CN108997570B - Dimer acid modified copolyester hot melt adhesive and preparation method thereof - Google Patents
Dimer acid modified copolyester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN108997570B CN108997570B CN201810849720.3A CN201810849720A CN108997570B CN 108997570 B CN108997570 B CN 108997570B CN 201810849720 A CN201810849720 A CN 201810849720A CN 108997570 B CN108997570 B CN 108997570B
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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
- C08G63/91—Polymers modified by chemical after-treatment
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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
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- Polyesters Or Polycarbonates (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a preparation method of dimer acid modified copolyester hot melt adhesive, which comprises the following steps: (1) adding dimer acid containing 36 carbon atoms, dihydric alcohol containing 2-8 carbon atoms and a catalyst into a reaction kettle according to a ratio, uniformly mixing, and finishing an esterification reaction at the temperature of 160-; (2) adding thermoplastic polyester and a stabilizer into the system after the esterification reaction in the step (1), heating to 250-260 ℃, keeping the temperature at constant temperature for 10-60min after the reaction system becomes clear and transparent, reducing the pressure to 60-140Pa at the constant temperature of 250-260 ℃, and performing polycondensation for 1-4h until the required viscosity is reached, and then discharging to obtain the copolyester hot melt adhesive. The preparation method has the advantages of quick reaction and high yield, and the prepared hot melt adhesive has the characteristics of high melting point, strong low-temperature tolerance, small melt viscosity and the like, and can meet the requirements of various industries on high-melting-point and low-temperature-resistant polyester hot melt adhesives.
Description
Technical Field
The invention relates to the technical field of copolyester hot melt adhesives, in particular to a dimer acid modified copolyester hot melt adhesive and a preparation method thereof.
Background
The polyester hot melt adhesive has the characteristics of strong bonding force, quick curing, good weather resistance and the like, and is widely applied. However, most of the existing middle-high grade polyester hot melt adhesives have poor low temperature resistance and are easy to become brittle due to high crystallinity and strong molecular chain rigidity, and the melt viscosity of the high molecular weight copolyester is often higher. These disadvantages have led to a major limitation in the field of application of polyester hotmelts.
Chinese patent CN103421460A discloses a preparation method of a crystalline and transparent high-melting-point copolyester hot melt adhesive. The product is crystalline and transparent, has strong bonding force, good dry cleaning resistance and high melting point, and has the advantage of being suitable for application under high temperature conditions.
Chinese patent CN1340585 shows a method for preparing a high melting point polyester hot melt adhesive. The product obtained by the method has the advantages of high crystallization speed, short solidification time and the like, and is suitable for being applied under the high-temperature condition.
Chinese patent CN102492388A provides a high-melting-point polyester hot melt adhesive with better fluidity. The hot melt adhesive has strong adhesiveness, and has good flow assurance and excellent wetting and leveling properties in high-temperature use.
The high melting point copolyester in the above patents has small proportion of methylene chain, ether bond and other flexible chain segments, has limited influence on low temperature resistance and melt viscosity of the material, and the performance needs to be improved.
Disclosure of Invention
The invention provides a dimer acid modified copolyester hot melt adhesive and a preparation method thereof, the preparation method has the advantages of quick reaction and high yield, and the prepared hot melt adhesive has the characteristics of high melting point, strong low-temperature tolerance, small melt viscosity and the like, and can meet the requirements of various industries on high-melting-point and low-temperature-resistant polyester hot melt adhesives.
The technical scheme of the invention is as follows: a preparation method of dimer acid modified copolyester hot melt adhesive comprises the following steps:
(1) adding dimer acid containing 36 carbon atoms, dihydric alcohol containing 2-8 carbon atoms and a catalyst into a reaction kettle according to a ratio, uniformly mixing, and finishing an esterification reaction at the temperature of 160-;
(2) adding thermoplastic polyester and a stabilizer into the system after the esterification reaction in the step (1), heating to 250-260 ℃, keeping the temperature at constant temperature for 10-60min after the reaction system becomes clear and transparent, reducing the pressure to 60-140Pa at the constant temperature of 250-260 ℃, and performing polycondensation for 1-4h until the required viscosity is reached, and then discharging to obtain the copolyester hot melt adhesive.
