阅读说明：本技术 一种二氧化碳基聚氨酯纤维及其制备方法 (Carbon dioxide-based polyurethane fiber and preparation method thereof ) 是由 张红明 赵强 王献红 王佛松 于 2020-05-22 设计创作，主要内容包括：本发明涉及聚氨酯纤维技术领域,尤其涉及一种二氧化碳基聚氨酯纤维及其制备方法,所述二氧化碳基聚氨酯纤维由包含如下重量份组分的纺丝原液经过纺丝制得：聚(碳酸酯-醚)二元醇180～350份；芳香族二醇3.5～7.8份；芳香族二异氰酸酯45～92份；有机溶剂650～1450份；胺类扩链剂11.5～18.7份；链终止剂0.8～2.1份；抗氧化剂0.03～0.11份；紫外吸收剂0.05～0.09份。本发明提供的二氧化碳基聚氨酯纤维耐高温性能和耐环境老化性能较优。实验表明,所述二氧化碳基聚氨酯纤维经过上述高温处理后,纤维丝的拉伸强力变化不低于72％,经过上述碱液处理后,纤维丝的拉伸强力变化不低于75％。(The invention relates to the technical field of polyurethane fibers, in particular to a carbon dioxide-based polyurethane fiber and a preparation method thereof, wherein the carbon dioxide-based polyurethane fiber is prepared by spinning a spinning solution which comprises the following components in parts by weight: 180-350 parts of poly (carbonate-ether) glycol; 3.5-7.8 parts of aromatic diol; 45-92 parts of aromatic diisocyanate; 650-1450 parts of an organic solvent; 11.5-18.7 parts of an amine chain extender; 0.8-2.1 parts of a chain terminator; 0.03-0.11 part of antioxidant; 0.05-0.09 part of ultraviolet absorbent. The carbon dioxide-based polyurethane fiber provided by the invention has better high temperature resistance and environmental aging resistance. Experiments show that after the carbon dioxide-based polyurethane fiber is subjected to the high-temperature treatment, the tensile strength change of the fiber filament is not less than 72%, and after the carbon dioxide-based polyurethane fiber is subjected to the alkali liquor treatment, the tensile strength change of the fiber filament is not less than 75%.)

1. The carbon dioxide-based polyurethane fiber is prepared by spinning a spinning solution which comprises the following components in parts by weight:

2. the carbon dioxide-based polyurethane fiber according to claim 1, wherein the molecular weight of the poly (carbonate-ether) diol is 2200 to 3800g/mol, and the content of carbonate in the poly (carbonate-ether) diol is 32.5 wt% to 56.8 wt%.

3. The carbon dioxide-based polyurethane fiber according to claim 1, wherein the aromatic diol is selected from hydroquinone bis hydroxyethyl ether, hydroquinone (β -hydroxyethyl) ether, dihydroxyethyl terephthalate, or dihydroxyethyl benzyl ether.

4. The carbon dioxide-based polyurethane fiber according to claim 1, wherein the aromatic diisocyanate is selected from diphenylmethane diisocyanate, m-xylylene isocyanate, naphthalene diisocyanate, or toluene-2, 4-diisocyanate.

5. The carbon dioxide-based polyurethane fiber according to claim 1, wherein the organic solvent is one or more selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone.

6. The carbon dioxide-based polyurethane fiber according to claim 1, wherein the amine-based chain extender is selected from the group consisting of 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, 2-methyl-1, 5-pentylenediamine, diethylenetriamine, isophoronediamine, 1, 3-cyclohexanediamine, hexafluorodiamine, and triethylenediamine;

the chain terminator is selected from dimethylamine, diethylamine, dipropylamine, di-n-butylamine, cyclohexylamine, n-pentylamine or ethanolamine.

7. The carbon dioxide-based polyurethane fiber according to claim 1, wherein the antioxidant is selected from chernox 1010, chernox 1076, chernox 1098, or chernox 1024;

the ultraviolet absorbent is selected from UV-326, UV-327, UV-328, UV-329, UV-234 or UV-531.

8. The method of preparing a carbon dioxide-based polyurethane fiber according to claim 1, comprising the steps of:

A) stirring and reacting poly (carbonate-ether) dihydric alcohol, aromatic diol and aromatic diisocyanate at 70-90 ℃ under the condition of protective gas to obtain a polyurethane prepolymer;

B) under the condition of protective gas, stirring and mixing the polyurethane prepolymer and an organic solvent at the temperature of 5-30 ℃ to obtain a prepolymer solution, adding an amine chain extender and a chain terminator into the prepolymer solution at the speed of 8-15 m L/min, and reacting to obtain polyurethane elastic fiber;

C) stirring and mixing the polyurethane elastic fiber, the antioxidant and the ultraviolet absorbent to obtain a polyurethane elastic fiber spinning solution;

D) and spinning the polyurethane elastic fiber spinning solution to obtain the carbon dioxide-based polyurethane fiber.

