CN104945432A - Phosphite ester antioxidant and preparation method thereof - Google Patents
Phosphite ester antioxidant and preparation method thereof Download PDFInfo
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- CN104945432A CN104945432A CN201410331828.5A CN201410331828A CN104945432A CN 104945432 A CN104945432 A CN 104945432A CN 201410331828 A CN201410331828 A CN 201410331828A CN 104945432 A CN104945432 A CN 104945432A
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Abstract
The invention discloses a phosphite ester antioxidant synthesized through a two-step method, wherein the phosphite ester antioxidant can be used for replacing a traditional assistant antioxidant to be used in the field of processing of polymers. A two-step catalytic condensation synthesis preparation process is adopted and has the technical advancements of short reaction time, easy control in reaction and easy post-treatment; the phosphite ester prepared by virtue of the process has the advantages that a spatial structure with very high hydrophobicity is formed by the binding of phosphorus atoms and a bisphenol compound with relatively large steric hindrance, and therefore the hydrolysis resistance of the antioxidant is enhanced; moreover, since multiple benzene rings exist in the molecule, the antioxidant has very high rigidity and is hardly damaged in a high-temperature processing process.
Description
Technical field
The present invention relates to antioxidant technology field, specifically a kind of phosphite ester kind antioxidant and preparation method thereof.
Background technology
Macromolecular material, in the course of processing or when using in high temperature, aerobic situation for a long time, there will be material degradation, and with phenomenons such as physical property reduction, bad orders, in order to prevent the deterioration of material, usually must add oxidation inhibitor in the material.Oxidation inhibitor is divided into primary antioxidant and auxiliary antioxidant.Primary antioxidant has aromatic amine oxidation inhibitor and Hinered phenols antioxidant.Auxiliary antioxidant has phosphorous acid esters etc.In general primary antioxidant and auxiliary anti-oxidant have synergy.
In the macromolecular material application processes such as polyolefine, styrene resin, engineering thermoplastic resin and powder coating, itself is often along with the processing conditions of high temperature and high humidity.This requires that oxidation inhibitor itself must have certain hydrolytic resistance and high temperature resistance, otherwise oxidation inhibitor will occur to decompose or destroy under high temperature, super-humid conditions, cannot play the function that oxidation inhibitor itself has.
Phosphorous acid esters of gallic acid oxidation inhibitor is the high-efficiency anti-oxidant of a class excellent performance, other oxidation inhibitor of comparing, and they can not only improve polymer processing stability, and have good heat-resistant stability and resistance to hydrolysis.Research finds, the stability to hydrolysis of phosphorous acid acid esters and pyrolytic decomposition are with sterically hindered around phosphorus atom in molecular structure and rigidity is relevant, in general, sterically hindered larger with rigidity, stability to hydrolysis and high thermal resistance better.
The auxiliary antioxidant principal item that high polymer processing uses in the market is phosphorous acid esters, such as three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (abbreviation irgasfos 168), two hard ester group pentaerythritol phosphites (abbreviation antioxidant 618) etc., but these oxidation inhibitor in use, due to configuration aspects, still there is certain defect in their stability to hydrolysis, high temperature resistance decomposability.
Summary of the invention
In order to overcome the above-mentioned defect of existing oxidation inhibitor, the invention discloses a kind of phosphite ester kind antioxidant with two step synthetic method, it can substitute the application of traditional auxiliary antioxidant in polymer processing field.
A kind of phosphite ester kind antioxidant, its structure is as follows:
。
A preparation method for phosphite ester kind antioxidant, its making step is as follows:
(1) solvent, 2,4-DTBP are put in reactor, stirring heating, control temperature of reaction, phosphorus trichloride is joined in reactor and carry out condensation reaction, after reaction for some time, be warming up to 40-50 DEG C, add the catalyzer by dissolution with solvents, reaction for some time;
(2), after generating intermediate, a certain amount of solvent and dihydroxyphenyl propane is added.React under being warming up to reflux state to tail gas absorption mouth place without hydrogen chloride gas release.Just product can be obtained again through subsequent processes.
