EP0000658B1 - Procédé de préparation d'isocyanurates contenant des doubles liaisons éthyléniques - Google Patents

Procédé de préparation d'isocyanurates contenant des doubles liaisons éthyléniques Download PDF

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Publication number
EP0000658B1
EP0000658B1 EP78300193A EP78300193A EP0000658B1 EP 0000658 B1 EP0000658 B1 EP 0000658B1 EP 78300193 A EP78300193 A EP 78300193A EP 78300193 A EP78300193 A EP 78300193A EP 0000658 B1 EP0000658 B1 EP 0000658B1
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Prior art keywords
process according
reaction
alcohol
trimerization
isocyanate
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EP0000658A1 (fr
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Kenneth Helmut Markiewitz
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Covestro Resins BV
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ICI Americas Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate

Definitions

  • This invention relates to a process for the preparation of ethylenically unsaturated isocyanurates. More particularly, this invention relates to a process for preparing an ethylenically unsaturated isocyanurate of a polyisocyanate and a monohydric alcohol containing a vinylidene group.
  • polyisocyanate when used in this application means a compound containing 2 or more NCO groups.
  • allyl group when used in the application means the group characterized by the formula:
  • aromatic polyisocyanate when used in this application means a compound containing at least 2 isocyanate groups each of which is attached directly to the carbon atom of an aromatic ring.
  • isocyanurate means a compound containing the structure:
  • ethylenically unsaturated isocyanurates may be prepared by a two-step process which comprises a first step of reacting a polyisocyanate with a monohydric alcohol containing a vinylidene group in the presence of a copper salt to form an isocyanate containing urethane and a second step of trimerizing the isocyanate containing urethane in the presence of an isocyanurate trimerization catalyst to form an ethylenically unsaturated isocyanurate.
  • R'" is a monovalent organic radical having the formula obtained by removing a hydroxyl group from a vinylidene carbonyl oxy alkanol
  • R" is an organic radical free of a group which is reactive with an isocyanate group and is the organic radical obtained by removing the isocyanate groups from a polyisocyanate
  • x is an integer which is one less than the number of isocyanate groups present in the polyisocyanate
  • each R' is independently selected from and with the proviso that each terminal R' is wherein x, R', R" and R"' are as defined above, and wherein the total number of isocyanurate rings is less then 400.
  • the isocyanurate compositions produced by the process of this invention may be monomeric, that is containing only one isocyanurate ring, or polymeric, that is containing more than one isocyanurate ring, but are usually mixtures of monomeric and polymeric species.
  • the solid isocyanurates of this invention Prior to curing, are fusible, that is they exhibit a softening point by the Ring and Ball method described in the A.S.T.M. Designation E28-58T.
  • thermoset resins The products of this invention may be generally classified as thermoset resins.
  • the prior art thermoset resins lack one or more important physical properties which would be desirable in their use. It is an object of this invention to prepare curable thermosetting compositions which combine excellent viscosity control at low as well as high dissolved solids concentrations; which are easily handled for laminate preparation; which may be blended with copper salts to yield a low exotherm on cure to prevent bubbling and warpage; which have a broad range of solubility in vinylidene monomers with which it is copolymerizable; which when cured form thermoset resins which exhibit good corrosion resistance in a variety of media, including water, acid and alkali; and which yield cured resins with superior stiffness and rigidity and excellent retention of physical properties at elevated temperatures.
  • the reaction of the polyisocyanate with the monohydric alcohol in the first step may be conducted in accordance with reaction conditions conventional in the prior art for reacting an alcohol with an isocyanate to form a urethane, provided that the reaction is carried out in the presence of a copper salt. It is essential, in accordance with the present invention, that the reaction of the monohydric alcohol with the polyisocyanate is carried out in the presece of a copper salt.
  • the copper salt used in the process of this invention may be any known copper salt, provided its anion does not interfere with the reaction.
  • the presence of iodide anions in the reaction will not interfere with the preparation of the ethylenically unsaturated isocyanurate, but iodide anions may interfere with the curing of the ethylenically unsaturated isocyanurates and thus iodide anions are preferably avoided.
  • the copper salt need not be soluble in the reactants or in any solvent which may be used.
  • copper salts which may be used include cupric acetate, cupric benzoate, cupric glycinate, cupric acetylacetonate, cupric sulfate, cupric oxalate, cupric chloride, cupric bromide, cupric nitrate, cupric naphthenate, cupric formate, mono- and di-cupric salts of ethylenediaminetetraacetic acid, cuprous chloride, cuprous bromide, cuprous cyanide, and cupric propionate. Mixtures of more than one copper salt may also be used.
  • a preferred catalyst is cupric acetate.
  • the use of a copper salt in the process of this invention serves several beneficial purposes.
  • the copper salt promotes the reaction of the aromatic polyisocyanate with the monohydric alcohol to form a urethane, helps prevent undesirable reactions which lead to gelation, improves the storage stability of the unsaturated isocyanurate product, permits the development of low exotherms when polymerizing the unsaturated isocyanurate product, promotes the formation of polymerized isocyanurate products having excellent physical properties, and allows the reaction to proceed in a safe and reproducible manner.
  • the amount of copper salt used will depend on the particular copper salt selected and on the particular polyisocyanate and monohydric alcohol used. In general, the amount of salt employed is from 0.001% to 1%, based on the total weight of polyisocyanate and alcohol. A preferred amount of copper salt is from 0.02% to 0.2%. Lower amounts of copper salt are less effective and, for practical purposes, produce no increased benefits. Larger amounts of copper salt may be used, but do not increase benefits and may interfere with polymerization of the unsaturated isocyanurate.
  • the polyisocyanate used in the process of this invention may be any trimerizable polyisocyanate which is conventionally used in the art for the preparation of isocyanurates.
  • the polyisocyanate may be saturated, unsaturated, monomeric or polymeric.
  • the only requirements are that the polyisocyanate contain at least two isocyanate groups, be trimerizable, and be free of any groups which interfere with the trimerization of isocyanate groups or which interfere in the reaction of an isocyanate group with a hydroxyl group.
  • Preferred isocyanates are aromatic isocyanates.
  • polyisocyanates which are particularly useful include: 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; m-phenylene diisocyanate; p-phenylene diisocyanate; 1,5-naphthalene diisocyanate; 4,4'-diphenyl ether diisocyanate; 4,4',4"-triphenylmethane triisocyanate; 2,4,4'-triisocyanatodiphenylmethane; 2,2',4-triisocyanato diphenyl; 4,4'-diphenylmethane diisocyanate; 4,4'-benzophenone diisocyanate; 2,2-bis(4-isocyanatophenyl)propane; 1,4-naphthalene diisocyanate; 4 - methoxy - 1,3 - phenylene diisocyanate; 4 - chloro - 1,3 - phenylenediisocyan
  • the monohydric alcohols which are useful in the process of this invention include any monohydric alcohol containing a vinylidene group but which does not contain an allyl group and, except for the alcoholic hydrogen, is free of radicals reactive with isocyanate groups.
