CN114231242A - Nylon 12 hot melt adhesive and preparation method thereof - Google Patents
Nylon 12 hot melt adhesive and preparation method thereof Download PDFInfo
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- CN114231242A CN114231242A CN202210049313.0A CN202210049313A CN114231242A CN 114231242 A CN114231242 A CN 114231242A CN 202210049313 A CN202210049313 A CN 202210049313A CN 114231242 A CN114231242 A CN 114231242A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention discloses a nylon 12 hot melt adhesive and a preparation method thereof, wherein the raw materials comprise: a) caprolactam, b) laurolactam, C) at least one nylon salt starting mixture of C6-C14 diacids and C5-C12 diacids, d) at least one nylon salt starting mixture of triamines and C2-C14 diacids, e) low molecular weight nylon 22, f) medium and low molecular weight olefin polymers with epoxy and/or maleic anhydride groups. The nylon 12 hot melt adhesive has the advantages of good crystallization property, less residual, good water resistance and dry cleaning resistance, high peel strength, good cohesive force and the like.
Description
Technical Field
The invention mainly relates to a nylon 12 hot melt adhesive and a preparation method thereof, belonging to the preparation process of organic polymer materials.
Background
The polyamide (nylon) hot melt adhesive is a hot melt adhesive obtained by copolycondensation of a plurality of aliphatic dicarboxylic acids and aliphatic diamines, has the advantages of low melting temperature, narrow melting range, convenient processing, wide application range, high bonding strength, better flexibility and wear resistance, excellent aging resistance and the like, can be applied to bonding of materials such as clothes, leather, wood, plastics, metals, ceramics and the like, and is a high-end material for the current high-grade clothes hot melt adhesive interlining and wireless sewing clothes.
The polyamide amide groups of the single component are orderly arranged, hydrogen bonds are easily formed among the amide groups, and the polyamide amide groups are easy to crystallize and have high melting points. Because the bonded material is limited in multiple aspects such as heat resistance, construction energy consumption and the like, the melting point of the nylon hot melt adhesive needs to be controlled between 80 ℃ and 140 ℃ and is not too high easily, so that the melting point of the product needs to be reduced by breaking the regular arrangement of amide groups of the nylon hot melt adhesive through random copolymerization of a plurality of monomers, but the crystallization performance of the nylon hot melt adhesive is also obviously reduced. The crystallization property is reduced, the opening time of the hot melt adhesive is prolonged, the construction efficiency is reduced, the cohesive strength is reduced, and the bonding effect of the product is reduced. The existing domestic nylon hot melt adhesive is a terpolymer or quadripolymer prepared by carrying out melt copolycondensation on caprolactam, nylon 66 salt, nylon 1010 salt, nylon 1012 salt and the like in a high-pressure reaction kettle, the carbon chain lengths of the used raw materials, namely long-carbon-chain nylon 1010, nylon 1012 and the like, are lower than that of nylon 12, and the prepared product has small adhesive force, large hardness, poor flexibility, poor wear resistance, poor water washing resistance and poor dry cleaning resistance. Therefore, the laurolactam component is introduced into the polymerization unit, so that the cohesiveness, flexibility, wear resistance and water washing resistance of the product can be improved; however, under the condition of no modification, the crystallization performance of the copolymerization product can be ensured only by ensuring the sufficient dosage of the long carbon chain nylon, and because the cost of the long carbon chain raw material is high and is not suitable for being added excessively, a modification method which can ensure the crystallization capacity of the product, can ensure the comprehensive conditions of flexibility, cohesiveness and the like and simultaneously controls the cost within an acceptable range is urgently needed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nylon 12 hot melt adhesive with excellent comprehensive performance and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a nylon 12 hot melt adhesive which comprises the following raw materials:
the total mass of the component a), the component b), the component c) and the component d) is 100 percent, and the mass percentage content is as follows:
a) caprolactam 20-45%, preferably 25-40%;
b) 25-60%, preferably 30-55% of laurolactam;
c) 20-30%, preferably 21-28% of at least one nylon salt raw material mixture consisting of C6-C14 dibasic acid and C5-C12 diamine;
d) at least one nylon salt raw material mixture composed of triamine and C2-C14 dibasic acid 1.0-4.0%, preferably 1.2-3.0%;
e) low molecular weight nylon 22(PA 22);
f) a medium to low molecular weight olefin polymer fraction having epoxy and/or maleic anhydride groups;
wherein the molar ratio of the triamine in the component e) to the component d) is 1.00-1.05: 1, preferably 1.00-1.01: 1;
the addition amount of the component f) is 0.1-10 percent of the total mass of the component a), the component b), the component c) and the component d), and the preferred addition amount is 0.1-5 percent.
