CN104926969A - Preparation method for polyisoprene resin - Google Patents
Preparation method for polyisoprene resin Download PDFInfo
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- CN104926969A CN104926969A CN201510138381.4A CN201510138381A CN104926969A CN 104926969 A CN104926969 A CN 104926969A CN 201510138381 A CN201510138381 A CN 201510138381A CN 104926969 A CN104926969 A CN 104926969A
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 10
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 150000001875 compounds Chemical group 0.000 claims description 6
- -1 titanium metal compound Chemical class 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- FWCTZJNNLCYVMA-UHFFFAOYSA-L butan-1-ol;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCCO.CCCCO FWCTZJNNLCYVMA-UHFFFAOYSA-L 0.000 claims 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical class [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 claims 1
- NSYCXGBGJZBZKI-UHFFFAOYSA-L dichlorotitanium;ethanol Chemical compound CCO.CCO.Cl[Ti]Cl NSYCXGBGJZBZKI-UHFFFAOYSA-L 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 claims 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002114 nanocomposite Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000000899 Gutta-Percha Substances 0.000 description 2
- 240000000342 Palaquium gutta Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920000588 gutta-percha Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method for high-strength polyisoprene resin. The preparation method for the polyisoprene resin comprises the step of subjecting isoprene to polymerization reaction in the presence of a supported Ziegler-Natta catalyst. The obtained polyisoprene resin has mooney viscosity (ML1+4, 100 DEG C) of 60 to 80 and tensile strength of 19 to 41 Mpa. The polyisoprene resin prepared in the invention has high mechanical property and good processing performance, and can be applied in preparation of automobile shock-absorbing products.
Description
Technical field
The present invention relates to a kind of high strength polyisoprene resin preparation method, be specifically related to a kind of load Ziegler-Natta catalyst and there is lower polyisoprene resin and preparation method thereof.
Background technology
Along with the high speed development of Domestic Automotive Industry, the demand of rubber tyre and various For Rubber Spare Parts for Automobiles increases fast.At present, China's rubber Year's consumption has reached 5,000,000 tons, ranks first in the world.And rubber sources is in situation in short supply at present, price rises.Due to China's geographical position reason, the quick speedup of production of domestic natural rubber is slow, the growth that cannot satisfy the demands, current year import natural rubber is more than 1,500,000 tons, account for more than 20% of Natural Rubber in The World total resources, natural rubber constantly raises in the demand of my rubber item especially tyre industry, and the industrial installation of domestic synthesis polyisoprene rubber is in continuous dilatation.Since two thousand five, the throughput of isoprene is increasing sharply, and get more and more from the isolated by product C 5 fraction of ethylene unit, this advances the development of synthetic polyisoprenes material to a great extent.
Polyisoprene resin and high trans-Isosorbide-5-Nitrae-polyisoprene (trans-1,4-polyisoprene, TPI), refer to containing anti-form-1, the synthetic materials that 4-structural content is greater than 96%, has natural gutta-percha and the similar stuctures and properties of gutta-percha.Studied persons think the optimal material being applied to shape memory functional material field, as medical orthotic material and temperature sensitive deformable material etc.Both at home and abroad to high trans-1, the study on the synthesis of 4-polyisoprene mainly contains vanadium system catalyst system (VCl3/AlEt3 and loaded modified type) (Industrial & EngineeringChemistry Product Research and Development, 1962, 1 (2): 82-85.), vanadium titanium mixed catalyst system (VCl3/TiCl3/AlEt3 and Ti (OR) 4/VCl3-TiO2/AlR3) (Journal of AppliedPolymer Science, 2001, 82 (1): 81-89) and titanium system catalyst system [TiCl4/Ti (OR) 4-Al (i-Bu) 3 loading type] (polymer journal, 1992, 1 (1): 116-119).Because the molecular chain of high trans-Isosorbide-5-Nitrae-polyisoprene has good order, therefore it has good machining property and dynamic properties.
