CN1113906C - Synthesis method of epoxidation trans-1,4-polyisoprene - Google Patents
Synthesis method of epoxidation trans-1,4-polyisoprene Download PDFInfo
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- CN1113906C CN1113906C CN 00123985 CN00123985A CN1113906C CN 1113906 C CN1113906 C CN 1113906C CN 00123985 CN00123985 CN 00123985 CN 00123985 A CN00123985 A CN 00123985A CN 1113906 C CN1113906 C CN 1113906C
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Abstract
The present invention provides a method for synthesizing epoxidized trans-1, 4-polyisoprene, which relates to the technology of synthesizing high molecular material. Loose powdery high trans-1, 4-polyisoprene synthesized by a precipitation polymerization method of organic peracid and a titanium carried main catalyst body is used as raw material, and phase suspension technology is adopted. A certain quantity of the raw material is suspended in water solution of organic peracid, which has a certain concentration and a certain pH value, to react, and the temperature is maintained while the mixed solution is stirred until products have a certain epoxidizing degree. After water washing and drying, the products are still loss power. With the advantages of simple technological process, high productive efficiency, low cost and adjustable epoxidizing degree within the range between 5% and 60%, the method of the present invention can be widely used in the industries of tyres, etc.
Description
The present invention relates to the macromolecular material synthetic technology, a kind of epoxidation trans-1 that is mainly used in tire and manufacturings such as other products of rubber and plastic, tackiness agent of more clearly saying so, the synthetic method of 4-polyisoprene.
Epoxidation trans-1,4-polyisoprene (be called for short ETPI) is a high trans-1, a kind of chemical modification product of 4-polyisoprene (being called for short TPI), promptly in the TPI molecular chain the two keys of part by product that epoxide group replaced.ETPI had both kept structure and the performance of original TPI, had increased many new premium propertiess because introduce new group in the molecular chain again, had extensive use, as rubber, plastics, tackiness agent etc.The epoxidation modification polydiolefin base polymer of having developed at present also has epoxidation natural gum (ENR), epoxidation rare-earth isoprene rubber (EIR) and epoxidation cis-1,4-polybutadiene rubber (EBR) etc., the lower ENR of epoxy content particularly, (NR) compares with natural gum, can produce very high wet road surface slip resistance, also show the performance that rose improves wear-resisting, anti-solvent, acid and alkali-resistance and anti-ozone-induced cracking, estimable more is: the low-rolling-resistance characteristic so the ENR that also do not lose NR when having improved wet and slippery gripping power are mainly used in tire industry.ETPI and ENR are in molecular composition, and structural similarity makes it that similar performance also be arranged.
The raw material of synthetic ETPI is TPI and organic peracid.Owing to the TPI output rareness that natural TPI promptly extracts from the skins of plants such as the bark of eucommia, leaf, seed, cost an arm and a leg, so the source of TPI is mainly by the polycoordination synthetic.The one, adopting vanadium or vanadium titanium catalyst system abroad is the blocky TPI of piece grain by solution polymerization process synthetic outward appearance, the one, and the employing load titanium catalyst system that the inventor invents is sulphur loose powder granulous TPI (Chinese invention patent ZL95110352.0) by bulk precipitation polymerization method synthetic outward appearance.Organic peracid can directly be bought or by hydrogen peroxide (H
2O
2) and organic acid (formic acid HCOOH, acetate CH
3COOH etc.) formulated.It is pointed out that before this patent invention, the synthetic of ETPI all adopted solution method, promptly TPI is dissolved into earlier in hydro carbons or the aromatic hydrocarbon solvent, and then the adding organic peracid carries out process for epoxidation.The kinetic viscosity of reaction system is very big like this, brought a series of difficulty for the mixing of reactor, heat transfer and aftertreatment, also limited simultaneously the concentration of still interpolymer, reduced throughput, also had problems such as the recovery of a large amount of solvents is refining thereby increased cost greatly.
The objective of the invention is to overcome the difficulty that above-mentioned traditional E TPI runs in synthetic, the problems that high kinetic viscosity was brought during the solution solution method was synthetic, get rid of the solvent recuperation operation, a kind of technical process of having simplified greatly is provided, enhance productivity, reduce production costs, the renewable recycling of reaction residue, a small amount of washing can be in alkali with acid-bearing wastewater and the back discharge, to the epoxidation trans-1 that environment can not pollute, the synthetic method of 4-polyisoprene.ETP1 of the present invention is used for the tire manufacturing, with making the existing good wet-sliding resistant performance of tire, keeps its low-rolling-resistance characteristic again, and over-all properties has bigger improvement.
