CN100441584C - Preparation method of tetramethylomethane phosphite ester antioxidant - Google Patents
Preparation method of tetramethylomethane phosphite ester antioxidant Download PDFInfo
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- CN100441584C CN100441584C CNB2005101125039A CN200510112503A CN100441584C CN 100441584 C CN100441584 C CN 100441584C CN B2005101125039 A CNB2005101125039 A CN B2005101125039A CN 200510112503 A CN200510112503 A CN 200510112503A CN 100441584 C CN100441584 C CN 100441584C
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Abstract
The present invention discloses a method for preparing pentaerythritol phosphate antioxidant. It is characterized by that it is made up by using pentaerythritol, solvent, phosphorus trichloride and 2,6-di-tert-butyl-p-cresol as raw material and using weak base type macroporous ion exchange resin as catalyst through a certain preparation process. Said catalyst is a solid, can be easily dispersed and recovered.
Description
Technical field
The present invention relates to a kind of preparation method who prepares phosphorous acid ester, more particularly, the present invention relates to a kind of preparation method of pentaerythritol phosphite oxidation inhibitor.
Background technology
Oxidation inhibitor is the important auxiliary agent of stabilization in fluoropolymer resin processing and the application process, and it is used and almost relates to all polymkeric substance and goods thereof.China's polymer product increase of production in recent years is rapid, and this development and application for oxidation inhibitor provides good market outlook.Pentaerythritol phosphite oxidation inhibitor is a kind of high-efficiency anti-oxidant of excellent performance, can not only improve polymer processing stability, and has a good color stability, therefore heat-resistant stability and excellent resistance to hydrolysis energy have good application prospects in macromolecular materials such as polyolefine, styrene resin and engineering thermoplastic resin.The structural formula of this kind antioxidant can be expressed as follows:
At present all to adopt liquid basified compound be catalyzer to bibliographical information synthesis of pentaerythritol phosphite antioxidant, as aminated compounds etc.Though such catalyzer has advantages such as reaction conditions gentleness and since the recovery of catalyzer with separates very difficultly, so production cost is higher, has restricted its industrial applications.Patent EP356688 proposes a kind of preparation method of this oxidation inhibitor, with dichloro pentaerythritol diphosphite and 2, the 6-toluene di-tert-butyl phenol is a raw material, and triethylamine or Tributylamine are catalyzer, behind the reaction certain hour, filtration washing obtains product under optimal temperature.It is catalyzer that this method adopts the liquid amine compounds, and the separation of post catalyst reaction and recovery be difficulty very, and easily environment is polluted, and is not suitable for suitability for industrialized production.
Summary of the invention
The present invention is the problem that can not separate and reclaim catalyzer after the reaction that produces of catalyzer in order to solve in the prior art with liquid basified compound, has proposed a kind of method of using solid catalyst to prepare pentaerythritol phosphite oxidation inhibitor.
Concrete technical scheme of the present invention is as follows.
The preparation method of the pentaerythritol phosphite oxidation inhibitor that the present invention proposes may further comprise the steps:
(1) synthetic dichloro pentaerythritol diphosphite: solvent, tetramethylolmethane, weak base type solid catalyst are added in the reactor, in anhydrous inert atmosphere with under stirring, be heated to 20～50 ℃, dropwise add phosphorus trichloride in the reactor, be heated to 50～100 ℃ then gradually, reacted 2～10 hours, and obtained containing the reaction solution of dichloro pentaerythritol diphosphite; Wherein the add-on of weak base type solid catalyst is 1～20% of a tetramethylolmethane quality, the mol ratio of phosphorus trichloride and tetramethylolmethane is 2～5:1, the add-on of solvent is 5～20ml/g tetramethylolmethane, and described weak base type solid catalyst is a weak base type macroporous ion exchange resin;
(2) synthesis of pentaerythritol phosphite antioxidant: the reaction solution that obtains to step (1) adds 2,6 ditertiary butyl p cresol, continuing to be heated to 80～120 ℃ under the stirring, reacts 8～24 hours; The mol ratio of 2,6 ditertiary butyl p cresol and dichloro pentaerythritol diphosphite is 2～4: 1;
(3) post-reaction treatment: the reacting liquor while hot that step (2) obtains is filtered, cooling, crystallization, washing, drying obtains antioxidant product of the present invention.
In described step (1), solvent, tetramethylolmethane, weak base type solid catalyst are added in the reactor, preferably be heated to 20～50 ℃, again phosphorus trichloride is dropwise added in the reactor.
