydrogen, substituted or unsubstituted alkyl radicals containing
from about 1 to about 18 carbon atoms, and substituted or
unsubstituted aryl radicals; X is a halogen; and Z is alkylene or
arylene; and n has a value from zero to about 4; R.sup.1 is
selected from the group of radicals consisting of hydrogen and
alkyl radicals containing from about 1 to about 4 carbon atoms,
preferably hydrogen or methyl, most preferably hydrogen; R.sup.2 is
independently selected from the group of radicals consisting of
hydrogen and alkyl radicals containing from about 1 to about 4
carbon atoms, preferably hydrogen or methyl, most preferably
hydrogen; R.sup.6 is independently selected from the group of
radicals consisting of hydrogen, substituted or unsubstituted alkyl
radicals containing from about 1 to about 18 carbon atoms, and
substituted or unsubstituted aryl radicals, preferably hydrogen or
phenyl or substituted or unsubstituted alkyl radicals containing
from about 1 to about 12 carbon atoms, most preferably hydrogen or
phenyl or substituted or unsubstituted alkyl radicals containing
from about 1 to about 6 carbon atoms; X is a halogen, preferably
chlorine; and Z is arylene or a C.sub.1 to C.sub.4 alkylene,
preferably phenylene, or methylene;
[0049] (b) from about 0.05 to about 65, preferably from about 0.1
to about 55, more preferably from about 0.5 to about 50 mole
percent of repeating units represented by the following formula
(II); 10
[0050] wherein Y, R.sup.1, R.sup.2, n, and X are as described for I
with the proviso that at least one Y is not hydrogen;
[0051] (c) from 0 to about 25, preferably from 0 to about 15, more
preferably from 0 to about 5 mole percent of repeating units
represented by the following formula (III); 11
[0052] wherein R.sup.1 and R.sup.2 are as described for I and
A.sup.1 is a sterically bulky, aliphatic or cycloaliphatic
substituent of up to about 20 carbons or R.sup.2 and A.sup.1
together form a ring system wherein the ring system formed by
A.sup.1 and R.sup.2 is optionally substituted with one or more
substituents selected from substituted and unsubstituted alkyl
radicals benzyl radicals, aryl radicals, and aralkyl radicals
containing up to about 18 carbon atoms, --X, --CH.sub.2X,
--C(O)R.sup.6, --(Z)--CO.sub.2H, --(Z)--SO.sub.3H, --NO.sub.2,
--C(O)OR.sup.6, --(Z)--OR.sup.6 ).sub.2, --(Z)--N(R.sup.6N).sub.2,
--P(OR.sup.6).sub.2, --(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.- 2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof; wherein R.sup.6, X, and Z are as defined above
for I; and
[0053] (d) from 35 to 99.95 mole percent of repeating units
represented by the following formula (IV); 12
[0054] wherein R.sup.3 and R.sup.4 are selected from the group
consisting of hydrogen and alkyl radicals having from 1 to 18
carbon atoms, with the proviso that R.sup.3 and R.sup.4 are
different alkyl radicals.
[0055] The terms "ester", "ether", "amine", "amide", for example
include both substituted and unsubstituted alkyl and aryl
derivatives thereof.
[0056] The functionalized, that is, transformed, interpolymers
described above may be prepared in a number of different ways
depending upon the interpolymer starting material and the number
and type of functional groups to be added. Some functional groups
may be added directly to the interpolymer by, for example, a
Friedel-Crafts reaction or other electrophilic substitution
reaction. Such functional groups include, for example,
unsubstituted or substituted alkylcarbonyl, arylcarbonyl, and
aralkyl groups; carboxylic acid or sulfonic acid groups or alkyl
groups substituted with carboxylic acid or sulfonic acid groups;
halogen, and NO.sub.2, which can subsequently be transformed to
NH.sub.2. Preferably such groups include acyl such as substituted
or unsubstituted phenylcarbonyl, carboxyalkylcarbonyl, and
substituted or unsubstituted carboxybenzyl. Particularly preferred
groups include --C(O)Me which can be further functionalized to, for
example, --CO.sub.2H; --C(O)--pC.sub.6H.sub.4--Me which in turn can
be further functionalized to, for example,
--CH(OH)--pC.sub.6H.sub.4--Me;, for example,
--CH(R.sup.5)CH.sub.2CH.sub.2CO.sub.2H;
--CH(R.sup.5)CH.sub.2CH.sub.2SO.s- ub.3H; and
--CH(R.sup.5)--pC.sub.6H.sub.4--CO.sub.2H, wherein R.sup.5 is
independantly selected from hydrogen or an alkyl group; and
--C(O)CH.sub.2CH.sub.2CO.sub.2H. The functional groups containing
acid groups can be converted to ionomeric salts, such as zinc
ionomers by neutralization. The electrophilic substitution
reactions which have been discovered to be advantageously useful
for the substantially random polymers described above may be
conducted as described in G. A. Olah, Friedel-Crafts and Related
Reactions, Vol. II, Part 2, J. Wiley & Sons, N.Y., 1964.
[0057] While many of the earlier described substituents may be
placed directly on the interpolymer by an electrophilic
substitution reaction, other substituents are not amenable to this
strategy. For this reason it is often advantageous to first
halomethylate the interpolymer and then transform the halomethyl
group into other substituents by suitable reactions, such as
nucleophilic substitution.
[0058] Such halomethylation typically employs the dissolution of
the interpolymer in a suitable solvent to perform halomethylation.
Generally, a suitable solvent is a compound which will not
significantly react with any component in the reaction mixture.
Preferably, the solvent is a liquid and remains a liquid at the
conditions employed in the reaction. While different types of
solvents may be used, preferred solvents include, for example,
chlorinated hydrocarbons such as 1,2-dichloroethane,
trichloromethane, methylene chloride, as well as, mixtures thereof.
Often, the halomethyl ether reactant itself may be used in excess
as a solvent.
[0059] Once dissolved, the interpolymer is then reacted with a
halomethyl ether having the following structure:
X--CH.sub.2--O--R.sup.4
[0060] wherein X represents a halogen and R.sup.4 represents an
inert group.
[0061] X is preferably chloro, bromo, fluoro, or iodo. More
preferably X is chloro or bromo. Most preferably X is chloro.
[0062] The R.sup.4 group is not particularly critical so long as
the halomethyl ether is capable of reacting with the interpolymer
to form a halomethylated interpolymer. Thus, R.sup.4 is an inert
group with respect to the reactants and reaction conditions
employed. Typically, R.sup.4 is a group selected from substituted
or unsubstituted hydrocarbyl. Preferably R.sup.4 is an alkyl group.
More preferably R.sup.4 is an alkyl group having from one to 20
carbon atoms. Most preferably R.sup.4 is an alkyl group having from
one to six carbon atoms such as, for example, methyl or ethyl.
[0063] The specific halomethyl ether which is employed in the
halomethylation reaction is generally selected based upon the
halomethylated interpolymer which is desired. For example, if a
chloromethylated interpolymer is desired then a chloromethyl ether
is employed. Similarly, if a bromomethylated interpolymer is
desired then a bromomethyl ether is employed. Preferred halomethyl
ethers include halomethyl alkyl ethers such as chloromethyl alkyl
ethers and bromomethyl alkyl ethers, for example, chloromethyl
methyl ether, chloromethyl ethyl ether, bromomethyl methyl ether,
bromomethyl ethyl ether.
[0064] The halomethyl ether is preferably mixed with the dissolved
interpolymer. However, as one skilled in the art will appreciate,
the halomethyl ether may also first be dissolved in a suitable
solvent and then the interpolymer may be dissolved in the same or a
different solvent. Additionally, the halomethyl ether may be formed
in situ.
[0065] The amount of halomethyl ether employed varies depending
upon such factors as the type of interpolymer, the desired degree
of halomethylation and the reaction conditions employed. Typically,
the higher the desired degree of halomethylation then the more
halomethyl-ether which is required.
[0066] The degree of halomethylation may be defined as the mole
percent of halomethylation per mole of polymer repeat unit
containing an aromatic group. In the case of ethylene-styrene
interpolymer for example, the degree of halomethylation is the mole
percent of phenyl rings which have a halomethyl group attached. For
ethylene-styrene interpolymers the mole percent may be from at
least 1, preferably at least 5 to 80 percent or even as much as 100
or 200 percent. As one skilled in the art will appreciate if the
degree of halomethylation is above 100 percent then some aromatic
groups will have more than one halomethyl group substitutuent.
[0067] Generally, the para position of the phenyl ring is most
active and the meta position is the least active. Thus, halomethyl
substitution first occurs predominantly at the para position of the
ethylene-styrene interpolymer and then at the ortho position. Both
the degree of halomethylation and the position of substitution may
be readily determined by NMR spectroscopy.
[0068] The interpolymer is preferably reacted with the halomethyl
ether in the presence of a catalytic amount of a suitable catalyst.
A suitable catalyst is a compound which is effective in catalyzing
chloromethylation as described in, for example, G. A. Olah,
Friedel-Crafts and Related Reactions, Vol. II, Part 2, p. 659, J.
Wiley & Sons, N.Y., 1964. Preferably, such catalysts include
mild Lewis acid catalysts such as tin tetrachloride, zinc chloride,
and titanium tetrachloride.
[0069] The specific catalyst employed is not critical so long as
the catalyst has the appropriate activity. As one skilled in the
art will appreciate, the higher the desired degree of
halomethylation then the more active a catalyst which may be
necessary. In some circumstances the catalyst may be so active that
crosslinking and/or gellation of the interpolymer may occur. If
crosslinking is not desired then a moderating agent may be added in
a sufficient amount to weaken the catalyst activity and reduce the
crosslinking. Such moderating agents are compounds such as, for
example, ethers. Thus, ethers such as alkyl ethers, aromatic ethers
and mixtures thereof will often moderate the catalyst activity. A
preferred ether which has shown effectiveness as a moderating agent
is diethyl ether.
[0070] The amount of catalyst added will vary depending upon such
factors as the particular catalyst employed, the type and amount of
interpolymer and halomethyl ether being reacted, as well as, the
desired degree of halomethylation. In general, however, the molar
ratio of halomethyl ether to catalyst often determines the degree
of halomethylation, as well as, the amount of crosslinking which
occurs. Therefore, for most applications the molar ratio of
halomethyl ether to catalyst is usually at least 5, preferably at
least 10, more preferably at least 20. On the other hand, the molar
ratio of halomethyl ether to catalyst is usually no more than 1000,
preferably no more than 100, more preferably no more than 50.
[0071] The pressure and temperature of the halomethylation reaction
should be regulated such that the reaction proceeds as desired.
Typically, the reaction is carried out at ambient to pressure.
However, other pressures may be employed so long as the reaction is
not hindered.
[0072] Many differerent temperatures may be employed. Typically, if
the temperature is low then the reaction proceeds slowly. On the
other hand, if the temperature is high then the reaction proceeds
more quickly and may even result in crosslinking. In general,
temperatures of at least -50, preferably at least 0, more
preferably at least 10.degree. C. may be employed. Correspondingly,
temperatures of less than 100, preferably less than 50, more
preferably less than 30.degree. C. may be employed.
[0073] The reaction should be allowed to proceed until the desired
degree of halomethylation has been reached. As one skilled in the
art will appreciate, such times will vary depending upon the
desired degree of halomethylation, as well as, the particular
catalyst employed and the reaction conditions. Typically, higher
degrees of halomethylation will require a longer reaction time.
However, generally reaction times may be reduced by employing more
halomethylating agent and/or more active catalysts and/or higher
temperatures. Generally, the reaction time is at least 0.5,
preferably at least 2, more preferably at least 8 hours.
Correspondingly, the reaction time is usually less than 72,
preferably less than 48, more preferably less than 24 hours.
[0074] The halomethylated interpolymer may be recovered by any
suitable means. A particularly advantageous recovery method is to
add a quenching amount of water when the desired degree of
halomethylation has been reached. The water which is added is
preferably at a temperature below that of the reaction and above
the water's freezing point at the pressure employed in the
reaction.
[0075] The actual amount and temperature of the water which is
added is not critical so long as the reaction is quenched and a
readily separable aqueous layer and an organic layer are formed.
The organic layer comprises halomethylated interpolymer and
solvent. The two layers may be separated and the halomethylated
interpolymer may then be isolated from the organic layer and dried.
While the isolation may be accomplished by any suitable means, a
convenient means of isolation is precipitation.
