CN101117405A - Method for preparing non-toxicity organophosphorus ester flame-proof plasticizing agent - Google Patents
Method for preparing non-toxicity organophosphorus ester flame-proof plasticizing agent Download PDFInfo
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- CN101117405A CN101117405A CNA2007100595553A CN200710059555A CN101117405A CN 101117405 A CN101117405 A CN 101117405A CN A2007100595553 A CNA2007100595553 A CN A2007100595553A CN 200710059555 A CN200710059555 A CN 200710059555A CN 101117405 A CN101117405 A CN 101117405A
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- cresols
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- plasticizing agent
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 231100000956 nontoxicity Toxicity 0.000 title claims description 13
- 150000002148 esters Chemical class 0.000 title claims description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 13
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 11
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000001896 cresols Chemical class 0.000 claims description 20
- 231100000419 toxicity Toxicity 0.000 claims description 11
- 230000001988 toxicity Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229940100630 metacresol Drugs 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical group CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 231100000460 acute oral toxicity Toxicity 0.000 claims description 2
- 231100000403 acute toxicity Toxicity 0.000 claims description 2
- 230000007059 acute toxicity Effects 0.000 claims description 2
- 239000003905 agrochemical Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract description 2
- 229930003836 cresol Natural products 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000011968 lewis acid catalyst Substances 0.000 abstract 1
- 239000004597 plastic additive Substances 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 10
- -1 dichloride phosphoric acid trimethylbenzene ester Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 102000021944 Butyrylcholinesterase Human genes 0.000 description 1
- 108010053652 Butyrylcholinesterase Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- NJFLMBDOPGVWLJ-UHFFFAOYSA-N phosphoric acid dihydrochloride Chemical compound Cl.Cl.OP(O)(O)=O NJFLMBDOPGVWLJ-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a method of producing an innocuous organophosphate flame retardant plasticizer. The producing method of the innocuous organophosphate flame retardant plasticizer (tricresyl phosphate) of the invention adopts phosphorus oxychloride and a mixture of m-cresol and p-cresol as material, reacting with the effect of the Lewis acid catalyst. The molar ratio of the phosphorus oxychloride to the cresol is better to be 1:30-1:5.0. The action material should be put in the reactor at one time, without impregnant, the action temperature should be 70-150 DEG C, in the vacuum of 30-720mmHg, getting the target production by distilling after the action. The technology of the invention is simple, without any impregnant in the action, environmentally-friendly, no discharging of waste water, waste gas and solid wastes. The technology is easy to be used in the production of industrialisation, and meet the trend of innocuity plastic additive and environment-protection completely.
Description
[technical field] the invention belongs to a kind of fire retardant, particularly a kind of preparation method who does not contain the Tritolyl Phosphate of ortho isomer.This phosphoric acid ester does not have or contains the volatile components to the HUMAN HEALTH disadvantageous effect of utmost point low levels, is a kind of resin flame-retardant additive of excellence, simultaneously with plasticity, but also can be used as synthetic fire prevention lubricating oil or lubrication oil antiwear agent.
[background technology] organophosphate is a kind of based flame retardant in the synthetic resins such as plastics, rubber, urethane that is widely used in.Synthetic resins mixes a certain amount of phosphate flame retardant in the course of processing, can effectively improve the required amount of oxygen (raising oxygen index) of synthetic resins burning and make it nonflammable.
Under present condition, the mankind improve day by day for environment and health demand, and pursuing asepsis environment-protecting and eco-friendly material has become a kind of common viewpoint.Because producing the toxicity of Dioxins and heavy metal based flame retardant, bromide burning back can cause certain problem.Phosphoric acid ester more becomes the focus of concern under these circumstances.
Put down in writing in the synthetic method of Tritolyl Phosphate such as the documents and materials, adopt the reaction of cresols and phosphorus trichloride, generate tricresyl phosphite.Tricresyl phosphite again with chlorine reaction, generate dichloride phosphoric acid trimethylbenzene ester, hydrolysis obtains Tritolyl Phosphate then.
CH
3C
6H
4OH+PCl
3→(CH
3C
6H
4O)
3P+3HCl?↑
(CH
3C
6H
4O)
3P+Cl
2→(CH
3C
6H
4O)
3PCl
2
(CH
3C
6H
4O)
3PCl
2+H
2O→(CH
3C
6H
4O)
3PO+2HCl?↑
Pilot process product dichloride phosphoric acid front three phenolic ester is a highly toxic substance, and all hydrolysis in next procedure can be present in the end article, cause this material classified in toxic chemicals.Its toxicity detects per os toxicity LD
50＜500mg/Kg.
