CN102344421A - Preparation method for phenoxy ester in water phase - Google Patents
Preparation method for phenoxy ester in water phase Download PDFInfo
- Publication number
- CN102344421A CN102344421A CN2011102127357A CN201110212735A CN102344421A CN 102344421 A CN102344421 A CN 102344421A CN 2011102127357 A CN2011102127357 A CN 2011102127357A CN 201110212735 A CN201110212735 A CN 201110212735A CN 102344421 A CN102344421 A CN 102344421A
- Authority
- CN
- China
- Prior art keywords
- phenol
- reaction
- preparation
- phenoxy
- phenoxy ester
- 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
Landscapes
- Fireproofing Substances (AREA)
Abstract
The invention relates to a preparation method for phenoxy ester in a water phase. The phenoxy ester is prepared by reaction between phenol and an esterifying agent. The preparation method for the phenoxy ester in the water phase is characterized by comprising the following steps: adding the phenol to aqueous solution of sodium hydroxide or potassium hydroxide to prepare the sodium salt or the kali salt of the phenol; dropwise adding the esterifying agent under the condition of controlling the temperature to be 0-25 DEG C; keeping the temperature; after low-temperature action is performed for certain time, enabling the temperature to rise to 40-100 DEG C to continue the reaction; and after the reaction is ended, cooling and separating to prepare the phenoxy ester. The esterifying agent is cyanuric chloride, phosphorus oxychloride, phosphorus trichloride or acyl chloride. The preparation method for the phenoxy ester compound in the water phase has a simple the process, short reaction time, high product quality and high yield. In the reaction process, only water is used as a reaction solvent, an organic solvent is not adopted, and solvent recovery and aftertreatment do not need to be performed, thereby, the environment is protected.
Description
Technical field
The present invention relates to a kind of preparation method of phenoxy ester, be specifically related to the preparation method that a kind of aqueous phase carries out phenoxy cyanurate, SULPHOSUCCINIC ACID ESTER, phosphorous acid ester or carboxylicesters.
Background technology
The cyanurate of phenoxy, SULPHOSUCCINIC ACID ESTER, phosphorous acid ester and carboxylicesters can be as the fire retardants of excellent property, and phosphorus-halogenated flame retardant has good synergistic effect owing to not only contain phosphorus but also contain bromine etc. in the molecule.
The preparation of the cyanurate of phenoxy, SULPHOSUCCINIC ACID ESTER, phosphorous acid ester or carboxylicesters generally adopts cyanuric chloride, POCl3, phosphorus trichloride or alkyl acyl chloride and (single or many) phenol or (single or many) bromophenol in solvent, to carry out catalyzed reaction (Mu Chunming, Shi Tiejun, Shi Xianlei; The research of synthetic three (tribromophenoxy) isocyanuric acid esters of solid acid catalysis and flame retardant polyurethane urea thereof, chemical propellant and macromolecular material, 2008; 6 (2): 37-39), this preparation method exists catalyzer, solvent to select and isolating problem the loaded down with trivial details (Jiang Danlei of aftertreatment; Song Jian, Zhang Qing, Han Tieliang; Lv Rihong, Qu Shihong, four-(2; The 6-xylyl) the Resorcinol biphosphonate is synthetic, petrochemical complex. and 2010,39 (5): 542-547).In addition; Also can process the phenol sodium water solution to (single or many) bromophenol with the reactant aqueous solution of sodium hydroxide earlier earlier; And then with methylene dichloride (or other solvents) solution reaction of cyanuric chloride, alkyl acyl chloride, POCl3 or phosphorus trichloride, under the effect of phase-transfer catalyst, make target product.
