CN102453109A - Stabilizing method and separation method of polyisoprene - Google Patents
Stabilizing method and separation method of polyisoprene Download PDFInfo
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- CN102453109A CN102453109A CN2010105300292A CN201010530029A CN102453109A CN 102453109 A CN102453109 A CN 102453109A CN 2010105300292 A CN2010105300292 A CN 2010105300292A CN 201010530029 A CN201010530029 A CN 201010530029A CN 102453109 A CN102453109 A CN 102453109A
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Abstract
The invention relates to a method for stabilizing polyisoprene synthesized in the presence of a catalyst. According to the invention, the catalyst is a product obtained by interaction of titanium tetrachloride and an aluminum organic compound. The method comprises the step of adding lignosulfonate into a synthesized polyisoprene solution. The method is extremely simple and convenient, is easy to operate and low in cost, and can be used for effectively reducing the content of titanium metal in a separated polymer. In the step of deactivating the catalyst, lignosulfonate is used instead of methanol, thereby reducing environment pollution.
Description
Technical field
The present invention relates to a kind of method of from contain catalyst solution, separating TR 301, said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound.The invention still further relates to the method for stablizing TR 301.The present invention is particularly useful for the TR 301 solution that contains the variable valency metal titanium is handled, and reducing the content of metal titanium in the isolated polymkeric substance, thereby guarantees the physical and mechanical properties of polymkeric substance.
Background technology
TR 301 can be divided into cis-1 according to its microtexture, 4-TR 301, anti-form-1,4-TR 301,3,4-TR 301 and 1,2-TR 301.Wherein, cis-1, the 4-TR 301 is commonly called as polyisoprene rubber, and its microtexture is similar with tree elastomer (like hevea, guayule).Polyisoprene rubber is widely used in making tire and other rubber items, is the main substitute of tree elastomer.
Many titaniums are that Ziegler-Natta catalyst can be used for synthesizing cis-1, the 4-TR 301.Usually only adopt TiCl on the industrial production
4-AlR
3And TiCl
4-gather two types of catalyzer of imido grpup aluminium alkane.Typically, carry out the polycoordination of isoprene with the solution polymerization mode.
Cis-1, the physical and mechanical properties of 4-TR 301 depend on the physicochemical property of polymkeric substance self, the influence that the while also receives processing formula and cure conditions.For the physicochemical property of the polymkeric substance that obtains in the stable polymerization reaction, must avoid the degraded of polymkeric substance in the post-treatment step.Therefore, polymers soln from polymerization process is deactivated and make it stable, from solution, separate polymkeric substance again.
To cis-1, it is very necessary that the 4-TR 301 carries out stabilizing treatment.This is that the 4-TR 301 has high degree of unsaturation, to a series of physics and chemical factor such as instabilities such as oxygen, ozone, light, high temperature and ultraviolet ray because of cis-1.Above-mentioned factor can make its degraded through the crosslinked and chain rupture of macromolecular chain.For preventing polymer degradation, the trace active catalyst in the polymers soln is deactivated, because they can not only make stablizer lose efficacy, even can become the initiator of degradation process.Research shows the active ingredient TiCl in the catalyzer
3At room temperature can generate such as Cl with the oxygen reaction
3Ti-O-O-TiCl
3Such superoxide.This superoxide decomposes the generation radical easily, as: Cl
3TiO, the degraded of the further initiated polymerization thing of this meeting.It is thus clear that the transition metal that exists in the polymkeric substance has very big influence to the degraded of polymkeric substance.In order to keep synthetic cis-1, the physical and chemical performance of 4-TR 301, deactivating and removing and the stabilization of polymkeric substance is seemed very important to the trace catalyzer.
Neat this storehouse of Olympic Competition is shown and mentioned methyl alcohol, ethanol, acetone in the book of " isoprene tactic polymerization " (Science Press, 1984) all is extraordinary catalyst deactivation agent.In the industrial production in early days, these deactivators are widely used.But these reagent and water dissolve each other fully, and reagent itself belongs to hazardous and noxious substances, bring very big pressure to water treatment and environment protection.
