Alkyl phenolic resin for improving adhesive property of GLR rubber adhesive and preparation method thereof

Abstract

The invention discloses an alkyl phenolic resin for improving the bonding performance of a GLR rubber adhesive and a preparation method thereof, and relates to the technical field of phenolic resin preparation, the alkyl phenolic resin comprises the following raw materials by weight: 60-70 parts of modified resin, 15-20 parts of modified EPDM, 2-4 parts of carbon fiber, 5-7 parts of naphthenic oil, and 0.8-1.0 part of an anti-aging agent. The modified resin is obtained by carrying out reaction grafting on methyl 3-dodecylthio-propionate, 5-amino-2-hydroxycycloheptyl-2, 4, 6-triene-1-ketone, punicic acid and the like, and then blending with alkyl phenolic resin. The modified EPDM is obtained by grafting a functional monomer and EPDM, wherein the functional monomer contains imidazole, amino, piperazine, phosphamide, hydroxyl and terminal carbon-carbon double bonds. The prepared alkyl phenolic resin has good corrosion resistance, toughness, antibacterial property, adhesion, oil resistance and flame retardance, and is worthy of popularization and application.

Description

Technical Field

[0001] The present invention relates to the technical field of phenolic resin preparation, and particularly relates to an alkyl phenolic resin for improving the bonding performance of GLR rubber adhesives and a preparation method thereof. Background Art

[0002] Adding alkyl phenolic resin to GLR rubber adhesives can significantly improve the bonding strength, durability and application range. However, the dense three-dimensional network structure and rigid skeleton in alkyl phenolic resin limit the movement of molecular segments, resulting in high elastic modulus and brittleness of the material, reducing the toughness of alkyl phenolic resin and restricting its use in GLR rubber adhesives.

[0003] After mixing ethylene propylene diene monomer (EPDM) with phenolic resin, the flexible main chain of EPDM can offset the rigidity of phenolic resin, reduce the brittleness of the material, absorb energy through the crazing-shear band mechanism under the action of external force impact, and inhibit crack propagation, thereby improving toughness. However, the compatibility between EPDM and alkyl phenolic resin is poor, and EPDM itself has poor oil resistance, flame retardancy, and poor adhesion to metal and polar polymer substrates, which has an adverse effect on the adhesion of alkyl phenolic resin, resulting in its inapplicability to improving the adhesion performance between steel cord and rubber in automotive rubber tires. When GLR rubber adhesives are used in antibacterial applications such as medical devices, food packaging, refrigerator seals, and automotive seals, higher requirements are put forward for the antibacterial properties of alkyl phenolic resin.

[0004] Therefore, it is necessary to develop appropriate modification methods to make up for the insufficient toughness of alkyl phenolic resin, improve the defects of poor oil resistance, flame retardancy and adhesion of EPDM, and at the same time enhance the antibacterial properties of alkyl phenolic resin, so as to obtain an alkyl phenolic resin with excellent comprehensive properties such as improving the adhesion performance between steel cord and rubber in automotive rubber tires. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides an alkyl phenolic resin for improving the bonding performance of GLR rubber adhesives and a preparation method thereof.

