MXPA00003245A - Water resistant unsaturated polyester resin compositions - Google Patents

Abstract

A curable thermoset resin composition usefulfor imparting water and/or solvent resistance to gel coated fiber-reinforced polymers comprising:(A) at least 5 wt.%of an at least partially end-capped unsaturated polyetherester resin;(B) an unsaturated polyester resin preferably modified with dicyclopentadiene having a ratio of the number average molecular weight to the average number of double bonds per polymer molecule in the range from about 200 to about 400, in an amount such that the weight ratio of polyester resin (B) to polyetherester resin (A) is in the range from about 10:90 to about 90:10;(C) about 10 to about 70 wt.%of at least one vinyl monomer;and (D) a curing agent. The composition is preferably used as a barrier layer between the fiber-reinforced polymer and the gel coat.

Description

"COMPOSITIONS OF UNSATURATED POLYESTER RESIN, WHICH HAVE WATER RESISTANCE" This invention relates to the field of resin systems including curable thermosettable resins, composite materials and surface laminates for composite materials, and processes for making same. Polymers reinforced with known gel-coated fibers are subject to blistering if immersed in water or solvents for a prolonged period of time, unless special measures are taken to prevent this phenomenon. The blisters are raised by localized swelling of the gel-coated laminate due to the diffusion of water to the compound and the presence of water-soluble constituents within the laminate. The blisters not only affect the external appearance of the gel-coated fiber reinforced polymer article, but also eventually lead to reduced strength of the composite. Various methods have been proposed to reduce blistering in gel-coated composites. U.S. Patent No. 4,724,173 discloses using a permeable gel layer to allow osmotically active molecules to diffuse from the osmotic centers through the gel layer at a defined transport rate whereby the osmotic pressure of the osmotic centers is reduced to reduce the formation of blisters. U.S. Patent No. 4,477,325 discloses a method of manufacturing a surface barrier having improved water resistance to protect the hydrolysis composite. U.S. Patent Nos. 4,480,077 and 4,525,544 disclose vinyl ester resin compositions which can be used in the laminate construction to impart greater resistance to water permeation and U.S. Patent No. 4,959,259 discloses a bisphenol polyester resin composition which can also be used to impart greater resistance to water permeation. The latter technique, using a laminated resin that has greater resistance to corrosion and / or water, is the most common technique used by the composite industry to reduce blistering. Those resins are typically vinyl ester resins or isophthalic polyester resins. Not only is this technique not always completely satisfactory, but it also increases the total cost of the composite material and / or reduces the flexibility to select the lamination resin due to other desired properties.

As a consequence of these and other reasons, improvements in the ability to prevent blistering are desirable. These and other objects are achieved by the present invention. One aspect of this invention is that of curable thermosettable resin compositions useful for imparting water and / or solvent resistance with gel-coated fiber reinforced polymers, comprising: (A) At least 5 percent by weight of an unsaturated polyether ester resin at least partially terminally blocked; (B) An unsaturated polyester resin having a number average molecular weight ratio to the average number of double bonds per polymer molecule within the range of 200 to about 400 in an amount such that the weight ratio of the polyester resin (B) to the polyether ester resin (A) is within the range of about 10:90 to about 90:10; (C) From about 10 percent to about 70 weight percent of at least one vinyl monomer; and (D) A healing agent.

- Another aspect of this invention is a method for making a curable thermosetting resin composition comprising combining: (A) At least 5 weight percent of an unsaturated polyether ester resin of at least partially terminal block; (B) An unsaturated polyester resin having a number-average molecular weight ratio to the average number of double bonds per polymer molecule within the range of about 200 to about 400, in an amount such that the ratio in weight of the polyester resin (B) to the polyether ester resin (A) is within the range of about 10:90 to about 90:10; (C) From about 10 percent to about 70 percent by weight of at least one vinyl monomer; and (D) A healing agent. A further aspect of this invention is an intermediate for making a curable thermosettable resin composition comprising: (A) At least 5 weight percent of an at least partially unsaturated polyether ester resin terminal block; B) An unsaturated polyester resin having a number average molecular weight ratio to the average number of double bonds per polymer molecule within the range of 200 to about 400, in an amount such that the weight ratio of the polyester resin (B) to the polyether ester resin (A) is within the range of about 10:90 to about 90:10; and (C) From about 20 percent to about 50 weight percent of at least one vinyl monomer. The term "terminal block compound" as used herein, means a compound having at least one functional group capable of reacting with at least one reactive end group of the unsaturated polyether ester resin such that the number of unsaturated polyether ester resin is reduced.

