CN100556986C - A kind of preparation method of tris (nonyl) phosphate anti-oxidant - Google Patents
A kind of preparation method of tris (nonyl) phosphate anti-oxidant Download PDFInfo
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- CN100556986C CN100556986C CN 200710056079 CN200710056079A CN100556986C CN 100556986 C CN100556986 C CN 100556986C CN 200710056079 CN200710056079 CN 200710056079 CN 200710056079 A CN200710056079 A CN 200710056079A CN 100556986 C CN100556986 C CN 100556986C
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- phosphite
- nonyl
- triethyl
- nonyl phenol
- oxidant
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Abstract
The present invention relates to a kind of preparation method of tris (nonyl) phosphate anti-oxidant.Constitute by nonyl phenol and triethyl-phosphite; The mole proportioning of nonyl phenol and triethyl-phosphite is: 3.1: 1.0～3.5: 1.0.With nonyl phenol and triethyl-phosphite is raw material, and rare gas element is protection gas, carries out the synthetic tris (nonyl) phosphate anti-oxidant of solvent-free transesterification reaction under catalyst action, and the by product ethanol in the reaction process can be recycled.Technology of the present invention is simple, and reaction process is easy to control, the reaction conditions gentleness, and the basic non-environmental-pollution of process, institute's synthetic product trinonylphengl phosphite is important oxidation inhibitor and stablizers such as rubber, natural rubber, polyolefin plastics and latex.
Description
Technical field:
The invention belongs to fine chemistry industry and technical field of polymer materials, particularly relate to a kind of preparation method of tris (nonyl) phosphate anti-oxidant.
Background technology:
Oxidation inhibitor is a kind of automatic oxidation reaction speed that can slow down plastics, rubber and other macromolecular materials, guarantees that it does not influence the auxiliary agent in its work-ing life in moulding, storage process.Trinonylphengl phosphite (trinonylphengl phosphite) oxidation inhibitor because have heat-resisting, resistance to oxidation, good characteristic such as pollution-free forms and is important auxiliary antioxidant, its consumption is a kind of of maximum in the phosphite ester kind antioxidant, has been widely used in plastics industry, the rubber industry.All be with nonyl phenol and PCl about the synthetic of trinonylphengl phosphite at present
3Be raw material, have the operational path of two quasi-representatives: the one, in solvent-free system, carry out, provide a kind of as U.S. Pat 5532401 with nonyl phenol and PCl
3For raw material directly prepares the method for trinonylphengl phosphite under condition of no solvent, this method need adopt thin film distillation to remove byproduct of reaction HCl, and these class methods have the thin film distillation troublesome poeration, the deficiency that facility investment is big; As Japanese Patent JP07039884 also is to react in solvent-free system, but catalyzer finally is difficult to remove in this method; The 2nd, in organic solvent system, carry out, Chinese patent CN1427064A also adopts nonyl phenol and PCl
3Be raw material, carry out the method that esterification prepares trinonylphengl phosphite in organic solvent, the temperature of reaction of this method and vacuum tightness will be divided three sections controls, and is not easy to operate, and organic solvent needs to steam entire reaction course energy consumption height with high temperature; There is raw material PCl in these technologies at present
3Belong to highly toxic substance and facile hydrolysis, or organic solvent aftertreatment difficulty or defective such as not easy to operate.
Technology contents:
For solving the problem that exists in the present antioxidant trinonylphengl phosphite production, it is raw material that the present invention has succeeded in developing with nontoxic triethyl-phosphite and nonyl phenol, carry out transesterify and produce the novel method of trinonylphengl phosphite under the organic solvent-free condition, its step and condition are:
Provided by the inventionly a kind ofly constitute by nonyl phenol and triethyl-phosphite about tris (nonyl) phosphate anti-oxidant; The mole proportioning of nonyl phenol and triethyl-phosphite is: 3.1: 1.0～3.5: 1.0.
A kind of preparation method provided by the invention about tris (nonyl) phosphate anti-oxidant, step and condition are as follows:
To be equipped with back heat up in a steamer prolong, nitrogen conduit, thermometer, dropping funnel the four-hole container in, the mole proportioning of pressing raw material nonyl phenol and triethyl-phosphite adds nonyl phenol, adopts N
2Or CO
2Rare gas element is protected, N
2Or CO
2Flow velocity be 10-50mL/min, under agitation press 0.5～1.8% of raw material gross weight and add catalyzer, be warmed up to 100～110 ℃, drip triethyl-phosphite gradually by the mole proportioning, in 0.5～1h, drip off, be warmed up to 110～130 ℃ then and react, under this temperature, react 2.5～3.0h, excessive nonyl phenol is removed in last underpressure distillation, obtains a kind of tris (nonyl) phosphate anti-oxidant;
The catalyzer of described usefulness is: anhydrous K
2CO
3, Na
2CO
3, CH
3ONa, (CH
3)
3CONa, Dibutyltin oxide, porcine pancreatic lipase (porcine pancreatic lipase model L3126, Type II, Sigma company), KNO
3/ γ-Al
2O
3, MgO-NaOH, phospho-wolframic acid, silicotungstic acid.
