CN116082400A - Synthesis method of efficient phosphite antioxidant pentaerythritol distearyl diphosphate - Google Patents
Synthesis method of efficient phosphite antioxidant pentaerythritol distearyl diphosphate Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 30
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- QAYPAJMIHQWDNR-UHFFFAOYSA-N [hydroxy-[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]phosphoryl] dioctadecyl phosphate Chemical compound O(P(OCCCCCCCCCCCCCCCCCC)(=O)OP(=O)(O)OCC(CO)(CO)CO)CCCCCCCCCCCCCCCCCC QAYPAJMIHQWDNR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 47
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 42
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims abstract description 40
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 26
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 23
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- 239000002904 solvent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
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- 230000002829 reductive effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- -1 pentaerythritol distearyl phosphate Chemical compound 0.000 abstract description 17
- 125000003003 spiro group Chemical group 0.000 abstract description 7
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- NPXUKNQBFIIIDW-UHFFFAOYSA-N dichlorophosphinite Chemical compound [O-]P(Cl)Cl NPXUKNQBFIIIDW-UHFFFAOYSA-N 0.000 abstract 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 11
- 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 8
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- 239000004033 plastic Substances 0.000 description 5
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- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- TYCLKLCKLGCVEZ-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C TYCLKLCKLGCVEZ-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- VMNKHSPZIGIPLL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OCC(CO)(CO)COP(O)O VMNKHSPZIGIPLL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 229940079593 drug Drugs 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
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- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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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)
Abstract
The invention discloses a method for synthesizing high-efficiency phosphite antioxidant pentaerythritol distearyl phosphate, which comprises the steps of adding pentaerythritol serving as a raw material, triethylamine serving as a catalyst and a reaction solvent into a reactor, dropwise adding phosphorus trichloride serving as the raw material, reacting at a reaction temperature, and continuously removing hydrogen chloride gas generated by the reaction to the outside of a system in the reaction process; after the first step of reaction is finished, stearyl alcohol and an acid binding agent are added into the system to carry out the second step of reaction, and after the reaction is finished, the finished product of the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate is obtained. The invention provides a one-pot method new process for synthesizing pentaerythritol distearyl diphosphate, which comprises the steps of firstly adding phosphorus trichloride and pentaerythritol to synthesize spiro dichlorophosphite, then adding stearyl alcohol, and obtaining the pentaerythritol distearyl diphosphate with high yield, high purity and high stability by using a proper acid binding agent and matching and setting the optimal process conditions.
Description
Technical Field
The invention relates to a method for synthesizing high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate.
Background
Substances which retard or prevent oxidation or autoxidation processes are known as antioxidants, which are chemical substances which, when present in small amounts in a polymer system, retard or inhibit the progress of the oxidation process of the polymer and retard the deterioration of materials, articles and articles during storage and use, and are therefore also known as "antioxidants". Generally, the amount of the catalyst is small, and most of the catalyst is a substance with reducing property. The general requirement for the antioxidant is that the dosage is small, the efficiency is high, the price is low, and no adverse effect exists.
Phosphite antioxidants have the advantages of decomposing polymer peroxide compounds and preventing the polymer peroxide compounds from being decomposed to induce the polymer to be degraded by thermal oxygen, are also called as peroxide decomposers, and are usually matched with main antioxidants for use, so that the phosphite antioxidants have good synergistic effect. Thereby remarkably improving the high-temperature processing stability of the polymer, inhibiting the change of the color and the melt index of the polymer during processing and improving the color and the melt index stability of the plastic product. At present, in the markets at home and abroad, the representative variety of the general phosphite antioxidant with larger usage amount is antioxidant 168, which is an aryl phosphite structure.
Compared with the general phosphite antioxidant, the antioxidant 626, the antioxidant 9228 and the antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate which are representative high-performance aryl phosphite antioxidants containing spiro rings, has a unique structure of the spiro rings and higher antioxidant activity, and can be widely applied to middle-high end formulas of general plastics and engineering plastics with harsh processing conditions. The antioxidant 618 is a representative spiro-ring-containing high-performance alkyl phosphite antioxidant, and long-chain alkyl imparts good compatibility with polyolefin and other materials, and is mainly applied to medium-high end formulas of polyethylene, polypropylene, polystyrene, polyvinyl chloride and other general-purpose plastics. The above high-efficiency antioxidants are getting more and more demands and attention with the trend of replacing steel with plastic and the rapid development of plastic composite materials.
Three typical high-efficiency aryl phosphite antioxidants with spiro unique structures
Typical high-efficiency alkyl phosphite antioxidant with spiro unique structure
There are two technological routes for the synthesis of antioxidant distearyl pentaerythritol diphosphite in literature or patents: one is the transesterification process and the other is the phosphorus trichloride process.
