CN102628218B - Phosphorus hybrid flame retardant and preparation method thereof - Google Patents
Phosphorus hybrid flame retardant and preparation method thereof Download PDFInfo
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- CN102628218B CN102628218B CN2012101278091A CN201210127809A CN102628218B CN 102628218 B CN102628218 B CN 102628218B CN 2012101278091 A CN2012101278091 A CN 2012101278091A CN 201210127809 A CN201210127809 A CN 201210127809A CN 102628218 B CN102628218 B CN 102628218B
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Abstract
The invention discloses a phosphorus hybrid flame retardant and a preparation method thereof. The flame retardant comprises the following raw materials by weight: 100 parts of 2-hydroxyethyl phenyl phosphinic acid, 30-50 parts of a graphene polyphosphazenes nano composite material, 10-15 parts of montmorillonite, 10-20 parts of sodium methylsiliconate, and 50-80 parts of inositol hexaphosphate. The phosphorus hybrid flame retardant provided by the invention is mainly composed of phosphorus 2-hydroxyethyl phenyl phosphinic acid, with other components added to the compound so as to obtain the hybrid flame retardant. Components of the flame retardant cooperate and synergize with each other, which overcomes the defect that single phosphorus compounds are liable to generate melted droplets and have poor water resistance. The flame retardant has the advantages of simple preparation, good thermal stability, good water resistance and high flame retardancy.
Description
Technical field
The present invention relates to a kind of weaving flame-retardant mixture and preparation method thereof, being specifically related to a kind of phosphorus is to mix fire retardant and preparation method thereof, belongs to the fire retardant technical field.
Background technology
Development along with modernization science and technology and textile industry, the kind of textiles is more and more, application in mankind's daily life is also more and more extensive, but textiles is all generally inflammable or combustible material, and a lot of fire are all caused or enlarged by the textiles quick igniting.Lift statistics, fire quantity and the death rate that textiles causes are all high than fire quantity and the death rate that other reasons causes, approximately 20% fire is all caused by textile combustion in the world.Therefore the fire-retardant problem of textiles has become the focus that the world instantly widely pays close attention to.
In order to reduce the flammability of textiles, a large amount of research has been carried out to the fire resistance of textiles one after another in countries in the world, and the research of fire retardant and use have reduced the hidden danger of fire effectively.At present, commonplace fire retardant has halogenated flame retardant and phosphorus flame retardant, but thereby halogenated flame retardant is very restricted application because produce noxious material in combustion process, so phosphorus flame retardant is the fire proofing of comparison safety and environmental protection.General phosphorus flame retardant is single phosphorus series compound, at flame retardant effect, melt on the problem of dripping and have certain deficiency.
Summary of the invention
Deficiency for existing fire retardant existence, the invention provides a kind of mixing fire retardant---fire retardant mixes in phosphorus system, fire retardant mixes take 2-ethoxy phenyl hypophosphorous acid as main fire proofing in this phosphorus system, add other composition, increased the overall performance of fire retardant, good flame retardation effect, produce safety and environmental protection without melting dropping.
It is the preparation method who mixes fire retardant that the present invention also provides phosphorus of the present invention, the method easy operating, and products obtained therefrom is functional.
Phosphorus flame retardant is present most widely used fire-retardant class material,, because it does not contain halogen element, can not endanger environment, so good flame retardation effect is favored, phosphorus flame retardant commonly used is the organophosphorus compound of single component, in combustion process, fire retardant produces phosphoric anhydride or phosphoric acid, impels the textiles dehydration carbonization, stops or reduce fuel gas to produce, in addition, phosphoric anhydride forms similar glassy fused mass and covers on fabric when thermal cracking, impel its oxidation to generate carbon dioxide, plays fire-retardant effect.But the phosphorus-containing compound of single component is easy to produce melt and drips phenomenon when burning, and WATER RESISTANCE is poor, also is subject to certain restrictions in application.
