CN105732713A - Amphiphilic compound containing hindered phenol and phosphite ester and synthetic method and application thereof - Google Patents
Amphiphilic compound containing hindered phenol and phosphite ester and synthetic method and application thereof Download PDFInfo
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- CN105732713A CN105732713A CN201410766897.9A CN201410766897A CN105732713A CN 105732713 A CN105732713 A CN 105732713A CN 201410766897 A CN201410766897 A CN 201410766897A CN 105732713 A CN105732713 A CN 105732713A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 150000008301 phosphite esters Chemical class 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title claims description 15
- -1 polypropylene Polymers 0.000 claims abstract description 52
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 239000004743 Polypropylene Substances 0.000 claims abstract description 11
- 229920001155 polypropylene Polymers 0.000 claims abstract description 11
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 109
- 238000006243 chemical reaction Methods 0.000 claims description 89
- 239000000376 reactant Substances 0.000 claims description 80
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 78
- 229910052757 nitrogen Inorganic materials 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 125000003944 tolyl group Chemical group 0.000 claims description 40
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 38
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 33
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 32
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 28
- 239000012043 crude product Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 26
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 238000004440 column chromatography Methods 0.000 claims description 22
- JJFOBACUIRKUPN-UHFFFAOYSA-N 2-bromoethoxybenzene Chemical class BrCCOC1=CC=CC=C1 JJFOBACUIRKUPN-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 230000006837 decompression Effects 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 12
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- TVWAVADIILZVIY-UHFFFAOYSA-N 1,3-ditert-butyl-2-methoxy-5-methylbenzene Chemical class COC1=C(C(C)(C)C)C=C(C)C=C1C(C)(C)C TVWAVADIILZVIY-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 208000035126 Facies Diseases 0.000 claims description 3
- 150000001298 alcohols Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000010511 deprotection reaction Methods 0.000 claims description 3
- GTQHJCOHNAFHRE-UHFFFAOYSA-N 1,10-dibromodecane Chemical compound BrCCCCCCCCCCBr GTQHJCOHNAFHRE-UHFFFAOYSA-N 0.000 claims description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 2
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 claims description 2
- XGQOMXPCQPOGSH-UHFFFAOYSA-N 2,3-ditert-butyl-1-methoxy-4-methylbenzene Chemical class COC1=CC=C(C)C(C(C)(C)C)=C1C(C)(C)C XGQOMXPCQPOGSH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 31
- 229920005989 resin Polymers 0.000 abstract description 31
- 150000003983 crown ethers Chemical group 0.000 abstract description 26
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000002274 desiccant Substances 0.000 description 16
- 229920002521 macromolecule Polymers 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 230000003064 anti-oxidating effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an amphiphilic compound comprising a hindered phenol unit, a phosphite unit, a crown ether unit, and a linear chain segment unit. The length of the straight chain segment unit is controlled to adjust the distance between the hindered phenol and the phosphite ester unit so as to control the synergistic effect of the hindered phenol and the phosphite ester unit, and the effective functional group content in the unit mass of the compound and the compatibility of the compound and the resin. The hindered phenol structural unit and the phosphite structural unit can be transferred to the surface layer of the resin through the transfer function of the crown ether unit, so that the oxidation in the air is more effectively eliminated; the hindered phenol unit and the phosphite ester unit can effectively prevent the crown ether unit from falling off from the surface of the resin due to the large space structure, and the antistatic time of the compound is prolonged. The compound of the invention can be used as an antistatic antioxidant for polypropylene or polyethylene.
Description
Technical field
The present invention relates to a kind of antioxidation, antistatic dual-function compound and synthetic method thereof, particularly relate to and a kind of unimolecule comprises hindered phenol and phosphite ester and the antioxidation of crown ether structures, antistatic compound and synthetic method thereof simultaneously.
Background technology
Hindered phenol compound is owing to can fight for, with polymer, the peroxy radical formed in autoxidation, by the transfer of hydrogen atom, form carboxylic acid and a kind of stable antioxidant free radical, this free radical has again the ability catching living radical, it is possible to the second kinetic chain of termination polymer chain type oxidation reaction.And peroxide is decomposed into stable product one by self to the conversion of phosphate compounds and plays the protective effect to polymer by phosphite ester compound.In the antioxidation of polymer, show extraordinary synergism between hindered phenol compound and phosphite ester compound, the antioxidant 1010 that produces such as Ciba, 1076 and 168 composite after be widely used among the antioxidant of the products such as polyolefin, ABS resin, synthetic rubber and polyester.
Hinered phenols antioxidant is usually generated by the mode of ester exchange in the basic conditions.As: US4716244, US5481023, US5563291, US6878843, US2003166962 describe with Lithamide., lithium acetate, sodium acetate, magnesium acetate, three b propanol aluminum, zinc acetate etc. for catalyst preparing Hinered phenols antioxidant (as antioxidant 1010,1076,245 and 1135) process.Phosphite ester kind antioxidant is usually alcohol compound by reacting prepared with Phosphorous chloride..As: CN200510112503.9, CN200710056079.X, CN200710176407.X describe tetramethylolmethane or nonyl phenol and Phosphorous chloride. in a solvent by the process of ester exchange acquisition phosphite ester kind antioxidant.
Amphiphilic compound can occur to migrate and move to resin surface and form dense arrangement in resin, surface concentration is higher than inside, and hydrophilic unit, towards air, forms conductive layer in conjunction with the moisture in air, the electrostatic charge making accumulation is dissipated, the effective gathering reducing deleterious charge.Amphiphilic compound antistatic additive is usually polycondensation reaction and prepares.As: CN200810046009.0, CN200810150057.4, CN02151546.8 describe the preparation process of the amphiphilic antistatic additive of different molecular structures.
Present stage Hinered phenols antioxidant, phosphorous acid esters auxiliary antioxidant and parents' class antistatic additive widely use in polyolefin products, Hinered phenols antioxidant and relatively uniform being dispersed among resin and play antioxidation of phosphorous acid esters auxiliary antioxidant, but it only has surface and air contact therefore to only have a small amount of Hinered phenols molecule and phosphite ester quasi-molecule to play antioxidation after resin forming, the synergism of hindered phenol and phosphite ester also cannot embody preferably simultaneously, thus greatly reduces antioxidant effect.
Summary of the invention
Weak point that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and the polyfunctional group antioxidation of a kind of function admirable, antistatic compound and synthetic method thereof are provided.
Under the structure of compound provided by the present invention such as formula (I):
Under the structure of compound provided by the present invention such as formula (I):
Wherein n is the positive integer of 3-16;M is the positive integer of 6-12.
The synthetic route of compound of the present invention is:
In synthetic route, the 1st step is hydroxyl protection, and hindered phenol is converted into methyl phenyl ethers anisole temporarily, in case hydroxyl is destroyed in bromo-reaction below;2nd step reaction is the α bromo of benzyl, is generally adopted the typical brominated reagents such as NBS and carries out;3rd step and the 4th step and the reaction of the 5th step be bromo-derivative under alkaline matter effect with the reaction of alcohol, this type of reaction can specifically carry out degree by what control that bromo-derivative and alcohols material mol ratio realize reaction;6th step reaction is the phosphating reaction of alcohol, after being generally under low temperature to be added drop-wise in alcoholic solution by Phosphorous chloride., solution adds hot preparation phosphite ester again;During the 7th step reaction, the methyl phenyl ethers anisole after the hydroxyl protection of the 1st step reaction being re-converted into hydroxyl, this type of reaction generally uses Boron tribromide, and reaction very easily carries out, and conversion ratio is very high.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of synthetic method of the novel antioxidant comprising difunctional, raw material includes: 2,6-di-tert-butyl methyl phenol, dimethyl sulfate, N-bromo-succinimide, azodiisobutyronitrile, straight diol, straight chain dibromoalkane, N, N-diethyl alcohol radical-1,10-diaza-18 crown-6, Phosphorous chloride., Boron tribromide diethyl ether solution.
