CN103665219A - Method for processing polyisoprene solution - Google Patents
Method for processing polyisoprene solution Download PDFInfo
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- CN103665219A CN103665219A CN201210338627.9A CN201210338627A CN103665219A CN 103665219 A CN103665219 A CN 103665219A CN 201210338627 A CN201210338627 A CN 201210338627A CN 103665219 A CN103665219 A CN 103665219A
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- Prior art keywords
- solution
- polyisoprene
- citric acid
- weight
- citrate
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 230000009849 deactivation Effects 0.000 claims abstract description 12
- -1 aluminum compound Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000000126 substance Substances 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 241001597008 Nomeidae Species 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000001508 potassium citrate Substances 0.000 claims description 5
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- 235000015870 tripotassium citrate Nutrition 0.000 claims description 5
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 4
- MPQPXMRGNQJXGO-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxamide Chemical compound NC(=O)CC(O)(C(N)=O)CC(N)=O MPQPXMRGNQJXGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 150000003608 titanium Chemical class 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 128
- 229960004106 citric acid Drugs 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000000178 monomer Substances 0.000 description 22
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 15
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 14
- 238000010908 decantation Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical class CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 150000003609 titanium compounds Chemical group 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical class CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 241000221020 Hevea Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001495453 Parthenium argentatum Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JIPKSNNYNSHSEK-UHFFFAOYSA-N hexane;phenoxybenzene Chemical compound CCCCCC.C=1C=CC=CC=1OC1=CC=CC=C1 JIPKSNNYNSHSEK-UHFFFAOYSA-N 0.000 description 1
- GWTMSNCNGOSQAD-UHFFFAOYSA-J hexane;tetrachlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].CCCCCC GWTMSNCNGOSQAD-UHFFFAOYSA-J 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a method for processing a polyisoprene solution, which is used for stabilizing the polyisoprene solution synthesized in the presence of a catalyst. The solution contains the catalyst which is the product of interaction of halogenated titanium with an organic aluminum compound and an electron donor. The method is characterized in that the polyisoprene solution comes into contact with citric acid compounds so as to deactivate the catalyst in the solution, wherein the citric acid compound is one or more than one of citric acid, citrate and derivatives of citric acid. The method is very simple and convenient, is easy to operate, is low in cost, and can effectively lower the metal content of titanium in the separated polymer. In the step of catalyst deactivation, citric acid compounds substitute methyl alcohol and the like and moreover the pollution to the environment is reduced also.
Description
Technical field
The present invention relates to a kind for the treatment of process of polyisoprene solution.
Background technology
Polyisoprene, according to its microtexture, can be divided into cis-Isosorbide-5-Nitrae-polyisoprene, anti-form-1,4-polyisoprene, 3,4-polyisoprene and 1,2-polyisoprene.Wherein, cis-Isosorbide-5-Nitrae-polyisoprene is commonly called as polyisoprene rubber, and its microtexture is similar to natural rubber (as hevea, guayule).Polyisoprene rubber is widely used in manufacturing tire and other rubber items, is the main substitute of natural rubber.
Many titaniums are that Ziegler-Natta catalyst can be used for synthesizing cis-Isosorbide-5-Nitrae-polyisoprene.In industrial production, conventionally only adopt TiCl
4-AlR
3and TiCl
4-poly-imido grpup aluminium alkane two class catalyzer.Typically, in solution polymerization mode, carry out the polycoordination of isoprene.
The physical and mechanical properties of cis-Isosorbide-5-Nitrae-polyisoprene depends on the physicochemical property of polymkeric substance self, the impact that the while is also subject to processing formula and cure conditions.For the physicochemical property of the polymkeric substance that obtains in stable polymerization reaction, must avoid the degraded of polymkeric substance in post-treatment step.Therefore, should first make deactivate and make it stable from the polymers soln of polymerization process, then polymkeric substance is separated from solution.
