CN109897062A - A kind of preparation and purification method of antioxidant 168 - Google Patents
A kind of preparation and purification method of antioxidant 168 Download PDFInfo
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- CN109897062A CN109897062A CN201711313176.2A CN201711313176A CN109897062A CN 109897062 A CN109897062 A CN 109897062A CN 201711313176 A CN201711313176 A CN 201711313176A CN 109897062 A CN109897062 A CN 109897062A
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- antioxidant
- irgasfos
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- methanol
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Abstract
The present invention provides a kind of preparation method of irgasfos 168, the present invention is used as catalyst using 4-dimethylaminopyridine and triethylamine mixing, catalyst amount is low, and effect is good, simple process, product yield is high, it can achieve 97% or more, and purity is high, there is good industrial production prospect, a kind of purification process of irgasfos 168, the method includes by crude product irgasfos 168 ethyl acetate: methanol=5: 1 mixed solvent recrystallizes 1-3 times；Obtain the irgasfos 168 crystal that purity is 99.5% or more.
Description
Technical field
The present invention relates to antioxidant, in particular to a kind of preparation and purification method of antioxidant 168.
Background technique
Irgasfos 168, melting range: 183~186 DEG C, density: 1.03g/cm3.Appearance is white crystals sprills, tasteless, nothing
Poison, volatility is low, not soluble in water, is slightly soluble in alcohols, is dissolved in various hydrocarbon solvents.
Irgasfos 168 is a kind of phosphite antioxidant haveing excellent performance, and is indispensable thermostabilization in resin processing
Agent, can be effectively prevented the generation of hydrogen halides in process, to greatly reduce the corrosion to mold, and can decompose poly-
It closes the hydroperoxides formed in object degradation and plays good synergistic effect.It is that general phosphorous acid esters are auxiliary in the world at present
One of aid anti-oxidants have good hydrolytic resistance, and high temperature resistant, volatility is small, and anti-extractibility is strong, and can significantly improve product
Photostability.Meanwhile irgasfos 168 is also thermal stabilization additive safer at present, oneself obtains U.S. FDA and ratifies, Germany,
Also oneself permits in the product for contacting food for the states such as Switzerland, Japan, Italy.Irgasfos 168 is assisted as phosphorous acid esters
Antioxidant is widely used in the processing of the products such as PP, HDPF, LLDPF, LDPF, ABS and polycarbonate.Especially suitable for various
In the process of polyolefin, polyolefin in process, due to heat, oxygen and the influence of shear, can make polyolefin generate drop
Solution or crosslinking.Either degradation or crosslinking can all cause irremediable as a result, damage product to the mechanical property of polyolefin
Appearance and performance.The addition of irgasfos 168 can be such that the degradation of polyolefin chain or crosslinking work in-process reduces.The especially production
Product are used cooperatively with Hinered phenols primary antioxidant, can effectively improve processing stability, the Heat-resistant stable of polyolefin resin
Property, modification of colour and weatherability, have good synergistic effect, be the mainstream kind of phosphorous acid esters auxiliary antioxidant, apply
Extensively, there is good development prospect.
Irgasfos 168 is developed and is commercially produced by Ciba-Geigy company, Switzerland earliest.With polyolefin industry and
The rapid development in plastics high temperature process molding market increasingly increases the demand of phosphite ester antioxidant, domestic market demand
Amount is about 1400 ~ 1600t/a, and constantly increases.The unit that China researchs and produces irgasfos 168 product at present has more than 10 families,
But mostly scale is less, and yield is lower.As Zhong You group begins to production irgasfos 168, but raw material Lan Hua company nineteen ninety
Import is relied on always, with self-produced raw material, there is product fusing point always and product quality requirement is not achieved, and product yield is lower asks
Topic.
Currently, the synthetic method of irgasfos 168 is mainly with 2,4-DTBP and phosphorus trichloride as raw material,
Target product three [ 2,4- di-tert-butyl-phenyl ] phosphite ester is generated under the action of basic catalyst.Previous production technology is all
Using single catalyst, catalytic efficiency is low, and reaction temperature is high, and purity is low, and yield is low (90% or so).Such as patent document CN
102485728 A disclose a kind of antioxidant 168, are made of following raw materials according according to following weight proportion: 2,4- bis- tertiary fourths
500-800 parts of base phenol, 150-200 parts of phosphorus trichloride, 5-10 parts of pyridine, resulting product yield is only 90% or more.It is anti-oxidant
The traditional preparation synthetic method yield 88% of agent 168, disposing mother liquor finished product yield about 2%, total recovery is 90% or more.In life
The noxious material that pollution environment can be generated during production endangers the health of worker, and produces at high cost.
But due to using single catalyst, effect is not good enough, although yield is also very high, the purity of product is not high, causes
Later period is higher to the purification requirements of product, and process flow is longer, and production cost is higher.
