CN101935399B - Method for preparing phosphorus-containing organosilicon flame retardant - Google Patents
Method for preparing phosphorus-containing organosilicon flame retardant Download PDFInfo
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Abstract
The invention relates to a method for preparing a phosphorus-containing organosilicon flame retardant, and provides a method for preparing a phosphorus-containing flame retardant, which has the advantages of rich raw materials, low cost, simple production technology, no HCl generated in a reaction, and recyclable by-products of the reaction to solve the technical problems. The preparation process comprises the following steps of: reacting an active phosphorus compound with a hydroxyl-containing polysiloxane in the presence of a catalyst, wherein the molar ratio of the active phosphorus compound to the hydroxyl-containing polysiloxane is 1:1-20; and after the reaction, filtering, and steaming to remove low-boiling-point substances to obtain the product of the phosphorus-containing organosilicon flame retardant.
Description
Technical field
The present invention relates to the fire retardant synthesis technical field, specifically be meant a kind of preparation method of phosphoric organic silicon fire retardant.This phosphoric organic silicon fire retardant can be applied to be used as fire retardant among polyolefine, polycarbonate, ABS, nylon, the PC/ABS, compares with traditional fire retardant, and high-efficiency low-toxicity is a kind of environment friendly flame retardant.
Background technology
Along with the development of China's synthetic material industry and the continuous expansion of Application Areas, fire retardant has vast market prospect in every field such as chemical building material, electronic apparatus, communications and transportation, space flight and aviation, household furniture, upholstery, clothing, food, lodging and transportion--basic necessities of life.
Organic phosphorus flame retardant is a kind of flame retardant properties fire retardant preferably, has fire-retardant plasticising dual-use function, can replace the halogenation flame retardant, is a kind of environment amenable fire retardant.Wherein, the SULPHOSUCCINIC ACID ESTER aboundresources, low price is used very extensively.But most of phosphate flame retardants are liquid, poor heat resistance, and volatility is big, and is not ideal with the consistency of polymkeric substance.Organic silicon fibre retardant is a kind of new and effective, low toxicity, anti-molten drop, eco-friendly halogen-free flame retardants, also is that a kind of charcoal becoming presses down fumicants.Organic silicon fibre retardant is being given outside the base material excellent flame-retardant, can also improve processing characteristics, resistance toheat of base material etc.Therefore, as the up-and-coming youngster of fire retardant, developed rapidly since the eighties in 20th century.
Adopt the phosphoric organic silicon fire retardant not only can reduce the toxicity of phosphorus fire retardant, have good cooperative flame retardant effect simultaneously.When the phosphoric organic silicon fire retardant used, at high temperature, the formation of charcoal was facilitated in phosphorus meeting catalysis, and silicon then increases the thermostability of these charcoal layers, thus performance phosphorus/silicon cooperative flame retardant effect.And when replacing silane with siloxanes, the fire-retardant synergy of phosphorus/silicon is further strengthened, because the stratiform silicon-dioxide that the siloxanes degraded forms has stoped the oxidation of charcoal layer, thereby has improved the stability of charcoal layer.
In technology in the past, mainly adopting POCl3 is raw material, through the amino reaction of phosphorus-chlorine key and silicoorganic compound, and preparation phosphorated organic silicon fibre retardant.But because phosphorus oxychloride reaction is active strong, hydrolysis easily, poor stability, and also when react with amino, generation HCl by product exerts an influence to environment easily.
Summary of the invention
The technical issues that need to address of the present invention are, the phosphonium flame retardant preparation method who provide that a kind of abundant raw material is inexpensive, production technique simple, no HCl generates in the reaction, and the recyclable utilization again of byproduct of reaction.