1st step, the protection of phenolic hydroxyl group:
By 2; 6-di-tert-butyl methyl phenol and dimethyl sulfate are 1 in molar ratio: (1.1~2) add reactor; it is simultaneously introduced reaction solvent A; the concentration making BHT is 0.1-0.4mol/L, under nitrogen protection; reaction temperature is 45 DEG C~61 DEG C; response time is 0.1h~2h, generates 2,6-di-t-butyl p-methyl anisoles;
Phenolic hydroxyl group protection course of reaction is:
Protect in course of reaction at phenolic hydroxyl group, use proton nmr spectra1The content of BHT in HNMR analysis monitoring reactant, until inspection does not measure BHT in reactant;Generally can every monitoring in 10 minutes once, it is possible to adopt unequal interval cycle monitoring.
By theoretical value, dimethyl sulfate should be 1/2nd of BHT, and during practical application, the dimethyl sulfate of addition is substantially excessive, to ensure the total overall reaction of BHT.In reaction, nitrogen plays the protective effect to reaction, it is prevented that oxygen or the interference for reacting of other impurity.
After reacting completely, reactant liquor being cooled to room temperature, add the solution of potassium carbonate 0.5-1.5L that concentration is 0.2-0.6mol/L and extract, repeat 3-5 time in reactant liquor, organic facies is evaporated after drying and can obtain 2,6-pure di-t-butyl p-methyl anisoles.
2nd step, the α bromo of 2,6-di-t-butyl p-methyl anisoles:
By 2; 6-di-t-butyl p-methyl anisole and N-bromo-succinimide are 1 in molar ratio: (1~1.5) adds reactor; it is simultaneously introduced reaction dissolvent B so that the concentration of 2,6-di-t-butyl p-methyl anisoles is 0.3-0.6mol/L; under nitrogen protection; under the catalytic action of azodiisobutyronitrile, reaction temperature 50 DEG C~77 DEG C, 2~5 hours response time; generate 2,6-di-t-butyls to bromomethyl methyl phenyl ethers anisole.Wherein azodiisobutyronitrile concentration in reaction dissolvent B is 0.002-0.004mol/L.
The equation of bromo-reaction is:
In bromo-reaction process, the color of observing response solution, when the orange color dissipated of reactant liquor, and there is white precipitate to continue reaction 1~2 hour after generating.
Intermediate product 2, the 6-di-t-butyl method purifying available recrystallization to bromomethyl methyl phenyl ethers anisole in the present invention, the solvent of selected recrystallization is normal hexane.
3rd step, 2, the 6-di-t-butyls alcoholization reaction to bromomethyl methyl phenyl ethers anisole:
By 2,6-di-t-butyl to bromomethyl methyl phenyl ethers anisole and glycol compound HO (CH2)nOH is 1 in molar ratio: (1.1~3) add reactor, adds and 2, the 6-di-t-butyls alkaline matter to bromomethyl methyl phenyl ethers anisole equimolar amounts, and this alkaline matter can be: sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate.It is simultaneously introduced reaction dissolvent C so that the concentration of bromomethyl methyl phenyl ethers anisole is 0.2-0.4mol/L by 2,6-di-t-butyls, under the catalytic action of alkaline matter, by reactant liquor heating to backflow, 5 hours~60 hours response time, generate 3,5-di-t-butyls to methyl oxygen base methyl phenyl ethers anisole alcohol.
The equation of bromo-reaction is:
Diol compound HO (CH used in reaction2)nIn OH, n is the positive integer of 3~16.
The shift value utilizing reactant and the product thin layer chromatography on silica gel plate during reaction is different, developing solvent is chloroform, methanol, monitoring 2,6-di-t-butyl is thin out till no longer change gradually to the colour developing point of bromomethyl methyl phenyl ethers anisole, stop heating, in reactant liquor, add distilled water after reactant liquor recovers room temperature extract, organic facies is dried, utilize column chromatography for separation to obtain clean product.
4th step, 3, the 5-di-t-butyls bromination reaction to methyl oxygen base methyl phenyl ethers anisole alcohol:
3 that upper step is prepared, 5-di-t-butyl is to methyl oxygen base methyl phenyl ethers anisole alcohol and dibromoalkane, such as 1,6-dibromo-hexane, 1,8-bis-bromooctane, 1,10-dibromo-decane etc., it is that 1 (3~5) add reactor according to mol ratio, adding and 3, the 5-di-t-butyls alkaline matter to methyl oxygen base methyl phenyl ethers anisole alcohol equimolar amounts, this alkaline matter can be: sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate.It is simultaneously introduced reaction dissolvent D, make 3, the concentration of methyl oxygen base methyl phenyl ethers anisole alcohol is 0.1-0.3mol/L by 5-di-t-butyl, reactant liquor is heated to reflux 10~48 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, after utilize column chromatography for separation to obtain bromo-derivative clean product.
Reaction equation prepared by described bromo-derivative is:
Wherein n is the positive integer of 3-16;M is the positive integer of 6-12.
Utilize thin layer chromatography monitoring reaction process, stopped reaction after when continuation heating 1-2 is little after the colour developing point of three-step reaction product is progressively reduced until and no longer changes.The method of the solid crude product column chromatography that decompression distillation obtains is easily separated purification.
5th step, the preparation of hindered phenol-crown ether Amphi-pathic compound:
The bromo-derivative that 4th step reaction is prepared and N, N-diethyl alcohol radical-1,10-diaza-18 crown-6 1:(1~3 in molar ratio) mixing, it is simultaneously introduced alkaline matter equimolar with bromo-derivative, this alkaline matter can be: sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate.It is simultaneously introduced reaction dissolvent E so that the concentration of the bromo-derivative that the 4th step reaction prepares is 0.3-0.6mol/L, and reactant liquor is heated to reflux 10~48 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, after utilize column chromatography for separation to obtain { [(3,5-di-t-butyls, 4-methoxyl group) tolyl, m-m alkyl] n-n glycol ether-ethyl }, 2-hydroxyethyl, N, the clean product of N-1,10-diaza-18 crown-6.
Wherein n is the positive integer of 3-16;M is the positive integer of 6-12.
Utilize thin layer chromatography monitoring reaction process, stopped reaction after when continuation heating 1-2 is little after the colour developing point of the bromo-derivative that the 4th step is obtained by reacting is progressively reduced until and no longer changes.The method of the solid crude product column chromatography that decompression distillation obtains is easily separated purification.
6th step, the preparation of phosphite ester:
{ [(3 that the reaction of upper step is prepared, 5-di-t-butyl, 4-methoxyl group) tolyl, m-m alkyl] n-n glycol ether-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6 adds reactor, it is simultaneously introduced reaction dissolvent F, make { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, m-m alkyl] n-n glycol ether-ethyl }, 2-hydroxyethyl, N, N-1, the concentration of 10-diaza-18 crown-6 is 0.2-0.4mol/L, under the protection of nitrogen, reactant liquor is controlled at 0 DEG C~20 DEG C, the Phosphorous chloride. that mole is alcohols material 1/1/3rd~bis-is dripped in reactant liquor, time for adding is 0.5~5 hour.It is added dropwise to complete after maintenance temperature continues reaction 2~10 hours and reactant liquor is heated to 130 DEG C~135 DEG C, reflux 2~5 hours under 0.02-0.05MPa, prepare three { [(3,5-di-t-butyl, 4-methoxyl group) tolyl, m-m alkyl] n-n glycol ether-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester.
Three [(3,5-di-t-butyls, 4-methoxyl group) tolyl, m-m alkyl] n-n glycol ether-ethyl, 2-hydroxyethyl, N, N-1, reaction equation prepared by 10-diaza-18 crown-6} phosphite ester is:
Wherein n is the positive integer of 3-16;M is the positive integer of 6-12.