In the invention, the main chain structure is formed by copolycondensation of the components a), b), c) and d), and the melting point of a copolymerization product can be controlled within a proper range by adjusting the proportion of the multi-component monomer.
In the invention, the component C) is prepared into nylon salt by the reaction of the C6-C14 dibasic acid and C5-C12 diamine;
preferably, the C6-C14 dibasic acid is selected from one or more of adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like;
preferably, the C5-C12 diamine is selected from one or more of pentanediamine, hexanediamine, decanediamine and the like;
the free combination of the monomers can form nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 1010 salt, nylon 1012 salt, nylon 1212 salt and the like, or form compound nylon salt, such as nylon 66/1010 salt, nylon 66/612 salt and the like.
The manner of preparing the nylon salt from the diacid and the diamine in component c) is known to those skilled in the art and can be prepared by any desired method, and the invention is not particularly limited;
preferably, the molar ratio of the C6-C14 dibasic acid to the C5-C12 diamine is 1.00-1.05: 1, preferably 1.00-1.01: 1.
in the invention, the triamine in the component d) reacts with the dibasic acid C2-C14 to prepare the nylon salt;
preferably, the triamine is selected from diethylenetriamine, triethylamine and the like;
preferably, the C2-C14 dibasic acid is selected from one or more of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like.
The manner of preparing the nylon salt from the dibasic acid and the triamine in the component d) is known to those skilled in the art, and can be prepared by any desired method, and the present invention has no specific requirement;
preferably, the molar ratio of the triamine to the C2-C14 dibasic acid is 1.00-1.02: 1, preferably 1.00: 1.
in the invention, the component e) low molecular weight nylon 22 is used as a modified component and added into a main chain structure of nylon 12, so that the crystallization performance of the product can be obviously improved.
In the invention, the component e) of the low molecular weight nylon 22 has the molecular weight of 300-2000, preferably 500-1500;
the nylon 22(PA22) is prepared from oxalic acid and ethylenediamine through polymerization reaction in a manner known to those skilled in the art, and can be prepared by any desired method, and the invention has no specific requirement;
preferably, the molar ratio of ethylenediamine to oxalic acid is 1 to 1.05: 1, preferably 1.00-1.01: 1; .
Preferably, the raw material for preparing the nylon 22 further comprises an end capping agent, wherein the end capping agent is selected from one or more of acetic acid, stearic acid, benzoic acid, adipic acid and the like, and is more preferably selected from one or more of acetic acid, stearic acid and benzoic acid; the amount of the end-capping agent is 1 to 15 wt%, preferably 1.5 to 10 wt%, of the total mass of the oxalic acid and the ethylenediamine.
Preferably, the raw materials for preparing the nylon 22 also comprise raw materials such as a catalyst, an antioxidant, water and the like;
the catalyst is selected from one or more of sodium phosphate, sodium hypophosphite and sodium hypophosphite; the dosage of the catalyst is preferably 0.1-1 wt% of the total mass of the oxalic acid and the ethylenediamine;
the antioxidant is selected from the compound of an antioxidant 1098 and an antioxidant 168, and the mixing mass ratio is preferably 1: 2; the dosage is preferably 1-5 wt% of the total mass of the oxalic acid and the ethylenediamine;
the amount of water used is preferably 5 to 40 wt% based on the total mass of oxalic acid and ethylenediamine.
In some specific embodiments, the nylon 22 is preferably prepared by a preparation method comprising the steps of mixing oxalic acid, ethylenediamine, a catalyst, an antioxidant, acetic acid and water, heating to 40-60 ℃ for reaction for 30-60min, then continuing to heat to 150-.
