CN101456944B - Refining method of high purity epoxy resins - Google Patents
Refining method of high purity epoxy resins Download PDFInfo
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- CN101456944B CN101456944B CN2007101792239A CN200710179223A CN101456944B CN 101456944 B CN101456944 B CN 101456944B CN 2007101792239 A CN2007101792239 A CN 2007101792239A CN 200710179223 A CN200710179223 A CN 200710179223A CN 101456944 B CN101456944 B CN 101456944B
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Abstract
The invention relates to a refining method for high-purity epoxide resin, which obtains high-purity powder epoxide resin product through a reverse-phrase diffusion method. Using the different solubility of the epoxide resin in different solvents, the method of the invention enables the good solvent for dissolving epoxide resin to be quickly dissolved in a resin poor solvent; meanwhile, the resin body is quickly solidified and separated out from the poor solvent to form resin micro-powder, and the non-adherent power resin with good exterior can be obtained after filtration and the like treatment. The obtained resin product has the advantages of high purity, good exterior, high quality and great production and application value.
Description
Technical field
The present invention relates to the process for purification of high purity epoxy resins, belong to the fine chemistry industry production technical field.
Background technology
Resins, epoxy is a kind of important high performance material, Resins, epoxy cooperates the back to form the 3 D stereo reticulated structure with solidifying agent, show excellent physicochemical property, electric property, chemical resistance etc., have a wide range of applications in national economy every field such as liquid crystalline polymers hot solids, epoxy resin fiber, matrix material, electronic apparatus and embedding, tackiness agent and coating, textile industry and material of construction.Along with Resins, epoxy progressively enlarges in the application aspect the hi-tech, performance to Resins, epoxy, requirement as thermotolerance, weathering resistance, flame retardant resistance, shock-resistance, low-stress, high strength, high bonding force, high reliability, erosion resistance etc. also improves constantly, especially in some high-tech sector, as powder coating special epoxy resin, copper-clad plate special epoxy resin, electrician cast special epoxy resin, automobile electrocoating paint special epoxy resin, electronic package special epoxy resin etc., the high purifying of special requirement Resins, epoxy.
The synthetic of Resins, epoxy mainly forms or formed by superoxide (hydrogen peroxide, peroxidation acetate etc.) bis oxide key with epoxy chloropropane condensation under alkaline condition by containing binary or multi-hydroxy (or reactive hydrogen) monomer (as polyvalent alcohol, phenol, carboxylic acid, amine etc.).Mainly comprise following several: (1) bis-phenol is a Resins, epoxy; (2) element type Resins, epoxy; (3) Racemic glycidol fundamental mode Resins, epoxy; (4) epoxidation of olefins such as aliphatic epoxy resin, cycloaliphatic epoxy resin; (5) heterocyclic Resins, epoxy such as tricyanic epoxy resin, extra large mattress Resins, epoxy; Acid imide Resins, epoxy etc.Wherein accounting for more than 95% of whole Resins, epoxy production by bis-phenol based compound synthetic bisphenol-type epoxy resin, is the important component part of Resins, epoxy.
Resins, epoxy synthetic be because the complicacy of reaction, no matter is epoxy chloropropane etherificate stage or taking off HCl becomes loop order section or bis oxide key stage, all exists main reaction and side reaction.Because reaction system viscosity is big, there is intermediate phase simultaneously, makes reaction not exclusively, form heterogeneous terminal group easily.With the epoxy chloropropane route is example, and this route is the main route of synthetic epoxy resin, and the research of this route is also maximum.Major impurity that it is generally acknowledged this route is to be the impurity and the epoxy chloropropane hydrolysate of end group with the organochlorine; Owing to the high viscosity of system, solvent is not easy evaporate to dryness and easy double team impurity in addition, and these reasons all may make the downgrade of Resins, epoxy, and especially some production technologies fall behind and manage poor unit, and the latter's influence may be also bigger than the former.The method for quality that improves Resins, epoxy at present generally is that employing improvement synthesis route, the heterogeneous terminal group of minimizing and two kinds of methods of aftertreatment washing are main, obtains product by underpressure distillation then.
