CN1948321B - Preparation method of bis(2,4-dicumylphenyl)pentaerythritol bisphosphite - Google Patents
Preparation method of bis(2,4-dicumylphenyl)pentaerythritol bisphosphite Download PDFInfo
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- CN1948321B CN1948321B CN2005100303931A CN200510030393A CN1948321B CN 1948321 B CN1948321 B CN 1948321B CN 2005100303931 A CN2005100303931 A CN 2005100303931A CN 200510030393 A CN200510030393 A CN 200510030393A CN 1948321 B CN1948321 B CN 1948321B
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- Prior art keywords
- dicumylphenyl
- phenol
- reaction
- jiajibianji
- bis
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZRXYYPBERCJDHZ-UHFFFAOYSA-N 1,1-bis[2,4-bis(2-phenylpropan-2-yl)phenyl]-2,2-bis(hydroxymethyl)propane-1,3-diol phosphorous acid Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C1=CC=CC=C1)C1=C(C=CC(=C1)C(C)(C)C1=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C1=CC=CC=C1)C(C)(C)C1=CC=CC=C1 ZRXYYPBERCJDHZ-UHFFFAOYSA-N 0.000 title abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- JBTXGEJRJCNRLU-UHFFFAOYSA-N [2-(dihydroxyphosphanyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] dihydrogen phosphite Chemical class OP(O)OCC(CO)(CO)COP(O)O JBTXGEJRJCNRLU-UHFFFAOYSA-N 0.000 claims description 15
- 229940059574 pentaerithrityl Drugs 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000011175 product filtration Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000005660 chlorination reaction Methods 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- FMUYQRFTLHAARI-UHFFFAOYSA-N 2,4-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 FMUYQRFTLHAARI-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000003292 diminished effect Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Abstract
本发明公开了一种双(2，4-二枯基苯基)季戊四醇双亚磷酸酯的制备方法。将2，4-双-(α，α-二甲基苄基)苯酚加入反应溶剂甲苯中，在催化剂，氮气的存在下，与三氯化磷进行氯化反应，与季戊四醇进行缩合反应，获得本发明的目标产物。用本发明制备方法得到的双(2，4-二枯基苯基)季戊四醇双亚磷酸酯，纯度达到98％以上，产率为87-89％。本发明与现有技术相比，具有反应时间短，产率提高，成本降低，产品纯度高的优点，适于工业化生产。The invention discloses a preparation method of bis(2,4-dicumylphenyl)pentaerythritol bisphosphite. 2,4-bis-(α,α-dimethylbenzyl)phenol is added to the reaction solvent toluene, and in the presence of catalyst and nitrogen, chlorination reaction is carried out with phosphorus trichloride, and condensation reaction is carried out with pentaerythritol to obtain The target product of the present invention. The bis(2,4-dicumylphenyl)pentaerythritol bisphosphite obtained by the preparation method of the invention has a purity of over 98% and a yield of 87-89%. Compared with the prior art, the present invention has the advantages of short reaction time, increased yield, reduced cost and high product purity, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites.
Background technology
Two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphite is a kind of antioxidant that is used for polymkeric substance, especially can be used as the antioxidant of preparation macromolecular material.Its structural formula is as follows:
In the prior art; disclosed preparation method is with 2 in PCT patent application (WO 94/170824); 4-pair-(α; α-Er Jiajibianji) phenol is raw material, adds catalyzer trolamine and reaction solvent, under protection of nitrogen gas; carry out chlorination reaction with phosphorus trichloride; carry out condensation reaction with tetramethylolmethane, obtain two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites.
The method of this patent report, the reaction times needs more than ten hours, adopts toluene and normal heptane as reaction solvent, and solvent consumption is big, reclaims difficulty, the cost height, productive rate is low.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites, to overcome long reaction time in the prior art, solvent load is big, cost height, the deficiency that productive rate is low.
Technical conceive of the present invention:
With 2,4-pair-(α, α-Er Jiajibianji) phenol adds in the reaction solvent toluene, at catalyzer, under the existence of nitrogen, carry out chlorination reaction with phosphorus trichloride, carry out condensation reaction with tetramethylolmethane, obtain two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites.