9. The method according to claim 8, wherein in step a), the shielding gas is nitrogen;

the stirring speed of the stirring reaction is 60-100 rpm, and the stirring reaction time is 1-3 h;

in the step B), the protective gas is nitrogen;

the stirring speed of the stirring and mixing is 75-130 rpm, and the stirring and mixing time is 20-40 min;

the reaction temperature is 5-30 ℃, and the reaction time is 0.5-1.5 h.

10. The preparation method according to claim 8, wherein in the step C), the stirring rate of the stirring and mixing is 150-200 rpm;

in the step D), the spinning method is dry spinning.

Technical Field

The invention relates to the technical field of polyurethane fibers, in particular to a carbon dioxide-based polyurethane fiber and a preparation method thereof.

Background

The polyurethane fiber is also called spandex, is a blend of polyurethane and polyurea-urethane, has the performance between rubber and plastic, has the performances of high elasticity, high strength, wear resistance, flexing resistance and the like, and is widely applied to the fields of knitted clothes, household articles and the like. The polyurethane fiber is prepared by pre-polymerization of diisocyanate and hydroxyl-terminated diol and chain extension of diamine, and comprises two types of fibers, namely polyester and polyether, wherein the polyester fiber has strong oxidation resistance and oil resistance, and the polyether fiber has mildew resistance and good elasticity. The resilience of the polyurethane fiber is up to 95 percent, the breaking elongation of the polyurethane fiber is 300 to 700 percent, the main acting force among the polyurethane fiber molecules is Van der Waals force, the soft segment molecules formed by the hydroxyl-terminated diol have relatively weak binding force to other molecules, so that the soft segment is curled and relaxed, and the soft segment is easy to move and elongate at normal temperature, which is the structural basis of the high elasticity of the fiber; strong polar groups in a hard chain segment formed by a carbamido group (-NHCONH-) and a carbamate group (-NHOCO-) are connected through hydrogen bond acting force, so that the polyurethane fiber has the characteristics of high glass transition temperature and easy crystallization, can prevent relative slippage of molecular chains when the molecular chains are stressed, can restore the soft chain segment to the original unstretched state after being stretched, prevents infinite elongation of polyurethane, and has the characteristics of high breaking elongation and high elastic recovery rate due to the structural characteristics of the soft and hard chain segments.

The invention patent 201310446184.X reports an efficient polyurethane elastic fiber production method, which comprises the steps of firstly carrying out prepolymerization reaction on polytetramethylene ether glycol, 4-diphenylmethane diisocyanate and an n-butyl alcohol end-capping agent, and then carrying out chain extension twice by sequentially using DMAC (dimethylacetamide) solution of glycol and mixed amine step by step to obtain the polyurethane fiber. The invention patent 201910758620.4 provides a novel polyurethane fiber material and a preparation method thereof, the polyurethane fiber material is prepared from a component A and a component B, wherein: the component A consists of polytetrahydrofuran ether glycol, polyether polyol, polyester polyol, TDI and a chain extender; the component B consists of silica sol, ultraviolet absorbent and antioxidant. The obtained polyurethane fiber material has the characteristics of high elasticity, stain resistance, aging resistance and the like. The polyurethane fiber needs to be dyed when the textile is manufactured, the dyeing treatment needs a long-time treatment at a high temperature of more than 130 ℃, however, the common polyurethane fiber has poor high temperature resistance, the fiber is broken under the high temperature condition, the performance of the polyurethane fiber is seriously damaged, and the high temperature resistant polyurethane fiber also receives general attention in recent years. Japanese patent H4-100919 improves the high temperature resistance of spandex fiber by adding triamine before spinning polyurethane fiber stock solution, however, in this method, the triamine is added into the high-viscosity spinning stock solution, so the dispersion uniformity of the stock solution cannot be ensured, and moreover, the mode of adding the triamine has great influence on the alkali resistance, thus greatly influencing the hydrolytic stability. The invention patent 201811408761.5 reports a spandex fiber with good heat resistance and low-temperature setting property and a preparation method thereof, wherein the heat resistance is improved by adding isocyanate trimer in the polymerization process, but the trimer obtains a cross-linked net structure rather than a linear structure, and the synthesis is difficult to control. The invention patent 201510535986.7 reports a preparation method of a high temperature resistant and fatigue resistant radiation cross-linked polyurethane fiber, which comprises the steps of firstly mixing polytetrahydrofuran glycol, polypropylene glycol polyether diol and diisocyanate to obtain isocyanate-terminated polyurethane prepolymer, then adding mixed amine solution to carry out chain extension reaction and chain termination reaction, wherein fluorine-containing aromatic diamine chain extender is adopted in the chain extension reaction to obtain 25-50% solid content polyurethane fiber solution, and the high temperature resistance is improved through ultraviolet radiation cross-linking, but the production cost is greatly increased by fluorine-containing aromatic diamine.

