CN109881290B - Fireproof protective clothing, fabric and fiber - Google Patents
Fireproof protective clothing, fabric and fiber Download PDFInfo
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- CN109881290B CN109881290B CN201910079417.4A CN201910079417A CN109881290B CN 109881290 B CN109881290 B CN 109881290B CN 201910079417 A CN201910079417 A CN 201910079417A CN 109881290 B CN109881290 B CN 109881290B
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Abstract
A method of producing a fire-blocking fiber, comprising: dissolving the phenolic aldehyde prepolymer in an alcohol solution of polyvinyl alcohol to form a phenolic aldehyde prepolymer solution; adding polyethylene glycol, phosphate, dihydric phosphate and an alkaline compound into the phenolic aldehyde prepolymer solution to form a spinning solution; carrying out wet spinning to obtain nascent fiber; and then curing the nascent fiber, and soaking the cured fiber in an organic solvent at the temperature of 30-60 ℃ to obtain the fireproof fiber. The fireproof fiber provided by the invention is a flame-retardant fiber, has high tensile strength, good air permeability and low density, and can be used for preparing comfortable, light and fireproof protective clothing. The invention also provides protective clothing containing the fireproof fiber.
Description
Technical Field
The invention relates to protective clothing and fibers of the protective clothing, in particular to protective clothing with fireproof performance, fibers for producing the protective clothing and a fiber production method.
Background
The protective clothing is used in special environment and is mainly applied to industries, departments or places such as fire fighting, military industry, petrifaction, disinfection, laboratories and the like.
The protective clothing for fire prevention is widely applied in the fields of fire fighting, electric welding, metallurgy and the like. Such as fire-proof firefighter uniform disclosed in CN109091772A, fire-retardant yarn and protective uniform disclosed in CN109056137A for preparing protective uniform, protective uniform made of fire-retardant viscose disclosed in CN101397710A, etc.
One of the fibers used for the existing fireproof protective clothing is a general fiber added with a flame retardant, for example, the fabric of the protective clothing disclosed in CN107636217A adopts a phosphorus flame retardant, and the fabric of the protective clothing disclosed in CN106638015A adopts a phosphorus-nitrogen intumescent flame retardant. In order to solve the problem that the flame retardant gradually loses efficacy or falls off after exudation after the protective clothing is used for a long time or is washed for many times, the flame retardant performance is reduced, and the flame retardant fiber disclosed in CN108866668A adopts a method that a silane coupling agent grafts a combustion improver onto a polypropylene copolymer main chain, but the method can only be applied to specific polymer materials and flame retardants.
The other is a flame-retardant fiber with aromatic heterocyclic ring, highly cross-linked, metal chelated structure, but the flame-retardant fiber which can be used for protective clothing at present can be produced by a few manufacturers, for example, aromatic amide imide fiber PAIF is basically produced by Kermel in France, polyetherimide fiber PEIF is produced by Colorado in Japan, polyphenylene sulfide fiber PPSF is produced by a few manufacturers such as Toray, melamine fiber MLF is produced by BASF, and the yield is only hundreds to thousands of tons per year. Only a plurality of phenolic fiber PNF manufacturers exist, the PNF has the long-term heat-resistant temperature of 150 ℃, can instantly resist the high temperature of 2405 ℃, has the LOI of 30-32, can not burn when meeting flame, has the surface carbonization effect of flame retardance, does not release harmful gas, but has the PNF strength of 1.5-1.8cN/dtex, and still needs to be improved.
Disclosure of Invention
In order to solve the problems in the prior art, the application provides a fiber with fire-proof performance, protective clothing produced by the fiber and a production method of the fiber.
In a first aspect, the present invention provides a method for producing a fire-resistant fiber, comprising:
providing a phenolic prepolymer; wherein, the molecular structure of the phenolic prepolymer is as follows:
dissolving the phenolic aldehyde prepolymer in an alcohol solution of polyvinyl alcohol to form a phenolic aldehyde prepolymer solution;
adding polyethylene glycol, phosphate, dihydric phosphate and an alkaline compound into the phenolic aldehyde prepolymer solution to form a spinning solution; carrying out wet spinning to obtain nascent fiber;
then the primary fiber is cured,
and soaking the cured fiber in an organic solvent at the temperature of 30-60 ℃ to obtain the fireproof fiber.
In a preferred embodiment of the present invention, the alcohol solution may be one or more of methanol, ethanol, propanol, isopropanol, and butanol solution.
In a preferred embodiment of the present invention, the organic solvent is an organic solvent capable of dissolving polyvinyl alcohol and polyethylene glycol, such as halogenated hydrocarbon, alcohol, ketone, ester solvent, preferably any one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, chlorobenzene, dichloromethane, chloroform, dichloroethane, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone.
In a preferred embodiment, the weight ratio of the polyethylene glycol to the phenolic prepolymer is preferably 1: 5-10, more preferably 1: 6-9, and more preferably 1: 7-8.
In a preferred embodiment of the invention, the phosphate is preferably an alkali metal phosphate, such as sodium phosphate, potassium phosphate.