Phosphoric organic silicon fire retardant preparation method of the present invention; It is characterized in that: in the presence of catalyzer; Active phosphorus compound and hydroxyl ZGK 5 are reacted (be preferably 80～150 ℃ of reactions 4～20h) down; Wherein the ratio of the mole number of hydroxyl is 1: 1～20 (be preferably 1: 3～12, more excellent is 1: 5～8) in the ZGK 5 of active phosphorus compound and hydroxyl; Reaction finishes, and filters, and steams and removes low-boiling-point substance, obtains the phosphoric organic silicon flame retardant products;
Described active phosphorus compound is SULPHOSUCCINIC ACID ESTER, phosphorous acid ester or its combination, specifically is selected from one or more mixtures in trimethyl phosphite 99, triethyl phosphate, triphenylphosphate, Trichloroethyl Phosphate, tributyl phosphate, methyl acid phosphate diethyl ester, trimethyl phosphite, triethyl-phosphite, triphenyl phosphite, phosphorous acid trichloro ethyl ester, the tributyl phosphate.
SULPHOSUCCINIC ACID ESTER in the active phosphorus compound and phosphorous acid ester are a kind of raw materials of important preparation phosphonium flame retardant.Its phosphine oxygen base key under catalyst action, can with hydroxy-containing compounds generation transesterification reaction, generate new P contained compound.Among the present invention, adopting SULPHOSUCCINIC ACID ESTER or phosphorous acid ester is raw material, under catalyst action, through with the silicoorganic compound generation transesterification reaction of hydroxyl, phosphorus atom is introduced in the silicoorganic compound, thereby is prepared the phosphorated organic silicon fibre retardant.
Said hydroxyl ZGK 5 has formula M
aM '
bD
cK
dD '
eP '
fT
gN
jT '
kQ
m, subscript a, b, c, d, e, f, g, j, k and m are 0 or positive integer (preferably being no more than 5000 positive integer) in the formula, and e and f sum be more than or equal to 1, wherein M has general formula R
1 3SiO
1/2,
M ' has general formula (X)
hR
2 3-hSiO
1/2,
D has general formula R
3R
4SiO
2/2,
K has general formula R
5R
6SiO
2/2,
D ' has general formula X R
7SiO
2/2,
P ' has general formula X R
8SiO
2/2,
T has general formula R
9SiO
3/2,
N has general formula R
10SiO
3/2,
T ' has general formula X SiO
3/2,
Q has general formula SiO
4/2,
Subscript h is 1 or 2 or 3 in the formula; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Be selected from C
1-30Alkyl, C
1-22Alkoxyl group, C
2-22Alkenyl, C
6-14Aryl, C
6-22The substituted aryl of alkyl, C
6-22Aralkyl or C
1-22Fluoroalkyl; X is a hydroxyl.
The hydroxyl ZGK 5 that above-mentioned hydroxyl ZGK 5 can be a kind of structure, or the arbitrary combination of multiple structural hydroxyl ZGK 5.For example, the hydroxyl ZGK 5 can be the hydroxyl methyl silicon resin, the methyl phenyl silicone resin of hydroxyl, the methyl vinyl silicone of hydroxyl, or their arbitrary combination.
Alkyl includes but not limited to methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, neo-pentyl, base, dodecyl, hexadecyl, octadecyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl and suberyl among the present invention.Aralkyl includes but not limited to phenmethyl, benzene butyl, hydrocinnamyl and styroyl.Aryl includes but not limited to phenyl, xenyl and naphthyl.Fluoroalkyl includes but not limited to trifluoro propyl.Aryloxy includes but not limited to phenoxy.Alkoxyl group includes but not limited to methoxyl group and oxyethyl group.Alkenyl includes but not limited to vinyl, allyl group.
Use catalyzer can effectively promote the transesterification reaction of phosphorus alkoxyl group and organic hydroxy silicate compound, catalyzer is selected from Pottasium Hydroxide, sodium hydroxide, Anhydrous potassium carbonate, soda ash light, sodium methylate, triethylamine, dibutyl tin dilaurate, dibutyltin diacetate or stannous octoate.
In the present invention, the applicant adopts SULPHOSUCCINIC ACID ESTER or phosphorous acid ester and hydroxyl silicoorganic compound under catalyst action, to react, and a step has prepared the phosphoric organic silicon fire retardant.Compared with prior art, the present invention adopts the phosphorus compound good stability, and said technological line is more easy, and no HCl generates in the reaction, can not impact environment, and the pure recyclable of generation utilizes again.