[0076] The properties of the halomethylated resins usually differ
widely depending upon the type of halogen, the type of
interpolymer, and the extent of halomethylation. Generally,
chloromethylation appears to have little effect on the glass
transition temperature and the thermal stability of
ethylene-styrene interpolymer. For example, the glass transition
temperature of ethylene styrene copolymer containing 70 weight
percent styrene increases from 26.5.degree. C. to 29.degree. C.
when 44 mole percent of the phenyl groups are chloromethylated and
the thermal stability appears comparable to that of the parent
interpolymer.
[0077] Once the interpolymer has been halomethylated, the
halomethyl groups may be transformed to other functional groups if
desired. The transformation may occur in solution or in an
interpolymer melt in, for example, an extruder. Numerous
transformations are possible. For example, the halomethyl group can
be used for simple crosslinking (by reaction with a Lewis acid, a
dinucleophile or water or induced by radiation), reactive
compatibilization with other polymers, or for introduction of a
plethora of other functional groups onto the polymer backbone.
Functional groups to which the halomethyl group can be transformed
include, for example, phosphonium, ammonium, sulfonium, ester,
hydroxyl, ether, amine, phosphine, thiol, cyano, carboxylic acid,
amide, or a functional group derived from reaction with
nucleophiles, and mixtures thereof within the interpolymer. Such
functionalization from halomethyl groups has been described in, for
example, U.S. Pat. No. 5,162,445; P. Hodge, "Polymers as Chemical
Reagents", Encyclopedia of Polymer Science and Engineering 2nd
Edition, pp. 618-658; and Monthead et al., "Chemical
Transformations of Chloromethylated Polystyrene," IMS-Review
Macromolecular Chemical Physics, 1988, pp. 503-592. Suitable such
methods may be used to form the transformed interpolymers. Some
examples of such functionalization are described below.
[0078] The transformed, that is, functionalized, interpolymers of
the present invention are preferably substantially random
interpolymers comprising repeating units derived from
[0079] (1) monomer units derived from
[0080] (i) at least one vinyl or vinylidene aromatic monomer,
or
[0081] (ii) at least one sterically hindered aliphatic or
cycloaliphatic vinyl or vinylidene monomer;
[0082] (iii) a combination of at least one vinyl or vinylidene
aromatic monomer and at least one sterically hindered aliphatic or
cycloaliphatic vinyl or vinylidene monomer; and
[0083] (2) monomer units derived from
[0084] (i) ethylene, or
[0085] (ii) C.sub.3-20 .alpha.-olefin;
[0086] (iii) or a combination (i) and (ii)
[0087] wherein the aromatic group of one or more of said vinyl or
vinylidene aromatic monomers is substituted subsequent to
interpolymer formation with one or more substituents independently
selected from the group consisting of substituted and unsubstituted
alkyl radicals, benzyl radicals, aryl radicals, and aralkyl
radicals containing up to 18 carbon atoms, --X, --CH.sub.2X,
--C(O)R.sup.6, --(Z)--CO.sub.2H, --(Z)--SO.sub.3H, --NO.sub.2,
--C(O)OR.sup.6, --(Z)--OR.sup.6, --N(R.sup.6).sub.2,
--(Z)--N(R.sup.6).sub.2, --P(OR.sup.6).sub.2,
--(Z)--P(OR.sup.6).sub.2, --P(R.sup.6).sub.2,
--(Z)--P(R.sup.6).sub.2, --P(O)(R.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --P(O)(OR.sup.6).sub.2,
--(Z)--P(O)(R.sup.6).sub.2, --(Z)--SR.sup.6, --CN, --(Z)--CN,
--CO.sub.2H, --C(O)N(R.sup.6).sub.2, --(Z)--C(O)N(R.sup.6).sub.2,
ionomeric salts of --CO.sub.2.sup.-, --(Z)--CO.sub.2.sup.-,
--(Z)--SO.sub.3.sup.-, --N.sup.+(R.sup.6).sub.3,
--(Z)--N.sup.+(R.sup.6).sub.3, --P.sup.+(R.sup.6).sub.3,
--(Z)--P.sup.+(R.sup.6).sub.3, --(Z)--S.sup.+(R.sup.6).sub.2, and
mixtures thereof; where R.sup.1 is selected from the group of
radicals consisting of hydrogen and alkyl radicals containing from
1 to 4 carbon atoms; R.sup.2 is independently selected from the
group of radicals consisting of hydrogen and alkyl radicals
containing from 1 to 4 carbon atoms; R.sup.6 is independently
selected from the group of radicals consisting of hydrogen,
substituted or unsubstituted alkyl radicals containing from 1 to 18
carbon atoms, and substituted or unsubstituted aryl radicals; X is
a halogen; and Z is alkylene or arylene; and n has a value from
zero to 4;
[0088] The phrase "substituted subsequent to interpolymer
formation" as used herein means that an substantially random
interpolymer is first formed and is then reacted to form a
functionalized substantially random interpolymer.
[0089] Preferred functional groups include, for example,
chloromethyl, bromomethyl, trialkyl ammonium such as triethyl
ammonium, alkyl phosphonium, aryl phosphonium such as triphenyl
phosphonium, acetate, hydroxyl, methoxy, phenoxy, cyano,
alkylcarbonyl, arylcarbonyl, and metal ionomers. It is preferred
that when Component (1) is styrene, and Component 2 is ethylene,
Component (1) is not substituted, subsequent to functionalization,
at the para position with a group having a formula
--CF(R.sup.7).sub.2 wherein R.sup.7 is hydrogen or alkyl. It is
also preferred that Component (1) is not a para
C.sub.1-C.sub.4-alkyl styrene when Component (2) is a
C.sub.4-C.sub.7 isoloefin.
[0090] The substantially random functionalized interpolymers and
compositions of the present invention can be utilized as a
component in polymer blends such as a compatabilizer and can be
used to produce a wide range of fabricated articles, including but
not limited to, calendered sheet, blown films, injection molded
parts,. The compositions can also be used in the manufacture of
fibers, foams and lattices. The compositions of the present
invention can also be utilized in adhesive and sealant
formulations. Some properties which might be desirable to modify
include, for example, processing characteristics, glass transition
temperature, modulus, hardness, viscosity, elongation, fire
retardation,use of functionalized polymers in membranes, as
components in bitumen/asphalt modification, in wire and cable, in
flooring/carpet systems, and as tie layers in multilayer film
structures, as coupling agents in filled polymer compositions
(including their use as minor components in ESI and other polymer
compositions. The functionalization can be performed on the resin
itself or on a surface layer of a pre-formed structure comprising
the unfunctionalized substantially random interpolymer which in
turn can have major effects on properties such as for example,
friction, blocking, and adhesion.
[0091] The following examples are illustrative of the invention,
but are not to be construed as limiting the scope of the invention
in any manner.
EXAMPLES
Preparation of Ethylene Styrene Interpolymers (ESI-1, ESI-2 and
ESI-3)
[0092] ESI's-1-3 were substantially random ethylene/styrene
interpolymers prepared using the following catalyst and
polymerization procedures.
[0093] Preparation of Catalyst A
(dimethyl[N-(1,1-dimethylethyl)-1,1-dimet-
hyl-1-[(1,2,3,4,5-.eta.)-1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl]silana-
minato(2-)-N]-titanium)
[0094] 1) Preparation of
3,5,6,7-Tetrahydro-s-Hydrindacen-1(2H)-one
[0095] Indan (94.00 g, 0.7954 moles) and 3-chloropropionyl chloride
(100.99 g, 0.7954 moles) were stirred in CH.sub.2Cl.sub.2 (300 mL)
at 0.degree. C. as AlCl.sub.3 (130.00 g, 0.9750 moles) was added
slowly under a nitrogen flow. The mixture was then allowed to stir
at room temperature for 2 hours. The volatiles were then removed.
The mixture was then cooled to 0.degree. C. and concentrated
H.sub.2SO.sub.4 (500 mL) slowly added. The forming solid had to be
frequently broken up with a spatula as stirring was lost early in
this step. The mixture was then left under nitrogen overnight at
room temperature. The mixture was then heated until the temperature
readings reached 90.degree. C. These conditions were maintained for
a 2 hour period of time during which a spatula was periodically
used to stir the mixture. After the reaction period crushed ice was
placed in the mixture and moved around. The mixture was then
transferred to a beaker and washed intermittently with H.sub.2O and
diethylether and then the fractions filtered and combined. The
mixture was washed with H.sub.2O (2.times.200 mL). The organic
layer was then separated and the volatiles removed. The desired
product was then isolated via recrystallization from hexane at
0.degree. C. as pale yellow crystals (22.36 g, 16.3% yield).
[0096] .sup.1H NMR (CDCl.sub.3): d2.04-2.19 (m, 2 H), 2.65 (t,
.sup.3J.sub.HH=5.7 Hz, 2 H), 2.84-3.0 (m, 4 H), 3.03 (t,
.sup.3J.sub.HH=5.5 Hz, 2 H), 7.26 (s, 1 H), 7.53 (s, 1 H).
[0097] .sup.13C NMR (CDCl.sub.3): d25.71, 26.01, 32.19, 33.24,
36.93, 118.90, 122.16, 135.88, 144.06, 152.89, 154.36, 206.50.
[0098] GC-MS: Calculated for C.sub.12H.sub.12O 172.09, found
172.05.
[0099] 2) Preparation of 1,2,3,5-Tetrahydro-7-phenyl-s-indacen.
[0100] 3,5,6,7-Tetrahydro-s-Hydrindacen-1(2H)-one (12.00 g, 0.06967
moles) was stirred in diethylether (200 mL) at 0.degree. C. as
PhMgBr (0.105 moles, 35.00 mL of 3.0 M solution in diethylether)
was added slowly. This mixture was then allowed to stir overnight
at room temperature. After the reaction period the mixture was
quenched by pouring over ice. The mixture was then acidified (pH=1)
with HCl and stirred vigorously for 2 hours. The organic layer was
then separated and washed with H.sub.2O (2.times.100 mL) and then
dried over MgSO.sub.4. Filtration followed by the removal of the
volatiles resulted in the isolation of the desired product as a
dark oil (14.68 g, 90.3% yield).
[0101] .sup.1H NMR (CDCl.sub.3): d2.0-2.2 (m, 2 H), 2.8-3.1 (m, 4
H), 6.54 (s, 1H), 7.2-7.6 (m, 7 H). GC-MS: Calculated for
C.sub.18H.sub.16 232.13, found 232.05.
[0102] 3) Preparation of 1,2,3,5-Tetrahydro-7-phenyl-s-indacene,
dilithium salt.
[0103] 1,2,3,5-Tetrahydro-7-phenyl-s-indacen (14.68 g, 0.06291
moles) was stirred in hexane (150 mL) as nBuLi (0.080 moles, 40.00
mL of 2.0 M solution in cyclohexane) was slowly added. This mixture
was then allowed to stir overnight. After the reaction period the
solid was collected via suction filtration as a yellow solid which
was washed with hexane, dried under vacuum, and used without
further purification or analysis (12.2075 g, 81.1% yield).
[0104] 4) Preparation of
Chlorodimethyl(1,5,6,7-tetrahydro-3-phenyl-s-inda-
cen-1-yl)silane.
[0105] 1,2,3,5-Tetrahydro-7-phenyl-s-indacene, dilithium salt
(12.2075 g, 0.05102 moles) in THF (50 mL) was added dropwise to a
solution of Me.sub.2SiCl.sub.2 (19.5010 g, 0.1511 moles) in THF
(100 mL) at 0.degree. C. This mixture was then allowed to stir at
room temperature overnight. After the reaction period the volatiles
were removed and the residue extracted and filtered using hexane.
The removal of the hexane resulted in the isolation of the desired
product as a yellow oil (15.1492 g, 91.1% yield).
[0106] .sup.1H NMR (CDCl.sub.3): d0.33 (s, 3 H), 0.38 (s, 3 H),
2.20 (p, .sup.3J.sub.HH=7.5 Hz, 2 H), 2.9-3.1 (m, 4 H), 3.84 (s, 1
H), 6.69 (d, .sup.3J.sub.HH=2.8 Hz, 1 H), 7.3-7.6 (m, 7 H), 7.68
(d, .sup.3J.sub.HH=7.4 Hz, 2 H).
[0107] .sup.13C NMR (CDCl.sub.3): d0.24, 0.38, 26.28, 33.05, 33.18,
46.13, 116.42, 119.71, 127.51, 128.33, 128.64, 129.56, 136.51,
141.31, 141.86, 142.17, 142.41, 144.62.
[0108] GC-MS: Calculated for C.sub.20H.sub.21ClSi 324.11, found
324.05.