SU689212 discloses and has used the passivator of maleic acid derivatives as catalyzer.But, in the catalyst deactivation process, still used methyl alcohol or ethanol.
Mention among the GB1317507 and use aliphatic diamine or polyamines as passivator.But its effect of removing metal titanium in the polymkeric substance is also bad in actual use.
This area still needs a kind of instead of methanol, ethanol or acetone with so that from the catalyst deactivation in the TR 301 solution of polymerization process, thus the method for the physical and chemical performance of stabilization of polymer.
Summary of the invention
The inventor finds to use sulfonated lignin can make from the catalyst deactivation in the TR 301 solution of polymerization process, thereby makes polymers soln stable after extensive, deep research, from solution, separates polymkeric substance again.Through the inventive method, can make the content of metal titanium in the isolated TR 301 drop to suitable scope, thereby guarantee synthetic cis-1, the physical and mechanical properties of 4-TR 301.This method is very easy, easy handling, cost are low, can effectively reduce the content of titanium metal in the isolated polymkeric substance.In catalyzer deactivation step, use sulfonated lignin to replace methyl alcohol, reduced environmental pollution.
An object of the present invention is to provide and a kind of synthetic TR 301 in the presence of catalyzer is carried out stable method, said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound.
Another object of the present invention provides a kind ofly carries out isolating method to synthetic TR 301 in the presence of catalyzer, and said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound.
Detailed Description Of The Invention
In the description of this invention, remove other and offer some clarification on hereinafter, the numerical value among the application all can be considered by word " approximately " to be modified.But the inventor has as far as possible accurately reported the numerical value among the embodiment, although these numerical value comprise certain error inevitably.
In this application, only if clearly get rid of, concrete perhaps preferred embodiment of the present invention can make up.In addition, each item key element of the application embodiment is the concrete preferred selection of the upper technical characterictic corresponding with it.If said upper technical characterictic can make up with other upper characteristic, the said key element of embodiment then, promptly said concrete preferred selection also can be made up with said other upper characteristic.These combinations should be regarded as the part of the original record content of the application.
According to an aspect of the present invention; Provide a kind of synthetic TR 301 in the presence of catalyzer has been carried out stable method; Said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound, and said method comprises in synthetic TR 301 solution and adds sulfonated lignin.
Said sulfonated lignin can be water-soluble sulfonated lignin, for example, but are not limited to sulfomethylated lignin acid alkali metal salt, sulfomethylated lignin acid alkaline earth metal salt and lignosulfonic acid quaternary ammonium salt.Preferred sulfonated lignin include, but not limited to sodium lignosulfonate, lignosulfonic acid potassium, calcium lignin sulphonate, magnesium lignosulfonate, ammonium lignosulphonate, more preferably sodium lignosulfonate.
Be applicable to that sulfonated lignin of the present invention can be the verivates of the waste product of cellulose paper and hydrolysis industry thereof.These sulfonated lignin can easily be purchased acquisition.
According to embodiments more of the present invention, said sulfonated lignin can add with the form of the aqueous solution.Preferably, the aqueous solution of sulfonated lignin can be prepared as follows: sulfonated lignin are dissolved in the water is formulated as the aqueous solution of 1～50% weight concentration.In use, preferably under agitation, be that the solution form of 5-14 joins in the TR 301 solution with the pH value.
Preferably, the molecular weight of said sulfonated lignin can be 4 * 10
2～10 * 10
6, its total hydroxy radical content is preferably 1.1-1.2/C
9Here, as well known in the art, C
9Hydrocinnamyl structural unit in the expression sulfonated lignin.
The consumption of said sulfonated lignin preferably is enough to provide 1～100 times hydroxyl, based on the metal titanium content meter that exists in the catalyzer.More preferably, the consumption of said sulfonated lignin is enough to provide 8～50 times hydroxyl, based on the metal titanium content meter that exists in the catalyzer.
