CN108047273A - The preparation method and application of liquid phosphite class compound - Google Patents
The preparation method and application of liquid phosphite class compound Download PDFInfo
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- CN108047273A CN108047273A CN201711431050.5A CN201711431050A CN108047273A CN 108047273 A CN108047273 A CN 108047273A CN 201711431050 A CN201711431050 A CN 201711431050A CN 108047273 A CN108047273 A CN 108047273A
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- preparation
- pentaerythrite
- methyl
- reaction
- alkali
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- -1 phosphite class compound Chemical class 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 157
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000003513 alkali Substances 0.000 claims abstract description 38
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 4
- 208000006278 hypochromic anemia Diseases 0.000 claims abstract description 4
- YGPLZBDXFXBLMZ-UHFFFAOYSA-N 1,1-dichloro-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)C(O)(Cl)Cl YGPLZBDXFXBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 93
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 48
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 28
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 claims description 27
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 25
- 235000019270 ammonium chloride Nutrition 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 12
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 11
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 9
- LWWJDXKGQVEZKT-UHFFFAOYSA-N 3-ethylhexan-1-ol Chemical class CCCC(CC)CCO LWWJDXKGQVEZKT-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- NVINYZLICSJRSI-UHFFFAOYSA-N 5-methyldodecane Chemical class CCCCCCCC(C)CCCC NVINYZLICSJRSI-UHFFFAOYSA-N 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 abstract description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 27
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 23
- 239000012467 final product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000376 reactant Substances 0.000 description 15
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 14
- 235000006708 antioxidants Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- RLGDVTUGYZAYIX-UHFFFAOYSA-N 4-ethylhexan-1-ol Chemical class CCC(CC)CCCO RLGDVTUGYZAYIX-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- GQJWRLJHGJGGIP-UHFFFAOYSA-N 1,1-dichloro-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)C(O)(Cl)Cl GQJWRLJHGJGGIP-UHFFFAOYSA-N 0.000 description 1
- SFRKSDZMZHIISH-UHFFFAOYSA-N 3-ethylhexane Chemical class CCCC(CC)CC SFRKSDZMZHIISH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000002530 phenolic antioxidant 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The present invention provides the preparation method and application of liquid phosphite class compound, wherein the preparation method of the liquid phosphite class compound, includes the following steps：(1) by pentaerythrite, with phosphorus trichloride, the reaction under the action of alkali prepares pentaerthiyldichlorodiphosphite；(2) generation mono- chloro pentaerythritol diphosphites of R are reacted with dichloro pentaerythritol diphosphites by R OH；And (3) are reacted with R chloros pentaerythritol diphosphites using R ' OH and prepare R, R ' pentaerythritol diphosphites, wherein the R and R ' is different alkyl.
Description
Technical field
The present invention relates to chemical processing field more particularly to a liquid phosphite class compound preparation method and should
With.
Background technology
Plastics will unavoidably be influenced in process be subject to factors such as heat, oxygen, mechanical shearings, often can therefore send out
Heat is degraded, and reduces melt viscosity, causes the reduction of end article physical property.The hydrogen formed in polyolefin thermal degradation process
Peroxide can further promote the light degradation of polyolefin.Phosphorous acid esters are that polyolefin processes main auxiliary antioxidant,
There is good synergistic effect with hindered phenol main anti-oxidant, the processing stability, heat-resisting steady of polyolefin can be effectively improved
Qualitative, modification of colour and weatherability；It is also showed that with hindered amine as light stabilizer compatibility and good cooperates with stablizing effect.
Important kind of the phosphite ester as auxiliary antioxidant, has been to be concerned by more and more people.Its reason is on the one hand
Itself excellent comprehensive stability performance is rooted in, on the other hand, they can cooperate with use with a variety of auxiliary agents, coordinate with phenolic antioxidant
Using assigning polymer excellent processing stability, heat-resistant stability, modification of colour and lasting weatherability, can adapt to current
The high temperature trend of world's plastic processing, thus it is particularly significant for the research of the exploitation of such antioxidant, application.
Liquid phosphite is one kind among industrial phosphite ester, and wherein liquid phosphite is compared to solid phosphorous
Acid esters has many advantages, such as convenient for pipeline transportation, facilitates metering, can be uniformly mixed in fluid product.
The content of the invention
The one of the present invention is designed to provide the preparation method and application of a liquid phosphite class compound, wherein described
Liquid phosphite class compound can be applied to as anti-oxidant machine in industrial production, especially the production of polyolefin.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
It is mild to state the reaction condition of the preparation method of liquid phosphite class compound, it is suitable for mass production.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
The liquidus behavior for stating liquid phosphite class compound makes it easier to mix with polyolefin, compensates for powder antioxidant and is mixing
The deficiency of method.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
State that the preparation method of liquid phosphite class compound is easy to operate, and the reaction time is shorter.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
It is high to state the preparation method yield of liquid phosphite class compound, has saved cost.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
Stating the solvent that the preparation method of liquid phosphite class compound utilizes can be recycled, with cost-effective.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
Stating the excessive raw material that the preparation method of liquid phosphite class compound utilizes can be recycled, with cost-effective.
Another object of the present invention is to provide the preparation method and application of a liquid phosphite class compound, wherein institute
Final product can be obtained by shirtsleeve operation by stating the preparation method of liquid phosphite class compound, and the net of complexity is not required
Change operation.
One side under this invention, the present invention provides one for manufacturing the preparation method of phosphite ester compound,
Including：
(1) by pentaerythrite, with phosphorus trichloride, the reaction under the action of alkali prepares dichloro pentaerythritol diphosphorous acid
Ester；
(2) generation mono- chloro pentaerythrite diphosphorous acids of R- are reacted with dichloro pentaerythritol diphosphites by R-OH
Ester；And
(3) reacted using R '-OH with R- chloros pentaerythritol diphosphites and prepare R, R '-pentaerythrite diphosphorous acid
Ester, wherein the R and R ' is different alkyl.
