CN107915846B - Polyamide copolymer and preparation method and application thereof - Google Patents
Polyamide copolymer and preparation method and application thereof Download PDFInfo
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a polyamide copolymer and a preparation method and application thereof. The structural formula of the polyamide of the invention is shown as formula I, [ NH- (CH)2)m―NH―CO―(CH2)n―CO]x―[NH―(CH2)p―NH―CO―(CH2)q―CO]yFormula I; in the formula I, when m is an odd number of 1-12, n is an even number of 1-12; when m is an even number of 1-12, n is an odd number of 1-12; wherein p and q are both an even number of 1-12; the ratio of x to y is 0.075-11.5: 1, x is 25 to 150, and y is 25 to 150. The polyamide blend is applied to the preparation of resin and/or fiber. The resin and the fiber prepared from the blend greatly increase the elongation at break and improve the toughness while maintaining the tensile modulus and the strength.
Description
Technical Field
The invention relates to a polyamide copolymer and a preparation method and application thereof, belonging to the technical field of chemical industry.
Background
Polyamide (PA, commonly called nylon) is one of important polymer materials in modern industry, and has the excellent comprehensive properties of high strength, heat resistance, good electrical property, wear resistance, shock resistance, sound absorption, oil resistance, weak acid and alkali resistance, organic solvents and the like. Therefore, the fiber is widely applied to automobiles, electrical equipment, mechanical parts, transportation equipment, textile, paper making machinery and the like. With the progress of miniaturization of automobiles, high performance of electronic and electrical devices, and weight reduction of mechanical devices becoming faster, demand for polyamides is becoming higher and larger. However, the mechanical properties, especially the elongation at break, of the polyamide of a single component are low, and the demand for products with high toughness requirements cannot be met. Therefore, there is a need to improve the mechanical properties of polyamides, in particular the toughness of the resins.
The polyamide toughening modification is mostly melt blended with other polymers, such as polyethylene, polypropylene, polystyrene and the like, or inorganic nanoparticles, such as carbon nanotubes, nanoclay and the like, for enhancing the toughness of polyamide. However, the quality of the blend performance depends on the interfacial compatibility of the blend components, so that a compatibilizer is also added to improve the mechanical properties of the blend resin. Patent 2015800181461 proposes that aliphatic nylon blended with semi-aromatic nylon can improve the mechanical properties of the material (s. buhaga. novel nylon blend for improved mechanical properties of mono-and multifilament fibers. application No. 2015800181461).
Disclosure of Invention
The invention aims to provide a polyamide copolymer, and a preparation method and application thereof.
The invention provides a polyamide copolymer, which is characterized in that: the structural formula of the polyamide copolymer is shown as a formula I,
―[NH―(CH2)m―NH―CO―(CH2)n―CO]x―[NH―(CH2)p―NH―CO―(CH2)q―CO]yformula I;
in the formula I, when m is an odd number of 1-12, n is an even number of 1-12; when m is an even number of 1-12, n is an odd number of 1-12;
wherein p and q are both an even number of 1-12;
the ratio of x to y is 0.075-11.5: 1, x is 25 to 150, and y is 25 to 150.
In the invention, the polyamide chain segment is formed by copolymerizing odd-even polyamide chain segments and even-even polyamide chain segments; and/or the presence of a gas in the gas,
the odd-even polyamide chain segment and the even polyamide chain segment are copolymerized.
In the invention, the mass ratio of the odd-even polyamide chain segment to the even polyamide can be 0.25-4: 1, in particular 4: 1. 1: 1. 0.25: 1, the mass ratio of x to y in the structural formula of the polyamide copolymer can be 0.075 to 11.5: and 1, converting to obtain.
In the present invention, the odd-even polyamide segment specifically includes at least one of a polyamide 56 segment, a polyamide 65 segment, a polyamide 69 segment, and a polyamide 96 segment;
the coupling polyamide segment specifically comprises at least one of polyamide 66, polyamide 610, polyamide 612 and polyamide 12 segments;
the even-numbered polyamide segments specifically comprise at least one of polyamide 6 and polyamide 12 segments.
In the present invention, the parity polyamide segment has a structure of [ NH- (CH)2)m―NH―CO―(CH2)n―CO]xX is 25 to 150;
specifically, when m is 5 and n is 4, polyamide 56 is;
polyamide 65 is when m is 6, n is 3;
polyamide 69 is when m is 6 and n is 7;
polyamide 96 is when m is 9 and n is 4;
the structure of the even polyamide chain segment and the even polyamide chain segment is [ NH- (-CH) -)2)p―NH―CO―(CH2)q―CO]yY is 25 to 150;
specifically, when p is 6 and q is 4, polyamide 66 is;
polyamide 610 is when p is 6, q is 8;
polyamide 612 is p-6, q-10;
polyamide 1010 is p-10, q-8;
polyamide 1212 when p is 12 and q is 10;
when polyamide 6 is p ═ q ═ 5;
when p ═ q ═ 11, polyamide 12 can be obtained.
