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WO2001016204A1 - Procede de production de resines epoxydes hautement moleculaires - Google Patents

Procede de production de resines epoxydes hautement moleculaires Download PDF

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Publication number
WO2001016204A1
WO2001016204A1 PCT/EP2000/008404 EP0008404W WO0116204A1 WO 2001016204 A1 WO2001016204 A1 WO 2001016204A1 EP 0008404 W EP0008404 W EP 0008404W WO 0116204 A1 WO0116204 A1 WO 0116204A1
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WIPO (PCT)
Prior art keywords
epoxy resin
reaction
liquid epoxy
solvent
resin
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Ceased
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PCT/EP2000/008404
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English (en)
Inventor
Simon Ming-Kung Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Resolution Research Nederland BV
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Shell Internationale Research Maatschappij BV
Resolution Research Nederland BV
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Priority to AU79039/00A priority Critical patent/AU7903900A/en
Publication of WO2001016204A1 publication Critical patent/WO2001016204A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols

Definitions

  • the present invention relates to an improved process for upstaging liquid epoxy resins to produce higher molecular weight resinous polyepoxides or hydroxy- terminated polyethers. More specifically, this invention relates to processes for the continuous production of epoxy resins or hydroxy-terminated polyethers in solvents. This invention also relates to the continuous production of epoxy resins or hydroxy-terminated polyethers having uniform consistency. The epoxy resin and hydroxy-terminated polyether products of the instant invention exhibits more uniformity and consistency.
  • This invention also relates to improvements in the production of thermosetting resinous polyepoxides, including processes and the products resulting therefrom.
  • the present invention also relates to the continuous production of higher molecular weight epoxy resins or hydroxy-terminated polyethers using sequentially staged reactors .
  • thermosetting resinous polyepoxides i.e., epoxy resins, hydroxy-terminated polyethers or phenoxy-terminated resins have in industries and scientific disciplines found application in many forms, principally as surface-coating materials combining toughness, flexibility, adhesion and chemical resistance to a nearly unparalleled degree.
  • the epoxy resins are fundamentally polyethers, but retain their epoxy nomenclature on the basis of their starting material and the presence of epoxide groups in the polymer before crosslinking or curing.
  • the most common types of resinous polyepoxides are produced by reaction of monomeric epoxy compounds, primarily epichlorohydrin, with dihydric phenols, such as bisphenol-A (BPA) , to give diglycidyl ethers.
  • BPA bisphenol-A
  • the resinous polyepoxide may vary from a viscous liquid to a high melting solid.
  • the higher molecular weight resinous polyepoxides or hydroxy-terminated polyethers can be made by a process known as "upstaging”, “upgrading”, fusion or “advancement”.
  • upstaging or advancement process an initial liquid resinous polyepoxide is reacted with a dihydric phenol in the presence of a catalyst until enough of the dihydric phenol is incorporated into the epoxy polymer chain to increase molecular weight to the desired level.
  • Such upstaging processes have in the past been conducted both on a batch basis and on a continuous basis. See, for example, U.S. Patent Nos . 3,547,881, 3,919,169 and 4,612,156.
  • the dihydric phenols and liquid polyepoxide together with a catalyst are admixed or otherwise contacted at a relatively low temperature and then heated up to the reaction temperature and held at reaction temperature for a time sufficient to produce the resinous polyepoxide or hydroxy-terminated polyether of higher molecular weight.
  • cycle times are typically relatively lengthy.
  • batch production involving bisphenol-A and a liquid polyepoxide consisting essentially of the diglycidyl ether of bisphenol-A can take from 8 to 12 hours of cycle time. This includes the charging of raw materials, reaction, and discharging and solidification/packaging of the product. Moreover, batch processes are generally labor intensive and equipment intensive. When a solid resin product is produced, long batch cycle time can lead to resin products with wider molecular weight distributions as well as higher softening points (Tg) and viscosities.
  • Tg softening points