According to one embodiment of present invention, the alkali is organic weak base.
According to one embodiment of present invention, the R '-OH are selected from 3- methyl lauryl alcohol, 4- methyl lauryl alcohol, 5- methyl
One kind of lauryl alcohol, different tridecanol composition.
According to one embodiment of present invention, the R-OH is selected from 3- ethyl hexanols, 4- ethyl hexanols, isooctanol composition
In one kind.
According to one embodiment of present invention, the R-OH：Equivalent proportion=1~1.2 of pentaerythrite:1.
According to one embodiment of present invention, the R '-OH：Equivalent proportion=1~1.2 of pentaerythrite:1
According to one embodiment of present invention, in the step (1), heated and reacted using gradient increased temperature, the chlorination of generation
Hydrogen is absorbed.
According to one embodiment of present invention, in the step (1), add in pentaerythrite into reaction vessel, alkali and have
Solvent and 15-20 DEG C add in phosphorus trioxide, pentaerythrite：Alkali：Molar ratio=1 of phosphorus trioxide:0.025~0.03：
0.1~0.12:2~2.2, pentaerythrite：The molar ratio of organic solvent is more than 1:5；First, the first stage heats：Reaction temperature
30-40 DEG C, second stage heating：110-115 DEG C of reaction temperature sponges the hydrogen chloride gas of generation in this heating period
Body after being warming up to 110-115 DEG C, is vacuumized and by the organic solvent of extraction rushing vacuum pump with water for reaction vessel
It is back in reaction vessel, steams organic solvent after extracting.
According to one embodiment of present invention, in the step (1), add in pentaerythrite into reaction vessel, alkali and have
Solvent and phosphorus trioxide, pentaerythrite are added under the conditions of ice-water bath：Alkali：Molar ratio=1 of phosphorus trioxide:0.025~
0.03：0.1~0.12:2~2.2, pentaerythrite：The molar ratio of organic solvent is more than 1:5；First, the first stage heats：Reaction
30-40 DEG C of temperature, second stage heating：110-115 DEG C of reaction temperature sponges the hydrogen chloride of generation in this heating period
Gas after being warming up to 110-115 DEG C, is vacuumized and by the organic molten of extraction rushing vacuum pump with water for reaction vessel
Agent is back in reaction vessel, is steamed organic solvent after extracting.
According to one embodiment of present invention, in the step (1), pentaerythrite, methyl three are added in into reaction vessel
Octyl group ammonium chloride, alkali and organic solvent and 15-20 DEG C add in phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：
Alkali：Molar ratio=1 of phosphorus trioxide:0.025~0.03：0.1~0.12:2~2.2, pentaerythrite：The molar ratio of organic solvent
More than 1:5；First, the first stage heats：30-40 DEG C of reaction temperature, second stage heating：110-115 DEG C of reaction temperature, at this
The hydrogen chloride gas of generation is sponged in a heating period, after being warming up to 110-115 DEG C, vacuum pump is being rushed for reaction with water
Container is vacuumized and the organic solvent of extraction is back in reaction vessel, steams organic solvent after extracting.
According to one embodiment of present invention, in the step (2), R-OH is added drop-wise to reaction at 100 to 120 DEG C
In container, keep the temperature to reaction and terminate, the R-OH：Equivalent proportion=1~1.2 of pentaerythrite:1.
According to one embodiment of present invention, in the step (3), R '-OH is added drop-wise to reaction at 100 to 120 DEG C and are held
In device, keep the temperature to reaction and terminate, the R '-OH：Equivalent proportion=1~1.2 of pentaerythrite:1.
According to one embodiment of present invention, the preparation method further comprises step (4), wherein the step (4)
For：
The alkali of a predetermined amount is added in neutralize solution, then removes remaining alkali, wherein the step (4) is located at institute
After stating step (3).
According to one embodiment of present invention, the preparation method further comprises step (4), wherein the step (4)
For：
If the R '-OH in the step (3) are excessive, the R '-OH are first removed, then add in the alkali of a predetermined amount
To neutralize solution, then remaining alkali removed, wherein the step (4) is located at after the step (3).
According to one embodiment of present invention, in the step (4) under 70-80 DEG C of temperature, normal pressure add in alkali in and.
According to one embodiment of present invention, the alkali in the step (4) is triethylamine, di-n-butylamine and tri-n-butylamine
In one or more.
According to one embodiment of present invention, remaining alkali is removed by way of evaporation in the step (4).
According to one embodiment of present invention, the preparation method further comprises step (5), wherein the step (5)
For：
Heat filtering is to obtain liquid phosphite class compound.
Another aspect under this invention, the present invention further provides a liquid phosphite class antioxidant, including above-mentioned
Phosphite ester compound is prepared in any preparation method of claim.
According to one embodiment of present invention, the phosphite ester compound be selected from diphosphorous acid (2- methyl heptane bases,
2- methyl dodecyl) pentaerythritol ester, diphosphorous acid (3- ethyl hexyl alkyl, 3- methyl dodecyl) pentaerythritol ester, two
Phosphorous acid (4- ethyl hexyl alkyl, 4- methyl dodecyl) pentaerythritol ester, diphosphorous acid (4- ethyl hexyl alkyl, 5- methyl ten
Dialkyl group) pentaerythritol ester, diphosphorous acid (3- ethyl hexyl alkyl, 5- methyl dodecyl) pentaerythritol ester, diphosphorous acid (2-
Methyl heptane base, 3- methyl dodecyl) pentaerythritol ester, diphosphorous acid (2- methyl heptane bases, 4- methyl dodecyl) season
Doutrate, diphosphorous acid (2- methyl heptane bases, 5- methyl dodecyl) pentaerythritol ester, diphosphorous acid (3- ethyl hexanes
Base, 4- methyl dodecyl) pentaerythritol ester, diphosphorous acid (3- ethyl hexyl alkyl, 2- methyl dodecyl) pentaerythritol ester,
Diphosphorous acid (4- ethyl hexyl alkyl, 2- methyl dodecyl) pentaerythritol ester, diphosphorous acid (4- ethyl hexyl alkyl, 3- methyl
Dodecyl) one or more in pentaerythritol ester.
