CN1028108C - 一氧化碳与烯属不饱和化合物的聚合物的制备方法 - Google Patents
一氧化碳与烯属不饱和化合物的聚合物的制备方法 Download PDFInfo
- Publication number
- CN1028108C CN1028108C CN90100394A CN90100394A CN1028108C CN 1028108 C CN1028108 C CN 1028108C CN 90100394 A CN90100394 A CN 90100394A CN 90100394 A CN90100394 A CN 90100394A CN 1028108 C CN1028108 C CN 1028108C
- Authority
- CN
- China
- Prior art keywords
- palladium
- complex
- phosphorus
- bidentate ligand
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 16
- 229920000642 polymer Polymers 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000003446 ligand Substances 0.000 claims abstract description 50
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 hydrocarbyl palladium halide Chemical class 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 150000003606 tin compounds Chemical class 0.000 description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- JHPBVORIWHFCDS-UHFFFAOYSA-N (3-diphenylphosphanyl-2,2-dimethylpropyl)-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC(C)(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 JHPBVORIWHFCDS-UHFFFAOYSA-N 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YQHRQVQNJGVQEM-UHFFFAOYSA-N [diphenylphosphanylmethyl(dimethyl)silyl]methyl-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C[Si](C)(C)CP(C=1C=CC=CC=1)C1=CC=CC=C1 YQHRQVQNJGVQEM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YNNYXLLXSONLCU-UHFFFAOYSA-N 3-phenylsulfanylpropylsulfanylbenzene Chemical compound C=1C=CC=CC=1SCCCSC1=CC=CC=C1 YNNYXLLXSONLCU-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- HJSFAHKFVZTLRU-UHFFFAOYSA-N benzyl(trimethyl)stannane Chemical compound C[Sn](C)(C)CC1=CC=CC=C1 HJSFAHKFVZTLRU-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- WBVCLUDHJDTUAU-UHFFFAOYSA-N tetrabenzylstannane Chemical compound C=1C=CC=CC=1C[Sn](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 WBVCLUDHJDTUAU-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- COHOGNZHAUOXPA-UHFFFAOYSA-N trimethyl(phenyl)stannane Chemical compound C[Sn](C)(C)C1=CC=CC=C1 COHOGNZHAUOXPA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
适合用于制备一氧化碳和一种或多种烯属不饱和化合物的共聚物的催化剂组合物由烃基卤化钯与含磷二齿配位体的络合物组成。
Description
本发明涉及以一种由钯化合物和含磷二齿配位体形成的络合物为基础的催化剂组合物，这种组合物适宜用作从一氧化碳和一种或多种烯属不饱和化合物制备聚合物的催化剂。
已经知道在由一氧化碳和一种或多种烯属不饱和化合物制备的线型聚合物中，由一氧化碳派生的链节单元和由所用的烯属不饱和化合物派生的链节单元是以交替形式出现的，这种聚合物可以通过将单体与由二卤化钯和通式为R1R2P-R-PR3R4的含磷二齿配位体形成的络合物为基础的催化剂组合物接触来制备，在通式中，R1，R2，R3，R4是相同的烃基或不同的随选性有极性基团取代的烃基，R为其桥中至少含有两个碳原子的二价有机桥基。
