Modified bio-based monomer resin as well as preparation method and application thereof

Abstract

The invention relates to modified bio-based monomer resin as well as a preparation method and application thereof, at least one of alpha-methyl styrene, styrene and vinyl toluene is used as a raw material to prepare monomer petroleum resin, and then bio-based anhydride is introduced for graft modification to obtain the modified bio-based monomer resin. The modified bio-based monomer resin is suitable for being applied to the fields of rubber mixing, casting wax, adhesives and the like, the physical performance of the casting wax can be effectively improved, the adhesiveness, thermal stability and durability of rubber are improved, the bonding strength of the adhesives is improved, and the application field of the adhesives is widened.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum resins, and particularly relates to a modified bio-based monomer resin and a preparation method and application thereof. Background Art

[0002] Pure aromatic monomer petroleum resin is made from a mixture of purified styrene, α-methylstyrene, and vinyltoluene monomers. The resulting monomer resin is water white and extremely stable to thermal and oxidative degradation. Products with different softening points and molecular weights can be obtained by changing the ratio of the monomers. Monomer resins with low softening points improve the viscosity of block copolymer formulations, while monomer resins with high softening points strengthen the end blocks and increase cohesion and high temperature resistance. Due to the high aromaticity of the monomer resins, they are extremely compatible with polymers containing styrene. They can effectively reduce the melt viscosity of the adhesive, increase the polymer melt index and fluidity, and maintain the colloid bonding strength. Monomer resins are used in EVA packaging adhesives to provide specific adhesive properties. Other uses for monomer resins include casting waxes, coatings, transparent sealants, laminating adhesives, rubber tires, and plastic modification. In adhesive applications, pure monomer resins can be used to modify the styrene ends in SBCs to balance viscosity, adhesion, and heat resistance.

[0003] Casting wax is a special wax material used in the casting process. Its main function is to make a casting model before casting to facilitate mold making in the casting process. Casting wax is divided into two categories: ordinary casting wax and precision casting wax. Ordinary casting wax is mainly used to make parts that do not require high precision, such as mold making and ordinary parts. Precision casting wax is used to make high-precision parts, such as jewelry, precision machine tools and other fields. Adding monomer petroleum resin to casting wax can improve the compatibility, anti-cracking performance and flexibility of casting wax.

[0004] Monomer petroleum resin plays a major role in viscosity enhancement, reinforcement, softening and plasticization in rubber mixing. It can significantly enhance the adhesion between rubber and fillers, skeleton materials and rubber layers, improve the dispersion of fillers in the rubber matrix, increase the self-adhesion of the mixed rubber and the peeling resistance of the final product, reduce the Mooney viscosity and hardness of the rubber during mixing, increase its plasticity and fluidity, make the rubber easier to shape during processing, and give the final product the required hardness and softness.

[0005] The application of monomer petroleum resin in adhesives is mainly reflected in improving viscosity, cohesion, improving processing performance and reducing costs.

[0006] In the current context of increasing global environmental awareness, bio-based materials have received extensive attention and research due to their renewable properties, while current monomer resin raw materials are all derived from petrochemical systems. Modification of bio-based materials is a hot topic in current research, and as a renewable resource, it has great development prospects. At the same time, when the monomer resin is used in hot melt adhesives, its wetting and plasticity are relatively weak after mixing with the base material, making the initial viscosity of the hot melt adhesive relatively low; and because of the nature of its raw materials, its molecular structure lacks polar groups, and its decomposition properties with other substances are poor when used. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide a modified bio-based monomer resin and a preparation method and application thereof. The resin is modified by introducing bio-based acid anhydride to enhance the polarity of the resin and improve the application effect of the product in the fields of casting wax, rubber mixing, adhesives, etc.

[0008] The invention provides a modified bio-based monomer resin. At least one of alpha-methylstyrene, styrene and vinyltoluene is used as a raw material to prepare a monomer petroleum resin, and then a bio-based acid anhydride is introduced for grafting modification to obtain the modified bio-based monomer resin.

[0009] Preferably, the bio-based anhydride is one or more of itaconic anhydride and citraconic anhydride.

