LU103177B1 - Method for synthesizing high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite - Google Patents
Method for synthesizing high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite Download PDFInfo
- Publication number
- LU103177B1 LU103177B1 LU103177A LU103177A LU103177B1 LU 103177 B1 LU103177 B1 LU 103177B1 LU 103177 A LU103177 A LU 103177A LU 103177 A LU103177 A LU 103177A LU 103177 B1 LU103177 B1 LU 103177B1
- Authority
- LU
- Luxembourg
- Prior art keywords
- reaction
- pentaerythritol diphosphite
- synthesizing
- phosphite antioxidant
- distearyl pentaerythritol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 42
- 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 title claims abstract description 40
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 36
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 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 38
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 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 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims 1
- -1 aryl phosphite Chemical compound 0.000 description 18
- 239000000126 substance Substances 0.000 description 10
- 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 10
- 125000003003 spiro group Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005580 one pot reaction Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material 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
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 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
- 238000010189 synthetic method Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HQTRGFZLVRBFPT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-octadecylhenicosane-1,3-diol Chemical compound CCCCCCCCCCCCCCCCCCC(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC HQTRGFZLVRBFPT-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound 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
- 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
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NPXUKNQBFIIIDW-UHFFFAOYSA-N dichlorophosphinite Chemical compound [O-]P(Cl)Cl NPXUKNQBFIIIDW-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- C07F9/547—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
Landscapes
- 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
Disclosed in the present invention is a method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite. According to the method, pentaerythritol serving as a raw material, triethylamine serving as a catalyst, and a reaction solvent are added into a reactor, phosphorus trichloride serving as a raw material is added dropwise, a reaction is performed at a reaction temperature, and hydrogen chloride gas generated by the reaction is continuously removed in a reaction process out of a system. After the first-step reaction is completed, octadecanol and an acid-binding agent are added to the system for a second-step reaction, and after the reaction is completed, post treatment is performed to obtain a finished product of the high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite.
Description
H109WO9LU-PCT23020 28.06.2023
METHOD FOR SYNTHESIZING HIGH-EFFICIENCY PHOSPHITE LU103177
ANTIOXIDANT OF DISTEARYL PENTAERYTHRITOL DIPHOSPHITE
[01] The present invention relates to a method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite.
[02] A substance capable of delaying or preventing an oxidation or automatic oxidation process is referred to as an antioxidant, which is a kind of chemical substance. The progress of a polymer oxidation process can be delayed or inhibited when only a small amount of the antioxidant exists in a polymer system, and deterioration of materials, articles and supplies during storage and use can be delayed, such that the antioxidant is also referred to as an anti-aging agent. Generally, a usage amount of the antioxidant is small, and most of antioxidants are substances with a reduction property. A small usage amount, high efficiency, a low price and no adverse consequences are general requirements on the antioxidant.
[03] Phosphite antioxidants have an effect of decomposing polymer peroxy compounds to prevent induction of thermo-oxidative degradation of polymers due to cracking of the polymer peroxy compounds, and are also referred to as peroxide decomposing agents, which are usually used in conjunction with a main antioxidant, and have a good synergistic effect, and therefore, high-temperature processing stability of the polymers can be remarkably improved, the color and melt index change during polymer processing can be inhibited, and the color and the melt index stability of plastic products can be improved. At present, on the market at home and abroad, a representative variety of general phosphite antioxidants with relatively large usage amounts is an antioxidant 168, which is an aryl phosphite structure.
[04] The antioxidant 626, the antioxidant 9228, and the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are representative high-performance aryl phosphite antioxidants containing spiro. Compared with the general 1
H109WO9LU-PCT23020 28.06.2023 phosphite antioxidants, the antioxidant 626, the antioxidant 9228, and the antioxidant of LU103177 bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are higher in antioxidant activity, and can be widely used in medium and high-end formulas of general plastics and engineering plastics with harsh processing conditions due to the unique spiro structures.
The antioxidant 618 is a representative high-performance alkyl phosphite antioxidant containing spiro, and endowed with good compatibility with polyolefin and other materials by means of long-chain alkyl, which is mainly applied to high-end formulas of general plastics such as polyethylene, polypropylene, polystyrene and polyvinyl chloride. The above-mentioned high-efficiency antioxidants get more and more demands and attention with the trend of “replacing steel with plastics” and rapid development of plastic composite materials.
