JPH058731B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention broadly relates to carboxy-modified vinyl ester urethane resins, methods for producing the resins, and compositions containing the resins. More narrowly, the present invention relates to carboxy-modified vinyl ester urethane resins having the following general formula: B-I [A-M-A-M] _{o -CO2H} where A is from polyoxyalkylene bisphenol A. M is a group derived from a dicarboxylic acid or its anhydride, I is an isocyanate-derived group having at least two isocyanate functionalities, and B is an acrylic or methacrylic hydroxyl group. A group derived from a terminal ester, where n is an integer equal to from 1 to about 10. Although other production methods are available, the above resins are made by reacting a polyisocyanate and a hydroxyl-terminated ester of acrylic or methacrylic acid with polyoxyalkylkylene bisphenol A and a dicarboxylic acid (or anhydride or mixture thereof). It can be produced by reacting with a condensation product. The above resins are particularly useful as thickeners in sheet molding formulations made by reaction with magnesium when mixed with unsaturated monomers, unsaturated resins, low profile agents, fillers and reinforcing agents. be. BACKGROUND OF THE INVENTION Non-carboxy modified vinyl ester urethane resins are known and disclosed in US Pat. No. 3,876,726. Thermosetting vinyl ester resin compositions containing reactive carboxylic acid groups are also described in U.S. Pat.
It is known and disclosed in US Pat. No. 3,466,259. Other vinyl ester resins containing reactive carboxylic acid groups are disclosed in US Pat. No. 3,548,030 and US Pat. No. 4,197,390.
However, none of these disclosed prior art resins are dissimilar to the resins of the present invention. Furthermore,
It has been unexpectedly discovered that the carboxy-modified resins of the present invention provide superior properties to magnesium oxide-containing compositions. According to the present invention, a carboxy-modified vinyl ester urethane resin having the following general formula is produced: B-I [A-M-A-M] _{o -CO2H} where A is polyoxyalkylene bisphenol. A
M is a group derived from a dicarboxylic acid or anhydride thereof, I is an isocyanate-derived group having at least two isocyanate functionalities, and B is an acrylic or methacrylic group. A group derived from a hydroxyl-terminated ester of an acid, and n is an integer equal to from 1 to about 10. Carboxy-modified vinyl ester urethane resins of the above general formula are typically maleate or fumarate esters of polyoxyalkylene bisphenol A (but saturated equivalents can also be used), and have an isocyanate functionality of about 2 to 3. It is manufactured from (three components) a polyisocyanate and a hydroxyl-terminated ester of acrylic or methacrylic acid. Each of those components that can be used to make the resins of the present invention is described in detail below. The carboxy-modified urethane resin of the present invention can be synthesized by several methods. In one method described in the Examples, a short chain dihydroxy terminated polyester is first made. This dihydroxy group-terminated polyester is bisphenol A
(diol) and dicarboxylic acid or dicarboxylic anhydride at a molar ratio of 3:2. One terminal hydroxyl group is reacted with an equimolar amount of unsaturated dicarboxylic acid or unsaturated dicarboxylic anhydride to produce a short-chain polyester having an average of one hydroxyl group and one carboxyl group per molecule. . The molecular weight of these polyester intermediates ranges from 600 to 8000, preferably from 1500 to 3000. It is not a requirement to produce the polyester oligomers in this way. This is because it is known in the art to condense all diols and dicarboxylic acids (or dicarboxylic acid anhydrides) with appropriate restrictions to obtain equivalent products. This condensation can be carried out neat without admixture of other materials, or it can be carried out in a suitable solvent such as an unsaturated monomer (eg styrene). It is preferred to carry out in a solvent, especially if the carboxy-modified resin is ultimately to be polymerized with such monomers. The above polyester oligomer has a total molar ratio of hydroxyl groups to isocyanate groups of 0.95 to
It can be reacted with equivalent weights of polyisocyanate and acrylic acid (or methacrylic acid) hydroxy ester to be in the range of 1.1. It is preferable to prevent unreacted isocyanate from remaining in the resin. The above reaction may be carried out in a solvent or without mixing other substances. The polyisocyanate may be first reacted with a hydroxyl-terminated oligomer or hydroxyacrylic (or methacrylic) acid ester such that at least one unreacted isocyanate group remains per molecule and then reacted with the remaining hydroxyl-containing component. . Alternatively, the polyisocyanate can be added (reacted) to a solvent mixture of both hydroxyl group-containing components as shown in the examples. In another method of synthesis, polyisocyanates are prepared in a solvent solution of stoichiometric amounts of dihydroxyl-terminated oligomeric polyesters and hydroxyacrylic (or methacrylic) esters in a total hydroxyl/isocyanate molar ratio of at least 3/3. 2 and is added such that at least one unreacted hydroxyl group remains per molecule. One mole of dicarboxylic acid is then added to this composition per equivalent of unreacted hydroxyl groups. 17
