CN111334240A - Reactive polyurethane hot melt adhesive and preparation method and application thereof - Google Patents
Reactive polyurethane hot melt adhesive and preparation method and application thereof Download PDFInfo
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
A reactive polyurethane hot melt adhesive and a preparation method and application thereof relate to the technical field of hot melt adhesives. The hot melt adhesive is prepared from the following raw materials in parts by weight: 20-50 parts of polyether polyol; 20-50 parts of polyester polyol; 10-30 parts of polyisocyanate; 5-20 parts of amino-terminated acrylate resin; 0.5-2 parts of antioxidant auxiliary agent; 0.05-0.5 part of catalyst. The reactive polyurethane hot melt adhesive has good high temperature resistance and cohesiveness. The invention also discloses a preparation method and application of the reactive polyurethane hot melt adhesive.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives. More particularly relates to a reactive polyurethane hot melt adhesive and a preparation method and application thereof.
Background
The polyurethane adhesive is a new chemical material of synthetic resin, and is adhesive resin containing carbamate (-NHCOO-) or isocyanate (-NCO) in molecular chain. The yield of the polyurethane adhesive in China in 2017 is 89.6 ten thousand tons, and is expected to reach 109.8 ten thousand tons in 2020. According to the yield data of nearly five years, the annual average growth rate of the polyurethane adhesive is 7.5%, wherein the reactive polyurethane hot melt adhesive (PUR) becomes the variety with the fastest development rate of the polyurethane adhesive industry with the characteristics of high performance, high added value and the like. The reactive polyurethane hot melt adhesive (PUR) is a reactive adhesive which can be subjected to moisture crosslinking and curing to continuously improve the bonding strength, has the characteristics of excellent initial bonding strength, heat resistance, high final bonding strength and the like, and has extremely high application value in the industries of 3C products, household appliances, automobile manufacturing and the like. Therefore, there is a need to consider how to better reduce the cost of its preparation and how to provide a polyurethane adhesive with better properties.
Disclosure of Invention
The first purpose of the invention is to provide a reactive polyurethane hot melt adhesive.
The second purpose of the invention is to provide a preparation method of the reactive polyurethane hot melt adhesive.
The third purpose of the invention is to provide the application of the reactive polyurethane hot melt adhesive.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a reactive polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight:
further, the hot melt adhesive is prepared from the following raw materials in parts by weight:
further, the polyester polyol is aromatic polyester polyol prepared by alcoholysis and esterification of PET products. The PET product includes but is not limited to waste PET products, such as waste PET bottles and the like. The polyester polyol provided by the method realizes the waste utilization of PET products on one hand, and has low cost; on the other hand, the inventor of the invention researches and discovers that the aromatic polyester polyol provided by the method has better heat resistance and adhesiveness after being used in polyurethane hot melt adhesive compared with the aromatic polyester polyol provided by the conventional method.
Further, the preparation of the polyester polyol comprises the following steps:
(1) alcoholysis of PET products: taking waste of the cleaned and dried PET product, sequentially adding a catalyst and a depolymerizing agent, carrying out alcoholysis for 2-6 hours at the reaction temperature of 150-200 ℃ in the nitrogen atmosphere, quickly heating and filtering reaction liquid, extracting the reaction liquid for three times by using boiling water, standing the reaction liquid for 8-12 hours at the low temperature of-10 ℃ to-20 ℃, separating out white crystals, washing the white crystals for three times by using distilled water to remove the catalyst and the depolymerizing agent, and carrying out vacuum drying for 2-6 hours at the temperature of 60 ℃ to obtain an alcoholysis product of the PET product;
the reaction equation is as follows:
(2) esterification of alcoholysis products of PET products: mixing the alcoholysis product of the PET product obtained in the step (1), aromatic dibasic acid and micromolecular dihydric alcohol according to a certain mass ratio, and carrying out esterification and dehydration for 10-15 hours at the reaction temperature of 150-220 ℃ in the nitrogen atmosphere, wherein the acid value is less than or equal to 20 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa (negative value represents lower than atmospheric pressure) at the rate of 0.02MPa/30min, wherein the reaction temperature is between 200 ℃ and 220 ℃; and then reacting for 1-2 hours under high vacuum degree, wherein the acid value is less than or equal to 2mgKOH/g, and obtaining the aromatic polyester polyol.