The patent of synthesis TPI is published in nineteen fifty-five (British Pat.834544 and Bairn Pat.553904) the earliest.From the sixties, Canadian Polysar, Britain Dunlop and Kuraray company etc. have successively built up the back yard industry device of hundreds of t/a.These patents and device are all adopt vanadium or vanadium/titanium mixed system, solution polymerization synthesis TPI in aromatic hydrocarbons or aliphatic solvents.Due to catalytic efficiency low (only 1 ~ 2kgTPI/gV), complex process, energy and material consumption is high, and scale is little again, and production cost is very high, and international market price at l3 ~ 15 $/more than kg, is mainly limited to the special purposes such as medical material always.
In current polyisoprene resin production, the most widely used supported catalyst is still using magnesium compound or silicon-dioxide as effective catalyst (the CN 103265654A of carrier; CN103288999A).We introduce functional supports carbon nanotube (CNTs) on this basis, use CNTs/MgCl
2composite carried catalyst prepares polyisoprene resin.Due to the constructional feature of CNTs one dimension carbon material, stronger with the interface binding power of olefin polymer, can also be scattered in polyolefin substrate with the form of filler, and under less addition, significantly improve the electrical property of polymkeric substance, mechanical property, thermostability, thermal conductivity and magnetic property.In this work, we adopt first with CNTs/MgCl
2for the load Ziegler-Natta catalyst of complex carrier, synthetic polyisoprenes resin, products therefrom has high-mechanical property and good processing characteristics concurrently, for the preparation of automobile shock goods.。
Summary of the invention
The object of this invention is to provide a kind of polyisoprene resin, mooney viscosity (the ML1+4 that described polyisoprene resin is recorded by mooney viscosity, 100 DEG C) be 60 ~ 80, tensile strength is 19 ~ 41Mpa, has high-mechanical property and good processing characteristics concurrently.
Present invention also offers a kind of preparation method of polyisoprene resin, described polyisoprene resin is the CNTs/MgCl by using titanium metal compound to form for promotor for Primary Catalysts aluminum contained compound
2load Ziegler-Natta catalyst; Preferably, described carrier is carbon nanotube/magnesium chloride (CNTs/MgCl
2), described titanium metal compound is titanium tetrachloride, described aluminum contained compound be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane one or both.
Present invention also offers a kind of polyisoprene preparation method, method comprises: reactor through pump drainage nitrogen replacement for several times, adds the isoprene of metering, aluminum contained compound, carbon nanotube/magnesium chloride (CNTs/MgCl successively
2) load titanium tetrachloride, wherein, the mol ratio of titanium and isoprene is 1 ~ 10-4:1, the mol ratio of aluminium and titanium is 15 ~ 30:1, through 0 DEG C of pre-polymerization 20min, with 15 ~ 40 DEG C of constant temperature polyase 13 ~ 9h, stop polyreaction with acidic ethanol, resulting polymers at 30 DEG C vacuum-drying to constant weight.
The present invention adopts carbon nanotube/magnesium chloride (CNTs/MgCl
2) complex carrier replaces conventional magnesium chloride (MgCl
2) carrier, enhance the interface binding power of catalyzer and olefin polymer, and carrier is scattered in polyisoprene resin matrix with the form of filler, and under less addition, the electrical property of polyisoprene resin, mechanical property, thermostability, thermal conductivity and magnetic property is made to significantly improve.
Present invention also offers described polyisoprene resin and have high-mechanical property and good processing characteristics concurrently, for the preparation of the purposes of automobile shock goods.
Embodiment
The polyisoprene resin preparation method that following specific embodiment is just invented makes detailed explanation.But these embodiments do not limit the scope of the invention, also should not be construed as and only have condition provided by the invention, parameter or numerical value to implement the present invention.
