CN103289000A - High molecular weight polyisoprene rubber and preparation method thereof - Google Patents
High molecular weight polyisoprene rubber and preparation method thereof Download PDFInfo
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- CN103289000A CN103289000A CN2013102700422A CN201310270042A CN103289000A CN 103289000 A CN103289000 A CN 103289000A CN 2013102700422 A CN2013102700422 A CN 2013102700422A CN 201310270042 A CN201310270042 A CN 201310270042A CN 103289000 A CN103289000 A CN 103289000A
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 47
- 229920001971 elastomer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 53
- 229910052782 aluminium Inorganic materials 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000004411 aluminium Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 15
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 13
- -1 iron halide Chemical class 0.000 claims description 12
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 7
- GBRSPKXOFRTAHS-UHFFFAOYSA-N 5-(4-nitrophenyl)-1,2-oxazole-3-carboxylic acid Chemical compound O1N=C(C(=O)O)C=C1C1=CC=C([N+]([O-])=O)C=C1 GBRSPKXOFRTAHS-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 6
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001868 water Inorganic materials 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 229910001848 post-transition metal Inorganic materials 0.000 abstract 1
- 235000010210 aluminium Nutrition 0.000 description 35
- 239000000463 material Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical class OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- UZEFVQBWJSFOFE-UHFFFAOYSA-N dibutyl hydrogen phosphite Chemical class CCCCOP(O)OCCCC UZEFVQBWJSFOFE-UHFFFAOYSA-N 0.000 description 1
- SULWMEGSVQCTSK-UHFFFAOYSA-N diethyl hydrogen phosphite Chemical class CCOP(O)OCC SULWMEGSVQCTSK-UHFFFAOYSA-N 0.000 description 1
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical class COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses high molecular weight polyisoprene rubber which simultaneously contains a 3,4-strucure, a cis-1,4 structure and a trans-4,4 structure, as well as a preparation method of the high molecular weight polyisoprene rubber and an adopted iron post-transition metal catalyst composition. The polyisoprene rubber disclosed by the invention has the characteristics of not only being good in slipper resistance, but also being low in generated heat, and is in particular suitable for a high-performance tyre and other rubber products. The catalyst system disclosed by the invention is insensitive to water, oxygen gas, carbon dioxide and the like, and gentle in experimental operation conditions.
Description
Technical field
The invention belongs to the polydiolefin field of rubber materials, contain 3 when more particularly relating to a kind of high molecular, the 4-structure), cis-1, the 4-structure) and anti-form-1, polyisoprene rubber of 4-structure and preparation method thereof and the iron that adopts are the late transition metal catalyst composition.
Background technology
The late transition metal catalyst that last century, the nineties occurred, showed very high catalytic activity, and the catalysis cost sometimes even also lower than ziegler natta catalyst, demonstrate good industrial applications potentiality [Coordination Chemistry Reviews (2010), 254:661-676].It shows lewis acidic characteristic, has good tolerance for polar group, provides possibility for suitability for industrialized production functional polyalkylene olefin product.Some Chinese invention patents have been introduced the preparation (200710064961.9 of late transition metal catalyst; 200910078174.9; 200910078595.1; 201210325646.8; 01118568.6 03153153.9; 200410005634.2; 200610134241.0), some rear transition metal catalyst system have been used to carry out the polymerization (01124240.X of ethene, propylene, vinylbenzene and acrylamide simultaneously; 02118523.9; 02113767.6; 200810034033.2; 200410087512.2; 201210299110.3; Euro Patent WO02102861 (2002); Euro Patent WO03018649 (2003)).The elimination of β-H but the rear transition metal catalyst system is highly advantageous to, therefore at present big portion all is applied to the research of olefin oligomerization.
