CN112760735A - Flame-retardant polyamide fiber - Google Patents
Flame-retardant polyamide fiber Download PDFInfo
- Publication number
- CN112760735A CN112760735A CN202110077251.XA CN202110077251A CN112760735A CN 112760735 A CN112760735 A CN 112760735A CN 202110077251 A CN202110077251 A CN 202110077251A CN 112760735 A CN112760735 A CN 112760735A
- Authority
- CN
- China
- Prior art keywords
- chlorinated paraffin
- modified
- acid
- reaction
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a flame-retardant polyamide fiber, which is obtained by melt spinning of polyamide copolymer, the preparation method of the polyamide copolymer comprises the steps of preparing carboxyl-containing chlorinated paraffin by the reaction of chlorinated paraffin and p-hydroxybenzoic acid, preparing chlorinated paraffin-modified dibasic acid by the esterification reaction of the carboxyl-containing chlorinated paraffin and 5-hydroxyisophthalic acid or 2, 5-dihydroxyterephthalic acid, then preparing chlorinated paraffin modified diamine by acylation, chlorinated paraffin modified 2, 5-dihydroxy terephthaloyl chloride and 1, 3-propane diamine reaction, then reacting with chlorinated paraffin modified 5-hydroxy isophthaloyl dichloride to prepare polyamide oligomer, and finally copolymerizing the oligomer and polyamide prepolymer to obtain chlorinated paraffin modified polyamide copolymer, wherein the prepared flame-retardant fiber has good mechanical property and flame-retardant heat resistance.
Description
Technical Field
The invention relates to a flame-retardant polyamide fiber, and belongs to the field of organic fiber materials.
Background
The polyamide 6 fiber has excellent strength, wear resistance, hygroscopicity and rebound resilience, and plays a significant role in civil and industrial fields. However, the limited oxygen index of polyamide 6 fiber is only about 21%, and the fiber is flammable, and the research on flame retardant polyamide 6 fiber is a problem to be solved urgently.
The chlorinated paraffin is a chlorinated derivative of paraffin, has the advantages of low volatility, flame retardance, good barrier property, low price and the like, can be used as additives such as a plasticizer, a flame retardant and the like, and is already used in a large amount in a flame retardant material, but the addition amount of an additive type flame retardant is relatively large, and the flame retardant property is general. As the service time is prolonged, the additive flame retardant is easy to migrate out of the polymer network, and the durability of flame retardance is reduced.
Disclosure of Invention
In view of the defects of the prior art in the application of chlorinated paraffin in polyamide fiber, the invention aims to provide a polyamide 6 copolymer with a molecular side chain containing chlorinated paraffin molecules.
The invention also aims to provide a method for preparing the flame-retardant polyamide 6 copolymer, which has the advantages of wide raw material source, simple operation and mild reaction conditions.
The invention discloses a flame-retardant polyamide 6 fiber, which is characterized in that the flame-retardant polyamide 6 fiber is obtained by melt spinning of chlorinated paraffin-modified polyamide 6 resin, wherein the chlorinated paraffin-modified polyamide 6 resin has a structure shown in a formula (I):
in the formula (I), R1、R2、R3Is a chlorinated paraffin chain segment.
The invention also provides a preparation method of the chlorinated paraffin-modified polyamide 6 copolymer, which comprises the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Carrying out phosphorus trichloride acylation on the chlorinated paraffin containing carboxyl obtained in the step (1) to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of modified chlorinated Paraffin dibasic acid
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of 5-hydroxyisophthalic acid or 2, 5-dihydroxyterephthalic acid and acid-binding agent triethylamine under the protection of nitrogen to perform esterification reaction to obtain modified chlorinated paraffin dibasic acid;
and (4): preparation of modified chlorinated Paraffin Dichloride
Carrying out phosphorus trichloride acylation on the modified chlorinated paraffin diacid obtained in the step (3) to obtain modified chlorinated paraffin diacid chloride;
and (5): preparation of chlorinated Paraffin modified diamines
Slowly dripping the chlorinated paraffin modified 2, 5-dihydroxy terephthaloyl chloride prepared in the step (4) into a mixed system of 1, 3-propane diamine and acid-binding agent triethylamine under the protection of nitrogen to perform amidation reaction to obtain chlorinated paraffin modified diamine;
and (6): preparation of chlorinated Paraffin-modified Polyamide oligomer
Slowly dropwise adding the chlorinated paraffin modified 5-hydroxy isophthaloyl dichloride obtained in the step (4) into a mixed system of chlorinated paraffin modified diamine and acid-binding agent triethylamine under the protection of nitrogen to perform amidation reaction to obtain chlorinated paraffin modified polyamide oligomer;
and (7): preparation of chlorinated Paraffin-modified Polyamide 6 copolymer
Adding the chlorinated paraffin modified polyamide oligomer into the polyamide 6 prepolymer, uniformly stirring, and reacting at the temperature of 220 ℃ and 230 ℃ for 8-10 h to obtain the chlorinated paraffin modified polyamide 6 copolymer.
