Preparation method of itaconic anhydride grafted polyethylene adhesive resin master batch

Abstract

The invention relates to the technical field of polymer adhesives, in particular to a preparation method of itaconic anhydride grafted polyethylene adhesive resin master batch. The problems that gel and crystal points are easily generated in the grafting process of itaconic anhydride grafted polyethylene adhesive resin master batch, and the bonding strength of an adhesive is reduced due to the influence of high temperature are solved. According to the preparation method, itaconic anhydride is grafted into polyethylene, the variety and dosage of monomers I and II used in the grafting process are controlled, the temperature and pressure intensity of introduced carbon dioxide are changed, and the variety and dosage of an initiator in the grafting process are controlled, so that the grafting rate is increased, and the number of crystal points is reduced. The fatty alcohol alkyl glycoside is prepared, and the glycoside is grafted into itaconic anhydride grafted polyethylene, so that the bonding strength of the bonding resin master batch is improved. The surface-treated para-aramid fiber is added, and the ethylene-vinyl acetate copolymer and the antioxidant are added, so that the bonding strength of the bonding resin master batch after high-temperature treatment is high.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer adhesives, and specifically to a preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch. Background Art

[0002] Polyethylene (PE) is a common general-purpose plastic with large production volume, good performance, and low price. It has good wear resistance and chemical corrosion resistance, but its tensile property is poor, and its toughness and fatigue resistance are insufficient. Therefore, it often needs to be combined with other materials, such as adding nylon 6, to improve the overall comprehensive performance of the material. During the process of compounding polyethylene and nylon 6, due to the lack of active groups on the surface of polyethylene, its adhesion to the polar material nylon 6 is poor. Therefore, an adhesive resin needs to be introduced to improve the affinity between the two materials.

[0003] The polar monomer maleic anhydride grafted polyethylene is often used as an adhesive resin masterbatch for polyolefins and polyamides, and usually has a high grafting rate. Common grafting methods include solid-phase grafting modification, solution grafting, melt grafting, suspension grafting, and radiation grafting. Among them, the melt grafting operation method is simple and is the most widely used in industry. Patent CN118272004B discloses a polyethylene adhesive and its preparation method. The adhesive is prepared from raw materials containing polyethylene, maleic anhydride grafted polyethylene, silicon-containing benzoxazine, and antioxidant 626, and has good mechanical properties and high temperature resistance. However, maleic anhydride has a pungent smell, which affects its daily use.

[0004] Itaconic anhydride is a bio-derived monomer with low price. Compared with maleic anhydride, it has the characteristics of non-toxic, odorless, and not easy to sublimate, so it is also used as a grafting substance. The research results of the literature Verbeek R J C, Hanipah H S. Grafting itaconic anhydride onto polyethylene using extrusion[J]. Journal of Applied Polymer Science, 2010, 116(6): 3118-3126. show that by grafting and modifying linear low-density polyethylene with itaconic anhydride, changing the concentrations of the monomer and the initiator can increase the grafting rate, but it is easy to crosslink and generate gels.

[0005] Patent CN118440636A discloses an itaconic anhydride grafted polyethylene adhesive resin masterbatch and its preparation method. The itaconic anhydride grafted polyethylene adhesive resin masterbatch is prepared by reacting and extruding polyethylene, itaconic anhydride, a synergist and a peroxide initiator through a twin-screw extruder, which improves the bonding strength between polyethylene and nylon 6 and does not produce crystals and fisheyes. Among them, acrylate monomers are used as synergists, which can improve the grafting rate of itaconic anhydride and reduce the crosslinking degree. However, after the itaconic anhydride grafted polyethylene adhesive resin masterbatch is treated under a harsh high-temperature environment, the bonding strength decreases and the high-temperature resistance is poor.

[0006] In addition, alkyl glycosides are also used as adhesives to improve the adhesiveness of wear-resistant wrapping paper. For example, patent CN105038654A discloses a hot melt adhesive for wear-resistant wrapping paper, which is prepared from raw materials containing EVA, a modified tackifying resin and alkyl glycosides, and has good bonding performance and heat resistance. However, the dispersion stability of the melt adhesive components is poor, and substances such as alkyl glycosides are separated, thus reducing the bonding strength, and this hot melt adhesive is not suitable for adhesives of polyethylene and nylon 6 materials.

[0007] In the prior art, there are still problems such as low grafting rate of itaconic acid grafted modified polyethylene, easy generation of gels, low bonding strength of the prepared adhesive resin masterbatch, and poor high-temperature resistance.

[0008] Therefore, a preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch is proposed. Summary of the Invention

[0009] The purpose of the present invention is to provide a preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch. By grafting itaconic anhydride onto polyethylene, controlling the types and dosages of monomer 1 and monomer 2 used in the grafting process, adjusting the dosages of grafted itaconic acid and monomer mixture, changing the temperature and pressure of carbon dioxide introduction, and controlling the types and dosages of initiator 1 and initiator 2 in the grafting process, the grafting rate of itaconic acid is increased. As an adhesive, the itaconic anhydride grafted polyethylene adhesive resin masterbatch reduces the number of crystal points in the bonding material prepared by bonding polyethylene and nylon 6. By preparing fatty alcohol alkyl glycosides and grafting the glycosides into itaconic anhydride grafted polyethylene, the fatty alcohol alkyl glycosides are chemically bonded with itaconic acid, improving the bonding strength of the adhesive resin masterbatch and the adhesiveness to low surface activity materials. By adding surface-treated para-aramid, and then adding ethylene-vinyl acetate copolymer and antioxidant, the bonding strength of the adhesive resin masterbatch is high after high-temperature treatment and the high-temperature resistance is improved.

