CN102863616A - Preparation method of low-melting-point copolyamide hot melt adhesive - Google Patents
Preparation method of low-melting-point copolyamide hot melt adhesive Download PDFInfo
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- CN102863616A CN102863616A CN2012101997456A CN201210199745A CN102863616A CN 102863616 A CN102863616 A CN 102863616A CN 2012101997456 A CN2012101997456 A CN 2012101997456A CN 201210199745 A CN201210199745 A CN 201210199745A CN 102863616 A CN102863616 A CN 102863616A
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Abstract
The invention discloses a preparation method of low-melting-point copolyamide hot melt adhesive. The preparation method includes that aliphatic dicarboxylic acid with 3-8 carbon number, aliphatic diamine with 3-8 carbon number, caprolactam, water and catalyst are added in a reaction kettle, simultaneously high-boiling-point monoamine is added to serve as a molecular weight regulator, the temperature rises to 170-250 DEG C under the protection of nitrogen, and finally the copolyamide hot melt adhesive is obtained through condensation reaction. The melting point of the obtained hot melt adhesive is below 115 DEG C and is particularly suitable for adhesion of heat-sensitive fiber fabric or leather fabric.
Description
Technical field
The present invention relates to a kind of preparation method of low-melting-point copolyamides hot melt adhesive.
Technical background
Polyamide hot is a kind of hot melt adhesive that aliphatic dibasic acid and diamines make by melt phase polycondensation,
From molecular structure, copolyamide exists powerful Intermolecular Forces and interface electrostatic attraction, and various materials are all had good affinity and tough cohesive force; Simultaneously the copolyamide hot melt adhesive have also that curing speed is fast, environmental protection is pollution-free, physical and chemical performance is stable, water insoluble, transportation and the advantage such as easy to use, thereby be widely used in the bonding of the materials such as fabric, metal, plastics, leather.The clothes fusible interlining is the important applied field of polyamide hot, and it requires material melting point low, and particularly some chemical ﹠ blended fabrics wish that the hot melt adhesive fusing point is lower than 110 ℃, in order to avoid damage cloth; Chinese patent CN88103468A and Chinese patent CN1590433 disclose respectively two kinds of dystectic copolyamide hot melt adhesives, fusing point is up to more than 300 ℃, be difficult to be applied to apparel industry, Chinese patent CN101705073B has proposed a kind of soybean oil-based dimeric acid type polyamide hot melt adhesive and preparation method thereof, gained hot melt adhesive fusing point is 98-120 ℃, owing to used dimeracid in its prescription, cause the product colour yellowing, inapplicable in some occasion.In order to overcome defects, the present invention proposes a kind of preparation method of low-melting-point copolyamides hot melt adhesive.
Summary of the invention
The object of the invention is to disclose a kind of preparation method of low-melting-point copolyamides hot melt adhesive, to satisfy the demand of relevant industries, it is characterized in that comprising the steps:
(1) aliphatic dibasic acid, aliphatic diamine and hexanolactam are joined in the reactor, add simultaneously molecular weight regulator, water and catalyzer, be warming up to 170 ~ 190 ℃ under nitrogen protection, pressure rises to 1.0 ~ 1.5MPa, stirring reaction 1.5 ~ 2.5 hours; Be warming up to 200 ~ 240 ℃, pressure is increased to 1.6 ~ 1.8MPa again, reacts 1 hour; Temperature continues to be increased to 250 ℃, and Pressure Drop is to normal pressure, reacts that discharging can get the target hot melt adhesive at last after 0.5 ~ 1.0 hour;
Said aliphatic dibasic acid is that carbonatoms is 3 ~ 8 diprotic acid, is selected from 1,3-propanedioic acid, Isosorbide-5-Nitrae-Succinic Acid, 1,5-pentanedioic acid, 1,6-hexanodioic acid and 2,4-dimethyl-1, more than one in the 6-hexanodioic acid;
Said aliphatic diamine is that carbonatoms is 3 ~ 8 diamine, is selected from 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 2, more than one in the 4-dimethyl hexanediamine;
Described molecular weight regulator is a kind of in amino dodecane, tetradecy lamine, cetylamine and the stearylamine;
Described catalyzer is a kind of in diphosphanetetroic acid and the phosphoric acid.
