CN1253140A

CN1253140A - Process for preparing viscosity-increasing resin dedicated to rubber and its product

Info

Publication number: CN1253140A
Application number: CN 99125258
Authority: CN
Inventors: 张兰英
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-12-01
Filing date: 1999-12-01
Publication date: 2000-05-17
Anticipated expiration: 2019-12-01
Also published as: CN1109697C

Abstract

A processfor preparing the viscosity-increaser dedicated to rubber includes such technological steps as fractionating the C9 fraction, catalytic polymerization reaction, removing catalyst, and then compound reaction to obtain the product. Its advantage is a scientific simple process. Said voscosity-increaser can be used to increase the ratio of synthetic rubber in tyre, the self-adhesive property of semifinished rubber and the qualified rate of products.

Description

Preparation method of special tackifying resin for rubber and product thereof

The invention relates to a preparation method of rubber resin, in particular to a preparation method of tackifying resin special for rubber and a product thereof.

A tackifier and a softener commonly used in the preparation of the bias rubber tire in the rubber industry are coumaroneC5 resin, and have certain defects in the use process, so that the development of the tire industry is restricted. With the development of petroleum industry, devices for preparing ethylene by cracking are increased, and a large amount of by-product C is produced₉Fraction, using C₉The comprehensive utilization of the fractions is very significant.

The invention aims to provide a by-product C for preparing ethylene by petroleum cracking₉A method for preparing tackifying resin special for rubber by using distillate as a raw material.

The invention also aims to provide a product prepared by the preparation method.

The preparation method of the tackifying resin special for rubber comprises the step of adding C₉The fraction is fractionated, catalyzed and polymerized, and then the catalyst is removed, and then the compound reaction is carried out to obtain the product of the tackifying resin special for rubber.

Wherein the fractionation is a byproduct C for preparing ethylene by cracking petroleum at normal pressure₉Fraction is fractionated for 8 hours, and the fraction within the temperature of 180-220 ℃ is obtained as the reactant of the next step; the byproduct C of ethylene preparation by petroleum cracking₉The distillate is a mixture composed of a plurality of compounds, the components are relatively complex and can be roughly divided into two categories, one category is unsaturated active components, such as styrene, vinyl toluene, indene, dicyclopentadiene and the like; another group is inactive components, mainly saturated hydrocarbons, according to C₉The active components in the distillate have different boiling points, and the distillate in different boiling range ranges is cut by normal pressure fractionation to obtain the distillate of themain raw material used by the invention; obtaining a fraction rich in xylene, styrene, cyclopentadiene and indene, wherein the specific components are shown in the following table:

component weight (%)

C₉0.74 vinyl toluene 15.82

Benzene 0.88 indene 10.96

Toluene 7.88 naphthalene 2.24

Ethylbenzene 1.94 meta-xylene 0.97

Styrene 9.20 o-xylene 3.30

Allyl benzene 1.93

The polymerization reaction comprises the steps of adding a catalyst into the reactants, and reacting for 5-7 hours at the temperature of 80-100 ℃ to obtain a polymer; in the above catalytic polymerization, C₉The active components of the fractions being reacted, e.g. styrene, indene, bicyclo-ringsPentadiene and vinyltoluene in the presence of cationic catalyst and the reactionThe agent is an electron-deficient substance, namely an electrophilic reagent of an electron acceptor, so that double bonds in unsaturated hydrocarbon are broken to form a trivalent carbon cation active center, and the resin with a branched chain and a long chain structure is generated.

The following is AICI₃For example, the reaction mechanism for fractional polymerization is written.

AICI₃

AICI₃AICI₃

AICI₃

CH₃-CHR-(CH₂-CHR)n-CH＝CHR+AICI₃

Wherein R represents styrene, indene and the like.

The polymer finally generated by the reaction is resin liquid with long-chain structure of styrene, indene, vinyl toluene and dicyclopentadiene. The amount of catalyst used in the polymerization is based on C₉The content of unsaturated components in the components is determined. If the amount of the catalyst added is too small, the reaction is not complete, and if the amount of the catalyst is too large, the quality of the resin is affected, and the catalyst removal is difficult. The addition amount of the catalyst is controlled to be 0.8-1.3% of the fraction. The catalyst may be aluminum trichloride or boron trifluoride.

The process for removing the catalystAdding water and a demulsifier into the polymer obtained by the reaction, and reacting at the temperature of 80-90 ℃ for 1.5-2.5 hours until water and oil are layered, and removing wastewater; the existence of the catalyst affects the quality of the resin, so the catalyst is removed completely in time after the polymerization reaction is finished; the catalyst can be removed by a continuous water washing method; the continuous water washing method has the advantages of simple equipment, low cost, capability of recycling the treated wastewater and the like, and has no influence on environmental protection. The demulsifier can be polyoxyethylene ether, and the addition amount is C₉0.5-1% of the fraction.

