CN109957108B - Polyesteramide hot melt adhesive and preparation method thereof - Google Patents
Polyesteramide hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109957108B CN109957108B CN201711420960.3A CN201711420960A CN109957108B CN 109957108 B CN109957108 B CN 109957108B CN 201711420960 A CN201711420960 A CN 201711420960A CN 109957108 B CN109957108 B CN 109957108B
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- 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
- C08G69/44—Polyester-amides
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- 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
- C09J177/12—Polyester-amides
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Abstract
The invention provides a preparation method of a polyesteramide hot melt adhesive, which is characterized in that reaction parameters such as polymerization temperature, polymerization pressure, reaction raw material proportion and the like are regulated and controlled by optimizing a process flow, and the prepared polyesteramide hot melt adhesive is low in yellow index, high in peel strength, low in peel strength loss rate after washing, excellent in performance and wide in application range.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a polyesteramide hot melt adhesive.
Background
The use of adhesives is becoming more and more widespread in everyday life and industrial production. In particular, in the fields of construction, textile, automobile traffic and the like, people have great demands for high-quality adhesives. As a solid adhesive, a hot melt type adhesive is used after melting the adhesive by heating, and generally, thermoplastic resins such as synthetic resins of polyurethane, polystyrene, polyacrylate, etc. are used, but these synthetic resins have high toxicity and serious pollution problems during production and use, so that the application range of the adhesive is more and more limited. As a biodegradable material, the polyesteramide has gained more and more attention in the fields of textiles, engineering plastics and the like, and the research and application of the polyesteramide hot melt adhesive have also gained rapid development. For example, in the clothing industry, the polyester amide hot melt adhesive used as the clothing adhesive can make clothing wear-resistant, straight and smooth, and is a fabric adhesive with excellent performance.
However, in the production and use of polyesteramides, yellowing occurs relatively easily, mainly due to oxidation of the amino groups present on the macromolecular chains. As an adhesive for clothes, the physical requirements of polyester amide hot melt adhesive products are high, the polyester amide hot melt adhesive products generally need to be light yellow or white colloid, if the Yellow Index (YI) is used for expressing the yellow degree of the products, the yellow Index value of the polyester amide hot melt adhesive synthesized in the prior art is often dozens or even hundreds, and the requirements are difficult to meet. In addition, the hot melt adhesive for clothing has to be further improved in water washing resistance and dry cleaning resistance.
Disclosure of Invention
Aiming at the defects of poor water resistance, yellowing color and the like of the polyesteramide in the prior art, the invention provides the preparation method of the polyesteramide hot melt adhesive.
In one aspect, the present invention provides a polyesteramide hot melt adhesive.
The polyesteramide hot melt adhesive disclosed by the invention comprises the following structural units:
x is an integer of 2-6; y is an integer of 2-13; n is an integer of 4 to 10.
The intrinsic viscosity of the polyesteramide hot melt adhesive is 0.3-0.7 dL/g.
The softening point of the polyesteramide hot melt adhesive is 142-153 ℃, the peel strength is 26-34N/2.5 cm, and the loss rate of the peel strength after washing is 13-29%;
the yellow index YI of the polyesteramide hot melt adhesive is below 20, and is preferably 7-15.
On the other hand, the invention also provides a preparation method of the polyesteramide hot melt adhesive, which comprises the following steps:
1) respectively preparing an alcohol ester oligomer and an amide oligomer, and mixing the obtained materials in a polycondensation kettle;
2) controlling the temperature in the kettle at 230-250 ℃, starting a vacuum device, raising the vacuum degree to 500-50 Pa, and discharging to obtain
Polyester amide hot melt adhesive.
The preparation process of the alcohol ester oligomer in the step 1) comprises the following steps: putting dibasic acid, dihydric alcohol and a catalyst into a reaction kettle, heating and stirring under the protection of nitrogen until a mixture is clear, continuing heating for reaction, draining water when the temperature is raised to 145-170 ℃ until the pressure in the kettle is reduced to 0 and the temperature is raised to 185-200 ℃, and draining water under normal pressure under the protection of nitrogen flow until no fraction is discharged to obtain an alcohol ester oligomer;
the polymerization degree of the obtained alcohol ester oligomer is 6-8.