The polyurethane elastic fiber material can meet different severe environmental conditions such as light, heat, oxygen, water and the like in the using process, so that the polyurethane is required to have good heat resistance, alkali resistance, ultraviolet light aging resistance and other properties, otherwise, the polyurethane structure is changed, the polyurethane elastic fiber is aged, the properties are gradually deteriorated, and the use value of the polyurethane elastic fiber material is lost. Therefore, the research on the environmental aging resistance of the polyurethane fiber material becomes the development direction in the field.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a carbon dioxide-based polyurethane fiber and a preparation method thereof.

The invention provides a carbon dioxide-based polyurethane fiber which is prepared by spinning a spinning solution containing the following components in parts by weight:

preferably, the molecular weight of the poly (carbonate-ether) glycol is 2200 to 3800g/mol, and the content of carbonate in the poly (carbonate-ether) glycol is 32.5 wt% to 56.8 wt%.

Preferably, the aromatic diol is selected from hydroquinone bis hydroxyethyl ether, hydroquinone (β -hydroxyethyl) ether, dihydroxyethyl terephthalate or dihydroxyethyl benzyl ether.

Preferably, the aromatic diisocyanate is selected from diphenylmethane diisocyanate, m-xylylene isocyanate, naphthalene diisocyanate or toluene-2, 4-diisocyanate.

Preferably, the organic solvent is one or more selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone.

Preferably, the amine chain extender is selected from 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, 2-methyl-1, 5-pentylenediamine, diethylenetriamine, isophoronediamine, 1, 3-cyclohexanediamine, hexafluorodiamine or triethylenediamine;

the chain terminator is selected from dimethylamine, diethylamine, dipropylamine, di-n-butylamine, cyclohexylamine, n-pentylamine or ethanolamine.

Preferably, the antioxidant is selected from chernox 1010, chernox 1076, chernox 1098, or chernox 1024;

the ultraviolet absorbent is selected from UV-326, UV-327, UV-328, UV-329, UV-234 or UV-531.

The invention provides a preparation method of the carbon dioxide-based polyurethane fiber, which comprises the following steps:

A) stirring and reacting poly (carbonate-ether) dihydric alcohol, aromatic diol and aromatic diisocyanate at 70-90 ℃ under the condition of protective gas to obtain a polyurethane prepolymer;

B) under the condition of protective gas, stirring and mixing the polyurethane prepolymer and an organic solvent at the temperature of 5-30 ℃ to obtain a prepolymer solution, adding an amine chain extender and a chain terminator into the prepolymer solution at the speed of 8-15 m L/min, and reacting to obtain polyurethane elastic fiber;

C) stirring and mixing the polyurethane elastic fiber, the antioxidant and the ultraviolet absorbent to obtain a polyurethane elastic fiber spinning solution;

D) and spinning the polyurethane elastic fiber spinning solution to obtain the carbon dioxide-based polyurethane fiber.

Preferably, in step a), the protective gas is nitrogen;

the stirring speed of the stirring reaction is 60-100 rpm, and the stirring reaction time is 1-3 h;

in the step B), the protective gas is nitrogen;

the stirring speed of the stirring and mixing is 75-130 rpm, and the stirring and mixing time is 20-40 min;

the reaction temperature is 5-30 ℃, and the reaction time is 0.5-1.5 h.

Preferably, in the step C), the stirring speed of the stirring and mixing is 150-200 rpm;

in the step D), the spinning method is dry spinning.