Utilize at present rear transition metal especially the iron system to carry out research and the patent of isoprene polymerization few.Three pyridine complexes that utilize iron of successes such as Yasuda and MMAO catalyst system synthesize many upright configurations [1,2(or 3,4) and 1,4] divinyl and isoprene copolymer, and showed catalytic efficiency [Macromolecules 2003,36:7953-7958] preferably.Honk recklessly, open and learn congruent human ferric acetyl acetonade (Fe (acac)
3Obtained the polyisoprene of 3,4 structures of high level (60%) under the effect of)/diethyl phosphorous acid ester (DEP) and modified methylaluminoxane (MMAO).[polymer material science and engineering, 2005,21:106-109].But the polyisoprene molecular weight that above-mentioned institute synthesizes is not high (≤50000) also, limited its application greatly.This research and utilization iron complex is Primary Catalysts, low-cost aluminum alkyls is optimized polymerization parameter as promotor, and successful synthetic molecular weight is at the polyisoprene rubber material more than 100,000, and can effectively regulate 3,4 structural contents in the binary form polyisoprene.
Summary of the invention
One of purpose of the present invention provides a kind of cis 1 that contains simultaneously, 4-structure, 3,4-structure and anti--1, the polyisoprene rubber material of 4-structure, described polyisoprene rubber is the cis-1 of 30-60% by molar fraction, 4-structure, molar fraction are 3 of 10-60%, 4-structure and molar fraction are anti-1 of 5-50%, the 4-structure is formed, and the weight-average molecular weight of described polyisoprene can reach 400,000 g/mol, molecular weight distribution 1-5.
Wherein, described polyisoprene rubber is by using the catalyst composition of being made up of as promotor and external electron donor as Primary Catalysts and aluminum alkyls three iron halide title complexs as follows synthetic, wherein, aluminium (Al) is 50-500:1 with the mol ratio of iron (Fe), the mol ratio of external electron donor and iron is 1-200:1
Described aluminum alkyl catalyst is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride;
Described external electron donor is selected from a kind of in dimethylphosphite, diethyl phosphite, dibutyl phosphite, triphenylphosphate, diethyl phosphoric acid and the diisooctyl phenyl phosphite.
Two of purpose of the present invention provides a kind of preparation method of described polyisoprene rubber, and this method comprises following method one or method two:
Method one: with the polymeric kettle pump drainage of dried and clean and through the nitrogen replacement several, in polymeric kettle, add isoprene (Ip), external electron donor, solvent, aluminum alkyl catalyst and the three iron halide title complexs that measure, wherein, the mol ratio of iron and isoprene is 1-100 * 10
-6: 1, aluminium (Al) is 50-500:1 with the mol ratio of iron (Fe), the mol ratio of external electron donor and iron is 1-200:1, the volume ratio of solvent and isoprene monomer is 1-10:1, in 10-90 ℃ of constant temperature polymerization 20min-24 hour, stop polymerization with 1% Muriatic industrial spirit, clean again three times with straight alcohol, resulting polymers is dried to constant mass in 40 ℃ of vacuum drying ovens, obtain described polyisoprene rubber;
Method two: with the polymeric kettle pump drainage of dried and clean and through the nitrogen replacement several, in polymeric kettle, add isoprene Ip, external electron donor, aluminum alkyl catalyst and the three iron halide title complexs that measure, wherein, the mol ratio of iron and isoprene monomer is 1-100 * 10
-6: 1, aluminium (Al) is 50-500:1 with the mol ratio of iron (Fe), the mol ratio of external electron donor and iron is 1-200:1, in 10-90 ℃ of constant temperature polymerization 20min-24 hour, stop polymerization with 0.1% Muriatic industrial spirit, clean three times with straight alcohol again, resulting polymers is dried to constant mass in 40 ℃ of vacuum drying ovens, obtain described polyisoprene rubber
Wherein, three iron halide title complexs as mentioned above;
Described aluminum alkyl catalyst is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride;
Described external electron donor is selected from a kind of in dimethylphosphite, diethyl phosphite, dibutyl phosphite, triphenylphosphate, diethyl phosphoric acid and the diisooctyl phenyl phosphite;
Described solvent is selected from one or both in toluene, hexane, normal heptane, tetrahydrofuran (THF), dimethylbenzene, hexanaphthene, chloroform and the tetracol phenixin.
Three of purpose of the present invention provides a kind of catalyst composition for the synthesis of described polyisoprene rubber, described catalyst composition is that Primary Catalysts and aluminum alkyls are that promotor and external electron donor are formed by three iron halide title complexs as implied above, wherein, the mol ratio of aluminium and iron is 50-500:1, and the mol ratio of external electron donor and iron is 1-200:1;
Described aluminum alkyl catalyst is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride;
Described external electron donor is selected from a kind of in dimethylphosphite, diethyl phosphite, dibutyl phosphite, triphenylphosphate, diethyl phosphoric acid and the diisooctyl phenyl phosphite.
Catalyst composition of the present invention adopts suitable aluminum alkyl catalyst to replace expensive aluminum alkoxide MAO, optimizes the ratio of external electron donor simultaneously, has realized to polyisoprene 3 regulation and control of 4-structure and molecular weight.Catalyst system of the present invention is insensitive to water, oxygen, carbonic acid gas etc., and the experimental implementation condition is not harsh.
Four of purpose of the present invention provides a kind of described polyisoprene rubber for the preparation of the tire with wet-sliding resistant performance, low-heat-generation characteristics and the purposes of other rubber items.
It is good that polyisoprene rubber of the present invention had both had an anti-slippery, has the low characteristics of the heat of giving birth to again, is specially adapted to high-performance tire and other rubber items.
Embodiment
Adopt
13Cis 1 in the C-NMR spectrum analysis polymkeric substance, the 4-structure, trans 1, distribution and the content of 4-structure and 3,4-structure: instrument: Switzerland Bruker-500 type nuclear magnetic resonance analyser; Test condition: sample size 10-20 mg, 25 ℃ of temperature, solvent C DCl
3, frequency 125 MHz are standard with the tetramethylsilane.
Adopt molecular weight and the molecular weight distribution of GPC test polymer, tetrahydrofuran (THF) is moving phase, and polystyrene is standard specimen.
Unless outside the specified otherwise, the method and apparatus that the application adopts is the method and apparatus of this area routine.
Embodiment 1
The iron trichloride title complex (C1) that adds 5.2 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 124 mg triphenylphosphates, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 350 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 30mol%, 3, the 4-structure accounts for 60mol%, and is anti-1, and the 4-structure accounts for 10mol%, molecular weight is 381 000 g/mol, and molecular weight distribution is 3.27.
Embodiment 2
The iron bromide title complex (C2) that adds 67.9 mg in the 300 mL polymeric kettles successively, 100 mL isoprene monomers, 62 mg triphenylphosphates and 85.5 mg triethyl aluminums, polymerization temperature is 10 ℃, polymerization time is 24 h.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 3 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 60mol%, 3, the 4-structure accounts for 10mol%, and is anti-1, and the 4-structure accounts for 30mol%, weight-average molecular weight is 27000 g/mol, and molecular weight distribution is 2.28.
Embodiment 3
The ferric iodide title complex (C3) that adds 84.8 mg in the 3 L polymeric kettles successively, 100 mL isoprene monomers, 6.2 g triphenylphosphates, 1000 mL solvent xylenes and 311 mg triisobutyl aluminiums, polymerization temperature is 90 ℃, polymerization time is 10 min.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 2.1 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 33mol%, 3, the 4-structure accounts for 17mol%, and is anti-1, and the 4-structure accounts for 50mol%, weight-average molecular weight is 210000 g/mol, and molecular weight distribution is 4.57.
Embodiment 4
The iron(ic) chloride title complex (C4) that adds 53.2 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 1.1 g dimethylphosphites, 1000 mL solvent chloroform and 240 mg diethyl monochlor(in)ate aluminium, polymerization temperature is 60 ℃, and polymerization time is 60 min.With 0.1wt% acidic alcohol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 26 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 50mol%, 3, the 4-structure accounts for 23mol%, and is anti-1, and the 4-structure accounts for 27mol%, weight-average molecular weight is 208000 g/mol, and molecular weight distribution is 3.04.
Embodiment 5
The iron(ic) chloride title complex (C5) that adds 53.2 mg in the 3 L polymeric kettles successively, 100 mL isoprene monomers, 13.8 mg diethyl phosphites, 1000 mL solvents tetrahydrofurane and 330 mg diisobutyl monochlor(in)ate aluminium, polymerization temperature is 50 ℃, and polymerization time is 6 h.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 5.1 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 40mol%, 3, the 4-structure accounts for 55mol%, and is anti-1, and the 4-structure accounts for 5mol%, weight-average molecular weight is 98600 g/mol, and molecular weight distribution is 4.30.
Embodiment 6
The iron bromide title complex (C6) that adds 66.6 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 19.4 mg dibutyl phosphites, 1000 mL solvent normal heptanes and 2.4 mg diethyl monochlor(in)ate aluminium, polymerization temperature is 30 ℃, and polymerization time is 60 min.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, final vacuum-drying obtains 125 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 42mol%, 3, the 4-structure accounts for 51mol%, and is anti-1, and the 4-structure accounts for 7mol%, weight-average molecular weight is 112400 g/mol, and molecular weight distribution is 3.7.
Embodiment 7
The iron(ic) chloride title complex (C7) that adds 53.2 mg in the 3 L polymeric kettles successively, 500 mL isoprene monomers, 18.6 mg diethyl phosphoric acids, 1000 mL solvent hexanes and 1025 mg diethyl monochlor(in)ate aluminium, polymerization temperature is 50 ℃, polymerization time is 10 h.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 110.5 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 32mol%, 3, the 4-structure accounts for 52mol%, and is anti-1, and the 4-structure accounts for 16mol%, weight-average molecular weight is 105500 g/mol, and molecular weight distribution is 3.3.
Embodiment 8
The iron(ic) chloride title complex (C8) that adds 58.8 mg in the 3 L polymeric kettles successively, 800 mL isoprene monomers, 38.8 diisooctyl phenyl phosphites, 800 mL solvent tetracol phenixin and 38 mg triethyl aluminums, polymerization temperature is 80 ℃, and polymerization time is 200 min.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 88 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 32mol%, 3, the 4-structure accounts for 52mol%, and is anti-1, and the 4-structure accounts for 16mol%, weight-average molecular weight is 34200 g/mol, and molecular weight distribution is 3.3.
Embodiment 9
The iron(ic) chloride title complex (C9) that adds 54.6 mg in the 3 L polymeric kettles successively, 800 mL isoprene monomers, 38.8 diisooctyl phenyl phosphites, 800 mL solvent tetracol phenixin and 38 mg triethyl aluminums, polymerization temperature is 80 ℃, and polymerization time is 200 min.With 0.1wt% salt acidifying ethanol 200 mL termination reactions, clean and remove solvent and unreacted monomer 3 times, vacuum-drying obtains 102 g polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 36mol%, 3, the 4-structure accounts for 52mol%, and is anti-1, and the 4-structure accounts for 12mol%, weight-average molecular weight is 56600 g/mol, and molecular weight distribution is 3.1.
Embodiment 10
The iron trichloride title complex (C10) that adds 57.4 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 155 mg triphenylphosphates, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 230 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 44mol%, 3, the 4-structure accounts for 20mol%, and is anti-1, and the 4-structure accounts for 36mol%, weight-average molecular weight is 191 000 g/mol, and molecular weight distribution is 3.55.
Embodiment 11
The iron trichloride title complex (C11) that adds 54.6 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 3.72 g triphenylphosphates, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 200 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 32mol%, 3, the 4-structure accounts for 58mol%, and is anti-1, and the 4-structure accounts for 10mol%, weight-average molecular weight is 178000 g/mol, and molecular weight distribution is 3.87.
Embodiment 12
The iron trichloride title complex (C12) that adds 57.4 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 1.2 g triphenylphosphates, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 326 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 34mol%, 3, the 4-structure accounts for 55mol%, and is anti-1, and the 4-structure accounts for 11mol%, weight-average molecular weight is 225000 g/mol, and molecular weight distribution is 3.87.
Embodiment 13
The iron trichloride title complex (C13) that adds 6.02 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 1.01 g triphenylphosphates, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 354 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 35mol%, 3, the 4-structure accounts for 35mol%, and is anti-1, and the 4-structure accounts for 30mol%, weight-average molecular weight is 125000 g/mol, and molecular weight distribution is 3.24.
Embodiment 14
The iron trichloride title complex (C14) that adds 5.60 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 0.54 g triphenylphosphate, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 394 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 44mol%, 3, the 4-structure accounts for 21mol%, and is anti-1, and the 4-structure accounts for 35mol%, weight-average molecular weight is 119800 g/mol, and molecular weight distribution is 3.14.
Embodiment 15
The iron trichloride title complex (C15) that adds 5.88 mg in the 3 L polymeric kettles successively, 1000 mL isoprene monomers, 0.76 g triphenylphosphate, 1000 mL toluene, the sesquialter ethylaluminium chloride of 13.7 mg, polymerization temperature is 40 ℃, polymerization time is 24 h.With 0.1% salt acidifying ethanol, 200 mL termination reactions, clean and take off aluminum removal and unreacted monomer 3 times, vacuum-drying obtains 247 gram polyisoprene rubber materials, cis-1 wherein, and the 4-structure accounts for 51mol%, 3, the 4-structure accounts for 31mol%, and is anti-1, and the 4-structure accounts for 18mol%, weight-average molecular weight is 186700 g/mol, and molecular weight distribution is 3.97.
Claims (10)
1. polyisoprene rubber, wherein, described polyisoprene rubber is the cis-1 of 30-60% by molar fraction, 4-structure, molar fraction are 3 of 10-60%, 4-structure and molar fraction are the anti-form-1 of 5-50%, the 4-structure is formed, and the weight-average molecular weight of described polyisoprene can reach 400,000 g/mol, molecular weight distribution 1-5.
2. polyisoprene rubber as claimed in claim 1, wherein, described polyisoprene rubber is by using the catalyst composition of being made up of as promotor and external electron donor as Primary Catalysts and aluminum alkyls three iron halide title complexs as follows synthetic, wherein, the mol ratio of aluminium and iron is 50-500:1, the mol ratio of external electron donor and iron is 1-200:1
3. polyisoprene rubber as claimed in claim 2, wherein, described aluminum alkyl catalyst is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride;
Described external electron donor is selected from a kind of in dimethylphosphite, diethyl phosphite, dibutyl phosphite, triphenylphosphate, diethyl phosphoric acid and the diisooctyl phenyl phosphite.
4. method for preparing the described polyisoprene rubber of claim 1, this method comprises following method one or method two:
Method one: with the polymeric kettle pump drainage of dried and clean and through the nitrogen replacement several, in polymeric kettle, add isoprene, external electron donor, solvent, aluminum alkyl catalyst and the three iron halide title complexs that measure, wherein, the mol ratio of iron and isoprene is 1-100 * 10
-6: 1, the mol ratio of aluminium and iron is 50-500:1, the mol ratio of external electron donor and iron is 1-200:1, the volume ratio of solvent and isoprene monomer is 1-10:1, in 10-90 ℃ of constant temperature polymerization 20min-24 hour, stop polymerization with 1% Muriatic industrial spirit, clean again three times with straight alcohol, resulting polymers is dried to constant mass in 40 ℃ of vacuum drying ovens, obtain described polyisoprene rubber;
Method two: with the polymeric kettle pump drainage of dried and clean and through the nitrogen replacement several, in polymeric kettle, add isoprene, external electron donor, aluminum alkyl catalyst and the three iron halide title complexs that measure, wherein, the mol ratio of iron and isoprene monomer is 1-100 * 10
-6: 1, the mol ratio of aluminium and iron is 50-500:1, the mol ratio of external electron donor and iron is 1-200:1, in 10-90 ℃ of constant temperature polymerization 20min-24 hour, stop polymerization with 0.1% Muriatic industrial spirit, clean three times with straight alcohol again, resulting polymers is dried to constant mass in 40 ℃ of vacuum drying ovens, obtain described polyisoprene rubber
Wherein, three iron halide title complexs are as follows:
。
5. method as claimed in claim 4, wherein, described aluminum alkyl catalyst is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride.
6. method as claimed in claim 4, wherein, described external electron donor is selected from a kind of in dimethylphosphite, diethyl phosphite, dibutyl phosphite, triphenylphosphate, diethyl phosphoric acid and the diisooctyl phenyl phosphite.
7. method as claimed in claim 4, wherein, described solvent is selected from one or both in toluene, hexane, normal heptane, tetrahydrofuran (THF), dimethylbenzene, hexanaphthene, chloroform and the tetracol phenixin.
8. catalyst composition for the synthesis of the described polyisoprene rubber of claim 1, described catalyst composition is that Primary Catalysts and aluminum alkyls are that promotor and external electron donor are formed by three iron halide title complexs as follows, wherein, the mol ratio of aluminium and iron is 50-500:1, the mol ratio of external electron donor and iron is 1-200:1
9. catalyst composition as claimed in claim 8, wherein, described aluminum alkyl catalyst is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride;
Described external electron donor is selected from a kind of in dimethylphosphite, diethyl phosphite, dibutyl phosphite, triphenylphosphate, diethyl phosphoric acid and the diisooctyl phenyl phosphite.
10. the described polyisoprene rubber of claim 1 is for the preparation of the purposes of the tire with excellent wet-sliding resistant performance, low-heat-generation and other rubber items.
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| CN105111344A (en) * | 2015-09-11 | 2015-12-02 | 江南大学 | Carbon nano tube/polyisoprene composite material and preparation method thereof |
| CN105968243A (en) * | 2016-06-05 | 2016-09-28 | 王金明 | Preparation method of polyisoprene catalyst |
| CN107674137A (en) * | 2016-08-01 | 2018-02-09 | 浙江众立合成材料科技股份有限公司 | Hydrogenation type styrene analog thermoplastic elastomer and its synthetic method and application |
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| CN1935852A (en) * | 2005-09-19 | 2007-03-28 | 青岛科技大学 | Method for preparing fatty alcohol modified load-type Titanium series catalyst and its use for diene polymerization |
| CN102086277A (en) * | 2009-12-07 | 2011-06-08 | 青岛科技大学 | Polyisoprene composite rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1935852A (en) * | 2005-09-19 | 2007-03-28 | 青岛科技大学 | Method for preparing fatty alcohol modified load-type Titanium series catalyst and its use for diene polymerization |
| CN102086277A (en) * | 2009-12-07 | 2011-06-08 | 青岛科技大学 | Polyisoprene composite rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105111344A (en) * | 2015-09-11 | 2015-12-02 | 江南大学 | Carbon nano tube/polyisoprene composite material and preparation method thereof |
| CN105968243A (en) * | 2016-06-05 | 2016-09-28 | 王金明 | Preparation method of polyisoprene catalyst |
| CN107674137A (en) * | 2016-08-01 | 2018-02-09 | 浙江众立合成材料科技股份有限公司 | Hydrogenation type styrene analog thermoplastic elastomer and its synthetic method and application |
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