CN1493602A - Long carbon chain nylon and its synthesis method - Google Patents
Long carbon chain nylon and its synthesis method Download PDFInfo
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Abstract
A C13-C18 nylon with long carbon chain is prepared from the dibasic acid with long carbon chain and prepared by fermentation method through synthesizing. Its advantages are low hydroscopicity, high size stability and toughness, and high resistance to low temp.
Description
Technical Field
The invention relates to a polyamide engineering plastic (nylon) and a synthesis method thereof.
Background
Polyamide engineering Plastics (PA), also known as nylon, are linear thermoplastic polymers having repeat structural units of amide groups (-CONH) in the main chain. Is obtained by condensation polymerization of dibasic acid and diamine or amino acid. The amide group of the nylon has polarity, and hydrogen bonds are formed among molecules, so the nylon has the excellent characteristics of toughness, wear resistance, impact resistance, fatigue resistance, corrosion resistance, oil resistance, solvent resistance, no toxicity, good self-extinguishing property, good electronic insulation property and the like. The composite material is mainly used for mechanical instruments, automobiles, textiles and the like to be used as bearings, gears, turbines, automobile parts, oil pipes, oil tanks and the like. Is one of the varieties which have the most extensive application, the fastest development and the most research at present.
In 1934 DuPont first developed PA66, which was commercialized in 1939, and PA6 was first commercialized in 1943 by Farben, Germany. Since PA66 and PA6 have short carbon chains, high water absorption and poor dimensional stability, PA engineering plastics with long carbon chains, low water absorption and good dimensional stability, such as PA610, PA1010, PA612, PA11 and PA12, are developed later. In the research process, the long-carbon-chain nylon has more excellent comprehensive performance than the short-carbon-chain nylon, and is particularly superior in the aspects of water absorption, dimensional stability, flexibility, wear resistance and low temperature resistance. Currently, the nylon varieties with the longest carbon chain are PA12 and PA 1212. PA12 was first developed in 1966 by Emser and Huls, and its synthesis method comprises trimerizing butadiene to cyclododecatriene, hydrogenating cyclododecatriene, oxidizing, oximating, Beckmann rearrangement to obtain laurolactam, and ring-opening polymerization of the dodecalactam to obtain PA 12. Because the synthesis steps are long and the yield of each step is not high, the price is high. In order to reduce the cost and improve the water absorption, dimensional stability and flexibility at the same time, zheng zhou university developed PA1212 (chinese patent 99108152.8), and although the cost of PA1212 was lower than that of PA12, the water absorption, dimensional stability and flexibility of PA1212 were not improved much more than that of PA12 because the carbon chain length of PA1212 was the same as that of PA 12. In order to improve the flexibility, wear resistance, low temperature resistance and other properties of the existing engineering plastics such as PA66, PA6, PA1010 and the like, one or more elastomers or inorganic fillers are added into polyamide. However, in the quality improvement process, it is often the case that an improvement in one characteristic results in a deterioration in another characteristic. In addition, in the hydrogenation process mentioned in the patent, potassium hydroxide is added as a medium, and after the reaction is finished, the long-chain diamine must be distilled out under reduced pressure. The increase of the reduced pressure distillation process not only increases the investment of equipment, electric power and manpower, but also reduces the yield of the product, so that the production cost of the product is improved.
Chinese patent 88104294.3 reports that blending a polyethylene graft copolymer with polar branches with PA1010 improves its low temperature properties: low temperature impact strength, elongation at break, however, results in deterioration of heat resistance and rigidity of the polyamide material. Japanese patent laid-open No. 62-253652 describes that a resin having a high glass transition temperature, such as a polyphenylene resin, a rubbery polymer, an unsaturated carboxylic acid and a polyamide are melt-kneaded to obtain a better impact strength and a better heat resistance while reducing the heat resistance and dimensional stability. Japanese patent No. Sho 61-36340 coats glass beads with more than 1% by weight of a surface coating agent such as a silane compound, a fluorocarbon compound or the like to control or suppress the decrease in impact strength or tensile elongation thereof, but the effect is not significant while other properties are affected. Practice has shown that it is difficult to ensure that one or more properties of the material are unchanged while the other properties are changed by adding one or more additives. Therefore, the preparation of the long carbon chain nylon becomes an effective means capable of simultaneously improving various properties of the nylon.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the long carbon chain nylon with better performance. Meanwhile, the invention also provides a synthesis process of the nylon, which has rich raw material sources, simple synthesis steps and low production cost.
