CN105085568A - Preparation method of tri(2-chloroisopropyl)phosphate (TCPP) - Google Patents
Preparation method of tri(2-chloroisopropyl)phosphate (TCPP) Download PDFInfo
- Publication number
- CN105085568A CN105085568A CN201510517020.0A CN201510517020A CN105085568A CN 105085568 A CN105085568 A CN 105085568A CN 201510517020 A CN201510517020 A CN 201510517020A CN 105085568 A CN105085568 A CN 105085568A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- acid ester
- tcpp
- chloro isopropyl
- preparation
- 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
Abstract
The invention relates to a preparation method of tri(2-chloroisopropyl)phosphate (TCPP). The TCPP is prepared by reacting dehydrated epoxypropane and phosphorus oxychloride. The invention particularly relates to a preparation method of TCPP with low TCPP ether impurity content and high product yield. The method comprises the following steps: before adding the epoxypropane to react, adding a dehydrating agent into the epoxypropane or passing the epoxypropane through a dehydrating-agent-filled dehydration tower to perform deep dehydration on the epoxypropane until the water content in the epoxypropane is less than 100 ppm, and reacting with the phosphorus oxychloride to obtain the TCPP. The TCPP ether content in the TCPP product is less than 1000 ppm. Compared with the TCPP obtained in the prior art, the method greatly lowers the TCPP ether content in the product and enhances the product yield.
Description
Technical field
The invention belongs to technical field of compound preparation, be specifically related to a kind of preparation method of low TCPP ether content three-(2-chloro isopropyl) phosphoric acid ester, it prepares three-(2-chloro isopropyl) phosphoric acid ester by through the propylene oxide of processed and phosphorus oxychloride reaction.
Background technology
Three-(2-chloro isopropyl) phosphoric acid ester, be called for short TCPP, it is a kind of fire retardant being widely used in the multiple polymers such as polyurethane soft foamed plastics, rigid foam.Urethane foam, especially rigid foam are widely used as all kinds of energy-saving and heat-insulating material, but it easily burns, and need add fire retardant and carry out flame-retardant modified.
The preparation of TCPP is known in those skilled in the art, mainly through utilizing phosphorus oxychloride and propylene oxide Reactive Synthesis under the such as Louis acid catalysis such as aluminum chloride, tetrabutyl titanate or titanium tetrachloride.The TCPP crude product that phosphorus oxychloride and propylene oxide reaction obtain, then obtain TCPP through processes such as alkali cleaning, washing, vacuum hydro-extraction, filtrations.TCPP is primarily of four kinds of isomer and phosphoric acid ester (the being called for short TCPP ether) composition with penton group.And low TCPP ether content is extremely important on the toxicological evaluation of TCPP product.
Patent US2610978, US3100220, US2008227997, DE-A1921504, the method adopting different catalyzer synthesis TCPP is described in EP0398095A2, but TCPP ether Producing reason and how effectively to reduce the preparation method of TCPP ether content in TCPP in all not mentioned TCPP.
Patent CN101235050A describes the TCPP product adopting aluminum trichloride catalyst to prepare and shows the isomer proportion more favourable than prior art, but also reduces the formation of by product as TCPP ether to a great extent.But do not mention the root that TCPP ether in TCPP produces, and the how preparation method of the content of TCPP ether in more effective reduction TCPP.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide and a kind ofly will prepare the method for three-(2-chloro isopropyl) phosphate flame retardants through the propylene oxide of processed and phosphorus oxychloride reaction, three-(2-chloro isopropyl) phosphate flame retardants obtained by the method have low TCPP ether content.
The present inventor finds after active research, in TCPP product, TCPP ether is that moisture owing to containing in propylene oxide participates in reaction and formed, moisture in propylene oxide and phosphorus oxychloride reaction generate by product, this by product again with propylene oxide reaction, simultaneously moisture at a certain temperature also can directly and propylene oxide reaction, thus the existence of moisture reduces the yield of product on the one hand, add the foreign matter content in product simultaneously, comprise the content of TCPP ether, and the moisture of industrial-grade epoxy propane usually containing about 300PPM, the present invention is in order to solve the problem, before propylene oxide adds reaction, by adding dewatering agent or propylene oxide is flow through after the dehydration tower being filled with dewatering agent carries out deep dehydration to propylene oxide in propylene oxide, the water-content in propylene oxide is made to be less than 100PPM, obtained TCPP is carried out again with phosphorus oxychloride reaction, the TCPP ether content of this TCPP is less than 1000PPM, compared with the TCPP obtained with prior art, greatly reduce the TCPP ether content in product.
