CN108164750A - Hindered amine antioxidant and polyethylene material - Google Patents
Hindered amine antioxidant and polyethylene material Download PDFInfo
- Publication number
- CN108164750A CN108164750A CN201611114276.8A CN201611114276A CN108164750A CN 108164750 A CN108164750 A CN 108164750A CN 201611114276 A CN201611114276 A CN 201611114276A CN 108164750 A CN108164750 A CN 108164750A
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- CN
- China
- Prior art keywords
- antioxidant
- polythene material
- amine antioxidant
- suffocated amine
- suffocated
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 95
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 89
- 150000001412 amines Chemical class 0.000 title claims abstract description 60
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 38
- -1 polyethylene Polymers 0.000 title claims abstract description 29
- 239000004698 Polyethylene Substances 0.000 title abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 27
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000012760 heat stabilizer Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 150000008301 phosphite esters Chemical class 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 3
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003490 Thiodipropionic acid Substances 0.000 claims description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical group [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 229930016911 cinnamic acid Natural products 0.000 claims description 3
- 235000013985 cinnamic acid Nutrition 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 235000019303 thiodipropionic acid Nutrition 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 2
- DKXULEFCEORBJK-UHFFFAOYSA-N magnesium;octadecanoic acid Chemical compound [Mg].CCCCCCCCCCCCCCCCCC(O)=O DKXULEFCEORBJK-UHFFFAOYSA-N 0.000 claims 1
- 230000003712 anti-aging effect Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 78
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 33
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 31
- 229940080818 propionamide Drugs 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000002156 mixing Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 15
- 239000003480 eluent Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical group ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 11
- 230000006698 induction Effects 0.000 description 11
- 238000010898 silica gel chromatography Methods 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005491 wire drawing Methods 0.000 description 10
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 7
- 150000005004 2-naphthylamines Chemical class 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- XFNJVKMNNVCYEK-UHFFFAOYSA-N 1-naphthaleneacetamide Chemical compound C1=CC=C2C(CC(=O)N)=CC=CC2=C1 XFNJVKMNNVCYEK-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 150000001793 charged compounds Chemical class 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- FFJWPGGBISIFHI-UHFFFAOYSA-N 1-methylnaphthalen-2-amine Chemical class C1=CC=C2C(C)=C(N)C=CC2=C1 FFJWPGGBISIFHI-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PCHYYOCUCGCSBU-UHFFFAOYSA-N 4-bromo-2-methylaniline Chemical class CC1=CC(Br)=CC=C1N PCHYYOCUCGCSBU-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a hindered amine antioxidant and a polyethylene material, wherein the hindered amine antioxidant comprises the following structure (I):wherein R is1Is alkyl, R2And R3Selected from hydrogen or the following general formula (II), and R2And R3At least one of them is selected from the following general formula (II):wherein R is4Is a chain hydrocarbon group, R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15Independently selected from hydrogen or alkyl. The hindered amine antioxidant has good compatibility with polymers, good migration resistance and solvent extraction resistance, and can be applied to the anti-aging of various high polymer materials; and the hindered amine antioxidant has light color and is not easy to color.
Description
Technical field
The present invention relates to a kind of suffocated amine antioxidant and polythene materials, belong to technical field of organic chemistry.
Background technology
Antioxidant is a kind of anti-aging agent often added in high molecular material, can prevent high molecular material in processing, storage
With use during due to by heat, oxygen act on and lose performance, common antioxidant have Hinered phenols antioxidant and by
Hindered amine antioxidant, wherein suffocated amine antioxidant can not only prevent high molecular material thermal oxide, but also be also prevented from light
Oxidation, therefore, is widely used in polymeric material field.
At present, the primary antioxidant used in polythene material is mostly Hinered phenols antioxidant, and amine antioxidants are generally held
Easy coloring is generally unsuitable in plastic products.But amine antioxidants have more excellent antioxygen compared with Hinered phenols antioxidant
Change performance, particularly phenyl-2-naphthylamine kind antioxidant, since there are electron-donating groups on phenyl ring, make hydrogen atom more active, eventually
Only the ability of free radical is stronger.Phenyl-2-naphthylamine was once widely used as rubber antioxidant, but due to its coloring and poison
Property, it is restricted its application.And (2- the naphthalenes) -1,4- phenylenediamines of N, N'- bis- are due to its excellent heat-proof aging, resistance to natural old
Advantages, the consumption proportion such as the property changed and low stain are continuously increased, and can be applied to the works such as ABS, polyformaldehyde and polyamide
In engineering plastics.
