JPS5910737B2 - Compositions containing half-esters of organic polyols, unsaturated monomers, epoxides and reinforcing fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to molding compositions that can be used in the production of molded articles, in particular in the production of fiber reinforced plastics.

Moldings made from the compositions of the invention are particularly suitable for automotive applications and household products. Fiberglass has been widely used as a reinforcing material in the manufacture of thermoset moldings.

These types of molded products are called “glass-reinforced plastics (G
RP) 1 and “Glass fiber reinforced plastic (FRP)
” is called. The fiberglass content in these thermoset moldings ranges from about 15 to about 75-80% by weight. over a range of. Polyester resins are often used as the resin component of these glass-reinforced thermosetting plastics. The unsaturated polyesters widely used in automotive GRP are made from maleic anhydride and propylene glycol.

However, new commercially available polyesters used in automotive applications are often becoming more complex in their structure due to the need for greater toughness. The polyesters are typically derived from the co-reaction of maleic anhydride and isophthalic or terephthalic acid or esters thereof with glycols such as propylene glycol, dipropylene glycol and/or ethylene glycol. Maleic anhydride or maleic acid is the starting component of these polyesters. The molecular weight (Mn) of these polyesters can range from about 500 to about 5,000. However, most industrial polyesters have molecular weights of about 1300 to about 2500 and are randomly terminated with carboxyl or hydroxyl moieties. H. C. “HalfEsterOfOrganicPolyol and a Process for Their Production” by Gardner et al.
OlsAIldAPrOcessFOrTheirPr
U.S. Patent Application Serial No. 129,884, filed March 27, 1980, titled
(a) The following empirical formula: where n is a number having an average value of from about 1.8 to less than about 4, and m is equal to the free valence of R' minus the average value of n; R' is a residue of an organic polyol having 2 to 4 (including 2 and 4) hydroxyl groups 0H in the above formula, without a hydroxyl group];
b) a homogeneous liquid of maleic anhydride; (c) an ethylenically unsaturated monomer that forms a liquid homogeneous mixture with the half ester and maleic anhydride and is copolymerizable; and (d) a basic compound. A composition comprising a mixture is described.

The composition may further contain one or more reinforcing fibers having a melting point or glass transition temperature of about 130°C or higher. Pelkey Patent No. 518,346 describes compositions containing triethylene glycol maleate, bisphenol A epoxy resin, and styrene as Examples 5 and 17 at 80° C. for 8 hours and then at 160° C. for 7 hours. A composition is described that upon curing forms a transparent hard resin.

This document does not describe the addition of fiber reinforcement to the composition. The present invention comprises a half ester of an organic polyol, maleic anhydride, an ethylenically unsaturated monomer, an epoxide having two or more 1,2-epoxide radicals, one or more reinforcing fibers, and optionally a base. A molding composition comprising:

By adding an epoxide having two or more 1,2-epoxide radicals to the composition of U.S. Patent Application Ser. was found to be formed at room temperature. Additionally, cured articles formed from the epoxide-containing compositions of the present invention have increased toughness as well as reduced moisture absorption compared to cured articles formed from the compositions of the aforementioned US Patent Application Serial No. 129β84. Said co-pending U.S. Patent Application Serial No. 129,8
No. 84 describes a number of half-esters of polyols suitable for forming intimate mixtures with vinyl monomers.

However, at room temperature, only a limited number of polyols exist that provide adducts with maleic anhydride that are soluble in styrene. The example is 2, 2, 4
-Trimethyl-1,3-pentanediol forms a soluble product with maleic anhydride. However, when styrene is added to the maleic anhydride reaction product of either propylene glycol or diethylene glycol, a two-phase liquid mixture is obtained. The inventor has now determined that at least two
It has been discovered that by adding an epoxide having 1,2-epoxide radicals to the two-phase mixture described above, a single homogeneous mixture can be formed at room temperature.
These mixtures are then cured to obtain parts of uniform stiffness. Furthermore, the compositions of the present invention can be formed into composites having high stiffness and strength with cure times of 25 minutes or less.

This is neither stated nor suggested in the Pelkey patent specification. The curable molding compositions of this invention are prepared by (a) the following empirical formula: R is a residue having no hydroxyl group of an organic polyol having 2 to 4 (including 2 and 4) 0H hydroxyl groups in the above formula (1)] (b) maleic anhydride; (c) an epoxide having two or more 1,2-epoxide radicals; and (d) a liquid homogeneous mixture of (a), (b) and (c). The ethylenically unsaturated monomers that form (
e) one or more reinforcing fibers having a melting point or glass transition temperature of about 130° C. or higher, and optionally a basic compound.

The half ester of the organic polyol is characterized by the following empirical formula:

This half ester is produced by the reaction of maleic anhydride with an organic polyol. The reaction product is at least about 1.5
It has ester groups. If the polyol has 4 hydroxyl groups, the reaction product can have up to 4 half-ester groups. If the number of half-ester groups is less than the number of hydroxyl groups available from the polyol, the reaction product will have residual hydroxyl groups. Typically, the maleic anhydride content in the composition totals about 20 mole percent of the amount of maleic anhydride used to form the half-ester.
not exceed. Reacts with maleic anhydride to form the above empirical formula (1
The organic polyols forming the half esters shown in ) typically have at least 2 carbon atoms and can have from 2 to 4 (inclusive) hydroxyl groups. These polyols include alkane diols, triols, and tetraols; aliphatic ether-containing diols, triols, and tetraols; cycloaliphatic-containing diols, triols, and tetraols; and aromatic-containing diols, triols, and tetraols. etc. Specific examples of organic polyols suitable for the practice of this invention include ethylene glycol, diethylene glycol, 2,2,4-trimethyl-1
, 3-pentanediol, dipropylene glycol, propylene glycol, 2,2=dimethyl-1,3-propanediol, polypropylene glycol having an average molecular weight of about 150 to about 600 and having 2 to 4 terminal hydroxyl groups; Ethylene glycol 1,4-cyclohexanedimethanol 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate, triethanolamine 1,3-butanedio[alpha]tetraethylene SS glycol , 2,2-bis(4-hydroxyphenyl)propane, ethylene oxide adduct and propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane, pentaerythritol, erythritol, glycerin, trimethylolpropane, 1 ,4-butanediol 1,6-hexanediol, tripropylene glycol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,2,
Includes 6-hexanetriol, 1,3-propanediol, and the like.