C produced by fermentation12～C18The long carbon chain nylon synthesized by using the long carbon chain diacid as a raw material is characterized by being represented by the following molecular formula:
wherein n: the number of carbon atoms of diamine, n is 6-18
m: the number of carbon atoms of the dibasic acid, m is 13 to 18
X: degree of polymerization, X is 20 to 400
Long carbon chain nylon (non-reinforced) properties:
specific gravity: 1.00-1.07;
melting point: 160-200 ℃;
breaking elongation: 300 to 900 percent
Water absorption (24h,%): 0.1 to 0.4
The long carbon chain nylon can be nylon formed by the same carbon chain dibasic acid and diamine, such as: PA1313, PA1414, PA1515, PA1616, PA1717, PA 1818. Also nylon formed by different carbon chain dibasic acids and diamine, PA613, PA1013, PA614, PA1015,PA616, PA1017, PA618, PA1213, PA1314, PA1214, PA1215, PA1615, PA1516, PA1617, PA1718 and the like.
When preparing the long carbon chain nylon, additives can be selected according to requirements, such as: stabilizers, plasticizers, lubricants, reinforcing modifiers, molecular weight regulators, and the like; the stabilizer can be selected from: finely dispersed carbon black and ultraviolet absorbers, etc.; the plasticizer can be selected from: aliphatic diols and aromatic chlorosulfonyl compounds; the lubricant can be selected from: paraffin, metal soaps, etc.; the reinforcing modifier can be selected from: glass fibers, minerals, and the like; the molecular weight regulator is preferably selected from long carbon chain monoacids or monoamines. The dosage of all the additives is 0.01-5.00 w%.
The invention relates to a method for synthesizing long carbon chain nylon 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 ethanol solution of the long-chain binary nitrile with hydrogen in the presence of a catalyst to obtain long-chain diamine;
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 to obtain the long carbon chain nylon.
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, a solvent and a catalyst into a reaction kettle, decompressing, pumping out gas in the reaction kettle, introducing hydrogen into the reaction kettle, keeping the pressure at 1.0-3.0 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 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 also can select metal reducing agents such as nickel, sodium, platinum, palladium and the like, the dosage is 5 w-50 w%, and preferably, the dosage is 10 w-20 w% of that of the long-chain binary nitrile, such as framework nickel, carrier nickel and the like. 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.
And 4, adding the long carbon chain nylon salt and various required additives into a polycondensation reaction kettle in proportion for polycondensation reaction, heating the mixture after nitrogen replacement until the temperature in the reaction kettle is 200-250 ℃, keeping the pressure at 1.0-2.0 MPa, starting pressure release after 1.0-2.0 hours of reaction, reducing the pressure to normal pressure within 1-2 hours, finishing the reaction within 0.5-2.0 hours under the protection of nitrogen, and reducing the temperature in the kettle to 180-210 ℃ for wire drawing and grain cutting to obtain the long carbon chain nylon product.
Compared with the prior art, the invention has the advantages that:
1. from the raw material perspective
The main raw material of nylon 12, namely the laurolactam, is butadiene which is used as a starting 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 hot melt adhesive (nylon 12 hot melt adhesive), and the nylon 12 hot melt adhesive has the advantages of low melting temperature, high bonding strength, good flexibility and wear resistance, excellent aging resistance, water washing resistance, dry cleaning resistance and the like, and not only has the high melting temperature at presentThe best material for the grade clothing hot melt lining and the wireless sewing clothing is the development direction of the polyamide hot melt adhesive in the world at present. With the development of industries such as automobiles, electronics, clothes and the like, the synthesis of both rubber and hot melt adhesive makes butadiene as a raw material in short supply. The long carbon chain nylon is liquid wax (C) which is a byproduct of petroleum refining13～C16) The raw materials are rich and easily available and have low price.