The reaction equation is (for illustration only) as:
furthermore, the alcoholysis in the step (1) is carried out by taking dihydric alcohol as a depolymerizing agent and catalyzing by a catalyst.
Further, the catalyst in the step (1) is selected from one or more of stannous chloride, zinc acetate, lead acetate, manganese acetate, titanium phosphate and ionic liquid.
Further, the weight of the catalyst in the step (1) is 0.01-0.2% of the weight of the PET product.
Further, the depolymerizing agent in the step (1) is one or more selected from ethylene glycol, diethylene glycol, propylene glycol and butanediol.
Further, the weight of the depolymerizing agent in the step (1) is 150-300% of the weight of the PET product.
Further, the alcoholysis product of the step (1) is glycol ester, preferably one or more of ethylene terephthalate, diethylene glycol terephthalate, trimethylene terephthalate and butylene terephthalate.
Further, the esterification method in the step (2) is as follows: and heating, esterifying and dehydrating the alcoholysis product, micromolecular dibasic acid and micromolecular dihydric alcohol to obtain the aromatic polyester polyol.
Further, the small molecule dibasic acid in the step (2) is selected from one or more of succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, phthalic anhydride and isophthalic acid.
Further, the small molecule diol in the step (2) is selected from one or more of ethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol.
Further, in the step (2), the molar ratios of the alcoholysis product of the PET product, the small-molecule dibasic acid and the small-molecule dihydric alcohol in the step (2) are respectively as follows: n (PET article alcoholysis product): n (small molecule dibasic acid): n (small molecule diol) ═ 1: 1-5: 1-5.
Further, the number average molecular weight of the polyester polyol is 1000-4000.
Further, the aromatic polyester polyol obtained by the method is selected from one or more of terephthalic acid polyol, phthalic acid polyol and phthalic anhydride polyester polyol.
Further, the polyether polyol has a number average molecular weight of 1000-4000.
Further, the polyether polyol is selected from polyether glycol, preferably one or more of polypropylene glycol, polytetramethylene ether glycol and polyethylene glycol.
Further, the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate and toluene diisocyanate.
Further, the amino-terminated acrylate resin is selected from one or more of amino methyl acrylate resin, amino ethyl acrylate resin and amino butyl acrylate resin.
Further, the molecular weight of the amino-terminated acrylate resin is 1000-30000.
Further, the antioxidant auxiliary agent is selected from one or more of arylamine antioxidants mainly comprising dialkyl diphenylamine, diaminotoluene derivatives and 1, 8-diaminonaphthalene derivatives.
Further, the catalyst is selected from one or more of dibutyltin dilaurate, dibutyltin diacetate, triethylenediamine and double-morpholino diethyl ether.
Furthermore, the total weight of the components in the raw materials of the reactive polyurethane hot melt adhesive is 100 parts.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of reactive polyurethane hot melt adhesive comprises the following steps:
mixing polyether polyol, polyester polyol, amino-terminated acrylate resin and an antioxidant auxiliary agent, heating to 110-130 ℃, stirring, vacuumizing and dehydrating for 1.0-3.0 hours; cooling to 85-100 ℃, adding polyisocyanate under the protection of nitrogen, and stirring and reacting at the temperature of 105-125 ℃ for 0.5-2.5 hours under the protection of nitrogen; adding a catalyst, reacting for 0.5-1.5 hours at the temperature of 105-125 ℃ under vacuum stirring, and discharging to obtain the reactive polyurethane hot melt adhesive.
