JPS6240356B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to isocyanurates. In particular, the present invention relates to isocyanurates that have excellent physical properties at elevated temperatures when cured. As used herein, the term "vinylidene group" is represented by the following formula CH ₂ =C (wherein the two free valence bonds are never both bonded to the same carbon atom). means a group that As used herein, the term "aromatic polyisocyanate" refers to compounds containing at least two isocyanate groups directly attached to carbon atoms of an aromatic ring. The term “isocyanurate” is defined by the formula means a compound containing an isocyanurate ring represented by The isocyanurates of the present invention can generally be classified as thermosetting resins. Prior art thermosets lack one or more important physical properties that are desirable for their use. It is an object of the present invention to combine excellent viscosity control at low as well as high dissolved solids concentrations, to be easy to handle for laminate production, and to provide a solids solution during curing by mixing with copper salts. It has low heat generation to prevent foaming and warping, has a wide range of solubility in copolymerizable vinylidene monomers, and when cured does well in a variety of media including water, acids, and alkalis. To produce an ethylenically unsaturated isocyanurate that forms a thermosetting resin that exhibits excellent corrosion resistance, has excellent stiffness and rigidity, and produces a cured resin that retains excellent physical properties even at high temperatures. . The wide range of applications of the isocyanurates of the present invention allows for the production of a wide range of products with properties superior to common polyester and isophthalate resins as well as other specialty vinyl ester resins. The isocyanurates of the present invention are also characterized by extremely high levels of aromatic and cyclic character derived from both the aromatic polyisocyanate and the isocyanurate rings. This high degree of aromatic and cyclic character appears to contribute substantially to the improved thermal stability and stiffness and stiffness of products made from the isocyanurates of the present invention.
The combination of these isocyanurates with a high degree of aromatic and cyclic character with unsaturated compounds, such as acrylates and methacrylates, is not easily obtainable with products of the prior art. A rapid curing system with excellent retention of physical properties becomes possible. This combination also allows for a wide range of solubility for the various comonomers copolymerized with the isocyanurates of the present invention. The isocyanurates of the present invention have a molecular weight range that allows for suitable solution viscosities (about 100 to about 1000 cps) for good handling and lay-up during laminate production. Isocyanurates of the present invention having solution viscosities greater than 1000 cps are also produced for use in applications requiring high viscosity. The isocyanurates of the present invention can be prepared at low solids concentrations and yet exhibit suitable viscosities for good handling. The isocyanurate of the present invention is an aromatic polyisocyanate and the following formula: and (In the above formula, R ₁ is hydrogen or an alkyl group containing 1 to 4 carbon atoms, and R ₂ is hydrogen, alkyl containing 1 to 12 carbon atoms, or chlorine containing 1 to 12 carbon atoms. a chlorinated, brominated or fluorinated alkyl group, R ₃ is hydrogen, an alkyl group containing 1 to 12 carbon atoms or a chlorinated, brominated or fluorinated alkyl group containing 1 to 12 carbon atoms; _R4
is hydrogen, a methyl group or an ethyl group, and n is 1 to 4, provided that R ₂ on the adjacent carbon atom
R ₃ must not be alkyl or chlorinated, brominated or fluorinated alkyl, i.e.
(provided that at least one of R ₂ and R ₃ must be hydrogen) isocyanurate obtained from an isocyanate group-containing urethane derived by reaction with at least one vinylidene carbonyloxyalkanol represented by It is. In order to obtain a cured product with an excellent combination of physical properties at elevated temperatures, the cured product should be based on at least a major amount of the isocyanurate moiety based on one or more vinylidenecarboxyoxyalkanols as defined above. It is essential that they be produced using unsaturated isocyanurates. Examples of such alkanols include hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
Included are hydroxyethyl acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and the diacrylates and dimethacrylates of trimethylolpropane, trimethylolethane, trimethylolmethane and glycerin. A preferred group of vinylidene carbonyloxyalkanols includes hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate and mixtures thereof. Another group of preferred such alkanols is blends of multifunctional acrylates or methacrylates such as pentaerythritol triacrylate, pentaerythritol trimethacrylate and blends thereof with hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate. It is a mixture with a monofunctional acrylate or methacrylate. The isocyanurate of the present invention must contain a moiety derived from one of the vinylidene carbonyloxyalkanols defined above, but the moiety derived from an aromatic polyisocyanate may include any trimerizable aromatic polyisocyanate. It can be based on In fact, any trimerizable aromatic polyisocyanate commonly used in the art for the production of isocyanurates can be used in the production of the isocyanurate compositions of the present invention. For example, aromatic polyisocyanates may or may not contain ethylenic unsaturation and may be monomeric or polymeric. Aromatic polyisocyanates contain at least two aromatic isocyanate groups, are capable of trimerization, and contain groups that interfere with the trimerization of the isocyanate groups or interfere with the reaction between the isocyanate groups and the hydroxyl groups. The only necessary condition is that it does not contain. Examples of aromatic polyisocyanates particularly useful in the preparation of the isocyanurates of the present invention include 4,4'-diphenyl ether diisocyanate; 4,4',4''-triphenylmethane triisocyanate; 4,4'-triisocyanatodiphenylmethane;2,2',4-
Triisocyanatodiphenyl; 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-
Phenyl diisocyanate; 4-bromo-1.
3-phenylene diisocyanate; 4-ethoxy-1,3-phenylene diisocyanate; 2.
4'-diisocyanatodiphenyl ether; 4.
4'-diisocyanatodiphenyl; 9,10-anthracene diisocyanate; 4,6-dimethyl-
1,3-phenylene diisocyanate; 4,4'-
Diisocyanatodibenzyl; 3,3'-dimethyl-
4.4′-diisocyanatodiphenylmethane; 3.
3'-dimethyl-4,4'-diisocyanatodiphenyl;3,3'-dimethoxy-4,4'-diisocyanatodiphenyl; 1,8-naphthalene diisocyanate; 2,4,6-tri Lentriisocyanate; 2,4,4'-triisocyanato diphenyl ether, diphenylmethane diisocyanate, trade names Mondur and Papi
Polymethylene polyphenylene polyisocyanate having an average functional group number of 2.1 to 2.7, commercially available as;
1,3-xylene-4,6-diisocyanate;
Included are aromatic isocyanate-terminated polyurethanes; and aromatic isocyanate-terminated prepolymers of polyesters. Preference is given to using all aromatic polyisocyanates, but also small amounts of aliphatic polyisocyanates, such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, or α,α'-diisocyanate.
p-xylene can also be used in combination with aromatic polyisocyanates. Small amounts of monoisocyanate may be present to modify the structure of the isocyanurate produced. The use of small amounts of monoisocyanate improves elongation and helps prevent gelling, especially when triisocyanates are used. The amount of monoisocyanate used is usually selected such that the ratio of isocyanate groups derived from the monoisocyanate to isocyanate groups derived from the polyisocyanate is about 0.5 or less, preferably about 0.3 or less. Typical examples of monoisocyanates that can be used include p-
Included are tolylisocyanate, phenyl isocyanate and n-butyl isocyanate. Preferred polyisocyanates are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenylene having an average functional group number of 2.1 to 2.7. polyisocyanates and mixtures thereof. As is clear from the above formulas (1) to (3), the isocyanurate of the present invention can also be said to be an ester of carboxyaminophenyl isocyanurate and vinylidene carbonyloxyalkanol. These esters contain one or more isocyanurate rings per molecule. Alternatively, as is usually the case, these esters may contain one isocyanurate ring per molecule and one isocyanurate ring per molecule.
It consists of a mixture with an ester containing more than one isocyanurate ring. These esters may or may not contain allophanate groups. The solid isocyanurates of the present invention are fusible prior to curing. i.e. ASTM designation
The softening point is shown by the ring and ball method described in E28-58T. Preferred isocyanurates of the present invention are 5.75-
6μ (carbonyl), 6.1~6.35μ (amide hydrogen), 6.9~7.2μ (isocyanurate), 10.15~
Shows an infrared characteristic (1R) peak at 10.85μ (vinyl). The preferred isocyanurate group is 5.8-5.95
μ, 6.2-6.3μ, 7.00-7.15μ and 10.2-10.75
There is an IR peak at μ. The isocyanurates of the present invention prepared with toluene diisocyanate and hydroxylpropyl methacrylate have a specific concentration of about 5.85μ, about 6.23μ, about 7.1μ and about 10.6μ in styrene.