本专利申请人在对这类催化剂组合物的研究中发现，用烃基取代二卤化钯/含磷二齿配位体络合物中的一个与钯相键联的卤素原子后催化聚合的活性获得极大的提高。本申请人还对上述的用烃基取代一个与钯相键联的卤素原子的取代反应进行了研究。刚开始时研究结果令人失望。试图通过用含二卤化钯的络合物与烃基镁化卤，烃基锂化合物或二烃基锌化合物反应来实现所需要的单取代反应的一切努力，看来都会造成两个卤原子均被烃基取代的结果。进一步的研究使研究者发现了一种方法，这种方法使得用烃基有可能只取代上述的二卤化钯/含磷二齿配位体络合物中的一个与钯相键联的卤原子。进一步的研究发现这种方法不仅可以用来取代二卤化钯/含磷二齿配位体络合物（这种含磷二齿配位体符合前面所给的通式）中的一个与钯相键联的卤素原子，而且还可以更普遍地用于含有构型为M-R5-M的二齿配位体的二卤化钯/二齿配位体络合物，其中R5代表一成桥基团，M部分选自磷，硫，氮，砷，锑和C＝C。当这类二齿配位体与二卤化钯络合时，钯原子与二齿配位体中的两M基团之间成键。所发现的用来取代二卤化钯/含磷二齿配位体络合物中一个卤素原子的方法包括将该络合物与含四个与锡相键联基团的锡化合物反应，四个基团中的三个是相同的或不同的烃基，余下的第四个基团既可以是烃基，也可以是氢或卤素原子。将这种方法用于二卤化钯/含磷二齿配位体络合物，其中含磷二齿配位体具有如下通式R1R2P-R-PR3R4，反应得到适合本发明催化剂组合物中使用的烃基卤化钯/含磷二齿配位体络合物。将这种方法用于含有其它二齿配位体的二卤化钯/二齿配位体络合物时，反应得到烃基卤化钯/二齿配位体络合物，将这种络合物与通式为R1R2P-R-PR3R4的化合物反应就可简单地制得所需要的烃基卤化钯/含磷二齿配位体络合物。
由烃基卤化钯和通式为R1R2P-R-PR3R4的含磷二齿配位体的络合物所组成的催化剂组合物是新型的催化剂。制备烃基卤化钯/二齿配位体络合物的方法也是新的，该方法是将二卤化钯和含有M-R5-M构型的二齿配位体的络合物与前文所述的锡化合物反应，随后，如果所得的络合物中所含的二齿配位体不符合通式R1R2P-R-PR3R4的要求，则将该络合物再与通式为R1R2P-R-PR3R4
的含磷二齿配位体反应转化为符合需要的络合物。
因此，本专利申请涉及以烃基卤化钯和通成为R1R2P-R-PR3R4的含磷二齿配位体的络合物为基础的新型的催化剂组合物。其次，本专利申请还涉及这种催化剂组合物在由一氧化碳和一种或多种烯属不饱和化合物制备聚合物中的应用，还涉及到由此制备的聚合物以及至少部分含有这种聚合物的制成品。最后，本专利申请涉及制备烃基卤化钯和构型为M-R5-M的二齿配位体络合物的方法，该方法是将二卤化钯和相应的二齿配位体的络合物与含有四个与锡相键联基团的锡化合物反应，该四个基团中的三个是相同的或不同的烃基，而第四个基团既可以是烃基，也可以是氢或是卤素原子;随后，如果所得到的络合物中所含的二齿配位体不符合通式R1R2P-R-PR3R4的要求，则将该络合物再与通式为R1R2P-R-PR3R4的含磷二齿配位体反应转化为符合要求的络合物。
在通式为R1R2P-R-PR3R4的含磷二齿配位体中，R1，R2，R3，R4是相同的基团为佳。非常适合本发明要求的则是其中R1，R2，R3和R4为未被取代苯基的含磷二齿配位体;和R1，R2，R3，R4为含有一个或多个烷氧基的苯环且其中至少有一个烷氧基处于与苯环相联的磷原子的邻位这种含磷二齿配位体。含磷二齿配位体中的桥基R最好是在桥中含有三个碳原子的桥基。适宜的桥基R的例子有-CH2CH2CH2-，-CH2-C（CH3）2-CH2-和-CH2-Si（CH3）2-CH2-。在络合物中的烃基卤化钯最好是甲基氯化钯。
如前所述，将二卤化钯和相应的二齿配位体的络合物与前面所述的锡化合物反应而制得烃基卤化钯与含构型为M-R5-M的二齿配位体的络合物。如果反应初始络合物中的二齿配位体符合通式R1R2P-R-PR3R4的要求，则其反应产物就是可以用于本发明催化剂组合物的络合物。如果反应初始络合物是含其它二齿配位体的络合物，则反应产物就是一种络合物，将它与通式为R1R2P-R-PR3R4的二齿配位体反应可制得适合用作本发明催化剂组合物的络合物。在用作反应初始原料的化合物中与二齿化钯络合的其它二齿配位体的例子有：其中M为氮原子的二齿配位体如2，2′-二吡啶和1，10-菲咯啉;其中M为磷原子的二齿配位体如双（二苯基膦基）甲烷;其中M为硫原子的二齿配位体如1，3-双（苯硫基）丙烷;其中M为C＝C基的二齿配位体如1，5-环辛二烯和降冰片二烯;其中M为砷原子的二齿配位体如1，3-双（二苯基砷基）丙烷。在制备过程中，初始络合物中的二齿化钯最好是二氯化钯。在本发明的方法中，为了用烃基取代一个与钯原子相键联的卤素原子，使用了锡化合物，在这种锡化合物中，与锡原子相键联的基团中的一个可以是氢或卤素原子，例如三丁基氢化锡和三甲基氯化锡。较好的锡化合物是其中的四个与锡原子相键联的基团都是烃基，尤其是四个基团都相同的锡化合物更好。适用的锡化合物的例子有四甲基锡，四乙基锡，四新戊基锡，四苄基锡，三甲基苯基锡及三甲基苄基锡。最好使用四个与锡原子相键联的基团都相同的锡化合物例如四甲基锡。使用本发明催化剂组合物的聚合反应最好是采用将单体与由聚合产物不溶或实质上不溶的稀释剂配成的催化剂组合物溶液相接触的办法进行。非常适宜的稀释剂是低级醇类如甲醇。如果需要，聚合反应也可以在气相条件下进行。利用本发明的催化剂组合物可以适当地与一氧化碳聚合的烯属不饱和化合物是一类完全由碳和氢组成的化合物以及除了碳氢外还含有一个或多个杂原子的化合物。本发明的催化剂组合物最好用于制备一氧化碳与一种或多种烯属不饱和化合物的共聚物。适宜的烃类单体的例子有乙烯以及其它α-烯烃如丙烯，1-丁烯，1-己烯和1-辛烯。本发明的催化剂组合物特别适用于制备一氧化碳与乙烯的共聚物和用于制备一氧化碳与乙烯及另一种α-烯烃（特别是丙烯）的三元共聚物。用于制备聚合物所需的催化剂溶液的用量是可以在很大范围内变动的。每摩尔欲聚合的烯属不饱和化合物所需要的催化剂用量以含有10-7-10-3摩尔钯较适合，最好是含有10-6-10-4摩尔钯。
