阅读说明：本技术 一种改性芳烃石油树脂的制备方法 (Preparation method of modified aromatic hydrocarbon petroleum resin ) 是由 王斌 孙向东 贾立朋 于 2019-09-20 设计创作，主要内容包括：本发明涉及一种改性芳烃石油树脂的制备方法,包括以甲基苯乙烯或其衍生物与二乙烯基苯作为配料,催化反应后再加入马来酸酐进行反应,最后脱除催化剂和溶剂以及低聚物得到改性芳烃石油树脂。本发明工艺简便,反应条件温和,制备得到的芳烃石油树脂具有色号浅、芳香度高、透明度高,拥有较强的分子刚性,与BR、SBR等橡胶相容性好,能有效提高其抗湿滑性能,且软化点和分子量易于调节,适用于橡胶、塑料、热熔型胶黏剂的改性。(The invention relates to a preparation method of modified aromatic hydrocarbon petroleum resin, which comprises the steps of taking methyl styrene or derivatives thereof and divinyl benzene as ingredients, adding maleic anhydride for reaction after catalytic reaction, and finally removing catalyst, solvent and oligomer to obtain the modified aromatic hydrocarbon petroleum resin. The invention has simple and convenient process and mild reaction condition, the prepared aromatic petroleum resin has light color number, high aromaticity, high transparency, stronger molecular rigidity and good compatibility with rubbers such as BR, SBR and the like, can effectively improve the wet skid resistance, has easily adjusted softening point and molecular weight, and is suitable for modifying rubbers, plastics and hot melt adhesives.)

1. A method for preparing a modified aromatic petroleum resin, comprising:

(1) mixing methyl styrene or a derivative thereof and divinyl benzene according to the mass ratio of 1: 0-0.05 to obtain a mixture; the total material mass of the stirred reaction kettle is firstly put in to be 40 to60 percent of solvent and 0.2 to 2.0 percent of Friedel-Crafts catalyst are filled with N₂protecting, and then dripping the ingredients at the temperature of minus 30-5 ℃ for reaction for 0.5-2 h;

(2) After the ingredients are added dropwise, heating to 25-50 ℃, adding maleic anhydride accounting for 0.2-1.0% of the total mass of the materials, and reacting for 10-30 min to obtain a polymeric resin liquid;

(3) Carrying out alkali washing on the polymerized resin solution obtained in the step (2), then washing with water to be neutral, and removing the catalyst; then, carrying out vacuum rectification under the vacuum degree of-0.08 to-0.09 MPa to 220 to 250 ℃, and removing the solvent and the oligomer to obtain the modified aromatic petroleum resin.

2. the method of claim 1, wherein: the methylstyrene or the derivative thereof in the step (1) is 4-methylstyrene, alpha-methylstyrene or 3-methylstyrene and the derivative thereof.

3. the method of claim 1, wherein: the solvent in the step (1) is one of cyclohexane, methylcyclohexane, benzene, toluene and xylene.

4. The method of claim 1, wherein: the Friedel-Crafts catalyst in the step (1) is one of gaseous boron trifluoride and boron trifluoride diethyl etherate.

5. The method of claim 1, wherein: and (4) washing the alkali in the step (3) by using a 10-15% sodium hydroxide solution.

6. The method of claim 1, wherein: the softening point of the modified aromatic hydrocarbon petroleum resin obtained in the step (3) is 90-130 ℃, and the Gardner color number is less than or equal to 4 #.

Technical Field

The invention belongs to the field of petroleum resin, and particularly relates to a preparation method of modified aromatic hydrocarbon petroleum resin.

Background

The petroleum resin is a solid or viscous liquid medium-low relative molecular weight polymer obtained by catalytic polymerization or free radical polymerization of byproducts C5, C9 fractions and the like of an ethylene device serving as main raw materials. The monomers and molecular structures constituting the resin can be roughly classified into aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, hydrogenated modified petroleum resins, and the like. Wherein the aromatic petroleum resin comprises C9 petroleum resin, C5/C9 copolymerized petroleum resin, styrene-indene resin, etc.

In the above conventional aromatic hydrocarbon petroleum resins, the polymerized monomers are usually mainly styrene, α -methylstyrene and indene and derivatives thereof. For example, U.S. Pat. No. 6,63, 16567 discloses a copolymer resin based on limonene, dicyclopentadiene, indene and alpha-methylstyrene. Patent CN1101650A discloses a method for preparing aromatic hydrocarbon petroleum resin suitable for rubber and tire industry by using C9 oil fraction rich in styrene and indene as raw material and selecting liquid composite aluminum trichloride dication complex (LAL) as catalyst. Patents CN102746460B and CN102746459A disclose a method for preparing copolymer resin which is light color, has high softening point and is suitable for paint and ink, from C9 raw material mainly comprising indene and methyl indene under the action of boron trifluoride catalyst. In patent CN106916264B, a mixed aromatic hydrocarbon containing C10, C15 and C20 as main components is used to modify C5 petroleum resin, so that it has good compatibility with SIS, SEBS and SBS.

