Melamine spinning solution, spinning solution and melamine fiber

文档序号：900696 发布日期：2021-02-26 浏览：25次中文

阅读说明：本技术 一种三聚氰胺纺丝原液、纺丝液及三聚氰胺纤维 (Melamine spinning solution, spinning solution and melamine fiber ) 是由刘绍英蒙延宗王公应于 2019-08-23 设计创作，主要内容包括：本发明公开了一种三聚氰胺纺丝原液、纺丝液及三聚氰胺纤维。所述纺丝原液是由包括以下组分的原料聚合而得：三聚氰胺100重量份；甲醛30～120重量份；催化剂0.1～3重量份；溶剂30～200重量份。所述溶剂为有机溶剂或者有机溶剂和水。本发明制备的三聚氰胺纺丝原液和纺丝液具有较好的贮存稳定性和可纺性,不需要添加助成纤剂可直接湿法纺丝或干法纺丝,纤维的力学性能较好,同时工艺简单、效率高、成本低。所制备的三聚氰胺纤维强度为1.2～2.6cN/dtex,断裂伸长率为11～16％,极限氧指数32～35,热分解温度大于370℃。(The invention discloses a melamine spinning solution, a spinning solution and melamine fiber. The spinning solution is obtained by polymerizing raw materials comprising the following components: 100 parts by weight of melamine; 30-120 parts by weight of formaldehyde; 0.1-3 parts by weight of a catalyst; 30-200 parts of a solvent. The solvent is an organic solvent or an organic solvent and water. The melamine spinning solution and the melamine spinning solution prepared by the invention have good storage stability and spinnability, can be directly used for wet spinning or dry spinning without adding a fiber forming aid, and have good mechanical properties, simple process, high efficiency and low cost. The strength of the prepared melamine fiber is 1.2-2.6 cN/dtex, the elongation at break is 11-16%, the limiting oxygen index is 32-35, and the thermal decomposition temperature is more than 370 ℃.)

1. The melamine spinning solution is characterized in that the spinning solution is obtained by polymerizing raw materials comprising the following components:

2. the melamine spin dope of claim 1 wherein:

3. the melamine spin dope of claim 1 wherein:

the solvent is an organic solvent or an organic solvent and water;

the organic solvent is one or a combination of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, propyl acetate, butyl acetate, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, methyl ethyl carbonate, diethyl carbonate, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and cyclohexanone.

4. A melamine spin dope according to claim 3 wherein:

the weight ratio of the water to the organic solvent is 1: 3-3: 1.

5. The melamine spin dope of claim 1 wherein:

the catalyst is one or a combination of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, magnesium oxide, ammonia water, triethylamine, triethanolamine and the like.

6. A process for the preparation of a melamine spin dope according to any one of claims 1 to 5, characterized in that it comprises:

the components are mixed according to the using amount, and the melamine fiber spinning solution is prepared after polymerization reaction, wherein the viscosity of the melamine fiber spinning solution is 5000-20000 mpa.s;

the reaction temperature is 70-100 ℃, and the reaction time is 60-180 min.

7. A melamine dope obtained from the melamine dope according to any one of claims 1 to 5, wherein the melamine dope is obtained by polymerizing raw materials comprising:

100 parts of melamine spinning solution;

0-5 parts by weight of a crosslinking agent; preferably 0.3 to 4 parts by weight;

the cross-linking agent is one or a combination of formic acid, acetic acid, glycolic acid, citric acid, p-toluenesulfonic acid, ethylenediamine tetraacetic acid, maleic acid, phosphoric acid and boric acid.

8. A process for the preparation of a melamine dope according to claim 7, characterised in that the process comprises:

the components are mixed according to the using amount, and the melamine spinning solution is prepared through polymerization reaction at the temperature of 50-70 ℃, and the viscosity of the melamine spinning solution is 9000-22000 map.s.

9. A melamine fiber made from the melamine dope of claim 7.

10. Melamine fiber according to claim 9, wherein:

the fiber strength is 1.2-2.6 cN/dtex, the elongation at break is 11-16%, the limiting oxygen index is 32-35, and the thermal decomposition temperature is more than 370 ℃.

Technical Field

The invention relates to the technical field of fibers, in particular to a melamine spinning solution, a spinning solution and melamine fibers.

Background

The melamine fiber is a novel high-performance fiber which is formed by weaving melamine formaldehyde resin serving as a main component, has higher flame retardance and high temperature resistance, good fiber whiteness and dyeing property, does not burn, melt or melt drop when being contacted with flame, does not generate toxic or harmful gas when being carbonized at high temperature, does not cause secondary disaster, can be used for preparing flame-retardant fabrics, fire-fighting clothes, clutch linings, heat-insulation and high-temperature-resistant filter materials and the like, is low in price and has wide application and development prospects.