In recent years, the market demand of high-end polythene material constantly increases, promoted high-end polythene material research and
Exploitation.It is found in high-end polythene material development process, surface is will appear in process and goes out spot and wrapping problem, this master
If since the Hinered phenols antioxidant one side polarity added in polythene material is larger, the compatibility with polythene material
It is poor, migration easily occurs and loses antioxygenic property；Another aspect Hinered phenols antioxidant facile hydrolysis makes it terminate free radical
Ability declines, and chain free radical interacts and crosslinks reaction, gel phenomenon occurs, leads to the processability of polythene material
It can decline.In order to meet the needs of high-end polythene material exploitation, a kind of antioxygen having compared with high-compatibility and difficult hydrolysis of exploitation
Agent is very necessary.
Invention content
It is a primary object of the present invention to provide a kind of suffocated amine antioxidant and polythene material, to overcome the prior art
Middle antioxidant poor compatibility, diffluent problem.
The object of the present invention is achieved like this, a kind of suffocated amine antioxidant, which includes as follows
Structure (I)：
Wherein R1For alkyl, R2And R3Selected from hydrogen or below formula (II), and R2And R3At least one of be selected from below formula
(Ⅱ)：
Wherein, R4For chain alkyl, R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15Independently selected from hydrogen or alkyl.
Suffocated amine antioxidant of the present invention, wherein, the R1Carbon atom number be preferably greater than 8 even number.
Suffocated amine antioxidant of the present invention, wherein, the suffocated amine antioxidant preferably has below formula：
Wherein, R1For alkyl, R1Middle carbon atom number is the even number more than 8.
The present invention also provides a kind of polythene material, above-mentioned suffocated amine antioxidant is included in the polythene material.
Polythene material of the present invention, wherein, which includes：
100 mass parts of polyvinyl resin；
Composite assistant 0.2-0.36 mass parts；
Wherein described composite assistant includes primary antioxidant, auxiliary antioxidant, heat stabilizer and rheological agent；The primary antioxidant
For above-mentioned suffocated amine antioxidant.
Polythene material of the present invention, wherein, the auxiliary antioxidant is preferably bis- (2,4- di-tert-butyl-phenyls)
Pentaerythritol diphosphites, three (2,4- di-tert-butyl-phenyls) phosphite esters, thiodipropionic acid dilauryl cinnamic acid ester and thio two
The double octadecyls of propionic acid form one or more of group.
Polythene material of the present invention, wherein, the heat stabilizer is preferably calcium stearate, magnesium stearate, tristearin
Sour zinc and aluminum stearate form one or more of group.
Polythene material of the present invention, wherein, the rheological agent is preferably fluorine rheological body.
Polythene material of the present invention, wherein, the primary antioxidant, auxiliary antioxidant, heat stabilizer and rheological agent
Mass ratio be preferably 1：0.5-1.5：0.25-0.75：0.05-0.15.
Beneficial effects of the present invention：
1st, suffocated amine antioxidant of the invention is simple organic by two kinds of amidation condensation and Michael addition reaction
Reaction can be prepared by, and reaction condition is mild.
2nd, not only contain in the suffocated amine antioxidant molecule there are two the anti-oxidant unit of hindered amine, but also also contain in molecule
There is the chain alkyl of excellent compatibility with high molecular material, so the compatibility of the suffocated amine antioxidant and polymer is good,
Anti-migration, anti-solvent extracting performance are good, can be applied to the anti-aging of a variety of high molecular materials；And the suffocated amine antioxidant
Color is shallower, not easy coloring.