[0006] The object of the present invention can be achieved by the following technical solutions: An alkyl phenolic resin for improving the bonding performance of GLR rubber adhesives, comprising the following raw materials in parts by weight: 60-70 parts of modified resin, 15-20 parts of modified EPDM, 2-4 parts of carbon fiber, 5-7 parts of naphthenic oil, and 0.8-1.0 part of antioxidant; The antioxidant is antioxidant RD; The alkylphenolic resin for improving the bonding performance of GLR rubber adhesive is prepared by the following steps: stirring modified resin, modified EPDM, carbon fiber, naphthenic oil and antioxidant at 130-140 °C for 15-20 min to obtain the alkylphenolic resin for improving the bonding performance of GLR rubber adhesive; The preparation of the modified resin includes the following steps: Step A1: Under the atmosphere of protective gas, reflux and stir methyl 3-dodecylthiopropionate, raise the temperature and stir, then cool down, add methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one and sodium methoxide, and stir to obtain Product 1; Step A2: Mix and stir Product 1, toluene and Alkaline Solution 1, and react with epichlorohydrin to obtain Product 2; Step A3: Under the atmosphere of protective gas, mix punicic acid, toluene and pyridine, then add Product 2, and stir to obtain Product 3; mix and stir Product 3, toluene and Alkaline Solution 2, then add epichlorohydrin and stir to obtain Product 4; Step A4: Add Product 4 and alkylphenolic resin into methanol, then add trimethylamine and stir to obtain the modified resin; Further, the preparation of the modified resin includes the following specific steps: Step A1: Under the atmosphere of protective gas, reflux and stir methyl 3-dodecylthiopropionate, raise the temperature to 100-110 °C, continue to stir for 30-40 min, then cool down to 55-60 °C, add methanol and 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one, then add sodium methoxide, and stir and react for 24-25 h to obtain Product 1; Further, the dosage ratio of methyl 3-dodecylthiopropionate, methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one and sodium methoxide is 29.5-30.5 g: 95-105 mL: 14-15 g: 1-2 g; During the reaction of Step A1, an ammonolysis reaction occurs between methyl 3-dodecylthiopropionate and the amino group of 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one to obtain Product 1 containing a thioether-containing alkane long chain and a hydroxy-containing cycloheptenone; Step A2: Add Product 1 to toluene, start stirring, then add Alkaline Solution 1, stir for 5-10 min, then add epichlorohydrin, and stir and react at room temperature for 7-7.5 h to obtain Product 2; Further, the dosage ratio of Product 1, toluene, Alkaline Solution 1 and epichlorohydrin is 45-47 g: 110-120 mL: 4-6 mL: 10-10.5 g; Alkaline Solution 1 is a sodium hydroxide solution with a mass fraction of 10-15%; During the reaction of step A2, the hydroxyl group on the cycloheptenone in product 1 reacts with epichlorohydrin to obtain product 2 containing an alkane long chain with a thioether and a cycloheptenone containing an epoxy group; Step A3: Under an inert gas atmosphere, stir and add punicic acid to toluene, heat up to 45 - 50 °C, add pyridine, then add product 2, stir and react for 9 - 10 h, then heat up to 110 - 120 °C and stir for 1 - 1.5 h to obtain product 3; After mixing and stirring product 3, toluene, and lye 2, add epichlorohydrin and stir and react at 40 - 45 °C for 6 - 7 h to obtain product 4; Furthermore, the dosage ratio of punicic acid, toluene, pyridine, and product 2 is 28 - 28.5 g : 160 - 170 mL : 0.8 - 0.9 g : 48 - 50 g; The dosage ratio of product 3, toluene, lye 2, and epichlorohydrin is 77 - 79 g : 190 - 200 mL : 15 - 20 mL : 14 - 15 g; Lye 2 is a sodium hydroxide solution with a mass fraction of 5 - 10%; During the reaction of step A3, the epoxy group of punicic acid and product 2 undergoes ring opening to obtain product 3 containing a hydroxyl group; The hydroxyl group of product 3 then reacts with epichlorohydrin to obtain product 4 containing an alkane long chain with a thioether, an alkane long chain with three conjugated double bonds, a cycloheptenone, and an epoxy group; Step A4: Add product 4 and alkylphenolic resin to methanol, then add trimethylamine, and reflux and stir and react at 110 - 120 °C for 4 - 4.5 h to obtain a modified resin; Furthermore, the dosage ratio of product 4, alkylphenolic resin, methanol, and trimethylamine is 45 - 47 g : 20 - 25 g : 150 - 160 mL : 2 - 3 g; During the reaction of step A4, the epoxy group on product 4 reacts with the hydroxymethyl group and phenolic hydroxyl group in the alkylphenolic resin to obtain a modified resin.

[0007] The preparation of the modified EPDM includes the following steps: Step B1: Mix 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride and tetrahydrofuran and adjust the pH to neutral, add diallyl chlorophosphate and triethylamine and stir to obtain product a; Step B2: Mix product a, toluene, and 3-chloroperoxybenzoic acid and stir to obtain product b; Under an inert gas atmosphere, mix 3-methylbut-3-enoic acid and toluene, add pyridine, then add product b and stir to obtain product c; Step B3: Mix product c, a hydrochloric acid solution of stannous chloride, and ethanol and stir to obtain a functional monomer; Mix EPDM, the functional monomer, and dicumyl peroxide and heat and melt to obtain modified EPDM; Furthermore, the preparation of the modified EPDM includes the following specific steps: Step B1: Mix 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride with tetrahydrofuran, adjust the pH to neutral, then, under an ice-water bath, add diallyl chlorophosphate and triethylamine and continue refluxing and stirring for 2 - 2.5 h. Then raise the temperature to 110 - 120 °C and continue refluxing and stirring for 1 - 1.5 h. Filter, wash with deionized water, and dry to obtain product a; Furthermore, the dosage ratio of 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride, tetrahydrofuran, diallyl chlorophosphate, and triethylamine is 31.5 - 32.5 g : 130 - 140 mL : 20 - 21 g : 22 - 24 g; the 0.1 mol / L sodium hydroxide solution is used to adjust the pH; During the reaction process of Step B1, the secondary amino group in 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride reacts with diallyl chlorophosphate to obtain product a containing imidazole, nitro, piperazine, phosphoramide, and terminal carbon-carbon double bond; Step B2: Mix product a with toluene and stir for 35 - 45 min, then add 3-chloroperoxybenzoic acid and stir at room temperature for 6 - 6.5 h to obtain product b; Under an inert gas atmosphere, stir and add 3-methylbut-3-enoic acid to toluene, raise the temperature to 45 - 50 °C, add pyridine, then add product b, stir and react for 9 - 9.5 h, then raise the temperature to 100 - 110 °C and stir for 1 - 1.5 h to obtain product c; Furthermore, the dosage ratio of product a, toluene, and 3-chloroperoxybenzoic acid is 53 - 55 g : 180 - 190 mL : 35 - 36 g; the dosage ratio of 3-methylbut-3-enoic acid, toluene, pyridine, and product b is 22 - 24 g : 160 - 170 mL : 0.4 - 0.6 g : 56 - 58 g; During the reaction process of Step B2, the terminal carbon-carbon double bond of product a is oxidized to an epoxy group to obtain product b; The epoxy group of product b undergoes ring-opening reaction with 3-methylbut-3-enoic acid to obtain product c containing imidazole, nitro, piperazine, phosphoramide, hydroxyl, and terminal carbon-carbon double bond; Step B3: Mix product c, hydrochloric acid solution of stannous chloride, and ethanol, then reflux and stir at 70 - 80 °C for 6 - 6.5 h to obtain the functional monomer; Mix EPDM, the functional monomer, and dicumyl peroxide and stir for 30 - 40 min, then heat and melt at 150 - 160 °C for 40 - 45 min to obtain modified EPDM; Furthermore, the dosage ratio of product c, stannous chloride hydrochloric acid solution, and ethanol is 80 - 82 g : 6 - 8 mL : 160 - 170 mL; the concentration of the stannous chloride hydrochloric acid solution is 0.1 g / mL, and the volume fraction of ethanol is 95%; the dosage ratio of EPDM, functional monomer, and dicumyl peroxide is 100 - 105 g : 3 - 5 g : 0.6 - 0.8 g; During the reaction in step B3, the nitro group in product c is selectively reduced to an amino group, obtaining a functional monomer containing imidazole, amino group, piperazine, phosphoramide, hydroxyl group, and terminal carbon-carbon double bond; under the initiation of dicumyl peroxide, the functional monomer is melt-grafted with EPDM to obtain modified EPDM.