  • Illustrative examples of such alcohols include 4-vinylbenzyl alcohol, hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 8-hydroxyoctyl acrylate, 12-hydroxydodecanyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2 - hydroxy - 3 - acryloyloxypropyl acrylate, 2 - hydroxy - 3 - phenoxypropyl acrylate, 2 - hydroxy - 3 - (o - chlorophenoxy)propyl
  • polyfunctional acrylates it is preferred to use them in combination with monofunctional acrylates and methacrylates to help minimize high working viscosities and possible gelation problems during the reaction.
  • Mixtures of monohydric alcohols containing a vinylidene group may also be used.
  • a preferred class of vinylidene alcohols are the ester alcohols, particularly the acrylates and methacrylates, containing one vinylidene group.
  • Preferred alcohols include hydroxypropyl methacrylate hydroxyethyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl acrylate.
  • all the monohydric alcohols used in the process of this invention contain a vinylidene group and are free of allyl groups
  • a minor amount of such alcohols may be replaced with other hydroxyl containing compounds, such as other monohydric alcohols, dihydric alcohols, monohydric phenols, or dihydric phenols.
  • the high temperature properties decrease as the amount of the monohydric alcohol containing a vinylidene group decreases, one may be willing to sacrifice somewhat on the high temperature properties in order to introduce other desirable properties. For example, in some applications, one may be willing to sacrifice some high temperature properties for the inclusion of flame-retardancy or low smoke properties.
  • the flame-retardancy properties may be introduced by substituting a minor amount of the monohydric vinylidene alcohol with a phosphorus or halogen containing alcohol or phenol.
  • low smoke properties may be introduced by substituting a minor amount of the monohydric, vinylidene alcohol with sulphur containing alcohols or phenols.
  • Saturated monohydric alcohols are particularly useful with polyisocyanates having a functionality greater than two in order to limit the degree of branching in the unsaturated isocyanurate.
  • Illustrative examples of monohydric alcohols which may be used to replace up to 49 mol percent of the monohydric alcohol containing a vinylidene group described above include: methanol, ethanol, propanol, butanol, isopropanol, isobutanol, octyl alcohol, cyclohexanol, benzyl alcohol, allyl alcohol, glycerol diallyl ether, trimethylolpropane diallyl ether, saturated halogenated alcohols, halogenated alcohols containing ethylenic unsaturation, halogenated allyl alcohols, halogenated monohydric alcohols such as 2-bromo ethanol, 3 - bromo - 1 - propanol; 4 - chloro - 1 - butanol, 2- chlorethanol, 4 - chloro - 1 - hexanol, 3 - chloro - 1 - propanol, 2,3 - dibromo
  • dihydric alcohols which may be used to replace up to 33 mol percent, and preferably up to 10 mol percent, of the monohydric alcohol containing a vinylidene group described above include: ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, compounds characterized by the formula: wherein R 1 is an alkyl group containing from 1 to 4 carbon atoms, 1,4-butane diol, pentamethylene glycol, hexamethylene glycol, glycerol methyl ether, glycerol monochlorohydrin, glycerol monostearate, and dihydroxy acetone.
  • phenols in small amounts (up to about 20%) that are reactive with aromatic isocyanates may be used in the practice of this invention.
  • the reactive phenols it is particularly important that essentially all of the phenolic hydroxyl groups are reacted with isocyanate groups so that unreacted hydroxyl groups will not be available to interfere with subsequent free radical curing reactions.
  • Phenols such as 4-hydroxyphenyl - 4' - chlorophenyl sulfone are especially useful because they characteristically improve the fire retardant and smoke properties of the product while still retaining elevated temperature retention of physical properties.
  • Phenol may also be used to block a minor portion of the isocyanate functionality which may later be regenerated at elevated temperature to produce products with improved bonding to a substrate, especially glass fibers. Nitrophenols do not react readily with isocyanates and are not within the scope of this invention.
  • the reaction of the polyisocyanate with the monohydric alcohol may be carried out at a temperature from 10°C to 130°C., and preferably from 40°C to 95°C. Lower temperatures result in a slow reaction whereas temperatures above 95°C may result in vinyl polymerization of the alcohol. It is preferred to run the urethane reaction at as low a temperature as possible in order to avoid vinyl polymerization of the alcohol.
  • a primary alcohol reacts to form a urethane at a lower temperature than a secondary or tertiary alcohol and an acrylate reacts at a lower temperature to give vinyl polymerization than a methacrylate.
  • a methacrylate of a secondary alcohol can be reacted at a relatively high temperature (reasonable rate of urethane formation, but no vinyl polymerization) but a primary alcohol acrylate requires a lower reaction temperature to avoid vinyl polymerization, but the primary alcohol group still undergoes the urethane reaction at a reasonable rate at the lower temperature.
  • the reaction of the polyisocyanate and the monohydric alcohol is continued until essentially all of the original hydroxyl groups have reacted.
  • the reaction product is an isocyanate-containing urethane product containing from 0.75 to 1.6 moles of unreacted isocyanate groups for each mole of starting polyisocyanate used.
  • the isocyanate-containing urethane product may be trimerized by any procedure conventional in the prior art for trimerizing isocyanates.
  • a preferred method of trimerizing the isocyanate-containing urethane comprises maintaining the urethane reaction product at a temperature from 0°C.
  • the trimerization catalyst used may be any trimerization catalyst known in the prior art for trimerizing isocyanates and which will not cause gelation of the isocyanurate.
  • Illustrative examples of such catalysts include tertiary amines such as N,N-dimethyl aniline. N-methyl morpholine, triethylene tetramine, tributyl phosphine, and N-benzyltrimethylammonium hydroxide.
  • the active trimerization catalyst is best employed in the range of from 0.04% to 1 %, based on the total weight of isocyanate and alcohol used. Higher levels may present difficulties in the control of the exothermic trimerization, and lower levels may be either ineffective of delay completion of the reaction.
  • the process of this invention may be conducted in the absence of a solvent, it is preferred to carry out the urethane forming reaction and the trimerization reaction in the presence of a solvent for the reactants.
  • the product formed is invariably a solid and therefore requires special processing which permits the easy removal of the heat generated by the reaction and prevents the reaction mixture from reaching high temperature which may induce insolubility and gelation of the products.
  • special processing techniques may be the trimerization of the monourethane in thin layers on moving temperature-controlled belts or in temperature-controlled trays.
  • a solvent When a solvent is used, it should be non-reactive, that is, the solvent should not contain any groups which would react with isocyanate groups or in any way interfere with the urethane forming reaction or the trimerization reaction. Thus, the solvent should not contain any hydroxyl, carboxy, or amine groups which might interfere with these reactions. This then limits the suitable solvents to esters, ethers, hydrocarbons and similar solvents containing non-reactive, non-functional groups.
