WO2020215501A1 - 一种具有阻燃功能的聚氨酯弹性纤维及其制备方法 - Google Patents

一种具有阻燃功能的聚氨酯弹性纤维及其制备方法 Download PDF

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WO2020215501A1
WO2020215501A1 PCT/CN2019/096374 CN2019096374W WO2020215501A1 WO 2020215501 A1 WO2020215501 A1 WO 2020215501A1 CN 2019096374 W CN2019096374 W CN 2019096374W WO 2020215501 A1 WO2020215501 A1 WO 2020215501A1
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flame
retardant
elastic fiber
polyurethane elastic
polyurethane
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PCT/CN2019/096374
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English (en)
French (fr)
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陈永军
马千里
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烟台泰和新材料股份有限公司
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Publication of WO2020215501A1 publication Critical patent/WO2020215501A1/zh
Priority to US17/504,514 priority Critical patent/US20220033997A1/en

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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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/5081—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
    • C08G18/5084—Phosphate compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes

Definitions

  • the invention relates to a preparation method of polyurethane elastic fiber, in particular to a polyurethane elastic fiber with flame retardant function and a preparation method thereof.
  • Polyurethane elastic fiber (commonly known as spandex) is a kind of textile fiber with high elasticity, which is widely used in knitted and woven elastic fabrics.
  • Spandex can usually be combined with nylon, nylon, cotton, linen and other fibers to make fabrics, giving the fabrics close-fitting shaping, free expansion and contraction, and no pressure, and can significantly improve the shape retention, drape and wrinkle resistance of clothing. It is applied in various textile and apparel fields, and is popularized and applied in the industrial textile fields such as automobile interior decoration.
  • Textiles are widely used, but because they are usually composed of flammable and combustible natural or synthetic fibers, they often become the first fire objects of fire.
  • the United States, Britain, Japan, Germany and other countries have introduced relevant laws and regulations on the flame retardancy of textile fibers, which are for the production of clothing for children, the elderly, and the disabled, indoor decoration fabrics, theater curtains, and transportation vehicles.
  • the textile materials used in the hotel and the uniforms of steel workers and soldiers have all put forward flame-retardant requirements.
  • flame-retardant fibers such as flame-retardant cotton, flame-retardant viscose, and flame-retardant polyester has been achieved through flame-retardant finishing or addition of flame-retardant agents; in addition, flame-retardant fibers such as aramid and poly Fibers such as imide and polyphenylene sulfide have also been mass-produced and used.
  • Spandex is an indispensable "MSG-like" textile material in the modern textile and garment industry, and there are few reports on its flame-retardant fiber.
  • Patent application CN 201511003945.X introduces a method for preparing flame-retardant polyurethane fibers by blending.
  • the polyurethane polymer is mixed with phenyl phosphate flame retardants and non-metal oxide synergistic flame retardants, and then spun into fibers.
  • the flame retardant is added by blending. When the addition amount is too small, the flame retardancy will not meet the requirements; when the addition amount is too large, the spinnability of the polymer and the mechanical properties of the fiber will be affected.
  • Patent application CN201310547567.6 introduces a method for preparing flame-retardant polyurethane fibers by copolymerization. Phosphorus-containing flame retardants and chain extenders are used to react with prepolymer to form copolymer flame-retardant polyurethane, and melamine flame retardants are added.
  • the blending of aluminum oxide flame retardant, etc. has a flame retardant effect. Since the hydroxyl group in the hydroxyl-containing phosphorus flame retardant is less reactive than the amino group, it is difficult to form an effective chemical bond when chain extension with amine. Therefore, the chemically introduced phosphorus content is limited, which limits the actual flame retardant effect, and other flame retardants need to be blended.
  • the present invention provides a polyurethane elastic fiber with flame-retardant function and a preparation method thereof to overcome the shortcomings of the prior art.
  • the polyurethane elastic fiber prepared by the invention has excellent flame-retardant properties while maintaining good stretchability of the polyurethane fiber. Long performance.
