CN107163474A - A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant - Google Patents
A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant Download PDFInfo
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- CN107163474A CN107163474A CN201710403265.XA CN201710403265A CN107163474A CN 107163474 A CN107163474 A CN 107163474A CN 201710403265 A CN201710403265 A CN 201710403265A CN 107163474 A CN107163474 A CN 107163474A
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- nitrogen phosphorus
- fire retardant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant, belong to technical field of flame retardant.Comprise the following steps：（1）Phosphoric acid and urea are added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe, is reacted after heating；（2）Cooled down after the completion of reaction, ammonia is passed through after cooling and carries out neutralization reaction, treats that pH value reaches 5 ~ 7, be cooled to room temperature, centrifugation obtains being ground into powder after white solid；（3）By step（2）White solid powder, lubricant, coupling agent, the SiO of preparation2, mix in the tertiary butyl ether input high speed mixer of poly- aryl ethane resin and diethylene glycol, be finally completed preparation.The preparation method is simple, and raw material is easy to get, it is easy to accomplish industrialization；Using nitrogen phosphorus as main ignition-proof element, high effect nontoxic, safety and environmental protection；On the premise of identical flame retardant effect is ensured, the consumption of only existing conventional flame retardants 1/3, and flame retardant rating reaches 0 grade of UL94 V, disclosure satisfy that polyethylene and polyacrylic processing request.
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of preparation side of low smoke and zero halogen nitrogen phosphorus composite fire retardant
Method and its application.
Background technology
Fire-retardant science and technology be in order to adapt to social safety production and life the need for, fire preventing occur, protect the people
Lives and properties and a science grown up.Fire retardant is application of the flame-retarded technology in real life, and it is that one kind is used for
Improve the special auxiliary chemicals of flammable combustible material combustibility, be widely used in the fire-retardant processing of all kinds of finishing materials.
Material after fire retardant is processed, when being attacked by extraneous burning things which may cause a fire disaster, can effectively prevent, delays or terminate the biography of flame
Broadcast, so as to reach fire-retardant effect.For the material of high polymer material flame resistance can be increased, it is mainly used in high polymer material such as modeling
Material, rubber, fiber etc., and most of these materials can burn.Particularly plastics, applied communications and transportation,
In terms of building, electrotechnical apparatus, aviation, space flight, it is felt to be desirable to solve its resistance to combustion problem.The use one of fire retardant
As should possess following condition：The physical property of high polymer material, such as heat resistance, mechanical strength, electric property are not reduced；Decompose temperature
Degree should not be too high, but at processing temperatures again can not decompose, it is inexpensive.
Red phosphorus is a kind of preferable fire retardant in non-halogen flame retardant, with addition is few, the high and low cigarette of flame retarding efficiency,
Low toxicity, it is widely used the advantages of；The inorganic combustion inhibitor compounding use such as red phosphorus and aluminium hydroxide, expansile graphite, is made compound
The non-halogen fire retardants such as phosphorus/magnesium, phosphorus/aluminium, phosphorus/graphite, usable flame retardant amount is greatly reduced, so as to improve the processing of plastic products
Performance and physical and mechanical properties.But common red phosphorus is oxidizable in atmosphere, moisture absorption, easily cause dust explosion, transport difficult, with
The defects such as high polymer material intermiscibility difference, application is restricted.
The content of the invention
The technical problem of solution：For above-mentioned technical problem, it is compound fire-retardant that the present invention provides a kind of low smoke and zero halogen nitrogen phosphorus
The preparation method and applications of agent, preparation method is simple, and raw material is easy to get, it is easy to accomplish industrialization；Using nitrogen phosphorus as main fire-retardant member
Element, high effect nontoxic, safety and environmental protection.
Technical scheme：A kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant, the preparation method includes following
Step：（1）It is 2 ~ 10 that mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe:1 phosphoric acid and urine
Element, is warming up to 40 ~ 90 min of reaction after 100 ~ 180 DEG C；
（2）Cooled down after the completion of reaction, be cooled to after 10 ~ 90 DEG C and be passed through ammonia progress neutralization reaction, treat that pH value reaches 5 ~ 7,
Room temperature is cooled to, centrifugation obtains being ground into powder after white solid；
（3）By step（2）White solid powder, lubricant, coupling agent, the SiO of preparation2, poly- aryl ethane resin and diethyl two
1 ~ 10 min of mixing in the tertiary butyl ether input high speed mixer of alcohol, wherein by weight, 50 ~ 75 parts of white solid powder, lubrication
0.5 ~ 2 part of agent, 0.5 ~ 2 part of coupling agent, SiO2 0.1 ~ 2 part, 3 ~ 5 parts of poly- aryl ethane resin and the tertiary butyl ether 11 ~ 15 of diethylene glycol
Part, it is finally completed preparation.