CN200610085221.9 discloses the compound method of a kind of fire retardant three (bromo phenoxy) cyanurate, carries out in mutually at the aqueous solution and organic solvent two, and step is following: bromophenol and sodium hydroxide reaction generate bromophenol sodium; The reaction under catalyzer, suitable temperature condition of bromophenol sodium and cyanuric chloride makes three (bromo phenoxy) cyanurate; Described catalyzer is phase-transfer catalyst quaternary ammonium salt and quaternary phosphine salt; Described suitable temperature condition is: the dropping temperature when the cyanuric chloride drips of solution is added in the bromophenol sodium water solution is 20 ℃~35 ℃; Temperature of reaction after dropwising is 40 ℃~55 ℃.Described bromophenol comprises: monobromophenol, dibromophenol or tribromophenol.
Adopt the mixed solvent of water and organic solvent, though reduced the usage quantity of organic solvent, make product cost reduce, because the toxicity and the inflammableness of organic solvent, still there is potential safety hazard in entire reaction course.And all need use phase-transfer catalyst in the described method.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of aqueous phase phenoxy ester can overcome the deficiency of prior art, and whole process of preparation only is solvent with water; Need not add organic solvent and phase-transfer catalyst; Technology is simple, and the reaction times is short, does not have solvent recuperation and aftertreatment problem.
The object of the invention is realized through following technical proposal:
A kind of preparation method of aqueous phase phenoxy ester is made by the reaction of phenol and esterifying agent, it is characterized in that: phenol is added sodium salt or the sylvite of processing phenol in the aqueous solution of sodium hydroxide or Pottasium Hydroxide; Controlled temperature drips esterifying agent down for 0 ℃-25 ℃; After keeping this thermotonus certain hour, elevated temperature to 40 ℃~100 ℃ continues reaction, after reaction finishes; Cooling separates making the phenoxy ester;
Described esterifying agent is cyanuric chloride, POCl3, phosphorus trichloride or acyl chlorides R-COCl.
Described phenoxy ester comprises phenoxy cyanurate, SULPHOSUCCINIC ACID ESTER, phosphorous acid ester or carboxylicesters.
Can make above-mentioned phenoxy ester according to the inventive method, method is respectively:
A) preparation method of phenoxy cyanurate is following: after the aqueous solution of (single, many) phenol or (single, many) fortified phenol and sodium hydroxide (or potassium) is processed phenol sodium (or potassium) salts solution; Controlled temperature adds cyanuric chloride for 0 ℃-25 ℃; After keeping the low-temp reaction certain hour, elevated temperature continues reaction, after reaction finishes; Cooling is filtered or separatory separates.
B) preparation method of phenoxy SULPHOSUCCINIC ACID ESTER is following: after the aqueous solution of (single, many) phenol or (single, many) fortified phenol and sodium hydroxide (or potassium) is processed phenol sodium (or potassium) salts solution; Controlled temperature drips POCl3 for 0 ℃-25 ℃; After keeping the low-temp reaction certain hour, elevated temperature continues reaction, after reaction finishes; Cooling is filtered or separatory separates.
C) preparation method of phenoxy phosphorous acid ester is following: after the aqueous solution of (single, many) phenol or (single, many) bromophenol and sodium hydroxide (or potassium) is processed phenol sodium (or potassium) salts solution; Controlled temperature drips phosphorus trichloride for 0 ℃-25 ℃; After keeping the low-temp reaction certain hour, elevated temperature continues reaction, after reaction finishes; Cooling is filtered or separatory separates.
D) preparation method of phenoxy carboxylic acid ester is following: after the aqueous solution of (single, many) phenol or (single, many) bromophenol and sodium hydroxide (or potassium) is processed phenol sodium (or potassium) salts solution; Controlled temperature drips alkyl acyl chloride for 0 ℃-25 ℃; After keeping the low-temp reaction certain hour, elevated temperature continues reaction, after reaction finishes; Cooling is filtered or separatory separates.
Described phenol comprises monohydric phenol or dihydric phenol.Monohydric phenol comprises phenol, alkylphenol or halogenated phenol, preferred phenol, C
1-C
4Alkylphenol, phenyl-monobromide phenol, dibrominated phenol or tribromo-benzene phenol.Dihydric phenol comprises dihydroxyphenyl propane, alkyl dihydroxyphenyl propane, halogenated bisphenol A, dihydroxy-benzene or halogeno-benzene diphenol, preferred dihydroxyphenyl propane, tetrabromo-bisphenol, pyrocatechol, Resorcinol, Resorcinol and (single, many) bromobenzene diphenol.