It is very necessary that cis-Isosorbide-5-Nitrae-polyisoprene is carried out to stabilizing treatment.This is because cis-Isosorbide-5-Nitrae-polyisoprene has high degree of unsaturation, as unstable in oxygen, ozone, light, high temperature and ultraviolet ray etc. to series of physical and chemical factor.Above-mentioned factor can make its degraded by the crosslinked and chain rupture of macromolecular chain.For preventing polymer degradation, need to make the trace active catalyst deactivation in polymers soln, because they can not only make stablizer lose efficacy, even can become the initiator of degradation process.Research shows the active ingredient TiCl in catalyzer
3at room temperature can generate such as Cl with oxygen reaction
3ti-O-O-TiCl
3such superoxide.This superoxide easily decomposes generation free radical, as: Cl
3tiO, the degraded of the further initiated polymerization thing of this meeting.Visible, the transition metal existing in polymkeric substance has a significant impact the degraded of polymkeric substance.In order to keep the physical and chemical performance of synthetic cis-Isosorbide-5-Nitrae-polyisoprene, to the deactivation of trace catalyzer and remove and the stabilization of polymkeric substance is seemed to very important.
This storehouse of neat Olympic Competition is shown and mentioned methyl alcohol, ethanol, acetone in < < isoprene tactic polymerization > > (Science Press, a 1984) book is all extraordinary catalyst deactivation agent.In industrial production in early days, these deactivators are widely used.But these reagent and water dissolve each other completely, and reagent itself belongs to hazardous and noxious substances, brings very large pressure to water treatment and environment protection.
SU689212 discloses and has used maleic acid derivatives as the passivator of catalyzer.But, in catalyst deactivation process, still used methyl alcohol or ethanol.
In GB1317507, mention and use aliphatic diamine or polyamines as passivator.But its effect of removing metal titanium in polymkeric substance is also bad in actual use.
This area still needs a kind of instead of methanol, ethanol or acetone and above-mentioned passivator with so that from the catalyst deactivation in the polyisoprene solution of polymerization process, thus the method for the physical and chemical performance of stabilization of polymer.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect of prior art, and a kind for the treatment of process of the polyisoprene solution that contains catalyzer is provided.
The inventor finds after extensive, deep research, one or more citric acid based compounds that use is selected from citric acid, Citrate trianion and citric acid derivant can make from the active catalyst inactivation in the polyisoprene solution of polymerization process, thereby make polymers soln stable, then can guarantee that the polymkeric substance that separation obtains has better physical and mechanical properties.
To achieve these goals, the invention provides a kind for the treatment of process of polyisoprene solution, described solution contains catalyzer, described catalyzer is halogenated titanium and organo-aluminium compound and the interactional product of electron donor, wherein, the method comprises described polyisoprene solution is contacted with citric acid based compound, makes the catalyst deactivation containing in described solution; Described citric acid based compound is selected from one or more in citric acid, Citrate trianion and citric acid derivant.
Pass through the inventive method, can effectively reduce content and the ash oontent of metal titanium in isolated polymkeric substance, make the content of metal titanium in polyisoprene drop to suitable scope, thereby good ageing-resistant performance and the physical and mechanical properties of synthetic cis-Isosorbide-5-Nitrae-polyisoprene have been guaranteed.In addition, very easy, the easy handling of method provided by the invention, cost are low.Moreover, adopt described citric acid based compound to replace traditional passivator methyl alcohol, also greatly reduced the pollution to environment.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the treatment process of polyisoprene solution provided by the invention, described method comprises described polyisoprene solution is contacted with citric acid based compound, makes the catalyst deactivation in described solution; Described citric acid based compound is selected from one or more in citric acid, Citrate trianion and citric acid derivant.
According to the present invention, under preferable case, described Citrate trianion is selected from one or more in alkali metal citrates (as one or more in Lithium Citrate de, Trisodium Citrate and Tripotassium Citrate) and ammonium citrate; Further preferably, described Citrate trianion is selected from one or more in Trisodium Citrate, Tripotassium Citrate and ammonium citrate.It should be explained that, the Trisodium Citrate of take in Citrate trianion is example, generally thinks, Trisodium Citrate refers to, the situation that the hydrogen in three carboxyls of citric acid is all replaced by sodium, i.e. trisodium citrate.