Technical conceive of the present invention is, utilizes the characteristics of raw material TPI for loose shape powder, its powder directly is suspended in the aqueous solution of organic peracid to carry out epoxidation.Therefore, how to regulate processing condition and prescription, eliminate side reaction, making epoxidation reaction steadily controlled is key of the present invention.
The present invention is characterized as water phase suspension, with organic peracid and the loose powder shape TPI of load titanium catalyst body precipitation polymerization method synthetic is raw material, earlier the TPI powder of certain mass is packed into when synthetic in the clean reaction vessel, disposable then or add the organic peracid aqueous solution of finite concentration and pH value in batches, the TPI powder is suspended in wherein, react at temperature control with under fully stirring, draw the reaction solution sample of certain mass behind the certain hour, the titration measuring reaction proceeds to the variation of organic peracid concentration in system this moment, just the process of this moment reaction and the epoxy content situation of product as can be known, thereby instruct control, reach the epoxy content that needs until product reaction.Product still for loose powder shape, can directly use behind simple washing and drying.Synthesis condition is: the mol ratio of the two keys of organic peracid/TPI is 0.1～1.5, the pH value of system is 1～6, and temperature of reaction is 0～40 ℃, 0.1～8 hour reaction times, by regulating above-mentioned synthesis condition, can obtain the epoxy content grade and be 5%～60% ETPI product.By determine the epoxy content of reaction process and product with the organic peracid consumption in the comprehensive drop reaction system, realize controlledly synthesis.
The present invention adopts loose powder shape high trans-1, and the 4-polyisoprene is a raw material, is convenient to react from the inside and outside of powder carry out simultaneously, strengthens reaction area, fast reaction speed greatly.External vanadium or the vanadium titanium catalyst system of adopting is that bonding is block by solution polymerization process synthetic TPI, is difficult to reaction.The granularity of the TPI that the present invention adopts is generally less than 3mm.
In influencing epoxidation reaction all multifactor, the pH value of selecting rational temperature of reaction and reaction system is the control reaction process, suppresses the key point of side reaction.The consumption of temperature rising peracid is accelerated speed of reaction and is improved greatly.Angle from the shortening reaction times enhances productivity needs high temperature of reaction.But temperature of reaction is too high, then exists reaction acutely to be difficult to control, the peracid decomposition aggravation, and shortcoming, temperature of reaction such as side reactions such as open loop also increase, the easy bonding of TPI particle are unsuitable too high again.Generally be advisable with 0～40 ℃, effect is best during with 15～25 ℃.
Epoxidation in the strongly-acid medium, side reactions such as open loop easily take place in the epoxide group of generation.Epoxidation in alkaline medium, organic peracid easily decomposes.So the pH value of reply reaction system is regulated, and is advisable with 1～6, and is best with 4.5 o'clock effects.Reaction times is too short, and the epoxy content of product is lower, the pellet density heterogeneity, and promptly epoxidation is inhomogeneous.Reaction times is long, and production efficiency reduces, and has wasted the time.Reaction times was advisable with 0.1～8 hour, and is best with 1～3 hour effect.
The proportioning of organic peracid and TPI all has considerable influence to speed of reaction and production cost.Organic peracid will make speed of reaction reduction, production efficiency reduce very little.Too much organic peracid causes the raising of waste and production cost again in reaction process.The mol ratio of the two keys of organic peracid/TPI is to be advisable in 0.1～1.5 o'clock.
The finished product of this synthetic method are loose powder shape, and its epoxy content grade is 5%～60%.When epoxy content was 20% left and right sides, ETPI had the excellent comprehensive performance: its low-rolling-resistance, low-heat-generation performance advantage do not have too many loss, and have significantly improved its wet-sliding resistant performance, can satisfy the requirement of high-performance tire.