  • the resin products are typically prepared by fusing the lower molecular weight epoxy resin (like EPON Resin 828, EPON is a trademark) with the corresponding component such as bisphenol-A or tetrabromobisphenol-A (TBBPA) in a batch reaction system by base catalysis using a catalyst like triphenyl phosphine (TPP) or triphenyl phosphonium ethyl iodide (TPPEI).
  • TPP triphenyl phosphine
  • TPPEI triphenyl phosphonium ethyl iodide
  • FIG. 1 is a schematic diagram of the reactor system used to upstage epoxy resins or hydroxy-terminated polyethers using the process of the present invention.
  • a primary object of the present invention is to provide improvements in the production of a higher molecular weight epoxy resins or hydroxy- terminated polyethers from liquid epoxy resins, which improvements significantly alleviate or do not incur the problems and disadvantages discussed above.
  • a further object of the present invention relates to a continuous process for upstaging thermosetting liquid resinous polyepoxides or hydroxy-terminated polyethers which uses sequentially staged reactors.
  • the present invention relates to a continuous process for upstaging epoxy resins or hydroxy-terminated polyethers, which process comprises continuously passing a feed solution comprising (i) a liquid epoxy resin, (ii) a compound having active hydrogens or reaction functional groups capable of reacting with a liquid epoxy resin such as polyhydric phenolic compound, (iii) an inert solvent or diluent such as acetone, xylene, or a mixture thereof, and (iv) a catalyst such as triphenyl phosphonium ethyl iodide catalyst through reaction chamber (s), such as a series of pipe reactors, optionally having mixing means such as static mixing means or dynamic mixing means, to produce a product stream comprising product epoxy resin or hydroxy-terminated polyethers; and removing said solvent from said product stream; wherein the equivalency ratios of said epoxy resin to said compound having active hydrogens or reaction functional groups capable of reacting with a liquid epoxy resin is from 3.3:1 to 0.5:1,
  • the present invention is directed to a process for the continuous upstage or upgrade of epoxy resins. It has been found now that by incorporating an inert solvent into the continuous reaction system, one could employ one or more simple and inexpensive reactor (s), with static-mixers or dynamic mixer (s), to make fusion resin solutions, without having to resort to the use of the more expensive reactors, such as extruder- reactor (s). Since longer residence time can be designed into this type of reactor, the catalyst amount used does not have to be elevated to a similarly high level as that used in certain prior art solventless continuous processes using the extruder-reactors.
  • An additional advantage of the present process resides in the fact that the solvent in the reaction system also serves as a heat sink for the high exotherm released from this type of reactions.
  • the resulting solution product can be diluted to the desired concentration, or blended with other additives or components as necessary to give the final product.
  • the feeds to the reaction system can be in the solution form (e.g., liquid EPON Resin 828, and BPA or TBBPA-based solutions where the solvent and the catalyst are combined with the respective phenolic components) for easier handling, especially in grassroot plants e.g., no solids dust handling to minimize potential for explosion and accurate metering.
  • solution form e.g., liquid EPON Resin 828, and BPA or TBBPA-based solutions where the solvent and the catalyst are combined with the respective phenolic components
  • a Continuous Solution Reaction Unit consisting of a single jacketed pressure feed vessel with an air- driven mixer, a feed pump, a series of four heat-traced pipe reactors with internal static elements, a heat exchanger pipe for cooling the exiting reaction product, and a back pressure regulator is used.
  • a schematic diagram of the reaction system is shown in Figure 1.
  • the feed consisting of the raw materials, catalyst and the solvent, is prepared externally in a 4-neck flask equipped with a stirrer, a thermocouple, and a condenser. Solid reactant and liquid epoxy resin are charged, mixed followed by the addition of solvent. Heat is applied only as needed.
  • reaction premix Upon full dissolution of the solids, catalyst is added and uniformly mixed into the solution. This reaction premix is then transferred into the feed vessel (pre-warmed as needed via the heat jacket), gently deaerated with nitrogen (pressurizing the vessel to 2.72 bar (25 psig) and released to ⁇ 1.35 bar ( ⁇ 5 psig) , repeated another 2 times, and finally pressurizing to 2.04-2.72 bar (15-25 psig) nitrogen atmosphere).