Specific embodiment
It is described below to disclose the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
The present invention basic principle can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
As used herein, term "comprising", " comprising ", " having " or their any other modification are intended to and cover non-row
His property includes.For example, composition, step, method, product or equipment comprising series of elements are not necessarily limited to those members
Element, and other not expressly listed elements or such composition, step, method, product or the intrinsic member of equipment can be included
Element.In addition, unless expressly stated to the contrary, "or" refers to the "or" of inclusive, without referring to exclusive "or".For example,
Following any one situation is satisfied by condition A or B：A is real (or existing) and B is false (or being not present), A
It is false (or being not present) and B is real (or existing) and A and B is real (or existing).Equally,
Be related to indefinite article of the number of element or component example (things occurred) before element of the present invention or component "one" or
" one kind " is intended to be non-limiting.Therefore, "one" or " one kind " should be interpreted as including one or at least one, and member
Element or the singulative of component also include plural number, and odd number is substantially represented unless there are digital.
Ratio general expression herein is the single number compared with numerical value 1；Such as ratio refers to 4: 1 for 4.Term
" equivalent ratio " refers to a kind of equivalents of the component (such as alkali) compared with another component being added in reaction mixture, recognizes
Know, some every mole of compounds can provide two equivalents or more equivalent.In above-mentioned statement, it is used alone or all in compound word
Term " alkyl " as used in " alkylthio group " or " halogenated alkyl " includes straight or branched alkyl, such as methyl, ethyl, positive third
Base, isopropyl or different butyl, amyl or hexyl isomers." alkoxy " includes such as methoxyl group, ethyoxyl, positive third oxygen
Base, isopropoxy and different butoxy, amoxy and hexyloxy isomers.
The present invention provides the preparation method of a phosphite ester compound, wherein the preparation method is first with trichlorine
Change phosphorus and pentaerythrite and carry out cyclization, generate intermediate pentaerthiyldichlorodiphosphite, then by intermediate with
Reactant reaction generates final product.
An embodiment according to the present invention, the preparation method of the phosphite antioxidant include the following steps：
(1) to addition raw material pentaerythrite, solvent and corresponding catalyst among reaction vessel；
(2) phosphorus trichloride is added at a certain temperature to generate intermediate pentaerthiyldichlorodiphosphite；
(3) R-OH is added at a certain temperature to generate R- chloro pentaerythritol diphosphites；And
(4) and then R '-OH are added in generate final product diphosphorous acid (R, R ') pentaerythritol ester.
R and R ' herein refers to different alkyl, can be straight chained alkyl or the alkyl with branch.
An embodiment according to the present invention, the preparation method of the phosphite antioxidant include the following steps：
(1) to addition raw material pentaerythrite, solvent and corresponding catalyst among reaction vessel；
(2) phosphorus trichloride is added at a certain temperature to generate intermediate pentaerthiyldichlorodiphosphite；
(3) isomerous tridecanol is added at a certain temperature to generate two phosphorous of 2- methyl dodecyl chloros pentaerythrite
Acid esters；And
(4) and then isooctanol is added in generate final product diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) season
Doutrate.
By above-mentioned preparation method, the compound of the pentaerythritol diphosphite with different alkyl can be obtained.And
In traditional preparation method, intermediate pentaerthiyldichlorodiphosphite often substitutes the double alkyl of generation by identical alkyl
Pentaerythritol diphosphite.
This can be passed through after final product diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) pentaerythritol ester is obtained
The method of field technology personnel Chang Zhi, the operations such as extraction, filtering, to separate the product.
It is worth noting that, the equivalent for the alcohols being firstly added is sub- no more than the intermediate dichloro pentaerythritol two
Twice of phosphate equivalent, to avoid the intermediate pentaerthiyldichlorodiphosphite-Cl by the alkoxy of alcohols
Substitute completely and then generate the identical product of both sides alkoxy.Optionally, the alcohols being firstly added：Intermediate dichloro-
The equivalent of pentaerythritol diphosphites is controlled 1:1 or so, to generate a chloro-product as far as possible ,-a Cl is left for follow-up
Alcohols occur substitution reaction.
Optionally, in another example of the present invention, the preparation method of the phosphite antioxidant includes following step
Suddenly：
(1) the raw material pentaerythrite of suitable equivalent, methyl tricapryl ammonium chloride, triethylamine and reaction are added in reaction vessel
Solvent,
(2) phosphorus trichloride of corresponding equivalent is added dropwise at a lower temperature in reaction solution；
(3) reaction temperature is raised after a period of time to promote reaction；
(4) treat to remove reaction dissolvent after completion of the reaction；
(5) A reactants are added under a preset temperature to generate a chloro alkyl pentaerythritol diphosphites；And
(6) treat to add in B reactants after reaction to generate final product R, R '-pentaerythritol diphosphites.
In the present embodiment, the pentaerythrite：Phosphorus trichloride：Triethylamine：The molar ratio of methyl tricapryl ammonium chloride=
1：2：0.1：0.025.
It is noted that in this example, methyl tricapryl ammonium chloride improves Ji Wusi as phase transfer catalyst
The reaction rate of alcohol and phosphorus trichloride, has been saved the reaction time, and then improves production efficiency.
In the example of the present invention, the pentaerythrite is set to larger than 1 with the molar ratio of reaction dissolvent:10.