[0109] 5) Preparation of
N-(1,1-Dimethylethyl)-1,1-dimethyl-1-(1,5,6,7-tet-
rahydro-3-phenyl-s-indacen-1-yl)silanamine.
[0110]
Chlorodimethyl(1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl)silane
(10.8277 g, 0.03322 moles) was stirred in hexane (150 mL) as
NEt.sub.3 (3.5123 g, 0.03471 moles) and t-butylamine-(2.6074 g,
0.03565 moles) were added. This mixture was allowed to stir for 24
hours. After the reaction period the mixture was filtered and the
volatiles removed resulting in the isolation of the desired product
as a thick red-yellow oil (10.6551 g, 88.7% yield).
[0111] .sup.1H NMR (CDCl.sub.3): d0.02 (s, 3 H), 0.04 (s, 3 H),
1.27 (s, 9 H), 2.16 (p, .sup.3J.sub.HH=7.2 Hz, 2 H), 2.9-3.0 (m, 4
H), 3.68 (s, 1 H), 6.69 (s, 1 H), 7.3-7.5 (m, 4 H), 7.63 (d,
.sup.3J.sub.HH=7.4 Hz, 2 H). .sup.13C NMR (CDCl.sub.3): d-0.32,
-0.09, 26.28, 33.39, 34.11, 46.46, 47.54, 49.81, 115.80, 119.30,
126.92, 127.89, 128.46, 132.99, 137.30, 140.20, 140.81, 141.64,
142.08, 144.83.
[0112] 6) Preparation of
N-(1,1-Dimethylethyl)-1,1-dimethyl-1-(1,5,6,7-tet-
rahydro-3-phenyl-s-indacen-1-yl) silanamine, dilithium salt.
[0113]
N-(1,1-Dimethylethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydro-3-phenyl-s-
-indacen-1-yl)silanamine (10.6551 g, 0.02947 moles) was stirred in
hexane (100 mL) as nBuLi (0.070 moles, 35.00 mL of 2.0 M solution
in cyclohexane) was added slowly. This mixture was then allowed to
stir overnight during which time no salts crashed out of the dark
red solution. After the reaction period the volatiles were removed
and the residue quickly washed with hexane (2.times.50 mL). The
dark red residue was then pumped dry and used without further
purification or analysis (9.6517 g, 87.7% yield).
[0114] 7) Preparation of
Dichloro[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1-
,2,3,4,5-.eta.)-1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl]silanaminato(2--
)-N]titanium
[0115]
N-(1,1-Dimethylethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydro-3-phenyl-s-
-indacen-1-yl)silanamine, dilithium salt (4.5355 g, 0.01214 moles)
in THF (50 mL) was added dropwise to a slurry of
TiCl.sub.3(THF).sub.3 (4.5005 g, 0.01214 moles) in THF (100 mL).
This mixture was allowed to stir for 2 hours. PbCl.sub.2 (1.7136 g,
0.006162 moles) was then added and the mixture allowed to stir for
an additional hour. After the reaction period the volatiles were
removed and the residue extracted and filtered using toluene.
Removal of the toluene resulted in the isolation of a dark residue.
This residue was then slurried in hexane and cooled to 0.degree. C.
The desired product was then isolated via filtration as a red-brown
crystalline solid (2.5280 g, 43.5% yield).
[0116] .sup.1H NMR (CDCl.sub.3): d0.71 (s, 3,H), 0.97 (s, 3 H),
1.37 (s, 9 H), 2.0-2.2 (m, 2 H), 2.9-3.2 (m, 4 H), 6.62 (s, 1 H),
7.35-7.45 (m, 1 H), 7.50 (t, .sup.3J.sub.HH=7.8 Hz, 2 H), 7.57 (s,
1 H), 7.70 (d, .sup.3J.sub.HH=7.1 Hz, 2 H), 7.78 (s, 1 H). .sup.1H
NMR (C.sub.6D.sub.6): d0.44 (s, 3 H), 0.68 (s, 3 H), 1.35 (s, 9 H),
1.6-1.9 (m, 2 H), 2.5-3.9 (m, 4 H), 6.65 (s, 1 H), 7.1-7.2 (m, 1
H), 7.24 (t, .sup.3J.sub.HH=7.1 Hz, 2 H), 7.61 (s, 1 H), 7.69 (s, 1
H), 7.77-7.8 (m, 2 H). .sup.13C NMR (CDCl.sub.3): d1.29, 3.89,
26.47, 32.62, 32.84, 32.92, 63.16, 98.25, 118.70, 121.75, 125.62,
128.46, 128.55, 128.79, 129.01, 134.11, 134.53, 136.04, 146.15,
148.93.
[0117] .sup.13C NMR (C.sub.6D.sub.6): d0.90, 3.57, 26.46, 32.56,
32.78, 62.88, 98.14, 119.19, 121.97, 125.84, 127.15, 128.83,
129.03, 129.55, 134.57, 135.04, 136.41, 136.51, 147.24, 148.96.
[0118] 8) Preparation of
Dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1-
,2,3,4,5-.eta.)-1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl]silanaminato(2--
)-N]titanium
[0119]
Dichloro[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-.eta.)-1,-
5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl]silanaminato(2-)-N]titanium
(0.4970 g, 0.001039 moles) was stirred in diethylether (50 mL) as
MeMgBr (0.0021 moles, 0.70 mL of 3.0 M solution in diethylether)
was added slowly. This mixture was then stirred for 1 hour. After
the reaction period the volatiles were removed and the residue
extracted and filtered using hexane. Removal of the hexane resulted
in the isolation of the desired product as a golden yellow solid
(0.4546 g, 66.7% yield).
[0120] .sup.1H NMR (C.sub.6D.sub.6): d0.071 (s, 3 H), 0.49 (s, 3
H), 0.70 (s, 3 H), 0.73 (s, 3 H), 1.49 (s, 9 H), 1.7-1.8 (m, 2 H),
2.5-2.8 (m, 4 H), 6.41 (s, 1 H), 7.29 (t, .sup.3J.sub.HH=7.4 Hz, 2
H), 7.48 (s, 1 H), 7.72 (d, .sup.3J.sub.HH=7.4 Hz, 2 H), 7.92 (s, 1
H). .sup.13C NMR (C.sub.6D.sub.6): d2.19, 4.61, 27.12, 32.86,
33.00, 34.73, 58.68, 58.82, 118.62, 121.98, 124.26, 127.32, 128.63,
128.98, 131.23, 134.39, 136.38, 143.19, 144.85.
[0121] Preparation of Cocatalyst E,
(Bis(hydrogenated-tallowalkyl)methylam- ine
[0122] Methylcyclohexane (1200 mL) was placed in a 2 L cylindrical
flask. While stirring, bis(hydrogenated-tallowalkyl)methylamine
(ARMEEN.RTM. M2HT, 104 g, ground to a granular form) was added to
the flask and stirred until completely dissolved. Aqueous HCl (1M,
200 mL) was added to the flask, and the mixture was stirred for 30
minutes. A white precipitate formed immediately. At the end of this
time, LiB(C.sub.6F.sub.5).sub.4.Et.sub.2O.3 LiCl (Mw=887.3; 177.4
g) was added to the flask. The solution began to turn milky white.
The flask was equipped with a 6" Vigreux column topped with a
distillation apparatus and the mixture was heated (140.degree. C.
external wall temperature). A mixture of ether and
methylcyclohexane was distilled from the flask. The two-phase
solution was now only slightly hazy. The mixture was allowed to
cool to room temperature, and the contents were placed in a 4 L
separatory funnel. The aqueous layer was removed and discarded, and
the organic layer was washed twice with H.sub.2O and the aqueous
layers again discarded. The H.sub.2O saturated methylcyclohexane
solutions were measured to contain 0.48 wt percent diethyl ether
(Et.sub.2O).
[0123] The solution (600 mL) was transferred into a 1 L flask,
sparged thoroughly with nitrogen, and transferred into the drybox.
The solution was passed through a column (1" diameter, 6" height)
containing 13.times. molecular sieves. This reduced the level of
Et.sub.2O from 0.48 wt percent to 0.28 wt percent. The material was
then stirred over fresh 13.times. sieves (20 g) for four hours. The
Et.sub.2O level was then measured to be 0.19 wt percent. The
mixture was then stirred overnight, resulting in a further
reduction in Et.sub.2O level to approximately 40 ppm. The mixture
was filtered using a funnel equipped with a glass frit having a
pore size of 10-15 .mu.m to give a clear solution (the molecular
sieves were rinsed with additional dry methylcyclohexane). The
concentration was measured by gravimetric analysis yielding a value
of 16.7 wt percent.
POLYMERIZATION
[0124] ESI-1 was prepared in a 6 gallon (22.7 L), oil jacketed,
Autoclave continuously stirred tank reactor (CSTR). A magnetically
coupled agitator with Lightning A-320 impellers provided the
mixing. The reactor ran liquid full at 475 psig (3,275 kPa).
Process flow was in at the bottom and out of the top. A heat
transfer oil was circulated through the jacket of the reactor to
remove some of the heat of reaction. At the exit of the reactor was
a micromotion flow meter that measured flow and solution density.
All lines on the exit of the reactor were traced with 50 psi (344.7
kPa) steam and insulated.
[0125] Toluene solvent was supplied to the reactor at 30 psig (207
kPa). The feed to the reactor was measured by a Micro-Motion mass
flow meter. A variable speed diaphragm pump controlled the feed
rate. At the discharge of the solvent pump, a side stream was taken
to provide flush flows for the catalyst injection line (1 lb/hr
(0.45 kg/hr)) and the reactor agitator (0.75 lb/hr (0.34 kg/hr)).
These flows were measured by differential pressure flow meters and
controlled by manual adjustment of micro-flow needle valves.
[0126] Uninhibited styrene monomer was supplied to the reactor at
30 psig (207 kpa). The feed to the reactor was measured by a
Micro-Motion mass flow meter. A variable speed diaphragm pump
controlled the feed rate. The styrene stream was mixed with the
remaining solvent stream. Ethylene was supplied to the reactor at
600 psig (4,137 kPa). The ethylene stream was measured by a
Micro-Motion mass flow meter just prior to the Research valve
controlling flow. A Brooks flow meter/controller was used to
deliver hydrogen into the ethylene stream at the outlet of the
ethylene control valve. The ethylene/hydrogen mixture combines with
the solvent/styrene stream at ambient temperature. The temperature
of the solvent/monomer as it enters the reactor was dropped to
.about.5.degree. C. by an exchanger with -5.degree. C. glycol on
the jacket. This stream entered the bottom of the reactor. The
three component catalyst system and its solvent flush also entered
the reactor at the bottom but through a different port than the
monomer stream. Preparation of the catalyst components took place
in an inert atmosphere glove box. The diluted components were put
in nitrogen padded cylinders and charged to the catalyst run tanks
in the process area. From these run tanks the catalyst was
pressured up with piston pumps and the flow was measured with
Micro-Motion mass flow meters. These streams combine with each
other and the catalyst flush solvent just prior to entry through a
single injection line into the reactor.
[0127] Polymerization was stopped with the addition of catalyst
kill (water mixed with solvent) into the reactor product line after
the micromotion flow meter measuring the solution density. Other
polymer additives can be added with the catalyst kill. A static
mixer in the line provided dispersion of the catalyst kill and
additives in the reactor effluent stream. This stream next entered
post reactor heaters that provide additional energy for the solvent
removal flash. This flash occurred as the effluent exited the post
reactor heater and the pressure was dropped from 475 psig (3,275
kPa) down to .about.250 mm of pressure absolute at the reactor
pressure control valve. This flashed polymer entered a hot oil
jacketed devolatilizer. Approximately 85 percent of the volatiles
were removed from the polymer in the devolatilizer. The volatiles
exited the top of the devolatilizer. The stream was condensed with
a glycol jacketed exchanger and entered the suction of a vacuum
pump and was discharged to a glycol jacket solvent and
styrene/ethylene separation vessel. Solvent and styrene were
removed from the bottom of the vessel and ethylene from the top.
The ethylene stream was measured with a Micro-Motion mass flow
meter and analyzed for composition. The measurement of vented
ethylene plus a calculation of the dissolved gasses in the
solvent/styrene stream were used to calculate the ethylene
conversion. The polymer separated in the devolatilizer was pumped
out with a gear pump to a ZSK-30 devolatilizing vacuum extruder.
The dry polymer exits the extruder as a single strand. This strand
was cooled as it was pulled through a water bath. The excess water
was blown from the strand with air and the strand was chopped into
pellets with a strand chopper.