Description of the drawings
Fig. 1 is the infrared spectrogram of suffocated amine antioxidant prepared by the embodiment of the present invention 1；
Fig. 2 is the mass spectrogram of suffocated amine antioxidant prepared by the embodiment of the present invention 1；
Fig. 3 is the infrared spectrogram of suffocated amine antioxidant prepared by the embodiment of the present invention 7；
Fig. 4 is the mass spectrogram of suffocated amine antioxidant prepared by the embodiment of the present invention 7；
Fig. 5 is the infrared spectrogram of suffocated amine antioxidant prepared by the embodiment of the present invention 8；
Fig. 6 is the mass spectrogram of suffocated amine antioxidant prepared by the embodiment of the present invention 8.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not forms any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
The invention discloses a kind of suffocated amine antioxidant, which can be made by the following method
It is standby：
(1) synthesis of intermediate (I)：First will be to halogenated amino benzenes compounds and accelerant N, N- diisopropylethylamine is molten
Solution is in tetrahydrofuran, and (preferably -5 DEG C~5 DEG C) dropwise addition acetyl halide compounds, react certain time (preferably 3 at room temperature at low temperature
~7h), after reaction, a certain amount of saturation NH is added in into reaction mixture4Cl aqueous solutions are so that reaction terminating, then with one
Quantitative ethyl acetate extraction organic phase, supernatant liquid is through Na2SO4It is dry, it is then dried in vacuum condition, obtains intermediate
(Ⅰ)。
(2) synthesis of intermediate (II)：Intermediate (I) is dissolved in ethyl alcohol, N2Protection, is added dropwise chain fatty at room temperature
The ethanol solution of amine reacts 60~80h at 70~90 DEG C, and reaction gained mixture is concentrated under vacuum, and concentrate uses silica gel
Column chromatography purifies, and obtains intermediate (II).
(3) synthesis of suffocated amine antioxidant：Intermediate (II) and 2- naphthylamine compounds are dissolved in methanol, N2It protects
Under shield, catalyst XPhos and Pd are added in2(dba)3With accelerating agent K2CO3, 5~10h is reacted at 70~90 DEG C, obtains hindered amines
Antioxidant crude product；Crude product is dissolved using the mixed solvent of ethyl acetate and tetrahydrofuran, after solution washing, gained organic phase
Through chromatography, suffocated amine antioxidant is obtained.
It is 1 to the molar ratio of halogenated amino benzenes compounds and acetyl halide compound in above-mentioned steps (1):1.1~1:1.5, promote
Dosage into agent n,N-diisopropylethylamine is 40% with acetyl halide compound gross mass, solvent four to halogenated amino benzenes compounds
The dosage of hydrogen furans is 10~15 times with acetyl halide compound gross mass, saturation NH to halogenated amino benzenes compounds4Cl aqueous solutions
Dosage be 0.5~1 times of reaction dissolvent volume, the dosage of ethyl acetate is 0.8~1.2 times of reaction dissolvent volume, vacuum
Dry temperature is 30 DEG C, and the vacuum drying time is for 24 hours.
The molar ratio of intermediate (I) and chain fatty amine is 2 in above-mentioned steps (2):1, the dosage of etoh solvent is centre
9 times of body (I) and chain fatty amine gross mass, reaction temperature are 70~90 DEG C, and the reaction time is 60~80h；It is concentrated in vacuo anti-
It is 5~10h that answer temperature, which be 50 DEG C, is concentrated in vacuo the reaction time；The volume ratio of eluent petroleum ether used in chromatography and ethyl acetate
It is 1:10.
Intermediate (II) and 2- naphthylamine compounds molar ratio are 1 in above-mentioned steps (3):2~1:2.5, solvent methanol
8~10 times for intermediate (II) and 2- naphthylamine compounds gross masses of dosage, accelerating agent K2CO3Dosage and intermediate (II)
Molar ratio is 1:7~1:11, catalyst is XPhos and Pd2(dba)3Dosage is respectively 1 with the molar ratio of intermediate (II):10,
Reaction time is 5~10h；Crude product dissolving solvent for use ethyl acetate dosage is the 0.5 of the volume for reacting solvent for use methanol
~1.5, the volume ratio of chromatography eluent petroleum ether and ethyl acetate is 5:1.
Wherein the present invention more specifically discloses antioxidant
It can be prepared by the following method：
(1) with acryloyl chloride substitution reaction generation intermediate (I) occurs for para-bromoaniline；
(2) the addition reaction generation intermediate (II) of carbon-carbon double bond occurs with chain fatty primary amine for intermediate (I)；And
(3) with 2- naphthylamines substitution reaction generation suffocated amine antioxidant (III) occurs for intermediate (II), and specific reaction equation is such as
Under：
Wherein, R12For alkyl, and carbon atom number is the even number more than 8.
