CN1907990A - Preparation method of 3,9-di[4-(1-methyl-1-benzoethyl)phenoxy]-2,4,8,10-tetraoxy-3,9-diphosphorspiro[5,5]hendecane - Google Patents
Preparation method of 3,9-di[4-(1-methyl-1-benzoethyl)phenoxy]-2,4,8,10-tetraoxy-3,9-diphosphorspiro[5,5]hendecane Download PDFInfo
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- CN1907990A CN1907990A CN 200610030205 CN200610030205A CN1907990A CN 1907990 A CN1907990 A CN 1907990A CN 200610030205 CN200610030205 CN 200610030205 CN 200610030205 A CN200610030205 A CN 200610030205A CN 1907990 A CN1907990 A CN 1907990A
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Abstract
The invention discloses a preparing method of 3, 9-double [4-(1- methyl-1- phenethyl) phenoxy]-2, 4, 8, 10-complex tetroxide-3, 9-diphosphoric spiral [5.5] undecane, which comprises the following steps: adopting pentaerythrite as raw material to react with triethyl phosphite acted by catalyst; obtaining intermediate pentaerythrite ethyl diphosphite to react with 4-(alpha, alpha-dimethyl benzyl) phenol; producing the product with over 97% purity and 90-93% productivity at 124.4-125.2 deg.c.
Description
Technical field
The present invention relates to organic changing into, more specifically refer to a kind of antioxidant 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2,4,8 of 9-, 10-four oxa-s-3, the undecanoic preparation method of 9-two phosphorus spiral shells [5.5].
Background technology
3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2,4,8 of 9-, 10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes are a kind of important auxiliary agents, especially can be as antioxidant in the macromolecular material preparation.Its structural formula is as follows:
In the prior art, " Chem.Papers " 43 (3), 421-432,1989 disclosed preparation methods are with 3,9-two chloro-2,4,8,10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes are raw material, with the dry-out benzene is that solvent, calcium chloride are that absorption agent, triethylamine are acid binding agent, reacts with 4-(α, α-Er Jiajibianji) phenol, obtain 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2,4 of 9-, 8,10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes.
The method of this report, with highly toxic benzene as solvent, operate dangerous, the hydrogen chloride gas that produces in the building-up process, difficult quilt absorbs fully, environment is polluted, and hydrogenchloride has severe corrosive to equipment, equipment loss is big, industrial prospect is undesirable.
Summary of the invention
The technical problem that the present invention solves provides a kind of 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2 of 9-, 4,8,10-four oxa-s-3, the undecanoic preparation method of 9-two phosphorus spiral shells [5.5], make solvent to overcome the highly toxic benzene of available technology adopting, operate dangerously, hydrogen chloride gas is to the pollution of environment, to the deficiency of equipment deep-etching.
Technical conceive of the present invention: with the tetramethylolmethane is raw material, with the triethyl-phosphite reaction, obtains intermediate tetramethylolmethane diphosphite ethyl ester under catalyst action, with 4-(α, α-Er Jiajibianji) phenol reactant, promptly obtains target product of the present invention then.
Reaction formula of the present invention is as follows:
Method of the present invention comprises the steps:
(1) with tetramethylolmethane, catalyzer and triethyl-phosphite, under 130～140 ℃ condition, reacted 1～2 hour, steam in the reaction and remove the by product ethanol that generates, after the reaction, steam and remove triethyl-phosphite excessive in the reaction product and remaining ethanol, obtain intermediate tetramethylolmethane diphosphite ethyl ester.
According to the present invention, said catalyzer is a Dibutyltin oxide, and the mass ratio of tetramethylolmethane and catalyzer is 10: 0.5～1.0, and the mol ratio of tetramethylolmethane and triethyl-phosphite is 1: 2～2.2.
(2) in the intermediate tetramethylolmethane diphosphite ethyl ester that step (1) is collected, add 4-(α, α-Er Jiajibianji) phenol, reacted under 50～60 ℃ the condition 3～4 hours, steam in the reaction and remove the by product ethanol that generates, after the reaction, steam and remove remaining ethanol in the reaction product, cooling, the white solid of separating out is target product of the present invention.