Present method is determined the epoxy content of reaction process and product by the organic peracid consumption in the tracking drop reaction system.After promptly stirring and control condition are reacted for some time, the clear liquid that the takes a morsel KMnO of 0.02M
4Na with 0.01M
2S
2O
3The reference liquid titration, the concentration of calculating organic peracid is with starting point concentration comparison, computable ring oxygen degree.The composite powder granule product is through suction filtration, and the water flushing at room temperature is dried to constant weight to neutral again.The reaction residue that suction filtration goes out is a large amount of organic acid aqueous solution, adds after a certain amount of hydrogen peroxide fully reacts, and just renewable is the organic peracid aqueous solution, for reusing.It does not have the refining problem of playback of a large amount of solvents, greatly reduces cost.And the kinetic viscosity of the reaction system of water phase suspension is little, has overcome that solution method mixes, the difficulty of heat transfer and aftertreatment, has improved throughput.Task comes to this and finishes.
Analytical results shows, does not have by product structures such as cyclic ethers, glycol basically among the synthetic ETPI of present method.Test result shows that the performance index of the synthetic ETPI of present method all can reach and surpass the index request of international like product.Because the science of present technique is simplified production technique, the production efficiency height is expected to reduce cost significantly, obtains considerable industrial value.Compare with the solution method in past, its production cost descends greatly, and its production efficiency then improves greatly.It can be widely used in the production of tire manufacturing and plastics, tackiness agent etc.Both kept with present method synthetic ETPI sizing material that the original rolling resistance of TPI is little, compression heat generation is low, the fatigue performance excellent characteristics, improved its anti-slippery, binding property, resistance to air loss and oil-proofness again greatly, can satisfy each side requirement better as the high-performance tire material.
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment 1. cleans oven dry with the 1000ml there-necked flask, adding employing load titanium catalyst body precipitation polymerization method synthetic particle diameter is the loose powder 60g of 80 purpose TPI, adding concentration with the two keys of the organic peracid/TPI=ratio of 1 (mol ratio) is 12.7% (mass ratio, the organic peracid aqueous solution 510g of pH=4.5 down together),, stirring is suspended in wherein the TPI powder, water-bath temperature control to 15 ℃ reacts under fully stirring.With the titrimetry of reaction solution sample, organic peracid concentration reduces to 9.9% after 1 hour, and this moment, the ETPI epoxy content was 22.0%; After 2 hours, organic peracid concentration reduces to 8.0%, and the ETPI epoxy content is 36.6%; After 3 hours, organic peracid concentration reduces to 7.5%, and the ETPI epoxy content is 40.7%; After 4 hours, organic peracid concentration reduces to 6.6%, and the ETPI epoxy content is 47.9%; After 5 hours, organic peracid concentration reduces to 6.3%, and discharging and with after product suction filtration washing, the drying at room temperature obtains epoxy content and be 50.2% the loose powder 67g of ETPI.Suction filtration goes out reaction residue 500g, and add concentration and the be 30% aqueous hydrogen peroxide solution 450g of (mass ratio, down with) placed after 48 hours, just can get concentration and be 11.6% the organic peracid aqueous solution, for repeated use.
Embodiment 2. synthetic methods with embodiment 1, synthesis condition are: adopting load titanium catalyst body precipitation polymerization method synthetic particle diameter is the loose powder 60g of 20 purpose TPI, adding concentration with the two keys of the organic peracid/TPI=ratio of 0.55 (mol ratio) is the organic peracid aqueous solution 310g of 11.6% (mass ratio), PH=4.5, stirring is suspended in wherein the TPI powder, water-bath temperature control to 25 ℃ reacts under fully stirring.After 3 hours, organic peracid concentration reduces to 1.1%, discharging and with behind the product washing and drying, obtain epoxy content and be 49.8% the loose powder 67g reaction residue 300g of ETPI, adding concentration is the aqueous hydrogen peroxide solution 400g of 30% (mass ratio, together following), places after 48 hours, just can get concentration and be 12.1% the organic peracid aqueous solution, for reusing.
Embodiment 3. adopts the 5000ml there-necked flask, it is that the loose powder 300g of 20 purpose TPI, concentration are 11.6% organic peracid 1550g that synthetic method and condition are removed the adding particle diameter, all the other are with embodiment 2, the result is also approaching with embodiment 2, illustrate that synthesizer amplifies easily, product structure and performance are not had influence.Cost has been saved in the renewable recycling of reaction residue, has avoided the refining problem of recovery of solution method.