Adopt this method to produce Tritolyl Phosphate, it is relatively poor that operational path complexity, complex steps and production process produce a large amount of high concentrated organic wastewaters, raw material consumption height, product quality indicator, can't satisfy the green clean production mechanism that current social is advocated.
In addition, the mould processing of plastics and goods thereof is carried out under higher temperatures.In the mould processing process, can cause some micromolecular phosphoric acid ester thermolysiss, volatilize or ooze out, make that the concentration of this material raises in the operating environment air.According to the literature, personnel once occur and contacted the incident of poisoning in the back.
And containing " phosphorous acid ortho-cresol ester " in the existing product tritolyl phosphate, its toxicity is more obvious, contacts this product and can make the people cause that central nervous system is speeded slow or pseudocholinesterase is paralysed, suppressed to spasm type.
Because the synthetic method difference of such compound under the historical conditions causes the difference on its physical properties and the chemical structure that the habitual understanding of people is misunderstood.
[summary of the invention] the objective of the invention is to solve the phosphate flame retardant toxicity problem of higher that original method is produced.Provide a kind of technological process simple, the preparation method of non-toxicity organophosphorus ester flame-proof plasticizing agent, by to the control of using raw material and production process to obtain avirulent Tritolyl Phosphate.
It is raw material that the preparation technology of non-toxicity organophosphorus ester flame-proof plasticizing agent provided by the invention (Tritolyl Phosphate) adopts the mixture of meta-cresol and p-cresol and phosphorus oxychloride, the Louis acid catalyst as: react under the effects such as aluminum chloride, magnesium chloride, titanium tetrachloride.The mol ratio of phosphorus oxychloride and cresols was advisable with 1: 3.0～1: 5.0.Mol ratio is less than under 1: 3.0 the condition, and reaction can not be carried out fully, and half ester content too much influences the stability to hydrolysis of the finished product; If mol ratio, reduces the operation efficiency of reactor greatly greater than 1: 5.0 then unreasonable economically, preferred 1: 3.0～1: 3.5 is good.The amount of catalyzer is advisable with 5 ‰ add-ons of phenolic compound.
Concrete as follows through step:
The first, adopting cresols and phosphorus oxychloride is starting raw material, wherein, cresols is the mixture of meta-cresol and p-cresol, and the quality percentage composition of meta-cresol is not less than 50% of cresols at least, and wherein the quality percentage composition of ortho-cresol is lower than 0.1% of cresols; The mol ratio of phosphorus oxychloride and cresols is 1: 3-1: 5;
The second, in the disposable adding reactor of above-mentioned reaction raw materials, do not use solvent, temperature of reaction is 70-150 ℃, and the Louis acid as catalyst under the vacuum condition of 30-720mmHg, after reaction finishes, obtains target product through distillation.
The inventive method is not used any solvent in reaction process.
The percentage composition of meta-cresol is preferably greater than 60% of cresols in the inventive method.
Preferred 1: 3.0～1: 3.5 of the mol ratio of phosphorus oxychloride and cresols.
The Louis acid catalyst is: aluminum chloride, magnesium chloride or titanium tetrachloride.
The consumption of Louis acid catalyst is 5 ‰ of a cresols quality.
Handle without washing after reaction is finished, carry out underpressure distillation subsequently, collect 265 ℃ of-285 ℃ of fractions, vacuum tightness 20mmHg obtains target product; The per os toxicity LD of this phosphoric acid ester
50＞10000mg/kg, according to the agricultural chemicals acute toxicity grading criteria, this true border of phosphoric acid ester acute oral toxicity nontoxicity.
Feed stock conversion can reach 70-80% under catalyst action.
Product of the present invention is a colourless transparent oil liquid, and odorless, stable, non-volatile has flame retardant resistance, water insoluble, be dissolved in benzene, ethers, alcohols, vegetables oil, mineral wet goods organic solvent, can with polyvinyl chloride, polystyrene, vinyl chloride copolymer, synthetic rubber and many cellulose families mix.
Advantage of the present invention and beneficial effect:
Operational path of the present invention is simple, does not use any solvent in reaction process, and is environmentally friendly, do not have three waste discharge in the production process substantially.Technology is easy to suitability for industrialized production.Fully satisfy current additives for plastics do not have poison, the trend trend of environmental protectionization.