According to the present invention, under preferable case, described citric acid derivant selects the citric mide that free general formula 1 represents and one or more in the citrate being represented by general formula 2;
In formula 1, R
1, R
2, R
3can be identical or different, respectively do for oneself-OH or-NR
7r
8, and R
1, R
2and R
3in at least one be-NR
7r
8, R
7, R
8identical or different, respectively do for oneself H or carbonatoms are the alkyl of 1-6, and wherein, described alkyl can be also branched-chain alkyl for straight chained alkyl, more preferably, and R
7, R
8be H or the carbonatoms of respectively doing for oneself is the alkyl of 1-2.Further preferably, described R
1, R
2and R
3be-NR
7r
8effect is better.More preferably in situation, described citric mide is the citric acid triamide with structure shown in following formula 3;
In formula 2, R
4, R
5, R
6can be identical or different, respectively do for oneself-OH or-OR
9, and R
4, R
5and R
6in at least one be-OR
9, R
9for the carbonatoms alkyl that is 1-8, the alkyl that more preferably carbonatoms is 1-4, wherein, described alkyl can be also branched-chain alkyl for straight chained alkyl.Further preferably, described R
4, R
5and R
6be-OR
9effect is better, and R
9for the carbonatoms alkyl that is 2-4.More preferably in situation, described citrate is the tributyl citrate with structure shown in following formula 4;
According to the present invention, as long as the consumption of described citric acid based compound can make the active catalyst inactivation in described polyisoprene solution, under preferable case, the amount of substance of described citric acid based compound be the metal titanium in described catalyzer amount of substance 1-100 doubly, be preferably 30-50 doubly.
According to the present invention, described citric acid based compound can be to use with the form of its pure substance, can be also to use with the form of its solution.For example, described citric acid and/or Citrate trianion can be used with the form of the aqueous solution; Described citric acid derivant can be used with the form of organic solution.Preferably, the concentration of the described aqueous solution is 1-50 % by weight; The concentration of described organic solution is 1-50 % by weight.Wherein, the organic solvent in described organic solution can be selected the normally used any organic solvent that reactive component is to inertia in this area, the organic solvent using while being preferably synthetic polyisoprenes.Such as, but not limited to, saturated aliphatic hydrocarbon or clicyclic hydrocarbon solvent, be preferably C
5-C
10alkane and/or naphthenic hydrocarbon, as be selected from one or more in pentane, iso-pentane, hexane, hexanaphthene, heptane and octane.
According to the present invention, the selectable range of the condition of described contact is wider, and under preferable case, the condition of contact comprises that the temperature of contact is 40-70 ℃, and the time of contact is 50-60 minute; Further preferably, the temperature of described contact is 10-50 ℃, and the time of contact is 20-40 minute.
According to the present invention, the mode of described contact can be variety of way, as long as can play the effect that makes catalyst deactivation, be preferably mixing, more preferably in situation, the described polyisoprene solution that contains catalyzer carried out with mixing under agitation of citric acid based compound, more preferably by citric acid based compound, or in the polyisoprene solution that contains catalyzer described in the solution of citric acid based compound (aqueous solution of citric acid and/or Citrate trianion, and/or the organic solution of citric acid derivant) joins.
According to the present invention, after the polyisoprene solution obtaining is contacted with citric acid based compound, just can play the effect that makes catalyst deactivation, that is, make polyisoprene solution-stabilized.For the catalyzer after inactivation is separated from system, under preferable case, method provided by the invention also comprises: the solution that Jiang Shui obtains after contacting with citric acid based compound with by described polyisoprene solution mixes, and carries out oily water separation.
Wherein, solution that Jiang Shui obtains after contacting with citric acid based compound with by the polyisoprene solution that contains catalyzer mixes can play abundant mixing, wash glue and reduce the effect of catalyst content in polymkeric substance, although as long as the solution that Jiang Shui obtains after contacting with citric acid based compound with by the described polyisoprene solution that contains catalyzer mixes, but, under preferable case, the weight of described polyisoprene solution of take is benchmark, the consumption of described water is 10-300 % by weight, is preferably 50-150 % by weight.