According to embodiments more of the present invention, the solvent of employed solution can be organic solvent during synthetic polyisoprenes.Said organic solvent has no particular limits, and can select that this area is normally used to be any organic solvent of inert to reactive component for use, for example, but is not limited to saturated aliphatic hydrocarbon or clicyclic hydrocarbon solvent, for example C
5～C
10Alkane or naphthenic hydrocarbon are like pentane, iso-pentane, hexane, hexanaphthene, heptane, octane or its mixture.
According to embodiments more of the present invention, said TR 301 solution can be the solution of 10～20% weight in above-mentioned solvent.
According to a further aspect in the invention, provide a kind of synthetic TR 301 in the presence of catalyzer is carried out isolating method, said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound, and said method comprises:
(i) aqueous solution of adding sulfonated lignin in synthetic TR 301 solution makes the catalyst deactivation in the TR 301 solution;
(ii) use the resulting inactivation solution of water washing,
(iii) water phase separated and
(iv) separate organic solvent used in the TR 301 solution.
The described sulfonated lignin of step (i) can be water-soluble sulfonated lignin, for example, but are not limited to sulfomethylated lignin acid alkali metal salt, sulfomethylated lignin acid alkaline earth metal salt and lignosulfonic acid quaternary ammonium salt.Preferred sulfonated lignin include, but not limited to sodium lignosulfonate, lignosulfonic acid potassium, calcium lignin sulphonate, magnesium lignosulfonate, ammonium lignosulphonate, more preferably sodium lignosulfonate.
Be applicable to that sulfonated lignin of the present invention can be the verivates of the waste product of cellulose paper and hydrolysis industry thereof.These sulfonated lignin can easily be purchased acquisition.
According to embodiments more of the present invention, said sulfonated lignin can add with the form of the aqueous solution.Preferably, the aqueous solution of sulfonated lignin can be prepared as follows: sulfonated lignin are dissolved in the water is formulated as the aqueous solution of 1～50% weight concentration.In use, preferably under agitation, be that the solution form of 5-14 joins in the TR 301 solution with the pH value.
Preferably, the molecular weight of said sulfonated lignin can be 4 * 10
2～10 * 10
6, its total hydroxy radical content is preferably 1.1-1.2/C
9Here, as well known in the art, C
9Hydrocinnamyl structural unit in the expression sulfonated lignin.
The consumption of said sulfonated lignin preferably is enough to provide 1～100 times hydroxyl, based on the metal titanium content meter that exists in the catalyzer.More preferably, the consumption of said sulfonated lignin is enough to provide 8～50 times hydroxyl, based on the metal titanium content meter that exists in the catalyzer.
According to embodiments more of the present invention, the solvent of employed solution can be organic solvent during synthetic polyisoprenes.Said organic solvent has no particular limits, and can select that this area is normally used to be any organic solvent of inert to reactive component for use, for example, but is not limited to saturated aliphatic hydrocarbon or clicyclic hydrocarbon solvent, for example C
5～C
10Alkane or naphthenic hydrocarbon are like pentane, iso-pentane, hexane, hexanaphthene, heptane, octane or its mixture.
According to embodiments more of the present invention, said TR 301 solution can be the solution of 10～20% weight in above-mentioned solvent.
According to embodiments more of the present invention, the amount of step used water in (ii) can be 10～300% weight, based on the polymers soln meter.Preferably, be 50～150% weight in the amount of step used water in (ii), based on the polymers soln meter.
According to embodiments more of the present invention, step (i) and/or (ii) in can add stablizer, for example inhibitor, photostabilizer.
Can mention as concrete stablizer: 4-methyl-2,6 di t butyl phenol, N-phenyl-N '-cyclohexyl Ursol D; 2; 2 '-methylene-bis-(4-methyl-6-tert butyl phenol), N-phenyl-N '-sec.-propyl Ursol D, octadecyl-3; In two (1, the 1-the dimethyl ethyl)-4-hydroxy benzoic propionates of 5-one or more.
Preferably, the consumption of aforementioned stable agent can be 0.1～2% weight based on the solid TR 301.
