CN100439350C - Benzofuranone-like stabilizer and its use - Google Patents
Benzofuranone-like stabilizer and its use Download PDFInfo
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- CN100439350C CN100439350C CNB2006100324078A CN200610032407A CN100439350C CN 100439350 C CN100439350 C CN 100439350C CN B2006100324078 A CNB2006100324078 A CN B2006100324078A CN 200610032407 A CN200610032407 A CN 200610032407A CN 100439350 C CN100439350 C CN 100439350C
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- tertiary butyl
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Abstract
The invention relates to a spacial blocking ester-containing benzofuran ketone stabilizer and the application thereof, and its general formula comprises R1, R6 and R7, C1-C10 alkyls; R2 and R5, C1-C10 alkyls; and R3 and R4, C1-C10 alkyls. When R1, R6 and R7 are all methyl groups, R3 and R4 are methyl groups, and R2 and R5 are tertbutyl groups, it is named pivalic acid 4-methyl-2-tertbutyl-6-(5-methyl-7- tertbutyl-2, 3-dihydro-2-oxo-3-benzofuranyl) phenyl ester. And the benzofuran ketone compound is used as a stabilizer for organic polymers and organic matters to resist degradation caused by heat, oxidization or photoinduction.
Description
Technical field
The invention relates to a kind of contain steric restriction ester group Benzopyranone kind stabilizer and application thereof.
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?232583(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
EP4158871991 same Patent: the US5175312 1992 that is correlated with
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: US6359148B1 US6346630B1 US5814692US5773631 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 also industrialization product occurs.
Chinese invention patent ublic specification of application CN1594301A has specifically reported the several 3-aryl-benzofuranones different with above-mentioned document with CN1785986A, and those several 3-substituted-phenyl-benzofuranones are especially suitable for use as heat, oxidation or photoinduction cause the degrading stablizer of organic polymer and organic substance;
The compound of the concrete report of CN1594301A:
5-methyl-7-the tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (the 3H)-benzofuranone acetate 4-methyl-2-tertiary butyl-6-(5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) the phenyl ester vinylformic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
The compound of the concrete report of CN1785986A:
The heptanaphthenic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
The present invention is the continuation research of CN1594301A and CN1785986A.
Summary of the invention
The purpose of this invention is to provide a kind of benzofuranones, be especially suitable for use as heat, oxidation or photoinduction cause the degrading stablizer of responsive organic polymer and organic substance, this compounds has better anti-oxidant function with respect to disclosed compound, and more stable, and has good thermostability; And plant corresponding succinct synthetic method of benzofuranones and related application therewith.
The invention provides its general structure for this reason and be and contain steric restriction ester group benzofuranones shown in the formula (1).
R in the formula (1)
1, R
6, R
7Be: C
1-C
10Alkyl; R
2, R
5Be: C
1-C
10Alkyl; R
3, R
4Be: C
1-C
10Alkyl.
The alkyl that will link to each other with ester carbonyl group is designed to the spatial obstacle that increases ester group that is intended that of steric restriction tertiary alkyl, in the hope of improving the stable effect and the stability of new compound, with the cycloalkyl structure that designs among the CN1785986A the different of essence is arranged.
Work as R
1, R
6, R
7All be: methyl;
R
3, R
4Be: methyl; R
2, R
5Be: the tertiary butyl; Structural formula as the formula (2),
Its called after: the trimethylacetic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester.
Benzofuranone use of a compound of the present invention is: cause the stablizer of degrading as organic polymer and organic substance opposing heat, oxidation or photoinduction.
The compounds of this invention can be shared with phenolic antioxidant, phosphorous acid ester and phosphinate oxidation inhibitor, as polyolefin stabilizers.
Disclosed 3-aryl-benzofuranone synthetic method is all quite loaded down with trivial details:
The need elder generation system aryl alcohol acid intermediate that has gets 3-aryl-benzofuranone parent through electrophilic substitution and while cyclic condensation, last chemically modified with corresponding alkylphenol reaction then; As US5367008, US5369159.