The step (1) carried out among suitable solvent, wherein the reaction dissolvent for alkali and pentaerythrite with
And phosphorus trichloride should be inert.The reaction dissolvent can be that single solvent also can be also mixed solvent.
In the example of the present invention, the reaction dissolvent can be dimethylbenzene, toluene, in thiacyclohexane either mesitylene
It is a kind of or a variety of.Those skilled in the art are not made the present invention it is to be understood that solvent species herein is only for example
Into limitation.
It is worth noting that, by raw material pentaerythrite, methyl tricapryl ammonium chloride, after triethylamine and reaction dissolvent mixing most
Another raw material phosphorus trichloride is just added in afterwards.Because the reaction of pentaerythrite and phosphorus trichloride will release substantial amounts of heat, therefore described
Step (2) operates at low ambient temperatures.Such as in ice-water bath.Optionally, in the example of the present invention, the step (2)
Reaction temperature be 0 DEG C~20 DEG C.Preferably, the reaction temperature of the step (2) is 15 DEG C~20 DEG C.
The phosphorus trichloride should be added dropwise to the pentaerythrite, avoid toppling over quickly trigger more side reactions and then
Influence yield.It is accurately controlled for the phosphorus trichloride with the ratio of the pentaerythrite, because tri-chlorination
The dosage of phosphorus, which crosses major general, makes cyclization incomplete, in turn results in the waste of raw material, once the dosage of phosphorus trichloride will excessively draw
Side reaction is sent out, makes the yield of product reduce.In the example of the present invention, pentaerythrite：Molar ratio=1 of phosphorus trichloride：2~
2.2 so that pentaerythrite reduces the side reaction that phosphorus trichloride triggers in the case of reacting completely as far as possible.
In order to further preferably control phosphorus trichloride and pentaerythrite reaction generation title intermediate-dichloro- Ji Wusi
Alcohol diphosphites rather than other by-products.In the step (2), phosphorus trichloride is slowly added dropwise.One in the present invention shows
It is 20min in example, the time required to the process.
It is noted that in the step (2), the reaction product of phosphorus trichloride and pentaerythrite except intermediate-
There is hydrogen chloride outside pentaerthiyldichlorodiphosphite, the aggregation of hydrogen chloride gas is so that the air pressure in reaction vessel increases
Greatly, therefore in the step (2), the step of further comprising a removal hydrogen chloride.Minimizing technology can be those skilled in the art
Common method, such as absorbed with water, with alkaline solution absorption etc..In the example of the present invention, absorbed with clear water three-level
Become hydrochloric acid.
In the example of the present invention, reaction temperature is raised to promote to react after a period of time in the step (3)
In generation, specifically, the step (3) further comprises following steps：
(3.1) 30-50 DEG C is warming up to, then reacts a period of time at this temperature；And
(3.2) 100-120 DEG C is warming up to, then reacts to reaction and finishes at this temperature.
Among the step (3.1), temperature-rise period needs to control in 20min, in the step (3.2),
Temperature-rise period needs to control in 30min.
In the example of the present invention, the warming temperature of the step (3.1) can be 30-40 DEG C, the step (3.2)
Warming temperature can refer to 110 DEG C, 115 DEG C.The reaction time can be at least 20min after the step (3.1) heating.Institute
The reaction time can be at least 10min after stating step (3.2) heating.
, it is necessary to which the hydrogen chloride gas of generation is removed among the process of the step (3).Can vacuum pump be filled by water
Removal.
The step (3) further comprises that a step (3.3) vacuumizes.In the example of the present invention, rushed using water true
Sky pump vacuumizes reaction vessel, may also take solvent away while extracting hydrogen chloride, and solvent can be returned by condenser
The mode of stream is returned among reaction vessel.It, can not by vacuum control in -60kpa in 10 minutes in the example of the present invention
It is too fast, prevent material from rushing out.It at 110-115 DEG C, extracts 30 minutes, mesitylene passes through condenser reflux to reaction
In bottle.
During the step (4), solvent is removed.In the example of the present invention, the step (4) includes
Under 130-136 DEG C of temperature, -99KPa pressure, mesitylene is steamed out.
During the step (5), reactant alkylol A is added in reaction vessel and reacts a period of time,
During this, 100 DEG C -120 DEG C are maintained the temperature at so that reaction carries out to reaction terminating.
During the step (6), reactant alkylol B is added in reaction vessel and reacts a period of time,
During this, 100 DEG C -120 DEG C are maintained the temperature at so that reaction carries out to reaction terminating.
It is noted that in the step (5), in order to avoid excessive reactant alkylol A and intermediate-dichloro
For the by-product of two substitution alkyl pentaerythritol diphosphites of pentaerythritol diphosphites generation, the reactant alkylol
The molar ratio of A and pentaerythrite is controlled in 1~1.2:1.Preferably, the reactant alkylol A and pentaerythrite rub
You are equal to 1 at ratio:1.
It is noted that in the step (6), in order to enable-one chlorine substituent of reactant alkylol B and intermediate
Fully two substitution alkyl pentaerythritol diphosphites of reaction generation-R, R '-pentaerythritol diphosphites, i.e. substitution have not
With the pentaerythritol diphosphites of alkyl, in the example of the present invention, the dosage of the reactant alkylol B is arranged to
Excessive.Optionally, the reactant alkylol B：The molar equivalent ratio of pentaerythrite is more than 1.That is, the reactant
The dosage of alkylol B is more than pentaerythrite.In the example of the present invention, the reactant alkylol B：Mole of pentaerythrite
Equivalent proportion=1~1.2:1.
