WO2022088852A1 - Polymère méta-aramide à allongement élevé et procédé de préparation s'y rapportant - Google Patents

Polymère méta-aramide à allongement élevé et procédé de préparation s'y rapportant Download PDF

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Publication number
WO2022088852A1
WO2022088852A1 PCT/CN2021/112535 CN2021112535W WO2022088852A1 WO 2022088852 A1 WO2022088852 A1 WO 2022088852A1 CN 2021112535 W CN2021112535 W CN 2021112535W WO 2022088852 A1 WO2022088852 A1 WO 2022088852A1
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WO
WIPO (PCT)
Prior art keywords
meta
amount
polar solution
aramid fiber
polar
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Application number
PCT/CN2021/112535
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English (en)
Chinese (zh)
Inventor
任仲恺
宋金苓
张爱华
关振虹
吕继平
Original Assignee
烟台泰和新材料股份有限公司
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Publication of WO2022088852A1 publication Critical patent/WO2022088852A1/fr

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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
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • 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
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides

Definitions

  • the invention belongs to the technical field of aramid fibers, and particularly relates to an aramid fiber polymer and a preparation method thereof.
  • Aramid fibers are divided into two types: para-type and meta-type according to different molecular structures.
  • Para-type products are generally used as high-strength and high-modulus fibers, and meta-type products are mainly used as high-temperature resistant fiber materials.
  • aramid fiber prepared by it is known as one of the three major high-performance fiber materials in the world today. It has high temperature resistance, intrinsic flame retardancy, electrical insulation, radiation resistance, chemical corrosion resistance, etc. Excellent characteristics; widely used in military and police safety protective clothing, high temperature environmental protection filter material, industrial safety protective clothing, high-end electrical insulation materials, aircraft and high-speed train secondary stress parts, industrial textiles and other fields, is an important basic material related to the national economy and people's death.
  • the purpose of the present invention is to provide a high elongation meta-aramid fiber polymer and a preparation method thereof, so as to improve the elongation of the meta-aramid fiber polymer and solve the above-mentioned technical problems.
  • a high elongation meta-aramid polymer the general structural formula is as follows:
  • R 1 is derived from a diphenylalkane compound.
  • R 1 is specifically:
  • amino groups are located in the symmetrical positions centered on the alkyl carbon on the two benzene rings, respectively.
  • a preparation method of a high elongation meta-aramid polymer comprising the following steps:
  • the preparation method of the first polar solution comprises: dissolving m-phenylenediamine in the first polar solvent, and then adding isophthaloyl chloride to fully react to obtain;
  • the preparation method of the first polar solution includes: dissolving the diamine compound in the first polar solvent, and then adding isophthaloyl chloride to fully react to obtain it;
  • step S3 neutralize the reaction product of step S2 to a pH value above 8.0 to obtain a highly elongated meta-aramid fiber polymer.
  • a further improvement of the present invention lies in that: in step S1, the ratio of the amount of the first polar solution meso-phenylenediamine dissolved to the first polar solvent is (40-44): (320-400); the first polar solution is prepared In solution, the added isophthaloyl chloride is 4/5 of the amount of m-phenylenediamine.
  • step S1 the ratio of the amount of the diamine compound and the second polar solvent in the second polar solution is (1-1.1): (16-18); In solution, the added isophthaloyl chloride is 4/5 of the amount of the diamine compound.
  • a further improvement of the present invention is: the general structural formula of the diamine compound is as follows:
  • a further improvement of the present invention is: in step S1, specifically: after dissolving m-phenylenediamine in the first polar solvent and cooling to below 20 DEG C, then adding isophthaloyl chloride to fully react;
  • step S1 specifically: after dissolving the diamine compound in the second polar solvent, cooling the temperature to below 20° C., then adding isophthaloyl chloride to fully react.
  • a further improvement of the present invention is: the amount of the isophthaloyl chloride added in the step S2 is the amount of the material of the first polar solution m-phenylenediamine in the step S2 and the amount of the diamine in the second polar solution in the step S2 1/5 of the sum of the amounts of the substances in the class of compounds.
  • a further improvement of the present invention is that: when the first polar solvent and the second polar solution are configured in step S1, the sufficient reaction time after adding isophthaloyl chloride is 1-1.5h, and the reaction temperature is below 20°C; In step S2, the reaction temperature is below 40°C, and the complete reaction time is 0.6-1.2 h.
  • the further improvement of the present invention lies in that: the prepared high elongation meta-aramid fiber polymer has a viscosity of 1000-1800 Po.
  • the further improvement of the present invention is that: the prepared high-elongation meta-aramid fiber polymer is coagulated and formed by an aqueous solution of dimethylacetamide containing 2% boric acid, and then subjected to washing, drawing, drying, heat setting, oiling, Crimping and cutting to form meta-aramid high elongation staple fibers.
  • the present invention has the following beneficial effects:
