CN101613261B - Method for synthesizing bisphenol A ethoxy compound - Google Patents
Method for synthesizing bisphenol A ethoxy compound Download PDFInfo
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- CN101613261B CN101613261B CN2009101832841A CN200910183284A CN101613261B CN 101613261 B CN101613261 B CN 101613261B CN 2009101832841 A CN2009101832841 A CN 2009101832841A CN 200910183284 A CN200910183284 A CN 200910183284A CN 101613261 B CN101613261 B CN 101613261B
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- bisphenol
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- bpa
- dihydroxyphenyl propane
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- MRJVFSASLCFQCI-UHFFFAOYSA-N CC(C)(CCO)Oc1ccc(C(C)(C)c(cc2)ccc2OCCO)cc1 Chemical compound CC(C)(CCO)Oc1ccc(C(C)(C)c(cc2)ccc2OCCO)cc1 MRJVFSASLCFQCI-UHFFFAOYSA-N 0.000 description 1
- LIPGWDOITZWUEA-UHFFFAOYSA-N CC(C)(c(cc1)ccc1O)C(C=C1)=CCC1O Chemical compound CC(C)(c(cc1)ccc1O)C(C=C1)=CCC1O LIPGWDOITZWUEA-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a method for synthesizing a bisphenol A ethoxy compound, which comprises the following steps: adding bisphenol A and a catalyst of dimethyl aminoethanol into a reactor, raising the temperature to a reaction temperature of between 110 and 125 DEG C by stirring and the protection of inert gas; and adding epoxyethane into the mixture to react at a pressure of between 0.1 and 0.35 MPa for 1 to 20 hours to prepare the bisphenol A ethoxy compound. The reaction equation is shown as follows, wherein n is between 1 and 5. The method achieves the solid polymerization of the bisphenol A and the epoxyethane, and selects the novel dimethyl aminoethanol as the catalyst so that the product is free from postprocessing. The product of the bisphenol A ethoxy compound has the advantages of shallow color phase which ranges from 10 to 30, no existence of metallic ions, 0.05 to 0.1 ppm of peroxide and the like.
Description
Technical field
The invention belongs to the synthetic field of new of organic chemistry, be specifically related to a kind of compound method of bisphenol A ethoxy verivate.
Background technology
The ethoxylation bis-phenol comprises BPA-2EO, BPA-4EO and BPA-10EO; Can prepare BPA (2EO) DA, BPA (4EO) DA and BPA (10EO) DA raw material respectively through acroleic acid esterification, be applied to the reactive monomer thinner of UV radiation curing.As the new technology of a fast development, the UV radiation curing technology has a wide range of applications like: microelectronics industry, PCB circuit card, aerospace, seal paper money, high-end aspect such as civilian at many high-technology fields; As in performance unique advantage aspect the sharp microelectronic component of height, top coat is controlled in the 30-300 nanometer, and it has erosion resistance, good wear-resisting wiping mechanical property, thermotolerance; Energy-conserving and environment-protective.Excellent greatly as in conventional solvent based coating and printing ink goods because of UV radiation curing product performance index, the UV uv radiation curing industry of China has obtained tremendous development in recent years, is just getting into the fast-developing phase at present.
Be that the compound method that raw material carries out ethoxylation mainly contains following two kinds with the dihydroxyphenyl propane:
First kind is that solid material and catalyzer are added in the reaction kettle, under protection of inert gas, is heated to the fusing point of material again with steam or oil bath, and then starts stirring; Add EO gradually, accomplish predetermined charging capacity, after reaction is improved, carry out the subsequent disposal operation according to designed molecules amount or mole number.The maximum shortcoming of this method is that the melting process temperature is uncontrollable; The solid materials melting process is to be abutted against nearly still wall high-temperature zone slowly to conduct heat, and this inhomogeneous meeting of being heated makes the material at the still wall produce thermolysis, particularly to the material such as the dihydroxyphenyl propane of poor heat stability; 180 ℃ of decomposition temperatures; The resolvent easy coloring forms superoxide, and under its melting temperature (Tm), reacts with EO, has exceeded the most appropriate temperature of reaction.Have a strong impact on the index such as color and luster, purity of additive derivative finished product.
