CN103880611A - Preparation method of bis(hydroxypropyl) bisphenol fluorene ether - Google Patents
Preparation method of bis(hydroxypropyl) bisphenol fluorene ether Download PDFInfo
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- CN103880611A CN103880611A CN201410099277.4A CN201410099277A CN103880611A CN 103880611 A CN103880611 A CN 103880611A CN 201410099277 A CN201410099277 A CN 201410099277A CN 103880611 A CN103880611 A CN 103880611A
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- bisphenol fluorene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a preparation method of bis(hydroxypropyl) bisphenol fluorene ether, belonging to the technical field of synthesis of organic compounds. The preparation method is characterized by using bisphenol fluorene as a raw material, adding a ferrocene catalyst, using methylbenzene as a solvent and then using propylene epoxide as a chain extension agent to synthesize bis(hydroxypropyl) bisphenol fluorene ether. Adopted to prepare bis(hydroxypropyl) bisphenol fluorene ether, the preparation method has the prominent advantages and positive effects that the process is simple; the energy consumption is low; the content of allyl alcohol byproduct substances is low; the content of bis(hydroxypropyl) bisphenol fluorene ether is high; the product has light color and stable properties.
Description
Technical field
The present invention relates to a kind of preparation method of bis-hydroxypropyl bisphenol fluorene ether, belong to the synthesis technical field of organic compound.
Background technology
Bis-hydroxypropyl bisphenol fluorene ether is white solid, can be applied to be called as and there is 5E feature UV coating, it is efficient that 5E is respectively 1. Efficient(), 2. Enabling(wide adaptability), 3. Economical(economy), 4. Energy Saving(is energy-conservation), 5. Environmental Friendly(environmental friendliness), be described as the green industry new technology of Twenty-First Century.With the functional thinner of acrylic or methacrylic acid-respons as UV coating, it not only has the effect of dissolving and diluting oligopolymer, regulation system viscosity, can also participate in photosensitive polymerization, affect the laser curing velocity of coating and the various performances of cured film, as physics, mechanical propertys such as hardness, wear resistance, sticking power, snappinesies.
Bis-hydroxypropyl bisphenol fluorene ether can also be used for glass fiber industry simultaneously, and with acid, acid anhydrides, polyvalent alcohol, play adhesive effect by drying polycondensation, as tackiness agent.Synthesize various resins with diprotic acid condensation: the performance of the resin being formed by dibasic alcohol, diprotic acid esterification directly depends on the molecular structure of alcohol, acid, and the molecular structure of dibasic alcohol seems particularly important.The industrial dibasic alcohol of using is morely ethylene glycol, but glycol molecule is simple in structure, and synthetic resin structure is also more single; And bis-hydroxypropyl bisphenol fluorene is owing to containing aromatic ring in its molecule, improve well structure and the performance of synthetic resins.People's discoveries such as Hirakouchi, after bis-hydroxypropyl bisphenol fluorene ether and aromatic binary carboxylic acid condensation, synthetic elastic resin is widely used in the fields such as machinery, building, automobile making, can completely cut off noise, reduces harmful vibrations.
With the carboxylate of unsaturated acid as synthetic resins monomer: the unsaturated acid esterifications such as bis-hydroxypropyl bisphenol fluorene and vinylformic acid, methacrylic acid, can be made into several functions high molecular polymerization monomer.Wherein, the polymkeric substance of the double methyl methacrylate of bis-hydroxypropyl bisphenol fluorene ether is because having good specific refractory power, light transmission, moderate solidification value and set time, therefore can be used as the clad material of optical fiber; It can also make photochromics, for the manufacture of optical element; It still prepares the principal monomer of anaerobic glue, and synthetic anaerobic glue, can fast setting in the time of room temperature in the situation that of isolated air, solvent-free, nontoxic, heat-resisting, acid and alkali-resistance and tablet corrosion vibration resistance, impact, be widely used as the tackiness agent on the assembly processes such as machinery, automobile, electric, aircraft; It also can be made into curable liquid resin composition, as wash primer, secondary coating, fibre-optic strip base material; In addition, because its biocompatibility is better, also can be used as traditional dentistry and repair enamel tackiness agent.