制备聚合物反应较好的是在温度低于75℃，压力分0.2-15兆帕条件下进行，最好在温度低于50℃，压力为0.5-10兆帕条件下进行。在欲聚合的混合物中烯属不饱和化合物与一氧化碳的摩尔比例以10∶1～1∶10为好，最好是5∶1～1∶5。
现在借助下列实施例对本发明进行阐述。
实施例1
甲基氯化钯和2，2-二甲基-1，3-双（二苯基膦基）-2-硅杂丙烷的等摩尔络合物按下述方法
制解。往由2mmol的二氯化钯与2，2-二甲基-1，3-双（二苯基膦基）-2-硅杂丙烷的等摩尔络合物与10ml二氯甲烷和10ml甲醇混合液组成的悬浮液中加入4mmol四甲基锡。在室温下搅拌二小时后，在减压下将反应混合物中的溶剂蒸出。残存物每次用5ml乙醚洗涤三次，然后在室温下真空干燥。所得产物为1.15克甲基氯化钯与2，2-二甲基-1，3-双（二苯基膦基）-2-硅杂丙烷的等摩尔络合物。
实施例2
甲基氯化钯和2，2-二甲基-1，3-双（二苯基膦基）丙烷的等摩尔络合物按下述方法制备。往由2mmol二氯化钯和2，2-二甲基-1，3-双（二苯基膦基）丙烷的等摩尔络合物和50ml二氯甲烷与50ml甲醇的混合液组成的悬浮液中加入4mmol四甲基锡。在氩气氛下迥流三小时后，在减压下将反应混合物中的溶剂蒸出。残留物溶于5ml二氯甲烷，然后加入25ml乙醚。过滤出所得固体物，用5ml乙醚洗涤后，在室温下真空干燥。所得产物为0.95克甲基氯化钯与2，2-二甲基-1，3-双（二苯基膦基）丙烷的等摩尔络合物。
实施例3
一氧化碳/乙烯共聚物按下述方法制备。往一容积为250ml搅拌着的高压釜中加入由100ml甲醇和0.1mmol按实施例1制得的甲基氯化钯与2，2-二甲基-1，3-双（二苯基膦基）-2-硅杂丙烷的等摩尔络合物所组成的催化剂溶液。将高压釜中的所有空气通过抽真空除去后，注入1∶1的一氧化碳/乙烯混合气达到4兆帕的压力为止。在室温下搅拌1.5小时之后，释放掉余压终止聚合反应。将生成的聚合物过滤出来，用甲醇洗涤后在室温下真空干燥，得到1.2克共聚物，聚合速度为75克共聚物/克钯·小时。
实施例4
采用与实施例3基本相同的方法制备一氧化碳/乙烯共聚物，只是做了如下变动：
a）用按实施例2制备的甲基氯化钯与2，2-二甲基-1，3-双（二苯基膦基）丙烷的等摩尔络合物作为催化剂溶液中的钯络合物组分，和
b）反应时间为4小时而不是1.5小时，得到1.5克共聚物，聚合速度为35克共聚物/克钯·小时。
实施例5
基本上重复一次实施例3的实验，不同之处只是在催化剂溶液中的钯络合物是二氯化钯而不是甲基氯化钯。结果是不发生聚合反应。
实施例6
基本上重复实施例4的实验，不同之处只是在催化剂溶液中的钯络合物是二氯化钯而不是甲基氯化钯。结果不发生聚合反应。
实施例7
采用与实施例3基本相同的方法制备一氧化碳/乙烯共聚物，只是做如下一些变动：
a）.催化剂溶液中含有0.1mmol二氯化钯与1，3-双（二苯基膦基）丙烷的等摩尔络合物作为钯络合物组分。
b）.反应温度为110℃而不是室温，
c）.反应时间为2小时而不是1.5小时。
得到1.5克共聚物。聚合速度为70克共聚物/克钯·小时，
在例1-7中，例1-4是本发明的实施例。在实施例1和2中，二氯化钯和含磷二齿配位体的络合物中的一个氯原子通过和四甲基锡反应而被甲基取代了。在实施例3和4中，将由此反应制得的钯络合物作为催化剂用于制备一氧化碳与乙烯的共聚物。在实施例5-7中，采用二氯化钯与含磷二齿配位体的络合物作为催化剂，这不属于本发明的范围，本专利申请中引用这些实施例作为比较用。当以二氯化钯和含磷二齿配位体的络合物为基础的催化剂组合物中的一个卤素原子被烃基取代后，催化剂活性增加，这一点通过将实施例5和6的结果分别与实施例3和4的结果相比较（聚合速度分别从0增加到75及35克共聚物/克钯·小时）得到确切的证实。通过比较实施例3和7的结果也证实上述的催化活性增加。在实施例3中，通过使用含甲基氯化钯与含磷二齿配位体络合物的催化剂组合物在室温下获得了75克共聚物/克钯·小时的聚合速度。在实施例7中，采用含二氯化钯络合物而不是含甲基氯化钯络合物的催化剂组合物时需要在110℃温度下反应才能达到相应的聚合速度（70克共聚物/克钯·小时）。
借助于13C-NMR分析获知按实施例3，4和7方法制备的一氧化碳/乙烯共聚物具有线型结构，且其中由一氧化碳派生的链节单元与由乙烯派生的链节单元是以交替形式出现。
Claims (5)
1、制备一氧化碳与一种或多种烯属不饱和化合物的聚合物的方法，其特征在于单体与以烷基钯卤化合物和含磷二齿配位体的络合物为基础的催化剂组合物相接触，所述烷基具有最多5个碳原子，含磷二齿配位体的通式R1R2P-R-PR3R4，式中R1，R2，R3和R4是相同的烃基或不同的随选性有极性基团取代的烃基，R是在其桥中至少含有两个碳原子的二价有机桥基。
2、权利要求1所述的方法，其特征在于在含磷二齿配位体中的R1，R2，R3和R4基团或是未被取代的苯基，或是含有一个或多个烷氧基取代的苯基且其中至少有一个烷氧基处于与苯环相键联的磷原子的邻位。
3、权利要求1所述的方法，其特征在于其中的烷基卤化钯是甲基氯化钯。
4、权利要求1-3任一项所述的方法，其特征在于将单体和用聚合产物不溶或实质不溶的稀释剂配成的催化剂组合物的溶液相接触。