Utilize thin layer chromatography monitoring reaction process, stopped reaction after the colour developing point of the 5th step product is progressively reduced until no longer change.Improve the vacuum of reaction system after having reacted, uniformly substantial amounts of dimethylbenzene and triethylamine are steamed from there-necked flask.Cooling, adds isobutanol washing, and reduces temperature of charge further, product crystallization, and filtration washing is dried and obtained product.
7th step, the deprotection reaction of hydroxyl:
null6th step is reacted the three { [(3 of gained,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl,2-hydroxyethyl,N,N-1,10-diaza-18 crown-6} phosphite ester joins among the there-necked flask containing reaction dissolvent G,Control three { [(3,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl,2-hydroxyethyl,N,N-1,The concentration of 10-diaza-18 crown-6} phosphite ester is 0.01-0.2mol/L,After reacting liquid temperature is down to 0 DEG C~-50 DEG C, the solution G being dissolved with Boron tribromide in advance is added drop-wise among flask,Three { [(3,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl,2-hydroxyethyl,N,N-1,10-diaza-18 crown-6} phosphite ester and Boron tribromide are 3 in molar ratio: (1~3),Time for adding is 1~5 hour,Stir 2~5 hours after reactant liquor is returned to after dripping room temperature.
The reaction equation of hydroxyl deprotection is:
Utilize thin layer chromatography monitoring reaction process, react the colour developing point of phosphite ester compound of gained when the 6th step and taper into until stopped reaction after disappearing.Reactant liquor is transferred in separatory funnel, add pH value distilled water between 7~8, dry 6~24 hours with anhydrous magnesium sulfate after organic layer being separated after repeatedly extracting, after being filtered to remove desiccant, obtain clean product by being evaporated under filter vacuum.
Synthesis step involved in above technical scheme is conventional methodology of organic synthesis, the reaction dissolvent that each step adopts is the Conventional solvents of such synthetic reaction applicable, those skilled in the art can carry out conventional selection according to the Professional knowledge grasped and general knowledge, is not specially limited in the present invention.In order to reach better reaction effect, the present invention provides the preferred version of reaction solvent A-G.Preferred version is:
A solvent is selected from following at least one: chlorobenzene, dichloromethane, chloroform, toluene;
B at least one in following: benzene, dichloromethane, chloroform, carbon tetrachloride;
C at least one in following: methanol, ethanol, acetone, dimethylformamide;
D at least one in following: triethylamine, ethanol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, dichloromethane, carbon tetrachloride, ethyl acetate;
E at least one in following: triethylamine, ethanol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, dichloromethane, carbon tetrachloride, ethyl acetate;
F at least one in following: triethylamine, ethanol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, dichloromethane, carbon tetrachloride, ethyl acetate;
G at least one in following: dichloromethane, chloroform, carbon tetrachloride.
The compound of present invention synthesis can as polypropylene or the antioxidant of polyethylene, antistatic additive use.This compounds is added in polypropylene or polyethylene base material by the different purposes according to goods according to mass content 0.05% to 0.15%, can play antioxidation, antistatic effectiveness after extruder grain.
The invention has the beneficial effects as follows:
The method utilizing chemosynthesis, is simultaneously introduced hindered phenol structure unit, phosphite ester construction unit and crown ether structures unit in same molecule.Hindered phenol structure is owing to can fight for, with polymer, the peroxy radical formed in autoxidation; by the transfer of hydrogen atom; form carboxylic acid and a kind of stable antioxidant free radical; this free radical has again the ability catching living radical; second kinetic chain of the polymer chain type oxidation reaction that can terminate; therefore hindered phenol structure unit exists as the antioxidation functional group of whole molecule, and peroxide is decomposed into stable product by self to the conversion of phosphate compounds and plays the protective effect to polymer by phosphite ester compound.In the antioxidation of polymer, extraordinary synergism is shown between hindered phenol compound and phosphite ester compound.Crown ether structures is a kind of typical hydrophilic thin fat structure, when compound containing crown ether structures joins in macromolecule resin, due to hydrophilic lipophobic interaction contains the compound of crown ether structures can to macromolecule resin surface migration, compound containing crown ether structures contacts with the water in air on macromolecule resin surface and forms the moisture film that can be led away by electric charge, in case macromolecule resin surface charge is piled up, therefore crown ether structures unit can use as the antistatic functional group of whole molecule.When same molecule had both contained hindered phenol structure unit, when phosphite ester construction unit contains again crown ether structures unit, three kinds of construction units are except the original antioxidation of each self-sustaining or anlistatig function, due to crown ether structures unit because hydrophilic lipophobic interaction can drive hindered phenol structure unit and phosphite ester construction unit from moving to resin surface inside resin and being enriched with at resin surface to macromolecule resin surface migration simultaneously, improve the quantity of resin surface hindered phenol structure unit and phosphite ester construction unit, strengthen the antioxidation of resin, thus better protection macromolecule resin product is from the impact of the hot oxygen environment in air.Have bigger sterically hindered simultaneously because hindered phenol structure unit, phosphite ester construction unit compare the chain structure unit such as alkyl, when crown ether structures unit is when macromolecule resin surface enrichment, the hindered phenol structure unit being connected with crown ether structures unit and phosphite ester structure effectively can be tangled with the long strand of macromolecule resin, this entanglement can supression crown ether structures come off from resin surface, increase product the antistatic cycle.
The compound of present invention synthesis is compared with common hindered phenol compound; when hindered phenol structure content is suitable; macromolecule resin is added as antioxidant; in the present invention, the compound of synthesis is because of containing phosphite ester construction unit; oxidized hindered phenol peroxide is reduced to hindered phenol structure by the conversion to phosphoric acid ester structure by phosphite ester structure again, plays the more excellent protective effect to polymer.The hydrophilic lipophobic interaction of crown ether structures unit forms the enrichment of hindered phenol and phosphite ester on macromolecule resin surface simultaneously, high concentration hindered phenol unit and the phosphite ester unit of local is formed at the interface of macromolecule resin with air contact, making its antioxidant effect be substantially better than common hindered phenol compound, the compound of present invention synthesis simultaneously is also equipped with obvious antistatic property compared with common hindered phenol compound.The compound of present invention synthesis is compared with common phosphite ester compound, when phosphite ester structural unit content is thought at that time, because of the compound of present invention synthesis contain hindered phenol structure its actively oxidation resistance be substantially better than common phosphite ester compound, because of the compound of present invention synthesis, it contains crown ether structures it also has the anti-static function not available for common phosphite simultaneously.
The compound of present invention synthesis is compared with common crown ether compound, when crown ether structures content is suitable, macromolecule resin is added as antistatic additive, because containing bigger sterically hindered hindered phenol structure unit and phosphite ester construction unit in the compound of synthesis in the present invention, at the hydrophilic lipophobic interaction of crown ether structures unit when the enrichment of macromolecule resin surface formation hindered phenol, the hindered phenol structure unit being connected with crown ether structures unit and phosphite ester construction unit effectively can tangle with the long strand of macromolecule resin, this entanglement can supression crown ether structures come off from resin surface, thus compared with common crown ether compound antistatic cycle of compound of present invention synthesis longer, the compound of present invention synthesis simultaneously also has antioxygenic property compared with common crown ether compound.
The compound of present invention synthesis and common hindered phenol compound, the mixture that phosphite ester compound forms with common crown ether compound is compared, when hindered phenol structure content, phosphite ester structural content and crown ether structures content are homogeneous at that time, macromolecule resin is added as antioxidant and antistatic additive, the compound of present invention synthesis is because of crown ether unit and hindered phenol unit, mutually collaborative its antioxidant effect of effect existed between phosphite ester unit three and anlistatig cycle are all better than common hindered phenol compound, the mixture of phosphite ester compound and common crown ether compound composition adds among macromolecule resin.The chain length utilizing selected glycol and diether carrys out the size of Molecular regulator, so can change this type of molecular weight of material thus changing its compatibility in naval stores, to play antioxidation and the antistatic effect of the best.