Described esterifying agent acyl chlorides R-COCl, the wherein preferred C of R
1-C
4Alkyl or alkylene.
In the described method, wherein the mol ratio of phenolic hydroxyl group and sodium hydroxide or Pottasium Hydroxide is 1:1.05-1.2.The preferred proportion that the present invention recommends is 1:1.08-1.12.
In described sodium hydroxide or the potassium hydroxide aqueous solution, the mass concentration 0.01~0.5g/mL of sodium hydroxide or Pottasium Hydroxide.
In the described method, the mol ratio of phenolic hydroxyl group and cyanuric chloride, POCl3, phosphorus trichloride is 3:1-1.5, with the mol ratio of acyl chlorides be 1:1.05-1.3.The preferred proportion that the present invention recommends is respectively 3:1-1.3 and 1:1.05-1.2.
Need not adopt phase-transfer catalyst in the described method.
Described method is controlled at 0 ℃-25 ℃ in esterifying agent dropping process, and keeps low-temp reaction, and the time of keeping reaction is 0.5~3 h.
Described method, heating back 40 ℃~100 ℃ reaction times is 2~6h.Preferred temperature of reaction is 40 ℃~60 ℃.
With single bromophenol is example (suitable equally to other phenol), and the inventive method synthetic main route is following:
Reaction formula 1
Reaction formula 2
Reaction formula 3
Reaction formula 4(R=C
1-C
4Alkyl or alkylene)
Reaction process is reduced to room temperature after accomplishing, and can directly obtain product after the washing through filtering or the separatory phase-splitting.
The unsaturated phenoxy ester of the present invention's preparation can also further obtain many bromos phenoxy ester with the bromine addition.
Beneficial effect of the present invention:
1, the overall yield of method products obtained therefrom of the present invention can reach more than 90% 85 ~ 98% usually.
2, do not use phase-transfer catalyst in the inventive method, directly can react with water as solvent, temperature is low, and energy consumption is little, and reaction conditions is gentle, and is easy to control.
3, the quality of the prepared phenoxy ester of the present invention flame retardant products is good, and product purity is high, and color and luster is better, does not need other decolouring to handle.
4, method of the present invention can prepare the phenoxy ester (having two keys like R in the reaction formula 4) that has two keys, and then product is a reactive flame retardant, can obtain the body flame retarded polymeric material with olefin-copolymerization, and its flame retardant properties is better, and is more lasting.
5, the inventive method is only reacted at aqueous phase, separates simply, does not have the recovery and the aftertreatment problem of organic solvent, environmental protection and with low cost more in process of production.
In a word, the inventive method technology is simple, and the reaction times is short, good product quality, and yield is high, and is environmentally friendly.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited claim.
Embodiment
Embodiment 1
In four-hole boiling flask, add entry 250g, sodium hydroxide 43g, temperature adds phenol 93 g after reducing to room temperature, places cryosel to bathe this solution; Treat that temperature reduces to below 25 ℃, begin to drip POCl3 51g, controlled temperature is lower than 25 ℃, drip finish reaction 1 h after; Elevated temperature to 40 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product, productive rate 92%.
Embodiment 2
In four-hole boiling flask, add entry 250g, sodium hydroxide 43g, temperature adds phenol 93 g after reducing to room temperature, places cryosel to bathe this solution; Treat that temperature reduces to below 25 ℃, begin to drip cyanuric chloride 62g, controlled temperature is lower than 25 ℃, drip finish reaction 0.5 h after; Elevated temperature to 40 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product, productive rate 90%.
Embodiment 3
In four-hole boiling flask, add entry 150g, sodium hydroxide 43g, temperature adds phenol 93 g after reducing to room temperature, places cryosel to bathe this solution; Treat that temperature reduces to below 25 ℃, begin to drip phosphorus trichloride 46g, controlled temperature is lower than 25 ℃, drip finish reaction 1 h after; Elevated temperature to 40 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product, productive rate 93%.