Minimum products with acid numbers in the range of -33 are most suitable for use with metal oxide thickeners for sheet molding formulations. In carrying out the urethane reaction, it is sometimes preferred to use a catalyst to promote the reaction between the hydroxyl groups and the isocyanate groups. Such catalysts are well known and include organic amines and organometallic compounds such as triethylenediamine and dibutyltin dilaurate. Bisphenol A Derivative The bisphenol A derivative used in the production of the vinyl ester urethane resin of the present invention can be said to be a condensate of bisphenol A and an alkylene oxide (eg, ethylene oxide or propylene oxide). As is well known to those skilled in the art, bisphenol A is the following compound: In addition to those of the above structure, substituted derivatives of bisphenol A can also be used to produce the resins of the present invention. When such substituted derivatives are used, those having the following general formula are preferably used. wherein X is selected from the group consisting of halogen and methyl, and a is an integer equal to 1 or 2. Particularly preferred bisphenol A derivatives are:
It is represented by the above general formula where X is selected from the group consisting of chlorine, bromine and fluorine. The polyoxyalkylene derivative of bisphenol A is produced by reacting the above bisphenol A with an alkylene oxide.
Examples of suitable alkylene oxides that may be used are ethylene oxide, propylene oxide, or butylene oxide. Preferred bisphenol A polyoxyalkylene derivatives that can be used in the present invention can be represented by the following general formula. where R' is an alkylene group having 2 to 4 carbon atoms, X is halogen or methyl, a is an integer equal to 0 to 2, and m and n are each at least is an integer equal to 1 and the sum of the two is equal to about 2 to about 16. The sum of m and n in the above formula is determined by the number of moles of alkylene oxide reacted with each mole of bisphenol A. Therefore, at least 2 moles of alkylene oxide should be reacted with each mole of bisphenol A in preparing the bisphenol A polyoxyalkylene derivatives that can be used in the present invention. A preferred result is that the number of moles of alkylene oxide used (i.e., the sum of m and n in the above formula) is from about 2 to about
Achieved if equal to 16. As the amount of alkylene oxide used increases, the properties of the resin change, improving some of its properties, such as flexural strength and elongation, while at the same time improving other properties, such as glass transition temperature and tensile strength. It was found that the Therefore, it is necessary to select the amount of alkylene oxide used so as to obtain a resin with desired properties.
It should be noted that although resins can be made from bisphenol A derivatives where the sum of m and n is greater than about 8, such resins are extremely soft and are therefore not preferred materials for the present invention. . A particularly favorable result is that m has a total of 2 to about 4
is achieved with bisphenol A derivatives equal to . In particularly preferred polyoxyalkene bisphenol A derivatives, R' in the above formula is an alkylene group containing 2 to 3 carbon atoms. Bisphenol A polyester oligomers useful in the production of vinyl ester urethane resins according to the present invention are produced by reacting the polyoxyalkene bisphenol A derivatives described above with dicarboxylic acids or dicarboxylic anhydrides. Unsaturated dicarboxylic acids that can be used to prepare the derivatives useful in this invention are, for example, maleic acid and fumaric acid. An example of a dicarboxylic anhydride that can be used is maleic anhydride. Although it is preferable to use an unsaturated dibasic acid as a substituent of the bisphenol A polyester oligomer, it is also possible to use a saturated dibasic acid or a mixture of a saturated dibasic acid and an unsaturated dibasic acid. . Some examples of saturated dibasic acids are azelaic acid, sebacic acid, etc., or ortho-, iso- and tere-phthalic acids. Reducing cross-link density by this method tends to reduce resin shrinkage upon curing and provide a better low profile surface. The concentration of the reactants must meet two requirements. The first requirement is that the hydroxyl equivalents used and the isocyanate equivalents used be equally balanced (however, the OH/NCO ratio is
It should be in the range of 0.90 to 1.1). The second requirement is that the final product containing the solvent has an acid number of 17-33. Esters of acrylic (or methacrylic) acid The hydroxyl-terminated esters of acrylic (or methacrylic) acid that can be used according to the invention are:
It has the following general formula: where R is hydrogen or methyl, ethyl, propyl, butyl, etc., R' is an alkyl group containing 2 to 4 carbon atoms, and n is an integer equal to from 1 to about 3. Such esters are prepared by reacting acrylic acid, or methacrylic acid or a suitable substituted acrylic acid, with an alkylene oxide selected from the group consisting of ethylene oxide and propylene oxide. This reaction is carried out in a manner well known in the art. The integer n in the above formula is determined by the number of moles of alkylene oxide used per mole of acrylic acid (or methacrylic acid). According to the present invention, the desired vinyl ester resin is