Existing at present a large amount of reports that improve synthesis route: patent CN200310114428.0 substitutes the NaOH aqueous solution/phase-transfer catalyst system with carbonate or anionite-exchange resin, do not use phase-transfer catalyst, reaction system is anhydrous, production technique is simple, product is easily handled, do not produce a large amount of waste water, the product purity height, viscosity is low.United States Patent (USP) [US 4,017,523] has been invented the method that a kind of continuous processing prepares the polyhydroxy polycarboxylic glycidyl ether, with the Resins, epoxy hydrolysis chlorine 0.01～0.001% that this method makes, combined chloride 0.1～0.15%.United States Patent (USP) [US 4,499,255] azeotropic vacuum hydro-extraction when adding alkali, the system alkali concn of making remains dense state, and the epoxy organochlorine that makes is no more than 0.02%.U.S. Resins, epoxy scientist has invented the method [US 4,684,701] that a kind of " intermediate phase transfer method " generates low chlorine content Resins, epoxy, the Resins, epoxy hydrolysis chlorine 0.0017%, the combined chloride 0.041% that make again.Japanese Patent [JP 6026058] is then studied and is successfully used the not method for preparing epoxy compounds of halogen-containing admixture.SUMITOMO CHEMICAL people from Jinchuan such as repaiies earlier with phenols and the synthetic linear resin that contains the allyl etherization structural unit of formaldehyde copolymerization in addition, at last with under the acetate low temperature two keys being oxidized to epoxy group(ing), chloride content＜0.002%.Japanese Patent [JP11181048; JP11130836; JP2001040065] in point out a kind of high purity epoxy resins that can be applicable in the semiconductor-encapsulating material.United States Patent (USP) [US5,077,375] had invented once that a kind of continuous processing in the presence of basic metal prepares the method for highly purified polyhydroxy polycarboxylic glycidyl ether with epoxy chloropropane and polar solvent with hydroxyl phenol.Also be to have pointed out a kind of method that in the presence of specific polarity solvent and amine salt, prepares the Resins, epoxy of utmost point low content of organic chlorine in the Japanese Patent [10095831].Patent [US6001873; JP10195175 (A)] a kind of preparation high purity epoxy resins has been proposed, the content of epoxy organochlorine is no more than 350ppm in the product that is obtained.Pointed out a kind of material that synthesizes hydroxyl earlier with phenol and formaldehyde copolymerization in the Japanese Patent [JP11060682], then at urea as 1, there are the method for preparing the Resins, epoxy of utmost point low content of organic chlorine down with epoxy chloropropane in 3-methylimidazole alkane ketone, organic solvent and alkali.Cl content 〉=the 1500ppm of preparation resin, epoxy amount≤200, fusing point ℃ have been pointed out a kind ofly to prepare the method for the Resins, epoxy of high purity, low-viscosity in the Japanese Patent [JP7109328] with Bisphenol F and epoxy chloropropane.
Reduce the Resins, epoxy of heterogeneous terminal group except above change synthesis route preparation is low, generally also adopt the way of aftertreatment washing.These methods are mainly concerned with the selection appropriate solvent, for example handle with buck in methylethylketone, can get hydrolyzable chloride content and be 0.041% Resins, epoxy.And under similarity condition, make solvent with toluene, the Resins, epoxy hydrolyzable chloride content that makes is 0.156%, also useful mixed solvent.Data shows, adds alkali metal compounds such as NaCl, KCl, LiCl, and phosphorus, boron, carboxylic acid and their salt can promote the HCl that takes off of Resins, epoxy to react [JP 87199222, and JP 88159376].Dow Chemical company [C085108970] adopts a kind of aftertreatment technology that the Resins, epoxy cl content is reduced to very low level, can get the cresols Resins, epoxy of the dihydroxyphenyl propane glycidyl ether of hydrolysis chlorine 0.0003%, combined chloride 0.054% or hydrolysis chlorine 0.0007%, combined chloride 0.0263%.Document [petrochemical complex, 2005,34,1091] report is a raw material with dihydroxyphenyl propane and epoxy chloropropane, has prepared liquid bisphenol A type Resins, epoxy by two-step approach, and is refining with NaH reaction carrying out aftertreatment again, remove the hydrolyzable chlorine of Resins, epoxy, make the Resins, epoxy of high-purity, low hydrolyzable chlorine content, the massfraction of hydrolyzable chlorine is lower than 0.005% in the gained Resins, epoxy, reaches the service requirements of microelectronics industry.Patent JP2004211028 has reported that also a kind of aftertreatment technology purity ring epoxy resins is so that reduce its cl content.
More than numerous improvement technology all be based on and reduce the heterogeneous terminal group that various side reactions generate and the content of other impurity, thereby improve the performance and the solidification reactivity of resin self, epoxy equivalent (weight) is risen and the decline of cured resin cross-linking density, facts have proved that these improvement are effectively and fabulous reference value is arranged.