The most preferred organic polyol is 2,2-dimethyl-3-
Hydroxypropyl 2,2-dimethyl-3-hydroxypropionate, 10pyrene glycol, diethylene glycol, and ethylene oxide and propylene oxide adducts of 2,2-bis(4-hydroxyphenyl)propane. The use of mixtures of the polyols mentioned above in the preparation of half-esters is highly preferred. As described below, the half ester of formula (1) above is produced by reacting maleic anhydride with a polyol.

Since the reaction is reversible, a portion of the initial charge of maleic anhydride is carried into the final product. The maleic anhydride/polyol reaction product therefore contains both the half ester of formula (1) above and maleic anhydride. Epoxides having two or more 1,2-epoxide radicals suitable for use in the present invention are of two general forms.

The first is one having a plurality of 1,2-epoxide groups derived from the reaction of a polyfunctional active hydrogen-containing compound with excess epihalohydrin under basic conditions. These epoxides are called polyglycidyl compounds.
When the active hydrogen compound is a polyhydric alcohol or a polyhydric phenol, the resulting epoxide composition has glycidyl ether groups. A preferred group of polyglycidyl compounds are prepared via a condensation reaction with 2,2-bis(4-hydroxyphenyl)propane, also known as pisphenol A, and have the following formula: (having a value of approximately 10).

These epoxides are bisphenol A epoxy resins. They are produced by Shell Chemical Company (ShellChem).
icalCO. ) to “EpOn 828”,
Under trade names such as [Kohon 1004] and "Kohon 1010", and under trade names such as "Kohon 1004" and "Kohon 1010",
C.O. ) to “DER33l” “DER332” and “
It is commercially available under the trade name DER334. The most preferred bisphenol A epoxy resins are those with n values between 0 and 2. Other polyfunctional active hydrogen-containing compounds can be used to prepare polyglycidyl adducts suitable for use in the practice of this invention.

These compounds include amines, amino alcohols and polycarboxylic acids. Adducts derived from amines and aminophenols include N,N-diglycidylpropylaniline, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 0,
N,N-triglycidyl-4-aminophenol or N,N'-dimethyl-N,N'-diglycidyl-4,4
'-diaminodiphenylmethane. 4,4'
Polyepoxides that are polyglycidyl ethers of -dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone, or tris(4-hydroxyphenyl)methane are useful in the present invention.

Glycidyl esters of carboxylic acids are also suitable for use in the present invention.

Such glycidyl esters include, for example, diglycidyl phthalate and diglycidyl adipate. Polyepoxides made from polyols such as pentaerythritol, glycerin, butanediol or trimethylolpropane and engineered pyhalohydrins are also useful. Polyepoxides such as triglycidyl cyanurate, triglycidyl isocyanurate, N,N-diglycidyl oxamide, N,N'glycidyl derivatives of hydantoins, diglycidyl esters of cycloaliphatic dicarboxylic acids, and polyglycidyl thioethers of polythiols are also used. can do. Other epoxy-containing materials are copolymers of acrylic esters of glycidol, such as glycidyl acrylate and glycidyl methacrylate, and one or more copolymerizable vinyl compounds.

Examples of such copolymers include 1:1 styrene-glycidyl methacrylate, 1:1 methyl methacrylate-glycidyl acrylate and 62,5:24:13.
．． 5, methyl methacrylate ethyl acrylate triglycidyl methacrylate. Silicone resins with epoxy functionality {e.g. 2,4,6,8,10-penta-scratch [3-(2,3-epoxypropoxy)propyl]-2,4,6,8,10-pentamethylcyclopentasiloxane; and diglycidyl ether of 1,3-bis-(3-hydroxypropyl)tetramethyl-disiloxane} can also be used.

A large number of suitable glycidyl compounds are commercially available. In addition to the bisphenol A epoxy resin mentioned above, these include flame-retardant epoxy resins (for example, DER-580, a brominated bisphenol type epoxy resin manufactured by Tau Chemical Co., Ltd.), 1
, 4-butanediol diglycidyl ether [e.g. Ciba-GeigyCOrpOra
"Araldite" from tiOn)
DR-2], polyglycidyl ethers of phenol-formaldehyde novolacs (e.g. "DEN-431" and "DEN-438" from Tau Chemical Company),
Polyglycidyl ether of cresol-formaldehyde novolac (e.g. “ECN” from Ciba Kirkey)
-1273"), N,N'-diglycidyl derivatives of dimethylhydantoin (for example, "X
B-2793''), resorcinol diglycidyl ether [e.g. KOppers CO. Inc.
．． ) and methylolated bisphenol epoxy resins [e.g. Schaefer Chemi.
calCO. ) manufactured by ApOgen 101]
includes. Another type of epoxide having a 1,2-epoxide radical is prepared by epoxidation of dienes or polyethylene.

