CN100427494C - Prepn of fire retardant resorcinol tetraphenyldiphosphate - Google Patents
Prepn of fire retardant resorcinol tetraphenyldiphosphate Download PDFInfo
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- CN100427494C CN100427494C CNB2006100852204A CN200610085220A CN100427494C CN 100427494 C CN100427494 C CN 100427494C CN B2006100852204 A CNB2006100852204 A CN B2006100852204A CN 200610085220 A CN200610085220 A CN 200610085220A CN 100427494 C CN100427494 C CN 100427494C
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- resorcinol
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- fire retardant
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003063 flame retardant Substances 0.000 title claims abstract description 12
- UQSHIDHNLKIYGN-UHFFFAOYSA-N diphenoxyphosphoryl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OP(=O)(OC=1C=CC=CC=1)OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 UQSHIDHNLKIYGN-UHFFFAOYSA-N 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 10
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 230000006837 decompression Effects 0.000 claims abstract description 3
- -1 triphenyl phosphate ester Chemical class 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 abstract 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- OBTARUYASFQRHM-UHFFFAOYSA-N benzene-1,3-diol;diphenoxyphosphoryl diphenyl phosphate Chemical compound OC1=CC=CC(O)=C1.C=1C=CC=CC=1OP(OP(=O)(OC=1C=CC=CC=1)OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 OBTARUYASFQRHM-UHFFFAOYSA-N 0.000 abstract 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
- 235000015320 potassium carbonate Nutrition 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 235000011118 potassium hydroxide Nutrition 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 1
- 229960001755 resorcinol Drugs 0.000 description 18
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation process of fire retardant resorcinol tetraphenyl diphosphate includes the first step of the reaction between phenol and phosphorus oxychloride in the presence of Lewis acid catalyst and under heating to produce triphenyl phosphate ester; and second step of ester interchange reaction between triphenyl phosphate ester and resorcinol in the conditions of catalysis, heating and decompression to obtain resorcinol tetraphenyl diphosphate. The reaction temperature is 80-260 deg.c; the catalyst for the first step is Lewis acid catalyst; and the catalyst for the second step is Lewis acid catalyst or alkali catalyst in the amount of 0.05-3 wt% of resorcinol. The acid catalyst is selected from MgCl2, ZnCl2, AlCl3 and TiCl4 and the alkali catalyst is selected from NaOH, KOH, Na2CO3, K2CO3 and sodium phenate. The present invention has the advantages of short reaction period, low power consumption, high product yield and less environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, be specifically related to a kind of preparation method of fire retardant resorcinol tetraphenyldiphosphate.
Background technology
Resorcinol tetraphenyldiphosphate is a kind of existing fire retardant.According to the present documents and materials of grasping, the synthetic method of reporting in the document mainly contains 3 kinds: 1. phosphorus oxychloride obtains Resorcinol tetrachloro biphosphonate with resorcin reaction, carries out end-blocking with phenol again, obtains target product; 2. after phosphorus oxychloride obtains diphenyl phosphoryl chloride with phenol reactant, get target product with resorcin reaction again; 3. replacing phenol with phenol sodium is raw material, promptly with sodium phenylate Resorcinol tetrachloro biphosphonate is carried out end capping and gets product.
Method one, at first, the first step is easy to generate polymer when preparing Resorcinol tetrachloro biphosphonate, and the by product HCl of generation is difficult to remove fully, and HCl is very big to the reaction influence of second step; The phenol of second step reaction is easy to and unreacted POCl
3Reaction generates triphenyl, makes that the purity of product is not enough, has influenced the performance of product.Secondly, the reaction times is long, energy consumption is high, and the first step is at 6～8h, 40 ℃～80 ℃ of temperature of reaction; Second step, 8～10h, about 140 ℃ of temperature of reaction.The 3rd, the thick product colour that obtains is darker, and viscosity is bigger, needs repeatedly washing decolouring, and is more serious to the damage ratio of environment.
The pure substance of method two, diphenyl phosphoryl chloride is difficult to synthetic, be easy to generate the mixture of a phenyl phosphoryl chloride, diphenyl phosphoryl chloride and triphenyl phosphide, then need mixture is carried out underpressure distillation as the needs diphenyl phosphoryl chloride, the productive rate of the product that obtains is not high.
Method three, this method are with respect to method one, and energy consumption reduces, but there is same problem in the first step reaction with the first step in the method one, and the preparation of sodium phenylate is relatively more difficult, and be oxidized because phenol is easy to.