The IR peak is shown at μ. The isocyanurates of the present invention, which are styrene solutions of isocyanurates based on toluene diisocyanate and hydroxylpropyl methacrylate, can also be characterized, within experimental error, by the following nuclear magnetic resonance absorption (NMR): i.e.
9.6±0.2, 8.8±0.2, 7.50, 7.48, 7.44, 7.41,
7.36, 7.33, 7.29, 7.26, 6.79, 6.71, 6.57,
There are signals at 5.93, 5.91, 5.70, 5.69, 5.33, 5.31, and 5.19. The isocyanurate of the present invention containing an allofuanate group has an NMR signal of 10.6±0.2. All NMR measurements cited in this application are 30
C, by proton magnetic resonance spectroscopy on a Varian CFT-20 operating at 79.4 MHz (80 MHz nominal). Dimethyl sulfoxide was used as a solvent. Results are expressed in chemical shifts (ppm) relative to tetramethylsilane as internal standard. All unsaturated isocyanurates of the present invention are soluble in at least one of the following free radically polymerizable ethylenically unsaturated monomers: Divinylbenzene, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butyl acrylate, butyl methacrylate, tetramethylene glycol diacrylate,
Trimethylolpropane triacrylate, pentaerythritol triacrylate, neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate, 2,3-dibromopropyl acrylate, 2,3-dibromopropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, chlorstyrene, acrylonitrile, vinylidene chloride, vinyl acetate, vinyltoluene, hexanediol diacrylate, hexanediol dimethacrylate and mixtures thereof . "Soluble" means at 25°C, at least one of the above
This means that at least 2 g of isocyanurate is dissolved in 100 g of the seed ethylenically unsaturated monomer. The ethylenically unsaturated isocyanurate of the present invention is produced by producing an isocyanate-containing urethane by reacting an aromatic polyisocyanate with the above-mentioned vinylidene carbonyloxyalkanol. It can be produced by trimerization until it reacts to form the ethylenically unsaturated isocyanurate of the present invention. It is of course possible that the isocyanurate obtained may contain small amounts of residual isocyanate groups. The solution viscosity of the unsaturated isocyanurate of the present invention can be varied over a wide range by adjusting the charging ratio of aromatic polyisocyanate and vinylidene carbonyloxy alcohol used during its synthesis and/or the trimerization temperature. be able to. Thus, by varying the degree of excess of isocyanate groups over hydroxy groups,
Production of high molecular weight species and solution viscosity at a given concentration can be controlled. Increasing the excess of isocyanate groups to hydroxyl groups favors the production of high molecular weight species and therefore tends to result in high viscosity, whereas decreasing the excess of isocyanate groups to hydroxyl groups favors the production of low molecular weight species. It is advantageous for the production of , and therefore tends to have a low viscosity. By appropriately controlling this excess, a polymerizable resin solution with a desired viscosity can be obtained. This can be done experimentally and it has been found that increasing solids concentration and reaction temperature also provide resins with high molecular weight and solution viscosity. The opposite is also true. Based on the number of moles of -OH per mole of polyisocyanate
The molar excess of NCO groups should be kept in the range of about 0.75 to about 1.6, preferably in the range of about 0.8 to about 1.4.
In a solution consisting of equal parts of a mixture of hydroxypropyl methacrylate and toluene diisocyanate and solvent, the molar excess of NCO groups for laminating applications is preferably from about 0.8 to about 1.05. "Excess mole number of NCO groups relative to the number of moles of -OH per mole of polyisocyanate" is the number of moles of NCO group used minus the number of moles of -OH used. means the number of moles of NCO groups equal to the number of moles of NCO group divided by the number of moles of NCO. According to the present invention, the step is to react a monohydric alcohol containing a vinylidene group but not containing an allyl group (vinylidene carbonyloxyalkanol) with a polyisocyanate in the presence of a copper salt to produce an isocyanate-containing urethane. After the above reaction, per mole of polyisocyanate used
A first step in which the amounts of monohydric alcohol and polyisocyanate are chosen to give 0.75 to 1.6 moles of unreacted isocyanate groups, and the isocyanate-containing urethane is trimerized in the presence of an isocyanate trimerization catalyst to form ethylene. It has been found that ethylenically unsaturated isocyanurate can be produced by a two-step method comprising a second step of producing systemically unsaturated isocyanurate. The isocyanurates produced by the process of the present invention may be monomeric, ie, isocyanurates containing only one isocyanurate ring, or polymeric, ie, isocyanurates containing more than one isocyanurate ring, but usually monomeric It is a mixture of body species and polymer species. The solid isocyanurates of the present invention are fusible before curing, ie they exhibit a softening point according to the ring and ball method according to ASTM designation E28-58T. The reaction between the polyisocyanate and the monohydric alcohol in the first step is a conventional method for producing urethane by reacting alcohol and isocyanate, provided that the reaction is carried out in the presence of a copper salt. This can be carried out depending on the reaction conditions.
In the production method of the present invention, it is essential to carry out the reaction between the monohydric alcohol and the polyisocyanate in the presence of a copper salt. The copper salt used in the method of the invention may be any known copper salt as long as its anion does not interfere with the reaction. During the reaction, the presence of iodine anions does not interfere with the production of ethylenically unsaturated isocyanurate, but does interfere with the polymerization reaction of ethylenically unsaturated isocyanurate. Therefore, it is preferable to avoid iodine anions. The copper salt need not be soluble in the reaction components or solvents used. The reaction between the polyisocyanate and the monohydric alcohol is preferably carried out in an organic solvent in the presence of a copper salt that is soluble in that solvent, although copper salts that are insoluble in the organic solvent or in the reaction components may also oxidize the reaction mixture. Vigorous stirring can be used. Obviously, the only requirement is that the copper salt be in intimate contact with the reactants. Examples of copper salts that can be used include cupric acetate,
Cupric benzoate, cupric glycine, cupric acetylacetone, cupric sulfate, cupric oxalate, cupric chloride, cupric bromide, cupric nitrate, cupric naphthenate, formic acid Includes cupric, mono- and dicupric salts of ethylenediaminetetraacetic acid, cuprous chloride, cuprous bromide, cuprous cyanide, cupric propionate. Mixtures of two or more copper salts can also be used. A preferred catalyst is cupric acetate. The use of copper salts in the method of the invention offers various advantages. In other words, the copper salt promotes the urethane-forming reaction between aromatic polyisocyanate and monohydric alcohol, helps prevent undesirable reactions that lead to gelation, improves the storage stability of the unsaturated isocyanurate produced, and has excellent properties. The present invention promotes the production of polymerizable isocyanurates with desirable physical properties, and allows the reaction to proceed in a safe and reproducible manner. The amount of copper salt used varies depending on the copper salt used and the polyisocyanate and monohydric alcohol used. Generally, the amount of copper salt used is from 0.001 to the total weight of polyisocyanate and alcohol.
1%, and the preferred amount of copper salt used is 0.02-0.2
%. Lower amounts are less effective;
Does not yield more benefits for practical purposes.
Higher amounts of copper salts can also be used, but may not provide as much benefit and may interfere with the polymerization reaction of the unsaturated isocyanurate. Solution viscosity also increases when increasing the temperature used for the trimerization reaction, but temperature is not as important a variable as the excess of isocyanurate groups to hydroxyl groups. However, because the trimerization reaction is slow at low temperatures and the vinyl groups can undergo premature polymerization at high temperatures, the trimerization temperature is most often between about 0 and about 95
kept at ℃. The preferred trimerization temperature is about 50 to about 90
It is ℃. The particular trimerization temperature chosen controls the amount of allophanate present in the isocyanurate. Generally, the higher the temperature, the lower the allofuanate content. Allophanate-free isocyanurates can be produced by carrying out the trimerization at temperatures above about 85°C. Allophanate-free isocyanurates can also be prepared by heating the allophanate-containing isocyanurates included in this invention in the presence of a trimerization catalyst, preferably to a temperature of about 85 to about 95°C. The isocyanurate of the present invention usually has an allofuanate:urethane stoichiometric ratio of about 0 to 0 as determined by NMR measurement.