Further, after the step (6), the preparation method includes a step (7), wherein the step (7)
For：Remove excessive reactant alkylol B.In the example of the present invention, excessive reactant alkylol B is steamed.Into one
Step ground, in at least example of the present invention, by excessive isooctanol under 150-160 DEG C of temperature, -80~-100KPa pressure
It is steamed out, in the example of the present invention, steams excessive isooctanol in -99KPa.
Further, after the step (7), the preparation method includes a step (8), wherein the step (8)
For：Removal impurity obtains more pure final product.In the example of the present invention, final product is obtained by the method for filtering
Liquid phosphite class compound.
In the example of the present invention, the step (8) includes the following steps：
(8.1) excess base is added in neutralize；
(8.2) the excessive alkali of removal；And
(8.2) desalination impurity.
In the step (8.1), the alkali can be organic weak base.Preferably, pyridine, triethylamine or N, N- bis-
The organic weak bases such as wopropyl ethyl amine.
In the step (8.2), the mode for removing excessive alkali can be by way of evaporation.One in the present invention shows
In example, the organic weak base is triethylamine, is steamed out excessive alkali under 110-120 DEG C of temperature, -99KPa pressure.In this hair
In other bright examples, excessive alkali is removed at 100-130 DEG C of temperature, the pressure of -90KPa to -100KPa.
In the step (8.3), the salinity impurity in product is removed by way of heat filtering.One in the present invention shows
In example, 80 DEG C of progress heat filterings are warming up to.In another example of the present invention, 75 DEG C of progress heat filterings are warming up to.In the present invention
Another example in, be warming up to 70 DEG C progress heat filterings.
Embodiment 1
(1) added in into reaction vessel pentaerythrite, methyl tricapryl ammonium chloride, triethylamine and mesitylene and
15-20 DEG C of addition phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Triethylamine：Molar ratio=1 of phosphorus trioxide:
0.025：0.1：2, pentaerythrite：Molar ratio=1 of mesitylene：14；First, the first stage heats：Reaction temperature 30-40
DEG C, react 20min, second stage heating：110-115 DEG C of reaction temperature is reacted 10min, is sponged in this heating period
The hydrogen chloride gas of generation.After being warming up to 110-115 DEG C, with water rush vacuum pump be evacuated to for reaction vessel-
The mesitylene of extraction is simultaneously back in reaction vessel by 60Kpa.After extracting by mesitylene 130-136 DEG C of temperature ,-
It is steamed under 99KPa pressure；
(2) in 115-120 DEG C, pressure -10KPa or so, isomerous tridecanol is added drop-wise in reaction vessel in 20 minutes,
Heat preservation to reaction terminates, the isomerous tridecanol：Molar equivalent ratio=1 of pentaerythrite:1；
(3) in 115-120 DEG C, pressure -10KPa or so, isooctanol is added drop-wise to reaction vessel in 20 minutes, heat preservation is extremely
Reaction terminates；And excessive isooctanol is steamed after the completion of reaction, the isooctanol：The molar equivalent ratio of pentaerythrite=
1:1；
(4) add in triethylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive triethylamine is steamed out under 99KPa pressure, the triethylamine：Molar equivalent ratio=6 of pentaerythrite:10；And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) pentaerythritol ester, yield is 95%.
Embodiment 2
(1) pentaerythrite, methyl tricapryl ammonium chloride, triethylamine and toluene are added in into reaction vessel and in 15-20
DEG C add in phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Triethylamine：Molar ratio=1 of phosphorus trioxide:0.025：
0.12：0.22, pentaerythrite：Molar ratio=1 of toluene：14；First, the first stage heats：30-40 DEG C of reaction temperature, reaction
20min, second stage heating：110-115 DEG C of reaction temperature reacts 10min, and the chlorine of generation is sponged in this heating period
Change hydrogen.After being warming up to 110-115 DEG C, carry out being evacuated to -60Kpa and incite somebody to action for reaction vessel rushing vacuum pump with water
The refluxing toluene of extraction is into reaction vessel.Toluene is steamed under 100-120 DEG C of temperature, -99KPa pressure after extracting；
(2) in 115-120 DEG C, pressure -10KPa or so, isomerous tridecanol is added drop-wise in reaction vessel in 20 minutes,
Heat preservation to reaction terminates, the isomerous tridecanol：Molar equivalent ratio=1 of pentaerythrite:1.2；
(3) in 115-120 DEG C, pressure -10KPa or so, isooctanol is added drop-wise to reaction vessel in 20 minutes, heat preservation is extremely
Reaction terminates；And excessive isooctanol is steamed after the completion of reaction, the isooctanol：The molar equivalent ratio of pentaerythrite=
1.2:1；
(4) add in triethylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive triethylamine is steamed out under 99KPa pressure, the triethylamine：Molar equivalent ratio=6 of pentaerythrite:10；And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) pentaerythritol ester, yield is 95% or so.
Embodiment 3
(1) pentaerythrite, methyl tricapryl ammonium chloride, triethylamine and hexamethylene are added in into reaction vessel and in 15-
20 DEG C of addition phosphorus trioxides, pentaerythrite：Methyl tricapryl ammonium chloride：Triethylamine：Molar ratio=1 of phosphorus trioxide:0.025：
0.12：0.22, pentaerythrite：Molar ratio=1 of hexamethylene：14；First, the first stage heats：30-40 DEG C of reaction temperature, instead
Answer 20min, second stage heating：110-115 DEG C of reaction temperature reacts 10min, generation is sponged in this heating period
Hydrogen chloride gas.After being warming up to 80-100 DEG C, -60Kpa be evacuated to simultaneously for reaction vessel rushing vacuum pump with water
The hexamethylene of extraction is back in reaction vessel.After extracting by hexamethylene under 80-100 DEG C of temperature, -99KPa pressure
It steams；
(2) in 115-120 DEG C, pressure -10KPa or so, 3- methyl lauryl alcohols are added drop-wise to reaction vessel in 20 minutes
It is interior, it keeps the temperature to reaction and terminates, the 3- methyl lauryl alcohol：Molar equivalent ratio=1 of pentaerythrite:1.2；
(3) in 115-120 DEG C, pressure -10KPa or so, 3- ethyl hexanols are added drop-wise to reaction vessel in 20 minutes, are protected
Temperature to reaction terminates；And excessive 3- ethyl hexanols are steamed after the completion of reaction, the 3- ethyl hexanols：Pentaerythrite
Molar equivalent ratio=1.2:1；
(4) add in triethylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive triethylamine is steamed out under 99KPa pressure, the triethylamine：Molar equivalent ratio=6 of pentaerythrite:10；And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (3- ethyl hexyl alkyl, 3- methyl dodecyl) pentaerythritol ester, yield is 95% or so.
