Blends and alloys of polycyclic polymers

Details Blends and alloys of polycyclic polymers Blends and alloys of polycyclic polymers

2000-10-04

2003-11-18

Mullis, Jeffrey (Department: 1711)

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C528S025000, C528S031000, C528S033000, C528S039000

Reexamination Certificate

active

06649707

ABSTRACT:

BACKGROUND OF THE INVENTION
Addition polymers derived from norbornene-type monomers exhibit a number of physical and mechanical properties, some of which are highly desirable while others are less desirable or even undesirable. For example, the addition homopolymer of norbornene, i.e., poly(bicyclo[2.2.1]hept-2-ene) exhibits some excellent characteristics such as optical clarity, low moisture absorption, and extremely high thermomechanical resistance having a glass transition temperature of about 380° C. On the other hand, this same homopolymer is very brittle requiring improved toughness for many applications. A well known effective method of improving the properties of a polymer is to blend or alloy the polymer with another polymer (or polymers) in order to optimize a given property, e.g., toughness or heat distortion temperature.
A polymer blend is simply a mixture of two or more polymers. The polymer blend, however, can be either immiscible or miscible depending on the value of the free energy of mixing between the polymeric species. For a negative free energy of mixing, the thermodynamics are favorable for a miscible polymer blend; typically a one-phase system results. For a positive free energy of mixing an immiscible polymer blend results giving, typically, a multi-phase system. To change the morphology of a blend, the interfacial properties of the blend must be changed. One method to accomplish this is to add a compatibilizing agent to the blend. According to L. A. Utracki (
Polymer Alloys and Blends. Thermodynamics and Rheology
. Hanser, Munich, 1989, p. 124) the “goal of compatibilization is to obtain a stable and reproducible dispersion which would lead to the desired morphology and properties.” This can be accomplished in the following ways: 1) add linear, graft, or random copolymers to a polymer blend; 2) coreact in the blend to generate in-situ either copolymer, interacting polymers or interpenetrating networks (by the synthesis of one of the polymers in the presence of the second polymeric constituent); or 3) modify the homopolymers by incorporation of functional groups. In many cases this may result in the formation of a polymer alloy, that is, an immiscible polymer blend having a modified interface or morphology. The morphology of the polymer alloy may be a very fine (sub-micron) dispersion or relatively large depending on the compatibilizer chosen, the amount of compatibilizer added, and the desired properties of the alloy.
Incompatibility is the rule rather than the exception, particularly in the case of hydrocarbon addition polymers derived from norbornene-type monomers (e.g., polynorbornene). Blends of incompatible polymers in most instances form large domains with properties inferior to the constituents, therefore compatibilizer techniques are usually employed to maximize the strengths of the constituents while overcoming their individual deficiencies. Various attempts have been undertaken to prepare polymer compositions that are easily processable and which possess improved physical properties. Compatibilization can provide for specific interactions between polymers. In this regard, methods have focused upon the preparation and use of functionalized polymers having pendant reactive groups which facilitate the grafting of coreactive materials and other polymers to form graft-modified polymers and polymer blends having improved physical properties. Typically a polymer can be functionalized by copolymerizing the monomer with monomer(s) having a functional substituent. However, polyolefins particularly polynorbornene-type addition polymers are generally more difficult to functionalize by copolymerization processes because of the tendency of the polar groups in the monomers to poison the catalyst. To our knowledge no attempts have been made to prepare blends and alloys of polycyclic addition polymers derived from norbornene-type monomers with a variety of other dissimilar polymers.
Accordingly, it would be highly desirable to provide blends and alloys of addition polymerized norbornene-type monomers with other polymer systems.
SUMMARY OF THE INVENTION
We have found that it is possible to functionalize polynorbornene-type polymers so as to make them compatible and hence alloyable with a variety of other polymers to generate families of new blends, alloys, and block copolymers with superior balance of properties.
It is a general object of this invention to provide a functionalized polycyclic addition polymer derived from NB-type monomers.
It is another object of this invention to provide polycyclic addition polymers containing a terminal functional group.
It is a further object of this invention to provide polycyclic addition polymers that contains pendant functional groups.
It is still a further object of the invention to provide free radical graft copolymers of polycyclic addition polymers having pendant polyvinylic side blocks and maleic anhydride grafts.
It is another object of this invention to provide in situ polymerization blends of polycyclic addition polymers and reactive and nonreactive elastomeric polymers.
It is still a further object of the invention to provide chlorinated polycyclic addition polymers.
It is another object of the invention to provide miscible blends of polycyclic addition polymers and polystyrene.
In still another object of the invention to provide methods that enable functional end groups and functional pendant groups to be tailored so that desired reactions can be effected.
It is still another object of the invention to prepare olefinic A-B block copolymers with pendant polynorbornene-type side blocks.
It is a further object to react the terminal functional polycyclic addition polymers of this invention with coreactive monofunctional and difunctional polymeric materials to make A-B and A-B-A block copolymers.
We have found that it is possible to functionalize polycyclic addition polymers derived from NB-type monomers to make new materials that can be utilized-as: 1) intermediates for the preparation of other functional containing polymers; 2) segment polymers for the preparation of block copolymers; 3) substrate polymers for the preparation of graft copolymers; 4) as constituent polymers in the preparation of in situ polymer blends; 5) polymers in miscible blends; 6) compatibilizers for polymer blends; and 7) thermosetting systems.
These and other objects of the present invention are accomplished by the following methods and functionalized PNB compositions. As used throughout the specification, the term PNB means polymers represented by structure II below.
DETAILED DESCRIPTION
The polycyclic addition polymers of this invention are derived from at least one norbornene-type (NB-type) monomer having the following structure:
wherein R
1
to R
4
independently represent hydrogen, linear and branched (C
1
-C
20
)alkyl; hydrocarbyl substituted and unsubstituted (C
5
-C
12
)cycloalkyl; substituted and branched (C
5
-C
12
)cycloalkenyl (C
6
-C
24
)aryl; (C
7
-C
15
)alkyl; linear and branched (C
2
-C
20
)alkenyl; (C
3
-C
20
)alkynyl; any of R
1
and R
2
or R
3
and R
4
can be taken together to form a (C
1
-C
10
)alkylidene group; R
1
and R
4
when taken together with the two ring carbon atoms to which they are attached can represent saturated and unsaturated cyclic groups of 4 to 12 carbon atoms or any aromatic ring of 6 to 17 carbon atoms; and n is 0, 1, 2, 3, or 4. When n is 0 in structures I and II and in all structures in the specification and claims, it will be recognized that a bicyclic structure will be present and that substituents R
1
to R
4
will be attached to the respective ring carbon atoms in the cicyclic ring. By hydrocarbyl is meant that the substituent is composed solely of carbon and hydrogen atoms. Representative hydrocarbyl substituents include linear and branched (C
1
-C
10
)alkyl, and linear and branched (C
2
-C
15
)alkenyl.
The term NB-type monomer as used throughout the present specification is meant to include norbornene as well as any higher cyclic derivative thereof so long as the monomer contains

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