The transesterification process has two main types: (1) Synthesizing distearyl pentaerythritol diphosphite by taking triphenyl phosphite, pentaerythritol and stearyl alcohol as raw materials; (2) The method is characterized in that the distearyl pentaerythritol diphosphite is synthesized by taking triethyl phosphite, pentaerythritol and stearyl alcohol as raw materials. Phosphorus trichloride method: the distearyl pentaerythritol diphosphite is synthesized by taking phosphorus trichloride, pentaerythritol and stearyl alcohol as raw materials.
The traditional process for producing the antioxidant 618 takes triphenyl phosphite, pentaerythritol and stearyl alcohol as raw materials, a catalyst is added, and a target product is synthesized by one-step transesterification. For example, US patent 4064100 discloses that distearyl pentaerythritol diphosphite is obtained by transesterification using triphenyl phosphite, pentaerythritol, and stearyl alcohol as raw materials and sodium methoxide as a catalyst. Yin Zhenyan et al report a solvent-free transesterification one-step process for the preparation of distearyl pentaerythritol diphosphite. The diphenyl phosphate, the stearyl alcohol and the pentaerythritol are used as raw materials, and the organotin is used as a catalyst to synthesize distearyl pentaerythritol diphosphite, so that the product yield reaches more than 98 percent.
However, the method for preparing distearyl pentaerythritol diphosphite by taking triphenyl phosphite, pentaerythritol and stearyl alcohol as raw materials uses sodium methoxide as a catalyst, so that the method has the advantages of poor effect, large consumption, high reaction temperature and long reaction time, aromatic hydrocarbon solvent is required to be added in the reaction process, and equipment investment is increased due to solvent recovery; the potassium carbonate or the organic tin is used as a catalyst, trace phenol in the product cannot be removed, and the product is easy to turn yellow, so that the application of the catalyst in the fields of foods and medicines is limited.
The method is characterized in that the distearyl pentaerythritol diphosphite is synthesized by taking triethyl phosphite, pentaerythritol and stearyl alcohol as raw materials. The method does not need to add organic solvents such as toluene, and the like, does not generate phenol in the product, and is a nontoxic, efficient and environment-friendly method. Both patent CN1765908A and patent CN111620905A report this method, and the product yield can reach more than 98%. However, the reaction temperature of the process is too high, the reaction can be carried out under a very low vacuum degree, the conditions are severe, the process is difficult to thoroughly carry out, a single product is difficult to generate, other byproducts appear, the separation and purification are difficult to carry out, the purity of the final product is not high, the reported yield of the prior patent is very high, but no reasonable 31P-NMR spectrum is proved. Product P of distearyl pentaerythritol diphosphite synthesized by using commercially available triethyl phosphite method 31 The (CDCl 3) spectrum is shown in FIG. 3, which is a mixture.
The phosphorus trichloride process is to synthesize distearyl pentaerythritol diphosphite with phosphorus trichloride, pentaerythritol and stearyl alcohol as material in two steps. The domestic patent CN101182330 discloses a process for preparing distearyl pentaerythritol diphosphite by a phosphorus trichloride two-step method, wherein the first step is to react phosphorus trichloride with substituted phenol or alkanol substances to generate an intermediate, and the second step is to react the generated intermediate with pentaerythritol to generate a final product. The process reports that the product yield is more than 95%, no byproducts are generated, but no reasonable spectrogram can be proved, and in addition, the second-step reaction is too long (more than 4 hours) under the heating condition, so that the energy consumption is not beneficial to saving.
In summary, for various existing synthesis processes of distearyl pentaerythritol diphosphite, the transesterification process has the defects of harsh reaction conditions, more byproducts, complex post-treatment process and low product purity. The different feeding sequences of the phosphorus trichloride process have great influence on the reaction temperature and time of the product, so that the product has low purity and poor stability.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a novel synthesis method for industrial production of the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate, which is favorable for providing an industrial product of the pentaerythritol distearyl diphosphate with high purity and good precipitation resistance.
The invention provides a simple and efficient synthesis method, which uses pentaerythritol, phosphorus trichloride and stearyl alcohol as raw materials, wherein in the first step of the reaction, fatty tertiary amine such as triethylamine is used as a catalyst to be matched with toluene as a reaction solvent, and in the second step, fatty tertiary amine such as triethylamine is used as an acid binding agent to be matched with toluene as the reaction solvent, so that a mixture of efficient novel phosphite compounds with spiro structures is synthesized by a one-pot method with high efficiency and high yield. The reaction equation is shown below:
the high-efficiency and high-yield one-pot synthesis method of the invention
The invention relates to a method for synthesizing high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate, which specifically comprises the following steps:
1) Adding pentaerythritol as a raw material, triethylamine as a catalyst and a reaction solvent into a reactor, dropwise adding phosphorus trichloride as a raw material, and reacting at a reaction temperature, wherein hydrogen chloride gas generated by the reaction is continuously removed out of the system in the reaction process;
2) After the reaction of the step 1), adding stearyl alcohol and an acid binding agent into the system to perform a second-step reaction, and performing post-treatment after the reaction is finished to obtain the finished product of the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate.