[0128] The various catalysts, co-catalysts and process conditions
used to prepare the ethylene styrene interpolymer are summarized in
Table 1 and its properties are summarized in Table 2.
1TABLE 1 PREPARATION CONDITIONS FOR ESI #'s 1-3 Solvent Ethylene
Styrene Reactor Flow Flow Hydrogen Flow Ethylene Temp lb/hr lb/hr
Flow lb/hr Conversion B/Ti MMAO.sup.e/Ti Co- ESI # .degree.C.
(kg/hr) (kg/hr) sccm.sup.f (kg/hr) % Ratio Ratio Catalyst Catalyst
ESI-1 78.4 40.99 2.17 3.5 21.0 96.42 3.5 6.0 A.sup.a C.sup.c
(18.59) (0.98) (9.52) ESI-2 101.8 19.20 1.99 4.0 7.0 87.38 1.25
10.0 B.sup.b D.sup.d (8.71) (0.90) (3.16) ESI-3 80.2 18.57 1.71
12.0 12.0 88.93 1.25 10.0 A.sup.a D.sup.d (8.42) (0.77) (5.42) a
Catalyst A is dimethyl[N-(1,1-dimethylethyl)-1,1-dimethy-
l-1-[(1,2,3,4,5-.eta.)-1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl]silanami-
nato(2-)-N]-titanium. b Catalyst B is (t-butylamido)dimethyl(tetra-
methylcyclopentadienyl)silane-titanium (II) 1,3-pentadiene prepared
as described in U.S. Pat. No. 5,556,928, Example 17 c Cocatalyst C
is tris(pentafluorophenyl)borane, (CAS#001109-15-5),. d Cocatalyst
D is bis-hydrogenated tallowalkyl methylammonium tetrakis
(pentafluorophenyl)borate. e a modified methylaluminoxane available
from Akzo Nobel as MMAO-3A (CAS#146905-79-5) f SCCM is standard
cm.sup.3/min
[0129]
2TABLE 2 PROPERTIES OF ESI #'s 1-3 Styrene.sup.a Styrene.sup.a
Atactic Polystyrene.sup.b Melt Index, I.sub.2 ESI # (wt %) (mol %)
(wt %) (g/10 min) ESI-1 70.0 38.6 3 1.26 ESI-2 35.0 12.7 6.0 --
ESI-3 58.0 27.1 3.0 1.0 a. the amount of styrene in the copolymer.
b. Based on the copolymer plus the atactic polystyrene content
APPARATUSES
[0130] Proton (300 MHz) and Carbon (75 MHz) nuclear magnetic
resonance (NMR) spectra were run in deuterochloroform and
referenced to tetramethylsilane (0 ppm). The NMR instrument was a
Varian Inova. Differential Scanning Calorimetry (DSC) was performed
on a Dupont DSC 2910 scanning at 10.degree. C./min. The glass
transition temperatures reported are the inflections of the step
transitions. Inherent viscosities were measured with a Schott
Gerate Capillary Viscometer in chloroform at 25.degree. C. at
concentration of 0.5 g/dL.
NMR ANALYSIS
[0131] The chloromethylated polymer (100 mg) was dissolved in 2 g
of CDCl.sub.3 and then placed in a 5 mm diameter NMR tube. Standard
proton and carbon spectra were then run. The extent of
chloromethylation was calculated from the integrated proton NMR
spectrum. The integral of the benzylic methylene hydrogens of the
chloromethyl group (4.53 ppm) and the integral of the total
aromatic region (6.6-7.6 ppm) were used in the calculation. The
calculation was performed as follows:
[0132] Let i'=number of chloromethylated phenyl groups
[0133] Let i=number of unsubstituted phenyl groups
[0134] Then, 2i'=integral of methylene hydrogens of chloromethyl
group and 5i+4i'=total integral of aromatic region, and
[0135] i'/(i'+i)=mole fraction of phenyl groups
chloromethylated=z.
[0136] For the purposes of this application, the mol % of total
functionalized repeating units, "x", was determined from the mole
fraction of phenyl groups functionalized, "z", using the following
equation:
x=100 z a/c
[0137] where;
[0138] "z" is the mole fraction of phenyl groups functionalized (as
determined by NMR);
[0139] "a" is the no. of moles of styrene repeat units in 100 g of
the starting interpolymer as calculated by a=100 y/104.15 (where y
is the wt fraction of styrene repeat units in the starting
interpolymer and 104.15 is the molecular weight of styrene.);
[0140] "b" is the no. of moles of ethylene repeat units in 100 g of
the starting interpolymer as calculated by b=100 (1-y)/28.05 (where
y is the wt fraction of styrene repeat units in the starting
interpolymer and 28.05 is the molecular weight of ethylene.)
and
[0141] "c"=a+b
[0142] The ESI samples contained no talc, calcium stearate or any
other additive or stabilizer. ESI-1 had a melt index (MI) of 1.26
g/10 minutes at 190.degree. C. under a 2.1 kg load and an inherent
viscosity of 1.16 dL/g in CHCl.sub.3 at a concentration of 0.5 g/dL
and a temperature of 25.degree. C. The glass transition temperature
of ESI-1 was 26.5.degree. C. (inflection of the step transition,
scan rate=10.degree. C./minute).
Example 1
Chloromethylation of ESI-1
[0143] A 1 L 3 neck flask equipped with mechanical stirrer, water
condenser, and nitrogen inlet was charged with 62.5 g (0.42 mols
styrene repeat units) of ESI-1 and 500 mL of methylene chloride.
After complete dissolution of the interpolymer (.about.3 hrs), 2.25
mL (2.25 mmol) of a 1 molar solution of zinc chloride in diethyl
ether was added to the flask and the reaction mixture became hazy.
Next, 5.0 g (52.9 mmol) of chloromethyl ethyl ether was added all
at once. The reaction mixture cleared and took on a light yellow
color. The reaction was stirred at ambient temperature for 30 hours
and then 200 mL of water was added to quench the reaction mixture.
After stirring vigorously for 5 minutes the contents of the flask
were transferred to a separatory funnel and the layers allowed to
separate (.about.2 hrs). The methylene chloride layer containing
the interpolymer was then passed through a column (radius=3.6 cm)
containing 300 mL of MSC-1H strong acid ion exchange beads to
remove the last traces of zinc and water. The chloromethylated
interpolymer was precipitated into 4 L of 50/50 v/v
acetone/methanol in explosion proof Waring blender and then
collected by filtration and dried in a vacuum oven. The final yield
of chloromethylated interpolymer was 49.6 g. Analysis of the sample
by proton to NMR (CDCl.sub.3) revealed a new peak at 4.53 (relative
to tetramethylsilane) due to the chloromethyl group. Integration of
the proton NMR spectrum showed that 1.6% of the phenyl groups bear
the chloromethyl group corresponding to 0.62 mol % of
functionalized repeating units. The dilute solution viscosity of
the interpolymer in chloroform (.about.0.5 g/dL, 25.degree. C.) was
1.26 dL/g.
Example 2
Chloromethylation of ESI-1
[0144] A 2 L, 4 neck flask equipped with mechanical stirrer, water
condenser, and nitrogen inlet was charged with 125 g (0.84 mol
styrene) of ESI-1 interpolymer and 1 L of methylene chloride. After
complete dissolution of the interpolymer (.about.3 hrs), 4.5 mL
(4.5 mmol) of a 1 molar solution of zinc chloride in diethyl ether
was added to the flask. The reaction mixture became hazy upon
addition of the catalyst solution. Next, 10.0 g (0.106 mol) of
chloromethyl ethyl ether was added all at once. The reaction
mixture cleared and took on a light yellow color. The reaction was
stirred at ambient temperature for 30 hours and then 400 mL of
water was added to quench the reaction. After stirring vigorously
for 5 minutes the contents of the flask were transferred to a
separatory funnel and the layers allowed to separate (.about.2
hrs). The methylene chloride layer containing the interpolymer was
then passed through a column (radius=3.6 cm) containing 200 mL of
Dowex MSC-1H.TM. strong acid ion exchange resin to remove the last
traces of zinc and water (the ion exchange resin was rinsed with
water, tetrahydrofuran, and finally methylene chloride prior to
use). The chloromethylated interpolymer solution was divided into
approximately two equal portions and each portion was precipitated
into 3.2 L of 50/50, v/v, acetone/methanol in an explosion proof
Waring.TM. blender and then collected by filtration on a glass
fritted funnel. The white interpolymer was rinsed with methanol,
air dried on the funnel and then dried in a vacuum oven at
30.degree. C. The final isolated yield of interpolymer was 115.3 g.
Analysis of the sample by proton NMR (CDCl.sub.3) revealed a new
peak at 4.53 ppm (relative to tetramethylsilane) due to the
chloromethyl group. Integration of the proton NMR spectrum showed
that 2.1 mole percent of the phenyl groups bear the chloromethyl
group corresponding to 0.81 mol % of functionalized repeating
units. This level of chloromethylation corresponds to 0.14 mmol of
CH.sub.2Cl groups/g of interpolymer. The dilute solution viscosity
of the chloromethylated interpolymer in chloroform (.about.0.5
g/dL, 25.degree. C.) was 1.26 dL/g and it had a glass transition
temperature of 23.0.degree. C.
Example 3
Bromethylation of ESI-1
[0145] A 120 mL wide mouth bottle was charged with 6.25 g (42 mmol
of styrene) of ESI-1, 50 mL of methylene chloride. The bottle was
capped with a teflon lined lid and placed on a shaker overnight to
dissolve the interpolymer. After the interpolymer had dissolved 0.9
mL (0.9 mmol) of tin(IV) bromide (1 molar solution in
CH.sub.2Cl.sub.2) was added to the bottle via a syringe and mixed
with the interpolymer solution. Next, 5 mL of diethyl ether and
2.25 g (10.1 mmol) of bromomethyloctyl ether were added to the
bottle. The bottle was then placed on a shaker. After 8 hours, an
aliquot of the reaction mixture was removed and precipitated into
methanol. The sample was then dried in a vacuum oven at ambient
temperature and then analyzed by proton NMR to reveal that 0.32
mole percent of the phenyl groups had been bromomethylated. After
31 hours, the remaining reaction mixture was precipitated into an
explosion proof Waring.TM. blender containing 500 mL of 50/50, v/v,
methanol/acetone. The bromomethylated interpolymer was collected by
filtration on a glass fritted funnel and was washed with an
additional 50 mL of methanol. The white interpolymer was air dried
on the funnel and then placed in a vacuum oven at 30.degree. C. for
final drying to yield 5.7 g of product. Analysis of the final
product by proton NMR showed that 0.7 mole percent of the phenyl
groups had been bromomethylated corresponding to 0.27 mol % of
functionalized repeating units.
Example 4
[0146] A 120 mL wide mouth bottle was charged with 6.25 g (42 mmol
of styrene) of ESI-1 and 50 mL of the desired solvent (methylene
chloride, 1,2-dichloroethane, or tetrahydrofuran). The bottle was
capped with a teflon lined lid and placed on a shaker overnight to
dissolve the interpolymer. After the interpolymer had dissolved,
tin tetrachloride was added to the bottle via a syringe and mixed
with the interpolymer solution. Next, the chloromethylating agent
and any other reagents (for example diethyl ether to moderate
catalyst activity) were added to the bottle. The bottle was then
placed on a shaker. At designated times aliquots of the reaction
mixture were removed and precipitated into methanol. The samples
were then dried in a vacuum oven at ambient temperature and then
analyzed by proton NMR for the extent of chloromethylation. At the
end of the run, the remaining reaction mixture was precipitated
into an explosion proof Waring.TM. blender containing 500 mL of
50/50, v/v, methanol/acetone. The chloromethylated interpolymer was
collected by filtration on a glass fritted funnel and was washed
with an additional 50 mL of methanol. The white interpolymer was
air dried on the funnel and then placed in a vacuum oven at
30.degree. C. for final drying. Results are shown in Table 3. Rapid
gellation of the reaction mixture occurred in Table 3 entries 1 and
2. At 45.degree. C., gellation occurred immediately after catalyst
addition. At 20.degree. C., gellation occurred 4 minutes after
catalyst addition. The solvent was eliminated as a candidate for
the agent responsible for crosslinking by performing experiments
without adding the chloromethylating agent. In these `blank`
experiments no gellation was observed (even after several days). It
appears that in the presence of a very active catalyst, the
benzylic chlorine group which is the product of the
chloromethylation reaction undergoes further reaction to form a
methylene bridge between two phenyl rings which crosslinks the
ESI-1 polymer.
