CN102628218A - Phosphorus hybrid flame retardant and preparation method thereof - Google Patents
Phosphorus hybrid flame retardant and preparation method thereof Download PDFInfo
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- CN102628218A CN102628218A CN2012101278091A CN201210127809A CN102628218A CN 102628218 A CN102628218 A CN 102628218A CN 2012101278091 A CN2012101278091 A CN 2012101278091A CN 201210127809 A CN201210127809 A CN 201210127809A CN 102628218 A CN102628218 A CN 102628218A
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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 with 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 human daily life also more and more widely, but textiles generally all is inflammable or combustible material, a lot of fire are all caused or are enlarged by the textiles quick igniting.Lift statistics, the fire quantity that textiles causes and the death rate are all high than the fire quantity and the death rate that other reasons causes, about in the world 20% fire is all caused by textile combustion.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 Study of Flame 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 makes application receive very big restriction because in combustion process, produce noxious material, 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 to existing fire retardant existence; The invention provides a kind of mixing fire retardant---fire retardant mixes in phosphorus system, and it is main fire proofing with 2-ethoxy phenyl hypophosphorous acid that fire retardant mixes in this phosphorus system, adds other composition; Increased the overall performance of fire retardant; Good flame retardation effect does not have and melts dropping generation, safety and environmental protection.
It is the preparation method who mixes fire retardant that the present invention also provides phosphorus of the present invention, this method easy operating, and products obtained therefrom is functional.
Phosphorus flame retardant is to use fire-retardant type of the widest material at present, because of 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, and fire retardant produces phosphoric anhydride or phosphoric acid in the combustion process; Impel the textiles dehydration carbonization, stop or reduce fuel gas to produce, in addition; Phosphoric anhydride forms glass-like shape fused mass and covers on the 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 when burning and drips phenomenon, and WATER RESISTANCE is poor, on using, also receives certain restriction.
The present invention is a main component with 2-ethoxy phenyl hypophosphorous acid, 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 the fire retardant, safety and environmental protection.The present invention realizes through following measure:
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 poly phosphazene 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 poly phosphazene 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 in preferred paraffin, 8 parts of melamines.
Phosphorus of the present invention is the preparation method who mixes fire retardant, it is characterized in that may further comprise the steps:
(1) uses ball-milling method to be ground to particle diameter imvite and be 20-50nm, get nano imvite;
(2) 2-ethoxy phenyl hypophosphorous acid, Graphene poly phosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, under 30-40 ℃, carry out sonicated 2-4h;
(3) add remaining raw material in the mixture after the sonicated, mix, promptly get phosphorus system and mix fire retardant.
Among the above-mentioned preparation method, supersonic frequency is that 20kHz, ultrasonic power are 400W.
Phosphorus of the present invention is that the mixing fire retardant is a main component with 2-ethoxy phenyl hypophosphorous acid; Composite Graphene poly phosphazene nano composite material, imvite, methyl silicon sodium alcoholate, cyclohexanol six phosphates are processed fire retardant; Contain Graphene, phosphorus, nitrogen component in the Graphene poly phosphazene nano composite material; Have the good flame effect, imvite is treated can insert in 2-ethoxy phenyl hypophosphorous acid and the Graphene poly phosphazene nano composite material, with the structural interaction in 2-ethoxy phenyl hypophosphorous acid and the nano composite material; Suppressed to melt and dripped phenomenon, promoted fire retardation.Methyl silicon sodium alcoholate has waterproof effect, joins the problem that can suppress fire retardant WATER RESISTANCE difference in the fire retardant, and cyclohexanol six phosphates can be fused to all the components together, can promote the waterproof action of methyl silicon sodium alcoholate in addition.Each performs its own functions for each composition in the prescription, and collaborative each other onset has overcome the problem that single phosphorus series compound is easy to melt dropping, WATER RESISTANCE difference; Strengthened the fire retardation of fire retardant; Make the mixing fire retardant that finally obtains, anti-water effective, do not have and melt dropping and produce safety and environmental protection.
The used Graphene poly phosphazene nano composite material of the present invention discloses in patent CN201110025542.0 (a kind of preparation method of Graphene poly phosphazene nano composite material); Belong to prior art; The structure and the preparation technology that disclose this Graphene poly phosphazene nano composite material that this patent is detailed; Those skilled in the art can obtain according to record wherein, and the present invention no longer details.
Used cyclohexanol six phosphates of the present invention have another name called six phosphate ester of cyclohexanhexanol, inositol hexaphosphate, can in market, buy, and its structural formula is:
Further, mix in the 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 the layer of protecting barrier between textiles and external environment; Fire-retardant effect is further played in the entering of blocking-up air, contains triazine ring in the melamine; Improved the heat endurance of fire retardant, and phosphorus, the composite fire resistance that more helps improving fire retardant of nitrogen.
It is that 2-ethoxy phenyl hypophosphorous acid is a main component with phosphorus that fire retardant mixes in phosphorus of the present invention system, adds other composition and carries out compositely, obtains mixing fire retardant; Each composition is worked in coordination in this fire retardant, and synergy has overcome single phosphorus series compound and has been easy to produce the shortcoming of melting dropping, WATER RESISTANCE difference; Preparation is simple; Heat stability is good, WATER RESISTANCE is good, good flame retardation effect.
The specific embodiment
Through specific embodiment the present invention is further explained below, should be understood that following explanation only is in order to explain the present invention, its content not to be limited.If no special instructions, raw materials used is weight portion.
Disclosed method makes among the Graphene poly phosphazene nano composite material employing patent CN201110025542.0 that uses among the following embodiment, 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 poly phosphazene nano composite materials, 15 parts of imvites; 17 parts of methyl silicon sodium alcoholates; 70 parts of cyclohexanol six phosphates prepare by following method: use ball-milling method to be ground to particle diameter imvite and be 20-50nm, get nano imvite; 2-ethoxy phenyl hypophosphorous acid, Graphene poly phosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates; Under 35 ℃, carry out sonicated 3h; Supersonic frequency is that 20kHz, ultrasonic power are 400W; Add remaining raw material in the mixture after the sonicated, mix, promptly get phosphorus system and mix fire retardant.
Embodiment 2
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 30 parts of Graphene poly phosphazene nano composite materials, 10 parts of imvites; 20 parts of methyl silicon sodium alcoholates; 50 parts of cyclohexanol six phosphates prepare by following method: use ball-milling method to be ground to particle diameter imvite and be 20-50nm, get nano imvite; 2-ethoxy phenyl hypophosphorous acid, Graphene poly phosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates; Under 30 ℃, carry out sonicated 4h; Supersonic frequency is that 20kHz, ultrasonic power are 400W; Add remaining raw material in the mixture after the sonicated, mix, promptly get phosphorus system and mix fire retardant.
Embodiment 3
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 40 parts of Graphene poly phosphazene nano composite materials, 13 parts of imvites; 15 parts of methyl silicon sodium alcoholates; 70 parts of cyclohexanol six phosphates prepare by following method: use ball-milling method to be ground to particle diameter imvite and be 20-50nm, get nano imvite; 2-ethoxy phenyl hypophosphorous acid, Graphene poly phosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates; Under 40 ℃, carry out sonicated 3h; Supersonic frequency is that 20kHz, ultrasonic power are 400W; Add remaining raw material in the mixture after the sonicated, mix, promptly get phosphorus system and mix fire retardant.
Embodiment 4
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 50 parts of Graphene poly phosphazene nano composite materials, 15 parts of imvites; 10 parts of methyl silicon sodium alcoholates; 80 parts of cyclohexanol six phosphates prepare by following method: use ball-milling method to be ground to particle diameter imvite and be 20-50nm, get nano imvite; 2-ethoxy phenyl hypophosphorous acid, Graphene poly phosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates; Under 40 ℃, carry out sonicated 2h; Supersonic frequency is that 20kHz, ultrasonic power are 400W; Add remaining raw material in the mixture after the sonicated, mix, promptly get phosphorus system and mix fire retardant.
Embodiment 5
Get 100 parts of 2-ethoxy phenyl hypophosphorous acid, 35 parts of Graphene poly phosphazene nano composite materials, 15 parts of imvites, 17 parts of methyl silicon sodium alcoholates, 15 parts in 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 poly phosphazene nano composite materials, 10 parts of imvites, 20 parts of methyl silicon sodium alcoholates, 20 parts in 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 poly phosphazene nano composite materials, 13 parts of imvites, 10 parts of methyl silicon sodium alcoholates, 10 parts in 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.
Carry out the test of heat endurance, limited oxygen index, fusion dropping number to mixing fire retardant according to the phosphorus system of such scheme preparation, the result sees the following form 1.
With phosphorus of the present invention is to mix fire retardant to be coated on the fiber; 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, and unit replacement cycle>=20 day, the POY full-rolling rate is " 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 result sees the following form 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 poly phosphazene nano composite material 30-50 part, imvite 10-15 part, methyl silicon sodium alcoholate 10-20 part, cyclohexanol six phosphate 50-80 parts.
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 poly phosphazene 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 in paraffin, 8 parts of melamines.
5. the preparation method of fire retardant mixes in claim 1 or 2 described phosphorus systems, it is characterized in that may further comprise the steps:
(1) uses ball-milling method to be ground to particle diameter imvite and be 20-50nm, get nano imvite;
(2) 2-ethoxy phenyl hypophosphorous acid, Graphene poly phosphazene nano composite material and nano imvite are joined in cyclohexanol six phosphates, under 30-40 ℃, carry out sonicated 2-4h;
(3) add remaining raw material in the mixture after the sonicated, mix, promptly get phosphorus system and mix fire retardant.
6. preparation method according to claim 5 is characterized in that: supersonic frequency is that 20kHz, ultrasonic power are 400W.
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| CN2012101278091A CN102628218B (en) | 2012-04-27 | 2012-04-27 | Phosphorus hybrid flame retardant and preparation method thereof |
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| CN2012101278091A CN102628218B (en) | 2012-04-27 | 2012-04-27 | Phosphorus hybrid flame retardant and preparation method thereof |
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Cited By (7)
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| CN104213406A (en) * | 2013-05-29 | 2014-12-17 | 中日合成化学股份有限公司 | Water-soluble flame-retardant composition and application thereof |
| CN104983100A (en) * | 2015-06-29 | 2015-10-21 | 安徽东锦服饰有限公司 | Processing method for waterproof flame-retardant functional clothing fabric |
| CN105603560A (en) * | 2016-01-25 | 2016-05-25 | 晋江市亿泰隆化纤制造有限公司 | Flame-retardant and antibacterial polyester fiber for mattress filling and manufacturing method of fiber |
| CN105647549A (en) * | 2015-11-25 | 2016-06-08 | 北京旭碳新材料科技有限公司 | Graphene flame-retardant film, and preparation method and application 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 |
| CN109713199A (en) * | 2018-12-28 | 2019-05-03 | 湖南农业大学 | A kind of heat-proof combustion-resistant composite diaphragm and its preparation method and application |
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Patent Citations (2)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104213406A (en) * | 2013-05-29 | 2014-12-17 | 中日合成化学股份有限公司 | Water-soluble flame-retardant composition and application thereof |
| CN104213406B (en) * | 2013-05-29 | 2016-02-24 | 中日合成化学股份有限公司 | Water-soluble flame-retardant composition and application thereof |
| CN104983100A (en) * | 2015-06-29 | 2015-10-21 | 安徽东锦服饰有限公司 | Processing method for waterproof flame-retardant functional clothing fabric |
| 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 |
| CN105647549A (en) * | 2015-11-25 | 2016-06-08 | 北京旭碳新材料科技有限公司 | Graphene flame-retardant film, and preparation method and application thereof |
| 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 |
| CN105603560A (en) * | 2016-01-25 | 2016-05-25 | 晋江市亿泰隆化纤制造有限公司 | Flame-retardant and antibacterial polyester fiber for mattress filling and manufacturing method of fiber |
| 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 |
| CN109713199A (en) * | 2018-12-28 | 2019-05-03 | 湖南农业大学 | A kind of heat-proof combustion-resistant composite diaphragm and its preparation method and application |
| 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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