CN1182162C - Production method of butylbenzene lithium series anionic polymers - Google Patents
Production method of butylbenzene lithium series anionic polymers Download PDFInfo
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- CN1182162C CN1182162C CNB021142858A CN02114285A CN1182162C CN 1182162 C CN1182162 C CN 1182162C CN B021142858 A CNB021142858 A CN B021142858A CN 02114285 A CN02114285 A CN 02114285A CN 1182162 C CN1182162 C CN 1182162C
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- butylbenzene
- hexanaphthene
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- anionic polymers
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Abstract
The present invention provides a production method of butylbenzene lithium series anionic polymers, which is characterized in that compound solvent comprising cyclohexane and C6 raffinate oil is used as solvent for the reaction of anions. The compound solvent has the advantages of low solidifying point and low cost.
Description
Technical field
The present invention relates to a kind of production method of butylbenzene lithium series anionic polymers.
Background technology
Butylbenzene lithium series anionic polymers comprises that specifically with divinyl (or isoprene), vinylbenzene be monomer, with the lithium alkylide is initiator, SBS, the SIS, SEBS, SEPS, the low-cis-polybutadiene rubber that form by anionic solution polymerization, solution polymerized butadiene styrene rubber or K-resin etc., in existing production technology, the solvent of above butylbenzene lithium series anionic polymers production usefulness mainly contains:
United States Patent (USP) 3,078,254 (1963) 3,198,774 (1965) disclose and have formed and as the production solvent of butadiene-styrene block copolymer SBS a kind of the cooperation in 9: 1 ratio with hexanaphthene or hexanaphthene and normal hexane.Be that solvent is the most commonly used wherein with pure hexanaphthene, but pure hexanaphthene zero pour is up to 6.5 ℃ Celsius, adopt pure cyclohexane give to be butylbenzene lithium series anionic polymers production solvent, when cold district tissue in winter is produced, solvent easily takes place freeze phenomenon, the influence safety in production is so the American adopts hexanaphthene to mix the technology of using with normal hexane.Because the zero pour of normal hexane is subzero 95 ℃ Celsius, hexanaphthene is with after normal hexane mixes, and the zero pour of mixed solvent system decreases than hexanaphthene, can solve butylbenzene lithium series anionic polymers and produce frozen problem winter.But hexanaphthene and normal hexane cost are higher, cause the production cost of whole butylbenzene lithium series anionic polymers higher, and simultaneously, the toxicity of normal hexane is big, and production process and product are difficult to compliance with environmental protection requirements.In addition, to disclose with benzene be solvent to " polymer use school " of France " SIS trial report " of delivering in 1975; At Hsieh.H.I.and.W.H:Rubb.chem.and.Technlo, announced in 43,32 (1970) with toluene and done the lab scale report that solvent prepares butylbenzene copolymer.In these two kinds of reports, the zero pour of solvent benzol though the toluene zero pour is lower, reaches subzero 94 ℃ up to easily freezing 5.5 ℃ of winters Celsius, is solvent with toluene, chain transfer reaction easily takes place influence quality product, and benzene, toluene is all toxic.
There is following defective in various degree in the solvent of more than synthetic butylbenzene lithium series anionic polymers: some solvent zero pour is higher, is unfavorable for that cold zone organizes industrial production; Some solvent prevailing price is higher, causes product cost higher.
Summary of the invention
The object of the invention is to overcome above two big defectives, in the production of butylbenzene lithium series anionic polymers, use a kind of double solvents, make it to guarantee the needs of butylbenzene lithium series anionic polymers polyreaction and product performance, this double solvents zero pour is descended, cost is lower.
The present invention adopts hexanaphthene and C
6It is compound by a certain percentage formulated to raffinate oil, wherein C
6The boiling range of raffinating oil is at 60 ℃～140 ℃, and iodine number is less than 0.1g/100g; C
6The main component of raffinating oil is the alkanes substance that contains six left and right sides carbon atoms, as pentane, pentamethylene, methylcyclopentane etc.C
6Raffinating oil, the quality percentage composition is 1%～45% in double solvents.In the double solvents, with C
6The increase zero pour of raffinating oil descends, and works as C
6The quality percentage composition of raffinating oil reaches at 40% o'clock, and the double solvents zero pour can reach subzero 47 ℃ Celsius, can satisfy China's cold zone needs of keeping the safety in production winter.While C
6Raffinate oil cost far below hexanaphthene, behind the employing double solvents, can reduce production costs.C
6The content of raffinating oil at double solvents can not be too high, C in double solvents
6When the content of raffinating oil reaches certain value, the solubility parameter of polystyrene section differs bigger in the solubility parameter of double solvents and the butylbenzene lithium series polymkeric substance, and polystyrene section solubleness in the double solvents system descends and precipitation is separated out, and influences quality product, therefore, C in the double solvents
6The content of raffinating oil generally is no more than 45%, and below the content, double solvents is to the solubility property of butylbenzene lithium series polymkeric substance at this, and polyreaction control and polymeric articles quality all do not have detrimentally affect.
