CN108059731A - A kind of preparation method of the ammonium polyphosphate flame retardant of not facile hydrolysis - Google Patents
A kind of preparation method of the ammonium polyphosphate flame retardant of not facile hydrolysis Download PDFInfo
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- CN108059731A CN108059731A CN201711321112.7A CN201711321112A CN108059731A CN 108059731 A CN108059731 A CN 108059731A CN 201711321112 A CN201711321112 A CN 201711321112A CN 108059731 A CN108059731 A CN 108059731A
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- ammonium polyphosphate
- preparation
- resin catalyst
- flame 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/405—Polyphosphates of ammonium
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Abstract
The present invention relates to a kind of preparation methods of the ammonium polyphosphate flame retardant of not facile hydrolysis.Reaction system carries out melt polymerization in liquefied ammonia environment, while introduces resin catalyst so that the ammonium polyphosphate product produced has the higher degree of polymerization, so as to improve its stability and service life in fire proofing.
Description
Technical field
The present invention relates to a kind of preparation method of ammonium polyphosphate, especially a kind of ammonium polyphosphate flame retardant of not facile hydrolysis
Preparation method.
Background technology
For the substance of high molecular material flame resistance can be increased, it is mainly used for high molecular material such as plastics, rubber, fiber
Deng, and most of these materials can burn.Particularly plastics are applied in communications and transportation, building, electricity Gong Qi
Material, aviation, space flight etc., it is felt to be desirable to solve its resistance to combustion problem.The use of fire retardant should generally possess following
Several conditions：The physical property of high molecular material is not reduced, such as heat resistance, mechanical strength, electric property;Decomposition temperature should not be too high,
But it cannot decompose again at processing temperatures;Durability is good;Good weatherability;It is inexpensive.Ammonium polyphosphate is also known as ammonium polyphosphate or contracting
Ammonium polyphosphate (abbreviation APP).Ammonium polyphosphate is non-toxic and tasteless, does not generate etchant gas, and hygroscopicity is small, and thermal stability is high, is a kind of
The non-halogen fire retardant of function admirable.
CN106832416A discloses a kind of preparation method of siliceous ammonium polyphosphate：By being introduced in ammonium polyphosphate skeleton
Organosilicon and iron content complex ions liquid, the anti-flammability of the siliceous ammonium polyphosphate flame retardant of generation are improved.
CN101570325B discloses a kind of method of modifying.The present invention solves existing ammonium polyphosphate as fire retardant
Facile hydrolysis causes flame retardant property to reduce the problem of being easily precipitated in the material with fire retardant.The method of the present invention is as follows：By modifying agent with
The mixed solution of dispersant is poured into ammonium polyphosphate, stirs, is static, being further continued for stirring, obtaining mixture, then by mixture in temperature
Spend for when drying 1~3 is small under conditions of 100 DEG C~250 DEG C to get modified ammonium polyphosphate.Modification is obtained using the present invention
The solubility of ammonium polyphosphate in water is 0.19g/100mL, and cladding activation grade is vertical for 98.1%~99.5%, 1.6mm battens
Up to V0 grades, oxygen index (OI) reaches more than 36 for burning, after the immersion when 168 is small, is with the addition of the polypropylene of ammonium polyphosphate modifying
The weight-loss ratio of material is small, is with the addition of the 1.6mm battens vertical combustion of polypropylene material of ammonium polyphosphate modifying still up to V0 grades,
Oxygen index (OI) can reach 33.6.
The existing solution for ammonium polyphosphate facile hydrolysis shortcoming mostly using coating or modified method, increases
The production cost of ammonium polyphosphate and complex process degree are added.
The content of the invention
Present invention aims at the above-mentioned technical problems in the prior art are solved, a kind of poly- phosphorus of not facile hydrolysis is provided
The preparation method of sour ammonium fire retardant.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of ammonium polyphosphate resistance of not facile hydrolysis
Fire the preparation method of agent, it is characterised in that preparation process includes：
1. the preparation of resin catalyst
By weight, 100 parts of vinylacetate, 3-6 parts of vinyltrimethoxysilane, allyl butyrate two are added in a kettle
It is 5-12 parts sour, 4,4'- 1-4 parts of dicarboxyl diphenylethlenes, 0.5-2 parts of benzoyl peroxide, 0.2-0.8 parts of polyvinyl alcohol, 1-
Pi-allyl -3- methylimidazoles are double（Fluoroform sulphonyl）0.0001-0.001 parts of inferior amine salt, 400-700 parts of water, nano-calcium carbonate
30-60 parts, be warming up to 80-95 DEG C after mixing, react 8-15h, after reaction with acetum wash away nano-calcium carbonate to get
To resin catalyst.
