CN110511239B - Production method of tris (1, 3-dichloropropyl) phosphonate - Google Patents
Production method of tris (1, 3-dichloropropyl) phosphonate Download PDFInfo
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- CN110511239B CN110511239B CN201910905140.6A CN201910905140A CN110511239B CN 110511239 B CN110511239 B CN 110511239B CN 201910905140 A CN201910905140 A CN 201910905140A CN 110511239 B CN110511239 B CN 110511239B
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- 239000007983 Tris buffer Substances 0.000 title claims abstract description 22
- OOKDJDMLPGZAMP-UHFFFAOYSA-N OP(=O)OC(Cl)CCCl Chemical compound OP(=O)OC(Cl)CCCl OOKDJDMLPGZAMP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 25
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000003930 superacid Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 18
- HXDMGFFCTHRNDE-UHFFFAOYSA-N OP(OC(CCl)CCl)=O Chemical compound OP(OC(CCl)CCl)=O HXDMGFFCTHRNDE-UHFFFAOYSA-N 0.000 claims description 8
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 7
- -1 1, 3-dichloro-2-propyl Chemical group 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 3
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a production method of tris (1, 3-dichloropropyl) phosphonate, which comprises the steps of continuously introducing phosphorus oxychloride, 1, 3-dichloropropanol and phosphorus oxychloride into a 1-3-stage filler reaction tower for catalytic esterification, carrying out alkali washing, water washing and distillation on an esterification product generated by the reaction to obtain tris (1, 3-dichloropropyl) phosphonate, and introducing hydrogen chloride gas generated by the reaction into a negative pressure absorption device through a gas discharge hole in the top of the reaction tower. Wherein, the filling material of each stage of reaction tower is any one of catalyst solid super acid or strong acid cation resin, and the filling material in the reaction tower is soaked in the raw material 1, 3-dichloropropanol before reaction. The method utilizes the catalyst as the filler of the esterification reaction tower, improves the esterification rate by controlling the reaction temperature of each stage of reaction tower to rise step by step, has high catalyst utilization rate and long cycle life, and can ensure that the product yield can reach more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a production method of tris (1, 3-dichloro-2-propyl) phosphonate.
Background
The phosphonic acid tri (1, 3-dichloro-2-propyl) ester is an additive type general chlorine-containing phosphorus-containing flame retardant, has flame retardant, plasticizing, damp-proof, static interference, tensile resistance and compression resistance, and halogen atoms generated by decomposition at high temperature have the function of trapping active free radicals in combustion so as to enable high-activity hydroxyl or hydrogen atoms to generate water or hydrogen, thereby interrupting chain oxidation reaction. And the thermal decomposition of the phosphonic acid tris (1, 3-dichloro-2-propyl) ester can be converted into the glassy polyvinylidene phosphate, a solid coke layer is formed on the surface of the material, and the air and the heat are isolated to prevent combustion. On the other hand, the phosphorus-halogen synergistic effect also effectively improves the flame retardant property of the phosphonic acid tris (1, 3-dichloro-2-propyl) ester, phosphorus halide and phosphorus oxide halide generated by thermal decomposition are good radical terminators, the boiling point is high, the specific gravity is high, the residence time in a combustion zone is long, the reaction with radicals is easier, and meanwhile, a coating layer can be formed on the surface of the material to isolate oxygen and heat to prevent combustion. Therefore, tris (1, 3-dichloro-2-propyl) phosphonate is widely used as a good flame retardant and flame retardant plasticizer in unsaturated polyesters, rigid and flexible polyurethane foams, epoxy resins, phenolic resins, flexible polyvinyl chloride, and the like.
The application of tris (1, 3-dichloro-2-propyl) phosphonate in the flame retardant field is wide, a large number of documents are reported abroad, Stauffer chemical company in the United states and Daba chemical company in Japan have been produced for a long time, and in recent years, many scholars in China have studied the synthesis of tris (1, 3-dichloro-2-propyl) phosphonate, and Chinese patents with publication numbers of CN102863468A, CN107556338A and CN102807581B respectively introduce epichlorohydrin and phosphorus oxychloride as raw materials and TiCl 102807581B4、AlCl3Or a preparation method using Lewis acid as a catalyst. Such preparation methods have serious disadvantages: firstly, the catalyst is unstable, extremely easy to decompose in the air, difficult to separate after reaction, unable to be recycled, and pollutes the environment; secondly, the epichlorohydrin is a product of cyclization of 1, 3-dichloro-2-propanol, is volatile, unstable, has a potential carcinogenic effect, is inflammable, and the steam and air thereof are easy to form an explosive mixture, and the reaction of the epichlorohydrin and phosphorus oxychloride is an exothermic reaction, so that the epichlorohydrin has a high requirement on temperature, is easy to accumulate when the temperature is low, and is easy to react instantly after reaching a certain amount to cause an explosive boiling phenomenon, and the epichlorohydrin is easy to undergo a self-polymerization reaction, so that the product has high chroma, more byproducts and low utilization rate of raw materials. Thirdly, the epoxy chloropropane is dripped, and the operation is complex.