When the terminal block compound has more than one functional group per molecule, then the functional groups are selected such that they have, under the same conditions, a greater propensity to react with a reactive end group of the unsaturated polyether ester resin and with another functional group of the terminal blocking compound to avoid substantial polymerization of the terminal blocking compound with itself. The functional groups of the blocking compound - terminal preferably are the same or are known to be essentially unreactive with one another. The term "cure" and "cure" refer to the formation of an essentially irreversible three-dimensional network of crosslinking in a curable polymer composition such that the polymer forms a structure that is essentially insoluble in the solvents for the non-crosslinked polymer. The term "bisphenol-A" refers to 2,2-bis (4-hydroxyphenylpropane). The term "unsaturated polyether ester resin" means intermediate molecular weight polymer resins containing non-ethylenic saturation available for free radical polymerization with a vinyl monomer, recurring ester units and recurring polyether blocks. The polyether blocks have repeating units of oxyalkylene groups (-O-alkylene-) which in a preferred embodiment have from 2 to 10 carbon atoms each (eg, oxypropylene, oxyethylene, etc ...), greater preference of 2 to 4 carbon atoms. Preferably, the unsaturated polyether ester resins have an ether / ester molar ratio of at least about 0.75, more preferably at least about 1, and preferably not greater than about 3. The number average molecular weight of these resins, preferably fall within the range of about 500 to about 10,000. They have terminal groups of alcohol and / or carboxylic acid that react with at least one of the terminal block compounds. Unless otherwise specified herein, the term "viscosity" refers to the viscosity of a polymer in a 65 weight percent styrene monomer of NVM (non-volatile material, see below) at 25 ° C. C, which is measured using a Broo field viscometer. The term "NVM" refers to a non-volatile material (also known as "solids") dispersed in a volatile substance (e.g., styrene monomer) that is measured according to the D1259 method of the American Society for the Testing of Materials. The term "ASTM" refers to a well-known collection of standard laboratory procedures for measuring the properties of materials published by the American Society for Testing and Materials. Unless otherwise specified, all ratios, percentages and parts are by weight. A more detailed description of each component of the curable thermosettable resin composition will be given below.

Component (A) Unsaturated polyether ester resins suitable for making the corresponding terminal block resins include the reaction products of polyethers and unsaturated carboxylic anhydrides or unsaturated di- or polycarboxylic acids. Preferred polyethers include polyether polyols such as polyoxyalkylene polyols, alkylene oxide-alkylene oxide copolymers and the like, wherein the alkylene group preferably has from 2 to 6 carbon atoms (eg, polyoxypropylene polyols), polyoxyethylene polyols, copolymers of ethylene oxide-propylene oxide, etc ...). These polyols preferably have average hydroxyl functionality within the range of about 2 to about 8, and preferably have a number average molecular weight within the range of about 250 to about 10,000. Unsaturated anhydrides are preferably cyclic anhydrides, such as maleic anhydride, succinic anhydride, italic anhydride and the like. Preferred di- or polycarboxylic unsaturated acids include branched and cyclic linear dicarboxylic acids of 3 to 40 carbon atoms and aromatic dicarboxylic acids of 8 to 40 carbon atoms, such as maleic acid, fumaric acid, phthalic acid and isophthalic acid . U.S. Patent No. 5,139,006, which is incorporated herein by reference, discloses a process for making the unsaturated polyether ester resins wherein the polyether is reacted with a cyclic unsaturated carboxylic anhydride in the presence of a Lewis acid catalyst. U.S. Patent Nos. 5,436,313 and 5,436,314, also incorporated herein by reference, describe preferred methods for preparing unsaturated polyether ester resins wherein the catalyst for inserting anhydrides and dicarboxylic acids into the polyethers are protic acids having a pKa of less than about 0 and metal salts thereof. The unsaturated polyether ester resins are terminally blocked with at least one terminal blocking compound such that the terminal block resin has a lower acid number than the resin prior to terminal block. Preferably, the acid number is decreased by at least 50 percent. The typical initial acid number is between 50 and 200 milligrams of KOH per gram, preferably between 70 and 170 milligrams of KOH per gram.