In the invention, the component f) is an olefin polymer with middle and low molecular weight and epoxy and/or maleic anhydride groups, is an olefin polymer with middle and low molecular weight and flexible structure, can react with free terminal amino in the tail end structure of the nylon 12 hot melt adhesive, further improves the flexibility and wear resistance of the nylon 12 hot melt adhesive without influencing the crystallization capacity of the main chain structure, and can improve the binding power with the non-polar part of the bound material; wherein
The epoxy functionality of the olefin polymer with the epoxy group and the medium and low molecular weight is 0.75-1.5, preferably 0.9-1.2, and the molecular weight is 100-1000, preferably 150-800;
the maleic anhydride group-containing olefin polymer with medium and low molecular weight has a maleic anhydride grafting rate of 0.1-5 wt%, preferably 0.2-1 wt%, and a molecular weight of 100-.
The raw materials of the nylon 12 hot melt adhesive also comprise optional auxiliary agents, wherein the auxiliary agents are preferably selected from antioxidants, catalysts, molecular weight regulators and the like;
the antioxidant is selected from the compound of an antioxidant 1098 and an antioxidant 168;
preferably, the dosage of the antioxidant is 1-5 wt% of the total mass of the raw material components a) -d);
the catalyst is selected from one or more of sodium phosphate, sodium hypophosphite and sodium hypophosphite;
preferably, the amount of the catalyst is 0.1 to 0.5 weight per thousand of the total mass of the raw material components a) to d);
the molecular weight regulator is selected from one or more of stearic acid, benzoic acid and glacial acetic acid;
preferably, the amount of the molecular weight regulator is 1-10 wt% of the total mass of the raw material components a) -d), and the amount of the molecular weight regulator can be determined by technical personnel according to the formula of the product and the viscosity of the product.
The invention also provides a preparation method of the nylon 12 hot melt adhesive, in particular to a preparation process for preparing the nylon 12 hot melt adhesive with good crystallization property by melting and polycondensation of multi-component monomers in a reaction kettle, and improving the water resistance and flexibility of the nylon 12 hot melt adhesive by screw modification to finally obtain a nylon 12 hot melt adhesive product, which comprises the following steps:
(1) adding the component a), the component b), the component c) and the component d) into a high-pressure reaction kettle for mixing, then adding optional auxiliary agents and water, heating to 100-295 ℃ under stirring for reaction for 30-90min, and then continuously heating to 280-295 ℃ for reaction for 3-6h to prepare the main chain structure of the nylon 12 hot melt adhesive;
(2) adding nylon 22 into a reaction kettle, replacing with nitrogen, heating to 240-260 ℃, reacting for 10-30min, granulating and drying to obtain nylon 12 colloidal particles;
(3) and (3) blending the nylon 12 colloidal particles obtained in the step (2) and the component f) by a double-screw extruder to prepare the nylon 12 hot melt adhesive.
In the step (3), the component f) is blended with nylon 12 colloidal particles in a double-screw extruder blending mode, and is grafted to the tail end of a main chain of a nylon 12 hot melt adhesive through a chemical reaction;
preferably, the blending specific method comprises the following steps: mixing the nylon 12 colloidal particles prepared in the step (2) with the component f) for 3-10min at the rotation speed of 20-100rpm and the temperature of 10-40 ℃ by a blender, feeding the mixture to a screw extruder, wherein the screw temperature is 180-230 ℃, preferably 190-220 ℃, and the rotation speed is 200-600rpm, preferably 220-400rpm, and performing extrusion granulation to obtain the nylon-12 colloidal particles.
According to the invention, the crystallization performance of the product is improved by introducing the low molecular weight nylon 22 (molecular weight of 300-2000) with a short chain structure into the branched chain of the nylon 12 hot melt adhesive, and the water washing resistance of the hot melt adhesive is improved by further introducing the flexible group (olefin structure containing epoxy or maleic anhydride functional group), so that the prepared nylon 12 hot melt adhesive has the advantages of good crystallization performance, less residual amount, good water and dry cleaning resistance, large peeling strength, good adhesion and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes the laurolactam as a part of the main structure of the nylon hot melt adhesive to ensure the basic flexibility, wear resistance and water washing resistance of the product.
According to the invention, the PA22 structure with high crystallinity and rapid crystallization is introduced into the branched chain structure of the nylon 12 hot melt adhesive, and the main structure of the nylon 12 hot melt adhesive is induced to crystallize through crystallization, so that the randomly copolymerized nylon hot melt adhesive is ensured to have certain crystallization capacity, thereby avoiding the improvement of the crystallization performance of the product by adding excessive laurolactam and long carbon chain monomers and the like, reducing the cost and simultaneously reducing the content of residual monomers.
