CN109054082A - One kind containing the organic ester stabilizer of phosphorous acid and its synthetic method - Google Patents
One kind containing the organic ester stabilizer of phosphorous acid and its synthetic method Download PDFInfo
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- CN109054082A CN109054082A CN201810810157.9A CN201810810157A CN109054082A CN 109054082 A CN109054082 A CN 109054082A CN 201810810157 A CN201810810157 A CN 201810810157A CN 109054082 A CN109054082 A CN 109054082A
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- CN
- China
- Prior art keywords
- acid
- stearic acid
- reaction
- pentaerythrite
- phosphorous
- Prior art date
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- Granted
Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 32
- 150000002895 organic esters Chemical class 0.000 title claims abstract description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 title claims description 18
- 238000010189 synthetic method Methods 0.000 title claims description 9
- -1 organic ester phosphite ester Chemical class 0.000 claims abstract description 40
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000004033 plastic Substances 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 235000021355 Stearic acid Nutrition 0.000 claims description 36
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 36
- 239000008117 stearic acid Substances 0.000 claims description 36
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LAFHJDSRGFVBHP-UHFFFAOYSA-N C(C(O)C)(=O)O.P(O)(O)O Chemical compound C(C(O)C)(=O)O.P(O)(O)O LAFHJDSRGFVBHP-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000005485 electric heating Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 235000011088 sodium lactate Nutrition 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical class OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 claims description 8
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 8
- 239000001540 sodium lactate Substances 0.000 claims description 8
- 229940005581 sodium lactate Drugs 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 7
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 5
- 150000008301 phosphite esters Chemical class 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 2
- RQWDXNAIEYQSPX-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)O.C(CCCCCCCCCCCCCCCCC)(=O)O.OP(O)OP(O)O.OCC(CO)(CO)CO Chemical class C(CCCCCCCCCCCCCCCCC)(=O)O.C(CCCCCCCCCCCCCCCCC)(=O)O.OP(O)OP(O)O.OCC(CO)(CO)CO RQWDXNAIEYQSPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 241000498779 Myristica Species 0.000 claims description 2
- 235000009421 Myristica fragrans Nutrition 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- MEEHILQTQNZOPZ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphite octadecanoic acid Chemical compound P(O)(O)OCC(CO)(CO)CO.C(CCCCCCCCCCCCCCCCC)(=O)O MEEHILQTQNZOPZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- PAPMYDUBILUNJX-UHFFFAOYSA-J calcium zinc tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ca++].[Zn++] PAPMYDUBILUNJX-UHFFFAOYSA-J 0.000 claims description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 2
- 229940001447 lactate Drugs 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 239000001702 nutmeg Substances 0.000 claims description 2
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 235000013618 yogurt Nutrition 0.000 claims 1
- 235000006708 antioxidants Nutrition 0.000 abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007812 deficiency Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 3
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
It is an object of the invention to overcome the above deficiencies in the existing technologies, and a kind of thermal stability with higher, antioxidant, weatherability and stability to hydrolysis resistance are provided, is mainly used as the stabilizer of plastic processing (such as polyvinyl chloride).The present invention uses organic ester phosphite ester antioxidant to be directly prepared into metallic salt and uses as stabilizer, is a kind of no phenol, no benzene, organic ester stabilizer of environment-protecting and non-poisonous phosphorous acid esters.Its characteristic is: the dendritic product of the high molecular weight with pentaerythrite structure；The stabilizer of response type characteristic with the good multiple functions of greasy property that is anti-oxidant, having had, plasticising performance；People are nontoxic to product to adapt to, environmentally friendly requirement.
Description
Technical field
The invention belongs to technical field of fine, in particular to one kind to contain the organic ester stabilizer product-of phosphorous acid
Two-(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc) and its synthetic method.
Background technique
Phosphite ester antioxidant is the faster a kind of product of development, the annual growth of global antioxidant in antioxidant kind
5%, and phosphite antioxidant annual growth reaches 7% or more, and development speed has leading in entire antioxidant
Position.Due to the rapid growth of plastics production capacity and yield, the growth of the production and consumption of antioxidant is stimulated and has pulled, the existing country
The growth of antioxidant is maintained at 10% growth rate.Domestic phosphite ester antioxidant receives more and more attention.