- The terminal blocking compound for example may be dicyclopentadiene, an epoxy-containing compound or both. The compound containing the epoxy group can be represented by the following formula: R * R3-C-CHR1 (i) \ / or wherein R, R and R represent a hydrogen atom or a hydrocarbyl group optionally having one or more heteroatoms, provided at least one of R1, R2 and R3 is not a hydrogen atom. The hydrocarbyl group may be methyl, aliphatic, cycloaliphatic or aromatic, combinations of two or more methyl, aliphatic, cycloaliphatic and aromatic residues, with or without heteroatoms. Heteroatoms, for example, may be oxygen or sulfur atoms present as ether or ester bonds between two or more methyl, aliphatic, cycloaliphatic or aromatic residues and / or the heteroatoms may be present in functional groups, such as additional groups of the formula (II). The hydrocarbyl group preferably does not contain functional groups with the epoxy group in the formula (II). Preferably, the epoxy-containing compound has at least two hydrocarbyl groups that do not contain residues reactive with the polyether ester resin (A). The number average molecular weight of the epoxide-containing compound is preferably not greater than 1500, preferably not greater than about 1000, and even more preferably not greater than 500. The compounds containing the epoxy group include, for example, glycidyl esters, glycidyl ethers, epoxy alkyls, epoxy cycloalkyls, epoxyalkylenes, aromatic epoxy compounds such as p-glycidyl styrenes and the like, and mixtures thereof. Specific examples of compounds containing the epoxy group include CARDURA resins (glycidyl esters obtainable from Shell Oil Company) such as Resin F CARDURA E-10 (a glycidyl ester of acid Versatic 10; GLYDEXX obtainable from Exxon Chemical Co. , such as GLYDEXX N-10 or ND-101, etc ...). Suitable aromatic epoxy compounds include glycidyl ethers obtainable by the reaction of epichlorohydrin with an aromatic compound containing at least one hydroxyl group carried under alkaline reaction conditions. The epoxy-containing compounds obtained when the compound containing the hydroxyl group is 2,2-bis (4-hydroxy-phenylpropane) (ie, bisphenol-A) are represented by the structure given below where n is zero or a number greater than 0, commonly within the scale of 0 to 10, preferably within the scale of 0 to 2.

Other suitable epoxy compounds can be prepared by the reaction of epichlorohydrin with di- and tri-hydroxyphenol mononuclear compounds, such as resorcinol and fluoroglycinol, polyhydroxy, polynuclear phenolic compounds, such as bis (p-hydroxyphenyl) methane and 4,4 '- dihydroxybiphenyl, or aliphatic polyols such as 1,4-butanediol and glycerol. Preferred diepoxy compounds include those designated EPON resin commercially available from Shell Oil Company, such as Resins.

EPON 825, 826 and 828, each of which are reaction products of epichlorohydrin and bisphenol A, where the n-value of the above formula is 0.04, 0.08 and 0.13, respectively.

EPON 828 which has a molecular weight of approximately 400 and one equivalent of epoxide (Method D-1652 of the American Society for the Testing of Materials) of about 185-192 is a preferred diepoxy compound due to its low viscosity, mechanical performance and commercial availability. Additional examples of suitable bisphenol A epoxide compounds include the D.E.R. TM obtainable from Dow Chemical Company, such as D.E.R. ™ 330, 331, 332 and 333, and ARALDITE ™ GY resins available from Ciba-Geigy such as ARALDITE ™ GY 6004, 6005, 6008, 6010 and 2600. In a preferred embodiment, at least one terminal block compound comprises at least a certain amount, more preferably, at least about 20 weight percent, even more preferably, at least about 50 weight percent and preferably less than or equal to about 80 weight percent DCPD and / or the monofunctional epoxy containing compound which can be obtained by reacting the same with the unsaturated polyether ester resin in the corresponding proportions . In one embodiment, at least one terminal block compound comprises a mixture of (a) DCPD and / or a monofunctional epoxy containing compound and (b) a di- or poly-functional epoxy containing compound, preferably, wherein the ratio of (a) to (b) is within the range of about 10:90 to about 90:10, more preferably, about 20:80 to about 80:20. In addition to the other advantages of this invention, curable thermosetting compositions containing these terminally blocked unsaturated polyester resins also have the advantage of ease of application due to the low viscosity of these resins. In a preferred embodiment, the viscosity of the terminal block unsaturated polyether ester resin does not exceed 1.5 Pa. s (1500 centipoise) and the viscosity of the curable thermosetting composition preferably does not exceed 0.50 Pa. s (500 centipoises). The at least partially unsaturated polyether ester resin of terminal block is present in the curable thermosetting resin composition in an amount of at least 5 weight percent, preferably at least about 10 weight percent, and up to about 80 weight percent, more preferably up to about 60 weight percent. Component B The polyester resins of dicyclopentadiene (DCPD) suitable as component (B) are preferably derived from dicyclopentadiene, maleic anhydride, and a polyhydric alcohol, preferably a glycol (eg, polypropylene alcohol, polyethylene alcohol, polyethylene alcohol, polypropylene alcohol, dipropylene alcohol) or mixtures of these). The preferred reaction is carried out in the presence of water under conditions to generate maleic acid, maleic anhydride to form dicyclopentadiene maleate and then esterify the maleate with the glycol to form the unsaturated polyester resin. The unsaturated polyester resin DCPD preferably has a viscosity no greater than about 0.50 Pa.s (500 centipoise). The preparation of DCPD polymer resins is described, for example, in U.S. Patent Nos. 3,933,757; 3,347,806; 3,883,612; 4,029,848; 4,148,765; 4,348,499 and 4,246,367; the teachings of which are incorporated by the present by reference. DCPD polyester resins can typically be obtained as solutions in vinyl aromatic monomers, such as styrene. To the extent that the aromatic vinyl monomer is already introduced by the DCPD polyester resin solution, that accounts for the presence of the vinyl monomer component (C). The ratio of the polyester resin DCPD to the polyether ester resin decreases within a weight ratio scale from about 10:90 to about 90:10, and preferably within the range from about 25:75 to about 75:25. .