Commercially available examples of these epoxides include vinylcyclohexene dioxide (e.g. Union Carbide Co., Ltd.).
UniOnCarbideCOrp. ) from “ERL
4206''), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (
For example, “ERL-422” from Union Carbide
1") 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate (for example, "
ERL-4201''), bis(3,4-epoxy-6-
Methylcyclohexylmethyl) adipate (e.g. "ERL-4289" from Union Carbide), bis(2,3-epoxycyclopentyl) ether (e.g. "ERL-0400" from Union Carbide)
, dipentene dioxide (e.g. [ERL-4269'' from Union Carbide), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane (e.g. Union Carbide) Other suitable epoxidized polyenes include soybean oil, tung oil and linseed oil. Including epoxidized natural oils.

These materials have a distribution of monounsaturated oligomers and polyunsaturated oligomers. Generally, epoxides have two or more 1,2-epoxide radicals.

Monoepoxides such as styrene oxide, propylene oxide, epoxycyclohexane, glycidyl ethers of monocarboxylic acids, etc. can be added to the epoxide component. Generally, these components contain two or more 1,2-diepoxide radicals. 50 weight based on total epoxide, which greatly reduces the water sorption tendency of the cured composition in a similar manner as epoxides having more than 50% by weight, based on total epoxide. Amounts of monoepoxide can be used. The ethylenically unsaturated monomer used in the composition of the present invention forms a liquid homogeneous mixture with maleic anhydride, the half-ester structure represented by formula (1) above, and the epoxide.

Furthermore, the ethylenically unsaturated monomer must be copolymerizable with maleic anhydride and the half ester.

Suitable ethylenically unsaturated monomers that can be used in the practice of this invention include -CH=C[ groups, preferably CH2=C
One or more monomers having groups.

These monomers include styrene and its derivatives and homologs; diacrylphthalate; divinylbenzene; derivatives of acrylic or methacrylic acid and their esters, amides or nitriles, such as methyl acrylate, methyl methacrylate, n-butyl Includes methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. Further, the monomer is, for example, vinyl acetate, vinyl propionate,
Vinyl ethers and vinyl esters such as methyl vinyl ether; triallyl cyanurate; 1,3
-butanediol dimethacrylate and the like.
Mixtures of the above monomers can also be effectively used in the practice of this invention. The most preferred ethylenically unsaturated monomer expected in the practice of this invention is styrene.

This is because styrene has the most significant industrial use for such purposes. The composition of the present invention comprises:
The molar ratio of half ester to maleic anhydride ranges from about 3:1 to about 200:1, preferably from about 6:1 to about 100:1.

In the most typical and preferred embodiments, the molar ratio of half ester to maleic anhydride is from about 10:1 to about 30:1. The composition of the present invention comprises maleic anhydride/
Preferably, it is produced by intermixing the organic polyol reaction product, the ethylenically unsaturated monomer, and the epoxide. Basic compounds can also be present in the maleic anhydride/organic polyol reaction product. The basic compound acts in particular as a catalyst for the anhydride/organic polyol reaction. The basic compound is selected from amines, metal salts of alcohols or carboxylic acids, or metal oxides or hydroxides.

Metal salts of alcohols include sodium methoxide, potassium methoxide and lithium isopropoxide.

Metal salts of carboxylic acids include sodium acetate and potassium benzoate. Metal oxides or hydroxides include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. Magnesium oxide is an example of a suitable metal oxide. The characteristics of all bases suitable for use in the present invention are that the basic compound 19 is combined with water 10
This means that the pH is greater than 7 when dissolved in 0a. Preferred basic compounds are secondary or tertiary amines.

These amines have a PKb ranging from 3 to 12.
Amines suitable for use in the practice of this invention include:

(In the above formula, R is CH8, C, H5, C8H7, C4H,
independently selected from alkyl having 1 to 8 carbon atoms such as and aralkyl having 7 to 15 carbon atoms such as independently selected from alkoxy and halogen).

Other amines suitable for use in the present invention include 1
,5-diazabicyclo[5.4.0]-undeca-5-
En;1,5-diazabicyclo[4.3.0]-non-
Includes 5-ene.

Components (a), (b), (c) and (d) of the present invention are about 2
A liquid mixture is formed at a temperature range of 0°C to about 70°C.

These mixtures typically contain 40% by weight of ethylenically unsaturated monomers such as styrene. having a room temperature viscosity in the range of about 10 to about 500 centiboads. Preferably, at this monomer level, the viscosity of the solution is between about 20 centiboads and about 300 centiboads. The half ester having the formula (1) in the present invention is about 250
having a molecular weight ranging from about 900 to about 900. The acid numbers of the anhydride/polyol reaction products of this invention range from about 70 to about 500. Preferably the acid value is about 100
and about 300. In order to produce the half ester of formula (1), a polyol and maleic anhydride are
Typically, a molar ratio of 1 mole of maleic anhydride per mole of hydroxyl groups is mixed in the absence of a solvent.

The reaction is heated at 60-130°C for 1-5 hours. These conditions are 75% of the initial charge of anhydride.
% or more is sufficient to convert more than % to half esters. If a catalytic amount of a basic compound is added to the reactant mixture, the reaction time can be reduced to 30 minutes or less. After about 70% of the maleic anhydride has reacted, the ethylenically unsaturated monomer can be added.

The temperature of the liquid is rapidly lowered to the desired temperature or room temperature. The lower temperature is optional and depends on the method employed to carry out the process, the type of equipment used, and the method of utilization of the product composition. The maleic anhydride/polyol reaction product can also be prepared directly in the presence of polymerizable monomers.