The invention provides a carbon dioxide-based polyurethane fiber which is prepared by spinning a spinning solution containing the following components in parts by weight: 180-350 parts of poly (carbonate-ether) glycol; 3.5-7.8 parts of aromatic diol; 45-92 parts of aromatic diisocyanate; 650-1450 parts of an organic solvent; 11.5-18.7 parts of an amine chain extender; 0.8-2.1 parts of a chain terminator; 0.03-0.11 part of antioxidant; 0.05-0.09 part of ultraviolet absorbent. The carbon dioxide-based polyurethane fiber provided by the invention has excellent high temperature resistance and environmental aging resistance. Experimental results show that after the carbon dioxide-based polyurethane fiber is subjected to the high-temperature treatment, the tensile strength change of the fiber filaments is not less than 72%; after the carbon dioxide-based polyurethane fiber is treated by the alkali liquor, the tensile strength change of the fiber filaments is not less than 75%.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a carbon dioxide-based polyurethane fiber which is prepared by spinning a spinning solution containing the following components in parts by weight:

in certain embodiments of the present invention, the poly (carbonate-ether) glycol has a molecular weight of 2200 to 3800 g/mol. In certain embodiments, the poly (carbonate-ether) glycol has a molecular weight of 2200g/mol, 3800g/mol, or 3000 g/mol. In certain embodiments of the invention, the carbonate content of the poly (carbonate-ether) glycol is from 32.5 wt% to 56.8 wt%. In certain embodiments, the carbonate content of the poly (carbonate-ether) diol is 56.8 wt%, 32.5 wt%, or 53.5 wt%. In certain embodiments of the present invention, the poly (carbonate-ether) glycol is prepared according to the method disclosed in chinese patent application No. 201711213266.4. In certain embodiments of the present invention, the poly (carbonate-ether) glycol is present in an amount of 180 parts, 350 parts, 210 parts, 285 parts, 260 parts, or 310 parts by weight.

In certain embodiments of the present invention, the aromatic diol is selected from hydroquinone bis hydroxyethyl ether, hydroquinone (β -hydroxyethyl) ether, dihydroxy ethyl terephthalate, or dihydroxy ethyl benzyl ether, in certain embodiments of the present invention, the weight fraction of the aromatic diol is 3.5 parts, 7.8 parts, 4.9 parts, 6.4 parts, 7.1 parts, or 6.5 parts.

In certain embodiments of the present invention, the aromatic diol is selected from hydroquinone bis hydroxyethyl ether, hydroquinone (β -hydroxyethyl) ether, dihydroxy ethyl terephthalate, or dihydroxy ethyl benzyl ether, in certain embodiments of the present invention, the weight fraction of the aromatic diisocyanate is 45 parts, 92 parts, 62 parts, 78 parts, 79 parts, or 85 parts.

In certain embodiments of the present invention, the organic solvent is selected from one or more of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone. In certain embodiments of the present invention, the organic solvent is present in 650 parts, 1450 parts, 800 parts, 1200 parts, 1320 parts, or 1180 parts by weight.

In certain embodiments of the present invention, the amine chain extender is selected from the group consisting of 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, 2-methyl-1, 5-pentylenediamine, diethylenetriamine, isophoronediamine, 1, 3-cyclohexanediamine, hexafluorodiamine, or triethylenediamine. In certain embodiments of the present invention, the weight fraction of the amine chain extender is 11.5 parts, 18.7 parts, 13.5 parts, 12.8 parts, 14.2 parts, or 14.8 parts.

In certain embodiments of the present invention, the chain terminator is selected from dimethylamine, diethylamine, dipropylamine, di-n-butylamine, cyclohexylamine, n-pentylamine, or ethanolamine. In certain embodiments of the present invention, the weight fraction of chain terminator is 0.8 parts, 2.1 parts, 1.2 parts, 1.4 parts, 1.5 parts, or 1.9 parts.

In certain embodiments of the present invention, the antioxidant is selected from hindered phenolic antioxidants. In certain embodiments, the antioxidant is selected from chernox 1010, chernox 1076, chernox 1098, or chernox 1024. In certain embodiments of the present invention, the antioxidant is present in an amount of 0.03 parts, 0.11 parts, 0.07 parts, 0.08 parts, 0.1 parts, or 0.09 parts by weight.

In certain embodiments of the present invention, the ultraviolet absorber is selected from the group consisting of UV-326, UV-327, UV-328, UV-329, UV-234, and UV-531. In certain embodiments of the present invention, the weight part of the ultraviolet absorber is 0.05 parts, 0.09 parts, 0.07 parts, 0.06 parts, or 0.08 parts.

The carbon dioxide-based polyurethane fiber provided by the invention has better high temperature resistance and environmental aging resistance.