Component (C) Vinyl aromatic monomers useful as component (C) of this invention include styrene, vinyl toluene, chlorostyrenes, tertiary butyl styrene, dimethylstyrenes, divinylbenzene, diallyl phthalate, mono- or multi-functional lower alkyl esters of the acids acrylic and methacrylic and the like, and mixtures thereof. Styrene is preferred. The aromatic vinyl monomer is present in an effective amount to result in a cured thermosetting product when reacted with the other components of the curable thermosetting resin composition in the presence of a free radical initiator. The amount of the vinyl aromatic monomer in the curable thermosetting resin is within the range of about 10 percent to about 70 percent by weight. Preferably, the vinyl monomer is present in an amount of at least about 20 weight percent, more preferably at least about 30 weight percent, up to about 60 weight percent, most preferably up to about 50 weight percent. percent by weight and even more preferred, up to about 36 weight percent. Component (D) The curing agent (D) comprises at least one free radical initiator. Useful free radical initiators are those which are well known and which can be obtained commercially in the unsaturated polyester industry. They include peroxide initiators and azo type initiators. Peroxide initiators include, for example, methylethyl ketone peroxide (MEK), benzoyl peroxide, tert-butylperbenzoate, tert-butyl peroxide, and the like, and mixtures thereof. The initiator is used in an amount effective to react the vinyl aromatic monomer and the other polymer components of the curable thermosetting resin to produce a cured thermosetting product. Typically, the amount is within the range of from about 0.5 percent to about 3 weight percent, more preferably from about 1 percent to about 2 percent by weight based on the weight of the curable thermosetting resin composition. An accelerator with free radical initiator is often combined in the curing agent to allow cure at lower temperatures. Examples of accelerators include dimethylaniline and transition metal salts (cobalt, iron, manganese, copper, zinc or vanadium), such as cobalt naphthenate, cobalt octanoate and the like.