Embodiment 4
(1) added in into reaction vessel pentaerythrite, methyl tricapryl ammonium chloride, triethylamine and mesitylene and
15-20 DEG C of addition phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Triethylamine：Molar ratio=1 of phosphorus trioxide:
0.025：0.1：2, pentaerythrite：Molar ratio=1 of mesitylene：14；First, the first stage heats：Reaction temperature 30-40
DEG C, react 20min, second stage heating：110-115 DEG C of reaction temperature is reacted 10min, is sponged in this heating period
The hydrogen chloride gas of generation.After being warming up to 110-115 DEG C, with water rush vacuum pump be evacuated to for reaction vessel-
The mesitylene of extraction is simultaneously back in reaction vessel by 60Kpa.After extracting by mesitylene 130-136 DEG C of temperature ,-
It is steamed under 99KPa pressure；
(2) in 115-120 DEG C, pressure -10KPa or so, 4- methyl lauryl alcohols are added drop-wise to reaction vessel in 20 minutes
It is interior, it keeps the temperature to reaction and terminates, the 4- methyl lauryl alcohol：Molar equivalent ratio=1 of pentaerythrite:1；
(3) in 115-120 DEG C, pressure -10KPa or so, 4- ethyl hexanols are added drop-wise to reaction vessel in 20 minutes, are protected
Temperature to reaction terminates；And excessive 4- ethyl hexanols are steamed after the completion of reaction, the 4- ethyl hexanols：Pentaerythrite
Molar equivalent ratio=1:1；
(4) add in triethylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive triethylamine is steamed out under 99KPa pressure, the triethylamine：Molar equivalent ratio=6 of pentaerythrite:10；And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (4- ethyl hexyl alkyl, 4- methyl dodecyl) pentaerythritol ester, yield is 90%.
Embodiment 5
(1) added in into reaction vessel pentaerythrite, methyl tricapryl ammonium chloride, tri-n-butylamine and mesitylene and
15-20 DEG C of addition phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Tri-n-butylamine：Molar ratio=1 of phosphorus trioxide:
0.025：0.1：2, pentaerythrite：Molar ratio=1 of mesitylene：14；First, the first stage heats：Reaction temperature 30-40
DEG C, react 20min, second stage heating：110-115 DEG C of reaction temperature is reacted 10min, is sponged in this heating period
The hydrogen chloride gas of generation.After being warming up to 110-115 DEG C, with water rush vacuum pump be evacuated to for reaction vessel-
The mesitylene of extraction is simultaneously back in reaction vessel by 60Kpa.After extracting by mesitylene 130-136 DEG C of temperature ,-
It is steamed under 99KPa pressure；(2) in 115-120 DEG C, pressure -10KPa or so, 5- methyl lauryl alcohols are added drop-wise in 20 minutes
In reaction vessel, keep the temperature to reaction and terminate, the 5- methyl lauryl alcohol：Molar equivalent ratio=1 of pentaerythrite:1；
(3) in 115-120 DEG C, pressure -10KPa or so, 4- ethyl hexanols are added drop-wise to reaction vessel in 20 minutes, are protected
Temperature to reaction terminates；And excessive 4- ethyl hexanols are steamed after the completion of reaction, the 4- ethyl hexanols：Pentaerythrite
Molar equivalent ratio=1:1；
(4) add in tri-n-butylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive tri-n-butylamine is steamed out under 99KPa pressure, the tri-n-butylamine：Molar equivalent ratio=6 of pentaerythrite:10；With
And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (4- ethyl hexyl alkyl, 5- methyl dodecyl) pentaerythritol ester, yield is 70%.
Embodiment 6
(1) added in into reaction vessel pentaerythrite, methyl tricapryl ammonium chloride, tri-n-butylamine and mesitylene and
15-20 DEG C of addition phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Tri-n-butylamine：Molar ratio=1 of phosphorus trioxide:
0.025：0.1：2, pentaerythrite：Molar ratio=1 of mesitylene：14；First, the first stage heats：Reaction temperature 30-40
DEG C, react 20min, second stage heating：110-115 DEG C of reaction temperature is reacted 10min, is sponged in this heating period
The hydrogen chloride gas of generation.After being warming up to 110-115 DEG C, with water rush vacuum pump be evacuated to for reaction vessel-
The mesitylene of extraction is simultaneously back in reaction vessel by 60Kpa.After extracting by mesitylene 130-136 DEG C of temperature ,-
It is steamed under 99KPa pressure；(2) in 115-120 DEG C, pressure -10KPa or so, 5- methyl lauryl alcohols are added drop-wise in 20 minutes
In reaction vessel, keep the temperature to reaction and terminate, the 5- methyl lauryl alcohol：Molar equivalent ratio=1 of pentaerythrite:1；
(3) in 115-120 DEG C, pressure -10KPa or so, 3- ethyl hexanols are added drop-wise to reaction vessel in 20 minutes, are protected
Temperature to reaction terminates；And excessive 3- ethyl hexanols are steamed after the completion of reaction, the 3- ethyl hexanols：Pentaerythrite
Molar equivalent ratio=1:1；
(4) add in tri-n-butylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive tri-n-butylamine is steamed out under 99KPa pressure, the tri-n-butylamine：Molar equivalent ratio=6 of pentaerythrite:10；With
And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (3- ethyl hexyl alkyl, 5- methyl dodecyl) pentaerythritol ester, yield is 70%.
