CN111909508B - Copolyamide hot-melt adhesive resin and preparation method thereof - Google Patents
Copolyamide hot-melt adhesive resin and preparation method thereof Download PDFInfo
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- CN111909508B CN111909508B CN202010866864.7A CN202010866864A CN111909508B CN 111909508 B CN111909508 B CN 111909508B CN 202010866864 A CN202010866864 A CN 202010866864A CN 111909508 B CN111909508 B CN 111909508B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a copolyamide hot-melt adhesive resin which comprises the following components in parts by weight: caprolactam: 80-120 parts of a solvent; nylon 66 salt: 80-100 parts of a solvent; and (3) modifying EVA: 10-20 parts; the modified ethylene-vinyl acetate copolymer is EVA resin with amide groups. According to the invention, after EVA is modified, an amide group is formed on a branched chain of a molecular chain, the modified EVA has better compatibility with nylon molecules due to the similarity of molecular structures, the modified EVA can be fully dispersed among the nylon molecules, resin is obtained through chemical copolymerization modification, the melting point can be effectively reduced, large-dose addition is not needed, and the obtained copolymer resin also has the amide group on the branched chain, so that the hot-melt adhesive bonding with nylon materials has better effect.
Description
Technical Field
The invention relates to the field of macromolecules, in particular to a copolyamide hot-melt adhesive resin and a preparation method thereof.
Background
In recent years, due to excellent service performance and processing and forming convenience of the nylon thermal fuse, the demand of the nylon thermal fuse in the industries of textile, clothing and the like is rapidly increased. Therefore, higher demands are made on the yield and properties of the polyamide resin (hereinafter referred to as "specialty material") as a raw material thereof. At present, no special material for the hot melt wire with strong pertinence exists in the market, the special material can be selected from general resin, the selectable resin is few in grade, and most of the special material is monopolized by foreign companies. Under the condition, the development of China in related fields and the development process of high-end products are severely restricted. Although a few domestic enterprises develop some related products according to market demands, the whole technology is lack of an autonomous core technology, the product quality stability is poor, and systematic research is also lack. The industrial production of the copolymer PA66/6 of Polyamide (PA)66 and PA6 has been carried out abroad, and several grades of general-purpose copolyamide resins have been developed successively, but the development demand for thermal fuses has not been fully satisfied. Therefore, the intensive research on the special material for the nylon hot melt and the development of the commodity meeting the global market demand are problems to be solved urgently.
At present, the special material for the nylon hot melt wire in the domestic market has the problems of high melting point, insufficient bonding strength and the like. Therefore, the invention develops a special material for the thermal fuse with low melting point and high bonding strength.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a copolyamide hot-melt resin and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a copolyamide hot-melt resin is disclosed,
comprises the following components in parts by weight:
caprolactam: 80 to 120 parts by weight of
Nylon 66 salt: 80 to 100 portions of
And (3) modifying EVA: 10-20 parts;
the modified ethylene-vinyl acetate copolymer is EVA resin with amide groups.
As a further improvement of the present invention,
the modified EVA comprises the following components in parts by weight:
ethylene: 280 to 300 portions of
Vinyl acetate: 80 to 100 portions of
Vinylamine: 40 to 50 portions of
The monoacid chloride compound: 80-200 parts.
As a further improvement of the present invention,
the preparation method of the modified EVA comprises the following steps:
adding ethylene, vinyl acetate and vinylamine monomers into a solvent by using n-hexane as a solvent, reacting for 3-5 hours at 30-150 ℃ under 5-7 MPa by using an azo compound as an initiator, cooling to room temperature, adding NaOH, adjusting the pH value to 8-9, adding a monoacid chloride compound, reacting for 0.5-2 hours at 20-30 ℃, cooling and washing to obtain the modified EVA.
As a further improvement of the present invention,
the azo compound is azobisisobutyronitrile, and the dosage of the azo compound is 0.5-2 parts.
As a further improvement of the present invention,
the monoacid chloride compound is acetyl chloride.
Another object of the present invention is to provide a method for preparing a copolyamide hot-melt resin, comprising:
adding nylon 66 salt into a reaction kettle, heating to 200-250 ℃, dissolving to a transparent solution, adding modified EVA, reacting at a constant temperature for 1-2 hours to obtain a milky solution, adding caprolactam, heating to 270-300 ℃, reacting at a constant temperature for 2-5 hours, cooling to 250-260 ℃, changing into a distillation device, draining, cooling after draining, performing a post-treatment process, removing impurities and drying to obtain the copolyamide hot melt filament resin.