[0010] To achieve the above purpose, the present invention provides the following technical solutions:

[0011] On the one hand, the present invention provides a method for preparing an itaconic anhydride grafted polyethylene adhesive resin masterbatch, and the preparation method comprises the following steps:

[0012] Add 0.3 - 0.7 parts of monomer mixture and 0.4 - 1.4 parts of itaconic anhydride to molten high-density polyethylene, and stir to obtain a molten mixture; the ratio of the number of parts of monomer one to monomer two in the monomer mixture is 1 - 2:1 - 3; introduce carbon dioxide into the molten mixture, set the temperature to 150 - 165 °C, and the pressure to 60 - 80 MPa, and stir to obtain a reactant to be reacted; add 0.12 - 0.3 parts of initiator mixture to the reactant to be reacted, and react to obtain itaconic anhydride grafted polyethylene; the initiator mixture is composed of initiator one and initiator two; add 0.01 - 0.03 parts of sodium acetate and 0.30 - 0.55 parts of fatty alcohol alkyl glycoside to the itaconic anhydride grafted polyethylene, and react to obtain fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene;

[0013] Add formic acid-hydrogen peroxide solution, 0.15 - 0.25 parts of modified para-aramid, 2 - 3.5 parts of ethylene-vinyl acetate copolymer, polyethylene wax, and 0.1 - 0.2 parts of antioxidant to the fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene to obtain a mixed material; put the mixed material into a twin-screw extruder and extrude at 85 - 205 °C to obtain the itaconic anhydride grafted polyethylene adhesive resin masterbatch;

[0014] The fatty alcohol alkyl glycoside is obtained by reacting glucose with 1.5 - 2.3 parts of fatty alcohol under the catalysis of 0.01 - 0.02 parts of p-toluenesulfonic acid;

[0015] The modified para-aramid is obtained by treating para-aramid with calcium chloride dispersion liquid and sodium hydroxide alcohol solution, and then adding 0.2 - 0.6 parts of dopamine; the ratio of the number of parts of anhydrous calcium chloride to ethanol in the calcium chloride dispersion liquid is 1 - 1.5:48.5 - 49; the ratio of the number of parts of sodium hydroxide to ethanol in the sodium hydroxide alcohol solution is 1 - 2:23 - 24.

[0016] Preferably, the monomer one is one of styrene, cyclohexylmethyl dimethoxysilane, and allyl silane.

[0017] Preferably, the monomer two is one of dimethylaminoethyl acrylate, glycidyl methacrylate, glycidyl acrylate, and ethyl methacrylate.

[0018] Preferably, the initiator one is one of 2,2'-azo-bisisobutyronitrile, 4-phenylazobenzoyl chloride, azobenzene-4,4'-dicarbonyl chloride, and polyacrylonitrile.

[0019] Preferably, the initiator II is one of tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyacetate, benzoyl peroxide, and diisopropylbenzene peroxide.

[0020] Preferably, the fatty alcohol is one of stearyl alcohol, tetradecyl alcohol, lauryl alcohol, undecyl alcohol, palmityl alcohol, and hyperbranched polyester polyol.

[0021] Preferably, the antioxidant is composed of antioxidant I and antioxidant II; antioxidant I is one of antioxidant 168, antioxidant 626, and triphenyl phosphite; antioxidant II is one of antioxidant 3125, octyl gallate, and antioxidant 1098; the dosage ratio of antioxidant I to antioxidant II is 1:1.

[0022] Preferably, the preparation method of the fatty alcohol alkyl glycoside is as follows: The glucose and the fatty alcohol are mixed evenly to obtain a sugar alcohol solution, which is added to a three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser; the sugar alcohol solution is heated to 110 °C, and after reflux reaction, p-toluenesulfonic acid is added thereto, and the reaction continues for 2 h to obtain a fatty alcohol alkyl glycoside precursor; when the reaction continues for 2 h, vacuum is intermittently pumped, and the vacuum degree is 0.075 MPa; the vacuum degree of the fatty alcohol alkyl glycoside precursor is increased to 0.080 MPa, and the excess alcohol and water are removed to obtain a fatty alcohol alkyl glycoside intermediate; the fatty alcohol alkyl glycoside intermediate is cooled to 80 °C, the pH is adjusted, and then it is layered and dried to obtain the fatty alcohol alkyl glycoside.

[0023] Preferably, the preparation method of the modified para-aramid is as follows: Calcium chloride anhydrous is dispersed in the ethanol at 15 °C to obtain a calcium chloride dispersion; the para-aramid is added to the calcium chloride dispersion, stirred for 1 h and then taken out, washed with distilled water and dried to obtain a modified para-aramid precursor; sodium hydroxide alcohol solution is added to the modified para-aramid precursor, stirred for 1 h and then taken out, washed with distilled water and dried to obtain a modified para-aramid intermediate; dopamine, dicyclohexylcarbodiimide, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added to the modified para-aramid intermediate, heated and stirred for reaction, washed and dried to obtain the modified para-aramid.

[0024] On the other hand, the present invention provides an itaconic anhydride grafted polyethylene adhesive resin masterbatch, which comprises fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene, modified para-aramid, ethylene-vinyl acetate copolymer, polyethylene wax and antioxidant; the itaconic anhydride grafted polyethylene adhesive resin masterbatch is obtained by the preparation method described in any one of the above; by adjusting the types and dosages of monomer one and monomer two, the grafting rate of itaconic anhydride in the itaconic anhydride grafted polyethylene is 0.11%-0.25%, and the number of crystal points of the adhesive material prepared by bonding polyethylene and nylon 6 with the itaconic anhydride grafted polyethylene adhesive resin masterbatch as the adhesive is 13-31; by adjusting the types and dosages of initiator one and initiator two, the grafting rate of the itaconic anhydride is 0.17%-0.32%, and the number of crystal points is 8-19; by adjusting the type and dosage of fatty alcohol, and the dosages of p-toluenesulfonic acid and fatty alcohol alkyl glycoside, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch is 68.5-88.1 N / 25 mm; by changing the preparation method and dosage of the modified para-aramid, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch is 84.0-89.1 N / 25 mm, and its bonding strength after high-temperature treatment is 88.0-88.9 N / 25 mm; by adjusting the dosages of the ethylene-vinyl acetate copolymer and antioxidant, the type of antioxidant and the reaction temperature, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch is 86.0-89.3 N / 25 mm, and its bonding strength after high-temperature treatment is 89.0-89.2 N / 25 mm.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] 1. By grafting itaconic anhydride onto high-density polyethylene and further preparing an itaconic anhydride grafted polyethylene adhesive resin masterbatch, a multi-layer adhesive material is obtained by using it to bond polyethylene and nylon 6 materials, and the number of crystal points is small. By changing the types of monomer one and monomer two, changing the dosage ratio of monomer one and monomer two, changing the dosages of the monomer mixture and itaconic anhydride, and changing the temperature and pressure of the introduced carbon dioxide, the number of crystal points of the adhesive material is reduced, and the grafting rate of itaconic anhydride in the itaconic anhydride grafted polyethylene is high.