Optional Ingredients Additional components may be added to the curable thermosetting resin compositions of this invention. These components include reinforcing agents such as fibers, for example, glass fibers, fibers or organic fibers which may be in crushed form or in the form of a cloth or mat; flame retardants (phosphorus or antimony compounds, aluminum trihydrate, halogenated waxes, etc ...), antioxidants, inhibitors of the free radical initiator (eg, to prevent the initiation of premature polymerization), pigments, dyes, release agents mold, inert filling materials (calcium carbonate, clays, talc, etc ...), low profile additives with low shrinkage, thickeners (magnesium oxide, magnesium hydroxide, calcium oxide, etc.), etc ... When the reinforcing fiber is used, the amount of fiber preferably is at least 5 weight percent, more preferably at least about 10 weight percent to about 80 weight percent, most preferably up to about 60 weight percent of the total weight of the composition. Utility of curable thermosettable resin composition The curable thermosettable resin compositions of this invention when combined with a reinforcing fiber can be used to obtain a fiber reinforced polymer composite by curing the thermosetting resin composition. The curable thermosettable resin composition of this invention can also be used to prepare an intermediate for making a surface laminate by combining the curable thermosettable resin composition with reinforcing fibers in the form of a sheet, which preferably has an average cross-sectional thickness , at least about 0.25 millimeter, more preferably from about 0.5 millimeter to about 5 millimeters, more preferably up to 2.5 millimeters, even more preferably up to 0.8 millimeter. This sheet preferably has a cross-sectional thickness less than 1 weight percent of its total surface area. The fiber content of the surface laminate is preferably within the range of about 25 percent to about 45 percent by weight. The fiber of preference is from about 1 to about 5 centimeters of crushed fiber or a shear stress of a continuous fiber mat. The intermediate surface laminate may be used between a gel layer and a fiber reinforced polymer layer t in a gel-coated polymer laminate to improve water and / or chemical resistance and also to improve the surface appearance of the laminate. The water and / or chemical resistance of the gel-coated polymer laminate can also be improved by just interposing the curable thermosetting resin composition, with or without optional components, between the gel-coating layer and the fiber-reinforced polymer layer. An advantage of interposing the thermosetting resin of the present invention between a gel layer and the fiber reinforced polymer layer is to prevent the formation of blisters due to the migration of water and / or other low molecular weight substances, such as organic solvents. , through the gel layer towards the fiber-reinforced polymer, causing -lining, delamination and other problems in the fiber-reinforced polymer layer. The swelling may cause an ampoule below the gel layer and the continuous migration of water and / or other solvents to the fiber reinforced polymer may eventually lead to loss of strength in the lamination of the fiber reinforced polymer.

In one embodiment, the blistering of a gel-reinforced fiber reinforced polymer is reduced by applying at least one layer of the curable thermosettable resin composition or the intermediate of the surface laminate between the gel layer and the reinforced polymer layer. fiber, and the curing of the curable thermosetting resin composition. Preferably, this is carried out by applying a gel layer composition to a mold, at least partially curing the gel layer composition, applying at least one curable thermosetting resin composition or the intermediate surface laminate to at least the partially cured gel layer, at least partially curing the curable thermosetting resin composition, by applying at least the fiber reinforced polymer layer to the thermosetting resin composition layer at least partially cured and cured of the resulting product to form the fiber reinforced polymer coated with gel. The polyester resin used to make the fiber reinforced polyester resin can be a general purpose polyester resin known in the art such as polyester resins based on orthophthalic acid. Preferred polyester resins are those with a double bond / molecular weight or a vinyl group factor (-C = C-) between about 150 and - about 500, more preferably between about 200 and about 350 (as will be further described in U.S. Patent Nos. 3,701,748, 4,295,907 and 5,637,630 which are incorporated herein by reference). These resins are made from a reaction of one or more of the glycols with an unsaturated dicarboxylic acid or its anhydride or with a mixture of unsaturated acid or its anhydride with a saturated dicarboxylic acid or its anhydride. The reaction mixture may also include dicyclopentadiene to control the molecular weight of the polyesters, as described in U.S. Patent Nos. 3,883,612 and 3,986,922 which are incorporated in Xa herein by reference. The unsaturated polyester resin typically has a number average molecular weight within the range of about 500 to about 5,000, preferably within the range of about 700 to about 2,000. Examples of the appropriate unsaturated polyester resins include the STYPOL polyester resins made by Cook Composites and Polymers, Inc. The polyester resin is applied to a matrix precursor and then cured, for example, using a curing agent that described above, for the polyether ester resin.

The gel layer composition can be any of those which are well known and which can be obtained in the art. The gel layer is typically 0.2 to 0.6 millimeter thick, and it is the surface coating of the molded part. The gel layer provides the finish color and the surface profile of the piece. Gel coatings are well known and various classes are commercially available. The selection of the gel layer will depend on the desired characteristics of the piece in relation to, among other things, impermeability, weathering, hydrolytic stability and surface finish. Examples of commercially available gel-coat materials include gel layer materials obtainable from Cook Composites and Polymers under the trademarks POLYCOR®, ARMORCOTE®, BUFFBACK®, ENVIROCOR® and LOVOCOR®. Examples of various types of reinforcing fibers that can be used in the practice of this invention are glass fibers, carbon fibers, various aramid fibers and other types of natural and synthetic fibers. The typical fiber content of the compound is between about 10 percent and 80 percent by weight. The compound and the molded part can and often are constructed in one operation. First, a gel layer is usually applied to the surface of the mold, at least partially cured, and then at least one layer of at least one curable thermosetting resin composition or at least one layer of an intermediate surface laminate is applied. applied over the gel layer at least partially cured. These are open mold operations. The precursor of the fiber reinforced polyester matrix is then applied, for example, by hand placement or spraying, or the fiber reinforcement is applied to the surface laminate, the mold is closed and the precursor of the polyester matrix is injected into the the closed mold, preferably with the mold closed under vacuum. The precursor is then allowed to cure with or without a thermal supplement and the article part is demoulded.

