CN1288142C - 3-substituted phenyl-benzo furanone stabilizer and preparing process thereof - Google Patents
3-substituted phenyl-benzo furanone stabilizer and preparing process thereof Download PDFInfo
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- CN1288142C CN1288142C CN 200410045039 CN200410045039A CN1288142C CN 1288142 C CN1288142 C CN 1288142C CN 200410045039 CN200410045039 CN 200410045039 CN 200410045039 A CN200410045039 A CN 200410045039A CN 1288142 C CN1288142 C CN 1288142C
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- methyl
- tertiary butyl
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- -1 3-substituted phenyl-benzo furanone Chemical class 0.000 title claims abstract description 68
- 239000003381 stabilizer Substances 0.000 title claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229920000620 organic polymer Polymers 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 11
- 125000003118 aryl group Chemical group 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 4
- 125000002252 acyl group Chemical group 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
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- 239000004743 Polypropylene Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 230000002596 correlated effect Effects 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010137 moulding (plastic) Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- VQTUMNNCKYTZSR-UHFFFAOYSA-N 3-hydroxy-3h-1-benzofuran-2-one Chemical compound C1=CC=C2C(O)C(=O)OC2=C1 VQTUMNNCKYTZSR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000010934 O-alkylation reaction Methods 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229920003052 natural elastomer Polymers 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical class Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound 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 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Furan Compounds (AREA)
Abstract
本发明是关于3-取代苯基-苯并呋喃酮稳定剂及其制备，其结构通式特征为(1)式所示，(1)式中R1是：氢、酰基、烷基、芳烷基、烯丙基；R2，R5是：氢、C1-C10烷基、C6-C10的环烷基或芳基、芳烷基；R3、R4是：C1-C10烷基、C6-C10的环烷基或芳基、芳烷基。此类3-取代苯基-苯并呋喃酮用作有机聚合物和有机物质抵抗热、氧化或光诱导所导致降解的稳定剂。
The present invention relates to a 3-substituted phenyl-benzofuranone stabilizer and its preparation. Its structural general formula is characterized by (1) formula, where R in ( 1 ) is: hydrogen, acyl, alkyl, aromatic Alkyl, allyl; R 2 , R 5 are: hydrogen, C 1 -C 10 alkyl, C 6 -C 10 cycloalkyl or aryl, aralkyl; R 3 , R 4 are: C 1 -C 10 alkyl, C 6 -C 10 cycloalkyl or aryl, aralkyl. Such 3-substituted phenyl-benzofuranones are used as stabilizers of organic polymers and organic substances against thermally, oxidatively or light-induced degradation.
Description
Technical field
The invention relates to 3-substituted-phenyl-benzofuranone stabilization agent and preparation thereof.
This type of 3-substituted-phenyl-benzofuranone causes the stablizer of degrading as organic polymer and organic substance opposing heat, oxidation or photoinduction.
Background technology
Indivedual 3-aryl-benzofuranones are openly reported the earliest:
M.H.Hubacher J.Org.Chem.24，1949(1959)；
J.Gripenberg Acta Chemica Scandinavia 23 2583(1969)
M.Auge Bull.Soc.Chim.Fr.1970 4024
J.Morvan Bull.Soc.Chim.Fr.1979 583
Some 3-aryl-benzofuranone starts from as the report of organic polymer and organic substance stablizer:
US4325863 1982
US4338224 1982
EP415887 1991 relevant same Patent: US5175312 1992
3-aryl-benzofuranone occurs in succession as the report of organic polymer and organic substance stablizer subsequently:
The DE4432732 same Patent of being correlated with: US6359148 B1 US6346630 B1 US5814692
US5773631 US5516920 CN1191229A CN1106809A
The CA2132132 same Patent of being correlated with: US5607624 CN1111627A
The EP0591102 same Patent of being correlated with: US5428162 CN1087906A
The DE4316611 same Patent of being correlated with: US5488117 US5369159
DE4316876 same Patent: the US5367008 that is correlated with
EP0589839 same Patent: the US5428177 that is correlated with
The EP0644190 same Patent of being correlated with: US5807505 US5693829 US5614572 CN1106032A
And industrialization product appears.
Disclosed by the invention is the class 3-aryl-benzofuranone different with above-mentioned bibliographical information, and this type of 3-substituted-phenyl-benzofuranone is especially suitable for use as heat, oxidation or photoinduction cause the degrading stablizer of organic polymer and organic substance.