2. From the synthetic route
The method for synthesizing nylon by using laurolactam comprises the following steps:
the petroleum fermentation method comprises the following steps:
the method for synthesizing nylon by using 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 continuouslyconverting 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 be distilled under reduced pressure after the reaction is finished. The increase of the reduced pressure distillation process not only increases the investment of equipment, electric power and manpower, but also reduces the yield of the product, so that the production cost of the product is improved.
4. From the aspect of long carbon chain nylon performance
The molecular chain of the nylon 12 polymerization unit is twelve carbons, the molecular chain of the long carbon chain nylon polymer polymerization unit is more than thirteen carbons, and the increase of the molecular chain of the polymer polymerization unit reduces the number of polar functional groups contained in the molecules in the polymer with the same molecular weight, and the polymer is better than nylon 12 and nylon 1212 in the aspects of water absorption, dimensional stability, flexibility and low temperature resistance.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
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.
30kg of tridecane dinitrile, 60kg of ethanol (95%), 3.0kg of skeleton nickel and 20kg of liquid ammonia are added into a high-pressure reaction kettle, gas in the reaction kettle is extracted under reduced pressure, hydrogen is introduced into the reaction kettle, the pressure is kept at 2Mpa, the temperature of the reaction kettle is controlled at 120 ℃, the temperature is reduced to 60 ℃ after 1 hour, the temperature in the reaction kettle is reduced to normal pressure, a catalyst is filtered, and the ethanol and the ammonia are evaporated 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 22kg of nylon 1313 salt, 0.13kg of phosphorous acid and 0.6kg of lauric acid into a polycondensation reaction kettle, heating to 100 ℃ in the reaction kettle, starting stirring, keeping the pressure at 1.3MPa when the temperature in the kettle is 250 ℃, starting pressure release after 2 hours, continuing to react for 1.0 hour after 1.5 hours to normal pressure, finishing the polycondensation reaction, drawing wires, and pelletizing to obtain the nylon 1313.
Example 2:
adding 40kg tetradecanedioic acid produced by fermentation method into a distillation reaction kettle with stirring, heating to 140 deg.C to melt tetradecanedioic acid, introducing ammonia gas, wherein the flow rate of ammonia gas is controlled at 60m3And/h, carrying out dehydration reaction for 12 hours, heating to 350 ℃, keeping for 4 hours, and distilling under reduced pressure to obtain tetradecanedinitrile.
Adding 30kg of tetradecanedinitrile, 60kg of ethanol (95%), 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 temperature of the reaction kettle at 120 ℃, cooling to 60 ℃ after 60 minutes, reducing the temperature to normal pressure in the reaction kettle, filtering out a catalyst, and evaporating out ethanol and ammonia to obtain tetradecanediamine.
Adding refined tetradecanedioic acid and ethanol at a ratio of 1: 8 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 23kg of nylon 1414 salt, 0.1kg of phosphorous acid and 0.3kg of lauric acid into a polycondensation reaction kettle, heating to 100 ℃ in the reaction kettle, starting stirring, keeping the pressure at 1.5MPa when the temperature in the kettle is 240 ℃, starting pressure release after 2 hours, continuing to react for 1.0 hour to normal pressure after 1.0 hour, and finishing the polycondensation reaction to obtain nylon 1414.
Example 3:
adding 40kg pentadecanedioic acid produced by fermentation method into a distillation reaction kettle with a stirrer, heating to 150 deg.C to melt pentadecanedioic acid, introducing ammonia gas, wherein the flow rate of ammonia gas is controlled at 60m3And h, performing dehydration reaction for 12 hours, heating to 350 ℃, keeping the temperature for 4 hours, and distilling under reduced pressure to obtain pentadecane dinitrile.
