CN102206234A - Preparation method of pentaerythritol diphosphite antioxidant - Google Patents
Preparation method of pentaerythritol diphosphite antioxidant Download PDFInfo
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- CN102206234A CN102206234A CN2011100874774A CN201110087477A CN102206234A CN 102206234 A CN102206234 A CN 102206234A CN 2011100874774 A CN2011100874774 A CN 2011100874774A CN 201110087477 A CN201110087477 A CN 201110087477A CN 102206234 A CN102206234 A CN 102206234A
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Abstract
The invention relates to a preparation method of an antioxidant. The method comprises the following steps: pentaerythritol and phosphorus trichloride which are treated as raw materials are subjected to a cyclization reaction to prepare dichloro pentaerythritol diphosphite, dichloro pentaerythritol diphosphite is subjected to a substitution reaction with hindered phenol to prepare pentaerythritol diphosphite, pentaerythritol diphosphite is separated, washed, dried and pulverized to obtain the antioxidant product. According to the present invention, a technology of a one pot method is employed to prepare the antioxidant, a ratio of the raw materials for the cyclization reaction is controlled, the cyclizaiton reaction process is monitored through <31>P NMR, intermediate product separation and purification can be omitted, and the production cost can be reduced. The purity of the obtained antioxidant product is high, and the antioxidant has the advantages of good high temperature antioxidant performance and color protection capability in the application of polypropylene resin.
Description
The present invention is the dividing an application of 200710176407.X " a kind of preparation method of pentaerythritol bis-phosphite antioxidant " in October 26 2007 applying date.
Technical field
The present invention relates to a kind of polymer processing aids, be specifically related to a kind of preparation method of pentaerythritol bis-phosphite antioxidant.
Background technology
Oxidation inhibitor is the important auxiliary agent 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.Because traditional phosphite ester kind antioxidant; as three-(2; the 4-di-t-butyl) benzene phosphorous acid ester (commercial 168 oxidation inhibitor that are called); easy xanthochromia under hot conditions; limited it in the high temperature process field as the application in spinning processing field, the heat-resistant stable and the color and luster protective capability that improve phosphorous acid ester are oxidation inhibitor research and development focuses always.Pentaerythritol bis-phosphite antioxidant is a kind of high-efficiency anti-oxidant of excellent performance, because it has high melt point, distinctive sterically hindered in higher phosphorus content and the molecular structure, therefore can not only improve polymer processing stability, and has a good color stability, therefore heat-resistant stability and resistance to hydrolysis energy have good application prospects in macromolecular materials such as polyolefine, styrene resin, engineering thermoplastic resin, trevira.
Synthetic this kind antioxidant of bibliographical information is a basic raw material with tetramethylolmethane, phosphorus trichloride and hindered phenol all at present, adopts two-step approach synthetic.At first the reaction of tetramethylolmethane and phosphorus trichloride generates intermediate product dichloro diphosphites, and after separation was purified, intermediate product and hindered phenol reaction generated the oxidation inhibitor crude product, obtain the pure product of oxidation inhibitor again after separating purification.Because intermediate product need be purified by recrystallization or vacuum distilling, not only consumed energy, and yield descends.Patent EP356688 proposes a kind of preparation method of this oxidation inhibitor, with tetramethylolmethane, phosphorus trichloride and hindered phenol is raw material, the liquid tertiary amine compound is a catalyzer, adopt two-step process, after the purifying intermediate products, carry out the reaction of second step again, behind the reaction certain hour, filtration washing obtains antioxidant product under optimal temperature.This method purifying intermediate products complex process, yield is not high, and cost increases, and is not suitable for suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is:
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of preparation method of pentaerythritol bis-phosphite antioxidant, need not intermediate product and separate purification step, simplify production process, reduce cost.
Technical scheme of the present invention is:
A kind of preparation method of pentaerythritol bis-phosphite antioxidant, raw material comprises: tetramethylolmethane, phosphorus trichloride and hindered phenol; May further comprise the steps:
The 1st step, cyclization:
Phosphorus trichloride and tetramethylolmethane are added reactor, in molar ratio,
Phosphorus trichloride: tetramethylolmethane=2～2.2: 1
Add reaction solvent simultaneously, described reaction solvent is selected from least a in following: toluene, dimethylbenzene, benzene, chlorobenzene, methylene dichloride, ethyl acetate;
Under nitrogen protection, under amine cyclization catalyst action, 50 ℃～120 ℃ of temperature of reaction, reaction times 2h～10h generates the dichloro pentaerythritol diphosphite;
The cyclization process is:
Used amine cyclization catalyzer is known conventional products, use be the catalyzer of state of the art.Usually, described amine cyclization catalyzer is selected from a kind of in following: triethylamine, Tributylamine, pyridine, weak anion resin.