The stabilizer being added in plastic processing is mainly now two major class, first is that organic tin, this kind of stabilizer has well
Stability is mostly used for the processing of clear plastic articles, but its deficiency is mainly manifested in three aspects, first is that most organotin
Stabilizer is toxic, second is that it, in addition to stability, without other functions, now all joined in most organic tin stabilizer other
Component (such as lubricant, auxiliary antioxidant, the compositions such as plasticizer), third is that price.Second is that fatty acid salt based article stabilizer is (such as
Fatty acid calcium/magnesium/zinc etc.), this kind of fatty acid salt asepsis environment-protecting has the function of lubricant, but it also has insufficient aspect,
If stability is not so good as organic tin stabilizer, it cannot be used for transparent article mostly, need to add other auxiliary agents when in use to rise
To synergy (such as antioxidant, auxiliary stabilizer etc.).
Summary of the invention
It is an object of the invention to overcome the above deficiencies in the existing technologies, and it is steady to provide a kind of heat with higher
Qualitative, antioxidant, weatherability and stability to hydrolysis resistance are mainly used as the stabilizer of plastic processing (such as polyvinyl chloride).This is
One kind containing the organic ester stabilizer of phosphorous acid, it is characterized in that title are as follows: two-(double stearic acid pentaerythrite phosphorous acid lactic acid)-calcium
(zinc), molecular structural formula are:
Double stearic acid pentaerythrite=phosphorous acid-lactic acid
Calcium (zinc)
Double stearic acid pentaerythrites=phosphorous acid-Ru Suan ∕
Molecular weight are as follows: 1610~1635；
Phosphorus content are as follows: 3.80~3.85%；
Calcium content are as follows: 1.2~1.25%；
Zinc content are as follows: 1.95~2.05%.
The synthetic method that the present invention contains phosphorous acid organic ester antioxidant is divided into the synthesis of four steps:
The first step is pentaerythrite and stearic lactate synthesis, produces double stearic acid pentaerythritol esters, chemical reaction equation
Formula:
2 stearic acid+pentaerythrite-→+2 water of bis- stearic acid pentaerythritol ester
The reaction process of the first step is:, will in the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed
Esterification is carried out in pentaerythrite and stearic acid in molar ratio 1:2 proportion addition reaction flask, catalyst is stannous chloride, dosage
0.3-0.2%, 150-220 DEG C of reaction temperature, reaction time 60-180 minute is cooled to 100 DEG C hereinafter, obtaining after reaction
The double stearic acid pentaerythritol esters of product；
Second step is the synthesis of double stearic acid pentaerythritol esters and triethyl phosphite, produces three-bis- stearic acid pentaerythrites two
Phosphite ester, chemical equation:
Double stearic acid pentaerythritol ester+triethyl phosphites
+ 2 ethyl alcohol of-→ bis- stearic acid pentaerythritol diphosphites
The reaction process of second step is: in the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed,
1:1 is matched in molar ratio for the double stearic acid pentaerythritol esters of the product that the first step is reacted and triethyl phosphite, and catalyst is
Phosphoric acid, dosage 0.4-0.8%, 140-200 DEG C of reaction temperature, reaction time 120-180 minute is cooled to 100 DEG C after reaction
It is filtered hereinafter, being kept the temperature through constant temperature oven, obtains phosphorous acid organic ester antioxidant product-bis- stearic acid pentaerythrite diphosphorous acid
Ester；
Third step is the synthesis of double stearic acid pentaerythritol ester phosphite esters and sodium lactate, produces double stearic acid pentaerythrite phosphorous
Sour sodium lactate, chemical equation:
Double stearic acid pentaerythritol phosphite+sodium lactates
- → bis- stearic acid pentaerythrite phosphorous acid sodium lactate+ethyl alcohol
The reaction process of third step is: in the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed,
1:1 is matched in molar ratio for the double stearic acid pentaerythritol ester phosphite esters of the product that second step reacts and sodium lactate, catalyst
For phosphoric acid, dosage 0.4-0.8%, in reaction time 120-180 minute, is cooled to 100 after reaction by 140-200 DEG C of reaction temperature
DEG C hereinafter, obtaining phosphorous acid organic ester antioxidant product-bis- stearic acid pentaerythrite phosphorous acid sodium lactate；
4th step is that double stearic acid pentaerythritol ester phosphorous acid sodium lactates are reacted with calcium hydroxide (zinc) progress double decomposition displacement, is made
Product two-(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc) is taken, chemical equation:
2 pairs of stearic acid pentaerythrite phosphorous acid sodium lactate+calcium hydroxides (zinc)
+ 2 sodium hydroxide of-→ bis--(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc)
The reaction process of 4th step is: in the jar that electric stirring, electric heating, temp measuring system are housed, reacting in third step
2:1 is matched in molar ratio for the double stearic acid pentaerythritol ester phosphorous acid sodium lactates of obtained product and calcium hydroxide (zinc), in water
Carry out double decomposition displacement to react, the ratio of water and material presses 8:1(%), 60-90 DEG C of reaction temperature, reaction time 100-120 point
Clock carries out centrifugal dehydration after reaction, removes water, is placed on 120 DEG C of constant temperature oven drying, obtains the organic ester stabilizer of phosphorous acid
Product-bis--(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc).