German patent DE2364091-B discloses a process for the preparation of melamine fibres, which was successful in the production of melamine fibres by dry spinning by adding polyvinyl alcohol as a co-fibre-forming agent to melamine formaldehyde resin, but the fibres were cured for a longer time at a spinning speed of about 10 m/min, while the addition of the co-fibre-forming agent reduced the stability of the spinning dope. European patents EP221330-A and EP93965-A firstly carry out substitution reaction on melamine, and then react the prepared substituted melamine with formaldehyde to prepare spinning solution. The Chinese patent CN101016658A adopts a wet process to prepare the melamine formaldehyde resin/polyvinyl alcohol mixed fiber, the fineness of the fiber is 3-10 dtex, the strength is 1-3 cN/dtex, and the elongation at break is 5-15%, but the addition of the polyvinyl alcohol reduces the stability of the spinning solution and the flame retardant property of the fiber. Chinese patent CN104928791A discloses a method for continuously preparing melamine fiber, which takes polyvinyl alcohol as a fiber forming aid, melamine formaldehyde resin solution and polyvinyl alcohol solution are mixed according to the mass ratio of 4:6-6:4, saturated sodium sulfate containing boric acid is used as a coagulating bath, and the fiber prepared by a wet spinning process has the strength of 2-4 cN/dtex, the elongation at break of 10-40% and the elastic modulus of 100-400 cN/dtex, but the fiber manufacturing process is complex, the stability of spinning stock solution is poor, and the flame retardant property of the fiber is low.

At present, pure water is used as a solvent in domestic and overseas researches, the prepared melamine spinning solution has poor fiber forming property and spinnability, and in order to improve the spinnability, the spinnability and the fiber forming property are mainly improved by adding a large amount of polyvinyl alcohol and the like, but the addition of a large amount of polyvinyl alcohol not only ensures that the stability of the spinning solution is poor, but also reduces the flame retardant property of fibers. Lidongyong et al (research on melamine fiber spinning solution for wet spinning, New chemical materials 2018, 46, 198-containing 201) take melamine and paraformaldehyde as raw materials, melamine spinning solution prepared by taking water as a solvent can be directly subjected to wet spinning without adding a fiber forming aid, the tensile strength of the fiber is 1.97cN/dtex, the elongation at break is 4.91%, the thermal decomposition temperature is more than 370 ℃, but the mechanical properties of the fiber cannot meet the requirements of practical application.

In the existing method for preparing melamine fiber, the prepared spinning solution has poor spinnability (or can not be spun), and can be spun only by adding a fiber forming aid (such as a large amount of polyvinyl alcohol, nylon and the like), but the addition of the polyvinyl alcohol and the like makes the spinning solution unstable and reduces the flame retardance; in order to achieve the purpose of flame retardance, a flame retardant is added; these lose the inherent unique properties of the fiber and can drip during burning causing secondary hazards (if essentially melamine blend fibers are prepared instead of strictly melamine fibers with the addition of a co-fiberizer).

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a melamine spinning solution, a spinning solution and melamine fiber. The invention can directly spin without adding auxiliary fiber forming agent, and the spinning method can be dry method or wet method, the mechanical property of the fiber is not reduced on the premise of keeping the inherent (or intrinsic) flame retardant property of melamine.

One of the purposes of the invention is to provide a melamine spinning solution.

Is obtained by polymerizing raw materials comprising the following components:

the solvent is an organic solvent or an organic solvent and water;

At present, the melamine fiber is researched at home and abroad by using water as a solvent to prepare a spinning solution, along with the increase of the molecular weight of melamine formaldehyde resin, the solubility of the spinning solution in water is poor, and the molecular weight of the spinning solution is low at a critical gel point, so that the spinnability is poor, and the spinnability needs to be improved by adding a PVA (polyvinyl alcohol) fiber forming aid, but the stability of the spinning solution and the flame retardance of the fiber are reduced by adding the PVA.

The melamine formaldehyde resin has good solubility in the solvent, the solvent has a diluting effect on the spinning solution, the molecular weight of the spinning solution is relatively high (the viscosity of the spinning solution is high) when the critical gel point is reached, the spinnability is good, the dry spinning or the wet spinning can be directly carried out without adding a fiber forming aid (both spinning methods are available), and the performance of the fiber is good.

Formed from water and organic solvents (H)₂O/DMF) composite solvent can improve the molecular weight (viscosity) of the spinning solution at the critical gel point, and the water and the organic solvent can form azeotropy in the fiber forming process, so that the speed of the solvent to be removed from the nascent fiber is improved, the structural defects of the fiber are reduced, and the performance of the fiber is better. Therefore, the combination of the organic solvent and water has more excellent effects.

The weight ratio of water to the organic solvent is preferably 1:3 to 3: 1.