Modifier and additive as high molecular polymer chain: bis-hydroxypropyl bisphenol fluorene ether is bonded in high molecular polymer chain by a certain percentage, can make polymkeric substance have better intensity, elasticity, bounding force and processibility.For example, bis-hydroxypropyl bisphenol fluorene ether is with different mol ratios and terephthalic acid polymerization, bisphenol fluorene group is inserted in polyester chain, can reduce the crystallization rate of polybutyleneterephthalate, make polymkeric substance there is good mechanical property, electric property and physical and chemical performance, the engineering plastics of making are widely used in automobile making, electric and electronic field.
The research of existing domestic bis-hydroxypropyl bisphenol fluorene ether has no report, only have similar bisphenol A polyethenoxy ether to have report: as patent 201210003017.3, invent a kind of bisphenol A epoxy ethane additive product, adopt trialkylamine to make catalyzer, make solvent synthesis of bisphenol A at 80-150 ℃ and become the preparation method of thing with ethers.The Master's thesis " synthesizing of narrow distribution dihydroxyphenyl propane polyethenoxy ether " of the Chen Chao of Southern Yangtze University has been studied a kind of synthetic method of dihydroxyphenyl propane polyethenoxy ether, first adopt KOH, NaOH and take hexanaphthene as solvent and band aqua complete synthesis dihydroxyphenyl propane be dihydroxyphenyl propane sylvite or sodium salt, again take dihydroxyphenyl propane sylvite or sodium salt as raw material, at 150-160 ℃, add propylene oxide reaction, after completion of the reaction, adopt sulfuric acid, add ethyl acetate to wash with water again 5 times, finally steam ethyl acetate and obtain finished product.But it is synthetic that this patent is not suitable for dihydroxyphenyl propane propoxylation: first, catalyzer trialkylamine catalytic activity is low, and propylene oxide than the reactive behavior of oxyethane a little less than, required catalytic amount is many, reaction time is long, and propylene oxide is easily isomerizated into vinylcarbinol or other by products; Secondly, reacting desired excess Temperature, also easily there is isomerization reaction and becomes by product vinylcarbinol or vinyl carbinol in propylene oxide, and product allyl alcohol-like substances content is all more than 0.1%.And the method for Master's thesis " synthesizing of narrow distribution dihydroxyphenyl propane polyethenoxy ether ", the product synthesizing distributes wide, about bis-hydroxypropyl content of bisphenol A is 70-80%, and under 150-160 ℃, high concentration alkali exist, easily there is isomerization reaction and become by product in propylene oxide, make by-products content high, product allyl alcohol-like substances content is all more than 0.1%, of poor quality.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of preparation technology simple, be easy to industrializing implementation, products obtained therefrom quality is good, the preparation method of stay-in-grade single stage method bis-hydroxypropyl bisphenol fluorene ether.
For achieving the above object, the technical scheme that the present invention takes is as follows:
A preparation method for bis-hydroxypropyl bisphenol fluorene ether, take bisphenol fluorene as raw material, adds ferrocene catalyzer, and toluene is solvent, then carries out the synthetic of bis-hydroxypropyl bisphenol fluorene ether with propylene oxide as chain extension agent.
For realizing result of use better, further arranging of technique scheme is as follows:
Described ferrocene catalyzer is 1,1 '-bis-(diphenylphosphine) ferrocene (CAS:12150-46-8).
In described building-up process, temperature of reaction is 40～75 ℃, and reaction pressure is-0.04～0.5MPa, and as preferably, temperature of reaction is 50-75 ℃, and reaction pressure is-0.4-0.5MPa.
Described bisphenol fluorene, propylene oxide, 1, the mol ratio 1: 1.8～3.0: 0.0003735～0.0022 of two (diphenylphosphine) ferrocene of 1'-.
The addition of described toluene is the 60-200% of bisphenol fluorene quality.
A bis-hydroxypropyl bisphenol fluorene ether that adopts aforesaid method to prepare, the allyl alcohol-like by-products content of described bis-hydroxypropyl bisphenol fluorene ether can reach≤and 0.01%, hydroxyl value is 242-245 mgKOH/g, color and luster is No. 5-30 (Pt-Co unit).