The molar ratio of the dibasic acid to the dihydric alcohol is 1: 1-1: 1.5;
the catalyst is one or more of tetraisopropyl titanate, tetrabutyl titanate, dibutyl tin dilaurate, sodium acetate, zinc acetate, ethylene glycol antimony or antimony trioxide, and the addition amount of the catalyst is 100ppm to 5000ppm of the total mass of the dibasic acid and the dihydric alcohol.
Wherein the preparation process of the amide oligomer in the step 1) comprises the following steps: adding dibasic acid, diamine and an auxiliary agent into a reaction kettle, replacing with nitrogen for three times, heating under the protection of nitrogen, draining when the temperature in the kettle rises to 205-225 ℃, and finishing draining when the pressure in the kettle falls to 0 and the temperature in the kettle rises to 230-240 ℃ to obtain an amide oligomer;
the degree of polymerization of the obtained amide oligomer is 15 to 25.
The molar ratio of the dibasic acid to the diamine is 1: 1-1: 1.1; the dibasic acid and the diamine may be replaced with a nylon salt formed from the dibasic acid and the diamine.
The auxiliary agent comprises one or more of sodium hypophosphite, trimethyl phosphate, p-hydroxybenzoic acid, lactic acid, benzoic acid or an antioxidant N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide (SEED), and the addition amount of the auxiliary agent is 0 wt% -10 wt% of the total amount of the dibasic acid and the diamine.
The dibasic acid in the invention comprises one or more of succinic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and pentadecanedioic acid;
the dihydric alcohol in the invention comprises one or more of ethylene glycol, propylene glycol, butanediol and hexanediol;
the diamine in the invention comprises one or more of butanediamine, pentanediamine, hexanediamine and decanediamine.
The invention has the beneficial effects that:
1. the preparation process is simple, the scheme of the invention can be obtained by simply adjusting the process parameters on the basis of the existing polyester amide preparation method, the alcohol ester and the amide oligomer are respectively prepared in the invention, the polymerization degrees of the alcohol ester and the amide oligomer are well controlled, and simultaneously, the performance of the obtained product is optimized by regulating and controlling reaction parameters such as polymerization temperature, polymerization pressure, the proportion of reaction raw materials and the like;
2. the polyesteramide hot melt adhesive prepared by the invention has the advantages of low yellow index, high peel strength, low peel strength loss rate after washing and wide application range.
Drawings
FIG. 1 is a HNMR spectrum of PEA-III obtained in example 3 (trifluoroacetic acid and DMSO-d) 6 As a solvent).
Detailed Description
The method for performance testing is as follows:
intrinsic viscosity: measured according to ASTM D4603-2003.
Softening point: measured according to GB/T15332-94
Peel strength: determination according to FZ/T80007.1-2006
Peel strength loss rate after washing: determination according to FZ/T80007.2-2006
Yellow Index (YI): determined according to HG/T3862-2006.
Example 1
800G of hexanediol and 1.5KG of dodecanedioic acid are weighed into a 5L reactor. Under the protection of nitrogen, starting heating to 130 ℃ of the temperature in the kettle, starting stirring, adding 1.5G of tetraisopropyl titanate under the protection of nitrogen, and continuing heating reaction after the mixture becomes clear liquid. In the presence of nitrogen flow, when the temperature in the kettle reaches 160 ℃, the water drainage is started until the pressure in the kettle is reduced to 0 (or the pressure of the nitrogen flow), the temperature is slowly increased to 190 ℃, and the water is drained under normal pressure under the protection of the nitrogen flow until no fraction is discharged. And (3) cooling, cooling the temperature in the kettle to 140 ℃, and discharging under nitrogen pressure while the kettle is hot to obtain a white solid hexanedioic acid diol ester oligomer.
A10L polymerization vessel was charged with 1.5KG of pure water and 240G of lactic acid, and 1.4KG of pentamethylenediamine and 2.9KG of dodecanedioic acid, respectively, were slowly added thereto. And replacing the nitrogen for three times, and starting heating to increase the temperature under the condition of nitrogen protection. When the temperature in the kettle rises to 212 ℃, the pressure in the kettle is 17KG, and a water outlet valve is opened to start water drainage. Controlling the water yield, ensuring the pressure in the kettle to be 17KG, and draining for 2 hours. Then, the water is drained continuously until the pressure in the kettle is reduced to 0 (or the pressure of the nitrogen flow), the temperature in the kettle is about 230 ℃, and the time is 2 hours. The temperature in the kettle is reduced to 185 ℃, the hexanediol dodecanedioate oligomer is added under the nitrogen condition, then the temperature is raised to 240 ℃ under the protection of nitrogen, a vacuum pump is started, the vacuum degree is raised to 50Pa from low to high, and the use time is 2 hours. The temperature of the discharge port is controlled at 240 ℃, nitrogen flow is increased to discharge, and yellowish polyester amide hot melt adhesive PEA-I is obtained.