It is better to keep the allofuanate content as low as possible, preferably between about 0 and 0.7. The properties of allofuanate-free isocyanurates are (1) low gas evolution when heated with peroxide addition and (2) shelf life of uncured resin in the presence of unpromoted peroxide. It is a long thing. Allophanate-free isocyanurates can be used for the production of thick laminates to minimize gassing at high temperatures. Generally, as the solids content of the resin solution decreases, the solution viscosity also decreases. To compensate for this reduced viscosity, which makes the laminate difficult to manufacture, the amount of high molecular weight polyisocyanurate structures is increased by increasing the excess of isocyanate groups to hydroxyl groups. The amount of this high molecular weight species can also be increased or decreased by adjusting the trimerization temperature. Table 1 below shows how vinylidene carbonyloxyalkanol-containing urethane isocyanurate solutions can be obtained over a wide viscosity range. Table 1 is for the reaction product from hydroxypropyl methacrylate (HPMA) and toluene diisocyanate (TDI) dissolved in styrene, but other polyisocyanates or vinylidene alcohol in other vehicle systems It will be clear to those skilled in the art that a similar relationship holds even when . The example in Table 1 shows the influence of three important reaction parameters on the viscosity of the final product. F and G and H and I indicate the effect of trimerization temperature on the viscosity of the final product. Examples D and F and J and L show the effect of concentration on viscosity, while Examples B and C, E and F and I, and J and K show the excess mole of NCO groups over hydroxyl groups per mole of polyisocyanate. shows the effect of viscosity on the final product viscosity. All reactions shown in Table 1 were carried to completion. That is, the residual isocyanate content is approximately zero.
Viscosity adjustment can also be achieved by stopping the reaction prematurely in the usual manner by adding active hydrogen compounds compatible with the system and/or by destroying the trimerization catalyst. You can do it even if you have to. All reaction experiments were conducted in styrene using HPMA and TDI. Reaction experiments B to L were conducted according to the method described in Example 1, while reaction experiment A was conducted according to the method described in Example 8. The method used in Experiment A uses a different polyisocyanate addition regime than that used in Experiments B-L and is used primarily for the synthesis of low concentration products.

[Table] In order to obtain cured products with excellent high-temperature properties, it is essential that the isocyanurates of the invention are based on at least one of the vinylidene carbonyloxyalkanols defined above;
In the present invention, a small amount of the moiety derived from vinylidene carbonyloxyalkanol (R in the above formulas (2) and (3)) is derived from other monohydric alcohols, dihydric alcohols, monohydric phenols, or dihydric phenols. It is also intended that parts can be substituted. Saturated monohydric alcohols are particularly useful when polyisocyanates with functionality greater than 2 are used. Although it has been found that decreasing the amount of vinylidene carbonyloxyalkanol reduces high temperature properties, some high temperature properties may be willingly sacrificed to introduce other desired properties. For example, certain applications may be willing to sacrifice certain high temperature properties to provide flame resistance or low smoke production. Flame retardancy can be introduced by replacing small amounts of the vinylidene carbonyloxyalkanol with phosphorous or fluorine, chlorine or bromine containing alcohols or phenols. Similarly, low smoke emission can be introduced by replacing small amounts of the vinylidene carbonyloxyalkanol with sulfur-containing alcohols or phenols. Although small amounts of hydroxyl or phenolic materials may be included in the polymerizable compositions containing the isocyanurates of the present invention, such compositions must be fusible and pass the solubility test described above. It should be remembered that it must contain at least a major amount of isocyanurate moieties derived from the vinylidene carbonyloxyalkanols listed above. Examples of monohydric alcohols and monohydric phenols that can be used to replace up to 49 mol% of the above vinylidene carbonyloxyalkanols include methanol, ethanol, propanol, butanol, isobutanol, octyl alcohol, cyclohexanol, benzyl Alcohols, allyl alcohol, glycerin diallyl ether, trimethylolpropane diallyl ether, saturated halogenated alcohols, halogenated alcohols containing ethylenically unsaturation, such as dibromneopentyl glycol monoacrylate and monomethacrylate, halogenated allyl alcohol, 2-bromine Ethanol, 3-bromo-1-propanol, 4-chloro-1-butanol, 2-
Chlorethanol, 4-chloro-1-hexanol, 3-chloro-1-propanol, 2,3-dibromo-1-propanol, 2,3-dichloro-
1-propanol, 2,2,2-trichloroethanol, 1-bromo-2-propanol, 1-chloro-2-propanol, 1,3-dibrom-2
- monohydric alcohols such as propanol, 1,3-dichloro-2-propanol, monoacrylate and monomethacrylate esters of A of alkoxylated bisphenols A and alkoxylated tetrabromobisphenols, and polyoxyethylene and monohydric phenols; Contains polyoxypropylene ether. Examples of dihydric alcohols that can be used to substitute up to 33 mol%, preferably up to 10 mol% of the above vinylidene carbonyloxyalkanols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, formula (In the above formula, R' ₁ is an alkyl group containing 1 to 4 carbon atoms), 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, glycerin methyl ether, bisphenol A These include polyoxyethylene and polyoxypropylene ethers of dihydric phenols such as, glycerin monochlorohydrin, glycerin monostearate, dihydroxyacetone, and monoesters of the above polyols with acrylic acid or methacrylic acid. In general, the invention can be practiced using small amounts (up to 20 mole percent) of phenols that are reactive with aromatic isocyanates. When using reactive phenols, it is especially important to react substantially all of the phenolic hydroxyl groups with isocyanate groups, thereby eliminating unreacted hydroxyl groups that would interfere with the subsequent free radical curing reaction. . Phenols, such as 4-hydroxyphenyl-4'-chlorophenyl sulfone, are particularly useful because they improve the flame and smoke properties of the cured product while retaining its physical properties at elevated temperatures.
