CN1493575A - Method of preparing phosphite ester - Google Patents
Method of preparing phosphite ester Download PDFInfo
- Publication number
- CN1493575A CN1493575A CNA021466076A CN02146607A CN1493575A CN 1493575 A CN1493575 A CN 1493575A CN A021466076 A CNA021466076 A CN A021466076A CN 02146607 A CN02146607 A CN 02146607A CN 1493575 A CN1493575 A CN 1493575A
- Authority
- CN
- China
- Prior art keywords
- acid ester
- ammonium
- phosphorous acid
- salt
- phosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 21
- 150000008301 phosphite esters Chemical class 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 5
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 phosphorous acid ester Chemical class 0.000 claims description 38
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000005886 esterification reaction Methods 0.000 claims description 16
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- FNDXFUBHPXBGMD-UHFFFAOYSA-N OP(O)O.OP(O)(O)=O Chemical compound OP(O)O.OP(O)(O)=O FNDXFUBHPXBGMD-UHFFFAOYSA-N 0.000 abstract 1
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Abstract
A process for preparing phosphate (phosphite) includes esterifying reaction between PCl3, phosphorus oxychloride, or phosphorus thiochloride and alcohol or phenol while introducing the liquid mixture of ammonium salt and sulphite for cooling the resultant, cooling to lower than 40 deg.C by condenser, collecting the resultant in said liquid mixture while introducing ammonia to it, filtering for removing ammonium chloride to obtain coarse product, and rectifying. Its advantages are high speed and high output rate.
Description
The present invention relates to the preparation method of industrial chemicals, specifically the preparation method of (Asia) phosphoric acid ester.
Phosphorous acid ester and phosphoric acid ester [hereinafter to be referred as (Asia) phosphoric acid ester] all are the intermediates of preparation organophosphorus pesticide.When preparing (Asia) phosphoric acid ester at present, generally all adopt phosphorus trichloride, phosphorus oxychloride or phosphorus thiochloride and alcohols (as methyl alcohol, ethanol) or phenols (as phenol) to carry out esterification, hydrogenchloride and other muriate are emitted in reaction; The mixture that contains liquid hydrogenchloride and thick ester that reaction generates obtains (Asia) phosphoric acid ester crude product after (promptly this mixture flows into the depickling jar after the condenser cooling, through heating, depickling) handled in depickling.Crude product promptly obtains the pure product of (Asia) phosphoric acid ester accordingly through vacuum fractionation again.This preparation method is because esterification reaction product just cools off by condenser, so speed of cooling is slow, and resultant of reaction also can dissolve a large amount of hydrogenchloride in temperature-fall period, thereby increased side reaction.Moreover, in deacidification, need could remove de-chlorine hydride, and can increase side reaction when heating up by heating, also can lose part (Asia) phosphoric acid ester simultaneously, thereby influence the yield of (Asia) phosphoric acid ester.Zhi Bei its yield of (Asia) phosphoric acid ester is usually at 70--80% as stated above.
Purpose of the present invention just provides the novel method of a kind of preparation (Asia) phosphoric acid ester, and this method can effectively suppress the side reaction in the preparation process, can significantly improve the yield of (Asia) phosphoric acid ester simultaneously.
The object of the present invention is achieved like this:
The inventive method includes following steps:
A, employing phosphorus trichloride, phosphorus oxychloride or phosphorus thiochloride and alcohol or phenol carry out esterification;
The proportion of raw materials amount can be calculated according to the mass ratio in the common esterification, appraise and decide.