[0010] Preferably, the vinyltoluene is a mixture of 2-vinyltoluene, 3-vinyltoluene and 4-vinyltoluene, wherein the ratio of 3-vinyltoluene to 4-vinyltoluene is 45-50wt%:50-55wt%.

[0011] The present invention also provides a method for preparing a modified bio-based monomer resin, comprising the following steps:

[0012] (1) mixing at least one of α-methylstyrene, styrene and vinyltoluene with an aromatic solvent in proportion, and conveying the mixture to a first polymerization kettle via a pump, adding a catalyst to the first polymerization kettle, and overflowing the resin liquid obtained from the first polymerization kettle to a second polymerization kettle via a pipeline to continue heat preservation polymerization, removing the catalyst from the resin liquid produced from the second polymerization kettle, and flash evaporating and dehydrating the mixture to obtain a monomer resin liquid;

[0013] (2) dissolving the bio-based acid anhydride and the initiator in an aromatic hydrocarbon solvent and adding the dissolved bio-based acid anhydride and the initiator to the monomer resin liquid obtained in step (1), and placing the dissolved bio-based acid anhydride and the initiator in a shell-and-tube reactor to generate a free radical reaction, thereby obtaining a modified bio-based monomer resin liquid; the resin liquid material is passed through a flash tower to remove the solvent, unreacted bio-based acid anhydride and oligomers, an antioxidant is added to the molten resin in the bottom of the tower, and the modified bio-based monomer resin is obtained through granulation.

[0014] Preferably, the aromatic hydrocarbon solvent in step (1) is selected from one or more of toluene, xylene, trimethylbenzene, and Solvesso 100# solvent oil; the aromatic hydrocarbon solvent accounts for 60-75wt% of the total feed amount.

[0015] Preferably, the catalyst in step (1) is boron trifluoride gas or boron trifluoride ether; the amount of the catalyst added is 1 to 2 wt% of the total amount of α-methylstyrene, styrene and vinyltoluene in the total material.

[0016] Preferably, the polymerization temperature of the first polymerization kettle in step (1) is -5 to 15°C, the polymerization temperature of the second polymerization kettle is 5 to 25°C, and the total polymerization time is 10 to 25 hours.

[0017] Preferably, the initiator in step (2) is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, diisopropyl peroxide, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, and diisopropyl peroxydicarbonate.

[0018] Preferably, the bio-based anhydride in step (2) is 3-15% of the solid content of the monomer resin liquid; and the added amount of the initiator is 1-5% of the mass of the bio-based anhydride.

[0019] Preferably, the temperature of the shell-and-tube reactor in step (2) is 100-250° C., and the reaction time is 1-10 h.

[0020] Preferably, the flash tower in step (2) is operated under vacuum conditions of -0.09 to -0.098 MPa and a bottom temperature of 240 to 260°C.

[0021] Preferably, the amount of antioxidant added in step (2) is 0.1 to 1 wt % of the liquid-solid content of the monomer resin.

[0022] The invention also provides an application of a modified bio-based monomer resin in casting wax.

[0023] Preferably, the casting wax comprises the following ingredients in parts by weight: 60-80 parts of paraffin wax, 10-20 parts of microcrystalline wax, 1-10 parts of EVA, and 10-20 parts of modified bio-based monomer resin.

[0024] Preferably, the paraffin wax is fully refined or semi-refined paraffin wax with a melting point of 56-70°C.

[0025] Preferably, the microcrystalline wax has a melting point of 60° C. and is mainly composed of C31-70 branched saturated hydrocarbons and contains a small amount of cyclic and straight-chain hydrocarbons.

[0026] Preferably, the EVA is copolymerized from ethylene and vinyl acetate, wherein the VA content is 28% and the melt index (MI) is 150 g / 10 minutes.

[0027] The present invention also provides an application of the modified bio-based monomer resin in tire rubber.

[0028] Preferably, the tire rubber comprises the following ingredients in parts by weight: 80-85 parts of styrene-butadiene rubber, 20-40 parts of butadiene rubber, 80-85 parts of carbon black, 1-5 parts of silane coupling agent, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, 20-30 parts of filler oil, and 1-10 parts of modified bio-based monomer resin.