According to the present invention, the condition that the solution that Jiang Shui obtains after contacting with citric acid based compound with by described polyisoprene solution mixes generally comprises the temperature of mixing and the time of mixing, the selectable range of the temperature of described mixing and the time of mixing is wider, under preferable case, the temperature of described mixing is 40-60 ℃, and the time of mixing is 20-40 minute.
According to the present invention, the solution that Jiang Shui obtains after contacting with citric acid based compound with by described polyisoprene solution mixes, and carry out oily water separation, can obtain water and oil phase, polyisoprene and finish solvent are present in oil phase, and wherein, the method for described oily water separation can adopt the method for well known to a person skilled in the art, for example, thus standingly in standing groove complete oily water separation.Wherein, described standing temperature can be 30-70 ℃, is preferably 40-60 ℃; The described standing time can be 15-50 minute, is preferably 20-40 minute.
According to the present invention, the method is also included in after oily water separation, the step of the polyisoprene in the oil phase that further separation obtains.Wherein, the method of described separation can adopt the method for well known to a person skilled in the art to carry out, for example, can adopt the mode of steam stripped, preferably, at 100-250 ℃, remove organic solvent and residual monomer in oil phase, and be preferably dried the polymkeric substance obtaining, complete dehumidifying, and separation obtains polymer poly isoprene.
According to the present invention, under preferable case, in order further to improve the ageing-resistant performance of rubber, the method also comprises: before polyisoprene solution is contacted with citric acid based compound, simultaneously or afterwards, and/or the solution that obtains after contacting with citric acid based compound with by polyisoprene solution of Jiang Shui mix before, simultaneously or afterwards, add stablizer.
Wherein, described stablizer can be the various stablizers that can function as described above, and is preferably antioxidant.Specifically, described antioxidant is preferably selected from 4-methyl-2,6-DI-tert-butylphenol compounds, N-phenyl-N '-cyclohexyl Ursol D, 2,2 '-methylene-bis-(4-methyl-6-tert-butylphenol), N-phenyl-N '-sec.-propyl Ursol D, octadecyl-3, one or more in two (1,1-the dimethyl ethyl)-4-hydroxy benzoic propionates of 5-.Further preferably, the weight of polyisoprene in described polyisoprene solution of take is benchmark, and the consumption of described stablizer is 0.1-2 % by weight.
In the polyisoprene obtaining according to method separation of the present invention, the content (mass content) of metal titanium can be controlled between 50-300ppm, and ash oontent can be reduced to below 0.3 % by weight.
Improvement of the present invention is the catalyst deactivation containing in the polyisoprene solution obtaining to make polyisoprene solution-stabilized, , polyisoprene solution is contacted with citric acid based compound, therefore, the present invention is not particularly limited the preparation method of polyisoprene solution, can adopt and well known to a person skilled in the art method preparation, for example, can be under solution polymerization condition, make to contain isoprene monomer, isoprene monomer polymerization in the mixture of catalyzer and finish solvent, obtain polyisoprene solution, wherein, described catalyzer refers to the catalyzer of heterogeneous state, contain the electron donor that halogenated titanium and organo-aluminium compound and selectivity contain.
For example, in the present invention, described isoprene monomer carries out solution polymerization under catalyst action.Therefore, described isoprene monomer is generally polymerization-grade, and it can be commercially available.
In the present invention, described catalyzer can be any suitable catalyst for the polymerization of catalysis isoprene monomer conventional in this area, for example, and Titanium series catalyst etc., described catalyzer can be commercially available, also can prepare according to the method for well known to a person skilled in the art.
Described Titanium series catalyst can be known in the art disclosed industrial Titanium series catalyst.More specifically, described heterogeneous Titanium series catalyst mainly contains halogenated titanium, general formula is AlR
3organo-aluminium compound (wherein, R can be the straight or branched alkyl of C1-C6) and preferably also contain electron donor, general formula is R
1-O-R
2ether (wherein, R
1and R
2can be identical or different, can be alkyl, cycloalkyl, alkylene or the aromatic yl group that contains 2-20 carbon atom independently of one another).Wherein, take every mole of halogenated titanium compound as benchmark, the content of described organo-aluminium compound can be 0.1-10 mole, is preferably 0.5-2.0 mole, 0.8-1.2 mole more preferably, and the content of described ether can be 0.001-20 mole, is preferably 0.2-2 mole.