Examples Resin A Resin A is a terminal block unsaturated polyether ester resin mixed with styrene monomer. The unsaturated polyether ester resin is prepared by charging a five liter flask equipped with agitator, condenser, thermometer and tube to introduce nitrogen gas with 1418 grams of ACCLAIM ™ 2200 Polyol (a 2000 molecular weight polyoxypropylene diol, obtainable from ARCO Chemical Company), 442 grams of propylene glycol, 1140 grams of maleic anhydride and 2.3 grams of p-toluenesulfonic acid monohydrate and heating the mixture at 195 ° C for 4 hours, while introducing nitrogen gas until the acid decreases up to 110 milligrams of KOH per gram. "Terminal blockade is carried out by reducing the temperature of the reaction mixture to 140 ° C, introducing 260 grams of DCPD per drop to the resulting mixture and maintaining the temperature of 140 ° C. for 4 hours until the acid number is reduced to approximately 84 milligrams of KOH per gram.The mixture is then loaded with 0.7 gram of DMP-30 (2,4,6-tris-dimethylaminomethyl phenol), is mixed and maintained at 140 ° C for 5 minutes after which 675 grams of the EPON 828 Ream (obtainable from Shell Oil Company) are added, and the reaction mixture continue to mix and maintain at a temperature of 140 ° C to 150 ° C until the acid number decreases to 30 milligrams of KOH per gram. The reaction product is mixed with 1500 grams of styrene monomer to form about 5000 grams of a crystalline resin solution containing the terminal blocking resin (Resin A) having a viscosity of 1100 Pa. s (1 100 centipoises) and 65 percent by weight of NVM. Resin B Resin B is also a terminal block unsaturated polyether ester resin mixed with styrene monomer. The unsaturated terminal block polyetherester resin is prepared in the same manner as Resin A with the exception of a mixture of 520 grams of the EPON 828 resin and 310 grams of CARDURA8 E-10 resin (a glycidyl ester obtainable from Shell Oil Company) instead of 675 grams of the EPON 828 Resin from the Resin A process. The terminal block unsaturated polyether ester resin (Resin B) is mixed with a styrene monomer in such a way that the mixture has a viscosity of 0.385 Pa s (385 centipoises) and 65 percent by weight of NVM. DCPD resin DCPD resin is an unsaturated polyester resin DCPD mixed with styrene. The unsaturated polyester resin DCPD is repaired by charging a resin container of 4 liters capacity equipped with a mechanical stirrer, nitrogen spray tube, a thermoelectric pair (to measure the temperature) and a distillation head, with 1032 grams of maleic anhydride, heating the maleic anhydride to 66 ° C, slowly adding approximately 207 grams of water to the maleic anhydride and allowing the temperature to rise to about 118 ° C due to the heat released by the exothermic reaction between the maleic anhydride and the water added and then when the temperature begins to decrease by itself, add 1392 grams of DCPD at a rate that keeps the temperature of the reactants between approximately 118 ° C and 129 ° C until the acid number of the reaction mixture is 245 milligrams of KOH per gram or less. Then, 415 grams of ethylene glycol are added to the resulting reaction mixture and the temperature of the reaction mixture is raised to 204 ° C and maintained at about that temperature until the acid number decreases to 42 milligrams of KOH per gram. . A vacuum (i.e., negative pressure differential) of 85 kPa is applied to the mixture for about 30 minutes as the reaction temperature is allowed to cool. The reaction product is then mixed with 1200 grams of styrene. Preparation of the curable thermosetting resins of the invention Resin A and DCPD Resin are combined in the proportions shown in Table 1 below to prepare the solid examples of this invention. For these examples, the styrene monomer is added to adjust the weight percent NVM from 65 weight percent to 60 weight percent. A catalyst system is added to cure each example at room temperature consisting of 1.63 weight percent MEK peroxide, 0.15 weight percent cobalt naphthenate and 0.12 weight percent N, N-dimethylacetoacetamide. The results obtained are shown in Table 1, which is presented below.