  • the present invention adopts the following technical solutions:
  • a preparation method of polyurethane elastic fiber with flame retardant function includes the following steps:
  • a polyol containing flame retardant elements is reacted with excess 4,4'-diphenylmethane diisocyanate to prepare an isocyanate-terminated prepolymer, and the prepolymer is dissolved in an organic solvent to form a prepolymer Body solution
  • the polypolyol containing flame-retardant elements in step (1) is a polyether diol containing phosphorus element or a polyester diol containing phosphorus element.
  • the polyether polyol containing phosphorus element contains a -PO- or -PC- structure, and the phosphorus content is 0.5 wt% to 5 wt%; the polyester polyol containing phosphorus element contains phosphate ester Structure, and the phosphorus content is 0.5wt%-10wt%, the acid value is below 3.0.
  • the phosphorus content in the polyether polyol containing phosphorus is 1% to 3% by weight; the phosphorus content in the polyester polyol containing phosphorus is 1% to 6% by weight, and the acid value is less than 2.0.
  • step (1) the molar ratio of 4,4'-diphenylmethane diisocyanate to the polypolyol containing flame retardant elements is (1.5:1) to (2.5:1).
  • the organic solvent in step (1) is one or a mixture of N,N-dimethylformamide and N,N-dimethylacetamide.
  • step (2) the molar ratio of the amino functional group in the diamine or the mixed amine of the diamine and the monoamine to the isocyanate at the end of the prepolymer is (1.00:1) to (1.05:1).
  • the diamine in step (2) is one or more of ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and 2-methyl-1,5-pentanediamine
  • One or more of dimethylamine, diethylamine, and methylethylamine are mixed in any ratio.
  • the molar ratio of the monoamine to the diamine is (0.02:1) to (0.15:1).
  • a polyurethane elastic fiber with flame-retardant function is prepared by the above-mentioned preparation method of a polyurethane elastic fiber with flame-retardant function, and the limiting oxygen index of the polyurethane elastic fiber is 25%-32%.
  • the present invention has the following beneficial technical effects:
  • the invention uses phosphorus-containing polypolyols as raw materials to introduce flame-retardant elements into the polyurethane molecules through reaction, which is intrinsically flame-retardant; during use, the flame-retardant function will not decrease due to the migration and precipitation of the flame-retardant ,
  • the flame-retardant effect is long-lasting; phosphorus element has excellent flame-retardant performance, and does not release hydrogen halide gas during combustion, which belongs to a class of environmentally friendly flame-retardant elements; the phosphorus element is added in a low amount and is evenly distributed in the molecule, which affects the flexibility of the molecular chain Small, the prepared fiber has good elongation properties.
  • the polyurethane elastic fiber prepared by the invention has excellent flame-retardant performance, the limiting oxygen index is between 25-32%, while maintaining the good elongation performance of the polyurethane fiber, and the elongation at break is between 360-600%. Therefore, the elastic fiber prepared by the present invention can be used with flame-retardant cotton, flame-retardant viscose, aramid and other flame-retardant fibers to make flame-retardant yarns, fabrics, etc., which can be applied to children's clothing, mattress fabrics, curtains , Vehicle interiors, protective tooling, fire-fighting clothing and other flame-retardant protective products.
  • a preparation method of polyurethane elastic fiber with flame retardant function includes the following steps:
  • a polypolyol with a molecular weight of 1000-3000 containing flame retardant elements is reacted with excess 4,4'-diphenylmethane diisocyanate (abbreviated as MDI) to prepare a prepolymer with isocyanate-terminated
  • MDI 4,4'-diphenylmethane diisocyanate
  • the polymer is dissolved in an organic solvent to form a pre-polymer solution with a certain concentration;
  • the polyol containing flame retardant elements refers to the polyether diol or polyester diol containing phosphorus
  • the polyether polyol containing phosphorus contains -PO- or -PC- structure, which contains phosphorus.