In this method, maleic anhydride, a polyol, a vinyl monomer, and a vinyl polymerization inhibitor are added in an amount of about 15 to about 60
A liquid mixture is prepared by blending at a temperature of °C. It is desirable to add to this mixture a catalytic amount of a basic compound such as a tertiary amine. The basic compound catalyzes the in situ half-ester formation from the reaction of the polyol with maleic anhydride. The amount of basic compound used is about 0.2 to about 2.0 weight of the total mixture? over a range of. 70% of maleic anhydride
The time required to react the above ranges from about 5 minutes to several days. In producing the polyol/anhydride reaction product, the reaction equilibrium between maleic anhydride and organic polyol is tilted toward the maximum reaction of maleic anhydride at the lowest temperature.
If the reaction is carried out at an elevated temperature, i.e. 80° C., an equilibrium composition in which about 80% of maleic anhydride reacts with the organic polyol to form a half ester is obtained.
OmpOsiiiOn) can be achieved within a reasonable time.

If the reaction mixture is cooled to about room temperature, i.e. 23°C, more maleic anhydride reacts with the organic polyol, resulting in approximately 87 moles of maleic anhydride. The above conversion rate is achieved. The preparation of the polyol/anhydride reaction mixture can be carried out under subatmospheric, atmospheric, and superatmospheric pressure conditions.

However, atmospheric pressure conditions are generally employed. The maleic anhydride/polyol reaction is desirably carried out in the absence of water.

In the actual operation of this invention, it is often not possible to ensure that all of the reactants are completely dry and that the atmosphere in which the reaction takes place is completely moisture-free. However, in the practical operation of the process of the invention, an amount of water equivalent to the amount that can theoretically convert 1% by weight of maleic anhydride used in the reaction to maleic acid can be tolerated. Preferably, this amount is considered a maximum amount. In normal cases, water is present in relatively trace amounts, 1 weight? A much smaller amount of maleic anhydride reacts to form maleic acid. In order to ensure that the amount of water that enters the reaction is as small as possible, it is desirable to use a moisture-free, inert atmosphere in carrying out the reaction.

This moisture-free atmosphere can be provided by a relatively dry gas such as dry nitrogen, carbon dioxide, methane, helium, argon, and the like. When carrying out the anhydride/polyol reaction, it is preferable to stir the reactants.

The degree of agitation is not critical; gentle agitation of the reaction mass is sufficient. To avoid any complication of the reaction, it is desirable to effectively disperse the basic catalyst (if used) throughout the composition. The resin portion of the present invention is prepared by blending a maleic anhydride/polyol reaction product, an ethylenically unsaturated monomer, and a component having two or more 1,2-epoxide groups.

Preferably, the last component is added to the mixture of the first two components. A homogeneous liquid mixture is produced by blending at a temperature between about 0 and about 90°C. When curing the compositions of the present invention, both radical-forming reactions and polar bond-forming reactions take place.

The ethylenically unsaturated monomer copolymerizes under free radical conditions with the carbon-carbon double bonds in the half-ester and in maleic anhydride. The terminal carboxyl group of the half-ester and the anhydride portion of the maleic anhydride condense with the 1,2-epoxide functionality to form the hydroxy ester via a polar mechanism. Furthermore, the homopolymerization of epoxides can be carried out via the polar route (POl
arPaihway) may occur simultaneously.
In a preferred embodiment, the composition is cured by using a source of both free radicals and an epoxide curing catalyst. Suitable free radical sources for curing the compositions of the present invention include the ``Organic Peroxide Review'' by Gallagher et al.
anicPer0xideReview), Plastics Design and Processing (Plast
icsDesign & PrOcessing) J, l9
July 1978 issue, pages 38-42, and August 1978 issue, pages 60-67 (38, 42 and 60, 67 respectively)
e-beam radiation, actinic radiation, azo curing agents, and peroxide curing agents such as those described on page 10-12.

The techniques disclosed in the above two papers are incorporated herein by reference. Selection of a specific peroxide polymerization initiator or azo polymerization initiator for curing the composition of the present invention is within the scope of those skilled in the art, and the above-mentioned peroxide polymerization initiator and azo polymerization initiator can be used to achieve the desired curing. The manner in which this is carried out is generally characterized in the above article. The compositions of the present invention can be cured in the absence of epoxide curing agents.

However, it is desirable to use epoxide curing catalysts to obtain faster cure speeds and improved properties. These catalysts are well known in the art and include, for example, boron trifluoride, aluminum chloride, zinc chloride, stannic chloride, ferric chloride, boron trifluoride-piperidine complex, boron trifluoride-1,6 - metal halide Lewis acids such as hexanediamine complex, boron trifluoride-monoethylamine complex, boron trifluoride-dimethyl ether complex, boron trifluoride-diethyl ether complex, boron trifluoride-dipropyl ether complex; For example, phosphoric acid,
Strong mineral acids such as polyphosphoric acid; aliphatic hydrocarbon sulfonic acids and aromatic acids such as ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, lower alkyl substituted benzenesulfonic acid, etc. Hydrocarbon sulfonic acids; aliphatic fluorosulfonic acids such as trifluoromethanesulfonic acid; examples include stannous acetate, stannous butyrate, stannous hexanoate, stannous octoate, stannous benzoate, etc. stannous acylates such as; stannous salts of perfluoroalkanesulfonic acids such as tin(l)bis(trifluoromethanesulfonate); such as stannic butoxide, stannic 2-ethylhexoxide, etc. stannic alkoxides; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc.; tertiary amines such as trimethylamine, triethylamine, etc. Boron trifluoride complexes and tin salts of perfluoroalkanesulfonic acids are highly preferred for curing compositions containing glycidyl epoxy side groups. Preferred catalysts for compositions containing epoxidized dienes or polyenes are stannous acylate and triboron trifluoride monoamine complexes. These catalysts are approximately 0% based on the weight of epoxide.
．． It is used in an amount of 0.01 to about 3.0%.

