CN104031265B - A kind of copolymerization transparent nylon and preparation method thereof - Google Patents

A kind of copolymerization transparent nylon and preparation method thereof Download PDF

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Publication number
CN104031265B
CN104031265B CN201410290321.XA CN201410290321A CN104031265B CN 104031265 B CN104031265 B CN 104031265B CN 201410290321 A CN201410290321 A CN 201410290321A CN 104031265 B CN104031265 B CN 104031265B
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monomer
mass content
transparent nylon
nylon
copolymerization transparent
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CN104031265A (en
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高原
梁效礼
杨冬
黄俊辉
张海春
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Chendong Yipuwan New Materials (Guangdong) Co.,Ltd.
GUANGZHOU CHENDONG NEW MATERIALS Co.,Ltd.
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Dongguan Epone Nylon Sci & Tech Co Ltd
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Abstract

The invention provides copolymerization transparent nylon, be polymerized by following each component: mass content is the monomer A of 80-96%: lactan; Mass content is the monomers B of 2-10%: mol ratio is the hexanodioic acid monomer of 1:1 and the mixture of m-xylene diamine monomer, poly-meta-xylylene adipamide (MXD6) salt or poly-meta-xylylene adipamide (MXD6) performed polymer; Mass content be the monomer E of 2-10%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine; Monomer D is aliphatic dibasic acid.This copolymerization transparent nylon is by monomer A, and monomers B, monomer C and monomer D, is polymerized jointly, comparatively conventional nylon 6, and nylon66 fiber and nylon 6/66 copolymer have the more excellent transparency and over-all properties.

Description

A kind of copolymerization transparent nylon and preparation method thereof
Technical field
The present invention relates to macromolecular material nylon synthesis technical field, particularly, relate to a kind of copolymerization transparent nylon and preparation method thereof.
Background technology
Wallace's Tomas Carothers of du pont company has invented polymeric amide in the thirties in 20th century.Polymeric amide has high mechanical strength, good shock resistance, and the good characteristics such as excellent thermotolerance, wear resistance and oil-proofness, are widely used in machinery and chemical industry, play very important effect in national economy fields such as water conservancy, national defence, traffic.
But the nylon transparency is poor, at some, higher field is required to material transparent, be difficult to play a role.For this reason, the research to transparent nylon is extensively launched both at home and abroad.Transparent nylon is generally amorphous polymer, and transmittance is close with opticglass, is widely used in aircraft industry, automobile making, electrical equipment industry, medical sector, food product pack, engineering and mechanical part, off-shore operation department, physical culture and Hi-Fi (high-fidelity)/image/fine groove floppy disk department.
In prior art, the transparent polyamide of synthesis mainly contains aliphatics transparent polyamide, aromatic series transparent polyamide, Semi-aromatic transparent polyamide.Wherein, aliphatics transparent polyamide is the random copolymerization of aliphatic dibasic acid and diamine, as nylon 6/66 copolymer, and nylon 6/12 multipolymer etc. of Emer company.But the destruction of straight-chain aliphatic monomer random copolymerization to Product Sequence regularity is limited, and polymeric amide crystallization velocity is very fast, and processing condition are difficult to control.And aromatic series transparent polyamide, Semi-aromatic transparent polyamide is because the existence of aromatic monomer, and technological process is comparatively complicated.Therefore, continue to carry out modification to its technique.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of copolymerization transparent nylon and preparation method thereof, this copolymerization transparent nylon passes through monomer A, monomers B, monomer C and monomer D, jointly be polymerized, comparatively conventional nylon 6, nylon66 fiber and nylon 6/66 copolymer have the more excellent transparency and over-all properties.
Technical scheme of the present invention is as follows: a kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 80-96%: lactan;
Mass content is the monomers B of 2-10%: mol ratio is the hexanodioic acid monomer of 1:1 and the mixture of m-xylene diamine monomer, poly-meta-xylylene adipamide (MXD6) salt or poly-meta-xylylene adipamide (MXD6) performed polymer;
Mass content be the monomer E of 2-10%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine; Monomer D is aliphatic dibasic acid.
Described lactan is caprolactam (CPL), lauryl lactan or the mixture of the two.
Described cycloalphatic diamine is 4,4′-diaminodicyclohexylmethane (PACM), isophorone diamine (IPDA) or the mixture of the two.
Described aliphatic dibasic acid is hexanodioic acid.
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Beneficial effect of the present invention is: copolymerization transparent nylon of the present invention passes through monomer A, monomers B, monomer C and monomer D, jointly be polymerized, preparation method is simple, comparatively conventional nylon 6, and nylon66 fiber and nylon 6/66 copolymer have the more excellent transparency, its light transmission rate can reach more than 82%, excellent combination property.
Embodiment
Embodiment 1:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 96%: caprolactam
Mass content is the monomers B of 2%: mol ratio is the hexanodioic acid monomer of 1:1 and the mixture of m-xylene diamine monomer;
Mass content be the monomer E of 2%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine PACM; Monomer D is aliphatic dibasic acid hexanodioic acid
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Embodiment 2:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 92.5%: caprolactam
Mass content is the monomers B of 5.5%: poly-meta-xylylene adipamide (MXD6) salt;
Mass content be the monomer E of 2%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine IPDA; Monomer D is aliphatic dibasic acid hexanodioic acid
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Embodiment 3:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 92.5%: caprolactam
Mass content is the monomers B of 2.5%: poly-meta-xylylene adipamide (MXD6) performed polymer;
Mass content be the monomer E of 5%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine IPDA; Monomer D is aliphatic dibasic acid hexanodioic acid
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out polycondensation dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Embodiment 4:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 90%: caprolactam
Mass content is the monomers B of 5%: mol ratio is the hexanodioic acid monomer of 1:1 and the mixture of m-xylene diamine monomer;
Mass content be the monomer E of 5%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine PACM; Monomer D is aliphatic dibasic acid hexanodioic acid.
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Embodiment 5:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 90%: caprolactam
Mass content is the monomers B of 7.5%: poly-meta-xylylene adipamide (MXD6) salt;
Mass content be the monomer E of 2.5%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is the mixture of cycloalphatic diamine PACM and IPDA; Monomer D is aliphatic dibasic acid hexanodioic acid
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Embodiment 6:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 90%: caprolactam
Mass content is the monomers B of 2.5%: poly-meta-xylylene adipamide (MXD6) salt;
Mass content be the monomer E of 7.5%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine IPDA; Monomer D is aliphatic dibasic acid hexanodioic acid
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
Embodiment 7:
A kind of copolymerization transparent nylon, is polymerized by following each component:
Mass content is the monomer A of 80%: caprolactam
Mass content is the monomers B of 10%: mol ratio is the hexanodioic acid monomer of 1:1 and the mixture of m-xylene diamine monomer;
Mass content be the monomer E of 10%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine PACM; Monomer D is aliphatic dibasic acid hexanodioic acid
The preparation method of described copolymerization transparent nylon, comprises the steps:
1) by monomer A, monomers B, monomer C and monomer D drop into the automatic control polymeric kettle with agitator device, at the temperature of the pressure of 1-27bar, 220-320 DEG C, carry out dehydration reaction;
2) after reacting, nitrogen injection discharges the moisture that reaction generates, and then copolymerization transparent nylon melt is discharged in pressurization, and melt is shaping by die head Cast Strip, through cooling and dicing, obtains described copolymerization transparent nylon.
In order to further illustrate the performance of copolymerization transparent nylon of the present invention, the present inventor detects the transmittance of described copolymerization transparent nylon prepared by embodiment 1-7, mist degree, tensile strength and tensile modulus,
Detected result record is as following table.
The transmittance of copolymerization transparent nylon described in table 1, embodiment 1-7, mist degree, tensile strength and tensile modulus detected result
Test item Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
Light transmission rate % 82 87.5 86.5 88 90 87.8 92
Mist degree % 80 5 6 2 1.5 2.5 1.0
Tensile strength MPa 80 85 83 85 90 84 89
Tensile modulus MPa 2700 2750 2800 2850 2890 2850 2880
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by submitted to claims.