According to the present invention, the mol ratio of reactant tetramethylolmethane and 4-(α, α-Er Jiajibianji) phenol is 1: 2～2.1.
Raw material 4-used in the present invention (α, α-Er Jiajibianji) phenol can be according to " Liaoming Petrochemical Univ's journal " 24 (4), 22-24, and 2004 reported method prepare.
With preparation method of the present invention obtain 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2,4 of 9-, 8,10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes, purity reaches more than 97%, productive rate is 90%-93%, fusing point is 124.4～125.2 ℃, consistent (document " Chem.Papers " 43 (3), 421-432 with bibliographical information, 1989 reported values: 124～126 ℃), identify the structure O (CH of product with nucleus magnetic resonance
2) C:3.33-4.61, C
6H
5C
6H
4: 6.90-7.25 (m, 18H), (CH
3)
2C:1.67 (s, 12H).
Beneficial effect:
The present invention has avoided highly toxic organic solvent, operational safety compared with prior art, avoided the pollution of hydrogen chloride gas to environment, the direction that meets the green chemical industry development, the by product ethanol that generates in the reaction process is recyclable to be utilized again, is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
In the reactor that has heating, stirring, thermometer, reflux condensing tube, add 13.62g (0.10mol) tetramethylolmethane, 34.89g (0.21mol) triethyl-phosphite, 0.82g (0.003mol) Dibutyltin oxide respectively, stirring at room, heating gradually, temperature of reaction is controlled at 130～140 ℃, reacted 2 hours, steam the by product ethanol (recycling) that generates in the reaction process in the reaction simultaneously, after reaction finishes, steam and remove triethyl-phosphite excessive in the reaction solution and remaining ethanol, obtain intermediate tetramethylolmethane diphosphite ethyl ester.
Having heating, stir, thermometer, the intermediate tetramethylolmethane diphosphite ethyl ester that adds above-mentioned gained in the reactor of reflux condensing tube, 42.46g (0.20mol) 4-(α, α-Er Jiajibianji) phenol, heating when stirring, temperature of reaction is controlled at 50～60 ℃, reacts 4 hours, steam simultaneously in the reaction and remove the by product ethanol (recycling) that generates in the reaction process, after reaction finishes, steam and remove remaining ethanol in the reaction solution, cooling, separate out white solid, filter, drying obtains 57.10g 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2 of 9-, 4,8,10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes, productive rate 92.6%, purity are 98.8%, and fusing point is 124.6～125.0 ℃.
Embodiment 2
In the reactor that has heating, stirring, thermometer, reflux condensing tube, add 27.23g (0.20mol) tetramethylolmethane, 68.13g (0.41mol) triethyl-phosphite, 1.36g (0.005mol) Dibutyltin oxide respectively, stirring at room, heating gradually, temperature of reaction is controlled at 130～140 ℃, reacted 1 hour, steam the by product ethanol (recycling) that generates in the reaction process in the reaction simultaneously, after reaction finishes, steam and remove triethyl-phosphite excessive in the reaction solution and remaining ethanol, obtain intermediate tetramethylolmethane diphosphite ethyl ester.
Having heating, stir, thermometer, the intermediate tetramethylolmethane diphosphite ethyl ester that adds above-mentioned gained in the reactor of reflux condensing tube, 87.04g (0.41mol) 4-(α, α-Er Jiajibianji) phenol, heating when stirring, temperature of reaction is controlled at 50～60 ℃, reacts 3 hours, steam simultaneously in the reaction and remove the by product ethanol (recycling) that generates in the reaction process, after reaction finishes, steam and remove remaining ethanol in the reaction solution, cooling, separate out white solid, filter, drying obtains 111.23g3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2 of 9-, 4,8,10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes, productive rate 90.2%, purity are 97.6%, and fusing point is 124.4～125.2 ℃.
