WO2022088852A1 - High-elongation meta-aramid polymer and preparation method therefor - Google Patents
High-elongation meta-aramid polymer and preparation method therefor Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meta
- amount
- polar solution
- aramid fiber
- polar
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004760 aramid Substances 0.000 title abstract description 18
- 229920003235 aromatic polyamide Polymers 0.000 title abstract description 15
- -1 polyisophthaloyl Polymers 0.000 claims abstract description 24
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical group 0.000 claims abstract description 5
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 35
- 229920006231 aramid fiber Polymers 0.000 claims description 29
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 21
- 239000002798 polar solvent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 4
- UHNUHZHQLCGZDA-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethyl]aniline Chemical group C1=CC(N)=CC=C1CCC1=CC=C(N)C=C1 UHNUHZHQLCGZDA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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.
Landscapes
- 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
Disclosed in the present invention are a high-elongation meta-aramid polymer and a preparation method therefor. The general structural formula of the polymer is as follows: formula (I); in the formula, R1 is a compound containing a diphenylalkane structure; and the viscosity of the obtained polymer is 1000-1800 Po. According to the high-elongation meta-aramid polymer involved in the present invention, the diphenylalkane structure is introduced on the basis of original polyisophthaloyl metaphenylene diamine, the molecular structure is optimized, the elongation at break after the polymer is prepared into a fiber is improved, and the original intrinsic properties of meta-aramid are retained; the polymer has greater advantages in the field of high-end individual protection applications, has a simple polymerization process, and is reasonable in cost and easy to achieve large-scale production.
Description
本发明属于芳纶聚合体技术领域，特别涉及一种芳纶聚合体及其制备方法。The invention belongs to the technical field of aramid fibers, and particularly relates to an aramid fiber polymer and a preparation method thereof.
芳香族聚酰胺纤维根据分子结构不同分为对位型与间位型两类。对位型产品一般作为高强高模纤维应用，间位型主要用作耐高温纤维材料。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.
间位芳香族聚酰胺聚合体制备的材料具有优异的特性，使其在多个领域得到发展及应用。目前发展最成熟的是其纤维领域的应用，其制备的芳纶纤维被誉为当今世界三大高性能纤维材料之一，具有耐高温、本质阻燃、电绝缘、抗辐射、耐化学腐蚀等优良特性；广泛应用于军警安全防护服、高温环保滤材、工业安全防护服、高端电器绝缘材料、飞机及高速列车次受力件、产业用纺织品等领域，是关系国计民生的重要基础材料。Materials prepared from meta-aromatic polyamide polymers have excellent properties, which make them developed and applied in many fields. At present, the most mature development is its application in the field of fibers. The 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 livelihood.
但是目前市场上间位芳纶纤维的伸长率普遍较低，所制得的面料舒适度较差，无法满足高端市场需求。However, the elongation of meta-aramid fibers currently on the market is generally low, and the resulting fabrics have poor comfort, which cannot meet the needs of the high-end market.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种高伸长间位芳纶聚合体及其制备方法，以提高间位芳纶聚合体的伸长率，解决上述技术问题。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.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种高伸长间位芳纶聚合体，结构通式如下：A high elongation meta-aramid polymer, the general structural formula is as follows:
其中，n＞m，R
1来源于一种二苯基烷烃类化合物。
Wherein, n>m, R 1 is derived from a diphenylalkane compound.
本发明进一步的改进在于：所述R
1具体为：
A further improvement of the present invention is: the R 1 is specifically:
一种高伸长间位芳纶聚合体的制备方法，包括以下步骤：A preparation method of a high elongation meta-aramid polymer, comprising the following steps:
S1、配置第一极性溶液和第二极性溶液；S1, configure the first polar solution and the second polar solution;
所述第一极性溶液的制备方法包括：将间苯二胺溶解于第一极性溶剂，然后加入间苯二甲酰氯充分反应后获得；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;
所述第一极性溶液的制备方法包括：将二胺类化合物溶解于第一极性溶剂，然后加入间苯二甲酰氯充分反应后获得；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;
S2、将第一极性溶液和第二极性溶液按比例混合均匀，并加入间苯二甲酰氯完全反应；S2, mix the first polar solution and the second polar solution in proportion, and add isophthaloyl chloride to react completely;
S3、中和步骤S2反应产物至PH值8.0以上，得到高伸长间位芳纶聚合体。S3, neutralize the reaction product of step S2 to a pH value above 8.0 to obtain a highly elongated meta-aramid fiber polymer.