A preparation method for phosphite ester kind antioxidant, its chemical equation is as follows:
The first step,
；
Second step,
。
Described solvent can be organic alkane, aromatic hydrocarbons; and their mixture; described catalyzer is pyridine and homologue thereof; the described the first step reaction times controls as 20-90min; it is 40 DEG C-50 DEG C that described the first step temperature of reaction controls; described reaction whole process uses nitrogen protection, and the hydrogenchloride sodium hydroxide of generation absorbs, and the fusing point of described product is 82 DEG C-86 DEG C.
Described subsequent processes comprises: distilled at ambient pressure by reaction solution and steam solvent, when system reach 150 DEG C and solvent-free steam time, under the pressure of about 5 KPa, underpressure distillation is to steam residual solvent in system, and in flask, product is that white is to light yellow viscous liquid; Poured into while hot in Stainless Steel Disc by product, be cooled to room temperature (about 20 DEG C), product is blocks of solid, and milling with mortar becomes white powder; White powder adds dehydrated alcohol and grinds for some time, and wherein impurity can dissolve in ethanol, and product is insoluble in ethanol, suction filtration, obtains filter cake and filtrate, wherein filtrate comparatively thickness, and filter cake is product.After repetitive operation dehydrated alcohol grinding steps twice, by filter cake vacuum-drying at 35 DEG C, obtain white solid powder product.
Compared with prior art: adopt two-stage catalysis condensation method synthesis and preparation process, there is the reaction times short, easy control of reaction system, the technical advances such as aftertreatment easily realizes, the phosphorous acid ester obtained by this technology is due to phosphorus atom and sterically hindered larger bisphenol cpd bonding, constitute the space structure that hydrophobicity is very strong, enhance the hydrolytic resistance of antioxidant product, simultaneously owing to having multiple benzene ring structure in molecule, it has very high rigidity, is not easy to be damaged in high temperature working processes.
Embodiment
Below in conjunction with concrete implementation column, the invention will be further described.
embodiment 1
In the 1L four-hole boiling flask that thermometer, electric stirring, reflux exchanger, generation gas absorbing device and gas export mouth are housed, under nitrogen protection, add 2,4-DI-tert-butylphenol compounds 141.9 g, toluene 100 mL, stir and add 30 mL phosphorus trichlorides after being heated to 45 DEG C, reacting 30 min; Be warming up to 55 DEG C, add the about 0.3 mL pyridine dissolved with 10 mL toluene, react 90 min; Then add 150 mL toluene, 39.2 g dihydroxyphenyl propanes, react to tail gas absorption mouth place without hydrogen chloride gas release (about 90 min) under being warming up to reflux state (about 115 DEG C), reaction terminates.
Reaction solution is distilled at ambient pressure and steams solvent, when system reach 150 DEG C and solvent-free steam time, under the pressure of about 5 KPa, underpressure distillation is to steam residual solvent in system, in flask product be white to light yellow viscous liquid; Poured into while hot in Stainless Steel Disc by product, be cooled to room temperature (about 20 DEG C), product is blocks of solid, and milling with mortar becomes white powder; White powder adds dehydrated alcohol and grinds for some time, and wherein impurity can dissolve in ethanol, and product is insoluble in ethanol, suction filtration, obtains filter cake and filtrate, wherein filtrate comparatively thickness, and filter cake is product.After repetitive operation dehydrated alcohol grinding steps twice, by filter cake vacuum-drying at 35 DEG C, obtain 141g white solid powder product, the fusing point of product: 82-84 DEG C.
embodiment 2
In the 1L four-hole boiling flask that thermometer, electric stirring, reflux exchanger, generation gas absorbing device and gas export mouth are housed, under nitrogen protection, add 2,4-DI-tert-butylphenol compounds 141.9 g, diethyl-dimethyl methane 100 mL, stir and add 30 mL phosphorus trichlorides after being heated to 40 DEG C, reacting 90 min; Be warming up to 55 DEG C, add the about 0.3 mL pyridine dissolved with 10 mL diethyl-dimethyl methane, react 90 min; Then add 150 mL diethyl-dimethyl methane, 39.2 g dihydroxyphenyl propanes, react to tail gas absorption mouth place without hydrogen chloride gas release (about 90 min) under being warming up to reflux state (about 87 DEG C), reaction terminates.
