CN1493639A - Long carbon chain nylon hot melt glue and its synthesis method - Google Patents
Long carbon chain nylon hot melt glue and its synthesis method Download PDFInfo
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Abstract
A hot-fusible adhesive of C13-C18 polyamide with long carbon chain is prepared from the dibasic acid prepared by fermenting method through synthesizing. Its advantages are high adhesion, softness and size stability, and excellent resistance to water washing.
Description
Technical Field
The invention relates to a long carbon chain nylon hot melt adhesive and a synthesis method thereof. In particular to a polyamide hot melt adhesive for preparing clothes and a synthesis method thereof.
Background
The polyamide hot melt adhesive (PA) is a hot melt adhesive obtained by copolycondensation of various aliphatic dicarboxylic acids, aliphatic diamine and the like, is mainly used for producing hot melt lining cloth of clothes, plays roles of reinforcing and sizing the framework of the clothes and the like in the hot melt lining cloth of the clothes, and is an essential auxiliary material for producing the clothes. The polyamide hot melt adhesive has the advantages of low melting temperature, narrow melting range, convenience in processing, wide application range, high bonding strength, good flexibility and wear resistance, excellent aging resistance, water washing resistance, dry cleaning resistance and the like, and is the best material for the current high-grade clothing hot melt lining and the wireless sewing clothing.
The amide groups of the polyamide with single component are orderly arranged, and the polarity of the amide groups and the function of intermolecular hydrogen bonds cause large crystallinity and high melting point, so that the low melting point requirement of the hot melt adhesive for the adhesive interlining can not be met. The structural order of the copolymerized polyamide is destroyed by the copolycondensation of a plurality of monomers, and the melting point of the copolymerized polyamide is greatly reduced. Currently, the main polymerization units used for preparing hot melt adhesives are nylon 6, nylon 66, nylon 1010, nylon 612, nylon 12, nylon 1212, etc., and three or more copolymers thereof. In the polymerization unit, the longer the carbon chain of the nylon component is, the higher the bonding strength of the hot melt adhesive is, and the better the flexibility, the wear resistance, the water washing resistance and the drapability are. Switzerland and Germany have more advantages in the synthesis technology and production of polyamide hot melt adhesives, and the PA6/66/12 (nylon 12 hot melt adhesive) terpolymer is commonly used by the Switzerland and Germany. The main raw material of dodecalactam for preparing nylon 12 hot melt adhesive is first developed and succeeded in 1966 by Emser company and Huls company, the synthesis method is that butadiene is trimerized into cyclododecatriene, the cyclododecatriene is hydrogenated, oxidized, oximated and Beckmann rearranged to prepare dodecalactam, and the dodecalactam is ring-opened and polymerized to obtain nylon 12 hot melt adhesive. Because the synthesis steps are long and the yield of each step is not high, the price is high.
At present, the longest carbon chain of the raw material for synthesizing the hot melt adhesive in China is nylon-1010, but the molecular chain of the nylon-1010 polymer is not as long as that of nylon-12, so the hot melt adhesive has better bonding strength, flexibility, dimensional stability, water washing resistance, drapability and the like than the hot melt adhesive containing the nylon-12. Zhengzhou university develops and develops a hot melt adhesive containing nylon 1212 (Chinese patent 99121120.0), and comprehensive evaluation results of performances of the hot melt adhesives containing nylon 12 and nylon 1212 show that the comprehensive performances of the hot melt adhesives containing nylon 1212 and nylon 12 are similar, and the cost of the hot melt adhesive containing nylon 1212 is slightly lower than that of the hot melt adhesive containing nylon 12.
In order to improve the bonding strength and flexibility of the hot melt adhesive, the molecular chains of the polymer are increased by adopting dimer acid, polyacid or polyether diamine in Chinese patent 97107743.6, US patent 4,045,389, US patent 4,024,116 and the like, and the number of polar functional groups is increased simultaneously when the molecular chains of the polymer are increased, so that the water washing resistance of the hot melt adhesive is poor.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide C with excellent performance13～C18Long carbon chain nylon hot melt adhesive. Meanwhile, the invention also provides a method for synthesizing the polyamide hot melt adhesive, which has the advantages of rich raw material sources, simple synthesis steps and low production cost.
