CN102675372A - Ethylenediamine bicyclo-tetra methylenemelamine phosphonate compound and preparation method thereof - Google Patents
Ethylenediamine bicyclo-tetra methylenemelamine phosphonate compound and preparation method thereof Download PDFInfo
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- CN102675372A CN102675372A CN2012101243232A CN201210124323A CN102675372A CN 102675372 A CN102675372 A CN 102675372A CN 2012101243232 A CN2012101243232 A CN 2012101243232A CN 201210124323 A CN201210124323 A CN 201210124323A CN 102675372 A CN102675372 A CN 102675372A
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Abstract
The invention relates to an ethylenediamine bicyclo-tetra methylene melamine phosphonate compound and a preparation method thereof, in particular to a novel ethylenediamine bicyclo-tetra methylene melamine phosphonate for polymer flame retardance and the preparation method thereof. The compound synthesized by a two-step method has the characteristics of high phosphor/nitrogen content, high thermal stability, good hydrolysis resistance and the like, wherein due to triazine ring and phosphor-oxygen-nitrogen six-membered heterocyclic ring in the molecular structure, the thermal stability of the compound is greatly improved, the decomposition temperature of the compound is higher than 280 DEG C; and the charing property and flame retardance of a flame retarding system can be greatly improved due to the triazine ring structure in the molecular structure, and the excellent synergetic flame retarding effect of organic phosphor and six-membered heterocyclic ring can be represented. The compound synthesized by the invention can be widely applied to flame retardance of various synthetic materials and textiles such as polyolefin, polyurethane, nylon and polyester; raw materials for synthesizing the compound are easy to obtain, the production process is simple, and is suitable for industrial production and application.
Description
Technical field
The present invention relates to a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound and preparation method thereof; Particularly relate to one type and can be used for fire-retardant novel ethylene diamine dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound of polymkeric substance and preparation method thereof, specifically relate to a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound that contains triazine ring and phosphorous oxynitride hexa-member heterocycle and preparation method thereof.
Background technology
Since the eighties in 20th century, fire retardant has become the maximum auxiliary agent of synthetic materials consumption that is only second to softening agent.Along with expanding economy, people have had large increase to environmental protection and awareness of safety, and ecotope and value of life are also more paid close attention to.Traditional halogenated flame retardant is used for the production of fire retardant material in a large number because its flame retarding efficiency is high, but when burning, produces a large amount of smog and deleterious corrosive gases because halogen is flame retardant products, hinders rescue and evacuating personnel, causes secondary disaster to take place.Therefore, halogen is that the application of flame retardant products is restricted.Halogen-free flame retardants is used widely owing to have environmentally friendly characteristics such as low cigarette, low toxicity.Use efficient, low cigarette, halogen-free flame retardants nontoxic or low toxicity will become the inexorable trend of following fire retardant material development.Inorganic in recent years filler and fire-retardant and phosphorus flame retardant receive common concern.
Phosphorus flame retardant enjoys attention because flame retarding efficiency is high in the halogen-free flame-retardant field.There is easy volatile in traditional phosphorus flame retardant great majority, and therefore defectives such as facile hydrolysis develop low volatility, and the phosphorus flame retardant of facile hydrolysis is not the emphasis of developing from now on.Chinese patent CN101429438A has described a kind of with 4-chloro-benzaldehyde, and isobutyric aldehyde, phosphoric acid and trimeric cyanamide are that raw material reacts and makes phosphor-nitrogen expansion type combustion inhibitor 5; 5-dimethyl--4-rubigan-1,3, the method for 2-dioxaphosphorinane phosphoric melamine salt; Its three steps of reaction needed carry out, and reaction process is more numerous and diverse, and product purity is not high; And the fire retardant that makes contains halogen, still can not satisfy environmental protection requirement.
Summary of the invention
The purpose of this invention is to provide a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound and preparation method thereof, the present invention is directed to the characteristics of phosphorus flame retardant majority and the composite use of nitrogenous compound, synthesized a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound; This compound has phosphorus, nitrogen content is high; Characteristics such as thermostability is high, and hydrolytic resistance is good are owing to contain triazine ring and phosphorous oxynitride hexa-member heterocycle in the molecular structure; Improved its thermostability greatly; Its decomposition temperature is more than 280 ℃, and synthesis material is easy to get, and is easy to realize industrial production and application; Because the triazine ring structure in the molecular structure has also improved the one-tenth charcoal property and the flame retardant resistance of flame-retardant system greatly, show the excellent cooperative flame retardant effect of organophosphorus and hexa-member heterocycle simultaneously.Synthetic compound of the present invention can be widely used in the fire-retardant of synthetic materialss such as various polyolefine, urethane, nylon and polyester and textiles.