  • the instant process exhibits good stability of reaction premix at the feed temperature over the duration of a typical continuous run ( ⁇ 12 hours) .
  • An illustrative example of premix stability results are given in Table 1.
  • Other suitable methods which can be used by one skilled in the art, for making reaction premix and/or for feeding to the feed vessel are also within the scope of the present process.
  • liquid epoxy resin feed and the compound having active hydrogen (s) are separately charged to the continuous reactor; the compound having active hydrogen (s) can be mixed with the inert solvent and catalyst before injected into the reactor.
  • the liquid epoxy resin feed, the compound having active hydrogen (s) and the inert solvent can be premixed, and the premix is injected to the reactor (s) separately from the catalyst.
  • the present process may utilize one reaction chamber or reactor, with one or more reaction zones, or two or more reaction chambers or reactors, each with one or more reaction zones.
  • a pipe reactor or a plurality of two or more staged pipe reactors with mechanical mixing means can be utilized.
  • the mechanical mixing means include, but not limit to, static mixing element (s) and dynamic mixer (s) .
  • the reaction chamber (s) or reactor (s) can optionally be heat traced by setting heat-tracing on the reactors or reaction chamber (s) and controlling temperature (s) via controllers.
  • the premix solution is delivered, e.g. via the diaphragm pump, continuously through a reaction chamber or a plurality of reactors in which the coupling reaction takes place.
  • the feed rate is gradually increased to the targeted flow rate and the temperature of each of the reaction zones is optionally adjusted as needed due to exotherm.
  • flow rates are checked during the run, and samples are taken, e.g. after 3-5 turnovers and analyzed.
  • Heat tracing may be applied in the reaction chamber (s) or reactor (s) to control the temperature in reaction zone(s) in the reaction chamber (s) or reactor (s) .
  • the temperature in the reactor (s) or chamber (s) will generally stay below 232 °C (450 °F), preferably below 216 °C (420 °F) and most preferably below 204 °C (400 °F) .
  • the temperatures in the reaction chamber (s) or reactors are typically from 49 °C (120 °F) to 216 °C (420 °F), preferably from 82 °C (180 °F) to 216 °C (420 °F) , more preferably from 93 °C (200 °F) to 204 °C (400 °F) .
  • the duration of the fusion reaction i.e. the amount of time the reactants/feedstock stay in the reaction chamber (s) before it is discharged as the product stream, is typically from 10 minutes to 180 minutes, preferably from 20 minutes to 120 minutes, and more preferably from 30 minutes to 60 minutes.
  • the present Continuous Solution Reaction Unit can be utilized to produce a variety of resin products.
  • Illustrative non-limiting examples of inert solvents which are suitable for preparing the reactive feedstock (liquid epoxy resin and phenolic components, with catalyst such as ethyl triphenyl-phosphonium iodide or triphenyl phosphine) include, but not limited to, acetone and xylene .
  • suitable inert solvents include, but by no means limited to, a solvent capable to solubilize the reactant epoxy resin (s).
  • the Reaction Unit is normally filled, flushed and cleaned with the solvent to be used in the next run from the feed vessel using the diaphragm pump.
  • solvents which can be used in the practice of the present invention include, but by no means limited to, benzene, toluene, sulpholane, diethylether, tetra- hydrofuran, dimethoxyethane, C5-C10 aliphatic hydro- carbons including all the branched isomers, ethylbenzene, cumene, 2-butanone and 2-methyl tetrahydrofuran, as well as mixtures thereof.
  • the reaction mixtures typically contain from 5 to 80 percent, preferably from 5 to 50 percent, and more preferably from 5 to 25 percent by weight of solvent (s) or diluent (s).
  • the ratio of the equivalent of catalyst to the equivalent of epoxy employed in the reaction mixture is typically from 5xl0 ⁇ 5 to 2xl0 ⁇ 3, preferably from lxl0 ⁇ to lxl0-3, and most preferably from 1.5x10" ⁇ to 5xl0 ⁇ 4 .
  • the equivalency ratio of liquid epoxy resin to the compound having active hydrogen (s) or reactive function groups capable of reacting with a liquid epoxy resin is from 3.3:1 to 0.5:1, most preferably from 1.6:1 to 0.65:1.
  • the equivalent ratio of liquid epoxy resin to the compound having active hydrogen (s) or reactive function groups capable of reacting with a liquid epoxy resin is from 3.3:1 to 1.3:1, more preferably from 2.7:1 to 2.5:1 to produce the product epoxy resin with advanced molecular weight .
  • Suitable starting materials having an average of more than one vicinal epoxy group per molecule which can be employed in the process of the present invention include, for example, those represented by the formulas:
