CN101514526A - Modified polyacrylonitrile fiber (fabric) with flame retardant or noncombustible performance and a preparation method thereof - Google Patents
Modified polyacrylonitrile fiber (fabric) with flame retardant or noncombustible performance and a preparation method thereof Download PDFInfo
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- CN101514526A CN101514526A CNA2009100461257A CN200910046125A CN101514526A CN 101514526 A CN101514526 A CN 101514526A CN A2009100461257 A CNA2009100461257 A CN A2009100461257A CN 200910046125 A CN200910046125 A CN 200910046125A CN 101514526 A CN101514526 A CN 101514526A
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Abstract
The invention relates to a modified polyacrylonitrile fibre with flame retardant or noncombustible performance and a preparation method thereof. The fiber is characterized in that: each 100kg fabric comprises the ingredients with the following contents: 0.75kg-14kg hydrazine hydrate, 2 kg-3kg sodium hydroxide, 3kg-5kg hydrochloric acid, 9kg-15kg organic amine, 0.5kg-1.50kg zinc sulfate or calcium carbonate, 0.7kg-1.50kg calcium chloride and 0.8kg-1.50kg copper sulfate. The preparation method comprises the following steps: firstly using amine aqueous solution with concentration of 18%-30% or hydrazine hydrate with concentration of 15%-28% for the fiber or fabric, then adding the deoiled fiber or fabric into the catalyst hydrazine hydrate at the temperature of 80 DEG C-100 DEG C by a bath ratio 1:15-25; keeping the temperature at 95 DEG C-100 DEG C and stirring the mixture for 38 minutes-45 minutes to obtain the modified fiber; adding the processed modified fiber into calcium salt solution or cupric salt solution or zinc sulfate solution while the bath ratio is 1:15-25, then processing the mixture for 30 minutes-60 minutes at the temperature of 80 DEG C-100 DEG C to ensure the water content of the fiber or fabric to reach about 28% of bound water and about 25% of chelated water and ensure the metal atom to be complex with cyano-group; washing and drying. The method improves the two shortcomings of the original PAN fiber or fabric, such as easy combustion and easy generation of static under the condition of friction.
Description
Technical field
The invention belongs to modified polyacrylonitrile fiber dimension and preparation field thereof, particularly relate to modified polyacrylonitrile fiber dimension (fabric) that has anti-combustion or do not fire and preparation method thereof.
Background technology
Polyacrylonitrile (acrylic fibers) fiber or fabric can be dyed bright-coloured color and luster, excellent abrasive, good warmth retention property (artificial wool), the feel of uniqueness and good characteristics such as flexibility with cation dyes, become one of current important synthetic fiber, and be widely used in daily life and the industrial production.But acrylic fiber or fabric have two big shortcomings: the one, very easily burn; The 2nd, very easily produce static, thereby limited its scope of application greatly.
In the fifties in last century, Houtz just finds that PAN fiber or fabric are heated to uniform temperature, will initial ring under catalyst action changes into to be the big molecule of trapezium structure:
Cu
+ 2Ion just with the ring in N atom generation bonding or chelating.
What produce table flame-retardant acrylic fibre fiber the earliest is U.S. carbonization company, the acrylic filaments that provided in the first batch to market in 1948 (An: Vcl is 40: 60).Vinyon N fire resistance fibre and fabric that this technology is simple, price is low to fire-retardant less demanding place, also have quite daily consumption at some so far.At present, fire resistance is the most effective in the worldwide surely belongs to " Kanekalon " that Japanese Zhong Yuan company produces.It is by propylene and vinyl chloride or vinylidene chloride and bromine ethylene copolymer, adds an amount of nanoscale Sb in spinning solution again
2O
3Powder is made fire resistance fibre, makes with the blend of 30-40% cotton fiber again.The fire resistance of Kanekalon reaches the flame-retardant standard of the U.S., Britain (West Europe), Japan and China fully, and its limited oxygen index (Limeting-Oxygen-Index is LoI) reaches 32.The method of testing of LoI is by following formula LoI=[o by standard GB 2406-80 before China
2]/([o
2]+[N
2]) * 100% records.More than these flame-retardant acrylic fibre fibers all be with halide and Sb
2O
3Make, it is fire-retardant to belong to gas phase, and its shortcoming can discharge HCl, BaCl when being burning
2, toxic gas such as HCN do not reach anti-combustion or noninflammability energy yet.
Summary of the invention
Technical problem to be solved by this invention provides modified polyacrylonitrile fiber dimension (fabric) that has anti-combustion and do not fire and preparation method thereof, and this method has greatly been improved former PAN fiber or fabric easy firing and be easy to generate two big shortcomings of static under friction.