  • the mass percentage is 0.5-5%, preferably 1-3%; the phosphorus-containing polyester polyol contains a phosphate structure, and the phosphorus-containing mass percentage is 0.5-10%, preferably 1-6%, and the acid value is below 3.0 , Preferably below 2.0; organic solvent is one or more of N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc); MDI and polyols containing flame retardant elements The ratio of moles is between 1.5:1 and 2.5:1;
  • the ratio of the total moles of amino functional groups in the diamine or mixed amine to the moles of isocyanate at the end of the prepolymer is between 1.00:1 and 1.05:1;
  • the diamine is ethylenediamine, 1 , One or more of 2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine (MPDA), which are reactive chain extenders;
  • monoamine is dimethylamine
  • diethylamine and methylethylamine are molecular weight regulators to control the reaction viscosity;
  • the molar ratio of the monoamine to the diamine is between 0.02:1 and 0.15:1;
  • Solution preparation Dilute the prepared polyurethane solution with a solvent to a polymer solution with a solid content of 10-15%; or the prepared fiber is washed to remove the surface oil, dried, dissolved and then formulated into a polymer Solution.
  • Test Use oxygen index to test its limiting oxygen index.
  • a constant-speed elongation type strength machine is used to test the elongation of the spandex when it breaks at a tensile speed of 500 mm/min.
  • the vacuum degree is -0.1 Atm
  • the residual monomers and volatile components in the crude product are removed, neutralized by adding phosphoric acid, absorbed by diatomaceous earth, filtered, and finally reacted to obtain a viscous transparent liquid product.
  • the hydroxyl value is 181mg/gKOH
  • the acid value is 0.2mg/gKOH
  • the number average molecular weight is 620; calculated according to the feed amount and product quality, the product contains 5wt% phosphorus.
  • the temperature of the above-mentioned prepolymer solution was lowered to 10° C., and a DMAc solution of a mixed amine of 1,2-propylene diamine and diethylamine was added for chain extension to obtain a polyurethane solution.
  • the molar ratio of diethylamine:(1,2-propylenediamine) is 0.15:1
  • the molar ratio (NHx:NCO) of the amino functional group in the mixed amine to the isocyanate functional group in the prepolymer is 1.05:1.
  • polyether diols containing 3%, 2%, 1%, and 0.5% phosphorus were prepared.
  • diethylene glycol it is necessary to add diethylene glycol to adjust the molecular weight when adding potassium hydroxide. See Table 1 for specific feeding amount and performance indicators.
  • the molar ratio of MDI to polyether glycol, the type and amount of chain extender are adjusted according to Table 2 .
  • the polyurethane solution is prepared, and then cured, defoamed, filtered, and then spun to obtain 40D or 560D polyurethane fibers.
  • the reaction product Relieve the pressure with nitrogen and lower the temperature.
  • the temperature drops to 80°C
  • the reaction product is taken out to obtain the phosphorus-containing polyester polyol.
  • the hydroxyl value is 36mg/gKOH
  • the acid value is 1.7mg/gKOH
  • the number average molecular weight is 3000. Calculated according to the feeding amount and product quality, the product contains 10wt% phosphorus.
  • 560D polyurethane fiber was prepared according to the preparation method of polyurethane fiber in Example 1.
  • the solvent is replaced by a mixed solvent of 80 wt% DMF and 20 wt% DMAc from DMAc
  • the yellow inhibitor is replaced by HN-150
  • the antioxidant is replaced by antioxidant 245.
  • polyester diol preparation method in Example 6 the polyester diols containing 6%, 3%, 1%, and 0.5% phosphorus were prepared. Among them, the solvent is replaced by a mixed solvent with pure DMF. See Table 3 for specific feeding amount and performance indicators.
  • polyester diols in the above Examples 7-10 as raw materials, according to the preparation method of the polyurethane fiber in Example 6, the molar ratio of MDI to polyether diol, the type and amount of chain extender were adjusted according to Table 4.