[0029] Preferably, the styrene-butadiene rubber is a polystyrene-butadiene copolymer, wherein the mass fraction of organic acid is 3% to 7.5%, the mass fraction of combined styrene is 22% to 25%, the raw rubber Mooney viscosity, ML (1+4), at 100°C is 40 to 60, the mixed rubber Mooney viscosity, ML (1+4), at 100°C is ≦90, the tensile strength (145°C, 35min) is ≧19Mpa, the elongation at break (145°C, 35min) is ≧360%, the 300% tensile stress (145°C, 25min) is 5 to 16Mpa, the 300% tensile stress (145°C, 35min) is 10 to 20Mpa, and the 300% tensile stress (145°C, 50min) is 12 to 20Mpa.

[0030] Preferably, the butadiene rubber is cis-1,4-polybutadiene rubber, wherein the tensile strength is 10-25 MPa, the elongation at break is 700-800%, the 300% modulus of tensile stress is 4-8 MPa, the tear strength is 55-65 KN / m, the Shore hardness A is 55-60 degrees, the resilience is 45-55%, and the Akron abrasion is 0.02-0.1 cm3 / (1.6 km).

[0031] Preferably, the carbon black has an iodine absorption value of 110 to 130 g / kg and a DBP absorption value of 110 to 120 10^(-5)m 3 / kg, CTAB adsorption specific surface area 100~115,10 3 ㎡ / kg.

[0032] Preferably, the filler oil has a flash point (opening) of 180-230° C., a kinematic viscosity (100° C.) of 15-45 mm 2 / s, and an aromatic content of 75-85%.

[0033] Preferably, the stearic acid has an iodine value of ≤4 gI2 / 100 g, a chromaticity (Hazen unit) of ≤500, and a saponification value of 200-220 mgKOH / g.

[0034] Preferably, the silane coupling agent is one or more of bis-(y-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, isobutyltriethoxysilane and the like.

[0035] The present invention also provides an application of a modified bio-based monomer resin in a hot melt adhesive.

[0036] Preferably, the hot melt adhesive comprises the following ingredients in parts by weight: 40-60 parts of Henghe HM-1000 hydrogenated resin, 10-20 parts of modified bio-based monomer resin, 20-30 parts of softener, 30-40 parts of SIS thermoplastic elastomer, and 1-3 parts of antioxidant.

[0037] Preferably, the SIS thermoplastic elastomer is a linear structure, wherein the mass fraction of styrene is 13% to 17%, and the melt index measured at 200° C. and 5 kg is 10 to 20 g / 10 min.

[0038] Preferably, the softener is at least one of hydrogenated naphthenic oil, dioctyl phthalate and paraffin.

[0039] Preferably, the antioxidant is at least one of a phosphite antioxidant and a hindered phenol antioxidant.

[0040] Beneficial Effects

[0041] (1) The monomer resin of the present invention is modified by introducing bio-based acid anhydride, thereby enhancing the polarity of the resin and improving the application effect of the product in the fields of casting wax, rubber mixing, adhesives, etc.

[0042] (2) The monomer resin prepared by the present invention is mainly used in the field of casting wax, which can effectively improve the bending strength and hardness of the casting wax; improve its compatibility and fluidity, so that the film material is easy to demold with low residue.

[0043] (3) The monomer resin prepared by the present invention is mainly used in the field of rubber mixing, specifically mainly in tire rubber, and can play a role in viscosity enhancement, softening, improving fluidity during vulcanization, and improving the tensile strength, wear resistance, and aging resistance of tire rubber. (4) The monomer resin prepared by the present invention is mainly used in the field of hot melt adhesives, mainly in improving the viscosity and cohesive strength of the adhesive.