Embodiment 7
(1) added in into reaction vessel pentaerythrite, methyl tricapryl ammonium chloride, triethylamine and mesitylene and
15-20 DEG C of addition phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Triethylamine：Molar ratio=1 of phosphorus trioxide:
0.025：0.1：2, pentaerythrite：Molar ratio=1 of mesitylene：14；First, the first stage heats：Reaction temperature 30-40
DEG C, react 20min, second stage heating：110-115 DEG C of reaction temperature is reacted 10min, is sponged in this heating period
The hydrogen chloride gas of generation.After being warming up to 110-115 DEG C, with water rush vacuum pump be evacuated to for reaction vessel-
The mesitylene of extraction is simultaneously back in reaction vessel by 60Kpa.After extracting by mesitylene 130-136 DEG C of temperature ,-
It is steamed under 99KPa pressure；
(2) in 115-120 DEG C, pressure -10KPa or so, isomerous tridecanol is added drop-wise in reaction vessel in 20 minutes,
Heat preservation to reaction terminates, the isomerous tridecanol：Molar equivalent ratio=1 of pentaerythrite:1；
(3) in 115-120 DEG C, pressure -10KPa or so, isooctanol is added drop-wise to reaction vessel in 20 minutes, heat preservation is extremely
Reaction terminates；And excessive isooctanol is steamed after the completion of reaction, the isooctanol：The molar equivalent ratio of pentaerythrite=
1:1；
(4) add in di-n-butylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive di-n-butylamine is steamed out under 99KPa pressure, the di-n-butylamine：Molar equivalent ratio=6 of pentaerythrite:10；With
And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) pentaerythritol ester, yield is 89%.
Embodiment 8
(1) added in into reaction vessel pentaerythrite, methyl tricapryl ammonium chloride, triethylamine and mesitylene and
15-20 DEG C of addition phosphorus trioxide, pentaerythrite：Methyl tricapryl ammonium chloride：Triethylamine：Molar ratio=1 of phosphorus trioxide:
0.03：0.12：22, pentaerythrite：Molar ratio=1 of mesitylene：5；First, the first stage heats：Reaction temperature 30-40
DEG C, react 20min, second stage heating：110-115 DEG C of reaction temperature is reacted 10min, is sponged in this heating period
The hydrogen chloride gas of generation.After being warming up to 110-115 DEG C, with water rush vacuum pump be evacuated to for reaction vessel-
The mesitylene of extraction is simultaneously back in reaction vessel by 60Kpa.After extracting by mesitylene 130-136 DEG C of temperature ,-
It is steamed under 99KPa pressure；
(2) in 115-120 DEG C, pressure -10KPa or so, isomerous tridecanol is added drop-wise in reaction vessel in 20 minutes,
Heat preservation to reaction terminates, the isomerous tridecanol：Molar equivalent ratio=1.2 of pentaerythrite:1；
(3) in 115-120 DEG C, pressure -10KPa or so, isooctanol is added drop-wise to reaction vessel in 20 minutes, heat preservation is extremely
Reaction terminates；And excessive isooctanol is steamed after the completion of reaction, the isooctanol：The molar equivalent ratio of pentaerythrite=
1.2:1；
(4) add in di-n-butylamine under 70-80 DEG C of temperature, normal pressure, neutralization reaction 10 minutes, 110-120 DEG C of temperature ,-
Excessive di-n-butylamine is steamed out under 99KPa pressure, the di-n-butylamine：Molar equivalent ratio=6 of pentaerythrite:10；With
And
(5) heat filtering at a temperature of 70-80 DEG C filters out the salinity in material, obtains as clear as crystal liquid, is exactly
Final product diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) pentaerythritol ester, yield is 89%.
It is understood that temperature and pressure data here are by way of example only, the present invention is not caused to limit.
It should be understood by those skilled in the art that the embodiment of the present invention shown in foregoing description be only used as citing and not
The limitation present invention.The purpose of the present invention has been fully and effectively achieved.The function and structural principle of the present invention is in embodiment
Middle displaying and explanation, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (20)
1. one is used to manufacture the preparation method of phosphite ester compound, which is characterized in that includes the following steps：
(1) by pentaerythrite, with phosphorus trichloride, the reaction under the action of alkali prepares pentaerthiyldichlorodiphosphite；
(2) generation mono- chloro pentaerythritol diphosphites of R- are reacted with dichloro pentaerythritol diphosphites by R-OH；With
And
(3) reacted using R '-OH with R- chloros pentaerythritol diphosphites and prepare R, R '-pentaerythritol diphosphites,
Described in R and R ' be different alkyl.
2. preparation method according to claim 1, wherein the alkali is organic weak base.
3. preparation method according to claim 2, wherein the R '-OH be selected from 3- methyl lauryl alcohol, 4- methyl lauryl alcohol,
One kind of 5- methyl lauryl alcohol, different tridecanol composition.
4. preparation method according to any one of claims 1 to 3, wherein the R-OH is selected from 3- ethyl hexanols, 4- ethyl hexyls
One kind in alcohol, isooctanol composition.
5. preparation method according to claim 1, wherein the R-OH：Equivalent proportion=1~1.2 of pentaerythrite:1.
6. preparation method according to claim 1, wherein the R '-OH：Equivalent proportion=1~1.2 of pentaerythrite:1 .
7. preparation method according to claim 1 wherein in the step (1), is heated using gradient increased temperature and reacted, production
Raw hydrogen chloride gas is absorbed.