Preferably, the reaction kettle in the step (1) is also added with dibasic fatty acid containing 6-18 carbon atoms and dibasic aromatic carboxylic acid containing 8 carbon atoms.
Preferably, the dibasic fatty acid is selected from one or more of 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid and octadecanedioic acid.
Preferably, the aromatic dicarboxylic acid is terephthalic acid or/and isophthalic acid.
Preferably, the dihydric alcohol is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol and diethylene glycol.
Preferably, the molar ratio of the dibasic fatty acid to the glycol is 1: 2.0 to 2.5.
Preferably, the catalyst is selected from titanium series, tin series or antimony series, and the total amount of the catalyst is 0.3-1.5% of the total mass sum of the dibasic fatty acid and the dihydric alcohol.
Preferably, the catalyst is tetrabutyl titanate.
Preferably, the thermoplastic polyester is selected from one or a combination of several of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT), and the total amount of the thermoplastic polyester is 0.5-3.0 times of the sum of the mass of the dibasic fatty acid and the mass of the dibasic alcohol.
Preferably, the stabilizer is triphenyl phosphite, and the dosage of the stabilizer is 0.1-1% of the total mass of the dibasic fatty acid and the dihydric alcohol.
The invention has the beneficial effects that: the preparation method of the dimer acid modified copolyester hot melt adhesive uses dimer acid to perform chemical copolymerization modification on the polyester hot melt adhesive, the preparation method has the advantages of quick reaction and high yield, the prepared hot melt adhesive has the characteristics of high melting point, strong low-temperature tolerance, small melt viscosity and the like, and the weather resistance, such as low-temperature tolerance, of the high-melting-point polyester hot melt adhesive and the processing and using properties of the high-melting-point polyester hot melt adhesive are greatly improved.
Detailed Description
In order to make the object, technical solution and technical effect of the present invention more apparent, the present invention will be further described with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of dimer acid modified copolyester hot melt adhesive comprises the steps of adding 168.3g of dimer acid, 54.1g of 1, 4-butanediol and 0.2133g of tetrabutyl titanate into a reaction kettle, rapidly heating to 160 ℃, heating to 210 ℃ at the rate of 60 ℃/h, and maintaining until the effluent reaches the theoretical value, thereby completing esterification; then adding 198.1g of PBT and 0.13g of triphenyl phosphite into the reaction system, heating to 255 ℃, keeping the temperature for 10min after the reaction system becomes clear and transparent, slowly reducing the pressure to 60Pa, carrying out polycondensation for 1.5h, then cooling to 220 ℃, discharging, and obtaining the copolyester hot melt adhesive. The melting point of the hot melt adhesive is 176 ℃ measured by a hot table melting point tester, the hot melt adhesive can resist low temperature of 40 ℃ below zero without brittle fracture measured by a low temperature folding test, and the viscosity of the hot melt adhesive at 230 ℃ is 10684cps measured by a Brookfield viscometer.
Example 2
A preparation method of dimer acid modified copolyester hot melt adhesive comprises the steps of adding 8.3g of isophthalic acid, 16.6g of terephthalic acid, 84.2g of dimer acid, 54.5g of 1, 4-butanediol and 0.5g of tetrabutyl titanate into a reaction kettle, rapidly heating to 160 ℃, heating to 210 ℃ at the rate of 60 ℃/h, and maintaining until the effluent reaches the theoretical value, thereby completing the esterification reaction; then adding 154.2g of PBT () and 0.11g of triphenyl phosphite to the reaction system, heating to 255 ℃, keeping the temperature for 10min after the reaction system becomes clear and transparent, slowly reducing the pressure to 60Pa, polycondensing for 1h, then cooling to 220 ℃ and discharging to obtain the high-melting-point copolyester hot melt adhesive. The melting point of the hot melt adhesive is 191 ℃ measured by a hot table melting point tester, the brittle failure temperature of the hot melt adhesive is-17 ℃ measured by a low-temperature folding endurance test, and the viscosity of the hot melt adhesive at 230 ℃ is 12245cps measured by a Brookfield viscometer.