  • the high-elongation meta-aramid fiber polymer involved in the present invention is based on the original meta-aramid fiber, and the molecular structure is modified by introducing a diphenylalkane structure, while retaining the meta-aramid fiber. It has its own characteristics and enhances the intermolecular force, so that the fibers made of this modified meta-aramid polymer have excellent spinnability, better tensile properties, and higher Elongation at break.
  • the high-elongation meta-aramid fiber polymer involved in the present invention adopts a simple and easy-to-operate polymerization method, has excellent cost advantages, and is easy to realize industrial production.
  • the polymer viscosity [Po]: BROOKFIELD DV-II+Pro is used to test the dynamic viscosity of the polymer solution, and the No. 4 rotor is selected, and the result is finally converted into the viscosity at the standard temperature (25°C) for characterization.
  • Fiber breaking strength [cN/dtex] and breaking elongation [%] The breaking strength and breaking elongation of fibers obtained by VP500 and VN500 of Lenzing Company of Austria were tested.
  • the present invention provides a kind of high elongation meta-aramid fiber polymer, the general structural formula is as follows:
  • the R 1 is specifically:
  • amino groups are located in the symmetrical positions centered on the alkyl carbon on the two benzene rings, respectively.
  • the present invention also provides a preparation method of a high elongation meta-aramid fiber polymer, comprising the following steps:
  • the preparation method of the first polar solution comprises: dissolving m-phenylenediamine in the first polar solvent, and then adding isophthaloyl chloride to fully react to obtain;
  • the preparation method of the first polar solution includes: dissolving the diamine compound in the first polar solvent, and then adding isophthaloyl chloride to fully react to obtain it;
  • step S3 neutralize the reaction product of step S2 to a pH value above 8.0 to obtain a highly elongated meta-aramid fiber polymer.
  • step S1 the ratio of the amount of the first polar solution m-phenylenediamine dissolved to the first polar solvent is (40-44): (320-400); when preparing the first polar solution, the added m-phenylene Diformyl chloride is 4/5 of the amount of m-phenylenediamine.
  • step S1 the ratio of the amount of the diamine compound to the second polar solvent in the second polar solution is (1-1.1): (16-18); when preparing the second polar solution, the added m-benzene Diformyl chloride is 4/5 of the amount of the diamine compound.
  • a further improvement of the present invention is: the general structural formula of the diamine compound is as follows:
  • the amount of the isophthaloyl chloride added in the step S2 is the amount of the first polar solution m-phenylenediamine in the step S2 and the amount of the diamine compound in the second polar solution in the step S2. 1/5 of the sum.
  • the prepared high elongation meta-aramid polymer has a viscosity of 1000-1800 Po.
  • the polar solvent involved in the above method can be selected from dimethylformamide, dimethylacetamide or N-methylpyrrolidone, but in actual production, considering that dimethylacetamide is compared with dimethylformamide, its High thermal stability, high hydrolytic stability, low corrosiveness and toxicity, the present invention preferably uses dimethylacetamide and N-methylpyrrolidone.
  • the polymer is coagulated and formed by a dimethylacetamide aqueous solution containing 2% boric acid, and then washed, drawn, dried, heat-set, oiled, and crimped. After cutting, the short fiber strength obtained by testing can reach 4.0 cN/dtex or more, elongation at break 50% or more.
  • This polymer is coagulated and formed by a dimethylacetamide aqueous solution containing 2% boric acid, and then washed with water, drawn, dried, heat-set, oiled, and crimped. After cutting, the short fiber strength obtained by testing can reach 4.0 cN/dtex or more, elongation at break 50% or more.
  • This polymer is coagulated and formed by an aqueous solution of N-methylpyrrolidone containing 2% boric acid, and then washed with water, drawn, dried, heat-set, oiled, and crimped. After cutting, the short fiber strength obtained by testing can reach 4.0 cN/dtex or more, elongation at break 50% or more.
  • This polymer is coagulated and formed by an aqueous solution of N-methylpyrrolidone containing 2% boric acid, and then washed with water, drawn, dried, heat-set, oiled, and crimped. After cutting, the short fiber strength obtained by testing can reach 4.0 cN/dtex or more, elongation at break 50% or more.
  • the high-elongation meta-aramid fiber polymer prepared by the invention is coagulated and formed by a dimethylacetamide aqueous solution containing 2% boric acid, and then washed with water, drawn, dried, heat-set, oiled, crimped, and cut to form Meta-aramid high elongation staple fiber.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne un polymère méta-aramide à allongement élevé et un procédé de préparation s'y rapportant. La formule de structure générale du polymère est la suivante : formule (I) ; dans la formule, R1 est un composé contenant une structure diphénylalcane ; et la viscosité du polymère obtenu est de 1000 à 1800 Po. Selon le polymère méta-aramide à allongement élevé selon la présente invention, la structure diphénylalcane est introduite sur la base de la polyisophtaloylméta-phénylènediamine d'origine, la structure moléculaire est optimisée, l'allongement à la rupture après la transformation du polymère en une fibre est amélioré et les propriétés intrinsèques d'origine du méta-aramide sont conservées ; le polymère a de plus grands avantages dans le domaine des applications de protection individuelle haut de gamme, a un procédé de polymérisation simple, a un coût raisonnable et permet facilement une production à grande échelle.
PCT/CN2021/112535 2020-10-27 2021-08-13 Polymère méta-aramide à allongement élevé et procédé de préparation s'y rapportant WO2022088852A1 (fr)