In the present invention, described solvent is generally inert hydrocarbon solvent.'inertia' in described inert hydrocarbon solvent be take not negative interference mixing and reaction process and/or be not principle with material component and reaction.For example, such as, but not limited to, saturated aliphatic hydrocarbon and/or clicyclic hydrocarbon solvent, C
5-C
10alkane or naphthenic hydrocarbon, specifically can be selected from one or more in pentane, iso-pentane, hexane, hexanaphthene, heptane and octane.
In the present invention, the gross weight of polymer reaction material is benchmark, and the concentration of the isoprene monomer in described polyreaction material can be 8-20 % by weight, is preferably 12-18 % by weight.The consumption of described catalyzer can the principle based on industrial economy suitably be selected, and for example, take every mole of isoprene monomer as benchmark, and the consumption of described Titanium series catalyst can be 1 * 10 conventionally
-4-5 * 10
-3molTi, is preferably 1.5 * 10
-4-2.5 * 10
-3molTi.
According to the present invention, when carrying out the solution polymerization of isoprene monomer, the condition of polyreaction can be conventional polymeric reaction condition, for example, polymeric reaction temperature can for subzero 30 ℃ to 80 ℃, be preferably 0-70 ℃, more preferably 10-60 ℃; Polymerization reaction time can be 20-300 minute, is preferably 100-200 minute.
For the mass parameter of described polyisoprene rubber product, as cis-Isosorbide-5-Nitrae-configuration content, number-average molecular weight and molecular weight distribution coefficient, can adopt any appropriate method well known in the art to measure.
Particularly, in the present invention, the microtexture of the polyisoprene rubber product of synthesized can adopt German Bruker Tensor 27 mid-infrared light spectrometers and German Bruker 400MHz nmr determination, and solvent is deuterochloroform; Number-average molecular weight and molecular weight distribution adopt Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 ℃.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will describe the present invention by embodiment.
In the present invention, adopt the IRIS/AP of company of Thermo Electron Corp. type entirely to compose the content that direct-reading ICP spectrograph (inductively coupled plasma atomic emission spectrometer) is measured metal titanium in isolated polyisoprene.Instrument parameter: high frequency power: 1150W, assisted gas: 0.5L/min, wriggling pump speed: 100 turn/min, integral time: 10s, nebulizer gas pressure: 32.06psi, sample size: 1.85mL/min.
Sample preparation: accurately take the dry glue of 2.000g in porcelain crucible, be placed in cascade raising temperature to 450 ℃ in high temperature resistance furnace, after ashing 3-4 hour, take out, add 5mL hydrochloric acid, on hot plate, slowly heating, until ash content dissolves completely, is steamed solution to dry to the greatest extent, add 3mL hydrochloric acid, proceed in 50mL volumetric flask, and water constant volume, prepare blank reagent solution simultaneously.
Determination of ash: take dry glue 2.000g, put into crucible charing (preventing that sample from catching fire) completely on electric furnace of constant weight.Then crucible is moved into calcination in 550 ℃ ± 25 ℃ muffle furnaces, during calcination, answer crack fire door, so that sufficient air to be provided, the whole carbonaceous of burning-off.Take out crucible slightly cold, in rear immigration drying basin, continue to be cooled to room temperature (25 ℃) to constant weight.Ash content calculation formula is as follows: total mass/sample mass after ash oontent (%)=calcination.
The preparation method of Titanium series catalyst described in following examples is: the hexane solution that titanium tetrachloride, triisobutyl aluminium and phenyl ether is mixed with respectively to 2mol/L concentration is standby.Solvent water number, lower than 20ppm, carries out deoxygenation processing with nitrogen before using; Aging reactor drying and deoxygenation are processed.