The invention also discloses a kind of polythene material, wherein, which includes：
100 mass parts of polyvinyl resin；
Composite assistant 0.2-0.36 mass parts；
Wherein described composite assistant includes primary antioxidant, auxiliary antioxidant, heat stabilizer and rheological agent；The primary antioxidant
For above-mentioned suffocated amine antioxidant.
The polythene material of the present invention, can be prepared by the following method：
In the prilling section of polyvinyl resin, polyethylene and the composite assistant of polyethylene quality 1.5-5% are added in, it is compound to help
Agent is by primary antioxidant, auxiliary antioxidant, heat stabilizer and rheological agent according to 1：0.5~1.5：0.25~0.75：0.05-0.15 matter
It measures percentage to prepare, primary antioxidant is above-mentioned suffocated amine antioxidant.
Auxiliary antioxidant is selected from bis- (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, three (2,4- di-t-butyls
Phenyl) phosphite ester, one kind in the double octadecyls of thiodipropionic acid dilauryl cinnamic acid ester and thio-2 acid or arbitrary several
Mixture.Hot heat stabilizer is one kind or arbitrary several mixed in calcium stearate, magnesium stearate, zinc stearate and aluminum stearate
Close object.Rheological agent is fluorine rheological body.
Technical solution of the present invention is described in detail below by specific embodiment.
The reaction that embodiment 1-6 is related to is：
The reaction that embodiment 7 is related to is：
The reaction that embodiment 8 is related to is：
Embodiment 1
The synthesis of N- (4- bromophenyls) acryloyl chloride：Accurately weigh 60g para-bromoaniline and 67.6g N, N- diisopropyl second
For amine solvent in 1.5L tetrahydrofurans, 0 DEG C is slowly added dropwise acryloyl chloride 34.7g while stirring, is reacted 4 hours under the conditions of 25 DEG C.
Saturation NH is added in into reaction mixture4Cl solution 1L, make reaction terminating, are then extracted using 3L ethyl acetate, Na2SO4It is de-
Water filters, and is dried in vacuo at 30 DEG C, obtains N- (4- bromophenyls) acrylamide.
The synthesis of 3,3' lauryl amines-two-(4- bromophenyl-hydrazines) amide：It is molten accurately to weigh 60g N- (4- bromophenyls) acryloyl chloride
Solution is in 1.0L ethyl alcohol, N2Lauryl amine 24.6g is slowly added dropwise under conditions of 25 DEG C, is reacted under the conditions of 85 DEG C while stirring for protection
72h.Mixed liquor after reaction is concentrated in vacuo, and is purified using silica gel column chromatography, eluent petroleum ether used:Ethyl acetate
=10:1, obtain 3,3' lauryl amines-two-(4- bromophenyl-hydrazines) amide.
The synthesis of 3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide：Accurately weigh 32.5g3,3' ten
Diamines-two-(4- bromophenyl-hydrazines) amide and 16.1g 2- naphthylamines are dissolved in the methanol of 600mL, then add in 2.4g XPhos,
28.2g K2CO3With the Pd of 4.7g2(dba)3, 85 DEG C, N2Under the conditions of isothermal reaction 8h.After reaction mixture is concentrated in vacuo；Using
700mL ethyl acetate dilutes concentrate at room temperature, filtering, then distills water washing 3 times using 700mL, 50 DEG C of vacuum are done
It is dry.Gained crude product is purified using silica gel column chromatography, eluent petroleum ether used：The volume ratio of ethyl acetate is 5:1, it obtains
3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide.
Infrared spectrum and mass spectral characteristi are carried out to novel suffocated amine antioxidant manufactured in the present embodiment, as a result such as Fig. 1 and
Shown in Fig. 2.
As seen from Figure 1：Wave number is in 3340cm-1It is the stretching vibration absworption peak of N-H, wave number 3045cm-1It is phenyl ring
The characteristic absorption peak of upper C-H, 1812cm-1Locate the absorption in over-frequency peak generated for the substitution of phenyl ring Isosorbide-5-Nitrae position, and wave number 2950cm-1With
2922cm-1There is the characteristic absorption peak of methyl and methylene, 2851cm respectively in place-1And 2817cm-1For the stretching vibration peak of C-N,
Wave number 1652cm-1Locate the stretching vibration absworption peak for amido bond C=O.As seen from Figure 2, m/z=762.6 is obstructed to be novel
The molecular ion peak of amine antioxidants.