Embodiment
The present invention will be elaborated to technical scheme of the present invention through following specific embodiment, but the present invention is not limited to the embodiment of following proposition.
Embodiment 1
The 250ml there-necked flask is loaded onto whisking appliance, TM and water distilling apparatus, adds the 2.5g triethylamine, (structural formula is Me to 79.9g (0.01 mol) hydroxyl methyl silicon resin
3SiO (Me
2SiO)
40(MeHOSiO)
20(MeSiO
3/2)
50SiMe
3, the hydroxyl mole number is 0.2) and 36.4g (0.2mol) triethyl phosphate, stirring and evenly mixing reacts 20h down at 80 ℃.Filter, steam and remove low-boiling-point substance, obtain 101.7g phosphoric organic silicon fire retardant, yield is 95%.
Fire-retardant application performance: with the phosphoric organic silicon fire retardant of ABS and preparation by weight for 85:15 puts into high-speed mixer, mixed at high speed 3 min, discharging is subsequent use.Raw material through mediating is at a high speed extruded on twin screw extruder, with melt extrusion at 100 ℃ of following vacuum-drying 6 h, compression moulding on press mold machine automatically then, the demoulding makes sample.Adopt the oxygen index of oxygen index instrument test sample to reach 29. 80%, the oxygen index that does not add the ABS of fire retardant is 21.5%.Adopt horizontal vertical burning determinator to carry out the testing vertical flammability of sample, the result shows can reach the UL94V-0 level, and the combustion test result who does not add fire retardant ABS is burning, explains that the ABS that adds the phosphoric organic silicon fire retardant has excellent flame-retardant performance.
Embodiment 2
The 1000ml there-necked flask is loaded onto whisking appliance, TM and water distilling apparatus, adds 15g sodium hydroxide, (structural formula is Me to 700g (0.1mol) hydroxyl methyl phenyl silicone resin
3SiO (Me
2SiO)
20(MeHOSiO)
10(PhHOSiO)
10(MeSiO
3/2)
48SiMe
3, the hydroxyl mole number is 2.0) and 12.4g (0.1mol) trimethyl phosphite, stirring and evenly mixing reacts 4h down at 130 ℃, filters, and steams and removes low-boiling-point substance, obtains 674.7g phosphoric organic silicon fire retardant.Yield is 96%.
Fire-retardant application performance:, in single screw extrusion machine, extrude sample with the mixed that the phosphoric organic silicon fire retardant and the Vestolen PP 7052 of preparation are pressed 30:70.Adopt oxygen index instrument test sample oxygen index to reach 29. 20%, the polyacrylic oxygen index that does not add fire retardant is 18.5%.Adopt horizontal vertical burning determinator to carry out the sample testing vertical flammability, the result shows can reach the UL94V-0 level, does not add the polyacrylic combustion test result of fire retardant and is burning, explains that the Vestolen PP 7052 that adds the phosphoric organic silicon fire retardant has excellent flame-retardant performance.
Embodiment 3
The 1000ml there-necked flask is loaded onto whisking appliance, TM and water distilling apparatus, adds the 20g dibutyl tin dilaurate, (structural formula is HOMe to 340g (0.01mol) hydroxyl methyl silicon resin
2SiO (MeHOSiO)
40(MeSiO
3/2)
440(HOSiO
3/2)
10SiMe
3, the hydroxyl mole number is 0.5), (structural formula is Me to 240g (0.01mol) hydroxyl methyl phenyl silicone resin
3SiO (Me
2SiO)
20(MeHOSiO)
70(PhSiO
3/2)
100(SiO
2)
70SiMe
3The hydroxyl mole number is 0.7), 26.6g (0.1mol) tributyl phosphate and 16.6g (0.1mol) triethyl-phosphite, stirring and evenly mixing at 150 ℃ of reaction 15h down, filters, and steams and removes low-boiling-point substance, obtains 552.2g phosphoric organic silicon fire retardant.Yield is 94%.