  • each A is independently a divalent hydrocarbyl group having from 1 to 10, preferably from 1 to 6 carbon atoms, more preferably R ⁇ -C-R 2 , wherein R 1 and R 2 are methyl or hydrogen; or A can be;
  • each R is independently hydrogen or a hydrocarbyl group having from about 1 to about 4 carbon atoms;
  • X is independently hydrogen, a halogen, preferably chlorine or bromine, or a hydrocarbyl or hydrocarbyloxy group having from 1 to 12 carbon atoms;
  • n has a value of zero or 1; and
  • q has an average value of from zero to 2, preferably from zero to 0.3.
  • the functionality of the epoxy resin is higher than 2, they are employed in combination with an epoxy resin having a functionality of 2 and is employed in small quantities with respect to the 2 functional material.
  • hydrocarbyl group means any aliphatic, cycloaliphatic or aromatic hydrocarbon group, which consists of hydrogen and carbon atoms.
  • hydrocarbyloxy group means those compounds represented by the formula —OR wherein R is a hydrocarbyl group as above defined.
  • Particularly suitable epoxy-containing materials include the glycidyl ethers of polyhydric phenols such as resorcinol, catechol, hydroquinone, bisphenol-A, bisphenol-F, tris-hydroxyphenyl methane, 2, 6, 2 ' , 6 ' -tetra- bromo-p, p ' -bisphenol-A, 2 , 6, 2 ' , 6 ' -tetramethyl-3, 5,3'- tribromo-p, p ' -biphenol, 2, 6, 2 ' , 6 ' -tetramethyl-3, 5, 3 ' , 5 ' - tetrabromo-p, p ' -biphenol, tetramethylbiphenol, bisphenol-E, mixtures thereof and the like.
  • polyhydric phenols such as resorcinol, catechol, hydroquinone, bisphenol-A, bisphenol-F, tris-hydroxyphenyl methane, 2,
  • liquid resinous polyepoxides generally possess a q value averaging less than 1, i.e., a liquid resinous polyepoxide consisting essentially of the diglycidyl ether of bisphenol-A.
  • a polyepoxide may have a weight per epoxide equivalent value between 180 and 240.
  • liquid means that the initial polyepoxide is in the liquid state at ambient conditions, i.e., 25 °C and 1 bar (760 mmHg) .
  • these polyepoxides are characterized by weight per epoxide equivalent values.
  • Weight per epoxide equivalent or "WPE” is defined and used herein to indicate the grams of resinous polyepoxide containing one gram equivalent of epoxy groups . Weight per epoxide equivalent is determined by the procedures described in "Epoxy Resins", pp. 133-135, Burge, Jr. and Geyer, Analytical Chemistry of Polymers, Part I, Kline, Ed. (Interscience 1959) .
  • the other reactant materials to make the resins of the present invention are preferably polyhydric phenolic materials which include, as non-limiting illustrative examples resorcinol, catechol, hydroquinone, bisphenol-A, bisphenol-F, dihydroxybiphenyl, tris-hydroxyphenyl methane, 2 , 6, 2 ' , 6 ' -tetrabromo-p, p ' -bisphenol-A, 2, 6, 2 ' , 6 ' -tetramethyl-3, 5,3' -tribromo-p, p ' -biphenol,
  • polyhydric phenolic materials which include, as non-limiting illustrative examples resorcinol, catechol, hydroquinone, bisphenol-A, bisphenol-F, dihydroxybiphenyl, tris-hydroxyphenyl methane, 2 , 6, 2 ' , 6 ' -tetrabromo-p, p ' -bisphenol-A
  • the amount of dihydric phenol and initial resinous polyepoxide to be employed in the process may vary over a wide range depending upon the type of reactants and the type of product to be desired.
  • the polyepoxide and the dihydric phenol reactants may be used in equivalency ratios of epoxide groups to phenolic (Ar—OH) of from 3.3:1 up to 0.5:1, more typically from 2.6:1 to 0.6:1, and preferably from 1.6:1 to 0.65:1.
  • the other preferred reactant of the present invention is a polyhydric phenolic material, other compounds having active hydrogens or other reactive groups may be used in the practice of the instant invention.
  • Such compounds containing groups reactive with the epoxy-containing material include, for example, those materials which contain an average of more than one organic hydroxyl, thiol, carboxyl, isocyanate, thioisocyanate or secondary amine group or any combination of such groups per molecule and those materials which contain only one primary amine group per molecule. These materials can be aliphatic or aromatic.
  • Suitable -COOH containing materials include dicarboxylic acids such as, for example, malonic acid, succinic acid, maleic acid, terephthalic acid, dinicotinic acid, mixtures thereof and the like.
  • Suitable materials containing thiol (—SH) groups include, as illustrative non-limiting examples, the thiol analogs to the aforementioned hydroxyl-containing materials.
  • Particularly suitable thiol materials include, for example, 1, 4-dimercaptobenzene, 1, 3-dimercapto- benzene, 1, 2-dimercaptobenzene, ethylene mercaptan, 1, 3-propanedithiol, 1, 4-butanedithiol, mixtures thereof and the like.