3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide, three (2,4- di-tert-butyl-phenyls) are sub-
Phosphate is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into powder and squeezes
Go out machine extrusion, obtain containing antioxidant 3, the composite assistant of 3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
Embodiment 2
According to-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide of reaction synthesis 3,3'- lauryl amines in embodiment 1.It will
3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide, three (2,4- di-tert-butyl-phenyls) phosphite esters, tristearin
Sour calcium, zinc stearate and fluorine rheological body are according to 1：1：0.5：0.5：0.1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature
It mixes, mixing 5~after twenty minutes, it is sent into powder extruder and squeezes out, obtain containing antioxidant 3,3'- lauryl amines-two-(N- (4- naphthalene second
Amide) aminobenzene) propionamide composite assistant packet.
In the prilling section of polyethylene, 0.31% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing simultaneously
It is granulated.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyethylene tree
The physical property measurement of fat the results are shown in Table 1.
Embodiment 3
According to-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide of reaction synthesis 3,3'- lauryl amines in embodiment 1.It will
3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide, three (2,4- di-tert-butyl-phenyls) phosphite esters, tristearin
Sour calcium, zinc stearate and fluorine rheological body are according to 1：1：0.75：0.75：0.1 mass ratio is put into high speed mixing smelting machine, at room temperature
Stirring, mixing 5~after twenty minutes, it is sent into powder extruder and squeezes out, obtain containing antioxidant 3,3'- lauryl amines-two-(N- (4- naphthalenes
Acetamide) aminobenzene) propionamide composite assistant packet.
In the prilling section of polyethylene, 0.36% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing simultaneously
It is granulated.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyethylene tree
The physical property measurement of fat the results are shown in Table 1.
Embodiment 4
According to-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide of reaction synthesis 3,3'- lauryl amines in embodiment 1.It will
3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide, calcium stearate, zinc stearate and fluorine rheological body is according to 1：
0.5：1：0.1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into powder extruder
It squeezes out, obtains containing antioxidant 3, the composite assistant packet of 3'- lauryl amines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide.
In the prilling section of polyethylene, 0.26% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing simultaneously
It is granulated.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyethylene tree
The physical property measurement of fat the results are shown in Table 1.
Embodiment 5
N- (4- bromophenyls) acryloyl chloride is synthesized according to the reaction in embodiment 1.Accurately weigh 60g N- (4- bromophenyls)
Acryloyl chloride is dissolved in 1.0L ethyl alcohol, N2Protection, is slowly added dropwise tetradecy lamine 28.3g under conditions of 25 DEG C while stirring, 85 DEG C
Under the conditions of react 72h.Mixed liquor after reaction is concentrated in vacuo, and is purified using silica gel column chromatography, eluent oil used
Ether:Ethyl acetate=10:1, obtain 3,3' tetradecy lamines-two-(4- bromophenyl-hydrazines) amide.
The synthesis of 3,3'- tetradecy lamines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide：Accurately weigh 33.9g3,3' ten
Tetramine-two-(4- bromophenyl-hydrazines) amide and 16.1g 2- naphthylamines are dissolved in the methanol of 600mL, then add in 2.4g XPhos,
28.2g K2CO3With the Pd of 4.7g2(dba)3, 85 DEG C, N2Under the conditions of isothermal reaction 8h.After reaction mixture is concentrated in vacuo；Using
700mL ethyl acetate dilutes concentrate at room temperature, filtering, then distills water washing 3 times using 700mL, 50 DEG C of vacuum are done
It is dry.Gained crude product is purified using silica gel column chromatography, eluent petroleum ether used：The volume ratio of ethyl acetate is 5:1.
3,3'- tetradecy lamines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide, three (2,4- di-tert-butyl-phenyls) are sub-
Phosphate is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into powder and squeezes
Go out machine extrusion, obtain containing antioxidant 3, the composite assistant of 3'- tetradecy lamines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
Embodiment 6
N- (4- bromophenyls) acryloyl chloride is synthesized according to the synthetic reaction in embodiment 1.Accurately weigh 60g N- (4- bromobenzenes
Base) acryloyl chloride is dissolved in 1.0L ethyl alcohol, N2Protection, is slowly added dropwise octadecylamine 35.7g under conditions of 25 DEG C while stirring, and 85
72h is reacted under the conditions of DEG C.Mixed liquor after reaction is concentrated in vacuo, and is purified using silica gel column chromatography, eluent stone used
Oily ether:Ethyl acetate=10:1, obtain 3,3' octadecylamines-two-(4- bromophenyl-hydrazines) amide.