According to the invention, the flexible olefin structure of an epoxy functional group or a maleic anhydride functional group is introduced into the tail end of the nylon 12 hot melt adhesive, so that the flexibility of the product is further improved while the crystallization capacity of the main structure is not influenced, and meanwhile, the flexible olefin structure has a positive effect on reducing the content of caprolactam and laurolactam residual monomers.
Detailed Description
The following examples further illustrate preferred embodiments within the scope of the present invention. These examples are merely illustrative and not intended to limit the scope of the invention, as many variations of the invention are possible without departing from the spirit and scope thereof.
The source information of the main raw materials adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
caprolactam: shanxi chemical industry, industrial grade;
laurolactam: wanhua chemical group, Inc., Industrial grade;
oxalic acid: jining Lanxing chemical Co., Ltd, a premium product;
adipic acid: huafeng group Limited, purified adipic acid, technical grade;
sebacic acid: hengshui Jinghua chemical Co., Ltd., industrial grade;
dodecanedioic acid: shandong Kaiser Biotechnology Co., Ltd., purity 99.7%, technical grade;
tetradecanedioic acid: shandong Kaiser Biotechnology Co., Ltd., purity 99.7%, technical grade;
ethylene diamine: Yangzhiti-Pasf Limited liability company, technical grade, purity 99.5%;
hexamethylene diamine: indovada, industrial grade;
pentanediamine: shandong Kaiser Biotech, Inc., Industrial grade;
decamethylenediamine: shandong Chi chemical Co., Ltd, technical grade;
triethylamine: kaiteng chemical Co., Ltd, Shandong, Industrial grade;
diethylenetriamine: shandong Shali environmental protection science and technology Limited, Industrial grade;
antioxidants 1098 and 168: basf, industrial grade;
sodium hypophosphite, and the like: beijing Yinuoka science and technology Co., Ltd, analytical grade;
epoxy-functional olefin polymers: nanjing Huadu scientific and technical industries, Inc.;
maleic anhydride grafted olefin polymer: nanjing Huadu scientific and technical industries, Inc.
The performance test method adopted by the embodiment of the invention comprises the following steps:
water washing resistance: measurement of washing Performance washing was performed according to the method specified in FZ/T01084-.
Dry cleaning resistance: measurement of Dry Wash Performance Water washing was carried out according to the method specified in FZ/T01083-.
Flexibility: the samples were tested for elongation at break according to the GB/T528-92 test method.
Wear resistance: and testing the mass loss rate of the sample according to the test method GB/T1768-2006.
Residual bills: dissolving a nylon 12 hot melt adhesive sample in a hexafluoroisopropanol solvent to prepare 10gL-1The dissolved solution is extracted by ethyl acetate, and then the content of monomer caprolactam and laurolactam is measured by adopting a gas chromatography.
Melting point and crystallization: according to the ISO 11357 test method, the temperature rising and lowering rate of the DSC instrument is set to be 10 ℃/min, and the temperature rising and lowering range is set to be 0-200 ℃.
Opening time: the test was performed according to the method specified in HG/T3716-2003.
Melt index: the test conditions are 2.16kg/160 ℃ according to the GB/T3682-2000 standard test.
Molecular weight: according to the test of GB/T27843-.
Example 1
(1) 1799.12g (19.98mol) of ethylenediamine, 1200.88g (19.98mol) of oxalic acid, 1.5g of sodium hypophosphite, 2.50g of antioxidant 1098, 5.00g of antioxidant 168, 180.15g of acetic acid and 600g of pure water are added into a high-pressure reaction kettle, stirring is started at 100rpm, heating is started to slowly raise the temperature of the materials to 50 ℃ for reaction for 45min, the temperature is continuously raised to 180 ℃ for heat preservation and pressure maintenance for reaction for 90min, the pressure is released to normal pressure through a pressure release valve, then the temperature is continuously raised to 290 ℃ for reaction for 40min, discharging and cutting into particles to prepare PA22, the average molecular weight is measured to be 1000, and the PA is dried for later use.