Disclosure of Invention
In order to solve the problems, the invention provides a production method for synthesizing tris (1, 3-dichloro-2-propyl) phosphonate by catalyzing the reaction of phosphorus oxychloride and 1, 3-dichloro-2-propanol by using a catalyst as a filler of an esterification reaction tower. Because the process of generating phosphonic acid tri-substituted ester by reacting phosphorus oxychloride with 1, 3-dichloro-2-propanol belongs to a step-by-step substitution esterification reaction mechanism, the speed and the temperature of each step of substitution esterification reaction have a direct relation from the viewpoints of reaction kinetics and thermodynamics, and the reaction temperature rises along with the increase of the substitution steps. Therefore, the method improves the esterification rate by controlling the reaction temperature of each stage of reaction tower to rise step by step, realizes high utilization rate of the catalyst, long cycle life and stable product quality, and the yield can reach more than 95 percent. The reaction mechanism involved in the present invention is as follows:
the purpose of the invention is realized by the following method:
a production method of phosphonic acid tris (1, 3-dichloro-2-propyl) ester comprises the following specific scheme: the method comprises the steps of continuously introducing phosphorus oxychloride and 1, 3-dichloropropanol which are reaction materials into a 1-3-level filler reaction tower according to a certain material mass ratio for catalytic esterification, carrying out alkali washing, water washing and distillation on an esterification product crude product generated by the reaction to obtain yellowish tris (1, 3-dichloropropyl) phosphonate, and allowing hydrogen chloride gas generated by the reaction to enter a negative pressure absorption device through a gas discharge port at the top of the reaction tower.
Wherein the mass ratio of the phosphorus oxychloride to the 1, 3-dichloropropanol of the reaction material can be mPhosphorus oxychloride：mDichloropropanol=1:（2.5~7.5）。
Preferably, the mass ratio of the phosphorus oxychloride to the 1, 3-dichloropropanol is mPhosphorus oxychloride：mDichloropropanol=1:（3~5）。
Wherein, the filler in the 1 to 3 stages of reaction towers is a catalyst for esterification reaction, and the raw material 1, 3-dichloropropanol needs to be soaked and activated in the initial stage of the reaction.
Wherein, the catalyst can be any one of composite solid super acid or sulfonic acid type cation resin.
Wherein the reaction temperature in the 1 to 3-stage reaction tower is controlled within the range of 110 to 120 ℃, 120 to 130 ℃ and 130 to 140 ℃ respectively.
Preferably, the control ranges of the reaction temperatures of the 1-grade to 3-grade are 115-118 ℃, 126-130 ℃ and 135-138 ℃.
The invention has the beneficial effects that:
(1) the method adopts the catalyst as the filler of the esterification reaction tower, so that the utilization rate of the catalyst and equipment is effectively improved;
（2）by usingPhosphorus oxychloride and 1The process of 3-dichloro-2-propanol reaction to generate phosphonic acid trisubstituted ester belongs to a stepwise substitution esterification reaction mechanism, and the esterification reaction increases the reaction temperature along with the increase of the substitution stage number. The methodBy controlling the reaction towers at different stages The reaction temperature is gradually increased, the esterification rate is improved, the product quality is stabilized, and the energy consumption is reduced;
(3) the method realizes high utilization rate of the catalyst, long cycle life and high product yield of over 90 percent, is simple and easy to operate, is easy to realize product continuity, is safe and environment-friendly, and is beneficial to industrial production.
Detailed Description
The production method of the present invention will be further described with reference to examples, but the following description is only for the purpose of explaining the present invention and does not limit the contents thereof.