But because the high viscosity of resin, general being difficult to distills out system fully with solvent; And easy curing of full-bodied product sticks to Polycondensation Reactor and Esterification Reactor, extremely difficult discharging behind the solvent evaporate to dryness; The resin that obtains lumps easily, is difficult to obtain outward appearance and the good powdery solid of grade.In the synthetic improvement technology of numerous resins, do not relate to the improvement technology of this respect substantially.How to solve high viscosity, discharging difficulty, easy caking, obtained outward appearance and high-grade powder-like product is exactly a problem to be solved in the present invention.
Summary of the invention
The present invention is based on above analysis, adopt the method for anti-phase diffusion to obtain the powdered epoxy product, the inventive method is utilized the difference of Resins, epoxy solubleness in different solvents, method by rapid diffusion can make the good solvent of dissolved epoxy dissolve in fast in the resin poor solvent, and this fast setting in poor solvent of resinite is separated out, form the resin micropowder, obtain the good powdery resin of inadherent outward appearance through processing such as filtrations.
Technical scheme of the present invention is:
Use solvent (i) dissolving back effectively to wash again after will directly removing reaction residual with reaction solvent or through steaming through reacted Resins, epoxy, evaporated in vacuo obtains high adhered resin crude product.Crude product with disperseing the good solvent dissolving, disperses the pulverulent solids that is suspended in a large number more fast in poor solvent.Technologies such as solid by filtration, aftertreatment, vacuum-drying obtain purity height, rosin products that outward appearance is good and of high grade.
The Resins, epoxy that the present invention relates to comprises the various compound of phenolic hydroxyl group and the various Resins, epoxy that epoxy chloropropane forms of containing, and the compound structure that contains two or more phenolic hydroxyl groups is as follows:
A is a phenol aromatic nucleus connector element in the formula, connector element is meant that a plurality of phenol aromatic nucleus are to be connected on the atom or directly coupling, connector element comprises ether (compound correspondence 4,4 '-dihydroxy diphenyl ether), sulfydryl (4,4 '-dihydroxyl diphenyl sulfide), methylene radical (Bisphenol F), 1,1-alkyl (dihydroxyphenyl propane D), two alkyl methylene radical (dihydroxyphenyl propane E), Cabbeen base (triphenol methylmethane), 1,1-two replaces ethyl (bis-phenol E), 1,1-two substituted propyls, 2,2-two substituted propyls (dihydroxyphenyl propane), 1,2-two substituted propyls (bis-phenol P), 2,2-two replaces butyl (bis-phenol D), 2,2-two replaces hexafluoro propyl group (hexafluoro Bisphenol F), 2,2-two substituted acetic acid ester groups, α, α-two replaces the fluorobenzene ethyl, α, α-dibasic various phenylpropyl alcohol Valerolactim bases, α, sulfonate group in α-dibasic various phenylpropyl alcohols penta, 1,1-two substituted cyclohexyls (bisphenol Z), 1,1,4,4,-four substituted cyclohexyls, 4,4 ,-two substituted cyclohexanone bases, sulfuryl (bisphenol S), 9,9-two replaces fluorenyl (bisphenol fluorene), 3, two (dioxan) (the bis-phenol PA) of 9-diethyl spiral shell, direct coupling ('-biphenyl diphenol) etc.Phenol aromatic nucleus number n is 2～6.X is the one or more substituting groups (m is 1～4) except that connecting atom and phenolic hydroxyl group on the phenol aromatic nucleus, comprises fluorine, bromine, chlorine, methyl, methylol etc.
Effectively washer solvent (i) is a water-immiscible solvent, is benzene, toluene, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloropropane and/or tetrachloroethane etc., preferred toluene and/or methylene dichloride.
Resin is dissolved in the cleaning solvent, successively add the aqueous solution and water washing, the aqueous solution contains certain density negatively charged ion, comprises sulfate ion, phosphate anion, polyphosphoric acid radical ion and/or di-sulfate ion etc., preferably phosphoric acid radical ion and/or polyphosphoric acid radical ion; Concentration is 10 * 10
-4M is between the 10M, and preferred 10
-2To 1M.Wash temperature is at 10 ℃ to 110 ℃, preferred 50 ℃ to 80 ℃; Washing time is from 1 minute to 48 hours, preferred 10 minutes to 4 hours.Resin solution is 1 to 10 time with the number of times of above solution washing, preferred 2 to 4 times.