The realization of the object of the invention, is mainly realized by following process.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, it is characterized in that obtaining by through the propylene oxide of processed and phosphorus oxychloride reaction, after propylene oxide dehydration, water-content is less than 100PPM.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, is characterized in that comprising the steps:
1) lewis acid catalyst is dissolved in phosphorus oxychloride the phosphorus oxychloride solution be mixed with containing catalyzer;
2) dewatering agent is used to carry out processed to propylene oxide;
3) phosphorus oxychloride solution and the step 2 containing the catalyzer that step 1) are obtained) propylene oxide reaction that dewaters of the process that obtains synthesizes three-(2-chloro isopropyl) phosphoric acid ester crude products;
4) by three-(2-chloro isopropyl) obtained for step 3) phosphoric acid ester crude products successively through alkali cleaning, washing, vacuum hydro-extraction, refilter three-(2-chloro isopropyl) phosphoric acid ester of obtained low TCPP ether foreign matter content.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, is characterized in that the lewis acid catalyst described in step 1) comprises aluminum trichloride (anhydrous), Magnesium Chloride Anhydrous, titanium tetrachloride, tetrabutyl titanate or isopropyl titanate.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, is characterized in that the lewis acid catalyst described in step 1) is aluminum trichloride (anhydrous).
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, it is characterized in that step 2) described dewatering agent refers to that having chemical reaction to water molecules removes or physical adsorption removal effect, and does not react with propylene oxide or adsorbing material.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, is characterized in that step 2) described dewatering agent comprises anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous, 3A molecular sieve, aluminium sesquioxide or calcium oxide, is preferably calcium oxide.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, is characterized in that the water-content of the propylene oxide through dewatering agent process is less than 100PPM.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, it is characterized in that in step 3), temperature of reaction is 40-80 DEG C, phosphorus oxychloride is 1:1.13-1.25 with the charge weight ratio of propylene oxide, continues 40-80 DEG C and be incubated to reacting completely after adding material in proportion.
The preparation method of described one three-(2-chloro isopropyl) phosphoric acid ester, it is characterized in that three-(2-chloro isopropyl) phosphate ester product are made up of four kinds of isomer and TCPP ether, described four kinds of isomer comprise: three-(2-chloro isopropyl) phosphoric acid ester, two-(2-chloro isopropyl) (2-chloropropyl) phosphoric acid ester, two-(2-chloropropyl) (2-chloro isopropyl) phosphoric acid ester, three-(2-chloropropyl) phosphoric acid ester, in product, the content of TCPP ether is less than 1000PPM.
Below describe commercial process of the present invention in detail.
1) in the phosphorus oxychloride metering kettle being equipped with feeder for solid materials, band stirring, first pump into phosphorus oxychloride, then add lewis acid catalyst by feeder for solid materials, stir under normal temperature, dissolve the obtained phosphorus oxychloride containing catalyzer;
2) propylene oxide continued through the dehydration tower being filled with dewatering agent and collect in test tank, the water-content controlling test tank oxypropylene is less than 100PPM;
3) in reactor, adding the phosphorus oxychloride containing catalyzer and step 2 that step 1) obtains simultaneously) propylene oxide after dehydration reacts, whole process control temperature of reaction is in 40-80 DEG C, the charge weight of both control is than being phosphorus oxychloride: propylene oxide=1:1.13-1.25,40 DEG C-80 DEG C insulations are continued to reacting completely, obtain three-(2-chloro isopropyl) phosphoric acid ester crude products after adding material in proportion;
4) step 3) be obtained by reacting three-(2-chloro isopropyl) phosphoric acid ester crude products carry out alkali cleaning, washing, vacuum hydro-extraction, refilter three-(2-chloro isopropyl) phosphate ester product of obtained low TCPP ether foreign matter content.
Embodiment
By following embodiment, comparing embodiment, further illustrate the present invention, they should not be considered limiting the scope of the invention.