Reaction formula of the present invention is:
In above-mentioned reaction process, adopt two (diphenylphosphine) ferrocene of 1,1'-as catalyzer, make reactive behavior, selectivity, controllability good, improved the overall activity of reaction; Because supplementary material exists different states of matter, adopt catalyzer of the present invention, coordinate the temperature of reaction, reaction pressure and the reaction atmosphere that match with it, by the control of product on suitable component state, reduce the formation of by product, reaction is more conducive to carry out to desired direction, has guaranteed that bis-hydroxypropyl bisphenol fluorene ether can one-step synthesis; Products obtained therefrom distributes rationally, product colour is shallow, and allyl alcohol-like by-products content is low, this is shallow with important diagnostic characteristics and the difference product color of additive method products obtained therefrom: pass through liquid-phase chromatographic analysis, allyl alcohol-like substances content is low, this allyl alcohol-like material (Main By product) content is lower than 0.003%, and bis-hydroxypropyl bisphenol fluorene ether content can reach more than 95%, and color and luster can reach 5-20 left and right (Pt-Co unit).
The problems such as it is initiator that the present invention adopts bisphenol fluorene,, has solved in routine techniques in complicated process of preparation for catalyzer with two (diphenylphosphine) ferrocene of 1,1'-, and processing step is many, and energy consumption is large, and comprehensive cost is high, poor product quality.Compared with prior art, there is following outstanding advantages and positively effect:
1, adopt technical solution of the present invention single stage method to synthesize bis-hydroxypropyl bisphenol fluorene ether, the content of this finished product is high, and the output capacity of bis-hydroxypropyl bisphenol fluorene ether is up to more than 95%.
2,, in the bis-hydroxypropyl bisphenol fluorene ether process of once preparing, by product allyl alcohol-like substances content can reach≤and 0.01%, color and luster≤No. 30 (Pt-Co unit), and product with stable quality, its color and luster mainly concentrates between No. 15-20.
3, prepare the technique of bis-hydroxypropyl bisphenol fluorene ether simple, catalyst consumption amount is extremely low, and finished product output capacity is higher, and whole preparation process energy consumption is low.
Embodiment
The preparation of reactor before implementing: first with distilled water, 2.5L autoclave is washed several times, until clean, oven dry reactor, is cooled to after normal temperature for subsequent use.
Embodiment 1:
In reactor, add bis-phenol 700g, two (diphenylphosphine) ferrocene 2.0g of 1,1'-, solvent toluene 300g, vacuumizes with vacuum pump, adopts N
2displace the air in reactor, replace after three times, under vacuum tightness>=-0.096MPa, close vacuum and start to be warming up to 70 ℃, continue to add propylene oxide 232g, control temperature of reaction at 70-75 ℃, reacting kettle inner pressure is at-0.40 ~ 0.5Mpa, add rear insulation and continue reaction, until pressure is only no longer reduced to.React complete, adopt after vacuum outgas 20min, in the situation that opening vacuum, be warming up to 120 ℃ of insulations until toluene solvant all removes recovery, after cool to 110 ℃ of blowings and obtain finished product.Product is through liquid-phase chromatographic analysis: allyl alcohol-like by-products content is 0.003%, and bis-hydroxypropyl bisphenol fluorene ether content is 98.5%; Range estimation No. 20, color and luster of sample (Pt-Co unit), chemical determination hydroxyl value is 242mgKOH/g.
Embodiment 2:
In reactor, add bisphenol fluorene 700g, 1,1 '-bis-(diphenylphosphine) ferrocene 1.7g, solvent toluene 500g, vacuumizes with vacuum pump, adopts N
2displace the air in reactor, replace after three times, under vacuum tightness>=-0.096MPa, close vacuum and start to be warming up to 60 ℃, continue to add propylene oxide 280g, control temperature of reaction at 60-65 ℃, reacting kettle inner pressure is at-0.40 ~ 0.5Mpa, add rear insulation and continue reaction, until pressure is only no longer reduced to.React complete, adopt after vacuum outgas 20min, in the situation that opening vacuum, be warming up to 120 ℃ of insulations until toluene solvant all removes recovery, after cool to 110 ℃ of blowings and obtain finished product.Product is through liquid-phase chromatographic analysis: allyl alcohol-like by-products content is 0.002%, and bis-hydroxypropyl bisphenol fluorene ether content is 95.5%; Range estimation No. 15, color and luster of sample (Pt-Co unit), chemical determination hydroxyl value is 245mgKOH/g.