Summary of the invention
In order to overcome the above-mentioned deficiency of prior synthesizing method, the present invention will provide a kind of new synthetic method, this method should be able to obtain the higher finished product of purity, reaction times short, energy consumption is lower; And can alleviate pollution to environment.
The scheme of finishing the foregoing invention task is, the preparation method of fire retardant resorcinol tetraphenyldiphosphate, and step is as follows:
(mol ratio is 3.00～3.05: 1) reaction generates triphenyl (TPP) for phenol and phosphorus oxychloride;
(mol ratio is 2.00～2.05: 1) carry out transesterification reaction under the condition of catalyzer, heating, decompression, obtain resorcinol tetraphenyldiphosphate for TPP and Resorcinol.
Reaction formula is as follows:
Method of the present invention is a raw material with phenol and phosphorus oxychloride, and keeping at a certain temperature under the effect of catalyzer, reaction generates TPP.And then add Resorcinol and react maintaining under certain temperature and the vacuum condition under the effect of catalyzer, crude product after filtration or washing remove impurity such as catalyzer, dehydration at last obtains product, the overall yield of products obtained therefrom is greater than 92%.
Adopt the inventive method, the temperature of reaction in two steps are generally 80～260 ℃ of scopes, and can obtain result preferably at 130～210 ℃.For the first step catalysts, can select Lewis an acidic catalyst such as MgCl
2, ZnCl
2, AlCl
3, TiCl
4Deng; The second step also available basic catalyst of the both available Lewis an acidic catalyst of catalysts such as NaOH, KOH, Na
2CO
3, K
2CO
3, sodium phenylate.It is good that the catalyst levels of two-step reaction all compares in 0.05%～3% scope, preferably between 0.1%～2%.Above-mentioned per-cent is to calculate according to the phenol of participating in reaction or the weight of Resorcinol.
The contrast experiment shows: the reaction of two steps only can realize " treating different things alike " with the Lewis an acidic catalyst, makes work simplification, and the time of reaction shortens, but the product acid number is higher, and color and luster is relatively poor.The Lewis an acidic catalyst is used in reaction as the first step, and basic catalyst is used in the reaction of second step instead, and the color and luster of product is better, and acid number is low, and viscosity is good, does not need other decolouring to handle.But processing step increases, and the time of reaction is longer.
What the present invention's second step reaction was adopted is reduced pressure, and vacuum tightness will have very big influence for the quality of reaction.The big more phenol that helps more of vacuum tightness is steamed from product, and the purity of product is just high more.General requirement vacuum tightness is under 10mmHg.
The present invention has overcome the deficiency of prior synthesizing method, and the reaction times is short, energy consumption is lower; The overall yield of products obtained therefrom is greater than 92%, and can alleviate the pollution to environment.
Embodiment
Embodiment 1. adds phenol 141.2g, catalyzer aluminum chloride 3.0g in the 250ml four neck flasks that reflux condensing tube (device for absorbing tail gas that connects suitable for reading), electric mixer and thermometer are housed.Open water of condensation, stir, be warming up to 50 ℃ and begin to drip POCl
376.65g, dripping off in 1～1.5 hour, temperature is raised to 80 ℃ gradually in the dropping process.Temperature is raised to 100 ℃ then, is incubated 1 hour, is raised to 140 ℃ of reactions 1 hour again, stops heating.
Add Resorcinol 27.5g, the stirring of heating, vacuum tightness is below 10mmHg, and 140～160 ℃ of reaction 60min collect phenol, and at 180～220 ℃ of about 90min of insulation, reaction finishes again.Stop heating, close vacuum pump when the liquid temperature drop is 120 ℃, while hot suction filtration.Thick product is yellow or brown transparent liquid, the by-product phenol recycling.Thick product is through alkali cleaning, washing and dry smart product 100.5g, the yield 70.1% of getting.
Embodiment 2. adds phenol 282.3g, catalyzer aluminum chloride 3.0g in the 500ml four neck flasks that reflux condensing tube (device for absorbing tail gas that connects suitable for reading), electric mixer and thermometer are housed.Open water of condensation, stir, be warming up to 50 ℃ and begin to drip POCl
3153.3g, dripping off in 1～1.5 hour, temperature is raised to 80 ℃ gradually in the dropping process. and temperature is raised to 100 ℃ then, is incubated 1 hour, is raised to 140 ℃ of reactions 1 hour again, stops heating.Unreacted phenol is removed in underpressure distillation, under 10mmHg vacuum tightness, collects 240～260 ℃ component, gets 293.0g, productive rate 90.0%.