本发明进一步的改进在于：步骤S1中第一极性溶液中间苯二胺溶和第一极性溶剂的物质的量之比为(40～44)：(320～400)；制备第一极性溶液时，加入的间苯二甲酰氯为间苯二胺的物质的量的4/5。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.
本发明进一步的改进在于：步骤S1中第二极性溶液中二胺类化合物和第二极性溶剂的物质的量之比为(1～1.1)：(16～18)；制备第二极性溶液时，加入的间苯二甲酰氯为二胺类化合物的物质的量的4/5。The further improvement of the present invention is: in 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.
本发明进一步的改进在于：所述二胺类化合物的结构通式如下：A further improvement of the present invention is: the general structural formula of the diamine compound is as follows:
NH
2-R
1-NH
2。
NH2 -R1 - NH2 .
本发明进一步的改进在于：步骤S1中，具体的：将间苯二胺溶解于第一极性溶剂后降温 至20℃以下后，再加入间苯二甲酰氯充分反应；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;
步骤S1中，具体的：将二胺类化合物溶解于第二极性溶剂后降温至20℃以下后，再加入间苯二甲酰氯充分反应。In 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.
本发明进一步的改进在于：步骤S2中第一极性溶液中间苯二胺的物质的量：第二极性溶液中二胺类化合物的物质的量＝(40～44)：(1～1.1)。A further improvement of the present invention is: in step S2, the amount of m-phenylenediamine in the first polar solution: the amount of diamine compounds in the second polar solution=(40～44): (1～1.1) .
本发明进一步的改进在于：步骤S2中加入的间苯二甲酰氯的物质的量为步骤S2中第一极性溶液中间苯二胺的物质的量与步骤S2中第二极性溶液中二胺类化合物的物质的量之和的1/5。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.
本发明进一步的改进在于：步骤S1中配置第一极性溶剂和第二极性溶液时，加入间苯二甲酰氯后充分反应的时间均为1-1.5h，反应温度均为20℃以下；步骤S2中，反应的温度为40℃以下，完全反应的时间为0.6-1.2h。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.
本发明进一步的改进在于：所制备高伸长间位芳纶聚合体的粘度为1000-1800Po。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.
本发明进一步的改进在于：所制备高伸长间位芳纶聚合体经过含有2％硼酸的二甲基乙酰胺水溶液进行凝固成型，然后进行水洗、牵伸、烘干、热定型、上油、卷曲、切断，形成间位芳纶高伸长短纤维。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.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明涉及的高伸长间位芳纶聚合体，是在原有间位芳纶的基础上，通过引入二苯基烷烃类结构，对分子结构进行了改性，同时保留间位芳纶本身的特性，且增强了分子间作用力，使得使用此改性间位芳纶聚合物制成的纤维在生产过程中具备了极佳的可纺性，更好的拉伸性能，更高的断裂伸长率。1. 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.
2、本发明涉及的高伸长间位芳纶聚合体采用简单易操作的聚合方式，极佳的成本优势，易于实现工业化生产。2. 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.
为进一步说明本发明，以下为具体实施例方式，但不应看作是对本发明的限制。在实施例和对比例中诸特性，均是按以下方法测定的。In order to further illustrate the present invention, the following are specific embodiments, but should not be regarded as a limitation of the present invention. The properties in the Examples and Comparative Examples were measured by the following methods.
本发明中，聚合物粘度[Po]：采用BROOKFIELD DV-Ⅱ+Pro测试聚合物溶液的动力粘度，选用4号转子，结果最终换算成标况温度下(25℃)的粘度进行表征。In the present invention, 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.
纤维断裂强度[cN/dtex]及断裂伸长率[％]：采用奥地利兰精公司VP500、VN500测试所制得的纤维断裂强度和断裂伸长率。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.