Embodiment 1
Under vacuum state, 750ml isoprene monomer is added in 3L reactor, and adding 1.2ml triisobutyl aluminium and 0.4 gram of MgCl2 load Ziegler-Natta catalyst successively, titanium elements mass percentage is 1.98wt%, and magnesium elements mass percentage is 23.48wt%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, and add acidic ethanol after being polymerized and stop polyreaction, vacuum-drying at 30 DEG C, obtains about 90 grams of polyisoprenes;
The data of the electronic tensile machine test of its II type dumbbell shaped batten are as table 1:
The electronic tensile machine test experiments result of table 1 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 118.99 | 6.09 | 10.61 | 19.00 | 162.60 | 439.24 | 19.00 | 439.24 |
Embodiment 2
Under vacuum state, 750ml isoprene monomer is added in 3L reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, titanium elements mass percentage is 2.58wt%, magnesium elements mass percentage is 21.09wt%, and carbon mass percentage is 9.28%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, add acidic ethanol after being polymerized and stop polyreaction, vacuum-drying at 30 DEG C, obtain about 100 grams of Dark grey polyisoprene nano composite materials provided by the invention, obtain content of carbon nanotubes about 0.04% matrix material in polymkeric substance.
The data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 2:
The electronic tensile machine test experiments result of table 2 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 125.93 | 6.40 | 9.45 | 22.04 | 169.24 | 506.77 | 21.53 | 506.94 |
Embodiment 3
Under vacuum state, 750ml isoprene monomer is added in 3L reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, titanium elements mass percentage is 0.96wt%, magnesium elements mass percentage is 12.02wt%, and carbon mass percentage is 48.04%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 10h, and add acidic ethanol after being polymerized and stop polyreaction, vacuum-drying at 30 DEG C, obtains about 200 grams of Dark grey polyisoprene nano composite materials provided by the invention.
The data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 3:
The electronic tensile machine test experiments result of table 3 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 135.84 | 7.26 | 12.51 | 36.56 | 334.90 | 527.20 | 35.55 | 527.35 |
Embodiment 4
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, wherein, titanium elements mass percentage is 2.01wt%, magnesium elements mass percentage is 21.22wt%, and carbon mass percentage is 9.27%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, and add acidic ethanol after being polymerized and stop polyreaction, vacuum-drying at 30 DEG C, obtains about 100 grams of Dark grey polyisoprene nano composite materials provided by the invention; Obtain content of carbon nanotubes about 0.04% matrix material in polymkeric substance.
The data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 4:
The electronic tensile machine test experiments result of table 4 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 125.69 | 6.69 | 17.30 | 28.68 | 252.41 | 466.92 | 27.27 | 467.10 |
Embodiment 5
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.5ml triisobutyl aluminium and 0.4 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, wherein, titanium elements mass percentage is 2.0wt%, magnesium elements mass percentage is 21.22wt%, and carbon mass percentage is 9.27%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains 105 grams of content of carbon nanotubes provided by the invention about 0.04% Dark grey polyisoprene nano composite material.
The data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 5:
The electronic tensile machine test experiments result of table 5 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 81.93 | 6.60 | 10.65 | 22.70 | 196.10 | 520.23 | 22.30 | 520.41 |
Embodiment 6
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.4 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, wherein, titanium elements mass percentage is 2.40wt%, magnesium elements mass percentage is 21.00wt%, and carbon mass percentage is 9.22%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 6h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains about 120 grams of content of carbon nanotubes provided by the invention about 0.04% Dark grey polyisoprene nano composite materials.After the composite sample obtained 135 DEG C of melting compressing tablets, the data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 6:
The electronic tensile machine test experiments result of table 6 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 139.06 | 6.45 | 11.76 | 26.42 | 207.15 | 545.03 | 25.30 | 545.16 |
Embodiment 7
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.8 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, wherein, titanium elements mass percentage is 1.15wt%, magnesium elements mass percentage is 11.96wt%, and carbon mass percentage is 47.99%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 10h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains about 250 grams of content of carbon nanotubes provided by the invention about 0.16% Dark grey polyisoprene nano composite materials.