Further, in the step 1), the feeding mass ratio of the pentaerythritol to the triethylamine catalyst is 100-150:1, preferably 130-135:1.
Further, in the step 1), the feeding mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1-4, preferably 1:1.5-2.5.
Further, in the step 1), the reaction solvent is toluene, and the feeding mass ratio of the pentaerythritol raw material to the reaction solvent is 1:3-6, preferably 1:4-5.
Further, the reaction pressure in the step 1) is normal pressure, the reaction temperature is 60-80 ℃, preferably 70 ℃, and the reaction time in the step 1) is 2-4 hours, preferably 3 hours.
Further, the mass ratio of the stearyl alcohol in the step 2) to the pentaerythritol in the step 1) is 3-5:1, preferably 4:1.
Further, the step 2) is to use triethylamine as the acid-binding agent, and the feeding mass ratio of the triethylamine acid-binding agent to the stearyl alcohol is 1:2-3, preferably 1:2.5-2.6.
Further, the reaction pressure in the step 2) is normal pressure, the reaction temperature is 70-90 ℃, the reaction rate can be improved, the triethylamine can be prevented from evaporating, and the reaction time in the step 2) is 40-80min, preferably 55-65min.
Further, the post-treatment step in step 2) is as follows: the reaction solution was filtered, and after adding celite to the filtrate and stirring, filtration was again performed, and then distillation was performed under reduced pressure so as to completely remove the solvent, that is, the treatment was completed.
The beneficial effects obtained by the invention are as follows:
the invention provides a method for synthesizing industrial products of pentaerythritol distearyl diphosphate with high purity and good precipitation resistance, and as a result, a novel one-pot process for synthesizing the pentaerythritol distearyl diphosphate is found, wherein phosphorus trichloride and pentaerythritol are firstly added to synthesize spiro bisphosphite, and then stearyl alcohol is directly added to synthesize the pentaerythritol distearyl diphosphate. The invention is completed by using proper acid binding agent and matching and setting the optimal process conditions to obtain the pentaerythritol distearyl diphosphate with high yield, high purity and high stability.
Drawings
FIG. 1 is a P of a novel phosphite compound obtained in example 1 of the present application 31 (CDCl 3 ) A spectrogram;
FIG. 2 is a FT-IR spectrum of a mixture of novel phosphite compounds obtained in example 1 of the present application;
FIG. 3 is a diagram showing the P of a distearyl pentaerythritol diphosphite synthesized by the triethyl phosphite process in the prior art 31 (CDCl 3 )。
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
A1000 ml flask having five ports was equipped with a stirrer, a nitrogen inlet pipe, a thermometer, a rectifying pipe and a cock (for sampling), and a moisture quantitative receiver and a cooling pipe were further installed at the front end of the rectifying pipe, and the above-mentioned apparatus was used as a reaction apparatus. Pentaerythritol (13.2 g) as a raw material, toluene (60 g) as a solvent, and triethylamine (0.1 g) as a catalyst were added to the flask, and phosphorus trichloride (28.8 g) as a raw material was added dropwise at normal pressure and a reaction temperature of 70 ℃. After the completion of the dropwise addition, the reaction temperature of the system was maintained at 70℃and the first-stage reaction was carried out while removing the hydrogen chloride formed outside the system. Ending the first step reaction when the content of the phosphorus trichloride in the raw material is less than 1% by HPLC analysisThe reaction time was 3 hours. A PTFE hose is used to introduce nitrogen below the liquid surface and stirring operation is performed to remove residual hydrogen chloride gas. Thereafter, stearyl alcohol (54.1 g) was added to the system, and triethylamine (21.0 g) as an acid-binding agent was added at normal pressure and a reaction temperature of 70 ℃. After the addition was completed, the system was gradually warmed to reflux (90 ℃ C.), and the second reaction was carried out. The second step reaction was terminated when less than 1% of the intermediate was analyzed by HPLC, and the reaction time was 1 hour. Then, filtration was carried out, diatomaceous earth (2 g) was added to the filtrate and stirred for 10 minutes, filtration was carried out again, and then distillation under reduced pressure was carried out so as to completely remove the solvent, thereby producing a novel phosphite compound represented by the above general formula (1) as a target compound in a yield of 95% and purity was measured using P 31 (CDCl 3 ) The nuclear magnetic method of (2) is determined to be 99.3 percent, and the purity is higher.