As a further improvement of the present invention,
the post-treatment step comprises crushing the resultant with a crusher, extracting with 60 deg.C hot water for 2 hr, and pre-drying in an air drying oven at 100 deg.C for 2 hr.
In the invention, molecular chain segments are mainly formed by polymerization of caprolactam and nylon 66 salt, modified EVA is added for copolymerization, and the melting point of the whole resin is reduced by adding the EVA.
However, in practical situations, when pure EVA is copolymerized with nylon, due to poor compatibility between EVA and nylon molecules, EVA cannot be well dispersed among nylon molecules, and finally the obtained resin has a situation that the local melting point is still high, and the melting point can be obviously reduced by adding a large amount of EVA.
According to the invention, after EVA is modified, an amide group is formed on a branched chain of a molecular chain, the modified EVA has better compatibility with nylon molecules due to the similarity of molecular structures, the modified EVA can be fully dispersed among the nylon molecules, resin is obtained through chemical copolymerization modification, the melting point can be effectively reduced, large-dose addition is not needed, and the obtained copolymer resin also has the amide group on the branched chain, so that the hot-melt adhesive bonding with nylon materials has better effect.
The EVA modification principle is as follows:
Detailed Description
The first embodiment is as follows:
a copolyamide hot-melt resin is disclosed,
comprises the following components in parts by weight:
caprolactam: 100 portions of
Nylon 66 salt: 100 portions of
And (3) modifying EVA: 10 parts of (A);
the modified EVA is EVA resin with amido.
The modified EVA comprises the following components in parts by weight:
ethylene: 300 portions of
Vinyl acetate: 100 portions of
Vinylamine: 40 portions of
The monoacid chloride compound: 150 parts.
The preparation method of the modified EVA comprises the following steps:
adding ethylene, vinyl acetate and vinylamine monomers into a solvent by using n-hexane as a solvent, reacting for 3-5 hours at 30-150 ℃ under 5-7 Mpa by using an azo compound as an initiator, cooling to room temperature, adding NaOH, adjusting the pH value to 8-9, adding a monoacid chloride compound, reacting for 0.5-2 hours at 20-30 ℃, cooling and washing to obtain the modified EVA.
The azo compound is azobisisobutyronitrile, and the dosage of the azo compound is 1 part.
The monoacid chloride compound is acetyl chloride.
The preparation method of the copolyamide hot melt resin comprises the following steps:
adding nylon 66 salt into a reaction kettle, heating to 250 ℃, dissolving to obtain a transparent solution, then adding modified EVA, reacting at constant temperature for 2 hours to obtain a milky solution, then adding caprolactam, heating to 300 ℃, reacting at constant temperature for 2-5 hours, then cooling to 260 ℃, changing into a distillation device, draining, cooling after draining, performing post-treatment, removing impurities and drying to obtain the copolyamide hot melt filament resin.
The post-treatment process comprises the steps of crushing the product by a crusher, extracting by hot water at 60 ℃ for 2 hours, and pre-drying for 2 hours in a forced air drying oven at 100 ℃.
Comparative example:
comprises the following components in parts by weight:
caprolactam: 100 portions of
Nylon 66 salt: 100 portions of
Commercial EVA: 10 parts of (A);
the preparation method of the copolyamide hot melt resin comprises the following steps:
adding nylon 66 salt into a reaction kettle, heating to 250 ℃, dissolving to a transparent solution, adding commercially available EVA, reacting at a constant temperature for 2 hours to obtain a milky solution, adding caprolactam, heating to 300 ℃, reacting at a constant temperature for 2-5 hours, cooling to 260 ℃, changing into a distillation device, draining, cooling after draining, performing a post-treatment process, removing impurities and drying to obtain the copolyamide hot melt filament resin.
The post-treatment step comprises crushing the resultant with a crusher, extracting with 60 deg.C hot water for 2 hr, and pre-drying in an air drying oven at 100 deg.C for 2 hr.
The examples and comparative examples were tested for softening point, hot melt index, and heat distortion temperature:
the softening point test method refers to the GB/T15332-94 standard for testing;
the test method of the melt index refers to the GB/T3682-2000 standard for testing;
the testing method of the thermal deformation temperature refers to the GB 20641-2006 standard for testing;
test methods for peel strength testing the peel strength was tested with reference to the HGT 3697-2016 standard.
Table one: and (3) detection results:
table two: raw material table:
as can be seen from the examples and comparative examples, the modified EVA prepared by the invention is adopted in the examples, and the commercially available EVA is adopted in the comparative examples, so that the softening point, the hot melt index and the thermal deformation temperature in the examples are obviously reduced.