  • Non- polymerizable solvents may also be used.
  • Illustrative of such solvents include benzene, toluene, xylene, dioxane, methyl ethyl ketone, ethyl acetate, and ethyl benzene.
  • the solvent may be removed when the reaction is complete to give a solid isocyanurate.
  • the solid isocyanurate may be dissolved in the same or a different solvent when it is to be cured.
  • Mixtures of solvents may also be used.
  • a preferred class of solvents are those which contain at least one polymerizable double bond.
  • a preferred solvent is styrene.
  • Other preferred solvents are a mixture of styrene and methyl methacrylate and a mixture of styrene and divinylbenzene.
  • the amount of solvent employed in the process of this invention may vary over a rather wide range.
  • the particular amount of solvent and the solvent used will depend somewhat of course on the nature of the solvent and on the solubility of the reactants used.
  • the reactants and the unsaturated isocyanurate products produced by the process of this invention are more soluble in polar solvents than in non-polar solvents.
  • the amount of solvent used will also depend, in the case of those solvents containing polymerizable double bonds, on the nature of the properties desired in the final product.
  • the high temperature properties of the final product will increase as the concentration of the styrene decreases.
  • the amount of solvent used will be from 0 to 95% by weight, and preferably from 30% to 80% by weight, based on the total weight of the reaction mixture.
  • the solution viscosity of the isocyanurates of this invention can be varied over a wide range by adjusting the stoichiometry of the aromatic polyisocyanates and hydroxy component employed in their synthesis and/or the temperature of the trimerization.
  • varying the degree of the excess isocyanate groups compared to hydroxyl groups it is possible to adjust the formation of high molecular weight species and solution viscosities at a fixed concentration.
  • Increasing the excess of isocyanate groups compared to hydroxyl groups favors higher molecular weight species and therefore higher viscosities
  • conversely lowering the excess isocyanate groups compared to hydroxyl groups favors lower molecular weight species and therefore lower viscosities.
  • the solution viscosity is increased as the temperature used in the trimerization reaction increases, but temperature variation is not as important a variable as the excess of isocyanate groups compared to hydroxyl groups.
  • the trimerization temperature must be maintained from 0°C. to 95°C., since too high a temperature will cause the vinylidene group to polymerize prematurely.
  • the amount of high molecular weight polyisocyanurate structures is increased by increasing the excess of isocyanate groups to hydroxyl groups.
  • the amount of these species may also be controlled by adjusting the trimerization temperature. As the solids levels decrease below 30% then extra care is needed with regard to the temperature profile. In some cases it may be necessary to alter the character of the solvent to keep the high molecular weight species in solution.
  • Table I illustrates ways to obtain vinylidene carbonyl oxy alkanol containing urethane isocyanurate solutions over a broad viscosity range.
  • Table I refers to the reaction products from hydroxypropylmethacrylate (HPMA) and toluene diisocyanate (TDI) dissolved in styrene, those skilled in the art will understand that similar relationships hold true for other solvent systems using other polyisocyanates or vinylidene alcohols.
  • the examples in Table I illustrate the effect of the three important reaction parameters on the viscosity of the final product. Examples F and G as well as H and I show the effect of trimerization temperature on the viscosity of the final product.
  • Examples D and F and J and L illustrate the effect of concentration on the viscosity
  • examples B and C, E, F, and I and also J and K demonstrate the effect of the molar excess of NCO groups compared to hydroxyl groups per mole of polyisocyanate, on the viscosity of the final product.
  • All reactions listed in the table were carried to completion, i.e., the residual isocyanate content was essentially zero. Additional viscosity control may be achieved also by stopping the reaction short of completion as can be done in the usual manner by adding active hydrogen compounds compatible with the system and/or destruction of the trimerization catalyst. All reaction runs are in styrene using HPMA and TDI.
  • reaction runs B through L were made using the procedure outlined in example 1 whereas reaction run A was made according to the procedure outlined in example 8.
  • the procedure used for run A involves a somewhat different mode of addition of polyisocyanate than used in runs B through L and is used primarily for the synthesis of low concentration products.
  • the addition of stabilizers is not necessary.
  • Exemplary of compounds which may be added to the final reaction product to neutralize the trimerization catalyst include acids such as acetic, phosphoric, sulfuric, oxalic, methanesulfonic, maleic, fumaric, acrylic, phthalic, isophthalic, and pyromellitic acids.
  • acids such as acetic, phosphoric, sulfuric, oxalic, methanesulfonic, maleic, fumaric, acrylic, phthalic, isophthalic, and pyromellitic acids.
  • the use of methanesulfonic acid or a mixture of methanesulfonic acid and oxalic acid are preferred.
  • the amount of acid to be added varies with the particular isocyanurate and percent of isocyanurate in solution. Generally the amount of acid should range between about 50 and 200 mole percent, and preferably from 100 to 175 mole percent, of the trimerization catalyst used. If the combination of methanesulfonic acid/oxalic
  • the addition of an acid to neutralize the trimerization catalyst is effective to impart extended shelf life to the isocyanurate products of this invention, particularly in the case of isocyanurate solutions containing at least 40% by weight of dissolved solids.
  • levels of residual isocyanurate content of up to 0.15% and even up to 0.2% at the time the trimerization reaction is terminated with an acid, such as methane sulfonic acid, do not cause serious stability problems.
  • levels of isocyanate content above 0.1 % in isocyanurate solutions having a concentration of less than 40% by weight of dissolved solids at the time the trimerization reaction is terminated with the addition of the acid may adversely affect the shelf stability of the isocyanurates.
  • these low solids solutions may be desirable for the shelf life of these low solids solutions to reduce the residual NCO to levels below 0.1 % through the addition of small amounts of compounds with labile hydrogen which react with NCO, such as alcohols and primary or secondary amines.
  • compounds with labile hydrogen which react with NCO, such as alcohols and primary or secondary amines.
  • Low molecular weight alcohols such as methanol, ethanol, propanols, and butanols and secondary amines are preferred.
  • Dibutyl amine is the most preferred of those compounds.
  • a small amount of a cbnventional polymerization inhibitor such as hydroquinone, tertiary butyl catechol and the methyl ether of hydroquinone should be incorporated in the reaction mixture prior to reaction.
  • the unsaturated isocyanurate compositions prepared by the process of this invention and solutions thereof in a copolymerizable solvent may be polymerized or cured in accordance with polymerization conditions conventional in the art for the polymerization of ethylenically unsaturated materials.
  • the polymerization may be carried out by reacting the unsaturated isocyanurate in the presence of a polymerization catalyst.
  • Suitable polymerization initiators include the various peroxide initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, di(2-ethylhexyl)peroxydicarbonate, t-butyl perbenzoate, dicumyl peroxide, and t-butyl hydroperoxide.