After the composite sample obtained 135 DEG C of melting compressing tablets, the data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 7:
The electronic tensile machine test experiments result of table 7 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 180.38 | 7.02 | 13.64 | 35.07 | 294.55 | 551.27 | 35.07 | 551.27 |
Embodiment 8
Under vacuum state, 750ml isoprene monomer is added in reactor, add 1.2ml triisobutyl aluminium and 0.8 gram of CNTs/MgCl2 load Ziegler-Natta catalyst successively, wherein, titanium elements mass percentage is 1.12wt%, magnesium elements mass percentage is 12.08wt%, and carbon mass percentage is 48.55%.Through 0 DEG C of pre-polymerization 20min, polymeric reaction temperature is 25 DEG C, polyreaction 10h, adds acidic ethanol and stop polyreaction after being polymerized, vacuum-drying at 30 DEG C, obtains about 260 grams of content of carbon nanotubes provided by the invention about 0.16% Dark grey polyisoprene nano composite materials.
After the composite sample obtained 135 DEG C of melting compressing tablets, the data of the electronic tensile machine test of II type dumbbell shaped mixture batten are as table 8:
The electronic tensile machine test experiments result of table 8 mixture batten
| Tensile modulus | Yield strength | Yield strain | Tensile strength | Maximum, force | Tension strain | Rupture stress | Elongation rate of tensile failure |
| 145.01 | 8.42 | 15.47 | 40.09 | 320.70 | 523.14 | 40.09 | 523.14 |
Claims (10)
1. a polyisoprene resin, is characterized in that, it is 60 ~ 80 that described polyisoprene resin records mooney viscosity (ML1+4,100 DEG C) by mooney viscosity machine.
2. polyisoprene resin according to claim 1, wherein, described polyisoprene resin tensile strength is 19 ~ 41Mpa.
3. a polyisoprene resin preparation method, described polyisoprene resin is the load Ziegler-Natta catalyst synthesis that titanium metal compound is Primary Catalysts by using, aluminum contained compound forms for promotor.
4. polyisoprene resin preparation method according to claim 3, wherein, described load Ziegler-Natta catalyst carrier is carbon nanotube/magnesium chloride (CNTs/MgCl
2).
5. polyisoprene resin preparation method according to claim 3, wherein, the general formula of described titanium metal compound is TiR
1 nx
(4-n), wherein, R
1for C
1~ C
20alkyl or alkoxyl group, X is halogen, n=0,1,2 or 3.
6. polyisoprene resin preparation method according to claim 5, wherein, described titanium metal compound be selected from titanium tetrachloride, titanous chloride, titanium tetrabromide, titanium tetra iodide, oxyethyl group titanous chloride, diethoxy titanium dichloride, triethoxy monochlor(in)ate titanium, methoxytitanium trichloride, dibutoxy titanium dichloride, three butoxy titanium chlorides one or more; Titan-alkoxide used is Ti (OEt) Cl
3, Ti (OEt)
2cl
2, Ti (OEt)
3cl, Ti (OEt)
4or Ti (OBu)
4.
7. polyisoprene resin preparation method according to claim 6, wherein, described titanium metal compound is preferably titanium tetrachloride.
8. the preparation method of isoprene resin according to claim 3, wherein, described aluminum contained compound be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or methylaluminoxane one or both.
9. a polyisoprene resin preparation method according to claim 3, it is characterized in that, preparation method is as follows: reactor through pump drainage nitrogen replacement for several times, adds the isoprene of metering, aluminum contained compound, carbon nanotube/magnesium chloride (CNTs/MgCl successively
2) load titanium tetrachloride, wherein, the mol ratio of titanium and isoprene is 1 ~ 10
-4: 1, the mol ratio of aluminium and titanium is 15 ~ 30:1, through 0 DEG C of pre-polymerization 20min, with 15 ~ 40 DEG C of constant temperature polyase 13 ~ 9h, stops polyreaction with acidic ethanol, resulting polymers at 30 DEG C vacuum-drying to constant weight.
10. the preparation method of polyisoprene resin according to claim 9, has high-mechanical property and good processing characteristics concurrently, for the preparation of automobile shock goods.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510138381.4A CN104926969A (en) | 2015-03-27 | 2015-03-27 | Preparation method for polyisoprene resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510138381.4A CN104926969A (en) | 2015-03-27 | 2015-03-27 | Preparation method for polyisoprene resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104926969A true CN104926969A (en) | 2015-09-23 |
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ID=54114409
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