The invention also provides a preparation method of the polyamide copolymer, which comprises the following steps:
(1) preparation of the polyamide salt: mixing odd diamine and even diacid in equal proportion to prepare polyamide salt A; mixing even diamine and odd diacid in equal proportion to prepare polyamide salt B; proportionally mixing the azo diamine and the dibasic acid to prepare polyamide salt C;
the structural formula of the polyamide salt A is NH3+―(CH2)m―NH3+COO――(CH2)n―COO―In the structural formula of the polyamide salt A, m is an odd number of 1-12, and n is an even number of 1-12;
the structural formula of the polyamide salt B is NH3+―(CH2)m―NH3+COO――(CH2)n―COO―In the structural formula of the polyamide salt B, m is an even number of 1-12, and n is an odd number of 1-12;
the structural formula of the polyamide salt C is NH3+―(CH2)p―NH3+COO――(CH2)q―COO―In the structural formula of the polyamide salt C, p and q are even numbers of 1-12;
(2) preparation of a Polyamide copolymer:
carrying out polycondensation reaction on the polyamide salt A or B to prepare an odd-even polyamide prepolymer M; and (3) carrying out polycondensation reaction on the polyamide salt C to prepare an even polyamide prepolymer N, and then mixing the even polyamide prepolymer M and the even polyamide prepolymer N for carrying out a polymerization expansion reaction to obtain the polyamide copolymer.
In the preparation method, the mixing temperature in the step (1) can be 30-60 ℃, specifically 40 ℃, 30-40 ℃, 40-60 ℃ or 35-50 ℃, and the time can be 1-4 h, specifically 2h, 1-2 h, 2-4 h or 1.5-3 h.
In the preparation method, the post-treatment in the step (1) is to slowly cool the mixture to room temperature, filter the mixture and wash the mixture for at least 3 times by using ethanol to obtain the polyamide salt.
In the preparation method, the temperature of the polycondensation and the diffusion polymerization in the step (2) can be 100-300 ℃, specifically, the reaction time can be 1-10 hours, specifically 2 hours, 1-2 hours, 2-10 hours or 1-8 hours.
In the preparation method, the mass ratio of M to N in the step (2) may be 0.25 to 4, and specifically may be 4: 1. 1: 1. 0.25: 1.
the polyamide copolymer is applied to preparing resin and/or fiber.
The invention has the following advantages:
the resin and the fiber prepared by the copolymer have larger elongation at break and greatly increased toughness.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of polyamide salt:
and (3) blending equimolar pentamethylene diamine and adipic acid aqueous solution, stirring for 2 hours at the temperature of 40 ℃, slowly cooling to room temperature, filtering, and washing for 3 times by using ethanol to obtain the polyamide 56 salt.
Mixing equimolar hexanediamine and adipic acid aqueous solution, stirring for 2h at 40 ℃, slowly cooling to room temperature, filtering, and washing with ethanol for 3 times to obtain the polyamide 66 salt.
Example 2, preparation of a copolymer of polyamides 56-66:
respectively carrying out polycondensation on polyamide 56 salt and polyamide 66 salt at 200 ℃ to obtain polyamide prepolymer, mixing the two prepolymers, and carrying out diffusion polymerization at 230 ℃ for 2h to obtain the polyamide 56-66 copolymer. The mass ratio of the two prepolymers is 4: 1. 1: 1. 0.25: 1.
example 3 mechanical Properties of Polyamide 56-66 copolymer
The mechanical properties of the polyamide 56-66 copolymer prepared in inventive example 2, wherein the polyamide 56 content is 80% by mass and the polyamide 66 content is 20% by mass, are determined as sample 2 in table 1. The elongation at break increased by 94.5% while keeping the tensile modulus and strength unchanged little.
Example 4 mechanical Properties of Polyamide 56-66 copolymer
The mechanical properties of the polyamide 56-66 copolymer prepared in inventive example 2, wherein the polyamide 56 content is 50% by mass and the polyamide 66 content is 50% by mass, are measured as sample 3 in table 1. While keeping the tensile modulus and strength unchanged, the elongation at break is increased by 165% compared with the single polyamide 56 and 107% compared with the single polyamide 66.
Example 5 mechanical Properties of Polyamide 56-66 copolymer
The mechanical properties of the polyamide 56-66 copolymer prepared in inventive example 2, wherein the polyamide 56 content is 20% by mass and the polyamide 66 content is 80% by mass, are measured as sample 4 in table 1. The elongation at break is increased by 35.0% slightly compared with single polyamide 66 while keeping the tensile modulus and strength unchanged slightly.