[0044] (5) The present invention uses raw materials such as α-methylstyrene, styrene, vinyltoluene, bio-based anhydrides, etc. that are partially or entirely derived from bio-based materials, replacing raw materials produced from petrochemicals, thereby reducing carbon footprint and reducing carbon dioxide emissions. DETAILED DESCRIPTION

[0045] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0046] Bio-based styrene aromatic monomers used in the examples:

[0047] Glucose is fermented or chemically catalyzed to obtain bio-based propylene, bio-based propylene and benzene are alkylated to obtain bio-based isopropyl benzene, and bio-based isopropyl benzene is catalytically dehydrogenated to obtain (bio-based) α-methylstyrene. Bio-based cinnamic acid is separated and purified by Perkin reaction to obtain (bio-based) styrene. Ethanol and toluene derived from crops such as corn can be used to prepare (bio-based) vinyl toluene by catalytic dehydrogenation. The vinyl toluene is a mixture of 3-vinyl toluene and 4-vinyl toluene, wherein the ratio of 3-vinyl toluene to 4-vinyl toluene is 45-50wt%: 50-55wt%.

[0048] Example 1

[0049] Raw material preparation: α-methylstyrene: styrene: vinyl toluene are prepared into raw material A in a mass ratio of 1:0.5:0.1, and then diluted with toluene, wherein the diluent solvent toluene accounts for 60% of the total weight of the ingredients. The prepared raw materials are added to the raw material tank, and the pressure is maintained at 0.3Mpa after being replaced with nitrogen three times. The feed pump is started to add the raw materials to the continuous polymerization kettle No. 1. After the liquid level reaches 50%, boron trifluoride gas or boron trifluoride ether catalyst is introduced through the flow meter. The amount of effective components added to the catalyst is 1.2% of the active components in the raw materials. The temperature of the continuous polymerization kettle No. 1 is controlled at 15°C, and the temperature of the No. 2 kettle is controlled at 20°C. The residence time of the No. 1 and No. 2 kettles is 5h each. After the raw materials are fully polymerized, the polymerization liquid enters the continuous alkali washing and water washing tanks to remove the catalyst, and the obtained monomer resin liquid is flashed and dehydrated, and the water content of the monomer resin liquid is required to be less than 100ppm. The monomer resin liquid, itaconic anhydride dissolved in toluene, and azobisisobutyronitrile dissolved in toluene are pumped into a shell-and-tube reactor, wherein the monomer resin yield in the monomer resin liquid is 60%, the addition ratio of itaconic anhydride is 3% of the solid content of the monomer resin liquid, and the addition ratio of azobisisobutyronitrile is 3% of the mass of itaconic anhydride. The temperature of the shell-and-tube reactor is 220°C, and the material residence time is 3h. The material coming out of the shell-and-tube reactor is removed from the solvent, unreacted bio-based anhydride and oligomers by a flash tower, wherein the vacuum degree is controlled to be above 0.095MPa, the distillation temperature is 240°C, and 0.2wt% of antioxidant 1010 is added to obtain a modified bio-based monomer resin.

[0050] Example 2

[0051] The difference from Example 1 is that the addition ratio of itaconic anhydride in this example is 5% of the liquid-solid content of the monomer resin, and the other conditions are the same as those in Example 1 to obtain a modified bio-based monomer resin.

[0052] Example 3

[0053] The difference from Example 1 is that the addition ratio of itaconic anhydride in this example is 8% of the liquid-solid content of the monomer resin, and the other conditions are the same as those in Example 1 to obtain a modified bio-based monomer resin.