Fire-retardant application performance: after 75:25 mixes in proportion with the phosphoric organic silicon fire retardant of PC and preparation, in twin screw extruder, extrude, pelletizing, make standard test specimen through injection moulding machine.Adopt oxygen index instrument test sample oxygen index to reach 30.2%, the oxygen index that does not add the PC of fire retardant is 25.6%.Adopt horizontal vertical burning determinator to carry out the sample testing vertical flammability, the result shows can reach the UL94V-0 level, and the combustion test result who does not add fire retardant PC is the UL94V-2 level, explains that the PC that adds the phosphoric organic silicon fire retardant has excellent flame-retardant performance.
Embodiment 4
The 500ml there-necked flask is loaded onto whisking appliance, TM and water distilling apparatus, adds the 5.0g sodium methylate, (structural formula is Me to 231.6g (0.00062mol) hydroxyl methyl vinyl silicone
3SiO (Me
2SiO)
30(MeHOSiO)
4800(ViHOSiO)
5(MeSiO
3/2)
50SiMe
3, the hydroxyl mole number is 3) and 66.8g (0.2mol) triphenylphosphate, stirring and evenly mixing reacts 16h down at 120 ℃.Filter, steam and remove low-boiling-point substance, obtain 217.8g phosphoric organic silicon fire retardant, yield is 90%.
Fire-retardant application performance:, in single screw extrusion machine, extrude sample with the mixed that the phosphoric organic silicon fire retardant and the nylon of preparation are pressed 10:90.Adopt oxygen index instrument test sample oxygen index to reach 32. 50%, the oxygen index that does not add the nylon of fire retardant is 26.5%.Adopt horizontal vertical burning determinator to carry out the sample testing vertical flammability, the result shows can reach the UL94V-0 level, and the combustion test result who does not add fire retardant nylon is the UL94V-2 level, explains that the nylon that adds the phosphoric organic silicon fire retardant has excellent flame-retardant performance.
Embodiment 5
The 1000ml there-necked flask is loaded onto whisking appliance, TM and water distilling apparatus, adds the 18g stannous octoate, (structural formula is HOMe to 340g (0.01mol) hydroxyl methyl silicon resin
2SiO (MeHOSiO)
40(MeSiO
3/2)
440(HOSiO
3/2)
10SiMe
3, the hydroxyl mole number is 0.5), (structural formula is Me to 240g (0.01mol) hydroxyl methyl phenyl silicone resin
3SiO (Me
2SiO)
20(MeHOSiO)
70(PhSiO
3/2)
100(SiO
2)
70SiMe
3The hydroxyl mole number is 0.7), 26.6g (0.1mol) tributyl phosphate, 9.1g (0.05mol) triethyl phosphate and 8.3g (0.05mol) triethyl-phosphite; Stirring and evenly mixing reacts 12h down at 140 ℃, filters; Steam and remove low-boiling-point substance, obtain 552.2g phosphoric organic silicon fire retardant.Yield is 94%.
Fire-retardant application performance: after 80:20 mixes in proportion with the phosphoric organic silicon fire retardant of PC and preparation, in twin screw extruder, extrude, pelletizing, make standard test specimen through injection moulding machine.Adopt oxygen index instrument test sample oxygen index to reach 31.5%, the oxygen index that does not add the PC of fire retardant is 25.6%.Adopt horizontal vertical burning determinator to carry out the sample testing vertical flammability, the result shows can reach the UL94V-0 level, and the combustion test result who does not add fire retardant PC is the UL94V-2 level, explains that the PC that adds the phosphoric organic silicon fire retardant has excellent flame-retardant performance.