Second method is with The suitable solvent starting material to be dissolved, and this solvent is good to the solidifying substance solvability, moderate boiling point and do not produce reaction with EO, and reaction after finishing is recycled solvent removal; The aftertreatment of carrying out subsequent step again is refining.The advantage of present method is to avoid material to cross thermolysis; Reducing temperature of reaction makes production process controlled.Shortcoming is to reclaim material consumption and the energy consumption increasing that solvent brings, and causes the increase of production cost.
Summary of the invention
The objective of the invention is to be to overcome the deficiency of above two kinds of prior arts, provide a kind of production technique simple, can obtain the compound method of high-quality bisphenol A ethoxy product.
The object of the invention can reach through following measure:
A kind of compound method of bisphenol A ethoxy compound; Dihydroxyphenyl propane and catalyzer dimethylaminoethanol are added in the reaction vessel; Be warming up to 110 ℃～125 ℃ of temperature of reaction in protection of inert gas and under stirring; Adding oxyethane then, is to react 1～20 hour under 0.1～0.35MPa at pressure, makes bisphenol A ethoxy compound; Its reaction equation is following:
The dihydroxyphenyl propane bisphenol A polyethenoxy ether
Wherein, n is 1～5.
The consumption of oxyethane is 1.8～11.5 times of dihydroxyphenyl propane molar weight among the present invention, is preferably 2～11 times.The consumption of catalyzer dimethylaminoethanol is 0.1 ‰～5 ‰ of dihydroxyphenyl propane and an oxyethane total mass, is preferably 1 ‰～5 ‰.Temperature of reaction is preferably 110 ℃～120 ℃.Rare gas element is selected nitrogen or helium etc.Pressure during reaction is preferably on normal pressure and be no more than 0.35MPa (pressure is greater than 0.1MPa and smaller or equal to 0.35MPa).
Stirring velocity when dihydroxyphenyl propane and the intensification of catalyzer dimethylaminoethanol is 30～100 rev/mins.Stirring velocity when when adding oxyethane or after adding oxyethane, reacting is 100～500 rev/mins, is preferably 100～180 rev/mins.
A kind of more concrete preparing method's method of the present invention is: earlier dihydroxyphenyl propane is added in the reaction kettle; Add catalyzer DMEA, under protection of inert gas, with the motor that the frequency modulation rotating speed is housed; Set motor speed; The beginning heat temperature raising drips EO in advance to reacting temperature required, and temperature is controlled at (as 110 ℃～125 ℃) about 120 ℃; Pressure is no more than 0.35Mpa.When temperature raises comparatively obviously, can accelerate rate of feeding, when adding the EO mol ratio, transfer that fast motor speed is the highest to be no more than 180 rev/mins at 1mol; Charging capacity until accomplishing design stops to feed in raw material.Keep temperature of reaction then, reaction keep-ups pressure and steadily accomplishes to reaction, is depressurized near being cooled to 80 ℃ behind the original pressure, under this temperature, removes remaining a spot of EO, gets into follow-up cooling discharge operation then.
This patent uses frequency modulation motor to stir; Add solid particulate raw material dihydroxyphenyl propane and DMEA catalyzer, start stirring at low speed in advance, stirring velocity is along with the increasing of charging capacity improves gradually; Suggestion is added to mole number in the time of 1: 1, the raising stirring velocity when dihydroxyphenyl propane and oxyethane ratio.Present method makes catalyzer and solid alcohol uniform mixing, avoids because of the irregular material decomposing phenomenon that takes place that is heated.120 ℃ of optimum temperature of reaction, the even polymerization of completion and EO, reaction pressure is controlled at and is no more than 0.35Mpa.Preparation gained verivate color and luster is good under this condition, productive rate is high, selectivity good.Narrow molecular weight distribution, non-metallic ion.
Bisphenol A polyethenoxy ether product of the present invention (like BPA-2EO, BPA-4EO, BPA-6EO, BPA-8EO, BPA-10EO) is liquid, and therefore post-processing steps such as the separation of reaction back end product, collection are simple.