In the preparation of the reactive polyurethane hot melt adhesive, the reaction conditions including reaction temperature, charging sequence and the like directly influence the performances of the obtained polyurethane hot melt adhesive including heat resistance, adhesiveness and the like. Therefore, in the preparation process of the hot melt adhesive, reaction conditions such as reaction temperature, time, feeding sequence and the like of each step need to be strictly controlled.
In order to achieve the third object, the present invention provides the application of the reactive polyurethane hot melt adhesive in general industry.
Further, the application of the reactive polyurethane hot melt adhesive in 3C products, household appliances or automobile manufacturing is provided.
Further, the reactive polyurethane hot melt adhesive can be used for bonding of PC/PC boards. And researches show that the polyurethane hot melt adhesive is particularly suitable for bonding PC boards, particularly thermal PC/PC boards.
The invention has the following beneficial effects:
in the reactive polyurethane hot melt adhesive provided by the invention, aromatic polyester polyol obtained by esterification based on the alcoholysis product of the recycled PET bottle flakes is used as the polyester polyol molecular chain structure, so that the hot melt adhesive has high tensile strength, elongation and adhesive property, and excellent high temperature resistance; the introduction of the amino-terminated acrylate resin can further enhance the bonding of different substrates, particularly polar surface materials; the polyisocyanate is used as a cross-linking agent, and the type and the dosage of the polyisocyanate can influence the molecular weight, the viscosity and the bonding performance of the hot melt adhesive; the catalyst can catalyze the reaction of NCO groups and moisture to promote crosslinking and curing; the small amount of antioxidant additive can effectively reduce the oxidative discoloration and degradation of the polyurethane prepolymer and enhance the heat resistance of the system.
In addition, the reactive polyurethane hot melt adhesive provided by the invention has excellent adhesion to different base materials such as plastics, metals, wood, glass and the like, is particularly good in adhesion to polar surface materials, has excellent high temperature resistance, and is widely applied to the fields of 3C products, household appliances, automobile manufacturing and the like.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The reactive polyurethane hot melt adhesive of the embodiment has the following raw material composition as shown in the following table 1:
TABLE 1
The preparation method of the reactive polyurethane hot melt adhesive comprises the following steps:
1) adding a mixture of polypropylene glycol, polyethylene glycol terephthalate polyester polyol, methyl aminoacrylate, dialkyl diphenylamine and a diaminotoluene derivative into a reaction kettle according to a metering ratio, heating to 120 ℃, and carrying out vacuum dehydration for 2 hours under stirring;
2) cooling to 90 ℃, adding diphenylmethane diisocyanate, and stirring and reacting for 1 hour at 115 ℃ under the protection of nitrogen;
3) adding dibutyltin dilaurate, vacuumizing, stirring and reacting for 1 hour at 115 ℃, and discharging to obtain the reactive polyurethane hot melt adhesive PUR1 #.
The ethylene terephthalate-based polyester polyol is prepared by the following method:
taking 10 parts of recovered PET bottle flakes after cleaning and drying, sequentially adding 0.05 part of stannous chloride and 25 parts of ethylene glycol, carrying out alcoholysis for 4 hours at the reaction temperature of 160 ℃ in the nitrogen atmosphere, quickly heating and filtering the reaction liquid, extracting the reaction liquid for three times by using boiling water, standing the reaction liquid for 10 hours at the low temperature of-20 ℃, washing the separated white crystals for three times by using distilled water, and carrying out vacuum drying for 4 hours at the temperature of 60 ℃ to obtain the ethylene glycol terephthalate;
mixing the obtained ethylene terephthalate, adipic acid and ethylene glycol according to the mass ratio of 30%/30%/40%, and carrying out esterification and dehydration for 15 hours at the reaction temperature of 180 ℃ in a nitrogen atmosphere, wherein the acid value is 18.5 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa at the rate of 0.02MPa/30min, wherein the reaction temperature is 210 ℃; followed by reaction under high vacuum for 2 hours to give an acid value of 0.68mgKOH/g, to obtain an ethylene terephthalate-based polyester polyol.