The preparation method of the chlorinated paraffin-modified polyamide 6 copolymer of the present invention further comprises the following preferred embodiments:
in the preferable scheme, the chlorinated paraffin and the p-hydroxybenzoic acid in the step (1) react at the temperature of 55-80 ℃ for 10-30 h to prepare the chlorinated paraffin containing carboxyl.
In the preferable scheme, the chlorinated paraffin containing carboxyl in the step (2) reacts with excessive phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
Further preferably, the mole ratio of the chlorinated paraffin containing acyl chloride to the 5-hydroxyisophthalic acid in the step (3) is 1-1.2: 1; the mole ratio of the chlorinated paraffin containing acyl chloride to the 2, 5-dihydroxy terephthalic acid is 2-2.2: 1.
Preferably, the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly dripped into the mixed solution of 5-hydroxyisophthalic acid or 2, 5-dihydroxyterephthalic acid and an acid binding agent at the temperature of 15-25 ℃ for reaction, and the reaction is continued for 3-5 hours after the dripping is finished.
Preferably, the modified chlorinated paraffin diacid reacts with excessive phosphorus trichloride for 4-6 hours at the temperature of 50-70 ℃ in the step (4) to prepare the modified chlorinated paraffin diacid chloride.
Further preferably, the molar ratio of the modified chlorinated paraffin diacid chloride reacted with the 1, 3-propane diamine in the step (5) is 1-1.1: 2.
Preferably, in the step (5), the reaction condition is that the modified chlorinated paraffin diacid chloride is slowly dripped into the mixed solution of the 1, 3-propane diamine and the acid-binding agent in an ice water bath for reaction, after the dripping is finished, the temperature is raised to 20-40 ℃, and the reaction is continued for 1-2 hours.
Further preferably, the molar ratio of the chlorinated paraffin-modified 5-hydroxyisophthaloyl dichloride to the chlorinated paraffin-modified diamine in the step (6) is 1: 1; the reaction condition is that firstly, the chlorinated paraffin modified 5-hydroxy isophthaloyl dichloride is slowly dripped into the mixed solution of the chlorinated paraffin modified diamine and the acid binding agent in an ice water bath for reaction, and the reaction is continued for 1-3 hours after the dripping is finished.
The invention has the beneficial effects that: according to the invention, traditional chlorinated paraffin molecules are introduced into a polyamide molecular chain through chemical bonds for the first time to form a novel polyamide oligomer, and then the novel polyamide oligomer and the polyamide 6 prepolymer are subjected to copolymerization reaction to prepare the chlorinated paraffin modified polyamide 6 copolymer. The whole preparation process has the advantages of easily available raw materials, low cost, simple operation and high yield, and meets the requirements of industrial production.
Drawings
FIG. 1 is an infrared image of a chlorinated paraffin-modified polyamide 6 copolymer obtained in example 2.