Employed solvent only otherwise the influence reaction is carried out just passable in the step (1).According to the character of reaction system of the present invention, described solvent can not be the proton acid, can not be polar material, carrying out and quality product and yield thereof that this two classes material all can react, and therefore described solvent is preferably aproticapolar solvent.The example of described aproticapolar solvent comprises benzene,toluene,xylene, ethylbenzene, propyl benzene, first and second benzene, isopropyl benzene, trimethylbenzene or two or more the mixture in them.In above-mentioned example, can be different isomerization body or its mixture, for example dimethylbenzene can be o-Xylol, m-xylene, p-Xylol or their mixture; First and second benzene can be o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene or their mixture.
There is no particular limitation for weak base type solid catalyst described in the step (1), but for the work-ing life that makes catalyzer longer, can use active constituent loading on the upper layer of catalyzer or adopt the macropore solid catalyst, be preferably weak base type macroporous ion exchange resin in the present invention.Described weak base type macroporous ion exchange resin is not had special requirement, and its example comprises that model is the weak base type macroporous ion exchange resin of D301 or D370, and the manufacturer of the ion exchange resin of these two kinds of models for example is Chemical Plant of Nankai Univ..In order to guarantee that reaction carries out smoothly, the tramp material in the preferred deionizing exchange resin, the ion exchange resin of buying from manufacturer will carry out pickling, alkali cleaning, distilled water and be washed till neutrality, final drying, and the ion exchange resin that obtains promptly can be used for reaction.
In step (1), when adding phosphorus trichloride, the reaction beginning.For reacting balance is carried out, avoid reacting too fast, dropwise add phosphorus trichloride.According to the size of reaction system, suitably regulate its adding speed.Add after the phosphorus trichloride, gradually temperature is increased to 50～100 ℃ temperature, carry out in order to guarantee reacting balance, its heat-up rate is not limited especially, those skilled in the art can carry out suitable control according to response situation.The factor that influences the adding speed of phosphorus trichloride and heat-up rate for example comprises the concentration of reaction raw materials in reaction system, proportioning raw materials, reactor apparatus etc.
After step (1) is finished, adopt the content of dichloro pentaerythritol diphosphite in the chromatograph analytical reaction liquid, according to the add-on of 2,6 ditertiary butyl p cresol in the amount determining step (2) of dichloro pentaerythritol diphosphite.
In step (1) and (2), along with the hydrogen chloride gas that produces of reaction.Hydrogen chloride gas in order discharge to produce in time will be equipped with an airway on reactor, hydrogen chloride gas is incorporated in the tail gas absorption bottle that sodium hydroxide solution is housed absorb, in order to avoid contaminate environment.From the angle of reaction generation hydrogenchloride, reaction system of the present invention will guarantee anhydrous state, otherwise reaction system becomes acidity, can't react.
After step (2) reaction is finished, from reaction solution, filter out catalyzer while hot, the filtrate cooling, the pentaerythritol phosphite antioxidant product crystallizes out from filtrate, washs then, can adopt the washing of ethanol or propyl alcohol, washing is to not containing till the reaction raw materials 2,6 ditertiary butyl p cresol.After the washing, carry out drying, desolvate to remove.Can adopt drying means known in the art such as oven drying and infrared lamp drying etc., temperature is 50～120 ℃.
Pentaerythritol phosphite antioxidant product of the present invention is by fusing point test, ultimate analysis, infrared test and difference formula weight thermal analyzer (DSC) analysis revealed, and product purity is more than 99%.By test of the processing heat stability in polypropylene material and long-term stable experiment, show that the like product performance of oxidation inhibitor of the present invention and import is suitable.
Catalyzer of the present invention is separate easily and recovery after reaction, and the repeated use of can regenerating, thereby reduces production costs significantly.The catalyzer that filters out in step (3) adopts TREATMENT OF ION EXCHANGE RESINS method conventional in the prior art, and carry out pickling, alkali cleaning, distilled water and be washed till neutrality, final drying, the catalyzer that obtains is promptly reusable.Test shows, uses regenerated catalyst suitable with the live catalyst effect, and under the identical situation of other conditions, the yield and the quality of gained oxidation inhibitor are as broad as long.Therefore preparation method of the present invention is fit to industrialization.
The present invention uses solid catalyst to replace liquid basified compound, avoids producing the waste liquor contamination environment.