  • the polyurethane solution is prepared, then cured, defoamed, filtered, and then spun to obtain 40D or 560D polyurethane fibers.
  • Example 4 The flame-retardant polyether diol in Example 4 was replaced with polytetrahydrofuran diol (PTMG), and a polyurethane solution was prepared according to the method of Example 4 and spun into a 40D polyurethane fiber.
  • PTMG polytetrahydrofuran diol

Abstract

本发明公开了一种具有阻燃功能的聚氨酯弹性纤维及其制备方法，所述聚氨酯弹性纤维以含有磷元素的聚醚二元醇或聚酯二元醇为原料，与4，4'-二苯甲基烷二异氰酸酯反应制成预聚物，并用有机胺扩链，得到聚氨酯溶液，由该聚合物溶液进行干法纺丝，制备聚氨酯纤维，制备得到的聚氨酯纤维的极限氧指数在25-32％之间。

Description

一种具有阻燃功能的聚氨酯弹性纤维及其制备方法 技术领域
本发明涉及一种聚氨酯弹性纤维的制备方法，具体涉及一种具有阻燃功能的聚氨酯弹性纤维及其制备方法。
背景技术
聚氨酯弹性纤维(俗称氨纶)是一种具有高弹性的纺织纤维，广泛用于针织和机织的弹力织物中。氨纶通常可与尼龙、锦纶、棉、麻等纤维制成织物，赋予织物贴身塑型，伸缩自如，无压迫感的特性，并能显著提高服装的保形性、悬垂性和抗褶皱性，广泛应用于各种纺织服装领域，并在汽车内饰等产业用纺织品领域得到推广应用。
纺织品应用广泛，但由于其通常由易燃、可燃的天然或合成纤维构成，常常成为火灾的最初着火物。为减少火灾发生，美、英、日、德等国对纺织纤维的阻燃性出台了相关法律规定，对制作儿童、老人、残疾人的服饰、室内铺饰用布、剧院幕布以及交通运输工具和旅馆内使用的纺织材料、炼钢工人及士兵制服等均提出了阻燃要求。
目前，通过阻燃整理或添加阻燃剂等方式，已实现阻燃棉、阻燃粘胶、阻燃涤纶等阻燃纤维的生产；另外，具有耐高温、本质阻燃纤维如芳纶、聚酰亚胺、聚苯硫醚等纤维也实现量产并得到应用。氨纶作为现代纺织服装工业必不可少的“类味精型”纺织原料，其阻燃型纤维的相关报道文献较少。专利申请CN 201511003945.X中介绍了共混法制备阻燃聚氨酯纤维的方法，在聚氨酯聚合物中混入苯基磷酸酯类阻燃剂、非金属氧化物协同阻燃剂，然后纺成纤维。通过共混方式加入阻燃剂，添加量过少时，阻燃性达不到要求；添加量过多时，聚合物可纺性以及纤维力学性能又会受到影响。专利申请CN201310547567.6中介绍了共聚法制备阻燃聚氨酯纤维的方法，采用含羟基的磷系阻燃剂、扩链剂一起与预聚体反应形成共聚阻燃聚氨酯，并添加三聚氰 胺类阻燃剂、三氧化二铝阻燃剂等共混起到阻燃效果。由于含羟基磷系阻燃剂中羟基比氨基反应活性弱，与胺一起扩链时，很难形成有效的化学结合。因此，化学方式引入的磷含量有限，限制了实际的阻燃效果，还需要共混其他阻燃剂。
发明内容
本发明提供一种具有阻燃功能的聚氨酯弹性纤维及其制备方法，以克服现有技术的不足，本发明制备得到的聚氨酯弹性纤维，具有优异的阻燃性能，同时保持了聚氨酯纤维良好的伸长性能。
为达到上述目的，本发明采用如下技术方案：
一种具有阻燃功能的聚氨酯弹性纤维的制备方法，包括以下步骤：