Ph Ph )
Abu Bır Sn x Ju od os 0 od - 0 0 - on Fa Pres, 7, esas, mi Som M Ve em mt bos XK po pm a 0 peo —
Vase Yd Nef nf Let FAR Sd fess Yer Neg oer? 626 9228 Bu PEP36 By
[05]
[06] Three typical high-efficiency aryl phosphite antioxidants with unique spiro structures 0 0
ANNAN NNN os À po \ / 0 0
[07] 618
[08] Typical high-efficiency alkyl phosphite antioxidant with unique spiro structure
[09] The pentaerythritol phosphite antioxidant 618 has a chemical name of distearyl pentaerythritol diphosphite, a molecular formula of C41H8206P2, a molecular weight of 733, a melting point of 54-56°C, a flash point of 260°C, and a commodity name of AP-618, which was first researched and developed and put into production by the US Borg-Warner
Chemicals Inc. at the end of the 1970s. The distearyl pentaerythritol diphosphite contains pentaerythritol and phosphite in the molecule, and compounds a radical scavenger and a hydroperoxide decomposing agent in one molecule, which is a molecular composite antioxidant and a heat stabilizer, has good processing stability, heat resistance stability, and a color and luster improvement property, is capable of improving weather resistance of 2
H109WO9LU-PCT23020 28.06.2023 products, is non-toxic and pollution-free, can be used for food packaging materials, and is LU103177 mainly used as an auxiliary antioxidant of various synthetic resin such as polyethylene, polypropylene, polyvinyl chloride, ABs resin, and polyester. This product was produced and applied by the US General Electric Company, Borg-Warner Inc. and Japan’s Johoku
Chemical Co., Ltd. at abroad and Jilin Chemical Company in China.
[10] There are two process routes for synthesizing the antioxidant of distearyl pentaerythritol diphosphite in the literature or patents, one is a transesterification method, and the other one is a phosphorus trichloride method.
[11] The transesterification method is mainly divided into two manners: (1) synthesizing distearyl pentaerythritol diphosphite by taking triphenyl phosphite, pentaerythritol and octadecanol as raw materials; and (2) synthesizing distearyl pentaerythritol diphosphite by taking triethyl phosphite, pentaerythritol and octadecanol as raw materials. In the phosphorus trichloride method, distearyl pentaerythritol diphosphite is synthesized by taking phosphorus trichloride, pentaerythritol and octadecanol as raw materials.
[12] A traditional process for producing the antioxidant 618 is as follows: taking triphenyl phosphite, pentaerythritol and octadecanol as raw materials, adding a catalyst, and synthesizing a target product by means of one-step transesterification. The method has a simple production process and mild reaction conditions. For example, a method is disclosed in the US Patent with the No. US4064100, where distearyl pentaerythritol diphosphite is obtained by means of transesterification by taking triphenyl phosphite, pentaerythritol, octadecanol as raw materials and sodium methoxide as a catalyst. A process for preparing distearyl pentaerythritol diphosphite by using a solvent-free transesterification one-step method is reported in the magazine Chemical World by YIN
Zhenyan, etc. Distearyl pentaerythritol diphosphite is synthesized by taking triphenyl phosphite, octadecanol and pentaerythritol as raw materials and organic tin as a catalyst, and a product yield reaches over 98%.
[13] However, for the method in which the distearyl pentaerythritol diphosphite is prepared by using the triphenyl phosphite, the pentaerythritol and the octadecanol as the raw materials, sodium methoxide is taken as a catalyst, which has a poor effect, large usage 3
H109WO9LU-PCT23020 28.06.2023 amount is large, high reaction temperature and a long time, and an aromatic solvent needs LU103177 to be added in a reaction process, such that apparatus investment will be increased due to solvent recovery. If potassium carbonate or organic tin is taken as a catalyst, trace phenol in a product cannot be removed, such that the product 1s likely to become yellow, which limits application of the product in the fields of food and medicine.
