CN117263821A - Mono-alicyclic diamide hindered phenol antioxidant and preparation method thereof - Google Patents
Mono-alicyclic diamide hindered phenol antioxidant and preparation method thereof Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 90
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 78
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 238000004220 aggregation Methods 0.000 claims abstract description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- -1 alicyclic diamine Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical group COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 19
- 150000004985 diamines Chemical class 0.000 description 11
- 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 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002000 scavenging effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 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 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 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 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
- C07C235/36—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the fields of organic synthesis and high polymer materials, in particular to a mono-alicyclic diamide hindered phenol antioxidant and a preparation method thereof. The structural formula of the mono-alicyclic diamide hindered phenol antioxidant is shown as formula I:wherein G is a mono-alicyclic diamine structure as shown in structural formulas I-1 and I-2 in the specification, and R' are each independently selected from methyl, ethyl, isopropyl or tert-butyl. The mono-alicyclic diamide hindered phenol antioxidant not only has excellent oxidation resistance, but also has the advantages of improving the thermal performance and micro-performance of the materialThe functions of aggregation performance, rheological performance and the like are observed, and the application value is higher; the preparation method of the mono-alicyclic diamide hindered phenol antioxidant provided by the invention has the advantages of simple process, high mono-alicyclic diamine conversion rate, recycling and reusing of excessive 3- (3, 5-alkyl-4-hydroxyphenyl) propionate and solvent, and strong market competitiveness.
Description
Technical Field
The invention relates to the fields of organic synthesis and high polymer materials, in particular to a mono-alicyclic diamide hindered phenol antioxidant and a preparation method thereof.
Background
The antioxidant is an additive for plastics and rubber industries, and is used for delaying the degradation and aging processes of plastics, rubber and other products, prolonging the service lives of the plastics, rubber and other products and improving the use value of the plastics, rubber and other products.
According to the difference of chemical structures, antioxidants are classified into amine antioxidants, phosphite antioxidants, sulfur-containing antioxidants and hindered phenol antioxidants. The hindered phenol antioxidant has the advantages of high antioxidant efficiency, good thermal stability, small volatility, good tinting strength, good compatibility with a base material and the like, and is the main antioxidant with the most application in the field of high-molecular materials.
Hindered phenolic antioxidants have sterically bulky groups, such as t-butyl groups, in the ortho position to the phenolic hydroxyl group. Although various hindered phenol antioxidants have been disclosed with varying properties such as octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate (2098), hexadecyl 2,2' -methylenebis- (4-methyl-6-tert-butylphenol) (2246), pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), tris (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanurate (antioxidant 3114), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-tert-butyl-4-hydroxybenzyl) benzene) (330), 2' -thiodiethylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1035), N ' - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine) (1098) and the like, the design and synthesis of the related polyphenols have been pursued.
Disclosure of Invention
In order to solve the problems, the invention researches and synthesizes the single alicyclic diamide hindered phenol antioxidant with improved material thermal property, micrococcumulation property and rheological property and the preparation method thereof, expands the variety of the hindered phenol antioxidant, and particularly overcomes the defects that the independent use effect of the existing hindered phenol antioxidant is poor and the composite use influences the material property.
Therefore, the invention provides the mono-alicyclic diamide hindered phenol antioxidant with a novel structure and the preparation method thereof, and the mono-alicyclic diamide hindered phenol antioxidant has the functions of keeping and/or improving the thermal stability, micro aggregation and the like of the material while improving the antioxidant property of the material.
Specifically, the invention provides a mono-alicyclic diamide hindered phenol antioxidant, and the structural formula of the mono-alicyclic diamide hindered phenol antioxidant is shown as formula I:
wherein G is selected from one of the following structural formulas:
wherein-NH in G each forms an amide bond with-c=o in formula I,
wherein R and R' are each independently selected from methyl, ethyl, isopropyl or tert-butyl.
The invention also provides a preparation method of the mono-alicyclic diamide hindered phenol antioxidant, which comprises the steps of preparing the mono-alicyclic diamide hindered phenol antioxidant shown in the formula I by nucleophilic addition-elimination reaction of mono-alicyclic diamine shown in the formula II and 3- (3, 5-alkyl-4-hydroxyphenyl) propionate shown in the formula III (hereinafter referred to as 3, 5-ester), wherein the reaction general formula is as follows:
wherein G' in formula II is selected from one of the following structural formulas:
wherein R and R' in formula III are each independently selected from methyl, ethyl, isopropyl or tert-butyl; and R 'is alkyl, preferably R' is methyl (-CH) 3 ) Or ethyl (-CH) 2 CH 3 )
Wherein G in formula I is selected from one of the following structural formulas:
wherein-NH in G each forms an amide bond with-c=o in formula I.