In a preferred embodiment of the invention, the phosphate is preferably an alkali metal phosphate, such as sodium dihydrogen phosphate, potassium dihydrogen phosphate.
More preferably, the molar ratio of the dihydrogen phosphate to the phosphate is preferably 1: 1.5-3, more preferably 1: 1.8-2.5, and more preferably 1: 2-2.3.
More preferably, the ratio of the total weight of the phosphate salt and the dihydrogen phosphate salt to the weight of the phenolic prepolymer is preferably 1: (20-50), more preferably 1: (25-40), and more preferably 1: (30-35).
In a preferred embodiment of the present invention, the basic compound is preferably a hydroxide, ammonia or an amine compound, more preferably an alkali metal hydroxide (e.g., NaOH, KOH, etc.), or triethanolamine, etc.
In a preferred embodiment of the present invention, the weight ratio of the alkaline compound to the phenolic prepolymer is preferably 1: 5-10, more preferably 1: 6-8.
More preferably, the pH of the dope is preferably 7 to 10, more preferably 8 to 9.
In a preferred embodiment of the invention, the fibres are soaked in the organic solvent for 1 to 5 hours, more preferably 1 to 3 hours.
In a preferred embodiment of the present invention, the curing treatment is preferably carried out at a temperature of 140 ℃ and 170 ℃, more preferably at a temperature of 150 ℃ and 160 ℃.
In a preferred embodiment of the present invention, the curing treatment time is preferably at least 30 minutes, more preferably 1 to 5 hours, more preferably 2 to 4 hours.
In a second aspect, the invention provides a fire-resistant fiber, which is prepared by the method.
The third aspect of the invention provides fireproof protective clothing which comprises the fireproof fiber.
More preferably, the fabric of the fireproof protective clothing is made of the fireproof fiber.
However, it should be understood that the fabric of the fire protective clothing may contain necessary components, pigments, etc. in addition to the fire-resistant fibers, for example, the components may be zippers, buttons, etc.
The fireproof fiber provided by the invention is a flame-retardant fiber, has high tensile strength, good air permeability and low density, and can be used for preparing comfortable, light and fireproof protective clothing.
Detailed Description
Example 1
Under the condition of alkali catalysis, formaldehyde and phenol are subjected to the following addition reaction:
during this reaction, a mixture of monohydric phenol alcohol and polyhydric phenol alcohol is formed.
Then, a molecular chain extension reaction is carried out, wherein the reaction process is carried out between adjacent para-hydrogen of hydroxymethyl and other phenol:
thereby obtaining a resol prepolymer.
10kg of the phenolic prepolymer was dissolved in a butanol solution of polyvinyl alcohol to form a phenolic prepolymer solution. The amount and concentration of the butanol solution of the polyvinyl alcohol are not limited in this embodiment, as long as the phenolic prepolymer solution meets the requirement of the wet spinning process for viscosity.
1.5kg of polyethylene glycol, 0.1kg of sodium dihydrogen phosphate, 0.2kg of sodium phosphate and 1kg of sodium hydroxide are added into the phenolic prepolymer solution to form an alkaline spinning solution.
And (3) carrying out wet spinning, dehydrating and removing aldehyde in a coagulating bath by adopting a saturated sodium sulfate solution of boric acid, and removing water generated by the reaction and excessive formaldehyde to obtain nascent fiber. If a relatively pure phenol-formaldehyde prepolymer is used, water and aldehyde are not present, and dehydration and aldehyde removal may not be performed.
The as-spun fibers were then heated at 150 ℃ for 4 hours to effect a curing and crosslinking treatment.
Soaking the cured fiber in 30-60 deg.C ethanol for 1-3 hr, taking out, and drying.
Example 2
10kg of the phenolic prepolymer was dissolved in a butanol solution of polyvinyl alcohol to form a phenolic prepolymer solution. The amount and concentration of the butanol solution of the polyvinyl alcohol are not limited in this embodiment, as long as the phenolic prepolymer solution meets the requirement of the wet spinning process for viscosity.
2kg of polyethylene glycol, 0.1kg of sodium dihydrogen phosphate, 0.2kg of sodium phosphate and 1.5kg of sodium hydroxide are added into the phenolic prepolymer solution to form an alkaline spinning solution.
And (3) carrying out wet spinning to obtain the nascent fiber, wherein the coagulating bath is subjected to dehydration and dealdehydizing treatment by adopting a saturated sodium sulfate solution of boric acid, and water generated by the reaction and excessive formaldehyde are removed to obtain the nascent fiber. If a relatively pure phenol-formaldehyde prepolymer is used, water and aldehyde are not present, and dehydration and aldehyde removal may not be performed.
The as-spun fibers were then heated at 150 ℃ for 2 hours for curing and crosslinking.
Soaking the cured fiber in ethyl acetate at 30-60 deg.c for 1-3 hr and taking out.
Example 3
10kg of the phenolic prepolymer was dissolved in a butanol solution of polyvinyl alcohol to form a phenolic prepolymer solution. The amount and concentration of the butanol solution of the polyvinyl alcohol are not limited in this embodiment, as long as the phenolic prepolymer solution meets the requirement of the wet spinning process for viscosity.