[14] For the method in which the distearyl pentaerythritol diphosphite is synthesized by taking the triethyl phosphite, the pentaerythritol and the octadecanol as the raw materials, an organic solvent such as toluene does not need to be added, and no phenol 1s generated in a product, such that the method is a non-toxic, high-efficiency and environment-friendly method. The method is reported in the patents with No. CN 1765908
A and No. CN 111620905 A, and a product yield reaches over 98%. However, a reaction temperature of the process is too high, the reaction can only be performed at a very low vacuum degree, conditions are harsh, the process is not easy to complete, a single product is difficult to generate, other byproducts appear, separation and purification are difficult, the purity of a final product 1s not high. À yield 1s reported to be very high in an existing patent, but no reasonable 31P-NMR spectrogram is used for proving. The P*! (CDCI3) spectrogram of the distearyl pentaerythritol diphosphite synthesized by using the triethyl phosphite method for market circulation is shown in FIG. 3, which is obviously a mixture.
[15] For a phosphorus trichloride process, the phosphorus trichloride, the pentaerythritol and the octadecanol are taken as the raw materials to synthesize the distearyl pentaerythritol diphosphite by using a two-step method. A process for preparing distearyl pentaerythritol diphosphite by using a phosphorus trichloride two-step method is disclosed in a domestic patent with No. CN 101182330, where in step 1, firstly, phosphorus trichloride reacts with substituted phenol or alkanol substances to generate an intermediate, and in step 2, the generated intermediate reacts with pentaerythritol to generate a final product. This process reports that a product yield is over 95%, no by-product is generated, but there is no reasonable spectrogram for proving. In addition, time of the reaction in step 2 is too long (greater than 4 h) under a heating condition, which is not conducive to energy consumption saving.
[16] In summary, for existing various synthesis processes for distearyl pentaerythritol 4
H109WO9LU-PCT23020 28.06.2023 diphosphite, the transesterification process has harsh reaction conditions, many by-products, LU103177 complicated post-treatment process, and low product purity. Different feeding sequences of the phosphorus trichloride process have large influence on a reaction temperature and time of a product, such that the product is low in purity and poor in stability.
[17] Aiming at the above-mentioned technical problems existing in the prior art, an objective of the present invention is to provide a new industrial-production-oriented method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite, which can provide high-purity and good-precipitation-resistance industrial products of the distearyl pentaerythritol diphosphite.
[18] The present invention provides a simple, convenient and high-efficiency synthetic method, where pentaerythritol, phosphorus trichloride and octadecanol are taken as raw materials, in a first-step reaction, fatty tertiary amine such as triethylamine is taken as a catalyst, and toluene is taken as a reaction solvent. In a second-step reaction, fatty tertiary amine such as triethylamine is taken as an acid-binding agent, and toluene is taken as a reaction solvent. A mixture of a new high-efficiency phosphite compound with a spiro structure is synthesized by using a high-efficiency and high-yield one-pot method. A reaction equation is shown as follows:
HO OH 0 a
P / \
X + a een OF X PC
HO—/ NOH “ ; ; od Nd]
Telvene soivent 2 NNN NNN PNA
TT Te te dan x JO Cr
Toiïmene solvent 9 ©
[19]
[20] High-efficiency and high-yield one-pot synthetic method of present invention
[21] The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite of the present invention specifically includes the following steps:
[22] 1) adding pentaerythritol serving as a raw material, triethylamine serving as a
H109WO9LU-PCT23020 28.06.2023 catalyst, and a reaction solvent into a reactor, dropwise adding phosphorus trichloride as a LU103177 raw material, performing a reaction at a reaction temperature, and continuously removing hydrogen chloride gas generated by the reaction in a reaction process out of a system; and
[23] 2) after the reaction in step 1) is completed, adding octadecanol and an acid-binding agent to the system for a second-step reaction, and after the reaction is completed, performing post treatment to obtain a finished product of the high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite.
[24] Furthermore, in step 1), a feeding mass ratio of the pentaerythritol to the triethylamine catalyst is 100-150:1 and preferably 130-135:1.
[25] Furthermore, in step 1), a feeding mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1-4 and preferably 1:1.5-2.5.
[26] Furthermore, in step 1), the reaction solvent is toluene, and a feeding mass ratio of the pentaerythritol raw material to the reaction solvent is 1:3-6 and preferably 1:4-5.
[27] Furthermore, in step 1), reaction pressure is normal pressure, a reaction temperature is 60-80°C and preferably 70°C, and reaction time in step 1) is 2-4 h and preferably 3 h.