  • Azo compounds such as azobisisobutyronitrile may be used in combination with peroxide initiators.
  • the amount of initiator employed is usually very small. For example, from 1 part of initiator per 1000 parts of the polymerizable mixture to 5 parts per 100 parts of said mixture.
  • Suitable accelerators include cobalt, manganese, lead, and iron compounds, such as cobalt naphthenate and manganese naphthenate, and tertiary amines such as dimethyl aniline.
  • the isocyanate product particularly when prepared as a solution in a copolymerizable monomer, may contain any of the additives which are conventionally employed in polymerization systems, tor example, antioxidants, U.V. absorbers, fillers, dyes and pigments.
  • Unsaturated isocyanurate products produced by the process of this invention have been found to be particularly useful in applications such as castings, coatings and laminates where it is desirable to have excellent combinations of flexural, tensile, and impact properties and good corrosion resistance at elevated temperatures.
  • the products of this invention are particularly useful in a variety of filament wound products such as pipes, ducts, and storage tanks and in molded products where they may be combined with fillers and fibers.
  • Laminates are prepared by rolling the indicated isocyanurate solution containing the curing reagents evenly onto glass fiber mats with a paint-type roller then rolling thoroughly with a grooved laminating roller.
  • the curing reagents are added to the solution of isocyanurate in copolymerizable solvent by first adding the indicated promoter and accelerator to the isocyanurate solution and then adding the indicated peroxide 3mm (1/8") thick laminates are prepared with two layers of split strand 457 g/m 2 (1 2 ounce) glass mats sandwiched between two 0.25 mm (10 mil) surfacing "C" glass mats.
  • the weight of the glass is 25% of the total resin glass weight.
  • 6 mm (1/4 inch) thick laminates are made by the following combination of glass mats impregnated with resin: 0.25 mm (10 mil) surfacing "C" glass mat, two layers of 457 g/m z (1 t ounce) chopped strand mat, 1 layer woven roving, one layer of 457 g/m 2 (1 t ounce) chopped strand mat, 1 layer of woven roving and a final layer of 457 g/m 2 (1-12 ounce) chopped strand glass mat.
  • the amount of resin used to make this 6 mm (1/4") laminate is adjusted to give a resin ratio of 70%.
  • Laminates are covered with a thin polyester film to exclude air from the surface during cure. After 18-24 hours at room temperature the cured laminates are heated for 1 hour at 100°C in an oven for postcure.
  • a three-neck, round-bottom, 5 liter glass flask, equipped with thermometer, air inlet, dropping funnel, stirrer, and condenser is charged with 865 ml of hydroxypropyl methacrylate, 2144 ml of styrene, 1.8 g of cupric acetate, and 800 mg of hydroquinone.
  • the solution is heated to 85°C., and 852 ml of toluene diisocyanate are slowly added over a 150 min. period.
  • the temperature of the reaction medium during the addition of the toluene diisocyanate is maintained between 88°C. and 90°C.
  • the temperature of the reaction mixture is maintained at about 90°C. for an additional 90 min.
  • the resulting dark green liquid is cooled to 55°C., and 5 ml of a 40% solution of benzyltrimethylammonium hydroxide dissolved in methanol is added over a 13 min. period. Heating is then continued at 55°C for 2 hrs. to form an ethylenically unsaturated isocyanurate.
  • the resulting clear, emerald green solution is cooled to 55°C., and 1.5 ml of a 40% solution of benzyltrimethylammonium hydroxide and methanol is added. The solution remains unchanged for several minutes and then begins to turn brown. The temperature of the solution is maintained at 55°C. until the isocyanate content falls to about 0.
  • the resulting product is a styrene solution of the ethylenically unsaturated isocyanurate of toluene diisocyanate and hydroxypropyl methacrylate.
  • Examples 3-5 are prepared according to the process recited in Example 2 except that the amounts of styrene, hydroxypropyl methacrylate (HPMA), hydroxyethyl methacrylate (HEMA), and toluene diisocyanate (TDI) used are those indicated in the following Table I.
  • HPMA hydroxypropyl methacrylate
  • HEMA hydroxyethyl methacrylate
  • TDI toluene diisocyanate
  • Example 1 According to the process of Example 1, 1314 grams of styrene, 232 grams of hydroxypropyl methacrylate, 4 ml. of a 10% solution of tertiary butyl catechol in styrene, and 920 milligrams of cupric acetate monohydrate are heated to 90°C. under an air sparge and nitrogen blanket and 335 grams of toluene diisocyanate (25% excess) are then added slowly over 60 minutes. The temperature is maintained at 90°C during the addition and for 60 minutes afterward. The product is cooled to 41 °C and 5 ml of 4% benzyltrimethylammonium hydroxide (Triton B registered trade mark at least in the United Kongdom) in methanol are added.
  • Triton B registered trade mark at least in the United Kongdom
  • the temperature is maintained at 45°C. for 4 hours.
  • 5 ml. of tertiary butyl catechol (10% solution in styrene) and 1.05 ml. of methanesulfonic acid are added and the product is cooled.
  • the resulting polymeric, ethylenically unsaturated polyisocyanurate contains a high proportion of product of molecular weight about 200,000 as determined by gel permeation chromatography.
  • the viscosity after sitting overnight at room temperature is about 10,000 centipoise.
  • a 3-liter, 4-neck flask equipped with temperature control, air sparge, N 2 blanket, condenser, addition funnel, and stirrer is charged with 1254 grams of styrene, 227grams of hydroxypropyl methacrylate (hydroxyl number 364), 460 milligrams of cupric acetate monohydrate, and 4.0 ml of 10% tertiary butyl catechol (TBC) in styrene.
  • TBC tertiary butyl catechol
  • TDI toluene diisocyanate
  • the temperature is maintained at 90°C for an hour and a half, after which the solution is cooled to 45°C. 5 cc. of a 40% solution of benzyltrimethylammonium hydroxide in methanol is added.
  • the resin turns very dark and an exotherm occurs which is controlled by means of a water bath so that the temperature does not exceed 50°C., and is restored to 45°C. and is maintained there.
  • 1.20 cc. of methanesulfonic acid is added and a cooling water bath is applied.
  • At 30°C. 5 ml. of 10% t-butyl catechol solution in styrene is added.
  • the resin is poured into cans.
  • the Brookfield viscosity is 395 cps. at 25°C. Physical properties are measured on a 3mm (1/8") casting that is postcured at 100°C. for 1 hour.
  • the cure system comprises 100 grams resin, 0.4 gram dimethyl aniline, 0.5 gram cobalt naphthenate, 0.5 gram Lupersol 224 (acetylacetone peroxide solution). (Lupersol is a registered trade mark at least in the United Kingdom) and 1.5 grams tertiary butyl perbenzoate.