本发明提供一种高伸长间位芳纶聚合体，结构通式如下：The present invention provides a kind of high elongation meta-aramid fiber polymer, the general structural formula is as follows:
其中，n＞m，R
1来源于一种二苯基烷烃类化合物；n:m＝(40-44)：(1-1.1)；整体分子量范围为32万-35万。所述R
1具体为：
Wherein, n>m, R 1 is derived from a diphenylalkane compound; n:m=(40-44): (1-1.1); the overall molecular weight range is 320,000-350,000. The R 1 is specifically:
本发明还提供一种高伸长间位芳纶聚合体的制备方法，包括以下步骤：The present invention also provides a preparation method of a high elongation meta-aramid fiber polymer, comprising the following steps:
S1、配置第一极性溶液和第二极性溶液；S1, configure the first polar solution and the second polar solution;
所述第一极性溶液的制备方法包括：将间苯二胺溶解于第一极性溶剂，然后加入间苯二甲酰氯充分反应后获得；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;
所述第一极性溶液的制备方法包括：将二胺类化合物溶解于第一极性溶剂，然后加入间苯二甲酰氯充分反应后获得；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;
S2、将第一极性溶液和第二极性溶液按比例混合均匀，并加入间苯二甲酰氯完全反应；S2, mix the first polar solution and the second polar solution in proportion, and add isophthaloyl chloride to react completely;
S3、中和步骤S2反应产物至PH值8.0以上，得到高伸长间位芳纶聚合体。S3, neutralize the reaction product of step S2 to a pH value above 8.0 to obtain a highly elongated meta-aramid fiber polymer.
步骤S1中第一极性溶液中间苯二胺溶和第一极性溶剂的物质的量之比为(40～44)：(320～400)；制备第一极性溶液时，加入的间苯二甲酰氯为间苯二胺的物质的量的4/5。In 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.
步骤S1中第二极性溶液中二胺类化合物和第二极性溶剂的物质的量之比为(1～1.1)：(16～18)；制备第二极性溶液时，加入的间苯二甲酰氯为二胺类化合物的物质的量的4/5。In 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.
本发明进一步的改进在于：所述二胺类化合物的结构通式如下：A further improvement of the present invention is: the general structural formula of the diamine compound is as follows:
NH
2-R
1-NH
2。
NH2 -R1 - NH2 .
步骤S2中第一极性溶液中间苯二胺的物质的量：第二极性溶液中二胺类化合物的物质的量＝(40～44)：(1～1.1)。In step S2, the amount of the meso-phenylenediamine in the first polar solution: the amount of the diamine compound in the second polar solution=(40-44): (1-1.1).
步骤S2中加入的间苯二甲酰氯的物质的量为步骤S2中第一极性溶液中间苯二胺的物质的量与步骤S2中第二极性溶液中二胺类化合物的物质的量之和的1/5。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.
所制备高伸长间位芳纶聚合体的粘度为1000-1800Po。The prepared high elongation meta-aramid polymer has a viscosity of 1000-1800 Po.
上述方法中涉及的极性溶剂可以选自二甲基甲酰胺、二甲基乙酰胺或N-甲基吡咯烷酮，但实际生产中考虑到二甲基乙酰胺与二甲基甲酰胺相比，其热稳定性、水解稳定性高、腐蚀性和毒性小，本发明优先选用二甲基乙酰胺和N-甲基吡咯烷酮。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.
实施例1Example 1
将按物质的量计的间苯二胺22份加入200份二甲基乙酰胺搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯17.6份，充分反应1h，此为溶液①。22 parts of m-phenylenediamine by the amount of substance was added to 200 parts of dimethylacetamide, stirred to dissolve, and cooled. Control the temperature below 20°C, add 17.6 parts of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride of 1:1, and fully react for 1 hour, this is solution ①.
将按物质的量计的4,4-二氨基二苯甲烷0.55份加入9份二甲基乙酰胺搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯0.44份，充分反应1h，此为溶液②。0.55 part of 4,4-diaminodiphenylmethane by the amount of substance was added to 9 parts of dimethylacetamide, stirred to dissolve, and cooled. Control the temperature below 20°C, add 0.44 part of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride of 1:1, and fully react for 1 hour, this is solution ②.