The composite reaction process is to add fatty acid zinc, tert-butyl phenolic resin, rosin resin and butyl resin into the polymer after the catalyst is removed, and react for 2-4 hours at the temperature of 180-220 ℃ to obtain the special tackifying resin for rubber. In the processing of rubber products, the special tackifying resin for rubber needs to be further subjected to complex reaction in order to achieve the characteristics of adhesion, softening, reinforcement, dispersion, compatibility and the like; in the heating process of the composite reaction, the discharged fractions can be used as a coating solvent, and after the composite reaction is completed, the temperature can be reduced, the materials can be discharged, crushed and packaged after the detection that the corresponding quality indexes are reached.

The preparation method of the tackifying resin special for rubber can also comprise the step of dehydrating by adopting a distillation method after the composite reaction.

The preparation method of the special tackifying resin for rubber is scientific, reasonable, simple and feasible, and all technical indexes of the prepared special tackifying resin for rubber can meet the index requirements after the detection of Qingdao quality inspection and the trial of users. The special tackifying resin for rubber can improve the processing performance, increase the viscosity, greatly reduce the rubber material cost and improve the proportion of synthetic rubber in the application of tires; the self-adhesive property of the semi-finished rubber material can be improved in the master batch, so that the semi-finished product has long viscosity retention time and good stiffness, and the qualification rate of the product is improved; the special tackifying resin for rubber has good compatibility, ensures that the semi-finished rubber material has good fluidity, reduces the Mooney viscosity of the rubber material, has small influence on the mechanical property of the rubber material, and is suitable for rubber formulas of various tires.

The present invention is further described below with reference to examples.

Examples

A process for preparing the special tackifying resin for rubber includes such steps as mixing 1200kgC₉The fraction is fractionated, catalyzed and polymerized, and then the catalyst is removed, and then the compound reaction is carried out to obtain the product of the tackifying resin special for rubber.

Wherein the fractionation is a byproduct C for preparing ethylene by cracking petroleum at normal pressure₉Fraction is fractionated for 8 hours, and the fraction within the temperature of 180-220 ℃ is obtained, and the fraction rich in xylene, styrene, cyclopentadiene and indene is obtained as the reactant of the next step. .

The polymerization reaction comprises the steps of adding aluminum trichloride into the reactants, and reacting for 6 hours at the temperature of 90 ℃ to obtain a polymer; the polymer finally generated by the reaction is resin liquid with long-chain structure of styrene, indene, vinyl toluene and dicyclopentadiene.

The process of removing the catalyst adopts a continuous washing method, and comprises the steps of adding 1kg of polyoxyethylene ether demulsifier into the polymer obtained by the reaction, reacting for 2 hours at the temperature of 85 ℃, and removing the wastewater;

the composite reaction process comprises the steps of adding 10kg of fatty acid zinc, 100kg of tert-butyl phenolic resin, 100kg of rosin resin and 50kg of butyl resin into the polymer without the catalyst, reacting for 3 hours at the temperature of 200 ℃, distilling to remove water, and cooling, discharging, crushing and packaging after detecting to reach corresponding quality indexes to obtain the special tackifying resin for rubber.

Claims

1. A process for preparing the tackifying resin specially used for rubber includes such steps as mixing C₉The fraction is fractionated, catalyzed and polymerized, and then the catalyst is removed, and then the compound reaction is carried out to obtain the product of the tackifying resin special for rubber.

2. The method for preparing a tackifying resin special for rubber according to claim 1, wherein said fractionation is a process of cracking petroleum at normal pressure to prepare ethylene as a by-product C₉The fraction was fractionated for 8 hours, and the fraction obtained at a temperature of 180 ℃ and 220 ℃ was used as the reactant for the next step.

3. The process for preparing tackifying resin special for rubber according to claim 1, wherein said polymerization reaction comprises adding a catalyst to the above reactants, and reacting at 80-100 ℃ for 5-7 hours to obtain a polymer.

4. The process for producing a tackifier resin for rubber according to claim 3, wherein the amount of the catalyst used in the polymerization is 0.5 to 1.5% by weight based on the distillate.

5. The method for preparing a tackifying resin special for rubber according to claim 3, wherein said catalyst is aluminum trichloride or boron trifluoride.

6. The method for preparing tackifying resin special for rubber according to claim 1, characterized in that the catalyst removal process comprises adding a demulsifier to the polymer obtained by the above reaction, reacting at a constant temperature of 80-90 ℃ for 1.5-2.5 hours, and removing wastewater after water and oil are layered; the demulsifier is polyoxyethylene ether.

7. The method for preparing a tackifying resin special for rubber according to claim 6, wherein the catalyst removal process adopts a continuous water washing method.

8. The method for preparing tackifying resin special for rubber as claimed in claim 1, wherein said complex reaction process comprises adding zinc fatty acid, rosin resin and butyl resin into the polymer after catalyst removal, reacting at 220 ℃ for 2-4 hours at 180-.

9. A special tackifying resin for rubber, which is characterized by being prepared by the preparation method of claims 1-8.