CN103304819A - Phosphor-containing epoxy resin flame retardant and preparation method thereof - Google Patents
Phosphor-containing epoxy resin flame retardant and preparation method thereof Download PDFInfo
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- CN103304819A CN103304819A CN2013102550016A CN201310255001A CN103304819A CN 103304819 A CN103304819 A CN 103304819A CN 2013102550016 A CN2013102550016 A CN 2013102550016A CN 201310255001 A CN201310255001 A CN 201310255001A CN 103304819 A CN103304819 A CN 103304819A
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Abstract
The invention discloses phosphor-containing epoxy resin flame retardant and a preparation method thereof. The preparation method of the phosphor-containing epoxy resin flame retardant comprises the following steps of: 1, enabling pentaerythritol and phosphorus oxychloride to react to obtain white powder pentaerythritol spirocyclic phosphate; and 2, enabling the pentaerythritol spirocyclic phosphate and phenol compound to react to obtain phosphor-containing flame retardant by using triethylamine as the catalyst. White powder or solid product is obtained by the steps including filtering, washing and the like after the reaction mixed solution is cooled. Relative to 100 weight parts of epoxy resin, 20 parts of flame retardant can be used for enabling the flame retardance of the composite material to reach UL94V-0 level. The phosphor-containing epoxy resin flame retardant provided by the invention is efficient halogen-free flame retardant, and can be used for various polymers by being used as the flame-retardant additive, so that the flame retardance of the polymer is improved.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, relate in particular a kind of phosphoric epoxy resin flame retardant and preparation method thereof.
Background technology
Resins, epoxy is widely used in the fields such as wrapping material, coating, building, building, tackiness agent, electronics and aviation with its good cohesiveness, erosion resistance, chemical resistant properties, heat-resisting and winter hardiness, electrical insulation capability and physical and mechanical properties.But the oxygen index of ordinary epoxy resin is about 19.8% only, belongs to combustible material, and its inflammableness and the lasting spontaneous combustion behind fire are restricted its application in a lot of fields.Therefore, the flame retardant properties that how to improve Resins, epoxy has caused domestic and international investigator's extensive concern.
At first, because halogen containing flame-retardant has higher flame retardant effect to epoxide resin material, so aspect polymer composite, use morely.Recently, because halogen containing flame-retardant can produce a large amount of smog in combustion processes and the gas that discharges is poisonous, corrodibility is large, and for the requirement of environment protection, the demand of halogen-free flameproof substitute technology is very urgent.
A kind of preparation method of brominated Fire Retardant of The Expoxy Resin is disclosed among the CN 102675600.Contain tetrabromo-bisphenol on this fire retardant main chain, can reach flame retardant effect, but owing to contain halogen, influential to environment.
Organic phosphorus flame retardant mostly belongs to additive flame retardant, has preferably characteristics of relatively low toxic side effect and flame retardant effect, is the halogen-free flame retardants of main development from now on.
Summary of the invention
The object of the present invention is to provide a kind of phosphoric epoxy resin flame retardant and preparation method thereof, this fire retardant is prepared by tetramethylolmethane, phosphorus oxychloride and phenolic compound, has higher flame retardant effect.
The technical solution used in the present invention: a kind of phosphoric epoxy resin flame retardant and preparation method thereof comprises the following steps:
The preparation of A, tetramethylolmethane spiro-phosphate
Tetramethylolmethane in molar ratio: phosphorus oxychloride=1:2-10 adds in the reactor, while stirring heating, and reaction is 2-12 hour under 60-140 ℃ of condition.Reaction mixture is cooled to room temperature, filters reaction mixture, use the washed with dichloromethane filter cake.Oven dry is 4-20 hour under 50-150 ℃ of condition, gets white powdery tetramethylolmethane spiro-phosphate.
The preparation of B, phosphonium flame retardant
Tetramethylolmethane spiro-phosphate in molar ratio: bisphenol S=1:0.6-1.4 adds in the reactor, adds after the solvent acetonitrile, drips triethylamine.Warming while stirring was to boiling, isothermal reaction 2-14 hour.Reaction mixture is cooled to room temperature, filters reaction mixture, use the acetonitrile washing leaching cake.Oven dry is 4-20 hour under 50-200 ℃ of condition, gets phosphonium flame retardant.
Tetramethylolmethane described in the steps A: the mol ratio of phosphorus oxychloride is preferably 1:3-9, and optimum mole ratio is 1:4-8; Described temperature of reaction is preferably 80-120 ℃, and optimal reaction temperature is 90-110 ℃; The described reaction times is preferably 4-10 hour, and optimum reacting time is 6-8 hour.