Claims (3)
1. phosphoric organic silicon fire retardant preparation method is characterized in that: in the presence of catalyzer, active phosphorus compound and hydroxyl ZGK 5 are reacted, wherein the ratio of the mole number of hydroxyl is 1: 1～20 in active phosphorus compound and the hydroxyl ZGK 5; Reaction finishes, and filters, and steams and removes low-boiling-point substance, obtains the phosphoric organic silicon flame retardant products;
Described active phosphorus compound is selected from one or more mixture of trimethyl phosphite 99, triethyl phosphate, triphenylphosphate, Trichloroethyl Phosphate, tributyl phosphate, methyl acid phosphate diethyl ester, trimethyl phosphite, triethyl-phosphite, triphenyl phosphite, phosphorous acid trichloro ethyl ester, tributyl phosphate;
Said hydroxyl ZGK 5 has formula M
aM '
bD
cK
dD '
eP '
fT
gN
jT '
kQ
m, subscript a, b, c, d, e, f, g, j, k and m are 0 or positive integer in the formula, and e and f sum be more than or equal to 1, wherein M has general formula R
1 3SiO
1/2,
M ' has general formula (X)
hR
2 3-hSiO
1/2,
D has general formula R
3R
4SiO
2/2,
K has general formula R
5R
6SiO
2/2,
D ' has general formula X R
7SiO
2/2,
P ' has general formula X R
8SiO
2/2,
T has general formula R
9SiO
3/2,
N has general formula R
10SiO
3/2,
T ' has general formula X SiO
3/2,
Q has general formula SiO
4/2,
Subscript h is 1 or 2 or 3 in the formula; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10Be selected from C
1-30Alkyl, C
1-22Alkoxyl group, C
6-14Aryl, C
6-22The substituted aryl of alkyl, C
6-22Aralkyl or C
1-22Fluoroalkyl; X is a hydroxyl.
2. phosphoric organic silicon fire retardant preparation method according to claim 1 is characterized in that described reaction conditions is, reacts 4～20h down at 80～150 ℃.
3. phosphoric organic silicon fire retardant preparation method according to claim 1 and 2 is characterized in that described catalyzer is selected from Pottasium Hydroxide, sodium hydroxide, Anhydrous potassium carbonate, soda ash light, sodium methylate, triethylamine, dibutyl tin dilaurate, dibutyltin diacetate or stannous octoate.
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| CN102504336B (en) * | 2011-11-03 | 2013-07-17 | 上海交通大学 | Flame retardant containing phosphorus and silicon and preparation method and application thereof |
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| CN110128836B (en) * | 2019-05-28 | 2021-06-22 | 常州大学 | Phosphorus-silicon-containing flame retardant and preparation method thereof |
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| CN112961363A (en) * | 2020-10-29 | 2021-06-15 | 广东广山新材料股份有限公司 | Polymeric phosphorus-silicon synergistic flame retardant and preparation method and application thereof |
| CN112480412A (en) * | 2020-10-31 | 2021-03-12 | 山东天一化学股份有限公司 | Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof |
| CN112409599B (en) * | 2020-10-31 | 2023-01-24 | 山东天一化学股份有限公司 | Hyperbranched silicon-based resin flame retardant containing phosphorus-oxygen functionalized and preparation method thereof |
| CN112625244B (en) * | 2020-12-30 | 2023-02-28 | 山东天一化学股份有限公司 | Hyperbranched phosphorus-containing organic silicon intumescent flame retardant, preparation method and flame-retardant polymer coating composition |
| CN112831052B (en) * | 2021-01-15 | 2022-08-05 | 万华化学集团股份有限公司 | Organosilicon flame retardant, preparation method thereof, epoxy resin composition prepared from organosilicon flame retardant and application of epoxy resin composition |
| CN113214316B (en) * | 2021-05-18 | 2023-04-18 | 杭州师范大学 | Phosphorous acid tri (tri-substituted siloxymethyl phenyl) ester, preparation method and application thereof |
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Effective date of registration: 20201130 Address after: Room 1302, No. 373, Century Avenue, Nantong, Jiangsu Province, 226000 Patentee after: Jiangsu Jinshi Electric Power Design Co.,Ltd. Address before: 226300 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee before: NANTONG WOTE OPTOELECTRONICS TECHNOLOGY Co.,Ltd. Effective date of registration: 20201130 Address after: 226300 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee after: NANTONG WOTE OPTOELECTRONICS TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310036 Xihu District Wenyi Road No. 222 Hangzhou Normal University Laboratory silicone Patentee before: Hangzhou Normal University |
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