CN112280518B - Elastic copolyester hot melt adhesive and preparation method thereof - Google Patents
Elastic copolyester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN112280518B CN112280518B CN202010983612.2A CN202010983612A CN112280518B CN 112280518 B CN112280518 B CN 112280518B CN 202010983612 A CN202010983612 A CN 202010983612A CN 112280518 B CN112280518 B CN 112280518B
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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
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an elastic copolyester hot melt adhesive and a preparation method thereof, wherein the main material comprises dibasic acid and dihydric alcohol, and the dibasic acid is formed by mixing terephthalic acid and isophthalic acid in proportion; the dihydric alcohol is formed by mixing 1, 3-propylene glycol, 1, 5-pentanediol and 1, 7-heptanediol according to a proportion; the auxiliary materials comprise a catalyst, a stabilizer and an antioxidant. The invention creatively adopts the dihydric alcohol used in the copolyester hot melt adhesive system to be the odd-numbered dihydric alcohol, and designs the unique material proportion, so that the copolyester hot melt adhesive prepared by the invention has the advantages of lower softening point suitable for sizing application, good bonding and water washing resistance meeting the bonding requirement on the basis of better resilience performance.
Description
Technical Field
The invention relates to an elastic copolyester hot melt adhesive and a preparation method thereof, in particular to a polyester hot melt adhesive which has good elasticity, good water washing resistance and proper pressing temperature and a preparation method thereof, can partially replace a thermoplastic polyurethane elastomer (TPU) hot melt adhesive, and is suitable for being applied to the fields of printing ink, reflecting materials, hot melt adhesive films, underwear, elastic bands of sports pants, printed clothing lining cloth, automotive interiors and the like.
Background
In 1972, dupont, usa and toyobo, japan, were leading to the development of thermoplastic polyester elastomers (TPEE) which has excellent resilience and excellent adhesion to materials such as ABS, PBT, PC, paint, glue, and metal.
The TPEE is mainly obtained by a hydroxyl-terminated polyether method, namely, dimethyl terephthalate and excessive micromolecule dihydric alcohol are subjected to ester exchange reaction under the action of a catalyst, and then the obtained substance and hydroxyl-terminated polyether are subjected to polycondensation reaction. However, methanol, which is a byproduct generated by the method, is gradually eliminated by the industry.
Other elastic polyester fibers, as disclosed in CN103642019A, CN110952161A and CN109651604A, mainly give elasticity to the material by adjusting the ratio of hard segments and soft segments of the polyester; an elastic polyester fiber disclosed in CN102691128A, which is obtained by mixing and copolymerizing a synthesized polyester oligomer having introduced rigid groups and a synthesized polyester oligomer having introduced flexible groups; both the two methods are relatively complicated in practical production application, and the melting point or softening point of the product is higher and is more than 160 ℃ generally, thus being not beneficial to industrial application.
Therefore, the polyester hot melt adhesive on the market at present has almost no elasticity, and the constant elongation recovery rate of most conventional copolyester hot melt adhesives is generally less than 20 percent, so that the polyester hot melt adhesive cannot be applied to the bonding fields with requirements on elasticity, such as elastic bands, underwear, printed clothes and the like.
Therefore, how to provide a novel polyester hot melt adhesive, which has elasticity, good bonding and water washing resistance, proper construction temperature and the like, becomes a problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problems and provides an elastic polyester hot melt adhesive and a preparation method thereof, so that the polyester hot melt adhesive prepared by the invention has elastic recovery performance, good bonding and water washing resistance and proper gluing temperature, and can partially replace the application field of TPU hot melt adhesives.
The technical scheme adopted by the invention is as follows: an elastic copolyester hot melt adhesive comprises main materials and auxiliary materials, wherein the main materials comprise dibasic acid and dihydric alcohol, and the dibasic acid is formed by mixing terephthalic acid and isophthalic acid according to a specific proportion; the dihydric alcohol is formed by mixing 1, 3-propylene glycol, 1, 5-pentanediol and 1, 7-heptanediol according to a specific proportion; the auxiliary materials comprise a catalyst, a stabilizer and an antioxidant.