Example 3
A preparation method of dimer acid modified copolyester hot melt adhesive comprises the steps of adding 8.3g of isophthalic acid, 16.6g of 1, 6-adipic acid, 84.2g of dimer acid, 54.5g of 1, 3-propylene glycol and 0.2133g of tetrabutyl titanate into a reaction kettle, rapidly heating to 160 ℃, heating to 210 ℃ at the speed of 60 ℃/h, and maintaining until effluent reaches a theoretical value to complete an esterification reaction; and then adding 35.55g of polytrimethylene terephthalate and 0.711g of triphenyl phosphite into the reaction system, heating to 250 ℃, keeping the temperature for 20min after the reaction system becomes clear and transparent, slowly reducing the pressure to 80Pa, performing polycondensation for 2h until the required viscosity is reached, discharging, cooling to 220 ℃, and discharging to obtain the high-melting-point copolyester hot melt adhesive. The melting point of the hot melt adhesive is 190 ℃ measured by a hot table melting point tester, the brittle failure temperature of the hot melt adhesive is-18 ℃ measured by a low-temperature folding endurance test, and the viscosity of the hot melt adhesive at 230 ℃ is 12245cps measured by a Brookfield viscometer.
Example 4
A preparation method of dimer acid modified copolyester hot melt adhesive comprises the steps of adding 8.3g of 1, 14-tetradecanedioic acid, 16.6g of terephthalic acid, 84.2g of dimer acid, 54.5g of neopentyl glycol and 0.8g of tetrabutyl titanate into a reaction kettle, rapidly heating to 160 ℃, heating to 210 ℃ at the speed of 60 ℃/h, and maintaining until the effluent reaches the theoretical value, thereby completing the esterification reaction; then 154.2g of polyethylene terephthalate and 0.11g of triphenyl phosphite are added into the reaction system, the temperature is raised to 260 ℃, after the reaction system becomes clear and transparent, the temperature is kept for 60min at constant temperature, the pressure is slowly reduced to 140Pa, polycondensation is carried out for 4h, then the temperature is reduced to 220 ℃, and discharging is carried out, thus obtaining the high-melting-point copolyester hot melt adhesive. The hot melt adhesive has a melting point of 190 ℃ as measured by a hot table melting point tester, a brittle failure temperature of-17.5 ℃ as measured by a low temperature folding endurance test, and a viscosity of 12250cps at 230 ℃ as measured by a Brookfield viscometer.
Example 5
A preparation method of dimer acid modified copolyester hot melt adhesive comprises the steps of adding 8.3g of octadecanedioic acid, 16.6g of terephthalic acid, 84.2g of dimer acid, 54.5g of diethylene glycol and 1.1665g of antimony system into a reaction kettle, rapidly heating to 160 ℃, heating to 210 ℃ at the rate of 60 ℃/h, and maintaining until the effluent reaches the theoretical value, thereby completing the esterification reaction; then adding 213.3g of polybutylene terephthalate and 0.5g of triphenyl phosphite into the reaction system, heating to 255 ℃, keeping the temperature for 10min after the reaction system becomes clear and transparent, slowly reducing the pressure to 100Pa, carrying out polycondensation for 3h, cooling to 220 ℃, discharging, and obtaining the high-melting-point copolyester hot melt adhesive. The melting point of the hot melt adhesive is 192 ℃ measured by a hot table melting point tester, the brittle failure temperature of the hot melt adhesive is-16 ℃ measured by a low-temperature folding endurance test, and the viscosity of the hot melt adhesive at 230 ℃ is 12250cps measured by a Brookfield viscometer.
Example 6
A preparation method of dimer acid modified copolyester hot melt adhesive comprises the steps of adding 8.3g of 1, 8-suberic acid, 16.6g of terephthalic acid, 84.2g of dimer acid, 54.5g of 1, 4-cyclohexanedimethanol and 1.0g of tin into a reaction kettle, rapidly heating to 160 ℃, heating to 210 ℃ at the rate of 60 ℃/h, and maintaining until effluent reaches a theoretical value, thereby completing esterification; then adding 200g of polytrimethylene terephthalate and 0.0711g of triphenyl phosphite into the reaction system, heating to 255 ℃, keeping the temperature for 10min after the reaction system becomes clear and transparent, slowly reducing the pressure to 60Pa, performing polycondensation for 1h, then cooling to 220 ℃ and discharging to obtain the high-melting-point copolyester hot melt adhesive. The melting point of the hot melt adhesive is 190 ℃ measured by a hot table melting point tester, the brittle failure temperature of the hot melt adhesive is-18 ℃ measured by a low-temperature folding endurance test, and the viscosity of the hot melt adhesive at 230 ℃ is 12230cps measured by a Brookfield viscometer.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the present invention pertains, the architecture form can be flexible and varied without departing from the concept of the present invention, and a series of products can be derived. But rather a number of simple derivations or substitutions are made which are to be considered as falling within the scope of the invention as defined by the appended claims.
Claims (5)
1. A preparation method of dimer acid modified copolyester hot melt adhesive is characterized by comprising the following steps:
(1) adding dimer acid containing 36 carbon atoms, dihydric alcohol containing 2-8 carbon atoms and a catalyst into a reaction kettle according to a ratio, uniformly mixing, and finishing an esterification reaction at the temperature of 160-;
(2) adding thermoplastic polyester and a stabilizer into the system after the esterification reaction in the step (1), heating to 250-;
adding a dibasic fatty acid containing 6-18 carbon atoms and a dibasic aromatic carboxylic acid containing 8 carbon atoms into the reaction kettle in the step (1); the dibasic fatty acid is selected from one or a mixture of more than one of 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid and octadecanedioic acid; the binary aromatic carboxylic acid is terephthalic acid or/and isophthalic acid;
the molar ratio of the dibasic fatty acid to the dihydric alcohol is 1: 2.0 to 2.5;
the thermoplastic polyester is selected from one or a combination of several of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT), and the total amount of the thermoplastic polyester is 0.5-3.0 times of the sum of the masses of the dibasic fatty acid and the dibasic alcohol.
2. The method for preparing dimer acid modified copolyester hot melt adhesive according to claim 1, wherein the diol is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol and diethylene glycol.
3. The method for preparing the dimer acid-modified copolyester hot melt adhesive according to claim 1, wherein the catalyst is selected from titanium system, tin system or antimony system, and the total amount of the catalyst is 0.3-1.5% of the total mass sum of the dibasic fatty acid and the glycol.
4. The method for preparing the dimer acid-modified copolyester hot melt adhesive according to claim 3, wherein the catalyst is tetrabutyl titanate.
5. The method for preparing the dimer acid-modified copolyester hot melt adhesive according to claim 1, wherein the stabilizer is triphenyl phosphite, and the dosage of the stabilizer is 0.1 to 1 percent of the total mass of the dibasic fatty acid and the dihydric alcohol.
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| CN201810849720.3A CN108997570B (en) | 2018-07-28 | 2018-07-28 | Dimer acid modified copolyester hot melt adhesive and preparation method thereof |
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| CN115232293A (en) * | 2022-07-14 | 2022-10-25 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing milled hot melt adhesive and preparation method thereof |
| CN115109242B (en) * | 2022-07-14 | 2024-05-28 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing antistatic type powder grinding hot melt adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340585A (en) * | 2000-08-29 | 2002-03-20 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
| CN102492388A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN103421460A (en) * | 2013-07-03 | 2013-12-04 | 上海天洋热熔胶有限公司 | Preparation method of crystalloid and transparent copolyester hot melt adhesive with high melting point |
| CN104629663A (en) * | 2013-11-11 | 2015-05-20 | 上海轻工业研究所有限公司 | Polyester hot melt adhesive |
| CN106189983A (en) * | 2016-07-27 | 2016-12-07 | 马爱芬 | A kind of footwear rapid link low melting point, high-adhesive-strength polyester hot-melt adhesive and its preparation method and application |
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- 2018-07-28 CN CN201810849720.3A patent/CN108997570B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340585A (en) * | 2000-08-29 | 2002-03-20 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
| CN102492388A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN103421460A (en) * | 2013-07-03 | 2013-12-04 | 上海天洋热熔胶有限公司 | Preparation method of crystalloid and transparent copolyester hot melt adhesive with high melting point |
| CN104629663A (en) * | 2013-11-11 | 2015-05-20 | 上海轻工业研究所有限公司 | Polyester hot melt adhesive |
| CN106189983A (en) * | 2016-07-27 | 2016-12-07 | 马爱芬 | A kind of footwear rapid link low melting point, high-adhesive-strength polyester hot-melt adhesive and its preparation method and application |
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