CN101498103A - Non-formaldehyde flame retardant for viscose fiber - Google Patents
Non-formaldehyde flame retardant for viscose fiber Download PDFInfo
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- CN101498103A CN101498103A CN 200910066578 CN200910066578A CN101498103A CN 101498103 A CN101498103 A CN 101498103A CN 200910066578 CN200910066578 CN 200910066578 CN 200910066578 A CN200910066578 A CN 200910066578A CN 101498103 A CN101498103 A CN 101498103A
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- flame retardant
- formaldehyde
- viscose
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- phosphite ester
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Abstract
The invention discloses a formaldehyde-free flame retardant for viscose fibers, which is a phosphate esters flame retardant of synthesizing acid amide by carrying out Michael addition reaction of phosphite ester and acrylamide compounds, and carrying out the reaction of generated acid amide functional groups and epoxy compounds. The structural formula of the flame retardant is shown above. The flame retardant, together with a cross-linking agent, a penetrating agent, a catalyst and a urea, is prepared into a flame retardant finishing liquid in proportion with water for fire retardant treatment of viscose fibers. The viscose fiber fabric after treatment has the advantages of good flame retardant effect, high durability, good hand touch, little strength reduction, good whiteness and the like.
Description
Technical field
The present invention relates to a kind of fire retardant new material, particularly a kind of non-formaldehyde flame retardant of viscose.
Background technology
Expert both domestic and external, scholar have developed a series of fire retardant and corresponding technologies that are applicable to cellulose fibre, as the Allbright﹠amp of flame retardant for cotton fabric with Britain; The THPC of wilson company.The Pyrovatex CP of Switzerland Ciba company is representative.THPC is a Tetrakis hydroxymethyl phosphonium chloride, but owing to may produce bischlormethyl ether in its building-up process, carcinogenic danger is arranged, and free formaldehyde content is higher, and the defective that these are inherent has limited its range of application.Pyrovatex CP formal name used at school is: N-methylol-3-(dimethoxy phosphoryl) propionamide, belong to the phosphate compounds of acid amides, and Pyrovatex CP is by dimethylphosphite and acrylamide generation Michael addition, carries out methylolation with formaldehyde again and gets.This fire retardant has synthetic simple, and it is convenient to use, advantages such as low toxicity.But its in synthetic process owing to use formaldehyde to carry out methylolation, so still have bigger formaldehyde residual.The present invention is directed to the too high problem of residual formaldehyde of Pyrovatex CP, adopt epoxide to replace formaldehyde, thereby in the process of post processing, reduce the residual quantity of formaldehyde.
Summary of the invention
The objective of the invention is in building-up process, may produce bischlormethyl ether in order to solve above-mentioned THPC, carcinogenic danger is arranged, and shortcoming that free formaldehyde content is higher and Pyrovatex CP in synthetic process owing to use formaldehyde to carry out methylolation, still have the residual shortcoming of bigger formaldehyde, and a kind of non-formaldehyde flame retardant of viscose is provided.
This fire retardant is the phosphate of acid amides, and its structural formula is as follows:
Wherein: R
1, R
2Can be the same or different, representative contains alkyl diradical or phenyl free radical, the wherein R of 1-4 carbon atom respectively
1, R
2Can be replaced by one or more halogen atoms; R
1, R
2Also can form an alkylidene bridge jointly, but the total number of carbon atoms can not surpass 4, the carbon atom in the alkylidene bridge can also be replaced by one or more halogen atoms; X wherein represents H or CH
3, Y represents Cl or Br or H.
The synthetic method of this fire retardant is:
With phosphite ester and acrylamides generation Michael addition, the amide functional group of generation and epoxy compounds reaction, the phosphate flame retardant of synthesizing amide;
Phosphite ester general formula wherein is:
Acrylic amide material general formula is:
Epoxy compounds meets following formula:
Said phosphite ester is dimethylphosphite or diethyl phosphite; Said amides compound is an acrylamide, said catalyst is for dividing sodium or phenol sylvite or alkali metal alcoholates, said epoxy compounds is expoxy propane or epoxychloropropane or epoxy bromopropane, and said inorganic additive is halide, oxide or the hydroxide of divalent metal.