Embodiment
Further explain the present invention in the mode of embodiment below, but the present invention is not limited to these embodiment.
Embodiment 1
(model D301, Chemical Plant of Nankai Univ. produces) joins respectively in the 500mL four-hole bottle with 0.1mol tetramethylolmethane, 100mL toluene and 0.5g ion exchange resin, logical N
2, open and stir, at room temperature begin to drip the PCl of 21ml
3, in 20 minutes, dropwise, slowly be heated to 80 ℃ then, reacting balance is carried out.Behind the reaction 8h, add the 2,6 ditertiary butyl p cresol of 0.25mol, be heated to 110 ℃, kept 10 hours, gained material filtered while hot, cooling, washing with alcohol is used in crystallization, and is dry under 120 ℃, obtains the 32.5g product.Show that by dsc analysis product purity can reach 99.1%.
Embodiment 2
(model D301, Chemical Plant of Nankai Univ. produces) joins respectively in the 500mL four-hole bottle with 0.1mol tetramethylolmethane, 100mL dimethylbenzene and 1.0g ion exchange resin, logical N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip the PCl of 21ml
3, in 20 minutes, dropwise, slowly be heated to 80 ℃ then, reacting balance is carried out.Behind the reaction 5h, add the 2,6 ditertiary butyl p cresol of 0.22mol then, be heated to 110 ℃, kept 10 hours, gained material filtered while hot, cooling, crystallization, dry under 100 ℃ with the propyl alcohol washing, obtain the 37.2g product.Show that by dsc analysis product purity can reach 99.1%.
Embodiment 3
(model D370, Chemical Plant of Nankai Univ. produces) adds respectively in the 500mL four-hole bottle with 0.1mol tetramethylolmethane, 100mL benzene and 1.3g ion exchange resin, logical N
2, to open and stir, heating in water bath when homo(io)thermism is 30 ℃, begins to drip the PCl of 21ml
3, in 20 minutes, dropwise, slowly be heated to 80 ℃ then, reacting balance is carried out.Behind the reaction 8h, add the 2,6 ditertiary butyl p cresol of 0.4mol then, be heated to 120 ℃, kept 10 hours, gained material filtered while hot, cooling, washing with alcohol is used in crystallization, and is dry under 60 ℃, obtains the 38.4g product.Show that by dsc analysis product purity can reach 99.2%.
Embodiment 4
(model D370, Chemical Plant of Nankai Univ. produces) adds respectively in the 500mL four-hole bottle with 0.1mol tetramethylolmethane, 100mL ethylbenzene and 1.5g ion exchange resin, logical N
2, to open and stir, heating in water bath when homo(io)thermism is 40 ℃, begins to drip the PCl of 21ml
3, in 20 minutes, dropwise, slowly be heated to 80 ℃ then, reacting balance is carried out.Behind the reaction 8h, add the 2,6 ditertiary butyl p cresol of 0.3mol then, be heated to 110 ℃, kept 10 hours, gained material filtered while hot, cooling, washing with alcohol is used in crystallization, and is dry under 120 ℃, obtains the 41.3g product.Show that by dsc analysis product purity can reach 99.3%.
Embodiment 5
The catalyzer that present embodiment uses is the catalyzer of catalyzer through regenerating and obtaining that uses among the embodiment 1, at first is washed till neutrality through overpickling, alkali cleaning and distilled water, can use after the vacuum-drying.
0.1mol tetramethylolmethane, 100mL toluene and 0.5g are added in the 500mL four-hole bottle logical N respectively through regenerated ion exchange resin
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip the PCl of 21ml
3, in 20 minutes, dropwise, slowly be heated to 75 ℃ then, reacting balance is carried out.Behind the reaction 8h, add the 2,6 ditertiary butyl p cresol of 0.25mol then, be heated to 110 ℃, kept 10 hours, gained material filtered while hot, cooling, washing with alcohol is used in crystallization, and is dry under 110 ℃, obtains the 28g product.Show that by dsc analysis product purity can reach 99.2%.
Embodiment 6
The catalyzer that present embodiment uses is the catalyzer of catalyzer through regenerating and obtaining that uses among the embodiment 3, at first is washed till neutrality through overpickling, alkali cleaning and distilled water, can use after the vacuum-drying.