The present invention, take 2-ethoxy phenyl hypophosphorous acid as main component, adds other composition,, with its synergy, has obtained new phosphorous flame-retardant agent composition, the mixing fire retardant better effects if of gained, and Halogen series elements not in fire retardant, safety and environmental protection.The present invention is achieved by the following measures:
A kind of phosphorus is to mix fire retardant, it is characterized in that comprising the raw material of following weight portion: 100 parts of 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material 30-50 part, imvite 10-15 part, methyl silicon sodium alcoholate 10-20 part, cyclohexanol six phosphate 50-80 parts.
Above-mentioned phosphorus is to mix fire retardant, preferably includes the raw material of following weight portion: 100 parts of 2-ethoxy phenyl hypophosphorous acid, 35 parts of graphene polyphosphazene nano composite materials, 15 parts of imvites, 17 parts of methyl silicon sodium alcoholates, 70 parts of cyclohexanol six phosphates.
On the basis of above-mentioned recipe ingredient, fire retardant of the present invention can also comprise paraffin 10-20 part, melamine 5-10 part, 15 parts, preferred paraffin, 8 parts of melamines.
Phosphorus of the present invention is the preparation method who mixes fire retardant, it is characterized in that comprising the following steps:
(1) imvite being ground to particle diameter with ball-milling method is 20-50nm, obtains nano imvite;
(2) 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 2-4h under 30-40 ℃;
(3) add remaining raw material in the mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
In above-mentioned preparation method, supersonic frequency is that 20kHz, ultrasonic power are 400W.
phosphorus of the present invention is to mix fire retardant take 2-ethoxy phenyl hypophosphorous acid as main component, composite graphene polyphosphazene nano composite material, imvite, methyl silicon sodium alcoholate, cyclohexanol six phosphates are made fire retardant, contain Graphene in graphene polyphosphazene nano composite material, phosphorus, nitrogen component, has good fire retardation, imvite is treated can insert in 2-ethoxy phenyl hypophosphorous acid and graphene polyphosphazene nano composite material, with the structural interaction in 2-ethoxy phenyl hypophosphorous acid and nano composite material, suppressed to melt a phenomenon, promoted fire retardation.Methyl silicon sodium alcoholate has the effect of waterproof, joins in fire retardant and can suppress the poor problem of fire retardant WATER RESISTANCE, and cyclohexanol six phosphates can be fused together all the components, can promote in addition the waterproof action of methyl silicon sodium alcoholate.In formula, Each performs its own functions for each composition, and collaborative onset, overcome single phosphorus series compound and be easy to melt dropping, the poor problem of WATER RESISTANCE mutually, strengthened the fire retardation of fire retardant, make the mixing fire retardant, the water resistant that finally obtain effective, produce safety and environmental protection without melting dropping.
The present invention's graphene polyphosphazene nano composite material used is in the preparation method of a patent CN201110025542.0(graphene polyphosphazene nano composite material) in open, belong to prior art, the structure that discloses this graphene polyphosphazene nano composite material and preparation technology that this patent is detailed, those skilled in the art can obtain according to record wherein, and the present invention no longer describes in detail.
The present invention's cyclohexanol six phosphates used have another name called six phosphate ester of cyclohexanhexanol, inositol hexaphosphate, can buy in market, and its structural formula is:
Further, mix in fire retardant and can also add paraffin, tripolycyanamide, the addition of paraffin is the 10-20 weight portion, preferred 15 weight portions, and the addition of melamine is the 5-10 weight portion, preferred 8 weight portions.Paraffin can produce one deck protective barrier between textiles and external environment; entering of blocking-up air, further play fire-retardant effect, contains triazine ring in melamine; improved the heat endurance of fire retardant, and phosphorus, the composite fire resistance that more is conducive to improve fire retardant of nitrogen.
Phosphorus of the present invention is that the mixing fire retardant is that 2-ethoxy phenyl hypophosphorous acid is as main component take phosphorus, add other composition to carry out composite, obtain mixing fire retardant, in this fire retardant, each composition is worked in coordination, and synergy has overcome single phosphorus series compound and has been easy to produce and melts dropping, the poor shortcoming of WATER RESISTANCE, preparation is simple, Heat stability is good, WATER RESISTANCE is good, good flame retardation effect.
The specific embodiment
Below by specific embodiment, the present invention is further explained, should be understood that following explanation is only in order to explain the present invention, does not limit its content.If no special instructions, raw materials used is weight portion.
The graphene polyphosphazene nano composite material that uses in following embodiment adopts disclosed method in patent CN201110025542.0 to make, and is not described in detail in this, and other compositions all can have been bought in market.
Embodiment 1
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 35 parts of graphene polyphosphazene nano composite materials, 15 parts of imvites, 17 parts of methyl silicon sodium alcoholates, 70 parts of cyclohexanol six phosphates, prepare by following method: it is 20-50nm that imvite is ground to particle diameter with ball-milling method, obtains nano imvite; 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 3h under 35 ℃, supersonic frequency is that 20kHz, ultrasonic power are 400W, add remaining raw material in mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
Embodiment 2
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 30 parts of graphene polyphosphazene nano composite materials, 10 parts of imvites, 20 parts of methyl silicon sodium alcoholates, 50 parts of cyclohexanol six phosphates, prepare by following method: it is 20-50nm that imvite is ground to particle diameter with ball-milling method, obtains nano imvite; 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 4h under 30 ℃, supersonic frequency is that 20kHz, ultrasonic power are 400W, add remaining raw material in mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
Embodiment 3
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 40 parts of graphene polyphosphazene nano composite materials, 13 parts of imvites, 15 parts of methyl silicon sodium alcoholates, 70 parts of cyclohexanol six phosphates, prepare by following method: it is 20-50nm that imvite is ground to particle diameter with ball-milling method, obtains nano imvite; 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 3h under 40 ℃, supersonic frequency is that 20kHz, ultrasonic power are 400W, add remaining raw material in mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
Embodiment 4
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 50 parts of graphene polyphosphazene nano composite materials, 15 parts of imvites, 10 parts of methyl silicon sodium alcoholates, 80 parts of cyclohexanol six phosphates, prepare by following method: it is 20-50nm that imvite is ground to particle diameter with ball-milling method, obtains nano imvite; 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 2h under 40 ℃, supersonic frequency is that 20kHz, ultrasonic power are 400W, add remaining raw material in mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
Embodiment 5
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 35 parts of graphene polyphosphazene nano composite materials, 15 parts of imvites, 17 parts of methyl silicon sodium alcoholates, 15 parts, paraffin, 8 parts of melamines, 70 parts of cyclohexanol six phosphates, make phosphorus system according to the method for embodiment 1 and mix fire retardant.
Embodiment 6
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 30 parts of graphene polyphosphazene nano composite materials, 10 parts of imvites, 20 parts of methyl silicon sodium alcoholates, 20 parts, paraffin, 5 parts of melamines, 50 parts of cyclohexanol six phosphates, make phosphorus system according to the method for embodiment 2 and mix fire retardant.
Embodiment 7
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 50 parts of graphene polyphosphazene nano composite materials, 13 parts of imvites, 10 parts of methyl silicon sodium alcoholates, 10 parts, paraffin, 10 parts of melamines, 80 parts of cyclohexanol six phosphates, make phosphorus system according to the method for embodiment 1 and mix fire retardant.
Fire retardant is mixed in phosphorus system according to the such scheme preparation carry out the test of heat endurance, limited oxygen index, melting dropping number, the results are shown in following table 1.
Be to mix fire retardant to be coated on fiber with phosphorus of the present invention, the spinnability of test fiber, spinnability during mainly from spinning several angles such as filter, unit replacement cycle, pre-oriented yarn (POY) full-rolling rate investigate, its classification standard is: filter replacement cycle 〉=72h, unit replacement cycle 〉=20 day, POY full-rolling rate are " good " more than 90%; Filter replacement cycle 〉=60h, unit replacement cycle 〉=15 day, the POY full-rolling rate is " better " more than 90%; Filter replacement cycle≤48h, unit replacement cycle≤12 day, the POY full-rolling rate is " poor " more than 90%, the results are shown in following table 2.