(1)采用含有阻燃元素的聚多元醇与过量的4，4’-二苯基甲烷二异氰酸酯反应制备成具有异氰酸酯封端的预聚体，将预聚体溶解在有机溶剂中，形成预聚体溶液；
(2)将二元胺或二元胺与一元胺的混合胺加入到预聚体溶液中进行扩链反应，得到聚氨酯溶液；
(3)将聚氨酯溶液与防黄剂、抗氧剂混合，再经过熟化、过滤、脱泡工序后，进行干法纺丝，得到具有阻燃功能的聚氨酯弹性纤维。
进一步地，步骤(1)中含有阻燃元素的聚多元醇为含有磷元素的聚醚二元醇或含有磷元素的聚酯二元醇。
进一步地，所述含有磷元素的聚醚多元醇中含有-P-O-或-P-C-结构，且含磷量为0.5wt％-5wt％；所述含有磷元素的聚酯多元醇中含有磷酸酯结构，且含磷量为0.5wt％-10wt％，酸值3.0以下。
进一步地，所述含有磷元素的聚醚多元醇中含磷量为1wt％-3wt％；所述含有磷元素的聚酯多元醇中含磷量为1wt％-6wt％，酸值2.0以下。
进一步地，步骤(1)中4，4’-二苯基甲烷二异氰酸酯与含有阻燃元素的 聚多元醇的摩尔比为(1.5：1)～(2.5：1)。
进一步地，步骤(1)中所述有机溶剂为N,N-二甲基甲酰胺和N,N-二甲基乙酰胺的一种或两种的混合。
进一步地，步骤(2)二元胺或二元胺与一元胺的混合胺中氨基官能团与预聚体端部的异腈酸酯的摩尔比为(1.00：1)～(1.05：1)。
进一步地，步骤(2)中二元胺为乙二胺、1，2-丙二胺、1，3-丙二胺、2-甲基-1，5-戊二胺中的一种或多种任意比例的混合；一元胺为二甲胺、二乙胺、甲乙胺中的一种或多种任意比例的混合。
进一步地，当步骤(2)中采用二元胺和一元胺的混合时，所述一元胺与二元胺的摩尔比为(0.02：1)～(0.15：1)。
一种具有阻燃功能的聚氨酯弹性纤维，采用上述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法制得，所述聚氨酯弹性纤维的极限氧指数为25％-32％。
与现有技术相比，本发明具有以下有益的技术效果：
本发明采用含磷聚多元醇为原料，通过反应将阻燃元素引入到聚氨酯分子中，属于本质阻燃；在使用过程中，不会因出现阻燃剂迁移、析出而导致阻燃功能的下降，阻燃效果持久；磷元素具有优异的阻燃性能，且燃烧时不释放卤化氢气体，属于一类环保阻燃元素；磷元素添加量低且在分子中均匀分布，对分子链柔韧性影响小，制备的纤维具有良好的伸长性能。本发明制备的聚氨酯弹性纤维具有优异的阻燃性能，极限氧指数在25-32％之间，同时保持了聚氨酯纤维良好的伸长性能，断裂伸长率在360-600％之间。因此，本发明所制备的弹性纤维可与阻燃棉、阻燃粘胶、芳纶等阻燃纤维一起使用，制成阻燃纱线、织物等，可应用于儿童服装、床垫面料、窗帘、交通工具内饰物、防护工装、消防服等阻燃防护用品。
具体实施方式
下面对本发明的实施方式做进一步详细描述：
一种具有阻燃功能的聚氨酯弹性纤维的制备方法，包括以下步骤：
(1)采用分子量为1000-3000的含有阻燃元素的聚多元醇与过量的4，4’-二苯基甲烷二异氰酸酯(简写为MDI)反应制备成具有异氰酸酯封端的预聚体，将预聚体溶解在有机溶剂中，形成一定浓度的预聚体溶液；
其中，含有阻燃元素的聚多元醇指含有磷元素的聚醚二元醇或聚酯二元醇，所述含有磷元素的聚醚多元醇中含有-P-O-或-P-C-结构，含磷质量百分数为0.5-5％，优选1-3％；所述含有磷元素的聚酯多元醇中含有磷酸酯结构，含磷质量百分数为0.5-10％，优选1-6％，酸值3.0以下，优选2.0以下；有机溶剂为N,N-二甲基甲酰胺(DMF)和N,N-二甲基乙酰胺(DMAc)的一种或几种；MDI与含有阻燃元素的聚多元醇摩尔数的比值在1.5：1～2.5：1之间；