The modified polyacrylonitrile fiber that has anti-combustion or do not fire of the present invention is tieed up (fabric), it is characterized in that comprising in every 100kg fabric the component of following content:
Hydrazine hydrate 0.75kg-14kg
NaOH 2kg-3kg
Hydrochloric acid 3kg-5kg
Organic amine 9kg-15kg
Zinc sulfate 0.5kg-1.50kg
Calcium chloride or calcium carbonate 0.7kg-1.50kg
Copper sulphate 0.8kg-1.50kg
Described calcium chloride must just can dissolve in hydrochloric acid solution, and zinc sulfate, copper sulphate use under neutrality or slightly acidic condition.
Described copper sulphate must dissolve in warm water earlier fully, and the form with solution adds again.
Make anti-combustion or do not fire, behind the conductive articles, must the abundant rinsing of water, solarization or oven dry become final products.
Preparation method with modified polyacrylonitrile fiber dimension (fabric) that anti-combustion or not of the present invention comprises:
This fiber or fabric are 18%-30% with concentration earlier, amine aqueous solution or concentration are 15%-28%, hydrazine hydrate, at 80 ℃-100 ℃, with bath raio is 1: 15-25 adds fiber or the fabric that deoiled, temperature remains on 95 ℃-100 ℃, stir 38min-45min and get modified fibre, is 10%-25%NaOH aqueous hydrolysis fiber with this modified fibre in concentration, be the further hydrolysis of 10%-25%HCl aqueous solution neutralization bases with concentration again, washing pH value remains on the acid range of 1-5, be 1 in bath raio afterwards: the modified fibre with above-mentioned processing under the 15-25 joins calcium salt or mantoquita calcium salt or mantoquita (calcium chloride, calcium carbonate or copper sulphate) or solution of zinc sulfate in or in the solution of zinc sulfate, locate 30min-60min at 80 ℃-100 ℃, make fiber or fabric moisture reach the chelating water of 28% right and left key Heshui and about 25%, and make metallic atom and cyano group complexing, clean oven dry.But hydrazine hydrate or organic amine solution catalysis acrylic fiber or fabric generation cyclized structure add copper sulphate or zinc sulfate or calcium chloride solution then.After the acrylic fiber cyclisation, also leave two on the nitrogen-atoms in the structure and be not easy to and metal cation generation bonding or chelating in conjunction with electronics, the product after the cyclisation also leaves a small amount of cyano group and also is easy to and metal cation generation bonding or chelating in addition.
This structurally-modified fiber or fabric burning can not emitted toxic substance and unpleasant gases such as hydrogen halides, sulfide, phosphide, cyanic acid.This fiber and fabric also have good washability.Using pure this noncombustible textile to can be used for space flight, spaceship, aviation, fireman etc., dress is this does not fire the clothes that thermal insulation is good
If with 50% cotton or acrylic fibers and fiber blend of the present invention or the fabric that interweaves, then can be used for the curtain chair cover tablecloth of use such as aircraft train vehicle steamer and carpet upper strata drape etc.; At indoor decorating cloth, carpet upper strata drape and woolen toy, children, old man's nightwear, the bedding etc. of can be used for.
The present invention is earlier with solution catalyzing acrylic fiber cyclisation such as amine aqueous solution or hydrazine hydrates, in this process fiber absorbs a large amount of hydrones, make metallic atom by the N atom in the cyclisation thing and remaining-CN bonding or chelating with slaine then, the big molecule of such cyclisation just has high anti-combustion, so that the fiber or the fabric that do not fire.
This anti-(no) fires fiber and fabric, not only reaches the anti-combustion standard of the U.S., Britain (West Europe), Japan and China fully, and LoI＞50, reaches the standard of noncombustible textile.This is because amine concentration and process conditions that catalytic cyclization is used are reasonable, the cyclisation product water absorption of production is increased, good flame resistance.