5、权利要求1-3任一项所述的方法，其特征在于聚合反应在低于75℃温度和0.2-15兆帕压力下进行，待聚合的混合物中烯属不饱和化合物对一氧化碳的摩尔比为10∶1-1∶10，并且每摩尔待聚合的烯属不饱和化合物要用的催化剂组合物的量是使其中含有10-7-10-3摩尔钯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8900184 | 1989-01-26 | ||
| NL8900184 | 1989-01-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044469A CN1044469A (zh) | 1990-08-08 |
| CN1028108C true CN1028108C (zh) | 1995-04-05 |
Family
ID=19854021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90100394A Expired - Fee Related CN1028108C (zh) | 1989-01-26 | 1990-01-24 | 一氧化碳与烯属不饱和化合物的聚合物的制备方法 |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US5025091A (zh) |
| EP (1) | EP0380162B1 (zh) |
| JP (1) | JP2857195B2 (zh) |
| KR (1) | KR900011792A (zh) |
| CN (1) | CN1028108C (zh) |
| AT (1) | ATE121108T1 (zh) |
| AU (1) | AU627830B2 (zh) |
| BR (1) | BR9000285A (zh) |
| CA (1) | CA2008443A1 (zh) |
| DE (1) | DE69018488T2 (zh) |
| ES (1) | ES2070993T3 (zh) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5171832A (en) * | 1990-04-27 | 1992-12-15 | Shell Oil Company | Polymerization of carbon monoxide/olefin with p bidentate ligand having (1) alkoxy phenyl p group and (2) monosubstituted divalent bridging group |
| US5229343A (en) * | 1990-04-27 | 1993-07-20 | Shell Oil Company | Polymerization process |
| NL9001114A (nl) * | 1990-05-10 | 1991-12-02 | Shell Int Research | Katalysatorcomposities. |
| DE69418088T2 (de) * | 1993-04-06 | 1999-08-12 | Bp Chemicals Ltd., London | Katalysatorzusammensetzung |
| GB9419762D0 (en) * | 1994-09-30 | 1994-11-16 | Bp Chem Int Ltd | Catalyst composition |
| DE19642886A1 (de) * | 1996-10-17 | 1998-04-23 | Fraunhofer Ges Forschung | Verfahren zur Herstellung eines thermooptischen variablen Polymerwerkstoffes und seine Anwendung |
| BRPI0411504B1 (pt) * | 2003-07-01 | 2013-09-17 | elemento filtrante, conjunto de cobertura, conjunto de filtro e processo para fixar e remover um elemento filtrante | |
| KR100789141B1 (ko) * | 2006-12-28 | 2007-12-28 | 주식회사 효성 | 폴리케톤의 제조방법 |
| EP2213643A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
| EP2213644A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl alkyl ether by catalyic allylation |
| EP2213645A1 (en) | 2009-01-28 | 2010-08-04 | Hexion Specialty Chemicals Research Belgium S.A. | Process for the preparation of an allyl aryl ether by catalytic o-allylation |