[0027] 2. By controlling the dosage of the initiator and the types of initiator one and initiator two during the preparation of the itaconic anhydride grafted polyethylene, itaconic anhydride and fatty alcohol alkyl glycoside are grafted onto the main chain of high-density polyethylene, and monomer two is promoted to copolymerize better, so that the grafting rate of the itaconic anhydride grafted polyethylene is further increased, the number of crystal points is reduced, and the phenomenon of gel generation during the grafting process is reduced.

[0028] 3. Using glucose and fatty alcohol as raw materials, fatty alcohol alkyl glycoside is synthesized under the action of an acidic catalyst. The synthesized fatty alcohol alkyl glycoside is used to synthesize fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene. Under the action of a sodium acetate catalyst, the itaconic anhydride grafted onto high-density polyethylene is ring-opened, and the ring-opened compound of fatty alcohol alkyl glycoside forms a polyester. Some of the double bonds contained in high-density polyethylene form epoxy groups and are ring-opened to form hydroxyl groups under the action of a formic acid-hydrogen peroxide solution, improving the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch.

[0029] 4. By using a calcium chloride dispersion and a sodium hydroxide alcohol solution to perform surface treatment on para-aramid, on the one hand, the surface roughness of para-aramid is improved, and on the other hand, by hydrolyzing the amide bond into a carboxyl group during the reaction process, the binding strength with the added dopamine is increased. The modified para-aramid reacts with the grafted fatty alcohol alkyl glycoside through a chemical bond. By controlling the ratio of the number of parts of anhydrous calcium chloride to ethanol, the ratio of the number of parts of sodium hydroxide to ethanol, and the amounts of dopamine and modified para-aramid, the itaconic anhydride grafted polyethylene adhesive resin masterbatch obtained has high bonding strength after high-temperature treatment.

[0030] 5. By adding ethylene-vinyl acetate copolymer during the preparation process of the itaconic anhydride grafted polyethylene adhesive resin masterbatch, the high-temperature resistance and bonding strength of the resin masterbatch are improved. By compounding and using a phosphate antioxidant and a phenolic antioxidant, the antioxidant stability of the resin masterbatch is improved. By controlling the reaction temperature during the preparation process, the itaconic anhydride grafted polyethylene adhesive resin masterbatch has good bonding strength after high-temperature treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic structural diagram of the itaconic anhydride grafted polyethylene adhesive resin masterbatch of Example 32 of the present invention;

[0032] Figure 2 It is a graph of the bonding strength results of the itaconic anhydride grafted polyethylene adhesive resin masterbatch of Examples 24, 29-40 and Comparative Example 8 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0034] Please refer to Figures 1 to 2 , the present invention provides a preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch, and the technical solution is as follows:

[0035] The substances involved in the present invention are as follows: p-toluenesulfonic acid CAS: 104-15-4; itaconic anhydride CAS: 2170-03-8; sodium acetate CAS: 127-09-3; ethylene-vinyl acetate copolymer CAS: 24937-78-8; styrene CAS: 100-42-5; dimethylaminoethyl acrylate CAS: 2439-35-2; glycidyl methacrylate CAS: 106-91-2; glycidyl acrylate CAS: 106-90-1; ethyl methacrylate CAS: 97-63-2; cyclohexylmethyldimethoxysilane CAS: 17865-32-6; allylsilane CAS: 1116-62-7; 2,2'-azobis(isobutyronitrile) CAS: 78-67-1; 4-phenylazobenzoyl chloride CAS: 104-24-5; azobenzene-4,4'-dicarbonyl chloride CAS: 10252-29-6; polyacrylonitrile CAS: 25014-41-9; tert-amyl peroxy-2-ethylhexanoate (LUPEROX 575) CAS: 70833-40-8; tert-amyl peroxyacetate (LUPEROX 531) CAS: 690-83-5; benzoyl peroxide (BPO) CAS: 94-36-0; dicumyl peroxide CAS: 80-43-3; stearyl alcohol CAS: 112-92-5; tetradecyl alcohol CAS: 112-72-1; lauryl alcohol CAS: 112-53-8; undecyl alcohol CAS: 112-42-5; palmityl alcohol CAS: 36653-82-4; antioxidant 168 CAS: 31570-04-4; antioxidant 626 CAS: 26741-53-7; triphenyl phosphite CAS: 101-02-0; antioxidant 3125 CAS: 34137-09-2; octyl gallate CAS: 1034-01-1; antioxidant 1098 CAS: 23128-74-7; dicyclohexylcarbodiimide (DCC) CAS: 538-75-0; 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) CAS: 25952-53-8. The hyperbranched polyester polyol was purchased from Shanghai Xibo New Materials Technology Co., Ltd.; the para-aramid was purchased from Yantai Taihe New Materials Co., Ltd.

[0036] It should be noted that the "high temperature" in this application is 50-80 °C, and specifically, the bond strength effects at 50 °C, 70 °C and 80 °C are used to represent in the examples.

[0037] Example 1

[0038] The preparation method of fatty alcohol alkyl glycoside is as follows: Mix 1 part of glucose and 2.3 parts of fatty alcohol (palmityl alcohol) evenly to obtain a sugar alcohol solution, and add it to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser; Heat the sugar alcohol solution to 110 °C, reflux for 10 min, then add 0.01 part of p-toluenesulfonic acid, and continue to react for 2 h to obtain a fatty alcohol alkyl glycoside precursor; Continue to react for 2 h and intermittently evacuate to a vacuum degree of 0.075 MPa; Raise the vacuum degree of the fatty alcohol alkyl glycoside precursor to 0.080 MPa, and extract the excess alcohol and water to obtain a fatty alcohol alkyl glycoside intermediate; Cool the fatty alcohol alkyl glycoside intermediate to 80 °C, adjust the pH to 8, then layer and dry to obtain fatty alcohol alkyl glycoside.