The subsequent processes of product, with example 1, finally obtains 136g white solid powder product.The fusing point of product: 83-85 DEG C.
embodiment 3
The resistant to hydrolysis performance of phosphite antioxidant prepared by the irgasfos 168 that test and comparison is commercially available as follows, antioxidant 618 and the present invention and pyrolytic decomposition performance.
Resistant to hydrolysis performance test:
Take 20g(and be accurate to 0.1g) experiment product, add in 500ml Erlenmeyer flask, then add 100ml distilled water, build bottle stopper and leave space.Sample plasma bottle is put in thermostat container, keep steady temperature to be 90 DEG C, start hydrolysising experiment, meter T1 writing time, when testing sample and being all converted into paste dope by crystal grain, hydrolysising experiment terminates, meter T2 writing time, the resistant to hydrolysis time Δ T=T2-T1 of product.
Resistance toheat is tested:
Adopt thermogravimetric analyzer, under nitrogen protection, test with the temperature rise rate of 20 DEG C/min and record temperature when institute's test sample product thermal weight loss reaches 10%.
Test result is in table 1.
Table 1
As can be seen from the experimental result of upper table, the resistant to hydrolysis performance of phosphite antioxidant of the present invention and pyrolytic decomposition performance are better than the irgasfos 168 and antioxidant 618 that existing market sells.
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (4)
1. a phosphite ester kind antioxidant, is characterized in that: its structure is as follows:
。
2. a preparation method for phosphite ester kind antioxidant, is characterized in that: its preparation process is as follows:
(1) solvent, 2,4-DTBP are put in reactor, stirring heating, control temperature of reaction, phosphorus trichloride is joined in reactor and carry out condensation reaction, after reaction for some time, be warming up to 40-50 DEG C, add the catalyzer by dissolution with solvents, reaction for some time;
(2) after generating intermediate, add a certain amount of solvent and dihydroxyphenyl propane, react under being warming up to reflux state to tail gas absorption mouth place without hydrogen chloride gas release, more just can obtain product through subsequent processes.
3. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2, is characterized in that: its chemical equation is as follows:
The first step,
；
Second step,
。
4. the preparation method of a kind of phosphite ester kind antioxidant according to claim 2, it is characterized in that: described solvent can be organic alkane, aromatic hydrocarbons, and their mixture, described catalyzer is pyridine and homologue thereof, the described the first step reaction times controls as 20-90min, it is 40 DEG C-50 DEG C that described the first step temperature of reaction controls, described reaction whole process uses nitrogen protection, the hydrogenchloride sodium hydroxide generated absorbs, the fusing point of described product is 82 DEG C-86 DEG C, described subsequent processes comprises: distilled at ambient pressure by reaction solution and steam solvent, when system reach 150 DEG C and solvent-free steam time, under the pressure of about 5 KPa, underpressure distillation is to steam residual solvent in system, in flask, product is that white is to light yellow viscous liquid, poured into while hot in Stainless Steel Disc by product, be cooled to room temperature (about 20 DEG C), product is blocks of solid, and milling with mortar becomes white powder, white powder adds dehydrated alcohol and grinds for some time, wherein impurity can dissolve in ethanol, and product is insoluble in ethanol, suction filtration, obtains filter cake and filtrate, wherein filtrate comparatively thickness, filter cake is product, after repetitive operation dehydrated alcohol grinding steps twice, by filter cake vacuum-drying at 35 DEG C, obtain white solid powder product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4724247A (en) * | 1986-07-18 | 1988-02-09 | Ethyl Corporation | Antioxidant aromatic diphosphites |
| CN101798325A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Preparation method of antioxidant product with stable performance |
-
2014
- 2014-07-11 CN CN201410331828.5A patent/CN104945432A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4724247A (en) * | 1986-07-18 | 1988-02-09 | Ethyl Corporation | Antioxidant aromatic diphosphites |
| CN101798325A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Preparation method of antioxidant product with stable performance |
Non-Patent Citations (1)
| Title |
|---|
| 夏娅娜 等: "一种新型双膦亚磷酸酯配体的合成及在1-己烯氢甲酰化反应中的应用", 《分子催化》 * |
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Application publication date: 20150930 |