FIG. 1: 3300cm-1Is the absorption peak of the stretching vibration of N-H, 2920cm-1And 2860cm-1Is the absorption peak of stretching vibration of methyl and methylene, 1470cm-1And 1370cm-1Bending vibration absorption peak of methyl group, 1745cm-1Is the stretching vibration absorption peak of C ═ O in the ester group, 1660cm-1Absorption peak of carbonyl group in amide, 1520cm-1Is a bending vibration absorption peak of N-H and a stretching vibration absorption peak of C-N in amide, 1480cm-Is the characteristic absorption peak of benzene ring, 1225cm-1And 1050cm-1Is a characteristic absorption peak of the C-O-C ether bond of 510cm-1Here is the stretching vibration peak of the C-Cl bond.
Detailed Description
The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.
Example 1
(1) Preparation of chlorinated paraffin 42 containing carboxyl group: 20g of chlorinated paraffin 42 is dissolved in 210mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 28g of potassium carbonate are added to react for 30h at 55 ℃ under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 42 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 42: adding 70mol of chlorinated paraffin 42 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.
(3) Preparation of chlorinated paraffin 42 modified 5-hydroxyisophthalic acid: adding 5-hydroxyisophthalic acid 100mol and an appropriate amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing chlorinated paraffin 42 containing acyl chloride 101mol at 15 ℃, continuing to react for 5h after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 42 modified 5-hydroxyisophthalic acid.
(4) Preparation of chlorinated paraffin 42-modified 2, 5-dihydroxyterephthalic acid: adding 50mol of 2, 5-dihydroxyterephthalic acid and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 101mol of chlorinated paraffin 42 containing acyl chloride at 15 ℃, continuing to react for 5 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 42 modified 2, 5-dihydroxyterephthalic acid.
(5) Preparation of chlorinated paraffin 42 modified 5-hydroxyisophthaloyl dichloride: adding 70mol of chlorinated paraffin 42 modified 5-hydroxyisophthalic acid into a reaction kettle, dropwise adding 100mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 modified 5-hydroxyisophthaloyl dichloride.
(6) Preparation of chlorinated paraffin 42 modified 2, 5-dihydroxy terephthaloyl chloride: adding 70mol of chlorinated paraffin 42 into a reaction kettle to modify 2, 5-dihydroxy terephthalic acid, dropwise adding 100mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 modified 2, 5-dihydroxy terephthaloyl chloride.
(7) Preparation of chlorinated paraffin 42 modified diamine: adding 100mol of anhydrous dichloromethane, 100mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 50mol of chlorinated paraffin 42-containing modified 2, 5-dihydroxy terephthaloyl chloride at 0 ℃, heating to 20 ℃ after dropwise adding, continuing to react for 2h, and washing and drying a reaction product to obtain chlorinated paraffin 42-modified diamine.
(8) Preparation of chlorinated paraffin 42-modified polyamide oligomer: adding 50mol of chlorinated paraffin 42 modified diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing chlorinated paraffin 42 modified 5-hydroxy isophthaloyl chloride at 0 ℃, continuing to react for 3 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 42 modified polyamide oligomer.
(9) Preparation of chlorinated paraffin 42-modified polyamide 6 copolymer: adding 100 parts by mass of caprolactam and 3 parts by mass of water into a reaction kettle, introducing nitrogen, uniformly stirring, heating to 250 ℃, keeping the temperature for reaction for 3 hours when the pressure reaches 0.8MPa, then reducing the pressure to normal pressure, adding 10 parts by mass of chlorinated paraffin 42-modified polyamide oligomer after the temperature is reduced to 230 ℃, uniformly stirring, and continuously reacting for 8 hours to obtain chlorinated paraffin 42-modified polyamide 6 copolymer C1.
Example 2
(1) Preparation of chlorinated paraffin 52 containing carboxyl group: 20g of chlorinated paraffin 52 is dissolved in 220mL of acetone, stirred and dissolved, and then 20g of p-hydroxybenzoic acid and 29g of potassium carbonate are added to react for 10 hours at 80 ℃ under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.
(2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.
(3) Preparation of chlorinated paraffin 52 modified 5-hydroxyisophthalic acid: adding 5-hydroxyisophthalic acid 100mol and an appropriate amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing chlorinated paraffin 52 containing acyl chloride 103mol at 25 ℃, continuing to react for 3h after dropwise adding, and washing and drying the reaction product to obtain the chlorinated paraffin 52 modified 5-hydroxyisophthalic acid.