[0054] Example 4

[0055] Raw material preparation: α-methylstyrene: styrene: vinyltoluene are prepared into raw material A in a mass ratio of 1:0.65:0.15, and then diluted with toluene, wherein the diluent solvent toluene accounts for 60% of the total weight of the ingredients. The prepared raw materials are added to the raw material tank, and the pressure is maintained at 0.3Mpa after being replaced with nitrogen three times. The feed pump is started to add the raw materials to the continuous polymerization kettle No. 1. After the liquid level reaches 50%, boron trifluoride gas or boron trifluoride ether catalyst is introduced through the flow meter. The amount of effective components added to the catalyst is 1.5% of the active components in the raw materials. The temperature of the continuous polymerization kettle No. 1 is controlled at 5°C, and the temperature of the No. 2 kettle is controlled at 8°C. The residence time of the No. 1 and No. 2 kettles is 8h each. After the raw materials are fully polymerized, the polymerization liquid enters the continuous alkali washing and water washing tanks to remove the catalyst, and the obtained monomer resin liquid is flashed and dehydrated, and the water content of the monomer resin liquid is required to be less than 100ppm. The monomer resin liquid, itaconic anhydride dissolved in toluene, and azobisisobutyronitrile dissolved in toluene are pumped into a shell-and-tube reactor, wherein the monomer resin yield in the monomer resin liquid is 60%, the addition ratio of itaconic anhydride is 3% of the solid content of the monomer resin liquid, and the addition ratio of azobisisobutyronitrile is 3% of the mass of itaconic anhydride. The temperature of the shell-and-tube reactor is 220°C, and the material residence time is 3h. The material coming out of the shell-and-tube reactor is removed from the solvent, unreacted bio-based anhydride and oligomers by a flash tower, wherein the vacuum degree is controlled to be above 0.095MPa, the distillation temperature is 240°C, and 0.2wt% of antioxidant 1010 is added to obtain a modified bio-based monomer resin.

[0056] Example 5

[0057] The difference from Example 4 is that the addition ratio of itaconic anhydride in this example is 5% of the liquid-solid content of the monomer resin, and the other conditions are the same as those in Example 4 to obtain a modified bio-based monomer resin.

[0058] Example 6

[0059] The difference from Example 4 is that the addition ratio of itaconic anhydride in this example is 8% of the liquid-solid content of the monomer resin, and the other conditions are the same as those in Example 4 to obtain a modified bio-based monomer resin.

[0060] Example 7

[0061] Raw material preparation: α-methylstyrene: styrene: vinyl toluene are prepared into raw material A in a mass ratio of 1:0.9:0.8, and then diluted with toluene, wherein the diluent solvent toluene accounts for 60% of the total weight of the ingredients. The prepared raw materials are added to the raw material tank, and the pressure is maintained at 0.3Mpa after being replaced with nitrogen three times. The feed pump is started to add the raw materials to the continuous polymerization kettle No. 1. After the liquid level reaches 50%, boron trifluoride gas or boron trifluoride ether catalyst is introduced through the flow meter. The amount of effective components added to the catalyst is 2% of the active components in the raw materials. The temperature of the continuous polymerization kettle No. 1 is controlled at -10°C, and the temperature of the No. 2 kettle is -5°C. The residence time of the No. 1 and No. 2 kettles is 10h respectively. After the raw materials are fully polymerized, the polymerization liquid enters the continuous alkali washing and water washing tanks to remove the catalyst, and the obtained monomer resin liquid is flashed and dehydrated, and the water content of the monomer resin liquid is required to be less than 100ppm. The monomer resin liquid, itaconic anhydride dissolved in toluene, and azobisisobutyronitrile dissolved in toluene are pumped into a shell-and-tube reactor, wherein the monomer resin yield in the monomer resin liquid is 60%, the addition ratio of itaconic anhydride is 3% of the solid content of the monomer resin liquid, and the addition ratio of azobisisobutyronitrile is 3% of the mass of itaconic anhydride. The temperature of the shell-and-tube reactor is 220°C, and the material residence time is 3h. The material coming out of the shell-and-tube reactor is removed from the solvent, unreacted bio-based anhydride and oligomers by a flash tower, wherein the vacuum degree is controlled to be above 0.095MPa, the distillation temperature is 240°C, and 0.2wt% of antioxidant 1010 is added to obtain a modified bio-based monomer resin.

[0062] Example 8

[0063] The difference from Example 8 is that the addition ratio of itaconic anhydride in this example is 5% of the liquid-solid content of the monomer resin, and the other conditions are the same as those in Example 8 to obtain a modified bio-based monomer resin.

[0064] Example 9

[0065] The difference from Example 8 is that the addition ratio of itaconic anhydride in this example is 8% of the liquid-solid content of the monomer resin, and the other conditions are the same as those in Example 8 to obtain a modified bio-based monomer resin.