Example 2
The reactive polyurethane hot melt adhesive of the embodiment has the following raw material composition shown in the following table 2:
TABLE 2
| Raw materials | Mass percent content (%) |
| Polypropylene glycol Mn 2000 | 35 |
| Diethylene glycol terephthalate-based polyester polyol Mn 2000 | 40 |
| Amino methyl acrylate Mn 8000 | 8 |
| Diphenylmethane diisocyanate | 15 |
| Dialkyl diphenylamine: diaminotoluene derivative ═ 1:1 (mass ratio) | 1.9 |
| Dimorpholinyl diethyl ether | 0.1 |
The preparation method of the reactive polyurethane hot melt adhesive comprises the following steps:
1) putting the mixture of polypropylene glycol, diethylene glycol terephthalate polyester polyol, methyl aminoacrylate, dialkyl diphenylamine and diaminotoluene derivatives into a reaction kettle according to a metering ratio, heating to 120 ℃, and carrying out vacuum dehydration for 2 hours under stirring;
2) cooling to 90 ℃, adding diphenylmethane diisocyanate, and stirring and reacting for 1 hour at 110 ℃ under the protection of nitrogen;
3) adding dimorpholinyl diethyl ether, stirring under vacuum, reacting at 110 deg.C for 1 hr, and discharging to obtain reactive polyurethane hot melt adhesive PUR2 #.
Wherein, the diethylene glycol terephthalate polyester polyol is prepared by the following method:
taking 10 parts of recovered PET bottle chips which are cleaned and dried, sequentially adding 0.1 part of zinc acetate and 30 parts of diethylene glycol, carrying out alcoholysis for 4 hours at the reaction temperature of 200 ℃ in a nitrogen atmosphere, quickly heating and filtering the reaction liquid, extracting the reaction liquid for three times by using boiling water, standing the reaction liquid for 12 hours at the low temperature of-10 ℃, washing the separated white crystals for three times by using distilled water, and carrying out vacuum drying for 4 hours at the temperature of 60 ℃ to obtain diethylene glycol terephthalate;
mixing diethylene glycol terephthalate, phthalic acid and diethylene glycol according to the mass ratio of 35%/25%/40%, and carrying out esterification and dehydration for 13 hours at the reaction temperature of 180 ℃ in a nitrogen atmosphere, wherein the acid value is 19.0 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa at the rate of 0.02MPa/30min, wherein the reaction temperature is 210 ℃; followed by reaction under high vacuum for 1.5 hours to give a diethylene glycol terephthalate-based polyester polyol having an acid value of 1.1 mgKOH/g.
Example 3
The reactive polyurethane hot melt adhesive of the embodiment has the following raw material composition shown in the following table 3:
TABLE 3
| Raw materials | Mass percent content (%) |
| Polypropylene glycol Mn 2000 | 45 |
| Terephthalic acid propylene glycol ester polyester polyol Mn ═ 4000 | 30 |
| Aminoacrylic acid ethyl ester Mn ═ 4000 | 7.4 |
| Diphenylmethane diisocyanate | 15 |
| Dialkyl diphenylamine | 2.5 |
| Dimorpholinyl diethyl ether | 0.1 |
The preparation method of the reactive polyurethane hot melt adhesive comprises the following steps:
1) adding polypropylene glycol, propylene glycol terephthalate polyester polyol, ethyl aminoacrylate and dialkyl diphenylamine into a reaction kettle according to a metering ratio, heating to 120 ℃, and carrying out vacuum dehydration for 2 hours under stirring;
2) cooling to 90 ℃, adding diphenylmethane diisocyanate, and stirring and reacting for 1 hour at 110 ℃ under the protection of nitrogen;
3) adding dimorpholinyl diethyl ether, stirring under vacuum, reacting at 110 deg.C for 1 hr, and discharging to obtain reactive polyurethane hot melt adhesive PUR3 #.