[0039] The preparation method of modified para-aramid is as follows: Disperse anhydrous calcium chloride in 50 parts of ethanol at 15 °C to obtain a calcium chloride dispersion, and the ratio of the number of parts of anhydrous calcium chloride to ethanol is 1.5:48.5; Add 1 part of para-aramid to 50 parts of the calcium chloride dispersion, stir for 1 h and then take it out, wash it with distilled water and dry it to obtain a modified para-aramid precursor; Add 50 parts of sodium hydroxide alcohol solution to the modified para-aramid precursor, continue to stir for 1 h and then take it out, wash it with distilled water and dry it to obtain a modified para-aramid intermediate; In 50 parts of sodium hydroxide alcohol solution, the ratio of the number of parts of sodium hydroxide to ethanol is 1:24, and ethanol is 48 parts; Add 0.5 part of dopamine, 0.01 part of DCC and 0.01 part of EDC to the modified para-aramid intermediate, raise the temperature to 140 °C, stir and react for 4 h, wash and dry to obtain modified para-aramid.

[0040] Melt 100 parts of high-density polyethylene in a reaction kettle to obtain molten high-density polyethylene; Add 0.5 part of monomer mixture and 1.2 parts of itaconic anhydride to the molten high-density polyethylene, and stir to obtain a molten mixture; The monomer mixture is composed of monomer one and monomer two in a ratio of 1:1; Monomer one is styrene; Monomer two is dimethylaminoethyl acrylate; Pass 150 parts of carbon dioxide into the molten mixture to discharge other gases, and adjust the temperature to 155 °C and the pressure to 65 MPa, and continue to stir for 30 min to obtain a reactant; Add 0.3 part of initiator mixture to the reactant, stir and react for 20 min to obtain itaconic anhydride-grafted polyethylene; The initiator mixture is composed of initiator one and initiator two in a ratio of 2:3; Initiator one is 2,2'-azobis(isobutyronitrile); Initiator two is LUPEROX 575; Add 1 part of squalane and 0.01 part of sodium acetate to the itaconic anhydride-grafted polyethylene and stir evenly, then add 0.55 part of fatty alcohol alkyl glycoside, react for 1.5 h, and cool to obtain fatty alcohol alkyl glycoside-itaconic anhydride-grafted polyethylene.

[0041] After mixing fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene with 0.02 parts of formic acid-hydrogen peroxide solution, 0.25 parts of modified para-aramid, 3 parts of ethylene-vinyl acetate copolymer, 0.1 part of dispersant polyethylene wax, and 0.2 part of antioxidant (antioxidant one-antioxidant 168 and antioxidant two-antioxidant 3125 are mixed in a ratio of 1:1) are added and mixed evenly, and then put into a twin-screw extruder. The temperatures of each zone are controlled to be 110°C, 150°C, 170°C, 200°C, 180°C, and 150°C in sequence, and the itaconic anhydride grafted polyethylene adhesive resin masterbatch is obtained by extrusion; the dosage ratio of formic acid to 30% hydrogen peroxide aqueous solution in the formic acid-hydrogen peroxide solution is 3:17.

[0042] Examples 2-14

[0043] Different from Example 1, the following preparation conditions are changed, as shown in Table 1 specifically.

[0044] Table 1 Preparation conditions of reactants to be prepared

[0045]

[0046]

[0047] Example 15

[0048] Different from Example 1, the temperature is 150°C and the pressure is 60 MPa.

[0049] Example 16

[0050] Different from Example 1, the temperature is 165°C and the pressure is 80 MPa.

[0051] Comparative Example 1

[0052] Different from Example 1, monomer one is not added.

[0053] Comparative Example 2

[0054] Different from Example 1, monomer two is not added.

[0055] Comparative Example 3

[0056] Different from Example 1, neither monomer one nor monomer two is added.

[0057] Comparative Example 4

[0058] Different from Example 1, carbon dioxide is not introduced.

[0059] Example 17

[0060] The grafting rates of the itaconic anhydride-grafted polyethylenes prepared in Examples 1-16 and Comparative Examples 1-4 were determined; the prepared adhesive resin masterbatch was melted and co-extruded with high-density polyethylene and nylon 6 to obtain an adhesive material, and the number of crystal points of the material was determined.

[0061] The grafting rate determination method is as follows: The itaconic anhydride-grafted polyethylenes prepared in the examples and comparative examples were purified. 0.5 parts of the purified itaconic anhydride-grafted polyethylene was dissolved in xylene, cooled at 70 °C for 5 min, then 10 mL of potassium hydroxide-ethanol solution was added, the conical flask was removed after refluxing for 15 min, 3 drops of phenolphthalein indicator were added thereto, and titration was carried out with acetic acid-xylene solution. When the color of the solution changed from red to white, the volume of acid consumed (V1) was recorded; a blank sample was weighed according to the same procedure, and the volume of acid consumed by the blank sample (V0) was titrated. The calculation formula for the grafting rate is as follows C is the concentration of the acetic acid-xylene solution. The crystal point number test method is as follows. The bonding material was cut into a size of 0.4 m × 0.4 m, and the total number of crystal points on 1 m 2 of the multi-layer bonding material was measured. The final results are shown in Table 2.