[0066] Comparative Example 1

[0067] Raw material preparation: α-methylstyrene: styrene: vinyltoluene are prepared into raw material A in a mass ratio of 1:0.5:0.1, and then diluted with toluene, wherein the dilution solvent toluene accounts for 60% of the total weight of the ingredients. The prepared raw materials are added to the raw material tank, and the pressure is maintained at 0.3Mpa after being replaced with nitrogen three times. The feed pump is started to add the raw materials to the continuous polymerization kettle No. 1. After the liquid level reaches 50%, boron trifluoride gas or boron trifluoride ether catalyst is introduced through the flow meter. The amount of effective components added to the catalyst is 1.2% of the active components in the raw materials. The temperature of the continuous polymerization kettle No. 1 is controlled at 15°C, and the temperature of the No. 2 kettle is controlled at 20°C. The residence time of the No. 1 and No. 2 kettles is 5h each. After the raw materials are fully polymerized, the polymerization liquid enters into a continuous alkali washing and water washing tank to remove the catalyst, and the obtained monomer resin liquid is passed through a flash tower to remove the solvent and oligomers, wherein the vacuum degree is controlled at above 0.095 MPa, the distillation temperature is 240°C, and after adding 0.2wt% of antioxidant 1010, the bio-based monomer resin can be obtained.

[0068] Comparative Example 2

[0069] Raw material preparation: α-methylstyrene: styrene: vinyltoluene are prepared into raw material A in a mass ratio of 1:0.65:0.15, and then diluted with toluene, wherein the dilution solvent toluene accounts for 60% of the total weight of the ingredients. The prepared raw materials are added to the raw material tank, and the pressure is maintained at 0.3Mpa after being replaced with nitrogen three times. The feed pump is started to add the raw materials to the continuous polymerization kettle No. 1. After the liquid level reaches 50%, boron trifluoride gas or boron trifluoride ether catalyst is introduced through the flow meter. The amount of effective components in the catalyst is 1.5% of the active components in the raw materials. The temperature of the continuous polymerization kettle No. 1 is controlled at 5°C, and the temperature of the No. 2 kettle is controlled at 8°C. The residence time of the No. 1 and No. 2 kettles is 8h each. After the raw materials are fully polymerized, the polymerization liquid enters into a continuous alkali washing and water washing tank to remove the catalyst, and the obtained monomer resin liquid is passed through a flash tower to remove the solvent and oligomers, wherein the vacuum degree is controlled at above 0.095 MPa, the distillation temperature is 250°C, and after adding 0.2wt% of antioxidant 1010, the bio-based monomer resin can be obtained.

[0070] Comparative Example 3

[0071] Raw material preparation: α-methylstyrene: styrene: vinyltoluene are prepared into raw material A in a mass ratio of 1:0.9:0.8, and then diluted with toluene, wherein the dilution solvent toluene accounts for 60% of the total weight of the ingredients. The prepared raw materials are added to the raw material tank, and the pressure is maintained at 0.3Mpa after being replaced with nitrogen three times. The feed pump is started to add the raw materials to the continuous polymerization kettle No. 1. After the liquid level reaches 50%, boron trifluoride gas or boron trifluoride ether catalyst is introduced through the flow meter. The amount of effective components in the catalyst is 2% of the active components in the raw materials. The temperature of the continuous polymerization kettle No. 1 is controlled at -10°C, and the temperature of the No. 2 kettle is -5°C. The residence time of the No. 1 and No. 2 kettles is 10h each. After the raw materials are fully polymerized, the polymerization liquid enters into a continuous alkali washing and water washing tank to remove the catalyst, and the obtained monomer resin liquid is passed through a flash tower to remove the solvent and oligomers, wherein the vacuum degree is controlled at above 0.095 MPa, the distillation temperature is 260°C, and after adding 0.2wt% of antioxidant 1010, the bio-based monomer resin can be obtained.

[0072] The monomer resins prepared in Examples 1-3 and Comparative Example 1 are applied in the field of casting wax, and the test contents are as follows: petroleum resin gel GPC molecular weight, compatibility, surface hardness (needle penetration, which refers to the depth of a standard needle penetrating a sample under a load of 100 g for 5 seconds), fluidity (viscosity, 90°C, MPa / s), linear shrinkage, flexural strength, and ash content.

[0073] The casting wax was tested for performance. The test method is as follows. The test results are shown in Table 1.