Method of the present invention is carried out according to following steps:
With 2,4-is two-and (α, α-Er Jiajibianji) phenol, catalyzer adds in the reaction solvent toluene, feeds nitrogen, be warming up to 70-80 ℃, drip phosphorus trichloride, reacted 1-2 hour, be cooled to 20-30 ℃, add tetramethylolmethane, reaction is 2-4 hour under 35-55 ℃ the condition, collects two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites of target product from reaction product.
According to the present invention, said catalyzer is a tetramethyl ammonium chloride; Reactant 2, the mass ratio of 4-pair-(α, α-Er Jiajibianji) phenol and catalyzer is 1000: 2-5; The weightmeasurement ratio of reactant and toluene solvant is 1: 1.0-2.0g/mL.
The consumption of phosphorus trichloride is 2,4-pair-(α, α-Er Jiajibianji) phenol: phosphorus trichloride=1: 1.0-1.5 mol ratio.The consumption of tetramethylolmethane is 2,4-pair-(α, α-Er Jiajibianji) phenol: tetramethylolmethane=1: 0.5-0.7 mol ratio.
Collect two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites of target product and comprise the steps: the reaction product filtration from reaction product, use absolute ethanol washing, the white solid that obtains is target product of the present invention.
Reaction formula of the present invention is as follows:
Raw material 2 used in the present invention, 4-pair-(α, α-Er Jiajibianji) phenol can prepare according to U.S. Pat 4275004 reported method.
With two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites that preparation method of the present invention obtains, purity reaches more than 98%, productive rate 87%-89%, fusing point 229.2-231.6 ℃ (the Aldrich melting point values is 229-232 ℃).
Good with catalyzer tetramethyl ammonium chloride selectivity of the present invention, the reaction times is short, uses the single reaction solvent to be easy to reclaim, and cost reduces, compared with prior art, have the reaction times weak point, productive rate improves, cost reduces, and the advantage that product purity is high is suitable for suitability for industrialized production.
Embodiment
Below by embodiment the invention will be further described the present invention, but embodiment does not limit protection scope of the present invention.
Embodiment 1
In the reactor that has stirring, thermometer, add 2 respectively, 4-pair-(α, α-Er Jiajibianji) phenol 165.2g (0.5mol), tetramethyl ammonium chloride 0.6g, toluene 220ml, stirring and dissolving, logical N
2Protection; be warming up to 70-75 ℃; drip phosphorus trichloride 68.7g (0.5mol); with the hydrogen chloride gas of emitting in the 40%NaOH alkaline solution absorption reaction; reacted 1.5 hours, cooling, controlled temperature is at 20-30 ℃; add tetramethylolmethane 40.8g (0.3mol); 40-45 ℃ was reacted 3 hours cooling, reaction product filtration under diminished pressure down; filter cake 20ml absolute ethanol washing; obtain two (2, the 4-dicumylphenyl) the pentaerythritol bis-phosphite 189.2g of white solid product, productive rate 88.7%; purity 98.8% (HPLC), fusing point: 229.7-231.3 ℃.
Embodiment 2
In the reactor that has stirring, thermometer, add 2 respectively, 4-pair-(α, α-Er Jiajibianji) phenol 165.2g (0.5mol), tetramethyl ammonium chloride 0.5g, toluene 260ml, stirring and dissolving, logical N
2Protection; be warming up to 75-80 ℃; drip phosphorus trichloride 82.4g (0.6mol); with the hydrogen chloride gas of emitting in the 40%NaOH alkaline solution absorption reaction; reacted cooling, controlled temperature 20-30 ℃ 2 hours; add tetramethylolmethane 34.1g (0.25mol); 35-40 ℃ was reacted 3.5 hours cooling, reaction product filtration under diminished pressure down; filter cake 20ml absolute ethanol washing; obtain two (2, the 4-dicumylphenyl) the pentaerythritol bis-phosphite 187.3g of white solid product, productive rate 87.8%; purity 98.5% (HPLC), fusing point: 229.4-231.4 ℃.
