CN109881290A - A kind of fire prevention protective garment, fabric and fiber - Google Patents

A kind of fire prevention protective garment, fabric and fiber Download PDF

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Publication number
CN109881290A
CN109881290A CN201910079417.4A CN201910079417A CN109881290A CN 109881290 A CN109881290 A CN 109881290A CN 201910079417 A CN201910079417 A CN 201910079417A CN 109881290 A CN109881290 A CN 109881290A
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Prior art keywords
fire proofing
phenolic aldehyde
proofing firbre
production
phosphate
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CN201910079417.4A
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CN109881290B (en
Inventor
蒋春燕
陈太球
王炳来
巫瑛
叶远丽
李飞
冯志忠
徐雪妮
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Swoto Protection and Technology Co Ltd
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Swoto Protection and Technology Co Ltd
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Abstract

A kind of production method of fire proofing firbre, comprising: phenolic aldehyde prepolymer is dissolved in the alcoholic solution of polyvinyl alcohol, forms phenolic aldehyde pre-polymer solution;Polyethylene glycol, phosphate, dihydric phosphate, alkali compounds are added in phenolic aldehyde pre-polymer solution and form spinning solution;It carries out wet spinning and obtains as-spun fibre;Then as-spun fibre is subjected to curing process, the fiber after solidification impregnates in 30-60 DEG C of organic solvent, obtains fire proofing firbre.The present invention also provides the fire proofing firbre of above method production, fire proofing firbre provided by the present invention is fire retardant grade fiber, and tensile strength is high, and good permeability, and density is low, can prepare comfortable, light, fireproof protective garment.The present invention also provides a kind of protective garments containing above-mentioned fire proofing firbre.

