CN102702267A - Method for preparing novel high-efficiency phosphite antioxidant - Google Patents
Method for preparing novel high-efficiency phosphite antioxidant Download PDFInfo
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- CN102702267A CN102702267A CN2012101983167A CN201210198316A CN102702267A CN 102702267 A CN102702267 A CN 102702267A CN 2012101983167 A CN2012101983167 A CN 2012101983167A CN 201210198316 A CN201210198316 A CN 201210198316A CN 102702267 A CN102702267 A CN 102702267A
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Abstract
The invention relates to a method for preparing a novel high-efficiency phosphite antioxidant. The method comprises the following step of: performing ester exchange on phosphite triester, pentaerythritol and fatty alcohol serving as raw materials in the presence of a catalyst to obtain fatty-alcohol-based pentaerythritol diphosphite with high phosphorus content. A one-pot method is adopted, a solvent is not added, the process is simple and environment-friendly, three wastes (waste gas, waste water and waste residues) are avoided, the using amount of the catalyst is small, yield is high, and the obtained product is high in phosphorus content, high-temperature oxidation resistance and color protection capability.
Description
Technical field
The present invention relates to a kind of phosphite ester kind antioxidant, in particular, the present invention relates to a kind ofly transesterification reaction take place in the presence of catalyzer, prepare a kind of new and effective phosphite antioxidant through tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18).
Background technology
The pentaerythritol diphosphites kind antioxidant is a kind of high-efficiency anti-oxidant of excellent performance; Owing to have the skeleton of spirane structure and high phosphorus content; Therefore can not only improve the processing stability of polymkeric substance; Also having good color stability, heat-resistant stability and resistance to hydrolysis, is one type of oxidation inhibitor with good application prospect.
At present, the method for synthetic this kind antioxidant mainly contains two kinds, and a kind of is ester-interchange method.Disclosing with triphenyl phosphite, tetramethylolmethane, decyl alcohol like U.S. Pat 3205250 is raw material; Sodium Metal 99.5 is a catalyzer; Synthesize didecyl alkyl pentaerythritol diphosphites through two step transesterifys, also disclose the synthetic of two dodecyl pentaerythritol diphosphites and two octadecyl pentaerythritol diphosphites simultaneously.Disclosing with triphenyl phosphite, tetramethylolmethane, stearyl alcohol like U.S. Pat 4064100 is raw material, and sodium methylate obtains two octadecyl pentaerythritol diphosphites as catalyzer through transesterify.Disclosing with triethyl-phosphite, tetramethylolmethane, hexadecanol like Chinese patent 200510037047.6 is raw material, and sodium methylate or sodium hydroxide are catalyzer, have prepared Dicetylpentaerythritesterhosphite esterhosphite.Another kind is the phosphorus trichloride method.Like U.S. Pat 6773624, US5917076.
The phosphorus trichloride method will be used solvent, and aftertreatment is loaded down with trivial details, the products obtained therefrom poor stability; And simple with tris phosphite ester-interchange method technology, need not with an organic solvent, yield is high, the products obtained therefrom good stability.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art
,It is raw material with tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) that the present invention provides a kind of, in the presence of catalyzer, obtains a series of efficient phosphite antioxidants through ester-interchange method.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of new and effective phosphite antioxidant; With tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) is raw material, and mol ratio is: 2.0:1.0:2.0, and its process step is: in the there-necked flask that TM, stirring are housed, add a certain amount of tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) and catalyzer; Stirring is warming up to 65～160 ℃; Regulating vacuum tightness is 10～760 mmhg, and to the absence of liq outflow, reaction finishes; Collect by-product, obtain having phosphite antioxidant suc as formula the I structure;
Ⅰ
In the formula, R is C
9～C
18Fatty Alcohol(C12-C14 and C12-C18) is like butanols, octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol and stearyl alcohol etc.
Tris phosphite can use trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite to replace.
Said catalyzer can be selected mineral alkali such as Pottasium Hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash etc. for use; Organic bases such as sodium methylate, aluminum isopropylate, amine etc.; Ester class such as tetrabutyl titanate etc.; Organic tin such as dibutyl tin laurate, Dibutyltin oxide etc. also can be two or more mixtures of above-mentioned catalyzer.
Said catalyzer is selected the mixed catalyst of salt of wormwood and Dibutyltin oxide for use.
The weight ratio of salt of wormwood and Dibutyltin oxide is 2:1 in the said mixed catalyst.
Said catalyst levels is 0.1%～0.5% of a tris phosphite weight.