B, in esterification reaction process, feed the mixed solution of forming by the salt of weak acid and the phosphorous acid ester of ammonium, with it reactant in a step is cooled off;
The salt of weak acid of ammonium generally is solid-state, when its with after phosphorous acid ester mixes, then become liquid state.Phosphorous acid ester in this mixed solution mainly plays cooling effect therein, and the salt of weak acid of ammonium mainly be with esterification reaction process in the hydrogenchloride that produces neutralize; The mixing match amount of the salt of weak acid of ammonium and phosphorous acid ester does not relatively have strict the qualification in this mixed solution, generally with the size decision of the hydrogenchloride amount that produced in the esterification, hydrogenchloride more for a long time, the amount of the salt of weak acid of ammonium strengthens, otherwise then reduces.The salt of weak acid of ammonium is 20～50: 100 with preferred weight part ratio of phosphorous acid ester in the mixed solution, helps the hydrogenchloride in the neutralization reactant in this ratio range most.
The salt of weak acid of ammonium can be selected ammonium phosphite, ammonium acetate, ammonium formiate for use, but with ammonium phosphite for most preferably.
The salt of weak acid of ammonium also can be substituted by amine substance (as methylamine, diethylamine, triethylamine), metal oxide (as calcium oxide, sodium oxide, potassium oxide), metal salt of weak acid (as lime carbonate, salt of wormwood, yellow soda ash) etc., and its effect is identical with effect;
The amount ratio of the salt of weak acid of ammonium and the mixed solution of phosphorous acid ester does not have strict the qualification, and is corresponding with the amount of esterification reaction product usually.Esterification reaction product is many, and the consumption of this mixed solution increases relatively, but with reach can in and hydrogenchloride accelerated reaction thing refrigerative effect.
C, be cooled to 40 ℃ below by condenser cooled resultant in the b step after, be collected in the storage tank of the salt of weak acid that is placed with ammonium and phosphorous acid ester mixed solution, and in storage tank, feed ammonia;
The mixed solution of forming by the salt of weak acid and the phosphorous acid ester of ammonium in the storage tank, the salt of weak acid of its ammonium and the weight proportion of phosphorous acid ester do not need strict control, and general with after resultant in the b step and the mixed solution effect, the pH value in the storage tank is neutrality and is as the criterion.
Ammonia in this step on the one hand and remaining hcl reaction, on the one hand with above-mentioned steps in the phosphorous acid reaction that produces.Ammonium phosphite in this step mixed solution mainly plays shock absorption, in case when feeding excessive ammonia, cause the liquid in the storage tank to be alkalescence.
The salt of weak acid of its ammonium of mixed solution of this step and the weight proportion of phosphorous acid ester are with 2～30: 100 for most preferably.Use this ratio, shock absorption the best of the salt of weak acid of ammonium.
Passing through the preferred temperature of condenser refrigerative in this step is-10 ℃-+10 ℃.Under this temperature, can further suppress the Decomposition of hydrogenchloride to phosphoric acid ester.
D, remove by filter in the above step ammonium chloride that reaction generates, obtain phosphorous acid ester and phosphoric acid ester crude product;
E, with the crude product in d step by rectifying, obtain the pure product of purified phosphorous acid ester or phosphoric acid ester.
The temperature of rectifying and pressure can be selected conventional parameter for use.
The inventive method is because in esterification reaction process, increased and used the mixed solution of forming by ammonium phosphite and phosphorous acid ester that it is cooled off, obviously accelerated cooling to resultant of reaction, weakened the Decomposition of hydrogenchloride to phosphoric acid ester, simultaneously also avoided resultant of reaction in temperature-fall period, to dissolve hydrogenchloride once more, thereby reduced the content of liquid hydrogen chloride, reduced the generation of side reaction.
The inventive method adopts the feeding ammonia to carry out depickling, thereby has avoided prior art heating in deacidification, and this step had both guaranteed that depickling was complete, had avoided the consume of (Asia) phosphoric acid ester in the deacidification again, thereby had guaranteed the yield of (Asia) phosphoric acid ester.
The inventive method is compared with original technology, and its speed of cooling and depickling speed all have significant quickening, uses this method can make the yield of (Asia) phosphoric acid ester reach 90--98%.