Embodiment 4
In four-hole boiling flask, add entry 200g, sodium hydroxide 43g, temperature adds phenol 93 g after reducing to room temperature, places cryosel to bathe this solution; Treat that temperature reduces to below 25 ℃, beginning dripping acetyl chloride 26.5g, controlled temperature is lower than 25 ℃, drip finish reaction 1 h after; Elevated temperature to 40 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product, productive rate 91%.
Embodiment 5
In four-hole boiling flask, add entry 150g, sodium hydroxide 43g, temperature adds phenol 93 g after reducing to room temperature, places cryosel to bathe this solution; Treat that temperature reduces to below 25 ℃, begin to drip POCl3 75g, controlled temperature is lower than 25 ℃, drip finish reaction 1 h after; Elevated temperature to 40 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product, productive rate 90%.
Embodiment 6
In four-hole boiling flask, add entry 150g, sodium hydroxide 43g, temperature adds phenol 93 g after reducing to room temperature, places cryosel to bathe this solution; Treat that temperature reduces to below 25 ℃, begin to drip POCl3 63g, controlled temperature is lower than 25 ℃; Elevated temperature to 40 ℃ reaction 2h behind dropping end reaction 1 h, stopped reaction, cooling; Filter, wash the finished product, productive rate 96%.
Embodiment 7,8,9,10, and with embodiment 1,2,3,4, difference is respectively phenol to be changed to tribromophenol 327 g.
Embodiment 11,12,13,14, and with embodiment 1,2,3,4, difference is respectively phenol to be changed to Resorcinol 54g.
Embodiment 15, and with embodiment 4, difference is Acetyl Chloride 98Min. is changed to acrylate chloride 30.5g.
Claims (10)
1. the preparation method of an aqueous phase phenoxy ester is made by phenol and esterifying agent reaction, it is characterized in that: phenol is added sodium salt or the sylvite of processing phenol in the aqueous solution of sodium hydroxide or Pottasium Hydroxide; Controlled temperature drips esterifying agent down for 0 ℃-25 ℃; After keeping this temperature low-temp reaction certain hour, elevated temperature to 40 ℃~100 ℃ continues reaction, after reaction finishes; Cooling separates making the phenoxy ester;
Described esterifying agent is cyanuric chloride, POCl3, phosphorus trichloride or acyl chlorides R-COCl.
2. the preparation method of phenoxy ester according to claim 1 is characterized in that: described phenoxy ester comprises phenoxy cyanurate, SULPHOSUCCINIC ACID ESTER, phosphorous acid ester or carboxylicesters.
3. the preparation method of phenoxy ester according to claim 1 is characterized in that: described phenol comprises phenol, alkylphenol, halogenated phenol, dihydroxyphenyl propane, alkyl dihydroxyphenyl propane, halogenated bisphenol A, dihydroxy-benzene or halogeno-benzene diphenol.
4. the preparation method of phenoxy ester according to claim 3 agent is characterized in that: described phenol is phenol, C
1-C
4Alkylphenol, phenyl-monobromide phenol, dibrominated phenol, tribromo-benzene phenol, dihydroxyphenyl propane, tetrabromo-bisphenol, pyrocatechol, Resorcinol, Resorcinol or bromobenzene diphenol.
5. the preparation method of phenoxy ester according to claim 1 is characterized in that: described acyl chlorides R-COCl, wherein R is C
1-C
4Alkyl or alkylene.
6. the preparation method of phenoxy ester according to claim 1 is characterized in that: the mol ratio of described phenolic hydroxyl group and sodium hydroxide or Pottasium Hydroxide is 1:1.05-1.2.
7. the preparation method of phenoxy ester according to claim 1 is characterized in that: in described sodium hydroxide or the potassium hydroxide aqueous solution, and the mass concentration 0.01~0.5g/mL of sodium hydroxide or Pottasium Hydroxide.