Purification process used at present includes recrystallization method, generallys use lower paraffin hydrocarbon, and ethyl alcohol equal solvent is recrystallized,
But existing recrystallization method is difficult to be effectively removed impurity, with the raising of quality standard, to the content of 2,4-DTBP
It is required that higher and higher, it is therefore desirable to which finding a kind of method can reduce impurity 2,4-DTBP in irgasfos 168
Content, while preparing a kind of good fluidity, the high irgasfos 168 of stability be in industrial production there is an urgent need to.
Summary of the invention
In order to compensate for the shortcomings of the prior art, the present invention provides a kind of preparation and purification methods of antioxidant 168.
The present invention is achieved through the following technical solutions:
A kind of preparation method of antioxidant 168, comprises the following steps:
1. 2,4-DTBP and catalyst are added in container, it is then slowly added into the mixing of dimethylbenzene and phosphorus trichloride
Liquid is warming up to 50 ~ 60 DEG C, reacts 2 ~ 5h；The catalyst is the mixture of 4-dimethylaminopyridine and triethylamine；2. by step
1. reaction solution obtained in is warming up to 130 ~ 160 DEG C, reacts 1.5 ~ 5h, is evaporated under reduced pressure out hydrogen chloride and dimethylbenzene；3. by step
2. reaction solution in after vacuum distillation is cooled to 90 DEG C, and isopropanol is added, and is cooled to room temperature after stirring 0.5 ~ 1.5h, filters, does
It is dry to obtain irgasfos 168.
The preparation method of antioxidant 168 of the invention, the amount of the catalyst are 2,4-DTBP quality
The mass ratio of 5%-7%, the 4-dimethylaminopyridine and triethylamine is 4:6-6:4.
The preparation method of antioxidant 168 of the invention, the molar ratio of the 2,4-DTBP and phosphorus trichloride
For 3.1:1, the mass ratio of dimethylbenzene and phosphorus trichloride is 5:1-7:1.
The purification process of antioxidant 168 of the invention, which is characterized in that steps are as follows:
Crude product irgasfos 168 ethyl acetate: methanol=5:1 is solvent recrystallization 1-3 times, wherein raw material proportioning crude product antioxidant
168: mixed solvent=l:10 of ethyl acetate and methanol.
The purification process of antioxidant 168 of the invention, the recrystallization number are 2 times.
The purification process of antioxidant 168 of the invention, steps are as follows: the second that irgasfos 168 crude product is measured with its 10 times
Acetoacetic ester and methanol=5:1 mixed solvent dissolution, are heated to reflux temperature, continue 20 minutes, and room temperature is let cool, and crystallization is precipitated, and is filtered
After obtain crystal, repeat above step, obtain second of recrystallized product, it is dry after up to irgasfos 168 sterling.
The beneficial effects of the present invention are:
The present invention using 4-dimethylaminopyridine and triethylamine by being mixed using 2,4-DTBP and phosphorus trichloride as raw material
Cooperation is catalyst, and catalyst amount is low, and effect is good, simple process, and product yield is high, can achieve 97% or more and purity is high,
With good industrial production prospect.The present invention can be used for the synthesis of irgasfos 168, and purification process crystal form is good, surely
Qualitative stronger, yield is high, and purification efficiency is high, simple process, it is low in cost, be suitble to large-scale production.
Specific embodiment
Embodiment 1
1. 8.8g 4-dimethylaminopyridine and 8.8g triethylamine are added to 500ml tri- by 252.15g 2,4-DTBP
In mouth flask, then the mixed liquor of 276g dimethylbenzene and 55.35g phosphorus trichloride is slowly added to, is warming up to 60 DEG C, reacts 2h；
2. by step 1. obtained in reaction solution be warming up to 130 DEG C, react 5h, be evaporated under reduced pressure out hydrogen chloride and dimethylbenzene；
3. the reaction solution after step 2. middle vacuum distillation is cooled to 90 DEG C, isopropanol is added, is cooled to room temperature after stirring 1h, takes out
Filter, dry 254.9g irgasfos 168, yield 98.5% (using phosphorus trioxide as benchmark calculated yield), fusing point for 184.3 ~
185.2 DEG C, purity 99.8%.
Irgasfos 168 crude product is measured to (w/v) ethyl acetate and methanol=5:1 mixed solvent (v/ of volume with 10 times of its weight
V) it dissolves, is heated to reflux temperature, continue 20 minutes, room temperature is let cool, and crystallization is precipitated, is crystallized after suction filtration, repeats the above step
Suddenly, second of recrystallized product is obtained, up to irgasfos 168 sterling, yield 96.2% after drying.It is detected by HPLC, gained is anti-
168 sterling of oxygen agent, purity 99.65%, impurity 1:2,4- DI-tert-butylphenol compounds and impurity 2:2,4- di-tert-butyl oxygen dichloride
The content of phosphorus is respectively less than 0.1%.