[0147] Moderation of the catalyst activity by adding diethyl ether
to the reaction mixture allowed for the chloromethylation of ESI-1
copolymer to proceed while crosslinking was suppressed (Table 3,
entry 3). The viscosity of the reaction mixture steadily increased
with time although gellation was not observed. A 10 fold reduction
in the amount of diethyl ether added led to gellation of the
reaction mixture after 8 hours (Table 3, entry 4). Similar results
were obtained in methylene chloride (Table 3, entries 5 and 6),
however no chloromethylation whatsoever was observed when
tetrahydrofuran was used as the solvent (Table 3, entry 7).
3TABLE 3 CHLOROMETHYLATION OF ESI WITH SNCL.sub.4 CATALYST
functionalized Solvent/ ROCH.sub.2Cl/ SnCl.sub.4 Et.sub.2O Temp %
chloro- repeating units Entry ESI.sup.1 (g) (mL) (mmol) (mmol) (mL)
(.degree. C.) Time (hr) methylation.sup.5 (mol %) 1 25
DCE.sup.2/200 R = octyl/42 3.55 0 45 0 gel gel 2 25 DCE / 200 R =
octyl/42 3.55 0 20 0.07 gel gel 3 6.25 DCE/50 R = octyl/10.1 0.88 5
20 5 1.5 0.58 50 33 1.27 94 4.5 1.74 4 6.25 DCE/50 R = ethyl/10.1
0.88 0.5 20 8 gel gel 5 6.25 MeCl.sub.2.sup.3/50 R = octyl/10.1
0.88 0 5 20 3.5 4.7 1.81 18 gel gel 6 6.25 MeCl.sub.2/50 R =
octyl/10.1 0.88 5 20 8 2.7 1.04 24 5.1 1.97 103 6.2 2.39 126.sup.8
8.0 3.09 7.sup.9 6.25 THF.sup.4/50 R = ethyl/10.1 0.88.sup.6 0 20 8
0 0 24.sup.7 0 0 126 0 0 .sup.1ESI-1, 70 wt % styrene containing
ethylene-styrene copolymer .sup.2DCE = 1,2-dichloroethane
.sup.3MeCl.sub.2 = methylene chloride .sup.4THF = tetrahydrofuran
.sup.5mole percent of phenyl groups chloromethylated determined by
proton NMR .sup.6reaction mixture heterogeneous upon addition of
catalyst .sup.7reaction mixture was originally heterogeneous but
became homogeneous before this time .sup.8reaction mixture very
dark and viscous .sup.9not an example of the invention
Example 5
[0148] A procedure was undertaken in a manner similar to Example 4
except that zinc chloride was employed as the chloromethylation
catalyst. The zinc chloride employed was a 1.0 molar anhydrous
solution in diethyl ether. The results are shown in Table 4.
4TABLE 4 CHLOROMETHYLATION OF ESI WITH ZNCL.sub.2 CATALYST
functionalized Solvent/ ROCH.sub.2Cl/ ZnCl.sub.2.sup.5 Temp %
chloro- repeating units Entry ESI.sup.1(g) (mL) (mmol) (mmol)
.degree. C. Time (hr) methylation.sup.6 (mol %) 1 6.25 DCE.sup.2/50
R = ethyl/10.6 0.9 20 8 3.3 1.27 24 4.2 1.62 77 5.5 2.12 126 6.3
2.43 2 6.25 MeCl.sub.2.sup.3/50 R = ethyl/10.6 0.9 20 8 5.3 2.05 24
6.3 2.43 77.sup.7 8.3 3.20 126 Gel gel 3.sup.8 6.25 THF.sup.4/50 R
= ethyl/10.1 0.9 20 8 0 0 24 0 0 126 0 0 .sup.1ESI-1, 70 wt %
styrene containing ethylene styrene interpolymer .sup.2DCE =
1,2-dichloroethane .sup.3MeCl.sub.2 = methylene chloride .sup.4THF
= tetrahydrofuran .sup.51 Molar solution of zinc chloride in
diethyl ether .sup.6mole percent of phenyl groups chloromethylated
as determined by proton NMR .sup.7reaction mixture was extremely
viscous .sup.8not an example of the invention
Example 6
[0149] A procedure was undertaken in a manner similar to Example 5
except that the parameters for chloromethylation of ESI-1 copolymer
in methylene chloride, utilizing chloromethyl ethyl ether and zinc
chloride were varied as shown in Table 5. The results of those
experiments are summarized in Table 5.
5TABLE 5 CHLOROMETHLATION OF ESI IN METHYLENE CHLORIDE WITH
CHLOROMETHYL ETHYL ETHER AND ZINC CHLORIDE functionalized
EtOCH.sub.2Cl mole ratio ZnCl.sub.2.sup.3 mole ratio % chloro-
repeating Entry.sup.1 (mmol) phenyl/ether.sup.2 (mmol)
ether/catalyst.sup.4 Time (hr) methylation.sup.5 units (mol %) 1
10.6 4 0.45 23.6 4 1.6 0.62 9 2.3 0.89 24 3.2 1.24 48 40 1.54 72
4.4 1.70 100 4.7 1.81 144 5.0 1.93 2 10.6 4 0.9 11.8 8 5.3 2.05 24
6.3 2.43 77.sup.6 8.3 3.20 126 gel gel 3 10.6 4 1.8 5.9 4 2.5 0.97
9 3.7 1.43 24 5.7 2 20 48 6.5 2.51 72 gel gel 4 5.3 8 0.9 5.9 4 1.4
0.54 9 2.2 0.85 24 3.3 1 27 48 3.7 1.43 72 4.2 1.67 100 4 4 1.70
122 gel gel 5 21.2 2 0.9 23.6 4 2.7 1.04 9 3.9 1.51 24 5.6 2.16 48
6.9 2.66 72 7.5 2.89 100 8.0 3.09 122 8.6 3.32 144 10.9 4.21 6 5.3
8 0.225 23.6 4 0.7 0.27 9 1.0 0.39 24 1.5 0.58 48 2.0 0.77 72 2.3
0.89 100 2.4 0.93 123 2.7 1.04 7 42.3 1 1.8 23.5 4 4.3 1.66 9 6.5
2.51 24 9.9 3.82 48 15.6 6.02 72 15.9 6.14 100 18.5 7.14 123 19.5
7.53 8 211.6 0.2 9 0 23.5 4 13.8 5.33 9 19.6 7.56 24 28.7 11.08 48
34.8 13.43 72 38.7 14.94 100 42.1 16.25 123 43.8 16.90 .sup.16.25 g
(42.1 mmol of styrenic repeat units) of ESI-1 dissolved in 50 mL of
methylene chloride, T = 20.degree. C. .sup.2ratio of moles of
phenyl groups on ESI to moles of chloromethyl ethyl ether added to
reaction mixture .sup.31 Molar solution of zinc chloride in diethyl
ether .sup.4ratio of moles of chloromethyl ethyl ether added to
reaction mixture to moles of zinc chloride added to reaction
mixture .sup.5mole percent of phenyl groups chloromethylated
determined by proton NMR .sup.6reaction mixture was extremely
viscous
Example 7
Triethylammonium Ionomer of ESI
[0150] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 1.0 g (0.42 mmol
chloromethyl groups) of chloromethylated interpolymer having 70
weight percent styrene(6.3 mole percent of phenyl groups in
interpolymer chloromethylated corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of chloroform. After the
interpolymer dissolved (.about.1 hr), 425 mg (4.2 mmol) of
triethylamine was added to the reaction mixture. The flask was
submerged in an oil bath thermostated at 60.degree. C. and stirred
for 20 hours. The treated interpolymer was then isolated by removal
of the solvent by rotary evaporation (bath temp=40.degree. C.) to
give 1.0 g of a clear, slightly yellow film which was dried at
25.degree. C. in vacuum oven. Analysis of the sample by proton NMR
(CDCl.sub.3) revealed a new peak at 4.65 ppm (relative to
tetramethylsilane) due to the benzylic methylene group of the
ionomer as well as new peals due to the ethyl groups bound to
nitrogen. Integration of the proton NMR spectrum showed that 83% of
the chloromethyl groups had been replaced by triethylammonium
groups corresponding to 2.02 mol % of functionalized repeating
units. The glass transition temperature of the interpolymer was
broad with the inflection occurring at 17.4.degree. C. A broad
endotherm centered at 172.degree. C. was also observed in the first
scan but it was absent in a second scan. The ionomer is potentially
useful in, for example, melt rheology modification, antistatic
agent, ion exchange films, and polymeric biocides.
Example 8
Triphenylphosphonium Ionomer of ESI
[0151] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 1.0 g (0.42 mmol
chloromethyl groups) of chloromethylated interpolymer having 70
weight percent styrene (6.3 mole percent of phenyl groups in
interpolymer chloromethylated corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of chloroform. After the
interpolymer dissolved (.about.1 hr), 1.0 g (3.81 mmol) of
triphenylphosphine was added to the reaction mixture. The flask was
submerged in an oil bath thermostated at 60.degree. C. and stirred
for 24 hours. The treated interpolymer was precipitated into 250 mL
of isopropanol in an explosion proof blender and collected by
vacuum filtration on a glass fritted funnel. The interpolymer was
then placed in a vacuum oven and dried at 25.degree. C. to yield
0.8 g of product. Analysis of the sample by proton NMR (CDCl.sub.3)
revealed a new peak at 5.2 ppm (relative to tetramethylsilane) due
to the benzylic methylene group of the ionomer as well as new peaks
due to the phenyl groups bound to phosphorous. Integration of the
proton NMR spectrum showed that 77% of the chloromethyl groups have
been replaced by triphenylphosphonium groups corresponding to 1.87
mol % of functionalized repeating units. The glass transition
temperature of the interpolymer was 24.3.degree. C. The ionomer is
potentially useful in, for example, melt rheology modification,
antistatic agent, ion exchange films, and polymeric biocides.
Example 9
Acetate Functional ESI
[0152] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 1.0 g (0.42 mmol
chloromethyl groups) of chloromethylated interpolymer having 70
weight percent styrene (6.3 mole percent of phenyl groups in
interpolymer chloromethylated corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of chloroform. After the
interpolymer dissolved (.about.1 hr), 1.6 g (4 mmol) of
tetraphenylphosphonium acetate was added to the reaction mixture.
The flask was submerged in an oil bath thermostated at 60.degree.
C. and stirred for 24 hours. The interpolymer was precipitated into
500 mL of 50/50, v/v, methanol/acetone in an explosion proof
blender and collected by vacuum filtration on a glass fritted
funnel. The interpolymer was then placed in a vacuum oven and dried
at 25.degree. C. to yield 0.96 g of product. Analysis of the sample
by proton NMR (CDCl.sub.3) revealed a new peak at 5.05 ppm
(relative to tetramethylsilane) due to the benzylic methylene
adjacent to the acetate group as well as a new peaks due to the
methyl of the acetate. Integration of the proton NMR indicated near
quantitative conversion of the chloromethyl group to the acetate.
The glass transition temperature of the interpolymer was
22.7.degree. C.
[0153] This type of ESI functionalization is potentially useful in,
for example, incorporating branch and graft sites into ESI by
reacting ESI-CH.sub.2Cl with fatty acids or polymers bearing
carboxylic acid groups; reacting an unsaturated acid (for example
acrylic acid) with chloromethylated ESI to provide a site for free
radical crosslinking or copolymerization with a host of vinyl
monomers; imparting some polar character to the polymer; and
attaching a variety of polymers to the ESI backbone (for example
PET, nylon) by reactive blending.
Example 10
Hydroxyl Functional ESI
[0154] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 0.5 g (0.20 mmol
acetate groups) of acetate functional interpolymer of Example 9
having 70 weight percent styrene (6.3 mole percent of phenyl groups
in interpolymer bear acetate group corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of tetrahydrofuran. After
the interpolymer dissolved, 0.65 g (1 mmol) of tetrabutylammonium
hydroxide (40 wt % solution in water) was added to the reaction
mixture. The flask was submerged in an oil bath thermostated at
60.degree. C. and stirred for 24 hours. The interpolymer was
precipitated into 500 mL of 50/50, v/v, methanol/acetone in an
explosion proof blender and collected by vacuum filtration on a
glass fritted funnel. The interpolymer was then placed in a vacuum
oven and dried at 25.degree. C. to yield 0.42 g of product.
Analysis of the sample by proton NMR (CDCl.sub.3) revealed a new
peak at 4.6 ppm (relative to tetramethylsilane) due to the benzylic
methylene adjacent to the hydroxyl group. Integration of the proton
NMR indicated quantitative conversion of the acetate group to the
hydroxyl group.