Under nitrogen protection; in 20L catalyzer aging reactor, add 600ml titanium tetrachloride hexane solution; the mixing solutions being comprised of 600ml triisobutyl aluminium hexane solution and 300ml phenyl ether hexane solution is slowly joined in aging reactor again to continuation ageing 24 hours under-30 ℃ and agitation condition.Catalyst concn is 6 * 10
-5mol/ml.
Embodiment 1
Under nitrogen protection, in 5L reactor, add 1700g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 17 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 15%.
At 60 ℃, to adding 132.61g mass percent concentration in above-mentioned polymers soln, it is the sodium citrate aqueous solution of 50 % by weight, and adding 6.3 grams containing 10 % by weight stablizers 2, the hexane solution of 2'-methylene-bis-(4-methyl-6-tert-butylphenol), stirs 30 minutes.
By 3L deionized water wash 1 time of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 94ppm, and ash content is 0.13 % by weight.
Embodiment 2
Under nitrogen protection, in 5L reactor, add 1980g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 15 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 12%.
At 60 ℃, to adding 787.23g mass percent concentration in above-mentioned polymers soln, be the Tripotassium Citrate aqueous solution of 1 % by weight, and add 8.75 grams containing the hexane solutions of 20 % by weight stablizer N-phenyl-N'-cyclohexyl Ursol D, stir 30 minutes.
By 3.5L deionized water wash 3 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 289ppm, and ash content is 0.29 % by weight.
Embodiment 3
Under nitrogen protection, in 5L reactor, add 2340g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 13 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 10%.
At 60 ℃, to adding 212.19g mass percent concentration in above-mentioned polymers soln, be the sodium citrate aqueous solution of 25 % by weight, and add 9.8 grams containing the hexane solutions of 20 % by weight stablizer N-phenyl-N'-sec.-propyl Ursol D, stir 30 minutes.
By 4.5L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 197ppm, and ash content is 0.21 % by weight.
Embodiment 4
Under nitrogen protection, in 5L reactor, add 2340g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 13 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 10%.
At 60 ℃, to adding 3978.7g mass percent concentration in above-mentioned polymers soln, be the sodium citrate aqueous solution of 1 % by weight, and add 9.8 grams containing the hexane solutions of 20 % by weight stablizer N-phenyl-N'-sec.-propyl Ursol D, stir 30 minutes.
By 4.5L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 273ppm, and ash content is 0.27 % by weight.
Embodiment 5
Under nitrogen protection, in 5L reactor, add 2340g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 13 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 10%.
At 60 ℃, to adding 199.98g mass percent concentration in above-mentioned polymers soln, be the ammonium citrate aqueous solution of 25 % by weight, and add 9.8 grams containing the hexane solutions of 20 % by weight stablizer N-phenyl-N'-sec.-propyl Ursol D, stir 30 minutes.
By 4.5L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 230ppm, and ash content is 0.23 % by weight.
Embodiment 6
Under nitrogen protection, in 5L reactor, add 2340g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 13 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 10%.
At 60 ℃, to adding 123.52g mass percent concentration in above-mentioned polymers soln, be the citric acid triamide solution (solvent is polymer solvent) of 25 % by weight, and add 9.8 grams containing the hexane solution of 20 % by weight stablizer N-phenyl-N'-sec.-propyl Ursol D, stir 30 minutes.
By 4.5L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 229ppm, and ash content is 0.23 % by weight.
Embodiment 7
Under nitrogen protection, in 5L reactor, add 1980g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 15 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 12%.
At 60 ℃, in above-mentioned polymers soln, add 296.35g to contain the oil solution (solvent is polymer solvent) of 25 % by weight tributyl citrates, and add 8.75 grams containing the hexane solution of 20 % by weight stablizer N-phenyl-N'-cyclohexyl Ursol D, stir 30 minutes.
By 3.5L deionized water wash 3 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 253ppm, and ash content is 0.26 % by weight.
Embodiment 8
Under nitrogen protection, in 5L reactor, add 1980g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 15 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 12%.
At 60 ℃, to adding 6297.81g mass percent concentration in above-mentioned polymers soln, be the Tripotassium Citrate aqueous solution of 1 % by weight, and add 8.75 grams containing the hexane solutions of 20 % by weight stablizer N-phenyl-N'-cyclohexyl Ursol D, stir 30 minutes.
