CN104962229A - Preparing method for polyamide hot melt adhesive - Google Patents
Preparing method for polyamide hot melt adhesive Download PDFInfo
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- CN104962229A CN104962229A CN201510357024.7A CN201510357024A CN104962229A CN 104962229 A CN104962229 A CN 104962229A CN 201510357024 A CN201510357024 A CN 201510357024A CN 104962229 A CN104962229 A CN 104962229A
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- melt adhesive
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- diamine
- polyamide hot
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Abstract
The invention relates to a preparing method for polyamide hot melt adhesive, in particular to a preparing method for polyamide hot melt adhesive resistant to high temperature, high in melting point and narrow in melting range. According to the technical scheme, the preparing method is characterized in that two kinds of binary acid, the proportion and design of two kinds of diamine, caprolactam and monobasic acid are carefully selected, and the polyamide hot melt adhesive resistant to high temperature, high in melting point and narrow in melting range is obtained by a common method. The performance requirements of special field application are met, and the cost can be effectively lowered. The polyamide hot melt adhesive prepared through the preparing method can meet the requirement for adhering to automobile components and electronic components of which the working condition temperature reaches 140 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of polyamide hot, particularly a kind of preparation method of high temperature resistant, fusing point is high, melting range is narrow polyamide hot.
Background technology
Polyamide hot is a kind of hot melt adhesive obtained by melt phase polycondensation by aliphatic dibasic acid and aliphatic diamine.Owing to containing amide group, amino, carboxyl isopolarity group in this hot melt adhesive, make it have good cementability to many polar materials, therefore polymeric amide colloidal sol is widely used in the fields such as chemical industry, automobile, lightization, weaving.
Chinese patent CN101307218 discloses a kind of high temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof, be the aliphatic dicarboxylic acid of 5 ~ 12 by carbonatoms, the carbonatoms aliphatics monocarboxylic acid that is 5 ~ 12, the carbon atom subnumber aliphatie diamine that is 6 ~ 15, carbonatoms be 6 ~ 12 lactan, water and stablizer react, then to dewater discharging, obtain polyamide hot.The method can obtain that molecular weight ranges is narrow, quick solidifying, hot melt adhesive that high temperature resistant water washing performance is good.
Chinese patent CN103525357 discloses the preparation method of the polyamide hot of a kind of amido inhibition.It is using a kind of monoamine as chain terminator, and by a kind of diacid, copolymerization hot melt adhesive prepared by a kind of diamines, nylon salt and lactan.Products obtained therefrom has the low easy coating of viscosity, feature that cohesive strength is high.
Chinese patent CN1990810 provides a kind of preparation method of daiamid composition.The polyamide hot fusing point that the method obtains is higher, and has the advantages such as lower temperature resistance is good, snappiness is good, oil-proofness is strong.
Above polyamide hot, all has the advantage of himself.But also there are some defects, as wider in its melting range of hot melt adhesive, melting point onset low (its first fusing point is all below 100 DEG C), and technique is more complicated, cannot meet the situation higher to hot melt adhesive requirement.As the automobile of running at high speed, around its tire, its ambient temperature is up to 120 DEG C; The bonding of conveying high-temperature medium pipeline; The car light of automobile, its operating ambient temperature can reach 140 DEG C; Need the adhesion problem of high-temperature sterilization clothes, also have the fields such as electronics.In these cases, above hot melt adhesive cannot meet the demands.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, a kind of preparation method of high temperature resistant, fusing point is high, melting range is narrow polyamide hot is provided.
The technical solution adopted in the present invention is, a kind of preparation method of polyamide hot, comprises the steps:
(1) diprotic acid, diamine, hexanolactam, monoprotic acid and water being preset proportioning by one joins in autoclave, and heating temperature in the kettle, to 230 ~ 260 DEG C, keeps still internal pressure 1.5 ~ 1.8Mpa, starts polycondensation 1.0 ~ 1.5h;
(2) reaction terminates rear beginning step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure;
(3) synthesis under normal pressure 1.0 ~ 1.5h under nitrogen protection;
(4), after synthesis under normal pressure terminates, logical nitrogen is in still, and pressure is 0.15 ~ 0.2Mpa, while hot discharging, obtains target product.
In above-mentioned steps (1), diprotic acid is the mixture of sebacic acid and hexanodioic acid, and diamine is the mixture of 1,5-pentamethylene diamine and hexanediamine, and monoprotic acid is selected from the one in phenylformic acid, acetic acid, propionic acid, stearic acid, and the mol ratio of each component is:
Diprotic acid: diamine=1:1.02 ~ 1.04;
Sebacic acid: hexanodioic acid=1:2.5 ~ 5.5;
1,5 pentamethylene diamines: hexanediamine=1:2.35 ~ 5.65;
Diprotic acid: hexanolactam: monoprotic acid=1:1.54 ~ 1.69:0.027 ~ 0.054.