Example 1
Respectively adding 307Kg of phosphorus oxychloride and 1228Kg of 1, 3-dichloropropanol into a material dropwise adding tank, setting the flow rate of the phosphorus oxychloride to be 150Kg/h and the flow rate of the 1, 3-dichloropropanol to be 605Kg/h, continuously adding the phosphorus oxychloride and the 1, 3-dichloropropanol into a 1-to 3-stage filler reaction tower at a constant speed, wherein the filler in each reaction tower is a mixed system of dichloropropanol and a sulfonic acid type cationic resin catalyst, wherein: the reaction temperature of the 1-stage reaction tower body is 115 ℃, the reaction temperature of the 2-stage reaction tower body is 128 ℃, and the reaction temperature of the 3-stage reaction tower body is 138 ℃. The total time from the material to the material from the bottom of the 1-stage reaction tower to the material from the bottom of the 3 rd-stage reaction tower is 4.5 hours, the esterification product crude product generated by the reaction is subjected to alkali washing, water washing and distillation to obtain the faint yellow tris (1, 3-dichloropropyl) phosphonate, the hydrogen chloride gas generated by the reaction enters a negative pressure absorption device through a gas discharge port at the top of the reaction tower, and the product yield is 95.07 percent based on the input amount of phosphorus oxychloride.
Example 2
Respectively adding 307Kg of phosphorus oxychloride and 1228Kg of 1, 3-dichloropropanol into a material dropwise adding tank, setting the flow rate of the phosphorus oxychloride to be 75Kg/h and the flow rate of the 1, 3-dichloropropanol to be 300Kg/h, continuously adding the phosphorus oxychloride and the 1, 3-dichloropropanol into a 1-to 3-stage filler reaction tower at a constant speed, wherein the filler in each reaction tower is a mixed system of dichloropropanol and a sulfonic acid type cationic resin catalyst, wherein: the reaction temperature of the 1-stage reaction tower body is 118 ℃, the reaction temperature of the 2-stage reaction tower body is 125 ℃, and the reaction temperature of the 3-stage reaction tower body is 135 ℃. The total discharge time from the material to the bottom of the 3 rd-level reaction tower is 6 hours, the esterification product crude product generated by the reaction is subjected to alkali washing, water washing and distillation to obtain the faint yellow tris (1, 3-dichloropropyl) phosphonate, the hydrogen chloride gas generated by the reaction enters a negative pressure absorption device through a gas discharge hole at the top of the reaction tower, and the product yield is 96.78 percent based on the input amount of phosphorus oxychloride.
Example 3
307Kg of phosphorus oxychloride and 921Kg of 1, 3-dichloropropanol are respectively put into a material dropwise adding tank, the flow rate of the phosphorus oxychloride is set to be 150Kg/h, the flow rate of the 1, 3-dichloropropanol is set to be 450Kg/h, and the phosphorus oxychloride is continuously put into a 1-level to 3-level filler reaction tower at a constant speed, other operation and process conditions are the same as those of the example 1 to obtain the yellowish tris (1, 3-dichloropropyl) phosphonate, and the product yield is 91.39% based on the input amount of the phosphorus oxychloride.
Comparative example 1
As in example 2: respectively adding 307Kg of phosphorus oxychloride and 1228Kg of 1, 3-dichloropropanol into a material dropwise adding tank, setting the flow rate of the phosphorus oxychloride to be 75Kg/h and the flow rate of the 1, 3-dichloropropanol to be 300Kg/h, continuously adding the phosphorus oxychloride and the 1, 3-dichloropropanol into a 1-to 3-stage filler reaction tower at a constant speed, wherein the filler in each reaction tower is a mixed system of dichloropropanol and a sulfonic acid type cationic resin catalyst, wherein: the temperature of the materials in the 1-3-stage reaction tower body is 138 ℃, the total time from the entry of all the materials into the 1-stage reaction tower to the discharge of all the materials from the bottom of the 3-stage reaction tower is 6 hours, the red-brown tris (1, 3-dichloropropyl) phosphonate is obtained by performing alkaline washing, water washing and distillation on the crude esterification product generated by the reaction, the hydrogen chloride gas generated by the reaction enters a negative pressure absorption device through a gas discharge port at the top of the reaction tower, and the product yield is 87.03% by the dosage of phosphorus oxychloride. (too high temperature throughout the process causes partial product carbonization, resulting in too high a material color).