It has been found that only ester materials can be produced in which the number of moles is equal to at least 1 up to about 3. If more than about 3 moles of alkylene oxide are used, the resulting resin has a lower heat distortion temperature and reduced physical properties (eg, tensile strength and flexural strength). Also,
It has been found that as the value of n decreases, the corrosion resistance of the resulting resin decreases. Therefore, it is desirable to keep this number as low as possible. Favorable results have been achieved with resins in which the value of n is equal to 1 to about 2. Representative acrylic (or methacrylic) ester materials that can be used include, for example, hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, polyoxyethylene
(2) Acrylate, polyoxyethylene (2) methacrylate, polyoxyethylene (3) acrylate, polyoxyethylene (3) methacrylate, polyoxypropylene (2) acrylate, polyoxypropylene (2) methacrylate, polyoxypropylene (3) ) acrylate and polyoxypropylene (3) methacrylate. Such acrylic or methacrylic esters can be used as a single compound or as a mixture of two or more compounds. Favorable results are obtained with hydroxypropyl methacrylate. The concentration of the reactants must meet two requirements. The first requirement is that the hydroxy equivalents used and the isocyanate equivalents used be equally balanced (however, the OH/NCO ratio may be in the range of 0.90 to 1.1). The second requirement is that the final product containing the solvent has an acid number of 17-33. The concentration of the reactant is initially set as follows. The hydroxyl functionality of the polyester oligomer must be calculated or determined experimentally. In the process step of reacting the polyester diol with maleic anhydride, the hydroxyl functionality is therefore reduced. Thus, the polyester diol with 2 equivalents of hydroxyl is 0.7
Reaction with equivalents of maleic anhydride leaves 1.3 equivalents of hydroxyl functionality. The acid value can be determined by measurement or calculation. The acid-modified polyester polyol is formulated such that the equivalent number of hydroxyls used from the diol is reacted with the same number of moles of isocyanate. For example, if the 1.3 equivalent weight of the product described above is reacted with toluene diisocyanate (TDI), 1.3 moles of TDI are used.
This isocyanate contains 2 equivalents of NCO per mole.
1.3 from vinyl alcohol
An equivalent amount of hydroxyl will be required. If we take the same acid-modified polyester polyol (1.3 equivalents) and react it with a polyphenylene polyisocyanate having an isocyanate functionality of 3.0, we will have 1.3 moles of that isocyanate compound and 2.6 equivalents of hydroxyl from the vinyl alcohol. will be needed.
Polymeric isocyanates are calculated on an equivalent weight basis (because their molecules do not have a single molecular weight). The acid number is calculated by the dilution method based on the initial acid number of the acid-modified polyester polyol, taking into account the total weight of reactants and solvents to be used. Polyisocyanates Preferred polyisocyanates for use in the present invention are aromatic derivatives that are liquid at normal temperatures. Such polyisocyanate materials are readily available commercially and are, for example, isomers of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and methylene-crosslinked polyestermethane polyisocyanates. Methylene crosslinked polyphenylmethane polyisocyanates have the general formula (For example, see Chapter 1 of "Polyurethane Technology" published by Intersign Publishers). Many polyphenyl polyethylene polyisocyanates (crude MDI) produced by aniline formaldehyde condensation and subsequent phosgenation; and carbodiimide, uretonimine, urethane, sulfonate, isocyanurate, urea groups, or Biuret group-containing polyisocyanates and their derivatives, many of which contain small amounts of pre-reacted low molecular weight polyols (e.g. ethylene glycol, propylene glycol, or hydroxy esters) to provide a suitable liquid. ; Can be used. Such combinations are readily available and well known in the urethane manufacturing industry. Examples are 2,4'- and 4,4'-
Contains diphenylmethane diisocyanate isomer and about 10% by weight, or about 0.1-0.3 mol%
There are compositions that are quasi-prepolymers containing low molecular weight polyols such as propylene glycol, butylene glycol, ethylene glycol, and poly-1,2-propylene ether glycols with molecular weights from 134 to 700. Of further interest to the present invention are ethylene glycol and molecular weight
carbodiimide and uretonimine modified derivatives of diphenylmethane diisocyanates which have been further modified by the addition of low molecular weight polyols, such as poly-1,2-propylene ether glycols of 134-700. The resulting vinyl ester urethane resin has been found to be particularly useful in compositions in which it is combined with 10-80% by weight of ethylenically unsaturated monomers in which it can be dissolved. As mentioned above, it is possible to make such compositions directly by including vinyl monomers in the reaction mixture. Alternatively, the vinyl ester urethane resin may be dissolved in a suitable vinyl monomer before use. Suitable vinyl monomers that can be used to prepare such compositions containing vinyl ester urethane resins are well known in the art and include, for example, styrene, chlorostyrene, t-butylstyrene, divinylbenzene, vinyltoluene. , vinyl acetate,
These include vinyl probionate, acrylic (and methacrylic) esters, diallyl phthalate, diallyl fumarate, and triallyl cyanurate.