According to embodiments more of the present invention, can carry out step separation (iii) with known profit phase detachment technique.Thereby these technology for example can include, but not limited to that aqueous glue is left standstill and make oily water separation in leaving standstill groove.
According to embodiments more of the present invention, can carry out step separation (iv) with the mode of steam stripped.Preferably, under 100-250 ℃, remove organic solvent and residual monomer, dry polymer is accomplished dehumidifying, isolates TR 301.
In the present invention, the weight ratio scope of the catalyzer in sulfonated lignin and the TR 301 solution can be at 0.25-30: 1, and preferably at 2-15: 1.At this moment, the content of metal titanium can be between 300-50ppm in the isolated TR 301, and ash oontent can be reduced to below 0.3.
Major advantage of the present invention and effect:
The present invention uses sulfonated lignin to replace methyl alcohol, has simplified aftertreatment technology.Because sulfonated lignin are verivates of the waste product of cellulose paper and hydrolysis thereof industry, so the present invention reduced cost, reduced environmental pollution.
The inventive method is very easy, easy handling, can effectively remove trace catalyzer in the polymers soln; Reduce titanium metal content and ash oontent in the isolated polymkeric substance; Thereby guarantee isolated cis-1, the 4-TR 301 has good aging properties and physical and mechanical properties.
Below, further specify the present invention with non-limiting example.But it should be noted that it is limitation of the present invention that these embodiment should not be regarded as.
Embodiment
In present specification, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
Test
In the present invention, isolated TR 301 is composed the content that direct-reading ICP spectrograph (inductively coupled plasma atomic emission spectrometer) is measured metal titanium entirely with the IRIS/AP of company of Thermo Electron Corp. type.
Instrument parameter: high frequency power: 1150W, auxiliary gas: 0.5L/min, the wriggling pump speed: 100 commentaries on classics/min, integral time: 10s, nebulizer gas pressure: 32.06psi, sample size: 1.85mL/min,
Specimen preparation: accurately take by weighing the 2.000g sample in porcelain crucible, place in the high temperature resistance furnace cascade raising temperature to 450 ℃, take out behind the ashing number hour; Add 5mL hydrochloric acid, slowly heat on the hot plate and dissolve fully, solution is steamed to doing to the greatest extent until ash content; Add 3mL hydrochloric acid; Change in the 50mL volumetric flask, and the water constant volume, prepare blank reagent solution simultaneously.
Embodiment
Embodiment 1
Under nitrogen protection, in the 5L reactor drum, add the 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 are 19wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 17% the polymers soln that contains active catalyst.
Under 60 ℃; In above-mentioned polymers soln, adding 206g, to contain the 50wt% molecular weight be 400 lignosulfonic acid sodium water solution, adds 6.3 grams simultaneously and contain 10wt% stablizer 2; 2 '-hexane solution of methylene-bis-(4-methyl-6-tert butyl phenol), stirred 30 minutes.
The polymers soln of handling is with 3L deionized water wash 1 time; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.
The content of measuring metal titanium in the isolated polymkeric substance is 94ppm, and ash content is 0.13wt%.
Embodiment 2
Under nitrogen protection, in the 5L reactor drum, add the 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 are 15wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 12% the polymers soln that contains active catalyst.
Under 60 ℃; In above-mentioned polymers soln; Adding 80g, to contain the 10wt% molecular weight be 1000 lignosulfonic acid sodium water solution, and adding 8.75 grams simultaneously, to contain stablizer N-phenyl-N '-cyclohexyl Ursol D weight percent be 20% hexane solution, stirred 30 minutes.The polymers soln of inactivation is with 3.5L deionized water wash 3 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 293ppm, and ash content is 0.29wt%.
Embodiment 3
Under nitrogen protection, in the 5L reactor drum, add the 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 are 13wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 10% the polymers soln that contains active catalyst.