For example, when G' in formula II is(i.e., the structural formula II-1, the corresponding mono-alicyclic diamine represented by the formula II is denoted as formula II-A), the mono-alicyclic diamide hindered phenol antioxidant (denoted as I-A) has the structural formula:
when G' in formula II is(i.e., the above structural formula II-1, the corresponding mono-alicyclic diamine represented by formula II is denoted as formula II-A), R and R 'in formula III are both tert-butyl groups, R' is methyl (the corresponding 3, 5-ester represented by formula III is denoted as III-A), the mono-alicyclic diamide hindered phenol antioxidant (I-A) is prepared as follows:
for example: when G' in formula II is(i.e., the above structural formula II-1, the corresponding mono-alicyclic diamine represented by formula II is denoted as formula II-A), R and R 'in formula III are methyl groups, R' is tert-butyl group (the corresponding 3, 5-ester represented by formula III is denoted as III-B), the mono-alicyclic diamide hindered phenol antioxidant (denoted as I-B) has the structural formula:
when G' in formula II is(i.e., the above structural formula II-1, the corresponding mono-alicyclic diamine represented by formula II is denoted as formula II-A), R and R 'in formula III are methyl groups, R' is tert-butyl group (the corresponding 3, 5-ester represented by formula III is denoted as III-B), the reaction formula for preparing the mono-alicyclic diamide hindered phenol antioxidant (I-B) is as follows:
further, the preparation method comprises the following steps: sequentially adding a solvent I, single alicyclic diamine shown in a formula II, 3- (3, 5-alkyl-4-hydroxyphenyl) propionate shown in a formula III (hereinafter referred to as 3, 5-ester) and a catalyst into a reactor, reacting for 2-12 h at 80-200 ℃, and tracking the reaction progress by TLC; after the reaction is finished, adding a solvent for secondary crystallization; filtering, washing the filter cake with solvent II, and finally vacuum drying at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant shown in the formula I.
Further, in the production method, the equivalent ratio of the mono-alicyclic diamine and the 3, 5-ester is: 1.0:2.0 to 4.0, preferably 1.0:2.2 to 3.0.
Further, in the preparation method, the ratio of the volume of the solvent one to the mass sum of the mono-alicyclic diamine and the 3, 5-ester is 2 to 6:1, preferably 2 to 4:1.
Further, in the preparation method, the catalyst is used in an amount of 1.0 to 12.0wt%, preferably 6 to 10wt%, based on the amount of 3, 5-ester.
Further, in the production method, the solvent is used in an amount of 20 to 150vol%, preferably 80 to 120vol%, based on the solvent.
Further, in the production method, the 3, 5-ester is methyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate and methyl 3- (3-methyl-5-t-butyl-4-hydroxyphenyl) propionate. Preferably, in the preparation method, the 3, 5-ester is methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further, in the production method, the solvent one is selected from toluene, xylene, solvent oil, chlorobenzene, dimethylsulfoxide, N-dimethylformamide, cyclohexane, isooctane, trimethylpentane, heptane, or 1, 2-dichloroethane. Preferably, in the preparation method, the solvent one is selected from xylene or solvent oil.
Further, in the production method, the catalyst is selected from dibutyltin oxide, stannous octoate, tetrabutyl titanate, triethylaluminum, copper acetate, copper chloride, and boron trifluoride. Preferably, in the preparation method, the catalyst is dibutyl tin oxide.
Further, in the preparation method, the solvent is selected from isopropanol, tert-butanol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether or methyl tert-butyl ether. Preferably, in the preparation method, the solvent is selected from isopropanol or ethylene glycol dimethyl ether.
In other aspects, the present invention also provides the use of a compound as defined hereinabove as shown in formula I as a mono-alicyclic diamide hindered phenolic antioxidant capable of improving the thermal, micro-aggregation and rheological properties of materials.