Preferably, the catalyst further include: sodium hydroxide, phosphoric acid, phosphorous acid, sodium bisulfate, four butyl ester of phthalandione,
Phthalandione isopropyl ester, stannous chloride, stannous oxide.
Preferably, the stearic acid further includes product synthesized by different fatty acid identical from its structural behaviour,
These fatty acid have: caprylic acid, isooctyl acid, pungent capric acid, n-capric acid, lauric acid/dodecanoic acid (lauric acid), tetradecylic acid (nutmeg acid), 16
Sour (palmitinic acid), stearic acid (stearic acid), different stearic acid, erucic acid etc..
Preferably, the synthetic method containing the organic ester stabilizer of phosphorous acid, it is characterized in that the raw material is matched
It is calculated than in molar ratio, the molecular weight of the compound needed for 1 mole of amount just refers to.
The stabilizer that the organic ester stabilizer of phosphorous acid of the present invention can be used as product of rubber and plastic processing uses.Its structure composition is shown
Show that there are also antioxygenic property and greasy properties, is the auxiliary agent of a multifunctional plastic processing.
The present invention uses organic ester phosphite ester antioxidant to be directly prepared into metallic salt and uses as stabilizer, is a kind of nothing
Phenol, no benzene, organic ester stabilizer of environment-protecting and non-poisonous phosphorous acid esters.Its characteristic is: the high score with pentaerythrite structure
The dendritic product of son amount；Response type characteristic with the good multiple functions of greasy property that is anti-oxidant, having had, plasticising performance
Stabilizer；People are nontoxic to product to adapt to, environmentally friendly requirement.
Compared with prior art, the present invention having the following advantages that and effect: the present invention is a new compound, by more
Step reaction synthesis, says in structure, by coupling phosphite ester, makes it have antioxygenic property, then couple metal produce it is organic
Salt makes it have stabilization function.The compound process in the production of existing stabilizer is directly connected into one compound,
Structure is provided simultaneously with multifunctionality.In plastic processing, to preventing from aoxidizing, improving color etc. has the function of for it;Itself
With thermal stability, weatherability and stability to hydrolysis resistance.
Specific embodiment
The present invention is further described by the following embodiment.
Example one.
In the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed, by 68 (molecule of pentaerythrite
Amount 136, similarly hereinafter) gram, stearic acid 284 (284) gram 0.7 gram of catalyst stannous chloride, is separately added into reaction flask, in vacuum item
Part protection is lower to carry out esterification, controls 150-220 DEG C of reaction temperature, the reaction time 150 minutes, is cooled to after reaction
100 DEG C hereinafter, addition triethyl phosphite 83 (166) gram, is added 2.1 grams of catalyst phosphoric acid, carries out second under nitrogen protection
Step reaction controls 140-200 DEG C of reaction temperature, the reaction time 150 minutes, is cooled to 100 DEG C after reaction hereinafter, cream is added
Phosphatase 11 gram is added in sour sodium 56 (112) gram, carries out third step reaction, under vacuum conditions, 140-200 DEG C of reaction temperature, reaction
Time 120-180 minute is cooled to 100 DEG C hereinafter, obtaining the double stearic acid pentaerythrite phosphorous acid lactic acid of product after reaction
Sodium (808).By the double stearic acid pentaerythritol ester phosphorous acid sodium lactates of product and calcium hydroxide (zinc), 2:1 is matched in molar ratio,
Carry out the 4th step double decomposition displacement in water to react, the ratio of water and material presses 8:1(%), 60-80 DEG C of reaction temperature, the reaction time
100-120 minutes, centrifugal dehydration is carried out after reaction, removes water, is placed on 120 DEG C of constant temperature oven drying, obtaining phosphorous acid has
Machine ester stabilizer product-bis--(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc).
Example two.