Embodiment 4. adopts the 5000ml there-necked flask, synthetic method and condition are the loose powder 300g of 20 purpose TPI except that adding particle diameter, all the other are with embodiment 1, react and extract reaction solution the sample titrimetry after 1 hour, recording at this moment, the product epoxy content is 21.9%, experience according to this epoxy content and embodiment 1, continue reaction discharging after 10 minutes, behind washing and drying, just obtained needed epoxy content and be 25% the loose powder of ETPI, explanation can be determined the epoxy content of reaction process and product by the organic peracid consumption in the tracking drop reaction system, thereby instruct control, realize controlledly synthesis, synthetic ETPI product of specifying epoxy content reaction.
Embodiment 5. is the loose powder 60g of 80 purpose TPI with adding particle diameter in the container, adding concentration with the two keys of the organic peracid/TPI=ratio of 1.5 (mol ratios) is 12.7% (mass ratio, the organic peracid aqueous solution 800g of pH=5 down together),, stirring is suspended in wherein the TPI powder, water-bath temperature control to 0 ℃ reacts under fully stirring.After 8 hours, organic peracid concentration reduces to 4%, and discharging and with behind the product washing and drying obtains epoxy content and be 60% the loose powder 69g of ETPI.
Embodiment 6. synthetic methods are with embodiment 1, synthesis condition is: adopting load titanium catalyst body precipitation polymerization method synthetic particle diameter is the loose powder 60g of 20 purpose TPI, adding concentration with the two keys of the organic peracid/TPI=ratio of 0.1 (mol ratio) is 1.3% (mass ratio), pH=4.5 organic peracid aqueous solution 500g, stirring is suspended in wherein the TPI powder, water-bath temperature control to 40 ℃ reacts under fully stirring.0.1 after hour, organic peracid concentration reduces to 0.6%, discharging and with behind the product washing and drying obtains epoxy content and is 5% the loose powder 61g of ETPI.
Embodiment 7. adopts the 500ml there-necked flask.The gram number that synthetic method and condition add TPI and organic peracid except that PH=1 reduces by half, all the other are with embodiment 1, react and extract reaction solution the sample titrimetry after 1 hour 40 minutes, recording at this moment, the product epoxy content is 31.8%, experience according to this epoxy content and embodiment 1, continue reaction discharging after 20 minutes, just having obtained the needed oxygen degree of going back behind washing and drying is 35% the loose powder 33g of ETPI.
Embodiment 8. synthetic methods are with embodiment 1, synthesis condition is: adopting supported catalyst bulk precipitation polymerization method synthetic particle diameter is the loose powder 60g of 20 purpose TPI, adding concentration with the two keys of the organic peracid/TPI=ratio of 0.2 (mol ratio) is the organic peracid aqueous solution 500g of 2.7% (mass ratio), pH=6, stirring is suspended in wherein the TPI powder, water-bath temperature control to 25 ℃ reacts under fully stirring.After 3 hours, organic peracid concentration reduces to 0.6%, discharging and with behind the product washing and drying, and obtaining epoxy content is the loose powder 62g of 15.7%ETPI.Illustrate that the factor that influences epoxidation reaction speed is more, the proportioning of temperature, TPI and organic peracid, the particle diameter of TPI and the concentration of organic peracid etc. are arranged.Wherein elevated temperature, the proportioning that increases organic peracid and concentration can make epoxidation reaction speed accelerate, and under identical reaction conditions, the granularity of TPI is little to the epoxy content influence, illustrates that loosen powder surface and inside all can carry out epoxidation reaction.
The Main physical mechanical property of the synthetic ETPI of present method and TPI contrast are as following table.As seen from the table, the over-all properties of ETPI is significantly improved than TPI.
Annotate: cross-linked rubber prescription (mass parts): 100 parts of rubbers, 35 parts of high wear-resistant carbon blacks, 5.0 parts in zinc oxide, 2.0 parts of stearic acid, 1 part of antioxidant 264,1 part of accelerant CZ, 5 parts of Sulfurs; Cure conditions is 150 ℃ * 20min, pressure 10MPa.