[0062] Table 2 Test results of grafting rate and crystal point number

[0063] Grafting rate (%) Number of crystal points (pcs) Example 1 0.20 31 Example 2 0.21 27 Example 3 0.20 22 Example 4 0.22 17 Example 5 0.19 18 Example 6 0.22 20 Example 7 0.21 16 Example 8 0.11 26 Example 9 0.15 23 Example 10 0.17 18 Example 11 0.20 20 Example 12 0.21 25 Example 13 0.20 29 Example 14 0.22 19 Example 15 0.22 17 Example 16 0.25 13 Comparative Example 1 0.12 27 Comparative Example 2 0.14 27 Comparative Example 3 0.03 42 Comparative Example 4 0.16 32

[0064] Table 2 shows that the grafting rate of itaconic anhydride in the itaconic anhydride-grafted polyethylene prepared by the present invention is 0.11%-0.25%. The itaconic anhydride-grafted polyethylene adhesive resin masterbatch prepared from the itaconic anhydride-grafted polyethylene as an adhesive has 13-31 crystal points in the adhesive material prepared by bonding polyethylene and nylon 6. The grafting rate of the comparative example is 0.03%-0.16%, and the number of crystal points is 27-42. In Examples 1-4, the type of monomer one was controlled to be styrene, which played an electron-donating role during the grafting reaction, promoted the grafting process, and significantly alleviated the β-chain scission reaction during the grafting process; by changing the type of monomer two, the grafting rate remained basically unchanged, and the number of crystals showed a gradually decreasing trend. The crystal points are mainly due to the fact that the molecular weight is higher than other parts of the material, the melt index is lower, the fluidity is weak and the viscosity is high. Therefore, during the extrusion and blown film processes of the adhesive material, it cannot be uniformly dispersed with other parts, so transparent spherical crystal points are formed and mixed in the adhesive material. When the type of monomer two is ethyl methacrylate, its conjugation effect and polarity are closest to those of itaconic anhydride, so its copolymerization reaction is more uniform and the number of crystal points is the least. Under the action of other monomer twos, alternating copolymerization occurs and the polymerization reaction is incomplete. The results of Examples 4-6 show that when the type of monomer two remains unchanged, by changing the type of monomer one, the number of crystal points changes. Among them, Example 4 uses styrene as monomer one and has the best effect. The results of Examples 4 and 7 show that by increasing the proportion of monomer two in monomer one and monomer two, the number of crystal points decreases. The results of Examples 7-10 show that when the amount of the monomer mixture is 0.5 parts, the grafting rate is high and the number of crystal points is small. The results of Examples 10-14 show that as the amount of itaconic anhydride increases, both the grafting rate and the number of crystal points first increase and then decrease. A small amount of itaconic anhydride is not conducive to the grafting reaction, and the grafting rate decreases; and it is not conducive to the adhesion between high-density polyethylene and nylon 6; when the amount is too high, the graftable sites in high-density polyethylene are certain, and a high amount results in incomplete grafting and a decrease in the grafting rate; when itaconic anhydride reaches a certain amount, on the one hand, it reduces the melt flow number of the bonding layer, and on the other hand, too much maleic anhydride is prone to cross-linking side reactions, the molecular weight becomes larger, and crystal points are generated. In Examples 1, 15, and 16, by changing the reaction temperature and pressure, carbon dioxide is changed into the form of supercritical fluid, thereby swelling high-density polyethylene and promoting the grafting reaction process. Under the conditions of Example 16, the grafting rate is the highest and the number of crystal points is the least. Comparative Example 1 and Comparative Example 2 do not add monomer one and monomer two respectively, the grafting rate decreases, and the number of crystal points increases. Comparative Example 3 does not add monomer one and monomer two, and the grafting rate and the number of crystal points are the worst among other groups. Comparative Example 4 does not add carbon dioxide, the grafting rate decreases, cross-linking is easy to occur, and the gel phenomenon is serious.

[0065] Examples 18-27

[0066] Different from Example 16, the following preparation conditions were changed, as specifically shown in Table 3.

[0067] Table 3 Dosage and type of initiator

[0068]

[0069]

[0070] Example 28

[0071] The grafting rate and the number of crystal points of the itaconic anhydride grafted polyethylene and the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared in Examples 18 - 27 and Comparative Example 7 were measured. The specific test method was referred to Example 17, and the final test results are shown in Table 3.

[0072] The grafting rate of itaconic anhydride in the itaconic anhydride grafted polyethylene prepared in the present invention is 0.17% - 0.32%. The itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared from the itaconic anhydride grafted polyethylene is used as an adhesive, and the number of crystal points of the adhesive material prepared by bonding polyethylene and nylon 6 is 8 - 19. The results of Examples 16, 18 - 20 show that by changing the type of initiator I, the grafting rate and the number of crystal points change. In Example 19, azobenzene - 4,4'-dicarbonyl chloride was used as initiator I, and the grafting rate was the highest and the number of crystal points was the least. The azo structure therein has a promoting effect on grafting itaconic anhydride and fatty alcohol alkyl glycoside onto high - density polyethylene, and its effect is the best compared with other initiator Is. And after the catalysis by the initiator is completed, the carboxyl group generated by its hydrolysis can also be connected with the hydroxyl group or amino group of the modified para - aramid through chemical bonds and become a fixed component in the itaconic anhydride grafted polyethylene adhesive resin masterbatch. The results of Examples 19, 21 - 23 show that in Example 24, azobenzene - 4,4'-dicarbonyl chloride and tert - amyl peroxyacetate were used in combination, and the grafting rate was the highest and the number of crystal points was the least. The results of Examples 21, 24 - 27 show that as the dosage of the initiator increases, the grafting rate shows a trend of first increasing and then decreasing, and the number of crystal points gradually decreases and then remains unchanged. The results of Comparative Examples 5 - 7 show that adding only one initiator or no initiator will result in a decrease in the grafting rate and a significant increase in the number of crystal points.

[0073] Examples 29 - 39

[0074] Different from Example 24, the preparation method of fatty alcohol alkyl glycoside and the dosage of fatty alcohol alkyl glycoside in the preparation process of fatty alcohol alkyl glycoside - itaconic anhydride grafted polyethylene were changed, as specifically shown in Table 4.

[0075] Example 40

[0076] Different from Example 24, the dosage of sodium acetate was 0.03 parts.

[0077] Table 4 Preparation conditions and dosages of fatty alcohol alkyl glycosides

[0078]

[0079] Comparative Example 8

[0080] Different from Example 24, fatty alcohol alkyl glycoside was not added during the preparation of fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene.

[0081] Comparative Example 9

[0082] Different from Example 24, the fatty alcohol was ethanol.

[0083] Example 41

[0084] The itaconic anhydride grafted polyethylene adhesive resin masterbatches prepared in Examples 24, 29-40 and Comparative Example 8 were subjected to a bond strength test. The specific test method was as follows: Referring to GB / T 2790-1995 "Test Method for 180° Peel Strength of Adhesives - Flexible Materials to Rigid Materials", a 180° peel experiment of polyethylene and nylon 6 was carried out. The specimen width was 25 mm and the tensile rate was 50 mm / min. The structure of the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared in Example 32 was as Figure 1 shown, and the final bond strength test results were as Figure 2 shown.