(2) 1750.00g of caprolactam, 2250.00g of laurolactam, 836.68g (5.73mol) of adipic acid, 665.27g (5.73mol) of hexamethylenediamine, 28.37g (0.27mol) of diethylenetriamine, 63.33g (0.27mol) of dodecanedioic acid, 41.95g of stearic acid, 1.40g of sodium hypophosphite, 4.66g of antioxidant 1098, 9.32g of antioxidant 168 and 1118.73g of water are added into a reaction kettle, after nitrogen replacement is carried out for 3 times, the temperature is increased to 115 ℃, after heat preservation and pressure maintaining reaction is carried out for 60min, the temperature is slowly increased to 290 ℃, after heat preservation and pressure maintaining reaction is carried out for 4.5h, the pressure is increased to normal pressure through a pressure relief valve, 274.98g of PA22 decompressed by the step (1) is put into the reaction kettle, after nitrogen replacement, the temperature is continuously increased to 250 ℃, after reaction is carried out for 15min, discharging, pelletizing and drying are carried out to obtain the nylon 12 colloidal particles.
(3) Mixing the nylon 12 colloidal particles obtained in the step (2) and 111.87g of epoxy-functional olefin polymer (epoxy functionality 0.9, molecular weight average 400) in a mixer for 10min at 20rpm and 10 ℃; then the mixture is melted and mixed in a double-screw extruder under the extrusion condition that the rotating speed of a screw is 200rpm, and the temperatures of the screw are set to be 190 ℃, 200 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃ and 210 ℃ from a feed inlet to a machine head in a segmented mode. The prepared nylon 12 hot melt adhesive is cut into granules, dried and then tested according to the standard, and the test results are shown in table 1.
Example 2
(1) 1559.24g (17.32mol) of ethylenediamine, 1040.76g (17.32mol) of oxalic acid, 0.26g of sodium hypophosphite, 2.60g of antioxidant 1098, 5.20g of antioxidant 168, 260.00g of acetic acid and 208.00g of pure water are added into a high-pressure reaction kettle, stirring is started at 100rpm, heating is started to slowly raise the temperature of the materials to 40 ℃ for reaction for 60min, the temperature is continuously raised to 160 ℃ for heat preservation and pressure maintenance for reaction for 90min, the pressure is released to normal pressure through a pressure release valve, then the temperature is continuously raised to 280 ℃ for reaction for 60min, discharging and cutting into particles to prepare PA22, the average molecular weight is 600, and drying is carried out for later use.
(2) 1300.00g of caprolactam, 3000.00g of laurolactam, 716.52g (2.77mol) of tetradecanedioic acid, 483.48g (2.77mol) of decamethylene diamine, 27.32g (0.27mol) of triethylamine, 39.46g (0.27mol) of adipic acid, 12.86g of acetic acid, 0.56g of sodium hypophosphite, 1.86g of antioxidant 1098, 3.72g of antioxidant 168 and 278.34g of water are added into a reaction kettle, after nitrogen replacement is carried out for 3 times, after the temperature is raised to 100 ℃, the reaction is kept at a constant temperature for 90min, after the temperature is slowly raised to 280 ℃, the reaction is kept at a constant temperature for 6h, the pressure is relieved to normal pressure through a pressure relief valve, 163.62g of PA22 prepared in the step (1) is put into the reaction kettle, after nitrogen replacement, the temperature is continuously raised to 240 ℃, after the reaction is continuously carried out for 30min, the material is discharged, cut into granules, and the nylon 12 colloidal particles are prepared by drying.
(3) Mixing the nylon 12 colloidal particles obtained in the step (2) and 250.51g of maleic anhydride grafted olefin polymer (the maleic anhydride grafting rate is 1 wt%, the molecular weight average value is 800) in a mixer for 10min, wherein the rotating speed is 20rpm, and the temperature is 10 ℃; then the mixture is melted and mixed in a double-screw extruder under the extrusion condition that the rotating speed of a screw is 200rpm, and the temperatures of the screw are set to be 190 ℃, 200 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃ and 210 ℃ from a feed inlet to a machine head in a segmented mode. The prepared nylon 12 hot melt adhesive is cut into granules, dried and then tested according to the standard, and the test results are shown in table 1.