Description

A kind of fire prevention protective garment, fabric and fiber
Technical field
The fiber taken the present invention relates to a kind of protective garment and protection more particularly to a kind of protection with fire protecting performance Clothes, the fiber for producing the protective garment, fiber production method.
Background technique
Protective garment is the clothes used under particular surroundings, is mainly used in the row such as fire-fighting, military project, petrochemical industry, disinfection, laboratory Industry, department or place.
The protective garment of fire prevention is widely used in fields such as fire-fighting, electric welding, metallurgy.Such as prevent disclosed in CN109091772A The flame-retardant yarn and protective garment, CN101397710A that protective garment is used to prepare disclosed in fiery fire-entry suit, CN109056137A disclose The production of fire-retardant viscose protective garment etc..
Fiber used in fire prevention protective garment at present, one is general fibers to add fire retardant, such as CN107636217A is disclosed The fabric taken of protection using phosphorus flame retardant, protective garment fabric disclosed in CN106638015A is swollen using phosphorus-nitrogen system Swollen type fire retardant.Fire retardant falls off after gradually failing or ooze out after protective garment long-time use is perhaps repeatedly washed, fire-retardant Performance decline, in order to solve this problem, fire resistance fibre disclosed in CN108866668A is using silane coupling agent by combustion adjuvant The method being grafted on polypropylene copolymer main chain, but this method may be only available for particular polymers material and fire retardant.
Another kind can be still used at present with heteroaromatic, highly cross-linked, the isostructural flame-resistant fibre of metal-chelating In this kind of fire resistance fibre of protective garment, the producer being able to produce is simultaneously few, such as fragrant amide imide fiber PAIF is substantially only There is French Kermel to produce, polyether-imide fiber PEIF only has the production of Kuraray company, and polyphenylene sulfide fibre PPSF is only There is east is beautiful to wait a small number of producers' productions, melacel MLF only has BASF production, and yield is only several hundred every year to arrive a few kiloton.Only phenol Aldehyde fiber PNF manufacturer is more, and the long-term heat resisting temperature of PNF is 150 DEG C, and moment is resistant to 2405 DEG C of high temperature, and LOI 30-32 is met Flame does not burn, and surface carbonation plays flame retardant effect, does not discharge pernicious gas, and still, PNF intensity only has 1.5-1.8cN/ Dtex, it is still to be improved.
Summary of the invention
Of the existing technology in order to solve the problems, such as, this application provides a kind of fibers with fire protecting performance, the fibre Tie up the protective garment of production and the production method of the fiber.
First aspect of the present invention is to provide a kind of production method of fire proofing firbre, comprising:
Phenolic aldehyde prepolymer is provided;Wherein, phenolic aldehyde prepolymer molecule structure are as follows:
Phenolic aldehyde prepolymer is dissolved in the alcoholic solution of polyvinyl alcohol, forms phenolic aldehyde pre-polymer solution;
Polyethylene glycol, phosphate, dihydric phosphate, alkali compounds are added in phenolic aldehyde pre-polymer solution and form spinning Stoste;It carries out wet spinning and obtains as-spun fibre;
Then as-spun fibre is subjected to curing process,
Fiber after solidification impregnates in 30-60 DEG C of organic solvent, obtains fire proofing firbre.
In one preferred embodiment of the invention, the alcoholic solution can be methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol One or more of solution.
In one preferred embodiment of the invention, the organic solvent is to be capable of the pure and mild polyethylene glycol of polyethylene dissolving Organic solvent, such as halogenated hydrocarbons, alcohol, ketone, esters solvent, preferably methanol, ethyl alcohol, propyl alcohol, isopropanol, ethylene glycol, chlorobenzene, two Chloromethanes, chloroform, dichloroethanes, methyl acetate, ethyl acetate, propyl acetate, acetone, espeleton, in methylisobutylketone Any one or more.
In an advantageous embodiment, the polyethylene glycol and phenolic aldehyde prepolymer weight ratio are preferably 1 ︰ (5-10), more Preferably 1 ︰ (6-9), more preferably 1 ︰ (7-8).
In one preferred embodiment of the invention, the phosphate is preferably alkali metal phosphate, such as sodium phosphate, phosphoric acid Potassium.
In one preferred embodiment of the invention, the phosphate is preferably alkali metal phosphate, as sodium dihydrogen phosphate, Potassium dihydrogen phosphate.
It is highly preferred that the dihydric phosphate and phosphatic molar ratio are preferably 1 ︰ (1.5-3), more preferably 1 ︰ (1.8-2.5), more preferably 1 ︰ (2-2.3).
It is highly preferred that the total weight and phenolic aldehyde prepolymer weight ratio of the phosphate and dihydric phosphate are preferably 1 ︰ (20-50), more preferably 1 ︰ (25-40), more preferably 1 ︰ (30-35).
In one preferred embodiment of the invention, the alkali compounds is preferably hydroxide, ammonia or amine compounds, More preferably alkali metal hydroxide (such as NaOH, KOH) or triethanolamine etc..
In one preferred embodiment of the invention, the alkali compounds and phenolic aldehyde prepolymer weight ratio are preferably 1 ︰ (5-10), more preferably 1 ︰ (6-8).
It is highly preferred that the spinning solution pH value is preferably 7-10, it is more selected as 8-9.
In one preferred embodiment of the invention, the fiber impregnates 1-5 hours, more preferably 1- in organic solvent 3 hours.
In one preferred embodiment of the invention, the curing process preferably carries out at a temperature of 140-170 DEG C, more It is carried out at a temperature of preferably 150-160 DEG C.
In one preferred embodiment of the invention, the curing process time is preferably at least 30 minutes, more preferably 1-5 hours, more preferably 2-4 hours.
The second aspect of the present invention is to provide a kind of fire proofing firbre, and the fire proofing firbre is prepared using the above method.
Third aspect of the present invention is to provide a kind of fire prevention protective garment, and the fire prevention protective garment includes that the fire prevention is fine Dimension.