Heat, oxygen, fuel are three fundamentals that any material (comprising fiber and fabric) is kept burning, remove wherein any one key element, all will stop burning to continue.We are around these three fire retardant mechanisms that will usually inquire into big molecule modified fibre and fabric.We are with the I in the example three
#, II
#, III
#Carry out differential scanning heat (DSC) respectively and measure, must figure two shown in: 1
#, number be fabric without flame treatment, have only an exothermic peak in burning; 2
#Number fabric be through amine aqueous solution after uniform temperature is handled certain hour, a series of cyclization takes place in acrylic fiber in the fabric, finds a strong endothermic peak to occur at 42.42 ℃ to 160 ℃, this is that the macromolecular physical absorption water evaporation of cyclisation is emitted due to the heat; 3
#Fabric fuel factor on DSC is more obvious, and 109.44 ℃ is the endothermic peak of the physical absorption water heating evaporation of fabric; 314.79 ℃-346.52 ℃ of two endothermic peaks are the bonding on the N atom or chelating water evaporation endothermic peaks that heat release occurred in the cyclisation flame-retardant textile; A part be with big molecule in cyano group form hydrogen bond water, another part is with complexing water, so two peaks occur; 413.01 a ℃ endothermic peak is in the flame-retardant textile due to the bonding evaporation of water.So various bound water evaporations absorb big calorimetric, are the one of the main reasons of modification cyclisation fire resistance fibre and fabric.Acrylic fiber or fabric water imbibition before and after modification brings up to 2 from 0.4%
#7.23% and 3 of number fabric
#10.2%, 3 of number fabric
#Water absorption is brought up to 25.50 times before and after number modification cyclisation fabric-modifying.Final combustion becomes charcoal cloth, then has very strong heat insulation and oxygen barrier effect, and stops fabric further to burn.
Do with hydrazine hydrate that macromolecular cyclization is roughly in the catalytic cyclization process:
This cyclized structure is equivalent to prepare pre-oxidation carbon fiber in the carbon fiber process with the acrylic fibers base.This pre-oxidation carbon fiber itself just has strong fire resistance and also have strong bound water ability under certain environment; For the second time add a certain amount of, as to have high conduction performance and chelating outlet capacity bivalent cupric ion more with this understanding, the performance that product is reached do not fire and conduct electricity.With amine aqueous solution catalysis, the fireproof fibre that adds mantoquita again places on as shown in the figure the gas lamp flame 1.5cm place (keeping flat) burning after 15 minutes, fabric sample is indeformable, just generates diameter such as flame diameter circular black charcoal cloth of a size, and this piece charcoal cloth also has certain intensity.If being heated to 2000--3000 ℃, just become the lamellar graphite fiber.
Use Cu
2+As chelated metal ions, not only right-CN base or=the N base has very strong bonding or chelation, and electric conductivity fine, the body resistivity of this modification PAN fiber or fabric is reduced to 10-11 the order of magnitude than former PAN fiber, and formation conductive fiber and fabric.This has just in time improved former PAN fiber or fabric easy firing greatly and be easy to generate static two big shortcomings under friction.
Description of drawings
Fig. 1 I
#, II
#, III
#The DSC curve of 3 samples, 1
#, number be fabric without flame treatment, 2
#Number fabric is through fiber or the fabric of amine aqueous solution after uniform temperature is handled certain hour, 3
#Fiber or fabric after processing fully.
Fig. 2: gas lamp flame part, 1 for the flame temperature highest region reaches 1570 ℃, and 2 is the flame second highest region, reaches 1540 ℃ of A for the burned flame band does not take place, and B is the reduction flame zone, and C is the oxidizing flame band, completing combustion, oxygen surplus.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The acrylic fiber precursor is a ternary polymerization acrylic staple fibre of selecting for use acrylic fibers subsidiary factory of Kingsoft general petrochemicals factory to produce, and it consists of acrylonitrile: methyl acrylate: Sodium methacrylate=92: 7: 1.The long 68mm of fiber, fiber number 5d.Modifier is the ZnSO of technical grade 40% hydrazine hydrate and chemical pure level
47H
2O.
The 15-28% hydrazine hydrate is made catalyst, adds in the reactor, be heated to 90 ℃ after, be 1 with bath raio: 15-25 adds the acrylic fiber of soaping and deoiling; Temperature remains on 95-100 ℃ of scope, under agitation handles after 38-45 minute and takes out, washing, oven dry.In bath raio is 1: solution of zinc sulfate is added in the modified fibre of above-mentioned processing under the 15-25, be heated to 95-100 ℃, under agitation handled 38-45 minute, the pH value remains on the acid range of 1-5 in the course of reaction.Promptly obtain the fiber of anti-combustion that color is a light violet magenta.The LoI value of this fiber of anti-the combustion is 35.And meet the BS 5722 of U.S. ASTM D 1230, Britain (West Europe), the JIS L1091 of Japan and the GB/T17591-2006 and the GB/T5455-1997 of China fully.After during burning, removing (point) burning things which may cause a fire disaster, slow burning fabric does not have afterflame, the phenomenon of glowing, fire end or remove (point) burning things which may cause a fire disaster after, the same size with the burning things which may cause a fire disaster cross-sectional area of slow burning fabric impaired area becomes carbonization in vertical direction; Dripless did not discharge any toxic gas yet when the length the same with the burning things which may cause a fire disaster height became carbon cloth and burning.The dry strength of this fiber of anti-the combustion descends 8.7%, and wet strength does not descend; And the lilac red color is not dark, and also available cation dyes are dyed shades of colour (except that white).At above two shortcomings, can respectively account for 50% with pure acrylic fiber or cotton fiber carries out blending or interweaves with fire resistance fibre, the LoI of this blending or intertexture is 30 and 32, this has reached aircraft, train, automobile, steamer and home-use slow burning fabric, and dry strength has only descended about 3.4%.