Described each component proportion meets following ranges, the mol ratio of described total diamine and total diamine be 1.02 ~ 1.05:1 in the gross weight of diprotic acid, diamine and hexanolactam, the weight percent of each component is respectively:
The weight of diprotic acid is 41.% ~ 51.1% of gross weight,
The weight of diamines is 39.7% ~ 50.0% of gross weight,
The weight of hexanolactam is 8.% ~ 13% of gross weight,
The weight of molecular weight regulator is 5.7% ~ 11.5% of gross weight,
Catalyst weight is 0.1% ~ 0.2% of gross weight,
Water is 5% ~ 10% of gross weight.
Innovation of the present invention is: adopt high boiling monoamine as molecular weight regulator, to have a fusing point low through detecting for prepared polyamide hot, and good stability of the dimension is water-fastness, the advantages such as viscosity is good can be applicable to the industries such as lining cloth, footwear industry, clothes and leather.
Performance test: the number-average molecular weight gel chromatography of products therefrom in the embodiment of the invention, the fusing point ISO 11357-1-1997 that adopts international standards measures.
Embodiment
Embodiment 1
With 10.4g 1,3-propanedioic acid, 26.4g 1,5-pentanedioic acid, 21.9g 1,6-hexanodioic acid, 17.4g 2,4-dimethyl-1,6-hexanodioic acid, 7.55g1,3-propylene diamine, 20.81g 1,5-pentamethylene diamine, 17.75g 1,6-hexanediamine, 14.69g 2,4-dimethyl hexanediamine, 11.9g hexanolactam, 8.53g amino dodecane, 0.15g diphosphanetetroic acid and 7.5g water join in the batch condensation polymerization reactor, pass into the air in the nitrogen replacement still.Temperature is increased to 170 ℃, and pressure rises to 1.0MPa, insulation reaction 2.0 hours; Pressure continues to rise to 1.7MPa, and temperature improves 200 ℃, reacts 1 hour; Pressure Drop is to normal pressure, and temperature is increased to 250 ℃, continues reaction 0.5 hour, and discharging obtains the copolyamide hot melt adhesive, and recording fusing point is 105.7 ℃, and number-average molecular weight is 16300.
Embodiment 2
With 23.6g 1,4-Succinic Acid, 19.8g 1,5-pentanedioic acid, 19g 1,6-hexanodioic acid, 20.88g 2,4-dimethyl-1,6-hexanodioic acid, 18.48g Putriscine, 16.7g 1,5-pentamethylene diamine, 15.83g 1,6-hexanediamine, 18.14g 2,4-dimethyl hexanediamine, 20.7g hexanolactam, 16.8g cetylamine, 0.21g phosphoric acid and 17.5g water join in the batch condensation polymerization reactor, pass into the air in the nitrogen replacement still.Temperature is increased to 185 ℃, and pressure rises to 1.5MPa, insulation reaction 1.5 hours; Pressure continues to rise to 1.7MPa, and temperature improves 220 ℃, reacts 1 hour; Pressure Drop is to normal pressure, and temperature is increased to 250 ℃, continues reaction 1.0 hours, and discharging obtains the copolyamide hot melt adhesive, and recording fusing point is 112.4 ℃, and number-average molecular weight is 19800.
Embodiment 3
With 10.4g 1,3-propanedioic acid, 11.8g 1,4-Succinic Acid, 29.2g 1,6-hexanodioic acid, 24.36g 2,4-dimethyl-1,6-hexanodioic acid, 7.7g1,3-propylene diamine, 9.15g Putriscine, 24.13g 1,6-hexanediamine, 20.97g 2,4-dimethyl hexanediamine, 13.62g hexanolactam, 17.4g stearylamine, 0.25g phosphoric acid and 10.2g water join in the batch condensation polymerization reactor, pass into the air in the nitrogen replacement still.Temperature is increased to 185 ℃, and pressure rises to 1.2MPa, insulation reaction 2.5 hours; Pressure continues to rise to 1.8MPa, and temperature is increased to 220 ℃, reacts 1 hour; Pressure Drop is to normal pressure, and temperature is increased to 250 ℃, continues reaction 1.0 hours, and discharging obtains the copolyamide hot melt adhesive, and recording fusing point is 107.5 ℃, and number-average molecular weight is 17600.