It is pointed out that many basic compounds that catalyze the polyol/maleic anhydride reaction also catalyze the reaction between epoxide groups and hydroacid groups as well as the reactions between epoxide groups and carboxylic acid groups. do. It is desirable to add polymerization inhibitors to the reaction mixture to avoid premature free radical polymerization.

These polymerization inhibitors include tert-butylcatechol, butyquinone monomethyl ether or butyquinone monoethyl ether, benzoquinone, tert-butylhydroquinone, methylhydroquinone and mixtures thereof (such as mixtures of hydroquinone monomethyl ether and methylhydroquinone). include. These polymerization inhibitors are used in amounts of about 30 to about 600 parts per million by weight. When effective levels of free radical polymerization inhibitors are present in the compositions of the present invention,
The pot life (i.e., the time the liquid portion of the composition becomes a non-flowing mixture due to initiation of cross-linking) is determined by the functionality of the epoxide, the nature of the epoxide, the functionality of the anhydride/polyol adduct, and the amount of vinyl monomer in the system. It depends on several factors, including the level of epoxy catalyst and the type and amount of epoxy catalyst.

For example, difunctional epoxy components (for trifunctional or tetrafunctional components), glycidyl epoxides (for epoxidized olefins, poxides), difunctional maleic anhydride/polyol adducts (for tris-half esters or tetra-scissified (relative to ester), the combination of large proportions of ethylenically unsaturated monomer and small amounts of epoxy catalyst all favor a long pot life. Under these conditions, low viscosity liquid mixtures can be stored at room temperature for many weeks. These mixtures can be easily cured by adding a free radical polymerization initiator and heating. On the other hand, the use of highly functionalized epoxide components obtained by epoxidation, low levels of ethylenically unsaturated monomers, and/or high concentrations of active epoxy catalysts makes the resins of the compositions of the invention The onset of gelation of the shaped portion can occur within 1 minute.

For example, 3,4-epoxycyclohexylmethyl 3,4-
Epoxy-cyclohexane carboxylate 50 weight?
, maleic anhydride/polyol adduct 40 weight? , 9% by weight of styrene and 1% by weight of stannous octoate? Prescriptions containing this category belong to this category. In view of this enhanced reactivity, formulations such as those described above are preferably mixed just prior to curing. Impingement mixing heads found in industrial polyurethane reaction injection molding machines
Mixing can be effectively accomplished using an in-line static mixer (mixing head) or an in-line static mixer.

The pot life characteristics of the resinous portion of the composition determine the optimal manufacturing schedule. Fibers suitable for use in the present invention as reinforcing agents have melting points or glass transition temperatures of about 130°C or higher. These fibers include fiberglass,
Carbon fiber, aromatic polyamide fiber [E. ■． Dupont Nemor (E.
■． Dupont Nemours), metal fibers (such as aluminum fibers and steel fibers), boron fibers, and the like. Carbon fibers include those having high Young's modulus and high tensile strength.

These carbon fibers can be made from "graphitizable" materials such as those described in US Pat. No. 4,005,183. Preferred fibers are fiberglass, carbon fibers and aromatic polyamide fibers.

Fibers suitable for use in the present invention are at least about 6 mm (1
/4 inch), with an average length of at least about 1
3 ml (1/2 inch).

Different lengths of fibers can be used, from about 67 nm (1/4 inch) onwards. However, at least about 50 fibers
% is about 13m77! (1/2 inch) or more. Preferably the length of the fibers is about 25 to about 50 mm (1 to 2 inches) or more. The compositions of the present invention contain from about 1 to about 60% by weight maleic anhydride/polyol reaction product (i.e., the half ester of formula (1) above plus maleic anhydride), preferably from about 5 to about 55% by weight. %, most preferably about 1
0 to about 50% by weight.

The ethylenically unsaturated monomer is present in the compositions of the present invention in an amount of about 1 to about 70% by weight. , preferably from about 3 to about 65?
, most preferably in an amount of about 5 to about 60% by weight.

The epoxide is present in the compositions of the present invention in an amount of about 1 to about 90% by weight, preferably about 3 to about 70% by weight. , most preferably in an amount of about 8 to about 60% by weight.

The composition may contain from about 15 to about 80 fibers by weight. , preferably about 35 to about 80% by weight, most preferably about 35 to about 70% by weight. Contains.