  • the casting (30% solids in styrene) has the following physical properties:
  • the reaction mixture is kept at 90 ⁇ 5°C. for an additional hour, then cooled over a 1 hour period to 35°C.
  • the trimerization reaction is terminated after 2.6 hours by addition of 14.9 grams dibutylamine; after 15 minutes, 1.49 ml. methanesulfonic acid (MSA) is added.
  • the resulting product has a viscosity of 998 cps. at 22.4°C.
  • a 3 mm (1/8") casting is made and cured according to the method described in Example 7.
  • the casting (25% solids in styrene) has the following properties:
  • methyl methacrylate (892 grams, 8.91 moles), hydroxypropyl methacrylate. (414 grams, 2.78 moles), copper acetate monohydrate (0.403 gram), and 10% tertiary butyl catechol/styrene solution (4.0 cc.).
  • methyl methacrylate 892 grams, 8.91 moles
  • hydroxypropyl methacrylate. (414 grams, 2.78 moles)
  • copper acetate monohydrate 403 gram
  • 10% tertiary butyl catechol/styrene solution 4.0 cc.
  • a 3 mm (1/8") laminate is prepared using two piles of 457 g/m 2 (1-lz ounce) chopped fibreglass strand mat between 0.25 mm (10 mil.) surfacing "C" glass mats and cured at 100°C, for one hour.
  • the casting and laminate have the following properties:
  • a 3-liter, 4-necked flask equipped with a mechanical stirrer, thermometer, air sparge, reflux condenser, dropping funnel and nitrogen inlet is charged with hydroxypropyl methacrylate (414 grams, 2.8 moles), styrene (772 grams, 7.4 moles), divinylbenzene (124 grams of a 72% active solution, 0.68 moles), cupric acetate monohydrate (0.45 gram), and 20% solution of tertiary butyl catechol in styrene (2 ml).
  • the mixture is heated to 40°C. and toluene diisocyanate (TDI) (80/20 mixture of 2,4- and 2,6-isomers, 486 grams, 2.8 moles) added over one hour.
  • TDI toluene diisocyanate
  • the reaction temperature is gradually increased to 90°C. by a combination of external heat and the exothermic nature of the reaction.
  • the reaction mixture is kept at 90° for an additional hour and then cooled over ninety minutes to 45 ⁇ 5°C.
  • Triton B 50% solution of benzyltrimethylammonium hydroxide in methanol, 5 ml.
  • the reaction mixture is kept at 55 ⁇ 5°C. for 2.5 hours and the trimerization reaction terminated by addition of methanesulfonic acid (1.2 ml.).
  • the product has a viscosity of 1060 cps. at 21°C.
  • a laminate is prepared and cured according to the method used in Example 9. The cured laminate has a flexural strength of 130 MN/m 2 (18,800 psi) at room temperature and 76.5 MN/m 2 (11,100 psi) at 177°C (350°F.).
  • Examples 18-20 are prepared according to the process of Example 17 except that the indicated amounts of toluene diisocyanate, unsaturated alcohol, solvent and catalyst used are those indicated in Table III.
  • Example 17 The procedure of Example 17 is used in Examples 21-26. The indicated reactants, catalysts and solvent and the amounts used are shown in Table IV.
  • the isocyanurate products of Examples 27-34 are prepared according to the procedure of Example 1, except for the variations in reactants, solvent and catalysts indicated in Table V.
  • a preferred method of this invention is as follows.
  • a chemical reactor equipped with agitator, condenser, gas pipe connections, vents, and port holes is first flushed with subsurface nitrogen.
  • an air sparge and nitrogen stream having relative flow rates of 1 to 3 are introduced into the reactor.
  • 2.7 parts of hydroxypropylmethacrylate (HPMA) are then charged to the reactor.
  • the air sparge and nitrogen streams are temporarily turned off and 0.0029 part of copper acetate monohydrate and 0.012 part of 20% solution of tertiary butyl catechol (TBC) in styrene are charged to the reactor under continuous agitation.
  • TBC tertiary butyl catechol
  • the air sparge and nitrogen blanket streams are turned on again and 5.7 parts of styrene are charged to the reactor.
  • the reaction mixture is then heated to about 40°C.
  • the incremental addition of an 80/20 mixture of 2,4- and 2,6-toluene diisocyanates (TDI) starts.
  • An overall amount of 3.1 parts of TDI are charged over about one hour period.
  • the exotherm of the reaction of TDI with the alcohol raises the temperature of the reaction mixture to about 90°C.
  • the temperature is lower or higher than 90° external heating or cooling is applied respectively to bring the temperature to about 90°C.
  • the reaction mixture remains at about 90°C. for at least one hour after the total amount of TDI has been added and until the NCO content of the reaction mixture drops to below 4.5% by weight.
  • the reaction product has a number average molecular weight of about 1160, a weight average molecular weight of about 2000, and a polydispersity of about 1.9.
  • About 95% of the isocyanurates present have a molecular weight of below about 5200 and contain some isocyanurates having a molecular weight above 5200 and below about 26,000.
  • This product corresponds to a product of formula II above where the number of isocyanurate rings in most of the isocyanurate molecules is less than 10.
  • This product has a ball and ring melting point of about 95°C. and a viscosity of about 400 - 600 cps at 25°C., and a refractive index of about 1.557 N D 20.
  • the infrared spectrum of this product shows absorption bands characteristic of isocyanurates and the essential absence of isocyanate functionality.
  • the hydroxyl number of the product is essentially zero.
  • the solution is maintained at 55°C for one hour.
  • the reaction is terminated by the addition of 1.3 ml. of a 10% solution in styrene of a 50/50 mixture of t-butyl catechol and mono-methyl ether of hydroquinone.
  • the product has a viscosity of 200 cps at 25°C.
  • Two-ply glass laminates (25% glass, 3mm (0.125 inch) thick) of the resulting 50% resin solution in styrene and which are cured with 0.1% dimethylaniline, 0.5% acetyl acetone peroxide solution (4% active oxygen), 1.5% tertiary butyl perbenzoate, and 0.1% of a 10% solution of tertiary butyl catechol in styrene, have the following physical properties measured at 150°C (300°F): flexural strength 121 MN/m 2 (17,600 psi); flexural modulus 3.31 x 10 3 MN/m 2 (0.48 x 10 6 psi); tensile strength 82 MN/m 2 (11,900 psi); tensile modulus 4.55 x 10 3 MN/m 2 (0.66 x 10 6 psi); Barcol hardness 25-28; elongation 2.2%; notched Izod 5.5J (4.05).
  • toluene diisocyanate 80/20 mixture of 2,4- and 2,6- isomers, 342 ml., 2,44 mole
  • TDI toluene diisocyanate
  • the product is allowed to cool to 40°C. and then removed from the pan to be ground into a fine powder.