Analysis of the present invention and test method illustrate:
In TCPP, TCPP ether content measures: with vapor-phase chromatography (GC)
Determination of moisture in propylene oxide: karl Fischer moisture volumetry
Embodiment 1
Be with in the phosphorus oxychloride metering kettle stirred being equipped with the 5000L of feeder for solid materials and first pump into phosphorus oxychloride 4600 kilograms, 15 kilograms of Catalyzed by Anhydrous Aluminium Chloride agent are added again by feeder for solid materials, stir under normal temperature, dissolve obtained phosphorus oxychloride solution, propylene oxide is continued through the dehydration tower being filled with dewatering agent calcium oxide and to collect in 10000L test tank totally 5300 kilograms, the water-content of test tank oxypropylene is 28PPM after testing, add the phosphorus oxychloride solution containing catalyzer and the propylene oxide after dewatering in 10000L reactor simultaneously, reinforced process control temperature of reaction is at 65 DEG C, the feed rate of reinforced both process control, its weight ratio is made to be phosphorus oxychloride: propylene oxide=1:1.152, continue 65 DEG C of insulations after adding material in proportion to reacting completely simultaneously, completely reacted TCPP crude product is turned the washing kettle of 16000L, add the sodium hydroxide solution of 5000 kilogram of 1% concentration, under temperature 70 C, stir 1 hour, leave standstill, divide lixiviating layer, add the deionized water of 5000 kilograms again, under temperature 70 C, stir 1 hour, leave standstill, branch vibration layer, washed TCPP crude product is proceeded in dehydrating kettle, intensification vacuum hydro-extraction, finally filter to obtain product 9715 kilograms, yield is 98.1%, analyze through GC, TCPP ether content is: 226PPM.
Comparative example 1
Except the industrial-grade epoxy propane being 270PPM except directly using water-content, other operation repeats embodiment 1, and final product 9613 kilograms, yield is 97.1%.Analyze through GC, TCPP ether content is: 2760PPM.
Embodiment 2-5
Except the use propylene oxide that water-content is different after different dewatering agent dehydration, other operation repeats embodiment 1, and net result sees the following form:
Table 1. propylene oxide water-content is on the impact of product yield and TCPP ether content
As can be seen from the data of embodiments of the invention 1-5 and comparative example, after adopting method of the present invention, in the product obtained, TCPP ether obviously reduces, and product yield also improves simultaneously.
Claims (9)
1. a preparation method for three-(2-chloro isopropyl) phosphoric acid ester, it is characterized in that obtaining by through the propylene oxide of processed and phosphorus oxychloride reaction, propylene oxide is after dehydration, and water-content is less than 100PPM.
2. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 1, is characterized in that comprising the steps:
1) lewis acid catalyst is dissolved in phosphorus oxychloride the phosphorus oxychloride solution be mixed with containing catalyzer;
2) dewatering agent is used to carry out processed to propylene oxide;
3) phosphorus oxychloride solution and the step 2 containing the catalyzer that step 1) are obtained) propylene oxide reaction that dewaters of the process that obtains synthesizes three-(2-chloro isopropyl) phosphoric acid ester crude products;
4) by three-(2-chloro isopropyl) obtained for step 3) phosphoric acid ester crude products successively through alkali cleaning, washing, vacuum hydro-extraction, refilter three-(2-chloro isopropyl) phosphoric acid ester of obtained low TCPP ether foreign matter content.
3. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 2, is characterized in that the lewis acid catalyst described in step 1) comprises aluminum trichloride (anhydrous), Magnesium Chloride Anhydrous, titanium tetrachloride, tetrabutyl titanate or isopropyl titanate.
4. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 3, is characterized in that the lewis acid catalyst described in step 1) is aluminum trichloride (anhydrous).
5. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 2, it is characterized in that step 2) described dewatering agent refers to that having chemical reaction to water molecules removes or physical adsorption removal effect, and does not react with propylene oxide or adsorbing material.
6. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 2, it is characterized in that step 2) described dewatering agent comprises anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous, 3A molecular sieve, aluminium sesquioxide or calcium oxide, is preferably calcium oxide.
7. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 2, is characterized in that the water-content of the propylene oxide through dewatering agent process is less than 100PPM.
8. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 2, it is characterized in that in step 3), temperature of reaction is 40-80 DEG C, phosphorus oxychloride is 1:1.13-1.25 with the charge weight ratio of propylene oxide, continues 40-80 DEG C and be incubated to reacting completely after adding material in proportion.