[0008] The beneficial effects of the present invention: The present invention discloses an alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive and its preparation method. The alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive is prepared from raw materials such as modified resin, modified EPDM, naphthenic oil, antioxidant, etc.

[0009] The modified resin is obtained by blending product 4 containing a long alkane chain with thioether, a long alkane chain with three conjugated double bonds, cycloheptenone, and epoxy group, which is obtained by reacting methyl 3-dodecylthiopropionate, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one, punicic acid, etc., with an alkylphenolic resin; due to the synergistic hydrophobic effect of cycloheptenone, long alkane chain, and long alkane chain with three conjugated double bonds, combined with the corrosion resistance of thioether, the corrosion resistance of the prepared alkylphenolic resin is significantly improved; the long alkane chain with thioether and the long alkane chain with three conjugated double bonds have strong flexibility, which can synergistically toughen the modified resin and enhance the impact strength of the prepared alkylphenolic resin; the hydroxyl group of 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one is epoxidized and then grafted with punicic acid, enhancing its own stability and also avoiding the adverse effects of pH changes on the antibacterial properties of cycloheptenone and punicic acid. The three conjugated double bonds in cycloheptenone and punicic acid synergistically antibacterial, endowing the prepared alkylphenolic resin with strong antibacterial properties.

[0010] The modified EPDM is obtained by grafting a functional monomer containing terminal carbon-carbon double bonds, imidazole, piperazine, hydroxyl groups, amino groups and phosphoramide, which is obtained by reacting 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride, diallyl chlorophosphate, 3-methylbut-3-enoic acid, etc., with EPDM; imidazole and piperazine can complex with metals to enhance the adhesion between the prepared alkylphenolic resin and the metal substrate; hydroxyl groups and amino groups can not only enhance the polarity of the modified EPDM molecular chain and the interfacial compatibility between the modified EPDM and the modified resin, thereby enhancing the oil resistance of the prepared alkylphenolic resin and the adhesion to the polar polymer substrate, but also complex with metals to enhance the adhesion between the prepared alkylphenolic resin and the metal substrate; phosphoramide and the nitrogen element with a relatively high content in imidazole and piperazine can not only promote the formation of a dense carbon layer to inhibit combustion, but also form a large amount of nitrogen-containing non-combustible gases to dilute combustible gases, forming a good flame retardant barrier in the condensed phase and the gas phase, and endowing the prepared alkylphenolic resin with good flame retardancy. Detailed implementation mode