In the cyclization process, with nucleus magnetic resonance phosphorus spectrum
31P
NMRThe content of phosphorus trichloride in the analysis monitoring reactant can not detect phosphorus trichloride in reactant; Usually can or monitor once half an hour every one hour, also can adopt the non-uniform distantance cycle monitoring, long pitch time in early stage in reaction, the reaction later stage increases monitors.
By theoretical value, phosphorus trichloride should be 2 times of tetramethylolmethane, and during practical application, the phosphorus trichloride of adding is slightly excessive, owing to the stripping effect of nitrogen, after this season penta tetrol complete reaction, continues stripping again until the phosphorus trichloride completely dissolve in reaction process.This moment, phosphorus trichloride and tetramethylolmethane reacted completely, no longer contained phosphorus trichloride and tetramethylolmethane in the material.
The present invention does not need intermediate product dichloro pentaerythritol diphosphite is purified, but directly carries out substitution reaction in reactor.
Before the 2nd step, structural formula is added above-mentioned reactor for the hindered phenol of (II) formula, in molar ratio, hindered phenol: tetramethylolmethane=2～5: 1
In the formula: R
1Be hydrogen, primary amine or tertiary amine, R
2Be hydrogen, primary amine or tertiary amine, R
3Be hydrogen, primary amine or tertiary amine;
The raw material hindered phenol of substitution reaction need add reactor before the 2nd step of beginning, when adding the substitution reaction catalyzer, just began to carry out the 2nd step.
The 2nd step, substitution reaction:
A certain amount of amine substitution reaction catalyzer is added above-mentioned reactor, under nitrogen protection, 80 ℃～130 ℃ of temperature of reaction, reaction times 8h～24h, the generating structure formula is the pentaerythritol bis-phosphite of (I) formula;
In the formula: R
1Be hydrogen, primary amine or tertiary amine, R
2Be hydrogen, primary amine or tertiary amine, R
3Be hydrogen, primary amine or tertiary amine;
Used amine substitution reaction catalyzer is known conventional products, use be the catalyzer of state of the art.Usually, described amine substitution reaction catalyzer is selected from a kind of in following: triethylamine, Tributylamine.
The substitution reaction process is:
In the 3rd step, product separates:
To reacted material of the 2nd step, separate, wash, dry, pulverizing, obtain pentaerythritol bis-phosphite antioxidant.
Separation can have different modes, and a kind of mode is repeatedly to wash:
Described the 3rd step product separates, and may further comprise the steps:
The 3.1st step, under 80 ℃～130 ℃ temperature, product is filtered, remove liquid phase;
The 3.2nd step, solid product is mixed with cleaning solvent, described cleaning solvent is selected from least a in following: Virahol;
Press mass ratio, cleaning solvent: solid product=4～15: 1
Under 80 ℃～130 ℃ temperature, stir, solid product is washed;
The 3.3rd step, said mixture is carried out solid-liquid separation, adopt and filter or the centrifugation mode, obtain solid product; Filter with centrifugation and all adopt known usual manner in the industry.
Usually, the 3.2nd step and the 3.3rd step will carry out repeatedly repeatedly, and impurity is washed off fully by solvent.
The 3.4th step, the gained solid product is mixed with non-polar solvent, described non-polar solvent is selected from least a in following: normal hexane, normal heptane;
Press mass ratio, non-polar solvent: solid product=2～5: 1
Under ℃ temperature of room temperature～50, stir, solid product is washed;
Non-polar solvent can be washed polar solvent off, also can wash the non polar impurities in the product off.
The 3.5th step, said mixture is carried out solid-liquid separation, adopt and filter or the centrifugation mode, obtain solid product; Filter with centrifugation and all adopt known usual manner in the industry.
In the 3.6th step, products therefrom is carried out drying, 80 ℃～130 ℃ of drying temperatures; Through air-flow or mechanical disintegration, obtaining particle diameter is the pentaerythritol bis-phosphite antioxidant product of 0.2mm～0.5mm.
Air stream drying can directly produce crushing effect usually.If the use drying mode need carry out mechanical disintegration again, as ball mill etc.