Wherein, the terephthalic acid propylene glycol ester polyester polyol is prepared by the following method:
taking 10 parts of recovered PET bottle chips which are cleaned and dried, sequentially adding 0.1 part of zinc acetate and 30 parts of 1, 3-propylene glycol, carrying out alcoholysis for 4 hours at the reaction temperature of 200 ℃ in a nitrogen atmosphere, quickly heating and filtering the reaction liquid, extracting for three times by using boiling water, standing for 12 hours at the low temperature of-10 ℃, separating out white crystals, washing for three times by using distilled water, and carrying out vacuum drying for 4 hours at the temperature of 60 ℃ to obtain trimethylene terephthalate;
mixing 30%/30%/40% of trimethylene terephthalate, phthalic acid and ethylene glycol according to the mass ratio, and carrying out esterification and dehydration for 14 hours at the reaction temperature of 200 ℃ in a nitrogen atmosphere, wherein the acid value is 19.3 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa at the rate of 0.02MPa/30min, wherein the reaction temperature is 220 ℃; then, the reaction was carried out for 1.5 hours under a high vacuum condition, and the acid value was 0.8mgKOH/g, thereby obtaining a propylene terephthalate-based polyester polyol.
Example 4
The reactive polyurethane hot melt adhesive of the embodiment has the following raw material composition shown in the following table 4:
TABLE 4
| Raw materials | Mass percent content (%) |
| Polypropylene glycol Mn 2000 | 45 |
| Polybutylene terephthalate-based polyester polyol Mn 4000 | 35 |
| Aminoacrylic acid ethyl ester Mn ═ 4000 | 8 |
| Toluene diisocyanate | 10 |
| Dialkyl diphenylamine: diaminotoluene derivative ═ 1:1 (mass ratio) | 1.85 |
| Dimorpholinyl diethyl ether | 0.15 |
The preparation method of the reactive polyurethane hot melt adhesive comprises the following steps:
1) adding a mixture of polypropylene glycol, polybutylene terephthalate polyester polyol, ethyl aminoacrylate, dialkyl diphenylamine and a diaminotoluene derivative into a reaction kettle according to a metering ratio, heating to 1200 ℃, and carrying out vacuum dehydration for 2 hours under stirring;
2) cooling to 70 ℃, adding toluene diisocyanate, and stirring and reacting for 1 hour at 80 ℃ under the protection of nitrogen;
3) adding dimorpholinyl diethyl ether, stirring under vacuum, reacting at 80 deg.C for 1 hr, and discharging to obtain reactive polyurethane hot melt adhesive PUR4 #.
The polybutylene terephthalate-based polyester polyol is prepared by the following method:
taking 10 parts of recovered PET bottle flakes after cleaning and drying, sequentially adding 0.1 part of ionic liquid and 20 parts of 1, 4-butanediol, carrying out alcoholysis for 4 hours at the reaction temperature of 200 ℃ in a nitrogen atmosphere, quickly heating and filtering the reaction liquid, extracting for three times by using boiling water, standing for 12 hours at the low temperature of-20 ℃, separating out white crystals, washing for three times by using distilled water, and carrying out vacuum drying for 5 hours at the temperature of 60 ℃ to obtain the butylene terephthalate;
mixing 30%/30%/40% by mass of butylene terephthalate, phthalic anhydride and ethylene glycol, and carrying out esterification and dehydration for 15 hours at the reaction temperature of 200 ℃ in a nitrogen atmosphere, wherein the acid value is 17.9 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa at the rate of 0.02MPa/30min, wherein the reaction temperature is 220 ℃; followed by reaction under high vacuum for 2 hours to give a butylene terephthalate-based polyester polyol having an acid value of 0.9 mgKOH/g.