[28] Furthermore, a feeding mass ratio of the octadecanol in step 2) to the pentaerythritol in step 1) is 3-5:1 and preferably 4:1.
[29] Furthermore, in step 2), triethylamine is used as the acid-binding agent, and a feeding mass ratio of the triethylamine acid-binding agent to the octadecanol is 1:2-3 and preferably 1:2.5-2.6.
[30] Furthermore, in step 2), reaction pressure is normal pressure, and a reaction temperature is 70-90°C, which not only can improve a reaction rate but also can prevent evaporation of triethylamine. Reaction time in step 2) is 40-80 min and preferably 55-65 min.
[31] Furthermore, the post-treatment in step 2) includes the steps: filtering a reaction solution, adding diatomite into filtrate for stirring, then performing filtration again, and finally performing reduced pressure distillation to completely remove the solvent, that is, treatment is completed.
[32] The present invention achieves the beneficial effects as follows: 6
H109WO9LU-PCT23020 28.06.2023
[33] In order to provide the method for synthesizing the high-purity and LU103177 good-precipitation-resistance industrial products of the distearyl pentaerythritol diphosphite, deep research is made in the present invention. It is found from results that in a new one-pot process for synthesizing the distearyl pentaerythritol diphosphite, firstly, the phosphorus trichloride and the pentaerythritol are added to synthesize spiro dichlorophosphite, and then the octadecanol is directly added for synthesizing the distearyl pentaerythritol diphosphite. The distearyl pentaerythritol diphosphite with high yield, high purity and high stability is obtained by using the suitable acid-binding agent and matching and setting optimal process conditions, thereby completing the present invention.
[34] FIG. 1 is a P*(CDCI>) spectrogram of a new phosphite compound obtained from
Example 1 of the present application;
[35] FIG. 2 is an FT-IR spectrogram of a mixture of a new phosphite compound obtained from Example 1 of the present application; and
[36] FIG. 3 is P*}(CDCl3) of an existing distearyl pentaerythritol diphosphite product synthesized by using a triethyl phosphite method and circulated in the market.
[37] The present invention is further described below in conjunction with particular examples, but the protection scope of the present invention is not limited herein.
[38] Example 1
[39] A 1000 ml flask with five mouths was equipped with a stirrer, a nitrogen inlet tube, a thermometer, a rectifying tube, and a cock (for sampling), then a moisture quantitative receiver and a cooling tube were further mounted at a tip of the rectifying tube, and the above devices were used as reaction devices. Pentaerythritol (13.2 g) serving as a raw material, toluene (60 g) serving as a solvent, and triethylamine (0.1 g) serving as a catalyst were added to the flask, and phosphorus trichloride (28.8 g) serving as a raw material was added dropwise at a reaction temperature of 70°C under normal pressure.
After completion of the dropwise addition, a system was kept at a reaction temperature of 7
H109WO9LU-PCT23020 28.06.2023 70°C, and a first-step reaction was performed while generated hydrogen chloride was LU103177 removed out of the system. The first-step reaction was ended when the raw material phosphorus trichloride was analyzed to be less than 1% by means of high performance liquid chromatography (HPLC), and the reaction time was 3 h. A polytetrafluoroethylene (PTFE) hose was used for introducing nitrogen below a liquid level, and stirring was performed to remove residual hydrogen chloride gas. Then, octadecanol (54.1 g) was added to the system, and triethylamine (21.0 g) serving as an acid-binding agent was added under normal pressure and at a reaction temperature of 70°C. After the addition was completed, the system was gradually heated to reflux (90°C) to perform a second-step reaction. The second-step was ended when an intermediate was analyzed to be less than 1% by means of
HPLC, and the reaction time was 1 hour. Then, filtration was performed, and diatomite (2 g) was added to filtrate for stirring for 10 minutes, and filtration was performed again. Finally, reduced pressure distillation was performed so as to completely remove the solvent, thereby producing a target product, the new phosphite compound represented by the above general formula (1), where a yield was 95%. Purity of 99.3% was determined by means of nuclear magnetic resonance of P*"(CDCIs), which was high.
[40] The new phosphite compound represented by the above general formula (1) was identified by means of nuclear magnetic resonance and infrared spectroscopy, and identification results were shown below.