The resin organic solvent is through after the water washing, and directly evaporated in vacuo obtains adhering to the product at the bottom of the evaporate to dryness still still.Resin behind the evaporate to dryness dissolves with good solvent, good solvent also can be dissolved in the solvent of poor solvent for the energy dissolving resin, be N, dinethylformamide, tetrahydrofuran (THF), dioxane, acetonitrile, N, N-N,N-DIMETHYLACETAMIDE and/or acetone etc., preferred N, dinethylformamide, dioxane and/or acetonitrile.The add-on of good solvent is 1～100 times of amount of resin, preferred 3～10 times.
The good solvent solution of resin is scattered in the poor solvent fast, and poor solvent is water and/or water mixed solution, and mixing solutions is methyl alcohol, ethanol, propyl alcohol and/or trolamine etc. and the mixing solutions of water.The amount of poor solvent is 10～1000 times of amount of resin, preferred 20～100 times.System temperature is at-30 ℃ to 80 ℃, preferred-10 ℃ to 20 ℃.Fast dispersion technology comprises that the limit stirs the limit fast and drip mixing reactor technology such as reinforced, Venturi is reinforced, membrane reactor and method (Li Dehua writes " Elementary Chemical Engineering " (second edition), Chemical Industry Press, 2007), the pulverulent solids that short mix is suspended after disperseing in a large number, non-caked, good dispersity.Filtration obtains powder-product, obtains the good powder epoxy resin of outward appearance through washing, aftertreatment and drying program again.
Process for refining of the present invention is particularly suitable for the production and large-scale production of high purity epoxy resins, not only obtain product high-purity, the product lover, and solved the agricultural technology problem that the Resins, epoxy high viscosity is brought, as react not exclusively, difficult, the easy material folding of discharging, evaporate to dryness difficulty, bonding, be difficult for problems such as drying, be highly suitable for the production of various Resins, epoxy.
Following specific embodiment describes the present invention in detail, but the present invention is not limited to this.
Embodiment
Embodiment 1:
The building-up reactions mixed solution decompression of bisphenol fluorene Resins, epoxy (about 6 grams) is steamed water and solvent, and temperature does not surpass 80 degree.Be cooled to room temperature behind the evaporate to dryness.Add toluene 30mL dissolving after the room temperature, add saturated NaH again
2PO
4/ Na
2HPO
4Solution 10ml adds 60-70 degree hot water 50mL water washing 10 minutes, 2 times.Back pure water washing 3 times.With regard to suction filtration, guarantee the organic phase clarification if any floss, tell organic phase, evaporate to dryness.Add dioxane 20mL dissolving then, drips of solution joins in the cold pure water of 100ML of quick stirring, obtains a large amount of white powders, continues to stir 20 minutes, filters, and product to the oven dry of neutral back, obtains pure white powder bisphenol fluorene Resins, epoxy with cold wash.
Embodiment 2:
The building-up reactions mixed solution decompression of bisphenol F epoxy resin (about 100 grams) is steamed solvent and lower boiling component, be cooled to room temperature.The 300mL that adds methylene chloride after room temperature dissolving was washed 10 minutes at 50 degree with 100mL 0.1M sodium polyphosphate/phosphoric acid solution again, and 3 times, back pure water washing 2 times.Tell organic phase, evaporate to dryness.Add N then, dinethylformamide 200mL dissolving, solution enriches in cold pure water/methyl alcohol (10: 1) solution of 10L with Venturi tube, obtain a large amount of buff powders, continue to stir 1 hour, filter, product to the oven dry of neutral back, obtains buff powder bisphenol F epoxy resin 80 grams with cold wash.
Embodiment 3:
The mixed solution (containing hexanaphthene) of bisphenol A epoxide resin (about 100 grams) building-up reactions is told waste liquid, with saturated Na
2SO
4Solution 30ml is dissolved in 70 degree hot water 500mL, washing reaction system 30 minutes, 2 times.Back pure water washing 2 times.Tell organic phase, evaporate to dryness.Add acetonitrile 200mL dissolving then, solution disperses fast with special reaction device and 20L cold water, obtains a large amount of white powders, filters, and product to the oven dry of neutral back, obtains pure white powder bisphenol A epoxide resin with cold wash.