The synthesis of 3,3'- octadecylamines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide：Accurately weigh 36.7g3,3' ten
Eight-two-(4- bromophenyl-hydrazines) amides of amine and 16.1g2- naphthylamines are dissolved in the methanol of 600mL, then add in 2.4g XPhos,
28.2g K2CO3With the Pd of 4.7g2(dba)3, 85 DEG C, N2Under the conditions of isothermal reaction 8h.After reaction mixture is concentrated in vacuo；Using
700mL ethyl acetate dilutes concentrate at room temperature, filtering, then distills water washing 3 times using 700mL, 50 DEG C of vacuum are done
It is dry.Gained crude product is purified using silica gel column chromatography, eluent petroleum ether used：The volume ratio of ethyl acetate is 5:1.
3,3'- octadecylamines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide, three (2,4- di-tert-butyl-phenyls) are sub-
Phosphate is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into powder and squeezes
Go out machine extrusion, obtain containing antioxidant 3, the composite assistant of 3'- octadecylamines-two-(N- (4- naphthaleneacetamide) aminobenzene) propionamide.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
Embodiment 7
The synthesis of N- (4- bromophenyls) acrylamide：Accurately weigh 60g para-bromoaniline and 67.6g N, N- diisopropyl second
For amine solvent in 1.5L tetrahydrofurans, 0 DEG C is slowly added dropwise acryloyl chloride 34.7g while stirring, reacts 4h under the conditions of 25 DEG C.To anti-
It answers and saturation NH is added in mixed liquor4Cl solution 1L, make reaction terminating, are then extracted using 3L ethyl acetate, Na2SO4Dehydration, mistake
It filters, is dried in vacuo at 30 DEG C, obtains N- (4- bromophenyls) acrylamide.
The synthesis of 3,3'- lauryl amines-two-(4- bromophenyl-hydrazines) propionamide：Accurately weigh 60g N- (4- bromophenyls) acryloyl
Chlorine is dissolved in 1.0L ethyl alcohol, N2Protection, is slowly added dropwise lauryl amine 24.6g under conditions of 25 DEG C while stirring, under the conditions of 85 DEG C
React 72h.Mixed liquor after reaction is concentrated in vacuo, and is purified using silica gel column chromatography, eluent petroleum ether used:Acetic acid
Ethyl ester=10:1, obtain 3,3'- lauryl amines-two-(4- bromophenyl-hydrazines) propionamide.
The synthesis of 3,3'- lauryl amines-two-(N- (1- methyl -4- naphthaleneacetamide) aminobenzene) propionamide：Accurately weigh
32.5g 3,3'- lauryl amines-two-(4- bromophenyl-hydrazines) propionamide and 17.6g 1- methyl -2- naphthylamines are dissolved in the methanol of 600mL
In, then add in 2.4g XPhos, 28.2g K2CO3With the Pd of 4.7g2(dba)3, 85 DEG C, N2Under the conditions of isothermal reaction 8h.Instead
After mixture is answered to be concentrated in vacuo；Concentrate is diluted at room temperature using 700mL ethyl acetate, filters, is then steamed using 700mL
Distilled water is washed 3 times, 50 DEG C of vacuum drying.Gained crude product is purified using silica gel column chromatography, eluent petroleum ether used:Acetic acid
The volume ratio of ethyl ester is 5:1, obtain 3,3'- lauryl amines-two-(N- (1- methyl -4- naphthaleneacetamide) aminobenzene) propionamide.
Infrared spectrum and mass spectral characteristi are carried out to novel suffocated amine antioxidant manufactured in the present embodiment, as a result such as Fig. 3 and
Shown in Fig. 4.
As seen from Figure 3：3340cm-1It is the stretching vibration absworption peak of N-H, wave number 3045cm-1It is C-H on phenyl ring
Characteristic absorption peak, 1811cm-1Locate the absorption in over-frequency peak generated for phenyl ring substitution, and wave number 2950cm-1And 2920cm-1Punishment
Do not occur the characteristic absorption peak of methyl and methylene, 2850cm-1And 2810cm-1For the stretching vibration peak of C-N, wave number 1655cm-1
Locate the stretching vibration absworption peak for amido bond C=O.As seen from Figure 4, m/z=789 is novel being obstructed of the synthesis of embodiment 3
The molecular ion peak of amine antioxidants.