TABLE 1 mechanical Properties of Polyamide 56-66 copolymer
Claims (5)
1. A method for preparing a polyamide copolymer, comprising the steps of:
(1) preparation of the polyamide salt: mixing odd diamine and even diacid in equal proportion to prepare polyamide salt A; mixing even diamine and odd diacid in equal proportion to prepare polyamide salt B; proportionally mixing the azo diamine and the dibasic acid to prepare polyamide salt C;
the structural formula of the polyamide salt A is NH3+―(CH2)m―NH3+COO――(CH2)n―COO―In the structural formula of the polyamide salt A, m is an odd number of 1-12, and n is an even number of 1-12;
the structural formula of the polyamide salt B is NH3+―(CH2)m―NH3+COO――(CH2)n―COO―In the structural formula of the polyamide salt B, m is an even number of 1-12, and n is an odd number of 1-12;
the structural formula of the polyamide salt C is NH3+―(CH2)p―NH3+COO――(CH2)q―COO―In the structural formula of the polyamide salt C, p and q are even numbers of 1-12;
(2) preparation of a Polyamide copolymer:
carrying out polycondensation reaction on the polyamide salt A or B to prepare an odd-even polyamide prepolymer M; carrying out polycondensation reaction on the polyamide salt C to prepare an even polyamide prepolymer N, and then mixing the even polyamide prepolymer M and the even polyamide prepolymer N for carrying out a polymerization expansion reaction to obtain the polyamide copolymer;
the structural formula of the polyamide copolymer is [ NH- (CH)2)m―NH―CO―(CH2)n―CO]x―[NH―(CH2)p―NH―CO―(CH2)q―CO]y―
Wherein when m is an odd number of 1-12, n is an even number of 1-12; when m is an even number of 1-12, n is an odd number of 1-12;
wherein p and q are both an even number of 1-12;
the ratio of x to y is 0.075-11.5: 1, x is 25 to 150, and y is 25 to 150.
2. The method of claim 1, wherein: in the step (1), the mixing temperature is 30-60 ℃, and the mixing time is 1-4 h.
3. The production method according to claim 1 or 2, characterized in that: the step (1) also comprises a post-treatment step; and the post-treatment comprises slowly cooling to room temperature, filtering, and washing with ethanol for at least 3 times to obtain the polyamide salt.
4. The production method according to claim 1 or 2, characterized in that: the temperature of the polycondensation and the diffusion polymerization in the step (2) is 100-300 ℃, and the reaction time is 1-10 h.
5. The production method according to claim 1 or 2, characterized in that: the mass ratio of M to N in the step (2) is 0.25-4.
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| CN111088123B (en) * | 2019-12-25 | 2021-06-25 | 广州立白企业集团有限公司 | Concentrated liquid detergent composition and process for producing the same |
| CN111171312B (en) * | 2020-01-21 | 2022-08-02 | 军事科学院系统工程研究院军需工程技术研究所 | Copolyamide 56/66 polymer and preparation method and application thereof |
| CN113321802A (en) * | 2021-06-21 | 2021-08-31 | 杭州聚合顺新材料股份有限公司 | Synthetic nylon 46/66 copolymer and preparation process thereof |
| CN115536838B (en) * | 2021-06-30 | 2024-02-09 | 上海凯赛生物技术股份有限公司 | Copolyamide resin, fiber, and preparation method and application thereof |
| CN115322366A (en) * | 2022-09-06 | 2022-11-11 | 东华大学 | Polyamide 6-modified high-strength high-toughness copolyamide and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5243024A (en) * | 1990-12-21 | 1993-09-07 | Amoco Corporation | High moduli polyimides |
| CN101443382A (en) * | 2006-05-16 | 2009-05-27 | 三菱化学株式会社 | Polyamide resin |
| CN106519219A (en) * | 2016-11-15 | 2017-03-22 | 中国纺织科学研究院 | Continuous polymerization process for PA6-5X copolymer, and PA6-5X copolymer |
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- 2017-11-22 CN CN201711171658.9A patent/CN107915846B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5243024A (en) * | 1990-12-21 | 1993-09-07 | Amoco Corporation | High moduli polyimides |
| CN101443382A (en) * | 2006-05-16 | 2009-05-27 | 三菱化学株式会社 | Polyamide resin |
| CN106519219A (en) * | 2016-11-15 | 2017-03-22 | 中国纺织科学研究院 | Continuous polymerization process for PA6-5X copolymer, and PA6-5X copolymer |
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Effective date of registration: 20220322 Address after: 100190 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee after: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee after: Institute of Quartermaster engineering technology, Academy of systems engineering, Academy of Military Sciences Address before: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee before: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
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