将上述①和②混合均匀，得到间苯二胺与4,4-二氨基二苯甲烷比例为40:1的溶液，控制温度在40℃以下加入间苯二甲酰氯4.51份，反应1.0h。反应完成后，加入丙胺进行中和，最终得到粘度为1725Po(25℃)的高伸长间位芳纶聚合体。Mix the above ① and ② evenly to obtain a solution with a ratio of m-phenylenediamine to 4,4-diaminodiphenylmethane of 40:1, control the temperature below 40°C, add 4.51 parts of isophthaloyl chloride, and react for 1.0 h. After the reaction is completed, propylamine is added for neutralization, and finally a high elongation meta-aramid polymer with a viscosity of 1725Po (25°C) is obtained.
将此聚合体经过含有2％硼酸的二甲基乙酰胺水溶液进行凝固成型，然后进行水洗、牵伸、烘干、热定型、上油、卷曲切断后，测试所得到的短纤维强度可达到4.0cN/dtex以上，断裂伸长率50％以上。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.
实施例2Example 2
将按物质的量计的间苯二胺20份加入180份二甲基乙酰胺搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯16份，充分反应1h，此为溶液①。Add 20 parts of m-phenylenediamine by the amount of substance to 180 parts of dimethylacetamide, stir and dissolve, and cool down. Control the temperature below 20°C, add 16 parts of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride of 1:1, and fully react for 1 hour, this is solution ①.
将按物质的量计的4,4'-二氨基联苄0.5份加入9份二甲基乙酰胺搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯0.4份，充分反应1h，此为溶液②。0.5 part of 4,4'-diaminobibenzyl based on the amount of substance was added to 9 parts of dimethylacetamide, stirred and dissolved, and the temperature was lowered. Control the temperature below 20°C, add 0.4 part of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride of 1:1, and fully react for 1 hour, this is solution ②.
将上述①和②混合均匀，得到间苯二胺与4,4'-二氨基联苄比例为40:1的溶液，控制温度在40℃以下加入间苯二甲酰氯4.1份，反应1.0h。反应完成后，加入丙胺进行中和，最终得到粘度为1610Po(25℃)的高伸长间位芳纶聚合体。Mix the above ① and ② evenly to obtain a solution with a ratio of m-phenylenediamine to 4,4'-diaminobibenzyl of 40:1, control the temperature below 40°C, add 4.1 parts of isophthaloyl chloride, and react for 1.0 h. After the reaction is completed, propylamine is added for neutralization, and finally a high elongation meta-aramid polymer with a viscosity of 1610 Po (25° C.) is obtained.
将此聚合体经过含有2％硼酸的二甲基乙酰胺水溶液进行凝固成型，然后进行水洗、牵伸、烘干、热定型、上油、卷曲切断后，测试所得到的短纤维强度可达到4.0cN/dtex以上，断裂伸长率50％以上。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.
实施例3Example 3
将按物质的量计的间苯二胺40份加入350份N-甲基吡咯烷酮搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯32份，充分反应1.5h， 此为溶液①。40 parts of m-phenylenediamine by the amount of substance was added to 350 parts of N-methylpyrrolidone, stirred to dissolve, and cooled. Control the temperature below 20°C, add 32 parts of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride 1:1, fully react for 1.5h, this is solution ①.
将按物质的量计的4,4-二氨基二苯甲烷1份加入16份N-甲基吡咯烷酮搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯0.8份，充分反应1.5h，此为溶液②。1 part of 4,4-diaminodiphenylmethane based on the amount of substance was added to 16 parts of N-methylpyrrolidone, stirred and dissolved, and the temperature was lowered. Control the temperature below 20°C, add 0.8 part of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride 1:1, and fully react for 1.5h, this is solution ②.
将上述①和②混合均匀，得到间苯二胺与4,4-二氨基二苯甲烷比例为40:1的溶液，控制温度在40℃以下加入间苯二甲酰氯8.2份，反应1.0h。反应完成后，加入丙胺进行中和，最终得到粘度为1582Po(25℃)的高伸长间位芳纶聚合体。Mix the above ① and ② evenly to obtain a solution with a ratio of m-phenylenediamine to 4,4-diaminodiphenylmethane of 40:1, control the temperature below 40°C, add 8.2 parts of isophthaloyl chloride, and react for 1.0 h. After the reaction is completed, propylamine is added for neutralization, and finally a highly elongated meta-aramid polymer with a viscosity of 1582 Po (25° C.) is obtained.