The present invention is directed to the characteristics of phosphorus flame retardant majority and the composite use of nitrogenous compound, synthesized a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound, this compound has phosphorus, nitrogen content is high; Characteristics such as thermostability is high, and hydrolytic resistance is good are owing to contain triazine ring and phosphorous oxynitride hexa-member heterocycle in the molecular structure; Improved its thermostability greatly; Its decomposition temperature is more than 280 ℃, and synthesis material is easy to get, and is easy to realize industrial production and application; Because the triazine ring structure in the molecular structure has also improved the one-tenth charcoal property and the flame retardant resistance of flame-retardant system greatly, show the excellent cooperative flame retardant effect of organophosphorus and hexa-member heterocycle simultaneously.Synthetic compound of the present invention can be widely used in the fire-retardant of synthetic materialss such as various polyolefine, urethane, nylon and polyester and textiles.
A kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound of the present invention, its structural formula of described compound is following:
As optimized technical scheme:
Aforesaid a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound, described compound be adopt ethylene diamine tetra methylene phosphonic acid and trimeric cyanamide through in and behind the salify, react through cyclodehydration again and make.
The present invention also provides a kind of preparation method of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound, and it is characterized in that: described preparation method adopts two-step reaction:
The first step: soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide again, attemperation also stirs, and after reaction finishes, filters, and drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt; Wherein, described temperature is 20～100 ℃, 2～8 hours reaction times; Trimeric cyanamide is 1: 0.20～1: 0.50 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid;
Second step: above-mentioned reaction intermediate is warming up to 160～260 ℃, 2～16 hours reaction times, make described reaction intermediate carry out the cyclodehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound, its structural formula does
Beneficial effect:
1, the first step reaction is simple acid-base reaction, as medium, reacts simple controllable with water, and reaction process does not have the hazardous and noxious substances generation.
2, the reaction of second step combines cyclization for dehydration, and environment is not polluted, and reaction process and conversion unit require simple, are applicable to industrial mass production.
3, synthetic quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound of the present invention has phosphorus, nitrogen content is high; Characteristics such as hydrolytic resistance is good; Owing to contain triazine ring and phosphorous oxynitride hexa-member heterocycle in the molecular structure, improved its thermostability greatly, its decomposition temperature is more than 280 ℃; And synthesis material is easy to get; Be easy to realize industrial production and application,, show the excellent cooperative flame retardant effect of organophosphorus and hexa-member heterocycle simultaneously because the triazine ring structure in the molecular structure has also improved the one-tenth carbon property and the flame retardant resistance of flame-retardant system greatly.Synthetic compound of the present invention can be widely used in the fire-retardant of synthetic materialss such as various polyolefine, urethane, nylon and polyester and textiles.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do this various changes or modification to the present invention after the content of having read the present invention's instruction, a little equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.20 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 60 ℃ and stirring; Sustained reaction 6 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 180 ℃, continues reaction 10 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound, its structural formula does
Through measuring its heat decomposition temperature is 283 ± 2 ℃.
Embodiment 2
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.31 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 100 ℃ and stirring; Sustained reaction 2 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 160 ℃, continues reaction 16 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound.
Through measuring its heat decomposition temperature is 285 ± 2 ℃.
Embodiment 3
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.50 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 20 ℃ and stirring; Sustained reaction 8 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 210 ℃, continues reaction 2 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound.
Through measuring its heat decomposition temperature is 287 ± 2 ℃.
Embodiment 4
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.25 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 80 ℃ and stirring; Sustained reaction 6 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 260 ℃, continues reaction 4 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound.
Through measuring heat decomposition temperature is 282 ± 2 ℃.
Embodiment 5
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.43 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 50 ℃ and stirring; Sustained reaction 4 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 240 ℃, continues reaction 6 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound.
Through measuring heat decomposition temperature is 281 ± 1 ℃.
Embodiment 6
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.36 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 55 ℃ and stirring; Sustained reaction 4 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 179 ℃, continues reaction 13 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound.
Through measuring heat decomposition temperature is 282 ± 1 ℃.
Embodiment 7
Soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide, trimeric cyanamide is 1: 0.27 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid; Adjust the temperature to 92 ℃ and stirring; Sustained reaction 4 hours after reaction finishes, is filtered; Drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt.Above-mentioned reaction intermediate is warming up to 230 ℃, continues reaction 10 hours, make midbody carry out dehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound.