| CN103102373B (zh) * | 2012-12-27 | 2015-11-11 | 中国科学院化学研究所 | 具有手性负抗衡离子的新型二价钯配合物及其制备方法 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2495286A (en) * | 1949-06-08 | 1950-01-24 | Du Pont | Interpolymers of carbon monoxide and method for preparing the same |
| GB1081304A (en) * | 1965-03-23 | 1967-08-31 | Ici Ltd | Improvements in or relating to chemical compounds |
| US3694412A (en) * | 1971-03-04 | 1972-09-26 | Shell Oil Co | Process for preparing interpolymers of carbon monoxide in the presence of aryl phosphine-palladium halide complex |
| GB1414662A (en) * | 1972-02-04 | 1975-11-19 | Dow Corning Ltd | Complexes containing phosphorus |
| ATE49010T1 (de) * | 1983-04-06 | 1990-01-15 | Shell Int Research | Verfahren zur herstellung von polyketonen. |
| NL8403035A (nl) * | 1984-10-05 | 1986-05-01 | Shell Int Research | Werkwijze ter bereiding van polyketonen. |
| IN166314B (zh) * | 1985-08-29 | 1990-04-07 | Shell Int Research | |
| IN167917B (zh) * | 1985-11-14 | 1991-01-05 | Shell Int Research | |
| IN168306B (zh) * | 1986-03-05 | 1991-03-09 | Shell Int Research | |
| CA1271877A (en) * | 1986-03-24 | 1990-07-17 | Johannes A.M. Van Broekhoven | Polymer preparation |
| EP0246683A3 (en) * | 1986-05-13 | 1988-01-27 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of polymers |
| IN171627B (zh) * | 1986-08-26 | 1992-11-28 | Shell Int Research | |
| NL8602164A (nl) * | 1986-08-26 | 1988-03-16 | Shell Int Research | Katalysatorcomposities. |
| KR0128998B1 (ko) * | 1987-07-23 | 1998-04-07 | 오노 알버어스 | 신규 촉매 조성물 및 이를 이용하여 중합체를 제조하는 방법 |
-
1990
- 1990-01-16 ES ES90200119T patent/ES2070993T3/es not_active Expired - Lifetime
- 1990-01-16 EP EP90200119A patent/EP0380162B1/en not_active Expired - Lifetime
- 1990-01-16 AT AT90200119T patent/ATE121108T1/de not_active IP Right Cessation
- 1990-01-16 DE DE69018488T patent/DE69018488T2/de not_active Expired - Fee Related
- 1990-01-17 US US07/466,559 patent/US5025091A/en not_active Expired - Fee Related
- 1990-01-23 KR KR1019900000779A patent/KR900011792A/ko not_active Withdrawn
- 1990-01-24 JP JP2014744A patent/JP2857195B2/ja not_active Expired - Lifetime
- 1990-01-24 CA CA002008443A patent/CA2008443A1/en not_active Abandoned
- 1990-01-24 CN CN90100394A patent/CN1028108C/zh not_active Expired - Fee Related
- 1990-01-24 AU AU48848/90A patent/AU627830B2/en not_active Ceased
- 1990-01-24 BR BR909000285A patent/BR9000285A/pt not_active Application Discontinuation
-
1991