Table 1 Result of the healing examples 1 and 2 of the invention Component / Property Example 1 Example 2 Resin A 80 60 Resin DCPD 20 40 Percentage of non-volatile material (NVM) 60 60 Gel time (min.) (1.63% DDM-9 (Lucidol)) 22 17 Gelification to the maximum exothermic reaction (min.) 11 13 Maximum exothermic temperature 150 ° C 186 ° C Gel-coated laminates are prepared by spraying a full type of ISO / NPG gel layer on a glass mold, pulling the gel layer down to 0.58 and 1.22 millimeters thick "wet" and then letting the gel layer cure for one hour at room temperature. A surface laminate is applied to the gel layer consisting of two layers of 42.5 grams of glass fiber mat saturated with either the resin mixture of Example 1 or Example 2, as indicated in Table 2 presented then, such that the surface laminate had a glass content of 30 percent by weight. The curing time for the surface laminate is two hours at room temperature. The main laminate consists of 4 layers of 42.5 grams of glass fiber mats with 35 weight percent glass content, which are applied after the surface lamination. A marine grade laminated resin, STYPOL 40-4822, is used. The laminate is cured at room temperature for at least 16 hours before the water boiling test is carried out. Table 2 shows the classifications of the surface profile.

Table 2 Before 100 hours 150 hours Example 1 Long wave, medium 1.8 64.1 81.8 Short wave, medium 1.3 59.0 58.4 Classification, medium 10.4 1.7 0.5 Classification of ANSI * 4.0 Example 2 Long wave, medium 1.2 51.2 74.1 Short wave, medium 0.8 42.5 60.3 Classification, medium 10.5 2.6 1.0 Classification of ANSI * 4.2 * ANSI refers to the American National Standards Institute. The "Classification of ANSI" refers to a test of 1 surface profile described in the publication of section ANSIZ124.1-1987 section 6.3. A lower ANSY rating indicates a better surface profile. A ANSI classification greater than 9 is considered a failure.

Wavy classification values (ACT Orange Release Standards TM) are typical industry visual test methods used to describe the appearance of the surface of an object. A BYK-Gardner wave scan is used to measure the appearance of the surface of different test panels. The wave scan can reveal the results in both long-term wavy (structure size greater than 0.6 millimeter) and short-term (structure size less than 0.6 millimeter). Both long-term and short-term undulations are classified from 0 to 100. The larger the number the greater the wavy is observed. The long-term and short-term undulations are then correlated mathematically with a surface classification value of 0 to 10. The higher the smoother number the surface appears.

Claims (22)

R E I V I N D I C A C I O N S

1. A curable thermosettable resin composition useful for imparting water and / or solvent resistance to polymers reinforced with gel coated fiber comprising: (A) At least 5 weight percent of a polyether ester resin at least partially unsaturated terminal blockage; (B) An unsaturated polyester resin having an average molecular weight ratio of ~ number to the average number of double bonds per polymer molecule within the range of about 200 to about 400, in an amount such that the ratio by weight of the polyester resin (B) to the polyether ester resin (A) is within the range of about 10:90 to about 90:10; (C) From about 10 percent to about 70 weight percent of at least one vinyl monomer; and (D) A healing agent.

The composition of claim 1, wherein the polyether ester resin (A) is capable of being obtained (1) by reacting at least one polyether and therefore less an ethylenically unsaturated anhydride or dicarboxylic acid in the presence of at least one catalyst effective to promote the insertion of the anhydride or dicarboxylic acid into the carbon-oxygen bonds of the polyether to produce unsaturated polyether ester resin polymer chains and ( 2) reacting the unsaturated polyether ester resin polymer chains with at least one terminal blocking compound to form the polyether ester resin with at least terminal block.

3. The composition according to claim 2, wherein at least one terminal block compound comprises dicyclopentadiene.

The composition according to claim 2 or 3, wherein at least one terminal blocking compound comprises at least one compound having at least one epoxy group.

5. The composition according to claim 4, wherein at least one compound having at least one epoxy group is a compound having the formula: R2 (I) R3-C-CHR1 / O wherein R, R and R represent a hydrogen atom or a hydrocarbyl group optionally having one or more heteroatoms, provided that at least one of R1, R2 and R is not a hydrogen atom.

The composition according to claim 4 or 5, wherein the compound having at least one epoxy group, has a molecular weight less than or equal to 500.