9. the preparation method of a kind of three-(2-chloro isopropyl) phosphoric acid ester according to claim 2, it is characterized in that three-(2-chloro isopropyl) phosphate ester product are made up of four kinds of isomer and TCPP ether, described four kinds of isomer comprise: three-(2-chloro isopropyl) phosphoric acid ester, two-(2-chloro isopropyl) (2-chloropropyl) phosphoric acid ester, two-(2-chloropropyl) (2-chloro isopropyl) phosphoric acid ester, three-(2-chloropropyl) phosphoric acid ester, in product, the content of TCPP ether is less than 1000PPM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510517020.0A CN105085568B (en) | 2015-08-21 | 2015-08-21 | A kind of preparation method of three (2 chloro isopropyl) phosphate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510517020.0A CN105085568B (en) | 2015-08-21 | 2015-08-21 | A kind of preparation method of three (2 chloro isopropyl) phosphate ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085568A true CN105085568A (en) | 2015-11-25 |
| CN105085568B CN105085568B (en) | 2017-03-08 |
Family
ID=54566978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510517020.0A Active CN105085568B (en) | 2015-08-21 | 2015-08-21 | A kind of preparation method of three (2 chloro isopropyl) phosphate ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085568B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674356A (en) * | 2016-11-28 | 2017-05-17 | 宣城市聚源精细化工有限公司 | Preparation method of fire retardants containing fiber-based phosphatidic acid |
| CN108864178A (en) * | 2018-07-19 | 2018-11-23 | 山东默锐科技有限公司 | A kind of synthesis tricresyl phosphate（2- chloropropyl）The micro- reaction method and device of ester |
| CN109912644A (en) * | 2019-04-09 | 2019-06-21 | 浙江万盛股份有限公司 | A kind of post-processing purifying technique of TCPP production crude product |
| CN110028644A (en) * | 2019-04-22 | 2019-07-19 | 烟台市顺达聚氨酯有限责任公司 | The high flame-retardant polyurethane spray foam and its method of TCPP crude product preparation |
| CN110054646A (en) * | 2019-05-15 | 2019-07-26 | 浙江万盛股份有限公司 | A kind of preparation method of green syt phosphate |
| CN110256483A (en) * | 2019-05-24 | 2019-09-20 | 佳化化学科技发展（上海）有限公司 | A kind of preparation process of phosphate flame retardant |
| CN111153934A (en) * | 2020-01-10 | 2020-05-15 | 江苏雅克科技股份有限公司 | Method for synthesizing tri- (2-chloroisopropyl) phosphate by solid catalysis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100220A (en) * | 1961-09-06 | 1963-08-06 | Celanese Corp | Improvement in process for making haloaliphatic phosphate esters |
| EP0398095A2 (en) * | 1989-05-19 | 1990-11-22 | Bayer Ag | Process for preparing tris (2-chloro isopropyl) ester of phosphoric acid |
| CN101235050A (en) * | 2007-02-02 | 2008-08-06 | 朗盛德国有限责任公司 | Production of propoxylated products containing phosphorous through use of aluminium trichloride |
| CN102887917A (en) * | 2011-10-14 | 2013-01-23 | 江苏大明科技有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN103408584A (en) * | 2013-07-30 | 2013-11-27 | 浙江万盛股份有限公司 | Preparation method for 3-(2-isopropyl chloride) phosphate ester fire-retardant with high resistance to hydrolysis |
-
2015
- 2015-08-21 CN CN201510517020.0A patent/CN105085568B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100220A (en) * | 1961-09-06 | 1963-08-06 | Celanese Corp | Improvement in process for making haloaliphatic phosphate esters |
| EP0398095A2 (en) * | 1989-05-19 | 1990-11-22 | Bayer Ag | Process for preparing tris (2-chloro isopropyl) ester of phosphoric acid |
| CN101235050A (en) * | 2007-02-02 | 2008-08-06 | 朗盛德国有限责任公司 | Production of propoxylated products containing phosphorous through use of aluminium trichloride |
| CN102887917A (en) * | 2011-10-14 | 2013-01-23 | 江苏大明科技有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN103408584A (en) * | 2013-07-30 | 2013-11-27 | 浙江万盛股份有限公司 | Preparation method for 3-(2-isopropyl chloride) phosphate ester fire-retardant with high resistance to hydrolysis |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674356A (en) * | 2016-11-28 | 2017-05-17 | 宣城市聚源精细化工有限公司 | Preparation method of fire retardants containing fiber-based phosphatidic acid |