Embodiment 4
With 10.4g 1,3-propanedioic acid, 11.8g 1,4-Succinic Acid, 19.8g 1,5-pentanedioic acid, 34.8g 2,4-dimethyl-1,6-hexanodioic acid, 7.62g 1,3-propylene diamine, 9.06g 1,4-butanediamine, 15.76g 1,5-pentamethylene diamine, 29.66g 2,4-dimethyl hexanediamine, 17.17g hexanolactam, 12.91g tetradecy lamine, 0.31g diphosphanetetroic acid and 12.5g water join in the batch condensation polymerization reactor, pass into the air in the nitrogen replacement still.Temperature is increased to 190 ℃, and pressure rises to 1.5MPa, insulation reaction 2.0 hours; Pressure continues to rise to 1.7MPa, and temperature is increased to 230 ℃, reacts 1 hour; Pressure Drop is to normal pressure, and temperature is increased to 250 ℃, continues reaction 0.5 hour, and discharging obtains the copolyamide hot melt adhesive, and recording fusing point is 109.5 ℃, and number-average molecular weight is 18500.
Embodiment 5
With 5.2g 1,3-propanedioic acid, 11.8g 1, the 4-Succinic Acid, 26.4g 1,5-pentanedioic acid, 29.2g 1,6-hexanodioic acid, 3.83g1,3-propylene diamine, 18.22g 1,4-butanediamine, 21.11g 1,5-pentamethylene diamine, 24.01g 1,6-hexanediamine, 20.89g hexanolactam, 15.11g stearylamine, 0.15g diphosphanetetroic acid and 7.5g water join in the batch condensation polymerization reactor, pass into the air in the nitrogen replacement still.Temperature is increased to 178 ℃, and pressure rises to 1.1MPa, insulation reaction 2.5 hours; Pressure continues to rise to 1.7MPa, and temperature improves 225 ℃, reacts 1 hour; Pressure Drop is to normal pressure, and temperature is increased to 250 ℃, continues reaction 0.6 hour, and discharging obtains the copolyamide hot melt adhesive, and recording fusing point is 103.5 ℃, and number-average molecular weight is 14700.
Claims (2)
1. the preparation method of a low-melting-point copolyamides hot melt adhesive is characterized in that comprising the steps:
(1) aliphatic dibasic acid, aliphatic diamine and hexanolactam are joined in the reactor, add simultaneously molecular weight regulator, water and catalyzer, be warming up to 170 ~ 190 ℃ under nitrogen protection, pressure rises to 1.0 ~ 1.5MPa, stirring reaction 1.5 ~ 2.5 hours; Be warming up to 200 ~ 240 ℃, pressure is increased to 1.6 ~ 1.8MPa again, reacts 1 hour; Temperature continues to be increased to 250 ℃, and Pressure Drop reacts and is down to room temperature after 0.5 ~ 1.0 hour to normal pressure, can get the target hot melt adhesive at last;
Said aliphatic dibasic acid is that carbonatoms is 3 ~ 8 diprotic acid, is selected from 1,3-propanedioic acid, Isosorbide-5-Nitrae-Succinic Acid, 1,5-pentanedioic acid, 1,6-hexanodioic acid and 2,4-dimethyl-1, more than one in the 6-hexanodioic acid;
Said aliphatic diamine is that carbonatoms is 3 ~ 8 diamine, is selected from 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 2, more than one in the 4-dimethyl hexanediamine;
Described molecular weight regulator is a kind of in amino dodecane, tetradecy lamine, cetylamine and the stearylamine;
Described catalyzer is a kind of in diphosphanetetroic acid, the phosphoric acid.
2. preparation method according to claim 1 is characterized in that, the mol ratio of described total diamine and total dicarboxylic acid is 1.02 ~ 1.05:1, and in the gross weight of diprotic acid, diamine and hexanolactam, the weight percent of each component is respectively:
The weight of diprotic acid is 41%-51.1% of gross weight,
The weight of diamine is 39.7%-50.0% of gross weight,
The weight of hexanolactam is 8%-13% of gross weight,
The weight of molecular weight regulator is 5.7%-11.5% of gross weight,
Catalyst weight is 0.1%-0.2% of gross weight,
Water is 5%-10% of gross weight.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525357A (en) * | 2013-10-23 | 2014-01-22 | 上海天洋热熔胶有限公司 | Preparation method of amino inhibited polyamide hot melt adhesive |
| CN103524731A (en) * | 2013-10-16 | 2014-01-22 | 上海天洋热熔胶有限公司 | Preparation method of polyamide hot melt adhesive with low surface energy for hot drills |
| CN105504271A (en) * | 2016-02-03 | 2016-04-20 | 温州华特热熔胶有限公司 | Low-melting-point copolyamide hot melt adhesive for clothes and processing method thereof |
| CN109503829A (en) * | 2018-10-10 | 2019-03-22 | 华峰集团有限公司 | There is light shaped silk spinning-grade polyamide 66 resin and preparation method thereof |
| CN109536119A (en) * | 2018-12-03 | 2019-03-29 | 上海天洋热熔粘接材料股份有限公司 | A kind of copolyamide hot melt adhesive and preparation method thereof |
| CN109970969A (en) * | 2019-04-10 | 2019-07-05 | 山东广垠新材料有限公司 | A kind of preparation method of ternary polymerization low melting point nylon |
| CN110330641A (en) * | 2019-06-06 | 2019-10-15 | 南京工程学院 | A kind of preparation method of nylon resin |
| CN110527083A (en) * | 2019-09-18 | 2019-12-03 | 温州华特热熔胶股份有限公司 | Copolyamide hot melt adhesive and preparation method thereof for spinning |
| CN112094619A (en) * | 2019-12-13 | 2020-12-18 | 上海铂淳胶粘技术有限公司 | Fiber composite hot melt adhesive and preparation method thereof |
| CN114656917A (en) * | 2020-12-23 | 2022-06-24 | 上海天洋热熔粘接材料股份有限公司 | Phenol yellowing resistant copolyamide hot melt adhesive and preparation method thereof |
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| CN1415686A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for preparing polyamide hot-melt adhesive |
| CN101705073A (en) * | 2009-11-13 | 2010-05-12 | 上海天洋热熔胶有限公司 | Soybean oil-based dimeric acid type polyamide hot melt adhesive and preparation method thereof |
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2012
- 2012-06-16 CN CN2012101997456A patent/CN102863616A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1415686A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for preparing polyamide hot-melt adhesive |
| CN101705073A (en) * | 2009-11-13 | 2010-05-12 | 上海天洋热熔胶有限公司 | Soybean oil-based dimeric acid type polyamide hot melt adhesive and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524731A (en) * | 2013-10-16 | 2014-01-22 | 上海天洋热熔胶有限公司 | Preparation method of polyamide hot melt adhesive with low surface energy for hot drills |
| CN103525357A (en) * | 2013-10-23 | 2014-01-22 | 上海天洋热熔胶有限公司 | Preparation method of amino inhibited polyamide hot melt adhesive |
| CN105504271A (en) * | 2016-02-03 | 2016-04-20 | 温州华特热熔胶有限公司 | Low-melting-point copolyamide hot melt adhesive for clothes and processing method thereof |
| CN109503829A (en) * | 2018-10-10 | 2019-03-22 | 华峰集团有限公司 | There is light shaped silk spinning-grade polyamide 66 resin and preparation method thereof |
| CN109503829B (en) * | 2018-10-10 | 2021-07-09 | 华峰集团有限公司 | Spinning-grade polyamide 66 resin for bright profiled yarn and preparation method thereof |
| CN109536119A (en) * | 2018-12-03 | 2019-03-29 | 上海天洋热熔粘接材料股份有限公司 | A kind of copolyamide hot melt adhesive and preparation method thereof |
| CN109970969B (en) * | 2019-04-10 | 2021-06-22 | 山东广垠新材料有限公司 | Preparation method of terpolymer low-melting-point nylon |
| CN109970969A (en) * | 2019-04-10 | 2019-07-05 | 山东广垠新材料有限公司 | A kind of preparation method of ternary polymerization low melting point nylon |
| CN110330641A (en) * | 2019-06-06 | 2019-10-15 | 南京工程学院 | A kind of preparation method of nylon resin |
| CN110330641B (en) * | 2019-06-06 | 2021-07-06 | 南京工程学院 | Preparation method of nylon resin |
| CN110527083A (en) * | 2019-09-18 | 2019-12-03 | 温州华特热熔胶股份有限公司 | Copolyamide hot melt adhesive and preparation method thereof for spinning |
| CN112094619A (en) * | 2019-12-13 | 2020-12-18 | 上海铂淳胶粘技术有限公司 | Fiber composite hot melt adhesive and preparation method thereof |
| CN114656917A (en) * | 2020-12-23 | 2022-06-24 | 上海天洋热熔粘接材料股份有限公司 | Phenol yellowing resistant copolyamide hot melt adhesive and preparation method thereof |
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Application publication date: 20130109 |