Claims (6)
1. the purified method of a Resins, epoxy, it is characterized in that: comprise the steps: that (b) utilizes the difference of Resins, epoxy solubleness in different solvents, method by rapid diffusion, the good solvent that is dissolved with Resins, epoxy is dissolved in the resin poor solvent fast, and this fast setting in poor solvent of resinite is separated out, form the resin micropowder, obtain the purified powder epoxy resin; Wherein said good solvent also can be dissolved in the solvent of poor solvent for the energy dissolved epoxy; Described poor solvent is the mixing solutions of water or methyl alcohol, ethanol, propyl alcohol, trolamine and water.
2. Resins, epoxy process for purification as claimed in claim 1 is characterized in that: described good solvent is selected from N, dinethylformamide, tetrahydrofuran (THF), dioxane, acetonitrile, N,N-dimethylacetamide and/or acetone.
3. Resins, epoxy process for purification as claimed in claim 1 is characterized in that: the add-on of described good solvent is 1～100 times of amount of resin.
4. Resins, epoxy process for purification as claimed in claim 1 is characterized in that: the amount of poor solvent is 10～1000 times of amount of resin.
5. Resins, epoxy process for purification as claimed in claim 1, it is characterized in that: also comprise the steps: before, reacted Resins, epoxy is directly effectively washed with reaction solvent or through steaming after using solvent (i) dissolving after the reaction residual again in step (b).
6. Resins, epoxy process for purification as claimed in claim 5, it is characterized in that: described solvent (i) is a water-immiscible solvent, is selected from benzene, toluene, normal hexane, hexanaphthene, ethyl acetate, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloropropane and/or tetrachloroethane; Described effective washing is successively to add the aqueous solution or water washing, and the aqueous solution contains negatively charged ion, and described negatively charged ion is selected from sulfate ion, phosphate anion, polyphosphoric acid radical ion, di-sulfate ion.
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| CN2007101792239A CN101456944B (en) | 2007-12-11 | 2007-12-11 | Refining method of high purity epoxy resins |
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| CN2007101792239A CN101456944B (en) | 2007-12-11 | 2007-12-11 | Refining method of high purity epoxy resins |
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| CN101456944A CN101456944A (en) | 2009-06-17 |
| CN101456944B true CN101456944B (en) | 2011-04-06 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816295B (en) * | 2011-06-10 | 2015-04-22 | 中国石油化工集团公司 | Bisphenol A liquid epoxy resin refining method |
| CN102633985A (en) * | 2012-04-10 | 2012-08-15 | 吉林大学 | Preparation method of high-purity bisphenol epoxy resin |
| CN102838726B (en) * | 2012-09-21 | 2014-12-24 | 黄山市向荣新材料有限公司 | Epoxy resin water washing auxiliary agent and using method thereof |
| CN103183851A (en) * | 2013-03-28 | 2013-07-03 | 宜兴市聚金信化工有限公司 | High flame resistance and high heat resistant synthetic rubber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017523A (en) * | 1974-05-30 | 1977-04-12 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the continuous preparation of polyglycidyl ethers of polyhydroxy phenols |
| CN1053798A (en) * | 1991-01-29 | 1991-08-14 | 江西省赣西化工厂 | Produce method of p-tert-butylphenol formaldehyde epoxy resin and products thereof |
| US6211389B1 (en) * | 2000-05-23 | 2001-04-03 | Dexter Corporation | Methods of reducing the chloride content of epoxy compounds |
| CN1546548A (en) * | 2003-12-03 | 2004-11-17 | 青岛帝科精细化学有限公司 | High purity low molecule biphenol A epoxy resin synthetic process |
-
2007
- 2007-12-11 CN CN2007101792239A patent/CN101456944B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017523A (en) * | 1974-05-30 | 1977-04-12 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the continuous preparation of polyglycidyl ethers of polyhydroxy phenols |
| CN1053798A (en) * | 1991-01-29 | 1991-08-14 | 江西省赣西化工厂 | Produce method of p-tert-butylphenol formaldehyde epoxy resin and products thereof |
| US6211389B1 (en) * | 2000-05-23 | 2001-04-03 | Dexter Corporation | Methods of reducing the chloride content of epoxy compounds |
| CN1546548A (en) * | 2003-12-03 | 2004-11-17 | 青岛帝科精细化学有限公司 | High purity low molecule biphenol A epoxy resin synthetic process |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2004-211028A 2004.07.29 |
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Assignee: Beijing Jin Yuan Xinhua Environmental Technology Co., Ltd. Assignor: Beijing CHARNA Chemicals Ltd. Contract record no.: 2011110000126 Denomination of invention: Refining method of high purity epoxy resins Granted publication date: 20110406 License type: Exclusive License Open date: 20090617 Record date: 20110802 |
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