Among these, it is preferable to use styrene, chlorostyrene, acrylic ester, or methacrylic ester. The amount of monomer used in such compositions can vary widely depending on the intended use of the particular composition. In addition to the vinyl ester urethane resin and monomer, the compositions of the present invention may contain any of the additives conventionally used in the manufacture of such compositions. Examples of such additives include free radical initiators to promote cross-linking reactions that occur when the composition cures; antioxidants to inhibit premature curing; and additives that impart color to the cured product. pigments for imparting; flame retardants; glasses, polypropylene, polyimides, for improving the strength and flexural modulus of products produced from the composition;
fibrous materials such as graphite; fillers such as antimony oxide, silicate oxide, magnesium oxide, and boron oxide to modify the physical properties of such products; and mold release agents. Thickeners Sheet molding compositions can be thickened by adding carboxy-reactive metal oxides (or metal hydroxides) such as magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide and basic calcium carbonate. , made using the carboxy-modified resin of the present invention. For any particular blend, the appropriate amount of thickener is determined experimentally and is based on the total weight of the carboxy-modified resin.
Even small amounts such as 0.5% are effective. In some instances, at least 1 mole of magnesium oxide per 2 moles of carboxy equivalents is most effective. Depending on the course of the synthesis of the carboxy-modified resin, it may be necessary to add a small amount of water of 0.2 to 1% by weight together with a thickener to act as a catalyst. Water may not be required if it is produced as a by-product in the polyester condensation reaction. Additional Resin Systems The carboxy-terminated polyurethane/vinyl monomer systems described above may contain up to 5% by weight of other ethylenically unsaturated resins prior to the addition of thickeners, fillers, etc. in the production of sheet molding formulations. When combined with 60% by weight, it can be used as a thickener. Ethylenically unsaturated resins that can be used are well known in the art and are prepared by reacting a carboxylic acid or anhydride with a polyhydric alcohol. Such resins range from 400 to 4000 (often
1000-3000). Such resins are produced in a reaction procedure in which at least one of both reactants has alpha-beta ethylenic unsaturation. Although such ethylenically unmixed resins are primarily linear, they can be made to contain branched chains by the addition of polyols or polycarboxylic acids with a functionality greater than 2.
Such resins usually contain a large number of ethylenically unsaturated bonds distributed along the backbone of the polymer chain. The use of alpha-beta ethylenically unsaturated carboxylic acids serves as a suitable method of introducing ethylenically unsaturation into polyester resins. Alpha acids such as maleic acid, fumaric acid, citraconic acid, gummy acid, gamma dimethyl citraconic acid, mezzaconic acid, itaconic acid, alpha methyl itaconic acid, gamma methyl itaconic acid, tetraconic acid, etc., and mixtures thereof.
Although it is preferred to use beta ethylenically unsaturated dicarboxylic acids, small amounts of alpha beta ethylenically unsaturated polycarboxylic acids having three or more carboxyl groups, such as aconitic acid, can also be used with the dicarboxylic acids. Anhydrides of any of the above alpha-beta ethylenically unsaturated polycarboxylic acids, if available, may be used in place of the acids. Additionally, examples of suitable saturated acids (or their anhydrides when available) that may be incorporated with unsaturated polyesters include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromphthalic acid, tetrabromophthalic acid, Chlorphthalic acid, adipic acid,
There may be zebacic acid, glutaric acid, pamelic acid or mixtures thereof. Of particular interest are mixtures of isophthalic acid (or orthophthalic acid) and fumaric acid/maleic acid. Any of a number of ethylenically unsaturated or saturated polyhydric alcohols can be used with any of the suitable mixtures described above. Dihydric alcohols, especially saturated aliphatic diols, are preferred as one of the reactants in polyester resin production. Particularly preferred among the dihydric alcohols that can be used are saturated aliphatic diols, such as ethylene glycol,
Propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol,
Triethylene glycol, tetraethylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, and mixtures thereof. Among the polyols having more than two hydroxyl groups, which can be used in small amounts to form branched chains, preferred are saturated aliphatic polyols, such as glycerol, trimethylolethane, trimethylolpropane, Pentaerythritol, arabitol, xylitol, delcitol, donnitol, sorbitol, mannitol, etc. and mixtures thereof. Furthermore, aliphatic aromatic diols and polyols and their halogenated and alkoxylated derivatives can also be used. In most cases, the condensation product has unreacted carboxylic acid groups or unreacted hydroxyl groups at the end of the chain branches. In the present invention, any remaining active hydrogen in the hydroxyl or carboxylic acid group may be removed by neutralization with a monohydroxy or monocarboxylic acid material. However, such precautions are not believed to be necessary to prevent cross-linking to the thickener chains. Other ethylenically unsaturated substances are
No. 3876726, No. 3297745, No. 3371056, No.