The influence of Vac content in common EVA on lowering the melting point is not large, which is probably caused by incompatibility of the EVA and nylon, the technical effect of better compatibility of the EVA and the nylon is achieved by modifying EVA and introducing acylamino in the scheme of the invention, and the effect of lowering softening point, hot melt index and thermal deformation temperature by adding the modified EVA is achieved, so that the EVA is more suitable for being used in a hot melt wire.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (6)
1. A copolyamide hot-melt resin characterized by:
comprises the following components in parts by weight:
caprolactam: 80 to 120 parts by weight of
Nylon 66 salt: 80 to 100 portions of
And (3) modifying EVA: 10-20 parts;
the modified EVA is EVA resin with amido;
the modified EVA comprises the following components in parts by weight:
ethylene: 280 to 300 portions of
Vinyl acetate: 80 to 100 portions of
Vinylamine: 40 to 50 portions of
The monoacid chloride compound: 80-200 parts.
2. A copolyamide hot-melt resin according to claim 1, characterised in that:
the preparation method of the modified EVA comprises the following steps:
adding ethylene, vinyl acetate and vinylamine monomers into a solvent by using n-hexane as a solvent, reacting for 3-5 hours at 30-150 ℃ under 5-7 MPa by using an azo compound as an initiator, cooling to room temperature, adding NaOH, adjusting the pH value to 8-9, adding a monoacid chloride compound, reacting for 0.5-2 hours at 20-30 ℃, cooling and washing to obtain the modified EVA.
3. A copolyamide hot-melt resin according to claim 2, characterised in that:
the azo compound is azobisisobutyronitrile, and the dosage of the azo compound is 0.5-2 parts.
4. A copolyamide hot-melt resin according to claim 3, characterised in that:
the monoacid chloride compound is acetyl chloride.
5. The process for the preparation of copolyamide hot melt resins according to any one of claims 1 to 4, characterized in that:
adding nylon 66 salt into a reaction kettle, heating to 200-250 ℃, dissolving to a transparent solution, adding modified EVA, reacting at a constant temperature for 1-2 hours to obtain a milky solution, adding caprolactam, heating to 270-300 ℃, reacting at a constant temperature for 2-5 hours, cooling to 250-260 ℃, changing into a distillation device, draining, cooling after draining, performing a post-treatment process, removing impurities and drying to obtain the copolyamide hot melt filament resin.
6. The method for preparing copolyamide hot-melt resin according to claim 5, wherein:
the post-treatment step comprises crushing the resultant with a crusher, extracting with 60 deg.C hot water for 2 hr, and pre-drying in an air drying oven at 100 deg.C for 2 hr.
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| CN202010866864.7A CN111909508B (en) | 2020-08-25 | 2020-08-25 | Copolyamide hot-melt adhesive resin and preparation method thereof |
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| CN202010866864.7A CN111909508B (en) | 2020-08-25 | 2020-08-25 | Copolyamide hot-melt adhesive resin and preparation method thereof |
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| CN111909508B true CN111909508B (en) | 2022-04-12 |
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| CN114685781B (en) * | 2020-12-31 | 2023-10-20 | 中国纺织科学研究院有限公司 | Polyamide functional masterbatch carrier resin and polyamide functional masterbatch |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997625A (en) * | 1973-05-30 | 1976-12-14 | Daicel, Ltd. | Hot melt adhesive for metals |
| CN105646875A (en) * | 2014-11-14 | 2016-06-08 | 辽宁银珠化纺集团有限公司 | Nylon 66 resin having a low melting point and a preparing method thereof |
| CN108410165A (en) * | 2018-02-12 | 2018-08-17 | 广东新会美达锦纶股份有限公司 | A kind of preparation method of high color fastness low melting point polyamide Masterbatch |
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2020
- 2020-08-25 CN CN202010866864.7A patent/CN111909508B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997625A (en) * | 1973-05-30 | 1976-12-14 | Daicel, Ltd. | Hot melt adhesive for metals |
| CN105646875A (en) * | 2014-11-14 | 2016-06-08 | 辽宁银珠化纺集团有限公司 | Nylon 66 resin having a low melting point and a preparing method thereof |
| CN108410165A (en) * | 2018-02-12 | 2018-08-17 | 广东新会美达锦纶股份有限公司 | A kind of preparation method of high color fastness low melting point polyamide Masterbatch |
Non-Patent Citations (1)
| Title |
|---|
| 用于尼龙织物的马来酸化乙烯-醋酸乙烯热熔胶的研究;林松柏 等;《化学世界》;19951231(第1期);第16-19页 * |
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