The beneficial effects of the invention are that
The mono-alicyclic diamide hindered phenol antioxidant provided by the invention not only has excellent oxidation resistance, but also has the functions of improving the thermal performance, micro aggregation performance, rheological property and the like of materials, and has larger application value; the preparation method of the mono-alicyclic diamide hindered phenol antioxidant provided by the invention has the advantages of simple process, high mono-alicyclic diamine conversion rate, recycling and reusing of excessive 3, 5-ester and solvent, and strong market competitiveness.
Description of the drawings:
FIG. 1 is a Mass Spectrum (MS) of a hindered phenol antioxidant I-A obtained in example 1 (ESI: M+Na) + ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is a Mass Spectrum (MS) diagram of the hindered phenol antioxidant I-A obtained in example 1, and B is a repetition of the hindered phenol antioxidant I-A obtained in example 1The resulting Mass Spectrum (MS) pattern was analyzed.
FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum of the hindered phenol antioxidant I-A obtained in example 1 1 H NMR) map.
FIG. 3 shows nuclear magnetic resonance spectrum of the hindered phenol antioxidant I-A obtained in example 1 13 C NMR) map.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Wherein G in formula I is respectivelyThe preparation of the mono-alicyclic diamide hindered phenol antioxidant is illustrated by the formula III in which R and R 'are both tert-butyl groups, R "is methyl (III-1) and R" is methyl, R' is tert-butyl (III-2), and the other preparation methods of the mono-alicyclic diamide hindered phenol antioxidant are the same except that G in formula I is->Skeleton changes, and changes in the R, R 'and R' groups in formula III.
Example 1
Xylene (110 mL), mono-alicyclic diamine II-1 (6.41 g,0.050 mol), 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate III-1 (38.57 g,0.110 mol) and dibutyltin oxide (3.20 g) were sequentially added to the reactor, reacted at 130℃to 140℃for 6 hours, TLC followed by crystallization by adding isopropanol (55 mL) after the mono-alicyclic diamine II-1 reaction site disappeared. Filtering, washing the filter cake with 60mL isopropanol three times, and finally vacuum drying at 60-100deg.C to obtain the mono-alicyclic diamide hindered phenol antioxidant I-A, wherein the molecular weight of I-A is 671.7 (calculated value is 648.5 and added sodium ion is 671.5) by mass spectrometry analysis as shown in figure 1. Nuclear magnetic resonance hydrogen spectrum of I-A 1 H NMR) and nuclear magnetic resonance carbon spectrum [ ] 13 C NMR) are shown in fig. 2 and 3, respectively.
Example 2
Xylene (160 mL), mono-alicyclic diamine II-1 (6.41 g,0.050 mol), 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate III-1 (36.55 g,0.125 mol) and dibutyltin oxide (2.10 g) were added in this order to react for 8h at 120-130 ℃, TLC followed by crystallization by adding isopropanol (110 mL) after the mono-alicyclic diamine II-1 reaction site disappeared. Filtering, washing the filter cake with 60mL of isopropanol for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-A.
Example 3
Solvent oil (200 mL), mono-alicyclic diamine II-1 (6.41 g,0.050 mol), 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate III-1 (43.86 g,0.150 mol) and dibutyl tin oxide (4.00 g) were added in this order to react for 10h at 80-100deg.C, TLC followed by crystallization, and after the point of mono-alicyclic diamine II-1 had disappeared, ethylene glycol dimethyl ether (160 mL) was added. Filtering, washing the filter cake with 60mL of ethylene glycol dimethyl ether for three times, and finally vacuum drying at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-A.
Example 4
Solvent oil (150 mL), mono-alicyclic diamine II-1 (6.41 g,0.050 mol), 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate III-1 (51.17 g,0.175 mol) and dibutyl tin oxide (2.30 g) were added in this order to react for 4h at 135-140 ℃, TLC followed by crystallization by acetonitrile (150 mL) after the reaction point of mono-alicyclic diamine II-1 disappeared. Filtering, washing the filter cake with 60mL of acetonitrile for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-A.
Example 5
Solvent oil (350 mL), mono-alicyclic diamine II-1 (6.41 g,0.050 mol), 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate III-1 (58.48 g,0.200 mol) and dibutyl tin oxide (3.90 g) were added in this order to react for 4h at 135-140 ℃, TLC followed by crystallization by acetonitrile (160 mL) after the reaction point of mono-alicyclic diamine II-1 disappeared. Filtering, washing the filter cake with 60mL of acetonitrile for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-A.