Phenol can also be used to sequester small amounts of isocyanate functional groups and later regenerate the isocyanate groups at elevated temperatures to obtain cured products with improved bonding to substrates, especially glass fibers. . Nitrophenols do not readily react with isocyanates and do not fall within the scope of this invention. The unsaturated isocyanurates of the present invention can be homopolymerized or copolymerized with one or more other ethylenically unsaturated, copolymerizable compounds. When the unsaturated isocyanurate of the present invention is copolymerized with a copolymerizable monomer, the isocyanurate may be dissolved in the copolymerizable monomer, or the ethylenically unsaturated isocyanurate of the present invention may be produced. In some cases, it may be desirable to use a copolymerizable compound as a solvent in the reaction system. When the ethylenically unsaturated copolymerizable monomer is used as a solvent for the production of the unsaturated isocyanurate of the present invention,
The solvent must be free of groups that react with isocyanate groups or that interfere with the urethane formation or trimerization reactions that occur during the production of the isocyanurates of the present invention. Therefore, the solvent must not contain hydroxyl, carboxyl or amino groups that could interfere with these reactions. Therefore, suitable solvents are esters, ethers,
Limited to hydrocarbons and similar solvents containing non-reactive groups. Examples of solvents that can be used in the production of the isocyanurates of the invention include divinylbenzene, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-methacrylate. Ethylhexyl, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, chlorstyrene, acrylonitrile, vinylidene chloride, vinyl acetate, vinyl stearate, vinyltolylene,
Hexanediol diacrylate, hexanediol dimethacrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, diallyl fumarate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate , 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, polyethylene glycol diacrylate, dimethylstyrene, ethylstyrene, propylstyrene, P-chloromethylstyrene, m-dibromoethylstyrene, bromstyrene, dimethylstyrene, Includes chlorostyrene, t-butylstyrene, vinyl propionate, and vinyl acetate. Non-polymerizable solvents such as benzene, toluene, xylene, ethylbenzene can also be used as reaction solvents. After the formation of the isocyanurate, such solvent can be removed from the reaction mixture to obtain a solid product. This solid product can be dissolved in a polymerizable solvent and then cured by a copolymerization reaction. Preferred polymerizable solvents are styrene, mixtures of styrene and methyl methacrylate, and mixtures of styrene and divinylbenzene. When producing the isocyanurates of the present invention without the use of solvents, the product is solid and the heat generated by the reaction can be easily removed and high temperatures that can result in insolubilization and gelation of the product special treatment is required to prevent the reactants from reaching the Among these special processing methods are monourethane trimerization on movable temperature controlled belts or in temperature controlled trays. The amount of solvent used to dissolve the isocyanurates of the present invention can vary widely. The amount of solvent used depends in part on the nature of the solvent and the solubility of the isocyanurate used. The isocyanurates of the present invention make it possible to maintain sufficient working viscosity with relatively low concentrations of dissolved solids. Polymerizable compositions containing isocyanurates can be obtained that allow sufficient laminating working viscosities of 100 to 1000 cps as measured on a Bruckfield viscometer model LVT, spindle #2, 30 rpm, 25°C. The amount of solvent also depends on the desired physical properties of the final cured product. Thus, for example, if one is interested in a copolymer of isocyanurate of a monourethane with tolylene diisocyanate and hydroxypropyl methacrylate and styrene, the high temperature properties of the final product improve with decreasing concentration of styrene. Generally, however, the amount of solvent used will be from 5 to 95%, preferably from 30 to 80%, by weight of the composition. A particularly preferred concentration is about 50% by weight. The unsaturated isocyanurates produced by the process of this invention can be polymerized or cured by polymerization conditions conventional in the art for polymerization of ethylenically unsaturated materials. The styrene solutions of the isocyanurates of the present invention, especially those made with tolylene diisocyanate or polymethylene polyphenylene polyisocyanate and hydroxypropyl methacrylate, hydroxyethyl methacrylate or hydroxypropyl acrylate, provide a surface that is dry to the touch. It is less sensitive to oxygen than regular vinyl. Generally, polymerization can be carried out by reacting unsaturated isocyanurates in the presence of a polymerization catalyst. Suitable polymerization initiators include benzoyl peroxide, methyl ethyl ketone peroxide, di(2-ethylhexyl) peroxydicarbonate, perbenzoic acid t.
Various peroxide initiators are included, such as -butyl, dicumyl peroxide and t-butyl hydroperoxide. Other polymerization catalysts that can be used include azo type initiators such as azobisisobutyronitrile. The amount of initiator used is usually very small. For example, from about 1 part of initiator per 1000 parts of polymerizable composition to about 5 parts of initiator per 100 parts of polymerizable composition. In many applications, it is desirable to initiate polymerization without externally applying heat. In such cases, an accelerator is usually added to the system. Suitable promoters include cobalt, manganese, lead and iron compounds such as cobalt naphthenate and manganese naphthenate, and tertiary amines such as dimethylaniline. Three illustrative examples of peroxide cocatalyst formulations that can be used to cure the unsaturated isocyanurates of the present invention are provided below. Formulation 1 Benzoyl peroxide 1% Dimethylaniline 0.2% Formulation 2 Dimethylaniline 0.02% Cobalt naphthenate 0.06% Methyl ethyl ketone peroxide 2.0% Formulation 3 Cobalt naphthenate 0.03% Acetylacetone peroxide (active oxygen 4%)
0.5% t-butyl perbenzoate 1.5% To prevent premature polymerization of the isocyanurate of the present invention, a small amount of a cupric salt such as cupric acetate or hydroquinone, the methyl ether of hydroquinone,
Conventional polymerization inhibitors such as phenothiazine and tert-butylcatechol can be added to the reaction mixture prior to isocyanurate production or to the final product, or both. The obtained isocyanurate, especially when prepared as a solution in copolymerizable monomers, may contain additives normally used in polymerization systems, such as antioxidants, UV absorbers, dyes and pigments. . It has been found that cured products containing unsaturated isocyanurates of the present invention are particularly useful in applications such as casting, coatings and laminations where it is desired to have excellent flexural and tensile properties as well as good corrosion resistance at elevated temperatures. Ta. Laminates made with wettable fibers contain at least 20% by weight isocyanurate and up to 80% by weight wettable fibers. The cured product obtained by polymerization of concentrated isocyanurate according to the present invention is
Stable at temperatures below 162.8℃ (325〓). The isocyanurate of the present invention may be used alone or in combination with one or more other ethylenically unsaturated monomers. In addition, the isocyanurate of the present invention may be an inorganic filler such as calcium carbonate, magnesium oxide, or alumina trihydrate;
Organic polymers such as polyethylene, polymethyl methacrylate and other additives to reduce shrinkage; and may also be used in combination with flame retardant additives or other polymeric resins such as general purpose polyesters. can. The isocyanurates of the present invention are particularly useful when used in the manufacture of reinforced structures such as laminates and pipes in combination with glass fibers, cellulosic fibers, aramid fibers or other fibers, and in combination with these fibers. Shows excellent wetting properties when used. The invention will be better understood by the examples given below. These examples are illustrative and should not be considered as limiting the scope of the invention. In the following examples, castings and laminates are manufactured as follows. The casting was made by pouring an isocyanurate solution containing the curing reagent between glass sheets separated by a distance of 1/8 inch (3.175 mm) with polytetrafluoroethylene-coated wire spacers. Manufactured. The curing reagent is added by first adding the necessary cocatalyst and accelerator to the copolymerizable solvent solution of the isocyanurate, and then adding the necessary peroxide. After keeping this casting at room temperature for 18-24 hours,
The resin is post cured by heating it at 100° C. for 1 hour in an oven. The production of the laminate is carried out by uniformly applying an isocyanurate solution containing a curing agent onto the glass fiber mat with a paint-type roller, followed by complete rolling with a grooved laminating roller. The curing reagent is added to the copolymerizable solvent solution containing isocyanurate by adding necessary cocatalysts and accelerators to the isocyanurate solution, and then
This is done by adding the necessary peroxide.
A 3.175mm thick laminate consists of two 0.254mm (10
2 layers between the "C" glass mats for the surface
Manufactured by sandwiching 1 1/2 oz. (42.45 g) split strand glass mat. The weight of glass is 25% of the total weight of resin and glass. The 6.35 mm (1/4 inch) thick laminate is manufactured by a combination of resin-impregnated glass mats as follows: i.e. 0.254mm
(10 mil) surface “C” glass mat, 2 layers
42.45 g (1 1/2 oz) chopped strand pine, one layer of woven roving and a final layer of
42.45 g (1 1/2 oz) chipped strand glass pine. The amount of resin used to make this 6.35 mm (1/4 inch) laminate is adjusted so that the resin ratio is 70%. The laminate is covered with a thin polyester film to exclude air from the surface during curing. After standing at room temperature for 18-24 hours, the cured laminate is post cured by heating at 100° C. for 1 hour in an oven. The physical properties of the castings and laminates produced in the following examples are determined by the ASTM test method set forth below. Physical properties ASTM test method Bending strength D790 Bending modulus D790 Tensile strength D638 Tensile modulus D638 % elongation D638 Izot impact strength D256 Barcol hardness D2583 Heating deflection temperature test (264psi) D648 Example 1 Thermometer, air introduction tube , 865 ml of hydroxypropyl methacrylate, 2144 ml of styrene, 1.8 g of cupric acetate, and hydroquinone in a 5 glass 3-necked round bottom flask equipped with a dropping funnel and condenser.