Summary of the invention
The purpose of this invention is to provide a new class 3-aryl-benzofuranone, be especially suitable for use as heat, oxidation or photoinduction cause the degrading stablizer of responsive organic polymer and organic substance, and with this type of 3-aryl-benzofuranone succinct synthetic method accordingly.
The invention provides its general structure for this reason and be the 3-substituted-phenyl-benzofuranone shown in (1) formula.
(1) in the formula
R
1Be: hydrogen, acyl group, alkyl, aralkyl, allyl group;
R
2, R
5Be: hydrogen, C
1-C
10Alkyl, C
6-C
10Cycloalkyl or aryl, aralkyl.
R
3, R
4Be: C
1-C
10Alkyl, C
6-C
10Cycloalkyl or aryl, aralkyl.
R wherein
1Be: hydrogen; R
3, R
4Be: methyl; R
2, R
5Be: the tertiary butyl;
Structural formula shown in (2) formula, its called after:
5-methyl-7-the tertiary butyl-3-(the 5-methyl-3-tertiary butyl-2-hydroxy phenyl)-2 (3H)-benzofuranones.
R wherein
1Be: ethanoyl; R
3, R
4Be: methyl; R
2, R
5Be: the tertiary butyl;
Structural formula shown in (3) formula, its called after:
The acetate 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester.
R wherein
1Be: acryl;
R
3, R
4Be: methyl;
R
2, R
5Be: the tertiary butyl;
Structural formula shown in (4) formula, its called after:
The vinylformic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester.
R wherein
1Be: methacryloyl;
R
3, R
4Be: methyl;
R
2, R
5Be: the tertiary butyl;
Structural formula shown in (5) formula, its called after:
The methacrylic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester.
The disclosed need that the 3-aryl-the benzofuranone synthetic method has relate to aryl alcohol acid intermediate, and what have will be through 3-hydroxyl-benzofuranone intermediate, all quite loaded down with trivial details.
The synthetic method of 3-substituted-phenyl-benzofuranone provided by the invention is corresponding more succinct.
Compound shown in general structure (S1) formula, (S1) in the formula:
R
1Be hydrogen, R
2, R
5Be: hydrogen, C
1-C
10Alkyl, C
6-C
10Cycloalkyl or aryl, aralkyl.R
3, R
4Be: C
1-C
10Alkyl, C
6-C
10Cycloalkyl or aryl, aralkyl.
(S1) formula comprises compound shown in (2) formula
The synthetic method of compound shown in general structure (S1) formula is:
With 2,4-disubstituted benzenes phenol or 4-fortified phenol and oxoethanoic acid condensation, esterification cyclization subsequently makes, and two-step reaction is finished in same reactor.
2, the mol ratio of 4-disubstituted benzenes phenol or 4-fortified phenol and oxoethanoic acid is 1.80-2.20: 0.90-1.10.Catalyzer is: alkylsulphonic acid, aryl sulfonic acid contains sulfonic ion exchange resin, mineral acid example hydrochloric acid, sulfuric acid.
Reaction can be solvent-free, and 130-200 ℃ of fusion at high temperature carried out.
Solvent is used in reaction, temperature of reaction between 30-150 ℃,
Optional solvent: halogenated alkane is as 1, the 2-ethylene dichloride,
Aromatic hydrocarbons such as toluene, benzene, dimethylbenzene
Aliphatic carboxylic acid is as acetate, propionic acid, formic acid.
Compound shown in general structure (S2) formula, (S2) in the formula:
R
6Be: C
1-C
20Alkyl, C
1-C
20Contain unsaturated link(age) alkyl, C
6-C
10Cycloalkyl, aryl, aralkyl,
R
2, R
5Be: hydrogen, C
1-C
10Alkyl, C
6-C
10Cycloalkyl or aryl, aralkyl.
R
3, R
4Be: C
1-C
10Alkyl, C
6-C
10Cycloalkyl or aryl, aralkyl.
(S2) formula comprises compound shown in (3), (4), (5) formula
The synthetic method of compound shown in general structure (S2) formula is: with general structure
(S1) reaction of compound shown in the formula and corresponding acid anhydrides or carboxylic acid halides makes,
The mol ratio of the compound shown in general structure (S1) formula and corresponding acid anhydrides or carboxylic acid halides is 0.90-1.10: 0.90-1.10.