  • the product is then dissolved in an equal weight of styrene, 1.5% tertiary butyl perbenzoate, 0.5% of a 6% solution of cobalt naphthenate, and 0.4% dimethylaniline are added and then 0.5% of acetylacetone peroxide solution (4% active oxygen) is added to the solution.
  • the solution containing the curing reagents is used for the preparation of a 3mm (1/8") laminate containing about 25% glass.
  • the physical properties of the laminate are as follows:
  • a 3mm (1/8") casting prepared from the same 50% solution of the solid VIC resin in styrene exhibits a heat deflection temperature of 124°C (255°F).
  • a 3-liter, 4-neck flask equipped with mechanical stirrer, thermometer, air sparge, reflux condenser, nitrogen inlet, and two dropping funnels is charged with 954.9 grams of styrene, 4 ml. of 10% solution of t-butyl catechol in styrene and 920 mg. of cupric acetate.
  • the mixture is heated to 65°C. and 426.4 ml. of toluene diisocyanate and 445 ml. of hydroxypropyl methacrylate added simultaneously over a one hour period. Heating is continued for an additional 1.5 hours at 65°C.
  • the reaction mixture is then cooled to 55°C.
  • a laminate is prepared and cured according to the method used in Example 9. The cured laminate has a flexural strength of 138 MN/m 2 (20,200 psi) at 150°C (300°F).
  • a four neck, 1000 ml. r.b. glass flask, equipped with stirrer assembly, pot thermometer, dropping funnel, air inlet and reflux condenser is charged with 24.6 ml. hydroxyethyl methacrylate, 243.2 grams benzene, 225 mg. cupric acetate, and 100 mg. hydroquinone.
  • the reaction mixture is heated to 79°C. and 34.8 grams toluene diisocyanate added over a 15-minute period. Heating at 80°C. is continued for an additional 40-minute period.
  • the product is then cooled to 55°C. and 1.5 ml. 40% methanolic benzyltrimethylammonium hydroxide added.
  • the reaction is maintained at 55°C for 52 minutes.
  • the product is an olive green liquid. After solvent removal, the product is isolated as a light brown powder.
  • a 150 ml. resin kettle, equipped with immersed thermometer, air inlet, addition funnel, and mechanized stirrer assembly is charged with 100 ml. carbon tetrachloride, 14.4 ml. hydroxypropyl methacrylate, 20 mg. cupric acetate, and 75 mg. hydroquinone.
  • the reaction mixture is heated to 77°C and 14.2 ml. toluene diisocyanate added over 14 minutes.
  • the product is maintained at 77°C. for an additional 31 minutes.
  • To 10 ml. of this product a clear yellow liquid, is added 2 drops of 40% methanolic benzyltrimethylammonium hydroxide and the product is maintained overnight at room temperature.
  • the reaction product in carbon tetrachloride is a yellow paste, showing only traces of an isocyanate peak.
  • Example 1 The procedure and apparatus of Example 1 are used herein. Into a solution of 955 grams styrene are charged 441 grams hydroxypropyl methacrylate, 920 mg. cuprous chloride, and 4 ml. of a 10% solution in styrene of t-butyl catechol. The solution is heated to 90°C. and 426.4 ml. toluene diisocyanate added dropwise over one hour. The reaction is maintained at 90°C. for an additional 40 minutes, and then cooled to 55°C. Thereupon 5 ml. of a 40% methanolic solution of benzyltrimethylammonium hydroxide is added, the exotherm controlled, and the reaction mixture maintained at 55°C. for 2 hours and 25 minutes. The product, a clear amber brown liquid, is cooled and stabilized by the addition of an additional 5 ml. t-butyl catechol solution, and -1.5 ml of methanesulfonic acid.

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Claims (30)

1. Procédé de préparation d'un isocyanurate à non-saturation éthylénique, caractérisé en ce qu'on fait réagir un polyisocyanate avec un constituant hydroxylé choisi entre
(a) un alcool monohydroxylé qui contient un radical vinylidène et qui ne contient pas de radical allyle;
(b) un alcool monohydroxylé tel que défini en (a) avec jusqu'à 49 moles % d'un alcool monohydroxylé qui ne contient pas de radical vinylidène et qui peut contenir éventuellement un radical allyle;
(c) un alcool monohydroxylé tel que défini en (a) avec jusqu'à 33 moles % d'un alcool dihydroxylé et
(d) un alcool monohydroxylé tel que défini en (a) avec jusqu'à 20 moles % d'un phénol; la réaction étant effectuée en la présence d'un sel de cuivre pour la formation d'un uréthanne contenant des radicaux isocyanate, les quantités de constituant hydroxylé et de polyisocyanate étant choisies pour procurer après la réaction 0,75 à 1,6 mole de radicaux isocyanate inchangés par mole de polyisocyanate mis en oeuvre, puis on ajoute une quantité catalytique d'un catalyseur de trimérisation des isocyanates qui amorce la trimérisation de l'uréthanne contenant des radicaux isocyanate sans provoquer de gélification et on conduit la trimérisation de l'uréthanne contenant des radicaux isocyanate pour former un isocyanurate à non-saturation éthylénique.
2. Procédé suivant la revendication 1, dans lequel le polyisocyanate organique est un polyisocyanate aromatique.
3. Procédé suivant la revendication 2, dans lequel l'alcool monohydroxylé est le méthacrylate d'hydroxypropyle, l'acrylate d'hydroxypropyle, le méthacrylate d'hydroxyéthyle, l'acrylate d'hydroxyéthyle, le triacrylate du pentaérythritol, le triméthacrylate du pentaérythritol ou un mélange de ces composés.
4. Procédé suivant la revendication 3, dans lequel l'isocyanate aromatique est un diisocyanato- toluène.
5. Procédé suivant là revendication 4, dans lequel le sel de cuivre est l'acétate cuivrique.
6. Procédé suivant la revendication 1 qui comprend (a) la préparation d'une solution d'un alcool monohydroxylé contenant un radical vinylidène, d'un sel de cuivre et d'un inhibiteur de polymérisation par radicaux libres dans un solvant qui est inerte à l'égard des radicaux isocyanate, (b) l'addition lente d'un polyisocyanate organique trimérisable à la solution en présence d'une quantité d'oxygène suffisante pour maintenir l'inhibiteur en activité tout en maintenant la température de la solution de 10 jusqu'à 130°C afin de former un monouréthanne contenant des radicaux isocyanate, (c) l'addition d'une quantité catalytique d'un catalyseur de trimérisation qui amorce la trimérisation du monouréthanne sans provoquer de gélification du monouréthanne et (d) le maintien de la température de 0 à 95°C pour la formation d'un isocyanurate.