Add 800mg. The solution is heated to 85° C. and 852 ml of toluene diisocyanate are added gradually over 150 minutes. During the addition of toluene diisocyanate, the temperature of the reaction medium is kept between 88°C and 90°C. After the addition of toluene diisocyanate is complete, the temperature of the reaction mixture is maintained at approximately 90° C. for an additional 90 minutes. The resulting dark green liquid is cooled to 55° C. and 5 ml of 40% benzyltrimethylammonium hydroxide methanol solution (40% methanol) are added over 13 minutes.
Heating is then continued at 55° C. for 2 hours to form ethylenically unsaturated isocyanurate. Example 2 To the reactor described in Example 1 are added 611.0 g of styrene, 33.1 g of hydroxypropyl methacrylate, 225 mg of cupric acetate, and 100 mg of hydroquinone. The resulting solution was heated to 90°C with vigorous stirring, at which point 34.8 g of toluene diisocyanate was added to 6
Add to reaction flask at a rate of ~10 ml/min. The temperature of the reaction medium is kept at 90° C. until the end of the addition of toluene diisocyanate and then at 90° C. for a further 40 minutes. The resulting clear emerald green solution
Cool to 55°C and add 1.5 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1.
Add. The color of the reaction solution does not change for several minutes and then begins to turn brown. The solution temperature is maintained at 55° C. until the isocyanate content has decreased to approximately zero.
The resulting product is a styrene solution of ethylenically unsaturated isocyanurate of toluene diisocyanate and hydroxypropyl methacrylate. Examples 3 to 5 are produced by the method described in Example 2. However, the amounts of styrene, hydroxypropyl methacrylate (HPMA), hydroxyethyl methacrylate (HEMA), and toluene diisocyanate (TDI) are as shown in Table 1.

[Table] Example 6 According to the method of Example 1, 1314 g of styrene, 232 g of hydroxypropyl methacrylate, 4 ml of a 10% styrene solution of tert-butylcatechol, and 920 mg of cupric acetate monohydrate were mixed in an atmosphere of air and nitrogen. After heating to 90℃, toluene diisocyanate
Add 335 g (25% excess) gradually over 60 minutes. The temperature was 90°C during the addition and for 60 minutes after the end of the addition.
Keep at ℃. The product is cooled to 41° C. and 5 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added. Maintain temperature at 45°C for 4 hours. Add 5 ml of tert-butylcatechol (10% styrene solution) and 1.05 ml of methanesulfonic acid;
Cool the product. The resulting ethylenically unsaturated polyisocyanurate composition contains a high proportion of polymeric product having a molecular weight of about 200,000 as determined by gel permeation chromatography.
The viscosity of the composition after standing overnight at room temperature is approximately
It is 10000cps. Example 7 1254 g of styrene, 227 g of hydroxypropyl methacrylate (hydroxyl value 364), and cupric acetate were placed in a 34-necked flask equipped with a temperature control device, air inlet tube, _N2 inlet tube, condenser, addition funnel, and stirrer. 460 mg of monohydrate, 10 of tert-butylcatechol (TBC)
Add 4.0 ml of % styrene solution. Then, heat the flask to 90℃, keeping the temperature between 90 and 98℃.
313 g of toluene diisocyanate (TDI) are added dropwise over 55 minutes. After the TDI addition is complete, the temperature is kept at 90°C for 1.5 hours and then the solution is cooled to 45°C. Add 5 c.c. of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1. The resin turns dark and generates heat, but the temperature can be lowered by adjusting it in a water bath.
Keep the temperature below 50℃ and keep at 45℃. 3. After 1 hour, add 1.2 cc of methanesulfonic acid and cool in a cooling water bath. At 30°C, 5 ml of a 10% tert-butylcatechol solution in styrene is added and at 25°C the polymerizable composition is poured into a can. The Bruckfield viscosity of this product is 395 cps at 25°C. 100℃
Thickness: 3.175mm post cured for 1 hour
Measure physical properties on (1/8 inch) cast objects. This curing system is based on the above composition 100
g, dimethylaniline 0.4 g, cobalt naphthenate 0.5 g, Lupersol 224 (acetylacetone peroxide solution) 0.5 g and tert-butyl perbenzoate 1.5 g. This casting (30% solids in styrene) exhibits the following physical properties. Tensile modulus (psi) 0.49±0.03×10 ⁶ Tensile strength (psi) 10900 % elongation 2.58 Bending strength (25℃, psi) 17300 Bending modulus (psi) 0.53×10 ⁶ Heat deflection temperature 111℃ Unnotched Izot impact value 2.91 Example 8 Stirrer, thermometer, air introduction tube, reflux condenser,
In 3 four-necked flasks equipped with _N2 inlet tubes were placed 171.0 g (1.14 eq.) of hydroxypropyl methacrylate, 1315.8 g (12.64 eq.) of styrene, 0.4535 g of cupric acetate monohydrate, and 10% tert-butylcatechol ( TBC) Add 3.75 ml of styrene solution and heat the mixture to 90 °C with stirring. 206.9 g (1.19 equivalents) of toluene diisocyanate (TDI) are added dropwise over 1 hour while maintaining the temperature at 90±5°C. The reaction mixture is kept at 90±5°C for an additional hour and then cooled to 35°C over a period of 1 hour. 62.1g TDI
After adding (0.36 equivalents), the mixture is further cooled to 30°C.
Next, 4.8 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added, and the generated exotherm is controlled by using a water bath. After 2.6 hours, the trimerization reaction is stopped by adding 14.9 g of dibutylamine, and after 15 minutes, 1.49 g of methanesulfonic acid (MSA) is added. The viscosity of the product obtained is 998 cps at 22.4°C. A casting having a thickness of 3.175 mm is made and cured as described in Example 7. This casting (30% solids in styrene) exhibits the following physical properties. Tensile modulus (psi) 0.55×10 ⁶ Tensile strength (psi) 9400 % elongation 2.28 Bending strength (psi) 16700 Unnotched Izot value (ft-lbs) 2.97 Heat deflection temperature 221〓 Bending modulus (psi) 0.85×10 ⁶ Example 9 Methyl methacrylate (892 g, 8.91 mol), hydroxypropyl methacrylate (414 g, 2.78 mol), Add cupric acetate monohydrate (0.403 g) and 10% tert-butylcatecholstyrene solution (4.0 cc).
The mixture is stirred and heated to 90°C and toluene diisocyanate (TDI) (468 g, 2.69 mol) is added slowly over 2 hours while maintaining the temperature at 90°C. After all the TDI has been added, the temperature is kept at 90°C for 1 hour with stirring and then cooled to 50°C. Add 5.0 ml of the benzyltrimethylammonium hydroxide methanol solution used in Example 1. An exothermic reaction occurs, but external cooling lowers the temperature of the reaction mixture to 55°C.
Keep at ℃. After keeping the mixture at 55° C. for 2 hours, it is cooled to room temperature and 1.2 ml of methanesulfonic acid is added.
The reaction product exhibits a viscosity of 1050 cps at 23°C. thickness
Make a 3.175mm (1/8″) caster,
Cured according to the method of Example 7. Two pieces of 0.254mm
(10 mil) 3.175 mm (1/8") thick laminate using two layers of 1 1/2 oz. chopped fiberglass strand mats sandwiched between two surface "C" glass mats. Making,
It was cured at 100°C for 1 hour. The properties of the casting and laminate are as follows.

【table】

[Table] Example 10 Hydroxypropyl methacrylate (414 g, 2.8 mol) and styrene (772 g , 7.4 mol), divinylbenzene (72% active substance solution 124
g, 0.68 mol) cupric acetate monohydrate (0.45 g) and a 20% styrene solution of tert-butylcatechol (2 ml) are added. The mixture was heated to 40°C and toluene diisocyanate (TDI) (80/20 mixture of 2,4- and 2,6-isomers, 486 g, 2.8
mol) over 1 hour. Combining external heating and the exothermic nature of the reaction to gradually increase the reaction temperature to 90°C
C. and the reaction mixture is left at 90.degree. C. for an additional hour before being cooled to 45.+-.5.degree. C. over 90 minutes. Next, 5 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 was added, and the heat generation was controlled in a water bath. The reaction mixture was heated at 55 ± 5 °C for 2.5
After a period of time, the trimerization reaction is stopped by adding methanesulfonic acid (1.2 ml). The viscosity of the product is
It is 1060 cps at 21℃. A laminate is made and cured using the method used in Example 9. The bending strength of cured laminate is 1321.64Kg/ ^cm2 at room temperature
(18800psi), 780.33Kg/cm ² at 176.7℃ (350〓)
(11100psi). Examples 11-17 Examples 11-17 use the apparatus and method of Example 1. Copper catalyst, tert-butylcatechol (TBC), and unsaturated alcohol in styrene at approximately 90°C.