The application of the phosphate flame retardant of the present invention's acid amides is to be made into fire retarding treating liquid by following prescription:
The phosphate flame retardant 500g of acid amides
Crosslinking agent 100g
Bleeding agent 2g
Catalyst 20g
Urea 20g
Thin up to one liter, crosslinking agent wherein is hexamethylol melamine resin (HMM), and catalyst is a phosphoric acid, and bleeding agent is fatty alcohol-polyoxyethylene ether (JFC).
Gluing fiber uses the processing method of fire retarding treating liquid to be:
Fiber two soaks two and rolls 160 ℃ of (3min) → alkali cleaning (Na of 108 ℃ of (pick-up 100%) → preliminary dryings (5min) → bake
2CO
3, 50g/L) → (20g/L, Na soap
2CO
3Soap flakes 2g/L) → washing → oven dry.
The fire-retardant sample of handled gluing fiber, oxygen index (OI) is 30 after testing, is 28.5 still can satisfy fire-retardant requirement after 50 washings, and is effective.
The invention has the beneficial effects as follows:
The present invention's fire retardant is a kind of reactive flame retardant, is the fire retardant that contains hydroxyl, phosphorus, nitrogen, halogen.Can use simultaneously with auxiliary agents such as crosslinking agent, bleeding agent, catalyst when using this fire retardant.The fabric that uses this fire retardant to handle has good flame retardation effect, the durability height, and good hand touch, intensity reduces few, and whiteness waits outstanding advantage well.
The specific embodiment
Concrete synthesis technique of the present invention be with phosphite ester and acrylic amide material by mole amount ratio 1.02:1, add reactor after the weighing.After treating that two components are dissolved each other, add halide, oxide, the hydroxide of divalent metal, fully stir, treat that it dissolves fully after, add catalyst; When the amount of catalyst adds about 50-60%, a violent exothermic reaction takes place, control exothermic reaction by the rate of addition of control catalyst this moment, makes temperature be no more than 70 ℃; Be added drop-wise to and no longer take place till the exothermic reaction, dripped the back insulation reaction 3 hours, after temperature drops to room temperature, obtain white crystal, i.e. the crude product of alkoxy phosphoryl propionamide.
Resulting intermediate crude product is dissolved in the distilled water in every mole of ratio that adds 100ml, be warmed up to 30 ℃ and treat to dissolve fully the NaOH solution that the back adds 20% concentration, adjust pH to 9.0, drip epoxide, addition is 1.5-2 a times of intermediate molal quantity, and the dropping time is controlled at about 30min; After dropwising, be warmed up to about 70-80 ℃, solution transfers clarification to by cloudy state behind the 1-2h, continues insulated and stirred 10h, and water and epoxide are removed in decompression distillation after reaction finishes, and the grease of gained is required fire retardant.
The raw material that uses in the present embodiment synthetic method is dimethylphosphite, acrylamide, epoxychloropropane, and inorganic additive is anhydrous MgCL
2, catalyst is CH
3The methanol solution of ONa.
Specific embodiments of the invention are:
Raw material dimethylphosphite and acrylamide 1.02:1 weighing in molar ratio is good, join in the reactor.Stir, treat that dimethylphosphite and acrylamide dissolve fully after, adding MgCL
2, addition is every mole of raw material 0.423g, stirs and treats MgCL
2After the dissolving, drip CH fully
3ONa solution is about 55% to be that violent exothermic reaction takes place when addition, and the rate of addition of control catalyst makes solution temperature be no more than 70 ℃, continues to drip CH
3ONa is till no exothermic phenomenon takes place, and heat release finishes the back at 70 ℃ of insulation reaction 3h, obtains white solid dimethoxy phosphoryl propionamide after being cooled to room temperature; In the gained intermediate, add distilled water, addition is that every mole of intermediate adds 100ml water, after treating to dissolve fully, the NaOH solution bar pH value to 9.0 of adding 20%, drip epoxychloropropane, addition is 1.5 times of intermediate molal quantity, and the dropping time is after 30min dropwises, be warmed up to 74 ℃, solution becomes clarification by muddiness after 1 hour; Continue insulation reaction 10h, after reaction finished, unreacted epoxychloropropane and water were removed in decompression distillation, and resulting colourless thick product is the phosphate flame retardant of acid amides, solid content 60%, pH value 6.0.