The present invention adopt method also have each step react in product yield higher, purify easier feature.
Nuclear-magnetism explanation
Wherein n is the positive integer of 3-16;M is the positive integer of 6-12.
1HNMR (500Hz, DMSO), δ: 9.05 (S, 3H), δ: 7.07 (S, 6H), δ: 4.45 (S, 6H), δ: 4.12 (t, 6H), δ: 3.47-3.39 (m, 78H), δ: 2.74-2.66 (m, 36H), δ: 2.45-1.82 (m, (6n+6m-24) H) δ: 1.26 (S, 54H).
In the nuclear-magnetism spectrum of compound, δ=9.05 represent hindered phenol structure, and δ=4.12 represent CH on straight chain adjacent with the oxygen atom that P atom links2-structure, δ: 3.47-3.39 represents on crown ether near the CH of oxygen atom2-structure, near the CH of nitrogen-atoms on δ: 2.74-2.66 crown ether2-representation.
Detailed description of the invention
The present invention is further described below in conjunction with embodiment.The scope of the present invention is not restricted by the embodiments, and the scope of the present invention proposes in detail in the claims.
The raw material sources and the specification thereof that use in an embodiment are as follows:
2,6-di-tert-butyl methyl phenol: Amresco analytical pure;
Dimethyl sulfate: Amresco analytical pure;
N-bromo-succinimide: chemical industry Reagent Company of traditional Chinese medicines group analytical pure;
Azodiisobutyronitrile: chemical industry Reagent Company of traditional Chinese medicines group analytical pure;
HO(CH2)nOH:FLUK analytical pure;
Br(CH2)nBr:FLUK analytical pure;
Phosphorous chloride.: lark prestige company analytical pure;
The diethyl ether solution of Boron tribromide: lark prestige company analytical pure;
Anhydrous magnesium sulfate, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, dichloromethane, chloroform, carbon tetrachloride, methanol, ethanol, acetone, dimethylformamide, triethylamine, toluene, benzene, dimethylbenzene, chlorobenzene, ethyl acetate, above solvent are Tianjin Tian Tai chemical company analytical pure;
Polypropylene powder used in Comparison study example derives from Lanzhou Petrochemical Company, for chemical products;Antioxidant 1010, irgasfos 168 and calcium stearate are that vapour Bagong department produces, for chemical pure;Antistatic additive hexadecyltrimethylammonium chloride vapour bar Products, for chemical pure.
Embodiment 1
Under nitrogen protection, 220g2,6-di-tert-butyl methyl phenol and 150g dimethyl sulfate are dissolved among the 2.5L chloroform dried.Reactant liquor is heated to 60 DEG C under stirring among the there-necked flask of 5L, reaction continues 1.5 hours.Repeatedly extracting four times with the solution of potassium carbonate of 1LO.5mol/L after reactant liquor is cooled to 25 DEG C, organic over anhydrous magnesium sulfate dries 24 hours.It is filtered to remove the anhydrous magnesium sulfate desiccant in solution, solvent is under reduced pressure evaporated off, obtain 2,6-di-t-butyl p-methyl anisole 215.3g, yield 92%.
Under nitrogen protection 215.3g2,6-di-t-butyl p-methyl anisole is joined equipped with among the 5L there-necked flask of 3L carbon tetrachloride.It is subsequently adding 161gN-bromo-succinimide and 2g azodiisobutyronitrile, heating is stopped after reactant liquor heating being continued 3 hours to 77 DEG C of reactions, after reactant liquor is cooled to 0 DEG C, it is filtered to remove white depositions, gained filtrate under reduced pressure removes solvent, and crude product utilizes normal hexane recrystallization, obtains 2,6-di-t-butyl is to bromomethyl methyl phenyl ethers anisole 175.7g, and productivity is 61%.
By 175.7g2,6-di-t-butyl to bromomethyl methyl phenyl ethers anisole and 65g1, ammediol joins among 5L there-necked flask, then adds 2L acetone solvent and 39g Anhydrous potassium carbonate in flask.After reactant liquor is heated to reflux 6 hours, remove heater, reactant liquor is cooled to 25 DEG C.Decompression is lower remove solvent after gained solid is dissolved among 1.5L ether, repeatedly extract three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and after hydrochloric acid weak solution extracting twice again, organic over anhydrous magnesium sulfate is dried 12 hours.After being filtered to remove desiccant, distillation under pressure removing solvent obtains solid crude product, and column chromatography (developing solvent is chloroform, methanol) obtains pure 1,3-PD list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole 117.6g, productivity 68%.
By 117.6g1, ammediol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole, 281.5g1,6-dibromo-hexane and 15.4g sodium hydroxide join in the there-necked flask containing 1.8L dehydrated alcohol 5L, are heated to reflux 10 hours.Heat filtering removes insoluble impurities, filtrate decompression is evaporated, obtains solid crude product, column chromatography (developing solvent dichloromethane, methanol) obtain pure [(3,5-di-t-butyls, 4-methoxyl group) benzyl, 6-bromohexane base] 1,3-third diether 97.3g, productivity 54%.
By 97.3g [(3, 5-di-t-butyl, 4-methoxyl group) benzyl, 6-bromohexane base] 1, 3-the third diether, N with 216.9g, N-diethyl alcohol radical-1, the mixing of 10-diaza-18 crown-6 is dissolved among the acetone of 500ml, it is simultaneously introduced the potassium carbonate of 28.5g, reactant liquor is heated to reflux 24 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, rear column chromatography for separation is utilized to obtain 93.3g pure { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 6-hexyl] 1, ammediol ether-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, productivity 61%.
By 93.3g{ [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 6-hexyl] 1, ammediol ether-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, join and among the there-necked flask containing 400mL dimethylbenzene and the 1L of the mixed solvent of 180mL triethylamine, the temperature of reactant liquor is controlled at 20 DEG C of Phosphorous chloride .s once starting afterwards to drip the 5mL being pre-added in Dropping funnel, dropping limit, limit is stirred, note observing response liquid temp, temperature is kept to continue stirring 3 hours after within 1 hour, dropwising, reactant liquor is heated to 130 DEG C~135 DEG C.Backflow 5 hours, then improve the vacuum of reaction system, uniformly substantial amounts of dimethylbenzene and triethylamine are steamed from there-necked flask under negative pressure.Cooling, adds isobutanol washing, and reduces temperature of charge further, product crystallization, filtration washing is dried and is obtained product three { [(3,5-di-t-butyls, 4-methoxyl group) tolyl, 6-hexyl] 1,3-PD ether-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 68.0g, productivity 72%.
Under nitrogen protection; by 68.0g tri-{ [(3,5-di-t-butyls, 4-methoxyl group) tolyl; 6-hexyl] 1; ammediol ether-ethyl, 2-hydroxyethyl, N; N-1; 10-diaza-18 crown-6} phosphite ester joins among the 3L there-necked flask containing 1L dichloromethane, is down to by reacting liquid temperature after-20 DEG C and is slowly added among flask by the 250mL dichloromethane solution Dropping funnel being dissolved with 22.7g Boron tribromide in advance, and time for adding is 2 hours.Stir 5 hours after reactant liquor is returned to after dripping room temperature.Reactant liquor is transferred in separatory funnel, add pH value distilled water between 7~8, after being separated by organic layer after repeatedly extracting three times, dry 24 hours with anhydrous magnesium sulfate, pure three { [(3 are obtained by being evaporated under filter vacuum after being filtered to remove desiccant, 5-di-t-butyl, 4-hydroxyl) tolyl, 6-hexyl] 1, ammediol ether-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 64.73g, productivity is 97%.