Bake out temperature described in the steps A is preferably 60-130 ℃, and best bake out temperature is 80-110 ℃; Described drying time is preferably 6-18 hour, and best drying time is 8-15 hour.
The spiro-phosphate of tetramethylolmethane described in the step B: the mol ratio of bisphenol S is preferably 1:0.8-1.2, and optimum mole ratio is 1:0.9-1.1; The described reaction times is preferably 4-12 hour, and optimum reacting time is 6-10 hour.
Bake out temperature described in the step B is preferably 70-160 ℃, and best bake out temperature is 80-140 ℃; Described drying time is preferably 8-15 hour, and best drying time is 10-13 hour.
Bisphenol S described in the step B can replace with other phenolic compounds, and phenolic compound is p-methyl phenol, phenol, or Resorcinol.
Embodiment
Below by embodiment the present invention is described in further detail, a kind of phosphoric epoxy resin flame retardant and preparation method thereof comprises the following steps:
The preparation of A, tetramethylolmethane spiro-phosphate
Tetramethylolmethane in molar ratio: phosphorus oxychloride=1:2-10 adds in the reactor, while stirring heating, and reaction is 2-12 hour under 60-140 ℃ of condition.Reaction mixture is cooled to room temperature, filters reaction mixture, use the washed with dichloromethane filter cake.Oven dry is 4-20 hour under 50-150 ℃ of condition, gets white powdery tetramethylolmethane spiro-phosphate.
The preparation of B, phosphonium flame retardant
Tetramethylolmethane spiro-phosphate in molar ratio: bisphenol S=1:0.6-1.4 adds in the reactor, adds after the solvent acetonitrile, drips triethylamine.Warming while stirring was to boiling, isothermal reaction 2-14 hour.Reaction mixture is cooled to room temperature, filters reaction mixture, use the acetonitrile washing leaching cake.Oven dry is 4-20 hour under 50-200 ℃ of condition, gets phosphonium flame retardant.
Tetramethylolmethane described in the steps A: the mol ratio of phosphorus oxychloride is preferably 1:3-9, and optimum mole ratio is 1:4-8; Described temperature of reaction is preferably 80-120 ℃, and optimal reaction temperature is 90-110 ℃; The described reaction times is preferably 4-10 hour, and optimum reacting time is 6-8 hour.Bake out temperature described in the steps A is preferably 60-130 ℃, and best bake out temperature is 80-110 ℃; Described drying time is preferably 6-18 hour, and best drying time is 8-15 hour.The spiro-phosphate of tetramethylolmethane described in the step B: the mol ratio of bisphenol S is preferably 1:0.8-1.2, and optimum mole ratio is 1:0.9-1.1; The described reaction times is preferably 4-12 hour, and optimum reacting time is 6-10 hour.Bake out temperature described in the step B is preferably 70-160 ℃, and best bake out temperature is 80-140 ℃; Described drying time is preferably 8-15 hour, and best drying time is 10-13 hour.Bisphenol S described in the step B can replace with other phenolic compounds, and phenolic compound is p-methyl phenol, phenol, or Resorcinol.
Embodiment 1
In the 250 ml four-hole bottles of being furnished with agitator, thermometer, nitrogen conduit and reflux condensing tube and device for absorbing tail gas, add tetramethylolmethane (20.42 g, 0.15 mol) (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group) and phosphorus oxychloride (122.66 g, 0.9 mol), while stirring heating, reaction is 6 hours under 120 ℃ of conditions.Reaction mixture is cooled to room temperature, filters reaction mixture, with methylene dichloride (analytical pure, East China, Shenyang City chemical reagent work) washing leaching cake.Oven dry is 12 hours under 100 ℃ of conditions, gets white powdery tetramethylolmethane spiro-phosphate A1, and yield is 63.5%, and fusing point is 229.3-233.7 ℃.
Embodiment 2
Except the mol ratio with tetramethylolmethane and phosphorus oxychloride changes into the 1:5, all the other get white powdery tetramethylolmethane spiro-phosphate A2 with embodiment 1, and yield is 62.4%, and fusing point is 228.1-232.5 ℃.
Embodiment 3
Except changing in the reaction times 8 hours, all the other get white powdery tetramethylolmethane spiro-phosphate A3 with embodiment 1, and yield is 52.4%, and fusing point is 230.4-234.3 ℃.