The selection of raw material of the present invention is a key of producing the low toxicity phosphoric acid trimethylbenzene phenolic ester.
Because of 3 mixed cresol has deleterious reason, be to contain a large amount of ortho-cresols.Detect through repetition test, we find to adopt M-and P-cresols is that the TCP toxicity that starting material (o-cresol content≤1%) production obtains obviously reduces, reach the low toxicity standard, so we may safely draw the conclusion: just become the major cause that the TCP that causes personated old man's production art to obtain has overt toxicity just because of containing about ortho-cresol of about 13%～25% in the cresols.
Because hot method production technique of the present invention has adopted new raw material and has added catalyzer and improve temperature of reaction, not only having shortened the production cycle greatly enhances productivity, the more important thing is and can not produce or seldom produce the intermediate product tricresyl phosphite in the production process, just can not produce toxic substance phosphorous acid ortho-cresol ester yet, realized that the low of TCP poison, enlarged the Application Areas of TCP.
[embodiment]
In the disposable at normal temperatures adding reactor of a certain amount of cresols, phosphorus oxychloride and catalyzer, apply heat by the outside it is reacted, temperature is brought up to 150 ℃ of afterreactions and is finished.Carry out towards target direction for the reaction that makes that reduces side reaction, need constantly will react the HCl that produces and remove.Preferred reaction is carried out under reduced pressure.The HCl that reaction generates absorbs through water and obtains hydrochloric acid.Reaction does not need any processing after finishing, and directly carries out underpressure distillation, collects the fraction of differing temps, obtains target product.
CH
3C
6H
4OH+POCl
3→(CH
3C
6H
4O)
3PO+3HCl?↑
The product that this technological process synthesizes detects through authoritative department toxicity, per os toxicity LD
50＞10000mg/Kg.True border nontoxicity.
Embodiment 1
In the 1000ml four-hole boiling flask that agitator, thermometer, condensing reflux pipe, hydrogen chloride absorption device are housed, add 230g (1.5mol) phosphorus oxychloride, 570g (5.25mol) M-and P-cresols (wherein meta-cresol quality percentage composition is greater than 50%), 2.5g AlCl
3Catalyzer fully stirs slow heat temperature raising down.Producing hydrogen chloride gas in the reaction process absorbs by the hydrogen chloride absorption device.Reach 150 ℃ through temperature after 3.5 hours, do not have HCl with the PH detection paper and emit, 265-285 ℃ fraction is collected in underpressure distillation (10mmHg).Obtain the 485g product, yield 87% (in phosphorus oxychloride), colourless transparent liquid.Acid number 0.05mgKOH/g, weight loss on heating 0.06,242 ℃ of flash-points (open cup), refractive index 1.556.
Embodiment 2
In being housed, agitator, thermometer, condensing reflux pipe, hydrogen chloride absorption device 1000ml four-hole boiling flask add 230g (1.5mol) phosphorus oxychloride, 570g (5.25mol) M-and P-cresols (wherein meta-cresol quality percentage composition is greater than 50%), 2.8g MgCl
2Catalyzer fully stirs down slow heat temperature raising.Producing hydrogen chloride gas in the reaction process absorbs by the hydrogen chloride absorption device.Reach 150 ℃ through temperature after 4 hours, do not have HCl with the PH detection paper and emit, 265-285 ℃ fraction is collected in underpressure distillation (10mmHg).Obtain the 505g product, yield 91% (in phosphorus oxychloride), colourless transparent liquid.Acid number 0.03mgKOH/g, weight loss on heating 0.02,245 ℃ of flash-points (open cup), refractive index 1.556.
Claims (6)
1. the preparation method of a non-toxicity organophosphorus ester flame-proof plasticizing agent is characterized in that this method is through following steps:
The first, adopting cresols and phosphorus oxychloride is starting raw material, wherein, cresols is the mixture of meta-cresol and p-cresol, and the quality percentage composition of meta-cresol is not less than 50% of cresols at least, and wherein the quality percentage composition of ortho-cresol is lower than 0.1% of cresols; The mol ratio of phosphorus oxychloride and cresols is 1: 3-1: 5;
The second, in the disposable adding reactor of above-mentioned reaction raw materials, do not use solvent, temperature of reaction is 70-150 ℃, and the Louis acid as catalyst under the vacuum condition of 30-720mmHg, after reaction finishes, obtains target product through distillation.