将此聚合体经过含有2％硼酸的N-甲基吡咯烷酮水溶液进行凝固成型，然后进行水洗、牵伸、烘干、热定型、上油、卷曲切断后，测试所得到的短纤维强度可达到4.0cN/dtex以上，断裂伸长率50％以上。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.
实施例4Example 4
将按物质的量计的间苯二胺20份加入160份N-甲基吡咯烷酮搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯16份，充分反应1h，此为溶液①。Add 20 parts of m-phenylenediamine by the amount of substance to 160 parts of N-methylpyrrolidone, stir and dissolve, and cool down. Control the temperature below 20°C, add 16 parts of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride of 1:1, and fully react for 1 hour, this is solution ①.
将按物质的量计的4,4'-二氨基联苄0.5份加入8份N-甲基吡咯烷酮搅拌溶解，降温。控制温度在20℃以下，按照二胺和酰氯1:1的反应比例向其中加入间苯二甲酰氯0.4份，充分反应1h，此为溶液②。0.5 part of 4,4'-diaminobibenzyl based on the amount of substance was added to 8 parts of N-methylpyrrolidone, stirred and dissolved, and the temperature was lowered. Control the temperature below 20°C, add 0.4 part of isophthaloyl chloride to it according to the reaction ratio of diamine and acid chloride of 1:1, and fully react for 1 hour, this is solution ②.
将上述①和②混合均匀，得到间苯二胺与4,4'-二氨基联苄比例为40:1的溶液，控制温度在40℃以下加入间苯二甲酰氯4.1份，反应1.0h。反应完成后，加入丙胺进行中和，最终得到粘度为1490Po(25℃)的高伸长间位芳纶聚合体。Mix the above ① and ② evenly to obtain a solution with a ratio of m-phenylenediamine to 4,4'-diaminobibenzyl of 40:1, control the temperature below 40°C, add 4.1 parts of isophthaloyl chloride, and react for 1.0 h. After the reaction is completed, propylamine is added for neutralization, and finally a highly elongated meta-aramid polymer with a viscosity of 1490 Po (25° C.) is obtained.
将此聚合体经过含有2％硼酸的N-甲基吡咯烷酮水溶液进行凝固成型，然后进行水洗、牵伸、烘干、热定型、上油、卷曲切断后，测试所得到的短纤维强度可达到4.0cN/dtex以上，断 裂伸长率50％以上。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.
本发明所制备高伸长间位芳纶聚合体经过含有2％硼酸的二甲基乙酰胺水溶液进行凝固成型，然后进行水洗、牵伸、烘干、热定型、上油、卷曲、切断，形成间位芳纶高伸长短纤维。抽样进行检测，样本长度：51mm；隔距长度：20mm；测试速度：20mm/min；张力：150mg；其性能参数如表1所示：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. Sampling for testing, sample length: 51mm; gauge length: 20mm; test speed: 20mm/min; tension: 150mg; its performance parameters are shown in Table 1:
表1短纤维性能测试表Table 1 Short fiber performance test table
以上所述实施例仅仅是本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案作出的各种变形和改进，均应落入本发明的权利要求书确定的保护范围内。The above-mentioned embodiments are only preferred embodiments of the present invention to describe, but do not limit the scope of the present invention. On the premise of not departing from the design spirit of the present invention, various modifications made by those of ordinary skill in the art to the technical solutions of the present invention and improvements, all should fall within the protection scope determined by the claims of the present invention.