[0085] Figure 2 The results showed that the bond strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared in the present invention was 68.5-88.9 N / 25 mm. The results of Examples 24, 29-32 showed that as the number of carbon atoms in the fatty alcohol increased, the bond strength showed a trend of increasing first and then decreasing. Under the action of p-toluenesulfonic acid, the glycosidic hydroxyl oxygen atom of glucose was rapidly protonated by the attack of the catalyst (H + ), and after the transition state sugar molecule became positively charged, the electronegativity of the oxygen increased, resulting in an increase in the positive charge of the anomeric carbon. To achieve its own stability, 1 molecule of water was rapidly removed to form an anomeric carbon cation. Then, the fatty alcohol carried out a nucleophilic process on the anomeric carbon cation, and the polymerization process of glucose and fatty alcohol was carried out. As the number of carbon atoms increased, the viscosity of the system gradually increased and the bonding ability improved. However, as the number of carbon atoms further increased, the polymerization reaction rate decreased and the polymerization reaction was incomplete. Therefore, as shown in Example 24, the bond strength decreased instead. Therefore, ethanol was used in the comparative example to synthesize alkyl glycoside, and the bond strength decreased. In Example 33, by adding hyperbranched polyester polyol, the bond strength was the highest. However, the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared from hyperbranched polyester polyol had strong fluidity in the molten state, which was not conducive to the bonding process. This was determined by the nature of hyperbranched polyester polyol itself. AsFigure 1 As shown, it is the structural diagram of the itaconic anhydride grafted polyethylene adhesive resin masterbatch in Example 32. First, itaconic anhydride is used for grafting, and then fatty alcohol alkyl glycoside and modified para-aramid are used for grafting to obtain the structure as shown in Figure 1 The structure of the itaconic anhydride grafted polyethylene adhesive resin masterbatch includes but is not limited to Figure 1 . The results of Examples 32, 34 - 36 show that as the amount of fatty alcohol increases, the bonding strength first increases and then decreases. The results of Examples 32 and 37 show that the amount of p-toluenesulfonic acid catalyst is within a reasonable range, so the bonding strength is high. The results of Examples 32, 38, and 39 show that as the amount of fatty alcohol alkyl glycoside decreases, the bonding strength decreases, and the amount of fatty alcohol alkyl glycoside is small. Then the content of polar groups containing hydroxyl groups decreases, and the bonding strength with the polar material nylon 6 decreases. The results of Examples 24 and 40 show that the amount of sodium acetate catalyst is within a reasonable range, and the bonding strength is high. Sodium acetate is used to catalyze the nucleophilic addition reaction of fatty alcohol alkyl glycoside to itaconic anhydride. The catalyst sodium acetate provides electrons for alkyl glycoside, and after the latter becomes negatively charged, it attacks the carbonyl carbon on itaconic anhydride, causing itaconic anhydride to ring open and react with it, thus increasing the bonding strength. In Comparative Example 8, no fatty alcohol alkyl glycoside is added, and the bonding strength is greatly reduced.

[0086] Examples 42 - 50

[0087] Different from Example 32, the preparation method and the amount of modified para-aramid are changed, as specifically shown in Table 5.

[0088] Table 5 Preparation method and amount of modified para-aramid

[0089]

[0090]

[0091] Comparative Example 10

[0092] Different from Example 32, no treatment is carried out using calcium chloride dispersion and sodium hydroxide alcohol solution.

[0093] Comparative Example 11

[0094] Different from Example 32, no modified para-aramid is added during the preparation of the itaconic anhydride grafted polyethylene adhesive resin masterbatch.

[0095] Example 51

[0096] The heat resistance of the itaconic anhydride grafted polyethylene adhesive resin masterbatches prepared in Examples 32, 42 - 50 and Comparative Examples 10 - 11 was tested. It included testing the bonding strength of the resin masterbatch at room temperature, and testing the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch after being placed at room temperature of 25°C, high temperatures of 50°C, 70°C, and 80°C for 10 h respectively. The testing method of the bonding strength referred to Example 41. The test results are shown in Table 6.

[0097] Table 6 Heat resistance effects of the adhesive resin masterbatches in Examples 32, 42 - 50 and Comparative Examples 10 - 11

[0098]

[0099] The bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared by the present invention is 84.0 - 89.1 N / 25 mm. After being treated at 50 °C, its bonding strength is 82.8 - 88.9 N / 25 mm. After being treated at 70 °C, its bonding strength is 82.6 - 88.8 N / 25 mm. After being treated at 80 °C, its bonding strength is 81.6 - 88.0 N / 25 mm. The results of Examples 32, 45, and 43 show that with the increase in the amount of anhydrous calcium chloride used in anhydrous calcium chloride and ethanol, the reduction value of the bonding strength after high-temperature treatment shows a trend of first decreasing and then increasing. The results of Examples 42 and 44 show that through the ratio of the number of parts of sodium hydroxide to ethanol, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch does not change significantly, but the reduction value of the bonding strength after high-temperature treatment changes. By using calcium chloride dispersion and sodium hydroxide alcohol solution to conduct surface treatment on para-aramid, controlling the fraction ratios of anhydrous calcium chloride and sodium hydroxide to ethanol respectively, the roughness of the para-aramid surface is improved. In addition, the amide bonds on the para-aramid surface are hydrolyzed into carboxyl groups, the surface groups are activated, and they react with the grafted fatty alcohol alkyl glycoside, and the high-temperature resistance of the aramid fiber improves the high-temperature resistance of the itaconic anhydride grafted polyethylene adhesive resin masterbatch. In Comparative Example 10, no treatment is performed using calcium chloride dispersion and sodium hydroxide alcohol solution, and the bonding strength does not change significantly compared with the examples, but the bonding strength decreases significantly after high-temperature treatment. The results of Examples 42, 45 - 47 show that with the increase in the amount of dopamine used, the reduction value of the bonding strength after high-temperature treatment shows a gradually decreasing trend. Dopamine reacts with the activated carboxyl groups on the para-aramid surface through hydroxyl groups, and the introduced dopamine improves the high-temperature resistance and wetting bonding performance of the itaconic anhydride grafted polyethylene adhesive resin masterbatch. The results of Examples 42, 48 - 50 show that with the increase in the amount of modified para-aramid used, the reduction value of the bonding strength after high-temperature treatment gradually decreases, and the high-temperature resistance is good. In Comparative Example 11, no modified para-aramid is added, and the bonding strength decreases significantly after high-temperature treatment. After high-temperature treatment at 50 °C and 70 °C, compared with the comparative examples, the reduction value of the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared in the examples is small. After testing the bonding strength after high-temperature treatment at 80 °C, the bonding strength of the examples decreases significantly compared with 50 °C and 70 °C, and the bonding strength of the comparative examples further decreases. In summary, by using calcium chloride dispersion and sodium hydroxide alcohol solution to treat para-aramid and then using dopamine for modification, the itaconic anhydride grafted polyethylene adhesive resin masterbatch prepared from the obtained modified para-aramid has high bonding strength, high bonding strength after high-temperature treatment, and good high-temperature resistance.