C of the invention13～C18The polyamide hot melt adhesive contains the following copolymerized units a, b and c:
a. caprolactam or epsilon-aminocaproic acid 15 w% -60 w%, preferably 20 w% -50 w%;
b. one or more C6～C12Dibasic acid and a plurality of C6～C1810 w-65 w%, preferably 20 w-50 w% of nylon salt formed by mixing equivalent diamine;
c. one or more C produced by petroleum fermentation method13～C18One or more C synthesized by dibasic acid and dibasic acid produced by petroleum fermentation method12～C18Nylon salt formed by mixing diamine with equivalent weight or C produced by one or more petroleum fermentation methods12～C18One or more C synthesized by dibasic acid and dibasic acid produced by petroleum fermentation method13～C1810 w-70 w%, preferably 20 w-60 w% of nylon salt formed by mixing equivalent diamine.
C as mentioned in b above6～C12The dibasic acid can be adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, or a mixture of several of them. C6～C18C in diamine11～C18The diamine can be C produced by petroleum fermentation11～C18Diamine synthesized by dibasic acid.
C produced by the above-mentioned petroleum fermentation method12～C18Dibasic acid and dibasic acid produced by petroleum fermentation methodSynthesized C12～C18The diamine can be nylon salt formed by the same carbon chain diacid and diamine, such as nylon 1313, nylon 1414, nylon 1515, nylon 1616, nylon 1717 or nylon 1818 salt. Nylon salts of different carbon chain diacids and diamines, such as nylon 1213, nylon 1314, nylon 1214, nylon 1215, nylon 1415, nylon 1516, nylon 1617, or nylon 1718 salts, may also be used.
In addition, in the hot melt adhesive, a molecular weight regulator, an anti-aging agent, a crystal nucleating agent, fluorescent powder, a polymerization initiator and the like can be selected and used, and additives such as an antioxidant, a preservative, an antistatic agent, a lubricant and the like can be selected and used according to specific needs.
Wherein the additives such as the anti-aging agent, the crystallization nucleating agent, the antioxidant, the preservative, the antistatic agent, the lubricant, the fluorescent powder and the like are any additives which can be used for preparing the polyamide hot melt adhesive, and the dosage is 0.01-5 w%, preferably 0.05-2 w%. The content of the fluorescent powder is 0.001-2 w%, preferably 0.01-1 w%
Wherein the molecular weight regulator comprises monocarboxylic acid or monoamine, the amount of monocarboxylic acid is generally 0.05-5 w% of the total amount of the dicarboxylic acid, or the amount of monoamine is generally 0.05-5 w% of the total amount of the diamine, and the amount of monoamine is generally 0.05-5 w% of the total amount of the diamineThe carboxylic acid or monoamine is preferably C8～C18A straight chain fatty acid or a fatty amine. The polymerization initiator is preferably water, and is added in an amount of 1 to 30 w%, preferably 5 to 10 w%.
The polyamide hot melt adhesive has the following characteristics: the melting point is 85-160 ℃, preferably 85-130 ℃, the melt index is 5-80 g/10min, preferably 18-40 g/10min, and the initial peel strength is more than 8kg/25 mm.
The invention relates to a long carbon chain polyamide hot melt adhesive synthesized by using long-chain dibasic acid produced by a fermentation method as a raw material, which comprises the following steps:
1. c produced by fermentation13～C18Preparing long-chain binary nitrile from the long-chain binary acid;
2. reacting the long-chain binary nitrile ethanol solution with hydrogen in the presence of a catalyst to obtain a long-chain diamine ethanol solution;
3. carrying out salt forming reaction on long-chain dibasic acid and long-chain diamine in an ethanol solution to obtain long-carbon-chain nylon salt;
4. and carrying out polycondensation reaction on the long carbon chain nylon salt and other two or more nylon salts to obtain the hot melt adhesive particles.
5. The long carbon chain polyamide hot melt adhesive powder is obtained by drying, freezing and crushing, screening, powder preparation and shaping the hot melt adhesive particles.
The process for preparing the dinitrile in step 1 is as follows: c produced by fermentation13～C18Adding long-chain dicarboxylic acid into a reaction kettle, heating to melt the long-chain dicarboxylic acid, introducing ammonia gas, performing dehydration reaction for 10-16 hours, heating to 320-360 ℃, keeping for 3-6 hours, performing reduced pressure distillation, and distilling out long-chain dicarboxylic nitrile.