The catalyst is one or a combination of alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, magnesium oxide, ammonia water, triethylamine, triethanolamine and the like.

The second purpose of the invention is to provide a preparation method of the melamine spinning solution.

The method comprises the following steps:

the reaction temperature is 70-100 ℃, and the reaction time is 60-180 min.

The method comprises the following specific steps:

according to the components, according to the using amount (wherein the using amount of the catalyst is used for regulating and controlling the pH value of the system to be 8-12), the polymerization reaction is carried out under the process conditions of 70-100 ℃ (preferably 80-98 ℃) and 60-180 min (preferably 90-150 min) of reaction time, and the melamine fiber spinning stock solution with the viscosity of 5000-18000 mpa.s (preferably 9000-13000 mpa.s) is prepared.

The invention also aims to provide a melamine spinning solution.

Is obtained by polymerizing raw materials comprising the following components:

100 parts of melamine spinning solution;

0-5 parts by weight of a crosslinking agent; preferably 0.3 to 4 parts by weight;

Inorganic nano materials such as aluminum oxide, titanium dioxide, silicon carbide, silicon nitride, magnesium hydroxide and the like can also be added. The mechanical property of the fiber can be improved by adding the nano material.

The fourth purpose of the invention is to provide a preparation method of the melamine spinning solution.

The method comprises the following steps:

The method specifically comprises the following steps:

the components react at the temperature of 50-70 ℃ according to the using amount (wherein the using amount of the cross-linking agent is that the pH value of a regulation system is 3.0-8.5) until the viscosity is 9000-16000 map.s, and the melamine fiber spinning solution is prepared.

The melamine fiber spinning solution prepared by the method can be stably stored for more than 30 days at 30 ℃, and the melamine fiber spinning solution can be stably stored for 100 hours at 60 ℃.

The fifth purpose of the invention is to provide a melamine fiber prepared by the melamine spinning solution.

The fiber strength is 1.2-2.6 cN/dtex, the elongation at break is 11-16%, the limiting oxygen index is 32-35, and the thermal decomposition temperature is more than 370 ℃.

The melamine spinning solution and the melamine spinning solution prepared by the invention have good storage stability and spinnability, can be directly used for wet spinning or dry spinning without adding a fiber forming aid, and have good mechanical properties, simple process, high efficiency and low cost. The strength of the prepared melamine fiber is 1.2-2.6 cN/dtex, the elongation at break is 11-16%, the limiting oxygen index is 32-35, and the thermal decomposition temperature is more than 370 ℃.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

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

Example 1

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 9.8, the reaction temperature is 90 ℃, and the reaction time is 130min, so that the melamine fiber spinning solution with the viscosity of 10400map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 0.8 part of formic acid, 4.6 of pH value, 60 ℃ of reaction temperature and 45min of reaction time, thus obtaining the melamine fiber spinning solution with the viscosity of 13500map.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.0cN/dtex, and the elongation at break is 9.8%; the breaking strength of the fiber prepared by dry spinning is 2.1cN/dtex, the elongation at break is 10.1 percent, and the limiting oxygen index is 35.

Example 2

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the amount, the reaction temperature is 90 ℃, the pH value is 9.7, and the reaction time is 120min, so that the melamine fiber spinning solution with the viscosity of 10800map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 1.5 parts of formic acid, 3.8 of pH value, 60 ℃ of reaction temperature and 28min of reaction time, and the melamine fiber spinning solution with the viscosity of 11800map.s is prepared.

Preparation of melamine fiber:

Example 3

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 10.5, the reaction temperature is 90 ℃, and the reaction time is 100min, so that the melamine fiber spinning solution with the viscosity of 12400map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 1.2 parts of acetic acid, 4.1 of pH value, 60 ℃ of reaction temperature and 25min of reaction time, and the melamine fiber spinning solution with the viscosity of 15800map.s is prepared.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 1.9cN/dtex, and the elongation at break is 10.4%; the fiber prepared by dry spinning has the breaking strength of 2.0cN/dtex, the elongation at break of 10.5 percent and the limited oxygen index of 33.

Example 4

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the amount, the pH value is 9.0, the reaction temperature is 90 ℃, and the reaction time is 140min, so that the melamine fiber spinning solution with the viscosity of 13700map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 2.2 parts of acetic acid, 4.0 of pH value, 60 ℃ of reaction temperature and 35min of reaction time, and the melamine fiber spinning solution with the viscosity of 17800map.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.6cN/dtex, and the elongation at break is 15.8%; the breaking strength of the fiber prepared by dry spinning is 2.8cN/dtex, the elongation at break is 16.7 percent, and the limiting oxygen index is 34.