Phenolic hydroxyl group in the compound shown in general structure (S1) formula also can carry out the O-alkylation, and H is replaced by alkyl, aralkyl, allyl group; The O-alkylating reagent is as benzylic type, allyl type halogenide, tertiary olefin, epoxy compounds, sulfuric ester, aromatic sulfonic acid ester etc.
3-substituted-phenyl-benzofuranone provided by the invention is especially suitable for use as heat, oxidation or photoinduction cause the degrading stablizer of responsive organic polymer and organic substance.
These to heat, oxidation or photoinduction cause degrading responsive organic polymer and organic substance as:
1, various olefin homos, multipolymer, olefin polymer mixture and modified olefin polymer thing.
2, α, the homopolymer of beta-unsaturated acid and derivative thereof, or with other monomeric multipolymers.
3, by unsaturated alcohol, amine or its acyl derivative, acetal derivant resulting polymers.
4, the homopolymer of cyclic ethers and multipolymer.
5, polyacetal.
6, polyphenylene oxide, polyphenylene sulfide, or with other mixture of polymers.
7, polymeric amide.
8, polyimide, polyureas, polybenzimidazole.
9, polyester, unsaturated polyester.
10, polycarbonate.
11, polysulfones, polyethersulfone, polyetherketone.
12, phenolic aldehyde, urea-formaldehyde resin.
13, Synolac.
14, Resins, epoxy.
15, natural polymer.
16, natural or synthesis of organic substance.
17, natural or synthetic rubber.
18, photosensitive imaging emulsion.
3-substituted-phenyl-benzofuranone provided by the invention also can be shared with following other stablizer or polymer builder,
1, phenolic antioxidant.
2, UV light absorber and photostabilizer.
3, metal passivator.
4, phosphorous acid ester and phosphinate.
5, peroxide scavenger.
6, polymeric amide stablizer.
7, alkaline auxiliary stablizer.
8, transparent nucleator.
9, fill toughener.
This type of 3-substituted-phenyl-benzofuranone is suitable as the photosensitive imaging emulsion stablizer of being made up of polymkeric substance and organism; With the shared polyolefin stabilizers that is suitable as very much of phenolic antioxidant, phosphorous acid ester and phosphinate.
Stablizer of the present invention is caught the restraint except that having the basic parent 3-of benzofuranone strong carbon radicals of position tertiary carbon and oxygen radical, its 3-bit substituent part also has traditional hindered phenol antioxygen active structure unit, that have in addition also contain unsaturated link(age) [compound shown in (4), (5) formula] can with combined with radical in addition with the macromolecular chain bonding, thereby efficient is higher, and anti-transport property is better.
Description of drawings
Fig. 1, the 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranone infrared spectras
Fig. 2, the 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranone proton nmr spectras
Fig. 3, the acetate 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester infrared spectra
Fig. 4, the acetate 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester proton nmr spectra
Fig. 5, the vinylformic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester infrared spectra
Fig. 6, the vinylformic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester proton nmr spectra
The invention will be further described for embodiment below the embodiment, but the present invention is not limited to following examples.
The embodiment 1 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranones are synthetic
Add 83.0 gram 4-methyl-2-tert.-butyl phenols in 500 milliliters of round-bottomed flasks, 48.0 gram oxoethanoic acids, 40% aqueous solution, 200 milliliters of acetate, 2 milliliters of vitriol oils, 4 milliliters of concentrated hydrochloric acids; The dress prolong; under the argon shield; begin heating, earlier 90 ℃ of degree reactions 2 hours, after refluxing then about 8 hours; be chilled to room temperature; suction filtration, with 100 ml waters washing three times, purifying obtains white powder crystalline solid product: the 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranones 55.6 grams; productive rate 60.0%, fusing point 210-212 ℃.