Example 5
Example 1 was repeated except that the raw materials were 35% by mass of polypropylene glycol and 35% by mass of ethylene terephthalate based polyester polyol, and the remaining conditions were unchanged, to prepare reactive polyurethane hot melt adhesive PUR5 #.
Example 6
Example 1 was repeated except that in the starting materials, polypropylene glycol was changed to polytetramethylene ether glycol, and the remaining conditions were not changed to prepare reactive polyurethane hot melt adhesive PUR6 #.
Comparative example 1
Example 1 was repeated except that the ethylene terephthalate-based polyester polyol prepared therein was replaced with a polyester polyol prepared by esterification of chemical raw materials, i.e., terephthalic acid, ethylene glycol, and adipate; and (3) keeping the other conditions unchanged, and preparing the reactive polyurethane hot melt adhesive.
Mixing terephthalic acid, adipic acid and ethylene glycol according to the mass ratio of 12.8%, 30% and 57.2%, and carrying out esterification and dehydration for 15 hours at the reaction temperature of 220 ℃ in a nitrogen atmosphere, wherein the acid value is 19.2 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa at the rate of 0.02MPa/30min, wherein the reaction temperature is 230 ℃; followed by reaction under high vacuum for 2 hours to give an acid value of 1.2mgKOH/g, to obtain an ethylene terephthalate-based polyester polyol.
Comparative example 2
Example 1 was repeated except that the amino methyl acrylate was replaced with hydroxy-terminated acrylate-carbonate copolyester and the remaining conditions were unchanged to prepare a reactive polyurethane hot melt adhesive.
The tensile strength, elongation at break and shear strength test results of the polyurethane hot melt adhesive obtained in the above examples and comparative examples under the GB/T7124 + 2008 standard and after being placed for 2 hours at different temperatures are shown in the following table 5:
TABLE 5
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. The reactive polyurethane hot melt adhesive is characterized by being prepared from the following raw materials in parts by weight:
2. the reactive polyurethane hot melt adhesive according to claim 1, wherein the hot melt adhesive is prepared from the following raw materials in parts by weight:
3. a reactive polyurethane hot melt adhesive according to claim 1 or 2, characterized in that the preparation of said polyester polyol comprises the steps of:
(1) alcoholysis of PET products: taking waste of the cleaned and dried PET product, sequentially adding a catalyst and a depolymerizing agent, carrying out alcoholysis for 2-6 hours at the reaction temperature of 150-200 ℃ in the nitrogen atmosphere, quickly heating and filtering reaction liquid, extracting the reaction liquid for three times by using boiling water, standing the reaction liquid for 8-12 hours at the low temperature of-10 ℃ to-20 ℃, separating out white crystals, washing the white crystals for three times by using distilled water to remove the catalyst and the depolymerizing agent, and carrying out vacuum drying to obtain an alcoholysis product of the PET product;
(2) esterification of alcoholysis products of PET products: mixing the alcoholysis product of the PET product obtained in the step (1), micromolecular dibasic acid and micromolecular dihydric alcohol according to a certain mass ratio, and carrying out esterification and dehydration for 10-15 hours under the condition of reaction temperature of 150-220 ℃ in nitrogen atmosphere, wherein the acid value is less than or equal to 20 mgKOH/g; then, starting to vacuumize, and increasing the vacuum degree of the system to-0.1 MPa according to the speed of 0.02MPa/30min, wherein the reaction temperature is between 200 ℃ and 220 ℃; and then reacting for 1-2 hours under high vacuum degree, wherein the acid value is less than or equal to 2mgKOH/g, and obtaining the aromatic polyester polyol.