Through measuring heat decomposition temperature is 285 ± 1 ℃.
Claims (3)
1. a quadrol dicyclo tetramethyl is pitched phosphonic acids trimeric cyanamide salt compound, and it is characterized in that: its structural formula of described compound is following:
2. a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound as claimed in claim 1, it is characterized in that described compound be adopt ethylene diamine tetra methylene phosphonic acid and trimeric cyanamide through in and behind the salify, react through cyclodehydration again and make.
3. the preparation method of a kind of quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound as claimed in claim 1 is characterized in that:
Described preparation method adopts two-step reaction:
The first step: soluble in water ethylene diamine tetra methylene phosphonic acid, add trimeric cyanamide again, attemperation also stirs, and after reaction finishes, filters, and drying obtains reaction intermediate ethylene diamine tetra methylene phosphonic acid melamine salt; Wherein, described temperature is 20～100 ℃, 2～8 hours reaction times; Trimeric cyanamide is 1: 0.20～1: 0.50 with the molar weight ratio that feeds intake of ethylene diamine tetra methylene phosphonic acid;
Second step: above-mentioned reaction intermediate is warming up to 160～260 ℃, 2～16 hours reaction times, make described reaction intermediate carry out the cyclodehydration reaction, obtain final product quadrol dicyclo tetramethyl fork phosphonic acids trimeric cyanamide salt compound, its structural formula does
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017163A (en) * | 2014-06-24 | 2014-09-03 | 北京理工大学 | Applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant |
| CN104031090A (en) * | 2014-06-24 | 2014-09-10 | 北京理工大学 | Preparation method of cyclic phosphorus-nitrogen synergistic halogen-free flame retardant |
| CN104072804A (en) * | 2014-06-24 | 2014-10-01 | 北京理工大学 | Cyclic phosphorus-nitrogen synergistic halogen-free flame retardant |
| 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 |
| CN111234462A (en) * | 2020-03-10 | 2020-06-05 | 南京同宁新材料研究院有限公司 | Ethylene diamine tetramethylene phosphonate metal salt/epoxy resin compound, preparation method and application thereof |
| CN111635559A (en) * | 2020-05-29 | 2020-09-08 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation method and application thereof |
| CN114407152A (en) * | 2022-02-15 | 2022-04-29 | 江山欧派门业股份有限公司 | Wood-bamboo fire retardant and preparation method thereof |
| CN114525095A (en) * | 2022-02-16 | 2022-05-24 | 江山花木匠家居有限公司 | Phenolic resin adhesive and production method thereof |
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| CN1162407C (en) * | 1998-07-08 | 2004-08-18 | 西巴特殊化学品控股有限公司 | Polyphosphate salt of 1,3,5-triazine compound with high degree of condensation and its use as flame retardent in polymer compositions |
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| EP1116773A1 (en) * | 1998-08-24 | 2001-07-18 | Nippon Chemical Industrial Company Limited | Flame retardant composition and flame-retardant resin composition |
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| 李到 等: "磷酸酯双三聚氰胺盐阻燃环氧树脂的燃烧性能和阻燃机理", 《功能高分子学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017163A (en) * | 2014-06-24 | 2014-09-03 | 北京理工大学 | Applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant |
| CN104031090A (en) * | 2014-06-24 | 2014-09-10 | 北京理工大学 | Preparation method of cyclic phosphorus-nitrogen synergistic halogen-free flame retardant |
| CN104072804A (en) * | 2014-06-24 | 2014-10-01 | 北京理工大学 | Cyclic phosphorus-nitrogen synergistic halogen-free flame retardant |
| CN104031090B (en) * | 2014-06-24 | 2016-05-11 | 北京理工大学 | A kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants |
| 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 |
| CN111234462A (en) * | 2020-03-10 | 2020-06-05 | 南京同宁新材料研究院有限公司 | Ethylene diamine tetramethylene phosphonate metal salt/epoxy resin compound, preparation method and application thereof |
| CN111635559A (en) * | 2020-05-29 | 2020-09-08 | 威海海润新材料科技有限公司 | Organic phosphide flame retardant and preparation method and application thereof |
| CN114407152A (en) * | 2022-02-15 | 2022-04-29 | 江山欧派门业股份有限公司 | Wood-bamboo fire retardant and preparation method thereof |
| CN114525095A (en) * | 2022-02-16 | 2022-05-24 | 江山花木匠家居有限公司 | Phenolic resin adhesive and production method thereof |
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Application publication date: 20120919 |