Example 3
(1) 1401.03g (23.31mol) oxalic acid, 2098.97g (23.31mol) ethylenediamine, 0.35g sodium hypophosphite, 5.83g antioxidant 1098, 11.70g antioxidant 168, 284.95g benzoic acid and 1050.00g pure water are added into a high-pressure reaction kettle, stirring is started at 100rpm, the materials are heated to 60 ℃ slowly and react for 30min, the temperature is increased to 200 ℃ continuously, heat preservation and pressure maintaining reaction is carried out for 120min, the pressure is released to normal pressure through a pressure release valve, then the temperature is increased to 290 ℃ continuously and reacts for 30min, discharging materials are cut into particles to prepare PA22, the average molecular weight is measured and 1500, and drying is carried out for later use.
(2) 2300.00g of caprolactam, 1650.00g of laurolactam, 387.75g (2.22mol) of decamethylene diamine, 512.24g (2.22mol) of dodecanedioic acid, 218.17g (2.13mol) of pentanediamine, 431.83g (2.14mol) of sebacic acid, 53.36g (0.53mol) of triethylamine, 106.64g (0.53mol) of sebacic acid, 46.08g of benzoic acid, 2.83g of sodium hypophosphite, 5.66g of antioxidant 1098, 11.32g of antioxidant 168 and 1698.00g of water are added into a reaction kettle, after nitrogen replacement is carried out for 3 times, after the temperature is increased to 120 ℃, after heat preservation and pressure maintenance reaction is carried out for 30min, after the temperature is slowly increased to 295 ℃, after heat preservation and pressure maintenance reaction is carried out for 3h, pressure is relieved to normal pressure through a pressure relief valve, 790.99g of PA22 prepared in the step (1) is put into the reaction kettle, after nitrogen replacement, the temperature is continuously increased to 260 ℃, after the reaction is carried out for 10min, discharging and grain cutting is carried out, and nylon 12 colloidal particles are prepared by drying.
(3) Mixing the nylon 12 colloidal particles obtained in the step (2) and 60.37g of epoxy functional olefin polymer (epoxy functionality is 1.2, molecular weight average is 180) in a mixer for 10min, wherein the rotating speed is 20rpm, and the temperature is 10 ℃; then the mixture is melted and mixed in a double-screw extruder under the extrusion condition that the rotating speed of a screw is 200rpm, and the temperatures of the screw are set to be 190 ℃, 200 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, 220 ℃ and 210 ℃ from a feed inlet to a machine head in a segmented mode. The prepared nylon 12 hot melt adhesive is cut into granules, dried and tested for performance, and the test results are shown in table 1.
Comparative example 1
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: and (2) not adding the component a, granulating and drying the prepared nylon 12 hot melt adhesive, and then testing the test performance of the hot melt adhesive, wherein the test result is shown in table 1.
Comparative example 2
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: and (3) not adding the component b, granulating and drying the prepared nylon 12 hot melt adhesive, and then testing the test performance of the hot melt adhesive, wherein the test results are shown in table 1.
Comparative example 3
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: and (3) not adding the component c, granulating and drying the prepared nylon 12 hot melt adhesive, and then testing the test performance of the hot melt adhesive, wherein the test results are shown in table 1.
Comparative example 4
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: and (3) not adding the component d, granulating and drying the prepared nylon 12 hot melt adhesive, and then testing the test performance of the hot melt adhesive, wherein the test results are shown in table 1.
Comparative example 5
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: the component e is not added, the prepared nylon 12 hot melt adhesive is cut into particles and dried, and then the test performance is tested, and the test result is shown in table 1.
Comparative example 6
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: and (3) not adding the component f, granulating and drying the prepared nylon 12 hot melt adhesive, and then testing the test performance of the hot melt adhesive, wherein the test results are shown in table 1.
Comparative example 7
Preparation of high molecular weight nylon 22 (molecular weight average 5000):
(1) 1120.82g (18.65mol) oxalic acid, 1679.18g (18.65mol) ethylenediamine, 1.40g sodium hypophosphite, 2.33g antioxidant 1098, 4.66g antioxidant 168, 33.63g acetic acid and 560.00g pure water are added into a high-pressure reaction kettle, stirring is started at 100rpm, the materials are heated to 50 ℃ slowly and react for 45min, the temperature is increased to 180 ℃ continuously, heat preservation and pressure maintaining reaction is carried out for 90min, the pressure is released to normal pressure through a pressure release valve, then the temperature is increased to 290 ℃ continuously, after reaction for 40min, discharging and granulating are carried out to obtain PA22, the average molecular weight is 5000, and drying is carried out for later use.