8. wherein in the step (1), Ji Wusi is added in into reaction vessel for preparation method according to claim 1
Alcohol, alkali and organic solvent and 15-20 DEG C add in phosphorus trioxide, pentaerythrite：Alkali：Molar ratio=1 of phosphorus trioxide:
0.025~0.03：0.1~0.12:2~2.2, pentaerythrite：The molar ratio of organic solvent is more than 1:5；First, the first stage adds
Heat：30-40 DEG C of reaction temperature, second stage heating：110-115 DEG C of reaction temperature sponges generation in this heating period
Hydrogen chloride gas, after being warming up to 110-115 DEG C, with water rush vacuum pump vacuumized for reaction vessel and will extraction
Organic solvent be back in reaction vessel, organic solvent is steamed after extracting.
9. wherein in the step (1), Ji Wusi is added in into reaction vessel for preparation method according to claim 1
Alcohol, alkali and organic solvent and phosphorus trioxide, pentaerythrite are added under the conditions of ice-water bath：Alkali：The molar ratio of phosphorus trioxide=
1:0.025~0.03：0.1~0.12:2~2.2, pentaerythrite：The molar ratio of organic solvent is more than 1:5；First, the first stage
Heating：30-40 DEG C of reaction temperature, second stage heating：110-115 DEG C of reaction temperature sponges production in this heating period
Raw hydrogen chloride gas, after being warming up to 110-115 DEG C, with water rush vacuum pump vacuumized for reaction vessel and will take out
The organic solvent gone out is back in reaction vessel, is steamed organic solvent after extracting.
10. wherein in the step (1), Ji Wusi is added in into reaction vessel for preparation method according to claim 1
Alcohol, methyl tricapryl ammonium chloride, alkali and organic solvent and 15-20 DEG C add in phosphorus trioxide, pentaerythrite：Methyl trioctylphosphine
Ammonium chloride：Alkali：Molar ratio=1 of phosphorus trioxide:0.025~0.03：0.1~0.12:2~2.2, pentaerythrite：Organic solvent
Molar ratio be more than 1:5；First, the first stage heats：30-40 DEG C of reaction temperature, second stage heating：Reaction temperature 110-
115 DEG C, the hydrogen chloride gas of generation is sponged in this heating period, after being warming up to 110-115 DEG C, vacuum is being rushed with water
Pump is vacuumized for reaction vessel and the organic solvent of extraction is back in reaction vessel, will be organic after extracting
Solvent steams.
11. preparation method according to claims 1 to 10, wherein in the step (2), at 100 to 120 DEG C by R-OH
It is added drop-wise in reaction vessel, keeps the temperature to reaction and terminate, the R-OH：Equivalent proportion=1~1.2 of pentaerythrite:1.
12. wherein in the step (3), R '-OH are added dropwise at 100 to 120 DEG C for preparation method according to claim 11
Into reaction vessel, keep the temperature to reaction and terminate, the R '-OH：Equivalent proportion=1~1.2 of pentaerythrite:1.
13. preparation method according to claim 12, wherein the preparation method further comprises step (4), wherein institute
Stating step (4) is：
The alkali of a predetermined amount is added in neutralize solution, then removes remaining alkali, wherein the step (4) is located at the step
(3) after.
14. preparation method according to claim 13, wherein the preparation method further comprises step (4), wherein institute
Stating step (4) is：
If the R '-OH in the step (3) are excessive, the R '-OH are first removed, then add in the alkali of a predetermined amount in
And solution, then remaining alkali is removed, wherein the step (4) is located at after the step (3).
15. preparation method according to claim 14, wherein adding in the step (4) under 70-80 DEG C of temperature, normal pressure
Enter alkali to neutralize.
16. according to any preparation method of claim 14, wherein the alkali in the step (4) is triethylamine, two positive fourths
One or more in amine and tri-n-butylamine.
17. preparation method according to claim 16, wherein removing residue by way of evaporation in the step (4)
Alkali.
18. according to any preparation method of claim 12 to 17, wherein the preparation method further comprises step
(5), wherein the step (5) is：
Heat filtering is to obtain liquid phosphite class compound.
A 19. liquid phosphite class antioxidant, which is characterized in that including any preparation methods of claim 1-18
Phosphite ester compound is prepared.
20. liquid phosphite class antioxidant according to claim 19, wherein the phosphite ester compound selects
From diphosphorous acid (2- methyl heptane bases, 2- methyl dodecyl) pentaerythritol ester, diphosphorous acid (3- ethyl hexyl alkyl, 3- first
Base dodecyl) pentaerythritol ester, diphosphorous acid (4- ethyl hexyl alkyl, 4- methyl dodecyl) pentaerythritol ester, two phosphorous
Sour (4- ethyl hexyl alkyl, 5- methyl dodecyl) pentaerythritol ester, diphosphorous acid (3- ethyl hexyl alkyl, 5- methyl dodecanes
Base) pentaerythritol ester, diphosphorous acid (2- methyl heptane bases, 3- methyl dodecyl) pentaerythritol ester, diphosphorous acid (2- methyl
Heptane base, 4- methyl dodecyl) pentaerythritol ester, diphosphorous acid (2- methyl heptane bases, 5- methyl dodecyl) Ji Wusi
Alcohol ester, diphosphorous acid (3- ethyl hexyl alkyl, 4- methyl dodecyl) pentaerythritol ester, diphosphorous acid (3- ethyl hexyl alkyl, 2-
Methyl dodecyl) pentaerythritol ester, diphosphorous acid (4- ethyl hexyl alkyl, 2- methyl dodecyl) pentaerythritol ester, two is sub-
One or more in phosphoric acid (4- ethyl hexyl alkyl, 3- methyl dodecyl) pentaerythritol ester.
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