The invention has the beneficial effects as follows: adopt " one kettle way ", solubilizing agent not, the simple environmental protection of technology does not have " three wastes ", and catalyst levels is little and yield is high, and the products obtained therefrom phosphorus content is high, has fabulous high-temperature oxidation resistant and color and luster protective capability.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
A kind of preparation method of new and effective phosphite antioxidant; With tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) is raw material, and mol ratio is: 2.0:1.0:2.0, and its process step is: in the there-necked flask that TM, stirring are housed, add a certain amount of tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) and catalyzer; Stirring is warming up to 65～160 ℃; Regulating vacuum tightness is 10～760 mmhg, and to the absence of liq outflow, reaction finishes; Collect by-product, obtain having phosphite antioxidant suc as formula the I structure;
Ⅰ
In the formula, R is C
9～C
18Fatty Alcohol(C12-C14 and C12-C18) is like butanols, octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol and stearyl alcohol etc.
Tris phosphite can use trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite to replace.
Said catalyzer can be selected mineral alkali such as Pottasium Hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash etc. for use; Organic bases such as sodium methylate, aluminum isopropylate, amine etc.; Ester class such as tetrabutyl titanate etc.; Organic tin such as dibutyl tin laurate, Dibutyltin oxide etc. also can be two or more mixtures of above-mentioned catalyzer.
Said catalyzer is selected the mixed catalyst of salt of wormwood and Dibutyltin oxide for use.
The weight ratio of salt of wormwood and Dibutyltin oxide is 2:1 in the said mixed catalyst.
Said catalyst levels is 0.1%～0.5% of a tris phosphite weight.
The present invention adopts " one kettle way ", solubilizing agent not, and the simple environmental protection of technology does not have " three wastes ", and catalyst levels is little and yield is high, and the products obtained therefrom phosphorus content is high, has fabulous high-temperature oxidation resistant and color and luster protective capability.
Embodiment 1:
In 1000 milliliters of there-necked flasks that have TM, a whisking appliance, add 124 gram trimethyl phosphites, 68 gram tetramethylolmethanes, the 74 gram trimethyl carbinols, 0.13 gram catalyzer; Stirring is warming up to 65～70 ℃; Be incubated 2～5 hours, be warming up to 80～100 ℃ flow out to absence of liq till, collect 95 gram methyl alcohol; Obtain di-t-butyl alkyl pentaerythritol diphosphites, yield is 99.0%.
The di-t-butyl pentaerythritol diphosphites is a colourless transparent liquid, phosphorus content: >=18.2%, and density (25 ℃): 0.98 g/mL, refractive index (25 ℃): 1.398.
Embodiment 2:
In 1000 milliliters of there-necked flasks that have TM, a whisking appliance, add 166 gram triethyl-phosphites, 68 gram tetramethylolmethanes, 130 gram isooctyl alcohol, 0.17 gram catalyzer; Stirring is warming up to 80～100 ℃; Be incubated 2～5 hours, be warming up to 120～140 ℃ flow out to absence of liq till, collect 137 gram ethanol; Obtain di-t-butyl alkyl pentaerythritol diphosphites, yield is 99.3%.
Two octane-iso base pentaerythritol diphosphites are colourless transparent liquid, phosphorus content: >=12.9%, and density (25 ℃): 1.02 g/mL, refractive index (25 ℃): 1.463.
Embodiment 3:
In 1000 milliliters of there-necked flasks that have TM, a whisking appliance, add 310 gram triphenyl phosphites, 68 gram tetramethylolmethanes, 158 gram isodecyl alcohols, 0.3 gram catalyzer; Regulating vacuum tightness is 10～15 mmhg; Stirring is warming up to 140～160 ℃, till flowing out to absence of liq, collects 281 phenol; Obtain two isodecyl alkyl pentaerythritol diphosphites, yield is 99.6%.
Two isodecyl alkyl pentaerythritol diphosphites are colourless transparent liquid, phosphorus content: >=12.1%, and density (25 ℃): 1.04 g/mL, refractive index (25 ℃): 1.475.
Embodiment 4:
In 1000 milliliters of there-necked flasks that have TM, a whisking appliance, add 310 gram triphenyl phosphites, 68 gram tetramethylolmethanes, 186 gram lauryl alcohols, 0.3 gram catalyzer; Regulating vacuum tightness is 10～15 mmhg; Stirring is warming up to 140～160 ℃, till flowing out to absence of liq, collects 280 gram phenol; Obtain two dodecyl pentaerythritol diphosphites, yield is 99.3%.
Two dodecyl pentaerythritol diphosphites are colourless transparent liquid, phosphorus content: >=11.5%, and density (25 ℃): 1.05 g/mL, refractive index (25 ℃): 1.485.
Embodiment 5:
In 1000 milliliters of there-necked flasks that have TM, a whisking appliance, add 310 gram triphenyl phosphites, 68 gram tetramethylolmethanes, 243 gram hexadecanols, 0.3 gram catalyzer; Regulating vacuum tightness is 10～15 mmhg; Stirring is warming up to 140～160 ℃, till flowing out to absence of liq, collects 280 gram phenol; Obtain Dicetylpentaerythritesterhosphite esterhosphite, yield is 99.3%.
Dicetylpentaerythritesterhosphite esterhosphite is a white waxy solid, phosphorus content: >=10.3%, and fusing point: 45～50 ℃.