[0155] The hydroxyl functional ESI is potentially useful in, for
example, compatibilizing ESI and other polymers such as epoxies,
urethanes, polyesters, polycarbonates.
Example 11
Methyl Ether Functional ESI
[0156] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 1.0 g (0.42 mmol
chloromethyl groups) of chloromethylated interpolymer having 70
weight percent styrene (6.3 mole percent of phenyl groups in
interpolymer chloromethylated corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of tetrahydrofuran. After
the interpolymer dissolved, 2 mL (4.85 mmol) of tetramethylammonium
hydroxide (25 wt % solution in methanol) was added to the reaction
mixture. The flask was submerged in an oil bath thermostated at
60.degree. C. and stirred for 24 hours. The interpolymer was
precipitated into 500 mL of 50/50, v/v, methanol/acetone in an
explosion proof blender and collected by vacuum filtration on a
glass fritted funnel. The interpolymer was then placed in a vacuum
oven and dried at 25.degree. C. to yield 0.98 g of product.
Analysis of the sample by proton NMR (CDCl.sub.3) revealed a new
peaks at 4.39 and 3.35 ppm (relative to tetramethylsilane) due to
the benzylic methylene adjacent to the methoxide group and the
methyl of the methoxide group respectively. Integration of the
proton NMR indicated quantitative conversion of the chloromethyl
group to the methyl ether. The glass transition temperature of the
interpolymer was 23.3.degree. C.
Example 12
Phenyl Ether Functional ESI
[0157] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 1.0 g (0.42 mmol
chloromethyl groups) of chloromethylated interpolymer having 70
weight percent styrene (6.3 mole percent of phenyl groups in
interpolymer chloromethylated corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of tetrahydrofuran. In a
second flask, 425 mg (2.14 mmol) of 4-hydroxybenzophenone was
dissolved in 25 mL of methylene chloride and treated with 600 mg
(1.64 mmol) of tetramethylammoniun hydroxide (25 wt percent in
methanol). The solvent (MeOH, CH.sub.2Cl.sub.2) was removed from
the phenate/phenol mixture by rotary evaporation. The residual
yellow viscous oil was taken up in 10 mL of THF and added to the
flask containing the interpolymer solution. The flask was submerged
in an oil bath thermostated at 60.degree. C. and stirred for 24
hours. The interpolymer was precipitated into 500 mL of 50/50, v/v,
methanol/acetone in an explosion proof blender and collected by
vacuum filtration on a glass fritted funnel. The interpolymer was
then placed in a vacuum oven and dried at 25.degree. C. to yield
1.0 g of product. Analysis of the sample by proton NMR (CDCl.sub.3)
revealed a new peak at 5.08 ppm (relative to tetramethylsilane) due
to the benzylic methylene adjacent to the new phenyl ether group
and new peaks in the aromatic region due to the new substituent.
Integration of the proton NMR indicated that 45 percent of the
chloromethyl groups have been converted to aromatic ether groups
corresponding to 1.09 mol % of functionalized repeating units.
[0158] 1. The phenyl ether functional ESI is potentially useful in,
for example, providing a good chromophore which may render ESI
crosslinkable with UV light. Similarly, displacement of the halide
with polymeric alcoholic or phenolic endgroups of PET,
polycarbonate, PPO, poly(alkylene)oxide, polyacetal,
polycaprolactone, etc. leads to grafting of these materials onto
ESI.
Example 13
Cyano Functional ESI
[0159] A 100 mL flask equipped with magnetic stirrer, water
condenser, and N.sub.2 inlet was charged with 1.0 g (0.42 mmol
chloromethyl groups) of chloromethylated interpolymer having 70
weight percent styrene (6.3 mole percent of phenyl groups in
interpolymer chloromethylated corresponding to 2.43 mol % of
functionalized repeating units) and 20 mL of tetrahydrofuran. After
the interpolymer dissolved, 537 mg (2 mmol) of tetrabutylammonium
cyanide was added to the reaction mixture. The flask was submerged
in an oil bath thermostated at 60.degree. C. and stirred for 24
hours. The interpolymer was precipitated into 500 mL of 50/50, v/v,
methanol/acetone in an explosion proof blender and collected by
vacuum filtration on a glass fritted funnel. The interpolymer was
then placed in a vacuum oven and dried at 25.degree. C. to yield
0.8 g of product. Analysis of the sample by proton NMR (CDCl.sub.3)
revealed a new peak at 3.65 ppm (relative to tetramethylsilane) due
to the benzylic methylene adjacent to the cyano group. Integration
of the proton NMR indicated near quantitative conversion of the
chloromethyl group to the cyano group.
[0160] The cyano functional ESI is potentially useful in, for
example, hydrolyzing the cyano group to a carboxylic amide or acid;
reducing the cyano group to give ESI with pendant aliphatic amine
groups; making ESI more polar.
Example 14
Reaction of ESI-1 with Acetyl Chloride
[0161] 6.15 g of an ethylene styrene interpolymer (ESI-1, 70 wt
percent styrene) was dissolved in 50 mL of dichloromethane. After
dissolution of the polymer, 0.86 g (10.9 mmol) of acetyl chloride
was added to the reaction mixture. Next, 17 mmol of aluminum
chloride (1 molar solution of aluminum chloride in nitrobenzene, 17
mL) was added to the reaction mixture. After 5 hours of mixing, the
yellow/brown reaction mixture was precipitated into 500 mL of 50/50
v/v methanol/acetone in a blender. The white polymer was collected
by filtration and then suspended in 500 mL of 0.1 M HCl for 20
minutes. The polymer was then collected by filtration and washed
twice with water and once with methanol and then dried in a vacuum
oven at 25.degree. C. to yield 6.4 g of white polymer. A 300 mg
portion of the polymer was pressed between teflon sheets into a
thin, clear, colorless, creasable film at 200.degree. C. with
20,000 lbs of load. Analysis of the film by infrared spectroscopy
showed an intense peak at 1685 cm.sup.-1 due to the ketone group.
The polymer (100 mg) was dissolved in 2 g of deuterochloroform and
analyzed by NMR spectroscopy. NMR chemical shifts referenced to
tetramethylsilane (0 ppm). In the proton NMR of the polymer, new
peaks were observed at 7.85 ppm (aromatic hydrogens alpha to acetyl
group), and 2.55 ppm (methyl hydrogens of the acetyl group).
Integration of the proton NMR spectrum revealed that 18.9 mole
percent of the phenyl groups in the polymer contained the acetyl
group corresponding to 7.29 mol % of functionalized repeating
units. The carbon 13 NMR spectrum of the polymer was consistent
with the assigned structure with the most distinguishing features
being peaks at 198 ppm (carbon of the ketone group), and 26.6 ppm
(methyl carbon of acetyl group). The glass transition temperature
(T.sub.g) of the polymer was 31.degree. C. as measured by
differential scanning calorimetry (DSC) at a scan rate of
10.degree. C./min. The inflection of the step transition was taken
as the T.sub.g.
Example 15
Oxidation of Acetylated ESI
[0162] 5 g of the acetylated ESI from Example 14 was dissolved in
100 mL of toluene in a 500 mL 3 neck flask equipped with mechanical
stirrer and condenser by heating and stirring at 60.degree. C. for
1 hour in an oil bath. After the polymer dissolved, 10 mL of
aqueous bleach (5.25 wt percent NaOCl) and 0.75 mmol of
cetyltrimethylammonium chloride (1 mL of a 25 wt % aqueous
solution) was added to the reaction mixture. The oil bath
surrounding the flask was heated to 110.degree. C. and the reaction
was allowed to proceed with vigorous stirring. Additional 10 mL
aliquots of bleach were added to the reaction mixture after 8 hrs,
24 hrs, and 48 hrs. After 72 hours, the thick white reaction
mixture was cooled and then precipitated into 500 mL of methanol in
a blender. The polymer was collected by filtration. The damp filter
cake (.about.10 g) was placed in 75 mL of tetrahydrofuran and
rapidly formed a tight, translucent gel. Addition of 10 mL of 1 M
HCl (in diethylether) to the tetrahydrofuran gel converts the
sodium salt of the ionomer to the free carboxylic acid and yields a
hazy nonviscous solution. The polymer solution was precipitated
into 500 mL of methanol in a blender and the resulting white
polymer collected by filtration, rinsed twice with 50 mL portions
of methanol and then dried in a vacuum oven at 25.degree. C. to
yield 4.6 g of a white powder. A 300 mg portion of the polymer was
pressed between teflon sheets into a thin, clear, colorless,
creasable film at 200.degree. C. with 20,000 lbs of load. Analysis
of the film by infrared spectroscopy showed two carbonyl stretched
at 1725 cm.sup.-1 and 1685 cm.sup.-1 due to both the carbonyl of
the newly formed acid groups and the carbonyl of unreacted acetyl
carbonyl groups respectively. The polymer (100 mg) was dissolved in
2 g of deuterochloroform and analyzed by NMR spectroscopy, NMR
chemical shifts referenced to tetramethylsilane (0 ppm) In the
proton NMR of the polymer a new peak were observed at 7.95 ppm
(aromatic hydrogens alpha to carboxyl group). Integration of the
proton NMR spectrum revealed that 4.8 mole percent of the phenyl
groups in the polymer contained the carboxylic acid group
corresponding to 1.85 mol % of functionalized repeating units and
that 15.3 mole percent of the phenyl groups in the polymer
contained the acetyl group corresponding to 5.9 mol % of
functionalized repeating units. The carbon 13 NMR spectrum of the
polymer was consistent with the assigned structure. The glass
transition temperature (T.sub.g) of the polymer was 33.5.degree. C.
as measured by differential scanning calorimetry (DSC) at a scan
rate of 10.degree. C./min. The inflection of the step transition
was taken as the T.sub.g.
Example 16
Reaction of ESI-1 with p-toluoyl Chloride
[0163] 6.25 g of an ethylene styrene interpolymer (ESI-1, 70 wt
percent styrene) was dissolved in 50 mL of dichloromethane. After
dissolution of the polymer, 1.62 g (10.5 mmol) of p-toluoyl
chloride was added to the reaction mixture. Next, 16 mmol of
aluminum chloride (1 molar solution of aluminum chloride in
nitrobenzene, 16 mL) was added to the reaction mixture. After 4
hours of mixing, the yellow/brown reaction mixture was precipitated
into 500 mL of 50/50 v/v methanol/acetone in a blender. The white
polymer was collected by filtration and then suspended in 500 mL of
0.1 M HCl for 30 minutes. The polymer was then collected by
filtration and washed twice with water and twice with methanol and
then dried in a vacuum oven at 25.degree. C. to yield 6.9 g of
white polymer. A 400 mg portion of the polymer was pressed between
teflon sheets into a thin, clear, colorless, creasable film at
200.degree. C. with 20,000 lbs of load. Analysis of the film by
infrared spectroscopy showed an intense peak at 1660 cm.sup.-1 due
to the ketone group. The polymer (100 mg) was dissolved in 2 g of
deuterochloroform and analyzed by NMR spectroscopy. NMR chemical
shifts referenced to tetramethylsilane (0 ppm). In the proton NMR
of the polymer several new features were observed the most
prominent of which were new peaks were at 7.7 ppm (aromatic
hydrogens alpha to ketone group), and 2.42 ppm (hydrogens of the
benzylic methyl group). Integration of the proton NMR spectrum
revealed that 16.3 mole percent of the phenyl groups in the polymer
contained the toluoyl ketone group corresponding to 6.29 mol % of
functionalized repeating units. The carbon 13 NMR spectrum of the
polymer was consistent with the assigned structure with the
assigned structure with the most distinguishing features being
peaks at 196 pm (carbon of the ketone group), and 21.6 pm (benzylic
methyl carbon). The glass transition temperature (T.sub.g) of the
polymer was 34.degree. C. as measured by differential scanning
calorimetry (DSC) at a scan rate of 10.degree. C./min. The
inflection of the step transition was taken as the T.sub.g.
Example 17
Reduction of ESI with Pendant Aromatic Ketone Groups
[0164] 3 g of the functionalized ESI from Example 16 was dissolved
in 100 mL of dry tetrahydrofuran in a 250 mL 3 neck flask equipped
with magnetic stirrer, condenser, and nitrogen inlet. After the
polymer dissolved (.about.2 hrs), 10 mmol of lithium aluminum
hydride (1M solution in diethylether, 10 mL) was added to the
reaction mixture via syringe. Upon addition of the reducing agent,
the viscosity of the reaction media increased dramatically making
stirring difficult. An oil bath was placed around the flask and the
apparatus was heated to 60.degree. C. and held there for 3 hours.