2. synthesize ammonium polyphosphate
By weight, 100 parts of one hydrogen amine of phosphoric acid, 30-50 parts of phosphorus pentoxide, melamine 15-25 are added in a kettle
Part, 2-5 parts of resin catalyst, 20-40 parts of liquefied ammonia is warming up to 220-250 DEG C, reacts 4-8h, isolates resin after reaction
Catalyst, product is filtered, washs, and dries, and crushes, obtains ammonium polyphosphate product.
The vinylacetate, vinyltrimethoxysilane, alkenyl succinic acid, 4,4'- dicarboxyl diphenylethlenes,
Benzoyl peroxide, polyvinyl alcohol, 1- pi-allyl -3- methylimidazoles are double（Fluoroform sulphonyl）Inferior amine salt, nano-calcium carbonate, phosphorus
A sour hydrogen amine, phosphorus pentoxide, melamine, liquefied ammonia is commercial product.
The present invention has the advantages that：
（1）Resin catalyst product has good thermal stability, non-breakable, can stablize performance catalysis in reaction temperature
Effect is effectively catalyzed the advantages of area is big, while service life is long, and can be repeated several times should in ammonium polyphosphate synthetic reaction is catalyzed
With.
（2）In ammonium polyphosphate synthesis step, by adding in liquefied ammonia and resin catalyst, the temperature of entire reaction system is made
Uniformly, Modulatory character is good；Catalyst degradation reaction required energy so that entire reaction process is stablized, and makes ammonium polyphosphate
The degree of polymerization of product is improved.
Specific embodiment
Following instance is only to further illustrate the present invention, and is not limitation the scope of protection of the invention.
Embodiment 1
The preparation of step 1. resin catalyst
In a kettle, vinylacetate 100g, vinyltrimethoxysilane 4.5g, alkenyl succinic acid 8.5g, 4,4'- are added in
Dicarboxyl diphenylethlene 2.5g, benzoyl peroxide 1.25g, polyvinyl alcohol 0.5g, 1- pi-allyl -3- methylimidazole are double（Three
Fluoromethane sulphonyl）Inferior amine salt 0.0005g, water 550g, nano-calcium carbonate 40g are warming up to 87 DEG C after mixing, react 11.5h,
Nano-calcium carbonate is washed away to get to resin catalyst with acetum after reaction.
Step 2. synthesizes ammonium polyphosphate
In a kettle, phosphoric acid one hydrogen amine 1000g, phosphorus pentoxide 450g, melamine 200g, resin catalyst 35g are added in,
Liquefied ammonia 300g is warming up to 235 DEG C, reacts 6h, isolates resin catalyst after reaction, and product is filtered, washs, drying,
It is broken, obtain ammonium polyphosphate product.
Embodiment 2
In a kettle, vinylacetate 100g, vinyltrimethoxysilane 3g, alkenyl succinic acid 5g, 4,4'- dicarboxyls are added in
Base diphenylethlene 1g, benzoyl peroxide 0.5g, polyvinyl alcohol 0.2g, 1- pi-allyl -3- methylimidazole are double（Fluoroform sulphur
Acyl）Inferior amine salt 0.0001g, water 400g, nano-calcium carbonate 30g are warming up to 80 DEG C after mixing, react 8h, after reaction
Nano-calcium carbonate is washed away to get to resin catalyst with acetum.
Step 2. synthesizes ammonium polyphosphate
In a kettle, phosphoric acid one hydrogen amine 1000g, phosphorus pentoxide 300g, melamine 150g, resin catalyst 20g are added in,
Liquefied ammonia 300g is warming up to 220 DEG C, reacts 4h, isolates resin catalyst after reaction, and product is filtered, washs, drying,
It is broken, obtain ammonium polyphosphate product.
Embodiment 3
In a kettle, vinylacetate 100g, vinyltrimethoxysilane 6g, alkenyl succinic acid 12g, 4,4'- bis- are added in
Carboxyl diphenylethlene 4g, benzoyl peroxide 2g, polyvinyl alcohol 0.8g, 1- pi-allyl -3- methylimidazole are double（Fluoroform sulphur
Acyl）Inferior amine salt 0.001g, water 700g, nano-calcium carbonate 50g are warming up to 95 DEG C after mixing, react 15h, after reaction
Nano-calcium carbonate is washed away to get to resin catalyst with acetum.