The mole ratio of the dibasic acid to the dihydric alcohol is as follows: 1: 1.6;
in the dibasic acid, the molar ratio of terephthalic acid to isophthalic acid is as follows: 1: 0.25-0.5;
in the dihydric alcohol, the mole ratio of 1, 3-propanediol, 1, 5-pentanediol and 1, 7-heptanediol is as follows: 1: 0.1-0.2: 0.2-0.4;
the catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.01-0.02% of the total mass of the dibasic acid;
the stabilizer is triphenyl phosphite, and the addition amount of the stabilizer is 0.01-0.015% of the total mass of the dibasic acid;
the antioxidant is 168 or 1010 in the amount of 0.01-0.015% of the total weight of the dibasic acid.
In the invention, all the dihydric alcohols are odd-carbon dihydric alcohols and are prepared and mixed according to a specific proportion. The product is endowed with elasticity by using the odd carbon effect, and the comprehensive performance of the product is ensured by combining the integral proportioning design.
Meanwhile, the applicant finds that the lower pressing temperature requirement of the hot melt adhesive cannot be met only by using a single glycol with odd carbon number through a plurality of tests; only any two odd-numbered diols are selected or the ratio of the three odd-numbered diols is changed randomly, which can generate adverse effects on the comprehensive basic performance and the cost of the product.
In addition, other diols with odd number of carbon atoms, such as 1, 9-nonanediol, can also be used as raw materials to be mixed, but the preparation process is more severe due to the lower boiling point, which is not favorable for industrial production.
The preparation method of the elastic copolyester hot melt adhesive comprises the following steps:
(1) sequentially adding terephthalic acid, isophthalic acid, 1, 3-propanediol, 1, 5-pentanediol, 1, 7-heptanediol and a catalyst into a reaction kettle according to a preset proportion for esterification reaction, wherein in the esterification reaction stage, the pressure is 0.1-0.2 MPa, the reaction temperature is 150-225 ℃, and when the amount of water generated by the reaction is more than 95% of the theoretical water yield, the esterification reaction is finished;
(2) adding a stabilizer into the product obtained in the step (1), performing reduced pressure polycondensation reaction at 230-240 ℃ under the condition of 30-60 Pa, and finishing the polycondensation reaction after 2-4 h;
(3) removing vacuum, adding antioxidant, vacuum stirring for reaction for 15min, introducing nitrogen gas to remove vacuum, and discharging when it is hot.
In the step (1), the boiling point of the 1, 3-propanediol is low, so that the esterification reaction stage needs to be carried out under pressure, otherwise, the 1, 3-propanediol is easy to overflow.
In the step (1), the dibasic acid and the dihydric alcohol can be mixed uniformly and then put into the reaction kettle for esterification.
The invention has the advantages that: the dihydric alcohol used in the copolyester hot melt adhesive system is creatively completely made of the dihydric alcohol with odd number of carbon atoms, and the unique material proportion is designed, so that the copolyester hot melt adhesive prepared by the invention has the advantages of good resilience, low softening point, suitability for sizing application, good bonding and water washing resistance, and meeting the bonding requirement.
Detailed Description
The present invention will be further specifically described with reference to the following examples, but the present invention is not limited thereto.
Example 1:
adding 265.81g of terephthalic acid, 66.45g of isophthalic acid, 187.32g of 1, 3-propanediol, 25.64 g of 1, 5-pentanediol, 65.08g of 1, 7-heptanediol and 0.033g of tetrabutyl titanate into a reaction kettle, gradually heating to 150 ℃, maintaining the pressure in the kettle at 0.1-0.2 MPa, starting stirring, starting distilling water when the temperature is close to 170 ℃, continuously and gradually heating to 225 ℃, and finishing the esterification reaction when the water yield reaches more than 95% of the theoretical value; then adding 0.033g of stabilizer, carrying out reduced pressure polycondensation reaction, gradually heating to 240 ℃, keeping the temperature, gradually reducing the pressure in the reaction kettle to 60Pa, and maintaining for 2-4 h; and (3) removing vacuum, adding 0.033g of antioxidant, vacuumizing again, stirring for 15min, introducing nitrogen, removing vacuum, and discharging while hot to obtain the target copolyester hot melt adhesive A1.