Get TPP68.7g (0.21mol), Resorcinol 11.6g (0.105mol), join in the 150ml three-necked flask that magnetic stirring apparatus and thermometer are housed, the stirring of heating adds 0.3g K
2CO
3, below 10mmHg, 120～130 ℃ of reaction 30min collect phenol in vacuum tightness, and at 150～200 ℃ of about 40min of insulation, reaction finishes again.Stop heating, close vacuum pump when the liquid temperature drop is 120 ℃, suction filtration while hot, thick product is a light yellow transparent liquid, the by-product phenol recycling.Thick product is through alkali cleaning, washing and dry smart product 53.2g, the yield 88.0% of getting.
Embodiment 3. adds phenol 282.3g, catalyzer aluminum chloride 3.0g in the 500ml four neck flasks that reflux condensing tube (device for absorbing tail gas that connects suitable for reading), electric mixer and thermometer are housed.Open water of condensation, stir, be warming up to 50 ℃ and begin to drip POCl
3153.3g, dripping off in 1～1.5 hour, temperature is raised to 80 ℃ gradually in the dropping process. and temperature is raised to 100 ℃ then, is incubated 1 hour, is raised to 140 ℃ of reactions 1 hour again, stops heating.Unreacted phenol is removed in underpressure distillation, under 10mmHg vacuum tightness, collects 240～260 ℃ component, gets 293.0g, productive rate 90.0%.
Get TPP68.7g (0.21mol), Resorcinol 11.6g (0.105mol), join in the 150ml three-necked flask that magnetic stirring apparatus and thermometer are housed, the stirring of heating, the stirring of heating, add the 0.2g sodium phenylate,, collect phenol at 130～140 ℃ of reactions of 10mmHg 30min, at 160～210 ℃ of about 30min of insulation, reaction finishes again.Stop heating, close vacuum pump when the liquid temperature drop is 120 ℃, suction filtration while hot, thick product is colourless or light yellow transparent liquid, the by-product phenol recycling.Thick product is through alkali cleaning, washing and dry smart product 54.8g, the yield 90.6% of getting.
Embodiment 4, and is substantially the same manner as Example 1, but the first step reaction is all adopted Lewis an acidic catalyst MgCl with the second step catalyst for reaction
2Catalyst consumption is 0.05% of phenol or a Resorcinol weight.Temperature of reaction is controlled at 80～260 ℃ of scopes.
Embodiment 5, and is substantially the same manner as Example 1, but the first step reaction is all adopted Lewis an acidic catalyst MgCl with the second step catalyst for reaction
2Catalyst consumption is 3% of phenol or a Resorcinol weight.
Embodiment 6, and is substantially the same manner as Example 1, but the first step reaction is all adopted Lewis an acidic catalyst ZnCl with the second step catalyst for reaction
2
Embodiment 7, and is substantially the same manner as Example 1, but the first step reaction is all adopted Lewis an acidic catalyst TiCl with the second step catalyst for reaction
4
Embodiment 8, and is substantially the same manner as Example 1, but the Lewis an acidic catalyst of the first step reaction adopts ZnCl
2The second step catalyst for reaction adopts basic catalyst NaOH.
Embodiment 9, and is substantially the same manner as Example 1, but the second step catalyst for reaction adopts basic catalyst KOH.
Embodiment 10, and is substantially the same manner as Example 1, but the second step catalyst for reaction adopts basic catalyst Na
2CO
3
Embodiment 11, and is substantially the same manner as Example 1, but the second step catalyst for reaction adopts basic catalyst K
2CO
3
Embodiment 10, and is substantially the same manner as Example 1, but the second step catalyst for reaction adopts the basic catalyst sodium phenylate.
Embodiment 11,12, and with embodiment 1,2 is basic identical respectively, but reactant and equipment all enlarge in proportion by technical scale.
