Modified copolymer of olefin and cycloolefin

Details Modified copolymer of olefin and cycloolefin Modified copolymer of olefin and cycloolefin

2001-12-28

2003-12-23

Choi, Ling-Siu (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S348000, C526S346000, C526S308000, C526S281000

Reexamination Certificate

active

06667379

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an olefin/cycloolefin/alkylstyrene copolymer, and more particularly to a functionalized olefin/cycloolefin/alkylstyrene copolymer which have enhanced properties such as good adhesion to a substrate and good compatibility with other polymers.
2. Description of the Prior Art
Non-functionalized cycloolefin copolymer (COC) are of high transparency and hardness and of low density. Furthermore, they are virtually chemically and moisture inert and are highly resistant to heat deformation. However, since non-functionalized COCs have non-polar molecular structure, they have poor adhesion to the substrate and poor compatibility with most other polymers.
Many researchers have drawn their attentions to synthesize functionalized cycloolefin copolymer in order to improve the adhesion properties and compatibility with other polymers. For example, Kreuder et al. in U.S. Pat. No. 5,756,623 have disclosed an ene-functionalized COC, which includes polymerized units of at least one cycloolefin, polymerized units of at least one olefin containing at least one double bond, polymerized units of at least alpha olefins, and polymerized units which possess at least two electron-withdrawing groups which are carbonyl or nitrile.
In JP 5279412, an unsaturated copolymer is obtained by compolymerizing C
2
-C
12
alpha olefin and a cyclic olefin containing alkylidene group or alkenyl group. Then, the unsaturated copolymer is oxidized with a peracid. Thus, the double bond of the alkylidene group or alkenyl group in the unsaturated copolymer is oxidized and epoxy group and/or OH group is introduced to the double bond.
In JP 5279413, an unsaturated copolymer similar to JP 5279412 is first obtained. Then, the unsaturated copolymer is reacted with a halogen or a hydrogen halide. As a result, the halogen group is introduced to the double bond in the unsaturated copolymer.
In JP 5287015, an unsaturated copolymer similar to JP 5279412 is first obtained. Then, amino group is introduced to the double bond in the unsaturated copolymer.
Chung et al. in U.S. Pat. No. 5,543,484 have disclosed a functionalized &agr;-olefin/para-alkylstyrene copolymer.
First, &agr;-olefin and para-alkylstyrene are copolymerized. The incorporation of p-alkylstyrene into the &agr;-olefin polymer results in the generation of benzylic protons, which are readily available for many chemical reactions, thereby introducing functional groups at the benzylic position under mild reaction conditions. Then, the olefin/p-alkylstyrene copolymer is functionalized by the functionalization of benzylic protons in p-alkylstyrene units. Such functionalization leads to improvement in the physical properties of the original olefin polymers.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an olefin/cycloolefin/alkylstyrene copolymer, and more particularly a functionalized olefin/cycloolefin/alkylstyrene copolymer. By the functionalization of benzylic protons in alkylstyrene units, the olefin/cycloolefin/alkylstyrene copolymer can have good adhesion to the substrate and good compatibility with other polymers.
To achieve the above-mentioned object, the olefin/cycloolefin/alkylstyrene copolymer of the present invention includes the following repeating units:
wherein
R
1
and R
2
are independently selected from the group consisting of hydrogen, alkyl, and primary and secondary haloalkyl,
X can be the same or different and is selected from the group consisting of (1) hydrogen, (2) a functional group, (3) a polymer moiety, (4) an alkali or alkaline earth metal, and (5) mixtures thereof, wherein the functional group is selected from a group containing halogen, oxygen, sulfur, silicon, nitrogen, carbon, phosphorus, and mixtures thereof;
wherein
a is an integer from 0 to 3,
R
3
, R
4
, R
5
, R
6
, R
8
, R
9
, R
10
, and R
11