What have will make 3-hydroxyl-benzofuranone intermediate with corresponding alkylphenol earlier, gets 3-aryl-benzofuranone parent, US5516920 with corresponding aromatic compound after electrophilic substitution connects the 3-aryl then.
The synthetic method of 3-substituted-phenyl-benzofuranones that the present invention adopts is corresponding more succinct.
The synthetic method of compound shown in the general structure (1) is:
Compound shown in the general structure formula (S) and corresponding carboxylic acid halides or anhydride reaction are made.R in the formula (S)
2, R
5Be: C
1-C
10Alkyl; R
3, R
4Be: C
1-C
10Alkyl.
The mol ratio of compound and corresponding acid anhydrides or carboxylic acid halides is 0.90-1.10: 0.90-1.10 shown in general structure (S) formula
The synthetic method of compound shown in the general structure (S) is:
With 2,4-disubstituted benzenes phenol and oxoethanoic acid condensation and esterification cyclization make,
Condensation and esterification cyclization are finished in same reactor;
The mol ratio of fortified phenol and oxoethanoic acid is 1.80-2.20: 0.90-1.10;
Catalyzer is: alkylsulphonic acid, and aryl sulfonic acid contains sulfonic ion exchange resin, mineral acid,
Mineral acid is hydrochloric acid or sulfuric acid;
Temperature of reaction is between 30-150 ℃; Solvent is used in reaction;
Optional solvent: aliphatic carboxylic acid, halogenated alkane or aromatic hydrocarbons,
Acetate in the aliphatic carboxylic acid, propionic acid, formic acid,
In the halogenated alkane 1,2-ethylene dichloride, or the toluene of aromatic hydrocarbons, benzene, dimethylbenzene.
Benzofuranones 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.
Benzofuranones 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.
Shared with phenolic antioxidant, phosphorous acid ester and phosphinate, be suitable as very much polyolefin stabilizers.
This type of cumarone ketone compound is suitable as the photosensitive imaging emulsion stablizer of being made up of polymkeric substance and organism.
Compound disclosed in this invention is not seen relevant report both domestic and external, and because the alkyl that the ester carbonyl group of its 3-substituted-phenyl-part of compound provided by the present invention links to each other is designed to the steric restriction tertiary alkyl, the similarly existing bigger change of substituted-phenyl benzofuranone stabilization agent of agent structure in the past relatively.On structure, the compound that the present invention discloses has a great difference with compound in the past.
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-substituted-phenyl-part also has potential tradition hindered phenol antioxygen active structure unit, energy and combined with radical, thereby efficient is higher.
The continuous alkyl of 3-substituted-phenyl-part ester carbonyl group is designed to the steric restriction tertiary alkyl in addition, and because of the spatial obstacle protection, new compound is stable, Heat stability is good.Improve stabilization effect, and himself thermostability of Benzopyranone kind stabilizer, expanding its use temperature scope is a very important use key element.
Description of drawings
Fig. 1: the 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranone infrared spectra IR.
Fig. 2: the 5-methyl-7-tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranone proton nmr spectra H
1NMR.
Fig. 3: the trimethylacetic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester infrared spectra IR.
Fig. 4: the trimethylacetic 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 H
1NMR.
Embodiment
The invention will be further described for following embodiment, but the present invention is not limited to following examples.
The embodiment 15-methyl-7-tertiary butyl-3-(the 5-methyl-3-tertiary butyl-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-(the 5-methyl-3-tertiary butyl-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) v 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) (3-substituted-phenyl-5 ' methyl H of 3 ' tertiary butyl H),
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) (3-substituted-phenyl-6 ', 4 ' H),
6.962 (1H), 7.134 (1H) (benzofuran-2-ones parent: 4,6 H).
The embodiment 2 trimethylacetic 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 toluene, and 5.2 gram triethylamines under 50 ℃ of degree, drip 6.2 cut valeryl chlorides, add back insulation 2 hours; Toluene is removed in washing then, and purifying gets white powder crystalline solid product: the trimethylacetic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-cumarone ketone group) phenyl ester 14.7 grams, productive rate 65.3%, fusing point 152-154 ℃.