Add the required amount of toluene diisocyanate dropwise under an atmosphere of nitrogen and air. When the NCO content has decreased to about half of its original value, the solution is cooled to about 55° C., the methanol solution of benzyl ammonium hydroxide used in Example 1 is added, and stirring is continued until the reaction is complete. Methanesulfonic acid and/or TBC are then added to stabilize the product. The reaction components, solvents, catalysts used and their amounts are shown in Table 2.

Table: Examples 18-20 Examples 18-20 are prepared according to the method of Example 17. However, the amounts of toluene diisocyanate, unsaturated alcohol, solvent and catalyst shown in Table 3 are used.

[Table] Examples 21-26 In Examples 21-26, the method of Example 17 is used. The reaction components, catalysts, and solvents used, as well as the amounts of each used, are shown in Table 4.

【table】

Table: Examples 27-34 The isocyanurate products of Examples 27-34 are prepared according to the method of Example 1. However, the reaction components,
The solvent and catalyst were changed and used as shown in Table 5.

[Table] Example 35 A preferred method for producing the isocyanurate of the present invention containing an allophanate group is as follows. A reactor equipped with a stirrer, condenser, gas line connections, vents and port holes is first flushed with nitrogen. Next, the relative velocity of air and nitrogen is 1:
3 gas streams are introduced into the reactor. Next, 2.7 parts of hydroxypropyl methacrylate (HPMA)
into the reactor. The air and nitrogen flow is temporarily stopped and 0.0029 parts of cupric acetate monohydrate and 0.012 parts of a 20% styrene solution of tert-butylcatechol (TBC) are added to the reactor under continuous stirring. Restart air and nitrogen flow and add 5.7 parts of styrene to the reactor. The reaction mixture was then heated to about 40°C, and when the temperature of the reaction mixture reached 40°C, 2,4- and 2,6-toluene diisocyanate (TDI)
Begin adding the 80/20 mixture in portions. A total of 3.1 parts of TDI is added over about 1 hour. During this period, the temperature of the reaction mixture rises to approximately 90°C due to the exothermic reaction of TDI and alcohol. If the temperature is lower or higher than 90° at the end of TDI addition, use external heating or cooling to bring the temperature to about 90°.
℃. The reaction mixture is maintained at about 90° C. for at least 1 hour after the addition of the entire amount of TDI and until the NCO content of the reaction mixture has fallen below 4.5% by weight. After both of the above conditions are satisfied, the reaction mixture is cooled to about 50°C. Next, 0.018 part of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added to this reaction mixture. Shortly after this addition, an exothermic reaction begins and the temperature of the reaction mixture is maintained at 50-60°C during the reaction period. From the onset of the exotherm, the viscosity and NCO content of the reaction mixture are monitored very closely. The viscosity of the reaction mixture is 400 ~
When 500 cps is reached and the NCO content drops below 0.2%, 0.007 parts of methanesulfonic acid is added to the reaction mixture and the mixture is cooled. When the temperature reaches about 35°C, 0.014 parts of TBC is added and the reaction mixture is cooled to room temperature. The vinyl isocyanurate obtained was transparent, pale yellowish brown in color, had a viscosity of about 400-500 cps, and had a shelf life of more than 3 months. From this isocyanurate solution, dimethylaniline 0.2%,
The laminate is manufactured using a curing system of 0.2% tert-butylcatechol, 0.2% benzoyl peroxide solution (50% active). Thickness manufactured from this resin
3.175mm (1/8″) two-layer laminate has over 80% of its room temperature bending and tensile strength at 149°C
(300〓) but still holds it. 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 about 5,200 or less, with a small amount of isocyanurates having a molecular weight of about 5,200 to about 26,000. This product has less than 10 isocyanurate rings in most isocyanurate molecules. This product has a ring and ball melting point of about 95°C, a viscosity of about 400-600 cps at 25°C, and a refractive index of about
1.557N ^2c _D. The infrared absorption spectrum of this product shows a characteristic absorption band of isocyanurate, with almost no isocyanate functionality. The hydroxyl value of the product is approximately 0. A 3.175 mm thick two-layer laminate made from this resin has over 80% of its room temperature bending and tensile strength.
Retains even at 149℃ (300℃). The curing reagent used to cure this resin was dimethylaniline 0.2
%, 10% styrene solution of tert-butylcatechol
0.2% and benzoyl peroxide (50% active) 2.0%
It is. Example 36 To a solution of 307 g of a mixture of 1- and 2-hydroxydecyl methacrylate dissolved in 481 g of methyl methacrylate, 0.3 g of cupric acetate monohydrate and 1.3 ml of a 10% solution of tert-butylcatechol in methyl methacrylate are added. . Heat this solution to 90°C,
Add 174 g of toluene diisocyanate over 30 minutes. The temperature is kept at 90 °C for an additional hour, the solution is cooled to 55 °C, and the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added.
Add 1.7ml. The reaction is completed by heating to 60° C. for an additional 3 hours. The reaction is stopped by adding 1.7 ml of 10% tert-butylcatechol methyl methacrylate and 0.5 ml of methanesulfonic acid. Example 37 To a solution of 165 g of 2-hydroxybutyl methacrylate in 71 g of styrene is added 313 mg of cupric acetate monohydrate and 0.75 g of a 10% styrene solution of a 50/50 mixture of tert-butylcatechol and the monomethyl ether of hydroquinone. Add ml. 90% solution
℃ and add 174 g of toluene diisocyanate over 1 hour. Continue heating at 90°C for 1 hour. Next, add 268.3g of styrene,
The solution was cooled to 55°C, and the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 was added.
Add 2.5ml. This solution is kept at 55°C for 1 hour.
10% styrene solution of a 50/50 mixture of tert-butylcatechol and monomethyl ether of hydroquinone
Add 1.3 ml to stop the reaction. The viscosity of the product is 200 cps at 25°C. Two-layer glass laminate made using a 50% styrene solution of the resulting resin [25% glass, 3.175 mm (0.125 inch) thick]
of dimethylaniline 0.1%, acetylacetone peroxide solution (active oxygen 4%) 0.5%, tert-butyl perbenzoate 1.5% and tert-butyl catechol.
cured with 0.1% 10% styrene solution] is 149
It exhibits the following physical properties at °C (300〓). bending strength
17600 psi, bending modulus 0.48 x ¹⁰⁶ psi, tensile strength 11900 psi, tensile modulus 0.66 x ¹⁰⁶ psi, Barcol hardness 25-28, elongation 2.2%, notched Izot value 4.05. Example 38 2 of 3 equipped with a stirrer, thermometer, and air introduction tube
In a neck flask, add toluene diisocyanate (TDI) (80/20 of the 2,4- and 2,6-isomers).
Add the mixture (342 ml, 2.44 mol) and heat the flask contents to 55°C. Cupric acetate monohydrate 0.4g
and 3.0 ml of tert-butylcatechol (360 ml, 2.44
mol) to the TDI dropwise from the addition funnel over 31 minutes. 49.4% of the original isocyanate concentration remains unreacted (as analyzed by infrared spectrophotometer) and the viscosity of the resulting green mixture is 550 cps. Add 20 g of tert-butylcatechol to 150 g of the above mixture at 40°C.
% toluene solution and 0.8 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1. Stir the mixture vigorously;
Immerse the bread in a constant temperature bath at 45°C. After 12 minutes, bubbles begin to form on the surface of this green mixture;
The color begins to turn brown after 35 minutes. At the same time, the temperature rises to 84°C in 16 minutes and the product solidifies. After cooling the product to 40°C, remove it from the pan and crush it.