| CN108864178A (en) * | 2018-07-19 | 2018-11-23 | 山东默锐科技有限公司 | A kind of synthesis tricresyl phosphate（2- chloropropyl）The micro- reaction method and device of ester |
| CN108864178B (en) * | 2018-07-19 | 2020-10-09 | 山东默锐科技有限公司 | Micro-reaction method and device for synthesizing tris (2-chloropropyl) phosphate |
| CN109912644A (en) * | 2019-04-09 | 2019-06-21 | 浙江万盛股份有限公司 | A kind of post-processing purifying technique of TCPP production crude product |
| CN109912644B (en) * | 2019-04-09 | 2021-08-03 | 浙江万盛股份有限公司 | Post-treatment purification process for TCPP (trichloropropylphosphate) production crude product |
| CN110028644A (en) * | 2019-04-22 | 2019-07-19 | 烟台市顺达聚氨酯有限责任公司 | The high flame-retardant polyurethane spray foam and its method of TCPP crude product preparation |
| CN110028644B (en) * | 2019-04-22 | 2021-03-19 | 烟台市顺达聚氨酯有限责任公司 | High-flame-retardant polyurethane spraying foam prepared from TCPP (trichloropropylphosphate) crude product and method thereof |
| CN110054646A (en) * | 2019-05-15 | 2019-07-26 | 浙江万盛股份有限公司 | A kind of preparation method of green syt phosphate |
| CN110054646B (en) * | 2019-05-15 | 2021-07-23 | 浙江万盛股份有限公司 | Preparation method of synthetic phosphate |
| CN110256483A (en) * | 2019-05-24 | 2019-09-20 | 佳化化学科技发展（上海）有限公司 | A kind of preparation process of phosphate flame retardant |
| CN111153934A (en) * | 2020-01-10 | 2020-05-15 | 江苏雅克科技股份有限公司 | Method for synthesizing tri- (2-chloroisopropyl) phosphate by solid catalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105085568B (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105085568A (en) | Preparation method of tri(2-chloroisopropyl)phosphate (TCPP) | |
| US10532990B2 (en) | Methods for converting cellulose to furanic products | |
| Tzeng et al. | Understanding the production of 5-hydroxymethylfurfural (HMF) from chitosan using solid acids | |
| EP3317359B1 (en) | A method for increasing the reactivity of lignin, a resin composition comprising said lignin and use of said resin composition | |
| CN102040732B (en) | Preparation method of polyether polyol cross-coupling agent | |
| CN112871191B (en) | Preparation method of magnetic phosphotungstic acid/attapulgite solid acid catalyst and application method thereof in lignocellulose liquefaction | |
| Peng et al. | Effect of metal salts existence during the acid-catalyzed conversion of glucose in methanol medium | |
| CN103408584B (en) | Preparation method for 3-(2-isopropyl chloride) phosphate ester fire-retardant with high resistance to hydrolysis | |
| CN105348351B (en) | The method for preparing 5ST | |
| CN107629086B (en) | A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants | |
| CN105392794B (en) | Method for producing the product containing fructoside | |
| CN104892418A (en) | Synthesis method of citric acid tributyl citrate | |
| CN108543525A (en) | The preparation method of the absorption resin of Phenol-Containing Wastewater Treatment | |
| KR101323631B1 (en) | A method to dehydrate polyols | |
| CN107673968A (en) | A kind of ionic liquid is directly catalyzed the method that agriculture and forestry organic waste material prepares levulinate | |
| EP2736614B1 (en) | Method of removing alkylene halogenohydrin from cellulose ether | |
| WO2000024700A1 (en) | PROCESS FOR THE MANUFACTURE OF α,α-BRANCHED CARBOXYLIC ACIDS | |
| KR101615963B1 (en) | Method for preparation of anhydrosugar alcohols by using a screw-type continuous reactor | |
| KR20140114439A (en) | Low-chloride lipf6 | |
| CN108929435A (en) | The synthetic method of the polyoxyethylene sorbitan monoleate of oligomeric D-sorbite content | |
| CN102850303A (en) | New application and using method of mesoporous solid acid catalyst | |
| CN103709039B (en) | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite | |
| WO2018038103A1 (en) | Process for producing sugar fatty acid ester using anion exchanger as catalyst | |
| CN104557807A (en) | Production process of 5-hydroxymethyl furfural | |
| CN115043871A (en) | Preparation method of hydrolysis-resistant TCPP flame retardant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |