CN108239509B - Polyether ester hot melt adhesive with good heat resistance and preparation method thereof - Google Patents
Polyether ester hot melt adhesive with good heat resistance and preparation method thereof Download PDFInfo
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- CN108239509B CN108239509B CN201611205121.5A CN201611205121A CN108239509B CN 108239509 B CN108239509 B CN 108239509B CN 201611205121 A CN201611205121 A CN 201611205121A CN 108239509 B CN108239509 B CN 108239509B
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polyether ester hot melt adhesive with good heat resistance and a preparation method thereof, wherein the polyether ester hot melt adhesive comprises the following components: a) the polyether ester polyol hot melt adhesive comprises a polyether ester polyol unit and b) a perfluoropolyether end-capping agent unit, wherein the weight-average molecular weight of the polyether ester hot melt adhesive is 20000-50000. The melting point of the polyether ester hot melt adhesive is 175-195 ℃, and the polyether ester hot melt adhesive has low viscosity, good low-temperature flexibility, good hydrolysis resistance and good thermal oxygen aging resistance.
Description
Technical Field
The invention relates to a polyether ester hot melt adhesive and a preparation method thereof, in particular to a polyether ester hot melt adhesive with good heat resistance and a preparation method thereof.
Background
Polyether esters are mostly used in the field of fiber materials and engineering plastics, but are also useful in the field of hot melt adhesives, such as patent publication CN96104247.8 (polyether ester for textile bonding) which discloses a polyether ester obtained by copolymerizing a polyalkylene ether glycol into a common polyether ester hot melt adhesive system, although it discloses solving the thermal oxygen aging resistance of polyether esters by adding an auxiliary agent; there is patent publication CN201110388483.3 (a polyether ester for textile adhesive bonding) which also uses the addition of polyalkylene ether glycol to a conventional polyether ester hot melt adhesive formulation to obtain a polyether ester, which is less susceptible to damage during processing and grinding and has a reduced melting point, making it easier to use.
In the above patent technologies, since polyether ester contains a large amount of ether bond components, thermal oxidation aging is easy, polyether absorbs water easily, and the occurrence of hydrolysis of the hot melt adhesive due to the action of water during storage and use of the hot melt adhesive also causes a large amount of bubbles to be generated during heating and use of the hot melt adhesive, thereby affecting use.
Therefore, there is a need in the art for a novel polyetherester hot melt adhesive material which can overcome the defects of the existing polyetherester hot melt adhesive that water is easily absorbed and degraded, so that the polyetherester hot melt adhesive has low viscosity, hydrolysis resistance, thermal-oxidative aging resistance and good low-temperature flexibility.
Disclosure of Invention
One aspect of the present invention provides a heat resistant polyetherester hot melt adhesive comprising:
a) polyether ester polyol units which are the polycondensation reaction product of a dicarboxylic acid component comprising terephthalic acid, isophthalic acid and optionally dimer acid, a diol component and a molecular weight increasing agent; the diol componentContaining C2-6Diols and aliphatic polyether diols;
b) the weight average molecular weight of the polyether ester hot melt adhesive is 20000-50000.
Another aspect of the present invention provides a method for preparing the heat-resistant polyether ester hot melt adhesive, which comprises polycondensing and end-capping the dicarboxylic acid component, the diol component, the molecular weight increasing agent and the perfluoropolyether end-capping agent in the presence of a catalyst.
The melting point of the polyether ester hot melt adhesive is 175-195 ℃, the fluorine-containing polyether ester hot melt adhesive has good hydrolysis resistance, thermal oxygen aging resistance and low viscosity, and the modified fluorine-containing polyether ester hot melt adhesive also has good low-temperature flexibility.
Detailed Description
In a preferred embodiment, the polyether ester polyol unit in the polyether ester hot melt adhesive comprises 49-60 wt% of dicarboxylic acid component, 39-50 wt% of diol component and 0.1-5 wt% of molecular weight increasing agent, preferably 49-60 wt% of dicarboxylic acid component, 39-50 wt% of diol component and 0.2-3 wt% of molecular weight increasing agent. .
In a more preferred embodiment, the content of terephthalic acid is 50 to 90% by weight, the content of isophthalic acid is 1 to 20% by weight, and the content of dimer acid is 0 to 40% by weight, based on the total weight of the dicarboxylic acid component in the polyetherester polyol unit.
In a more preferred embodiment, the content of terephthalic acid is 55 to 85 wt%, the content of isophthalic acid is 3 to 15 wt%, and the content of dimer acid is 10 to 40 wt%, based on the total weight of dicarboxylic acid components in the polyetherester polyol unit.
The dimer acid used in the present invention is C32－40Dimer acids, e.g. C16～C20Dimer of unsaturated fatty acids or alcohols, which may be dimer acids derived from linoleic acid, oleic acid, linolenic acid, elaidic acid, linoleic acid, eleostearic acid or tall oil. Preferred are dimer acids derived from C18 unsaturated fatty acids, e.g., tall oil, linoleic acid, oleic acidOr dimer acid obtained by dimerization of linolenic acid and the like, and hydrogenated dimer acid obtained by hydrogenation of the dimer acid, or dimer alcohol, wherein the use amount of the dimer acid is 1-40% of the mol content of the total diacid, preferably 5-30%;
in a more preferred embodiment, C is based on the total weight of the diol component in the polyetherester polyol units2-6The content of the dihydric alcohol is 80-96 wt% and the content of the aliphatic polyether dihydric alcohol is 4-20 wt%.
In a more preferred embodiment, C is2-6The diol component comprises at least one diol selected from ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexylene glycol. The above-mentioned diols may be used alone or in combination of two or more.
In a preferred embodiment of the present invention, the above-mentioned aliphatic polyether glycol comprises a polyether glycol represented by the formula C1-4Aliphatic diols, preferably from C2-4The molecular weight of the polyether glycol polymerized by the aliphatic diol is 1500-2500, and the preferred molecular weight is 1600-2400. Examples of aliphatic polyether diols include, but are not limited to, polyethylene glycol, polypropylene glycol, polybutanol, polytetrahydrofuran ether (PTMEG), polypropylene oxide glycol, or mixtures thereof. Polypropylene oxide glycol is preferably used.
In a more preferred embodiment, the molecular weight increasing agent is one commonly used in the art, for example, comprising a polyol, a polyacid, or a mixture thereof. Examples of the molecular weight increasing agent include, for example, glycerol, pentaerythritol, 1,3, 5-benzenetricarboxylic acid, trimethylolmethane, trimethylolpropane, β -hydroxyalkylamide, or a mixture thereof.
In a preferred embodiment, the perfluoropolyether capping agent units are derived from perfluoropolyether carbinols, perfluoropolyether formic acids, or mixtures thereof, and the perfluoropolyether capping agent has a molecular weight of 1500 to 2500, preferably 1800 to 2300.
In a more preferred embodiment, the perfluoropolyether capping agent units constitute 0.1 to 5 wt%, preferably 0.2 to 1 wt%, of the total weight of the polyetherester polyol units. (alternatively, the perfluoropolyether capping agent unit accounts for 1 to 50 mol%, preferably 2 to 10 mol%, of the total mol of the polyetherester polyol units).
For example, the above perfluoropolyether carbinol can be represented by the following general formula (1):
wherein n is the number of perfluoropropylene oxide monomers, and is generally 1-50, preferably 7-14 (corresponding to molecular weight of 1500-.
In a preferred embodiment of the present invention, the ratio of the total moles of copolymerized units of dicarboxylic acid to the total moles of copolymerized units of diol and molecular weight increasing agent in the polyether ester hot melt adhesive of the present invention is 0.95 to 1.05: 1.0 to 1.05, preferably 1: 1.
while not wishing to be bound by a particular theory, the present inventors have discovered that by partially or fully capping the polyetherester polyol with a perfluoropolyether capping agent, the resulting polyetherester hot melt adhesives can be made to have good hydrolysis resistance, thermal oxygen aging resistance, low viscosity characteristics, and low temperature flexibility, particularly for textile bonding applications.
The preparation method of the polyether ester hot melt adhesive comprises the following steps: the dibasic acid component, the dibasic alcohol component, the molecular weight increasing agent and the perfluoropolyether end-capping agent are subjected to esterification reaction under the action of a catalyst, wherein the reaction temperature range is 120-250 ℃, and preferably 180-220 ℃. In order to increase the reaction conversion and to achieve the above-mentioned ratio of the total moles of copolymerized units of the dicarboxylic acid to the total moles of copolymerized units of the diol and the molecular weight increasing agent, a slight stoichiometric excess of the diol (particularly, aliphatic diol) is generally made in the reaction raw materials. Therefore, in a particularly preferred embodiment, the total molar ratio of the dibasic acid to the glycol in the reaction raw materials of the polyether ester hot melt adhesive is 1 (1.1-2.2), preferably 1 (1.6-1.9).
Catalysts conventional in the art, such as alkyl titanates, preferably C-titanate, may be used in the esterification reaction described above1-5Alkyl esters, such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate.
The amount of the catalyst used in the present invention is about 0.020 to 0.15 wt%, preferably 0.025 to 0.1 wt%, based on the total weight of the raw material monomers.
When the water distilled out of the reaction system reaches more than 95% of the theoretical amount, adding a polycondensation catalyst and a thermal oxygen stabilizer, continuously and gradually increasing the temperature to 230-270 ℃, preferably 240-260 ℃, applying vacuum of less than 100Pa, and performing polycondensation reaction to remove residual water and monomers from the reaction system. And after about 2-4 hours, obtaining a melt with certain viscosity, stopping the reaction, pouring the material into cold water while the material is hot, and cooling to obtain the polyether ester hot melt adhesive.
The polycondensation catalyst can be the above-mentioned alkyl titanate, and is added in an amount of about 0.02 to 0.10% by weight, preferably 0.025 to 0.05% by weight based on the total weight of the raw material monomers.
The thermal oxygen stabilizer comprises a heat stabilizer and an antioxidant.
Examples of the heat stabilizer include phosphoric acid esters and phosphorous acid esters, and examples of the phosphoric acid esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate; examples of phosphites include triphenyl phosphite, triethyl phosphite, and tributyl phosphite. The heat stabilizer is added in an amount of about 0.020 to about 0.10 wt%, preferably about 0.025 to about 0.05 wt%, based on the total weight of the resulting polyetherester.
Examples of antioxidants include IRGANOX 1010, IRGANOX 245, IRGANOX 1076, IRGANOX 1098, IRGANOX 168, IRGANOX B900, antioxidant 264, and the like, which are available from Ciba, and are added in an amount of about 0.02 to 1% by weight, preferably about 0.05 to 1% by weight, based on the total weight of the copolyetherester produced.
The above reaction may also be added with additives commonly used in the art, such as nucleating agents, flame retardants, etc. Examples of nucleating agents include talc, sodium carboxylate salts, ultra-fine or nano silica, and the like. The addition amount of the nucleating agent is 0.1-2 wt% of the total weight of the polyether ester, and preferably 0.1-1 wt%.
The melting point of the polyether ester hot melt adhesive is 175-195 ℃, and the preferred melting point is 178-190 ℃; the weight average molecular weight is 20000 to 50000, preferably 25000-40000; the specific viscosity is 0.35-0.45, preferably 0.36-0.40; the melt viscosity is 10000-20000 mPa.s/232 ℃; the glass transition temperature (Tg) is-40 to-20 ℃, and the glass is not brittle at low temperature.
Example (b):
the following examples are intended to further illustrate the present invention, but it should be understood that they are not intended to limit the scope of the invention.
The polyether ester hot melt adhesives prepared in the respective examples or comparative examples were tested for various properties according to the following methods:
melt viscosity: measured according to HG/T3660. An 11g sample of polyester hot melt adhesive was accurately weighed, dried in an oven for moisture, tested using a Brookfield DV-E rotational viscometer, spindle number S27, and the melt viscosity value displayed on the dial after the rotor had spun for 30min was recorded.
Specific viscosity increase: according to the test of national standard GB/T1632, the specific viscosity increase test is carried out by adopting the Ubbelohde viscometer method for representing the molecular weight, and the used solvent is phenol-tetrachloroethane (the weight ratio is 1: 1).
Melting point and glass transition temperature: and (4) DSC method test, after the heat history is eliminated, heating at a heating rate of 20 ℃/min, and testing the peak value (Tm) of the melting peak and the glass transition temperature (Tg).
Adhesion peel strength of canvas-canvas: the tensile rate was 50mm/min according to the GB/T2791 test.
And (3) testing and judging the hydrolysis resistance of the polyether ester hot melt adhesive: the polyether ester particle sample is placed in a hot water bath at 80 ℃ for carrying out a water boiling aging resistance test, the polyether ester particle sample is taken out after 12 hours and dried in an oven at 100 ℃ for 3 hours, the polyether ester particle sample is cooled under the normal temperature drying condition, the specific viscosity of the polyether ester particle sample is tested, the specific viscosity reduction range of the polyether ester particle sample can be tested as the following formula, the viscosity reduction range is less than 15%, and the polyether ester particle sample is considered to have better hydrolysis resistance.
Viscosity reduction [ (. eta.) ]0-η1)/η0]×100％
η0-specific viscosity increase of the sample before hydrolysis treatment;
η1the specific viscosity increase of the samples after the hydrolysis treatment.
Low temperature flexibility test: the mandrel used for the flexibility test, as tested by HG/T4222, had a diameter of 12.8mm and sample dimensions of 75mm (length) x10 mm (width) x 1.25mm (thickness).
Evaluation of thermal oxidation aging resistance: after baking the polyether ester in an oven at 230 ℃ for 5 hours, the sample was cast into a 2mm thick sheet and, after cooling, tested according to HG/T4222 using a mandrel of 12.8mm diameter and a test temperature of 25 ℃.
Comparative example 1
A2000 ml stainless steel reactor equipped with a thermometer, mechanical stirrer, fractionating column and condenser was charged with 242g of terephthalic acid, 24g of isophthalic acid, 300g of 1, 4-butanediol, 40g of PPG (Hoodian petrochemical plant, Jiangsu province, PPG-2000, molecular weight 2000), 100g of dimer acid (Croda Pripol 1013), 0.23g of n-butyl titanate, 0.2g of triphenyl phosphate, and 3g of trimethylolmethane as a molecular weight increasing agent. Stirring, heating and raising the temperature, when the temperature in the kettle reaches 180-190 ℃, starting esterification, slowly raising the temperature in the kettle to 220 ℃, keeping the distillation temperature at 95-100 ℃, collecting distilled water to 64g, after the esterification is finished, adding 5g of antioxidant IRGONAX1010, raising the temperature to 250 ℃, starting a vacuum pump, carrying out polycondensation reaction in the kettle under the vacuum condition of 100pa, discharging after the reaction is finished, measuring the increase specific viscosity of 0.37, the weight average molecular weight of 36300, the melt viscosity of 46850mPa.s, the melting point of 187 ℃, the glass transition temperature (Tg) -8 ℃, the canvas-canvas adhesive strength of 1.7N/mm, the hydrolysis resistance test viscosity reduction range of 19%, the low-temperature flexibility test result is that the canvas-canvas adhesive strength is not brittle at the temperature of 25 ℃, and the thermal oxidation resistance aging performance test result is that the sample is brittle.