By 3.5L deionized water wash 3 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 260ppm, and ash content is 0.26 % by weight.
Embodiment 9
Under nitrogen protection, in 5L reactor, add 1490g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 19 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 17%.
At 60 ℃, to adding 172.8g mass percent concentration in above-mentioned polymers soln, be the Citric acid monohydrate Food grade aqueous solution of 25 % by weight, add 8.75 grams containing the hexane solutions of 20 % by weight stablizer 4-methyl-2,6 di t butyl phenols simultaneously, stir 30 minutes.
By 3.5L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 276ppm, and ash content is 0.28 % by weight.
Comparative example 1
Under nitrogen protection, in 5L reactor, add 1700g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 17 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 15%.
At 60 ℃, in above-mentioned polymers soln, add 82g to contain the aqueous solution of 10 % by weight methyl alcohol, and add 8.75 grams containing the hexane solution of 20 % by weight stablizer 4-methyl-2,6 di t butyl phenols, stir 30 minutes.
By 3L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 315ppm, and ash content is 0.32 % by weight.
Comparative example 2
Under nitrogen protection, in 5L reactor, add 1700g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 17 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 15%.
At 60 ℃, in above-mentioned polymers soln, add 149g to contain the aqueous solution of 10 % by weight acetone, and add 8.75 grams containing the hexane solution of 20 % by weight stablizer 4-methyl-2,6 di t butyl phenols, stir 30 minutes.
By 3L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 337ppm, and ash content is 0.34 % by weight.
Comparative example 3
Under nitrogen protection, in 5L reactor, add 1700g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 17 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 15%.
At 60 ℃, in above-mentioned polymers soln, add 77.2g to contain the aqueous solution of 10 % by weight quadrols, and add 8.75 grams containing the hexane solution of 20 % by weight stablizer 4-methyl-2,6 di t butyl phenols, stir 30 minutes.
By 3L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 582ppm, and ash content is 0.61 % by weight.
Comparative example 4
Under nitrogen protection, in 5L reactor, add 1700g hexane, 350g IP, adds TiCl
4the hexane solution of/triisobutyl aluminium/phenyl ether (three's mol ratio is 1.0:1.0:0.5) catalyzer, catalyst levels is 1.0 * 10
-3mol Ti/mol IP, monomer concentration is 17 % by weight.At 20 ℃, react the polymers soln containing active catalyst that to obtain polymkeric substance (polyisoprene) weight percentage for 2 hours be 15%.
At 60 ℃, in above-mentioned polymers soln, add 41g to contain the methanol solution of 90 % by weight ethyl maleates, and add 8.75 grams containing the hexane solution of 20 % by weight stablizer 4-methyl-2,6 di t butyl phenols, stir 30 minutes.
By 3L deionized water wash 2 times of the polymers soln through above-mentioned processing; Standing 30 minutes subsequently, carry out oily water separation; After decantation water, use steam stripped oil phase, vacuum drying, obtains removing trace catalyzer stable polyisoprene.
The content of measuring metal titanium in isolated polymkeric substance is 467ppm, and ash content is 0.54 % by weight.
Claims (13)
1. the treatment process of a polyisoprene solution, described solution contains catalyzer, described catalyzer is halogenated titanium and organo-aluminium compound and the interactional product of electron donor, it is characterized in that, the method comprises described polyisoprene solution is contacted with citric acid based compound, makes the catalyst deactivation containing in described solution; Described citric acid based compound is selected from one or more in citric acid, Citrate trianion and citric acid derivant.
2. treatment process according to claim 1, wherein, described Citrate trianion is selected from one or more in alkali metal citrates and ammonium citrate; Described citric acid derivant selects the citric mide that free general formula 1 represents and one or more in the citrate being represented by general formula 2;
In formula 1, R
1, R
2, R
3identical or different, respectively do for oneself-OH or-NR
7r
8, and R
1, R
2and R
3in at least one be-NR
7r
8, R
7, R
8identical or different, respectively do for oneself H or carbonatoms are the alkyl of 1-6;
In formula 2, R
4, R
5, R
6identical or different, respectively do for oneself-OH or-OR
9, and R
4, R
5and R
6in at least one be-OR
9, R
9for the carbonatoms alkyl that is 1-8.