Example 2:
adding 255.58g of terephthalic acid, 76.68g of isophthalic acid, 177.75g of 1, 3-propanediol, 29.19 g of 1, 5-pentanediol, 77.20g of 1, 7-heptanediol and 0.040g of tetrabutyl titanate into a reaction kettle, gradually heating to 150 ℃, keeping the pressure in the kettle at 0.1-0.2 MPa, starting stirring, starting distilling water when the temperature is close to 170 ℃, continuously and gradually heating to 225 ℃, and finishing the esterification reaction when the water yield reaches more than 95% of a theoretical value; then adding 0.040g of stabilizer, carrying out reduced pressure polycondensation reaction, gradually heating to 240 ℃, keeping the temperature, gradually reducing the pressure in the reaction kettle to 60Pa, and maintaining for 2-4 h; and (3) removing vacuum, adding 0.040g of antioxidant, vacuumizing again, stirring for 15min, introducing nitrogen, removing vacuum, and discharging while hot to obtain the target copolyester hot melt adhesive A2.
Example 3:
adding 246.12g of terephthalic acid, 86.14g of isophthalic acid, 169.11g of 1, 3-propanediol, 32.40g of 1, 5-pentanediol, 88.13g of 1, 7-heptanediol and 0.050g of tetrabutyl titanate into a reaction kettle, gradually heating to 150 ℃, keeping the pressure in the kettle at 0.1-0.2 MPa, starting stirring, starting distilling water when the temperature is close to 170 ℃, continuously and gradually heating to 225 ℃, and finishing the esterification reaction when the water yield reaches more than 95% of a theoretical value; then adding 0.050g of stabilizer, carrying out reduced pressure polycondensation reaction, gradually heating to 240 ℃, keeping the temperature, gradually reducing the pressure in the reaction kettle to 60Pa, and maintaining for 2-4 h; and (3) removing vacuum, adding 0.043g of antioxidant, vacuumizing again, stirring for 15min, introducing nitrogen, removing vacuum, and discharging while the mixture is hot to obtain the target copolyester hot melt adhesive A3.
Example 4:
adding 237.33g of terephthalic acid, 94.93g of isophthalic acid, 161.27g of 1, 3-propanediol, 35.31g of 1, 5-pentanediol, 98.06g of 1, 7-heptanediol and 0.066g of tetrabutyl titanate into a reaction kettle, gradually heating to 150 ℃, maintaining the pressure in the kettle at 0.1-0.2 MPa, starting stirring, starting distilling water when the temperature is close to 170 ℃, continuously and gradually heating to 225 ℃, and finishing the esterification reaction when the water yield reaches more than 95% of a theoretical value; then adding 0.050g of stabilizer, carrying out reduced pressure polycondensation reaction, gradually heating to 240 ℃, keeping the temperature, gradually reducing the pressure in the reaction kettle to 60Pa, and maintaining for 2-4 h; and (3) removing vacuum, adding 0.047g of antioxidant, vacuumizing again, stirring for 15min, introducing nitrogen, removing vacuum, and discharging while the mixture is hot to obtain the target copolyester hot melt adhesive A4.
Example 5:
adding 221.51g of terephthalic acid, 110.75g of isophthalic acid, 152.20g of 1, 3-propanediol, 41.66g of 1, 5-pentanediol, 105.76g of 1, 7-heptanediol and 0.050g of tetrabutyl titanate into a reaction kettle, gradually heating to 150 ℃, keeping the pressure in the kettle at 0.1-0.2 MPa, starting stirring, starting distilling water when the temperature is close to 170 ℃, continuously and gradually heating to 225 ℃, and finishing the esterification reaction when the water yield reaches more than 95% of a theoretical value; then adding 0.033g of stabilizer, carrying out reduced pressure polycondensation reaction, gradually heating to 240 ℃, keeping the temperature, gradually reducing the pressure in the reaction kettle to 60Pa, and maintaining for 2-4 h; and (3) removing vacuum, adding 0.050g of antioxidant, vacuumizing again, stirring for 15min, introducing nitrogen, removing vacuum, and discharging while hot to obtain the target copolyester hot melt adhesive A5.