Make into a fine powder. The product is then dissolved in an equal weight of styrene and 1.5% of tert-butyl perbenzoate, 0.5% of a 6% cobalt naphthenate solution and 0.4% of dimethylaniline are added, and this solution is then dissolved in an acetylacetone peroxide solution (active Add 0.5% (4% oxygen). Using this solution containing the curing reagent, the glass is approx.
A 3.175 mm (1/8") thick laminate containing 25% is prepared. The physical properties of the laminate are as follows.

[Table] This solid resin was manufactured from a 50% styrene solution.
3.175mm (1/8″) caster is 123.9℃
(255〓) indicates the heating deflection temperature. Example 39 This example demonstrates the production of alphaanate-free isocyanurates from isocyanurates containing high amounts of allophanate. Allofuanato:urethane ratio was determined by NMR analysis.
0.45 isocyanurate prepared as described in Example 35 is placed in a small reactor. to this,
Add 0.4 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 and 0.5 ml of a 10% solution of equal volumes of tert-butylcatechol and hydroquinone monomethyl ether. Heat the resulting mixture at 95° C. for 1.5 hours. The final product includes
There was no detectable allofuanate bond by NMR analysis. Example 40 Toluene diisocyanate (TDI) (2,4-isomer and 2,6-isomer) was added to a 500 ml three-necked flask equipped with a stirrer, thermometer, air inlet, reflux condenser and addition funnel. Add 28.1 g of an 80/20 mixture with 300 ml of dry benzene. this mixture
Heat to 55°C and add 21.3 g of hydroxypropyl methacrylate over 6 minutes. After keeping the reaction mixture at 55 °C for another 16 min, hydroquinone 0.37
g, phenyl isocyanate 8.9 g (0.07 mol)
Then, 0.75 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added. Continue heating at 50 °C for 45 min. The white precipitate that forms is removed by filtration. IR analysis confirmed that this precipitate was an isocyanurate containing both phenyl and tolyl groups. Example 41 A preferred method for producing the allofuanate-free isocyanurate of the present invention is as follows. 430 g of hydroxypropyl methacrylate, 856 g of styrene, 0.43 g of cupric acetate monohydrate, and tert-butyl catechol in a four-necked, round-bottomed glass flask equipped with a thermometer, air and nitrogen inlets, addition funnel, and condenser. Add 3.6 ml of styrene solution.
The solution is heated to 40° C. and 426 g of toluene diisocyanate are added over 45 minutes. During the addition of toluene diisocyanate, the temperature of the reaction medium gradually increases. The exothermic nature of this reaction is combined with external heating to bring the final temperature to 90°C. After the toluene diisocyanate addition is complete, the temperature of the reaction mixture is kept at 90° C. for an additional 15 minutes. The obtained dark green liquid was cooled to 70°C, and a methanol solution of benzyltrimethylammonium hydroxide used in Example 1 was added.
Add 2.8ml at once. The reaction mixture is exothermic
After reaching 90℃, keep the temperature at 90℃ for 1 hour. Methanesulfonic acid (1.33 ml) is then added, the reaction mixture is cooled and 4.4 ml of a 10% styrene solution of tert-butylcatechol is added. The NMR spectrum of the product does not contain any proton signals from allofuanate at about 10.6 ppm. This resin is 1%
Stability towards benzoyl peroxide at room temperature for at least 7 hours. Example 42 Hydroxypropyl methacrylate 860 in a 4-neck, round-bottom, 5-glass flask equipped with a thermometer, air and nitrogen inlet tubes, addition funnel and condenser.
g, styrene 1735g, cupric acetate monohydrate 0.86g
and 10% styrene solution of tert-butylcatechol
Add 7.2ml. The solution is heated to 41° C. and 876 g of toluene diisocyanate are added over 45 minutes. The temperature of the mixture is gradually raised to 90° C. during this 45 minute period using a combination of the exothermic reaction and external heating. After the addition of toluene diisocyanate is complete, the temperature of the reaction mixture is kept at 90° C. for an additional 15 minutes. The resulting dark green liquid is cooled to 67° C. (over 37 minutes) and 10 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added in one portion. Heat the mixture to 70°C for 5 minutes.
After another 5 minutes, a fever of 94°C is observed. After cooling externally to 90°C, keep at 90°C for an additional 131 minutes. 10% styrene solution of tert-butylcatechol
Add 8.8 ml and cool the reaction to 60°C. reactant
Remove 1000 ml and add 1.9 ml of methanesulfonic acid to the remaining bulk of the reaction. The NMR spectrum of this product does not contain any proton signal originating from 10.6 ppm allofuanate. This product is 1
% benzoyl peroxide for at least 8 hours. Example 43 In a 4-neck, round-bottom, 5-glass flask equipped with a thermometer, air and nitrogen inlet tubes, addition funnel, and condenser, 876 g of toluene diisocyanate and styrene were added.
Add 1736 g of cupric acetate monohydrate, 0.86 g of cupric acetate monohydrate, and 7.2 ml of a 10% styrene solution of tert-butylcatechol.
The solution is heated to 40° C. and 860 g of hydroxypropyl methacrylate are added over 45 minutes.
Combining the exothermic nature of the reaction with external heating makes this 45
Gradually raise the temperature of the reaction mixture to 90°C during the course of a minute. After the addition of the toluene diisocyanate was complete, the temperature of the reaction mixture was kept at 90°C for an additional 15 minutes, and the resulting dark green liquid was cooled to 72°C over 30 minutes to add the benzyltrimethylammonium hydroxide used in Example 1. Add 10 ml of methanol solution at once. 71℃
After 18 minutes, a fever of 90.5°C was observed for 5 minutes. The reaction mixture is kept at 90° C. for 59 minutes and 2.66 ml of methanesulfonic acid are added followed by 8.8 ml of a 10% styrene solution of tert-butylcatechol. next,
The reaction mixture is cooled to room temperature and stored. The NMR spectrum of this product does not contain a proton signal originating from 10.6 ppm allofuanate. A 3.175 mm (1/8″) two-layer laminate of this resin containing 25% glass was cured overnight at room temperature with 1% benzoyl peroxide and 0.2% dimethylaniline, followed by a 1 hour post-cure at 100°C. (post cure) has the following properties.

[Table] Example 44 In a 4-neck, round-bottom, 5-glass flask equipped with a thermometer, air and nitrogen inlets, two addition funnels, and a condenser, 1736 g of styrene and 0.86 g of cupric acetate monohydrate were added. g and 7.2 ml of a 10% styrene solution of tert-butylcatechol. The solution was heated to 41 °C and 860 g of hydroxypropyl methacrylate and 876 g of toluene diisocyanate were added simultaneously at 44 °C.
Add over a period of minutes. Due to a combination of the exothermic reaction and external heating, the temperature of the mixture gradually increases to 90° C. during this 45 minute period. After the addition is complete, the temperature of the reaction mixture is kept at 90° C. for 15 minutes. The resulting liquid was poured over 25 minutes.
Cool to 70° C. and add 10 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 at once. After 15 minutes at 71°C, for 4 minutes
Fever to 90.5℃ is observed. Reaction mixture at 90℃
Hold for 59 minutes, add 2.66 ml of methanesulfonic acid, then 10% styrene solution of tert-butylcatechol
Add 8.8ml. Cool the reaction mixture to room temperature.
The NMR spectrum of this product does not contain a proton signal originating from 10.6 ppm allofuanate. 3.175 mm (1/8 inch) containing 25% glass, cured overnight at room temperature with 1% benzoyl peroxide and 0.2% dimethylaniline, then post cured at 100°C for 1 hour. The two-layer laminate has the following properties.