These compositions can be formed by a number of different methods and equipment. A preferred procedure for producing molded articles from the compositions of the invention is described by R. Angiel Giunia (Ang
ell Jr., filed on April 14, 1980.
US Patent Application Serial No. 135,906 entitled ``USTherefore'' (incorporated herein by reference). This patent application describes a rapid fabrication method for fiber-reinforced thermoset products.
The fiber reinforcement consists of one or more fibers having a melting point or transition temperature of about 130°C or higher. The method is (a
) 1 having a melting point or glass transition temperature of 130°C or higher
(b) feeding the seed or more fibers in the form of a superimposed mass into a suitable heated metal die; supplying to one or more accumulator zones a liquid body of a thermosetting organic material having a temperature of about 100 nm, and capable of hardening into a thermoset resin composition when heated; (c) closing the mold containing the web; maintaining the viscosity of the liquid in the accumulator zone at a temperature below the temperature at which substantial curing of the liquid occurs; (d) injecting at least a portion of the thermosetting organic material from the accumulator zone into the mold under pressure, thereby filling the mold cavity; and (e) heating the mold. heating the substance to a temperature equal to or higher than the temperature at which curing of the substance begins;
(f) opening the mold and removing the cured thermoset article from the mold. No. 135,906, the apparatus includes: (a) having one or more cavities therein, further opening and closing the mold to expose the cavities; (b) means coupled to the mold; (b) means coupled to the mold; when the mold is opened to expose the cavity and before the thermosetting organic liquid is injected into the cavity when the mold is closed, (c) accumulator means coupled to the mold and capable of containing a thermosetting liquid, wherein the thermosetting liquid (d) is coupled to the means for regulating the injection of said liquid into said cavity, thereby said and a cooling means for keeping the temperature of the liquid in the injection means below the temperature of the mold.

Another device that can be used is a pressure bag former. Owing to the low viscosity of its liquid portion, the molding composition of the present invention easily flows over, near, and into the entire area of the mold and the fibrous material therein.
A homogeneous distribution of the reaction products within the final molded article is achieved.

For liquid portions of the compositions of the invention having a pot life of several hours or more, the aforementioned U.S. Patent Application Serial No. 135,906 having one or two accumulator zones
The apparatus described therein is perfectly suitable for producing fiber-reinforced composite articles.

However, if the liquid portion of the composition has a short pot life, it is desirable to mix the two reactive streams rapidly just before they enter the mold. This creates an impingement mixing head within the nozzle.
ixinhead) or by inserting a static mixer and using two accumulator zones. In this arrangement, the polyol/anhydride adduct and epoxide components can be kept separate until the part is constructed. The ethylenically unsaturated monomer can be stored in either or both accumulator zones. The liquid portion of the compositions of the invention can also be utilized in impregnation of textile fabrics, in the production of combined laminated structures for electrical potting, and in casting processes for protecting motors, windings, etc.

The following examples illustrate specific embodiments of the invention.

The examples are not intended to limit the scope of the invention. Example 1 Paddle type stirrer, nitrogen inlet/outlet, therm-o watch (
Melt 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3- in a 3 liter, 3-neck round bottom flask equipped with a thermometer fitted with a Therm-0-Watch control and an electric heating mantle. Charged were 408,529 (2.0 moles) of hydroxypropionate and 392,249 (4.0 moles) of molten maleic anhydride.

The solution was heated to 110° C. and kept at this temperature by using a cooling bath until the exotherm of the reaction subsided. 1.2
The temperature was maintained at 110±5° C. over time.

The mixture was then cooled to room temperature and poured into bottles for storage. The sample was titrated with aqueous pyridine. Acid value is 316~KO
It was H/9. Proton NMR analysis after 16 days shows that the maleic anhydride derived component is 91% maleate (almost exclusively maleate half esters, with less than 5% maleic acid or maleate diester) and 9% unreacted anhydride. showed that.

No fumarate-containing products were detected. Example 2
~4 The series of polyols described in Example 1 above and maleic anhydride were reacted at the temperatures and reaction times listed in Table 1 in a molar ratio of 1 mole of maleic anhydride per mole of hydroxyl groups. Example 1 above was repeated.

All products contained less than 15 mole percent unreacted maleic anhydride. Except for the adduct from propylene glycol, the fumarate content in all products was less than 8 mole percent of the initial charge of maleic anhydride. In the case of propylene glycol, the adduct contained 27 mol% of the initial charge of maleic anhydride in the form of fumarate. Z
O The reaction products of Examples 1-4 were used in the preparation of polyester/epoxy resins in the following examples.

Example 5 The apparatus described in Example 1 above was charged with 547.39 ml of dipropylene glycol and 8009 ml of maleic anhydride.

The mixture was heated to 43°C and stirred vigorously.
N-methylimidazole 5.23a (0.
4% by weight) was added. The reaction mixture immediately turned from colorless to dark brown. Over the next 18 minutes, the temperature of the mixture was increased to 120°C by intermittent heating. Twenty minutes after adding the catalyst, a sample was removed for analysis by titration. The amount of unreacted maleic anhydride present was 23% of the initial charge. The reaction temperature was gradually lowered from 120°C to 63°C over the next 60 minutes. At the end of this time a sample was taken for NMR analysis and 0.319 g of hydroquinone was added. NMR analysis showed that the distribution of the maleic anhydride-containing product was as follows: Maleate (half ester, diester and maleic acid) 88 mol% Fumarate 0.5 mol% Unreacted maleic anhydride 11.5 mol? Less than 2% of the initial charge of maleic anhydride was present as either maleic acid or maleic diester.

Examples 6 and 7 Examples 6 and 7 below demonstrate how a diepoxide is added to a two-phase liquid mixture containing maleic anhydride capped polyol and styrene to form a homogeneous liquid mixture (which is cured to make it rigid). It will be shown that a heat-cured cast product can be obtained.

Example 6 Reaction product 309 of maleic anhydride and propylene glycol and styrene 3 produced in Example 2 above
09 into approximately 2279 (8 oz.) bottles.

The two-phase mixture was inhibited with 500 ppm of t-butylhydroquinone. stirring the mixture;
It was heated to 80° C. to determine whether solubility was induced by heating. No homogeneous solution was obtained. The mixture was cooled to room temperature.

An epoxy resin made from bisphenol A and epichlorohydrin (Union Carpart Co., Ltd. ERL 2774) was added incrementally to the mixture.