4. The reactive polyurethane hot melt adhesive according to claim 3, wherein in the preparation method of the polyester polyol, the reaction equation in the step (1) is as follows:
one reaction equation of step (2) is:
5. the reactive polyurethane hot melt adhesive according to claim 3 or 4, wherein the alcoholysis in the step (1) is carried out by taking dihydric alcohol as a depolymerizing agent under the catalysis of a catalyst; the catalyst in the step (1) is selected from one or more of stannous chloride, zinc acetate, lead acetate, manganese acetate, titanium phosphate and ionic liquid; the weight consumption of the catalyst in the step (1) is 0.01-0.2% of the weight of the PET product; the depolymerizing agent in the step (1) is one or more selected from ethylene glycol, diethylene glycol, propylene glycol and butanediol; the weight consumption of the depolymerizing agent in the step (1) is 150-300% of the weight of the PET product; the alcoholysis product in the step (1) is diol ester, preferably one or more of ethylene terephthalate, diethylene glycol terephthalate, trimethylene terephthalate and butylene terephthalate;
the esterification method in the step (2) comprises the following steps: heating, esterifying and dehydrating the alcoholysis product, micromolecular dibasic acid and micromolecular dihydric alcohol to obtain the aromatic polyester polyol; the micromolecular dibasic acid in the step (2) is selected from one or more of succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, phthalic anhydride and isophthalic acid; the small molecular dihydric alcohol in the step (2) is selected from one or more of ethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol; in the step (2), the molar ratios of the alcoholysis product of the PET product, the micromolecular dibasic acid and the micromolecular dihydric alcohol are respectively as follows: n (PET article alcoholysis product): n (small molecule dibasic acid): n (small molecule diol) ═ 1: 1-5: 1-5.
6. The reactive polyurethane hot melt adhesive as claimed in claim 3 or 4, wherein the number average molecular weight of the polyester polyol is 1000-4000; the aromatic polyester polyol obtained by the method is selected from one or more of terephthalic acid polyol, phthalic acid polyol and phthalic anhydride polyester polyol.
7. The reactive polyurethane hot melt adhesive according to claim 1 or 2, wherein the polyether polyol has a number average molecular weight of 1000-4000; the polyether polyol is selected from polyether glycol, preferably one or more of polypropylene glycol, polytetramethylene ether glycol and polyethylene glycol; the antioxidant auxiliary agent is selected from arylamine antioxidant which is mainly one or more of dialkyl diphenylamine, diaminotoluene derivatives and 1, 8-diaminonaphthalene derivatives;
the catalyst is selected from one or more of dibutyltin dilaurate, dibutyltin diacetate, triethylenediamine and double-morpholino diethyl ether.
The polyisocyanate is selected from one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate and toluene diisocyanate;
the amino-terminated acrylate resin is selected from one or more of amino methyl acrylate resin, amino ethyl acrylate resin and amino butyl acrylate resin; the molecular weight of the amino-terminated acrylate resin is 1000-30000;
the total weight of the components in the raw materials of the reactive polyurethane hot melt adhesive is 100 parts.
8. The preparation method of the reactive polyurethane hot melt adhesive as claimed in claim 1 or 2, which is characterized by comprising the following steps:
mixing polyether polyol, polyester polyol, amino-terminated acrylate resin and an antioxidant auxiliary agent, heating to 110-130 ℃, stirring, vacuumizing and dehydrating for 1.0-3.0 hours; cooling to 85-100 ℃, adding polyisocyanate under the protection of nitrogen, and stirring and reacting at the temperature of 105-125 ℃ for 0.5-2.5 hours under the protection of nitrogen; adding a catalyst, reacting for 0.5-1.5 hours at the temperature of 105-125 ℃ under vacuum stirring, and discharging to obtain the reactive polyurethane hot melt adhesive.
9. Use of the reactive polyurethane hot melt adhesive of claim 1 or 2 in 3C products, household appliances or automobile manufacturing.
10. Use according to claim 9, wherein the reactive polyurethane hotmelt is used for bonding PC/PC boards, in particular for bonding PC boards to one another and for bonding PC/PC boards thermally.
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