Adding 30kg of pentadecane dinitrile, 60kg of ethanol, 4.5kg of skeleton nickel and 18kg 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 1.5MPa, raising the temperature to control the temperature of the reaction kettle at 120 ℃, cooling to 60 ℃ after 60 minutes, reducing the temperature to normal pressure in the reaction kettle, filtering out a catalyst, and evaporating out ethanol and ammonia to obtain pentadecane diamine.
Adding refined pentadecanedioic acid and ethanol at a ratio of 1: 6 into a reaction kettle, heating to 60 deg.C, adding ethanol solution of pentadecanedioamine while stirring to adjust pH to 7.4, cooling to 10 deg.C, and filtering to obtain nylon 1515 salt.
Adding 20kg of nylon 1515 salt, 0.1kg of phosphorous acid and 0.2kg of lauric acid into a polycondensation reaction kettle, heating to 100 ℃ in the reaction kettle, starting stirring, keeping the pressure at 1.5MPa when the temperature in the kettle is 250 ℃, starting pressure release after 2 hours, continuing to react for 1.0 hour after 1.5 hours to normal pressure, and finishing the polycondensation reaction to obtain the nylon 1515.
Example 4:
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 sebacic diamine under stirring to make pH of the solution 7.4, cooling to below 20 deg.C, and filtering to obtain nylon 1013 salt.
Nylon 1013 was prepared by adding 0.1kg of phosphorous acid and 0.3kg of lauric acid to a polycondensation reaction vessel under the same polycondensation conditions as in example 3.
Example 5:
in example 4, instead of using purified tridecanedioic acid, purified tetradecanedioic acid was used, and an ethanol solution of hexamethylenediamine was used instead of an ethanol solution of decamethylenediamine, and nylon 614 was prepared by the same process.
Comparative example 1:
nylon 1212 was prepared according to the method of the example in CN 1255507A.
The properties of the long carbon chain nylon pellets (soft) are shown in table 1.
TABLE 1 comparison of the Properties of Long carbon chain Nylon pellets (Soft)
| Performance of | Nylon 1313 | Nylon 1414 | Nylon 1515 | Nylon 1013 | Nylon 1212 | Nylon 12 | Nylon 11 |
| Appearance of the product | Is transparent | Is transparent | Is transparent | Is transparent | Is transparent | Is transparent | Is transparent |
| Melting Point C | 178 | 174 | 174 | 176 | 180 | 181 | 182 |
| Relative density g/cm3 | 1.04 | 1.04 | 1.03 | 1.05 | 1.05 | 0.04 | 1.05 |
| Tensile yield strength MPa | 23.1 | 31.4 | 22.8 | 29.2 | 32.8 | 29.6 | 37.6 |
| Tensile section attack strength MPa | 48.2 | 46.6 | 49.4 | 46.3 | 43.8 | 45.8 | 43.6 |
| Elongation at break% | 727 | 664 | 763 | 608 | 567 | 541 | 353 |
| The water absorption rate is w% | 0.3 | 0.2 | 0.2 | 0.3 | 0.4 | 0.4 | 0.6 |
It can be seen from table 1 that the longer the carbon chain of nylon, the higher the breaking elongation, the better the flexibility, and the lower the water absorption.
Claims (11)
1. A long carbon chain nylon is characterized in that the molecular formula of the nylon is as follows:
wherein n: the number of carbon atoms of diamine, n is 6-18
m: the number of carbon atoms of the dibasic acid, m is 13 to 18
X: the degree of polymerization, X, is 20 to 400, and is characterized in that the nylon is
2. The long carbon chain nylon of claim 1, wherein the nylon has:
specific gravity: 1.00 to 1.07
Melting point: 160-200 DEG C
Breaking elongation: 300 to 900 percent
Water absorption: 0.1 to 0.4 percent
3. The long carbon chain nylon of claim 1, wherein the nylon is C produced by fermentation13～C18The long carbon chain diacid is synthesized by raw materials.