After cooling the reaction was quenched by the slow addition of 10
mL of methanol. The viscous reaction mixture was precipitated into
500 mL of 1.25M aqueous sulfuric acid in a blender. The polymer was
collected by filtration and rinsed twice with 50 mL portions of
methanol and then dried on the filter. The damp filter cake
(.about.6 g) was placed in 80 mL of tetrahydrofuran and the mixture
shaken until all of the polymer dissolved (overnight). The polymer
solution was precipitated into 500 mL of methanol in a blender and
the resulting white polymer collected by filtration, rinsed twice
with 50 mL portions of methanol and then dried in a vacuum oven at
25.degree. C. to yield 2.8 g of a light yellow powder. A 300 mg
portion of the polymer was pressed between teflon sheets into a
thin, clear, colorless, creasable film at 200.degree. C. with
20,000 lbs of load. Analysis of the film by infrared spectroscopy
showed broad peak centered at 3175 cm.sup.-1 due to the hydroxyl
functionality and the noticeable absence of a peak in the carbonyl
region. The polymer (100 mg) was dissolved in 2 g of
deuterochloroform and analyzed by NMR spectroscopy. NMR chemical
shifts referenced to tetramethylsilane (0 ppm). In the proton NMR
of the polymer the peaks due to the ketone precursor were absent
and new peaks were observed at 5.75 ppm (methine hydrogen alpha to
hydroxyl group) and 3.75 ppm (hydrogen of hydroxyl group).
Integration of the proton NMR spectrum revealed that 17.2 mole
percent of the phenyl groups in the polymer contained the new
hydroxyl group corresponding to 6.64 mol % of functionalized
repeating units. The carbon 13 NMR spectrum of the polymer was
consistent with the assigned structure with the most noticeable
features being the absence of a peak in the carbonyl region and the
presence of a new peak at 75.9 ppm (carbon attached to hydroxyl
group). The glass transition temperature (T.sub.g) of the polymer
was 34.7.degree. C. as measured by differential scanning
calorimetry (DSC) at a scan rate of 10.degree. C./min.
[0165] The inflection of the step transition was taken as the
T.sub.g.
Example 18
Reaction of ESI-1 with Gamma-valerolactone
[0166] 1.25 g of an ethylene styrene interpolymer (ESI-1, 70 wt
percent styrene) was dissolved in 50 mL of dichloromethane. After
dissolution of the polymer, 0.2 g (1.5 mmol) of aluminum chloride
solid was added to the reaction mixture in one portion. Upon
addition of AlCl.sub.3, the reaction mixture turned pale yellow.
Next, 84 mg (0.84 mmol) of gamma-valerolactone was added to the
reaction mixture and the reaction mixture became homogeneous except
for a few small clumps of AlCl.sub.3. After 1 hour the clear,
orange, viscous reaction mixture was precipitated into 500 mL of
50/50 v/v methanol/acetone in a blender. The white, fibrous polymer
was collected by filtration and then suspended in 500 to mL of 0.1
M aqueous HCl for 15 minutes. The polymer was then collected by
filtration and washed twice with water and once with methanol and
then dried in a vacuum oven at 25.degree. C. to yield 1.11 g of a
white fibrous polymer. A 300 mg portion of the polymer was pressed
between teflon sheets into a thin, clear, colorless, creasable film
at 200.degree. C. with 20,000 lbs of load. Analysis of the film by
infrared spectroscopy showed a broad peak at 3500 to 3000 cm.sup.-1
due to the carboxylic acid group and a carbonyl stretch at 1710
cm.sup.-1. The polymer (50 mg) dissolved in 3 g of 90/10 v/v
chloroform/methanol to give a viscous solution.
Example 19
Reaction of ESI-1 with 2,4-butanesulfone
[0167] 1.25 g of an ethylene styrene interpolymer (ESI-1, 70 wt
percent styrene) was dissolved in 50 mL of dichloromethane. After
dissolution of the polymer, 0.237 g (1.78 mmol) of aluminum
chloride solid was added to the reaction mixture in one portion.
Upon addition of AlCl.sub.3, the reaction mixture turned pale
yellow. Next, 135 mg (0.99 mmol) of 2,4-butanesulfone was added to
the reaction mixture and the reaction mixture became homogenous
except for a few small clumps of AlCl.sub.3. After 1 hour the
viscous reaction mixture was precipitated into 500 mL of 50/50 v/v
methanol/acetone in a blender. The white polymer was collected by
filtration and then suspended in 500 mL of 0.1 M aqueous
H.sub.2SO.sub.4 for 15 minutes. The polymer was then collected by
filtration with washed twice and water and once with methanol and
then dried in a vacuum oven at 25.degree. C. to yield 1.26 g of a
white polymer. A 300 mg portion of the polymer was pressed between
teflon sheets into a thin, clear, light yellow, creasable film at
260 C. with 24,000 lbs of load. Analysis of the film by infrared
spectroscopy showed a broad peaks at 1300 and 1140 cm.sup.-1 due to
the sulfonic acid group. The polymer (50 mg) dissolved in 3 g of
90/10 v/v chloroform/methanol to give a viscous solution.
Example 20
Reaction of ESI-1 with Succinic Anhydride
[0168] 6.25 g of an ethylene styrene interpolymer (ESI-1, 70 wt
percent styrene) was dissolved in 50 mL of dichloromethane. After
dissolution of the polymer, 0.42 g (4.2 mmol) of succinic anhydride
was added to the reaction mixture. The anhydride did not completely
dissolve. Next, 8.4 mmol of aluminum chloride (1 molar solution of
aluminum chloride in nitrobenzene, 8.4 mL) was added to the
reaction mixture. Upon addition of AlCl.sub.3, the reaction mixture
turns yellow and the succinic anhydride dissolves. After 10 minutes
of mixing, the reaction mixture was thick and gelatinous. After 2
hours, the reaction mixture was precipitated into 500 mL of 50/50
v/v methanol/acetone in a blender. The white polymer was collected
by filtration and then suspended in 200 mL of 0.2 M HCl for 48
hours. The polymer was then collected by filtration and washed
twice with water and twice with methanol and then dried in a vacuum
oven at 25 C. to yield 7.1 g of a granular powder. The polymer (50
mg) dissolved in 1.5 g of 80/20 v/v tetrahydrofuran/methanol to
give a viscous solution. A 300 mg portion of the polymer was
pressed between teflon sheets into a thin, clear, and creasable
film at 250 C. with 20,000 lbs of load. Analysis of the polymer
film by infrared spectroscopy showed a broad peak at 3500 to 3000
cm.sup.-1 due to the carboxylic acid group and two carbonyl
stretches at 1690 and 1610 cm.sup.-1.
Example 21
Reaction of ESI-2 with 4-Vinylbenzoic Acid
[0169] 40 g of an ethylene styrene interpolymer (35 wt percent
Copolymer Styrene, 6.0 wt percent atactic Polystyrene, ESI-2) was
added to a Brabender mixer at 190.degree. C. To the polymer melt,
1.2 g (8 mmol) of powdered vinylbenzoic acid was added. Finally,
107 .mu.L of dodecylbenzenesulfonic acid was added and the molten
mixture blended at 80 rpm for 5 minutes. After the allotted time,
the Brabender was opened and the tan polymer melt was removed to
yield 36.3 g of product. A 300 mg portion of the polymer was
pressed between teflon sheets into a thin, clear, and creasable
film at 210 C. with 20,000 lbs of load. Analysis of the film by
infrared spectroscopy showed a broad peak at 3500 to 3000 cm.sup.-1
due to the carboxylic acid group and a carbonyl stretch at 1695
cm.sup.-1. Dissolution of the polymer in warm xylene (15 mL/g of
polymer) followed by precipitation into methanol did not change the
IR spectrum of the product indicating that the vinylbenzoic acid
was indeed grafted to the ethylene styrene copolymer and that the
product was not simply a physical mixture of the two
components.
Example 22
Reaction of ESI-3 with Chloromethylbenzoic Acid
[0170] 40.0 of ethylene/styrene interpolymer (58 wt percent
Copolymer Styrene, 3.0% atactic Polystyrene, ESI-3) was mixed with
0.080 g (0.49 mmol) FeCl.sub.3 in a ZIPLOC.TM. bag. The mixture was
added to a Haake Rheocord System 9000 Torque Rheometer equipped
with a Haake 600 mixing bowl with roller style blades. The bowl
temperature was 190.degree. C. and the sample was mixed at 60 RPM.
After 4 minutes, 1.5 g (8.8 mmol) of 4-chloromethylbenzoic acid was
sprinkled into the mixing bowl. Over a period of 9 minutes, the
torque increased from an initial value of 600 m.g to 1000 m.g. At
t=20 minutes, the sample was removed from the mixing bowl. After
compression molding, the tensile properties and TMA performance
were measured.
Example 23
Reaction of ESI-3 with Chloromethylbenzoic Acid and Subsequent
Conversion to the Zinc Ionomer via Addition of Zinc Oxide
[0171] 40.0 of ethylene/styrene interpolymer (58 wt percent
Copolymer Styrene, 3.0% atactic Polystyrene, ESI-3) was mixed with
0.080 g (0.49 mmol) FeCl.sub.3 in a ZIPLOC.TM. bag. The mixture was
added to a Haake Rheocord System 9000 Torque Rheometer equipped
with a Haake 600 mixing bowl with roller style blades. The bowl
temperature was 190.degree. C. and the sample was mixed at 60 RPM.
After 4 minutes, 1.5 g (8.8 mmol) of 4-chloromethylbenzoic acid was
sprinkled into the mixing bowl. At t=10 minutes, 2.0 g of zinc
oxide was added and the torque immediately increased from 800 m.g
to 2100 m.g. At t=20 minutes, the sample was removed from the
mixing bowl. After compression molding, the tensile properties and
TMA performance were measured.
Example 24
Reaction of ESI-3with Chloromethylbenzoic Acid and Subsequent
Conversion to the Zinc Ionomer via Addition of Zinc Oxide
[0172] 40.0 of ethylene/styrene interpolymer (58 wt percent
Copolymer Styrene, 3.0% atactic Polystyrene, EST-3) was mixed with
0.080 g (0.49 mmol) FeCl.sub.3 in a ZIPLOC.TM. bag. The mixture was
added to a Haake Rheocord System 9000 Torque Rheometer equipped
with a Haake 600 mixing bowl with roller style blades. The bowl
temperature was 190.degree. C. and the sample was mixed at 60 rpm.
After 4 minutes, 3.0 g (17.2 mmol) of 4-chloromethylbenzoic acid
was sprinkled into the mixing bowl. At t=10 minutes, 2.8 g of zinc
oxide was added and the torque immediately increased from 800 m.g.
to 2600 m.g. At t=20 minutes, the sample was removed from the
mixing bowl. After compression molding, the tensile properties and
TMA performance were measured.
Example 25
Reaction of ESI-3 with Chloromethylbenzoic Acid and Subsequent
Conversion to the Zinc Ionomer via Addition of Zinc Oxide Followed
by Plasticization with Zinc Stearate
[0173] 40.0 of ethylene/styrene interpolymer (58 wt percent
Copolymer Styrene, 3.0 wt percent atactic Polystyrene, ESI-3) was
mixed with 0.080 g (0.49 mmol) FeCl.sub.3 in a ZIPLOC.TM. bag. The
mixture was added to a Haake Rheocord System 9000 Torque Rheometer
equipped with a Haake 600 mixing bowl with roller style blades. The
bowl temperature was 190.degree. C. and the sample was mixed at 60
RPM. After 4 minutes, 1.5 g (8.8 mmol) of 4-chloromethylbenzoic
acid was sprinkled into the mixing bowl. At t=10 minutes, 2.0 g of
zinc oxide was added and the torque immediately increased from 800
m.g to 2100 m.g. At t=15 minutes, 4.0 g of zinc stearate was added
over a period of 3 minutes. At t=20 minutes, the sample was
removed, and a final torque reading of 700 m.g was recorded. After
compression molding, the tensile properties and TMA performance
were measured.
[0174] Examples 22-25 illustrate how functionalization of ESI can
be used to increase the temperature resistance and tensile strength
of ESI.