Ultimate analysis C
29H
38O
4Theoretical value C 77.30%, and H 8.50%
Measured value C 77.08%, H 8.26%
Infrared spectra IR (KBr compressing tablet) v cm
-1(referring to accompanying drawing 3)
1812.03cm
-1(benzofuranone carbonyl) 1747.99cm
-1(special pentyl ester carbonyl)
Proton nmr spectra
1H-NMR (CDCl
3) δ ppm (referring to accompanying drawing 4)
(9H) 1.370 (tertiary butyl H on the special pentyl ester base of 3-substituted-phenyl-2 ' position)
1.435 (9H), 2.192 (3H) (3-substituted-phenyl-5 ' methyl H of 3 ' tertiary butyl H),
1.435 (9H), 2.291 (3H) (5 methyl H of 7 tertiary butyl H of benzofuran-2-ones parent),
4.607 (1H) (the benzofuran-2-ones parent: 3 H),
(6.399 1H broad peak), 7.070 (1H) (3-substituted-phenyl-6 ', 4 ' H),
(6.954 1H broad peak), 7.154 (1H) (benzofuran-2-ones parent: 4,6 H).
Proton nmr spectra:
The benzofuran-2-ones parent: 4,6 H,
The 3-substituted-phenyl-6 ', 4 ' H particular location, referring to formula (S1)
X=H, acyl group
Infrared spectrometer IR Perkin-Elmer Spectrum One
Nuclear magnetic resonance analyser NMR Bruker-400
Three extruding pelletization stability of embodiment 3 polypropylene application experiment A
0.5 kilogram polypropylene powder
(the long petrochemical industry polypropylene powder Q/SHCL 2-2002 of company limited that contains in China Petrochemical Corporation Hunan)
(230 ℃, 2.16 kilograms of melting index measured values 5.4),
Do not add stablizer of the present invention,
Or only add 0.03% embodiment of the invention, 2 products,
Or only add 0.03%CN1785986 embodiment 2 products: the heptanaphthenic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
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
Three extruding pelletization stability of embodiment 4 polypropylene application experiment B
0.5 kilogram polypropylene powder
(the long petrochemical industry polypropylene powder Q/SHCL 2-2002 of company limited that contains in China Petrochemical Corporation Hunan)
(230 ℃, 2.16 kilograms of melting index measured values 5.4),
Add 0.05% antioxidant 1010 earlier:
Four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester
With 0.02% oxidation inhibitor 168: tricresyl phosphite (2, the 4-di-tert-butyl) ester
Add 0.01% embodiment of the invention, 2 product used as stabilizers again,
Or add 0.01%CN1785986 embodiment 2 products 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 1010 and 0.02% oxidation inhibitor 168)
A:5-methyl-7-the tertiary butyl-3-(5-methyl-3 tertiary butyls-2-hydroxy phenyl)-2 (3H)-benzofuranones
B: the vinylformic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
C: the acetate 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
D: the heptanaphthenic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
E: the trimethylacetic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
A, B, C, D, the experiment of five compounds self of E heat-resistant stability
Compound sample is sandwiched between two thin glass sheets of surveying fusing points, is placed in the heating cabinet of micro-fusing point instrument (the X-4 numeral shows micro-fusing point instrument, Tyke, Beijing Instr Ltd.),
Slowly evenly heat up from room temperature to 305 ℃, the observation sample fusing, and the complete colourless top temperature after the fusing, observe initial discoloring temperature, initial variable color degree and rise to 300 ℃ of variable color degree.
Initial discoloring temperature is healed high compound self heat-resistant stability better, the results are shown in Table 3:
Table 3A, B, C, D, the experiment of five compounds self of E heat-resistant stability
Five extruding pelletization stability of embodiment 6 polypropylene application experiment,
Experimental technique is identical with embodiment 1 with material
Only add 0.03% embodiment of the invention, 2 products: the trimethylacetic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester (compd E)
Or only add 0.03%CN1785986 embodiment 2 products: the heptanaphthenic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3 dihydro-2-oxo-s-3-benzofuryl) phenyl ester (Compound D)
With twin screw extruder at 260 ℃ of five extruding pelletizations,
Survey melting index (230 ℃, 2.16 kilograms) then.
