CN1109697C - Process for preparing viscosity-increasing resin dedicated to rubber and its product - Google Patents
Process for preparing viscosity-increasing resin dedicated to rubber and its product Download PDFInfo
- Publication number
- CN1109697C CN1109697C CN99125258A CN99125258A CN1109697C CN 1109697 C CN1109697 C CN 1109697C CN 99125258 A CN99125258 A CN 99125258A CN 99125258 A CN99125258 A CN 99125258A CN 1109697 C CN1109697 C CN 1109697C
- Authority
- CN
- China
- Prior art keywords
- rubber
- product
- viscosity
- resin dedicated
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a preparing method for special tackifying resin for rubber and a product of special tackifying resin for rubber. The preparing method comprises the steps: a compound reaction is performed on a C9 distillation fraction after a fractionating reaction and a catalytic polymerization reaction are performed on the C9 distillation fraction to remove a catalyst to obtain the product of the special tackifying resin for rubber. The preparing method of special tackifying resin for rubber has the advantages of scientificity, reasonability and simple and easy operation. The product can raise the proportion of synthetic rubber in tyre application. The product used in rubber masterbatch can improve the autohesion of semifinished rubber stock, so that the semifinished product has the advantages of long tack holding time, good stiffness and product qualified rate improvement. In addition, the product is suitable for rubber formulas of various tyres.
Description
The present invention relates to preparation method of the preparation method of rubber resin, particularly a kind of viscosity-increasing resin dedicated to rubber and products thereof.
Tackifier and tenderizer commonly used when the oblique rubber tire tire in the rubber industry prepares are " coumarone C5 resins ", and certain defective is in use arranged, the development of restriction tyre industry.Along with the development of petroleum industry, the cracking ethylene preparation device increases, and has produced a large amount of by product C
9Fraction uses C
9The comprehensive utilization meaning of fraction is very big.
The purpose of this invention is to provide a kind of by product C with petroleum cracking system ethene
9Fraction is the preparation method of feedstock production viscosity-increasing resin dedicated to rubber.
Another object of the present invention provides the product that a kind of above-mentioned preparation method makes.
The preparation method of viscosity-increasing resin dedicated to rubber of the present invention comprises C
9Fraction is through fractionation, catalytic polymerization, carries out the product that complex reaction obtains viscosity-increasing resin dedicated to rubber again after removing catalyzer.
Wherein, described fractionation is with the by product C of petroleum cracking system ethene under normal pressure
9Fraction fractionation 8 hours, the cut that intercepts in the 180-220 ℃ of temperature is next step reactant; The by product C of described petroleum cracking system ethene
9Fraction is the mixture that multiple compound is formed, and the composition more complicated can be divided into two big classes substantially, and a class is the active ingredient that insatiable hunger is closed, as vinylbenzene, Vinyl toluene, indenes and dicyclopentadiene etc.; Another kind of is inactive ingredients, mainly is saturated hydrocarbons, according to C
9Active ingredient boiling point difference in the fraction adopts normal pressure fractionation cutting, the method for fraction in the intercepting different boiling ranges scope, the fraction of the used body material of acquisition the present invention; Promptly obtain being rich in the fraction of dimethylbenzene, vinylbenzene, cyclopentadiene, indenes, concrete component sees the following form:
Component weight (%) component weight (%)
C
90.74 Vinyl toluene 15.82
Benzene 0.88 indenes 10.96
Toluene 7.88 naphthalenes 2.24
Ethylbenzene 1.94 m-xylenes 0.97
Vinylbenzene 9.20 o-Xylols 3.30
Phenyl allyloxy 1.93
Described polyreaction is included in the above-mentioned reactant and adds catalyzer, and reaction is 5-7 hour under 80-100 ℃ of temperature, obtains polymkeric substance; In above-mentioned catalyzed polymerization, C
9The active principle of fraction reacts, as vinylbenzene, indenes, dicyclo
Pentadiene, Vinyl toluene begin reaction after meeting cationic catalyst, these catalyzer all are the electron deficiency materials, be the electrophilic reagent of electron acceptor, make two bond ruptures formation trivalent carbon cationic activities center in the unsaturated hydrocarbons, generate the resin that has side chain, backbone.
Be with AICI below
3Be example, the fraction polymeric reaction mechanism of writing out.
CH
2＝CHR+AICI
3→CH
2＝CHR
AICI
3
CH
2＝CHR+CH
2＝CHR→CH
3-CHR-CH＝CHR
AICI
3 AICI
3
CH
3-CHR-CH＝CHR+CH2+CHR→CH
2-CHR-CH
3-CHR-CH＝CHR→----
AICI
3 AICI
3
CH
3-CHR-(CH
2-CHR)n-CH＝CHR
AICI
3
CH
3-CHR-(CH
2-CHR)n-CH＝CHR→
AICI
3
CH
3-CHR-(CH
2-CHR)n-CH＝CHR+AICI
3
R represents vinylbenzene, indenes etc. in the formula.