Embodiment 6:
In 1000 milliliters of there-necked flasks that have TM, a whisking appliance, add 310 gram triphenyl phosphites, 68 gram tetramethylolmethanes, 271 gram stearyl alcohol, 0.3 gram catalyzer; Regulating vacuum tightness is 10～15 mmhg; Stirring is warming up to 140～160 ℃, till flowing out to absence of liq, collects 275 gram phenol; Obtain two octadecyl pentaerythritol diphosphites, yield is 97.5%.
Two octadecyl pentaerythritol diphosphites are white waxy solid, phosphorus content: >=8.5%, and fusing point: 55～60 ℃.
Claims (6)
1. the preparation method of a new and effective phosphite antioxidant; It is characterized in that process step is: with tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) is raw material, and mol ratio is: 2.0:1.0:2.0 adds a certain amount of tris phosphite, tetramethylolmethane, Fatty Alcohol(C12-C14 and C12-C18) and catalyzer in the there-necked flask that TM, stirring are housed; Stirring is warming up to 65～160 ℃; Regulating vacuum tightness is 10～760 mmhg, and to the absence of liq outflow, reaction finishes; Collect by-product, obtain having phosphite antioxidant suc as formula the I structure;
Ⅰ
In the formula, R is C
9～C
18Fatty Alcohol(C12-C14 and C12-C18) is like butanols, octanol, decyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol and stearyl alcohol etc.
2. the preparation method of new and effective phosphite antioxidant according to claim 1 is characterized in that tris phosphite can use trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite to replace.
3. the preparation method of new and effective phosphite antioxidant according to claim 1; It is characterized in that: said catalyzer can be selected mineral alkali such as Pottasium Hydroxide, sodium hydroxide, salt of wormwood, yellow soda ash etc. for use; Organic bases such as sodium methylate, aluminum isopropylate, amine etc.; Ester class such as tetrabutyl titanate etc., organic tin such as dibutyl tin laurate, Dibutyltin oxide etc. also can be two or more mixtures of above-mentioned catalyzer.
4. like the preparation method of the said new and effective phosphite antioxidant of claim 3, it is characterized in that: said catalyzer is selected the mixed catalyst of salt of wormwood and Dibutyltin oxide for use.
5. like the preparation method of the said new and effective phosphite antioxidant of claim 3, it is characterized in that: the weight ratio of salt of wormwood and Dibutyltin oxide is 2:1 in the said mixed catalyst.
6. like the preparation method of the said new and effective phosphite antioxidant of claim 3, it is characterized in that: said catalyst levels is 0.1%～0.5% of a tris phosphite weight.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012483A (en) * | 2012-12-04 | 2013-04-03 | 浙江海普顿新材料股份有限公司 | Phenol-free phosphite ester, as well as preparation method and application thereof |
| CN103509055A (en) * | 2013-10-10 | 2014-01-15 | 中国海洋石油总公司 | Microwave synthesis method for tri(3,3'-di-tert-butyl-5,5'-dimethoxy-2,2'-diphenol) biphosphite |
| 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 |
| 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 |
| CN111620905A (en) * | 2020-06-02 | 2020-09-04 | 营口风光新材料股份有限公司 | Preparation method of high-performance phosphorus-containing antioxidant 618 |
| CN113651849A (en) * | 2021-07-23 | 2021-11-16 | 江苏常青树新材料科技股份有限公司 | Polymeric phenol-free low-odor phosphite ester and preparation method thereof |
| CN114181248A (en) * | 2021-06-26 | 2022-03-15 | 吉林市博禹祥实工贸有限公司 | Antioxidant, preparation method and application thereof |
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2012
- 2012-06-16 CN CN2012101983167A patent/CN102702267A/en active Pending
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012483A (en) * | 2012-12-04 | 2013-04-03 | 浙江海普顿新材料股份有限公司 | Phenol-free phosphite ester, as well as preparation method and application thereof |
| CN103509055A (en) * | 2013-10-10 | 2014-01-15 | 中国海洋石油总公司 | Microwave synthesis method for tri(3,3'-di-tert-butyl-5,5'-dimethoxy-2,2'-diphenol) biphosphite |
| CN103509055B (en) * | 2013-10-10 | 2016-08-17 | 中国海洋石油总公司 | A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester |
| 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 |
| 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 |
| CN111620905A (en) * | 2020-06-02 | 2020-09-04 | 营口风光新材料股份有限公司 | Preparation method of high-performance phosphorus-containing antioxidant 618 |
| CN114181248A (en) * | 2021-06-26 | 2022-03-15 | 吉林市博禹祥实工贸有限公司 | Antioxidant, preparation method and application thereof |
| CN113651849A (en) * | 2021-07-23 | 2021-11-16 | 江苏常青树新材料科技股份有限公司 | Polymeric phenol-free low-odor phosphite ester and preparation method thereof |
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Application publication date: 20121003 |