And 2, adding the long-chain binary nitrile, ethanol and the catalyst into a reaction kettle, decompressing, pumping out gas in the reaction kettle, introducing hydrogen into the reaction kettle, keeping the pressure at 1-3 MPa, raising the temperature to control the temperature of the reaction kettle at 80-130 ℃, cooling to below 60 ℃ after 30-120 minutes, reducing the temperature in the reaction kettle to normal pressure, filtering out the catalyst, and evaporating the ethanol to obtain the long-chain binary amine and a small amount of unreacted long-chain binary nitrile.
The catalyst used in step 2 may be selected from metal hydrides such as: lithium aluminum hydride, sodium borohydride and the like, and metal reducing agents such as nickel, sodium, platinum, palladium and the like can be selected, wherein the dosage is 5-50 w%, and framework nickel, carrier nickel and the like are preferably selected, and the dosage is 10-20 w%. The solvent can be selected from low molecular weight solvents such as water, alcohol, ether, acid, tetrahydrofuran, etc., preferably ethanol. The pH value of the medium is preferably under an alkaline condition, and a small amount of auxiliary agent can be selectively added, wherein the auxiliary agent is liquid ammonia, and the dosage of the auxiliary agent is 0.001-0.1 w% of the long-chain binary nitrile.
And 3, adding the long-chain dicarboxylic acid and the ethanol into a reaction kettle, heating to 50-70 ℃, adding an ethanol solution of the long-chain diamine under stirring to ensure that the pH value of the solution is 7.0-7.4, cooling to below 30 ℃, preferably below 15 ℃, and filtering to obtain the long-carbon-chain nylon salt.
The other two or more nylon salts in the step 4 are two or more of nylon 6, nylon 66, nylon 1010, nylon 612, nylon 12, nylon 1212 and the like, preferably nylon 6 and nylon 66, wherein the nylon 6 accounts for 10 w% -60 w% of the total weight, the nylon 66 accounts for 10 w% -60 w% of the total weight, and the long carbon chain nylon salt accounts for 10 w% -60 w% of the total weight. The process comprises the steps of adding various required reaction raw materials into a polycondensation reaction kettle according to a proportion for polycondensation reaction, heating to 60-150 ℃ in the reaction kettle, and starting stirring, preferably 80-120 ℃. And when the temperature reaches more than 200 ℃, starting polycondensation reaction, keeping the reaction temperature at 250-280 ℃, keeping the pressure at 1.7-2.0 MPa, starting pressure release after reacting for 1.5-2.5 hours, reducing the pressure to normal pressure within 1-2 hours, finishing the reaction within 0.5-1.5 hours under the protection of nitrogen, reducing the temperature in the kettle to 180-220 ℃, drawing wires, and granulating to obtain the hot melt rubber particles.
Compared with the prior art, the invention has the advantages that:
1. from the raw material perspective
The main raw material of the nylon 12 hot melt adhesive, namely the laurolactam, is butadiene which is used as a starting raw material for synthesizing butadiene rubber with the largest current yield, butadiene rubber with the second yield, chloroprene rubber, butyronitrile and other synthetic rubbers. The dodecalactam synthesized by the butadiene is a raw material for synthesizing the polyamide engineering plastic 12, and the engineering plastic 12 has the excellent characteristics of toughness, wear resistance, impact resistance, fatigue resistance, corrosion resistance, oil resistance and the like, and is the current international development direction of the engineering plastic. With the development of industries such as automobiles, electronics and the like, the synthesis of both rubber and engineering plastics 12 will make butadiene as a raw material short of supply. The long carbon chain polyamide hot melt adhesive is liquid wax (C) which is a by-product of petroleum refining13～C16) The raw materials are rich and easily available, and the price is low.
2. From the synthetic route
The method for synthesizing the hot melt adhesive by using the laurolactam comprises the following steps:
the petroleum fermentation method comprises the following steps:
the method for synthesizing the hot melt adhesive by the laurolactam has multiple synthesis steps and low yield in each step. The petroleum fermentation method has few synthesis steps and high yield in each step.