Embodiment 2
Under nitrogen protection, 220g2,6-di-tert-butyl methyl phenol and 150g dimethyl sulfate are dissolved among the 2.5L chloroform dried.Reactant liquor is heated to 60 DEG C under stirring among the there-necked flask of 5L, reaction continues 1.5 hours.Repeatedly extracting four times with the solution of potassium carbonate of 1LO.5mol/L after reactant liquor is cooled to 25 DEG C, organic over anhydrous magnesium sulfate dries 24 hours.It is filtered to remove the anhydrous magnesium sulfate desiccant in solution, solvent is evaporated off in pressurization, obtain 2,6-di-t-butyl p-methyl anisole 215.3g, yield 92%.
Under nitrogen protection 215.3g2,6-di-t-butyl p-methyl anisole is joined equipped with among the 5L there-necked flask of 3L carbon tetrachloride.It is subsequently adding 161gN-bromo-succinimide and 2g azodiisobutyronitrile, heating is stopped after reactant liquor heating being continued 3 hours to 77 DEG C of reactions, after reactant liquor is cooled to 0 DEG C, it is filtered to remove white depositions, gained filtrate under reduced pressure removes solvent, and crude product utilizes normal hexane recrystallization, obtains 2,6-di-t-butyl is to bromomethyl methyl phenyl ethers anisole 175.7g, and productivity is 61%.
Bromomethyl methyl phenyl ethers anisole and 101g1,6-hexanediol are joined among 5L there-necked flask by 175.7g2,6-di-t-butyl, then in flask, adds 2L acetone solvent and 39g Anhydrous potassium carbonate.After reactant liquor is heated to reflux 10 hours, remove heater, reactant liquor is cooled to 25 DEG C.Decompression is lower remove solvent after gained solid is dissolved among 1.5L ether, repeatedly extract three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and after hydrochloric acid weak solution extracting twice again, organic over anhydrous magnesium sulfate is dried 12 hours.After being filtered to remove desiccant, distillation under pressure removing solvent obtains solid crude product, and column chromatography (developing solvent is chloroform, methanol) obtains pure 1,6-hexanediol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole 127.8g, productivity 65%.
By 127.8g1,6-hexanediol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole, 299.7g1,8-bis-bromooctane and 14.7g sodium hydroxide join in the there-necked flask containing 1.8L dehydrated alcohol 5L, are heated to reflux 12 hours.Heat filtering removes insoluble impurities, filtrate decompression is evaporated, obtains solid crude product, column chromatography (developing solvent dichloromethane, methanol) obtain pure [(3,5-di-t-butyls, 4-methoxyl group) benzyl, 8-bromooctane base] 1,6-own diether 100.8g, productivity 51%.
By 100.8g [(3, 5-di-t-butyl, 4-methoxyl group) benzyl, 8-bromooctane base] 1, the own diether of 6-, N with 195.6g, N-diethyl alcohol radical-1, the mixing of 10-diaza-18 crown-6 is dissolved among the acetone of 500ml, it is simultaneously introduced the potassium carbonate of 25.7g, reactant liquor is heated to reflux 24 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, rear column chromatography for separation is utilized to obtain 89.0g pure { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 8-octyl] 1, oneself two ethers-ethyl of 6-}, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, productivity 59%.
By 89.0g{ [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 8-octyl] 1, oneself two ethers-ethyl of 6-}, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, join and among the there-necked flask containing 400mL dimethylbenzene and the 1L of the mixed solvent of 180mL triethylamine, the temperature of reactant liquor is controlled at 20 DEG C of Phosphorous chloride .s once starting afterwards to drip the 4.9mL being pre-added in Dropping funnel, dropping limit, limit is stirred, note observing response liquid temp, temperature is kept to continue stirring 3 hours after within 1 hour, dropwising, reactant liquor is heated to 130 DEG C~135 DEG C.Backflow 5 hours, then improve the vacuum of reaction system, uniformly substantial amounts of dimethylbenzene and triethylamine are steamed from there-necked flask under negative pressure.Cooling, adds isobutanol washing, and reduces temperature of charge further, product crystallization, filtration washing is dried and is obtained product three { [(3,5-di-t-butyls, 4-methoxyl group) tolyl, 8-octyl] 1,6-oneself two ethers-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 63.9g, productivity 71%.
Under nitrogen protection; by 63.9g tri-{ [(3,5-di-t-butyls, 4-methoxyl group) tolyl; 8-octyl] 1; oneself two ethers-ethyl of 6-, 2-hydroxyethyl, N; N-1; 10-diaza-18 crown-6} phosphite ester joins among the 3L there-necked flask containing 1L dichloromethane, is down to by reacting liquid temperature after-20 DEG C and is slowly added among flask by the 250mL dichloromethane solution Dropping funnel being dissolved with 19.5g Boron tribromide in advance, and time for adding is 2 hours.Stir 5 hours after reactant liquor is returned to after dripping room temperature.Reactant liquor is transferred in separatory funnel, add pH value distilled water between 7~8, after being separated by organic layer after repeatedly extracting three times, dry 24 hours with anhydrous magnesium sulfate, pure three { [(3 are obtained by being evaporated under filter vacuum after being filtered to remove desiccant, 5-di-t-butyl, 4-hydroxyl) tolyl, 8-octyl] 1, oneself two ethers-ethyl of 6-, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 60.9g, productivity is 97%.
Embodiment 3
Under nitrogen protection, 220g2,6-di-tert-butyl methyl phenol and 150g dimethyl sulfate are dissolved among the 2.5L chloroform dried.Reactant liquor is heated to 60 DEG C under stirring among the there-necked flask of 5L, reaction continues 1.5 hours.Repeatedly extracting four times with the solution of potassium carbonate of 1LO.5mol/L after reactant liquor is cooled to 25 DEG C, organic over anhydrous magnesium sulfate dries 24 hours.It is filtered to remove the anhydrous magnesium sulfate desiccant in solution, solvent is under reduced pressure evaporated off, obtain 2,6-di-t-butyl p-methyl anisole 215.3g, yield 92%.
Under nitrogen protection 215.3g2,6-di-t-butyl p-methyl anisole is joined equipped with among the 5L there-necked flask of 3L carbon tetrachloride.It is subsequently adding 161gN-bromo-succinimide and 2g azodiisobutyronitrile, heating is stopped after reactant liquor heating being continued 3 hours to 77 DEG C of reactions, after reactant liquor is cooled to 0 DEG C, it is filtered to remove white depositions, gained filtrate under reduced pressure removes solvent, and crude product utilizes normal hexane recrystallization, obtains 2,6-di-t-butyl is to bromomethyl methyl phenyl ethers anisole 175.7g, and productivity is 61%.
Bromomethyl methyl phenyl ethers anisole and 147g1,10-decanediol are joined among 5L there-necked flask by 175.7g2,6-di-t-butyl, then in flask, adds 2L anhydrous ethanol solvent and 22.6g sodium hydroxide.After reactant liquor is heated to reflux 15 hours, remove heater, reactant liquor is cooled to 25 DEG C.Decompression is lower remove solvent after gained solid is dissolved among 1.5L ether, repeatedly extract three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and after hydrochloric acid weak solution extracting twice again, organic over anhydrous magnesium sulfate is dried 24 hours.After being filtered to remove desiccant, distillation under pressure removing solvent obtains solid crude product, and column chromatography (developing solvent is chloroform, methanol) obtains pure decamethylene-glycol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole 141.5g, productivity 62%.
By 141.5g1,10-decanediol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole, 315g1,10-dibromo-decane and 14.0g sodium hydroxide join in the there-necked flask containing 1.8L dehydrated alcohol 5L, are heated to reflux 16 hours.Heat filtering removes insoluble impurities, filtrate decompression is evaporated, obtains solid crude product, column chromatography (developing solvent dichloromethane, methanol) obtain pure [(3,5-di-t-butyls, 4-methoxyl group) benzyl, 10-bromo-decane base] 1,10-the last of the ten Heavenly stems diether 102.5g, productivity 47%.