Claims (5)
1, a kind of preparation method of fire retardant resorcinol tetraphenyldiphosphate, step is as follows:
Phenol and phosphorus oxychloride are reacted under the condition of catalyzer, heating and are generated triphenyl, and the mol ratio of phenol and phosphorus oxychloride is 3.00～3.05: 1;
Triphenyl and Resorcinol carry out transesterification reaction under the condition of catalyzer, heating, decompression, obtain resorcinol tetraphenyldiphosphate, and the mol ratio of triphenyl and Resorcinol is 2.00～2.05: 1;
The temperature of reaction of described two steps is 80～260 ℃;
Described catalyzer, the first step reaction is the Lewis an acidic catalyst; The reaction of second step is Lewis an acidic catalyst or basic catalyst, and catalyst consumption is 0.05%～3% of phenol or a Resorcinol weight;
Described Lewis an acidic catalyst is selected from: MgCl
2, ZnCl
2, AlCl
3, TiCl
4Described basic catalyst is selected from: NaOH, KOH, Na
2CO
3, K
2CO
3, sodium phenylate.
According to the preparation method of the described fire retardant resorcinol tetraphenyldiphosphate of claim 1, it is characterized in that 2, the Lewis an acidic catalyst is used in described the first step reaction, and basic catalyst is used in the reaction of second step instead.
3, according to the preparation method of claim 1 or 2 described fire retardant resorcinol tetraphenyldiphosphates, it is characterized in that, the temperature of reaction of described two steps is 130-210 ℃, and described catalyst consumption is between the 0.1%-2% of phenol or Resorcinol weight.
4, according to the preparation method of the described fire retardant resorcinol tetraphenyldiphosphate of claim 3, it is characterized in that, also be provided with following steps: suction filtration while hot, thick product, the by-product phenol recycling; Thick product is through alkali cleaning, washing and dry smart product.
According to the preparation method of the described fire retardant resorcinol tetraphenyldiphosphate of claim 4, it is characterized in that 5, the control process of temperature of reaction is: the first step reaction, phenol 141.2g, catalyzer aluminum chloride 3.0g is warming up to 50 ℃ and begins to drip POCl
376.65g, dripping off in 1～1.5 hour, temperature is raised to 80 ℃ gradually in the dropping process, and temperature is raised to 100 ℃ then, is incubated 1 hour, is raised to 140 ℃ of reactions 1 hour again, stops heating; The reaction of second step adds Resorcinol 27.5g, the stirring of heating, and vacuum tightness is below 10mmHg, 140～160 ℃ of reaction 60min collect phenol, and at 180～220 ℃ of about 90min of insulation, reaction finishes again, stop heating, close vacuum pump when the liquid temperature drop is 120 ℃, while hot suction filtration.
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| CN101538279A (en) * | 2009-02-05 | 2009-09-23 | 上海华谊（集团）公司 | Method for preparing phosphite ester oligomer as phosphoric fire retardant |
| CN101899064B (en) * | 2009-12-22 | 2013-06-12 | 江苏雅克科技股份有限公司 | Preparation method of dihydric phenol di(dialkyl phenyl organic phosphate) |
| CN105254666B (en) * | 2015-11-11 | 2018-04-13 | 朱正直 | A kind of preparation method of Triphenyl phosphate |
| CN106222770A (en) * | 2016-07-05 | 2016-12-14 | 孙中志 | A kind of terylene chemical fibre fire retardant preparation method |
| CN106317107A (en) * | 2016-07-22 | 2017-01-11 | 上海石化西尼尔化工科技有限公司 | Preparation method of liquid flame retardant |
| CN110818736A (en) * | 2019-10-30 | 2020-02-21 | 南京师范大学镇江创新发展研究院 | Method for removing Lewis acid ionic liquid catalyst in phosphate ester flame retardant product |
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| US5344468A (en) * | 1991-06-14 | 1994-09-06 | Ethyl Petroleum Additives, Inc. | Organic phosphates and their use as wear inhibitors |
| US5750756A (en) * | 1994-11-01 | 1998-05-12 | Akzo Nobel Nv | Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) |
| US6489502B2 (en) * | 2000-10-16 | 2002-12-03 | Bayer Aktiengesellschaft | Process for preparing phosphoric acid esters |
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2006
- 2006-06-05 CN CNB2006100852204A patent/CN100427494C/en not_active Expired - Fee Related
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|---|---|---|---|---|
| US5344468A (en) * | 1991-06-14 | 1994-09-06 | Ethyl Petroleum Additives, Inc. | Organic phosphates and their use as wear inhibitors |
| US5750756A (en) * | 1994-11-01 | 1998-05-12 | Akzo Nobel Nv | Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) |
| US6489502B2 (en) * | 2000-10-16 | 2002-12-03 | Bayer Aktiengesellschaft | Process for preparing phosphoric acid esters |
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