3. From the viewpoint of synthetic method
The catalyst used in the step 2 is selected from skeleton nickel or carrier nickel, the solvent is selected from ethanol, and the pH of the medium is adjusted by liquid ammonia. After the reaction is finished, filtering out the catalyst, and distilling out ethanol and ammonia at normal pressure to obtain long-chain diamine and a small amount of unreacted long-chain dinitrile. And (3) dissolving the unreacted long-chain binary nitrile in the ethanol solution in the step (3) to separate the unreacted long-chain binary nitrile from the long-carbon-chain nylon salt of the insoluble ethanol solution, filtering the long-carbon-chain nylon salt, continuously using the ethanol solution containing the long-chain binary nitrile in the step (2), and continuously converting the unreacted long-chain binary nitrile into the long-chain diamine. Chinese patent 99108152.8 reports that in the hydrogenation process, potassium hydroxide is added as a medium, and long-chain diamine must bedistilled under reduced pressure after the reaction is finished. The method of the invention saves the reduced pressure distillation equipment, thereby saving the investment of equipment, electric power and manpower, improving the yield of the product and reducing the production cost of the product.
4. From the viewpoint of comprehensive performance of the hot melt adhesive
The longest molecular chain of the nylon 12 hot melt adhesive polymer is twelve carbons, the molecular chain of the long carbon chain hot melt adhesive polymer unit is more than thirteen carbons, and the increase of the molecular chain of the polymer unit is superior to the polyamide hot melt adhesive containing nylon 12 and nylon 1212 in bonding strength, flexibility, drapability, dimensional stability and particularly in water washing resistance.
Detailed Description
Example 1:
adding 40kg of tridecanedioic acid produced by fermentation method into a distillation reaction kettle with a stirrer, heating to 130 deg.C to melt tridecanedioic acid, introducing ammonia gas, wherein the flow rate of ammonia gas is controlled at 60m3And h, performing dehydration reaction for 10 hours, heating to 350 ℃, keeping for 4 hours, and distilling under reduced pressure to obtain the tridecane dinitrile.
Adding 30kg of tridecane dinitrile, 60kg of ethanol, 3.0kg of skeleton nickel and 20kg of liquid ammonia into a high-pressure reaction kettle, decompressing and extracting gas in the reaction kettle, introducing hydrogen into the reaction kettle, keeping the pressure in the reaction kettle at 3MPa, raising the temperature to control the temperature of the reaction kettle at 120 ℃, cooling to 40 ℃ after 1 hour, reducing the temperature in the reaction kettle to normal pressure, filtering out a catalyst, and evaporating the ethanol and the ammonia to obtain the tridecane diamine.
Adding refined tridecanedioic acid and ethanol at a ratio of 1: 8 into a reaction kettle, heating to 60 deg.C, adding ethanol solution of tridecanediamine under stirring to make pH of the solution 7.2, cooling to 15 deg.C, and filtering to obtain nylon 1313 salt.
Adding caprolactam, nylon 66 salt and nylon 1313 salt (6/66/1313) in a ratio of 32: 35: 33, the total amount of which is 100kg, 0.25kg of phosphorous acid and 1kg of lauric acid into a polycondensation reaction kettle, adding 10kg of water, heating until the temperature in the reaction kettle is 100 ℃, starting stirring, keeping the pressure at 1.8MPa when the temperature in the kettle is 270 ℃, starting releasing the pressure after 2 hours, reaching the normal pressure after 1.5 hours, continuing to react for 1.0 hour under the protection of nitrogen, finishing the polycondensation reaction, drawing wires, and cutting into granules to obtain the nylon 1313 hot melt adhesive granules.
Example 2:
adding 40kg tetradecanedioic acid produced by fermentation method into a distillation reaction kettle with stirring, and heating to 130%Melting tetradecane dibasic acid, introducing ammonia gas, controlling the flow rate of ammonia gas at 60m3And/h, carrying out dehydration reaction for 13 hours, heating to 330 ℃, keeping for 6 hours, and distilling under reduced pressure to obtain tetradecanedinitrile.
Adding 30kg of tetradecanedinitrile, 70kg of ethanol, 3.6kg of skeletal nickel and 24kg of liquid ammonia into a high-pressure reaction kettle, decompressing and extracting gas in the reaction kettle, introducing hydrogen into the reaction kettle, keeping the pressure at 2.5MPa, raising the temperature to control the temperatureof the reaction kettle at 120 ℃, cooling to 50 ℃ after 1 hour, reducing the temperature to normal pressure in the reaction kettle, filtering out a catalyst, and evaporating ethanol and ammonia to obtain tetradecanediamine.