can be the same or different and are selected from the group consisting of hydrogen, halogen, C
1-10
alkyl, and haloalkyl and
R
12
and R
13
can be the same or different and are selected from the group consisting of hydrogen, halogen, C
1-10
alkyl, haloalkyl, aryl, haloaryl, alcohol, ester, and acid, or R
12
and R
13
can be bonded together to form formula (III)
wherein
R
14
and R
15
can be the same or different and are selected from the group consisting of hydrogen, halogen, C
1-10
alkyl, and haloalkyl and
b is an integer from 3 to 5; and
wherein
R′ is C
1
to C
18
linear and branched alkyl, and most preferably R′ is C
1
to C
5
primary or secondary alkyl.
DETAILED DESCRIPTION OF THE INVENTION
The feature of the present invention is to introduce an alkylstyrene unit to an olefin/cycloolefin copolymer in order to obtain an olefin/cycloolefin/alkylstyrene copolymer. It is the first an olefin/cycloolefin/alkylstyrene copolymer is synthesized.
The incorporation of the alkylstyrene unit into the olefin/cycloolefin copolymer results in the generation of benzylic protons, which are readily available for many chemical reactions. Many functional groups can be introduced to the benzylic position under mild reaction conditions. By the functionalization, the adhesion to the substrate and the compatibility with other polymers can be improved compared with the non-functionalized olefin/cycloolefin/alkylstyrene copolymer.
The general process for preparing the olefin/cycloolefin/alkylstyrene copolymer of the present invention will be described below.
First, monomers (A), (B), (C), and optionally (D) are copolymerized to form an olefin/cycloolefin/alkylstyrene copolymer.
Monomer (A) is in an amount of 0.1-50 molt and is an alkylstyrene represented by formula (I)
R
1
and R
2
are independently selected from the group consisting of hydrogen, alkyl, and primary and secondary haloalkyl. Preferably, R
1
and R
2
are independently selected from the group consisting of hydrogen, C
1
to C
5
alkyl, and C
1
to C
5
primary and secondary haloalkyl.
Monomer (3) is in an amount of 1-99 molt and is an cycloolefin represented by formula (II)
wherein
a is an integer from 0 to 3,
R
3
, R
4
, R
5
, R
6
, R
8
, R
9
, R
10
, and R
11
can be the same or different and are selected from the group consisting of hydrogen, halogen, C
1-10
alkyl, and haloalkyl and
R
12
and R
13
can be the same or different and are selected from the group consisting of hydrogen, halogen, C
1-10
alkyl, haloalkyl, aryl, haloaryl, alcohol, ester, and acid, or R
12
and R
13
can be bonded together to form formula (III)
R
14
and R
15
can be the same or different and are selected from the group consisting of hydrogen, halogen, C
1-10
alkyl, and haloalkyl and
b is an integer from 3 to 5.
Monomer (C) is in an amount of 0.1-98.9 mol % and is ethylene, an C
3-20
&agr;-olefin, or mixtures thereof.
Monomer (D) is in an amount of 0-50 mol % and is a non-conjugated diene.
The olefin/cycloolefin/alkylstyrene copolymer obtained above contains an alkylstyrene unit represented by
wherein
R
1
and R
2
are independently selected from the group consisting of hydrogen, alkyl, and primary and secondary haloalkyl.
Then, the alkyltyrene unit-containing copolymer is subjected to halogenation to obtain a cycloolefin copolymer containing the repeating unit (vi) At (vi)
wherein X contains halogen.
The halogenated copolymer is very reative on the halogen group and is readily to undergo various reaction to form other functional groups. For example, the halogenated copolymer can be reacted with a nucleophile selected from a compound containing oxygen, sulfur, silicon, nitrogen, carbon, and phosphorus to obtain a cycloolefin copolymer containing the following repeating unit (vi)
wherein X contains an element selected from the group consisting of oxygen, sulfur, silicon, nitrogen, carbon, and phosphorus.
When some of the X groups contain oxygen, the oxygen-containing group can be alkoxides, phenoxides or carboxylates.
When some of the X groups contain sulfur, the sulfur-containing group can be thiolates, thiophenolates, thioethers, thiocarboxylates, dithiocarboxylates, thioureas, dithi

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