Example 6
Xylene (110 mL), mono-alicyclic diamine II-2 (6.41 g,0.050 mol), 3- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate III-2 (27.53 g,0.110 mol) and dibutyltin oxide (3.00 g) were added in this order to react for 6h at 130-140 ℃, TLC followed by crystallization by adding isopropanol (55 mL) after the mono-alicyclic diamine II-2 reaction site disappeared. Filtering, washing the filter cake with 60mL of isopropanol for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-B.
Example 7
Xylene (160 mL), mono-alicyclic diamine II-2 (6.41 g,0.050 mol), 3- (3-methyl-5-tertiary butyl-4-hydroxy phenyl) propionate III-2 (31.29 g,0.125 mol) and dibutyl tin oxide (2.00 g) were added in this order to react for 8h at 120-130 ℃, TLC followed by crystallization by adding isopropanol (110 mL) after the mono-alicyclic diamine II-2 reaction point disappeared. Filtering, washing the filter cake with 60mL of isopropanol for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-B.
Example 8
Solvent oil (200 mL), mono-alicyclic diamine II-2 (6.41 g,0.050 mol), 3- (3-methyl-5-tertiary butyl-4-hydroxy phenyl) propionate III-2 (37.54 g,0.150 mol) and dibutyl tin oxide (4.00 g) are sequentially added into a reactor, the reaction is carried out for 10h at 80-100 ℃, TLC tracks the reaction progress, and after the reaction point of the mono-alicyclic diamine II-2 disappears, ethylene glycol dimethyl ether (160 mL) is added for crystallization. Filtering, washing the filter cake with 60mL of ethylene glycol dimethyl ether for three times, and finally vacuum drying at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-B.
Example 9
Solvent oil (150 mL), mono-alicyclic diamine II-2 (6.41 g,0.050 mol), 3- (3-methyl-5-tertiary butyl-4-hydroxy phenyl) propionate III-2 (43.80 g,0.175 mol) and dibutyl tin oxide (2.20 g) are sequentially added into a reactor, the reaction is carried out for 4h at 135-140 ℃, TLC tracks the reaction progress, and acetonitrile (150 mL) is added for crystallization after the reaction point of the mono-alicyclic diamine II-2 disappears. Filtering, washing the filter cake with 60mL of acetonitrile for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-B.
Example 10
Solvent oil (300 mL), mono-alicyclic diamine II-2 (6.41 g,0.050 mol), 3- (3-methyl-5-tertiary butyl-4-hydroxy phenyl) propionate III-2 (58.48 g,0.200 mol) and dibutyl tin oxide (3.60 g) are sequentially added into a reactor, the reaction is carried out for 4h at 135-140 ℃, TLC tracks the reaction progress, and acetonitrile (150 mL) is added for crystallization after the reaction point of the mono-alicyclic diamine II-2 disappears. Filtering, washing the filter cake with 60mL of acetonitrile for three times, and finally drying in vacuum at 60-100 ℃ to obtain the mono-alicyclic diamide hindered phenol antioxidant I-B.
The PA6 is taken as a base material, the antioxidants I-A and I-A synthesized in the examples are respectively added, the antioxidant 1010 and the antioxidant 1098 are respectively compounded with the antioxidant 168 for use, and the PA6 composite material is prepared, and the detailed formula is shown in Table 1.
Table 1 formulation of PA6 composite
Extruding and granulating by using a Labtech double-screw extruder, wherein the processing temperature is (DEG C): 225. 240, 240 240, 220, 200. The prepared PA6 composite material was subjected to Thermal Gravimetric Analysis (TGA) in a nitrogen atmosphere, pure PA6 and initial decomposition temperature (T 5％ ) Temperature at 50% thermal weight loss (T 50％ ) At maximum thermal weight loss rate (T max ) The results are shown in Table 2.