(4) Preparation of chlorinated paraffin 52-modified 2, 5-dihydroxyterephthalic acid: adding 50mol of 2, 5-dihydroxyterephthalic acid and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 103mol of chlorinated paraffin 52 containing acyl chloride at 25 ℃, continuing to react for 3 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 52 modified 2, 5-dihydroxyterephthalic acid.
(5) Preparation of chlorinated paraffin 52 modified 5-hydroxyisophthaloyl dichloride: adding 70mol of chlorinated paraffin 52 modified 5-hydroxyisophthalic acid into a reaction kettle, dropwise adding 100mol of phosphorus trichloride, stirring and heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 modified 5-hydroxyisophthalic acid chloride.
(6) Preparation of chlorinated paraffin 52 modified 2, 5-dihydroxy terephthaloyl chloride: adding 70mol of chlorinated paraffin 52 into a reaction kettle to modify 2, 5-dihydroxy terephthalic acid, dropwise adding 100mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 modified 2, 5-dihydroxy terephthaloyl chloride.
(7) Preparation of chlorinated paraffin 52 modified diamine: adding 100mol of anhydrous dichloromethane, 100mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 50mol of chlorinated paraffin 52-modified 2, 5-dihydroxy terephthaloyl chloride at 0 ℃, heating to 40 ℃ after dropwise adding, continuing to react for 1h, and washing and drying a reaction product to obtain chlorinated paraffin 52-modified diamine.
(8) Preparation of chlorinated paraffin 52-modified polyamide oligomer: adding 50mol of chlorinated paraffin 52 modified diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing chlorinated paraffin 52 modified 5-hydroxy isophthaloyl dichloride at 0 ℃, heating to 50 ℃ after dropwise adding, continuing to react for 1h, and washing and drying a reaction product to obtain the chlorinated paraffin 52 modified polyamide oligomer.
(9) Preparation of chlorinated paraffin 52-modified polyamide 6 copolymer: adding 100 parts by mass of caprolactam and 3 parts by mass of water into a reaction kettle, introducing nitrogen, uniformly stirring, heating to 250 ℃, keeping the temperature for reaction for 3 hours when the pressure reaches 0.8MPa, then reducing the pressure to normal pressure, adding 10 parts by mass of chlorinated paraffin 42-modified polyamide oligomer after the temperature is reduced to 220 ℃, uniformly stirring, and continuously reacting for 10 hours to obtain chlorinated paraffin 52-modified polyamide 6 copolymer C2.
Example 3
(1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 70 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 70 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.
(3) Preparation of chlorinated paraffin 70 modified 5-hydroxyisophthalic acid: adding 5-hydroxyisophthalic acid 100mol and an appropriate amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 102mol of chlorinated paraffin 70 containing acyl chloride at 20 ℃, continuing to react for 4h after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 70 modified 5-hydroxyisophthalic acid.
(4) Preparation of chlorinated paraffin 70-modified 2, 5-dihydroxyterephthalic acid: adding 50mol of 2, 5-dihydroxyterephthalic acid and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 102mol of chlorinated paraffin 70 containing acyl chloride at 20 ℃, continuing to react for 4 hours after dropwise adding, and washing and drying a reaction product to obtain the chlorinated paraffin 70 modified 2, 5-dihydroxyterephthalic acid.
(5) Preparation of chlorinated paraffin 70 modified 5-hydroxyisophthaloyl dichloride: adding 70mol of chlorinated paraffin 70 modified 5-hydroxyisophthalic acid into a reaction kettle, dropwise adding 100mol of phosphorus trichloride, stirring and heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 70 modified 5-hydroxyisophthalic acid chloride.
(6) Preparation of chlorinated paraffin 70 modified 2, 5-dihydroxy terephthaloyl chloride: adding 70mol of chlorinated paraffin 70 into a reaction kettle to modify 2, 5-dihydroxy terephthalic acid, dropwise adding 100mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 52 modified 2, 5-dihydroxy terephthaloyl chloride.