This had two 1,2-epoxide groups per molecule and a weight of 190 per epoxy equivalent.
Diepoxide 20f! A homogeneous solution formed after the addition (approximately 5 minutes). The solution could not be separated by centrifugation. The appearance of the solution did not change after 24 hours. Example 7 The reaction product 309 of propylene glycol and maleic anhydride produced in Example 2 above and styrene 3
A two-phase mixture was prepared from 0.09 and t-butylhydroquinone 0.039.

This mixture was treated with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (ERL-422 sold by Union Carbide).
Processed at room temperature in increments of 1). After addition of diepoxide 309 (approximately 5 minutes) a homogeneous solution was formed which could not be separated by centrifugation. Examples 8-10 Examples 8-10 below describe the production of glass fiber reinforced composites by injecting resin into fiber-filled molds.

Example 8 Reaction mixture 110.49 prepared as described in Example 1 above from 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate and maleic anhydride; 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ERL-4221) 60.09 and styrene 12
9.69 and Zelec UN mold release agent 4.4
A solution was prepared from 9, 1.09 parts of stannous octoate, and 3.09 parts of t-butyl perbenzoate.

A portion of this resin was placed in a 5-fly (949) PPG type AKM cut strand mat (PPG, Inc., Pittsburgh, Pennsylvania, USA) in a heated mold approximately 8 inches square. Injected in seconds. The mold was pressurized at a pressure of approximately 6.3 kg/CIIL (90 psi). Approximately 3 mm (1/8 inch) of the composite was cured for 5 minutes at 150°C, then the composite was tested according to ASTM D-6
Tensile strength, modulus, and elongation by AS
Deflection strength and modulus were measured using TMD-790. The glass content was also determined by ashing. Example 9 The reaction product 55.29 of dipropylene glycol and maleic anhydride prepared as in Example 3 above and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (ERL- 422
1) 30.09, styrene 64.89, t-butyl perbenzoate 1.59, stannous octoate 0
．． A solution was prepared from Zeretsu UN2.29 and Zeretsu UN2.29.

A portion of this resin was placed in a heated mold approximately 20 CrfL (8 inches) square of poly(vinyl acetate) binder by 8 weights. Random glass mats containing excess were injected. The mat was a 447 type ROving cut to a length of approximately 2.5CT11 (1 inch).
Owens Corning, Toledo, Ohio, USA
Fiberglass (0wensC0rningFibe
RG1AS), Inc.]. 1 composite with a thickness of approximately 311 (1/8 inch)
It was cured at 50° C. for 5 minutes and removed from the mold. This composite was tested as described in Example 8 above. The results are shown in Table 1.

Example 10 Reaction product of propylene glycol and maleic anhydride prepared as described in Example 2 above 95.79
, epoxidized polybutadiene 52.09, styrene 112.39, and 1-butyl perbenzoate 2,6
A solution was prepared from 9.9% and Zeretsu UN Mold Release Agent 2.99%.

The epoxidized polybutadiene has a molecular weight of about 750 and an epoxide group weight of about 7.5? Contained. A portion of this resin was injected into a 5 fly (949) PPG type AKM cut strand mat in a heated mold approximately 20α (8 inches) square. Approximately 3n (1/8 inch) of the composite was cured for 5 minutes at 130°C. The composite was tested as described in Example 8 above. The results are shown in Table 1.

Examples 11 to 15 In Examples 11 to 15 below, pressure bag molding was employed to produce glass reinforced composites.

The resin was injected into the mold containing the glass reinforcement. Example 1
1 Reaction product of maleic anhydride and propylene glycol, prepared as described in Example 2 above 55.29
and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ERL-42
21) 30.09, styrene 64.89, Zeretsu UNm type agent 2.29, and 1-butylperbenzoe per day.
A solution was prepared from 59% of stannous octoate and 0.29% of stannous octoate.

Approximately 20cm x 20? The resin was applied to a 5 fly (105.69) PPG type AKM glass mat in a mold having a cavity of 8 inches x 8 inches x 1/8 inch. The composite was subjected to a programmed heating cycle of 5 minutes (130°C); 3 minutes (130°C);
~150°C): Cured in a press using 5 minutes (150°C). The composite was demolded and tested as described in Example 8 above. Example 12 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3 prepared as described in Example 1 above.
- 110.4 g of the reaction product of hydroxypropionate and maleic anhydride, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ERL-4221) 609, and styrene 129
．． 69, Zeretsu UN mold release agent 4.49, and stannous octoate for one day. 0f1 and i-butyl penbenzoate 3
．． A solution was prepared from 09.

The resin was applied to a 5 fly (105.69) PPG type AKM glass mat in a mold having a cavity of approximately 20 CTIL x 20 cm x 0.3 cm (8 inches x 8 inches x 1/8 inch).

The composite was cured at 90°C for 15 minutes and at 130°C for 10 minutes. The composite was removed from the mold and tested as described in Example 8 above. The results are shown in Table 1.

Example 13 The reaction product of propylene glycol and maleic anhydride, prepared as described in Example 2, 73.09;
3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ERL-422
1) A solution was prepared from 39.679 g of styrene, 85.79 g of styrene, 2409 g of t-butyl perbenzoate, 0.69 g of stannous octoate, and 2.99 g of Zeretsu UN mold release agent.