Preferably, the step（1）The mass fraction of phosphoric acid is 85%.
Preferably, the step（1）Mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe
For 4:1 phosphoric acid and urea, is warming up to after 150 DEG C and reacts 65 min.
Preferably, the step（2）It is cooled to after 65 DEG C and is passed through ammonia and carries out neutralization reaction, treats that pH value reaches 7, then
It is cooled to room temperature.
Preferably, the step（2）The amount for being passed through ammonia is the 4% ~ 18% of phosphoric acid quality.
Preferably, the step（3）Middle lubricant is stearic acid or calcium stearate, and the coupling agent is coupled for titanate esters
Agent.
Preferably, the step（3）8 min of mixing in high speed mixer are put into, batch mixer rotating speed is 1500 r/min.
Further, the step（3）In by weight, 65 parts of white solid powder, 1 part of lubricant, coupling agent 1
Part, SiO2 12 parts of 1.5 parts, 4 parts of poly- aryl ethane resin and the tertiary butyl ether of diethylene glycol.
Another technical scheme of the present invention is application of the described preparation method in polypropylene and polyethylene anti-flaming.
Beneficial effect：（1）Preparation method of the present invention is simple, and raw material is easy to get, it is easy to accomplish industrialization；Based on nitrogen phosphorus
Want ignition-proof element, high effect nontoxic, safety and environmental protection；（2）Product phosphorus content is more than 27%, and nitrogen content is more than 15%, and decomposition temperature is more than
350 DEG C, moisture is less than 0.5%, it is proposed that addition 12 ~ 18；（3）Compared to existing halogen-free flame retardants, ensureing identical flame retardant effect
On the premise of, consumption greatly reduces, the consumption of only existing conventional flame retardants 1/3, and flame retardant rating reaches V-0 grades of UL94,
It disclosure satisfy that polyethylene and polyacrylic processing request.
Embodiment
Embodiment 1
A kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant, the preparation method comprises the following steps：
（1）It is 2 that mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe:1 85wt.% phosphoric acid and urine
Element, is warming up to after 100 DEG C and reacts 40 min；
（2）Cooled down after the completion of reaction, be cooled to after 10 DEG C and be passed through ammonia progress neutralization reaction, the amount for being passed through ammonia is phosphoric acid
The 4% of quality, treats that pH value reaches 5, is cooled to room temperature, and centrifugation obtains being ground into powder after white solid；
（3）By step（2）White solid powder, lubricant, coupling agent, the SiO of preparation2, poly- aryl ethane resin and diethyl two
1 min of mixing in the tertiary butyl ether input high speed mixer of alcohol, wherein by weight, 50 parts of white solid powder, lubricant 0.5
Part, 0.5 part of coupling agent, SiO2 11 parts of 0.1 part, 3 parts of poly- aryl ethane resin and the tertiary butyl ether of diethylene glycol, are finally completed preparation.
Lubricant is stearic acid, and coupling agent is titanate coupling agent.
By mass parts, take 10 parts of polypropylene or polyethylene and 3 parts of this products to put into high speed mixer, add simultaneously
0.03 part of white oil and 0.05 stearic acid or zinc stearate, are sufficiently mixed 10 min.Then granulated in twin screw extruder machine,
Extrusion carries out vacuum exhaust, and mechanograph then is made with injection machine.
High speed mixer rotating speed is 1500 r/min.
Product phosphorus content is more than 18.5%, and nitrogen content is more than 17%, and decomposition temperature is more than 350 DEG C, and moisture is less than 0.7%, it is proposed that
Addition 22 ~ 30.
Compared to existing halogen-free flame retardants, on the premise of identical flame retardant effect is ensured, consumption greatly reduces, only existing
The consumption of conventional flame retardants 1/3, and flame retardant rating reaches V-0 grades of UL94, disclosure satisfy that polyethylene and polyacrylic processing will
Ask.
Preparation method of the present invention is simple, and raw material is easy to get, it is easy to accomplish industrialization；Using nitrogen phosphorus as main ignition-proof element,
High effect nontoxic, safety and environmental protection.
Embodiment 2
A kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant, the preparation method comprises the following steps：
（1）It is 10 that mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe:1 85wt.% phosphoric acid and
Urea, is warming up to after 180 DEG C and reacts 90 min；
（2）Cooled down after the completion of reaction, be cooled to after 90 DEG C and be passed through ammonia progress neutralization reaction, the amount for being passed through ammonia is phosphoric acid
The 18% of quality, treats that pH value reaches 7, is cooled to room temperature, and centrifugation obtains being ground into powder after white solid；
（3）By step（2）White solid powder, lubricant, coupling agent, the SiO of preparation2, poly- aryl ethane resin and diethyl two
10 min of mixing in alcohol tertiary butyl ether input high speed mixer, wherein by weight, 75 parts of white solid powder, 2 parts of lubricant,
2 parts of coupling agent, SiO2 15 parts of 2 parts, 5 parts of poly- aryl ethane resin and the tertiary butyl ether of diethylene glycol, are finally completed preparation.Lubricant is
Calcium stearate, coupling agent is titanate coupling agent.High speed mixer rotating speed is 1500 r/min.