Table 2 thermogravimetric data of PA6 composite in nitrogen atmosphere
Table 2 shows that novel antioxidants I-A and their resistanceThe composite system of oxygen 1010 or 1098 and antioxidant 168, respectively, has an initial decomposition temperature (T 5％ ) Substantially unaffected, but the novel combination of antioxidant I-A and antioxidant 168 gives a substrate PA6 with a temperature (T) at which the thermal weight loss of 50% 50％ ) Increasing from 445.79 ℃to 456.97 ℃at maximum thermal weight loss rate (T max ) The temperature of the mixture is increased from 445.09 ℃ to 461.12, which is superior to a composite system formed by 1010 or 1098 and the antioxidant 168 respectively. The biggest advantage of I-A is that the PA6 composite material has excellent performance when used alone, and the temperature (T) 50％ ) At maximum thermal weight loss rate (T max ) The temperature of (2) is respectively increased to 462.26 ℃ and 468.31 ℃, which is not only higher than that of the base material PA6, but also better than that of a composite system formed by 1010 or 1098 and the antioxidant 168 respectively.
Differential Scanning Calorimetric (DSC) analysis of the PA6 composite, pure PA6 and first time Peak to Peak (Peak) of the PA6 composite 1 ) First cooling peak (T) C ) Peak of second temperature rise (T) m ) The other main parameters are shown in Table 3.
TABLE 3 main DSC data for PA6 composite
X in Table 3 C Calculated from the following formula:
w in the formula PA6-x Delta H is the mass percent of PA6 in the composite material 0 m The melting enthalpy of 100% crystalline PA6 is 230.1J/g.
Table 3 shows that the use of I-A alone or in combination with antioxidant 168 in a composite system does not substantially affect the thermal properties and crystallinity of PA 6.
Rheological experiments were performed using a MARS type III rheometer with 20mm diameter PP20 in oscillatory shear mode, and the rheological properties of the PA6 composite are shown in Table 4, with a 10rad/s frequency for samples 1mm thick at 255℃in the strain range of 0.1% to 1000%.
Table 4 table PA6 composite rheology time data
PA6 is a crystalline resin, and its melt viscosity becomes small when the temperature exceeds its melting point. Table 4 shows that the addition of the antioxidant I-A or I-A and the antioxidant 168 forms a composite system, and the composite system formed by the antioxidant 168 and I-A or I-A leads the PA6 composite material to have excellent melt flowability and better processability from the point of view of the corresponding time of the maximum viscosity or the corresponding time of the sudden viscosity drop.
The absolute ethyl alcohol is used as a solvent, the antioxidants I-A and 1098 to be detected are respectively prepared into a series of solutions with molar concentration, and simultaneously, the 1, 1-diphenyl-2-picrylhydrazine free radical (DPPH) is dissolved in the absolute ethyl alcohol and stored in dark. The respective DPPH radical scavenging capacity of antioxidants I-A and 1098 was determined by the Brand-Williams method.
Mixing an absolute ethanol solution of DPPH with an antioxidant solution to be detected (the absolute ethanol is used for blank comparison to replace the antioxidant solution), standing for 0.5h at 25 ℃, and measuring absorbance A at a wavelength of 517nm by an ultraviolet-visible photometer until equilibrium is reached, wherein the clearance (a) of the antioxidant for eliminating DPPH free radicals is calculated by adopting the following formula:
in which A Blank space Absolute ethyl alcohol without antioxidant, A Antioxidant Is an absolute ethanol solution of an antioxidant. Similar to antioxidant 1098, the clearance of DPPH radical by antioxidant I-A (a) increases with increasing concentration at lower concentrations. When the concentrations of antioxidants I-A and 1098 are the same, the a values differ little.
According to the scavenging rate of the antioxidant for scavenging DPPH free radical and the concentration of the absolute ethanol solution of the antioxidantA relation curve, calculating the addition amount (half effective concentration, EC) of each antioxidant when the original mass concentration of DPPH free radical in the system is reduced to 50 percent (steady state) 50 ) And the time taken to reach half the effective concentration (TC 50 ) The Antioxidant Efficiency (AE) of the antioxidant is then calculated from the formula:
EC of antioxidants I-A and 1098 50 And TC 50 And calculated AE values are shown in table 5.
TABLE 5 EC of antioxidants I-A and 1098 50 、TC 50 And AE value
EC 50 The smaller the antioxidant, the stronger the antioxidant capacity of the antioxidant, TC 50 The larger the antioxidant is, the slower the reaction of scavenging the free radical is, the reaction speed of scavenging DPPH free radical by the antioxidant I-A is slightly faster than 1098, and the antioxidant capacity of the antioxidant I-A is also stronger than 1098. The antioxidant I-A and the antioxidant 1098 both contain two phenolic hydroxyl groups in the molecule, the active proton numbers of the two phenolic hydroxyl groups are the same when the molar concentration is the same, and the antioxidant efficiency AE of the I-A and the antioxidant 1098 is 1.76X10 respectively -3 And 1.52×10 -3 It is shown that at the same concentration, the antioxidant I-A provides hydrogen protons more strongly than 1098 and more efficiently than 1098.