The above publications basically relate to the participation of styrene and its derivatives as main comonomers in Friedel-Crafts alkylation catalyzed by Lewis acid and the like, and a large number of conjugated diene groups in the reaction monomers undergo different Diels-Alder addition reactions under the action of temperature to produce ring structures, so that the molecular structure is complex in similar synthetic resins, the molecular weight distribution is wide, the glass transition temperature is high, and the application range is limited.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method of modified aromatic hydrocarbon petroleum resin, the aromatic hydrocarbon petroleum resin prepared by the method has the advantages of light color number, high aromaticity, high transparency, stronger molecular rigidity, good compatibility with rubbers such as BR and SBR, effectively improved wet skid resistance, easily adjustable softening point and molecular weight, and suitability for modification of rubber, plastic and hot melt adhesives.

The invention provides a preparation method of modified aromatic hydrocarbon petroleum resin, which comprises the following steps:

(1) Mixing methyl styrene or a derivative thereof and divinyl benzene according to the mass ratio of 1: 0-0.05 to obtain a mixture; firstly putting a solvent accounting for 40-60% of the total material mass and a Friedel-Crafts catalyst accounting for 0.2-2.0% of the total material mass into a reaction kettle with a stirrer, and filling N₂Protecting, and then dripping the ingredients at the temperature of minus 30-5 ℃ for reaction for 0.5-2 h;

(2) After the ingredients are added dropwise, heating to 25-50 ℃, adding maleic anhydride accounting for 0.2-1.0% of the total mass of the materials, and reacting for 10-30 min to obtain a polymeric resin liquid;

(3) Carrying out alkali washing on the polymerized resin solution obtained in the step (2), then washing with water to be neutral, and removing the catalyst; then, carrying out vacuum rectification under the vacuum degree of-0.08 to-0.09 MPa to 220 to 250 ℃, and removing the solvent and the oligomer to obtain the modified aromatic petroleum resin.

The methylstyrene or the derivative thereof in the step (1) is 4-methylstyrene, alpha-methylstyrene or 3-methylstyrene and the derivative thereof. In the present invention, 4-methylstyrene is preferred.

The solvent in the step (1) is one of cyclohexane, methylcyclohexane, benzene, toluene and xylene.

The Friedel-Crafts catalyst in the step (1) is one of gaseous boron trifluoride and boron trifluoride diethyl etherate.

And (4) washing the alkali in the step (3) by using a 10-15% sodium hydroxide solution.

The softening point of the modified aromatic hydrocarbon petroleum resin obtained in the step (3) is 90-130 ℃, and the Gardner color number is less than or equal to 4 #.

4-Methylstyrene (4-methyl styrene, abbreviated as 4-MS) is a common styrene (St) derivative, and its chemical properties are similar to those of alpha-Methylstyrene (alpha-MS), and it is a polymerizable monomer with strong activity. Divinylbenzene (DVB) is a chemically active, widely used crosslinking agent that improves heat resistance, impact resistance, abrasion resistance, resistance to staining, strength, transparency, and the like of resins. Maleic Anhydride (MAH), also known as maleic anhydride, is an important unsaturated organic anhydride, and has wide applications in organic synthesis.

Under the action of a Friedel-Crafts catalyst, the methyl styrene and the derivatives thereof can synthesize a medium-low molecular weight polymer with the weight average molecular weight Mw of 500-3000, and the performance of the polymer is similar to that of petroleum resin. Compared with high molecular weight polystyrene resin (PS), the resin has the glass transition temperature of less than or equal to 100 ℃, has the thermal melting property, and is suitable for mechanical processing. In the conventional preparation method, the control of the resin molecular weight is usually realized by changing the type and the amount of the catalyst and adjusting the reaction conditions. In the invention, a proper amount of DVB is introduced as a modified monomer, and a proper amount of MAH is introduced as a terminal group, so that the resin has a proper molecular weight range and improved performance.

Advantageous effects

(1) The invention has simple and convenient process and mild reaction condition, the prepared aromatic petroleum resin has light color number, high aromaticity, stronger molecular rigidity and good compatibility with rubbers such as BR, SBR and the like, can effectively improve the wet skid resistance, has easily adjustable softening point and molecular weight, and is suitable for modifying rubbers, plastics and hot melt adhesives.

(2) The invention takes divinylbenzene as a modified component, enhances the polymerization degree of styrene and derivatives thereof under a Friedel-Crafts catalytic system, and can improve the heat resistance and the light transmittance of the resin.

(3) The invention takes maleic anhydride as a terminal group, regulates and controls the degree of polymerization reaction, controls the molecular weight of resin and prevents the generation of explosive polymers;

(4) The resin prepared by the invention has very low fluorescence intensity under ultraviolet light, and is suitable for modification of corresponding characteristics.

Drawings

FIG. 1 shows the fluorescence intensity of different resins.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.