CN110563875B

CN110563875B - Preparation method of modified aromatic hydrocarbon petroleum resin

Info

Publication number: CN110563875B
Application number: CN201910890924.6A
Authority: CN
Inventors: 王斌; 孙向东; 贾立朋
Original assignee: Ningbo Yonghua Resin Co ltd; Henghe Materials and Science Technology Co Ltd
Current assignee: Ningbo Yonghua Resin Co ltd; Henghe Materials and Science Technology Co Ltd
Priority date: 2019-09-20
Filing date: 2019-09-20
Publication date: 2021-12-21
Anticipated expiration: 2039-09-20
Also published as: CN110563875A

Abstract

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.

Description

Preparation method of modified aromatic hydrocarbon petroleum resin

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.

Example 1

Mixing 4-MS and DVB according to the mass ratio of 1:0.02 to obtain a mixture, firstly putting methylcyclohexane accounting for 50 percent of the total material mass and a boron trifluoride diethyl etherate catalyst accounting for 0.8 percent of the total material mass into a reaction kettle with a stirrer, and filling N₂Protecting, and slowly dripping the ingredients at the temperature of minus 20 ℃ for reaction for 1 h;after the dropwise addition, heating to 45 ℃, adding MAH accounting for 0.2 percent of the total material mass, and reacting for 20min to obtain a polymeric resin solution; washing the polymerized resin liquid with 15% sodium hydroxide lye, washing the polymerized resin liquid with water for multiple times until the polymerized resin liquid is neutral, and removing the catalyst; then, the mixture is decompressed and rectified to 240 ℃ under the vacuum degree of-0.085 MPa, and the solvent and the oligomer are removed, thus obtaining the modified aromatic hydrocarbon petroleum resin with the softening point of 101.5 ℃, the Gardner color number of 2.5#, the Mw of 940 and the aromaticity of 44.6 percent.

Examples 2 to 4

4-MS and DVB are used as raw materials, and under the same process conditions as those in the example 1, the content of DVB in the ingredients is changed, and the influence on the performance of the modified aromatic hydrocarbon petroleum resin is as follows:

DVB ratio

Softening point

Color number

Thermal stability

Mw

Light transmittance

Degree of aromaticity

Example 2

0∶1

93.5℃

2.1

6.0

875

75％

52.2

Example 3

0.03∶1

105.6℃

2.3

5.5

1090

86％

42.8

Example 4

0.05∶1

114.0℃

2.5

5.4

1240

90％

40.1

From the above table, the softening point, color number, weight average molecular weight Mw and light transmittance of the modified aromatic petroleum resin all increase with the increase of the DVB proportion in the formulation, while the thermal stability is rather gradually decreased. Namely, DVB as a modifying component can increase the degree of internal crosslinking of resin molecules, increase the molecular weight and softening point, and improve the light transmittance of the resin, but if added in an excessive amount, it may also slightly deteriorate the color number of the resin.

Examples 5 to 8

In examples 5 to 8, the other process conditions were the same as in example 1.

From the above table, it is understood that the softening point and Mw of the modified aromatic petroleum resin are both significantly decreased and the acid value is increased with the increase of the addition amount of MAH, but the color number of the resin is significantly deteriorated. By adjusting the MAH reaction time, the method has little influence on the performance of the modified aromatic hydrocarbon petroleum resin and only slightly increases the color number and acid value of the resin.

Example 9

Mixing alpha-MS and DVB according to the mass ratio of 1:0.01 to obtain a mixture, firstly putting methylcyclohexane accounting for 50 percent of the total material mass and a gaseous boron trifluoride catalyst accounting for 0.3 percent of the total material mass into a reaction kettle with a stirrer, and filling N₂Protecting, and slowly dripping the ingredients at the temperature of-15 ℃ for reaction for 1.5 h; after the dropwise addition is finished, heating to 50 ℃, adding MAH accounting for 0.2 percent of the total mass of the materials, and reacting for 20min to obtain a polymeric resin solution; washing the polymerized resin liquid with 15% sodium hydroxide lye, washing the polymerized resin liquid with water for multiple times until the polymerized resin liquid is neutral, and removing the catalyst; then, the mixture is decompressed and rectified to 240 ℃ under the vacuum degree of-0.085 MPa, and the solvent and the oligomer are removed, thus obtaining the modified aromatic hydrocarbon petroleum resin with the softening point of 99.0 ℃, the Gardner color number of 1.5#, the Mw of 1085, the light transmittance of 86 percent and the aromaticity of 47.0 percent.

Example 10

Mixing alpha-MS and DVB according to the mass ratio of 1:0.05 to obtain a mixture, firstly putting methylcyclohexane accounting for 40 percent of the total material mass and a gaseous boron trifluoride catalyst accounting for 0.5 percent of the total material mass into a reaction kettle with a stirrer, and filling N₂Protecting, and slowly dripping the ingredients at the temperature of minus 30 ℃ for reaction for 2.0 h; after the dropwise addition is finished, heating to 50 ℃, adding MAH accounting for 0.2 percent of the total mass of the materials, and reacting for 20min to obtain a polymeric resin solution; washing the polymerized resin liquid with 15% sodium hydroxide lye, washing the polymerized resin liquid with water for multiple times until the polymerized resin liquid is neutral, and removing the catalyst; then, the mixture is decompressed and rectified to 240 ℃ under the vacuum degree of-0.085 MPa, and the solvent and the oligomer are removed, thus obtaining the modified aromatic hydrocarbon petroleum resin with the softening point of 127.5 ℃, the Gardner color number of 1.9#, the Mw of 2750, the light transmittance of 89 percent and the aromaticity of 41.5 percent.

Example 11

The petroleum resin contains a conjugated double bond structure due to incomplete saturation, has a small amount of aromatic groups and derivative groups thereof capable of absorbing ultraviolet rays, and can generate strong fluorescence. Although the fluorescence is naturally generated and has no obvious influence on human health, the requirement of high fluorescence is eliminated as much as possible in fields with high requirement on fluorescence, such as food packaging, sanitation, clarifying sealant and the like. In the embodiment, the fluorescence spectrum of the resin under a 340nm ultraviolet light source is tested by a fluorescence spectrometer to qualitatively judge the fluorescence intensity of the resin; wherein, the resin (i) is the conventional cold polymerization C9 petroleum resin, and the resin (ii) and the resin (iii) are DVB modified aromatic hydrocarbon resins with different aromaticity, which are respectively the resins obtained in the embodiment 3 and the embodiment 9. By comparison, the modified aromatic petroleum resin of the invention has lower fluorescence intensity than the common C9 resin.

Claims

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

mixing methyl styrene or a derivative thereof and divinylbenzene according to a mass ratio of 1: 0.01-0.05 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;

after the addition of the ingredients is completed, 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;

step (3) carrying out alkali washing on the polymerized resin liquid obtained in the step (2), then washing with water to neutrality, 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 #.