专利号:US-6066705-A 优先权日:1995-08-31 标 题 :Vapor phase synthesis of cis-1, 4-Polyisoprene 发明人:CALDERON NISSIM; CASTNER KENNETH FLOYD; COLVIN HOWARD ALLEN; MUSE JR JOEL 权利人:GOODYEAR TIRE & RUBBER 摘要:By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of: (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure; (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35 DEG C. to about 70 DEG C.; and (3) withdrawing said cis-1,4-polyisoprene from said reaction zone. It has been determined that gel formation can be reduced by conducting the polymerization of isoprene monomer in the presence of a diarylamine, such as para-styrenated diphenylamine.
专利号:US-5859156-A 优先权日:1995-08-31 标 题 :Vapor phase synthesis of rubbery polymers 发明人:CALDERON NISSIM; MUSE JR JOEL; COLVIN HOWARD ALLEN; CASTNER KENNETH FLOYD 权利人:GOODYEAR TIRE & RUBBER 摘要:By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of: (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure; (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene in said reaction zone at a temperature within the range of about 0 DEG C. to about 100 DEG C. in the presence of a diarylamine, wherein said reaction zone is a horizontal, stirred reactor of substantially circular cross section containing a centrally-located drive shaft extending longitudinally through said reactor to which are attached a plurality of adjacently located paddles, which paddles cause essentially no forward or backward movement of the cis-1,4-polyisoprene contained in said reactor; and (3) withdrawing said cis-1,4-polyisoprene from said reaction zone.
专利号:US-7081504-B2 优先权日:2004-08-30 标 题:Synthesis of 1,4-polybutadiene 发明人:RACHITA MICHAEL JOSEPH; JOHNSON SCOTT EDWARDS 权利人:GOODYEAR TIRE & RUBBER 摘要:This invention is based upon the unexpected discovery that alkylated diphenylamines can be used in conjunction with nickel based catalyst systems which contain (a) an organonickel compound, (b) an organoaluminum compound, and (c) a fluorine containing compound to produce cis-1,4-polybutadiene having reduced molecular weight and an increased level of branching. This results in the cis-1,4-polybutadiene exhibiting good processability without sacrificing cold flow characteristics. Additionally, the alkylated diphenylamine which remains in the rubber acts in a manner which provides it with antioxidant protection. In other words, the use of alkylated diphenylamines accomplishes the three major objectives that are realized by employing para-styrenated diphenylamines (reduced molecular weight, regulated polymer macrostructure through branching and antidegradant protection). However, the utilization of alkylated diphenylamines, unlike para-styrenated diphenylamines, offers the additional advantage of being soluble in aliphatic solvents. By virtue of this increased level of solubility in aliphatic solvents, such as hexane, alkylated diphenylamines can be employed at greatly reduced levels of aromatic solvents. Likewise, when mixed catalyst streams containing alkylated diphenyl amines are combined precipitation is minimized compared to para-styrenated diphenylamine significantly improving issues related to fouling. The subject invention more specifically discloses a process for producing cis-1,4-polybutadiene having a reduced molecular weight and improved processability which comprises polymerizing 1,3-butadiene in the presence of (a) an organonickel compound, (b) an organoaluminum compound, (c) a fluorine containing compound, and (d) an alkylated diphenylamine; wherein the alkylated diphenylamine has alkyl groups that contain from 2 to 18 carbon atoms, and wherein the organoaluminum compound and the fluorine containing compound are brought together in the presence of the alkylated diphenylamine.
专利号:US-11155505-B2 优先权日:2017-02-17 标题 :Synthesis of pheromones and related materials via olefin metathesis 发明人:WAMPLER KEITH M; BUI VU; ROZZELL DAVID; COELHO PEDRO; FLORUTI ARTHUR; ONDI LEVENTE; MEHDI HASAN; EROS GABOR 权利人:PROVIVI INC 摘要:Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.
专利号:EP-3583088-B1 优先权日:2017-02-17 标 题:Synthesis of pheromones and related materials via olefin metathesis
专利号:US-2006047033-A1 优先权日:2004-08-30 标题 :Synthesis of 1,4-polybutadiene
摘要:Taylor, R. E.; Diène, C. R.; Daly, E. M., Science of Synthesis, (2009) 46, 552. 摘要:Matsumoto, K.; Katsuki, T.; Arends, I. W. C. E., Science of Synthesis: Stereoselective Synthesis, (2011) 1, 101. 摘要:Ho, C.-Y.; Raja, D., Science of Synthesis: Knowledge Updates, (2023) 2, 340.