By 102.5g [(3, 5-di-t-butyl, 4-methoxyl group) benzyl, 10-bromo-decane base] 1, 10-diether in the last of the ten Heavenly stems, N with 172.2g, N-diethyl alcohol radical-1, the mixing of 10-diaza-18 crown-6 is dissolved among the acetone of 500ml, it is simultaneously introduced the potassium carbonate of 22.6g, reactant liquor is heated to reflux 24 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, rear column chromatography for separation is utilized to obtain 83.6g pure { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 10-decyl] 1, 10-two ethers in the last of the ten Heavenly stems-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, productivity 57%.
By 83.6g{ [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 10-decyl] 1, 10-two ethers in the last of the ten Heavenly stems-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, join and among the there-necked flask containing 400mL dimethylbenzene and the 1L of the mixed solvent of 180mL triethylamine, the temperature of reactant liquor is controlled at 20 DEG C of Phosphorous chloride .s once starting afterwards to drip the 4.7mL being pre-added in Dropping funnel, dropping limit, limit is stirred, note observing response liquid temp, temperature is kept to continue stirring 3 hours after within 1 hour, dropwising, reactant liquor is heated to 130 DEG C~135 DEG C.Backflow 5 hours, then improve the vacuum of reaction system, uniformly substantial amounts of dimethylbenzene and triethylamine are steamed from there-necked flask under negative pressure.Cooling, adds isobutanol washing, and reduces temperature of charge further, product crystallization, filtration washing is dried and is obtained product three { [(3,5-di-t-butyls, 4-methoxyl group) tolyl, 10-decyl] 1,10-the last of the ten Heavenly stems two ethers-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 58.3g, productivity 69%.
Under nitrogen protection; by 58.3g tri-{ [(3,5-di-t-butyls, 4-methoxyl group) tolyl; 10-decyl] 1; 10-two ethers in the last of the ten Heavenly stems-ethyl, 2-hydroxyethyl, N; N-1; 10-diaza-18 crown-6} phosphite ester joins among the 3L there-necked flask containing 1L dichloromethane, is down to by reacting liquid temperature after-20 DEG C and is slowly added among flask by the 200mL dichloromethane solution Dropping funnel being dissolved with 16.1g Boron tribromide in advance, and time for adding is 1.5 hours.Stir 5 hours after reactant liquor is returned to after dripping room temperature.Reactant liquor is transferred in separatory funnel, add pH value distilled water between 7~8, after being separated by organic layer after repeatedly extracting three times, dry 24 hours with anhydrous magnesium sulfate, pure three { [(3 are obtained by being evaporated under filter vacuum after being filtered to remove desiccant, 5-di-t-butyl, 4-hydroxyl) tolyl, 10-decyl] 1,10-two ethers in the last of the ten Heavenly stems-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 55.7g, productivity is 97%.
Embodiment 4
Under nitrogen protection, 220g2,6-di-tert-butyl methyl phenol and 150g dimethyl sulfate are dissolved among the 2.5L chloroform dried.Reactant liquor is heated to 60 DEG C under stirring among the there-necked flask of 5L, reaction continues 1.5 hours.Repeatedly extracting four times with the solution of potassium carbonate of 1LO.5mol/L after reactant liquor is cooled to 25 DEG C, organic over anhydrous magnesium sulfate dries 24 hours.It is filtered to remove the anhydrous magnesium sulfate desiccant in solution, solvent is under reduced pressure evaporated off, obtain 2,6-di-t-butyl p-methyl anisole 215.3g, yield 92%.
Under nitrogen protection 215.3g2,6-di-t-butyl p-methyl anisole is joined equipped with among the 5L there-necked flask of 3L carbon tetrachloride.It is subsequently adding 161gN-bromo-succinimide and 2g azodiisobutyronitrile, heating is stopped after reactant liquor heating being continued 3 hours to 77 DEG C of reactions, after reactant liquor is cooled to 0 DEG C, it is filtered to remove white depositions, gained filtrate under reduced pressure removes solvent, and crude product utilizes normal hexane recrystallization, obtains 2,6-di-t-butyl is to bromomethyl methyl phenyl ethers anisole 175.7g, and productivity is 61%.
By 175.7g2,6-di-t-butyl to bromomethyl methyl phenyl ethers anisole and 171.2g1,12-12 glycol join among 5L there-necked flask, then in flask, add 2L anhydrous ethanol solvent and 22.6g sodium hydroxide.After reactant liquor is heated to reflux 18 hours, remove heater, reactant liquor is cooled to 25 DEG C.Decompression is lower remove solvent after gained solid is dissolved among 1.5L ether, repeatedly extract three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and after hydrochloric acid weak solution extracting twice again, organic over anhydrous magnesium sulfate is dried 24 hours.After being filtered to remove desiccant, distillation under pressure removing solvent obtains solid crude product, and column chromatography (developing solvent is chloroform, methanol) obtains pure 1,12-12 glycol list-(3,5-di-t-butyl, 4-methoxyl group) methyl phenyl ethers anisole 146.4g, productivity 60%.
By 146.4g1,12-12 glycol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole, 305.1g1,10-dibromo-decane and 13.6g sodium hydroxide join in the there-necked flask containing 1.8L dehydrated alcohol 5L, are heated to reflux 20 hours.Heat filtering removes insoluble impurities, filtrate decompression is evaporated, obtain solid crude product, column chromatography (developing solvent dichloromethane, methanol) obtains pure [(3,5-di-t-butyls, 4-methoxyl group) benzyl, 10-bromo-decane base] 1,12-ten two diether 97.0g, productivity 44%.
By 97.0g [(3, 5-di-t-butyl, 4-methoxyl group) benzyl, 10-bromo-decane base] 1, 12-12 diether, N with 153.9g, N-diethyl alcohol radical-1, the mixing of 10-diaza-18 crown-6 is dissolved among the acetone of 500ml, it is simultaneously introduced the potassium carbonate of 20.2g, reactant liquor is heated to reflux 24 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, rear column chromatography for separation is utilized to obtain 74.3g pure { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 10-decyl] 1, 12-12 ethers-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, productivity 55%.
By 74.3g{ [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 10-decyl] 1, 12-12 ethers-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, join and among the there-necked flask containing 400mL dimethylbenzene and the 1L of the mixed solvent of 180mL triethylamine, the temperature of reactant liquor is controlled at 20 DEG C of Phosphorous chloride .s once starting afterwards to drip the 4.5mL being pre-added in Dropping funnel, dropping limit, limit is stirred, note observing response liquid temp, temperature is kept to continue stirring 3 hours after within 1 hour, dropwising, reactant liquor is heated to 130 DEG C~135 DEG C.Backflow 5 hours, then improve the vacuum of reaction system, uniformly substantial amounts of dimethylbenzene and triethylamine are steamed from there-necked flask under negative pressure.Cooling, adds isobutanol washing, and reduces temperature of charge further, product crystallization, filtration washing is dried and is obtained product three { [(3,5-di-t-butyls, 4-methoxyl group) tolyl, 10-decyl] 1,12-ten two two ethers-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 51.0g, productivity 68%.
Under nitrogen protection; by 51.0g tri-{ [(3,5-di-t-butyls, 4-methoxyl group) tolyl; 10-decyl] 1; 12-12 ethers-ethyl, 2-hydroxyethyl, N; N-1; 10-diaza-18 crown-6} phosphite ester joins among the 3L there-necked flask containing 1L dichloromethane, is down to by reacting liquid temperature after-20 DEG C and is slowly added among flask by the 200mL dichloromethane solution Dropping funnel being dissolved with 13.7g Boron tribromide in advance, and time for adding is 1.5 hours.Stir 5 hours after reactant liquor is returned to after dripping room temperature.Reactant liquor is transferred in separatory funnel, add pH value distilled water between 7~8, after being separated by organic layer after repeatedly extracting three times, dry 24 hours with anhydrous magnesium sulfate, pure three { [(3 are obtained by being evaporated under filter vacuum after being filtered to remove desiccant, 5-di-t-butyl, 4-hydroxyl) tolyl, 10-decyl] 1,12-12 ethers-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 48.2g, productivity is 96%.