[0011] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0012] Example 1 A modified resin, the preparation of which comprises the following steps: Step A1: In a nitrogen atmosphere, methyl 3-dodecylthiopropionate (CAS No. 19759-75-2, supplier: Dayang Chem (Hangzhou) Co., Ltd.) is heated to 100 °C under reflux stirring, and stirring is continued for 30 min, then cooled to 55 °C, methanol and 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one are added, and then sodium methoxide is added, and the reaction is stirred for 24 h to obtain Product 1; the dosage ratio of methyl 3-dodecylthiopropionate, methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one and sodium methoxide is 29.5 g: 95 mL: 14 g: 1 g; Step A2: Product 1 is added to toluene, stirring is started, and then alkali solution 1 is added. After stirring for 5 min, epichlorohydrin is added, and the reaction is stirred at room temperature for 7 h to obtain Product 2; the dosage ratio of Product 1, toluene, alkali solution 1, and epichlorohydrin is 45 g: 110 mL: 4 mL: 10 g; alkali solution 1 is a sodium hydroxide solution with a mass fraction of 10%. Step A3: Under a nitrogen atmosphere, stir and add punicic acid to toluene, heat up to 45 °C, add pyridine, then add Product 2, stir and react for 9 h, then heat up to 110 °C and stir for 1 h to obtain Product 3; After mixing and stirring Product 3, toluene, and Alkaline Solution 2, add epichlorohydrin and stir and react at 40 °C for 6 h to obtain Product 4; The dosage ratio of punicic acid, toluene, pyridine, and Product 2 is 28 g: 160 mL: 0.8 g: 48 g; The dosage ratio of Product 3, toluene, Alkaline Solution 2, and epichlorohydrin is 77 g: 190 mL: 15 mL: 14 g; Alkaline Solution 2 is a sodium hydroxide solution with a mass fraction of 5%; Step A4: Add Product 4 and alkylphenolic resin (Supplier: Shandong Apu Chemical Technology Co., Ltd.) to methanol, then add trimethylamine, and reflux and stir and react at 110 °C for 4 h to obtain a modified resin; The dosage ratio of Product 4, alkylphenolic resin, methanol, and trimethylamine is 45 g: 20 g: 150 mL: 2 g.

[0013] Example 2 A modified resin, the preparation of which comprises the following steps: Step A1: Under a nitrogen atmosphere, heat methyl 3-dodecylthiopropionate (CAS No. 19759-75-2, Supplier: Dayang Chem (Hangzhou) Co., Ltd.) to 105 °C with reflux stirring, continue stirring for 35 min, then cool down to 58 °C and add methanol and 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one, then add sodium methoxide, and stir and react for 24.5 h to obtain Product 1; The dosage ratio of methyl 3-dodecylthiopropionate, methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one, and sodium methoxide is 30.0 g: 100 mL: 14.5 g: 1.5 g; Step A2: Add Product 1 to toluene, start stirring, then add Alkaline Solution 1, stir for 8 min, then add epichlorohydrin, and stir and react at room temperature for 7.3 h to obtain Product 2; The dosage ratio of Product 1, toluene, Alkaline Solution 1, and epichlorohydrin is 46 g: 115 mL: 5 mL: 10.3 g; Alkaline Solution 1 is a sodium hydroxide solution with a mass fraction of 13%; Step A3: Under a nitrogen atmosphere, stir and add punicic acid to toluene. Heat up to 48 °C, add pyridine, then add Product 2. Stir and react for 9.5 h, then heat up to 115 °C and stir for 1.3 h to obtain Product 3. After mixing and stirring Product 3, toluene, and Alkaline Solution 2, add epichlorohydrin and stir and react at 43 °C for 6.5 h to obtain Product 4. The dosage ratio of punicic acid, toluene, pyridine, and Product 2 is 28.3 g: 165 mL: 0.85 g: 49 g; the dosage ratio of Product 3, toluene, Alkaline Solution 2, and epichlorohydrin is 78 g: 195 mL: 18 mL: 14.5 g; Alkaline Solution 2 is a sodium hydroxide solution with a mass fraction of 8%. Step A4: Add Product 4 and alkylphenol formaldehyde resin (Supplier: Shandong Apu Chemical Technology Co., Ltd.) to methanol, then add trimethylamine, and reflux and stir and react at 115 °C for 4.3 h to obtain a modified resin. The dosage ratio of Product 4, alkylphenol formaldehyde resin, methanol, and trimethylamine is 46 g: 23 g: 155 mL: 2.5 g.

[0014] Example 3 A modified resin, the preparation of which comprises the following steps: Step A1: Under a nitrogen atmosphere, heat methyl 3-dodecylthiopropionate (CAS No. 19759-75-2, Supplier: Dayang Chem (Hangzhou) Co., Ltd.) to 110 °C with reflux stirring, continue stirring for 40 min, then cool down to 60 °C and add methanol and 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one, and then add sodium methoxide, and stir and react for 25 h to obtain Product 1. The dosage ratio of methyl 3-dodecylthiopropionate, methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one, and sodium methoxide is 30.5 g: 105 mL: 15 g: 2 g; Step A2: Add Product 1 to toluene, start stirring, then add Alkaline Solution 1, stir for 10 min, then add epichlorohydrin, and stir and react at room temperature for 7.5 h to obtain Product 2. The dosage ratio of Product 1, toluene, Alkaline Solution 1, and epichlorohydrin is 47 g: 120 mL: 6 mL: 10.5 g; Alkaline Solution 1 is a sodium hydroxide solution with a mass fraction of 15%. Step A3: Under a nitrogen atmosphere, stir and add punicic acid to toluene. Heat the mixture to 50°C, add pyridine, then add Product 2. Stir and react for 10 h, then heat to 120°C and stir for 1.5 h to obtain Product 3. After mixing and stirring Product 3, toluene, and Alkaline Solution 2, add epichlorohydrin and stir and react at 45°C for 7 h to obtain Product 4. The dosage ratio of punicic acid, toluene, pyridine, and Product 2 is 28.5 g: 170 mL: 0.9 g: 50 g. The dosage ratio of Product 3, toluene, Alkaline Solution 2, and epichlorohydrin is 79 g: 200 mL: 20 mL: 15 g. Alkaline Solution 2 is a 10% sodium hydroxide solution by mass. Step A4: Add Product 4 and alkylphenolic resin (Supplier: Shandong Apu Chemical Technology Co., Ltd.) to methanol, then add trimethylamine, and reflux and stir and react at 120°C for 4.5 h to obtain a modified resin. The dosage ratio of Product 4, alkylphenolic resin, methanol, and trimethylamine is 47 g: 25 g: 160 mL: 3 g.