- 1991-04-04 US US07/680,443 patent/US5145823A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69018488D1 (de) | 1995-05-18 |
| EP0380162A3 (en) | 1991-08-21 |
| JP2857195B2 (ja) | 1999-02-10 |
| EP0380162A2 (en) | 1990-08-01 |
| CN1044469A (zh) | 1990-08-08 |
| US5025091A (en) | 1991-06-18 |
| CA2008443A1 (en) | 1990-07-26 |
| JPH02233724A (ja) | 1990-09-17 |
| ATE121108T1 (de) | 1995-04-15 |
| AU627830B2 (en) | 1992-09-03 |
| DE69018488T2 (de) | 1995-09-21 |
| AU4884890A (en) | 1990-08-02 |
| KR900011792A (ko) | 1990-08-02 |
| EP0380162B1 (en) | 1995-04-12 |
| ES2070993T3 (es) | 1995-06-16 |
| US5145823A (en) | 1992-09-08 |
| BR9000285A (pt) | 1990-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1037000C (zh) | 催化剂组合物及其聚合应用 | |
| CN107001502B (zh) | 低聚烯烃的方法 | |
| AU605903B2 (en) | Catalytic compositions for the polymerization of carbon monoxide with an olefin | |
| CN1028108C (zh) | 一氧化碳与烯属不饱和化合物的聚合物的制备方法 | |
| US4740625A (en) | Catalyst compositions and a process for polymerizing carbon monoxide and olefins | |
| US4859764A (en) | Copolymerization of carbon monoxide and olefin with nitrogen containing phosphine ligand catalyst | |
| JP2903483B2 (ja) | 一酸化炭素とオレフィン状不飽和化合物との重合体製造用触媒組成物 | |
| CN87106786A (zh) | 催化剂组合物和烯烃与一氧化碳共聚的方法 | |
| CN1030708A (zh) | 催化剂组合物 | |
| JP2862610B2 (ja) | 触媒組成物 | |
| CN1019976C (zh) | 取代的二芳基磷化物的制备 | |
| JPH06172514A (ja) | オレフィン／一酸化炭素交互コポリマー製造用不均質触媒系 | |
| CA2136636C (en) | A process for the preparation of co-polymers of carbon monoxide and ethylenically unsaturated compounds | |
| EP0702045A2 (en) | Gas phase process for the copolymerization of carbon monoxide and ethylenically unsaturated compounds | |
| EP0390292B1 (en) | Catalyst compositions for the preparation of copolymers of carbon monoxide | |
| JPH10502683A (ja) | 線状一酸化炭素／α−オレフィンコポリマー製造用触媒 | |
| CN1078220C (zh) | 一种一氧化碳、乙烯和另一种烯属不饱和化合物的线性交替共聚物的制备方法 | |
| FI97059C (fi) | Uusi polymerointikatalyytti ja sen käyttö | |
| WO2000006299A1 (en) | Catalyst composition | |
| AU6678694A (en) | Preparation of copolymers of carbon monoxide | |
| CN1036020A (zh) | 一氧化碳和乙烯的聚合物 | |
| DE CLERCQ et al. | Ghent University, Krijgslaan 281 (S3), 9000 Ghent, BELGIUM. | |
| CN1107483A (zh) | 催化剂组合物及制备聚合物的方法 | |
| JPH08269192A (ja) | 一酸化炭素とエチレン系不飽和化合物との気相共重合プロセス | |
| GB2370516A (en) | Catalyst composition for the preparation of copolymers of carbon monoxide and an olefinically unsaturated compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |