CN108690156A - A kind of new method of high monomer conversion ratio synthesis of trans -1,4- polyisoprene - Google Patents
A kind of new method of high monomer conversion ratio synthesis of trans -1,4- polyisoprene Download PDFInfo
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- CN108690156A CN108690156A CN201810384555.9A CN201810384555A CN108690156A CN 108690156 A CN108690156 A CN 108690156A CN 201810384555 A CN201810384555 A CN 201810384555A CN 108690156 A CN108690156 A CN 108690156A
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- nitrae
- isosorbide
- polyisoprene
- tpi
- polymerization
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 238000013016 damping Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 3
- 125000002370 organoaluminium group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 class Chemical class 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 4
- 229910052782 aluminium Inorganic materials 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- GOKQOZYJEDDDOC-UHFFFAOYSA-N C(=O)OC.C1=CC=CC=C1 Chemical compound C(=O)OC.C1=CC=CC=C1 GOKQOZYJEDDDOC-UHFFFAOYSA-N 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- 229910010386 TiI4 Inorganic materials 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229960002380 dibutyl phthalate Drugs 0.000 claims 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000013013 elastic material Substances 0.000 abstract 1
- 239000012567 medical material Substances 0.000 abstract 1
- 239000012781 shape memory material Substances 0.000 abstract 1
- 239000012815 thermoplastic material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 239000000899 Gutta-Percha Substances 0.000 description 6
- 240000000342 Palaquium gutta Species 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229920000588 gutta-percha Polymers 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001887 crystalline plastic Polymers 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- KRNJJBUNWGLWNB-UHFFFAOYSA-N 2-methylbuta-1,3-diene hydrate Chemical compound O.CC(=C)C=C KRNJJBUNWGLWNB-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of high trans -1, the preparation method of 4- polyisoprene (TPI), isoprene polymerization is catalyzed using supported titanium catalyst, synthetic powder shape or block-like high trans -1 are synthesized in solution slurries method, 4- polyisoprene, catalyst efficiency and monomer conversion are high, have reached industrialization standard.The TPI that the present invention synthesizes is easily crystallization, high rigidity and the excellent material of dynamic property under a kind of room temperature.TPI is with a wide range of applications, and in zero cross-linking stage, TPI is a kind of thermoplastic material, is usually used in medical material;At the low cross-linking stage, TPI is a kind of thermoelastic material, is usually used in shape-memory material;When crosslink density is more than certain value, TPI then becomes a kind of rubber-type highly elastic material.Currently, TPI shows big advantage in green tire and two aspect of high temperature damping material, therefore it is a kind of material having very much application value.
Description
Technical field
The invention belongs to macromolecule synthesising technology field, more particularly to anti-form-1, the preparation method of 4- polyisoprene and
The trans-1,4-iroprene polymer being prepared by this method.
Background technology
Anti-form-1,4- polyisoprene (Trans-1,4-polyisoprene), abbreviation TPI, also known as artificial synthesized Cortex Eucommiae
Glue, with gutta-percha, gutta-percha and Ba Lata glue anti-form-1 having the same, 4- configurations, only difference is that natural Du
Secondary glue is with ester terminated, and TPI, gutta-percha and Ba Lata glue are with hydroxy-end capped.The chemical composition and natural rubber of TPI
(NR) identical, only in strand double bond structure on the contrary, two methines of TPI in the both sides of double bond connecting shaft line, and
For two methines of NR in the same side of double bond connecting shaft line, this leads to the two, and there are larger differences in performance, are mainly shown as
NR is non-Crystalline plastics at room temperature, and hardness and tensile strength are relatively low, and TPI rapid crystallizations when less than 60 DEG C,
It is a kind of Crystalline plastics with higher hardness and larger tensile strength.Double bond structure, chain compliance and trans- order
It is the typical three big structures features of TPI, this give the excellent dynamic properties of TPI, such as excellent flex fatig resistance, low dynamic is given birth to
Heat and rolling resistance and abrasion resistance.
During the application of TPI, researcher is found that three stages of TPI vulcanizations:When in the first stage, TPI
The degree of cross linking be zero, have stronger crystallizing power because the trans- order of strand is high, show as crystal type on TPI is microcosmic
Linear polymeric macroscopically then shows as thermoplastic hard material;In second stage, the degree of cross linking of TPI is relatively low, strand because
Crosslinking and network-type is changed by line style, but still have certain crystallizing power, show as crystal type network high score on TPI is microcosmic
Son macroscopically then shows as thermoelasticity hard material;In the phase III, the degree of cross linking of TPI reaches critical value and (divides between crosslinking points
Son amount Mc2924) or more for, TPI becomes soft elastomer.TPI vulcanizes the announcement of three stage features and its excellent dynamic
Performance plays great impetus to the application of TPI, and TPI is at two aspect of green tire and high temperature region damping material at present
Show huge application prospect.
There are natural extraction and artificial synthesized two kinds of approach in the source of trans-1,4-iroprene polymer.Natural extraction mainly has
Mechanical Method, alkali process method and solvent method, but these methods generally have that purity is low, glue yield rate is not high, complicated for operation and be unfavorable for
The shortcomings of large-scale production;And the gutta-percha quality homogeneity of different parts (leaf, seed, skin) is poor;Price is even more the tens of of NR
As many as times, this is difficult to receive on the General Purpose Rubbers product such as tire and damping material.Artificial synthesized gutta-percha mainly uses
Vanadium system, vanadium/titanium mixed catalyst solution polymerization and titanium system supported catalyst mass polymerization.Vanadium system or vanadium/titanium catalytic body
The catalyst efficiency of system is low, and polymerization technique is complicated, and reaction system viscosity is high, and energy consumption and material consumption are all very high, cost and price
Suitable with gutta-percha, therefore, it is difficult to the applications that puts it over;Catalyst efficiency is higher when titanium system supported catalyst mass polymerization,
But stirring power is big, and requires low temperature polymerization, and the reaction time is long, reacts later stage substantially solid graininess, therefore heat of polymerization
The problems such as being difficult to distribute, easily lead to hot-spot, cause implode causes defect rate higher, to influence the quality of product.This
Outside, Zhejiang University researcher has invented a kind of method that gas-phase polymerization prepares high trans-Isosorbide-5-Nitrae-polyisoprene in 2013,
The cohesion of this method and separation process are simple, and processing safety is high, and environmental pollution is few, but that there are mobility of particle is poor, radiates
Difficult and catalyst is easy the problems such as inactivation.
Invention content
The object of the present invention is to provide a kind of methods of high monomer conversion ratio synthesis of trans-Isosorbide-5-Nitrae-polyisoprene, are green
Colour wheel tire and high temperature region damping material, which provide, a kind of to be had excellent flex fatig resistance, low-rolling-resistance and abrasion and to go out
The raw material of color dynamic property, that is, the load-type Titanium series catalyst for using infusion process to prepare, with solution slurries method synthetic powder shape
Or block-like high trans-1,4-iroprene polymer.The present invention is compared to the above, the advantage is that:(1) catalyst efficiency ratio
Higher, polymerization process is steady, and heat is easy to distribute in polymerization, and the quality of polymer is easily controllable, is suitble to large-scale industry metaplasia
Production;(2) directionality of supported titanium catalyst is high, the anti-form-1 of product, and the molar content of 4- configurations is more than 98%;(3) polymerization speed
Rate is very fast, and reaction 6h substantially reduces the production cycle i.e. up to higher monomer conversion;(4) present invention can be poly- by controlling
The polymerization process conditions such as temperature, stirring intensity and form are closed to regulate and control the form of polymer, can be obtained powdered or block-like
Polymer, wherein polymer powder are easy to pipeline.
The method of high monomer conversion ratio synthesis of trans -1,4- polyisoprene carries out according to the following steps in the present invention:It will be anti-
It answers container to clean, dries, vacuumizes, for several times with nitrogen displacement, under dry nitrogen atmosphere, quantitative isoprene list is added
Body, n-hexane solvent, organo-aluminium and supported titanium catalyst, first pre-polymerization for a period of time, is then transferred to perseverance at a certain temperature
It polymerize in tepidarium, finally terminates polymerization with the ethanol solution containing antioxidant 264 (mass content 1%) that hydrochloric acid is acidified,
After product is taken out and above-mentioned ethanol solution is used to wash repeatedly, product is placed in 40 DEG C of vacuum drying chambers and is dried to constant weight.Root
Monomer conversion and catalyst efficiency are calculated according to product quality, and characterizes the microstructure and its performance of product.
Used polymerizing condition is:The load titanium rate of supported titanium catalyst be 1~8% (mass content), Al/Ti be 10~
220 (molar ratios), Ti/Ip are 1~10 × 10-4(molar ratio), monomer concentration are 1~10mol/L, and pre-polymerization temperature is -20~30
DEG C, the pre-polymerization time is 0~100min, and polymerization temperature is 10~90 DEG C, polymerization reaction time 1~for 24 hours.
Description of the drawings
Fig. 1:Supported titanium catalyst solution slurries method synthesizes TPI's1H-NMR spectrum;
Fig. 2:Supported titanium catalyst solution slurries method synthesizes TPI's13C-NMR spectrograms;
Fig. 3:Supported titanium catalyst solution slurries method synthesizes the DSC figures of TPI;
Fig. 4:Supported titanium catalyst solution slurries method synthesizes the TG figures of TPI.
1In H-NMR spectrums, the peak at chemical shift 5.14ppm is trans- Isosorbide-5-Nitrae-configuration and cis- Isosorbide-5-Nitrae-configuration isoprene
Peak at proton peak in unit double bond, 4.75ppm and 4.67ppm is the proton in 3,4- configuration isoprene unit double bonds
Peak at peak, 2.06ppm and 1.98ppm is the proton on trans- Isosorbide-5-Nitrae-configuration and cis- Isosorbide-5-Nitrae-configuration isoprene unit methylene
Peak, the peak at 1.74ppm are the proton peak on cis- Isosorbide-5-Nitrae-configuration isoprene unit methyl, and the peak at the places 1.69ppm is 3,4- structures
Proton peak on type isoprene unit methyl, the peak at 1.62ppm are the matter on trans- Isosorbide-5-Nitrae-configuration isoprene unit methyl
Sub- peak.According to the integrated intensity at this few place peak, it can be calculated that trans- Isosorbide-5-Nitrae-structure contents are 98.3%, cis--Isosorbide-5-Nitrae-configuration
Content is 0.9%, and 3,4- structure contents are 0.8%.
13In C-NMR spectrums, the peak at chemical shift 134.97ppm and 124.97ppm is trans- Isosorbide-5-Nitrae-configuration isoprene
Peak at carbon atom peak in unit double bond, 39.80ppm and 26.78ppm is trans- Isosorbide-5-Nitrae-configuration isoprene unit methylene
On carbon atom peak, the peak at chemical shift 16.07ppm is the carbon atom peak in trans- Isosorbide-5-Nitrae-configuration isoprene unit double bond,
Do not occur cis--Isosorbide-5-Nitrae-configuration, 3,4- configurations and 1 in spectrogram, the characteristic peak of 2- configurations illustrates product with trans- Isosorbide-5-Nitrae-configuration
Based on.
In DSC figures, solid line is a heating curve of product, it can be seen that the original crystal form of product is with α-crystal form
Based on, fusing point is 69.5 DEG C, melting enthalpy 80.8J/g, is 43.3% according to can be calculated the crystallinity of product;Dotted line is product
The secondary temperature elevation curve after thermal history is eliminated, it can be seen that the crystal form of product is beta-crystal at this time, fusing point is 48.5 DEG C, is melted
It is 35.3J/g to melt enthalpy, is 25.0%. according to can be calculated the crystallinity of product
The temperature of the maximum weight loss rate of product is 381 DEG C it can be seen from TG figures, and thermal stability and natural rubber are very
It is close.
Specific implementation mode
Example given below further illustrates the present invention, but is not limiting the scope of the invention, the neck
The technical staff in domain still falls within the protection of the present invention according to some nonessential modifications and adaptations that aforementioned present invention content is made
Range.
Following embodiment raw materials of the present invention:
Supported titanium catalyst:Polymer grade is prepared using infusion process;Isoprene:Polymer grade, the limited public affairs of Shanghai Jinshan petrochemical industry
Department;N-hexane:Analyze pure, the Tianjin chemical inc Bo Di;Alkyl aluminum:Monomer concentration is 4mol/L, with just when use
Hexane is diluted to 0.4mol/L;High pure nitrogen:99.999%, Qingdao He Li gases Co., Ltd;4A type molecular sieves:Chinese medicines group
Chemical reagent Co., Ltd;Antioxidant 264:Nanjing Rong Ji Chemical Co., Ltd.s;Potassium hydroxide:Analyze pure, Dihua work is won in Tianjin
Limited liability company;Calcium hydride:Analyze pure, one factory of Shanghai reagent;Metallic sodium:Chemical pure, Shanghai Xinhua chemical plant.
Raw material disposal:
1, the activation of 4A types molecular sieve
6h is activated at 150 DEG C in vacuum drying chamber, is transferred in wide-mouth bottle immediately, is sealed.
2, the rectifying of isoprene
Isoprene is placed in the narrow-mouthed bottle equipped with potassium hydroxide before rectifying, impregnates 12h to remove partial impurities, then
Isoprene is transferred in three-necked flask, a small amount of molecular sieve and calcium hydride is added, is heated to reflux 6h, makes containing for isoprene
Water and oxygen content are below l0ppm, then air-distillation, collect 34 ± 1 DEG C of fractions.Fraction is transferred to equipped with appropriate activation
In the narrow-mouthed bottle of good molecular sieve, the air in nitrogen discharge wide-mouth bottle is finally blasted, is sealed.
3, the rectifying of n-hexane
The activated molecular sieve of n-hexane is impregnated 12h to remove partial impurities before rectifying, then n-hexane is shifted
Into three-necked flask, a small amount of molecular sieve and sodium piece is added, is heated to reflux 4h, the water content of n-hexane and oxygen content is made to be below
68 ± 1 DEG C of fractions are collected in 10ppm, then air-distillation.Fraction is transferred to the wide-mouth bottle equipped with appropriate activated molecular sieve
In, the air in nitrogen discharge narrow-mouthed bottle is finally blasted, is sealed.
Embodiment 1
Clean 30ml polymerization pipes are toasted into 2h at 100 DEG C, High Purity Nitrogen displacement are used in combination for several times, after cooling, dry
In nitrogen atmosphere, isoprene monomer, n-hexane and triisobutyl aluminium and supported titanium catalyst are sequentially added, in 0 DEG C of ice bath
With prepolymerization 30min under stirring condition, it is then transferred in 30 DEG C of water-baths and continues to polymerize 6h, finally inject and contain into polymerization pipe
The ethanol solution of antioxidant 264 terminates reaction.Mixture is taken out and is washed repeatedly with above-mentioned ethanol solution, obtains what nothing was cohered
Product is put into 40 DEG C of vacuum drying chamber and dried to constant weight by powdery granule polymer.According to the quality of product, calculates and urge
Agent efficiency is 2824.1g/gTi, monomer conversion 59.7%;According to1H-NMR is composed, and calculates the anti-form-1 of product, 4- structures
Type content is 98.2%, and cis--Isosorbide-5-Nitrae-structure contents are 1.3%, and 3,4- structure contents are 0.5%.
Embodiment 2
Clean 1000ml three-necked flasks are toasted into 2h at 100 DEG C and are replaced for several times with High Purity Nitrogen, after cooling, in drying
Nitrogen atmosphere in, sequentially add n-hexane, triisobutyl aluminium and supported titanium catalyst first, then inject a small amount of isoamyl
Diene injects remaining isoprene again after a period of time, then the prepolymerization 30min under 0 DEG C of ice bath and stirring condition is shifted
To polymerization 6h is continued in 30 DEG C of water-baths, the ethanol solution containing antioxidant 264 is finally injected into three-necked flask to terminate reaction.
Mixture is taken out and is washed repeatedly with above-mentioned ethanol solution, obtains, without the powdery granule polymer cohered, product being put into
40 DEG C of vacuum drying chamber is dried to constant weight.According to the quality of product, it is 3094.4g/gTi, monomer to calculate catalyst efficiency
Conversion ratio is 65.3%;According to1H-NMR is composed, and calculates the anti-form-1 of product, and 4- structure contents are 98.1%, cis--Isosorbide-5-Nitrae-structure
Type content is 1.1%, and 3,4- structure contents are 0.8%.Catalyst efficiency and product structure and embodiment 1 are very close to illustrating this
Polyplant easily amplifies.
Embodiment 3
Polymerization is a difference in that and polymerize in 60 DEG C of water-baths with case study on implementation 1, post-treated, obtains bulk polymer.
According to the quality of product, it is 2851.1g/gTi, monomer conversion 60.2% to calculate catalyst efficiency;According to1H-NMR is composed,
The anti-form-1 of product is calculated, 4- structure contents are 98.3%, and cis--Isosorbide-5-Nitrae-structure contents are 1.0%, and 3,4- structure contents are
0.7%.
Embodiment 4
Polymerization is a difference in that and polymerize in 60 DEG C of water-baths with case study on implementation 2, post-treated, obtains bulk polymer.
According to the quality of product, it is 3141.9g/gTi, monomer conversion 66.4% to calculate catalyst efficiency;According to1H-NMR is composed,
The anti-form-1 of product is calculated, 4- structure contents are 98.5%, and cis--Isosorbide-5-Nitrae-structure contents are 0.8%, and 3,4- structure contents are
0.7%.Catalyst efficiency and product structure and embodiment 3 are very close to illustrating that the polyplant easily amplifies.
The TPI performances of this method synthesis are as follows:
Claims (9)
1. the present invention relates to a kind of preparation methods of high trans-Isosorbide-5-Nitrae-polyisoprene, it is characterized in that:Using supported titanium catalyst
It is catalyzed isoprene polymerization, with solution slurries method synthetic powder shape or block-like high trans-Isosorbide-5-Nitrae-polyisoprene, catalyst effect
Rate and monomer conversion are high, have reached industrialization standard.
2. according to the preparation method of high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, it is characterized in that:Supported titanium is catalyzed
Agent is prepared using infusion process, and a certain amount of third component is added to improve catalyst efficiency and regulate and control the regularity of product, i.e., instead
Formula -1,4- structure contents.
3. according to the preparation method of high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, implement according to the following steps, it is special
Sign is:In dry nitrogen atmosphere, quantitative isoprene, solvent, organo-aluminium and supported titanium catalysis are added into polymerization bottle
Agent, is then transferred in relevant temperature water-bath and polymerize first pre-polymerization certain time at a certain temperature, finally terminates reaction, removing
Unreacted monomer and solvent are dried to obtain powdered or block-like high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one.
4. according to the preparation method of high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, it is characterized in that:It is used poly-
Conjunction condition is:Supported titanium catalyst carry titanium rate be 1~8% (mass ratio), Al/Ti be 10~220 (molar ratios), Ti/Ip be 1~
10×10-4(molar ratio), monomer concentration are 1~10mol/L, and pre-polymerization temperature is -20~30 DEG C, and the pre-polymerization time is 0~100min,
Polymerization temperature is 10~90 DEG C, polymerization reaction time 1~for 24 hours.
5. according to the preparation method of high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, it is characterized in that:It is used molten
Agent is one kind in hexamethylene, n-hexane, normal heptane or toluene;Organo-aluminium is triethyl aluminum, triisobutyl aluminium, monomethyl dichloro
Change one kind in aluminium, dimethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diethyl monochlor(in)ate aluminium or diisobutyl monochlor(in)ate aluminium;
Titanium compound in supported titanium catalyst is selected from TiCl4,TiBr4Or TiI4In one kind;Carrier is selected from SiO2,MgCl2Or
MgCl2/SiO2One kind in mixture.
6. according to the supported titanium catalyst preparation method described in claim two, used third component is esters, ethers, ketone
The compounds such as class, anhydride or silanes, preferred third component are selected from benzoic acid, phenylacetic acid, P-methoxybenzoic acid, benzene
Methyl formate, phenyltrimethoxysila,e, Dicyclohexyldimethoxysilane, propyl trimethoxy silicane, phthalic acid two
One or more kinds of mixtures in butyl ester, o-benzene butyl phthalate ester.
7. according to high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, it is characterized in that:The polymer anti-form-1,4- structures
Type content is more than 98.0%, contains a small amount of cis--Isosorbide-5-Nitrae-configuration and 3,4- configurations simultaneously.
8. according to high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, it is characterized in that:The crystal form of the polymer is with α-crystalline substance
Based on type, for fusing point between 60~70 DEG C, crystallinity also contains a small amount of beta-crystal between 35%~45%.
9. according to high trans-Isosorbide-5-Nitrae-polyisoprene described in claim one, it is characterized in that:The dynamic property of the polymer is excellent
Different, if wearability is good, low-rolling-resistance and heat, flex fatigue property is excellent, especially suitable for green tire and high temperature
Damping material.
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