No. 3509234, No. 3641199, No. 3642943 and No.
It can be added with polyester resins such as vinyl ester urethane resins as described in US Pat. No. 3,677,920. These polyurethane resins contain unreacted −
It must be substantially free of NCO groups. Ethylenically unsaturated polyesters include typical ethylenically unsaturated polyepoxy condensation products, which are condensation polyethers such as those made from epichlorohydrin and diols (e.g. bisphenol A), and their ethylenically unsaturated condensation products. It may be included. Epoxidized polybutadiene is also useful. The ethylenically unsaturated polymeric material is poly(1,
3,5-tri-R substituted S-triazine-2,4,
(6-trione) (where R may contain ethylenically unsaturation or may contain a group reactive with ethylenically unsaturated materials). R groups may also be combined with epoxy, polyurethane and polyurethane resins. Such isocyanates are described in U.S. Pat.
No. 3821098, No. 3850770, No. 3719638, No.
No. 3437500, No. 3947736 and No. 3762269. In addition to the above, low profile
Various amounts of resins known in the art as profile resins can be included. Examples of such resins include polyvinyl acetate, polycaprolactone resins designated as LP-40, LP-90, and LP-90™ from Union Carbide; polymethylene methacrylate from Rohm and Haas. ;
[Solprene] by Philips Petroleum
(Trademark); Cellulose acetate lactate manufactured by Eastman;
and Exxon's CDB rubber (trademark). These compositions can be used as cast products, laminates, composites,
and filament manufacturing. Solid vinyl ester urethane resins are also useful, for example, in making molded and cast articles. The vinyl ester urethane resins of the invention are characterized by improved properties, especially when compared to previously available vinyl urethane resins. The resin of the present invention has a high heat distortion temperature,
It exhibits excellent corrosion resistance (especially against hypochlorite solutions) and is useful in compositions that cure more rapidly and require less catalyst. Yet another advantage of the resins of the present invention is the surprisingly low peak temperature (ie, the exothermic peak temperature reached during curing of the resin). These low peak temperatures facilitate processing and allow for the production of thicker laminates with homogeneous properties. Additionally, products made from the resins of the present invention exhibit less crazing, cracking, foaming, warping, and delamination. It has also been found that the properties of the vinyl ester urethane resin of the present invention can be changed depending on the value of y in the above general formula. It is therefore possible to create a series of resins whose properties vary over a considerable range depending on the end use of the resin. Finally, the vinyl ester urethane resins of the present invention can be manufactured as solid materials, and such solid materials are particularly useful in a variety of applications. EXAMPLES In order to further understand the present invention, examples are given below. It will be understood that these Examples are for illustrative purposes only, and that the present invention is not limited to the specific matters in these Examples. All quantitative ratios in the examples are by weight unless otherwise indicated. In these examples, the following standard tests:
Manipulations and ingredients used. Cast products are produced by pouring the resin-containing composition into a mold made of two glass plates (each coated with a release agent in advance) sealed on three sides and spaced 1/8 inch (approximately 3 mm) apart. did. After pouring the composition into the mold, the fourth side was sealed and the composition was allowed to cure at room temperature for 24 hours. At the end of this time, the composition
It was post-cured by heating in an oven at 100° C. for 4 hours, then it was cooled, demolded and tested. A laminate was made by impregnating glass fiber mat with a resin synthetic composition. The procedure used was as follows. a A sheet of polyethylene terephthalate film was placed on a flat surface and coated with a layer of resin composition. b A mat of continuous glass fibers was placed on top of this layer, pressed into intimate contact with the layer, and covered with a layer of resin composition. c. A chopped glass fiber mat was placed on top of the layer, pressed into intimate contact with the layer, and covered with a layer of resin composition. d Similarly, a second chopped glass fiber mat, another continuous glass fiber mat, and a second sheet of polyethylene terephthalate film were further added, each individually separated by a layer of resin-containing composition. The article thus obtained was cured for 24 hours at room temperature. At the end of this time it was post-cured by heating in an oven at 100° C. for 4 hours. The polyethylene terephthalate films were removed and the physical properties of the laminates were measured. Curability, ie gelation time, gelation to peak (exotherm) time, and peak temperature value, were measured by the following procedure. 