[41] A P*'(CDCI4) spectrogram of the new phosphite compound represented by the above general formula (1) is shown in FIG. 1. Chemical shifts of the new phosphite compound as the main component and represented by general formula (1) are 124.78 ppm, 124.83 ppm, 124.89 ppm, 124.95 ppm, and 125.02 ppm, showing a quintet peak. Chemical shifts of the C'*(CDCI3) spectrogram of the new phosphite compound as the main component and represented by general formula (1) are 14.16 ppm, 22.73 ppm, 25.52 ppm, 25.81 ppm, 29.31 ppm, 29.40 ppm, 29.61 ppm, 29.63 ppm, 29.70 ppm, 29.74 ppm, 31.24 ppm, 31.30 ppm, 31.96 ppm, 37.07 ppm, 37.12 ppm, 37.17 ppm, 61.45 ppm, 61.91 ppm, 61.93 ppm, 63.49 ppm, 63.68 ppm, 125.33 ppm, 128.25 ppm, and 129.06 ppm.
[42] An FT-IR spectrogram of the new phosphite compound represented by the above general formula (1) is shown in FIG. 2. 8
H109WO9LU-PCT23020 28.06.2023
[43] Examples 2-5 and Comparative examples 1-3: LU103177
[44] Operating steps of Examples 2-5 and Comparative examples 1-3 are repetition of the steps in Example 1. Difference is only that a temperature of the second step was adjusted, and reaction time was correspondingly changed in the step of ending the second step reaction when an intermediate was analyzed to be less than 1% by means of HPLC, and the other operating conditions are repetition of those of Example 1. Reaction results of temperatures in the second step and reaction time of the second step and corresponding product yields and purity of Examples 2-5 and Comparative examples 1-3 are summarized in Table 1.
[45] Table 1. Influence of reaction temperature on yield and purity of synthesized product
Second-step Product Second-step
Summary of reaction Product yield temperature of purity reaction time results (%) one-pot reaction (%) (min)
Fe ee
Example sos fe feo Je
Cee mee
Cle ee Je
Comparative example 3 110 78 92.2 150
Comparative example
[46] It can be seen from Table 1 that 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 means of suitable conditions.
[47] The contents of this description are merely a list of the forms in which the invention concept is implemented, and the protection scope of the present invention should not be regarded as limited to the specific forms stated in the examples. 9
Claims (9)
1. A method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite, comprising the following steps: 1) adding pentaerythritol serving as a raw material, triethylamine serving as a catalyst, and a reaction solvent into a reactor, dropwise adding phosphorus trichloride as a raw material, performing a reaction at a reaction temperature, and continuously removing hydrogen chloride gas generated by the reaction in a reaction process out of a system; and 2) after the reaction in step 1) is completed, adding octadecanol and an acid-binding agent to the system for a second-step reaction, and after the reaction is completed, performing post treatment to obtain a finished product of the high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite.
2. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein in step 1), a feeding mass ratio of the pentaerythritol to the triethylamine catalyst is 100-150:1 and preferably 130-135:1.
3. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein in step 1), a feeding mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1-4 and preferably 1:1.5-2.5.
4. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein in step 1), the reaction solvent is toluene, and a feeding mass ratio of the pentaerythritol raw material to the reaction solvent is 1:3-6 and preferably 1:4-5.
5. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein in step 1), reaction pressure is normal pressure, a reaction temperature is 60-80°C and preferably 70°C, and reaction time in step 1) is 2-4 h and preferably 3 h.
6. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein a feeding mass ratio of the octadecanol in step 2) to the pentaerythritol in step 1) is 3-5:1 and preferably 4:1. 1
H109WO9LU-PCT23020 28.06.2023
7. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl LU103177 pentaerythritol diphosphite according to claim 1, wherein in step 2), triethylamine is used as the acid-binding agent, and a feeding mass ratio of the triethylamine acid-binding agent to the octadecanol is 1:2-3 and preferably 1:2.5-2.6.
8. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein in step 2), reaction pressure is normal pressure, a reaction temperature is 70-90°C, and reaction time in step 2) is 40-80 min and preferably 55-65 min.