[0015] Example 4 A modified EPDM, the preparation of which comprises the following steps: Step B1: Mix 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride and tetrahydrofuran, adjust the pH to neutral, then under an ice-water bath, add diallyl chlorophosphate and triethylamine and continue to reflux and stir for 2 h. Then heat to 110°C and continue to reflux and stir for 1 h. Filter, wash with deionized water, and dry to obtain Product a. The dosage ratio of 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride, tetrahydrofuran, diallyl chlorophosphate, and triethylamine is 31.5 g: 130 mL: 20 g: 22 g. The 0.1 mol / L sodium hydroxide solution is used to adjust the pH. Step B2: After mixing and stirring Product a and toluene for 35 min, add 3-chloroperoxybenzoic acid and stir at room temperature for 6 h to obtain Product b. Under a nitrogen atmosphere, stir and add 3-methylbut-3-enoic acid to toluene. Heat the mixture to 45°C, add pyridine, then add Product b, stir and react for 9 h, then heat to 100°C and stir for 1 h to obtain Product c. The dosage ratio of Product a, toluene, and 3-chloroperoxybenzoic acid is 53 g: 180 mL: 35 g. The dosage ratio of 3-methylbut-3-enoic acid, toluene, pyridine, and Product b is 22 g: 160 mL: 0.4 g: 56 g. Step B3: Mix product c, a hydrochloric acid solution of stannous chloride, and ethanol, and then reflux and stir the mixture at 70 °C for 6 h to obtain a functional monomer; mix EPDM, the functional monomer, and dicumyl peroxide and stir for 30 min, and then heat and melt the mixture at 150 °C for 40 min to obtain modified EPDM; the dosage ratio of product c, the hydrochloric acid solution of stannous chloride, and ethanol is 80 g: 6 mL: 160 mL; the concentration of the hydrochloric acid solution of stannous chloride is 0.1 g / mL, and the volume fraction of ethanol is 95%; the dosage ratio of EPDM, the functional monomer, and dicumyl peroxide is 100 g: 3 g: 0.6 g.

[0016] Example 5 A modified EPDM, the preparation of which comprises the following steps: Step B1: Mix 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride and tetrahydrofuran, adjust the pH to neutral, then add diallyl chlorophosphate and triethylamine under an ice-water bath and continue to reflux and stir for 2.3 h, then raise the temperature to 115 °C and continue to reflux and stir for 1.3 h, filter, wash with deionized water, and dry to obtain product a; the dosage ratio of 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride, tetrahydrofuran, diallyl chlorophosphate, and triethylamine is 32.0 g: 135 mL: 20.5 g: 23 g; the 0.1 mol / L sodium hydroxide solution is used to adjust the pH. Step B2: Mix product a and toluene and stir for 40 min, then add 3-chloroperoxybenzoic acid and stir at room temperature for 6.3 h to obtain product b; under a nitrogen atmosphere, stir and add 3-methylbut-3-enoic acid to toluene, raise the temperature to 48 °C, add pyridine, then add product b, stir and react for 9.3 h, and then raise the temperature to 105 °C and stir for 1.3 h to obtain product c; the dosage ratio of product a, toluene, and 3-chloroperoxybenzoic acid is 54 g: 185 mL: 35.5 g; the dosage ratio of 3-methylbut-3-enoic acid, toluene, pyridine, and product b is 23 g: 165 mL: 0.5 g: 57 g. Step B3: Mix product c, a hydrochloric acid solution of stannous chloride, and ethanol, and then reflux and stir the mixture at 75 °C for 6.3 h to obtain a functional monomer; mix EPDM, the functional monomer, and dicumyl peroxide and stir for 35 min, and then heat and melt the mixture at 155 °C for 43 min to obtain modified EPDM; the dosage ratio of product c, the hydrochloric acid solution of stannous chloride, and ethanol is 81 g: 7 mL: 165 mL; the concentration of the hydrochloric acid solution of stannous chloride is 0.1 g / mL, and the volume fraction of ethanol is 95%; the dosage ratio of EPDM, the functional monomer, and dicumyl peroxide is 103 g: 4 g: 0.7 g.