6 Sample TMA (c) Break Stress (PSI) % elongation Example 22 64 800
470 Example 23 98 2000 300 Example 24 108 2500 250 Example 25 85
2700 370 Comparative Example 52 411 910 (unmodified ESI-3)
Example 26
Bromination of ESI-1
[0175] A 500 mL 3 neck flask equipped with a thermal well,
mechanical stirrer, dry ice condenser with exit attached to a gas
scrubber, and an addition funnel, and nitrogen inlet was charged
with 25 g (0.17 mol styrene repeat units) of ESI-1 and 250 mL of
methylene chloride. After complete dissolution of the interpolymer
(.about.5 hrs), 1.7 mL (1.7 mmol) of a 1 molar solution of aluminum
chloride in nitrobenzene was added to the apparatus. The flask was
then wrapped in aluminum foil to exclude light and dry ice and
acetone was added to the condenser. Bromine (27.2 g, 0.17 mol) was
added dropwise to the flask from the addition funnel over the
course of 1 hr. After the addition of bromine was complete, the
reaction mixture was stirred for an additional hour with the dry
ice condenser in place. The condenser was then removed and replaced
with a gas outlet adapter which was also attached to the gas
scrubber. The reaction mixture was stirred and swept with nitrogen
for an additional hour. The reaction mixture was poured into a
separatory funnel and washed with a solution of 15 g of sodium
bisulfite in 100 ml of water and then twice with 100 ml portions of
water. The polymer solution was then precipitated into 3 L of 50/50
v/v acetone/methanol in explosion proof Waring blender and the
off-white polymer crumb was collected by vacuum filtration on a
glass fritted funnel, washed once with 500 ml of methanol, air
dried on the funnel and dried in a vacuum oven at 35.degree. C. The
isolated yield of brominated polymer was 33.75 g. Total bromine
content of the sample 32.+-.1 wt. percent (theoretical value is
35.3 wt. percent if each phenyl ring has one --Br substituent).
Backbone halogenation was below the limit of detection (<0.1
wt.). By NMR approximately 90% of the phenyl rings were brominated
corresponding to 34.7 mol % of functionalized repeating units,,also
by NMR the observed ratio of ortho:meta;para bromine relative to
the attachment point of the phenyl ring to the polymer backbone is
19:0:81. The glass transition temperature of the brominated polymer
was 54.5.degree. C. and the dilute solution viscosity of the
interpolymer in chloroform (.about.0.5 g/dL, 25.degree. C.) was
0.97 dL/g.
Example 27
Nitration of ESI-1 (High Level)
[0176] A 1 L, 3 neck flask equipped with mechanical stirrer,
condenser, nitrogen inlet, and thermocouple was charged with 350 mL
of chloroform and 15 g (.about.0.1 mol of styrene repeat units) of
ESI-1. The reaction mixture was stirred at ambient temperature
under a nitrogen atmosphere to dissolve the polymer (.about.2.5
hrs). After the polymer dissolved, 8.0 g (0.1 mol) of finely ground
ammonium nitrate was added to the flask. Next, 46 mL (68.4 g, 0.326
mol) of trifluoroacetic anhydride was added in one portion. Upon
addition of the anhydride, part of the polymer precipitated from
solution but rapidly redissolved. As the reaction proceeded the
ammonium nitrate slowly dissolved and the reaction mixture took on
a yellow/orange color. After 70 hours the reaction mixture was
precipitated into 3 L of 50/50, v/v, methanol/acetone in an
explosion proof Waring blender. The polymer was collected by
filtration on a glass fritted funnel and was washed with an
additional 2 L of methanol. The granular light yellow polymer was
air dried on the funnel and then placed in a vacuum oven at
30.degree. C. for final drying. The isolated yield of nitrated
polymer was 18.8 g.
[0177] A 300 mg sample of the polymer was pressed into a thin film
at 200.degree. C. between teflon sheets backed with stainless steel
plates on a heated Carver laboratory press. The polymer film was
clear and light yellow in color. The film was tough, bendable,
creasable and significantly stiffer than a similar film of the
unmodified ethylene styrene material (ESI-1). Analysis of the film
by IR revealed new stretches at 1525, 1350, and 870 cm.sup.-1 which
are consistent with a material bearing nitro groups. The glass
transition temperature of the polymer was 65.degree. C. and it had
a inherent solution viscosity of 0.45 dL/g (CHCl.sub.3, 25.degree.
C.). Proton NMR analysis of the nitrated ethylene styrene copolymer
was consistent with mono nitration of the majority of the pendant
phenyl rings with the nitro group positioned in both the ortho and
para positions. A new peak in the proton NMR spectrum at
approximately 8.1 ppm is interpreted as arising from the two
hydrogen atoms adjacent to the nitro group in the para position of
the phenyl ring relative to the attachment point of the polymer
backbone. Aromatic peaks unique for the material nitrated ortho and
meta to the attachment point of the polymer backbone occured in the
range of 7.5-8.0 ppm. A peak in the aliphatic region of the proton
NMR at 2.9 ppm is unique for the benzylic methine proton of repeat
units bearing a nitro group on the ortho position of the aromatic
ring. The benzylic methine proton adjacent to unsubstituted phenyl
rings and those bearing a nitro group in the meta or para positions
of the aromatic ring form a broad singlet at 2.2-2.6 ppm. A ratio
of the integral of the new aromatic peaks unique to the nitrated
repeat units to the integral for all aromatic hydrogen atoms
revealed that approximately 84 mole percent of the phenyl groups
had been nitrated (4.5 mmol NO.sub.2/g of polymer corresponding to
32.4 mol % of functionalized repeating units). Due to the
overlapping of peaks, the ratio of ortho: meta: para ratio for
nitration of the phenyl rings could not be determined from the
proton NMR spectrum. The carbon 13 NMR spectrum of the nitrated
material was used to determine the ortho: meta: para substitution
ratio from the ratio of the integrated area of the peaks at 151.2,
148.2, and 146.3 ppm in the carbon spectrum (which are due to the
aromatic ring carbons bearing the nitro group of ortho, meta, and
para substituted species respectively). From these peaks the ratio
of ortho:meta:para nitration is 8.7:3.1:88.2.
Example 28
Nitration of ESI-1 (Low Level)
[0178] A 500 mL, 3 neck flask equipped with mechanical stirrer,
condenser, nitrogen inlet, and thermocouple was charged with 250 mL
of chloroform and 30 g (.about.0.2 mol of styrene repeat units) of
ESI-1. The reaction mixture was stirred at ambient temperature
under a nitrogen atmosphere to dissolve the polymer (.about.2.5
hrs). After the polymer dissolved, 1.6 g (0.02 mol) of ammonium
nitrate was added to the flask. Next, 10 mL (14.9 g, 0.07 mol) of
trifluoroacetic anhydride was added in one portion. As the reaction
proceeded the ammonium nitrate slowly dissolved and the reaction
mixture took on a yellow/orange color. After 24 hours the reaction
mixture was precipitated into 3 L of 50/50, v/v, methanol/acetone
in an explosion proof Waring blender. The polymer was collected by
filtration on a glass fritted funnel and was washed with an
additional 2 L of methanol. The granular light yellow polymer was
air dried on the funnel and then placed in a vacuum oven at
25.degree. C. for final drying. The isolated yield of nitrated
polymer was 29.5 g. The glass transition temperature of the polymer
was 24.degree. C. Proton NMR analysis of the nitrated ethylene
styrene copolymer indicates that approximately 1.3 mole percent of
the phenyl groups have been nitrated (0.09 mmol NO.sub.2/g of
polymer corresponding to 0.50 mol % of functionalized repeating
units).
Example 30
Phenylhydrazine Reduction of Highly Nitrated Copolymer
[0179] A 100 mL flask equipped with a magnetic stir bar was charged
with 540 mg of highly nitrated copolymer prepared as for Example 27
(.about.2.5 mmol NO.sub.2 groups) and 20 mL of phenyl hydrazine. A
water condenser topped with a nitrogen inlet was placed on the
flask and the flask submerged in an oil bath at 150.degree. C.
After 10 minutes a clear orange solution resulted. The reaction
mixture was stirred in the bath under a pad of nitrogen for 4.5
hours and then the bath temperature was increased to 200.degree. C.
The reaction mixture was held at 200.degree. C. for 1 hour and then
the flask containing the now golden yellow reaction mixture was
removed from the bath and cooled to room temperature. The cooled
polymer solution was precipitated into 500 mL of 85/15, v/v,
water/methanol in an explosion proof blender. The polymer was
collected by filtration on a glass fritted funnel and was washed 3
times with 40 mL portions of methanol. The granular gray polymer
was air dried on the funnel and then placed in a vacuum oven at
30.degree. C. for final drying. The isolated yield of polymer was
442 mg.
[0180] The glass transition temperature of the polymer was
66.degree. C. The polymer dissolved easily in chloroform (100 mg of
polymer in 2 g CDCl.sub.3) to give a clear homogeneous solution but
upon standing the solution gelled. We believe that the gellation
was the result of the pendant amino groups reacting with chloroform
(a multifunctional alkylating agent). The polymer was easily
dissolved in tetrahydrofuran (70 mg polymer in 1 g THF-d8). No
gellation was observed in THF even after several days. Proton NMR
analysis of the aminated polymer in THF-d8 yielded a spectrum
consistent with that expected for ES bearing amino functionality.
The resonances due to the aromatic protons were shifted
significantly upfield (>1 ppm) for the aminated polymer relative
to those observed for the nitrated polymer. Additionally, a new
peak positioned at approximately 4.2 ppm due to the hydrogen atoms
on the nitrogen of the newly formed aniline functionality was
observed. As in the case of the nitrated material, multiple peaks
were observed for the benzylic methine protons along the polymer
backbone arising from the different magnetic environments of these
protons depending upon the substitution of the aromatic ring
adjacent to it. A weighted ratio of the integral of the peak due to
the amine hydrogens (4.2 ppm) to the total integral of the aromatic
region revealed that approximately 83 mole percent of the phenyl
groups bear the amino group corresponding to 32 mol % of
functionalized repeating units. This is in excellent agreement with
the calculated degree of nitration of the starting polymer.
Example 31
Sulfurated Borohydride Reduction of Low Nitrated Copolymer
[0181] A 100 mL flask equipped with a magnetic stir bar was charged
with 500 mg of "low" nitrated ES copolymer (.about.0.045 mmol
NO.sub.2 groups) prepared as in Example 29. The flask was sealed
with a septum and swept with nitrogen with one needle attached to a
N.sub.2 supply and a second needle piercing the septum and acting
as a vent. The vent needle was then removed and the flask was kept
under a pad of nitrogen. Dry tetrahydrofuran (25 mL) was added to
the flask via syringe and the reaction mixture was stirred at
ambient temperature to dissolve the polymer (1 hr). When the
polymer had dissolved, sulfur (0.289 g, 9 mmol) was added to the
reaction mixture rapidly in one portion by removing the septum.
After the addition the septum was replaced and the reaction mixture
stirred to dissolve the sulfur. When the sulfur had dissolved, 1.5
mL (3 mmol) of a 2 molar solution of lithium borohydride in
tetrahydrofuran was added dropwise via a syringe (added over 1
minute). Upon addition of the borohydride, the reaction mixture
becomes intensely yellow and gas is evolved. After gas evolution
subsided, the septum was replaced with a condenser (topped with N2
inlet) and the flask was submerged in an oil bath and the reaction
mixture gently refluxed. After approximately 30 minutes, the
reaction mixure became a greenish/yellow gelatinous mass. Heating
was continued overnight (total heating 17 hrs). The reaction
mixture was then cooled to room temperature. The loose gel was
precipitated into 500 mL of 50/50, v/v, methanol/water in an
explosion proof blender to yield a yellowish colored polymer. The
polymer was collected by filtration on a glass fritted funnel and
was washed twice with 20 mL portions of methanol. The polymer was
air dried on the funnel and then placed in a vacuum oven at
30.degree. C. for final drying. The isolated yield of polymer was
510 mg.
[0182] The glass transition temperature of the polymer was
21.7.degree. C. The polymer dissolved easily in chloroform (100 mg
of polymer in 2 g CDCl.sub.3) to give a clear homogeneous solution.
No gellation problems were observed as noted above for the more
highly functionalized material. Proton and carbon-13 NMR analysis
of the aminated polymer in CDCl.sub.3 yielded spectra consistent
with that expected for ES bearing amino functionality but
quantitation was difficult due to the low level of
functionalization. A weighted ratio of the integral of the peak due
to the amine hydrogens to the total integral of the aromatic region
reveals that approximately 2 mole percent of the phenyl groups bear
the amino group corresponding to 0.77 mol % of functionalized
repeating units. This number is higher than expected (the starting
material had 1.3 mole percent of phenyl groups nitrated) but the
error on the number is high as it is near the detection limit for
the NMR analysis.
* * * * *