Claims (6)
1. one kind 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2,4,8 of 9-, 10-four oxa-s-3, the undecanoic preparation method of 9-two phosphorus spiral shells [5.5] comprises the steps:
(1) with tetramethylolmethane, catalyzer and triethyl-phosphite, under 130～140 ℃ condition, reacted 1～2 hour, from reaction product, collect intermediate tetramethylolmethane diphosphite ethyl ester;
(2) in the intermediate tetramethylolmethane diphosphite ethyl ester that step (1) is collected, add 4-(α, α-Er Jiajibianji) phenol, reacted under 50～60 ℃ the condition 3～4 hours, and from reaction product, collected target product 3, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2 of 9-, 4,8,10-four oxa-s-3,9-two phosphorus spiral shell [5.5] undecanes.
2. method according to claim 1 is characterized in that, said catalyzer is a Dibutyltin oxide.
3. method according to claim 1, the mass ratio that it is characterized in that tetramethylolmethane and catalyzer is 10: 0.5～1.0.
4. method according to claim 1, the mol ratio that it is characterized in that tetramethylolmethane and triethyl-phosphite is 1: 2～2.2.
5. method according to claim 1 is characterized in that the mol ratio of tetramethylolmethane and 4-(α, α-Er Jiajibianji) phenol is 1: 2～2.1.
6. according to each described method of claim 1～5, it is characterized in that,
(1) step (1) is collected the by product ethanol that intermediate tetramethylolmethane diphosphite ethyl ester steam to remove generates in comprising the steps: to react from reaction product, after the reaction, steam and remove triethyl-phosphite excessive in the reaction product and remaining ethanol, obtain intermediate tetramethylolmethane diphosphite ethyl ester;
(2) step (2) is collected target product 3 from reaction product, two [4-(1-methyl isophthalic acid-styroyl) phenoxy groups]-2 of 9-, 4,8,10-four oxa-s-3 steam during 9-two phosphorus spiral shell [5.5] undecanes comprise the steps: to react and remove the by product ethanol that generates, after the reaction, steam and remove remaining ethanol in the reaction product, cooling, the white solid of separating out is target product of the present invention.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610030205XA CN1907990B (en) | 2006-08-18 | 2006-08-18 | Preparation method of 3,9-di[4-(1-methyl-1-benzoethyl)phenoxy]-2,4,8,10-tetraoxy-3,9-diphosphorspiro[5,5]hendecane |
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| CN200610030205XA CN1907990B (en) | 2006-08-18 | 2006-08-18 | Preparation method of 3,9-di[4-(1-methyl-1-benzoethyl)phenoxy]-2,4,8,10-tetraoxy-3,9-diphosphorspiro[5,5]hendecane |
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| CN1907990A true CN1907990A (en) | 2007-02-07 |
| CN1907990B CN1907990B (en) | 2011-07-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107268043A (en) * | 2017-07-04 | 2017-10-20 | 电子科技大学 | A kind of inhibitor and electrolytic copper plating bath that filling perforation is electroplated for copper-connection HDI |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4290976A (en) * | 1975-03-24 | 1981-09-22 | Borg-Warner Chemicals, Inc. | Process for the preparation of phenol-free phosphites |
| JPH0686453B2 (en) * | 1985-06-13 | 1994-11-02 | 住友化学工業株式会社 | Process for producing hydroxyphenyl propionate |
| CN1044371C (en) * | 1994-11-23 | 1999-07-28 | 深圳泛胜塑胶助剂有限公司 | Preparation method for phosphite ester stabilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107268043A (en) * | 2017-07-04 | 2017-10-20 | 电子科技大学 | A kind of inhibitor and electrolytic copper plating bath that filling perforation is electroplated for copper-connection HDI |
| CN107268043B (en) * | 2017-07-04 | 2019-11-05 | 电子科技大学 | A kind of inhibitor and electrolytic copper plating bath for copper-connection HDI plating filling perforation |
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