Before anti-combustion process was handled, the fabric that will handle or fiber were with the finish on washing powder flush away fabric or the fiber earlier, and the fiber (I) that makes the part cyclisation is washed, dried to the amine aqueous solution of then using 20-30% then in the cyclisation of 80-95 ℃ of following catalysis acrylic fiber; Then with 10-25%NaOH aqueous hydrolysis (I) fiber, wash again, dry fiber (II); Again with the 10-25%HCl aqueous solution neutralization bases one-step hydrolysis of going forward side by side, wash, dry fiber (III); Use calcium (Ca) saline solution to handle again, make it and fiber (III) bonding or chelating, wash again, dry, make fiber (IV).More than per step all dry after handling, be to handle sample and all will carry out analytical test for per step.And in reality is produced in batches, just needn't every products obtained therefrom be dried, as long as carry out before next step operation on the clean sample with the treatment fluid of previous step operation.After above four steps handle, prepared flame-retardant acrylic fibre, mainly be to be used for carrying out blending with untreated pure acrylic fiber (O), be used for making general slow burning fabric, this blending flame-retardant acrylic fibre has reached airline carriers of passengers and train, automobile, the employed anti-combustion standard GB/T5455 of steamer and FZ/T01028, after promptly vertically lighting a fire 12 seconds, self-extinguishing time＜15 second, burning length＜203mm, no toxic gas and smog are emitted, no dropping.And it is home-use as curtain, bedding, clothing, carpet or pluse cloth etc.
Performance such as the following table of fiber after above anti-combustion processing procedure
| Sample number into spectrum | Color sample | Resistance oxygen index (OI) LoI | Strength damage % |
| (I) | White | 20.20 | 7.7 |
| (II) | Salmon pink | 24.60 | 23.60 |
| (III) | Orange colour | 23.60 | 27.60 |
| (IV) | Shallow salmon pink | 32.80 | 14.70 |
| (IV)-10 * | 32.20 |
*(IV)-10
*Be the sample of sample (final products) after pressing 10 water washings of GB/T5713 regulation
Example three
Acrylic fiber or fabric with ternary polymerization are made sample, earlier former acrylic fibers sample are washed with washing powder or liquid detergent, to remove original sample surface oil agent gained fibrillation (I
#).With the amine aqueous solution of 18-25% and add under the oxygen condition and handle fibrillation 30min down at 85-98 ℃, make it cyclisation, wash then, dry, modified fibre (II
#).With 10-25% aqueous hydrochloric acid solution neutralization bases, the one-step hydrolysis of going forward side by side, water is clear, make the fiber of anti-combustion the (III after the oven dry
#).Use copper salt solution (25% aqueous solution) to handle modified fibre II down again at 80-90 ℃
#30min cleans, dries, and makes fireproof fibre (IV
#).In continuous, large-scale production, more than two steps handle and just needn't dry.The modified acrylic fibres after above each step handles or the performance of fabric see Table 2
Table 2, the performance indications after each goes on foot anti-combustion and does not fire processing
IV
#Sample is after the III sample washes 10 times with water by the GB/T5711 established procedure, the sample after oven dry or the air dry.
Claims (5)
1. have the modified polyacrylonitrile fiber dimension that anti-combustion or not, it is characterized in that comprising in every 10kg fiber (fabric) component of following content:
Hydrazine hydrate 0.75kg-14kg
NaOH 2kg-3kg
Hydrochloric acid 3kg-5kg
Organic amine 9kg-15kg
Zinc sulfate 0.5kg-1.50kg
Calcium chloride or calcium carbonate 0.7kg-1.50kg
Copper sulphate 0.8kg-1.50kg.
2. the modified polyacrylonitrile fiber dimension that has anti-combustion or do not fire according to claim 1, it is characterized in that: described calcium chloride must just can dissolve in acid solution (as ammonium hydroxide), and zinc sulfate, copper sulphate use under neutrality or slightly acidic condition.
3. the modified polyacrylonitrile fiber dimension that has anti-combustion or do not fire according to claim 1, it is characterized in that: described copper sulphate must dissolve in warm water earlier fully, and the form with solution adds again.