Claims (5)
1, a kind of non-formaldehyde flame retardant of viscose, its structural formula is as follows:
Wherein: R
1, R
2Can be the same or different, representative contains alkyl diradical or phenyl free radical, the wherein R of 1-4 carbon atom respectively
1, R
2Can be replaced by one or more halogen atoms; R
1, R
2Also can form an alkylidene bridge jointly, but the total number of carbon atoms can not surpass 4, the carbon atom in the alkylidene bridge can also be replaced by one or more halogen atoms; X wherein represents H or CH
3, Y represents Cl or Br or H.
2, the synthetic method of the non-formaldehyde flame retardant of a kind of viscose as claimed in claim 1, this method is with phosphite ester and acrylamides generation Michael addition, amide functional group that generates and epoxy compounds reaction, the phosphate flame retardant of synthesizing amide;
Phosphite ester general formula wherein is:
Acrylic amide material general formula is:
Epoxy compounds meets following formula:
3, the synthetic method of the non-formaldehyde flame retardant of a kind of viscose according to claim 2, wherein said phosphite ester is dimethylphosphite or diethyl phosphite; Said amides compound is an acrylamide; Said catalyst is for dividing sodium or phenol sylvite or alkali metal alcoholates; Said epoxy compounds is expoxy propane or epoxychloropropane or epoxy bromopropane; Said inorganic additive is halide, oxide or the hydroxide of divalent metal.
4, a kind of fire retarding treating liquid of the non-formaldehyde flame retardant of viscose according to claim 1 that contains, the proportioning of this fire retarding treating liquid is as follows:
The phosphate flame retardant 500g of acid amides
Crosslinking agent 100g
Bleeding agent 2g
Catalyst 20g
Urea 20g
Thin up to one liter, crosslinking agent wherein is a hexamethylol melamine resin, and catalyst is a phosphoric acid, and bleeding agent is a fatty alcohol-polyoxyethylene ether.
5, fire retarding treating liquid as claimed in claim 3 is used for the flame treatment of gluing fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910066578 CN101498103A (en) | 2009-02-16 | 2009-02-16 | Non-formaldehyde flame retardant for viscose fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910066578 CN101498103A (en) | 2009-02-16 | 2009-02-16 | Non-formaldehyde flame retardant for viscose fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101498103A true CN101498103A (en) | 2009-08-05 |
Family
ID=40945365
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| CN 200910066578 Pending CN101498103A (en) | 2009-02-16 | 2009-02-16 | Non-formaldehyde flame retardant for viscose fiber |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701423B (en) * | 2009-10-28 | 2011-06-08 | 长春工业大学 | Phosphorus flame retardant for viscose fibers and production method and application thereof |
| CN101781572B (en) * | 2010-01-19 | 2012-12-05 | 陕西科技大学 | Method for preparing retanning-type leather fire retardant |
| CN103290682A (en) * | 2012-03-01 | 2013-09-11 | 聚隆纤维股份有限公司 | Preparation method for natural cellulose melt-blown non-woven fabric with burning-resistant function |
| CN103290502A (en) * | 2012-02-24 | 2013-09-11 | 聚隆纤维股份有限公司 | Manufacture method of native cellulose fiber with flameproof function |
| CN103572592A (en) * | 2012-07-27 | 2014-02-12 | 广东德美精细化工股份有限公司 | Cotton flame retardant and preparation method thereof |
| TWI561693B (en) * | 2012-02-24 | 2016-12-11 | ||
| CN106930106A (en) * | 2017-04-05 | 2017-07-07 | 苏州联胜化学有限公司 | Cotton is with without aldehyde permanent flame-retardant and its preparation method and application method |