The production method of butylbenzene lithium series anionic polymers: adding measures double solvents, monomer styrene, activator tetrahydrofuran (THF) in handling clean polymeric kettle, stir and be warming up to 40-60 ℃, add and measure the initiator n-Butyl Lithium, begin one section reaction, top temperature control well less than 60 ℃, reaction 30min, after question response is finished, add as required and measure vinylbenzene and carry out three sections reactions or add the coupler that measures carrying out linked reaction, depending on the circumstances or the needs of the situation hydrogenation reaction is carried out in hydrogenation again.After question response is finished, add the antioxidant 264 (2,6-di-t-butyl-4-toluol-benzene phenol) of dried glue weight 0.50%, glue carries out rerum natura and detects after condensing drying.Specific embodiment can be with reference to nineteen ninety " the theoretical and application of anionoid polymerization ", Xue Lianbao, the safe collaboration of Golden Customs, China Friendship Publishing Co..The preparation of double solvents is to add a certain proportion of C in the hexanaphthene that measures
6Raffinate oil, mix and get final product.
Specific embodiment
Embodiment 1
At N
2Handle in the round-bottomed flask that clean band stirs C
6Raffinate oil and hexanaphthene is made into composite solution by following quality proportioning respectively: 0/100,10/90,20/80,30/70,40/60.The even back of the solution stirring for preparing, is surveyed the zero pour data of this double solvents and is listed in table 1 to 20ug/g with molecular sieve dehydration by GB510-83.
The different C of table 1
6Raffinate oil and hexanaphthene proportioning double solvents zero pour
| Proportioning | 0/100 | 10/90 | 20/80 | 30/70 | 40/60 | 45/55 | 50/50 |
| Zero pour ℃ | 6.5 | -10.8 | -21.7 | -32.7 | -47.2 | -58.3 | -69.3 |
By implementing 1 as can be seen, in the double solvents with C
6The increase of raffinating oil and adding, zero pour descends in the double solvents system, and zero pour can reach-47.2 ℃ when proportioning reaches 40/60, can satisfy the northern China needs of keeping the safety in production cold local winter.
Embodiment 2
Utilize the 1 double solvents system for preparing of enforcement, press S/B=30/70 (mass ratio), design molecular weight Mn=10 ten thousand carries out type SBS polyreaction synthetic test, and the test products physical data is listed in table 2.
The different proportioning double solventss of table 2 synthesize type SBS product rerum natura table
*300% tensile modulus, tensile strength, tensile yield, tension set are carried out by GB GB/T528-92.
Shore hardness is carried out by GB GB/T531-92.
By embodiment 2 as can be seen, C in double solvents
6The content of raffinating oil increases gradually, 45% when following, adopt double solvents synthetic SBS and adopts pure hexanaphthene (0/100) synthetic SBS product performance roughly suitable.Work as C
6The content of raffinating oil surpasses at 50% o'clock, and the tensile strength of product, hardness can descend.Work as C
6The content of raffinating oil surpasses at 45% o'clock, because this double solvents is relatively poor to the solubility property of one section reaction, causes product performance to descend.
Embodiment 3
The double solvents that utilizes embodiment 1 to prepare is pressed S/B=30/70 (mass ratio), and design molecular weight Mn=23 ten thousand carries out star-shaped sbs polyreaction synthetic test, and the test products physical data is listed in table 3.
The different proportioning double solventss of table 3 synthesize star-shaped sbs rerum natura situation
By embodiment 3 as can be seen, in the double solvents with C
6C is worked as in the raffinate oil increase gradually of content
6Raffinate oil content 40% when following, and double solvents is worked as C to star-shaped sbs polyreaction and the not influence of sintetics rerum natura
6The content of raffinating oil reaches 50%, and the tensile strength of sintetics, hardness descend.
Embodiment 4
C in the double solvents
6Raffinate oil and hexanaphthene proportioning employing 0/100 and 40/60, investigate different S/B ratio type SBS sintetics performances respectively, data are listed in table 4.
Table 4 double solvents is produced the product performance of different S/B
By embodiment 4 as can be seen, use C
6Raffinate oil with hexanaphthene by the 40/60 double solvents system that is made into when adopting pure hexanaphthene (0/100) to produce the SBS product of different proportionings as solvent, the quality product that two kinds of solvent systems are produced is suitable substantially.
Embodiment 5
The double solvents that utilizes embodiment 1 to prepare is pressed S/I=30/70 (mass ratio, I represents isoprene), and design molecular weight Mn=12 ten thousand carries out line style SIS polyreaction synthetic test, and the test products physical data is listed in table 5.