Comparative example 2
A2000 ml stainless steel reactor equipped with a thermometer, mechanical stirrer, fractionating column and condenser was charged with 242g of terephthalic acid, 23g of isophthalic acid, 300g of 1, 4-butanediol, 30g of PPG (Hoodian petrochemical plant, Jiangsu province, PPG-2000, molecular weight 2000), 68g of dimer acid (Croda Pripol 1013), 0.23g of tetraethyl titanate, 0.2g of trimethyl phosphate, and 3g of Trimethylolpropane (TMP), a molecular weight increasing agent. Stirring, heating and raising the temperature, when the temperature in the kettle reaches 180-190 ℃, starting esterification, slowly raising the temperature in the kettle to 220 ℃, keeping the distillation temperature at 95-100 ℃, collecting distilled water to 64g, after the esterification is finished, adding 5g of antioxidant IRGONAX1010, raising the temperature to 250 ℃, starting a vacuum pump, carrying out polycondensation reaction in the kettle under the vacuum condition of 100pa, discharging after the reaction is finished, measuring the increase specific viscosity of 0.38, the weight average molecular weight of 35000, the melt viscosity of 38870mPa.s, the melting point of 184 ℃, the glass transition temperature (Tg) -10 ℃, the canvas-canvas adhesive strength of 1.4N/mm, the hydrolysis resistance test viscosity reduction range of 17%, the low-temperature flexibility test result is that the canvas-canvas adhesive strength is not brittle at the temperature of 25 ℃, and the thermal oxidation resistance aging performance test result is that the sample is brittle.
Example 1
A2000 ml stainless steel reactor equipped with a thermometer, a mechanical stirrer, a fractionating column and a condenser was charged with 242g of terephthalic acid, 12g of isophthalic acid, 300g of 1, 4-butanediol, 40g of PPG (PPG-2000, molecular weight 2000, Jiangsu Haian petrochemical plant, PPG-2000), 152g of dimer acid (Croda Pripol 1013), 3g of perfluoropolyether methanol (OH-4200, molecular weight 2000, available from F.C. Ltd., Hunan, Ltd.), 0.23g of tetraethyltitanate, 0.2g of triphenyl phosphate, and 3g of a molecular weight increasing agent, Trimethylolmethane (TMP). Stirring and heating to raise the temperature, when the temperature in the kettle reaches 190 ℃ of 180-.
Example 2
A2000 ml stainless steel reactor equipped with a thermometer, a mechanical stirrer, a fractionating column and a condenser was charged with 242g of terephthalic acid, 30g of isophthalic acid, 300g of 1, 4-butanediol, 40g of PPG (PPG-2000, molecular weight 2000, Jiangsu Haian petrochemical plant, PPG-2000), 91g of dimer acid (Croda Pripol 1013), 3g of perfluoropolyether methanol (OH-4200, molecular weight 2000, available from F.C. Ltd., Hunan, 2000), 0.23g of tetraethyl titanate, 0.2g of trimethyl phosphate, and 3g of Trimethylolpropane (TMP), a molecular weight increasing agent. Stirring and heating to raise the temperature, when the temperature in the kettle reaches 190 ℃ of 180-.