Used catalyzer is preferably preferred Anhydrous potassium carbonate or Dibutyltin oxide.
If used catalyzer is porcine pancreatic lipase (porcine pancreatic lipase, model L3126, Type II, a Sigma company), reaction conditions is: the Na that adds 1.5mL pH=7.8
2HPO
4～NaH
2PO
4Damping fluid, catalyst levels are 0.9% of raw material gross weight, and temperature of reaction is 45 ℃, and the reaction times is 8.0～12.0h; All the other conditions are the same.
This operational path does not use deleterious raw material, and raw material is easy to get, and reaction process is to carry out in solvent-free system, avoids the generation of " three wastes ", and is simple to operate, and a greenization technology route can be provided for the production of tris (nonyl) phosphate anti-oxidant.
Embodiment
Embodiment 1:
In the four-hole boiling flask that the 500mL that heats up in a steamer prolong, nitrogen conduit, thermometer, dropping funnel is housed back, add the 211.2g nonyl phenol, use N
2After the replacement(metathesis)reaction system, under agitation add the 3.9g anhydrous K
2CO
3Catalyzer is warmed up to 105 ℃, drips the 49.8g triethyl-phosphite gradually, dropwises in the 0.5h, is warmed up to 120 ℃, keeps this thermotonus 2.5h, and excessive nonyl phenol is removed in last underpressure distillation, obtains trinonylphengl phosphite product 193.5g.
Trinonylphengl phosphite product physical parameter is: light yellow transparent liquid, relative density are 0.9920 (25 ℃), and acid number is 0.02mgKOH/g, refractive index n
D 25Be 1.5264, phosphorus content 4.35%, yield are 93.6%.
Embodiment 2:
Add 217.8 nonyl phenols in the four-hole boiling flask of in embodiment 1, describing, use CO
2After the replacement(metathesis)reaction system, under agitation add 4.7gCH
3The ONa catalyzer is warmed up to 110 ℃, drips the 49.8g triethyl-phosphite gradually, dropwises in the 1.0h, is warmed up to 130 ℃, keeps this thermotonus 2.5h, and excessive nonyl phenol is removed in last underpressure distillation, obtains trinonylphengl phosphite product 173.8g.
Trinonylphengl phosphite product physical parameter is: light yellow transparent liquid, relative density are 0.9890 (25 ℃), and acid number is 0.05mgKOH/g, refractive index n
D 25Be 1.5258, phosphorus content 4.13%, yield are 84.1%.
Embodiment 3:
In the four-hole boiling flask described in the embodiment 1, add the 211.2g nonyl phenol, use N
2After the replacement(metathesis)reaction system, under agitation add 3.2g Dibutyltin oxide catalyzer, be warmed up to 105 ℃, drip the 49.8g triethyl-phosphite gradually, 0.5h in dropwise, be warmed up to 130 ℃, keep this thermotonus 2.5h, excessive nonyl phenol is removed in last underpressure distillation, obtains trinonylphengl phosphite product 186.4g.
Trinonylphengl phosphite product physical parameter is: light yellow transparent liquid, relative density are 0.9913 (25 ℃), and acid number is 0.02mgKOH/g, refractive index n
D 25Be 1.5275, phosphorus content 4.29%, yield are 90.2%.
Embodiment 4:
In the four-hole boiling flask described in the embodiment 1, add the 224.4g nonyl phenol, use N
2After the replacement(metathesis)reaction system, under agitation add 4.4g KNO
3/ γ-Al
2O
3, be warmed up to 100 ℃, drip the 49.8g triethyl-phosphite gradually, dropwise in the 0.5h, be warmed up to 120 ℃, keep this thermotonus 2.5h, excessive nonyl phenol is removed in last underpressure distillation, obtains trinonylphengl phosphite product 166.8g.
Trinonylphengl phosphite product physical parameter is: light yellow transparent liquid, relative density are 0.9875 (25 ℃), and acid number is 0.03mgKOH/g, refractive index n
D 25Be 1.5269, phosphorus content 4.20%, yield are 80.7%.
Embodiment 5:
In the four-hole boiling flask described in the embodiment 1, add the 231.0g nonyl phenol, use N
2After the replacement(metathesis)reaction system, under agitation add the 4.0g phospho-wolframic acid, be warmed up to 105 ℃, drip the 49.8g triethyl-phosphite gradually, 0.5h in dropwise, be warmed up to 120 ℃, keep this thermotonus 2.5h, excessive nonyl phenol is removed in last underpressure distillation, obtains trinonylphengl phosphite product 162.7g.