Embodiment 2
1. 8.5g 4-dimethylaminopyridine and 5.7g triethylamine are added to 500 ml by 252.15g 2,4-DTBP
In three-necked flask, then the mixed liquor of 332g dimethylbenzene and 55.35g phosphorus trichloride is slowly added to, is warming up to 55 DEG C, reaction
3.5h；
2. by step 1. obtained in reaction solution be warming up to 145 DEG C, react 3.5h, be evaporated under reduced pressure out hydrogen chloride and dimethylbenzene；
3. the reaction solution after step 2. middle vacuum distillation is cooled to 90 DEG C, isopropanol is added, is cooled to room temperature after stirring 1h, takes out
Filter, dry 253.4g irgasfos 168, yield 97.9% (using phosphorus trioxide as benchmark calculated yield), fusing point for 184.1 ~
185.4 DEG C, purity 99.7%.
Irgasfos 168 crude product is measured to (w/v) ethyl acetate and methanol=5:1 mixed solvent (v/ of volume with 10 times of its weight
V) it dissolves, is heated to reflux temperature, continue 20 minutes, room temperature is let cool, and crystallization is precipitated, is crystallized after suction filtration, repeats the above step
Suddenly, second of recrystallized product is obtained, up to irgasfos 168 sterling, yield 96.2% after drying.It is detected by HPLC, gained is anti-
168 sterling of oxygen agent, purity 99.65%, impurity 1:2,4- DI-tert-butylphenol compounds and impurity 2:2,4- di-tert-butyl oxygen dichloride
The content of phosphorus is respectively less than 0.1%.
Specific implementation of the invention is described in detail above, but is intended only as an example, the present invention is not
It is limited to specific implementation case described above, also within protection scope of the present invention to the equivalent modifications that carry out of the present invention.
Claims (6)
1. a kind of preparation method of antioxidant 168, which is characterized in that comprise the following steps:
1. 2,4-DTBP and catalyst are added in container, it is then slowly added into the mixing of dimethylbenzene and phosphorus trichloride
Liquid is warming up to 50 ~ 60 DEG C, reacts 2 ~ 5h；The catalyst is the mixture of 4-dimethylaminopyridine and triethylamine；2. by step
1. reaction solution obtained in is warming up to 130 ~ 160 DEG C, reacts 1.5 ~ 5h, is evaporated under reduced pressure out hydrogen chloride and dimethylbenzene；3. by step
2. reaction solution in after vacuum distillation is cooled to 90 DEG C, and isopropanol is added, and is cooled to room temperature after stirring 0.5 ~ 1.5h, filters, does
It is dry to obtain irgasfos 168.
2. the preparation method of antioxidant 168 according to claim 1, it is characterised in that: the amount of the catalyst is 2,
The mass ratio of the 5%-7% of 4- DI-tert-butylphenol compounds quality, the 4-dimethylaminopyridine and triethylamine is 4:6-6:4.
3. the preparation method of antioxidant 168 according to claim 1, it is characterised in that: 2, the 4- di-tert-butyl
The molar ratio of phenol and phosphorus trichloride is 3.1:1, and the mass ratio of dimethylbenzene and phosphorus trichloride is 5:1-7:1.
4. the purification process of antioxidant 168 according to any one of claims 1-4, which is characterized in that steps are as follows:
Crude product irgasfos 168 ethyl acetate: methanol=5:1 is solvent recrystallization 1-3 times, wherein raw material proportioning crude product antioxidant
168: mixed solvent=l:10 of ethyl acetate and methanol.
5. the purification process of the antioxidant 168 of claim 5, which is characterized in that recrystallization number is 2 times.
6. the purification process of the antioxidant 168 of claim 5, which is characterized in that steps are as follows: irgasfos 168 crude product is used
Its 10 times ethyl acetate measured and methanol=5:1 mixed solvent dissolution, are heated to reflux temperature, continue 20 minutes, and room temperature is let cool,
Crystallization is precipitated, crystal is obtained after suction filtration, repeats above step, second of recrystallized product is obtained, up to irgasfos 168 after drying
Sterling.
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| CN201711313176.2A CN109897062A (en) | 2017-12-09 | 2017-12-09 | A kind of preparation and purification method of antioxidant 168 |
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| CN201711313176.2A CN109897062A (en) | 2017-12-09 | 2017-12-09 | A kind of preparation and purification method of antioxidant 168 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590834A (en) * | 2019-09-23 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Preparation method of antioxidant 168 |
| CN110959800A (en) * | 2019-11-28 | 2020-04-07 | 梁山新翔新材料有限公司 | Preparation method of compound antioxidant |
-
2017
- 2017-12-09 CN CN201711313176.2A patent/CN109897062A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590834A (en) * | 2019-09-23 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Preparation method of antioxidant 168 |
| CN110590834B (en) * | 2019-09-23 | 2022-03-04 | 黄河三角洲京博化工研究院有限公司 | Preparation method of antioxidant 168 |
| CN110959800A (en) * | 2019-11-28 | 2020-04-07 | 梁山新翔新材料有限公司 | Preparation method of compound antioxidant |
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Application publication date: 20190618 |