Another kind of separate mode is a means re-crystallization:
Described the 3rd step product separates, and may further comprise the steps:
The 3.1st step, under 80 ℃～130 ℃ temperature, product is filtered, remove liquid phase;
The 3.2nd step, solid product is mixed with recrystallization solvent, described recrystallization solvent is selected from least a in following: toluene, dimethylbenzene, chlorobenzene;
Press mass ratio, recrystallization solvent: solid product=3～6: 1
Under 90 ℃～110 ℃ temperature, stir, solid product is dissolved;
In the 3.3rd step,,, obtain solid product after filtering liquid phase to the crystallization at room temperature of above-mentioned solution;
The 3.4th step, the gained solid product is mixed with non-polar solvent, described non-polar solvent is selected from least a in following: normal hexane, normal heptane;
Press mass ratio, non-polar solvent: solid product=2～5: 1
Under ℃ temperature of room temperature～50, stir, solid product is washed;
The 3.5th step, said mixture is carried out solid-liquid separation, adopt and filter or the centrifugation mode, obtain solid product;
In the 3.6th step, products therefrom is carried out drying, 80 ℃～130 ℃ of drying temperatures; Through air-flow or mechanical disintegration, obtaining particle diameter is the pentaerythritol bis-phosphite antioxidant product of 0.2mm～0.5mm.
Usually, the reaction solvent described in the 1st step is toluene, dimethylbenzene, chlorobenzene preferably, especially preferred toluene, dimethylbenzene.
The preferred toluene of recrystallization solvent described in the 3rd step.
The preferred normal hexane of non-polar solvent described in the 3rd step.
Described hindered phenol can add reactor simultaneously with phosphorus trichloride and tetramethylolmethane, and described hindered phenol also can add reactor after cyclization is finished.No matter whether hindered phenol exists when cyclization, can not react with intermediate product, has only after adding the substitution reaction catalyzer, just can react.
When industrial application, in the 1st step, can carry out according to known usual manner with the HCl tail gas of alkaline solution absorption reactor thermally discharge.
Described reaction solvent, cleaning solvent, recrystallization solvent all can recycle.Recycle design can be carried out according to industrial usual manner.
The invention has the beneficial effects as follows:
The present invention adopts one kettle way prepared pentaerythritol bis-phosphite antioxidant, accurately controls the first step reaction raw materials proportioning, by
31P
NMRThe analysis monitoring reaction process reacts completely tetramethylolmethane and phosphorus trichloride simultaneously, and intermediate product can be without separation, directly enter next step reaction, separate purification step owing to removed intermediate product from, therefore help production cost and reduce, be fit to suitability for industrialized production.The gained antioxidant product shows that through fusing point test, infrared analysis and ultimate analysis product purity is very high.In addition, the applicating evaluating in acrylic resin shows that oxidation inhibitor of the present invention has good high-temperature antioxygen property and color and luster protective capability.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1
With 1mol tetramethylolmethane, 2.5mol hindered phenol, 1000mL toluene solvant, add in the four-hole bottle of 5L, add the 0.5g pyridine as cyclization catalyst.Feed N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip PCl
3After dropwising, slowly be heated to 80 ℃, cyclization is steadily carried out.Behind the reaction 8h, adopt
31P
NMRThe analysis monitoring reaction process reacts completely simultaneously until tetramethylolmethane and phosphorus trichloride, adds the 1000mL triethylamine as replacing catalyzer, is heated to 110 ℃, keeps 10 hours.Gained material filtered while hot adds the 3256mL Virahol, is heated to 70 ℃ of stirrings, filters, and adds the 1321mL normal hexane then and stirs, filters, and obtains the 325g product after 90 ℃ of dryings of gained filter cake, and yield is 51.4%.
Embodiment 2
With the 1mol tetramethylolmethane, the 1000mL toluene solvant adds in the 5L four-hole bottle, adds the 0.65g weak anion resin as cyclization catalyst.Feed N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip PCl
3After dropwising, slowly be heated to 80 ℃, cyclization is steadily carried out.Behind the reaction 5h, adopt
31P
NMRThe analysis monitoring reaction process reacts completely simultaneously until tetramethylolmethane and phosphorus trichloride.Add 2 of 2.2mol then, the 6-ditertbutylparacresol adds the 800mL Tributylamine simultaneously as replacing catalyzer, is heated to 110 ℃, kept 10 hours, gained material filtered while hot adds toluene then and is heated to boiling, crystallizing at room temperature, filtration, filter cake adds the normal heptane washing, after the filtration, obtain the 372g product behind the gained filtration cakes torrefaction, yield is 58.9%.