Ultimate analysis C
24H
30O
3Theoretical value C 78.65%, and H 8.25%
Measured value C 78.46%, H 8.02%
Infrared spectra IR (KBr compressing tablet) ν cm
-1(referring to accompanying drawing 1)
1776.09cm
-1(benzofuranone carbonyl) 3434.20cm
-1(phenolic hydroxyl group)
Proton nmr spectra
1H-NMR (CDCl
3) δ ppm (referring to accompanying drawing 2)
1.411 (9H), 2.203 (3H) (5 ' methyl H of 3 ' tertiary butyl H of 3-substituted-phenyl),
1.452 (9H), 2.384 (3H) (5 methyl H of 7 tertiary butyl H of benzofuran-2-ones parent),
5.232 (1H) (the benzofuran-2-ones parent: 3 H),
(6.5856.581 1H is bimodal), 7.0787.074 (1H is bimodal) (6 ', 4 ' H of 3-substituted-phenyl),
6.962 (1H), 7.134 (1H) (benzofuran-2-ones parent: 4,6 H).
The embodiment 2 acetate 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester is synthetic
150 milliliters of round-bottomed flasks add the 18.3 gram 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranones, 50 milliliters of dimethylbenzene, and under 50 ℃ of degree, Dropwise 5 .3 restrains diacetyl oxide, adds back insulation 2 hours; Washing then removes removal xylene, and purifying gets white powder crystalline solid product: the acetate 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-cumarone ketone group) phenyl ester 13.3 grams, productive rate 65.0%, fusing point 166-169 ℃.
Ultimate analysis C
26H
32O
4Theoretical value C 76.44%, and H 7.90%
Measured value C 76.27%, H 7.63%
Infrared spectra IR (KBr compressing tablet) ν cm
-1(referring to accompanying drawing 3)
1798.48cm
-1(benzofuranone carbonyl) 1758.40cm
-1(acetyl carbonyl)
Proton nmr spectra
1H-NMR (CDCl
3) δ ppm (referring to accompanying drawing 4)
1.357 (9H), 2.247 (3H) (5 ' methyl H of 3 ' tertiary butyl H of 3-substituted-phenyl),
1.428 (9H), 2.283 (3H+3H) (7 tertiary butyl H of benzofuran-2-ones parent
Methyl H in 5 methyl H and the ethanoyl),
4.687 (1H) (the benzofuran-2-ones parent: 3 H),
(6.549 1H broad peak), 7.059 (1H) (6 ', 4 ' H of 3-substituted-phenyl),
(6.919 1H broad peak), 7.193 (1H) (benzofuran-2-ones parent: 4,6 H).
The embodiment 3 vinylformic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester is synthetic
150 milliliters of round-bottomed flasks add the 18.3 gram 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranones, 50 milliliters of dimethylbenzene, 5.3 gram triethylamine, under 50 ℃ of degree, drip 4.8 gram acrylate chlorides, add back insulation 2 hours: washing then, remove removal xylene, purifying gets white powder crystalline solid product: the vinylformic acid 4-methyl-2-tertiary butyl-6-(5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-cumarone ketone group) phenyl ester 12.6 grams, productive rate 60.0%, fusing point 160-163 ℃.
Ultimate analysis C
27H
32O
4Theoretical value C 77.11%, and H 7.67%
Measured value C 76.92%, H 7.41%
Infrared spectra IR (KBr compressing tablet) ν cm
-1(referring to accompanying drawing 5)
1812.88cm
-1(benzofuranone carbonyl) 1736.03cm
-1(acryloyl carbonyl)
Proton nmr spectra
1H-NMR (CDCl
3) δ ppm (referring to accompanying drawing 6)
1.349 (9H), 2.248 (3H) (5 ' methyl H of 3 ' tertiary butyl H of 3-substituted-phenyl),
1.410 (9H), 2.284 (3H) (5 methyl H of 7 tertiary butyl H of benzofuran-2-ones parent),
4.670 (1H) (the benzofuran-2-ones parent: 3 H),
(6.049 1H broad peak), 7.036 (1H) (6 ', 4 ' H of 3-substituted-phenyl),
(6.629 1H broad peak), 7.199 (1H) (the benzofuran-2-ones parent: 4,6 H),
(6.356 1H broad peak) (relative carbonyl is at two key opposite side H in the acryl),
(6.526 1H broad peak) (in acryl with carbonyl adjacent carbons on H),
(6.949 1H broad peak) (in acryl with carbonyl at two keys the same side H).