9. The method for synthesizing a high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite according to claim 1, wherein the post-treatment in step 2) comprises the steps: filtering a reaction solution, adding diatomite into filtrate for stirring, then performing filtration again, and finally performing reduced pressure distillation to completely remove the solvent, that is, treatment is completed. 2
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310011583.7A CN116082400A (en) | 2023-01-05 | 2023-01-05 | Synthesis method of efficient phosphite antioxidant pentaerythritol distearyl diphosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| LU103177B1 true LU103177B1 (en) | 2024-07-12 |
Family
ID=86213310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LU103177A LU103177B1 (en) | 2023-01-05 | 2023-06-06 | Method for synthesizing high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN116082400A (en) |
| LU (1) | LU103177B1 (en) |
| WO (1) | WO2024146066A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082400A (en) * | 2023-01-05 | 2023-05-09 | 浙江万盛股份有限公司 | Synthesis method of efficient phosphite antioxidant pentaerythritol distearyl diphosphate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4290976A (en) * | 1975-03-24 | 1981-09-22 | Borg-Warner Chemicals, Inc. | Process for the preparation of phenol-free phosphites |
| CN102061203A (en) * | 2009-11-16 | 2011-05-18 | 济南开发区星火科学技术研究院 | High-temperature diesel antioxidant and preparation method thereof |
| CN105949243B (en) * | 2016-05-12 | 2018-11-06 | 营口风光新材料股份有限公司 | A kind of preparation method of phosphite ester kind antioxidant 9228 |
| CN116082400A (en) * | 2023-01-05 | 2023-05-09 | 浙江万盛股份有限公司 | Synthesis method of efficient phosphite antioxidant pentaerythritol distearyl diphosphate |
-
2023
- 2023-01-05 CN CN202310011583.7A patent/CN116082400A/en active Pending
- 2023-06-06 WO PCT/CN2023/098546 patent/WO2024146066A1/en active IP Right Grant
- 2023-06-06 LU LU103177A patent/LU103177B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024146066A1 (en) | 2024-07-11 |
| CN116082400A (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Trost et al. | Palladium-catalyzed enantioselective allylic alkylations through CH activation. | |
| LU103176B1 (en) | Method for synthesizing phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite | |
| AU2017238018A1 (en) | Acrylic acid, and methods of producing thereof | |
| LU103177B1 (en) | Method for synthesizing high-efficiency phosphite antioxidant of distearyl pentaerythritol diphosphite | |
| CN102086271A (en) | Preparation method of high-transparent high heat resistance liquid calcium-zinc heat stabilizer | |
| Turner et al. | Polymerization of ethylene by an alkylidene hydride catalyst | |
| US20250074860A1 (en) | Intramolecular complex hindered phenol compound, preparation method therefor and use thereof | |
| CN113372389B (en) | Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application | |
| Bauer et al. | α-Hydroxy carboxylic acids as ligands for enantioselective diethylzinc additions to aromatic and aliphatic aldehydes | |
| CN109232652B (en) | Preparation method of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite | |
| CN108250240A (en) | A kind of 626 synthesis technology of antioxidant | |
| Oshiki et al. | The reactions of optically pure menthyloxymethylphenylphosphine-borane with organolithium reagents. | |
| CN101089005A (en) | Prepn process of cyclic phosphonate compound | |
| CN114163474B (en) | Polyketone catalyst ligand and synthesis method thereof | |
| Zhu et al. | Recent Advances in the Synthesis of Commercially Available Phosphite Antioxidants | |
| CN114195659B (en) | Polyphenol type antioxidant and preparation method and application thereof | |
| CN102491951B (en) | Production process of triallyl cyanurate | |
| CN109369490A (en) | The synthetic method of tert-butyl hydroperoxide carbonic ester | |
| CN113651849A (en) | Polymerized phenol-free, low-odor phosphite and preparation method thereof | |
| CN113603720A (en) | Organic ligand, preparation method thereof, catalytic system and ethylene oligomerization method | |
| JP5678489B2 (en) | Method for producing fumarate ester | |
| CN113292597B (en) | Method for preparing triethyl phosphate compound by recovering sodium diethylphosphate and ethyl chloride | |
| CN104478930B (en) | The synthesis technique of phosphorus part compounds | |
| US6180813B1 (en) | Benzylidenecyanoacetates and a method for making benzylidenecyanoacetates | |
| CN113024484B (en) | Method for purifying and preparing high-purity promoter CZ and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FG | Patent granted |
Effective date: 20240712 |