Embodiment 4
In the 100ml four-hole bottle of being furnished with agitator, thermometer, nitrogen conduit and reflux condensing tube and device for absorbing tail gas, add tetramethylolmethane spiro-phosphate (2.97 g, 0.01 mol), bisphenol S (4.76 g, 0.019 mol) (chemical pure, Chemical Reagent Co., Ltd., Sinopharm Group) and solvent acetonitrile (analytical pure, Rui Jin, Tianjin special chemical company limited), then drip triethylamine (4.04 g, mol) 0.04 (analytical pure, the special chemical in Rui Jin, Tianjin company limited).Warming while stirring is to boiling, isothermal reaction 6 hours.Reaction mixture is cooled to room temperature, filters reaction mixture, use the acetonitrile washing leaching cake.Oven dry is 12 hours under 100 ℃ of conditions, gets white powdery combustion inhibitor B1, and yield is 86.1%, and fusing point is 224.7-244.0 ℃.
Embodiment 5
Except the mol ratio with tetramethylolmethane spiro-phosphate and bisphenol S changes into the 1:1.05, all the other get white powdery combustion inhibitor B2 with embodiment 1, and yield is 92.7%, and fusing point is 225.2-244.8 ℃.
Embodiment 6
Except bisphenol S being changed into outside the methylphenol (chemical pure, Chemical Reagent Co., Ltd., Sinopharm Group), all the other get white powdery combustion inhibitor B3 with embodiment 4, and yield is 61.2%, and fusing point is 177.7-182.2 ℃.
Embodiment 7
Except bisphenol S being changed into outside the phenol (analytical pure, Tianjin forever large chemical reagent development centre), all the other get white powdery combustion inhibitor B4 with embodiment 4, and yield is 74.4%, and fusing point is 198.4-215.5 ℃.
Embodiment 8
Except bisphenol S being changed into outside the Resorcinol (analytical pure, the special chemical in Rui Jin, Tianjin company limited), all the other get white solid shape fire retardant B5 with embodiment 4, and yield is 82.3%, and fusing point is 229.3-290 ℃.
Embodiment 9
Get fire retardant (B1-B5) 20 g that above embodiment 4-8 makes, Resins, epoxy (E-44, Feicheng, Shandong De Yuan chemical industry company limited) 100 grams and 4,4 '-diaminodiphenyl-methane (chemical pure, Chemical Reagent Co., Ltd., Sinopharm Group) 26 g stirred 1 hour under 80 ° of C conditions, under reduced pressure deviate from bubble, be poured in the mould, 110
oSolidified 1 hour 140 under the C
oSolidified 2 hours 170 under the C
oSolidified 1 hour under the C, at last cooling, the demoulding.The gained batten all can reach the fire-retardant rank of UL94 V-0 through the test of vertical combustion instrument.
Claims (6)
1. phosphoric epoxy resin flame retardant and preparation method thereof comprises the following steps:
A. the preparation of tetramethylolmethane spiro-phosphate: tetramethylolmethane in molar ratio: phosphorus oxychloride=1:2-10 adds in the reactor, while stirring heating, and reaction is 2-12 hour under 60-140 ℃ of condition; Reaction mixture is cooled to room temperature, filters reaction mixture, use the washed with dichloromethane filter cake; Oven dry is 4-20 hour under 50-150 ℃ of condition, gets white powdery tetramethylolmethane spiro-phosphate;
B. the preparation of phosphonium flame retardant: tetramethylolmethane spiro-phosphate in molar ratio: bisphenol S=1:0.6-1.4 adds in the reactor, adds after the solvent acetonitrile, drips triethylamine; Warming while stirring was to boiling, isothermal reaction 2-14 hour; Reaction mixture is cooled to room temperature, filters reaction mixture, use the acetonitrile washing leaching cake; Oven dry is 4-20 hour under 50-200 ℃ of condition, gets phosphonium flame retardant.
2. described phosphoric epoxy resin flame retardant and preparation method thereof according to claim 1, it is characterized in that: tetramethylolmethane described in the steps A: the mol ratio of phosphorus oxychloride is preferably 1:3-9, and optimum mole ratio is 1:4-8; Described temperature of reaction is preferably 80-120 ℃, and optimal reaction temperature is 90-110 ℃; The described reaction times is preferably 4-10 hour, and optimum reacting time is 6-8 hour.
3. described phosphoric epoxy resin flame retardant and preparation method thereof according to claim 1, it is characterized in that: bake out temperature described in the steps A is preferably 60-130 ℃, and best bake out temperature is 80-110 ℃; Described drying time is preferably 6-18 hour, and best drying time is 8-15 hour.
4. described phosphoric epoxy resin flame retardant and preparation method thereof according to claim 1, it is characterized in that: the spiro-phosphate of tetramethylolmethane described in the step B: the mol ratio of bisphenol S is preferably 1:0.8-1.2, and optimum mole ratio is 1:0.9-1.1; The described reaction times is preferably 4-12 hour, and optimum reacting time is 6-10 hour.