7. The composition according to claim 6, in wherein at least one compound having at least one epoxy group is a reaction product of epichlorohydrin and bisphenol A.

8. The composition according to any of claims 2 to 7, wherein at least one blocking compound terminal has been added until the acid number of the unsaturated polyether ester of the terminal block (A) (2) is less than about 50 weight percent of the acid number of the unsaturated polyether ester (A) (1) before blocking terminal.

The composition according to any of claims 1 to 8, wherein the unsaturated polyester resin (B) is derived from at least one of dicyclopentadiene, a non-saturated carboxylic anhydride and a glycol. -

10. The composition according to any of claims 1 to 9, wherein the vinyl monomer (C) is styrene.

The composition according to any of claims 1 to 10, wherein the curing agent (D) comprises a free radical initiator and an accelerator.

The composition according to any of claims 1 to 11, wherein at least the at least partially unsaturated terminally blocked polyether ester has a viscosity not greater than 1.5 Pa. s (1500 centipoise) and is present in an amount of about 10 weight percent to about 80 weight percent, and the weight ratio of the polyester resin (B) to the polyether ester resin (A) is within the scale from about 25:75 to about 75:25.

13. An intermediate for making a surface laminate comprising reinforcing fibers and the curable thermosettable resin composition according to any of claims 1 to 12, in the form of a sheet having a cross-sectional thickness of less than 1 percent of its total surface area.

14. A fiber reinforced polymer composite obtainable by combining a curable thermosettable resin composition according to any of claims 1 to 12, with a reinforcing fiber and curing the curable thermosettable resin composition.

15. A fiber reinforced polymer coated with -gel comprising the fiber reinforced composition of claim 14 and a gel layer.

16. A gel-coated polymer laminate comprising at least one layer of fiber reinforced polymer, at least one layer of gel and at least one layer of thermosetting resin interposed between at least one layer of polymer reinforced with fiber and at least one layer of gel, wherein at least one layer of thermosetting resin is capable of being obtained by applying the curable thermosetting resin composition of any of claims 1 to 12 or the surface rolling intermediate of claim 13 as a barrier layer between the gel coating layer and the fiber reinforced polymer layer and curing the curable thermosetting resin composition.

17. The gel-coated laminate of claim 16, wherein the fiber reinforced polymer layer comprises a reinforcing fiber and a polyester resin. - -

18. A method for making a curable thermosetting resin composition comprising combining: (A) At least 5 weight percent of an unsaturated polyether ester resin with at least partially a terminal block; (B) An unsaturated polyester resin having a number average molecular weight ratio to the average number of double bonds per polymer molecule within the range of about 200 to about 400 in an amount such that the weight ratio from the polyester resin (B) to the polyether ester resin (A) is within the range of about 10:90 to about 90:10; (C) From about 10 percent to about 70 weight percent of at least one vinyl monomer; and (D) A healing agent.

19. An intermediate for making a curable thermosettable resin composition comprising: (A) At least 5 weight percent of a terminally blocked unsaturated polyether ester resin at least partially; (B) An unsaturated polyester resin having a number average molecular weight ratio at - average number of double bonds per polymer molecule within the range of about 200 to about 400, in an amount such that the weight ratio of the polyester resin (B) to the polyether ester resin (A) falls within the scale from about 10:90 to about 90:10; (C) From about 20 percent to about 50 weight percent of at least one vinyl monomer.

20. A method for reducing the blistering of a gel-coated fiber reinforced polymer comprising: (1) Applying at least one layer of the curable thermosetting resin composition of any of claims 1 to 12 or the intermediate of the The surface laminate of claim 13, between a gel coating layer and a fiber reinforced polymer layer, and (2) Curing the curable thermosetting resin composition.

The method according to claim 20, wherein the method comprises: (1) (a) Applying a gel layer composition to a mold, (b) At least partially cure the gel layer composition of the step (a) (c) Applying at least one layer of at least one curable thermosetting resin composition according to any of claims 1 to 12, or at least one layer of the intermediate of the surface laminate of claim 13 to the coating of step gel (b), (2) At least partially cure the curable thermosettable resin composition of step "1 (c); and (3) (a) Apply at least one layer of fiber-reinforced polymer to the layer of thermosetting resin composition, at least partially cured from step (2) and (b) Cure the product from step 3 (a) to form the gel-reinforced fiber reinforced polymer

22. An article obtainable by the method of Claim 19 or 20.