The UV radiation curing that present method can make (coating, printing ink) bisphenol A ethoxy propylene ester raw material monomer---the bisphenol A ethoxy verivate of molecular weight in 316～670 scopes.This method makes solid dihydroxyphenyl propane (BPA, fusing point 150-152 ℃) and oxyethane (EO) realize solid polymerization; And selected novel dimethylaminoethanol (DMEA) as catalyzer, product does not need aftertreatment.It is shallow that product of the present invention has form and aspect, in the 10-30 scope (GB/T605); Non-metallic ion; Superoxide is in advantages such as 0.05-0.1ppm.
Embodiment
Below in conjunction with specific examples, further specify the present invention:
Embodiment 1: bisphenol A polyethenoxy ether, the polymerization degree are 4, the preparation of BPA-4EO.
Reaction formula is following:
This instance is typical bisphenol A polyethenoxy ether; Called after BPA-4EO, this product produce bisphenol A polyethenoxy ether diacrylate, english abbreviation 4EOBPDA behind acroleic acid esterification; The BPA-4EO proportioning is mole number BPA: EO=1: 4, and hydroxyl value requires 280 ± 10mgKOH/g.
Earlier 1000 gram dihydroxyphenyl propanes and 2 gram dimethylaminoethanols are added in the reaction kettle; Under nitrogen protection, set 50 rev/mins of frequency modulation motor rotating speeds then, with 120 ℃ of addings of carrying out EO of steam heating intensification; After dropping into 190 gram EO, stirring velocity is brought up to 180 rev/mins gradually.Accomplish until EO being thrown, guarantee that temperature is no more than 120 ℃ to 763 grams; Pressure is no more than 0.35Mpa, reacts 4.5 hours, makes BPA4EO, yield 97.5%, products obtained therefrom hydroxyl value 283mgKOH/g, look numbers No. 20, superoxide 0.08ppm.
Embodiment 2: bisphenol A polyethenoxy ether, the polymerization degree are 6, the preparation of BPA-6EO.
Reaction formula is following:
This instance is typical bisphenol A polyethenoxy ether; Called after BPA-6EO, this product produce bisphenol A polyethenoxy ether diacrylate, english abbreviation 6EOBPDA behind acroleic acid esterification; The BPA-6EO proportioning is mole number BPA: EO=1: 6, and hydroxyl value requires 230 ± 10mgKOH/g.
Earlier 800 gram dihydroxyphenyl propanes and 2.6 gram dimethylaminoethanols are added in the reaction kettle; Under nitrogen protection, set 50 rev/mins of frequency modulation motor rotating speeds then, with 120 ℃ of addings of carrying out EO of steam heating intensification; After dropping into 154 gram EO, stirring velocity is brought up to 180 rev/mins gradually.Accomplish until EO being thrown, guarantee that temperature is no more than 120 ℃ to 926 grams; Pressure is no more than 0.35Mpa, reacts 6 hours, makes BPA6EO, yield 98%, products obtained therefrom hydroxyl value 233mgKOH/g, look numbers No. 30, superoxide 0.1ppm.
Embodiment 3: bisphenol A polyethenoxy ether, the polymerization degree are 10, the preparation of BPA-10EO.
Reaction formula is following:
This instance is 10 moles of products of bisphenol A polyethenoxy ether; Called after BPA-10EO, this product produce bisphenol A polyethenoxy ether diacrylate, english abbreviation 10EOBPDA behind acroleic acid esterification; Proportioning is mole number BPA: EO=1: 10, and hydroxyl value requires 170 ± 10mgKOH/g.
Earlier 600 gram dihydroxyphenyl propanes and 5.3 gram dimethylaminoethanols are added in the reaction kettle; Under nitrogen protection, set 50 rev/mins of frequency modulation motor rotating speeds then, with 115 ℃ of addings of carrying out EO of steam heating intensification; After dropping into 110 gram EO, stirring velocity is brought up to 180 rev/mins gradually.Accomplish until EO being thrown, guarantee that temperature is no more than 120 ℃ to 1158 grams; Pressure is no more than 0.35Mpa, reacts 8 hours, makes BPA10EO, yield 98%, products obtained therefrom hydroxyl value 172mgKOH/g, look numbers No. 30, superoxide 0.08ppm.
