Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-12-14
2002-11-05
Teskin, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S135000, C526S171000, C526S308000
Reexamination Certificate
active
06476167
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to novel, end-functionalized, linear, non-crosslinked polyolefins without pendant chain branched groups, and to a process for the preparation of these end-functionalized, linear, non-crosslinked polyolefins without pendant chain branched groups. This process is improved over other known processes in that it utilizes a chain transfer agent free of protecting groups, and hence forms the end-functionalized, linear, non-crosslinked polyolefins directly, without the need of further purification or deprotection after polymerization.
Hydroxyl-end functionalized polybutadienes synthesized via Ring Opening Metathesis Polymerization (or ROMP) are disclosed in Chung et. al. (U.S. Pat. No. 5,247,023), Grubbs, et. al. (U.S. Pat. No. 5,750,815) and Nubel, et al (U.S. Pat. Nos. 5,512,635, 5,559,190, 5,519,101 and 5,403,904). However, these polybutadienes are synthesized in a 2-step process where the first step involves polymerization and the second step involves conversion of the polymer chain ends to hydroxyl functionality.
The use of transition metal complexes to catalyze metathesis reactions with functionalized olefins is well known. U.S. Pat. Nos. 6,048,993, 6,111,121, 5,917,071, 5,831,108, 5,710,298, 5,342,909 and 5,312,940 describe the synthesis of various metathesis catalysts useful for this purpose. U.S. Pat. Nos. 5,880,231, 5,849,851, 5,750,815, 5,728,917 and 5,559,190 describe processes by which these catalysts are used to make functionalized polymers. U.S. Pat. Nos. 6,060,570, 5,731,383, 5,880,231 and 5,990,340 describe processes for making end-functionalized linear non-crosslinked polyolefins without chain branched groups where the cyclic olefin (1,5-cyclooctadiene) and a functionalized chain transfer agent (1,4-diacetoxy-2-butene) were used for the synthesis of linear end-functionalized materials. The use of a difunctional chain transfer agent such as 1,4-diacetoxy-2-butene creates hydroxyl end-functionalized polybutadienes having a functionality of 2.0. In these examples, however, after polymerization, the chain ends must be converted into hydroxyl functionality to form the end-functionalized polyolefin.
The present invention relates to the use of a chain transfer agent that is designed to ensure efficient reaction with traditional metathesis catalysts and 1,5-cyclooctadiene but forms a hydroxyl end-functionalized polybutadiene directly, without the need for further purification of the polymer. U.S. Pat. No. 5,360,863 describes the synthesis of these CTAs and the subsequent incorporation of these materials in coating compositions.
Polyurethane elastomers made from these hydroxyl end-functionalized polybutadienes have been described previously (U.S. Pat. No. 5,589,543 and
Cell Polym
1996, 15(6), 395). As described therein, hydroxyl end-functionalized polybutadiene was reacted with diisocyanates and extended with chain extenders to produce polyurethanes. In one example of using the one-shot procedure, molten diphenyl-methyl diisocyanate (MDI) and butane diol are blended with the hydroxyl end-functionalized polybutadiene and the reaction mixture is compressed under elevated temperature and pressure to form the polyurethane. In another example, toluene diisocyanate (TDI) and the hydroxyl end-functionalized polybutadiene are reacted to form a prepolymer, and the resultant prepolymer was chain extended with methylene-bis-ortho chloroaridine (MbOCA). The mixture is then compressed under elevated temperature and pressure to form a polyurethane. The polyurethanes formed under these conditions had improved hydrolytic stability and reasonable mechanical properties. U.S. Pat. No. 5,990,340 also describes prepolymers made with hydroxyl end-functionalized polybutadiene and various diisocyanates.
Co-pending U.S. application Ser. No. 09/140,208 filed on Aug. 26, 1998, now U.S. Pat. No. 6,166,166which is commonly assigned, relates to a process for preparing thermoplastic polyurethane materials. This process comprises a) casting an NCO-terminated prepolymer with 1,4-butanediol to form a casting composition, b) extruding the casting composition to form a polyurethane elastomer, c) pelleting the polyurethane elastomer to form pellets, and d) processing the pellets to form a thermoplastic material. Suitable NCO-terminated prepolymers comprise the reaction product of a polyisocyanate with an end-functionalized, linear, non-crosslinked polyolefin without pendant chain-branched groups which is prepared by reacting 1,4-diacetoxy-2-butene with 1,5-cyclooctadiene in the presence of a ruthenium complex catalyst.
The processes known and described in the art relate to the synthesis of hydroxyl end-functionalized polybutadienes and require large quantities of organic solvents such as, for example, tetrahydrofuran (or similar solvent) to saponify acetate end-groups into hydroxyl functionality. Additionally, large quantities of methanol (or similar non-solvents) must be used in the polymer purification. These solvents increase both production costs and disposal costs. Tetrahydrofuran is a hazardous material, and thus, its use and treatment is expensive and environmentally unacceptable. Accordingly, it is desirable to develop a process for the production of hydroxyl end-functionalized, linear, non-crosslinked, polyolefins without pendant chain branched groups that does not require enormous quantities of these organic solvents.
In general, improvements in the production of hydroxyl end group functionalized polyolefins have focused on the catalysts used in the polymerization. It is the object of the present invention, however, to provide a process for the synthesis and purification of hydroxyl end-functionalized, linear, non-crosslinked, polyolefins without pendant chain branched groups through improvements to the chain transfer agent, and, thereby eliminating the need for purification or further processing after polymerization.
SUMMARY OF THE INVENTION
This invention relates to a novel, end-functionalized, linear, non-crosslinked polyolefin that is free of pendant chain branched groups, and to a process for the preparation of these end-functionalized, linear, non-crosslinked polyolefins that are free of pendant chain branched groups.
As used herein, the terminology “free from pendant chain branched groups” describes a polymer where no pendant chain branched group(s) is (are) created during the process of making the polymer. Polymerization of monomers or chain transfer agents containing pendant side chains such as phenyl rings, pendant functionality, alkyl chains, etc, which therefore create pendant chain branched groups in the resultant polymers are, however, considered to be within the scope of the present application. In other words, polymers having pendant chain branched groups which correspond to the pendant chain branched groups of the monomers used to prepare the polymers are within the scope of the present application. For example: the polymerization of 4-methylpentene creates a polymer which contains a pendant methyl group attached to every 5
th
carbon atom. Since this methyl group was present in the starting monomer, the resultant polymer is considered to be within the scope of the present invention.
The end-functionalized, linear, non-crosslinked polyolefin without pendant chain branched groups comprise the reaction product of: (A) a cyclic olefin monomer, with (B) a chain transfer agent comprising the reaction product of an unsaturated dihydric alcohol and an alkylene oxide, in the presence of (C) a catalyst, wherein the functionality of the polyolefin as defined by vapor phase osmometry (VPO) and end group titration ranges from 1.7 to 2.2, and the polyolefin has a structure corresponding to:
wherein:
R
1
: represents a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms;
R
2
: represents a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms;
m: represents an integer from 0 to 1,000, preferably from 0 to 5;
p: represents an integer from 0 to 1,000, preferably from 0 to 5;
Bayer Corporation
Brown N. Denise
Gil Joseph C.
Teskin Fred
LandOfFree
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