  • Suitable materials containing isocyanate groups include, but not limited to, any isocyanate-containing material such as aromatic or aliphatic or cycloaliphatic isocyanate-containing materials.
  • Particularly suitable isocyanate-containing materials include, for example, hexamethylene-1, 6-diisocyanate, benzene-1, 4-diisocyanate, toluene diisocyanate, methylenediphenylisocyanate, mixtures thereof and the like.
  • Suitable materials containing thiocyanate groups include, as non-limiting illustrative examples, the thiol analogs to the aforementioned isocyanate-containing materials.
  • Particularly suitable thiol materials include, for example, hexamethylene-1, 6-dithiocyanate, benzene-1, 4- dithiocyanate, toluenedithiocyanate, methylene- diphenylthiocyanate, mixtures thereof and the like.
  • Suitable materials containing secondary amine groups include any aromatic or aliphatic or cycloaliphatic secondary amine-containing materials.
  • Particularly suitable secondary amine-containing materials include, as illustrative and non-limiting examples, piperazine, ethoxylated ethylenediamine, mixtures thereof and the like .
  • Particularly suitable materials which contain only one primary amine group per molecule include, as non- limiting illustrative examples, aniline, halogenated and alkylated aniline, hexylamine, heptylamine, long chain aliphatic amine, cyclohexylamine, cycloheptylamine and alkylated cyclicamine, mixtures thereof and the like.
  • the amounts of other reactive materials and initial resinous polyepoxide to be employed in the process may vary over a wide range depending upon the type of reactants and the type of products.
  • the compound having reactive functional groups and the polyepoxide reactants may be used in equivalency ratios of epoxy groups to reactive functional group of from 3.3:1 to 0.5:1, more typically from 2.6:1 to 0.6:1, and most preferably from 1.6:1 to 0.65:1.
  • the preferred fusion catalysts that are useful in the practice of the present invention include but not limited to the tetra organic substituted phosphonium halides of the tri-organic radical substituted phosphines and the like.
  • Preferred phosphonium halides are those conforming to the formula :
  • X is a halogen atom
  • R]_, R 2 , 3 and R4 are the same or different and represent hydrocarbon residues which may or may not be substituted by one or more functional groups, such as halogen atoms.
  • These phosphonium halides may generally be prepared by mixing in approximately equimolar proportions of a phosphine with a halide. The mixing may be carried out with or without the application of heat, alone or in the presence of an inert solvent such as, for example, diethylether, benzene, chloroform or carbon tetrachloride .
  • Preferred phosphines include but not limited to the organic phosphines, i.e., compounds of the formula
  • R is an organic radical and the other R's are hydrogen or organic radicals and preferably hydrocarbon radicals or substituted hydrocarbon radicals which may contain no more than 25 carbon atoms.
  • phosphines include but not limited to triphenyl phosphine, tri (tolyl) phosphine, tributyl phosphine, trilauryl phosphine, tricyclohexyl phosphine, trihexyl phosphine, triallyl phosphine, tridodecyl phostrieicosadecyl phosphine, trichlorobutyl phosphine, triethoxybutyl phosphine, trihexenyl phosphine, trixylyl phosphine, trinaphthyl phosphine, tricyclohexenyl phosphine, tri (3, 4-diethyloctyl) - phosphine, trioctadecyl phosphine, dioctyldecyl phosphine, dicyclohexyl phosphine, dicycl
  • Particularly preferred phosphines to be employed include the trihydrocarbyl, dihydrocarbyl and monohydrocarbyl phosphines wherein the hydrocarbyl radicals (hydrocarbon radicals) contain from 1 to
  • hydrocarbon radicals are alkyl cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, arylalkyl, and the like radicals.
  • the phosphines containing at least one and preferably three aromatic radicals are the phosphines containing at least one and preferably three aromatic radicals.
  • organic halides are those wherein the organic radical is a hydrocarbon radical, preferably having from 1 to 10 carbon atoms.
  • organic halides include methylchloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, propyl iodide, n-butyl iodide, sec-butyl iodide and n-decyl iodide, and the like, and mixtures thereof .
  • Examples of the above-noted phosphonium catalysts include, among others, methyltriphenyl phosphonium iodide, ethyltriphenyl phosphonium iodide, propyl- triphenyl phosphonium iodide, n-butyltriphenyl phosphonium iodide, iso-butyltriphenyl phosphonium iodide, sec-butyltriphenyl phosphonium iodide, n-pentyltriphenyl phosphonium iodide, n-decyltriphenyl phosphonium iodide, methyl tributyl phosphonium iodide, ethyltributyl phosphonium iodide, propyl tributyl phosphonium iodide, methyl triphenyl phosphonium chloride, ethyl tri(p-tolyl) phospho