[0100] Examples 52 - 61

[0101] Different from Example 45, the conditions for preparing the itaconic anhydride grafted polyethylene adhesive resin masterbatch by the twin-screw extruder are changed, as shown in Table 7 specifically.

[0102] Table 7 Preparation Conditions of Itaconic Anhydride Grafted Polyethylene Adhesive Resin Masterbatch

[0103]

[0104]

[0105] Comparative Example 12

[0106] Different from Example 45, ethylene-vinyl acetate copolymer is not added.

[0107] Comparative Example 13

[0108] Different from Example 45, antioxidant 3125 is not added.

[0109] Comparative Example 14

[0110] Different from Example 45, antioxidant 168 is not added.

[0111] Example 62

[0112] The itaconic anhydride grafted polyethylene adhesive resin masterbatches prepared in Examples 52 - 61 and Comparative Examples 12 - 14 were subjected to heat resistance tests. This included testing the bonding strength of the resin masterbatch at room temperature, and testing the bonding strength after placing the itaconic anhydride grafted polyethylene adhesive resin masterbatch at room temperature of 25°C and high temperatures (50°C, 70°C, 80°C) for 10 h. The specific test method was referred to Example 51, and the final test results are shown in Table 8.

[0113] Table 8 Test Results of Bonding Strength of Examples 52 - 61 and Comparative Examples 12 - 14

[0114]

[0115]

[0116] The bonding strength of the itaconic anhydride-grafted polyethylene bonding resin masterbatch prepared by the present invention is 86.0 - 89.3 N / 25 mm. After treatment at 50 °C, its bonding strength is 85.5 - 89.2 N / 25 mm. After treatment at 70 °C, its bonding strength is 85.1 - 89.2 N / 25 mm. After treatment at 80 °C, its bonding strength is 84.7 - 89.0 N / 25 mm. For the itaconic anhydride-grafted polyethylene bonding resin masterbatch prepared in the examples, after treatment at 50 °C and 70 °C, the reduction value of its bonding strength compared to the treatment at room temperature of 25 °C is small. After treatment at 80 °C, its bonding strength decreases significantly. Among them, the bonding strength of the examples is better than that of the comparative examples. The results of Examples 45, 52 - 54 show that as the dosage of ethylene-vinyl acetate copolymer increases, the bonding strength shows a gradually increasing trend. This is because the ethylene-vinyl acetate copolymer has the properties of both polar and non-polar compounds, so the adhesiveness between the bonding resin masterbatch and high-density polyethylene and nylon 6 increases. And as its dosage increases, the reduction value of the bonding strength after high-temperature treatment is gradually lower than that after room-temperature treatment. The results of Examples 52, 55 and 56 show that by changing the types of hindered phenol and amine antioxidants, the reduction value of the bonding strength after high-temperature treatment changes compared to that after room-temperature treatment. Among them, in Example 52, antioxidant 3125 is used, which has more effective antioxidant functional groups compared with other antioxidants, and the heat-resistant stability of the bonding resin masterbatch is improved. The results of Examples 52, 57, 58 show that by changing the types of phosphoric acid ester antioxidants, among which in Example 57, antioxidant 626 is used as the phosphoric acid ester antioxidant, the heat-resistant stability of the resin masterbatch is the best. And by changing the dosage of ethylene-vinyl acetate copolymer and changing the types and dosages of antioxidant one and antioxidant two, the reduction value after high-temperature treatment is small. For the resin masterbatch of Example 57, the reduction value of the bonding strength after treatment at 50 °C compared to that at 25 °C is 0.1 N / 25 mm, the reduction value of the bonding strength after treatment at 70 °C compared to that at 25 °C is 0.1 N / 25 mm, and the reduction value of the bonding strength after treatment at 80 °C compared to that at 25 °C is 0.2 N / 25 mm. The reduction value of the bonding strength after high-temperature treatment is small. The results of Examples 52, 59 show that reducing the dosage of antioxidants reduces the heat-resistant effect of the bonding resin masterbatch. The results of Examples 52, 60, 61 show that reducing the temperature of the reaction process gradually reduces the bonding strength. In Comparative Example 12, no ethylene-vinyl acetate copolymer is added, and the bonding strength of the bonding resin masterbatch decreases, and the bonding strength further decreases after high-temperature treatment. In Comparative Examples 13 and 14, no hindered phenol, amine antioxidant and phosphoric acid ester antioxidant are added respectively. The bonding strength is equivalent to that of Example 53, but the bonding strength decreases significantly after high-temperature treatment.