Embodiment 3
1mol tetramethylolmethane, 1000mL toluene solvant are added in the 5L four-hole bottle, add the 0.5g pyridine as cyclization catalyst.Feed N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip PCl
3After dropwising, slowly be heated to 80 ℃, cyclization is steadily carried out.Behind the reaction 8h, adopt
31P
NMRThe analysis monitoring reaction process reacts completely simultaneously until tetramethylolmethane and phosphorus trichloride.Add 2 of 4mol then, the 4-di-tert-butylphenol adds triethylamine simultaneously as replacing catalyzer, is heated to 120 ℃, kept 10 hours, gained material filtered while hot adds dimethylbenzene and is heated to boiling, crystallizing at room temperature, filtration, filter cake adds the normal heptane washing, after the filtration, obtain the 384g product behind the gained filtration cakes torrefaction, yield 63.8%.
Embodiment 4
1mol tetramethylolmethane, 1000mL toluene solvant are added in the 5L four-hole bottle, add the 0.5g pyridine as cyclization catalyst.Feed N
2, to open and stir, heating in water bath when homo(io)thermism is 50 ℃, begins to drip PCl
3After dropwising, slowly be heated to 85 ℃, cyclization is steadily carried out.Behind the reaction 8h, adopt
31P
NMRThe analysis monitoring reaction process reacts completely simultaneously until tetramethylolmethane and phosphorus trichloride.Add 2 of 4mol then, the 6-ditertbutylparacresol adds Tributylamine simultaneously as replacing catalyzer, is heated to 120 ℃, kept 10 hours, gained material filtered while hot adds the 3956mL Virahol, is heated to 60 ℃ of stirrings, filter, add the 2325mL normal hexane then and stir, filter, obtain the 445g product after 85 ℃ of dryings of gained filter cake, yield is 70.5%.
Application examples 1
Polypropylene powder and oxidation inhibitor of the present invention are mixed in high-speed mixer with the massfraction in the prescription and other an amount of auxiliary agent, use the single screw extrusion machine extruding pelletization, the single screw extrusion machine screw speed is 80 rev/mins, the material melt temperature is 260 ℃, by above condition extruding pelletization, extrude through 7 times screw rods so repeatedly, get 1,3,5,7 time pellet and survey its melt flow rate (MFR).The gained result is as shown in the table.
Table 1 difference is extruded the melt polypropylene flow rate value (g/10min) of number of times
| Number of times | Blank sample | Oxidation inhibitor sample of the present invention |
| 1 | 10.3 | 4.86 |
| 3 | 28.8 | 5.52 |
| 5 | 56.0 | 6.47 |
| 7 | Can't measure too greatly | 7.88 |
Application examples 2
Temperature is injected into the standard batten up to gained polypropylene granules under 260 ℃ of conditions, its aging prescription is: polypropylene powder is 100 parts, 1010 is 0.01 part, 0.1 part of calcium stearate, 0.1 part in 168 oxidation inhibitor or oxidation inhibitor of the present invention are placed on respectively in 150 ℃ of thermal ageing baking ovens, make it be subjected to the effect of heat and oxygen simultaneously, measure the initial efflorescence time, the gained result is as shown in table 2.
The initial efflorescence time (h) of the aging back of table 2 polypropylene
| Blank sample | 168 oxidation inhibitor samples | Oxidation inhibitor sample of the present invention |
| 16 | 182 | 358 |
Claims (6)
1. the preparation method of a pentaerythritol bis-phosphite antioxidant, raw material comprises: tetramethylolmethane, phosphorus trichloride and hindered phenol; It is characterized in that, may further comprise the steps:
The 1st step, cyclization:
Phosphorus trichloride and tetramethylolmethane are added reactor, in molar ratio,
Phosphorus trichloride: tetramethylolmethane=2～2.2: 1
Add reaction solvent simultaneously, described reaction solvent is selected from least a in following: toluene, dimethylbenzene, benzene, chlorobenzene, methylene dichloride, ethyl acetate;
Under nitrogen protection, under amine cyclization catalyst action, 50 ℃～120 ℃ of temperature of reaction, reaction times 2h～10h generates the dichloro pentaerythritol diphosphite;
In the cyclization process, the content with phosphorus trichloride in the nucleus magnetic resonance phosphorus spectrum analysis monitoring reactant can not detect phosphorus trichloride in reactant;
Before the 2nd step, structural formula is added above-mentioned reactor for the hindered phenol of (II) formula, in molar ratio, hindered phenol: tetramethylolmethane=2～5: 1
In the formula: R
1Be hydrogen, primary amine or tertiary amine, R
2Be hydrogen, primary amine or tertiary amine, R
3Be hydrogen, primary amine or tertiary amine;