Embodiment 3
In the reactor that has stirring, thermometer, add 2 respectively, 4-pair-(α, α-Er Jiajibianji) phenol 165.2g (0.5mol), tetramethyl ammonium chloride 0.7g, toluene 300ml, stirring and dissolving, logical N
2Protection is warming up to 70-75 ℃, drips phosphorus trichloride 96.1g (0.7mol); with the hydrogenchloride of emitting in the 40%NaOH alkaline solution absorption reaction, reacted cooling 1 hour; controlled temperature 20-30 ℃ adds tetramethylolmethane 38.1g (0.28mol), and 40-45 reacted 2 hours down, cooling; the reaction product filtration under diminished pressure; filter cake 20ml absolute ethanol washing obtains two (2, the 4-dicumylphenyl) the pentaerythritol bis-phosphite 186.0g of white solid product; productive rate 87.2%, purity 98.3% (HPLC).Fusing point: 229.2-231.6 ℃.
Claims (7)
1. the preparation method of two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites is characterized in that comprising the steps:
With 2,4-is two-and (α, α-Er Jiajibianji) phenol, catalyzer adds in the reaction solvent toluene, feeds nitrogen, be warming up to 70-80 ℃, drip phosphorus trichloride, reacted 1-2 hour, be cooled to 20-30 ℃, add tetramethylolmethane, reaction is 2-4 hour under 35-55 ℃ the condition, collects two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphites of target product from reaction product.
2. method according to claim 1 is characterized in that said catalyzer is a tetramethyl ammonium chloride.
3. method according to claim 1 is characterized in that, 2, and the mass ratio of 4-pair-(α, α-Er Jiajibianji) phenol and catalyzer is 1000: 2-5.
4. method according to claim 1 is characterized in that, 2, and the weightmeasurement ratio of 4-pair-(α, α-Er Jiajibianji) phenol and toluene solvant is 1: 1.0-2.0g/mL.
5. method according to claim 1, the consumption that it is characterized in that phosphorus trichloride is 2,4-pair-(α, α-Er Jiajibianji) phenol: phosphorus trichloride=1: 1.0-1.5 mol ratio.
6. method according to claim 1, the consumption that it is characterized in that tetramethylolmethane is 2,4-pair-(α, α-Er Jiajibianji) phenol: tetramethylolmethane=1: 0.5-0.7 mol ratio.
7. according to each described method of claim 1-6, it is characterized in that, from reaction product, collect target product two (2, the 4-dicumylphenyl) pentaerythritol bis-phosphite comprises the steps: the reaction product filtration, use absolute ethanol washing, the white solid that obtains is target product of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005100303931A CN1948321B (en) | 2005-10-11 | 2005-10-11 | Preparation method of bis(2,4-dicumylphenyl)pentaerythritol bisphosphite |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2005100303931A CN1948321B (en) | 2005-10-11 | 2005-10-11 | Preparation method of bis(2,4-dicumylphenyl)pentaerythritol bisphosphite |
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| Publication Number | Publication Date |
|---|---|
| CN1948321A CN1948321A (en) | 2007-04-18 |
| CN1948321B true CN1948321B (en) | 2010-04-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2005100303931A Expired - Fee Related CN1948321B (en) | 2005-10-11 | 2005-10-11 | Preparation method of bis(2,4-dicumylphenyl)pentaerythritol bisphosphite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104403290B (en) * | 2014-11-28 | 2016-06-22 | 上海锦湖日丽塑料有限公司 | The PC/ABS Alloy And Preparation Method that a kind of weather resistance is excellent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137798A (en) * | 1993-08-30 | 1996-12-11 | 多弗化学公司 | Hydrolytically stable pentaerythritol diphosphite |
| US5919966A (en) * | 1998-03-26 | 1999-07-06 | General Electric Company | Process for the preparation of spiro bis-phosphites |
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- 2005-10-11 CN CN2005100303931A patent/CN1948321B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137798A (en) * | 1993-08-30 | 1996-12-11 | 多弗化学公司 | Hydrolytically stable pentaerythritol diphosphite |
| US5919966A (en) * | 1998-03-26 | 1999-07-06 | General Electric Company | Process for the preparation of spiro bis-phosphites |
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| Publication number | Publication date |
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| CN1948321A (en) | 2007-04-18 |
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Granted publication date: 20100428 Termination date: 20121011 |