Claims (4)
1. the compound method of a bisphenol A ethoxy compound; It is characterized in that dihydroxyphenyl propane and catalyzer dimethylaminoethanol are added in the reaction vessel; Be warming up to 110 ℃～125 ℃ of temperature of reaction in protection of inert gas and under stirring; Adding oxyethane then, is to react 1～20 hour under 0.1～0.35MPa at pressure, makes bisphenol A ethoxy compound; Stirring velocity when wherein dihydroxyphenyl propane and catalyzer dimethylaminoethanol heat up is 30～100 rev/mins, and the stirring velocity when reacting when adding oxyethane or behind the adding oxyethane is 100～500 rev/mins; Its reaction equation is following:
Wherein, n is 1～5.
2. compound method according to claim 1, the consumption that it is characterized in that described oxyethane are 1.8～11.5 times of dihydroxyphenyl propane molar weight.
3. compound method according to claim 1, the consumption that it is characterized in that described catalyzer dimethylaminoethanol are 0.1 ‰～5 ‰ of dihydroxyphenyl propane and oxyethane total mass.
4. compound method according to claim 1 is characterized in that described temperature of reaction is 110 ℃～120 ℃.
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| CN2009101832841A CN101613261B (en) | 2009-07-30 | 2009-07-30 | Method for synthesizing bisphenol A ethoxy compound |
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| CN2009101832841A CN101613261B (en) | 2009-07-30 | 2009-07-30 | Method for synthesizing bisphenol A ethoxy compound |
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| CN101613261B true CN101613261B (en) | 2012-05-23 |
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| CN102320936A (en) * | 2011-09-28 | 2012-01-18 | 宜兴市宏博乳化剂有限公司 | Synthesis method for pentaerythritol ethyoxyl or propyl compound |
| EP3070149B1 (en) * | 2015-03-20 | 2017-07-12 | Authentix, Inc. | Method for detecting adulteration of a fuel |
| CN113024358A (en) * | 2021-03-15 | 2021-06-25 | 沧州临港丰亚化工有限公司 | Method for catalytically synthesizing phenyl diether fluorene by ethylene oxide |
| CN113372203A (en) * | 2021-06-04 | 2021-09-10 | 浙江皇马科技股份有限公司 | Hydrophilic UV (ultraviolet) photocuring monomer, aqueous emulsion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4846996A (en) * | 1988-02-11 | 1989-07-11 | Milliken Research Corporation | Liquid, non-crystallizing two mole diphenol alkoxylate mixtures |
| US6624333B1 (en) * | 1999-06-22 | 2003-09-23 | Basf Aktiengesellschaft | Method for producing bisphenol alcoxylates |
| CN1656147A (en) * | 2002-05-24 | 2005-08-17 | 巴斯福股份公司 | Method for producing polyetherols |
| CN101367714A (en) * | 2008-08-25 | 2009-02-18 | 杭州白浪助剂有限公司 | Preparation method of bisphenol A polyethenoxy ether toughening agent |
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- 2009-07-30 CN CN2009101832841A patent/CN101613261B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4846996A (en) * | 1988-02-11 | 1989-07-11 | Milliken Research Corporation | Liquid, non-crystallizing two mole diphenol alkoxylate mixtures |
| US6624333B1 (en) * | 1999-06-22 | 2003-09-23 | Basf Aktiengesellschaft | Method for producing bisphenol alcoxylates |
| CN1656147A (en) * | 2002-05-24 | 2005-08-17 | 巴斯福股份公司 | Method for producing polyetherols |
| CN101367714A (en) * | 2008-08-25 | 2009-02-18 | 杭州白浪助剂有限公司 | Preparation method of bisphenol A polyethenoxy ether toughening agent |
Non-Patent Citations (1)
| Title |
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| 邵文华.新型水溶性增韧剂双酚A聚氧乙烯醚的合成.《第五次全国环氧树脂应用技术学术交流会论文集》.1993,80-83. * |
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Address after: Wan Shi Zhen Nan Cao Cun, Jiangsu city of Yixing province 214217 Patentee after: YIXING ZHIBO ADVANCED MATERIAL TECHNOLOGY CO., LTD. Address before: Wan Shi Zhen Nan Cao Cun, Jiangsu city of Yixing province 214217 Patentee before: Yixing Hongbo Emulsifier Co., Ltd. |
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Granted publication date: 20120523 Termination date: 20120730 |