It is highly preferred that the fabric of the fire prevention protective garment is prepared by the fire proofing firbre.
However, it should be understood that it is described fire prevention protective garment fabric can containing in addition to fire proofing firbre necessary parts, Pigment etc., for example, the component can be zipper, button etc..
Fire proofing firbre provided by the present invention is fire retardant grade fiber, and tensile strength is high, and good permeability, and density is low, can Prepare comfortable, light, fireproof protective garment.
Specific embodiment
Embodiment 1
Under the conditions of base catalysis, formaldehyde and phenol carry out following addition reaction:
In the reaction process, the mixture of unitary phenolic alcohol Yu polynary phenolic alcohol is generated.
Then, molecule chain propagation reaction is carried out, which carries out between methylol and the ortho para position hydrogen of other phenol:
To obtain soluble phenolic aldehyde prepolymer.
10kg phenolic aldehyde prepolymer is dissolved in the butanol solution of polyvinyl alcohol, phenolic aldehyde pre-polymer solution is formed.Polyvinyl alcohol Butanol solution dosage and concentration, the present embodiment with no restrictions, as long as phenolic aldehyde pre-polymer solution is enabled to meet Wet-spinning Requirement of the silk technique to viscosity.
Polyethylene glycol 1.5kg, sodium dihydrogen phosphate 0.1kg, sodium phosphate 0.2kg, sodium hydroxide 1kg are added to phenolic aldehyde prepolymer In solution, alkaline spinning solution is formed.
Wet spinning is carried out, coagulating bath is dehydrated using the saturation metabisulfite solution of boric acid, full gear is handled, removal reaction The water of generation and excessive formaldehyde obtain as-spun fibre.If be not present using more pure phenolic aldehyde prepolymer Water and aldehyde, can be without dehydration, full gear processing.
Then as-spun fibre heats 4 hours at 150 DEG C and carries out solidification crosslinking Treatment.
Fiber after solidification is immersed in 30-60 DEG C of ethyl alcohol, is taken out after impregnating 1-3 hours, it is dry.
Embodiment 2
10kg phenolic aldehyde prepolymer is dissolved in the butanol solution of polyvinyl alcohol, phenolic aldehyde pre-polymer solution is formed.Polyvinyl alcohol Butanol solution dosage and concentration, the present embodiment with no restrictions, as long as phenolic aldehyde pre-polymer solution is enabled to meet Wet-spinning Requirement of the silk technique to viscosity.
Polyethylene glycol 2kg, sodium dihydrogen phosphate 0.1kg, sodium phosphate 0.2kg, sodium hydroxide 1.5kg are added to phenolic aldehyde prepolymer In solution, alkaline spinning solution is formed.
Carry out wet spinning obtain as-spun fibre, wherein coagulating bath using boric acid saturation metabisulfite solution be dehydrated, Full gear processing, the water and excessive formaldehyde that removal reaction generates, obtains as-spun fibre.If using more pure phenol Water and aldehyde is then not present in aldehyde prepolymer, can be without dehydration, full gear processing.
Then as-spun fibre heats 2 hours at 150 DEG C and carries out solidification crosslinking Treatment.
Fiber after solidification is immersed in 30-60 DEG C of ethyl acetate, is taken out after impregnating 1-3 hours.
Embodiment 3
10kg phenolic aldehyde prepolymer is dissolved in the butanol solution of polyvinyl alcohol, phenolic aldehyde pre-polymer solution is formed.Polyvinyl alcohol Butanol solution dosage and concentration, the present embodiment with no restrictions, as long as phenolic aldehyde pre-polymer solution is enabled to meet Wet-spinning Requirement of the silk technique to viscosity.
Polyethylene glycol 1.5kg, sodium dihydrogen phosphate 0.1kg, sodium phosphate 0.2kg, sodium hydroxide 1.5kg are added to phenolic aldehyde pre-polymerization In object solution, alkaline spinning solution is formed.
It carries out wet spinning and obtains as-spun fibre.
Then as-spun fibre heats 3 hours at 150 DEG C and carries out solidification crosslinking Treatment.
Fiber after solidification is immersed in 30-60 DEG C of ethyl acetate, is taken out after impregnating 1-3 hours.
Comparative example 1
10kg phenolic aldehyde prepolymer is dissolved in the butanol solution of polyvinyl alcohol, phenolic aldehyde pre-polymer solution is formed.Polyvinyl alcohol Butanol solution dosage and concentration, the present embodiment with no restrictions, as long as phenolic aldehyde pre-polymer solution is enabled to meet Wet-spinning Requirement of the silk technique to viscosity.
Sodium hydroxide 2kg is added in phenolic aldehyde pre-polymer solution, forms alkaline spinning solution.
Referring to embodiment 1, carries out wet spinning and obtain as-spun fibre.Then as-spun fibre is heated 3 hours at 150 DEG C and is carried out Solidify crosslinking Treatment.
LOI Tensile strength Density Fabric Air permenbility
Embodiment 1 36 4.5cN/dtex 1.05g/km 720.1L/m2·s
Embodiment 2 36 4.4cN/dtex 1.10g/km 718.3L/m2·s
Embodiment 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
It can be seen that by above-mentioned comparison compared to traditional phenolic fibre wet spinning, the application fiber obtained LOI is significantly improved and (has significant difference), improves the fire protecting performance of phenolic fibre.This may be due to phosphate and/ Or during phenolic fibre crosslinking curing esterification occurs for dihydric phosphate, to form fire retardant;Additionally, it is also possible to be The removal of polyvinyl alcohol is more thorough, and polyvinyl alcohol is avoided to reduce the performance of phenolic fibre.
In addition, the phenolic fibre that the application method obtains obtains smaller close in the case where not influencing tensile strength Degree and better Air permenbility, this may be due to: formed in phenolic fibre during removing polyvinyl alcohol, polyethylene glycol Stomata.
Meanwhile the presence of phosphate and dihydric phosphate, the violent variation of spinning solution pH value can be prevented, poly- second is avoided Esterification between enol and polyethylene glycol and phenolic aldehyde prepolymer, it is ensured that spinning is gone on smoothly, and the performance of final fiber Holding.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and Modification, all should be contained within the scope of the invention.

