Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-12-14
2002-05-21
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
active
06391978
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 the known process in that it utilizes water and base to remove protecting groups during processing rather than large amounts of organic solvents.
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.
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 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. 09/140,238 filed on Aug. 26, 1998, which 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 with improvements in the end-group removal and purification steps. The process of the present invention uses only water and based in the end-group removal and purification steps.
SUMMARY OF THE INVENTION
This invention relates to a process for the synthesis and purification of hydroxyl end-group functionalized, linear, non-crosslinked polyolefins without pendant chain branched groups. The process comprises polymerizing a cyclic olefin monomer with a chain transfer agent in the presence of a suitable catalyst thereby forming a protected end-group functionalized polyolefin, and adding a mixture comprising water and caustic to the protected end-group functionalized polyolefin to remove the protecting groups thereby forming a hydroxyl end-group functionalized, linear, non-crosslinked polyolefin without pendant chain branched groups.
DETAILED DESCRIPTION OF THE INVENTION
A protected end-group functionalized polyolefin is formed, step (I), from the reaction product of: (A) a cyclic olefin monomer, with (B) a chain transfer agent, in the presence of (C) a suitable catalyst. After polymerization, a mixture of water and caustic is added to the protected end-group functionalized polyolefin, step (II), to remove the protecting groups thus forming the hydroxyl end-group functionalized, linear, non-crosslinked polyolefins of the present invention.
The hydroxyl end-group functionalized, linear, non-crosslinked polyolefins of the present invention are characterized as being free of pendant branched groups. These polyolefins are preferably polybutadienes, but other suitable examples include polyethylene, polypropylene, polystyrene, poly(methylpentene), polynorbornene, poly(oxanonorbornene), and similar compounds. Polyolefins of the present invention have functionalities in the range of from 1.7 to 2.2, preferably from 1.95 to 2.05, and most preferably of 2.0, as defined by vapor phase osmometry (VPO) and end group titration.
In accordance with the present invention, it is, of course, possible to use a solvent during polymerization. This is, however, less preferred. Suitable solvents include compounds such as, for example, cyclohexane, tetrahydrofuran, methylene chloride, etc.
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 p
Bayer Corporation
Brown N. Denise
Gil Joseph C.
Lipman Bernard
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