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: and e, replacing the component e with the high molecular weight nylon 22 with the molecular weight average value of 5000, cutting into particles, drying, and then testing the performance of the prepared nylon 12 hot melt adhesive, wherein the test results are shown in Table 1.
Comparative example 8
Nylon 12 hot melt adhesive was prepared according to the method of example 1, except that: the component f is replaced by high molecular weight epoxy olefin polymer (Shenzhen Jinda full-technology Limited, Jinquan brand A-510, molecular weight mean value of 3000), the prepared nylon 12 hot melt adhesive is granulated and dried, and then the test performance is tested, and the test result is shown in Table 1.
Table 1 comparative and example performance test results
The homopolymerization reactions of the comparative examples and examples yielded polymers with a certain degree of polymerization as determined by the melt index and the residual monomer content of the product. Comparative examples 1 to 3 have a melting point of more than 150 ℃ and a rapid crystallization due to their simple main structure, and thus cannot be used as hot melt adhesives. The residual monomer content of the product can be significantly reduced by introducing reactive groups component e) PA22 and component f). Through contrast crystallization enthalpy, open time, bond strength data can know, PA22 can induce the product crystallization, shortens the open time when the product bonds, and its bond strength also has obvious promotion simultaneously, and simultaneously, f component can promote water-fast washing, pliability and the wear resistance of product.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the scope of the present invention is not limited thereto. All changes and modifications that come within the spirit of the invention are desired to be protected.
Claims (10)
1. The nylon 12 hot melt adhesive is characterized by comprising the following raw materials:
the total mass of the component a), the component b), the component c) and the component d) is 100 percent, and the mass percentage content is as follows:
a) caprolactam 20-45%, preferably 25-40%;
b) 25-60%, preferably 30-55% of laurolactam;
c) 20-30%, preferably 21-28% of at least one nylon salt raw material mixture consisting of C6-C14 dibasic acid and C5-C12 diamine;
d) at least one nylon salt raw material mixture composed of triamine and C2-C14 dibasic acid 1.0-4.0%, preferably 1.2-3.0%;
e) low molecular weight nylon 22(PA 22);
f) a medium to low molecular weight olefin polymer fraction having epoxy and/or maleic anhydride groups;
wherein the molar ratio of the triamine in the component e) to the component d) is 1.00-1.05: 1, preferably 1.00-1.01: 1;
the addition amount of the component f) is 0.1-10 percent of the total mass of the component a), the component b), the component c) and the component d), and the preferred addition amount is 0.1-5 percent.
2. The nylon 12 hot melt adhesive as claimed in claim 1, wherein component C) the C6-C14 dibasic acid reacts with C5-C12 diamine to produce a nylon salt;
preferably, the C6-C14 dibasic acid is selected from one or more of adipic acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid;
preferably, the C5-C12 diamine is selected from one or more of pentanediamine, hexanediamine and decanediamine;
preferably, the molar ratio of the C6-C14 dibasic acid to the C5-C12 diamine is 1.00-1.05: 1, more preferably 1.00 to 1.01: 1.
3. the nylon 12 hot melt adhesive as claimed in claim 1 or 2, wherein component d) the triamine is reacted with a C2-C14 dibasic acid to prepare a nylon salt;
preferably, the triamine is selected from diethylenetriamine and/or triethylamine;
preferably, the C2-C14 dibasic acid is selected from one or more of adipic acid, azelaic acid, sebacic acid and dodecanedioic acid;
preferably, the molar ratio of the triamine to the C2-C14 dibasic acid is 1.00-1.02: 1, more preferably 1.00: 1.
4. the nylon 12 hot melt adhesive according to any one of claims 1 to 3, wherein component e) the low molecular weight nylon 22 has a number average molecular weight of 300-2000, preferably 500-1500;
the nylon 22 is prepared from oxalic acid and ethylenediamine through polymerization reaction;
preferably, the molar ratio of ethylenediamine to oxalic acid is 1 to 1.05: 1, more preferably 1.00 to 1.01: 1.