2. the preparation method of non-toxicity organophosphorus ester flame-proof plasticizing agent according to claim 1 is characterized in that reacting finishing afterwards and handles without washing, carries out underpressure distillation subsequently, collects 265 ℃ of-285 ℃ of fractions, and vacuum tightness 20mmHg obtains target product; The per os toxicity LD of this phosphoric acid ester
50＞10000mg/kg, according to the agricultural chemicals acute toxicity grading criteria, this true border of phosphoric acid ester acute oral toxicity nontoxicity.
3. the preparation method of non-toxicity organophosphorus ester flame-proof plasticizing agent according to claim 1 and 2 is characterized in that the percentage composition of meta-cresol is preferably greater than 60% of cresols.
4. the preparation method of non-toxicity organophosphorus ester flame-proof plasticizing agent according to claim 1 and 2 is characterized in that preferred 1: 3.0～1: 3.5 of the mol ratio of phosphorus oxychloride and cresols.
5. the preparation method of non-toxicity organophosphorus ester flame-proof plasticizing agent according to claim 1 and 2 is characterized in that the Louis acid catalyst is: aluminum chloride, magnesium chloride or titanium tetrachloride.
6. the preparation method of non-toxicity organophosphorus ester flame-proof plasticizing agent according to claim 4, the consumption that it is characterized in that the Louis acid catalyst is 5 ‰ of a cresols quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100595553A CN101117405A (en) | 2007-09-11 | 2007-09-11 | Method for preparing non-toxicity organophosphorus ester flame-proof plasticizing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100595553A CN101117405A (en) | 2007-09-11 | 2007-09-11 | Method for preparing non-toxicity organophosphorus ester flame-proof plasticizing agent |
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|---|---|
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ID=39053678
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504751A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Flame-retardant polyurethane sealant and preparation method thereof |
| CN102558226A (en) * | 2011-12-15 | 2012-07-11 | 上海馨晟试化工科技有限公司 | Method for preparing aviation tricresyl phosphate additive |
| CN103223349A (en) * | 2013-04-09 | 2013-07-31 | 天津市联瑞阻燃材料有限公司 | Calcium-magnesium composite catalysts and preparation method thereof |
| CN105696100A (en) * | 2016-02-25 | 2016-06-22 | 东华大学 | Green carbon source copolymerized anti-flaming polylactic acid fiber and preparation method thereof |
| WO2018098829A1 (en) * | 2016-12-03 | 2018-06-07 | 苏州大学张家港工业技术研究院 | Biomass-based phosphate flame retardant and preparation method thereof |
| CN109593099A (en) * | 2017-09-30 | 2019-04-09 | 中国石油天然气股份有限公司 | A kind of preparation method of high-purity tricresyl phosphate |
| CN109868089A (en) * | 2019-01-28 | 2019-06-11 | 东莞市澳中电子材料有限公司 | A kind of PI film non-flammable adhesive tape |
-
2007
- 2007-09-11 CN CNA2007100595553A patent/CN101117405A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504751A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Flame-retardant polyurethane sealant and preparation method thereof |
| CN102504751B (en) * | 2011-11-22 | 2014-05-07 | 东莞市普赛达密封粘胶有限公司 | Flame-retardant polyurethane sealant and preparation method thereof |
| CN102558226A (en) * | 2011-12-15 | 2012-07-11 | 上海馨晟试化工科技有限公司 | Method for preparing aviation tricresyl phosphate additive |
| CN103223349A (en) * | 2013-04-09 | 2013-07-31 | 天津市联瑞阻燃材料有限公司 | Calcium-magnesium composite catalysts and preparation method thereof |
| CN105696100A (en) * | 2016-02-25 | 2016-06-22 | 东华大学 | Green carbon source copolymerized anti-flaming polylactic acid fiber and preparation method thereof |
| WO2018098829A1 (en) * | 2016-12-03 | 2018-06-07 | 苏州大学张家港工业技术研究院 | Biomass-based phosphate flame retardant and preparation method thereof |
| CN109593099A (en) * | 2017-09-30 | 2019-04-09 | 中国石油天然气股份有限公司 | A kind of preparation method of high-purity tricresyl phosphate |
| CN109593099B (en) * | 2017-09-30 | 2021-04-30 | 中国石油天然气股份有限公司 | Preparation method of high-purity tricresyl phosphate |
| CN109868089A (en) * | 2019-01-28 | 2019-06-11 | 东莞市澳中电子材料有限公司 | A kind of PI film non-flammable adhesive tape |
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