In the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed, 68 grams of pentaerythrite (are divided
Son amount 136, similarly hereinafter), isooctyl acid 144(144) gram, it 0.5 gram of stannous oxide catalyst, is separately added into reaction flask, in vacuum item
Part protection is lower to carry out esterification, controls 150-200 DEG C of reaction temperature, reaction time 150-180 minute cools down after reaction
To 100 DEG C hereinafter, triethyl phosphite 83 (166) gram are added .4 grams of catalyst phosphatase 11 is added, carries out the under nitrogen protection
The reaction of two steps controls 140-180 DEG C of reaction temperature, the reaction time 120 minutes, is cooled to 100 DEG C after reaction hereinafter, being added
Phosphatase 11 gram is added in sodium lactate 56 (112) gram, carries out third step reaction under vacuum conditions, 140-200 DEG C of reaction temperature, reacts
Time 120-180 minute is cooled to 100 DEG C hereinafter, obtaining the double isooctyl acid pentaerythrite phosphorous acid lactic acid of product after reaction
Sodium.By the double isooctyl acid pentaerythritol ester phosphorous acid sodium lactates of product and calcium hydroxide (zinc), 2:1 is matched in molar ratio, in water into
The ratio of the 4th step double decomposition of row displacement reaction, water and material presses 8:1(%), 60-80 DEG C of reaction temperature, reaction time 100-120
Minute, centrifugal dehydration is carried out after reaction, removes water, is placed on 110 DEG C of constant temperature oven drying, is obtained phosphorous acid organic ester and stablize
Agent product-bis--(double isooctyl acid pentaerythrite phosphorous acid lactic acid) calcium (zinc).
Example three.
In the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed, 68 grams of pentaerythrite (are divided
Son amount 136, similarly hereinafter), palmitinic acid 256(256) gram, 1.7 grams of four butyl ester of catalyst phthalandione is separately added into reaction flask, in vacuum
Condition protection is lower to carry out esterification, controls 160-220 DEG C of reaction temperature, the reaction time 150 minutes, is cooled to after reaction
100 DEG C hereinafter, addition triethyl phosphite 83 (166), is added 1.5 grams of catalyst phosphorous acid, carries out second under nitrogen protection
Step reaction, control 140-200 DEG C of reaction temperature, reaction time 120-150 minute, be cooled to after reaction 100 DEG C hereinafter, plus
Enter sodium lactate 56 (112) gram, be added 1 gram of phosphorous acid, under vacuum conditions progress third step reaction, 140-200 DEG C of reaction temperature,
Reaction time 180 minutes, it is cooled to 100 DEG C after reaction hereinafter, obtaining the double palmitinic acid pentaerythrite phosphorous acid lactic acid of product
Sodium.By the double stearic acid pentaerythritol ester phosphorous acid sodium lactates of product and calcium hydroxide (zinc), 2:1 is matched in molar ratio, in water into
The ratio of the 4th step double decomposition of row displacement reaction, water and material presses 8:1(%), 60-90 DEG C of reaction temperature, reaction time 100-120
Minute, centrifugal dehydration is carried out after reaction, removes water, is placed on 120 DEG C of constant temperature oven drying, is obtained phosphorous acid organic ester and stablize
Agent product-bis--(double palmitinic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc).
Claims (6)
1. one kind contains the organic ester stabilizer of phosphorous acid, it is characterized in that title are as follows: two-(double stearic acid pentaerythrite phosphorous yogurts
Acid)-calcium (zinc), molecular structural formula is:
Double stearic acid pentaerythrite=phosphorous acid-lactic acid
Calcium (zinc)
Double stearic acid pentaerythrites=phosphorous acid-Ru Suan ∕
Molecular weight are as follows: 1610~1635；
Phosphorus content are as follows: 3.80~3.85%；
Calcium content are as follows: 1.2~1.25%；
Zinc content are as follows: 1.95~2.05%.
2. according to claim 1 contains the organic ester stabilizer of phosphorous acid: two-(double stearic acid pentaerythrite phosphorous acid
Lactic acid)-calcium (zinc) synthetic method, it is characterized in that being divided into the synthesis of four steps:
The first step is pentaerythrite and stearic lactate synthesis, produces double stearic acid pentaerythritol esters, chemical reaction equation
Formula:
2 stearic acid+pentaerythrite-→+2 water of bis- stearic acid pentaerythritol ester
The reaction process of the first step is:, will in the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed
Esterification is carried out in pentaerythrite and stearic acid in molar ratio 1:2 proportion addition reaction flask, catalyst is stannous chloride, dosage
0.3-0.2%, 150-220 DEG C of reaction temperature, reaction time 60-180 minute is cooled to 100 DEG C hereinafter, obtaining after reaction
The double stearic acid pentaerythritol esters of product；
Second step is the synthesis of double stearic acid pentaerythritol esters and triethyl phosphite, produces three-bis- stearic acid pentaerythrites two
Phosphite ester, chemical equation:
Double stearic acid pentaerythritol ester+triethyl phosphites
+ 2 ethyl alcohol of-→ bis- stearic acid pentaerythritol diphosphites
The reaction process of second step is: in the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed,
1:1 is matched in molar ratio for the double stearic acid pentaerythritol esters of the product that the first step is reacted and triethyl phosphite, and catalyst is
Phosphoric acid, dosage 0.4-0.8%, 140-200 DEG C of reaction temperature, reaction time 120-180 minute is cooled to 100 DEG C after reaction
It is filtered hereinafter, being kept the temperature through constant temperature oven, obtains phosphorous acid organic ester antioxidant product-bis- stearic acid pentaerythrite diphosphorous acid
Ester；
Third step is the synthesis of double stearic acid pentaerythritol ester phosphite esters and sodium lactate, produces double stearic acid pentaerythrite phosphorous
Sour sodium lactate, chemical equation:
Double stearic acid pentaerythritol phosphite+sodium lactates
- → bis- stearic acid pentaerythrite phosphorous acid sodium lactate+ethyl alcohol
The reaction process of third step is: in the reaction flask that electric stirring, electric heating, reflux condenser, temp measuring system are housed,
1:1 is matched in molar ratio for the double stearic acid pentaerythritol ester phosphite esters of the product that second step reacts and sodium lactate, catalyst
For phosphoric acid, dosage 0.4-0.8%, in reaction time 120-180 minute, is cooled to 100 after reaction by 140-200 DEG C of reaction temperature
DEG C hereinafter, obtaining phosphorous acid organic ester antioxidant product-bis- stearic acid pentaerythrite phosphorous acid sodium lactate；
4th step is that double stearic acid pentaerythritol ester phosphorous acid sodium lactates are reacted with calcium hydroxide (zinc) progress double decomposition displacement, is made
Product two-(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc) is taken, chemical equation:
2 pairs of stearic acid pentaerythrite phosphorous acid sodium lactate+calcium hydroxides (zinc)
+ 2 sodium hydroxide of-→ bis--(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc)
The reaction process of 4th step is: in the jar that electric stirring, electric heating, temp measuring system are housed, reacting in third step
2:1 is matched in molar ratio for the double stearic acid pentaerythritol ester phosphorous acid sodium lactates of obtained product and calcium hydroxide (zinc), in water
Carry out double decomposition displacement to react, the ratio of water and material presses 8:1(%), 60-80 DEG C of reaction temperature, reaction time 100-120 point
Clock carries out centrifugal dehydration after reaction, removes water, is placed on 120 DEG C of constant temperature oven drying, obtains the organic ester stabilizer of phosphorous acid
Product-bis--(double stearic acid pentaerythrite phosphorous acid lactic acid) calcium (zinc).
3. the organic ester stabilizer of phosphorous acid according to claim 1, it is characterized in that can be used as the stabilization of product of rubber and plastic processing
Agent uses.
4. the synthetic method according to claim 2 containing the organic ester stabilizer of phosphorous acid, it is characterized in that the catalysis
Agent further include: sodium hydroxide, phosphoric acid, sodium bisulfate, four butyl ester of phthalandione, phthalandione isopropyl ester, stannous chloride, stannous oxide.
5. the synthetic method according to claim 2 containing the organic ester stabilizer of phosphorous acid, it is characterized in that the tristearin
Acid further includes product synthesized by different fatty acid identical from its structural behaviour, these fatty acid have: caprylic acid, isooctyl acid,
Pungent capric acid, n-capric acid, lauric acid/dodecanoic acid (lauric acid), tetradecylic acid (nutmeg acid), hexadecylic acid (palmitinic acid), stearic acid (stearic acid),
Different stearic acid, erucic acid etc..
6. the synthetic method according to claim 2 containing the organic ester stabilizer of phosphorous acid, it is characterized in that the raw material
Proportion calculates in molar ratio, the molecular weight of the compound needed for 1 mole of amount just refers to.
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| CN114057997A (en) * | 2021-11-26 | 2022-02-18 | 北京理工大学鲁南研究院 | Glycerol ester based chlorine-containing plastic heat stabilizer and stepwise esterification method production method thereof |
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