Claims (10)
- 一种高伸长间位芳纶聚合体，其特征在于，结构通式如下：A kind of high elongation meta-aramid fiber polymer is characterized in that, the general structural formula is as follows:
其中，n＞m，R 1来源于一种二苯基烷烃类化合物。 Wherein, n>m, R 1 is derived from a diphenylalkane compound. - 根据权利要求1所述的一种高伸长间位芳纶聚合体，其特征在于，所述R 1具体为： A kind of high elongation meta-aramid fiber polymer according to claim 1, is characterized in that, described R 1 is specifically:且氨基分别位于两个苯环上的以烷基碳为中心的对称位置。
And the amino groups are located in the symmetrical positions centered on the alkyl carbon on the two benzene rings, respectively. - 一种高伸长间位芳纶聚合体的制备方法，其特征在于，包括以下步骤：A kind of preparation method of high elongation meta-aramid fiber polymer is characterized in that, comprises the following steps:S1、配置第一极性溶液和第二极性溶液；S1, configure the first polar solution and the second polar solution;所述第一极性溶液的制备方法包括：将间苯二胺溶解于第一极性溶剂，然后加入间苯二甲酰氯充分反应后获得；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;所述第二极性溶液的制备方法包括：将二胺类化合物溶解于第一极性溶剂，然后加入间苯二甲酰氯充分反应后获得；The preparation method of the second polar solution comprises: dissolving the diamine compound in the first polar solvent, and then adding isophthaloyl chloride to fully react to obtain it;S2、将第一极性溶液和第二极性溶液按比例混合均匀，并加入间苯二甲酰氯完全反应；S2, mix the first polar solution and the second polar solution in proportion, and add isophthaloyl chloride to react completely;S3、中和步骤S2反应产物至PH值8.0以上，得到高伸长间位芳纶聚合体。S3, neutralize the reaction product of step S2 to a pH value above 8.0 to obtain a highly elongated meta-aramid fiber polymer.
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，步骤S1中第一极性溶液中间苯二胺溶和第一极性溶剂的物质的量之比为(40～44)：(320～400)；制备第一极性溶液时，加入的间苯二甲酰氯为间苯二胺的物质的量的4/5。The method for preparing a high elongation meta-aramid fiber polymer according to claim 3, wherein in step S1, the amount of the first polar solution meta-phenylenediamine dissolved and the amount of the first polar solvent is equal to The ratio is (40-44): (320-400); when preparing the first polar solution, the added isophthaloyl chloride is 4/5 of the amount of m-phenylenediamine.
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，步骤S1中第二极性溶液中二胺类化合物和第二极性溶剂的物质的量之比为(1～1.1)：(16～18)；制备第二极性溶液时，加入的间苯二甲酰氯为二胺类化合物的物质的量的4/5。The method for preparing a high-elongation meta-aramid fiber polymer according to claim 3, wherein in step S1, the amount of the diamine compound and the amount of the second polar solvent in the second polar solution is the same The ratio is (1-1.1): (16-18); when preparing the second polar solution, the added isophthaloyl chloride is 4/5 of the amount of the diamine compound.
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，所述二胺类化合物的结构通式如下：The preparation method of a kind of high elongation meta-aramid fiber polymer according to claim 3, is characterized in that, the general structural formula of described diamine compound is as follows:NH 2-R 1-NH 2。 NH2 -R1 - NH2 .
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，步骤S1中，具体的：将间苯二胺溶解于第一极性溶剂后降温至20℃以下后，再加入间苯二甲酰氯充分反应；The method for preparing a high elongation meta-aramid fiber polymer according to claim 3, wherein in step S1, specifically: dissolving m-phenylenediamine in the first polar solvent and then cooling to 20°C After the following, add isophthaloyl chloride to fully react;步骤S1中，具体的：将二胺类化合物溶解于第二极性溶剂后降温至20℃以下后，再加入间苯二甲酰氯充分反应。In 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.
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，步骤S2中第一极性溶液中间苯二胺的物质的量：第二极性溶液中二胺类化合物的物质的量＝(40～44)：(1～1.1)。The method for preparing a high elongation meta-aramid fiber polymer according to claim 3, wherein in step S2, the amount of m-phenylenediamine in the first polar solution: two in the second polar solution: Amount of substance of amine compound=(40-44):(1-1.1).
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，步骤S2中加入的间苯二甲酰氯的物质的量为步骤S2中第一极性溶液中间苯二胺的物质的量与步骤S2中第二极性溶液中二胺类化合物的物质的量之和的1/5。The method for preparing a high-elongation meta-aramid fiber polymer according to claim 3, wherein the amount of isophthaloyl chloride added in step S2 is the middle of the first polar solution in step S2 1/5 of the sum of the amount of phenylenediamine and the amount of diamine compounds in the second polar solution in step S2.