Example 2
A5-liter polymerization vessel was charged with 850G of hexanediol, 8.5G of ethylene glycol antimony, and 1.45KG of sebacic acid. And replacing the nitrogen for three times, and starting heating to increase the temperature under the condition of nitrogen protection. When the temperature in the kettle rises to 125 ℃, the temperature is kept for 10 minutes, and stirring is started. And (3) continuing heating reaction, and starting draining when the temperature in the kettle reaches 145 ℃ until the pressure in the kettle is reduced to 0 (or the pressure of nitrogen flow) for 3 hours. The temperature in the kettle rises to 190 ℃, and the water is drained under normal pressure under the protection of nitrogen flow until no fraction is discharged. The temperature in the kettle is reduced to 145 ℃, and then the hot material is discharged under the protection of nitrogen. A white solid hexanediol sebacate oligomer is obtained.
A10-liter polymerization vessel was charged with 2KG of pure water, 4KG of PA1010 salt (Dacron, Jian lake county) and 3G of the antioxidant SEED. And replacing the nitrogen for three times, and starting heating to increase the temperature under the condition of nitrogen protection. When the temperature in the kettle rises to 220 ℃, the pressure in the kettle is 18KG, and a water outlet valve is opened to start water drainage. Controlling the water yield, ensuring the pressure in the kettle to be 18KG, and draining for 2 hours. Then, the water is drained continuously until the pressure in the kettle is reduced to 0 (or the pressure of nitrogen flow), the temperature in the kettle is raised to about 230 ℃, and the time is taken for 2 hours. And (3) reducing the temperature in the kettle to 180 ℃, and adding the synthesized hexane diol sebacate oligomer under the protection of nitrogen. Then, under the protection of nitrogen, the temperature is raised to 250 ℃, a vacuum device is started, the vacuum degree is increased from low to high, and finally 100Pa is reached, and the use time is 3 hours. The temperature of the discharge port is controlled at 250 ℃, nitrogen flow is increased to discharge, and the polyester amide hot melt adhesive PEA-II is obtained.
Example 3
8KG of pure water and 10 PA66 salt (Henan Shenma nylon chemical) were added into a 30L polymerizer in a polycondensation kettle. After the nitrogen replacement was carried out three times, heating was started under the nitrogen protection condition. When the temperature in the kettle rises to 205 ℃, the pressure in the kettle is 16KG, and a water outlet valve is opened to start water drainage. The water yield is controlled well, the pressure in the kettle is ensured to be 16KG, and the water is drained for 3 hours. Then, the water was drained until the pressure in the autoclave decreased to 0 (or the pressure of the nitrogen stream) and the temperature in the autoclave increased to about 235 ℃ for 3 hours. Then the materials are continuously stirred under the conditions of nitrogen protection and the temperature in the kettle of 185 ℃ for standby.
In an esterification kettle of a 30L polymerization kettle, 3.2KG of hexanediol and 3.5KG of adipic acid were added. Heating to 135 ℃ in the kettle under the protection of nitrogen, starting stirring, adding 3.0G of tetrabutyl titanate under the protection of nitrogen to obtain a clear liquid, and then continuing heating for reaction. In the presence of nitrogen flow, when the temperature in the kettle reaches 170 ℃, the water drainage is started until the pressure in the kettle is reduced to 0 (or the pressure of the nitrogen flow), the temperature in the kettle slowly rises to 190 ℃, and the water is drained under normal pressure under the protection of the nitrogen flow until no fraction is discharged. The ethylene adipate oligomer in the esterification kettle was then pressed with nitrogen into a 30 liter polycondensation kettle at 190 ℃. And (3) starting a vacuum device at 235 ℃ in the polycondensation kettle, wherein the vacuum degree is increased from low to high and finally reaches 150Pa, and the time is 3 hours. The temperature of the discharge port is controlled at 235 ℃, nitrogen flow is increased to discharge, and the polyester amide hot melt adhesive PEA-III is obtained.
Example 4
A10L polymerization vessel was charged with 2KG of pure water and 4KG of PA1010 salt (Dahlong nylon, Jian lake county). And replacing the nitrogen for three times, and starting heating to increase the temperature under the condition of nitrogen protection. When the temperature in the kettle rises to 210 ℃, the pressure in the kettle is 17KG, and a water outlet valve is opened to start water drainage. The water yield is controlled well, and the water is drained for 2 hours under the pressure of 17KG in the kettle. Then, the water is continuously drained until the pressure in the kettle is reduced to 0 (or the pressure of the nitrogen flow), the temperature in the kettle is about 240 ℃, and the time is 1 hour. And controlling the temperature of a discharge port at 240 ℃, increasing nitrogen flow, and discharging to obtain the PA1010 oligomer.
700G of ethylene glycol and 3G of tetraisopropyl titanate are added into a 10L polymerization kettle, 2KG of sebacic acid is added, heating is started under the condition of nitrogen protection, and stirring and dissolving are started to be uniform. When the temperature in the kettle rises to 160 ℃, the drainage is started until the pressure in the kettle drops to 0 (or the pressure of nitrogen flow), the temperature in the kettle rises to 200 ℃ until no moisture is discharged, and the time is 1 hour. Adding the synthesized PA1010 oligomer, starting a vacuum device at the temperature of 245 ℃ in the kettle, and keeping the vacuum degree from low to high and finally reaching 50Pa for 3 hours. The temperature of the discharge port is controlled at 245 ℃, nitrogen flow is increased for discharging, and the polyester amide hot melt adhesive PEA-IV is obtained.
Example 5
2KG of pure water and 280G of p-hydroxybenzoic acid were placed in a 10L polymerization vessel, and 1.6KG of pentamethylenediamine and 3KG of sebacic acid, respectively, were slowly added thereto. And replacing the nitrogen for three times, and starting heating to increase the temperature under the condition of nitrogen protection. When the temperature in the kettle rises to 213 ℃, the pressure in the kettle is 17KG, and a water outlet valve is opened to start water drainage. The water yield is controlled well, the pressure in the kettle is ensured to be 17KG, and the water is drained for 2 hours. Then, the water is continuously drained until the pressure in the kettle is reduced to 0 (or the pressure of the nitrogen flow), the temperature in the kettle is about 235 ℃, and the time is 2 hours. The temperature of the discharge port is controlled at 235 ℃, and the nitrogen flow is increased to discharge.
700G of ethylene glycol and 3G of tetraisopropyl titanate are added into a 10L polymerization kettle, 2KG of sebacic acid is added, heating is started under the protection of nitrogen, and stirring and dissolving are started to be uniform. When the temperature in the kettle rises to 170 ℃, the water begins to be drained until the pressure in the kettle drops to 0 (or the pressure of nitrogen flow), the temperature in the kettle rises to 235 ℃ until no moisture is drained, and the time is 1 hour. Adding the synthesized PA510 oligomer, starting a vacuum device at the temperature of 235 ℃ in the kettle, and keeping the vacuum degree from low to high and finally reaching 80Pa for 3 hours. The temperature of the discharge port is controlled at 235 ℃, nitrogen flow is increased to discharge, and the polyester amide hot melt adhesive PEA-V is obtained.
Claims (16)
1. The polyester amide hot melt adhesive is characterized by comprising the following structural units:
wherein x is an integer of 2-6; y is an integer of 2 to 13; n is an integer of 4-10; the intrinsic viscosity of the polyesteramide hot melt adhesive is 0.3-0.7 dL/g;
the polyesteramide hot melt adhesive is formed by the polycondensation of an alcohol ester oligomer and an amide oligomer, and the yellow index YI of the polyesteramide hot melt adhesive is less than 20;
the preparation method of the polyesteramide comprises the following steps:
(1) respectively preparing the alcohol ester oligomer and the amide oligomer, and mixing the obtained materials in a polycondensation kettle;
(2) controlling the temperature in the kettle at 230-250 ℃, starting a vacuum device, raising the vacuum degree to 500-50 Pa, and discharging to obtain the polyesteramide hot melt adhesive.