The last polymkeric substance that generates of reaction is the resin liquid of vinylbenzene, indenes, Vinyl toluene, dicyclopentadiene backbone.Catalyst consumption is according to C in this polyreaction
9The content of unsaturated component is determined in the component.The catalyzer add-on is on the low side, and then reaction is incomplete, and catalyst excess then influences the quality of resin, and brings the denitrating catalyst difficulty.General catalyzer add-on is controlled at the 0.5-1.5% of fraction weight, is preferably 0.8-1.3%.Described catalyzer can be aluminum chloride or boron trifluoride.
The described process that removes catalyzer is included in the polymkeric substance that above-mentioned reaction obtains and adds entry and emulsion splitter, is reaction 1.5-2.5 hour under the 80-90 ℃ of temperature in temperature, removes waste water to water oil content layer; The existence of catalyzer influences the quality of resin, so should be in time that catalyst removal is clean after polyreaction finishes; Removing of catalyzer can be adopted the continuous washing method; This continuous washing method has advantages such as equipment is simple, cost is low, waste water can be recycled after treatment, and environmental protection is not had influence.Described emulsion splitter can be Soxylat A 25-7, and add-on is C
9The 0.5-1% of fraction.
Described complex reaction process is to add fatty acid zinc, tert butyl phenolic resin, Gum Rosin and butylated resin in having removed the polymkeric substance behind the catalyzer, and reacts 2-4 hour under 180-220 ℃ of temperature, can obtain viscosity-increasing resin dedicated to rubber.Viscosity-increasing resin dedicated to rubber wants to reach characteristics such as bonding, softening, reinforcement, dispersion, intermiscibility in rubber item processing, must further complex reaction; In the temperature-rise period of complex reaction, the fraction of discharge can be as paint solvent, complex reaction fully after, detect and reach can lower the temperature after the respective quality index blowing, fragmentation, packing.
The preparation method of viscosity-increasing resin dedicated to rubber of the present invention adopts distillating method to dewater after can also comprising complex reaction.
The preparation method of viscosity-increasing resin dedicated to rubber of the present invention is scientific and reasonable, and is simple, and the viscosity-increasing resin dedicated to rubber that makes is on probation through Qingdao quality inspection detection and user, the requirement that all can touch the mark of each technical indicator.Use this viscosity-increasing resin dedicated to rubber can improve processing characteristics, increase viscosity, reduce the sizing material cost significantly, improve the ratio of synthetical glue in tire applications; Can improve the self-adhesion performance of work in-process sizing material in master batch, make that the work in-process tack retention hour is long, very property is good, has improved the qualification rate of product; This viscosity-increasing resin dedicated to rubber has good consistency, makes the work in-process rubber mobility good, has reduced the sizing material mooney viscosity, and is little to the influence of sizing material mechanical property, is applicable to the rubber compounding of various tires.
Further describe the present invention below in conjunction with embodiment.
Embodiment
A kind of preparation method of viscosity-increasing resin dedicated to rubber, it comprises 1200kgC
9Fraction is through fractionation, catalytic polymerization, carries out the product that complex reaction obtains viscosity-increasing resin dedicated to rubber again after removing catalyzer.
Wherein, described fractionation is with the by product C of petroleum cracking system ethene under normal pressure
9Fraction fractionation 8 hours intercepts the cut in the 180-220 ℃ of temperature, obtains being rich in the reactant of the fraction of dimethylbenzene, vinylbenzene, cyclopentadiene, indenes for next step.。
Described polyreaction is included in the above-mentioned reactant and adds aluminum chloride, and reaction is 6 hours under 90 ℃ of temperature, obtains polymkeric substance; The last polymkeric substance that generates of reaction is the resin liquid of vinylbenzene, indenes, Vinyl toluene, dicyclopentadiene backbone.
The described process that removes catalyzer adopts the continuous washing method, is included in the Soxylat A 25-7 emulsion splitter that adds 1kg in the polymkeric substance that above-mentioned reaction obtains, and reaction is 2 hours under 85 ℃ of temperature, removes waste water;
Described complex reaction process is to have added fatty acid zinc 10kg, tert butyl phenolic resin, Gum Rosin 100kg and butylated resin 50kg in having removed the polymkeric substance behind the catalyzer, and under 200 ℃ of temperature, reacted 3 hours, remove moisture content through distillation again, detection reaches can lower the temperature after the respective quality index blowing, fragmentation, packing, obtains viscosity-increasing resin dedicated to rubber.
Claims (6)
1, a kind of preparation method of viscosity-increasing resin dedicated to rubber is characterized in that comprising C
9Fraction is through fractionation, catalytic polymerization, carries out the product that complex reaction obtains viscosity-increasing resin dedicated to rubber again after removing catalyzer;
Described fractionation is with the by product C of petroleum cracking system ethene under normal pressure
9Fraction fractionation 8 hours, the cut that intercepts in the 180-220 ℃ of temperature is next step reactant;
The described process that removes catalyzer is included in the polymkeric substance that above-mentioned reaction obtains and adds emulsion splitter, is reaction 1.5-2.5 hour under the 80-90 ℃ of constant temperature in temperature, removes waste water to water oil content layer; Described emulsion splitter is a Soxylat A 25-7;
Described complex reaction process is to add fatty acid zinc, Gum Rosin and butylated resin in having removed the polymkeric substance behind the catalyzer, and reacts 2-4 hour lower the temperature afterwards blowing, fragmentation under 180-220 ℃ of temperature.