Example 3
A2000 ml stainless steel reactor equipped with a thermometer, a mechanical stirrer, a fractionating column and a condenser was charged with 242g of terephthalic acid, 48g of isophthalic acid, 300g of 1, 4-butanediol, 40g of PPG (PPG-2000, molecular weight 2000, Jiangsu Haian petrochemical plant, PPG-2000), 97g of dimer acid (Croda Pripol 1013), 3g of perfluoropolyether methanol (OH-4200, molecular weight 2000, available from F.C. Ltd., Hunan, N-butyl titanate 0.23g, triphenyl phosphite 0.2g, and pentaerythritol 3g as a molecular weight increasing agent. Stirring, heating and raising the temperature, when the temperature in the kettle reaches 180-190 ℃, starting esterification, slowly raising the temperature in the kettle to 220 ℃, keeping the distillation temperature at 95-100 ℃, collecting distilled water to 64g, after the esterification is finished, adding 5g of antioxidant IRGONAX1010, raising the temperature to 250 ℃, starting a vacuum pump, carrying out polycondensation reaction in the kettle under the vacuum condition of 100pa, discharging after the reaction is finished, measuring the increase specific viscosity of 0.39, the weight average molecular weight of 38000, the melt viscosity of 15600mPa.s, the melting point of 185 ℃, the glass transition temperature (Tg) -23 ℃, the canvas-canvas adhesive strength of 1.8N/mm, the hydrolysis resistance test viscosity reduction range of 6%, the low-temperature flexibility test result is that the canvas-15 ℃ temperature is not brittle, and the thermal oxidation aging resistance test result is that the sample is not brittle.
Examples 4 to 7
The procedure was as in example 1, and the general table formulation and properties are shown in the following table.
Claims (10)
1. A polyetherester hot melt adhesive comprising:
a) polyether ester polyol units which are the polycondensation reaction product of a dicarboxylic acid component comprising terephthalic acid, isophthalic acid and optionally dimer acid, a diol component and a molecular weight increasing agent; the diol component contains C2-6Diols and aliphatic polyether diols;
b) the weight average molecular weight of the polyether ester hot melt adhesive is 20000-50000.
2. The polyether ester hot melt adhesive of claim 1, which comprises 49 to 60 wt% of the dicarboxylic acid component, 39 to 50 wt% of the glycol component, and 0.1 to 5 wt% of the molecular weight increasing agent, based on the total weight of the polyether ester polyol units.
3. The polyether ester hot melt adhesive according to claim 1 or 2, wherein the content of terephthalic acid is 50 to 90 wt%, the content of isophthalic acid is 1 to 20 wt%, and the content of dimer acid is 0 to 40 wt%, based on the total weight of dicarboxylic acid components in the polyether ester polyol unit.
4. The polyether ester hot melt adhesive of claim 3, wherein the content of terephthalic acid is 55-85 wt%, the content of isophthalic acid is 3-15 wt%, and the content of dimer acid is 10-40 wt%, based on the total weight of dicarboxylic acid components in the polyether ester polyol unit.
5. Polyetherester hotmelt adhesives according to claim 1 or 2, wherein the adhesive is a polyetherester hotmelt adhesiveTotal weight of diol component in the above polyether ester polyol unit, C2-6The content of the dihydric alcohol is 80-96 wt% and the content of the aliphatic polyether dihydric alcohol is 4-20 wt%.
6. The polyether ester hot melt adhesive of claim 5, wherein the aliphatic polyether diol comprises polyethylene glycol, polypropylene glycol, polybutylene glycol, or a mixture thereof, and the molecular weight of the polyether diol is 1500-2500.
7. The polyether ester hot melt adhesive of claim 1 or 2, wherein the molecular weight increasing agent comprises glycerol, pentaerythritol, 1,3, 5-benzenetricarboxylic acid, trimethylolmethane, trimethylolpropane, β -hydroxyalkylamide, or a mixture thereof.
8. The polyether ester hot melt adhesive of claim 1 or 2, wherein the perfluoropolyether capping agent unit is derived from perfluoropolyether carbinol, perfluoropolyether formic acid, or mixtures thereof, the perfluoropolyether capping agent has a molecular weight of 1500-2500, and the perfluoropolyether capping agent unit comprises 0.1-5 wt% of the total weight of the polyetherester polyol units.
9. The process for preparing a polyetherester hot melt adhesive according to any one of claims 1 to 8, which comprises polycondensing and capping the dicarboxylic acid component, the diol component, the molecular weight increasing agent and the perfluoropolyether capping agent in the presence of a catalyst.
10. The method of claim 9, wherein the catalyst is a titanate.
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