Beneficial effect of the present invention, by selected two kinds of diprotic acid, two kinds of diamines, hexanolactam and a kind of monacid proportion design, utilize ordinary method, prepare high temperature resistant, that fusing point is high, melting range is narrow polyamide hot, meet the performance requriements of special dimension application, and can effectively reduce costs.
Embodiment
Below by embodiment, the present invention is set forth further, but not as limit.
Embodiment 1:
Hexanolactam 237.3g, hexanodioic acid 131.4g, hexanediamine 109.04g, sebacic acid 80.8g, 1,5-pentamethylene diamine 40.8g, stearic acid 14.79g and water 200ml is added in the CNC high-pressure reactor of 2L.Being heated to temperature in the kettle is 230 ~ 245 DEG C, starts polycondensation, now, keeps still internal pressure to be that 1.6 ~ 1.8Mpa reacts 1.5h; After reaction terminates, start step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure; At N
2the lower synthesis under normal pressure 1.0h of protection; After synthesis under normal pressure terminates, logical nitrogen is 0.15 ~ 0.2Mpa, while hot discharging to still internal pressure, obtains target product P1.
Embodiment 2:
Hexanolactam 226g, hexanodioic acid 160.6g, hexanediamine 132.24g, sebacic acid 40.4g, 1,5-pentamethylene diamine 20.4g, phenylformic acid 7.38g and water 150ml is added in the CNC high-pressure reactor of 2L.Being heated to temperature in the kettle is 245 ~ 260 DEG C, starts polycondensation, now, keeps still internal pressure to be that 1.5 ~ 1.6Mpa reacts 1.5h; After reaction terminates, start step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure; At N
2the lower synthesis under normal pressure 1.5h of protection; After synthesis under normal pressure terminates, logical nitrogen is 0.15 ~ 0.2Mpa, while hot discharging to still internal pressure, obtains target product P2.
Embodiment 3:
Hexanolactam 237.3g, hexanodioic acid 146g, hexanediamine 110.2g, sebacic acid 60.6g, 1,5-pentamethylene diamine 40.8g, acetic acid 4.21g and water 150ml is added in the CNC high-pressure reactor of 2L.Being heated to temperature in the kettle is 245 ~ 260 DEG C, starts polycondensation, now, keeps still internal pressure to be that 1.5 ~ 1.7Mpa reacts 1.2h; After reaction terminates, start step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure; At N
2the lower synthesis under normal pressure 1.5h of protection; After synthesis under normal pressure terminates, logical nitrogen is 0.15 ~ 0.2Mpa, while hot discharging to still internal pressure, obtains target product P3.
Embodiment 4:
Hexanolactam 248.6g, hexanodioic acid 146g, hexanediamine 120.64g, sebacic acid 60.6g, 1,5-pentamethylene diamine 30.6g, propionic acid 2.60g and water 200ml is added in the CNC high-pressure reactor of 2L.Being heated to temperature in the kettle is 240 ~ 250 DEG C, starts polycondensation, now, keeps still internal pressure to be that 1.5 ~ 1.7Mpa reacts 1.0h; After reaction terminates, start step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure; At N
2the lower synthesis under normal pressure 1.2h of protection; After synthesis under normal pressure terminates, logical nitrogen is 0.15 ~ 0.2Mpa, while hot discharging to still internal pressure, obtains target product P4.
Embodiment 5:
Hexanolactam 226g, hexanodioic acid 146g, hexanediamine 119.48g, sebacic acid 60.6g, 1,5-pentamethylene diamine 30.6g, stearic acid 12.94g and water 200ml is added in the CNC high-pressure reactor of 2L.Being heated to temperature in the kettle is 240 ~ 255 DEG C, starts polycondensation, now, keeps still internal pressure to be that 1.6 ~ 1.7Mpa reacts 1.2h; After reaction terminates, start step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure; At N
2the lower synthesis under normal pressure 1.2h of protection; After synthesis under normal pressure terminates, logical nitrogen is 0.15 ~ 0.2Mpa, while hot discharging to still internal pressure, obtains target product P5.
Performance test:
The first fusing point of products obtained therefrom and whole fusing point reference standard ISO 11357-3-2011; The tensile strength of products obtained therefrom and elongation at break reference standard GB/T 1701-2001; The stripping strength reference standard FZ/T 01085-2009 of products obtained therefrom; Gel chromatography is adopted to measure the molecular weight of product.
Shown in the test result following table 1 of product:
Table 1: each embodiment products obtained therefrom index test result.