  • phosphines could also be used without further modification as catalysts of the present invention.
  • Non-limiting examples of such phosphines include triphenylphosphine, tri-p-tolyl- phosphine, tris-p-chloro-phenylphosphine, tri-n-butyl- phosphine, dibutylallylphosphine, trilaurylphosphine, trihexenylphosphine, tridodecylphosphine, dicyclohexyl- phosphine, trinaphthyl-phosphine, triethoxybutyl- phosphine, tris-p-methoxyphenylphosphine, tris-p-fluoro- phenylphosphine, and the like, as well as mixtures thereof.
  • the amount of the fusion catalyst will vary over a wide range. In general, amount of catalyst will vary from
  • the reaction conditions at each reaction zone may be maintained, i.e., the polyepoxide may be allowed to increase in molecular weight and weight per epoxide equivalent, for a period of time sufficient to produce the thermosetting polyepoxide, phenoxy-terminated resin, or hydroxy-terminated polyether upstaged or advanced to the desired molecular weight or weight per epoxide equivalent.
  • the average value of q may be allowed to increase by at least 2, and preferably by 4 to 12, from its initial value.
  • the molecular weight of the feed epoxy resin is from 340 to 800 preferably from 360 to 450, and most preferably from 370 to 420.
  • the fused product epoxy resin has an average molecular weight from 600 to 10000, preferably from 800 to 6000 and most preferably from 900 to 5000.
  • the Continuous Solution Reaction Unit consists of a single jacketed pressure feed vessel with an air-driven mixer, a feed pump, a series of four heat-traced pipe reactors (at 50, 100, 100, 100 ml volumes respectively) with internal static elements, a heat exchanger pipe (100 ml volume) for cooling the exiting reaction product, and a back pressure regulator.
  • a schematic diagram is shown in Figure 1.
  • the feed consisting of the raw materials, catalyst and the solvent, is prepared externally in a 4-neck flask equipped with a stirrer, a thermocouple, and a condenser. Solid reactant and liquid epoxy resin are charged, mixed followed by the solvent. Heat is applied only as needed. Upon full dissolution of the solids, catalyst is added and uniformly mixed into the solution. This reaction premix is then transferred into the feed vessel (pre- warmed as needed via the heat jacket) , gently deaerated with nitrogen (pressurizing the vessel to 25 psig and released to ⁇ 5 psig, repeated another 2 times, and finally pressurizing to 15-25 psig nitrogen atmosphere) .
  • the Continuous Solution Reaction Unit can be utilized to produce a variety of resin products.
  • Acetone and xylene are the primary solvents in the preparation of the reactive feedstock (liquid epoxy resin and phenolic components, with catalyst such as ethyl triphenyl- phosphonium iodide or triphenyl phosphine) .
  • the Reaction Unit is normally filled, flushed and cleaned with the solvent to be used in the next experiment from the feed vessel using the diaphragm pump. After cleaning the reactors, the pump is stopped, and excess solvent drained from the feed vessel. The feed vessel is then charged with the reaction mixture (see Feed Preparation section above) .
  • the premix solution is delivered via the diaphragm pump continuously through a series of heat-traced static mixer-reactors in which the coupling reaction takes place.
  • the feed rate is gradually increased to the targeted flow rate and the temperature of each of the reaction zones is fine-adjusted as needed due to exotherm. Flow rates are checked during the run, and samples are taken after 3-5 turnovers (1400-2200 ml) and analyzed.
  • BPA Bisphenol-A
  • g 756
  • Triphenyl phosphonium ethyl iodide g: 1.9
  • BPA Bisphenol-A
  • BPA Bisphenol-A
  • g 756
  • Triphenyl phosphonium ethyl iodide g: 2.4
  • Triphenyl phosphonium ethyl iodide g: 2.7 Solvent, g: 526 (xylene)
  • EPON Resin 828 g: 1939 Bisphenol-A (BPA), g: 612
  • Triphenyl phosphonium ethyl iodide g: 2.3
  • BPA Bisphenol-A
  • Triphenyl phosphonium ethyl iodide g: 3.0
  • EPON Resin 828 g: 2068 Bisphenol-A (BPA), g: 653 Triphenyl phosphonium ethyl iodide, g: 2.5
  • Premix Composition Low Molecular weight solid epoxy resin @ 535 g/eq epoxy, g: 3144 Bisphenol-A (BPA), g: 465
  • EPON Resin 828 g: 1573 Bisphenol-A (BPA), g: 832
  • EPON Resin 828 g: 2385 Bisphenol-A (BPA), g: 959
  • TBPA Tetrabromo bisphenol-A
  • TBPA Tetrabromo bisphenol-A
  • TBPA Tetrabromo bisphenol-A
  • Triphenyl phosphine g: 2.8 Solvent, g: 900 (acetone)
  • Acetone regular font
  • Xylene Bold, Italic and Underlined