Adding refined tetradecanedioic acid and ethanol at a ratio of 1: 6 into a reaction kettle, heating to 60 deg.C, adding ethanol solution of tetradecanediamine under stirring to make pH of the solution 7.4, cooling to 10 deg.C, and filtering to obtain nylon 1414 salt.
Adding caprolactam, nylon 66 salt and nylon 1414 salt (6/66/1414) in a ratio of 32: 20: 40, wherein the total amount is 100kg, adding 0.25kg of phosphorous acid and 1kg of lauric acid into a polycondensation reaction kettle, adding 20kg of water, heating until the temperature in the reaction kettle is 100 ℃, starting stirring, keeping the pressure at 2.0MPa when the temperature in the kettle is 270 ℃, starting releasing the pressure after 2 hours, keeping the pressure at normal pressure after 1.5 hours, continuing to react for 1.0 hour under the protection of nitrogen, finishing the polycondensation reaction, drawing wires, and cutting into granules to obtain the nylon 1414 hot melt adhesive granules.
Examples 3 to 7:
the polyamide hot melt adhesive synthesized by the method has different formula compositions under the same process conditions as the example 1.
Comparative example 1:
nylon 1212 hot melt adhesives were prepared according to the CN1283662A example.
The formulation compositions and the analytical results of the examples are shown in Table 1.
TABLE 1 Polyamide thermosol of different formulation compositions and analysis results
| Numbering | Formulation composition | Raw material ratio w％ | Polymerization inhibitor kg | Melting range ℃ | Melting Index of refraction g/10min | Initial peel strength Degree kg/25mm |
| Example 1 | 6/66/1313 | 32/35/33 | 0.2 | 120-130 | 18 | 13.0 |
| Example 2 | 6/66/1414 | 32/20/48 | 0.4 | 130-140 | 20 | 13.7 |
| Example 3 | 6/66/1515 | 24/36/40 | 0.8 | 110-120 | 22 | 14.2 |
| Example 4 | 6/66/1213 | 24/20/56 | 1.0 | 125-135 | 28 | 12.8 |
| Example 5 | 6/66/1214 | 30/30/40 | 0.6 | 105-115 | 24 | 13.2 |
| Example 6 | 6/66/1315 | 34/34/32 | 0.8 | 100-110 | 22 | 13.8 |
| Example 7 | 6/66/1416 | 40/30/30 | 0.2 | 120-130 | 18 | 14.0 |
| Comparative example 1 | 6/66/1212 | 36/31/33 | 0.16 | 110-120 | 28 | 11.8 |
The measuring method of the melting point, the melt index and the initial peeling strength is carried out according to the industry standard of the textile hot melt adhesive.
Claims (12)
1. The long carbon chain nylon hot melt adhesive is characterized by comprising the following copolymerization units a, b and c:
a. 15 w% -60 w% of caprolactam or epsilon-aminocaproic acid;
b. one or more C6～C12Dibasic acid and a plurality of C6～C1810 w% -65 w% of nylon salt formed by mixing equivalent diamine;
c. one or more C produced by petroleum fermentation method13～C18One or more C synthesized by dibasic acid and dibasic acid produced by petroleum fermentation method12～C18Diamine, nylon salt formed by mixing equivalent; or one or more C produced by petroleum fermentation12～C18One or more C synthesized by dibasic acid and dibasic acid produced by petroleum fermentation method13～C18Diamine, and nylon salt formed by mixing with equivalent weight of 10 w% -70 w%.
2. A hot-melt adhesive according to claim 1, wherein the content of copolymerized units a caprolactam or epsilon-aminocaproic acid is from 20 w% to 50 w%.
3. A hot-melt adhesive according to claim 1, wherein the content of copolymerized units b nylon salt is 20 to 50% by weight.
4. A hot-melt adhesive according to claim 1, wherein the content of copolymerized units c nylon salt is 20 to 60% by weight.
5. The hot melt adhesive according to claim 1, wherein said nylon salt in c is nylon 1313, nylon 1414, nylon 1515, nylon 1616, nylon 1717, nylon 1818 salt or nylon 1213, nylon 1314, nylon 1214, nylon 1215, nylon 1415, nylon 1516, nylon 1617, nylon 1718 salt.