The inventive method adopts phosphorus trichloride, phosphorus oxychloride or phosphorus thiochloride and corresponding alcohol or phenol reaction can be prepared corresponding dimethylphosphite, diethyl phosphite, the phosphorous acid diphenyl ester, triethyl-phosphite, triphenyl phosphite, the sulfenyl dimethyl phosphate, oxygen base diethyl phosphoric acid, oxygen base diphenyl phosphate, the sulfenyl trimethyl phosphite 99, the sulfenyl triethyl phosphate, the sulfenyl triphenylphosphate, oxygen base trimethyl phosphite 99, oxygen base triethyl phosphate, (Asia) phosphoric acid ester such as oxygen base triphenylphosphate.
Be described in further detail the present invention below in conjunction with embodiment.
Embodiment 1 preparation dimethylphosphite
Its preparation method is:
A, adopt 1.61 tons of 2.21 tons of phosphorus trichlorides and methyl alcohol, methyl alcohol put into reactor earlier, with phosphorus trichloride with 10 hours slowly input wherein carry out esterification.The hydrogenchloride and the methyl chloride of emitting in the reaction are discharged it by vacuum pump.
B, in esterification reaction process, adopt 10 tons of the mixed solutions (ammonium phosphite and phosphorous acid ester weight proportion are 30: 100) formed by ammonium phosphite and phosphorous acid ester, slowly dropped into 10 hours, the reactant in a step (this reactant includes phosphorous acid ester and hydrogenchloride) is cooled off.
When esterification, feed the mixed solution of forming by ammonium phosphite and phosphorous acid ester, this mixed solution can be to the reactant refrigerative simultaneously, ammonium phosphite and hydrogenchloride are reacted, be dissolved in the liquid, thereby effectively reduced the generation of side reaction to avoid a large amount of hydrogenchloride.
C, be after the mixture of phosphorous acid ester, ammonium chloride, phosphorous acid and remaining hydrogenchloride is cooled to 20 ℃ by condenser with cooled product in the b step, be collected in the storage tank that is placed with ammonium phosphite and phosphorous acid ester mixed solution, mixed solution is 2 tons, and the ammonium phosphite in the mixed solution and the weight proportion of phosphorous acid ester are 3: 100.Simultaneously in storage tank, feed ammonia.
Ammonia in this step on the one hand and remaining hcl reaction, on the one hand with above-mentioned steps in the phosphorous acid reaction that produces.Ammonium phosphite in this step mixed solution mainly plays shock absorption, in case when feeding excessive ammonia, cause the liquid in the storage tank to be alkalescence.
D, the ammonium chloride that produces in the above-mentioned steps is removed by filter, promptly obtain the crude product of dimethylphosphite.
E, with crude product through underpressure distillation, be 40 mmhg in 140～158 ℃, pressure, fractionation gets the pure product of dimethylphosphite.Its yield is 98%.
Embodiment 2
The preparation triphenyl phosphite
Adopt phosphorus trichloride and phenol to feed intake in 1: 3.01 in molar ratio, carry out esterification, its method steps is with embodiment 1, and the yield of triphenyl phosphite is 97%.
Claims (5)
1, a kind of method for preparing phosphorous acid ester and phosphoric acid ester is characterized in that it may further comprise the steps:
A, employing phosphorus trichloride, phosphorus oxychloride or phosphorus thiochloride and alcohol or phenol carry out esterification;
B, in esterification reaction process, feed the mixed solution of forming by the salt of weak acid and the phosphorous acid ester of ammonium, with it reactant in a step is cooled off;
C, cooled resultant in the b step is cooled to below 40 ℃ by condenser, is collected in the storage tank that is placed with the mixed solution of forming by the salt of weak acid and the phosphorous acid ester of ammonium, and in storage tank, feeds ammonia;
D, remove by filter in the above step ammonium chloride that reaction generates, obtain phosphorous acid ester and phosphoric acid ester crude product;
E, with the crude product in the d step by rectifying, obtain the pure product of purified phosphorous acid ester or phosphoric acid ester.