Step 2. synthesizes ammonium polyphosphate
In a kettle, phosphoric acid one hydrogen amine 1000g, phosphorus pentoxide 600g, melamine 250g, resin catalyst 50g are added in,
Liquefied ammonia 400g is warming up to 250 DEG C, reacts 15h, isolates resin catalyst after reaction, and product is filtered, washs, drying,
It is broken, obtain ammonium polyphosphate product.
Comparative example 1
Vinyltrimethoxysilane is added without, other conditions are the same as embodiment 1.
Comparative example 2
Alkenyl succinic acid is added without, other conditions are the same as embodiment 1.
Comparative example 3
4,4'- dicarboxyl diphenylethlenes are added without, other conditions are the same as embodiment 1.
Comparative example 4
It is double to be added without 1- pi-allyl -3- methylimidazoles（Fluoroform sulphonyl）Inferior amine salt, other conditions are the same as embodiment 1.
Comparative example 5
Resin catalyst is added without, other conditions are the same as embodiment 1.
Embodiment 4
Respectively refer to the ammonium polyphosphate product that standard HG/T2770-1996 examines embodiment 1-3 and comparative example 1-5 to be produced
The degree of polymerization.It is shown in Table 1.
Table 1：The ammonium polyphosphate product degree of polymerization that different process is produced.
Claims (2)
1. a kind of preparation method of the ammonium polyphosphate flame retardant of not facile hydrolysis, it is characterised in that include the following steps：By weight
Meter adds in 100 parts of one hydrogen amine of phosphoric acid, 30-50 parts of phosphorus pentoxide, 15-25 parts of melamine, resin catalyst in a kettle
2-5 parts, 20-40 parts of liquefied ammonia is warming up to 220-250 DEG C, reacts 4-8h, isolates resin catalyst, product warp after reaction
Filtering is washed, and is dried, and is crushed, is obtained ammonium polyphosphate product.
A kind of 2. preparation method of the ammonium polyphosphate flame retardant of not facile hydrolysis according to claim 1, it is characterised in that institute
The preparation method for the resin catalyst stated includes the following steps：By weight, vinylacetate 100 is added in a kettle
Part, 3-6 parts of vinyltrimethoxysilane, 5-12 parts of alkenyl succinic acid, 4,4'- 1-4 parts of dicarboxyl diphenylethlenes, peroxidating
0.5-2 parts of benzoyl, 0.2-0.8 parts of polyvinyl alcohol, 1- pi-allyl -3- methylimidazoles are double（Fluoroform sulphonyl）Inferior amine salt
0.0001-0.001 parts, 400-700 parts of water, 30-60 parts of nano-calcium carbonate is warming up to 80-95 DEG C after mixing, react 8-15h, instead
Should after with acetum wash away nano-calcium carbonate to get to resin catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113775A (en) * | 2013-01-23 | 2013-05-22 | 四川卓安消防材料有限公司 | Intumescent flame retardant including N-P cage type macromolecules and preparation technology thereof |
| CN105482160A (en) * | 2016-01-14 | 2016-04-13 | 中山康诺德新材料有限公司 | Preparation method and application for grafted modified ammonium polyphosphate with ultralow water sliding property and hydrolysis resistance |
| CN106586998A (en) * | 2016-12-18 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of ammonium polyphosphate having high polymerization degree |
| CN106586997A (en) * | 2016-12-16 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of type II ammonium polyphosphate |
-
2017
- 2017-12-12 CN CN201711321112.7A patent/CN108059731B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113775A (en) * | 2013-01-23 | 2013-05-22 | 四川卓安消防材料有限公司 | Intumescent flame retardant including N-P cage type macromolecules and preparation technology thereof |
| CN105482160A (en) * | 2016-01-14 | 2016-04-13 | 中山康诺德新材料有限公司 | Preparation method and application for grafted modified ammonium polyphosphate with ultralow water sliding property and hydrolysis resistance |
| CN106586997A (en) * | 2016-12-16 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of type II ammonium polyphosphate |
| CN106586998A (en) * | 2016-12-18 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of ammonium polyphosphate having high polymerization degree |
Non-Patent Citations (1)
| Title |
|---|
| 潘德韬等: "一步法制备高聚合度聚磷酸铵的中试研究", 《化工矿物与加工》 * |
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Effective date of registration: 20190522 Address after: No. 2 Zhongshan No. 7 Road, North District of Yancheng Coastal Chemical Industry Park, Yancheng City, Jiangsu Province Applicant after: Haibin Yoke Chemical Co., Ltd. Address before: 432009 Tongqutai Suitable Residential Area East of Dong Yong Road, Xiaogan City, Hubei Province Applicant before: Xiaogan Ruxi New Material Technology Co., Ltd. |
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