Under 60 ℃, in above-mentioned polymers soln, it is 1 * 10 that adding 515g contains the 4wt% molecular weight
5The lignosulfonic acid sodium water solution, adding 9.8 grams simultaneously, to contain stablizer N-phenyl-N '-sec.-propyl Ursol D weight percent be 20% hexane solution, stirred 30 minutes.The polymers soln of inactivation is with 4.5L deionized water wash 2 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 197ppm, and ash content is 0.21wt%.
Embodiment 4
Under nitrogen protection, in the 5L reactor drum, add the 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 are 17wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 15% the polymers soln that contains active catalyst.
Under 60 ℃; In above-mentioned polymers soln, adding 515g, to contain the 10wt% molecular weight be 10000 lignosulfonic acid sodium water solution, adds 8.75 grams simultaneously and contain stablizer 4-methyl-2; 6-DI-tert-butylphenol compounds weight percent is 20% hexane solution, stirs 30 minutes.The polymers soln of inactivation is with 3.5L deionized water wash 2 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 116ppm, and ash content is 0.16wt%.
Embodiment 5(Comparative Examples)
Under nitrogen protection, in the 5L reactor drum, add the 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 are 17wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 15% the polymers soln that contains active catalyst.
Under 60 ℃, in above-mentioned polymers soln, add 82g and contain the 10wt% methanol aqueous solution, adding 8.75 grams simultaneously, to contain stablizer 4-methyl-2,6 di t butyl phenol weight percent be 20% hexane solution, stirred 30 minutes.The polymers soln of inactivation is with 3L deionized water wash 2 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 315ppm, and ash content is 0.32wt%.
Embodiment 6(Comparative Examples)
Under nitrogen protection, in the 5L reactor drum, add the 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 are 17wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 15% the polymers soln that contains active catalyst.
Under 60 ℃, in above-mentioned polymers soln, add 149g and contain the 10wt% aqueous acetone solution, adding 8.75 grams simultaneously, to contain stablizer 4-methyl-2,6 di t butyl phenol weight percent be 20% hexane solution, stirred 30 minutes.The polymers soln of inactivation is with 3L deionized water wash 2 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 337ppm, and ash content is 0.34wt%.
Embodiment 7(Comparative Examples)
Under nitrogen protection, in the 5L reactor drum, add the 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 are 17wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 15% the polymers soln that contains active catalyst.
Under 60 ℃, in above-mentioned polymers soln, add 77.2g and contain the 10wt% ethylenediamine solution, adding 8.75 grams simultaneously, to contain stablizer 4-methyl-2,6 di t butyl phenol weight percent be 20% hexane solution, stirred 30 minutes.The polymers soln of inactivation is with 3L deionized water wash 2 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 582ppm, and ash content is 0.61wt%.
Embodiment 8(Comparative Examples)
Under nitrogen protection, in the 5L reactor drum, add the 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 are 17wt%.20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 15% the polymers soln that contains active catalyst.
Under 60 ℃, in above-mentioned polymers soln, add 41g and contain 90wt% ethyl maleate methanol solution, adding 8.75 grams simultaneously, to contain stablizer 4-methyl-2,6 di t butyl phenol weight percent be 20% hexane solution, stirred 30 minutes.The polymers soln of inactivation is with 3L deionized water wash 2 times; Left standstill oily water separation subsequently 30 minutes; Behind the decantation water, use steam stripped, vacuum drying obtains removing trace catalyzer and stable TR 301.The content of measuring metal titanium in the isolated polymkeric substance is 467ppm, and ash content is 0.54wt%.
Though the present invention is described with regard to some embodiment, the present invention is not limited to more disclosed embodiments or embodiment, but hopes to cover by the purport of the present invention of appended claims definition and the whole improved forms in the scope.
Claims (11)
1. one kind is carried out stable method to synthetic TR 301 in the presence of catalyzer, and said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound, and said method comprises in synthetic TR 301 solution and adds sulfonated lignin.
2. one kind is carried out isolating method to synthetic TR 301 in the presence of catalyzer, and said catalyzer is titanium tetrachloride and the interactional product of aluminum organic compound, and said method comprises:
(i) aqueous solution of adding sulfonated lignin in synthetic TR 301 solution makes the catalyst deactivation in the TR 301 solution;
(ii) use the resulting inactivation solution of water washing,
(iii) water phase separated and
(iv) separate organic solvent used in the TR 301 solution.