7. Procédé suivant la revendication 6, dans lequel le polyisocyanate organique est un diisocyanate aromatique.
8. Procédé suivant la revendication 6, dans lequel le polyisocyanate organique est un diisocyanato- toluène.
9. Procédé suivant la revendication 7, dans lequel l'alcool est le méthacrylate d'hydroxypropyle.
10. Procédé suivant la revendication 7, dans lequel l'alcool est le méthacrylate d'hydroxyéthyle.
11. Procédé suivant la revendication 7, dans lequel l'alcool est l'acrylate d'hydroxyéthyle.
12. Procédé suivant la revendication 7, dans lequel l'alcool monohydroxylé est l'acrylate d'hydroxypropyle.
13. Procédé suivant la revendication 7, dans lequel l'alcool est un mélange de méthacrylate d'hydroxypropyle et de méthacrylate d'hydroxyéthyle.
14. Procédé suivant la revendication 7, dans lequel le solvant est un hydrocarbure aromatique.
15. Procédé suivant la revendication 7, dans lequel le solvant est un monomère vinylidénique.
16. Procédé suivant la revendication 7, dans lequel le solvant est choisi entre le styrène, le benzène, le méthacrylate de méthyle, le divinylbenzène, le méthacrylate d'éthyle, le dioxanne, l'acrylate d'éthyle, l'acétate d'éthyle et la méthyléthylcétone.
17. Procédé suivant la revendication 7, dans lequel le catalyseur de trimérisation est la tributyl- phosphine.
18. Procédé suivant la revendication 7, dans lequel le catalyseur de trimérisation est l'hydroxyde de N-benzyltriméthylammonium.
19. Procédé suivant la revendication 7, dans lequel la température de trimérisation est de 20 à 60°C.
20. Procédé suivant la revendication 7, dans lequel la quantité de solvant est de 30 à 80% en poids, sur la base du poids de la composition complète.
21. Procédé suivant la revendication 7, dans lequel le sel de cuivre est l'acétate cuivrique.
22. Procédé suivant la revendication 20, dans lequel l'alcool monohydroxylé est choisi entre le méthacrylate d'hydroxypropyle, le méthacrylate d'hydroxyéthyle, l'acrylate d'hydroxyéthyle, l'acrylate d'hydroxypropyle et leurs mélanges, le solvant est le styrène le polyisocyanate est un diisocyanato- toluène, le sel de cuivre est l'acétate cuivrique, le catalyseur de trimérisation est l'hydroxyde de N-benzyltriméthylammonium et la température de trimérisation est de 20 à 60°C.
23. Procédé suivant la revendication 22, dans lequel l'inhibiteur de polymérisation par radicaux libres est l'hydroquinone, le t-butylcatéchol, l'éther monométhylique d'hydroquinone ou un mélange de ces composés.
24. Procédé suivant la revendication 1, dans lequel le catalyseur de trimérisation est neutralisé à l'aide d'un acide après la formation de l'isocyanurate à non-saturation éthylénique.
25. Procédé suivant la revendication 24, dans lequel l'acide est l'acide méthanesulfonique ou un mélange d'acide méthanesulfonique et d'acide oxalique.
26. Procédé suivant la revendication 24, dans lequel un alcool ou une amine secondaire de bas poids moléculaire est ajouté avant que l'acide soit ajouté.
27. Procédé suivant la revendication 3, dans lequel le sel de cuivre est un sel cuivrique.
28. Procédé suivant la revendication 3, dans lequel le sel de cuivre est un sel cuivreux.
29. Procédé suivant la revendication 3, dans lequel la réaction formant l'uréthanne et la réaction de trimérisation sont conduites en l'absence de solvant.
30. Procédé suivant la revendication 1, dans lequel l'alcool monohydroxylé contient un radical ester.
EP78300193A 1977-07-27 1978-07-25 Procédé de préparation d'isocyanurates contenant des doubles liaisons éthyléniques Expired EP0000658B1 (fr)

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Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2854192A1 (de) * 1978-12-15 1980-06-26 Basf Ag Polyurethan-beschichtungsmittel
US4451610A (en) * 1979-06-11 1984-05-29 Premix, Inc. Preparation of curable solid polyester resin pellets and powders
US4352906A (en) * 1981-08-06 1982-10-05 Ici Americas Inc. Blister resistant calcium carbonate filled polyisocyanurate resin molding compositions
DE3318147A1 (de) * 1983-05-18 1984-11-22 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von, isocyanuratgruppen und olefinische doppelbindungen aufweisenden verbindungen, die nach diesem verfahren erhaeltlichen verbindungen und ihre verwendung als bindemittel bzw. bindemittelkomponente in ueberzugsmitteln
EP0132451B2 (fr) * 1983-07-26 1992-10-28 Dainippon Ink And Chemicals, Inc. Composition de résine durcissable et son utilisation
US4648843A (en) * 1985-07-19 1987-03-10 Minnesota Mining And Manufacturing Company Method of dental treatment using poly(ethylenically unsaturated) carbamoyl isocyanurates and dental materials made therewith
DE3737244A1 (de) * 1987-11-03 1989-05-18 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen und olefinische doppelbindungen aufweisenden verbindungen und ihre verwendung als bindemittel
DE4015155A1 (de) * 1990-05-11 1991-11-14 Bayer Ag Verfahren zur herstellung von isocyanuratpolyisocyanaten, die nach diesem verfahren enthaltenen verbindungen und ihre verwendung
US5095069A (en) * 1990-08-30 1992-03-10 Ppg Industries, Inc. Internally-curable water-based polyurethanes
JPH0541134A (ja) * 1991-08-02 1993-02-19 Matsushita Electric Ind Co Ltd 照光ボタン装置
JPH0534622U (ja) * 1991-10-15 1993-05-07 松下電器産業株式会社 自照式釦
US5763042A (en) * 1994-06-28 1998-06-09 Reichhold Chemicals, Inc. Reinforcing structural rebar and method of making the same
US6197844B1 (en) * 1996-09-13 2001-03-06 3M Innovative Properties Company Floor finish compositions
AU730440B2 (en) 1996-10-07 2001-03-08 Marshall Industries Composites Reinforced composite product and apparatus and method for producing same
US5777024A (en) * 1997-04-30 1998-07-07 The Valspar Corporation Urethane resins and coating compositions and methods for their use