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Epoxy Resins (AREA)

Abstract

L'invention concerne un procédé continu permettant d'obtenir des résines époxydes hautement moléculaires, afin de produire des résines possédant un poids moléculaire plus élevé, Ce procédé consiste à (a) faire passer de manière continue une solution d'un composé doté de groupes hydrogène actifs ou de groupes fonctionnels réactifs pouvant réagir avec une résine époxyde liquide, un solvant inerte, et un catalyseur par une série de chambres de réaction au cours de diverses phases organisées en séquence; (b) les taux d'équivalence dudit composé possédant des groupes de protons actifs ou des groupes fonctionnels réactifs à la résine époxyde liquide introduite dans les chambres de réaction, étant compris entre 3.3:1 et 0.5:1 environ; la température dans les chambres de réaction est elle incluse entre 49 °C et 216 °C (120 °F-420 °F), et augmente de chambre en chambre, en gardant la pression à un niveau normal ou au-dessus de la normale dans lesdites chambres de réaction, et en mélangeant les matériaux au cours de la réaction de ceux-ci, avec des moyens adaptés; et (d) décharger le produit de résine époxyde au poids moléculaire accru ou produit polyléther hydroxy-terminé de la chambre de réaction de la phase ultime.
PCT/EP2000/008404 1999-08-30 2000-08-25 Procede de production de resines epoxydes hautement moleculaires Ceased WO2001016204A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU79039/00A AU7903900A (en) 1999-08-30 2000-08-25 Process for upstaging epoxy resins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38533199A 1999-08-30 1999-08-30
US09/385,331 1999-08-30