- 根据权利要求3所述的一种高伸长间位芳纶聚合体的制备方法，其特征在于，步骤S1中配置第一极性溶剂和第二极性溶液时，加入间苯二甲酰氯后充分反应的时间均为1-1.5h，反应温度均为20℃以下；The method for preparing a high elongation meta-aramid fiber polymer according to claim 3, characterized in that, when configuring the first polar solvent and the second polar solution in step S1, after adding isophthaloyl chloride The sufficient reaction time is 1-1.5h, and the reaction temperature is below 20°C;步骤S2中，反应的温度为40℃以下，完全反应的时间为0.6-1.2h。In step S2, the reaction temperature is below 40°C, and the complete reaction time is 0.6-1.2 h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011175357.5A CN112341619A (en) | 2020-10-27 | 2020-10-27 | High-elongation meta-aramid polymer and preparation method thereof |
| CN202011175357.5 | 2020-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022088852A1 true WO2022088852A1 (en) | 2022-05-05 |
Family
ID=74355654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/112535 WO2022088852A1 (en) | 2020-10-27 | 2021-08-13 | High-elongation meta-aramid polymer and preparation method therefor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112341619A (en) |
| WO (1) | WO2022088852A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341619A (en) * | 2020-10-27 | 2021-02-09 | 烟台泰和新材料股份有限公司 | High-elongation meta-aramid polymer and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0007632A1 (en) * | 1978-07-31 | 1980-02-06 | Teijin Limited | Aromatic polyamide composition |
| CN103597013A (en) * | 2011-03-23 | 2014-02-19 | 阿克伦聚合物体系有限公司 | Aromatic polyamide films for transparent flexible substrates |
| CN107522858A (en) * | 2017-09-07 | 2017-12-29 | 湖南化工研究院有限公司 | Meta-aramid resin polymerization liquid and preparation method thereof, meta-aramid resin and meta-aramid fibre fibrid |
| KR20180012539A (en) * | 2016-07-27 | 2018-02-06 | 주식회사 휴비스 | Meta-Aramid Fiber for reducing Electromagnetic wave and Method for Preparing the Same |
| CN107814928A (en) * | 2017-11-07 | 2018-03-20 | 东华大学 | A kind of modification poly of cation dye chromophil and its preparation method and application |
| CN110527082A (en) * | 2019-08-30 | 2019-12-03 | 烟台泰和新材料股份有限公司 | It is a kind of easily to contaminate modified meta-aramid and preparation method thereof |
| CN110565197A (en) * | 2019-09-20 | 2019-12-13 | 株洲时代新材料科技股份有限公司 | Preparation method of heterocyclic aramid 1313 fiber |
| CN112341619A (en) * | 2020-10-27 | 2021-02-09 | 烟台泰和新材料股份有限公司 | High-elongation meta-aramid polymer and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835212B2 (en) * | 1974-10-03 | 1983-08-01 | 帝人株式会社 | Polyamide clay block |
| JPS62177021A (en) * | 1986-01-29 | 1987-08-03 | Toray Ind Inc | Aromatic polyamide copolymer |
| US5621067A (en) * | 1995-03-30 | 1997-04-15 | Industrial Technology Research Institute | Wholly aromatic polyamides with improved flame resistance |
| JP2771469B2 (en) * | 1995-03-30 | 1998-07-02 | 財団法人工業技術研究院 | Wholly aromatic polyamides with improved flame resistance |
| JP2007154355A (en) * | 2005-12-05 | 2007-06-21 | Teijin Techno Products Ltd | Meta-aromatic polyamide fiber and method for producing the same |
| CN110592707A (en) * | 2019-09-20 | 2019-12-20 | 株洲时代新材料科技股份有限公司 | Preparation method of copolymerization modified aramid 1313 fiber |
-
2020
- 2020-10-27 CN CN202011175357.5A patent/CN112341619A/en not_active Withdrawn
-
2021
- 2021-08-13 WO PCT/CN2021/112535 patent/WO2022088852A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0007632A1 (en) * | 1978-07-31 | 1980-02-06 | Teijin Limited | Aromatic polyamide composition |
| CN103597013A (en) * | 2011-03-23 | 2014-02-19 | 阿克伦聚合物体系有限公司 | Aromatic polyamide films for transparent flexible substrates |
| KR20180012539A (en) * | 2016-07-27 | 2018-02-06 | 주식회사 휴비스 | Meta-Aramid Fiber for reducing Electromagnetic wave and Method for Preparing the Same |
