CN1101650A - Method for producing styrene indene resin - Google Patents
Method for producing styrene indene resin Download PDFInfo
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- CN1101650A CN1101650A CN 94110604 CN94110604A CN1101650A CN 1101650 A CN1101650 A CN 1101650A CN 94110604 CN94110604 CN 94110604 CN 94110604 A CN94110604 A CN 94110604A CN 1101650 A CN1101650 A CN 1101650A
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- Prior art keywords
- resin
- vinylbenzene
- indene resin
- fraction
- phosphite
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Abstract
The invention uses C9 oil distillate with rich phenyl ethylene and indan as the raw material and LAL liquid as catalyst for a polymerization process for 0.5-3 hours. At the end of it, a chain stopping agent of phosphite ester is introduced to stop the reaction. After treatment of the product for removal of catalyst and solvent naphtha, the final product is phenyl ethylene-indan resin and 200# solvent naphtha. The product produced by the invented method has stable softening point, lower value of weight reduction in heating and all indices in conformity with the specified requirements, thus suitable for wide application in rubber tier industry.
Description
The present invention relates to a kind of preparation of rubber product additive vinylbenzene-indenes, belong to aromatic hydrocarbons petroleum resin manufacturing process technology field.
Aromatic hydrocarbons petroleum resin based thermoplastic, high aromatic hydrocarbons, non-reacted hydrocarbon resin have good intermiscibility with natural rubber and synthetic rubber, and have good heat and chemical stability, are tire and other rubber item ideal tackifier and tenderizer.The development of radial is China's tire industry developing direction, and expectation year 2000 program radial tyre production ability is played 1,800,000 covers, therefore is badly in need of solving domestic material and high-quality problem.Radial available tackifier are a lot, mainly contain: octyl phenol resin, butylphenol urea formaldehyde, hydrocarbon binder resin, vinylbenzene-indene resin etc., wherein, vinylbenzene-indene resin is because aboundresources, moderate, excellent property is the rubber tackifier and the tenderizer of relatively praising highly both at home and abroad, is widely used in tire and other rubber items.
Vinylbenzene-indene resin has multiple production process route, for example: can utilize the waste material of coking production, get through distillation as the polymkeric substance that obtains in the distillation Residual oil of crude benzol processing and the crude benzol workshop section regenerating wash oil process.In addition, also can be with the byproduct C of oil pyrolysis system ethene
9Fraction is polymerized, the existing C that uses
9The technology of fraction synthesizing styrene-indene resin generally adopts Lewis acid and organometallic compound to make the catalyzer of polyreaction, and commonly used have an AlCl
3, BF
3And BF
3Etherate.Polymeric molecular resin amount wider distribution is macromole, middle molecule and small molecules admixture under these catalyst actions, so softening temperature is unfixing.The softening temperature of gained resin can only be controlled by distillation temperature, for example, requires to produce the resin of 100 ℃ of softening temperatures, proofreads softening temperature again after must determining according to this temperature earlier and determines next distillation temperature.Simultaneously, this class methods gained resin has many low-boiling-point substances and small molecules and lower-molecular substance to evaporate in heat-processed, and the softening temperature of resin itself and form and aspect also with great changes will take place, are added and subtracted the caloric value height, are difficult to reach the requirement of production and technical indication.Be not suitable for the production of radial.
The objective of the invention is to remedy the deficiency of prior art, select the compound aluminum chloride dication of a kind of new liquid catalyzer for use, make high-quality vinylbenzene-indene resin with the olefinic polymerization of rich in styrene-indenes.
C
9The composition more complicated of fraction can be divided into two big classes from the angle of synthetic resins, and a class is polymerisable active constituent, as vinylbenzene, vinyl toluene, indenes and dicyclopentadiene etc.; Another kind is non-active constituent, mainly is alkylbenzene and condensed-nuclei aromatics.When polymerization, this part nonactive component is steamed when aftertreatment as solvent.For C
9Coarse raw materials can carry out pre-treatment with the cracking of routine, the method for intercepting fraction, helps the fraction of rich in styrene-indenes with extraction.
