Copolymers of norbornene and functional norbornene monomers

Details Copolymers of norbornene and functional norbornene monomers Copolymers of norbornene and functional norbornene monomers

2002-04-10

2003-01-28

Henderson, Christopher (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C525S326800, C525S327300, C525S327200

Reexamination Certificate

active

06512065

ABSTRACT:

FIELD OF THE INVENTION
The present invention is directed to polymer compositions. More particularly, the present invention is directed to polymer compositions obtained by ring-opening metathesis polymerization of functional norbornene monomers.
BACKGROUND OF THE INVENTION
Cycloolefin polymers (e.g. norbornene-based polymers) and copolymers have received a great deal of attention in recent years. They have found application in dielectric, optical, and photolithographic applications. In addition, the utility of these materials as engineering thermoplastics has been explored. As such, new cyclic olefin copolymers and catalysts for the efficient preparation of cyclic olefin polymers are constantly being sought.
The addition polymer of norbornene, i.e., polynorbornene or poly(bicyclo[2.2.1]hept-2-ene, was described in U.S. Pat. No. 2,721,189. In this patent, two types of norbornene polymers were prepared. The first polymer was prepared by the addition polymerization of norbornene giving a fully saturated cyclic olefin polymer.
The second polymer was formed by “Ring-Opening Metathesis Polymerization” (ROMP) giving an unsaturated polymer backbone.
Throughout the years, work in many academic and industrial institutions have led to the development of ring-opening metathesis polymerization catalysts that are tolerant of functional groups. Most notably, are the molybdenum and ruthenium complexes that Schrock and Grubbs have developed (U.S. Pat. No. 4,681,956; U.S. Pat. No. 4,883,851; WO 96/04289). A variety of polymers with pendant functional groups have thus been prepared by ROMP. Further processing of the unsaturated polymers has been attempted in order to achieve materials with better properties. Physical blends (WO 93/06171) and chemical modification of the polymer structure by hydrogenation (U.S. Pat. No. 5,115,037), photolysis (EP 904767 A2) and others U.S. Pat. No. 5,603,985) are all examples illustrating technologies involved in the making of ROMP polymers.
Despite all advances in the new materials prepared by ROMP, there however remains a need to polymerize monomers with functional groups, such as epoxides and dioxalanes, which allow further chemical reactions to give polymers having desired physical properties.
SUMMARY OF THE INVENTION
The present invention relates to a polymer composition having the formula:
—[A]
S
—[B]
T
—
wherein A is a monomer repeat unit derived from one or more monomers selected from the group consisting of:
and B is a monomer unit derived from one or more functional norbornene monomers selected from the group consisting of:
wherein
R
7a
and R
7b
are independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl;
R
8a
and R
8b
are independently selected from H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, C(O)—R
9
;
R
9
is hydrocarbyl or substituted hydrocarbyl;
R
5a
and R
5b
are each independently H, hydrocarbyl, halogen, halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
R
6a
and R
6b
are each independently H, hydrocarbyl, halogen, halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
R
5a-b
and R
6a-b
may be taken together to form a ring, and S and T represent the mole fraction of the respective monomer unit and sum to one with the proviso that T>0; and k=0-3 and j=1-6.
The present invention is further a process for preparing functionalized polymers comprising the ring opening metathesis of functional norbornene to form homopolymers of norbornene or copolymers of norbornene wherein at least one of the monomers is a functional norbornene. The copolymers may be random, alternating or block copolymers.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to polymers having the formula:
—[A]
S
— and —[B]
T
—
wherein A is a monomer repeat unit derived from one or more monomers selected from the group consisting of:
and B is a monomer unit derived from one or more functional norbornene monomers selected from the group consisting of.
wherein
R
7a-b
is H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl;
R
8a-b
is H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl, C(O)—R
9
where R
9
is hydrocarbyl or substituted hydrocarbyl;
R
5a-b
and R
6a-b
are each independently H, hydrocarbyl, halogen, halohydrocarbyl, heteroatom connected hydrocarbyl or heteroatom connected substituted hydrocarbyl;
R
5a-b
and R
6a-b
may be taken together to form a ring, and S and T represent the mole fraction of the respective monomer unit and sum to one with the proviso that T>0; and k=0-3 and j=1-6.
In one embodiment of the present invention, the polymers herein described are prepared by a process including a ring-opening metathesis polymerization of cyclic olefins using metal complexes containg a metal-carbon double-bond which can undergo metathesis with a carbon-carbon double bond present in the monomers. Complexes such as the Schrock-type molybdenum alkylidene or the Grubbs-type ruthenium carbene complexes are preferred catalysts used in this invention.
As means of an example, ring-opening metathesis polymerization of monomers A1 and B4 is illustrated to give a polymer I, where neither the stereochemistry or the nature of end groups are implied by the drawing:
As used herein, the phrase “a monomer repeat unit derived from one or more norbornene, substituted norbornene or functional norbornene monomers” refers to the polymer product of the transition metal catalyzed ring-opening metathesis polymerization of said monomers as depicted by polymer I. It is understood that polymer I only depicts one combination of A1 and B4 monomers and that many other combinations of A1 and B4 are possible.
The polymers products described in this disclosure can be filter hydrogenated to give a saturated backbone. For instance, polymerization of monomers A1 and B4 by ring-opening metathesis polymerization produces polymer I as illustrated above. Polymer I can then be hydrogenated to give a polymer with a polyethylene cyclopentane-type structure, polymer II, where neither the stereochemistry or the nature of the end groups are implied by the drawing:
The polymers described in this disclosure can be further hydrolized to give pendant hydroxy moieties. Polymerization of monomers A1 and B4 by ring-opening metathesis polymerization will, upon treatment with strong acids, give a polymer containing hydroxyl group. Similarly, the formation of free radicals is also possible from epoxide-containing monomer units such as those originating from B2.
In ring-opening metathesis polymerization, one polymer chain is produced per active site. An acyclic olefin can be used as a chain-transfer agent. Addition of an acyclic olefin of formula III, shown below, allows improved control over the molecular weight of the polymer and over the processibility of the reaction mixture as compared to reactions that do not utilize chain transfer agents:
wherein R
10a
and R
10b
are hydrogen atom, hydrocarbyl, and substituted hydrocarbyl.
In this disclosure, symbols ordinarily used to denote elements in the PeriodicTable take their ordinary meaning, unless otherwise specified. Thus, N, O and S stand for nitrogen, oxygen and sulfur, respectively.
A “hydrocarbyl” group means a monovalent or divalent, linear, branched or cyclic group which contains only carbon and hydrogen atoms. Examples of monovalent hydrocarbyls include the following: C
1
-C
20
alkyl; C
1
-C
20
alkyl substituted with one or more groups selected from C
1
-C
20
alkyl, C
3
-C
8
cycloalkyl, and aryl; C
3
-C
8
cycloalkyl; C
3
-C
8
cycloalkyl substituted with one or more groups selected from C
1
-C
20
alkyl, C
3
-C
8
cycloalkyl, and aryl; C
6
-C
14
aryl; and C
6
-C
14
aryl substituted with one or more groups selected from C
1
-C
20
alkyl, C
3
-C
8
cycloalkyl, and aryl; where the term “aryl” preferably denotes a phenyl, napthyl, or anthracenyl group. Examples of divalent (bridging) hydrocarbyls include: —CH
2
—, —CH
2
CH
2

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