Trinonylphengl phosphite product physical parameter is: light yellow transparent liquid, relative density are 0.9810 (25 ℃), and acid number is 0.05mgKOH/g, refractive index n
D 25Be 1.5255, phosphorus content 4.13%, yield are 78.7%.
Embodiment 6:
In the four-hole boiling flask of the same terms described in the embodiment 1, add the 231.0g nonyl phenol, use N
2After the replacement(metathesis)reaction system, under agitation add 2.4g porcine pancreatic lipase (PPL, model L3126, Type II, Sigma company), add the Na of 1.5mL pH=7.8
2HPO
4～NaH
2PO
4Damping fluid is warming up to 45 ℃, drips the 49.8g triethyl-phosphite then gradually, dropwises in the 1h, and constant temperature reacts 11h down for 45 ℃, and excessive nonyl phenol is removed in last underpressure distillation, obtains trinonylphengl phosphite product 145.5g.
Trinonylphengl phosphite product physical parameter is: light yellow transparent liquid, relative density are 0.9887 (25 ℃), and acid number is 0.04mgKOH/g, refractive index n
D 25Be 1.5259, phosphorus content 4.10%, yield are 70.4%.
Claims (2)
1, a kind of preparation method of tris (nonyl) phosphate anti-oxidant is characterized in that, its step and condition are:
Described oxidation inhibitor is made of nonyl phenol and triethyl-phosphite; The mole proportioning of nonyl phenol and triethyl-phosphite is: 3.1: 1.0～3.5: 1.0;
To be equipped with back heat up in a steamer prolong, nitrogen conduit, thermometer, dropping funnel the four-hole container in, the mole proportioning of pressing raw material nonyl phenol and triethyl-phosphite adds nonyl phenol, adopts N
2Or CO
2Rare gas element is protected, N
2Or CO
2Flow velocity be 10-50mL/min, under agitation press 0.5～1.8% of raw material gross weight and add catalyzer, be warmed up to 100～110 ℃, drip triethyl-phosphite gradually by proportioning, in 0.5～1h, drip off, be warmed up to 110～130 ℃ then and react, keep this thermotonus 2.5～3.0h, excessive nonyl phenol is removed in last underpressure distillation, obtains a kind of tris (nonyl) phosphate anti-oxidant;
Described catalyzer is: anhydrous K
2CO
3, Na
2CO
3, CH
3ONa, (CH
3)
3CONa, Dibutyltin oxide, KNO
3/ γ-Al
2O
3, MgO-NaOH or phospho-wolframic acid or silicotungstic acid.
2, the preparation method of a kind of tris (nonyl) phosphate anti-oxidant as claimed in claim 1 is characterized in that, described catalyzer is Anhydrous potassium carbonate or Dibutyltin oxide.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294758A (en) * | 2015-11-24 | 2016-02-03 | 淄博亿丰中铁高分子材料有限公司 | Phosphite antioxidant and preparation method thereof |
| CN106279266A (en) * | 2016-07-14 | 2017-01-04 | 山东省临沂市三丰化工有限公司 | A kind of preparation method of liquid phosphite kind antioxidant |
| GB2562466B (en) * | 2017-05-04 | 2022-01-05 | Si Group Switzerland Chaa Gmbh | Composition |
| CN108398497B (en) * | 2018-02-11 | 2021-07-02 | 上海市食品药品包装材料测试所 | High performance liquid chromatography detection method of tris (nonylphenol) phosphite ester |
| CN108707164A (en) * | 2018-07-05 | 2018-10-26 | 营口风光新材料股份有限公司 | A kind of synthetic method of phosphite ester kind antioxidant 38 |
| CN113444527A (en) * | 2021-06-29 | 2021-09-28 | 江苏品和石油科技有限公司 | Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1058845A (en) * | 1963-04-24 | 1967-02-15 | Gen Aniline & Film Corp | Process for producing phosphate esters |
| CN1427064A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气集团公司 | Preparation method of antioxidant trinonylphengl phosphite |
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2007
- 2007-09-18 CN CN 200710056079 patent/CN100556986C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1058845A (en) * | 1963-04-24 | 1967-02-15 | Gen Aniline & Film Corp | Process for producing phosphate esters |
| CN1427064A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气集团公司 | Preparation method of antioxidant trinonylphengl phosphite |
Non-Patent Citations (3)
| Title |
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| 亚磷酸酯抗氧剂TNP的合成及评价. 刘文艳，金玉顺.弹性体，第11卷第5期. 2001 * |
| 亚磷酸酯类抗氧剂的开发及应用. 丁慧萍，邢翠萍.云南化工，第31卷第1期. 2004 * |
| 抗氧剂三（壬苯基）亚磷酸酯生产工艺改进. 郑维彬.贵州化工，第27卷第4期. 2002 * |
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