(7) Preparation of chlorinated paraffin 70 modified diamine: adding 100mol of anhydrous dichloromethane, 100mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a solution containing 50mol of chlorinated paraffin 70-modified 2, 5-dihydroxy terephthaloyl chloride dichloromethane at 0 ℃, heating to 35 ℃ after dropwise adding, continuing to react for 1h, and washing and drying a reaction product to obtain chlorinated paraffin 70-modified diamine.
(8) Preparation of chlorinated paraffin 70-modified polyamide oligomer: adding 50mol of chlorinated paraffin 70 modified diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing chlorinated paraffin 70 modified 5-hydroxy isophthaloyl dichloride at 0 ℃, heating to 40 ℃ after dropwise adding, continuing to react for 2 hours, and washing and drying a reaction product to obtain chlorinated paraffin 70 modified polyamide.
(9) Preparation of chlorinated paraffin 70-modified polyamide 6 copolymer: adding 100 parts by mass of caprolactam and 3 parts by mass of water into a reaction kettle, introducing nitrogen, uniformly stirring, heating to 250 ℃, keeping the temperature for reaction for 3 hours when the pressure reaches 0.8MPa, then reducing the pressure to normal pressure, adding 10 parts by mass of chlorinated paraffin 42-modified polyamide oligomer after the temperature is reduced to 230 ℃, uniformly stirring, and continuously reacting for 9 hours to obtain chlorinated paraffin 70-modified polyamide 6 copolymer C3.
Comparative example 1
(1) Preparation of poly (1, 3-propanediamyl terephthalamide) oligomer: adding 50mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing terephthaloyl chloride at 0 ℃, continuing to react for 2h after dropwise adding, and washing and drying the reaction product to obtain the poly (1, 3-propane diamine) oligomer.
(2) Preparation of the polyamide 6 copolymer: adding 100 parts by mass of caprolactam and 3 parts by mass of water into a reaction kettle, introducing nitrogen, uniformly stirring, heating to 250 ℃, keeping the temperature for reaction for 3 hours when the pressure reaches 0.8MPa, then reducing the pressure to normal pressure, adding 10 parts by mass of poly (1, 3-propane-diamine) terephthalamide oligomer after the temperature is reduced to 230 ℃, uniformly stirring, continuously reacting for 10 hours, and then adding 5 parts by mass of chlorinated paraffin 42 to obtain the polyamide 6 copolymer C4.
Comparative example 2
(1) Preparation of poly (1, 3-propanediamyl terephthalamide) oligomer: adding 50mol of 1, 3-propane diamine and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding 50mol of dichloromethane solution containing terephthaloyl chloride at 0 ℃, continuing to react for 2h after dropwise adding, and washing and drying the reaction product to obtain the poly (1, 3-propane diamine) oligomer.
(2) Preparation of the polyamide 6 copolymer: adding 100 parts by mass of caprolactam and 3 parts by mass of water into a reaction kettle, introducing nitrogen, uniformly stirring, heating to 250 ℃, keeping the temperature for reaction for 3 hours when the pressure reaches 0.8MPa, then reducing the pressure to normal pressure, adding 10 parts by mass of poly (1, 3-propane-diamine) terephthalamide oligomer after the temperature is reduced to 230 ℃, uniformly stirring, continuously reacting for 10 hours, and then adding 5 parts by mass of chlorinated paraffin 52 to obtain the polyamide 6 copolymer C5.
Preparation of Polyamide 6 fibers
And (3) cutting the prepared polyamide 6 copolymer into particles to obtain polyamide 6 copolymer chips, drying the chips in a vacuum drying oven at 100 ℃ for 24 hours, adding the chips into a melt spinning machine, and carrying out melt spinning at 265 ℃ to obtain the polyamide 6 fiber. The mechanical properties and flame retardant and heat resistance of the polyamide 6 fibers were tested according to national standards and the test results are shown in table 1.
TABLE 1 flame-retardant Polyamide 6 fiber Performance test results
Note: v-0 is the fire test rating of class V, and NR indicates failure of the test.