The 2nd step, substitution reaction:
A certain amount of amine substitution reaction catalyzer is added above-mentioned reactor, under nitrogen protection, 80 ℃～130 ℃ of temperature of reaction, reaction times 8h～24h, the generating structure formula is the pentaerythritol bis-phosphite of (I) formula;
In the formula: R
1Be hydrogen, primary amine or tertiary amine, R
2Be hydrogen, primary amine or tertiary amine, R
3Be hydrogen, primary amine or tertiary amine;
In the 3rd step, product separates, and may further comprise the steps:
The 3.1st step, under 80 ℃～130 ℃ temperature, the 2nd product that goes on foot is filtered, remove liquid phase;
The 3.2nd step, the solid product after filtering is mixed with recrystallization solvent, described recrystallization solvent is selected from least a in following: toluene, dimethylbenzene, chlorobenzene;
Press mass ratio, recrystallization solvent: the solid product after the filtration=3～6: 1
Under 90 ℃～110 ℃ temperature, stir, with the solid product dissolving after filtering;
In the 3.3rd step,,, obtain the solid product behind the recrystallization after filtering liquid phase to the crystallization at room temperature of above-mentioned solution;
The 3.4th step, the solid product behind the gained recrystallization is mixed with non-polar solvent, described non-polar solvent is selected from least a in following: normal hexane, normal heptane;
Press mass ratio, non-polar solvent: the solid product behind the recrystallization=2～5: 1
Under ℃ temperature of room temperature～50, stir, the solid product behind the recrystallization is washed;
The 3.5th step, said mixture is carried out solid-liquid separation, adopt and filter or the centrifugation mode, obtain through the solid product after recrystallization and the washing;
In the 3.6th step, the solid product after gained process recrystallization and the washing is carried out drying, 80 ℃～130 ℃ of drying temperatures; Through air-flow or mechanical disintegration, obtaining particle diameter is the pentaerythritol bis-phosphite antioxidant product of 0.2mm～0.5mm.
2. the preparation method of pentaerythritol bis-phosphite antioxidant according to claim 1 is characterized in that:
Reaction solvent described in the 1st step is selected from least a in following: toluene, dimethylbenzene, chlorobenzene.Preferred toluene, dimethylbenzene.
3. the preparation method of pentaerythritol bis-phosphite antioxidant according to claim 1 is characterized in that:
Non-polar solvent described in the 3rd step is a normal hexane.
4. the preparation method of pentaerythritol bis-phosphite antioxidant according to claim 1 is characterized in that:
Recrystallization solvent described in the 3rd step is a toluene.
5. according to the preparation method of the described pentaerythritol bis-phosphite antioxidant of one of claim 1 to 4, it is characterized in that:
In the 1st step, with the HCl tail gas of alkaline solution absorption reactor thermally discharge.
6. according to the preparation method of the described pentaerythritol bis-phosphite antioxidant of one of claim 1 to 4, it is characterized in that:
Described reaction solvent, recrystallization solvent all recycle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204879A (en) * | 2013-02-21 | 2013-07-17 | 吉林市吉溧化工有限责任公司 | Synthesis process of phosphate flame retardant |
| CN109503663A (en) * | 2018-12-25 | 2019-03-22 | 萧县新秀新材料有限公司 | A kind of industrialized preparing process of bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol phosphites |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968188A (en) * | 1974-02-04 | 1976-07-06 | Monsanto Company | Process for preparing the pentaerythritol ester of phosphorohalidous acid |
| CN1948319A (en) * | 2005-10-10 | 2007-04-18 | 中国石油化工股份有限公司 | Preparation method of tetramethylomethane phosphite ester antioxidant |
-
2007
- 2007-10-26 CN CN 201110087477 patent/CN102206234B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968188A (en) * | 1974-02-04 | 1976-07-06 | Monsanto Company | Process for preparing the pentaerythritol ester of phosphorohalidous acid |
| CN1948319A (en) * | 2005-10-10 | 2007-04-18 | 中国石油化工股份有限公司 | Preparation method of tetramethylomethane phosphite ester antioxidant |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204879A (en) * | 2013-02-21 | 2013-07-17 | 吉林市吉溧化工有限责任公司 | Synthesis process of phosphate flame retardant |
| CN109503663A (en) * | 2018-12-25 | 2019-03-22 | 萧县新秀新材料有限公司 | A kind of industrialized preparing process of bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol phosphites |
| 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 |
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