[0117] Although embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of itaconic anhydride grafted polyethylene adhesive resin masterbatch, characterized in that: The preparation method includes the following steps: Add 0.3 - 0.7 parts of monomer mixture and 0.4 - 1.4 parts of itaconic anhydride to molten high-density polyethylene, and stir to obtain a molten mixture; the ratio of the number of parts of monomer one to monomer two in the monomer mixture is 1 - 2:1 - 3; introduce carbon dioxide into the molten mixture, set the temperature at 150 - 165 °C and the pressure at 60 - 80 MPa, and stir to obtain a reactant to be reacted; add 0.12 - 0.3 parts of initiator mixture to the reactant to be reacted, and react to obtain itaconic anhydride-grafted polyethylene; the initiator mixture is composed of initiator one and initiator two; add 0.01 - 0.03 parts of sodium acetate and 0.30 - 0.55 parts of fatty alcohol alkyl glycoside to the itaconic anhydride-grafted polyethylene, and react to obtain fatty alcohol alkyl glycoside-itaconic anhydride-grafted polyethylene; Add formic acid-hydrogen peroxide solution, 0.15 - 0.25 parts of modified para-aramid, 2 - 3.5 parts of ethylene-vinyl acetate copolymer, polyethylene wax, and 0.1 - 0.2 parts of antioxidant to the fatty alcohol alkyl glycoside-itaconic anhydride-grafted polyethylene to obtain a mixed material; put the mixed material into a twin-screw extruder and extrude at 85 - 205 °C to obtain the itaconic anhydride-grafted polyethylene adhesive resin masterbatch; The fatty alcohol alkyl glycoside is obtained by reacting glucose with 1.5 - 2.3 parts of fatty alcohol under the catalysis of 0.01 - 0.02 parts of p-toluenesulfonic acid; The modified para-aramid is obtained by treating para-aramid with calcium chloride dispersion liquid and sodium hydroxide alcohol solution, and then adding 0.2 - 0.6 parts of dopamine; the ratio of the number of parts of anhydrous calcium chloride to ethanol in the calcium chloride dispersion liquid is 1 - 1.5:48.5 - 49; the ratio of the number of parts of sodium hydroxide to ethanol in the sodium hydroxide alcohol solution is 1 - 2:23 - 24.

2. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The monomer one is one of styrene, cyclohexylmethyldimethoxysilane, and allylsilane.

3. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The monomer two is one of dimethylaminoethyl acrylate, glycidyl methacrylate, glycidyl acrylate, and ethyl methacrylate.

4. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The initiator one is one of 2,2'-azo-bis-isobutyronitrile, 4-phenylazobenzoyl chloride, azobenzene-4,4'-dicarbonyl chloride, and polyacrylonitrile.

5. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The initiator two is one of tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyacetate, benzoyl peroxide, and diisopropylbenzene peroxide.

6. The preparation method of an itaconic anhydride-grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The fatty alcohol is one of stearyl alcohol, myristyl alcohol, lauryl alcohol, undecyl alcohol, palmityl alcohol, and hyperbranched polyester polyol.

7. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The antioxidant is composed of antioxidant one and antioxidant two; the antioxidant one is one of antioxidant 168, antioxidant 626, and triphenyl phosphite; the antioxidant is one of antioxidant 3125, octyl gallate, and antioxidant 1098; the dosage ratio of antioxidant one to antioxidant two is 1:

1.

8. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The preparation method of the fatty alcohol alkyl glycoside is as follows: The glucose and the fatty alcohol are mixed evenly to obtain a sugar alcohol solution, which is added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser; the sugar alcohol solution is heated to 110 °C, and after reflux reaction, p-toluenesulfonic acid is added thereto, and the reaction continues for 2 h to obtain a fatty alcohol alkyl glycoside precursor; when the reaction continues for 2 h, vacuum is intermittently pumped, and the vacuum degree is 0.075 MPa; the vacuum degree of the fatty alcohol alkyl glycoside precursor is increased to 0.080 MPa, and the excess alcohol and water are removed to obtain a fatty alcohol alkyl glycoside intermediate; the fatty alcohol alkyl glycoside intermediate is cooled to 80 °C, the pH is adjusted, and then it is layered and dried to obtain the fatty alcohol alkyl glycoside.

9. The preparation method of an itaconic anhydride grafted polyethylene adhesive resin masterbatch according to claim 1, characterized in that: The preparation method of the modified para-aramid is as follows: Anhydrous calcium chloride is dispersed in the ethanol at 15 °C to obtain a calcium chloride dispersion; the para-aramid is added to the calcium chloride dispersion, stirred for 1 h and then taken out, washed with distilled water and dried to obtain a modified para-aramid precursor; The sodium hydroxide alcohol solution is added to the modified para-aramid precursor, stirred for 1 h and then taken out, washed with distilled water and dried to obtain a modified para-aramid intermediate; dopamine, dicyclohexylcarbodiimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added to the modified para-aramid intermediate, heated and stirred for reaction, washed and dried to obtain the modified para-aramid.

10. An itaconic anhydride grafted polyethylene adhesive resin masterbatch, characterized in that: The itaconic anhydride grafted polyethylene adhesive resin masterbatch includes fatty alcohol alkyl glycoside-itaconic anhydride grafted polyethylene, modified para-aramid, ethylene-vinyl acetate copolymer, polyethylene wax and antioxidant; the itaconic anhydride grafted polyethylene adhesive resin masterbatch is obtained by the preparation method according to any one of claims 1-9; by adjusting the types and amounts of monomer one and monomer two, the grafting rate of itaconic anhydride in the itaconic anhydride grafted polyethylene is 0.11%-0.25%, and the number of crystal points of the adhesive material prepared by bonding polyethylene and nylon 6 with the itaconic anhydride grafted polyethylene adhesive resin masterbatch as an adhesive is 13-31; by adjusting the types and amounts of initiator one and initiator two, the grafting rate of the itaconic anhydride is 0.17%-0.32%, and the number of crystal points is 8-19; by adjusting the type and amount of fatty alcohol, the amounts of p-toluenesulfonic acid and fatty alcohol alkyl glycoside, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch is 68.5-88.1 N / 25 mm; by changing the preparation method and amount of the modified para-aramid, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch is 84.0-89.1 N / 25 mm, and its bonding strength after high-temperature treatment is 88.0-88.9 N / 25 mm; by adjusting the amounts of the ethylene-vinyl acetate copolymer and antioxidant, the type of antioxidant and the reaction temperature, the bonding strength of the itaconic anhydride grafted polyethylene adhesive resin masterbatch is 86.0-89.3 N / 25 mm, and its bonding strength after high-temperature treatment is 89.0-89.2 N / 25 mm.

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