Claims (10)

1. a kind of production method of fire proofing firbre characterized by comprising
Phenolic aldehyde prepolymer is provided;Wherein, phenolic aldehyde prepolymer molecule structure are as follows:
Phenolic aldehyde prepolymer is dissolved in the alcoholic solution of polyvinyl alcohol, forms phenolic aldehyde pre-polymer solution;
Polyethylene glycol, phosphate, dihydric phosphate, alkali compounds are added in phenolic aldehyde pre-polymer solution and form spinning original Liquid;It carries out wet spinning and obtains as-spun fibre;
Then as-spun fibre is subjected to curing process,
Fiber after solidification impregnates in 30-60 DEG C of organic solvent, obtains fire proofing firbre.
2. the production method of fire proofing firbre according to claim 1, which is characterized in that the organic solvent is that can dissolve The organic solvent of polyvinyl alcohol and polyethylene glycol.
3. the production method of fire proofing firbre according to claim 1, which is characterized in that the polyethylene glycol and phenolic aldehyde pre-polymerization Object weight ratio is 1 ︰ (5-10).
4. the production method of fire proofing firbre according to claim 1, which is characterized in that the dihydric phosphate and phosphate Molar ratio be 1 ︰ (1.5-3).
5. the production method of fire proofing firbre according to claim 1 or 4, which is characterized in that the phosphate and di(2-ethylhexyl)phosphate The total weight and phenolic aldehyde prepolymer weight ratio of hydrogen salt are 1 ︰ (20-50).
6. the production method of fire proofing firbre according to claim 1, which is characterized in that the alkali compounds and phenolic aldehyde are pre- Polymers weight ratio is 1 ︰ (5-10).
7. the production method of fire proofing firbre according to claim 1, which is characterized in that the spinning solution pH value is 7- 10。
8. the production method of fire proofing firbre according to claim 1, which is characterized in that the curing process preferably exists It is carried out at a temperature of 140-170 DEG C at least 30 minutes.
9. a kind of fire proofing firbre of claim 1 the method production.
10. a kind of fire prevention protective garment, which is characterized in that the fire prevention protective garment includes the fire proofing firbre.
CN201910079417.4A 2019-01-28 2019-01-28 Fireproof protective clothing, fabric and fiber Active CN109881290B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110629300A (en) * 2019-08-30 2019-12-31 中国科学院山西煤炭化学研究所 Preparation method of continuous filament bundle phenolic fiber

Citations (4)

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Publication number Priority date Publication date Assignee Title
KR101370868B1 (en) * 2011-04-11 2014-03-27 주식회사 포스포 Carbonfiber by polyfurfuryl alcohol and its manufacturing method for thereof
CN106521715A (en) * 2015-09-11 2017-03-22 五邑大学 Preparing method of microporous carbon fiber with high specific surface area
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KR101370868B1 (en) * 2011-04-11 2014-03-27 주식회사 포스포 Carbonfiber by polyfurfuryl alcohol and its manufacturing method for thereof
CN106521715A (en) * 2015-09-11 2017-03-22 五邑大学 Preparing method of microporous carbon fiber with high specific surface area
CN106811822A (en) * 2016-12-19 2017-06-09 山东圣泉新材料股份有限公司 A kind of phenol-formaldehyde resin modified fiber and its production and use
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Publication number Priority date Publication date Assignee Title
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