4. The long carbon chain nylon of claim 1 wherein said nylon is PA1313, PA1414, PA1515, PA1616, PA1717, PA 1818.
5. The long carbon chain nylon of claim 1, wherein said nylon is selected from the group consisting of PA613, PA1014, PA614, PA1015, PA616, PA1017, PA618, PA1213, PA1314, PA1214, PA1215, PA1615, PA1516, PA1617, and PA 1718.
6. A method for synthesizing the long carbon chain nylon of claim 1, which comprises the following steps:
(1) c produced by fermentation13～C18Preparing long-chain binary nitrile from the long-chain binary acid;
(2) reacting long-chain binary nitrile with hydrogen to obtain an ethanol solution of long-chain diamine;
(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) and carrying out polycondensation reaction on the long carbon chain nylon salt to obtain the long carbon chain nylon.
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 0.001-0.1 w% of the long-chain binary nitrile.
7. The synthesis method according to claim 5, wherein the conditions for preparing the dinitrile in step (1) are as follows: c produced by fermentation13～C18The long-chain dicarboxylic acid is used as a raw material, and is subjected to dehydration reaction for 10-16 hours in the presence of ammonia gas, then the temperature is increased to 320-360 ℃, and the temperature is kept for 3-6 hours.
8. The synthesis method according to claim 5, wherein the hydrogenation reaction conditions in the step (2) are as follows: the pressure is 2.0-3.0 MPa, the temperature is 80-130 ℃, and the reaction time is 30-60 minutes.
9. The synthesis method according to claim 5, 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.
10. The synthesis method according to claim 5, wherein the polycondensation reaction in step (4) is carried out by heating to a temperature of 200 to 250 ℃ in the reaction vessel, maintaining the pressure at 1.0 to 2.0MPa, starting pressure release after 1.0 to 2.0 hours of reaction, reducing the pressure to normal pressure within 1 to 2 hours, and finishing the reaction for 0.5 to 2.0 hours under the protection of nitrogen.
11. The synthesis method according to any one of claims 5 to 9, characterized in that one or more of a stabilizer, a plasticizer, a lubricant, a reinforcing modifier and a molecular weight regulator are added when the long carbon chain nylon is prepared, and the dosage of each additive is 0.01-5.00 w%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102076497A (en) * | 2008-06-24 | 2011-05-25 | 赢创德固赛有限责任公司 | Component with top layer of a pa613 moulding compound |
| CN103975018A (en) * | 2011-08-29 | 2014-08-06 | 纳幕尔杜邦公司 | Composite wheel for a vehicle |
| 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 |
| CN109180931A (en) * | 2018-08-16 | 2019-01-11 | 郑州大学 | A kind of preparation method and product of long carbon chain nylon PA1313 |
| CN111732726A (en) * | 2020-06-19 | 2020-10-02 | 山东东辰瑞森新材料科技有限公司 | High-fluidity body flame-retardant long-carbon-chain nylon and preparation method thereof |
-
2002
- 2002-11-02 CN CN 02144535 patent/CN1230460C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102076497A (en) * | 2008-06-24 | 2011-05-25 | 赢创德固赛有限责任公司 | Component with top layer of a pa613 moulding compound |
| CN103975018A (en) * | 2011-08-29 | 2014-08-06 | 纳幕尔杜邦公司 | Composite wheel for a vehicle |
| 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 |
| CN109180931A (en) * | 2018-08-16 | 2019-01-11 | 郑州大学 | A kind of preparation method and product of long carbon chain nylon PA1313 |
| CN109180931B (en) * | 2018-08-16 | 2021-02-02 | 郑州大学 | Preparation method of long-carbon-chain nylon PA1313 and product |
| CN111732726A (en) * | 2020-06-19 | 2020-10-02 | 山东东辰瑞森新材料科技有限公司 | High-fluidity body flame-retardant long-carbon-chain nylon and preparation method thereof |
| CN111732726B (en) * | 2020-06-19 | 2022-04-08 | 山东东辰瑞森新材料科技有限公司 | High-fluidity body flame-retardant long-carbon-chain nylon and preparation method thereof |
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