The different proportioning double solvents of table 5 line style SIS product rerum natura table
By embodiment 5 as can be seen, along with C in the double solvents
6C is worked as in the raffinate oil increase of content
6Raffinate oil content below 45%, do the not obviously reduction of solvent synthetic SIS quality product with adopting pure hexanaphthene (0/100) with the SIS quality product that this double solvents synthesizes.C in this explanation double solvents
6Raffinate oil content below 45%,, work as C the not influence of SIS quality product
6Raffinated oil content at 50% o'clock, utilize the synthetic SIS of this solvent all descending aspect tensile strength and the hardness obviously.
Embodiment 6
The double solvents that utilizes embodiment 1 to be made into is pressed S/B=30/70 (mass ratio), design molecular weight Mn=6 ten thousand, and degree of hydrogenation 〉=98% carries out line style SEBS polymerization hydrogenation, and the product physical and mechanical properties is listed in table 6.
The different proportioning double solvents of table 6 SEBS product rerum natura situation
By implementing 6 as can be seen, work as C in the double solvents
6Raffinated oil content at 45% o'clock, and double solvents synthetic SEBS product physical and mechanical properties is with to be solvent synthetic SEBS with pure hexanaphthene roughly suitable.C in double solvents
6The content of raffinating oil reaches at 50% o'clock, and synthetic SEBS product performance descend, and C is described
6The double solvents system of raffinating oil and being made into hexanaphthene is at C
6Raffinate oil content below 45%, can be used as the compound solvent of using of producing SEBS.
Embodiment 7
By the double solvents that embodiment 1 is made into, press S/B=75/25 (mass ratio), synthetic monomorphism line style K-resin is shown in the synthetic K-rosin products performance table 7.
K-resin property situation under the different proportioning double solventss of table 7
By embodiment 7 as can be seen, work as C in the double solvents
6Raffinated oil content at 40% o'clock, and it is suitable to do solvent synthetic product performance with double solvents synthetic K-rosin products performance and the pure hexanaphthene of use, C in double solvents
6The content of raffinating oil reaches at 50% o'clock, and synthetic K-resin property greatly descends.
Embodiment 8
Get embodiment 2 synthetic SBS products, carry out infrared spectra and detect, the microtexture of analyzing polyhutadiene section among the SBS is 1,4 structure and 1,2 structural content, detects data and lists in table 8.
Table 8
By embodiment 8 as can be known, with C in the double solvents
6The raffinate oil increase of content, the microtexture end is with C in the double solvents in the SBS product
6The increase of raffinating oil changes, and illustrates to adopt double solvents of the present invention to produce the microtexture that the butylbenzene lithium series polymkeric substance does not change product.
Claims (3)
1, a kind of production method of butylbenzene lithium series anionic polymers adopts general anionoid polymerization technology, hexanaphthene and C
6The solvent that the double solvents formed of raffinating oil is used as anionic reactive is characterized in that C
6Raffinating oil, the quality percentage composition is 1%～45% in double solvents.
2, method according to claim 1 is characterized in that C in the double solvents
6The boiling range of raffinating oil is at 60 ℃～140 ℃, and iodine number is less than 0.1g/100g.
3, method according to claim 1 and 2, the preparation that it is characterized in that double solvents are to add a certain proportion of C in the hexanaphthene that measures
6Raffinate oil, mix and get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021142858A CN1182162C (en) | 2002-07-20 | 2002-07-20 | Production method of butylbenzene lithium series anionic polymers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021142858A CN1182162C (en) | 2002-07-20 | 2002-07-20 | Production method of butylbenzene lithium series anionic polymers |
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| Publication Number | Publication Date |
|---|---|
| CN1394883A CN1394883A (en) | 2003-02-05 |
| CN1182162C true CN1182162C (en) | 2004-12-29 |
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| CNB021142858A Expired - Lifetime CN1182162C (en) | 2002-07-20 | 2002-07-20 | Production method of butylbenzene lithium series anionic polymers |
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- 2002-07-20 CN CNB021142858A patent/CN1182162C/en not_active Expired - Lifetime
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Owner name: CHINA PETROCHEMICAL CORPORATION; BALING PETROCHEM Free format text: FORMER OWNER: BALING PETROCHEMICAL CO., LTD., SINOPEC Effective date: 20070622 |
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Effective date of registration: 20070622 Address after: 100029 No. 6, Xin Xin Street East, Beijing, Chaoyang District Co-patentee after: China Petrochemical Group Baling Petroleum Co.,Ltd. Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: 414014 Yunxi District, Hunan, Yueyang Patentee before: China Petrochemical Group Baling Petroleum Co.,Ltd. |
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