[0017] Example 6 A modified EPDM, the preparation of which comprises the following steps: Step B1: Mix 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride with tetrahydrofuran, adjust the pH to neutral, then under an ice-water bath, add diallyl chlorophosphate and triethylamine and continue refluxing and stirring for 2.5 h, then raise the temperature to 120 °C and continue refluxing and stirring for 1.5 h, filter, wash with deionized water, and dry to obtain product a; the dosage ratio of 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride, tetrahydrofuran, diallyl chlorophosphate, and triethylamine is 32.5 g: 140 mL: 21 g: 24 g; the 0.1 mol / L sodium hydroxide solution is used to adjust the pH; Step B2: Mix product a with toluene and stir for 45 min, then add 3-chloroperoxybenzoic acid and stir at room temperature for 6.5 h to obtain product b; under a nitrogen atmosphere, stir and add 3-methylbut-3-enoic acid to toluene, raise the temperature to 50 °C, add pyridine, then add product b, stir and react for 9.5 h, then raise the temperature to 110 °C and stir for 1.5 h to obtain product c; the dosage ratio of product a, toluene, and 3-chloroperoxybenzoic acid is 55 g: 190 mL: 36 g; the dosage ratio of 3-methylbut-3-enoic acid, toluene, pyridine, and product b is 24 g: 170 mL: 0.6 g: 58 g; Step B3: Mix product c with a hydrochloric acid solution of stannous chloride and ethanol, and reflux and stir at 80 °C for 6.5 h to obtain a functional monomer; mix EPDM, the functional monomer, and dicumyl peroxide and stir for 40 min, then heat and melt at 160 °C for 45 min to obtain the modified EPDM; the dosage ratio of product c, the hydrochloric acid solution of stannous chloride, and ethanol is 82 g: 8 mL: 170 mL; the concentration of the hydrochloric acid solution of stannous chloride is 0.1 g / mL, and the volume fraction of ethanol is 95%; the dosage ratio of EPDM, the functional monomer, and dicumyl peroxide is 105 g: 5 g: 0.8 g.

[0018] Example 7 An alkylphenolic resin for improving the bonding performance of GLR rubber adhesives, comprising the following raw materials in parts by weight: 60 parts of modified resin, 15 parts of modified EPDM, 2 parts of carbon fiber, 5 parts of naphthenic oil, and 0.8 part of antioxidant; the antioxidant is antioxidant RD; The preparation of the alkylphenolic resin for improving the bonding performance of GLR rubber adhesives comprises the following steps: Stir the modified EPDM obtained in Example 4, the modified resin obtained in Example 1, carbon fiber (supplier: Hangzhou Gaoke Composite Materials Co., Ltd.), naphthenic oil (supplier: Dezhou Hongchen Chemical Co., Ltd.), and antioxidant at 130 °C for 15 min to obtain the alkylphenolic resin for improving the bonding performance of GLR rubber adhesives.

[0019] Example 8 An alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive, comprising the following raw materials in parts by weight: 65 parts of modified resin, 18 parts of modified EPDM, 3 parts of carbon fiber, 6 parts of naphthenic oil, 0.9 part of antioxidant; the antioxidant is antioxidant RD; The preparation of the alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive comprises the following steps: stirring the modified EPDM obtained in Example 5, the modified resin obtained in Example 2, carbon fiber (supplier: Hangzhou Gaoke Composite Materials Co., Ltd.), naphthenic oil (supplier: Dezhou Hongchen Chemical Co., Ltd.) and antioxidant at 135 °C for 18 min to obtain the alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive.

[0020] Example 9 An alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive, comprising the following raw materials in parts by weight: 70 parts of modified resin, 20 parts of modified EPDM, 4 parts of carbon fiber, 7 parts of naphthenic oil, 1.0 part of antioxidant; the antioxidant is antioxidant RD; The preparation of the alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive comprises the following steps: stirring the modified EPDM obtained in Example 6, the modified resin obtained in Example 3, carbon fiber (supplier: Hangzhou Gaoke Composite Materials Co., Ltd.), naphthenic oil (supplier: Dezhou Hongchen Chemical Co., Ltd.) and antioxidant at 140 °C for 20 min to obtain the alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive.

[0021] Comparative Example 1 Compared with Example 9, methyl 3-dodecylthiopropionate in the preparation process of the modified resin was replaced with methyl 3-methylthiopropionate, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive.

[0022] Comparative Example 2 Compared with Example 9, punicic acid in the preparation process of the modified resin was replaced with α-linolenic acid, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive.

[0023] Comparative Example 3 Compared with Example 9, punicic acid in the preparation process of the modified resin was replaced with sorbic acid, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive.

[0024] Comparative Example 4 Compared with Example 9, product 4 in the preparation process of the modified resin was replaced with a mixture of product 1 and punicic acid used in a mass ratio of 1:1, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin for improving the adhesion performance of GLR rubber adhesive.