100 grams of the resin-containing composition and catalyst were added to an 8 ounce jar and the mixture was stirred. The time between the addition of the catalyst and the point at which the free-flowing resin solution became sticky (as indicated by the appearance of a jelly-like mass) was determined as the "gel time." At this point, a thermocouple connected to a recorder was inserted into the center of the composition to about 1/2 inch from the bottom of the jar. The time between the gelation time and the time to reach the maximum exothermic temperature is referred to as the "gelation to peak exothermic time." The maximum exothermic temperature is the "peak temperature"
It is called. Tensile strength was measured by the method of ASTM D-638-71a. Bending strength was measured by the method of ASTM D-790-71. Barcol hardness was measured by the method of ASTM D-2583-67. The tensile strength was measured by the method of ASTM D-638-71a. Heat distortion temperature (HDT) is ASTM D-648-72
It was measured using the method. Shalpey impact and Izod impact are
Measured by ASTM D-256 method. The acid number (AN) of a resin is the number of mg of potassium hydroxide required to neutralize 1 g of resin. Percent free NCO was determined by titration using the method described on page 24 of Union Carbide Bulletin F-41146 entitled "Urethane Coatings Chemicals." Saponification number (SAP) is the number of mg of potassium hydroxide required to saponify 1 g of resin. Hydroxyl number (OH) is the mg of potassium hydroxide required to titrate unreacted acetic acid from the acetylation reaction of acetic anhydride of 1 g of sample. The hydroxypropyl methacrylate used was
The purity was 96% by weight. IONOL is an antioxidant identified as 2,6-di-t-butyl-4-methylphenol from Shell Chemical Company. The invention is further illustrated in the following examples. Preparation A Into two reaction flasks equipped with a stirrer, thermometer, nitrogen inlet tube and distillation head, add bisphenol.
Polyoxypropylene bisphenol A containing an average of 2.2 moles of propylene oxide per mole of A.
1318g (3.72mol) and 182g of maleic anhydride
g (1.86 mol) was added. The resulting mixture is heated to 210~
Heated to 215°C for 5 hours. At this point, the acid value is 11
was descending to The reaction mixture was then subjected to vacuum pressure for 1 hour while maintaining the temperature at 210-215°C. After releasing the vacuum pressure, 0.75 g of hydroquinone was added. The acid value was 7. The obtained hydroxy group-terminated polyester oligomer was cooled to 140°C and
g (1.67 mol) of maleic anhydride was added. The temperature dropped to 126°C. This temperature was maintained for 1/2 hour. The analytical values of the final product are AN=67, SAP=240,
OH=96. Example 1 Two reaction flasks equipped with a stirrer, a thermometer, a dry air inlet tube and a distillation head were charged with 633% of the hydroxy-terminated polyester oligomer from Preparation A above.
g (0.7 mol) was charged. Increase temperature to 88℃, 282℃
g of styrene was added. Then 211 g (1.37 moles) of 94% hydroxypropyl methacrylate were added. The temperature dropped to 58°C. Diphenylmethane diisocyanate (Trade Mark:
Rubinate M) 283 g (0.79 mol) were added dropwise. The temperature rose to 78°C due to the exothermic urethane reaction. The temperature was raised to 80-85°C and maintained for 4 hours. At this point there was no detectable amount of free NCO by IR analysis. 100 ppm of phenothiazine was added followed by 470 g of styrene to obtain 60% resin solids in styrene. This resin
The styrene solution had a viscosity of 1200 centipoise (No. 2, @12) at room temperature. The analytical values of this resin/styrene solution are AN=25, SAP=135 and OH=
It was 21. Preparation B Into two reaction flasks equipped with a stirrer, thermometer, nitrogen inlet tube and distillation head, add bisphenol.
Polyoxypropylene bisphenol A containing an average of 2.2 moles of propylene oxide per mole of A.
1267 g (3.58 moles) and 175 g of maleic anhydride
g (1.79 mol) was added. The resulting mixture was heated for 5 hours.
