Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From hydrocarbon reactant
Reexamination Certificate
2000-05-02
2002-02-05
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From hydrocarbon reactant
C528S396000, C528S397000, C528S422000, C525S242000, C525S191000, C585S262000, C585S506000, C585S422000
Reexamination Certificate
active
06344538
ABSTRACT:
BACKGROUND OF THE INVENTION
Interest in the field of functionalized polymeric materials stems from the desire to combine the unique properties of a functional group with those of a high molecular weight polymer.
Functionalized polymers have the potential for crosslinking via ionic interactions and covalent bonds, leading to improved properties for applications such as polymer blends. The introduction of specifically interacting groups is a particularly versatile route to miscibility enhancement. Other applications of these materials are in membranes, packaging, dispersants, adhesives and coatings. In addition, functionalized polymers may be used in the modification of existing materials to alter their adhesion, processability, solubility, dyeability, thermal, mechanical, and other properties.
Functional groups can be introduced into a polymer by two general approaches: (1) chemical modification of a nonfunctionalized, preformed polymer, or (2) polymerization or copolymerization of monomers containing the functionality. The second method has the advantages of producing a more homogeneous polymer with more uniform functionalization, the ability to analyze the monomers prior to polymerization, and the ability to control loading and distribution of functional groups along the polymer backbone.
A number of different functional or other polar groups have been incorporated into various polyolefin and polyvinyl materials. Successful functionalization is typically performed after polymer formation. In many instances, only terminal functionalization is achieved. Where functionalized monomers have been polymerized to prepare functional group-bearing polymers, the extra steps of masking the monomer functionality prior to polymerization, and then subsequently removing the mask, have been required. Limited success has previously been achieved in the polymerization of functionalized diene monomers, although such monomers have enormous commercial significance and utility in materials such as elastomers, adhesives, sealants, coatings, molded mechanical articles, and the like.
Initial work with nonsilicon-containing functionalized dienes was reported by Petzhold et al., which focused on anionic polymerization of N,N-diethylaminoisoprene and elucidation of microstructures. Petzhold, C., et al., (
Makromol. Chem., Rapid Commun
1993, 14, 33-43) refers to low yields (<50%) of low molecular weight (number-average molecular weight 5,000 g/mol) polymers obtained by anionic and radical polymerization of 2-(N,N-diisopropyl-aminomethyl)-1,3-butadiene. Petzhold, C., et al., (
Macromolecules
1994, 27, 3707-13) refers to low yields of low molecular weight polymers obtained by anionic polymerization of a series of 2-(N,N-dialkylaminomethyl)-1,3-butadienes.
What is needed are new functionalized diene monomers and methods for preparing and polymerizing functionalized dienes to produce high yields of functionalized diene polymers, without the requirements of masking and unmasking the functional group, or of adding the functionality only after polymerization.
SUMMARY OF THE INVENTION
The present invention provides functionalized diene monomers and methods for preparing and polymerizing such functional group-bearing monomers to prepare high yields of functionalized polymers and copolymers.
The diene monomers and functionalized polymers of the invention include, but are not limited to, butadiene monomers and polymerized functionalized butadiene monomers such as: 2-(N,N-dimethylaminomethyl)-1,3-butadiene (Compound 1a), 2-(N,N-diethylaminomethyl)-1,3-butadiene (Compound 1b), 2-(N,N-di-n-propylaminomethyl)-1,3-butadiene (Compound 1c), 2-(cyanomethyl)-1,3-butadiene (Compound 2), 2-(aminomethyl)-1,3-butadiene (Compound 3), 2-(hydroxymethyl)-1,3-butadiene (Compound 4), 2-(carboxymethyl)-1,3-butadiene (Compound 5), 2-(acetoxymethyl)-1,3-butadiene (Compound 6), 2-(2-alkoxy-2-oxoethyl)-1,3-butadiene (Compound 7), as well as disubstituted functionalized diene monomers and polymerized disubstituted functionalized diene monomers such as 2,3-bis(cyanomethyl)-1,3-butadiene (Compound 8), 2,3-bis(dialkylaminomethyl)-1,3-butadiene (Compound 9), 2,3-bis(4-ethoxy-4-oxobutyl)-1,3-butadiene (Compound 10) and the 2,3-bis(3-cyanopropyl)-1,3-butadiene (Compound 11). Also provided herein are methods for synthesizing these and other functionalized diene monomers, polymers, and copolymers.
The resulting polymers and copolymers may be used as is or blended with other materials to make a variety of new products, including adhesives, sealants, surfactants, elastomers, ionomers for, e.g., coatings and membranes, and may also be employed as functionalized polyolefin precursors. The resulting functionalized polymers or polymer blends may be quaternized, hydrogenated, cross-linked, or subject to other known polymer reactions to enhance properties for specific applications, as described in detail herein.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objects and advantages of the invention will be attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the presently preferred embodiments of the invention, which together with the following examples, serve to explain the principles of the invention.
Functionalized Diene Monomers
The present invention provides functionalized diene monomers of the formula:
Compound 1: Y=NR
2
(1a: R=methyl; 1b: R=ethyl; 1c: R=n-propyl)
Compound 2: Y=CN
Compound 3: Y=NH
2
Compound 4: Y=OH
Compound 5: Y=COOH
Compound 6: Y=OCOCH
3
Compound 7: Y=COOR (R=any alkyl group)
and similar functionalized monomers, having various functional groups, which may be synthesized by following the teachings provided herein.
The present invention also provides disubstituted functionalized diene monomers of the formula:
Compound 8: Y=CN
Compound 9: Y=NR
2
(9a: R=methyl; 9b: R=ethyl; 9c: R=n-propyl)
and similar disubstituted functionalized diene monomers , having various functional groups, which may be synthesized by following the teachings provided herein. The invention further provides disubstituted functionalized diene monomers of the formula:
Compound 10: Y=COOEt
Compound 11: Y=CN
and similar disubstituted functionalized monomers, having various functional groups, all of which may be synthesized by one of ordinary skill in the art given the teachings provided herein.
Monomer Synthesis and Purification
Compounds 1-9 and similar functionalized diene monomers are preferably synthesized by the techniques discussed below, although any suitable method may be used. The invention, including the polymers and polymerization products and processes of the invention, should be understood as not being limited to the following preferred monomers or monomer syntheses.
Compounds 1, 2, 3, 4 and 6 can be synthesized from the monobromide precursor, 2-(bromomethyl)-1,3-butadiene in several ways. Two methods are described below for the synthesis of the monobromide. The second method gives improved yields and purity.
The first method for the synthesis of 2-(bromomethyl)-1,3-butadiene involves the synthesis of 1,4-dibromo-2-methyl-2-butene by reacting isoprene with bromine at a temperature in the range of about 20° C. or below. The dibromide may then be reacted at elevated temperature in the range of about 120° C. with 1,3-dimethyl-3,4,5-6-tetrahydro-2(1H)-pyrimidinone (DMPU). The resulting 2-(bromomethyl)-1,3-butadiene is then reacted with the desired dialkylamine, sodium cyanide, phthalamide then hydrazine, potassium acetate then base, and potassium acetate to give 1, 2, 3, 4 and 6, respectively.
The second method for the synthesis of 2-(bromomethyl)-1,3-butadiene is preferred as it leads to higher yields of higher pu
Dickstein , Shapiro, Morin & Oshinsky, LLP
Iowa State University & Research Foundation, Inc.
Truong Duc
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