By mass parts, take 10 parts of polypropylene or polyethylene and 3 parts of this products to put into high speed mixer, add simultaneously
0.03 part of white oil and 0.05 stearic acid or zinc stearate, are sufficiently mixed 10 min.Then granulated in twin screw extruder machine,
Extrusion carries out vacuum exhaust, and mechanograph then is made with injection machine.
High speed mixer rotating speed is 1500 r/min.
Product phosphorus content is more than 25%, and nitrogen content is more than 7%, and decomposition temperature is more than 350 DEG C, and moisture is less than 0.6%, it is proposed that add
Dosage 15 ~ 23.
Compared to existing halogen-free flame retardants, on the premise of identical flame retardant effect is ensured, consumption greatly reduces, only existing
The consumption of conventional flame retardants 1/3, and flame retardant rating reaches V-0 grades of UL94, disclosure satisfy that polyethylene and polyacrylic processing will
Ask.
Preparation method of the present invention is simple, and raw material is easy to get, it is easy to accomplish industrialization；Using nitrogen phosphorus as main ignition-proof element,
High effect nontoxic, safety and environmental protection.
Embodiment 3
A kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant, the preparation method comprises the following steps：
（1）It is 4 that mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe:1 85wt.% phosphoric acid and urine
Element, is warming up to after 150 DEG C and reacts 65 min；
（2）Cooled down after the completion of reaction, be cooled to after 65 DEG C and be passed through ammonia progress neutralization reaction, the amount for being passed through ammonia is phosphorus
The 18% of sour quality, treats that pH value reaches 7, is cooled to room temperature, and centrifugation obtains being ground into powder after white solid；
（3）By step（2）White solid powder, lubricant, coupling agent, the SiO of preparation2, poly- aryl ethane resin and diethyl two
8 min of mixing in alcohol tertiary butyl ether input high speed mixer, wherein by weight, 65 parts of white solid powder, 1 part of lubricant,
1 part of coupling agent, SiO212 parts of 1.5 parts, 4 parts of poly- aryl ethane resin and the tertiary butyl ether of diethylene glycol, are finally completed preparation.Lubrication
Agent is stearic acid, and coupling agent is titanate coupling agent.
By mass parts, take 10 parts of polypropylene or polyethylene and 3 parts of this products to put into high speed mixer, add simultaneously
0.03 part of white oil and 0.05 stearic acid or zinc stearate, are sufficiently mixed 10 min.Then granulated in twin screw extruder machine,
Extrusion carries out vacuum exhaust, and mechanograph then is made with injection machine.
High speed mixer rotating speed is 1500 r/min.
Product phosphorus content is more than 27%, and nitrogen content is more than 15%, and decomposition temperature is more than 350 DEG C, and moisture is less than 0.5%, it is proposed that add
Dosage 12 ~ 18.
Compared to existing halogen-free flame retardants, on the premise of identical flame retardant effect is ensured, consumption greatly reduces, only existing
The consumption of conventional flame retardants 1/3, and flame retardant rating reaches V-0 grades of UL94, disclosure satisfy that polyethylene and polyacrylic processing will
Ask.
Preparation method of the present invention is simple, and raw material is easy to get, it is easy to accomplish industrialization；Using nitrogen phosphorus as main ignition-proof element,
High effect nontoxic, safety and environmental protection.
Claims (9)
1. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant, it is characterised in that the preparation method includes following
Step：（1）It is 2 ~ 10 that mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe:1 phosphoric acid and urine
Element, is warming up to 40 ~ 90 min of reaction after 100 ~ 180 DEG C；
（2）Cooled down after the completion of reaction, be cooled to after 10 ~ 90 DEG C and be passed through ammonia progress neutralization reaction, treat that pH value reaches 5 ~ 7,
Room temperature is cooled to, centrifugation obtains being ground into powder after white solid；
（3）By step（2）White solid powder, lubricant, coupling agent, the SiO of preparation2, poly- aryl ethane resin and diethylene glycol
1 ~ 10 min of mixing in tertiary butyl ether input high speed mixer, wherein by weight, 50 ~ 75 parts of white solid powder, lubricant
0.5 ~ 2 part, 0.5 ~ 2 part of coupling agent, SiO2 11 ~ 15 parts of 0.1 ~ 2 part, 3 ~ 5 parts of poly- aryl ethane resin and the tertiary butyl ether of diethylene glycol,
It is finally completed preparation.
2. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1, it is characterised in that institute
State step（1）The mass fraction of phosphoric acid is 85%.
3. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1 or 2, its feature exists
In the step（1）It is 4 that mass ratio is added in the four-hole boiling flask equipped with agitator, thermometer and breather pipe:1 phosphoric acid and
Urea, is warming up to after 150 DEG C and reacts 65 min.
4. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1, it is characterised in that institute
State step（2）It is cooled to after 65 DEG C and is passed through ammonia progress neutralization reaction, treats that pH value reaches 7, be cooled to room temperature.
5. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1 or 4, its feature exists
In the step（2）The amount for being passed through ammonia is the 4% ~ 18% of phosphoric acid quality.
6. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1, it is characterised in that institute
State step（3）Middle lubricant is stearic acid or calcium stearate, and the coupling agent is titanate coupling agent.
7. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1, it is characterised in that institute
State step（3）8 min of mixing in high speed mixer are put into, batch mixer rotating speed is 1500 r/min.
8. a kind of preparation method of low smoke and zero halogen nitrogen phosphorus composite fire retardant according to claim 1,6 or 7, its feature exists
In the step（3）In by weight, 65 parts of white solid powder, 1 part of lubricant, 1 part of coupling agent, SiO2 1.5 parts, it is poly-
12 parts of 4 parts of aryl ethane resin and the tertiary butyl ether of diethylene glycol.
9. application of the preparation method according to claim 1 in polypropylene and polyethylene anti-flaming.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710403265.XA CN107163474A (en) | 2017-06-01 | 2017-06-01 | A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant |
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| CN201710403265.XA CN107163474A (en) | 2017-06-01 | 2017-06-01 | A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107761377A (en) * | 2017-10-17 | 2018-03-06 | 江苏尼美达科技有限公司 | The synthesis and application of the cotton of the formaldehydeless release of the Halogen permanent flame-retardant of nitrogen phosphorus collaboration system |
| CN109749044A (en) * | 2018-11-29 | 2019-05-14 | 四川大学 | The pure and mild fire-retardant anti-static polyurethane elastomer prepared therefrom of phosphorus contained multicomponent and their preparation method |
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| CN1807552A (en) * | 2006-02-09 | 2006-07-26 | 朱凯琴 | Novel phosphor nitrogen composite combustion inhibitor |
| CN101230275A (en) * | 2007-12-28 | 2008-07-30 | 华东理工大学 | High thermal-stability bittern-free phosphorous-nitrogen system flame-proof material |
| CN101851399A (en) * | 2009-03-30 | 2010-10-06 | 山东兴强阻燃科技有限公司 | Halogen-free flame retardant polyester product and preparation method thereof |
| CN102516551A (en) * | 2011-11-24 | 2012-06-27 | 寿光卫东化工有限公司 | Phosphorus-nitrogen halogen-free flame retardant and preparation method thereof |
| CN102532599A (en) * | 2011-12-15 | 2012-07-04 | 青海师范大学 | Liquid halogen-free phosphorus-nitrogen collaboration flame retardant and preparation method thereof |
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2017
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|---|---|---|---|---|
| CN1807552A (en) * | 2006-02-09 | 2006-07-26 | 朱凯琴 | Novel phosphor nitrogen composite combustion inhibitor |
| CN101230275A (en) * | 2007-12-28 | 2008-07-30 | 华东理工大学 | High thermal-stability bittern-free phosphorous-nitrogen system flame-proof material |
| CN101851399A (en) * | 2009-03-30 | 2010-10-06 | 山东兴强阻燃科技有限公司 | Halogen-free flame retardant polyester product and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107761377A (en) * | 2017-10-17 | 2018-03-06 | 江苏尼美达科技有限公司 | The synthesis and application of the cotton of the formaldehydeless release of the Halogen permanent flame-retardant of nitrogen phosphorus collaboration system |
| CN107761377B (en) * | 2017-10-17 | 2019-10-11 | 江苏尼美达科技有限公司 | The synthesis and application of the cotton of the formaldehydeless release of the Halogen permanent flame-retardant of nitrogen phosphorus collaboration system |
| CN109749044A (en) * | 2018-11-29 | 2019-05-14 | 四川大学 | The pure and mild fire-retardant anti-static polyurethane elastomer prepared therefrom of phosphorus contained multicomponent and their preparation method |
| CN109749044B (en) * | 2018-11-29 | 2021-05-21 | 四川大学 | Phosphorus-containing polyol, flame-retardant antistatic polyurethane elastomer prepared from phosphorus-containing polyol and preparation method of flame-retardant antistatic polyurethane elastomer |
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Application publication date: 20170915 |