[0074] The flexural strength test method in the present invention is "Method for Determination of Flexural Strength of Investment Casting Mold Materials (GB / T14235.2-1993)".

[0075] The surface hardness test method in the present invention is "Asphalt Penetration Test Method" (GB / T 4509-2010).

[0076] The method for testing the linear shrinkage rate of the present invention is "Method for Determining the Linear Shrinkage Rate of Investment Casting Mold Materials (GB / T 14235.4-93)".

[0077] Table 1

[0078]

[0079]

[0080] It can be seen from the mold material performance test results in Table 1 that, compared with Comparative Example 1 and commercially available standard samples, the mold material configured with the modified bio-based monomer resin in the embodiment of the present invention has a lower wax cloud point and linear shrinkage, and the surface hardness and flexural strength are improved, which can meet the precision requirements of precision castings. However, in Examples 1-3, as the introduction ratio of the bio-based anhydride monomer increases, the configured mold material has an improved surface hardness, but the mold material becomes brittle and the flexural strength deteriorates. At the same time, the modified bio-based monomer resin obtained in the embodiment of the present invention has improved compatibility with paraffin wax, etc., which can significantly improve the precipitation of materials during the heating and demolding process of the mold material, and avoid leaving residues on the inner wall of the demolding to affect the quality of the mold. At the same time, the mold material configured with the modified bio-based monomer resin has a lower viscosity at high temperature, which can reduce the residue during the demolding process.

[0081] The monomer resins prepared in Examples 4-6 and Comparative Example 2 are applied in the field of rubber mixing, and the test contents are as follows: Shore hardness, Mooney viscosity, Mooney scorch, rheological properties, initial stretch, aging stretch, glass transition temperature (Tg), loss factor, DIN abrasion test, etc.

[0082] The performance test of the mixed rubber was carried out as follows. The test results are shown in Table 2.

[0083] The Shore A hardness (Type A) test method in the present invention is the "Vulcanized Rubber Shore A Hardness Test Method (GB / T531)".

[0084] The Mooney viscosity test method in the present invention is "Determination of Mooney viscosity of unvulcanized rubber (GB / T 1232)".

[0085] The Mooney scorch test method in the present invention is "Extrusion plastometer to measure the melt flow rate of thermoplastics (STMD1238)".

[0086] The tensile property test method in the present invention is "Rubber Tensile Property Test Method (GB / T 531-1999)".

[0087] The DIN abrasion test method in the present invention is "Method for Determination of Wear Resistance of Vulcanized Rubber or Thermoplastic Rubber (GB / T9867-2008)".

[0088] Table 2

[0089]

[0090]

[0091]

[0092] From the test data in Table 2 above, it can be seen that compared with Comparative Example 2 and the commercially available standard sample, after the modified bio-based monomer resin obtained in Examples 4-6 of the present invention is added to the tire rubber, the hardness of the rubber is increased, and the DIN wear of the tire is significantly reduced, indicating that the proportion of grafted bio-based anhydride in the monomer resin is increased, which can improve the wear resistance of the tire. At the same time, the glass transition temperature is low, and the loss factor (0℃tanδ) can effectively improve the anti-wet skid ability of the tire as the addition ratio of the bio-based anhydride monomer increases, but as the addition ratio further increases, the anti-wet skid ability of the loss factor (0℃tanδ) decreases, and the rolling resistance of the loss factor (60℃tanδ) increases, resulting in poor tire performance.

[0093] Therefore, the modified bio-based monomer resin prepared by the present invention is used in tire rubber, and its wear resistance is significantly improved. When the addition ratio of bio-based acid anhydride is controlled within a certain range, the anti-slip performance and rolling resistance of the tire can be improved.

[0094] The monomer resins prepared in Examples 7-9 and Comparative Example 3 are mainly used in the field of adhesives, mainly in improving the viscosity and cohesive strength of the adhesives, thereby improving the performance of the adhesives. The test contents are as follows: initial adhesion, lasting adhesion, peel strength, etc.

[0095] The performance test of the hot melt adhesive is carried out as follows. The test results are shown in Table 3.