Claims (6)
1. fire retardant mixes in a phosphorus system, it is characterized in that comprising the raw material of following weight portion:
100 parts of 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material 30-50 part, imvite 10-15 part, methyl silicon sodium alcoholate 10-20 part, cyclohexanol six phosphate 50-80 parts; Its preparation method is:
(1) imvite being ground to particle diameter with ball-milling method is 20-50nm, obtains nano imvite;
(2) 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 2-4h under 30-40 ℃;
(3) add remaining raw material in the mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
2. phosphorus according to claim 1 is to mix fire retardant, it is characterized in that comprising the raw material of following weight portion: 100 parts of 2-ethoxy phenyl hypophosphorous acid, 35 parts of graphene polyphosphazene nano composite materials, 15 parts of imvites, 17 parts of methyl silicon sodium alcoholates, 70 parts of cyclohexanol six phosphates.
3. phosphorus according to claim 1 and 2 is to mix fire retardant, it is characterized in that: also comprise paraffin 10-20 part, melamine 5-10 part.
4. phosphorus according to claim 3 is to mix fire retardant, it is characterized in that: also comprise 15 parts, paraffin, 8 parts of melamines.
5. the described phosphorus of claim 1 or 2 is the preparation method who mixes fire retardant, it is characterized in that comprising the following steps:
(1) imvite being ground to particle diameter with ball-milling method is 20-50nm, obtains nano imvite;
(2) 2-ethoxy phenyl hypophosphorous acid, graphene polyphosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, carry out ultrasonic processing 2-4h under 30-40 ℃;
(3) add remaining raw material in the mixture after ultrasonic processing, mix, obtain phosphorus system and mix fire retardant.
6. preparation method according to claim 5, it is characterized in that: supersonic frequency is that 20kHz, ultrasonic power are 400W.
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| TWI475100B (en) * | 2013-05-29 | 2015-03-01 | Sino Japan Chemical Co Ltd | Water-soluble flame retardant composition and application thereof |
| CN104983100B (en) * | 2015-06-29 | 2016-08-24 | 安徽东锦服饰有限公司 | Water proof fire retardant functional clothing fabric processing method |
| CN105647549B (en) * | 2015-11-25 | 2018-02-16 | 北京旭碳新材料科技有限公司 | A kind of graphene fire-retardant film and its preparation method and application |
| CN105603560B (en) * | 2016-01-25 | 2017-12-05 | 晋江市亿泰隆化纤制造有限公司 | Filling mattress flame-proof antibiotic polyester fiber and preparation method thereof |
| CN107629806A (en) * | 2017-09-14 | 2018-01-26 | 绵竹耀隆化工有限公司 | A kind of basic zirconium phosphate fire retardant and preparation method thereof |
| CN108948838A (en) * | 2018-05-24 | 2018-12-07 | 河北晨阳工贸集团有限公司 | Anti-flaming dope and preparation method thereof |
| CN109713199B (en) * | 2018-12-28 | 2020-04-07 | 湖南农业大学 | Heat-resistant flame-retardant composite diaphragm and preparation method and application thereof |
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| CN102020766A (en) * | 2009-09-23 | 2011-04-20 | 四川富尔新纺织阻燃材料有限公司 | Method for preparing flame-retardant copolymerized and modified polyester |
| CN102153870A (en) * | 2011-01-24 | 2011-08-17 | 江苏大学 | Method for preparing graphene polyphosphazene nano composite material |
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| CN102020766A (en) * | 2009-09-23 | 2011-04-20 | 四川富尔新纺织阻燃材料有限公司 | Method for preparing flame-retardant copolymerized and modified polyester |
| CN102153870A (en) * | 2011-01-24 | 2011-08-17 | 江苏大学 | Method for preparing graphene polyphosphazene nano composite material |
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