And (3) performance testing:
the product obtained in each embodiment is subjected to performance test with PES hot melt adhesive with a conventional softening point and TPU hot melt adhesive with common elasticity, wherein the softening point test standard is as follows: GB/T15332-; glass transition temperature test standard: GB/T19466.2-2004; elastic recovery performance test standard: ASTM D2594-2004 (2012) tensile recovery at 200% elongation; elongation at break test standard: (ii) a GB/T13022-1991; peel strength test standard: GB/T11402-.
The results of the relevant performance tests on the samples obtained are shown in table 1 below:
| index (I) | A1 | A2 | A3 | A4 | A5 | Commercially available PES Hot melt adhesive 1 | Commercially available PES Hot melt adhesive 2 | Commercially available TPU hot melt adhesive |
| Softening Point (. degree. C.) | 135 | 127 | 120 | 113 | 110 | 130 | 125 | -20 |
| Glass transition temperature (. degree. C.) | -3 | -7 | -11 | -13 | -15 | -8 | -15 | -20 |
| Percent recovery from constant elongation (%) | 40 | 55 | 59 | 65 | 80 | 16 | 20 | 90 |
| Elongation at Break (%) | 517 | 550 | 610 | 665 | 720 | 550 | 708 | 750 |
| Shell strong (N/5 cm) | 31.3 | 31.7 | 32.5 | 32.1 | 33.2 | 31.7 | 32.5 | 31.5 |
| Stripping strength after washing at 40 ℃ (N/5 cm) | 26.4 | 26.2 | 27.0 | 26.4 | 27.3 | 26.1 | 26.5 | 23.4 |
| Stripping strength after washing at 60 ℃ (N/5 cm) | 23.2 | 22.7 | 23.6 | 23.3 | 24.5 | 23.4 | 23.2 | 18.1 |
Table 1: and (5) performance test results.
As is apparent from the above table 1, the softening point of the copolyester hot melt adhesive prepared by the method is between 110 ℃ and 135 ℃, so that the copolyester hot melt adhesive has a low pressing temperature and is suitable for industrial application; but compared with the conventional copolyester hot melt adhesive with the melting point of 110-135 ℃, the elastic property of the product obtained by the invention is obviously improved, and the fixed elongation recovery rate is more than or equal to 40 percent and even reaches 80 percent; although the elastic recovery performance of the product obtained by the invention can not reach the TPU hot melt adhesive, compared with the TPU hot melt adhesive, the product has better water washing resistance. Therefore, the elastic copolyester hot melt adhesive prepared by the invention has elastic recovery performance, lower construction pressing temperature, better bonding performance and water washing resistance, can partially replace TPU hot melt adhesives, and is applied to the fields of reflective materials, underwear, elastic bands of sports pants, printed clothing linings, automotive interiors and the like.
Claims (6)
1. The elastic copolyester hot melt adhesive comprises main materials and auxiliary materials, wherein the main materials comprise dibasic acid and dihydric alcohol, and the elastic copolyester hot melt adhesive is characterized in that: the dibasic acid is prepared by mixing terephthalic acid and isophthalic acid in proportion; the dihydric alcohol is formed by mixing 1, 3-propylene glycol, 1, 5-pentanediol and 1, 7-heptanediol in proportion;
the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.6;
in the dibasic acid, the molar ratio of terephthalic acid to isophthalic acid is as follows: 1: 0.25-0.5;
in the dihydric alcohol, the mole ratio of 1, 3-propanediol, 1, 5-pentanediol and 1, 7-heptanediol is as follows: 1: 0.1-0.2: 0.2-0.4;
the auxiliary materials comprise a catalyst, a stabilizer and an antioxidant, and the addition amount of the catalyst is 0.01-0.02% of the total mass of the dibasic acid; the addition amount of the stabilizer is 0.01-0.015% of the total mass of the dibasic acid; the addition amount of the antioxidant is 0.01-0.015% of the total mass of the dibasic acid.