| CN106939511A (en) * | 2017-04-21 | 2017-07-11 | 齐齐哈尔大学 | A kind of phosphorus nitrogen chlorine-resistant fire retardant and its synthetic method |
| TWI596247B (en) * | 2012-03-01 | 2017-08-21 | Preparation of natural cellulose meltblown nonwovens with flame resistance | |
| CN108018715A (en) * | 2017-12-08 | 2018-05-11 | 天津工业大学 | A kind of preparation method of antiflaming finishing agent and fire-retardant regenerated cellulose fiber |
| CN108166125A (en) * | 2018-03-07 | 2018-06-15 | 芜湖航飞科技股份有限公司 | A kind of woven high temperature casing and preparation method thereof |
| CN108193345A (en) * | 2018-03-07 | 2018-06-22 | 芜湖航飞科技股份有限公司 | A kind of self-rolling woven high temperature casing and preparation method thereof |
| CN111648132A (en) * | 2020-06-11 | 2020-09-11 | 周晓珊 | Colorless-change environment-friendly composite flame retardant, and preparation method and application thereof |
| CN112358502A (en) * | 2020-11-09 | 2021-02-12 | 山东省海洋化工科学研究院 | Double-hydroxyl high-phosphorus-nitrogen-content flame-retardant functional monomer and preparation method thereof |
-
2009
- 2009-02-16 CN CN 200910066578 patent/CN101498103A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701423B (en) * | 2009-10-28 | 2011-06-08 | 长春工业大学 | Phosphorus flame retardant for viscose fibers and production method and application thereof |
| CN101781572B (en) * | 2010-01-19 | 2012-12-05 | 陕西科技大学 | Method for preparing retanning-type leather fire retardant |
| TWI561693B (en) * | 2012-02-24 | 2016-12-11 | ||
| CN103290502A (en) * | 2012-02-24 | 2013-09-11 | 聚隆纤维股份有限公司 | Manufacture method of native cellulose fiber with flameproof function |
| CN103290502B (en) * | 2012-02-24 | 2016-02-10 | 聚隆纤维股份有限公司 | The method for making of the native cellulose fibre of the resistance to combustion function of tool |
| CN103290682A (en) * | 2012-03-01 | 2013-09-11 | 聚隆纤维股份有限公司 | Preparation method for natural cellulose melt-blown non-woven fabric with burning-resistant function |
| TWI596247B (en) * | 2012-03-01 | 2017-08-21 | Preparation of natural cellulose meltblown nonwovens with flame resistance | |
| CN103290682B (en) * | 2012-03-01 | 2016-02-10 | 聚隆纤维股份有限公司 | The method for making of the native cellulose melt spraying non-woven fabrics of the resistance to combustion function of tool |
| CN103572592A (en) * | 2012-07-27 | 2014-02-12 | 广东德美精细化工股份有限公司 | Cotton flame retardant and preparation method thereof |
| CN103572592B (en) * | 2012-07-27 | 2015-09-16 | 广东德美精细化工股份有限公司 | A kind of cotton fire retardant and preparation method thereof |
| CN106930106A (en) * | 2017-04-05 | 2017-07-07 | 苏州联胜化学有限公司 | Cotton is with without aldehyde permanent flame-retardant and its preparation method and application method |
| CN106939511A (en) * | 2017-04-21 | 2017-07-11 | 齐齐哈尔大学 | A kind of phosphorus nitrogen chlorine-resistant fire retardant and its synthetic method |
| CN108018715A (en) * | 2017-12-08 | 2018-05-11 | 天津工业大学 | A kind of preparation method of antiflaming finishing agent and fire-retardant regenerated cellulose fiber |
| CN108166125A (en) * | 2018-03-07 | 2018-06-15 | 芜湖航飞科技股份有限公司 | A kind of woven high temperature casing and preparation method thereof |
| CN108193345A (en) * | 2018-03-07 | 2018-06-22 | 芜湖航飞科技股份有限公司 | A kind of self-rolling woven high temperature casing and preparation method thereof |
| CN111648132A (en) * | 2020-06-11 | 2020-09-11 | 周晓珊 | Colorless-change environment-friendly composite flame retardant, and preparation method and application thereof |
| CN112358502A (en) * | 2020-11-09 | 2021-02-12 | 山东省海洋化工科学研究院 | Double-hydroxyl high-phosphorus-nitrogen-content flame-retardant functional monomer and preparation method thereof |
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Open date: 20090805 |