(2)将低分子量二元胺或二元胺与一元胺的混合胺加入到上述预聚体溶液中进行扩链反应，得到聚氨酯溶液；
其中，二元胺或混合胺中氨基官能团的总摩尔数与预聚体端部的异腈酸酯摩尔数的比值在1.00：1～1.05：1之间；二元胺为乙二胺、1，2-丙二胺、1，3-丙二胺、2-甲基-1，5-戊二胺(MPDA)中的一种或几种，为反应扩链剂；一元胺为二甲胺、二乙胺、甲乙胺中的一种或几种，为分子量调节剂，控制反应粘度；所述一元胺与二元胺的摩尔比在0.02：1～0.15：1之间；
(3)将聚氨酯溶液与各种防黄剂(如TAS-011、HN-150)、抗氧剂(如HW-245、抗氧剂1790)等添加剂混合后，再经过熟化、过滤、脱泡等工序后，进行干法纺丝，得到聚氨酯弹性纤维；根据该方法制备的聚氨酯纤维的极限氧指数(LOI)达到25-32％。
下面结合实施例对本发明做进一步详细描述：
实施例中采用如下方法来测量聚氨酯纤维的性能。
极限氧指数的评价
(1)溶液制备：将所制备的聚氨酯溶液，用溶剂稀释至固含量为10-15％聚合物溶液；或将所制备的纤维经洗涤除去表面油剂后，干燥、溶解后配制成聚合物溶液。
(2)制膜：搅拌均匀后，放置一段时间，使溶液脱除气泡。然后，将溶液加热至40-60℃，在光洁的玻璃片上，流延成膜。室温放置12小时后，100℃干燥2小时。得到厚度约为2mm的薄膜。
(3)测试：使用氧指数议测试其极限氧指数。
断裂伸长率的评价
采用等速伸长型强力机，在拉伸速度500mm/min条件下，测试氨纶拉断时的伸长率。
实施例1
含磷聚醚二元醇制备：
将800g苯基磷酸投入5L反应器中，在不断搅拌混合的情况下，将反应温度加热到90℃后，将696g氧化丙烯(第一次投料)在4个小时内添加到反应釜中，反应至反应压力降至常压，继续加入氢氧化钾20g，将中间产品抽真空1小时，真空度为-0.1atm。然后继续将1722g氧化丙烯(第二次投料)在8个小时内添加到反应釜中，反应至反应压力降至常压，得到的粗产品，将粗产品抽真空1小时，真空度为-0.1atm，将残余在粗产品中的单体及挥发组分清除干净，加入磷酸中和，硅藻土吸附，过滤，最终反应得到粘性透明液体产品。经测试，羟值为181mg/gKOH，酸值为0.2mg/gKOH，数均分子量为620；根据投料量及产物质量计算出，产品含磷量为5wt％。
聚氨酯纤维制备：
将上述制备的含磷聚醚二醇与相当于它1.5倍摩尔数的4，4’-二苯甲基烷二异氰酸酯(MDI)，在干燥氮气保护、机械搅拌下，80℃反应3小时，得 到带-NCO封端的预聚物。降至室温后，加入N，N-二甲基乙酰胺(DMAc)，溶解形成预聚物溶液。
将上述预聚物溶液降温至10℃，加入1,2-丙二胺和二乙胺混合胺的DMAc溶液扩链，得到聚氨酯溶液。其中，二乙胺：(1,2-丙二胺)的摩尔比值为0.15:1，混合胺中氨基官能团与预聚物中异氰酸酯官能团的摩尔比(NHx:NCO)为1.05：1。向该聚氨酯溶液加入聚合物重量0.5wt％的防黄剂TAS-011和0.5wt％抗氧剂1790，混合均匀后，再经熟化、脱泡、过滤后，进行干法纺丝，得到560旦尼尔(简写为D)的聚氨酯纤维。
实施例2-5
含磷聚醚二元醇制备：
按实施例1中聚醚二元醇制备方法，制备含磷3％、2％、1％、0.5％的聚醚二元醇。为控制分子量，制备较低含磷量的聚醚二元醇时，需在加入氢氧化钾时，同时加入二甘醇用于调节分子量。具体投料量及性能指标见表1。
表1 含磷聚醚二元醇投料及性能指标
Figure PCTCN2019096374-appb-000001
Figure PCTCN2019096374-appb-000002
聚氨酯纤维制备：
以上述实施例2-5中聚醚二元醇为原料，按实施例1中聚氨酯纤维制备方法，将MDI与聚醚二元醇的摩尔比值、扩链剂种类及用量按照表2进行调整后，制备聚氨酯溶液，再经熟化、脱泡、过滤后，纺丝得到40D或560D的聚氨酯纤维。
聚氨酯纤维极限氧指数及断裂伸长率见表2。
表2 含磷聚醚二元醇型聚氨酯纤维投料及性能指标
Figure PCTCN2019096374-appb-000003
Figure PCTCN2019096374-appb-000004
实施例6
含磷聚酯二元醇制备：
将218g己二酸、2200g 2-羧乙基苯基次磷酸(CEPPA)和1248g 1,4-丁二醇加入5L反应釜中，加入1.5g催化剂钛酸四丁酯，在氮气保护下搅拌，逐渐升温至125-150℃，水开始被分馏出，控制在此反应温度范围下，反应2-8小时；然后继续升温至180℃，在此温度下抽真空至20-5000帕，缓慢升温至235℃，反应2-4小时后，每间隔30分钟测试酸值和羟值，酸值和羟值合格后，停止加热。用氮气泄压，降温，当温度降至80℃，取出反应产物，得到含磷聚酯多元醇。经测试，羟值为36mg/gKOH，酸值为1.7mg/gKOH，数均分子量为3000。根据投料量及产物质量计算出，产品含磷量为10wt％。
聚氨酯纤维制备：
以上述聚酯二元醇为原料，按实施例1聚氨酯纤维制备方法，制备560D聚氨酯纤维。其中，溶剂由DMAc替换为80wt％DMF和20wt％DMAc混合溶剂，防黄剂替换为HN-150和抗氧剂替换为抗氧剂245。
实施例7-10
含磷聚酯二元醇制备：
按实施例6中聚酯二元醇制备方法，制备含磷6％、3％、1％、0.5％的聚酯二元醇。其中，溶剂由混合溶剂替换为纯DMF。具体投料量及性能指标见表3。
表3 含磷聚酯二元醇投料及性能指标
Figure PCTCN2019096374-appb-000005
Figure PCTCN2019096374-appb-000006
聚氨酯纤维制备：
以上述实施例7-10中聚酯二元醇为原料，按实施例6聚氨酯纤维制备方法，将MDI与聚醚二元醇的摩尔比值、扩链剂种类及用量按照表4进行调整后，制备聚氨酯溶液，再经熟化、脱泡、过滤后，纺丝得到40D或560D的聚氨酯纤维。
聚氨酯纤维极限氧指数及断裂伸长率见表4。
表4 含磷聚酯二元醇型聚氨酯纤维投料及性能指标
Figure PCTCN2019096374-appb-000007
Figure PCTCN2019096374-appb-000008
对比实施例1
将实施例4中阻燃聚醚二元醇替换为聚四氢呋喃二元醇(PTMG)，按实施例4的方法制备聚氨酯溶液，并纺制成40D的聚氨酯纤维。
对比实施例2
按对比实施例1的方法制备聚氨酯溶液，并加入聚合物重量2％的高氮阻燃剂HT-211作为阻燃助剂，经混合、熟化、过滤、脱泡后，干法纺制成40D的聚氨酯纤维。
对比实施例3
按实施例4的方法制备聚氨酯溶液，并加入聚合物重量2％的高氮阻燃剂HT-211作为阻燃助剂，经混合、熟化、过滤、脱泡后，干法纺制成40D的聚氨酯纤维。
对比实施例4
按实施例9的方法制备聚氨酯溶液，并加入聚合物重量5％的高氮阻燃剂HT-211作为阻燃助剂，经混合、熟化、过滤、脱泡后，干法纺制成560D的聚氨酯纤维。
表5 不同对比实施例投料及性能指标
Figure PCTCN2019096374-appb-000009

Claims (10)