Embodiment 5
Under nitrogen protection, 220g2,6-di-tert-butyl methyl phenol and 150g dimethyl sulfate are dissolved among the 2.5L chloroform dried.Reactant liquor is heated to 60 DEG C under stirring among the there-necked flask of 5L, reaction continues 1.5 hours.Repeatedly extracting four times with the solution of potassium carbonate of 1LO.5mol/L after reactant liquor is cooled to 25 DEG C, organic over anhydrous magnesium sulfate dries 24 hours.It is filtered to remove the anhydrous magnesium sulfate desiccant in solution, solvent is under reduced pressure evaporated off, obtain 2,6-di-t-butyl p-methyl anisole 215.3g, yield 92%.
Under nitrogen protection 215.3g2,6-di-t-butyl p-methyl anisole is joined equipped with among the 5L there-necked flask of 3L carbon tetrachloride.It is subsequently adding 161gN-bromo-succinimide and 2g azodiisobutyronitrile, heating is stopped after reactant liquor heating being continued 3 hours to 77 DEG C of reactions, after reactant liquor is cooled to 0 DEG C, it is filtered to remove white depositions, gained filtrate under reduced pressure removes solvent, and crude product utilizes normal hexane recrystallization, obtains 2,6-di-t-butyl is to bromomethyl methyl phenyl ethers anisole 175.7g, and productivity is 61%.
By 175.7g2,6-di-t-butyl to bromomethyl methyl phenyl ethers anisole and 191.5g1,16-16 glycol join among 5L there-necked flask, then in flask, add 2L anhydrous ethanol solvent and 31.6g potassium hydroxide.After reactant liquor is heated to reflux 24 hours, remove heater, reactant liquor is cooled to 25 DEG C.Decompression is lower remove solvent after gained solid is dissolved among 1.5L ether, repeatedly extract three times with 1L distilled water, organic layer dilute solution of sodium bicarbonate and after hydrochloric acid weak solution extracting twice again, organic over anhydrous magnesium sulfate is dried 24 hours.After being filtered to remove desiccant, distillation under pressure removing solvent obtains solid crude product, and column chromatography (developing solvent is chloroform, methanol) obtains pure 1,16-16 glycol list-(3,5-di-t-butyl, 4-methoxyl group) methyl phenyl ethers anisole 151.6g, productivity 55%.
By 151.6g1,16-16 glycol list-(3,5-di-t-butyls, 4-methoxyl group) methyl phenyl ethers anisole, 305.1g1,12-dibromo-dodecane and 12.4g sodium hydroxide join in the there-necked flask containing 1.8L dehydrated alcohol 5L, are heated to reflux 24 hours.Heat filtering removes insoluble impurities, filtrate decompression is evaporated, obtain solid crude product, column chromatography (developing solvent dichloromethane, methanol) obtains pure [(3,5-di-t-butyls, 4-methoxyl group) benzyl, 12-bromo-dodecane base] 1,16-ten six diether 95.6g, productivity 42%.
By 95.6g [(3, 5-di-t-butyl, 4-methoxyl group) benzyl, 12-bromo-dodecane base] 1, 16-16 diether, N with 136.2g, N-diethyl alcohol radical-1, the mixing of 10-diaza-18 crown-6 is dissolved among the acetone of 500ml, it is simultaneously introduced the potassium carbonate of 17.9g, reactant liquor is heated to reflux 24 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, rear column chromatography for separation is utilized to obtain 70.5g pure { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 12-dodecyl] 1, 16-16 ethers-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, productivity 54%.
By 70.5g{ [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, 12-dodecyl] 1, 16-16 ethers-ethyl }, 2-hydroxyethyl, N, N-1, 10-diaza-18 crown-6, join and among the there-necked flask containing 400mL dimethylbenzene and the 1L of the mixed solvent of 180mL triethylamine, the temperature of reactant liquor is controlled at 20 DEG C of Phosphorous chloride .s once starting afterwards to drip the 4.3mL being pre-added in Dropping funnel, dropping limit, limit is stirred, note observing response liquid temp, temperature is kept to continue stirring 3 hours after within 1 hour, dropwising, reactant liquor is heated to 130 DEG C~135 DEG C.Backflow 5 hours, then improve the vacuum of reaction system, uniformly substantial amounts of dimethylbenzene and triethylamine are steamed from there-necked flask under negative pressure.Cooling, adds isobutanol washing, and reduces temperature of charge further, product crystallization, filtration washing is dried and is obtained product three { [(3,5-di-t-butyls, 4-methoxyl group) tolyl, 12-dodecyl] 1,16-ten six two ethers-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 46.3g, productivity 65%.
Under nitrogen protection; by 46.3g tri-{ [(3,5-di-t-butyls, 4-methoxyl group) tolyl; 12-dodecyl] 1; 16-16 ethers-ethyl, 2-hydroxyethyl, N; N-1; 10-diaza-18 crown-6} phosphite ester joins among the 3L there-necked flask containing 1L dichloromethane, is down to by reacting liquid temperature after-20 DEG C and is slowly added among flask by the 150mL dichloromethane solution Dropping funnel being dissolved with 11.4g Boron tribromide in advance, and time for adding is 1.2 hours.Stir 5 hours after reactant liquor is returned to after dripping room temperature.Reactant liquor is transferred in separatory funnel, add pH value distilled water between 7~8, after being separated by organic layer after repeatedly extracting three times, dry 24 hours with anhydrous magnesium sulfate, pure three { [(3 are obtained by being evaporated under filter vacuum after being filtered to remove desiccant, 5-di-t-butyl, 4-hydroxyl) tolyl, 12-dodecyl] 1,16-16 ethers-ethyl, 2-hydroxyethyl, N, N-1,10-diaza-18 crown-6} phosphite ester 43.4g, productivity is 95%.
Application examples:
Formulation samples: by 100 mass parts polypropylene powders and 1 mass parts Additives Products mix homogeneously in high-speed mixer, using double screw extruder extruding pelletization, double-screw extruder screw rotating speed is 120 revs/min, and material melt temperature is 220 DEG C.In comparative example three [1,16-16 glycol list-(3,5-di-t-butyl, 4-hydroxyl) methyl phenyl ethers anisole] phosphite ester presses in CN103319523A method described in embodiment 6 and obtains, two [1,16-ten six glycol list-(3,5-di-t-butyls, 4-hydroxyl) methyl phenyl ethers anisole] base pentaerythritol diphosphite presses in CN103319537A method described in embodiment 6 and obtains, and non-oxidizability and the antistatic behaviour of formulation samples is measured result as shown in the table:
Table 1, formulation samples the test of non-oxidizability and antistatic behaviour
By the result of table 1 it can be seen that when polypropylene is without antioxidant and antistatic additive in comparative example 1, product is very easy to oxidized, showing that melting means is big, yellow colour index is high, and the initial efflorescence time is short;Its resin surface resistance is high simultaneously, and internal electric charge cannot be overflowed by surface, it is easy to produce electrostatic.When comparative example 2 and comparative example 3 with the addition of primary antioxidant 1010 or auxiliary antioxidant 168 in polypropylene, product is not easy oxidized, but sheet resistance is high, and internal electric charge cannot be overflowed by surface, it is easy to produce electrostatic.With the addition of in comparative example 4 polypropylene after antistatic additive N, N-bis--(cetyl)-1,10-diaza-18 crown-6 that it shows certain antistatic behaviour, but product is very easy to oxidized, shows that melting means is big, yellow colour index is high, and the initial efflorescence time is short.Comparative example 5 is simultaneously introduced antioxidant 1010,168 and antistatic additive N, N-bis--(cetyl)-1,10-diaza-18 crown-6, two kinds of auxiliary agents all maintain its antioxidation having or antistatic effect, but manifest without collaborative reinforced effects between two kinds of auxiliary agents.Comparative example 6 and comparative example 7 with the addition of the difunctional antioxidant of hindered phenol phosphite ester of CN103319523A and CN103319537A synthesis respectively in polypropylene, its antioxidant effect is better, show as the initial efflorescence time longer, but it does not possess antistatic effect, show as but sheet resistance is high, internal electric charge cannot be overflowed by surface, it is easy to produces electrostatic.After acrylic resin in application examples with the addition of hindered phenol, phosphite ester and the crown ether trifunctional compound synthesized in embodiment, not only showing non-oxidizability but also show antistatic behaviour, the synergism between hindered phenol, phosphite ester and crown ether trifunctional makes antioxidation, antistatic property all be strengthened.