[0025] Comparative Example 5 Compared with Example 9, the functional monomer in the preparation process of the modified EPDM was replaced with Product c, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin that improves the adhesion performance of the GLR rubber adhesive.

[0026] Comparative Example 6 Compared with Example 9, the functional monomer in the preparation process of the modified EPDM was replaced with Product a, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin that improves the adhesion performance of the GLR rubber adhesive.

[0027] Comparative Example 7 Compared with Example 9, 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride in the preparation process of the modified EPDM was replaced with 4-nitroaniline, and the rest was exactly the same as Example 9, to obtain an alkylphenolic resin that improves the adhesion performance of the GLR rubber adhesive.

[0028] Next, further effect tests were conducted on the alkylphenolic resin prepared by the present invention to improve the adhesion performance of the GLR rubber adhesive, and the test results are as follows.

[0029] Impact strength: The impact strength of the alkylphenolic resin was tested with reference to GB / T6328-2021 "Test Method for Shear Impact Strength of Adhesives"; Corrosion resistance: A neutral salt spray test was carried out in a salt spray chamber. The solution used was a 5% sodium chloride solution by mass fraction. The size of the specimen was 150 mm × 100 mm × 1.0 mm. The test temperature was 35 °C. The specimen was placed at a 45° angle to the horizontal plane for 72 h. The weight of the specimen was weighed before and after the experiment and the weight change was calculated to calculate the corrosion rate; Corrosion rate (g / (m 2 ·h)) = weight change / (specimen exposure area × corrosion time); Antibacterial property: Using Escherichia coli and Staphylococcus aureus as the test strains, the antibacterial rate was tested with reference to QB / T2591-2023‌; Tensile shear strength: Tensile shear strength tests were carried out with reference to GB / T7124-2008 "Determination of Tensile Shear Strength of Adhesives (Rigid Material to Rigid Material)" to evaluate the adhesion. Metal steel and PET were used as substrates respectively. The length of the bonding surface was 12.5 mm, the thickness of the substrate was 2.0 mm, and the thickness of the specimens of the examples and comparative examples on the substrate was 0.2 mm. The curing conditions of the specimens of the examples and comparative examples on the substrate were 180 °C, 400 MPa, and 35 min; Oil resistance: The specimens of the examples and comparative examples were soaked in IRM standard oil for 7 d, and the retention rate of the tensile shear strength on metal steel was tested; Flammability: The limiting oxygen index of the examples and comparative examples was tested with reference to GB / T2406.2-2009; The results are recorded in Table 1; Table 1: Test Results

[0030] According to the data in Table 1, the alkylphenolic resin for improving the adhesion performance of GLR rubber adhesives of the present invention has excellent toughness, corrosion resistance, antibacterial property, adhesiveness, oil resistance and flammability. Comparing Example 9 with Comparative Example 1, it can be seen that when methyl 3-dodecylthiopropionate in the preparation process of the modified resin is replaced by methyl 3-methylthiopropionate, the synergistic hydrophobic effect decreases and the synergistic toughening effect weakens, resulting in a decrease in corrosion resistance and impact strength. Comparing Example 9 with Comparative Example 2, it can be seen that when punicic acid in the preparation process of the modified resin is replaced by α-linolenic acid, the antibacterial property weakens. Comparing Example 9 with Comparative Example 3, it can be seen that when punicic acid in the preparation process of the modified resin is replaced by sorbic acid, the antibacterial property weakens, and the synergistic hydrophobic effect and synergistic toughening effect weaken, and both corrosion resistance and impact strength decrease. Comparing Example 9 with Comparative Example 4, it can be seen that when Product 4 in the preparation process of the modified resin is replaced by a mixture of Product 1 and punicic acid in a mass ratio of 1:1, the intramolecular synergistic effect cannot be achieved, and the antibacterial property, impact strength and corrosion resistance decrease significantly. Comparing Example 9 with Comparative Example 5, it can be seen that when the functional monomer in the preparation process of the modified EPDM is replaced by Product c, that is, the nitro group of Product b is not reduced to an amino group, the enhancing effect on the oil resistance of EPDM weakens, and the adhesiveness with metal steel and polar polymer PET decreases. Comparing Example 9 with Comparative Example 6, it can be seen that when the functional monomer in the preparation process of the modified EPDM is replaced by Product a, and Product a does not contain amino and hydroxyl groups, the enhancing effect on the oil resistance of EPDM weakens more, and the adhesiveness with metal steel and polar polymer PET decreases more. Comparing Example 9 with Comparative Example 7, it can be seen that when 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride in the preparation process of the modified EPDM is replaced by 4-nitroaniline, the adhesiveness with the metal substrate decreases, the nitrogen element decreases, and the synergistic flame retardancy decreases.