In conclusion, the invention firstly introduces the traditional chlorinated paraffin molecules into the polyamide molecular chain through chemical bonds to form a novel polyamide oligomer, and then the novel polyamide oligomer and the polyamide 6 prepolymer are subjected to copolymerization reaction to prepare the chlorinated paraffin modified polyamide 6 copolymer, because the molecular side chain contains a large amount of chlorinated paraffin molecules, and the molecular main chain contains rigid benzene rings and flexible fatty chains, the polyamide copolymer is endowed with excellent flame-retardant heat resistance and good mechanical properties, and the prepared flame-retardant polyamide 6 fiber has good mechanical properties and flame-retardant heat resistance.
Claims (10)
1. A flame-retardant polyamide fiber obtained by melt-spinning a chlorinated paraffin-modified polyamide resin having a structure represented by the formula (I):
in the formula (I), R1、R2、R3Is a chlorinated paraffin chain segment.
2. The preparation method of the chlorinated paraffin-modified polyamide copolymer is characterized by comprising the following steps of:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Carrying out phosphorus trichloride acylation on the chlorinated paraffin containing carboxyl obtained in the step (1) to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of modified chlorinated Paraffin dibasic acid
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of 5-hydroxyisophthalic acid or 2, 5-dihydroxyterephthalic acid and acid-binding agent triethylamine under the protection of nitrogen to perform esterification reaction to obtain modified chlorinated paraffin dibasic acid;
and (4): preparation of modified chlorinated Paraffin Dichloride
Carrying out phosphorus trichloride acylation on the modified chlorinated paraffin diacid obtained in the step (3) to obtain modified chlorinated paraffin diacid chloride;
and (5): preparation of chlorinated Paraffin modified diamines
Slowly dripping the chlorinated paraffin modified 2, 5-dihydroxy terephthaloyl chloride prepared in the step (4) into a mixed system of 1, 3-propane diamine and acid-binding agent triethylamine under the protection of nitrogen to perform amidation reaction to obtain chlorinated paraffin modified diamine;
and (6): preparation of chlorinated Paraffin-modified Polyamide oligomer
Slowly dropwise adding the chlorinated paraffin modified 5-hydroxy isophthaloyl dichloride obtained in the step (4) into a mixed system of chlorinated paraffin modified diamine and acid-binding agent triethylamine under the protection of nitrogen to perform amidation reaction to obtain chlorinated paraffin modified polyamide oligomer;
and (7): preparation of chlorinated Paraffin-modified Polyamide copolymers
Adding the chlorinated paraffin modified polyamide oligomer into the polyamide prepolymer, uniformly stirring, and reacting at the temperature of 220 ℃ and 230 ℃ for 4-6 h to obtain the chlorinated paraffin modified polyamide copolymer.
3. The method according to claim 2, wherein the chlorinated paraffin containing a carboxyl group is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at a temperature of 55-80 ℃ for 10-30 hours.
4. The preparation method according to claim 2, wherein the chlorinated paraffin containing carboxyl groups in the step (2) is reacted with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
5. The method according to claim 2, wherein the acid chloride-containing chlorinated paraffin is reacted with 5-hydroxyisophthalic acid in the step (3) at a molar ratio of 1 to 1.2: 1; the mole ratio of the chlorinated paraffin containing acyl chloride to the 2, 5-dihydroxy terephthalic acid is 2-2.2: 1.
6. The preparation method according to claim 2, wherein the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly added dropwise into a mixed solution of 5-hydroxyisophthalic acid or 2, 5-dihydroxyterephthalic acid and an acid-binding agent at a temperature of 15-25 ℃ for reaction, and the reaction is continued for 3-5 hours after the dropwise addition is completed.
7. The method according to claim 2, wherein the modified chlorinated paraffin diacid in the step (4) reacts with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to obtain the modified chlorinated paraffin diacid chloride.
8. The method according to claim 2, wherein the modified chlorinated paraffin diacid chloride is reacted with 1, 3-propane diamine in a molar ratio of 1 to 1.1:2 in step (5).
9. The preparation method of claim 2, wherein the reaction conditions in the step (5) are that the modified chlorinated paraffin diacid chloride is slowly dripped into the mixed solution of the 1, 3-propane diamine and the acid-binding agent in an ice-water bath for reaction, after the dripping is completed, the temperature is raised to 20-40 ℃, and the reaction is continued for 1-2 hours.