The experimental result shows that the hindered phenol antioxidant has excellent oxidation resistance and can better prolong the service life of the material. The hindered phenol antioxidant also has the function of maintaining or improving the thermal performance, crystallinity and rheological property of PA6, and shows more excellent characteristics. The performance of the hindered phenol antioxidant provided by the invention is related to the structural characteristics thereof, namely, the hindered phenol antioxidant has a rigid six-membered ring framework, and amino is directly bonded on an alicyclic ring of a rigid structure. The diamine with the rigid structure is used as the same type of antioxidant of the central framework, and the stability is generally better than that of a flexible chain structure.
It should be noted that the description of the present invention and the accompanying drawings illustrate preferred embodiments of the present invention, but the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, which are not to be construed as additional limitations of the invention, but are provided for a more thorough understanding of the present invention. The above-described features are further combined with each other to form various embodiments not listed above, and are considered to be the scope of the present invention described in the specification; further, modifications and variations of the present invention may be apparent to those skilled in the art in light of the foregoing teachings, and all such modifications and variations are intended to be included within the scope of this invention as defined in the appended claims.
Claims (10)
1. The mono-alicyclic diamide hindered phenol antioxidant is characterized by having a structural formula shown in a formula I:
wherein G is selected from one of the following structural formulas:
wherein-NH in G each forms an amide bond with-c=o in formula I,
wherein R and R' are each independently selected from methyl, ethyl, isopropyl or tert-butyl.
2. The method for preparing a mono-alicyclic diamide hindered phenol antioxidant capable of extending the time corresponding to the abrupt decrease in material viscosity according to claim 1, wherein the method for preparing comprises: sequentially adding a solvent I, single alicyclic diamine shown in a formula II, 3- (3, 5-alkyl-4-hydroxyphenyl) propionate shown in a formula III and a catalyst into a reactor, reacting for 2-12 h at 80-200 ℃, and tracking the reaction progress by TLC; after the reaction is finished, adding a solvent for secondary crystallization; filtering, washing the filter cake with solvent II, vacuum drying at 60-100deg.C to obtain mono-alicyclic diamide hindered phenol antioxidant shown in formula I,
wherein G' in formula II is selected from one of the following structural formulas:
wherein R and R' in formula III are each independently selected from methyl, ethyl, isopropyl or tert-butyl; r' is alkyl.
3. The process of claim 2 wherein R "in formula III is methyl or ethyl.
4. The process according to claim 2, wherein the equivalent ratio of mono-alicyclic diamine to 3- (3, 5-alkyl-4-hydroxyphenyl) propionate is: 1.0:2.0-4.0; the ratio of the volume of the solvent I to the mass sum of the mono-alicyclic diamine and the 3- (3, 5-alkyl-4-hydroxy phenyl) propionate is 2-6:1; the dosage of the catalyst is 1.0 to 12.0 weight percent of the dosage of 3- (3, 5-alkyl-4-hydroxyphenyl) propionate; the second solvent is 20-150 vol% of the first solvent.
5. The method according to claim 2, wherein the 3- (3, 5-alkyl-4-hydroxyphenyl) propionate is methyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate or methyl 3- (3-methyl-5-t-butyl-4-hydroxyphenyl) propionate.
6. The process according to claim 2, wherein the solvent one is selected from toluene, xylene, solvent oil, chlorobenzene, dimethylsulfoxide, N-dimethylformamide, cyclohexane, isooctane, trimethylpentane, heptane or 1, 2-dichloroethane.
7. The preparation method according to claim 2, wherein the catalyst is selected from dibutyltin oxide, stannous octoate, tetrabutyl titanate, triethylaluminum, copper acetate, copper chloride and boron trifluoride.
8. The method of claim 2, wherein the catalyst is dibutyl tin oxide.
9. The method of claim 2, wherein the solvent is selected from isopropanol, t-butanol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether or methyl t-butyl ether.
10. The use of a compound of formula I as defined in claim 1 as a mono-alicyclic diamide hindered phenolic antioxidant capable of improving the thermal, micro-aggregation and rheological properties of materials.
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