8. the preparation method of phenoxy ester according to claim 1 is characterized in that: in the described method, the mol ratio of phenolic hydroxyl group and cyanuric chloride, POCl3, phosphorus trichloride is 3:1-1.5, with the mol ratio of acyl chlorides be 1:1.05-1.3.
9. the preparation method of phenoxy ester according to claim 1 is characterized in that: in the described method, 0 ℃-25 ℃ times of keeping reaction are 0.5~3 h.
10. the preparation method of phenoxy ester according to claim 1 is characterized in that: in the described method, 40 ℃~100 ℃ reaction times are 2~6 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110212735.7A CN102344421B (en) | 2011-07-28 | 2011-07-28 | Preparation method for phenoxy ester in water phase |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110212735.7A CN102344421B (en) | 2011-07-28 | 2011-07-28 | Preparation method for phenoxy ester in water phase |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102344421A true CN102344421A (en) | 2012-02-08 |
CN102344421B CN102344421B (en) | 2014-03-26 |
Family
ID=45543534
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201110212735.7A Expired - Fee Related CN102344421B (en) | 2011-07-28 | 2011-07-28 | Preparation method for phenoxy ester in water phase |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102344421B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102643199A (en) * | 2012-04-25 | 2012-08-22 | 中国石油化工股份有限公司 | Synthesis method of diphenyl isophthalate |
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 |
CN104151604A (en) * | 2013-05-14 | 2014-11-19 | 常熟市沈氏塑业有限公司 | Bromine-containing phosphate ester flame retardant and preparation method thereof |
CN105669448A (en) * | 2016-03-03 | 2016-06-15 | 国药集团化学试剂有限公司 | Preparation method of pentaerythritol triacrylate |
CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
CN108912065A (en) * | 2018-08-29 | 2018-11-30 | 潍坊玉成化工有限公司 | One kind three(Pentabromo- phenoxy group)The preparation method of chlorinated isocyanurates |
CN110152630A (en) * | 2019-06-04 | 2019-08-23 | 南京信息工程大学 | A kind of new and effective adsorbent and its application |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1049848A (en) * | 1989-08-29 | 1991-03-13 | 中国科学院长春应用化学研究所 | The new preparation process of tri aromatic ester of phosphic acid |
CN1888014A (en) * | 2006-06-05 | 2007-01-03 | 南京师范大学 | Synthesis of fire retardant tri (bromophenoxy) cyanurate |
CN101328153A (en) * | 2008-06-12 | 2008-12-24 | 杭州捷尔思阻燃化工有限公司 | Preparation of tris(tri-bromophenoxy) triazine by nonsolvent method |
CN101948486A (en) * | 2010-08-20 | 2011-01-19 | 洛阳市中达化工有限公司 | Synthesis method of 2,2'-methylene-bis(4,6-dibert-butylphenol) phosphate |
-
2011
- 2011-07-28 CN CN201110212735.7A patent/CN102344421B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1049848A (en) * | 1989-08-29 | 1991-03-13 | 中国科学院长春应用化学研究所 | The new preparation process of tri aromatic ester of phosphic acid |
CN1888014A (en) * | 2006-06-05 | 2007-01-03 | 南京师范大学 | Synthesis of fire retardant tri (bromophenoxy) cyanurate |
CN101328153A (en) * | 2008-06-12 | 2008-12-24 | 杭州捷尔思阻燃化工有限公司 | Preparation of tris(tri-bromophenoxy) triazine by nonsolvent method |
CN101948486A (en) * | 2010-08-20 | 2011-01-19 | 洛阳市中达化工有限公司 | Synthesis method of 2,2'-methylene-bis(4,6-dibert-butylphenol) phosphate |
Non-Patent Citations (2)
Title |
---|
武锐,等: "分子筛催化酚的酯化反应", 《厦门大学学报(自然科学版)》 * |
顾慧丹,等: "三(三溴苯基)氰尿酸酯的合成新方法", 《南京师范大学学报(工程技术版)》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102643199A (en) * | 2012-04-25 | 2012-08-22 | 中国石油化工股份有限公司 | Synthesis method of diphenyl isophthalate |
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 |