| CN107522858A (en) * | 2017-09-07 | 2017-12-29 | 湖南化工研究院有限公司 | Meta-aramid resin polymerization liquid and preparation method thereof, meta-aramid resin and meta-aramid fibre fibrid |
| CN107814928A (en) * | 2017-11-07 | 2018-03-20 | 东华大学 | A kind of modification poly of cation dye chromophil and its preparation method and application |
| CN110527082A (en) * | 2019-08-30 | 2019-12-03 | 烟台泰和新材料股份有限公司 | It is a kind of easily to contaminate modified meta-aramid and preparation method thereof |
| CN110565197A (en) * | 2019-09-20 | 2019-12-13 | 株洲时代新材料科技股份有限公司 | Preparation method of heterocyclic aramid 1313 fiber |
| CN112341619A (en) * | 2020-10-27 | 2021-02-09 | 烟台泰和新材料股份有限公司 | High-elongation meta-aramid polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112341619A (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020182111A1 (en) | Molybdenum disulfide hybrid flame retardant coated with phosphorus-nitrogen-zinc two-dimensional supramolecule and application thereof | |
| CN101735455B (en) | Method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof | |
| CN109930230A (en) | A kind of copolyamide industrial yarn and preparation method thereof | |
| CN112878036B (en) | Kevlar-based deprotonation method for preparing aramid nanofibers and nanofibers prepared by using method | |
| WO2016127833A1 (en) | Acetic nitrile fibre and preparation method therefor | |
| CN108559077B (en) | Heterocyclic aramid solution and preparation method thereof, preparation method of heterocyclic aramid finished yarn and heterocyclic aramid product | |
| CN109208103B (en) | Preparation method of flame-retardant cellulose fiber | |
| CN109183170B (en) | Preparation method of cellulose graphene composite short fiber | |
| CN109267164B (en) | Preparation method of cellulose graphene composite filament | |
| WO2022088852A1 (en) | High-elongation meta-aramid polymer and preparation method therefor | |
| CN109208104B (en) | Preparation method of conductive cellulose fiber | |
| CN106835332A (en) | Compound para-aramid fiber of high performance Graphene and preparation method thereof, application | |
| CN102383217B (en) | Polyimide fiber and preparation method thereof | |
| CN112500561B (en) | High-strength meta-aramid polymer and preparation method thereof | |
| CN105463621B (en) | Organic modification nano imvite strengthens the preparation method of polyimide fiber | |
| CN102677225B (en) | Aromatic polyamide/aromatic polyimide blended fiber and preparation method thereof | |
| CN114437366A (en) | Intumescent flame retardant, preparation method and application thereof, flame-retardant polyacrylonitrile fiber and preparation method thereof | |
| CN110804767B (en) | Aramid 1313 fiber and preparation method and application thereof | |
| CN112251825B (en) | Preparation method of polyamide-imide copolymer fiber | |
| CN105696103B (en) | Carpet silk fire-retardant fiber of ultraviolet resistant nylon 6 of copoly type and preparation method thereof | |
| CN105986474A (en) | High temperature-resistant flame retardation polyacrylonitrile fiber and production method thereof | |
| CN114736371B (en) | Polyimide film with high heat conductivity and preparation method thereof | |
| CN106087243A (en) | Filter felt that a kind of polyimides and polysulfonamides are blended and preparation method thereof | |
| CN114016187A (en) | Flame-retardant and arc-proof composite fabric and preparation method and application thereof | |
| CN114182388A (en) | Multifunctional high-crimp viscose fiber and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21884584 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21884584 Country of ref document: EP Kind code of ref document: A1 |