1.5kg of polyethylene glycol, 0.1kg of sodium dihydrogen phosphate, 0.2kg of sodium phosphate and 1.5kg of sodium hydroxide are added into the phenolic prepolymer solution to form an alkaline spinning solution.
And carrying out wet spinning to obtain the nascent fiber.
The as-spun fibers were then heated at 150 ℃ for 3 hours to effect a curing and crosslinking treatment.
Soaking the cured fiber in ethyl acetate at 30-60 deg.c for 1-3 hr and taking out.
Comparative example 1
10kg of the phenolic prepolymer was dissolved in a butanol solution of polyvinyl alcohol to form a phenolic prepolymer solution. The amount and concentration of the butanol solution of the polyvinyl alcohol are not limited in this embodiment, as long as the phenolic prepolymer solution meets the requirement of the wet spinning process for viscosity.
2kg of sodium hydroxide was added to the phenolic prepolymer solution to form an alkaline spinning dope.
Referring to example 1, a wet spinning was performed to obtain a nascent fiber. The as-spun fibers were then heated at 150 ℃ for 3 hours to effect a curing and crosslinking treatment.
| LOI | Tensile strength | Density of | Air permeability of fabric | |
| Example 1 | 36 | 4.5cN/dtex | 1.05g/km | 720.1L/m2·s |
| Example 2 | 36 | 4.4cN/dtex | 1.10g/km | 718.3L/m2·s |
| Example 3 | 36 | 4.5cN/dtex | 1.08g/km | 718.7L/m2·s |
| Comparative example 1 | 31 | 4.4cN/dtex | 1.26g/km | 546.5L/m2·s |
Compared with the traditional phenolic fiber wet spinning method, the LOI of the fiber obtained by the method is obviously improved (has obvious difference), and the fireproof performance of the phenolic fiber is improved. This may be due to the esterification of the phosphate and/or dihydrogen phosphate during the cross-linking and curing of the phenolic fibres, thereby forming a flame retardant; in addition, the polyvinyl alcohol can be removed more completely, and the performance of the phenolic fiber is prevented from being reduced by the polyvinyl alcohol.
In addition, the phenolic fiber obtained by the method of the application obtains smaller density and better air permeability without influencing tensile strength, which is probably due to the following reasons: pores are formed in the phenolic fibers in the process of removing the polyvinyl alcohol and the polyethylene glycol.
Meanwhile, the existence of phosphate and dihydric phosphate can prevent the drastic change of the pH value of the spinning solution, avoid the esterification reaction between the polyvinyl alcohol and the polyethylene glycol and the phenolic prepolymer, ensure the smooth spinning and the maintenance of the performance of the final fiber.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (3)
1. A method of producing a fire-resistant fiber, comprising:
providing a phenolic prepolymer; wherein, the molecular structure of the phenolic prepolymer is as follows:
dissolving the phenolic aldehyde prepolymer in an alcohol solution of polyvinyl alcohol to form a phenolic aldehyde prepolymer solution;
adding polyethylene glycol, phosphate, dihydric phosphate and an alkaline compound into the phenolic aldehyde prepolymer solution to form a spinning solution; carrying out wet spinning to obtain nascent fiber; wherein the weight ratio of the polyethylene glycol to the phenolic prepolymer is 1: 5-10; the molar ratio of the dihydric phosphate to the phosphate is 1: 1.5-3; the ratio of the total weight of the phosphate and the dihydric phosphate to the weight of the phenolic prepolymer is 1: 20-50; the pH value of the spinning solution is 7-10; the alkaline compound is NaOH, KOH or triethanolamine;
then the primary fiber is cured,
and soaking the cured fiber in an organic solvent capable of dissolving polyvinyl alcohol and polyethylene glycol at 30-60 ℃ to obtain the fireproof fiber.
2. The method for producing the flameproof fiber of claim 1, wherein the ratio by weight of the basic compound to the phenolic prepolymer is 1: 5-10.
3. The method for producing a flameproof fiber according to claim 1, wherein the curing treatment is carried out at a temperature of 140 ℃ and 170 ℃ for at least 30 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910079417.4A CN109881290B (en) | 2019-01-28 | 2019-01-28 | Fireproof protective clothing, fabric and fiber |
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| CN201910079417.4A CN109881290B (en) | 2019-01-28 | 2019-01-28 | Fireproof protective clothing, fabric and fiber |
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| CN109881290B true CN109881290B (en) | 2021-10-29 |
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| KR101370868B1 (en) * | 2011-04-11 | 2014-03-27 | 주식회사 포스포 | Carbonfiber by polyfurfuryl alcohol and its manufacturing method for thereof |
| CN106521715B (en) * | 2015-09-11 | 2019-08-30 | 五邑大学 | A kind of preparation method of high specific surface micro-pore carbon fiber |
| CN106811822B (en) * | 2016-12-19 | 2020-05-05 | 山东圣泉新材料股份有限公司 | Modified phenolic resin fiber and preparation method and application thereof |
| CN109112666B (en) * | 2018-07-27 | 2021-01-26 | 中原工学院 | Method for preparing phenolic fiber through wet spinning |
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