  1. 一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，包括以下步骤：
    (1)采用含有阻燃元素的聚多元醇与过量的4，4’-二苯基甲烷二异氰酸酯反应制备成具有异氰酸酯封端的预聚体，将预聚体溶解在有机溶剂中，形成预聚体溶液；
    (2)将二元胺或二元胺与一元胺的混合胺加入到预聚体溶液中进行扩链反应，得到聚氨酯溶液；
    (3)将聚氨酯溶液与防黄剂、抗氧剂混合，再经过熟化、过滤、脱泡工序后，进行干法纺丝，得到具有阻燃功能的聚氨酯弹性纤维。
  2. 根据权利要求1所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，步骤(1)中含有阻燃元素的聚多元醇为含有磷元素的聚醚二元醇或含有磷元素的聚酯二元醇。
  3. 根据权利要求2所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，所述含有磷元素的聚醚多元醇中含有-P-O-或-P-C-结构，且含磷量为0.5wt％-5wt％；所述含有磷元素的聚酯多元醇中含有磷酸酯结构，且含磷量为0.5wt％-10wt％，酸值3.0以下。
  4. 根据权利要求3所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，所述含有磷元素的聚醚多元醇中含磷量为1wt％-3wt％；所述含有磷元素的聚酯多元醇中含磷量为1wt％-6wt％，酸值2.0以下。
  5. 根据权利要求1所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，步骤(1)中4，4’-二苯基甲烷二异氰酸酯与含有阻燃元素的聚多元醇的摩尔比为(1.5：1)～(2.5：1)。
  6. 根据权利要求1所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，步骤(1)中所述有机溶剂为N,N-二甲基甲酰胺和N,N-二甲基乙酰胺的一种或两种的混合。
  7. 根据权利要求1所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，步骤(2)二元胺或二元胺与一元胺的混合胺中氨基官能团与预聚体端部的异腈酸酯的摩尔比为(1.00：1)～(1.05：1)。
  8. 根据权利要求1所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，步骤(2)中二元胺为乙二胺、1，2-丙二胺、1，3-丙二胺、2-甲基-1，5-戊二胺中的一种或多种任意比例的混合；一元胺为二甲胺、二乙胺、甲乙胺中的一种或多种任意比例的混合。
  9. 根据权利要求1所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法，其特征在于，当步骤(2)中采用二元胺和一元胺的混合时，所述一元胺与二元胺的摩尔比为(0.02：1)～(0.15：1)。
  10. 一种具有阻燃功能的聚氨酯弹性纤维，采用权利要求1-9任一项所述的一种具有阻燃功能的聚氨酯弹性纤维的制备方法制得，其特征在于，所述聚氨酯弹性纤维的极限氧指数为25％-32％。
PCT/CN2019/096374 2019-04-22 2019-07-17 一种具有阻燃功能的聚氨酯弹性纤维及其制备方法 WO2020215501A1 (zh)

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