CN104151604A (en) * | 2013-05-14 | 2014-11-19 | 常熟市沈氏塑业有限公司 | Bromine-containing phosphate ester flame retardant and preparation method thereof |
CN105669448A (en) * | 2016-03-03 | 2016-06-15 | 国药集团化学试剂有限公司 | Preparation method of pentaerythritol triacrylate |
CN105669448B (en) * | 2016-03-03 | 2018-02-09 | 国药集团化学试剂有限公司 | A kind of preparation method of pentaerythritol triacrylate |
CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
CN108912065A (en) * | 2018-08-29 | 2018-11-30 | 潍坊玉成化工有限公司 | One kind three(Pentabromo- phenoxy group)The preparation method of chlorinated isocyanurates |
CN108912065B (en) * | 2018-08-29 | 2022-03-11 | 潍坊玉成化工有限公司 | Preparation method of tri (pentabromophenoxy) isocyanurate |
CN110152630A (en) * | 2019-06-04 | 2019-08-23 | 南京信息工程大学 | A kind of new and effective adsorbent and its application |
CN110152630B (en) * | 2019-06-04 | 2022-03-22 | 南京信息工程大学 | Efficient adsorbent and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN102344421B (en) | 2014-03-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102344421B (en) | Preparation method for phenoxy ester in water phase | |
CN104371031B (en) | Cellulose-based nitrogen-phosphorus flame retardant and preparation method thereof | |
CN102775442B (en) | Oligomer phosphonate and its production and use | |
CN102757579A (en) | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof | |
CN106336435B (en) | A kind of preparation method of improved hexaphenoxycyclotriphosphazene | |
CN101921407A (en) | Bromine-containing pentaerythritol phosphoester retardant and preparation method thereof | |
CN102807581A (en) | Preparation method for synthesizing phosphotriester under catalysis of Lewis acid ionic liquid | |
CN102603800A (en) | Preparation method of phosphonitrile flame retardant | |
CN103772740A (en) | Phosphorus-containing flame retardant and preparation method thereof | |
CN104610571A (en) | Cardanol-based phosphatefire-retardant plasticizer and preparation method thereof | |
CN104356242B (en) | Halogen-free cellulose based phosphorus flame retardant and preparation method thereof | |
CN103408584B (en) | Preparation method for 3-(2-isopropyl chloride) phosphate ester fire-retardant with high resistance to hydrolysis | |
CN102924749A (en) | Ionic liquid-type phosphate fire retardant and preparation method thereof | |
CN104725668A (en) | Fluorophenyl and phosphate structure-containing novel phosphorus-silicon flame retardant and preparation method and application thereof | |
CN103435643A (en) | Preparation method of monohydroxy dialkyl phosphinic acid metal salt fire retardant | |
CN102702413A (en) | Phosphate flame retardant containing styrene structure and synthesis method of phosphate flame retardant | |
CN101830816B (en) | Method for preparing rosinyl di-quaternary ammonium salt cationic surfactant | |
CN101723970B (en) | Method for preparing retardant resorcin phosphate | |
CN102775445A (en) | Resorcinol-di(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)phosphate (RDD) and preparation method thereof | |
CN103539814A (en) | Fire retardant containing styrene structure and phosphorus and nitrogen elements and synthetic method thereof | |
CN103073581B (en) | Method for compositing alkyl phosphonic acid dialkyl ester | |
CN102942586B (en) | The preparation method of ethyl 2-methacrylate base phenmethyl phosphoric acid ester | |
CN102757026A (en) | Preparation method of fluoro phosphonitrile compound | |
CN105061715A (en) | HFC-245eb type combined polyether for polyurethane plastics for boards and preparation method of HFC-245eb type combined polyether | |
CN102604157A (en) | Flame retardant and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140326 Termination date: 20210728 |
|
CF01 | Termination of patent right due to non-payment of annual fee |