2. The elastic copolyester hot melt adhesive according to claim 1, wherein: the catalyst is tetrabutyl titanate; the stabilizer is triphenyl phosphite; the grade of the antioxidant is 168 or 1010.
3. The preparation method of the elastic copolyester hot melt adhesive is characterized by comprising the following steps of:
(1) sequentially adding dibasic acid consisting of terephthalic acid and isophthalic acid, dihydric alcohol consisting of 1, 3-propanediol, 1, 5-pentanediol and 1, 7-heptanediol and a catalyst into a reaction kettle according to a preset proportion for esterification reaction, wherein in the esterification reaction stage, the pressure is 0.1-0.2 MPa, the reaction temperature is 150-225 ℃, and when the amount of water produced by the reaction is more than 95% of the theoretical water yield, the esterification reaction is finished;
(2) adding a stabilizer into the product obtained in the step (1), performing reduced pressure polycondensation reaction at 230-240 ℃ under the condition of 30-60 Pa, and finishing the polycondensation reaction after 2-4 h;
(3) removing vacuum, adding antioxidant, vacuum stirring for reaction for 15min, introducing nitrogen to remove vacuum, and discharging when it is hot;
in the step (1), the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.6;
in the dibasic acid, the molar ratio of terephthalic acid to isophthalic acid is as follows: 1: 0.25-0.5;
in the dihydric alcohol, the mol ratio of 1, 3-propanediol, 1, 5-pentanediol and 1, 7-heptanediol is as follows: 1: 0.1-0.2: 0.2-0.4.
4. A process for preparing an elastic copolyester hot melt adhesive as claimed in claim 3, wherein: in the step (1), the catalyst is tetrabutyl titanate, and the addition amount of the tetrabutyl titanate is 0.01-0.02% of the total mass of the dibasic acid.
5. The process for preparing an elastic copolyester hot melt adhesive according to claim 3, wherein: in the step (2), the stabilizer is triphenyl phosphite, and the addition amount of the stabilizer is 0.01-0.015% of the total mass of the dibasic acid.
6. The process for preparing an elastic copolyester hot melt adhesive according to claim 3, wherein: in the step (3), the antioxidant is 168 or 1010 in grade, and the addition amount of the antioxidant is 0.01-0.015 percent of the total mass of the dibasic acid.
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| WO2009010324A2 (en) * | 2007-07-17 | 2009-01-22 | Evonik Degussa Gmbh | Moisture-curing hot-melt adhesive with good adhesion |
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| CN104479118A (en) * | 2014-12-23 | 2015-04-01 | 安徽助成信息科技有限公司 | Method for preparing PNT (para nitro toluene) copolyester hot melt adhesive used for film manufacturing |
| CN107090078A (en) * | 2017-05-22 | 2017-08-25 | 浙江大学 | Polyester of HMW high crystalline and its preparation method and application |
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| WO2009010324A2 (en) * | 2007-07-17 | 2009-01-22 | Evonik Degussa Gmbh | Moisture-curing hot-melt adhesive with good adhesion |
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Address after: 226413 group 9, Gangcheng village, Changsha Town, Rudong County, Nantong City, Jiangsu Province Applicant after: NANTONG TIANYANG NEW MATERIAL CO.,LTD. Applicant after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Applicant after: Kunshan Tianyang New Material Co.,Ltd. Address before: 226413 group 9, Gangcheng village, Changsha Town, Rudong County, Nantong City, Jiangsu Province Applicant before: NANTONG TIANYANG NEW MATERIAL CO.,LTD. Applicant before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Applicant before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd. |
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Address after: 226413 group 9, Gangcheng village, Changsha Town, Rudong County, Nantong City, Jiangsu Province Patentee after: NANTONG TIANYANG NEW MATERIAL CO.,LTD. Patentee after: Tianyang New Material (Shanghai) Technology Co.,Ltd. Patentee after: Kunshan Tianyang New Material Co.,Ltd. Address before: 226413 group 9, Gangcheng village, Changsha Town, Rudong County, Nantong City, Jiangsu Province Patentee before: NANTONG TIANYANG NEW MATERIAL CO.,LTD. Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee before: Kunshan Tianyang New Material Co.,Ltd. |