2, the method for preparing phosphorous acid ester and phosphoric acid ester according to claim 1 is characterized in that the mixed solution that salt of weak acid and phosphorous acid ester by ammonium in the said b step are formed, and the salt of weak acid of its ammonium and the weight part ratio of phosphorous acid ester are 20～50: 100.
3, the method for preparing phosphorous acid ester and phosphoric acid ester according to claim 1, the salt of weak acid that it is characterized in that said ammonium is an ammonium phosphite.
4, the method for preparing phosphorous acid ester and phosphoric acid ester according to claim 1 is characterized in that the mixed solution be made up of the salt of weak acid and the phosphorous acid ester of ammonium in the said c step, and the salt of weak acid of its ammonium and the weight part ratio of phosphorous acid ester are 2～30: 100.
5, the method for preparing phosphorous acid ester and phosphoric acid ester according to claim 1 and 2 is characterized in that in the c step the cooled resultant of b step being cooled to-10 ℃～+ 10 ℃ by condenser.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146607 CN1212326C (en) | 2002-10-28 | 2002-10-28 | Method of preparing phosphite ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146607 CN1212326C (en) | 2002-10-28 | 2002-10-28 | Method of preparing phosphite ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493575A true CN1493575A (en) | 2004-05-05 |
| CN1212326C CN1212326C (en) | 2005-07-27 |
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ID=34232805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02146607 Expired - Lifetime CN1212326C (en) | 2002-10-28 | 2002-10-28 | Method of preparing phosphite ester |
Country Status (1)
| Country | Link |
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| CN (1) | CN1212326C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374450C (en) * | 2006-07-21 | 2008-03-12 | 申厚宝 | Triethyl phosphite production process |
| CN100376589C (en) * | 2006-07-21 | 2008-03-26 | 申厚宝 | Trimethyl phosphite production process |
| CN101775033B (en) * | 2010-01-19 | 2012-08-29 | 青岛大学 | Preparation method of phosphite ester by using dividing wall tower reaction rectification technique |
| CN103224529A (en) * | 2013-04-09 | 2013-07-31 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphite |
| CN103801400A (en) * | 2014-03-07 | 2014-05-21 | 中国天辰工程有限公司 | Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed |
-
2002
- 2002-10-28 CN CN 02146607 patent/CN1212326C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374450C (en) * | 2006-07-21 | 2008-03-12 | 申厚宝 | Triethyl phosphite production process |
| CN100376589C (en) * | 2006-07-21 | 2008-03-26 | 申厚宝 | Trimethyl phosphite production process |
| CN101775033B (en) * | 2010-01-19 | 2012-08-29 | 青岛大学 | Preparation method of phosphite ester by using dividing wall tower reaction rectification technique |
| CN103224529A (en) * | 2013-04-09 | 2013-07-31 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphite |
| CN103801400A (en) * | 2014-03-07 | 2014-05-21 | 中国天辰工程有限公司 | Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed |
| CN103801400B (en) * | 2014-03-07 | 2015-12-02 | 中国天辰工程有限公司 | A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1212326C (en) | 2005-07-27 |
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Effective date of registration: 20070803 Address after: Wutongqiao District Qiao Gou Zhen 614800 Sichuan city of Leshan Province Patentee after: Sichuan Leshan Fuhua Agricultural Science Investment Group Co.,Ltd. Address before: 052260, Hebei City, Jinzhou Province North Little Village White Secretary Patentee before: Liu Deliang |
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Owner name: FUHUA TONGDA PESTICIDE SCIENCE AND TECHNOLOGY CO. Free format text: FORMER OWNER: SICHUAN LESHAN FUHUA AGRICULTURAL SCIENCE INVESTMENT GROUP CO., LTD. Effective date: 20080822 |
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Effective date of registration: 20080822 Address after: Wutongqiao District Bridge Town Sichuan city of Leshan Province Patentee after: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. Address before: Wutongqiao District Bridge Town Sichuan city of Leshan Province Patentee before: Sichuan Leshan Fuhua Agricultural Science Investment Group Co.,Ltd. |
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Granted publication date: 20050727 |
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