| Sample | TPI | ETPI | ||||
| Epoxy content, % | 0 | 17 | 25 | 36 | 50 | |
| The rubber performance | Density, g/cm 3 | 0.964 | 0.979 | 0.991 | 1.004 | 1.018 |
| Fusing point, ℃ | 59～62 | 49～51 | 41～43 | 39～41 | 37～39 | |
| Hardness, Shao A | 98 | 91 | 85 | 90 | 95 | |
| 100% tensile modulus, MPa | 5.33 | 3.70 | 3.19 | 3.92 | 4.78 | |
| 300% tensile modulus, MPa | 12.09 | 7.65 | 6.72 | 8.46 | ||
| Tensile strength, MPa | 24.65 | 13.01 | 12.15 | 10.23 | 5.28 | |
| Tensile yield, % | 550 | 450 | 470 | 380 | 130 | |
| Mooney viscosity, ML 1+4 100℃ | 87.4 | 119.6 | 135.3 | 135.7 | 148.7 | |
| Cured properties | Hardness, Shao A | 76 | 81 | 89 | 92 | 97 |
| 100% tensile modulus, MPa | 3.27 | 4.66 | 5.46 | 10.21 | 15.56 | |
| 300% tensile modulus, MPa | 9.82 | |||||
| Tensile strength, MPa | 13.48 | 13.06 | 13.64 | 14.88 | 16.54 | |
| Tear strength, MPa | 41.44 | 36.58 | 40.71 | 32.48 | 53.94 | |
| Tensile yield, % | 400 | 240 | 250 | 250 | 110 | |
| 0 ℃ of rebound resilience, % | 40.0 | 22.7 | 21.4 | 23.7 | 27.7 | |
| 70 ℃ of rebound resiliences, % | 67.5 | 60.0 | 40.5 | 26.8 | 21.9 | |
Claims (3)
1. epoxidation trans-1, the synthetic method of 4-polyisoprene, it is characterized in that with organic peracid and loose powder shape high trans-1, the 4-polyisoprene is a raw material, adopt water phase suspension technology, when synthetic with high trans-1,4-polyisoprene powder is suspended in the organic peracid aqueous solution and reacts, its processing condition are: the mol ratio of the two keys of organic peracid/TPI is 0.1～1.5, the pH value is 1～6, temperature is 0～40 ℃, reaction times is 0.1～8 hour, temperature control stirs, when reaching the epoxy content that needs, washing and drying leaches product, and the epoxy content of reaction process and product is determined by the organic peracid consumption of following the tracks of in the drop reaction system, the epoxy content grade of product is 5%～60%, and product is similar to raw material also to be loose powder shape.
2. according to claim 1 described epoxidation trans-1, the synthetic method of 4-polyisoprene, it is characterized in that the optimum process condition of said water phase suspension is: the pH value is 4～5, temperature of reaction is that 15～25 ℃, reaction times are 1～3 hour.
3. according to claim 1 or 2 described epoxidation trans-1, the synthetic method of 4-polyisoprene is characterized in that said washing and drying technology for the reaction solution suction filtration, is washed to neutrality, at room temperature is dried to constant weight.
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| CN1113906C true CN1113906C (en) | 2003-07-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3101876A1 (en) | 2019-10-14 | 2021-04-16 | Compagnie Generale Des Etablissements Michelin | Process for preparing an epoxidized diene elastomer. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014108958A1 (en) * | 2013-01-09 | 2014-07-17 | 東洋ゴム工業株式会社 | Modified-diene-type polymer and method for producing same, rubber composition, and pneumatic tire |
| CN103570848B (en) * | 2013-10-24 | 2016-01-20 | 沈阳化工大学 | The synthetic method of epoxidation natural gutta-percha |
| CN103910816B (en) * | 2014-04-12 | 2016-06-15 | 青岛科技大学 | The epoxidation trans polyisoprene rubber preparation method of a kind of improvement |
| KR20180123585A (en) * | 2016-04-05 | 2018-11-16 | 쿠퍼 타이어 앤드 러버 캄파니 | Process for the preparation of epoxidized polymers |
| CN105801725B (en) * | 2016-04-06 | 2018-04-13 | 河北科技大学 | A kind of preparation method of epoxidation isoprene rubber |
| CN107200820A (en) * | 2017-06-27 | 2017-09-26 | 江门盈骅光电科技有限公司 | Epoxidation vinyl benzene butadiene double-heptene block copolymer and its production and use |
| CN113354758A (en) * | 2021-06-29 | 2021-09-07 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing epoxidized trans-1, 4-polyisoprene by using micro-reaction device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3101876A1 (en) | 2019-10-14 | 2021-04-16 | Compagnie Generale Des Etablissements Michelin | Process for preparing an epoxidized diene elastomer. |
| WO2021074507A1 (en) | 2019-10-14 | 2021-04-22 | Compagnie Generale Des Etablissements Michelin | Method for preparing an epoxidised diene elastomer |
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