5. the nylon 12 hot melt adhesive as claimed in any one of claims 1 to 4, wherein the nylon 22 raw material also comprises an end capping agent, and the end capping agent is selected from one or more of acetic acid, stearic acid, benzoic acid and adipic acid, preferably from one or more of acetic acid, stearic acid and benzoic acid; the amount of the end capping agent is 1 to 15 weight percent of the total mass of the oxalic acid and the ethylenediamine, preferably 1.5 to 10 weight percent;
preferably, the raw materials for preparing the nylon 22 also comprise a catalyst, an antioxidant and water;
the catalyst is selected from one or more of sodium phosphate, sodium hypophosphite and sodium hypophosphite; the dosage of the catalyst is preferably 0.1-1 wt% of the total mass of the oxalic acid and the ethylenediamine;
the antioxidant is selected from the compound of an antioxidant 1098 and an antioxidant 168, and the mixing mass ratio is preferably 1: 2; the dosage of the antioxidant is preferably 1-5 wt% of the total mass of the oxalic acid and the ethylenediamine;
the amount of the water is 5-40 wt% of the total mass of the oxalic acid and the ethylenediamine.
6. The nylon 12 hot melt adhesive according to any one of claims 1 to 5, wherein the nylon 22 is prepared by mixing oxalic acid, ethylenediamine, a catalyst, an antioxidant, acetic acid and water, heating to 40-60 ℃ for reaction for 30-60min, then continuing to heat to 150-.
7. The nylon 12 hot melt adhesive according to any one of claims 1 to 6, wherein component f) the medium and low molecular weight olefin polymer having epoxy and/or maleic anhydride groups; wherein the content of the first and second substances,
the epoxy functionality of the olefin polymer with the epoxy group and the medium and low molecular weight is 0.75-1.5, preferably 0.9-1.2, and the molecular weight is 100-1000, preferably 150-800;
the maleic anhydride group-containing olefin polymer with medium and low molecular weight has a maleic anhydride grafting rate of 0.1-5 wt%, preferably 0.2-1 wt%, and a molecular weight of 100-.
8. The nylon 12 hot melt adhesive according to any one of claims 1 to 6, characterized in that the raw materials further comprise optional auxiliary agents, preferably antioxidants, catalysts, molecular weight regulators;
the antioxidant is selected from the compound of an antioxidant 1098 and an antioxidant 168;
preferably, the dosage of the antioxidant is 1-5 wt% of the total mass of the raw material components a) -d);
the catalyst is selected from one or more of sodium phosphate, sodium hypophosphite and sodium hypophosphite;
preferably, the amount of the catalyst is 0.1 to 0.5 weight per thousand of the total mass of the raw material components a) to d);
the molecular weight regulator is selected from one or more of stearic acid, benzoic acid and glacial acetic acid;
preferably, the amount of the molecular weight regulator is 1-10 wt% of the total mass of the raw material components a) -d).
9. The preparation method of the nylon 12 hot melt adhesive as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) adding the component a), the component b), the component c) and the component d) into a high-pressure reaction kettle for mixing, then adding optional auxiliary agents and water, heating to 100-295 ℃ under stirring for reaction for 30-90min, and then continuously heating to 280-295 ℃ for reaction for 3-6h to prepare the main chain structure of the nylon 12 hot melt adhesive;
(2) adding nylon 22 into a reaction kettle, replacing with nitrogen, heating to 240-260 ℃, reacting for 10-30min, granulating and drying to obtain nylon 12 colloidal particles;
(3) and (3) blending the nylon 12 colloidal particles obtained in the step (2) and the component f) by a double-screw extruder to prepare the nylon 12 hot melt adhesive.
10. The preparation method according to claim 9, wherein in the step (3), the component f) is blended with nylon 12 colloidal particles by means of a twin-screw extruder blending manner, and grafted on the ends of the nylon 12 hot melt adhesive main chain by means of a chemical reaction;
preferably, the blending specific method is as follows: mixing the nylon 12 colloidal particles prepared in the step (2) with the component f) for 3-10min at the rotation speed of 20-100rpm and the temperature of 10-40 ℃ by a blender, feeding the mixture to a screw extruder, wherein the screw temperature is 180-230 ℃, preferably 190-220 ℃, and the rotation speed is 200-600rpm, preferably 220-400rpm, and performing extrusion granulation to obtain the nylon-12 colloidal particles.
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| CN114231242B (en) | 2023-05-30 |
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