10. The method according to claim 2, wherein the molar ratio of the chlorinated paraffin-modified 5-hydroxyisophthaloyl chloride to the chlorinated paraffin-modified diamine in step (6) is 1: 1; the reaction condition is that firstly, the chlorinated paraffin modified 5-hydroxy isophthaloyl dichloride is slowly dripped into the mixed solution of the chlorinated paraffin modified diamine and the acid binding agent in an ice water bath for reaction, and the reaction is continued for 1-3 hours after the dripping is finished.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110077251.XA CN112760735A (en) | 2021-01-20 | 2021-01-20 | Flame-retardant polyamide fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110077251.XA CN112760735A (en) | 2021-01-20 | 2021-01-20 | Flame-retardant polyamide fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112760735A true CN112760735A (en) | 2021-05-07 |
Family
ID=75701889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110077251.XA Withdrawn CN112760735A (en) | 2021-01-20 | 2021-01-20 | Flame-retardant polyamide fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112760735A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801319A (en) * | 2021-09-22 | 2021-12-17 | 浙江新力新材料股份有限公司 | Rigid high-temperature-resistant nylon resin, and preparation method and application thereof |
-
2021
- 2021-01-20 CN CN202110077251.XA patent/CN112760735A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801319A (en) * | 2021-09-22 | 2021-12-17 | 浙江新力新材料股份有限公司 | Rigid high-temperature-resistant nylon resin, and preparation method and application thereof |
| CN113801319B (en) * | 2021-09-22 | 2023-08-01 | 浙江新力新材料股份有限公司 | Rigid high-temperature-resistant nylon resin, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2191556A (en) | Polyamides | |
| US3049518A (en) | Polyamides from n, n'-bis (3-aminophenyl)-isophthalamide | |
| CN1266445A (en) | Polymer-bound non-halogen fire resistant compositions | |
| CN113527669A (en) | Organic phosphorus copolymerized flame-retardant polyamide and preparation method thereof | |
| US5093464A (en) | Wholly aromatic polyamide from N,N'-bis (4-amino phenyl)-isophthalamide | |
| CN115141451A (en) | High-flame-retardancy polypropylene composite material and preparation method thereof | |
| CN113981559A (en) | Degradable aramid fiber and preparation method thereof | |
| CN107118344A (en) | A kind of anti-oxidant flame retardant type partially aromatic polyamide of color inhibition and preparation method thereof | |
| CN112760735A (en) | Flame-retardant polyamide fiber | |
| US4278786A (en) | Aromatic polyamides containing ether linkages and process for producing same | |
| CN111423579B (en) | Flame-retardant nylon resin and preparation method thereof | |
| US3472819A (en) | Polyamides of the recurring benzamide unit | |
| CN111621161A (en) | Crosslinked polymer flame retardant and preparation method thereof | |
| US2281576A (en) | Polyamides and process of making same | |
| CN113912838A (en) | Flame-retardant anti-dripping copolymerized nylon and preparation method and application thereof | |
| CN112760736A (en) | Flame-retardant polyamide fiber and preparation method thereof | |
| US3335114A (en) | Polycarbonamides from p-phenylenebis(dimethylacetic acid) and its derivatives | |
| CN102585225B (en) | Preparation method of diaza-naphthalenone-biphenyl-polybenzoxazole, monomer and polymer | |
| CN105153417A (en) | Halogen-free flame-retardant high-temperature nylon | |
| US4914180A (en) | Polyamides prepared from 2-(3-aminophenyl)-2-(4-aminophenyl) hexafluoro propane | |
| CN112812500A (en) | Flame-retardant epoxy plastic plate | |
| CN112898736A (en) | Flame-retardant fireproof epoxy plastic plate and preparation method thereof | |
| CN112759893A (en) | Flame-retardant epoxy plastic plate and preparation method thereof | |
| JPH01207322A (en) | Polycarbonamide of bis(2-(4-carboxyphenyl) hexafluoroisopropyl)diphenyl ether | |
| CN112920402B (en) | High-temperature-resistant nylon and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210507 |
|
| WW01 | Invention patent application withdrawn after publication |