6. The hot melt adhesive according to claim 1, characterized in that it has the following features: the melting point is 85-160 ℃, the melt index is 5-80 g/10min, and the initial peel strength is more than 8kg/25 mm.
7. A hot-melt adhesive according to claim 1 or 6, characterized in that it has the following features: the melting point is 85-130 ℃, and the melt index is 18-40 g/10 min.
8. A method for synthesizing a hot melt adhesive according to claim 1, comprising the steps of:
(1) c produced by fermentation13～C18Preparing long-chain binary nitrile from the long-chain binary acid;
(2) reacting the ethanol solution of the long-chain binary nitrile with hydrogen in the presence of a catalyst to obtain an ethanol solution of the long-chain binary amine;
(3) reacting long-chain dibasic acid and long-chain diamine in an ethanol solution to form salt, so as to obtain long-carbon-chain nylon salt;
(4) carrying out polycondensation reaction on long carbon chain nylon salt and other two or more nylon salts to obtain hot melt adhesive particles;
(5) and drying, freezing and crushing, screening, powder blending and shaping the hot melt adhesive particles to obtain the long carbon chain polyamide hot melt adhesive powder.
Wherein an auxiliary agent is required to be added in the step (2), and the auxiliary agent is liquid ammonia, and the using amount of the auxiliary agent is 0.005-0.1 w% of the long-chain binary nitrile.
9. The synthesis method according to claim 8, whereinthe conditions for preparing the dinitrile in step (1) are as follows: in the presence of ammonia gas, carrying out dehydration reaction for 10-16 hours, then heating to 320-360 ℃, and keeping for 3-6 hours.
10. The synthesis method according to claim 8, wherein the hydrogenation reaction conditions in the step (2) are as follows: the pressure is 2-3 MPa, the temperature is 80-130 ℃, and the reaction time is 30-60 minutes.
11. The synthesis method according to claim 8, wherein the salt formation reaction conditions in step (3) are as follows: the temperature is 50-70 ℃, and the pH value of the solution is 7.0-7.4.
12. The synthesis method according to claim 8, wherein the polycondensation reaction conditions in the step (4) are: the reaction temperature is 250-280 ℃, the pressure is 1.7-2.0 MPa, and the reaction time is 1.5-2.5 hours.
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| CN 02144534 CN1202195C (en) | 2002-11-02 | 2002-11-02 | Long carbon chain nylon hot melt glue and its synthesis method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200543B (en) * | 2006-12-15 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Preparation method for improving performance of high-temperature nylon |
| CN101307218B (en) * | 2008-06-20 | 2011-06-22 | 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 |
| CN104447350A (en) * | 2014-09-17 | 2015-03-25 | 河南省君恒实业集团生物科技有限公司 | Method for preparing C14 diamine and long carbon chain nylon PA1414 |
| CN108203508A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of modified nylon-6 material and preparation method thereof |
| CN111518271A (en) * | 2020-06-18 | 2020-08-11 | 广州鸿为新材料科技有限公司 | Nylon material for laser 3D printing and preparation method |
| CN111944475A (en) * | 2020-09-02 | 2020-11-17 | 河源市可顺绝缘材料有限公司 | Self-adhesive glue and self-adhesive insulated wire using same |
-
2002
- 2002-11-02 CN CN 02144534 patent/CN1202195C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200543B (en) * | 2006-12-15 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Preparation method for improving performance of high-temperature nylon |
| CN101307218B (en) * | 2008-06-20 | 2011-06-22 | 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 |
| CN104447350A (en) * | 2014-09-17 | 2015-03-25 | 河南省君恒实业集团生物科技有限公司 | Method for preparing C14 diamine and long carbon chain nylon PA1414 |
| CN108203508A (en) * | 2016-12-16 | 2018-06-26 | 中国石油化工股份有限公司 | A kind of modified nylon-6 material and preparation method thereof |
| CN111518271A (en) * | 2020-06-18 | 2020-08-11 | 广州鸿为新材料科技有限公司 | Nylon material for laser 3D printing and preparation method |
| CN111944475A (en) * | 2020-09-02 | 2020-11-17 | 河源市可顺绝缘材料有限公司 | Self-adhesive glue and self-adhesive insulated wire using same |
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| Publication number | Publication date |
|---|---|
| CN1202195C (en) | 2005-05-18 |
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