3. treatment process according to claim 2, wherein, described Citrate trianion is selected from one or more in Trisodium Citrate, Tripotassium Citrate and ammonium citrate; Described citric mide is the citric acid triamide with structure shown in following formula 3, and described citrate is the tributyl citrate with structure shown in following formula 4;
4. treatment process according to claim 1, wherein, the amount of substance of described citric acid based compound be the metal titanium in described catalyzer amount of substance 1-100 doubly, be preferably 30-50 doubly.
5. according to the treatment process described in any one in claim 1-4, wherein, described citric acid and/or Citrate trianion are used with the form of the aqueous solution, and the concentration of the described aqueous solution is preferably 1-50 % by weight; Described citric acid derivant is used with the form of organic solution, and the concentration of described organic solution is 1-50 % by weight.
6. treatment process according to claim 1, wherein, the temperature of contact is 40-70 ℃, the time of contact is 10-60 minute.
7. treatment process according to claim 1, wherein, the method also comprises that the solution obtaining after Jiang Shui contacts with citric acid based compound with by described polyisoprene solution mixes, and carries out oily water separation.
8. treatment process according to claim 7, wherein, the weight of described polyisoprene solution of take is benchmark, the consumption of described water is 10-300 % by weight, is preferably 50-150 % by weight.
9. treatment process according to claim 7, wherein, the temperature of mixing is 30-70 ℃, preferably 40-60 ℃; The time of mixing is 15-50 minute, preferably 20-40 minute.
10. according to the treatment process described in claim 1,7 or 8, wherein, the weight of described polyisoprene solution of take is benchmark, and the content of described polyisoprene is 8-20 % by weight.
11. treatment processs according to claim 7, wherein, the method also comprises: after oily water separation, the step of the polyisoprene in the oil phase that further separation obtains.
12. according to the method described in claim 1 or 7, wherein, the method also comprises: before polyisoprene solution is contacted with citric acid based compound, simultaneously or afterwards, and/or the solution that obtains after contacting with citric acid based compound with by polyisoprene solution of Jiang Shui mix before, simultaneously or afterwards, add stablizer.
13. methods according to claim 12, wherein, described stablizer is selected from 4-methyl-2,6-DI-tert-butylphenol compounds, N-phenyl-N '-cyclohexyl Ursol D, 2,2 '-methylene-bis-(4-methyl-6-tert-butylphenol), N-phenyl-N '-sec.-propyl Ursol D, octadecyl-3, one or more in two (1,1-the dimethyl ethyl)-4-hydroxy benzoic propionates of 5-; The weight of polyisoprene in polyisoprene solution of take is benchmark, and the consumption of described stablizer is 0.1-2 % by weight.
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| CN106292118A (en) * | 2016-08-31 | 2017-01-04 | 广州奥翼电子科技股份有限公司 | Electrophoresis showed micro unit, electric ink, electrophoresis showed diaphragm and electrophoretic display |
| CN107417813A (en) * | 2016-05-23 | 2017-12-01 | 北京利和知信科技有限公司 | A kind of ingredient of solid catalyst and catalyst for olefinic polymerization |
| CN116655842A (en) * | 2023-06-06 | 2023-08-29 | 中国石油天然气股份有限公司 | Polymer deashing method |
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| CN107417813A (en) * | 2016-05-23 | 2017-12-01 | 北京利和知信科技有限公司 | A kind of ingredient of solid catalyst and catalyst for olefinic polymerization |
| CN106292118A (en) * | 2016-08-31 | 2017-01-04 | 广州奥翼电子科技股份有限公司 | Electrophoresis showed micro unit, electric ink, electrophoresis showed diaphragm and electrophoretic display |
| CN116655842A (en) * | 2023-06-06 | 2023-08-29 | 中国石油天然气股份有限公司 | Polymer deashing method |
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| CN103665219B (en) | 2016-03-30 |
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