5. described phosphoric epoxy resin flame retardant and preparation method thereof according to claim 1, it is characterized in that: bake out temperature described in the step B is preferably 70-160 ℃, and best bake out temperature is 80-140 ℃; Described drying time is preferably 8-15 hour, and best drying time is 10-13 hour.
6. described phosphoric epoxy resin flame retardant and preparation method thereof according to claim 1, it is characterized in that: the bisphenol S described in the step B can replace with other phenolic compounds, and phenolic compound is p-methyl phenol, phenol, or Resorcinol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111687A (en) * | 2015-09-01 | 2015-12-02 | 沈阳化工大学 | Halogen-free epoxy resin flame retardant and preparation method thereof |
| CN107674408A (en) * | 2017-11-08 | 2018-02-09 | 安徽省瑞发复合材料制造有限公司 | A kind of high tenacity high flame-retardant polyurethane circuit board material |
| CN107778836A (en) * | 2017-11-08 | 2018-03-09 | 安徽省瑞发复合材料制造有限公司 | A kind of special compound polyurethane material of circuit board |
| CN112210273A (en) * | 2020-10-29 | 2021-01-12 | 浩力森化学科技（江苏）有限公司 | Halogen-free flame-retardant cationic electrodeposition coating |
| CN112321800A (en) * | 2020-06-16 | 2021-02-05 | 台州耘智科技有限公司 | Preparation method of flame-retardant epoxy resin |
| CN113773347A (en) * | 2021-10-25 | 2021-12-10 | 安徽大学 | Preparation method of spiro phosphate flame retardant for spandex fiber and flame-retardant spandex fiber based on spiro phosphate flame retardant |
| CN116120562A (en) * | 2022-12-09 | 2023-05-16 | 江苏宝源高新电工有限公司 | Halogen-free flame retardant, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414000A (en) * | 2002-09-26 | 2003-04-30 | 东北林业大学 | Sythetic method of pentaerythrite diphosphate ester diacid chlorine |
| CN102731790A (en) * | 2012-07-10 | 2012-10-17 | 合肥工业大学 | Phosphorus-nitrogen-carbon intumescent flame retardant and preparation method thereof |
| CN102964630A (en) * | 2012-11-23 | 2013-03-13 | 张家港顺昌化工有限公司 | Preparation method of fire retardant containing phosphorus |
-
2013
- 2013-06-25 CN CN2013102550016A patent/CN103304819A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414000A (en) * | 2002-09-26 | 2003-04-30 | 东北林业大学 | Sythetic method of pentaerythrite diphosphate ester diacid chlorine |
| CN102731790A (en) * | 2012-07-10 | 2012-10-17 | 合肥工业大学 | Phosphorus-nitrogen-carbon intumescent flame retardant and preparation method thereof |
| CN102964630A (en) * | 2012-11-23 | 2013-03-13 | 张家港顺昌化工有限公司 | Preparation method of fire retardant containing phosphorus |
Non-Patent Citations (2)
| Title |
|---|
| 侯旭锋: "耐热高磷含量磷酸酯阻燃剂的合成与应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 05, 15 May 2007 (2007-05-15) * |
| 王洋: "有机磷系阻燃剂的合成与应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 03, 15 March 2008 (2008-03-15) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111687A (en) * | 2015-09-01 | 2015-12-02 | 沈阳化工大学 | Halogen-free epoxy resin flame retardant and preparation method thereof |
| CN105111687B (en) * | 2015-09-01 | 2017-07-18 | 沈阳化工大学 | A kind of halogen-free ethoxyline resin antiflaming agent and preparation method thereof |
| CN107674408A (en) * | 2017-11-08 | 2018-02-09 | 安徽省瑞发复合材料制造有限公司 | A kind of high tenacity high flame-retardant polyurethane circuit board material |
| CN107778836A (en) * | 2017-11-08 | 2018-03-09 | 安徽省瑞发复合材料制造有限公司 | A kind of special compound polyurethane material of circuit board |
| CN112321800A (en) * | 2020-06-16 | 2021-02-05 | 台州耘智科技有限公司 | Preparation method of flame-retardant epoxy resin |
| CN112210273A (en) * | 2020-10-29 | 2021-01-12 | 浩力森化学科技（江苏）有限公司 | Halogen-free flame-retardant cationic electrodeposition coating |
| CN113773347A (en) * | 2021-10-25 | 2021-12-10 | 安徽大学 | Preparation method of spiro phosphate flame retardant for spandex fiber and flame-retardant spandex fiber based on spiro phosphate flame retardant |
| CN116120562A (en) * | 2022-12-09 | 2023-05-16 | 江苏宝源高新电工有限公司 | Halogen-free flame retardant, and preparation method and application thereof |
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Application publication date: 20130918 |