2. The polyesteramide hot melt adhesive of claim 1, having a yellowness index YI of from 7 to 15.
3. The polyesteramide hot melt adhesive according to claim 1 or 2, wherein the softening point of the polyesteramide hot melt adhesive is 142-153 ℃, the peel strength is 26-34N/2.5 cm, and the loss rate of the peel strength after washing is 13-29%.
4. A process for preparing a polyesteramide hotmelt adhesive according to any of claims 1 to 3, comprising the steps of:
(1) respectively preparing the alcohol ester oligomer and the amide oligomer, and mixing the obtained materials in a polycondensation kettle;
(2) controlling the temperature in the kettle at 230-250 ℃, starting a vacuum device, raising the vacuum degree to 500-50 Pa, and discharging to obtain the polyesteramide hot melt adhesive.
5. The method for preparing the polyesteramide hot melt adhesive according to claim 4, wherein the preparation process of the alcohol ester oligomer in the step (1) is as follows: and (2) putting the dibasic acid, the dihydric alcohol and the catalyst into a reaction kettle, heating and stirring under the protection of nitrogen until a mixture is clear, continuing heating for reaction, draining water when the temperature is raised to 145-170 ℃ until the pressure in the kettle is reduced to 0 and the temperature is raised to 185-200 ℃, and draining water under normal pressure under the protection of nitrogen flow until no fraction is discharged to obtain the alcohol ester oligomer.
6. The method for preparing the polyesteramide hot melt adhesive according to claim 5, wherein the diol comprises one or more of ethylene glycol, propylene glycol, butylene glycol and hexylene glycol.
7. The preparation method of the polyesteramide hot melt adhesive according to claim 5 or 6, wherein the molar ratio of the dibasic acid to the glycol is 1: 1-1: 1.5.
8. The method for preparing the polyesteramide hot melt adhesive according to claim 5, wherein the catalyst is one or more of tetraisopropyl titanate, tetrabutyl titanate, dibutyl tin dilaurate, sodium acetate, zinc acetate, ethylene glycol antimony or antimony trioxide, and the amount of the catalyst added is 100ppm to 5000ppm of the total mass of the dibasic acid and the dibasic alcohol.
9. The method for preparing polyesteramide hot melt adhesive according to claim 4, wherein the preparation process of the amide oligomer in the step (1) is as follows: and (2) adding dibasic acid, diamine and an auxiliary agent into a reaction kettle, replacing with nitrogen for three times, heating under the protection of nitrogen, draining when the temperature in the kettle rises to 205-225 ℃, and finishing draining when the pressure in the kettle falls to 0 and the temperature in the kettle rises to 230-240 ℃ to obtain the amide oligomer.
10. The method for preparing the polyesteramide hot melt adhesive according to claim 9, wherein the diamine comprises one or more of butanediamine, pentanediamine, hexanediamine and decanediamine.
11. The preparation method of the polyesteramide hot melt adhesive according to claim 9 or 10, wherein the molar ratio of the dibasic acid to the diamine is 1: 1-1: 1.1.
12. The method for preparing polyesteramide hot melt adhesive according to claim 9, wherein said diacid and said diamine are replaced by nylon salt formed by said diacid and said diamine.
13. The method for preparing polyesteramide hot melt adhesive according to claim 9, wherein the auxiliary agent comprises one or more of sodium hypophosphite, trimethyl phosphate, p-hydroxybenzoic acid, lactic acid, benzoic acid or antioxidant N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, and the addition amount of the auxiliary agent is 0 wt% -10 wt% of the total amount of the dibasic acid and the diamine.
14. The method for preparing polyesteramide hot melt adhesive according to claim 5, 6, 8, 9, 10, 12 or 13, wherein the dibasic acid comprises one or more of succinic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid.
15. The method for preparing the polyesteramide hot melt adhesive according to claim 7, wherein the dibasic acid comprises one or more of succinic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid.
16. The method for preparing the polyesteramide hot melt adhesive according to claim 11, wherein the dibasic acid comprises one or more of succinic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid.
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| CN112322249B (en) * | 2020-11-11 | 2022-04-01 | 温州华特热熔胶股份有限公司 | Polyesteramide silane enhanced hot melt adhesive and preparation method thereof |
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