Publications (1)

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WO2001016204A1 true WO2001016204A1 (fr) 2001-03-08

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JP (1) JP2001064353A (fr)
AU (1) AU7903900A (fr)
WO (1) WO2001016204A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046287A1 (fr) * 1999-12-21 2001-06-28 Resolution Research Nederland B.V. Procede continu integre permettant de produire des resines epoxydes a plus haut poids moleculaire
CN100519609C (zh) * 2004-08-19 2009-07-29 旭有机材工业株式会社 生产酚醛清漆树脂的方法
US8242234B2 (en) 2008-06-30 2012-08-14 Basf Coatings Gmbh Process for continuous production of epoxy resins
US8686095B2 (en) 2008-06-30 2014-04-01 Basf Corporation Process for continuous production of epoxy resins

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101502647B1 (ko) * 2008-03-14 2015-03-13 디아이씨 가부시끼가이샤 우레탄(메트)아크릴레이트의 제조 방법
US20090326099A1 (en) * 2008-06-30 2009-12-31 Basf Corporation Process for continuous production of epoxy resins

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Publication number Priority date Publication date Assignee Title
US3919169A (en) * 1974-02-20 1975-11-11 Dow Chemical Co Continuous process for the production of solid epoxy resins
US4105634A (en) * 1976-08-11 1978-08-08 Celanese Corporation Production of thermosetting resinous polyepoxides
JPH03122112A (ja) * 1989-10-05 1991-05-24 Dainippon Ink & Chem Inc 固形ビスフェノールａ型エポキシ樹脂の連続重合製造法
EP0434124A1 (fr) * 1989-12-15 1991-06-26 Shell Internationale Researchmaatschappij B.V. Réacteur à multistage
US5824752A (en) * 1996-04-19 1998-10-20 Shell Oil Company Process for the preparation of advanced resins

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919169A (en) * 1974-02-20 1975-11-11 Dow Chemical Co Continuous process for the production of solid epoxy resins
US4105634A (en) * 1976-08-11 1978-08-08 Celanese Corporation Production of thermosetting resinous polyepoxides
JPH03122112A (ja) * 1989-10-05 1991-05-24 Dainippon Ink & Chem Inc 固形ビスフェノールａ型エポキシ樹脂の連続重合製造法
EP0434124A1 (fr) * 1989-12-15 1991-06-26 Shell Internationale Researchmaatschappij B.V. Réacteur à multistage
US5824752A (en) * 1996-04-19 1998-10-20 Shell Oil Company Process for the preparation of advanced resins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 015, no. 324 (C - 0859) 19 August 1991 (1991-08-19) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046287A1 (fr) * 1999-12-21 2001-06-28 Resolution Research Nederland B.V. Procede continu integre permettant de produire des resines epoxydes a plus haut poids moleculaire
CN100519609C (zh) * 2004-08-19 2009-07-29 旭有机材工业株式会社 生产酚醛清漆树脂的方法
US8242234B2 (en) 2008-06-30 2012-08-14 Basf Coatings Gmbh Process for continuous production of epoxy resins
US8686095B2 (en) 2008-06-30 2014-04-01 Basf Corporation Process for continuous production of epoxy resins

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Publication number Publication date
AU7903900A (en) 2001-03-26
JP2001064353A (ja) 2001-03-13

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