By 3,3'- lauryl amines-two-(N- (1- methyl -4- naphthaleneacetamide) aminobenzene) propionamide, three (2,4- di-t-butyls
Phenyl) phosphite ester is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it send
Enter powder extruder extrusion, obtain containing antioxidant 3,3'- lauryl amines-two-(N- (1- methyl -4- naphthaleneacetamide) aminobenzene) third
The composite assistant of amide.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
Embodiment 8
The synthesis of N- (2- methyl -4- bromophenyls) acrylamide：Accurately weigh 65g 2- methyl -4- bromanilines and 67.6g
N,N-diisopropylethylamine is dissolved in 1.5L tetrahydrofurans, and 0 DEG C is slowly added dropwise acryloyl chloride 34.7g, 25 DEG C of items while stirring
4h is reacted under part.Saturation NH is added in into reaction mixture4Cl solution 1L, make reaction terminating, are then extracted using 3L ethyl acetate
It takes, Na2SO4Dehydration is filtered, and is dried in vacuo at 30 DEG C, is obtained N- (2- methyl -4- bromophenyls) acrylamide.
The synthesis of 3,3'- lauryl amines-two-(2- methyl -4- bromophenyl-hydrazines) propionamide：Accurately weigh 67g N- (2- methyl -4-
Bromophenyl) acryloyl chloride is dissolved in 1.0L ethyl alcohol, N2It protects, lauryl amine is slowly added dropwise while stirring under conditions of 25 DEG C
24.6g reacts 72h under the conditions of 85 DEG C.Mixed liquor after reaction is concentrated in vacuo, and is purified using silica gel column chromatography, used
Eluent petroleum ether:Ethyl acetate=10:1, obtain 3,3'- lauryl amines-two-(2- methyl -4- bromophenyl-hydrazines) propionamide.
The synthesis of 3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) 2- methyl amino phenyls) propionamide：Accurately weigh 34.5g
3,3'- lauryl amines-two-(2- methyl -4- bromophenyl-hydrazines) propionamide and 17.6g 1- methyl -2- naphthylamines are dissolved in the methanol of 600mL
In, then add in 2.4g XPhos, 28.2g K2CO3With the Pd of 4.7g2(dba)3, 85 DEG C, N2Under the conditions of isothermal reaction 8h.Instead
After mixture is answered to be concentrated in vacuo；Concentrate is diluted at room temperature using 700mL ethyl acetate, filters, is then steamed using 700mL
Distilled water is washed 3 times, 50 DEG C of vacuum drying.Gained crude product is purified using silica gel column chromatography, eluent petroleum ether used:Acetic acid
The volume ratio of ethyl ester is 5:1, obtain 3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) 2- methyl amino phenyls) propionamide.
As seen from Figure 5：Wave number is in 3342cm-1It is the stretching vibration absworption peak of N-H, wave number 3047cm-1It is phenyl ring
The characteristic absorption peak of upper C-H, 1810cm-1Locate the absorption in over-frequency peak generated for phenyl ring substitution, and wave number 2952cm-1And 2920cm-1
There is the characteristic absorption peak of methyl and methylene, 2855cm respectively in place-1And 2819cm-1For the stretching vibration peak of C-N, wave number
1650cm-1Locate the stretching vibration absworption peak for amido bond C=O.As seen from Figure 6, m/z=819 is the new of the synthesis of embodiment 2
The molecular ion peak of type suffocated amine antioxidant.
By 3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) 2- methyl amino phenyls) propionamide, three (2,4- di-tert-butyls
Base) phosphite ester is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into
Powder extruder squeezes out, and obtains containing antioxidant 3,3'- lauryl amines-two-(N- (4- naphthaleneacetamide) 2- methyl amino phenyls) propionyl
The composite assistant of amine.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
Comparative example 1
[β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester and three (2,4- di-tert-butyl-phenyls) is sub-
Phosphate is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into powder and squeezes
Go out machine extrusion, obtain the composite assistant containing antioxidant [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
Comparative example 2
By 1,3,5- trimethyls -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyls) benzene and three (2,4- di-tert-butyls
Base) phosphite ester is according to 1：1 mass ratio is put into high speed mixing smelting machine, is stirred at room temperature, and mixing 5~after twenty minutes, it is sent into
Powder extruder squeezes out, and obtains containing 1,3,5- trimethyl -2,4 of antioxidant, 6- (3,5- di-t-butyl -4- hydroxyphenylmethyls) benzene
Composite assistant packet.