The identification of the novel phosphite compounds represented by the above general formula (1) was carried out using nuclear magnetism and infrared, and the identification results are shown below.
P of novel phosphite Compound represented by the above general formula (1) 31 (CDCl 3 ) The spectrum is shown in FIG. 1, and the chemical shifts of the novel phosphite ester compound represented by the general formula (1) as the main component are 124.78ppm, 124.83ppm, 124.89ppm, 124.95ppm and 125.02ppm, and the novel phosphite ester compound shows five-fold peaks; novel phosphite Compound C represented by general formula (1) as a main component 13 (CDCl 3 ) The chemical shifts of the spectra were 14.16ppm, 22.73ppm, 25.52ppm, 25.81ppm, 29.31ppm, 29.40ppm, 29.61ppm, 29.63ppm, 29.70ppm, 29.74ppm, 31.24ppm, 31.30ppm, 31.96ppm, 37.07ppm, 37.12ppm, 37.17ppm, 61.45ppm, 61.91ppm, 61.93ppm, 63.49ppm, 63.68ppm, 125.33ppm, 128.25ppm, 129.06ppm.
The FT-IR spectrum of the novel phosphite compound represented by the above general formula (1) is shown in FIG. 2.
Examples 2 to 5 and comparative examples 1 to 3:
the procedure of examples 2-5 and comparative examples 1-3 were repeated for example 1, except that "the temperature of the second step was adjusted, and the reaction time period for ending the second step reaction was changed when the intermediate was less than 1% by HPLC analysis", and the remaining procedure conditions were repeated for example 1. The second step temperatures, second step reaction durations, and corresponding product yields and purities of examples 2-5 and comparative examples 1-3 are summarized in Table 1.
TABLE 1 influence of reaction temperature on yield and purity of the synthesized product
As can be seen from table 1: the second step temperature of the one-pot reaction has obvious influence on the yield and purity of the product, and the product with high yield and high purity can be prepared by adapting the conditions.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (9)
1. The synthesis method of the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate is characterized by comprising the following steps of:
1) Adding pentaerythritol as a raw material, triethylamine as a catalyst and a reaction solvent into a reactor, dropwise adding phosphorus trichloride as a raw material, and reacting at a reaction temperature, wherein hydrogen chloride gas generated by the reaction is continuously removed out of the system in the reaction process;
2) After the reaction of the step 1), adding stearyl alcohol and an acid binding agent into the system to perform a second-step reaction, and performing post-treatment after the reaction is finished to obtain the finished product of the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate.
2. The method for synthesizing the efficient phosphite antioxidant pentaerythritol distearyl diphosphate according to claim 1, wherein in the step 1), the feeding mass ratio of the pentaerythritol to the triethylamine catalyst is 100-150:1, preferably 130-135:1.
3. The method for synthesizing the efficient phosphite antioxidant pentaerythritol distearyl diphosphate according to claim 1, wherein in the step 1), the feeding mass ratio of pentaerythritol to phosphorus trichloride is 1:1-4, preferably 1:1.5-2.5.
4. The method for synthesizing the efficient phosphite antioxidant pentaerythritol distearyl diphosphate according to claim 1, wherein in the step 1), the reaction solvent is toluene, and the mass ratio of the pentaerythritol raw material to the reaction solvent is 1:3-6, preferably 1:4-5.
5. The method for synthesizing the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate as claimed in claim 1, wherein the reaction pressure in the step 1) is normal pressure, the reaction temperature is 60-80 ℃, preferably 70 ℃, and the reaction time in the step 1) is 2-4 hours, preferably 3 hours.
6. The method for synthesizing the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate according to claim 1, wherein the mass ratio of stearyl alcohol in the step 2) to pentaerythritol in the step 1) is 3-5:1, preferably 4:1.
7. The method for synthesizing the efficient phosphite antioxidant pentaerythritol distearyl diphosphate as claimed in claim 1, wherein in the step 2), triethylamine is used as an acid-binding agent, and the feeding mass ratio of the triethylamine acid-binding agent to stearyl alcohol is 1:2-3, preferably 1:2.5-2.6.
8. The method for synthesizing the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate as claimed in claim 1, wherein the reaction pressure in the step 2) is normal pressure, the reaction temperature is 70-90 ℃, and the reaction time in the step 2) is 40-80min, preferably 55-65min.
9. The method for synthesizing the high-efficiency phosphite antioxidant pentaerythritol distearyl diphosphate, which is characterized in that the post-treatment step in the step 2) is as follows: the reaction solution was filtered, and after adding celite to the filtrate and stirring, filtration was again performed, and then distillation was performed under reduced pressure so as to completely remove the solvent, that is, the treatment was completed.
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