The invention also provides a preparation method of the carbon dioxide-based polyurethane fiber, which comprises the following steps:

A) stirring and reacting poly (carbonate-ether) dihydric alcohol, aromatic diol and aromatic diisocyanate at 70-90 ℃ under the condition of protective gas to obtain a polyurethane prepolymer;

B) under the condition of protective gas, stirring and mixing the polyurethane prepolymer and an organic solvent at the temperature of 5-30 ℃ to obtain a prepolymer solution, adding an amine chain extender and a chain terminator into the prepolymer solution at the speed of 8-15 m L/min, and reacting to obtain polyurethane elastic fiber;

C) stirring and mixing the polyurethane elastic fiber, the antioxidant and the ultraviolet absorbent to obtain a polyurethane elastic fiber spinning solution;

D) and spinning the polyurethane elastic fiber spinning solution to obtain the carbon dioxide-based polyurethane fiber.

In the preparation method of the carbon dioxide-based polyurethane fiber provided by the invention, the components and the mixture ratio of the adopted raw materials are the same as those in the above, and are not described again.

In the invention, under the condition of protective gas, poly (carbonate-ether) dihydric alcohol, aromatic diol and aromatic diisocyanate are stirred to react at 70-90 ℃ to obtain a polyurethane prepolymer.

In certain embodiments of the invention, the shielding gas is nitrogen.

In certain embodiments of the invention, the temperature of the stirred reaction is 70 ℃, 90 ℃, 80 ℃, 85 ℃ or 75 ℃. In some embodiments of the present invention, the stirring speed of the stirring reaction is 60 to 100 rpm. In certain embodiments, the agitation rate of the agitation reaction is 95rpm, 85rpm, 90rpm, 80rpm, 100rpm, or 60 rpm. In some embodiments of the invention, the stirring reaction time is 1-3 h. In certain embodiments, the stirring reaction time is 3 hours, 1 hour, 2 hours, 1.5 hours, or 2.5 hours.

And (2) stirring and mixing the polyurethane prepolymer and an organic solvent at 5-30 ℃ under the condition of protective gas to obtain a prepolymer solution, adding an amine chain extender and a chain terminator into the prepolymer solution at the speed of 8-15 m L/min, and reacting to obtain the polyurethane elastic fiber.

In certain embodiments of the invention, the shielding gas is nitrogen.

In certain embodiments of the invention, the temperature of the agitation mixing is 5 ℃, 30 ℃, 10 ℃, 20 ℃, 15 ℃ or 20 ℃. In some embodiments of the present invention, the stirring rate of the stirring and mixing is 75-130 rpm. In certain embodiments, the agitation rate of the agitation mixing is 120rpm, 90rpm, 110rpm, 130rpm, or 75 rpm. In some embodiments of the present invention, the stirring and mixing time is 20-40 min. In certain embodiments, the time of the stirring and mixing is 20min, 40min, 35min, 25min, 30min, or 22 min.

In certain embodiments of the present invention, the amine chain extender and chain terminator are added to the prepolymer solution at a rate of 8 to 15m L/min, in certain embodiments at a rate of 11.5m L/min, 13.5m L/min, 13m L/min, 11m L/min, 15m L/min, or 8m L/min.

In some embodiments of the invention, the reaction temperature is 5-30 ℃, and the reaction time is 0.5-1.5 h. In certain embodiments, the temperature of the reaction is 5 ℃, 30 ℃, 10 ℃, 20 ℃, or 15 ℃. In certain embodiments, the reaction time is 1.5h, 1h, or 0.5 h.

And after obtaining the polyurethane elastic fiber, stirring and mixing the polyurethane elastic fiber, the antioxidant and the ultraviolet absorbent to obtain the polyurethane elastic fiber spinning solution.

In some embodiments of the present invention, the stirring rate of the stirring and mixing is 150 to 200 rpm. In certain embodiments, the agitation rate of the agitation mixing is 150rpm, 200rpm, 180rpm, 185rpm, or 195 rpm.

In certain embodiments of the invention, the agitating mixing is performed under a nitrogen blanket.

And spinning the polyurethane elastic fiber spinning solution to obtain the carbon dioxide-based polyurethane fiber.

In certain embodiments of the invention, the method of spinning is dry spinning.

In certain embodiments of the present invention, the dry spinning specifically comprises:

extruding the polyurethane elastic fiber spinning solution from the capillary holes of the spinneret plate, feeding the solution into a spinning channel, enabling the solvent in the solution trickle to be quickly volatilized through hot nitrogen in the spinning channel and taken away by hot gas, concentrating and solidifying the solution trickle while gradually removing the solvent, and stretching and thinning the solution under the action of winding tension to form fibers.

The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.

In order to further illustrate the present invention, the following examples are provided to describe the carbon dioxide-based polyurethane fiber and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.

The starting materials used in the following examples are all generally commercially available.