In the prilling section of polyethylene, 0.2% above-mentioned composite assistant is added, by extruder melting extrusion wire drawing and is made
Grain.Then the melt flow rate (MFR) of polyvinyl resin, mechanical property and oxidation induction period are tested.The polyvinyl resin
Physical property measurement the results are shown in Table 1.
1 polyvinyl resin of table analyzes test result
1 to 7 gained polyvinyl resin of embodiment is only that antioxidant used is different from the difference of comparative example 1 and 2, from table 1
Data, which can be seen that antioxidant used in embodiment, can significantly improve the oxidation induction period of polyvinyl resin, make it have excellent
Different antioxygenic property.
Beneficial effects of the present invention：
1st, suffocated amine antioxidant of the invention is simple organic by two kinds of amidation condensation and Michael addition reaction
Reaction can be prepared by, and reaction condition is mild.
2nd, not only contain in the suffocated amine antioxidant molecule there are two the anti-oxidant unit of hindered amine, but also also contain in molecule
There is the chain alkyl of excellent compatibility with high molecular material, so the compatibility of the suffocated amine antioxidant and polymer is good,
Anti-migration, anti-solvent extracting performance are good, can be applied to the anti-aging of a variety of high molecular materials；And the suffocated amine antioxidant
Color is shallower, not easy coloring.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
1. a kind of suffocated amine antioxidant, which is characterized in that the suffocated amine antioxidant includes such as lower structure (I)：
Wherein R1For alkyl, R2And R3Selected from hydrogen or below formula (II), and R2And R3At least one of be selected from below formula (II)：
Wherein, R4For chain alkyl, R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15Independently selected from hydrogen or alkyl.
2. suffocated amine antioxidant according to claim 1, which is characterized in that the R1Carbon atom number be idol more than 8
Number.
3. suffocated amine antioxidant according to claim 1, which is characterized in that the suffocated amine antioxidant has as follows
General formula：
Wherein, R1For alkyl, R1Middle carbon atom number is the even number more than 8.
4. a kind of polythene material, which is characterized in that be obstructed in the polythene material comprising claim 1-3 any one of them
Amine antioxidants.
5. polythene material according to claim 4, which is characterized in that the polythene material includes：
100 mass parts of polyvinyl resin；
Composite assistant 0.2-0.36 mass parts；
Wherein described composite assistant includes primary antioxidant, auxiliary antioxidant, heat stabilizer and rheological agent；The primary antioxidant is power
Profit requires 1-3 any one of them suffocated amine antioxidants.
6. polythene material according to claim 5, which is characterized in that the auxiliary antioxidant is bis- (2,4- bis- tertiary fourths
Base phenyl) pentaerythritol diphosphites, three (2,4- di-tert-butyl-phenyls) phosphite esters, thiodipropionic acid dilauryl cinnamic acid ester and
The double octadecyls of thio-2 acid form one or more of group.
7. polythene material according to claim 5, which is characterized in that the heat stabilizer is calcium stearate, stearic acid
Magnesium, zinc stearate and aluminum stearate form one or more of group.
8. polythene material according to claim 5, which is characterized in that the rheological agent is fluorine rheological body.
9. according to claim 5-8 any one of them polythene materials, which is characterized in that the primary antioxidant, auxiliary antioxygen
The mass ratio of agent, heat stabilizer and rheological agent is 1：0.5-1.5：0.25-0.75：0.05-0.15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611114276.8A CN108164750B (en) | 2016-12-07 | 2016-12-07 | Hindered amine antioxidant and polyethylene material |
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| CN113512232A (en) * | 2020-04-10 | 2021-10-19 | 中国石油天然气股份有限公司 | Macromolecular hindered phenol antioxidant and preparation method and application thereof |
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| CN102459173A (en) * | 2009-06-08 | 2012-05-16 | 巴斯夫欧洲公司 | Sterically hindered amine stabilizers |
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| CN113512232A (en) * | 2020-04-10 | 2021-10-19 | 中国石油天然气股份有限公司 | Macromolecular hindered phenol antioxidant and preparation method and application thereof |
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