4. according to the described modified polyacrylonitrile fiber dimension that has anti-combustion or do not fire of claim 1-3, it is characterized in that: make anti-combustion or do not fire, behind the conductive articles, must the abundant rinsing of water, solarization or oven dry become final products.
5. the preparation method of the modified polyacrylonitrile fiber dimension that has anti-combustion or do not fire comprises:
This fiber or fabric are that 18%-30% amine aqueous solution or concentration are the 15%-28% hydrazine hydrate with concentration earlier, at 80 ℃-100 ℃, with bath raio is 1: 15-25 adds fiber or the fabric that deoiled, temperature remains on 95 ℃-100 ℃, stir 38min-45min and get modified fibre, is 10%-25%NaOH aqueous hydrolysis fiber with this modified fibre in concentration, be the further hydrolysis of 10%-25%HCl aqueous solution neutralization bases with concentration again, washing pH value remains on the acid range of 1-5, be 1 in bath raio afterwards: the modified fibre with above-mentioned processing under the 15-25 joins calcium salt or mantoquita (calcium chloride, calcium carbonate or copper sulphate) or solution of zinc sulfate in, handle 30min-60min at 80 ℃-100 ℃, making the fiber or the fabric chelating water yield is 25%-30% bonding water 20%-28%, and make nitrogen-atoms complexing in metallic atom and cyano group and the cyclisation thing, clean oven dry.But hydrazine hydrate or organic amine solution catalysis acrylic fiber or fabric generation cyclized structure add copper sulphate or zinc sulfate or calcium chloride solution then.After the acrylic fiber cyclisation, also leave two on the nitrogen-atoms in the structure and be not easy to and metal cation generation bonding or chelating in conjunction with electronics, the product after the cyclisation also leaves a small amount of cyano group and also is easy to and metal cation generation bonding or chelating in addition.
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|---|---|---|---|
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|---|---|---|---|
| CN2009100461257A CN101514526B (en) | 2009-02-12 | 2009-02-12 | Modified polyacrylonitrile fiber (fabric) with flame retardant or noncombustible performance and a preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845748A (en) * | 2010-05-05 | 2010-09-29 | 山东理工大学 | Method for modifying flame retardance for acrylic fiber yarns, acrylic fiber knitting wools or acrylic fiber woolen yarns |
| CN101724965B (en) * | 2009-11-19 | 2012-12-12 | 汕头市奥山服饰有限公司 | Antistatic flame-retardant textile |
| CN104988724A (en) * | 2015-06-10 | 2015-10-21 | 四川大学 | Polyvinyl alcohol reinforcement modification halogen-free flame retardant polyacrylic composite fiber and preparation method thereof |
| CN103952916B (en) * | 2014-04-28 | 2016-01-20 | 绍兴文理学院 | A kind of preparation method of flame-retardant acrylic fibre |
| CN105986474A (en) * | 2015-02-13 | 2016-10-05 | 吉林吉盟腈纶有限公司 | High temperature-resistant flame retardation polyacrylonitrile fiber and production method thereof |
-
2009
- 2009-02-12 CN CN2009100461257A patent/CN101514526B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724965B (en) * | 2009-11-19 | 2012-12-12 | 汕头市奥山服饰有限公司 | Antistatic flame-retardant textile |
| CN101845748A (en) * | 2010-05-05 | 2010-09-29 | 山东理工大学 | Method for modifying flame retardance for acrylic fiber yarns, acrylic fiber knitting wools or acrylic fiber woolen yarns |
| CN103952916B (en) * | 2014-04-28 | 2016-01-20 | 绍兴文理学院 | A kind of preparation method of flame-retardant acrylic fibre |
| CN105986474A (en) * | 2015-02-13 | 2016-10-05 | 吉林吉盟腈纶有限公司 | High temperature-resistant flame retardation polyacrylonitrile fiber and production method thereof |
| CN105986474B (en) * | 2015-02-13 | 2018-09-04 | 吉林吉盟腈纶有限公司 | A kind of heat-resistant fireproof polyacrylonitrile fibre and preparation method thereof |
| CN104988724A (en) * | 2015-06-10 | 2015-10-21 | 四川大学 | Polyvinyl alcohol reinforcement modification halogen-free flame retardant polyacrylic composite fiber and preparation method thereof |
| CN104988724B (en) * | 2015-06-10 | 2017-05-03 | 四川大学 | Polyvinyl alcohol reinforcement modification halogen-free flame retardant polyacrylic composite fiber and preparation method thereof |
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|---|---|
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