The polymerization of unsaturated hydrocarbons such as above-mentioned active constituent vinylbenzene, indenes belongs to cationic polymerization, adopts BF
3Or AlCl
3When the lewis acid catalyst, must there be promotors such as the water of trace or HX to exist, make it produce positively charged ion, just can reach and start catalytic purpose.This reaction is lentamente at the beginning, chain is to the reaction that a side increases, only reach the regular hour after, reaction is just more and more fierce.Because the reaction faster or slower, having steadily has fierceness, and therefore, synthetic molecular resin amount is just inhomogeneous, has formed the gesture of large, medium and small mixing, so the softening temperature of resin and form and aspect are also unstable, the weight loss on heating value is also high, does not reach the requirement of technical indicator.
The present invention selects the compound aluminum chloride dication of liquid complex compound (LAL) to make catalyzer (seeing Chinese patent application 92113970.5 for details), and this catalyst structure formula is as follows:
-Cl
4Al
+R
+AlCl
- 4Wherein, R=-CH
2CH
2-,-CH
2CH
2CH
2-,
Because this catalyzer is a liquid, itself is the positively charged ion state, therefore needn't itself can be formed directly in the active centre, and have two active centre by the promotor initiation.Polyreaction is the center at the very start with the dication, and chain evenly increases fast to both sides, quantitatively adds catalyzer according to desired molecule amount size, makes its homogeneous reaction.When stopping chain, be chain terminator with a kind of auxiliary agent phosphorous acid ester of Heat stability is good, the activity centre, two ends simultaneously under the chain terminator effect end-blocking stop chain.Its reaction mechanism reaction formula following (is example with vinyl toluene and indenes copolymerization):
Polyreaction begins:
Owing to be that dication is the center, chain increases to both sides simultaneously, and the reaction times has shortened 2/3rds.The molecular resin amount of Sheng Chenging is even like this, and easy to control, the Heat stability is good of softening temperature heats the resin that generates repeatedly, and its softening temperature still remains unchanged, and the weight loss on heating value is low, sees the following form:
How much determining of catalyzer and chain terminator consumption according to the requirement of softening temperature.After fraction was determined, general catalyzer and chain termination dosage and molecular weight were inversely proportional to, and molecular weight is little, and softening temperature is low; Molecular weight is big, the softening temperature height.It is considered herein that this catalyzer LAL consumption is generally at the 1-3%(weight percent) be advisable, especially with 2% for well.
Chain terminator consumption 0.5-5%(weight percent, down together).
Chain terminator: phosphorous acid ester, liquid.Concrete can be trimethyl phosphite, triethyl-phosphite, triphenyl phosphite, dimethylphosphite.
Above-mentioned polyreaction is to carry out under stirring at normal temperature, reaction times 0.5-3 hour, temperature of reaction 20-90 ℃, adds chain terminator and reacts 1-2 hour again.
It is not omissible that the vinylbenzene-indene resin mixed solution that finishes for polymerization carries out necessary aftertreatment; The aftertreatment of resin comprises denitrating catalyst and desolventizing, and the method for aftertreatment adopts the ordinary method in this area to get final product.For example, denitrating catalyst, have alcohol wash in method, the ammonia and WATER-WASHING METHOD, ammonia in and filtration method, ammonia neutralized alcohol to wash method, continuous washing method etc. multiple.That the present invention advocates is simple with equipment, cost is lower, and the continuous washing method of no waste residue is for well.
Desolventizing not only will remove unpolymerized class hydrocarbon, also will remove the low-molecular(weight)polymer that generates in the polymerization process, and this is very important for the performance that improves vinylbenzene-indenes.Adopt the method for conventional underpressure distillation desolventizing, above-mentioned solvent can be distilled, use as industrial solvent.
Vinylbenzene-indene resin that the inventive method makes has excellent thermostability and the good intermiscibility of rubber, and to the incipient scorch of sizing material, sulfurizing time and physical and mechanical properties have no adverse effect.
The C of flycatcher mountain petrochemical industry to the north of the embodiment 1.
9Oil is raw material, 4 tons.
(1) the fraction composition such as the following table of extraction rich in styrene-indenes:
(2) add LAL catalyzer (the sharp company of Shandong University's Nowe produces) 2%, in 2 hours reaction times, 25 ℃ of temperature (initial)-90 ℃ (the highest) add chain terminator technical grade trimethyl phosphite 2%(weight percent).
(3) above-mentioned products therefrom is used continuous washing method denitrating catalyst, underpressure distillation desolventizing.Get 2 tons of 200# industrial solvents.