Comparative example 2
As in example 2: respectively adding 307Kg of phosphorus oxychloride and 1228Kg of 1, 3-dichloropropanol into a material dropwise adding tank, setting the flow rate of the phosphorus oxychloride to be 75Kg/h and the flow rate of the 1, 3-dichloropropanol to be 300Kg/h, continuously adding the phosphorus oxychloride and the 1, 3-dichloropropanol into a 1-to 3-stage filler reaction tower at a constant speed, wherein the filler in each reaction tower is a mixed system of dichloropropanol and a sulfonic acid type cationic resin catalyst, wherein: the temperature of the materials in the 1-3-stage reaction tower body is 118 ℃, the total time from the entry of all the materials into the 1-stage reaction tower to the discharge of all the materials from the bottom of the 3-stage reaction tower is 6 hours, the esterification product crude product generated by the reaction is subjected to alkali washing, water washing and distillation to obtain the faint yellow tris (1, 3-dichloropropyl) phosphonate, the hydrogen chloride gas generated by the reaction enters a negative pressure absorption device through a gas discharge hole in the top of the reaction tower, and the product yield is 67.44% based on the input amount of phosphorus oxychloride. (higher content of mono-substituted ester).
Claims (4)
1. A method for producing tris (1, 3-dichloro-2-propyl) phosphonate is characterized by comprising the following specific operations: phosphorus oxychloride and 1, 3-dichloropropanol are continuously introduced into a grade-1 filler reaction tower according to a certain material mass ratio, an esterification product crude product is generated through a catalytic esterification reaction of the grade-1 to grade-3 filler reaction tower, the crude product is subjected to alkali washing, water washing and distillation to obtain tris (1, 3-dichloropropyl) phosphonate, and hydrogen chloride gas generated by the reaction enters a negative pressure absorption device through a gas discharge port at the top of the reaction tower;
the mass ratio of the phosphorus oxychloride to the 1, 3-dichloropropanol can be m phosphorus oxychloride: m dichloropropanol =1: 2.5-7.5;
the reaction temperature in the 1-3 stages of reaction towers is 110-120 ℃, 120-130 ℃ and 130-140 ℃ respectively.
2. The method for producing tris (1, 3-dichloro-2-propyl) phosphonate according to claim 1, wherein the packing in the reaction column from stage 1 to stage 3 is a catalyst for esterification.
3. The method of claim 2, wherein the catalyst is selected from the group consisting of a composite solid super acid and a sulfonic acid type cationic resin.
4. The method for producing tris (1, 3-dichloro-2-propyl) phosphonate according to any one of claims 2 or 3, wherein the packing material in the reaction column is activated by immersion in the starting material 1, 3-dichloropropanol at the initial stage of the reaction.
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| CN201910905140.6A CN110511239B (en) | 2019-09-24 | 2019-09-24 | Production method of tris (1, 3-dichloropropyl) phosphonate |
| PCT/CN2020/102469 WO2021057207A1 (en) | 2019-09-24 | 2020-07-16 | Method for producing tris(1,3-dichloropropyl)phosphate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366122A (en) * | 2016-08-24 | 2017-02-01 | 浙江万盛股份有限公司 | Continuous preparation method of tri(2,3-dichloropropyl)phosphate |
| CN108997416A (en) * | 2018-08-28 | 2018-12-14 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (the chloro- 2- propyl of 1,3- bis-) ester |
| CN109438506A (en) * | 2018-12-06 | 2019-03-08 | 山东泰和水处理科技股份有限公司 | A method of preparing tricresyl phosphate (bis- chloropropyl of 1,3-) ester |
| CN210252272U (en) * | 2019-06-24 | 2020-04-07 | 山东泰和水处理科技股份有限公司 | Production device of phosphonic acid tris (1, 3-dichloropropyl) ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106366122A (en) * | 2016-08-24 | 2017-02-01 | 浙江万盛股份有限公司 | Continuous preparation method of tri(2,3-dichloropropyl)phosphate |
| CN108997416A (en) * | 2018-08-28 | 2018-12-14 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of phosphonic acids three (the chloro- 2- propyl of 1,3- bis-) ester |
| CN109438506A (en) * | 2018-12-06 | 2019-03-08 | 山东泰和水处理科技股份有限公司 | A method of preparing tricresyl phosphate (bis- chloropropyl of 1,3-) ester |
| CN210252272U (en) * | 2019-06-24 | 2020-04-07 | 山东泰和水处理科技股份有限公司 | Production device of phosphonic acid tris (1, 3-dichloropropyl) ester |
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| CN110511239A (en) | 2019-11-29 |
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