From in upper table 1, can obviously find out, good by the over-all properties of the polyamide hot prepared by the present invention, and just fusing point is all higher, is greater than 140 DEG C, whole fusing point is also higher, be greater than 160 DEG C, and melting range relative narrower, be generally less than 25 DEG C, the narrowlyest can reach 18.51 DEG C, the demand of special application field can be met.
Claims (1)
1. a preparation method for polyamide hot, is characterized in that, comprises the steps:
Diprotic acid, diamine, hexanolactam, monoprotic acid and water are preset proportioning by one to be joined in autoclave, and heating temperature in the kettle, to 230 ~ 260 DEG C, keeps still internal pressure 1.5 ~ 1.8Mpa, starts polycondensation 1.0 ~ 1.5h;
Reaction terminates rear beginning step-down, within 1.0 ~ 1.5h, still internal pressure is slowly down to normal pressure;
Synthesis under normal pressure 1.0 ~ 1.5h under nitrogen protection;
After synthesis under normal pressure terminates, logical nitrogen is in still, and pressure is 0.15 ~ 0.2Mpa, while hot discharging, obtains target product;
Described diprotic acid is the mixture of sebacic acid and hexanodioic acid, and described diamine is the mixture of 1,5-pentamethylene diamine and hexanediamine, and described monoprotic acid is selected from the one in phenylformic acid, acetic acid, propionic acid, stearic acid, and the mol ratio of each component is respectively:
Diprotic acid: diamine=1:1.02 ~ 1.04;
Sebacic acid: hexanodioic acid=1:2.5 ~ 5.5;
1,5 pentamethylene diamines: hexanediamine=1:2.35 ~ 5.65;
Diprotic acid: hexanolactam: monoprotic acid=1:1.54 ~ 1.69:0.027 ~ 0.054.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250433A (en) * | 2017-12-19 | 2018-07-06 | 浙江恒逸锦纶有限公司 | A kind of PA6-56 copolymeric materials and preparation method thereof |
| CN108690550A (en) * | 2018-05-14 | 2018-10-23 | 启东鑫天鼎热熔胶有限公司 | A kind of formula and preparation method thereof of weaving high temperature resistant water washing polyamide hot-melt adhesive |
| CN110330641A (en) * | 2019-06-06 | 2019-10-15 | 南京工程学院 | A kind of preparation method of nylon resin |
| CN113214474A (en) * | 2020-01-21 | 2021-08-06 | 上海凯赛生物技术股份有限公司 | Polyamide hot melt adhesive and preparation method thereof |
| CN116042169A (en) * | 2022-12-27 | 2023-05-02 | 南通天洋新材料有限公司 | Preparation method of phenol yellowing-resistant copolyamide hot melt adhesive |
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| CN1597826A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Thermosol of polyamide and preparation process thereof |
| CN101307218A (en) * | 2008-06-20 | 2008-11-19 | 上海天洋热熔胶有限公司 | High temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof |
| CN101463243A (en) * | 2009-01-15 | 2009-06-24 | 上海天洋热熔胶有限公司 | Polyamide thermosol for net film and preparation thereof |
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2015
- 2015-06-25 CN CN201510357024.7A patent/CN104962229B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597826A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Thermosol of polyamide and preparation process thereof |
| CN101307218A (en) * | 2008-06-20 | 2008-11-19 | 上海天洋热熔胶有限公司 | High temperature resistant water washing polyamide hot-melt adhesive for clothes and preparation method thereof |
| CN101463243A (en) * | 2009-01-15 | 2009-06-24 | 上海天洋热熔胶有限公司 | Polyamide thermosol for net film and preparation thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250433A (en) * | 2017-12-19 | 2018-07-06 | 浙江恒逸锦纶有限公司 | A kind of PA6-56 copolymeric materials and preparation method thereof |
| CN108690550A (en) * | 2018-05-14 | 2018-10-23 | 启东鑫天鼎热熔胶有限公司 | A kind of formula and preparation method thereof of weaving high temperature resistant water washing polyamide hot-melt adhesive |
| 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 |
| CN113214474A (en) * | 2020-01-21 | 2021-08-06 | 上海凯赛生物技术股份有限公司 | Polyamide hot melt adhesive and preparation method thereof |
| CN116042169A (en) * | 2022-12-27 | 2023-05-02 | 南通天洋新材料有限公司 | Preparation method of phenol yellowing-resistant copolyamide hot melt adhesive |
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| CN104962229B (en) | 2017-03-08 |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: Kunshan Tianyang New Material Co.,Ltd. Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd. |
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Address after: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee after: Tianyang New Material (Shanghai) Technology Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: Kunshan Tianyang New Material Co.,Ltd. Address before: 201802 Shanghai City, Jiading District Hui Ping Lu Nanxiang Town, No. 505 Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: Kunshan Tianyang New Material Co.,Ltd. |