[Table] Although the process of the present invention has been described above with respect to specific reaction conditions and reaction components, other different and equivalent reaction components and operating conditions that are within the scope of the invention may be used with respect to the specifically indicated reaction components above. It is clear that it can be used instead of operating conditions. Example 45 Hydroxypropyl methacrylate (441 g, 2.94 mol), styrene (954.9 g, 9.15 mol), acetic acid are added to three four-neck flasks equipped with a stirrer, thermometer, air inlet, reflux condenser, and addition funnel. Cupric monohydrate (0.92 g) and equal amounts of tert-butylcatechol and hydroquinone monomethyl ether
Add 4 ml of 10% solution. Heat the mixture to 90°C,
Toluene diisocyanate (TDI) (80/20 mixture of 2,4- and 2,6-isomers, 496.2 g,
2.85 mol) over 30 minutes. The reaction mixture is kept at 90°C for 15 minutes and then cooled to 65°C within 10 minutes. Next, 5 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 was added and heated to raise the reaction temperature to 85°C over 10 minutes, and then to 95°C over 35 minutes. The reaction mixture is stabilized by the addition of 2.5 ml of a 10% solution of equal volumes of tert-butylcatechol and hydroquinone monomethyl ether. The trimerization reaction is stopped by the addition of methanesulfonic acid (1.5 ml). As a result of NMR analysis, no allophanate group was detected. Example 46 Hydroxypropyl methacrylate (441 g, 2.94 g.
mol), styrene (954.9 g, 9.15 mol), cupric acetate monohydrate (0.92 g) and 4 ml of a 10% solution of equal volumes of tert-butylcatechol and hydroquinone monomethyl ether are added. The mixture was heated to 90°C and toluene diisocyanate (TDI) (2.
80/20 mixture of 4- and 2,6-isomers,
522.3 g, 3.00 mol) over 1 hour. After keeping the reaction mixture at 90°C for an additional hour,
Cool to 55°C within 20 minutes. Next, 5 ml of the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 is added, and heat generation is controlled using a water bath. The exothermic reaction brings the temperature to 65°C. As the reaction progresses, the temperature gradually decreases, so maintain it at 55°C by adding heat. 2 hours later, IR
The analytical isocyanate peak completely disappeared. The trimerization reaction is stopped by the addition of methanesulfonic acid (15 ml) and stabilized by the addition of 5 ml of a 10% solution of equal volumes of tert-butylcatechol and hydroquinone monomethyl ether. This product is
Allofuanato:urethane ratio was determined by NMR analysis.
Indicates 0.1. Example 47 A reactor equipped with a stirrer, condenser, gas line connections, vents, and port holes is first flushed with nitrogen. Next, a flow of air and nitrogen with a relative flow rate of 1:3 is introduced into the reactor. Then 2.7
of hydroxypropyl methacrylate (HPMA) is added to the reactor. The air and nitrogen flow is suspended and 0.0029 parts of cupric acetate monohydrate and 0.012 parts of a 20% styrene solution of tert-butylcatechol (TBC) are added to the reactor under continuous stirring. Restart air and nitrogen flow and add 5.7 parts of styrene to the reactor. The reaction mixture is then heated to approximately 40°C. When the temperature of the reaction mixture reaches 40°C, 2.
Begin the portionwise addition of an 80/20 mixture of 4- and 2,6-toluene diisocyanate (TDI). A total of 3.1 parts of TDI is added over about 1 hour. During this period, the temperature of the reaction mixture rises to approximately 90°C due to the exothermic reaction of TDI and alcohol. If the temperature is below or above 90°C at the end of the TDI addition, external heating or cooling brings the temperature to about 90°C. After adding the entire amount of TDI,
at 90°C for at least 1 hour and the reaction mixture
The reaction mixture is maintained at approximately 90° C. until the NCO content falls below 4.5% by weight. After both of the above conditions are met, the reaction mixture is cooled to about 50°C. Next, the methanol solution of benzyltrimethylammonium hydroxide used in Example 1 was added to the reaction mixture.
Add 0.018 parts. Shortly after this addition, an exothermic reaction begins. During this period, the temperature of the reaction mixture is
Keep at 50℃. From the onset of the exotherm, the viscosity and NCO content of the reaction mixture are monitored very closely.
When the viscosity of the reaction mixture reaches 400-500 cps and the NCO content drops below 0.2%, 0.007 part of methanesulfonic acid is added to the reaction mixture and the mixture is then cooled. When the temperature is about 35°C, 0.014 parts of TBC is added and the reaction mixture is then cooled to room temperature. The vinyl isocyanurate obtained was clear, light tan in color, had a viscosity of about 400-500 cps, and a shelf life of more than 3 months. NMR of the product shows an allofuanate:urethane ratio of 0.46. A laminate is prepared from this isocyanurate solution using 0.2% dimethylaniline, 0.2% tert-butylcatechol and 2.0% benzoyl peroxide solution (50% active). A 3.175mm (1/8″) two-layer laminate made from this resin has more than 80% of its room temperature flexural and tensile strength at 149°C (300〓).
But I keep it.

Claims (1)

[Scope of Claims] 1 The following general formula, ( ₁ ) R″(R′) is an aromatic group obtained by removing isocyanate groups from isocyanate, X is an integer one less than the number of isocyanate groups present in the polyisocyanate, and each R' is independently: or , where at least one R′ is The condition is that (In formulas (2) and (3), R is the following formula; and (In formulas (4) to (8), R ₁ is hydrogen or an alkyl group containing 1 to 4 carbon atoms, R ₂ is hydrogen, 1 to 12
alkyl containing 1 to 12 carbon atoms, or a chlorinated, brominated or fluorinated alkyl group containing 1 to 12 carbon atoms, and R ₃ is hydrogen, alkyl containing 1 to 12 carbon atoms, or 1 to 12 carbon atoms; a chlorinated, brominated or fluorinated alkyl group containing ~12 carbon atoms, R ₄ is hydrogen, methyl or ethyl and n is 1 to 4, with the proviso that on adjacent carbon atoms removing a hydroxyl group from one or more vinylidene carbonyl alkanols selected from the group consisting of R ₂ and R ₃ are both not alkyl or chlorinated, brominated or fluorinated alkyl; R represents -H or [formula]], and each molecule contains the following formula: Ethylenically unsaturated isocyanurate containing 400 or less isocyanurate rings represented by: 2. The isocyanurate according to claim 1, wherein the aromatic polyisocyanate is tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, xylene diisocyanate, or a mixture thereof. . 3. The isocyanurate according to claim 1, wherein the vinylidene carbonyloxyalkanol is hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, or a mixture thereof. . 4. The isocyanurate according to claim 1, wherein the stoichiometric ratio of allofuanate groups to urethane groups (allofuanate groups: urethane groups) is about 0.7 or less. Quintic formula; and (In the above formula, R ₁ is hydrogen or an alkyl group containing 1 to 4 carbon atoms, and R ₂ is hydrogen, an alkyl group containing 1 to 12 carbon atoms, or an alkyl group containing 1 to 12 carbon atoms. a chlorinated, brominated or fluorinated alkyl group, where R ₃ is hydrogen, an alkyl group containing 1 to 12 carbon atoms, or a chlorinated, brominated or fluorinated alkyl group containing 1 to 12 carbon atoms; , R ₄ is hydrogen, methyl group or ethyl group, and n is 1 to 4, provided that R ₂ and R ₃ on adjacent carbon atoms are both alkyl or chlorinated, brominated or fluorinated alkyl ) is reacted with an aromatic polyisocyanate in the presence of a copper salt to produce 0.75 to 1.6 moles of unreacted isocyanate per mole of the polyisocyanate used. A method for producing an ethylenically unsaturated isocyanurate containing 400 or less isocyanurate rings, which comprises a first step of producing a urethane having an isocyanate group, and a second step of trimerizing the isocyanate group-containing urethane using a trimerization catalyst. 6. The method for producing ethylenically unsaturated isocyanurate according to claim 5, which is carried out using an ethylenically unsaturated copolymerizable monomer as a solvent. 7. The method for producing ethylenically unsaturated isocyanurate according to claim 5, wherein the trimerization reaction is carried out at about 50 to 90°C.