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CN202011175357.5 2020-10-27
CN202011175357.5A CN112341619A (zh) 2020-10-27 2020-10-27 一种高伸长间位芳纶聚合体及其制备方法

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Publication number Priority date Publication date Assignee Title
CN112341619A (zh) * 2020-10-27 2021-02-09 烟台泰和新材料股份有限公司 一种高伸长间位芳纶聚合体及其制备方法

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CN110565197A (zh) * 2019-09-20 2019-12-13 株洲时代新材料科技股份有限公司 一种杂环芳纶1313纤维的制备方法
CN112341619A (zh) * 2020-10-27 2021-02-09 烟台泰和新材料股份有限公司 一种高伸长间位芳纶聚合体及其制备方法

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Publication number Priority date Publication date Assignee Title
EP0007632A1 (fr) * 1978-07-31 1980-02-06 Teijin Limited Composition à base de polyamides aromatiques
CN103597013A (zh) * 2011-03-23 2014-02-19 阿克伦聚合物体系有限公司 用于透明柔性基材的芳族聚酰胺膜
KR20180012539A (ko) * 2016-07-27 2018-02-06 주식회사 휴비스 전자파 저감 메타아라미드 섬유 및 그의 제조방법
CN107522858A (zh) * 2017-09-07 2017-12-29 湖南化工研究院有限公司 间位芳纶树脂聚合液及其制备方法、间位芳纶树脂及间位芳纶沉析纤维
CN107814928A (zh) * 2017-11-07 2018-03-20 东华大学 一种阳离子染料易染的改性聚间苯二甲酰间苯二胺及其制备方法和应用
CN110527082A (zh) * 2019-08-30 2019-12-03 烟台泰和新材料股份有限公司 一种易染改性间位芳纶及其制备方法
CN110565197A (zh) * 2019-09-20 2019-12-13 株洲时代新材料科技股份有限公司 一种杂环芳纶1313纤维的制备方法
CN112341619A (zh) * 2020-10-27 2021-02-09 烟台泰和新材料股份有限公司 一种高伸长间位芳纶聚合体及其制备方法

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