Proton nmr spectra: benzofuran-2-ones parent: 4,6 H,
6 ', 4 ' H particular location of 3-substituted-phenyl is referring to (1) formula
Infrared spectra IR instrument model Perkin-Elmer Spectrum One
Nuclear magnetic resonance nmr instrument model Bruker-400
Embodiment 4 polypropylene are extruding pelletization stability experiment A repeatedly
1.5 kilogram polypropylene powder
(the polypropylene powder 075-1 of plastic molding and processing plant of Jinling Petrochemical Co. of China Petrochemical Corporation)
(230 ℃, 2.16 kilograms of melting index measured values 11.0),
Do not add stablizer of the present invention,
Or only add one of 0.03% embodiment, 1,2,3 products used as stabilizers,
With twin screw extruder at 260 ℃ of three extruding pelletizations,
(the parallel parallel dual-screw extruding machine SJSH-30 of Nanjing Rubber-Plastic Machinery Plant)
Survey melting index (230 ℃, 2.16 kilograms) then,
(melt flow rate (MFR) instrument XNR-400 Chengde gold is built detecting instrument company limited)
Melting index raises, and chain degradation takes place meaning, and stability degenerates.
The results are shown in Table 1:
Three extruding pelletization stability experiments of table 1 polypropylene powder A
| The compounds of this invention | Melting index restrains/10 fens 230 ℃, 2.16 kilograms |
| ----------------- | 100.0 11.1 9.8 9.3 |
1.5 kilogram polypropylene powder
(the polypropylene powder 075-1 of plastic molding and processing plant of Jinling Petrochemical Co. of China Petrochemical Corporation)
(230 ℃, 2.16 kilograms of melting index measured values 11.0),
Add 0.05% antioxidant 3114 earlier:
1,3,5-(3,5-di-t-butyl-4 hydroxybenzyl) guanamine, 4,6-(1H, 3H, 5H) triketone
With 0.02% oxidation inhibitor 168: tricresyl phosphite (2, the 4-di-tert-butyl) ester
Add one of 0.01% embodiment, 1,2,3 products used as stabilizers again,
With twin screw extruder at 260 ℃ of three extruding pelletizations,
(the parallel parallel dual-screw extruding machine SJSH-30 of Nanjing Rubber-Plastic Machinery Plant)
Survey melting index (230 ℃, 2.16 kilograms) then,
(melt flow rate (MFR) instrument XNR-400 Chengde gold is built detecting instrument company limited)
Melting index raises, and chain degradation takes place meaning, and stability degenerates.
The results are shown in Table 2:
Three extruding pelletization stability experiments of table 2 polypropylene powder B
(having added earlier 0.05% antioxidant 3114 and 0.02% oxidation inhibitor 168)
| The compounds of this invention | Melting index restrains/10 fens 230 ℃, 2.16 |
| Embodiment | |
| 1 product 0.01 | 11.8 10.9 10.2 |
Claims (4)
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|---|---|---|---|---|
| CN108586404A (en) * | 2018-06-12 | 2018-09-28 | 湖南大学 | A kind of synthetic method of N- aryl naphtho- furanone imine compound |
| CN108947948A (en) * | 2018-06-12 | 2018-12-07 | 湖南大学 | A kind of N- aryl naphtho- furanone imine compound and its synthetic method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345836C (en) * | 2005-10-17 | 2007-10-31 | 湘潭大学 | Benzopyranone kind stabilizer and its application |
| CN100439350C (en) * | 2006-10-16 | 2008-12-03 | 湘潭大学 | Benzofuranone stabilizers and their applications |
| ES2701529T3 (en) * | 2014-08-05 | 2019-02-22 | Basf Se | 3-Phenyl-benzofuran-2-one diphosphite derivatives as stabilizers |
| CN109694362B (en) * | 2017-10-23 | 2023-05-09 | 江苏裕事达新材料科技有限责任公司 | 3-arylbenzofuranone propionamide compound, composition formed by same, preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586404A (en) * | 2018-06-12 | 2018-09-28 | 湖南大学 | A kind of synthetic method of N- aryl naphtho- furanone imine compound |
| CN108947948A (en) * | 2018-06-12 | 2018-12-07 | 湖南大学 | A kind of N- aryl naphtho- furanone imine compound and its synthetic method |
| CN108947948B (en) * | 2018-06-12 | 2021-07-20 | 湖南大学 | A kind of N-aryl naphthofuranone imine compound and its synthetic method |
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