Claims (13)
1. one kind comprises hindered phenol and phosphite ester Amphi-pathic compound, it is characterised in that structural formula is:
Wherein n is the positive integer of 3-16;M is the positive integer of 6-12.
2. the synthetic method of an Amphi-pathic compound as claimed in claim 1, it is characterised in that comprise the steps:
1st step; the protection of phenolic hydroxyl group: by 2; 6-di-tert-butyl methyl phenol and dimethyl sulfate are 1: 1.1~2 addition reactors in molar ratio; it is simultaneously introduced reaction dissolvent; under nitrogen protection, reaction temperature is 45 DEG C~61 DEG C, and the response time is 0.1h~2h; generate 2,6-di-t-butyl p-methyl anisoles;
2nd step; 2; the α bromo of 6-di-t-butyl p-methyl anisole: by 2,6-di-t-butyl p-methyl anisoles and N-bromo-succinimide be in molar ratio 1: 1~1.5 add reactors, be simultaneously introduced reaction dissolvent; under nitrogen protection; under the catalytic action of azodiisobutyronitrile, reaction temperature 50 DEG C~77 DEG C, 2~5 hours response time; generate 2,6-di-t-butyls to bromomethyl methyl phenyl ethers anisole;
3rd step, 2, the 6-di-t-butyl alcoholization reaction to bromomethyl methyl phenyl ethers anisole: be 1: 1.1~3 addition reactors in molar ratio to bromomethyl methyl phenyl ethers anisole and glycol compound by 2,6-di-t-butyls, add and 2, the 6-di-t-butyl alkaline matter to bromomethyl methyl phenyl ethers anisole equimolar amounts, it is simultaneously introduced reaction dissolvent, by reactant liquor heating to backflow, 5 hours~60 hours response time, generate 3,5-di-t-butyls to methyl oxygen base methyl phenyl ethers anisole alcohol;
4th step, 3, the 5-di-t-butyl bromination reaction to methyl oxygen base methyl phenyl ethers anisole alcohol: 3 that upper step is prepared, methyl oxygen base methyl phenyl ethers anisole alcohol and dibromoalkane are 1 3~5 add reactors according to mol ratio by 5-di-t-butyl, add and 3, the 5-di-t-butyl alkaline matter to methyl oxygen base methyl phenyl ethers anisole alcohol equimolar amounts, it is simultaneously introduced reaction dissolvent, reactant liquor is heated to reflux 10~48 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, then utilizes column chromatography for separation to obtain bromo-derivative clean product;
5th step, the preparation of hindered phenol-crown ether Amphi-pathic compound: the bromo-derivative that the 4th step reaction is prepared and N, N-diethyl alcohol radical-1, 10-diaza-18 crown-6 1:1~3 in molar ratio mix, it is simultaneously introduced alkaline matter equimolar with bromo-derivative, it is simultaneously introduced reaction dissolvent, reactant liquor is heated to reflux 10~48 hours, heat filtering removes insoluble impurities, decompression is distilled off solvent and obtains solid crude product, after utilize column chromatography for separation to obtain { [(3, 5-di-t-butyl, 4-methoxyl group) tolyl, m-m alkyl] n-n glycol ether-ethyl }, 2-hydroxyethyl, N, N-1, the clean product of 10-diaza-18 crown-6;
null6th step,The preparation of phosphite ester: { [(3 that the reaction of upper step is prepared,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl },2-hydroxyethyl,N,N-1,10-diaza-18 crown-6 adds reactor,It is simultaneously introduced reaction dissolvent,Under the protection of nitrogen,Reactant liquor is controlled at 0 DEG C~20 DEG C,The Phosphorous chloride. that mole is alcohols material 1/1/3rd~bis-is dripped in reactant liquor,Time for adding is 0.5~5 hour,It is added dropwise to complete after maintenance temperature continues reaction 2~10 hours and reactant liquor is heated to 130 DEG C~135 DEG C,Reflux 2~5 hours under 0.02-0.05MPa,Prepare three { [(3,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl,2-hydroxyethyl,N,N-1,10-diaza-18 crown-6} phosphite ester;
null7th step,The deprotection reaction of hydroxyl: the 6th step is reacted the three { [(3 of gained,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl,2-hydroxyethyl,N,N-1,10-diaza-18 crown-6} phosphite ester joins among the there-necked flask containing reaction dissolvent,After reacting liquid temperature is down to 0 DEG C~-50 DEG C, the solution G being dissolved with Boron tribromide in advance is added drop-wise among flask,Three { [(3,5-di-t-butyl,4-methoxyl group) tolyl,M-m alkyl] n-n glycol ether-ethyl,2-hydroxyethyl,N,N-1,10-diaza-18 crown-6} phosphite ester and Boron tribromide are 3:1~3 in molar ratio,Time for adding is 1~5 hour,Stir 2~5 hours after reactant liquor is returned to after dripping room temperature.
3. synthetic method as claimed in claim 2, after it is characterized in that the 1st step reacts completely, reactant liquor is cooled to room temperature, in reactant liquor, add the solution of potassium carbonate 0.5-1.5L that concentration is 0.2-0.6mol/L extract, repeat 3-5 time, organic facies is evaporated after drying and obtains 2,6-pure di-t-butyl p-methyl anisoles.
4. synthetic method as claimed in claim 2, it is characterised in that the diol compound molecular formula described in the 3rd step is HO (CH2)nOH, wherein n is the positive integer of 3~16.
5. synthetic method as claimed in claim 2, it is characterised in that the alkaline matter described in 3-5 step is selected from sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate.
6. synthetic method as claimed in claim 2, it is characterised in that the dibromoalkane described in the 4th step is selected from 1,6-dibromo-hexane, 1,8-bis-bromooctane or 1,10-dibromo-decane.
7. preparation method as claimed in claim 2, it is characterised in that at least one in chlorobenzene, dichloromethane, chloroform, toluene of the reaction dissolvent described in the 1st step.
8. synthetic method as claimed in claim 2, it is characterised in that at least one in benzene, dichloromethane, chloroform, carbon tetrachloride of the reaction dissolvent described in the 2nd step.
9. synthetic method as claimed in claim 2, it is characterised in that at least one in methanol, ethanol, acetone, dimethylformamide of the reaction dissolvent described in the 3rd step.
10. synthetic method as claimed in claim 2, it is characterised in that at least one in triethylamine, ethanol, dimethylformamide, toluene, dimethylbenzene, benzene, chlorobenzene, dichloromethane, carbon tetrachloride, ethyl acetate of the reaction dissolvent described in 4-6 step.
11. synthetic method as claimed in claim 2, it is characterised in that the reaction dissolvent described in the 7th step is selected from least one of dichloromethane, chloroform, carbon tetrachloride.
12. the application of an Amphi-pathic compound as claimed in claim 1, it is characterised in that described Amphi-pathic compound uses as antioxidant and the antistatic additive of polypropylene or polyethylene.
13. apply as claimed in claim 12, it is characterised in that described compound is 0.05%~0.15% add in polypropylene or polyethylene base material according to mass percent.
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