Heated to 210-215°C. At this point, the acid value had dropped to 10. Vacuum pressure was applied to the reaction mixture for 1 hour while maintaining the temperature at 210-215°C. After releasing the vacuum pressure, 0.76 g of hydroquinone was added. Acid value is 7
It was hot. The obtained hydroxy group-terminated polyester oligomer was cooled to 140° C., and 123 g (1.26 mol) of maleic anhydride was added thereto. The temperature dropped to 127°C. This temperature was maintained for 1/2 hour. The analytical values of the final product were AN=54, SAP=221 and OH=106. Example 2 Into two reaction flasks equipped with a stirrer, a thermometer, a dry air inlet tube and a distillation head, the hydroxy-terminated polyester oligomer of Preparation B above was added.
g (0.44 mol) was charged. Raise the temperature to 85℃,
282g of styrene was added. Then 233 g (1.52 moles) of 94% hydroxypropyl methacrylate
added. The temperature dropped to 53°C. Dropwise addition of 313 g (0.88 mol) of diphenylmethane diisocyanate (Rubinate M) over 1 hour resulted in an exothermic urethane reaction that brought the temperature to 81°C.
rose to The temperature was increased to 80-85°C and maintained at this temperature for 4 hours. At this point there was no detectable amount of free NCO by IR analysis. 100 ppm of phenothiazine was added followed by 470 g of styrene to give 60% resin solids in the styrene. This resin-styrene solution had a viscosity of 1350 centipoise (No. 2, @12) at room temperature. The analytical values of this resin/styrene solution are AN=18.6, SAP
= 128 and OH = 18. Preparation C Bisphenol A1 was added to two reaction flasks equipped with a stirrer, thermometer, nitrogen inlet tube and distillation head.
Polyoxide propylene bisphenol A containing an average of 2.2 moles of propylene oxide per mole.
1414 (4 moles) and 196 g of maleic anhydride
(2 mol) was added. The resulting mixture was heated to 210-215℃
and maintained at this temperature for 5 hours. At this point, the acid value had dropped to 11.7. Then set the temperature to 210
Vacuum pressure was applied to the reaction mixture for 1 hour while maintaining the temperature at ~215°C. After the vacuum pressure was released, 0.18 g of hydroquinone was added. The resulting hydroxy-terminated polyester oligomer was then cooled and poured out. . The final product was an amber semi-solid with AN=8.9, SAP=142 and OH=155. Example 3 569 g of the hydroxy-terminated polyester oligomer of Preparation C above were placed in two reaction flasks equipped with a stirrer, a thermometer, a dry air inlet and a distillation head.
(0.72 mol) was charged. The temperature was raised to 80° C. and 64 g (0.65 mol) of maleic anhydride was added. temperature
The temperature was raised to 105-110°C and maintained for 1/2 hour. 282 g of styrene was added followed by 211 g (1.35 moles) of 94% hydroxypropyl methacrylate.
The temperature dropped to 56°C. 283g over 1 hour
(0.8 mol) of Rubinate M was added dropwise.
The exothermic urethane reaction raised the temperature to 75°C. The temperature was raised to 80-85°C and maintained for 4 hours. At that point, there is a detectable amount of free NCO by IR analysis.
did not exist. 100ppm phenothiazine,
Then 470g of styrene was added to give 60% resin solids in the styrene. This resin/styrene solution has a viscosity of 1350 centipoise (No.
2, @12). The analytical values of this resin/styrene solution were AN=25, SAP=134 and OH=22. Example 4 797 g of the hydroxy-terminated polyester oligomer of Preparation A above was placed in two reaction flasks equipped with a stirrer, thermometer, dry air inlet tube, and distillation head.
(0.91 mol) was charged. Increase temperature to 98℃, 282
g of styrene was added, followed by dropwise addition of 174 g (1 mol) of toluene diisocyanate (TDI), and the exothermic urethane reaction brought the temperature to 90° C.
The temperature rose to ℃. Then 156 g (1 mole) of 94% hydroxypropyl methacrylate was added. The temperature was maintained at 90-95°C for 3 hours. At this point, the IR
There were no analytically detectable amounts of free NCO. 100 ppm of phenothiazine was added followed by 470 g of styrene to give 60% resin solids in the styrene. This resin/styrene solution had a viscosity of 625 centipoise (cps) at room temperature (No. 2, @30). The analytical values for this resin/styrene solution are AN=31, SAP=156 and OH=12.
It was hot. Example 5 658 g of the hydroxy-terminated polyester oligomer of Preparation C above was added to two reaction flasks equipped with a stirrer, a thermometer, a dry air inlet tube, and a distillation head.
(0.77 mol) was charged. Increase temperature to 97℃, 247℃
g of styrene was added, then 156 g (1 mole) of
Upon addition of 94% hydroxypropyl methacrylate, the temperature dropped to 69°C. 174 g (1 mol) of toluene diisocyanate (TDI) was added dropwise over the course of 1 hour, and the temperature rose to 86° C. due to the exothermic urethane reaction. Temperature 90~
Maintained at 95°C for 3.5 hours. There was no detectable amount of free NCO by IR analysis at that time.