Embodiment 3:
In reactor, add bisphenol fluorene 700g, two (diphenylphosphine) ferrocene 1.5g of 1,1'-, solvent toluene 600g, vacuumizes with vacuum pump, adopts N
2displace the air in reactor, replace after three times, under vacuum tightness>=-0.096MPa, close vacuum and start to be warming up to 70 ℃, continue to add propylene oxide 300g, control temperature of reaction at 70-75 ℃, reacting kettle inner pressure is at-0.40 ~ 0.5Mpa, add rear insulation and continue reaction, until pressure is only no longer reduced to.React complete, adopt after vacuum outgas 20min, in the situation that opening vacuum, be warming up to 120 ℃ of insulations until toluene solvant all removes recovery, after cool to 110 ℃ of blowings and obtain finished product.Product is through liquid-phase chromatographic analysis: allyl alcohol-like by-products content is 0.003%, and bis-hydroxypropyl bisphenol fluorene ether content is 97.5%; Range estimation No. 20, color and luster of sample (Pt-Co unit), chemical determination hydroxyl value is 243mgKOH/g.
Embodiment 4:
In reactor, add bisphenol fluorene 700g, two (diphenylphosphine) ferrocene 2.3g of 1,1'-, solvent toluene 900g, vacuumizes with vacuum pump, adopts N
2displace the air in reactor, replace after three times, under vacuum tightness>=-0.096MPa, close vacuum and start to be warming up to 50 ℃, continue to add propylene oxide 348g, control temperature of reaction at 50-55 ℃, reacting kettle inner pressure is at-0.40 ~ 0.5Mpa, add rear insulation and continue reaction, until pressure is only no longer reduced to.React complete, adopt after vacuum outgas 20min, in the situation that opening vacuum, be warming up to 120 ℃ of insulations until toluene solvant all removes recovery, after cool to 110 ℃ of blowings and obtain finished product.Product is through liquid-phase chromatographic analysis: allyl alcohol-like by-products content is 0.002%, and bis-hydroxypropyl bisphenol fluorene ether content is 98.7%; Range estimation No. 15, color and luster of sample (Pt-Co unit), chemical determination hydroxyl value is 243.5mgKOH/g.
After tested, specific targets are as follows for the prepared bis-hydroxypropyl bisphenol fluorene of the various embodiments described above ether:
Preparation method's reactive behavior of the present invention is high, can one-step synthesis bis-hydroxypropyl bisphenol fluorene ether, products obtained therefrom distributes rationally, product colour is shallow, and allyl alcohol-like by-products content is low, this is shallow with important diagnostic characteristics and the difference product color of additive method products obtained therefrom: pass through liquid-phase chromatographic analysis, allyl alcohol-like substances content is low, this allyl alcohol-like material (Main By product) content is lower than 0.003%, bis-hydroxypropyl bisphenol fluorene ether content/output capacity can reach more than 95%, color and luster can reach 5-20 left and right (Pt-Co unit), product with stable quality, its color and luster is stabilized between 15-20.
Above content is the further description of provided technical scheme being done in conjunction with the preferred embodiment of the present invention; can not assert that the concrete enforcement of the present invention is confined to above-mentioned these explanations; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (6)
1. a preparation method for bis-hydroxypropyl bisphenol fluorene ether, is characterized in that: take bisphenol fluorene as raw material, add ferrocene catalyzer, toluene is solvent, then carries out the synthetic of bis-hydroxypropyl bisphenol fluorene ether with propylene oxide as chain extension agent.
2. the preparation method of a kind of bis-hydroxypropyl bisphenol fluorene ether as claimed in claim 1, is characterized in that: described ferrocene catalyzer is 1,1 '-bis-(diphenylphosphine) ferrocene.
3. the preparation method of a kind of bis-hydroxypropyl bisphenol fluorene ether as claimed in claim 1, is characterized in that: in described building-up process, temperature of reaction is 40～75 ℃, and reaction pressure is-0.4～0.5MPa.