0.1mol tetramethylolmethane, 100mL toluene and 2.7g are added in the 500mL four-hole bottle logical N respectively through regenerated ion exchange resin
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip the PCl of 21ml
3, in 20 minutes, dropwise, slowly be heated to 75 ℃ then, reacting balance is carried out.Behind the reaction 10h, add the 2,6 ditertiary butyl p cresol of 0.3mol then, be heated to 110 ℃, kept 24 hours, gained material filtered while hot, cooling, washing with alcohol is used in crystallization, and is dry under 110 ℃, obtains the 39.7g product.Show that by dsc analysis product purity can reach 99.1%.
Claims (7)
1. the preparation method of a pentaerythritol phosphite oxidation inhibitor is characterized in that, it may further comprise the steps:
(1) synthetic dichloro pentaerythritol diphosphite: solvent, tetramethylolmethane, weak base type solid catalyst are added in the reactor, in anhydrous inert atmosphere with under stirring, dropwise add phosphorus trichloride in the reactor, be heated to 50～100 ℃ then gradually, reacted 2～10 hours, and obtained containing the reaction solution of dichloro pentaerythritol diphosphite; Wherein the add-on of weak base type solid catalyst is 1～20% of a tetramethylolmethane quality, the mol ratio of phosphorus trichloride and tetramethylolmethane is 2～5: 1, the add-on of solvent is 5～20ml/g tetramethylolmethane, and described weak base type solid catalyst is a weak base type macroporous ion exchange resin;
(2) synthesis of pentaerythritol phosphite antioxidant: the reaction solution that obtains to step (1) adds 2,6 ditertiary butyl p cresol, under agitation, is heated to 80～120 ℃, reacts 8～24 hours; The mol ratio of 2,6 ditertiary butyl p cresol and dichloro pentaerythritol diphosphite is 2～4: 1;
(3) post-reaction treatment: the reacting liquor while hot that step (2) obtains is filtered, cooling, crystallization, washing, drying obtains antioxidant product of the present invention.
2. preparation method according to claim 1 is characterized in that, solvent is an aproticapolar solvent described in the step (1).
3. preparation method according to claim 2, it is characterized in that, solvent described in the step (1) is benzene,toluene,xylene, ethylbenzene, propyl benzene, first and second benzene, isopropyl benzene, trimethylbenzene or two or more mixture in them, and described first and second benzene are o-methylethylbenzene, m-methyl ethylbenzene, p-methyl-ethylbenzene or their mixture.
4. preparation method according to claim 1 is characterized in that, weak base type solid catalyst described in the step (1) is that model is the weak base type macroporous ion exchange resin of D301 or D370.
5. preparation method according to claim 1 is characterized in that, in described step (1), solvent, tetramethylolmethane, weak base type solid catalyst is added in the reactor, is heated to 20～50 ℃, phosphorus trichloride is dropwise added in the reactor again.
6. preparation method according to claim 1 is characterized in that, washing described in the step (3) is extremely not contain 2,6 ditertiary butyl p cresol with ethanol or propyl alcohol washing.
7. preparation method according to claim 1 is characterized in that, drying described in the step (3) is to dry under 50～120 ℃ of temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023206791A1 (en) | 2022-04-26 | 2023-11-02 | 浙江新和成股份有限公司 | Method for preparing phosphorus-containing ligand |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206234B (en) * | 2007-10-26 | 2013-07-03 | 中国石油化工股份有限公司 | Preparation method of pentaerythritol diphosphite antioxidant |
| CN101418018B (en) * | 2007-10-26 | 2011-07-06 | 中国石油化工股份有限公司 | Method for preparing pentaerythritol bis-phosphite antioxidant |
| CN109503663B (en) * | 2018-12-25 | 2020-11-27 | 萧县新秀新材料有限公司 | Industrial production method of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226557A (en) * | 1998-02-20 | 1999-08-25 | 奇钛科技有限公司 | Liquid phosphorous antioxidant and use thereof |
| WO2004060900A1 (en) * | 2003-01-06 | 2004-07-22 | Teijin Chemicals Ltd. | Process for the production of pentaerythritol diphosphonates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226557A (en) * | 1998-02-20 | 1999-08-25 | 奇钛科技有限公司 | Liquid phosphorous antioxidant and use thereof |
| WO2004060900A1 (en) * | 2003-01-06 | 2004-07-22 | Teijin Chemicals Ltd. | Process for the production of pentaerythritol diphosphonates |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023206791A1 (en) | 2022-04-26 | 2023-11-02 | 浙江新和成股份有限公司 | Method for preparing phosphorus-containing ligand |
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