The resin was applied to a 5 fly (105.69) PPG type AKM glass mat in a mold having a cavity of approximately 20 CTn x 20 c7rL x 0.3 crn (8 inches x 8 inches x 1/8 inch). The composite was cured at 130°C for 5 minutes, 130-150°C for 2 minutes, and 150°C for 5 minutes. The composite was removed from the mold and tested as described in Example 8 above. The results are shown in Table 1. Example 14 Reaction product 509 of neopentyl glycol and maleic anhydride prepared as described in Example 4 above.
and bisphenol-A epoxy resin (Kohon 828)
509, styrene 509, t-butylhydroquinone 0.049, t-butyl penbenzoate 1.29, tin(1) bis(trifluoromethane sulfonate) [Minnesota Mining and Manufacturing Company] L-442 currently on sale
9] aqueous solution 1.09% and Zeretsu UN mold release agent 0.59%
A solution was prepared from.

Approximately 25c7n x 25c! NXO. 25C! Random glass mats (PPG type AK) in molds with cavities of RL (10 inches x 1/10 inches)
The resin was applied to 1579 of M). 153 of the compound
Cure for 6 minutes. The composite was removed from the mold and tested as described in Experiment 8 above. Example 15 Reaction product 2449 of dipropylene glycol and maleic anhydride prepared as described in Example 5 above.
, styrene 1319, and i-butylhydroquinone 0.
109 and polyglycidyl ether of phenol-formaldehyde novolac (weight 1 per epoxy equivalent)
80) [D. E. N. 438] 37.59, Zeretsu UN mold release agent 3.09 and t-butyl perbenzoate 4.49
A solution was prepared from 1.5% of an aqueous solution of tin SS(1) bis(trifluoromethanesulfonate) [L-4429].

Approximately 25cm x 25CTfLX0.25C! Random glass mat (PPG type AKM) in a mold with a cavity of RL (10 inches x 10 inches x 1/10 inch)
), a portion of the resin was applied to 1329. The composite was cured for 3 minutes at 157°C. The yellow translucent composite was removed from the mold and tested as described in Example 8 above. These results are shown in Table 1. The data in Table 1 demonstrate that composites made using compositions containing epoxides according to the invention have an excellent combination of mechanical properties.

Claims (1)

[Claims] 1 (a) The following experimental formula: (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, n
is a number having an average value of about 1.5 to about 4 or less,
m is equal to the value obtained by subtracting the average value of n from the free valence of R, and R has a hydroxyl group of an organic polyol having 2 to 4 (including 2 and 4) hydroxyl groups OH in the above formula (I). (b) maleic anhydride; (c) an epoxide having two or more 1,2-epoxide radicals; and (d) the above half-ester, anhydride. an ethylenically unsaturated monomer that forms a liquid homogeneous mixture with maleic acid and an epoxide; and (e) one or more reinforcing fibers having a melting point or glass transition temperature of about 130°C or higher. A curable molding composition. 2. The organic polyol is ethylene glycol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, propylene glycol, dipropylene glycol and has an average molecular weight between about 150 and about 600, and Polypropylene glycol with 4 terminal hydroxyl groups, 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate, ethylene oxide and propylene oxide adducts of pisphenol A, 2,2- dimethyl-1,3-
Propanediol, 1,3-butanediol and 1,4
-butanediol. 3. The composition according to claim 1, wherein the organic polyol is a mixture of polyols. 4. The composition of claim 1, wherein the total content of maleic anhydride does not exceed about 25 mole percent of the amount of maleic anhydride used to form the half-ester of (a). 5. The composition of claim 1, wherein the combined amount of half ester of formula (I) and maleic anhydride is from about 1 to about 60% by weight. 6. The composition according to claim 1, wherein the epoxide is a polyglycidyl compound. 7. The composition of claim 1, wherein the epoxide is derived from epoxidation of a diene or polyene. 8 Epoxide is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
3,4-epoxy-6-methylcyclohexylmethyl 3
, 4-epoxy-6-methylcyclohexanecarboxylate, bis(2,3-epoxy-cyclopentyl) ether, epoxidized polybutadiene, epoxidized soybean oil, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, vinyl Cyclohexene dioxide, 2-(3,4-epoxycyclohexyl-5,5
2. A composition according to claim 1, wherein the composition is selected from -spiro-3,4-epoxy)cyclohexane-metadioxane and dipentene dioxide. 9. The composition according to claim 1, wherein the epoxide is a copolymer of acrylic acid ester of glycidol. 10. The composition of claim 1, wherein the composition contains a monoepoxide. 11. The composition of claim 1, wherein the epoxide is present in an amount of about 1 to about 90% by weight. 12. The composition of claim 1, wherein the ethylenically unsaturated monomer is selected from ethylene, alpha-methylstyrene, lower alkyl esters of acrylic acid and methacrylic acid, and acrylonitrile. 13. The composition of claim 1, wherein the ethylenically unsaturated monomer is present in an amount of about 1 to about 70% by weight. 14. The composition according to claim 1, wherein the reinforcing fibers are fiberglass, carbon fibers or polyamide fibers. 15. The composition according to claim 14, wherein the reinforcing fiber is fiberglass. 16. The composition of claim 1, wherein the composition contains from about 15 to about 80% by weight reinforcing fibers. 17. The composition of claim 15 containing from about 35 to about 75% by weight of reinforcing fibers. 18. The composition according to claim 1, which contains a basic compound. 19. A composition according to claim 18, wherein the basic compound is selected from amines, metal hydroxides or metal salts of organic acids or alcohols. 20. The composition of claim 18, wherein the basic compound is present in an amount of about 0.005 to about 5% by weight based on the combined amount of polyol and maleic anhydride. 21. The composition according to claims 1 to 18, which contains an epoxide curing catalyst. 22. A composition according to claims 1 to 18, which is cured by a free radical source.