3. method according to claim 1 and 2; Wherein said sulfonated lignin are water-soluble sulfonated lignin; Preferred said sulfonated lignin are selected from sulfomethylated lignin acid alkali metal salt, sulfomethylated lignin acid alkaline earth metal salt and lignosulfonic acid quaternary ammonium salt; More preferably be selected from sodium lignosulfonate, lignosulfonic acid potassium, calcium lignin sulphonate, magnesium lignosulfonate, ammonium lignosulphonate, most preferably be sodium lignosulfonate.
4. according to each described method of claim 1-3, wherein said sulfonated lignin add with aqueous solution form, are preferably the aqueous solution of 1～50% weight concentration.
5. according to each described method of claim 1-4, wherein said sulfonated lignin are that the solution form of 5-14 joins in the TR 301 solution with the pH value.
6. according to each described method of claim 1-5, the molecular weight of wherein said sulfonated lignin is 4 * 10
2～10 * 10
6, total hydroxy radical content is 1.1-1.2/C
9
7. according to each described method of claim 1-6, the consumption of wherein said sulfonated lignin is enough to provide 1～100 times hydroxyl, preferably is enough to provide 8～50 times hydroxyl, based on the metal titanium content meter that exists in the catalyzer.
8. according to each described method of claim 1-7, wherein the weight ratio scope of the catalyzer in sulfonated lignin and the TR 301 solution is at 0.25-30: 1, and preferably at 2-15: 1.
9. method according to claim 2, wherein the amount of step used water in (ii) is 10～300% weight, 50～150% weight preferably are based on the polymers soln meter.
10. according to claim 2 or 9 described methods, wherein step (i) and/or (ii) in add stablizer, for example inhibitor, photostabilizer; Be preferably selected from 4-methyl-2,6 di t butyl phenol, N-phenyl-N '-cyclohexyl Ursol D; 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol), N-phenyl-N '-sec.-propyl Ursol D; Octadecyl-3, one or more in two (1, the 1-the dimethyl ethyl)-4-hydroxy benzoic propionates of 5-.
11., wherein carry out step separation (iv) with the mode of steam stripped according to claim 2,9 or 10 described methods.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254332A (en) * | 2012-02-20 | 2013-08-21 | 中国石油化工股份有限公司 | Polyisoprene preparation method and prepared polyisoprene |
| CN103665219A (en) * | 2012-09-13 | 2014-03-26 | 中国石油化工股份有限公司 | Method for processing polyisoprene solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3544542A (en) * | 1967-12-21 | 1970-12-01 | Bayer Ag | Process for isolating cis-1,4-polyisoprene from hydrocarbon solutions |
| SU788675A1 (en) * | 1979-07-16 | 1992-02-28 | V P Alekseenko | Method of obtaining cis-1,4-polyisoprene |
-
2010
- 2010-10-28 CN CN2010105300292A patent/CN102453109A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3544542A (en) * | 1967-12-21 | 1970-12-01 | Bayer Ag | Process for isolating cis-1,4-polyisoprene from hydrocarbon solutions |
| SU788675A1 (en) * | 1979-07-16 | 1992-02-28 | V P Alekseenko | Method of obtaining cis-1,4-polyisoprene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254332A (en) * | 2012-02-20 | 2013-08-21 | 中国石油化工股份有限公司 | Polyisoprene preparation method and prepared polyisoprene |
| CN103254332B (en) * | 2012-02-20 | 2015-07-22 | 中国石油化工股份有限公司 | Polyisoprene preparation method and prepared polyisoprene |
| CN103665219A (en) * | 2012-09-13 | 2014-03-26 | 中国石油化工股份有限公司 | Method for processing polyisoprene solution |
| CN103665219B (en) * | 2012-09-13 | 2016-03-30 | 中国石油化工股份有限公司 | A kind for the treatment of process of polyisoprene solution |
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