EP2337808B1 (fr) * 2008-09-29 2017-03-15 Scott Bader Company Limited Composition réticulable de moulage
WO2012012481A1 (fr) * 2010-07-21 2012-01-26 Nike International Ltd. Balle de golf et procédé de fabrication d'une balle de golf
US8920264B2 (en) 2010-07-21 2014-12-30 Nike, Inc. Golf ball and method of manufacturing a golf ball
KR101697404B1 (ko) * 2013-09-30 2017-01-17 주식회사 엘지화학 편광판 및 이를 포함하는 화상표시장치
JP6434825B2 (ja) * 2014-03-04 2018-12-05 三井化学株式会社 ポリイソシアヌレート組成物の製造方法
FR3019489B1 (fr) 2014-04-03 2016-12-23 European Aeronautic Defence & Space Co Eads France Procede et installation de realisation d'une piece en materiau composite
CN109923143B (zh) * 2016-11-14 2022-04-22 科思创德国股份有限公司 由前体制造物体的方法和可自由基交联的树脂在增材制造法中的用途
TW201823343A (zh) * 2016-12-23 2018-07-01 奇美實業股份有限公司 熱可塑性樹脂組成物及其所形成的成型品
KR20200023416A (ko) * 2017-06-29 2020-03-04 메르크 파텐트 게엠베하 반도체 발광 나노입자를 포함하는 조성물
ES2981974T3 (es) * 2017-11-14 2024-10-14 Covestro Deutschland Ag Productos semiacabados basados en el mecanismo de reticulación dual
US20210328336A1 (en) * 2018-11-01 2021-10-21 Hewlett-Packard Development Company, L.P. Housings for electronic devices
CN109694460B (zh) * 2018-12-11 2021-04-20 万华化学集团股份有限公司 多官能度不饱和异氰酸酯三聚体及其制备和在分散体稳定剂中的应用

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2894950A (en) * 1959-07-14 Method of producing triallyl
GB629015A (en) * 1947-02-14 1949-09-09 Richard Geoffrey Roberts New polymerisable materials and polymers thereof
US3437715A (en) * 1955-04-15 1969-04-08 Pittsburgh Plate Glass Co Resin composition
US2952665A (en) * 1955-12-08 1960-09-13 Mobay Chemical Corp High molecular weight cyclic trimers containing blocked isocyanate groups
GB809809A (en) * 1956-11-16 1959-03-04 Ici Ltd Polymeric isocyanates and their manufacture
US2947736A (en) * 1956-12-31 1960-08-02 American Cyanamid Co Resin compositions
US2993870A (en) * 1957-08-20 1961-07-25 Us Rubber Co Process of trimerizing organic isocyanates
US3041313A (en) * 1958-04-16 1962-06-26 Shawinigan Resins Corp Polyspirane resins composition
US3065231A (en) * 1958-08-06 1962-11-20 Allied Chem Production of triallyl isocyanurate
US2958704A (en) * 1958-09-02 1960-11-01 Goodrich Co B F Alkenyl isocyanate-substituted carbamates
US3061591A (en) * 1959-11-27 1962-10-30 American Cyanamid Co Tris-p-vinyl benzyl isocyanurate and polymers thereof
NL270400A (fr) * 1960-10-20
US3168483A (en) * 1961-01-17 1965-02-02 Air Prod & Chem Diazabicyclooctane-alkylene oxide catalyst compositions
US3297745A (en) * 1962-04-05 1967-01-10 Robertson Co H H Ethylenically unsaturated di-and tetra-urethane monomers
US3154522A (en) * 1962-04-20 1964-10-27 Air Prod & Chem Polyisocyanurate preparation using a triethylene diamine and a tertiary imine co-catalyst
DE1495844A1 (de) * 1964-11-20 1969-11-13 Bayer Ag Verfahren zur Herstellung von Urethanoelen
US3450648A (en) * 1967-11-13 1969-06-17 Bayer Ag Process of producing cellular polyurethanes employing tertiary amines and certain organic metallic compounds as catalyst system
US3763269A (en) * 1968-03-25 1973-10-02 Allied Chem Polyesters from tris(2-hydroxyalkyl)isocyanurate homopolymers
GB1234728A (en) * 1968-09-11 1971-06-09 Takeda Chemical Industries Ltd Method for producing organic isocyanate polymers
US3872035A (en) * 1968-10-01 1975-03-18 Union Carbide Corp N-(2-hydroxyethyl)-ethyleneimines as catalysts for polyisocyanurate foam formation
US3658801A (en) * 1969-06-10 1972-04-25 Dart Ind Inc Trisubstituted isocyanurates
US3850770A (en) * 1969-10-24 1974-11-26 Kansai Paint Co Ltd Radiation curable compositions from acrylurethane resins
US3719638A (en) * 1969-10-29 1973-03-06 T Miranda Radiation curable acrylic urethane monomers
US3943075A (en) * 1970-06-19 1976-03-09 Dunlop Holdings Limited Polyurethane foams
US3642943A (en) * 1970-07-08 1972-02-15 Lord Corp Acrylic urethane composition of acrylic polymer with pendant isocyanate groups and isocyanate containing urethane prepolymer
US3694415A (en) * 1970-07-15 1972-09-26 Kiyoshi Honda Coating resinous composition
US3849349A (en) * 1971-05-12 1974-11-19 K Frisch Polyisocyanurate foam and process for producing the same
CH546798A (de) * 1971-08-17 1974-03-15 Ciba Geigy Ag Verfahren zum haerten von acrylsaeureesterderivaten mit ionisierenden strahlen.
US3852220A (en) * 1972-01-12 1974-12-03 Marathon Oil Co Isocyanurate-based polyelectrolyte detergent composition
JPS504719B2 (fr) * 1972-03-18 1975-02-22
US3723367A (en) * 1972-03-27 1973-03-27 Union Carbide Corp Alkali metal mercaptides as urethaneisocyanurate catalysts
US3786030A (en) * 1972-04-05 1974-01-15 Minnesota Mining & Mfg Catalyst for trimerizing polyisocyanates
JPS5339476B2 (fr) * 1972-07-03 1978-10-21
JPS5232391B2 (fr) * 1972-09-13 1977-08-20
GB1467632A (en) * 1973-05-08 1977-03-16 Ici Ltd Tertiary amines
US3925335A (en) * 1973-05-29 1975-12-09 Ici America Inc Vinyl urethane resins from halogenated diols and phosphonate diols
BE816887A (fr) * 1973-06-27 1974-12-27 Solutions de polyisocyanates physiologiquement sans danger
US3821067A (en) * 1973-07-05 1974-06-28 Atlantic Richfield Co Fire retardant polyurethane compositions
US3860673A (en) * 1973-07-31 1975-01-14 Du Pont Elastomeric compositions
US3932401A (en) * 1974-01-31 1976-01-13 Minnesota Mining And Manufacturing Company Mixed acrylic acid/methacrylic acid esters of tris (hydroxyalkyl) isocyanurates

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AU517552B2 (en) 1981-08-06
AU3817078A (en) 1980-01-24
DE2861008D1 (en) 1981-11-26
BR7804849A (pt) 1979-04-17
JPS60106819A (ja) 1985-06-12
CA1084497A (fr) 1980-08-26
IT1097348B (it) 1985-08-31
EP0000658A1 (fr) 1979-02-07
US4128537A (en) 1978-12-05
JPS6044328B2 (ja) 1985-10-03
IT7826192A0 (it) 1978-07-27
MX150756A (es) 1984-07-12
AR224727A1 (es) 1982-01-15

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