Claims (2)

1. a copolymerization transparent nylon, is characterized in that, is polymerized by following each component:
Mass content is the monomer A of 80-96%: lactan;
Mass content is the monomers B of 2-10%: mol ratio is the hexanodioic acid monomer of 1:1 and the mixture of m-xylene diamine monomer, poly-meta-xylylene adipamide (MXD6) salt or poly-meta-xylylene adipamide (MXD6) performed polymer;
Mass content be the monomer E of 2-10%: monomer C and monomer D be obtained by reacting monomer E with mol ratio 1:1, wherein monomer C is cycloalphatic diamine, described cycloalphatic diamine is 4,4′-diaminodicyclohexylmethane (PACM), isophorone diamine (IPDA) or the mixture of the two; Monomer D is aliphatic dibasic acid, and described aliphatic dibasic acid is hexanodioic acid.
2. copolymerization transparent nylon as claimed in claim 1, it is characterized in that, described lactan is caprolactam (CPL), lauryl lactan or the mixture of the two.
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CN107337794B (en) * 2017-07-07 2020-07-17 株洲时代新材料科技股份有限公司 Copolymerized nylon containing six-membered ring and preparation method thereof
CN108084431A (en) * 2017-12-19 2018-05-29 山东东辰瑞森新材料科技有限公司 A kind of ultraviolet curing transparent nylon and preparation method thereof
CN109265678B (en) * 2018-09-19 2021-07-06 中仑塑业(福建)有限公司 Polyamide resin, preparation method thereof and molded product
CN111978713A (en) * 2020-09-11 2020-11-24 广州辰东新材料有限公司 Highlight spraying-free copolymerized transparent nylon modified material
CN112679729A (en) * 2020-12-15 2021-04-20 广州辰东新材料有限公司 Transparent nylon material and preparation method thereof
CN113698594B (en) * 2021-09-08 2023-08-04 湖南工业大学 Polyamide resin and preparation method thereof
CN115403923A (en) * 2022-09-06 2022-11-29 董泽民 Transparent flame-retardant nylon and preparation method thereof

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CN1746208A (en) * 2005-09-21 2006-03-15 中北大学 Block copolyamide and preparation thereof
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Address after: Room 312, ITT plant, No.5, Gongye North 4th Road, Songshanhu high tech Industrial Development Zone, Dongguan City, Guangdong Province

Patentee after: Chendong Yipuwan New Materials (Guangdong) Co., Ltd.

Address before: Park Songshan Lake Science and Technology Industrial Park in the northern industrial city of Guangdong Province, 523808 small enterprises of science and technology of Dongguan city building 4 Dongguan epone nylon Polytron Technologies Inc

Patentee before: Dongguan Epone Nylon Sci & Tech Co., Ltd.

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Effective date of registration: 20210910

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Patentee after: GUANGZHOU CHENDONG NEW MATERIALS Co.,Ltd.

Patentee after: Chendong Yipuwan New Materials (Guangdong) Co.,Ltd.

Address before: 523000 room 312, ITT workshop, No.5, Gongye North 4th Road, Songshanhu high tech Industrial Development Zone, Dongguan City, Guangdong Province

Patentee before: Chendong Yipuwan New Materials (Guangdong) Co.,Ltd.