(4) get 1 ton of vinylbenzene-indene resin, 90 ℃ of softening temperatures, weight loss on heating 0.2%(65 ℃), the water extract pH value is 6.
Embodiment 2. is as embodiment 1, and different is: LAL catalyzer 1%, 3 hours reaction times, chain terminator SILVER REAGENT triethyl-phosphite 0.5%, 100 ℃ of gained vinylbenzene-indene resin softening temperature, weight loss on heating 0.21%(65 ℃), water extract PH is 6.5.
The detection method of each technical indicator of the present invention is:
(1) mensuration of softening temperature is measured by the method for stipulating among the GB2294.
(2) mensuration of ash is pressed the GB2295 standard test, 550 ℃ of Heating temperatures.
(3) mensuration of PH is pressed the GB4318 standard test.
(4) mensuration of form and aspect is pressed the GB120071 standard test, and resin dissolves is made into homogeneous solution in toluene, sample and toluene mass ratio 1: 1.
(5) mensuration of weight loss on heating gets final product according to a conventional method.
Claims (4)
1, the manufacture method of vinylbenzene-indene resin, comprise the fraction that from the C9 fraction, extracts rich in styrene, indenes, under catalyst action, carry out polyreaction, vinylbenzene-indene resin is extracted in the resin liquid aftertreatment, it is characterized in that, catalyst system therefor is liquid compound aluminum chloride dication network and thing, add-on 1-3% (weight percent), and the phosphorous acid ester that adds 0.5-5% (weight percent) when polymerization is finished is made chain terminator.
2, the method for claim 1 is characterized in that, described phosphorous acid ester chain terminator is one of following:
(a) trimethyl phosphite (b) triethyl-phosphite
(c) triphenyl phosphite (d) dimethylphosphite
3, the method for claim 1 is characterized in that, polymerization reaction time is 0.5-3 hour.
4, the method for claim 1 is characterized in that, with the catalyzer in the continuous washing method wash-out resin liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110604A CN1048505C (en) | 1994-05-24 | 1994-05-24 | Method for producing styrene indene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110604A CN1048505C (en) | 1994-05-24 | 1994-05-24 | Method for producing styrene indene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101650A true CN1101650A (en) | 1995-04-19 |
| CN1048505C CN1048505C (en) | 2000-01-19 |
Family
ID=5034552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110604A Expired - Fee Related CN1048505C (en) | 1994-05-24 | 1994-05-24 | Method for producing styrene indene resin |
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| Country | Link |
|---|---|
| CN (1) | CN1048505C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109697C (en) * | 1999-12-01 | 2003-05-28 | 张兰英 | Process for preparing viscosity-increasing resin dedicated to rubber and its product |
| WO2011094973A1 (en) * | 2010-02-03 | 2011-08-11 | Gong Xiangqin | Rubber tyre extender oil for improving low hysteresis loss of rubber tyre and preparation method thereof |
| CN102746459A (en) * | 2012-06-27 | 2012-10-24 | 宁波职业技术学院 | Preparation method of cold polymerized styrene-indene resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53145896A (en) * | 1977-05-26 | 1978-12-19 | Sumitomo Chem Co Ltd | Preparation of petroleum resin |
| ATE97921T1 (en) * | 1988-05-09 | 1993-12-15 | Exxon Chemical Patents Inc | PETROLEUM RESINS AND PROCESS FOR THEIR MANUFACTURE. |
-
1994
- 1994-05-24 CN CN94110604A patent/CN1048505C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109697C (en) * | 1999-12-01 | 2003-05-28 | 张兰英 | Process for preparing viscosity-increasing resin dedicated to rubber and its product |
| WO2011094973A1 (en) * | 2010-02-03 | 2011-08-11 | Gong Xiangqin | Rubber tyre extender oil for improving low hysteresis loss of rubber tyre and preparation method thereof |
| CN102746459A (en) * | 2012-06-27 | 2012-10-24 | 宁波职业技术学院 | Preparation method of cold polymerized styrene-indene resin |
| CN102746459B (en) * | 2012-06-27 | 2014-01-01 | 宁波职业技术学院 | Preparation method of cold polymerized styrene-indene resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1048505C (en) | 2000-01-19 |
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