100 ppm of phenothiazine was added followed by 412 g of styrene to give 60% resin solids in the styrene. This resin/styrene solution can be heated to room temperature.
The viscosity was 628 sps (No. 2, @30). The analytical values of this resin/styrene solution are AN=24, SAP=
132 and OH=15. Example 6 Into two reaction flasks equipped with a stirrer, a thermometer, a dry air inlet tube and a distillation head were added 605 g of the hydroxy-terminated polyester oligomer of Preparation C above.
(0.77 mol) was charged. Increase the temperature to 80℃, 53
g (0.54 mol) of maleic anhydride was added. The temperature was increased to 105-110°C and maintained for 1/2 hour. then
Add 247g styrene, then 156g (1.0 mole)
of 94% hydroxypropyl methacrylate, the temperature dropped to 58°C. Over 1 hour, 174 g (1 mol) of TDI was added dropwise, and the exothermic urethane reaction caused the temperature to rise to 78°C. The temperature was increased to 80-85°C and maintained for 4 hours. There were no detectable amounts of free NCO by IR analysis at that time. Add 100 ppm of phenothiazine, then add 412 g of styrene,
The resin was given at 60% solids in styrene. This resin/styrene solution has a viscosity of 632 cps at room temperature.
(No. 2, @30). The analytical values of this resin/styrene solution are AN=25, SAP=150 and OH=
I was 18. Example 7 568 g of the hydroxy-terminated polyester oligomer of Preparation B above was added to two reaction flasks equipped with a stirrer, a thermometer, a dry air inlet tube, and a distillation head.
(0.77 mol) was charged. Increase temperature to 80℃, 156
g (1 mol) of 94% hydroxypropyl methacrylate was added. Over 1/2 hour, 174g (1
When TDI (mol) was added dropwise, the temperature rose to 108°C due to the exothermic urethane reaction. The temperature was increased to 110°-115°C and maintained for 1 hour. At that point, a detectable amount is released by IR analysis.
There were no NCOs. The molten resin was poured out and cooled to give an amber solid with a melting point of 82°C (ball-ring method). Analysis value is AN
=40, SAP=241 and OH=25. Although these resins were intended for sheet molding, cast and laminate data were obtained to establish their physical properties as cured styrene copolymers.

【table】

[Table] Bending strength retention rate 1

Claims (1)

[Claims] 1 The following general formula: B-I[A-M-A-M] _o -CO ₂ H (where B is derived from a hydroxyl-terminated ester of acrylic acid or methacrylic acid) group, I is a group derived from aromatic polyisocyanate, A is polyoxyalkylene bisphenol A
or a group derived from a derivative thereof, M is a group derived from a dicarboxylic acid or anhydride thereof, and n is an integer equal to 1 to 10. ) A sheet molding composition comprising a carboxyl group-terminated vinyl ester urethane polymer. 2. The composition of claim 1, wherein I is selected from the group consisting of groups derived from toluene diisocyanate, diphenylmethane diisocyanate, and methylene-bridged diphenylmethane diisocyanate. 3 A is a general formula: -(OR ¹ ) _o OPH(X) _a -C(CH ₃ ) ₂ -PH(X) _a -O(R ¹ O) _n - (where R ¹ is 2 to 4 PH is a phenyl group; X is halogen or methyl; n and m are each an integer equal to at least 1; , and a is an integer from 0 to 2). 4. A composition according to claim 1, wherein M is selected from the group consisting of groups derived from fumaric acid and maleic acid. 5 Styrene, chlorostyrene, t-butylstyrene, divinylbenzene, vinyltoluene, vinyl acetate, vinyl propionate, acrylic acid, methacrylic ester, substituted acrylic ester, diallyl phthalate, diallyl fumarate, triallyl cyanurate and trivinyl The composition of claim 1 further comprising 10 to 60% by weight of an ethylenically unsaturated monomer selected from the group consisting of isocyanurates. 6. Claim No. 6 further comprising 0.5 to 10% by weight of a carboxyl-reactive thickener selected from magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide and basic magnesium carbonate, and an equal amount of water. Composition according to item 5. 7. The composition according to claim 6, further comprising a free radical generating catalyst, a filler and a reinforcing agent. 8. The composition according to claim 1, further comprising 5 to 60% by weight of an ethylenically unsaturated resin selected from the group consisting of polyester resins, polyurethane resins, and polyvinyl isocyanurate resins. 9. A composition according to claim 1 having an acid value within the range of 12 to 33.