Example 5

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the amount, the pH value is 8.5, the reaction temperature is 90 ℃, the reaction time is 160min, and the melamine fiber spinning solution with the viscosity of 13900map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution by weight, the pH value of 8.5, the reaction temperature of 60 ℃ and the reaction time of 80min are adopted to prepare the melamine fiber spinning solution with the viscosity of 16300 map.s.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.4cN/dtex, and the elongation at break is 11.3%; the breaking strength of the fiber prepared by dry spinning is 2.6cN/dtex, the elongation at break is 12.1 percent, and the limiting oxygen index is 35.

Example 6

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 10.7, the reaction temperature is 100 ℃, the reaction time is 100min, and the melamine fiber spinning solution with the viscosity of 14800map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 1.6 parts of formic acid, 4.3 of pH value, 50 ℃ of reaction temperature and 25min of reaction time, and the melamine fiber spinning solution with the viscosity of 16200map.s is prepared.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.0cN/dtex, and the elongation at break is 9.5%; the breaking strength of the fiber prepared by dry spinning is 1.9cN/dtex, the elongation at break is 9.3 percent, and the limiting oxygen index is 34.

Example 7

Preparation of melamine spinning solution: (reduce the solvent proportion, solid content-76%)

The raw material ratio is as follows:

the components are used according to the dosage, the pH value is 8.7, the reaction temperature is 98 ℃, and the reaction time is 140min, so that the melamine fiber spinning solution with the viscosity of 10800map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 3.5 parts of phosphoric acid, 3.2 parts of pH value, 60 ℃ of reaction temperature and 35min of reaction time, and the melamine fiber spinning solution with the viscosity of 16400map.s is prepared.

Preparation of melamine fiber:

Example 8

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 10.3, the reaction temperature is 75 ℃, and the reaction time is 180min, so that the melamine fiber spinning solution with the viscosity of 9600map.s is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 2.0 parts of citric acid, 4.4 of pH value, 65 ℃ of reaction temperature and 55min of reaction time, thus obtaining the melamine fiber spinning solution with the viscosity of 14800 map.s.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.1cN/dtex, and the elongation at break is 9.8%; the breaking strength of the fiber prepared by dry spinning is 2.1cN/dtex, the elongation at break is 9.6 percent, and the limiting oxygen index is 32.

Example 9

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 8.9, the reaction temperature is 95 ℃, the reaction time is 130min, and the melamine fiber spinning solution with the viscosity of 11800map.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 2.5 parts of formic acid, 3.3 of pH value, 60 ℃ of reaction temperature and 45min of reaction time, and the melamine fiber spinning solution with the viscosity of 16100map.s is prepared.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.1cN/dtex, and the elongation at break is 12.3%; the breaking strength of the fiber prepared by dry spinning is 2.2cN/dtex, the elongation at break is 12.5 percent, and the limiting oxygen index is 35.

Example 10

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 9.3, the reaction temperature is 90 ℃, and the reaction time is 130min, so that the melamine fiber spinning solution with the viscosity of 9400map.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 2.5 parts of formic acid, 3.3 of pH value, 60 ℃ of reaction temperature and 25min of reaction time, and the melamine fiber spinning solution with the viscosity of 10100map.s is prepared.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 1.9cN/dtex, and the elongation at break is 9.5%; the breaking strength of the fiber prepared by dry spinning is 2.0cN/dtex, the elongation at break is 10.5 percent, and the limiting oxygen index is 35.

Example 11

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 10.4, the reaction temperature is 90 ℃, the reaction time is 130min, and the 14600map.s melamine fiber spinning solution is prepared.

Preparation of melamine spinning solution:

100 parts of the melamine spinning solution, 2.0 parts of formic acid, 3.0 of pH value, 60 ℃ of reaction temperature and 25min of reaction time to prepare the melamine fiber spinning solution with the viscosity of 19800map.

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 2.1cN/dtex, and the elongation at break is 12.8%; the breaking strength of the fiber prepared by dry spinning is 2.2cN/dtex, the elongation at break is 13.4 percent, and the limiting oxygen index is 32.

Example 12

Preparation of melamine spinning solution:

the raw material ratio is as follows:

the components are used according to the dosage, the pH value is 10.4, the reaction temperature is 90 ℃, and the reaction time is 130min, so that the 15800map.s melamine fiber spinning solution with the viscosity is prepared.

Preparation of melamine spinning solution:

Preparation of melamine fiber:

wet spinning and dry spinning are respectively adopted, and the performance of the fiber is respectively as follows: the breaking strength of the fiber prepared by wet spinning is 1.6cN/dtex, and the elongation at break is 8.5%; the fiber prepared by dry spinning has the breaking strength of 1.7cN/dtex, the elongation at break of 9.3 percent and the limited oxygen index of 33.

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Melamine spinning solution, spinning solution and melamine fiber

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