Five extruding pelletization stability experiments of table 4 polypropylene powder
It is more stable that the result shows that the product compound E of the present invention that 3-substituted-phenyl-part links to each other with ester carbonyl group alkyl is designed to the steric restriction tertiary alkyl is in a ratio of open-chain hydrocarbons based compound B, C, and thermostability also better; With CN1785986 embodiment 2 products be that Compound D is suitable; There is not the compd A stability of esterification the poorest.
Five extruding pelletization stability of polypropylene application experiment shows the product trimethylacetic acid 4-methyl of the present invention-2-tertiary butyl-6-(5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) to stablize effect than the CN1785986 embodiment 2 product heptanaphthenic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester good for phenyl ester.
Claims (4)
1, a kind of Benzopyranone kind stabilizer, its general structure are characterized as shown in the formula (1), R in the formula (1)
1, R
6, R
7Be: C
1-C
10Alkyl; R
2, R
5Be: C
1-C
10Alkyl; R
3, R
4Be: C
1-C
10Alkyl
2, R is worked as in benzofuranone stabilization agent according to claim 1
1, R
6, R
7All be: methyl; R
3, R
4Be: methyl; R
2, R
5Be: the tertiary butyl; Structural formula is shown in the formula (2), its called after: the trimethylacetic acid 4-methyl-2-tertiary butyl-6-(the 5-methyl-7-tertiary butyl-2,3-dihydro-2-oxo--3-benzofuryl) phenyl ester
3, the purposes of claim 1 or 2 described benzofuranone stabilization agent causes the stablizer of degrading as organic polymer resist heat, oxidation or photoinduction.
4, the purposes of claim 1 or 2 described benzofuranone stabilization agent, shared with phenolic antioxidant, phosphorous acid ester and phosphinate oxidation inhibitor, as polyolefin stabilizers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100324078A CN100439350C (en) | 2006-10-16 | 2006-10-16 | Benzofuranone-like stabilizer and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100324078A CN100439350C (en) | 2006-10-16 | 2006-10-16 | Benzofuranone-like stabilizer and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1935801A CN1935801A (en) | 2007-03-28 |
| CN100439350C true CN100439350C (en) | 2008-12-03 |
Family
ID=37953567
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|---|---|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6559224B2 (en) * | 2014-08-05 | 2019-08-14 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 3-Phenyl-benzofuran-2-one diphosphite derivatives as stabilizers |
| TWI669298B (en) * | 2017-08-29 | 2019-08-21 | 和新化學工業股份有限公司 | Antioxidant agent and plastic article having the same |
| EP3710145A4 (en) * | 2017-11-14 | 2021-09-15 | Basf Se | Polycarbonate compositions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000122243A (en) * | 1998-10-06 | 2000-04-28 | Agfa Gevaert Ag | Color photographic silver halide material |
| US6284447B1 (en) * | 1999-04-14 | 2001-09-04 | Agfa-Gevaert | Color photographic silver halide material |
| CN1594301A (en) * | 2004-07-14 | 2005-03-16 | 湘潭大学 | 3-substituted phenyl-benzo furanone stabilizer and preparing process thereof |
| CN1785986A (en) * | 2005-10-17 | 2006-06-14 | 湘潭大学 | Benzopyranone kind stabilizer and its application |
-
2006
- 2006-10-16 CN CNB2006100324078A patent/CN100439350C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000122243A (en) * | 1998-10-06 | 2000-04-28 | Agfa Gevaert Ag | Color photographic silver halide material |
| US6284447B1 (en) * | 1999-04-14 | 2001-09-04 | Agfa-Gevaert | Color photographic silver halide material |
| CN1594301A (en) * | 2004-07-14 | 2005-03-16 | 湘潭大学 | 3-substituted phenyl-benzo furanone stabilizer and preparing process thereof |
| CN1785986A (en) * | 2005-10-17 | 2006-06-14 | 湘潭大学 | Benzopyranone kind stabilizer and its application |
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| Publication number | Publication date |
|---|---|
| CN1935801A (en) | 2007-03-28 |
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