2, the preparation method of viscosity-increasing resin dedicated to rubber as claimed in claim 1 is characterized in that described polyreaction is included in the above-mentioned reactant and adds catalyzer, and reaction is 5-7 hour under 80-100 ℃ of temperature, obtains polymkeric substance.
3, the preparation method of viscosity-increasing resin dedicated to rubber as claimed in claim 2 is characterized in that catalyst consumption is the 0.5-1.5% of fraction weight in the polyreaction.
4, the preparation method of viscosity-increasing resin dedicated to rubber as claimed in claim 2 is characterized in that described catalyzer is aluminum chloride or boron trifluoride.
5, the preparation method of viscosity-increasing resin dedicated to rubber as claimed in claim 1 is characterized in that the described process that removes catalyzer adopts the continuous washing method.
6, a kind of viscosity-increasing resin dedicated to rubber is characterized in that adopting the product that makes as each described preparation method of claim 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99125258A CN1109697C (en) | 1999-12-01 | 1999-12-01 | Process for preparing viscosity-increasing resin dedicated to rubber and its product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99125258A CN1109697C (en) | 1999-12-01 | 1999-12-01 | Process for preparing viscosity-increasing resin dedicated to rubber and its product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253140A CN1253140A (en) | 2000-05-17 |
| CN1109697C true CN1109697C (en) | 2003-05-28 |
Family
ID=5283824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99125258A Expired - Fee Related CN1109697C (en) | 1999-12-01 | 1999-12-01 | Process for preparing viscosity-increasing resin dedicated to rubber and its product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1109697C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52108489A (en) * | 1976-03-09 | 1977-09-10 | Toyo Soda Mfg Co Ltd | Preparation of petroleum resins |
| CN1072187A (en) * | 1992-12-29 | 1993-05-19 | 大庆石油化工总厂研究院 | Lightweight oil cracking by-product C 9The technology of synthesizing petroleum resin |
| CN1101650A (en) * | 1994-05-24 | 1995-04-19 | 青岛琴波化工有限公司 | Method for producing styrene indene resin |
-
1999
- 1999-12-01 CN CN99125258A patent/CN1109697C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52108489A (en) * | 1976-03-09 | 1977-09-10 | Toyo Soda Mfg Co Ltd | Preparation of petroleum resins |
| CN1072187A (en) * | 1992-12-29 | 1993-05-19 | 大庆石油化工总厂研究院 | Lightweight oil cracking by-product C 9The technology of synthesizing petroleum resin |
| CN1101650A (en) * | 1994-05-24 | 1995-04-19 | 青岛琴波化工有限公司 | Method for producing styrene indene resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1253140A (en) | 2000-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1217966C (en) | Process for producing hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin obtained by the process | |
| US6310154B1 (en) | Solid acids as catalysts for the preparation of hydrocarbon resins | |
| US6479598B1 (en) | Petroleum resins and their production with BF3 catalyst | |
| US8962765B2 (en) | Method for preparing telechelic oligomers from tire waste | |
| KR0170755B1 (en) | Resin use for tackification | |
| JPS5914044B2 (en) | petroleum resin | |
| CN1928025A (en) | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof | |
| JPS632966B2 (en) | ||
| JP4863566B2 (en) | Process for producing modified conjugated diene polymer | |
| CN1109697C (en) | Process for preparing viscosity-increasing resin dedicated to rubber and its product | |
| JPS6195013A (en) | Petroleum resin and its production | |
| CN108239224A (en) | It is a kind of to be used to produce high-performance copolymer resins product of tire tread glue and preparation method thereof | |
| JPS6213967B2 (en) | ||
| EP1208125A1 (en) | Petroleum resins and their production with bf 3?catalyst | |
| CN1923869A (en) | Preparation method of petroleum resin | |
| CN108219216A (en) | Abietyl modified C9 Petropols and its preparation method and application | |
| CN107841009B (en) | Easily-processed anti-aging styrene butadiene rubber and preparation method thereof | |
| US2523926A (en) | Rubbery butadiene-styrene copolymenr compounded with an acid soluble hydrocarbon oil | |
| JP2004346154A (en) | Nonaromatic hydrocarbon resin and method for producing the same | |
| CN106699972B (en) | A kind of preparation method and its device of C5/C10 copolymer resins | |
| CN1048505C (en) | Method for producing styrene indene resin | |
| KR20020015380A (en) | Petroleum resins and their production with supported catalyst | |
| KR20160001424A (en) | Petroleum Resin, Adhesive Composition Comprising the Same and Adhesive Tape | |
| CN1269370A (en) | Petroleum resin modified with the by product of styrene and its paint material and production process | |
| EP0048141A2 (en) | Multi-ring hydrocarbons and their use in elastomer-containing compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030528 Termination date: 20101201 |