[0031] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. An alkylphenol-formaldehyde resin for improving the bonding performance of a GLR rubber adhesive, characterized in that: The invention comprises the following raw materials in parts by weight: 60-70 parts of modified resin, 15-20 parts of modified EPDM, 2-4 parts of carbon fiber, 5-7 parts of naphthenic oil and 0.8-1.0 parts of antioxidant; The modified resin is prepared by the following steps: Step A1, in a protective gas atmosphere, heating 3-dodecylthiopropionic acid methyl ester with stirring and cooling, adding methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one and sodium methoxide, and stirring to obtain product 1; Step A2, mixing product 1, toluene and alkali solution 1, and reacting with epichlorohydrin to obtain product 2; Step A3, in a protective gas atmosphere, mix pomegranate acid, toluene, and pyridine, then add product 2, and stir to obtain product 3; after mixing product 3, toluene, and alkali solution 2, add epichlorohydrin, and stir to obtain product 4; Step A4, adding product 4 and alkylphenol-formaldehyde resin into methanol, and then adding trimethylamine, and stirring to obtain a modified resin.

2. The alkylphenol-formaldehyde resin for improving the bonding performance of GLR rubber adhesive according to claim 1, characterized in that: In step A1, the usage ratio of methyl 3-dodecylthiopropionate, methanol, 5-amino-2-hydroxycyclohepta-2,4,6-trien-1-one and sodium methoxide is 29.5-30.5 g: 95-105 mL: 14-15 g: 1-2 g.

3. The alkylphenol-formaldehyde resin for improving the bonding performance of GLR rubber adhesive according to claim 1, characterized in that: In step A2, the amount ratio of product 1, toluene, alkali solution 1, and epichlorohydrin is 45-47 g: 110-120 mL: 4-6 mL: 10-10.5 g; in step A4, the amount ratio of product 4, alkylphenol-formaldehyde resin, methanol, and trimethylamine is 45-47 g: 20-25 g: 150-160 mL: 2-3 g.

4. The alkylphenol-formaldehyde resin for improving the bonding performance of a GLR rubber adhesive according to claim 1, characterized in that: In step A3, the usage ratio of pomegranate acid, toluene, pyridine and product 2 is 28-28.5 g: 160-170 mL: 0.8-0.9 g: 48-50 g; the usage ratio of product 3, toluene, alkali solution 2 and epichlorohydrin is 77-79 g: 190-200 mL: 15-20 mL: 14-15 g.

5. The alkylphenol-formaldehyde resin for improving the bonding performance of GLR rubber adhesive according to claim 1, characterized in that: The modified EPDM is prepared by the following steps: Step B1, 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride and tetrahydrofuran were mixed and the pH was adjusted to neutral, and diallyl chlorophosphate and triethylamine were added and stirred to obtain product a; Step B2, mixing product a, toluene and 3-chloroperbenzoic acid and stirring to obtain product b; in a protective gas atmosphere, mixing 3-methylbut-3-enoic acid and toluene, adding pyridine, and then adding product b, stirring to obtain product c; Step B3, mixing the product c, a hydrochloric acid solution of stannous chloride and ethanol, and stirring to obtain a functional monomer; mixing EPDM, the functional monomer and dicumyl peroxide, heating and melting to obtain a modified EPDM.

6. The alkylphenol-formaldehyde resin for improving the bonding performance of GLR rubber adhesive according to claim 5, characterized in that: In step B1, the usage ratio of 1-(5-(1H-imidazol-1-yl)-2-nitrophenyl)piperazine dihydrochloride, tetrahydrofuran, diallyl chlorophosphate and triethylamine is 31.5-32.5 g: 130-140 mL: 20-21 g: 22-24 g.

7. The alkylphenol-formaldehyde resin for improving the bonding performance of GLR rubber adhesive according to claim 5, characterized in that: In step B2, the usage ratio of product a, toluene, and 3-chloroperoxybenzoic acid is 53-55 g:180-190 mL:35-36 g; the usage ratio of 3-methylbut-3-enoic acid, toluene, pyridine, and product b is 22-24 g:160-170 mL:0.4-0.6 g:56-58 g.

8. The alkylphenol-formaldehyde resin for improving the bonding performance of a GLR rubber adhesive according to claim 5, characterized in that: In step B3, the usage ratio of product c, stannous chloride hydrochloric acid solution and ethanol is 80-82 g: 6-8 mL: 160-170 mL.

9. The alkylphenol-formaldehyde resin for improving the bonding performance of GLR rubber adhesive according to claim 5, characterized in that: In step B3, the concentration of the stannous chloride hydrochloric acid solution is 0.1 g / mL; the usage ratio of EPDM, functional monomer, and dicumyl peroxide is 100-105 g: 3-5 g: 0.6-0.8 g.

10. A method for preparing an alkylphenol-formaldehyde resin for improving the bonding performance of a GLR rubber adhesive according to any one of claims 1 to 9, characterized in that: The steps include: The modified resin, modified EPDM, carbon fiber, cyclohexane oil and antioxidant are stirred at 130-140° C. for 15-20 minutes to obtain an alkylphenolic resin for improving the bonding performance of the GLR rubber adhesive.

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