4. the preparation method of a kind of bis-hydroxypropyl bisphenol fluorene ether as claimed in claim 1, is characterized in that: described bisphenol fluorene, propylene oxide, 1, the mol ratio 1: 1.8～3.0: 0.0003735～0.0022 of two (diphenylphosphine) ferrocene of 1'-.
5. the preparation method of a kind of bis-hydroxypropyl bisphenol fluorene ether as claimed in claim 1, is characterized in that: the addition of described toluene is the 60-200% of bisphenol fluorene quality.
6. the bis-hydroxypropyl bisphenol fluorene ether that described in employing claim 1-5 any one prepared by method, it is characterized in that: bis-hydroxypropyl bisphenol fluorene ether content >=90% of described bis-hydroxypropyl bisphenol fluorene ether product, allyl alcohol-like by-products content can reach≤and 0.01%, hydroxyl value is 242-245 mgKOH/g, and color and luster is No. 5-30.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523905A (en) * | 2016-01-14 | 2016-04-27 | 浙江皇马科技股份有限公司 | Method for synthesizing hydroquinone dihydroxyl diethyl ether |
| CN106478381A (en) * | 2016-10-16 | 2017-03-08 | 武汉轻工大学 | A kind of method that bis ether fluorenes is prepared by catalyzing epoxyethane |
| CN109651093A (en) * | 2019-01-04 | 2019-04-19 | 浙江皇马科技股份有限公司 | A kind of preparation method of bis-hydroxyethyl bisphenol fluorenes ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359362A (en) * | 1999-06-22 | 2002-07-17 | Basf公司 | Method for producing bisphenol alcoxylates |
| US20040181099A1 (en) * | 2002-07-26 | 2004-09-16 | Yoshiaki Hirano | Aromatic ethers and process for producing aromatic ethers |
| CN1621431A (en) * | 2004-10-19 | 2005-06-01 | 中山大学 | Sulfonated fluorine-containing poly-arylether (arone) and its preparing method and use |
| JP2009167267A (en) * | 2008-01-15 | 2009-07-30 | National Institute Of Advanced Industrial & Technology | Method for efficiently producing fluorene-containing polyester |
-
2014
- 2014-03-18 CN CN201410099277.4A patent/CN103880611B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359362A (en) * | 1999-06-22 | 2002-07-17 | Basf公司 | Method for producing bisphenol alcoxylates |
| US20040181099A1 (en) * | 2002-07-26 | 2004-09-16 | Yoshiaki Hirano | Aromatic ethers and process for producing aromatic ethers |
| CN1621431A (en) * | 2004-10-19 | 2005-06-01 | 中山大学 | Sulfonated fluorine-containing poly-arylether (arone) and its preparing method and use |
| JP2009167267A (en) * | 2008-01-15 | 2009-07-30 | National Institute Of Advanced Industrial & Technology | Method for efficiently producing fluorene-containing polyester |
Non-Patent Citations (1)
| Title |
|---|
| N. MAISURADZE: "Synthesis of Dioles Containing Fluorene Group of Card-Type", 《BULLETIN OF THE GEORGIAN ACADEMY OF SCIENCES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523905A (en) * | 2016-01-14 | 2016-04-27 | 浙江皇马科技股份有限公司 | Method for synthesizing hydroquinone dihydroxyl diethyl ether |
| CN105523905B (en) * | 2016-01-14 | 2018-03-20 | 浙江皇马科技股份有限公司 | A kind of synthetic method of the double hydroxyl ether of hydroquinones |
| CN106478381A (en) * | 2016-10-16 | 2017-03-08 | 武汉轻工大学 | A kind of method that bis ether fluorenes is prepared by catalyzing epoxyethane |
| CN106478381B (en) * | 2016-10-16 | 2019-06-21 | 武汉轻工大学 | A method of bis ether fluorenes is prepared by catalyzing epoxyethane |
| CN109651093A (en) * | 2019-01-04 | 2019-04-19 | 浙江皇马科技股份有限公司 | A kind of preparation method of bis-hydroxyethyl bisphenol fluorenes ether |
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