[0096] The initial adhesion test method in the present invention is "GB / T 31125-2014 Ring initial adhesion test method".

[0097] The peel strength test method in the present invention is "GB / T2792-2014 Test method for peel strength of adhesive tape".

[0098] The test method for the holding force in the present invention is "GB / T 4851-2014 Test method for holding force of adhesive tape".

[0099] Table 3

[0100]

[0101]

[0102] According to the performance test results in Table 3, the peel strength and holding force of the hot melt adhesives prepared from Examples 7-9, Comparative Example 3 and the commercially available standard sample E-140 show an increasing trend as the proportion of bio-based anhydride increases. With the increase of the acid value, the holding force and peel strength are significantly improved, mainly because the carboxyl group can react chemically with the conjugated double bonds in SIS to improve the bonding effect, indicating that after the monomer resin is modified with bio-based anhydride, the viscosity and cohesive strength of the adhesive can be improved, thereby improving the performance of the adhesive. However, the initial adhesion of the adhesive decreases as the proportion of bio-based anhydride increases, but the adhesive prepared by adding 3-5% bio-based anhydride to obtain a modified bio-based monomer resin still has better initial adhesion than the unmodified monomer resin. Therefore, the hot melt pressure-sensitive adhesive of the present invention has good peel strength and initial adhesion strength.

[0103] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A modified bio-based monomer resin, characterized in that: At least one of alpha-methylstyrene, styrene and vinyltoluene is used as a raw material to prepare a monomer petroleum resin, and then a bio-based acid anhydride is introduced for graft modification to obtain a modified bio-based monomer resin.

2. The modified bio-based monomer resin according to claim 1, characterized in that: The bio-based acid anhydride is one or more of itaconic anhydride and citraconic anhydride.

3. A method for preparing a modified bio-based monomer resin, comprising the following steps: (1) mixing at least one of α-methylstyrene, styrene and vinyltoluene with an aromatic solvent in proportion, and conveying the mixture to a first polymerization kettle via a pump, adding a catalyst to the first polymerization kettle, and overflowing the resin liquid obtained from the first polymerization kettle to a second polymerization kettle via a pipeline to continue heat preservation polymerization, removing the catalyst from the resin liquid produced from the second polymerization kettle, and flash evaporating and dehydrating the mixture to obtain a monomer resin liquid; (2) dissolving the bio-based acid anhydride and the initiator in an aromatic hydrocarbon solvent and adding the dissolved bio-based acid anhydride and the initiator to the monomer resin liquid obtained in step (1), and placing the dissolved bio-based acid anhydride and the initiator in a shell-and-tube reactor to generate a free radical reaction, thereby obtaining a modified bio-based monomer resin liquid; the resin liquid material is passed through a flash tower to remove the solvent, unreacted bio-based acid anhydride and oligomers, an antioxidant is added to the molten resin in the bottom of the tower, and the modified bio-based monomer resin is obtained through granulation.

4. The preparation method according to claim 3, characterized in that: The aromatic hydrocarbon solvent in step (1) is selected from one or more of toluene, xylene, trimethylbenzene, and Solvesso 100# solvent oil; the aromatic hydrocarbon solvent accounts for 60-75wt% of the total feed amount.

5. The preparation method according to claim 3, characterized in that: The catalyst in step (1) is boron trifluoride gas or boron trifluoride ether; the amount of the catalyst added is 1 to 2 wt% of the total amount of α-methylstyrene, styrene and vinyltoluene in the total material.

6. The preparation method according to claim 3, characterized in that: The polymerization temperature of the first polymerization kettle in the step (1) is -5 to 15°C, the polymerization temperature of the second polymerization kettle is 5 to 25°C, and the total polymerization time is 10 to 25 hours.

7. The preparation method according to claim 3, characterized in that: The initiator in step (2) is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dicumyl peroxide, benzoyl peroxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, and diisopropyl peroxydicarbonate.

8. Use of the modified bio-based monomer resin according to claim 1 in casting wax.

9. Use of the modified bio-based monomer resin as claimed in claim 1 in tire rubber.

10. Use of the modified bio-based monomer resin according to claim 1 in a hot melt adhesive.

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