CS202376B1 - Hardenable composition based on epoxide resins and unsaturated polyester resins - Google Patents

Description

The invention relates to new types of curable compositions comprising as a binder component a mixture of epoxy and unsaturated polyester resin. These compositions, after curing, have superior properties over the known types.

Epoxy resins are organic compounds containing at least one epoxy group per molecule, but usually two. Among the best known are resin type dian. They are cured by the addition of hardeners, e.g., addition compounds containing at least two primary or secondary amino groups in the molecule, ionic catalysts based on the reaction products of hydrofluoric acid and boric acid, respectively. modified with nitrogen containing compounds. These systems are suitable for applications at temperatures ranging from 5 to 30 ° C. Dicarboxylic anhydrides, preferably polyanhydrides with added catalysts, can be used for curing at elevated temperatures of about 80 to 200 ° C. The mechanical properties of the cured compositions can be adjusted by selecting a suitable hardener over a relatively wide range. With the exception of the reduced outdoor weather resistance of the compositions, the chemical resistance is also satisfactory.

Unsaturated polyester resins are polyesters prepared from polyols such as glycols, glycol ethers, dianols and the like, saturated dicarboxylic acids such as phthalic acid, adipic acid, and the like. their halogenated derivatives and the like, and unsaturated dicarboxylic acids, most preferably maleic anhydride, which during the synthesis is predominantly converted to fumaric acid. The solvents and the cross-linking component are unsaturated monomers containing at least one double bonded polymerization, such as styrene,

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202 370 alkyl esters of acrylic or methacrylic acid, etc. The properties of unsaturated polyester resins can be modified by the type and amount of the individual components used to a very large extent. The resins are usually divided into low, medium and high reactive gelling times. Their reactivity is determined primarily by the content of fumarate units in the molecule, the type and amount of monomer. They can be cured chemically or by radiation. In particular, various types of initiators in the form of organic peroxides, such as alkyl peroxides such as di-tert-butyl peroxide, diaeyl peroxides such as benzoyl peroxide, hydroperoxides such as cumene peroxide, ketone peroxides such as cyclohexanone or methylcyclohexanone peroxide, peroxycarbonates di-sec-butylperoxycarbonate, peroxyesters such as t-butylperoxyacetate, sulfonylacylperoxides such as acetylcyclohexanesulfonylpsroxide, tertiary alkylperketals and others.

Suitable accelerator types are selected to accelerate the curing reaction, i.e., copolymerization and polymerization of the components. For example, they are a target for diaeyl peroxides. amines, e.g. dimethyaniline, for ketone peroxides cobalt and vanadium salts, usually as naphthenates or octoates, inorganic Li salts, e.g. in combination with ascorbic acid. By suitable selection of the initiator system, the curing process can be controlled primarily in relation to temperature and time.

Air-cured unsaturated polyester coatings up to ca 80 ° C have a surface inhibited by air oxygen. This inhibition is manifested in particular by the permanent adhesion of the coating, which can be removed by heating above 100 ° C or by dissolving the adhesive layer, for example in ketones. The inhibition by air is prevented by the addition of waxy substances forming a continuous separation layer on the surface which prevents air ingress. However, the addition of waxy materials has an adverse effect on the adhesion of the compositions to the substrates. By modifying unsaturated polyesters such as allyl ethers, non-sticking of the surfaces is achieved, but at the cost of reducing their hardness. By using crosslinking aids such as isocyanates, the surface tack can also be greatly reduced. Since unsaturated polyesters, and especially initiators, always contain less water, there is a risk of bubbles or foaming of the composition.

Additions of saturated polyesters containing unsaturated fatty acids (alkyds) to epoxy compositions are known, which can then be crosslinked under atmospheric oxygen or elevated temperature oxypolymerization under appropriate conditions (U.S. Pat. No. 117,402). The addition of unsaturated polyesters, alkyds and epoxyesters to catalysts based on an equilibrium mixture of hydrofluoric acid and boric acid protects the brit. U.S. Pat. A combination of epoxy resins with unsaturated polyesters is also described in a number of patents, e.g. U.S. Pat.

077 610 1,275,650; NSR pat. No. 1,077,420; Cancer. U.S. Pat. No. 181,962; švéd. Hush. No. 165,986;

švýc. U.S. Pat. No. 371,897; US Pat. Nos. 2,809,952 and 3,303,234; Briton. U.S. Pat. Nos. 742 532 and 789 297). These combinations provide homogeneous compositions that cure at room temperature or by heating in the presence of initiators, e.g., org. peroxides and accelerators (metal naphthenes), as well as epoxy hardeners, i.e. polyamines and polyanhydrides. The disadvantages of these mixtures are, in particular, the considerable yellowing of the cured compositions and the very limited selection of organic peroxide initiators suitable for curing the unsaturated polyester resins mixed with epoxy resins at temperatures up to 25 ° C.

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These drawbacks have no curable compositions based on the epoxy and unsaturated polyester resins, reactive monomers, polymerization initiators, catalysts and optionally accelerators, plasticizers, pigments and fillers that are the subject of the present invention. It consists in that the composition for every 100 parts by weight of a mixture of epoxy resin having a molecular weight of 200 to 600 with an unsaturated polyester resin based on saturated and unsaturated dicarboxylic acids and polyols, in wt. The ratio of 1: 9 to 9: 1 contains 2 to 55 wt. parts by weight of unsaturated monomers selected from the group consisting of styrene, its methyl and halo derivatives and alkyl esters of acrylic acid having a carbon number in the alkyl group of 1 to 8, 0.3 to 15 wt. parts of an organic peroxide type initiator and 1 to 25 wt. parts of the ionic polymerization catalyst based on equilibrium mixtures of hydrofluoric acid and boric acid. In addition to these components, up to 0.04 wt. Up to 20 wt.% of parts based on metal content, accelerators from the group of organic cobalt and vanadium salts and inorganic lithium salts. parts of plasticizer and up to 100 wt. parts of pigments and / or fillers.

The most preferred weight ratio of epoxy resin to unsaturated polyester resin is 1: 1 to 2: 1, and in the case of unsaturated polyester resins it is best to use types containing bound halogen, especially chlorine or bromine. Preferred plasticizers for these compositions are, in particular, chlorinated alkanes, in particular chlorinated paraffin, and / or chlorinated diphenyl; ratio of 1: 1 to 1: 3.

Epoxy compounds suitable for use in the compositions of this invention include, but are not limited to:

Glycidyl ethers prepared by the condensation reaction of epichlorohydrin, 4-methylepichlorohydrin or glycerin, dichlorohydrin with phenols (phenol, cresol, xylenol, resorcinol, hydroquinone, floroglucin) or bisphenols (2,2-bis- (4-hydroxyphenyl) propane, 2,2bis (4) (hydroxy-phenyl) ethane, bis (4-hydroxyphenyl) sulfone) and tris- and tetrakisphenols (condensation products of phenols or its homologues with glyoxal and other dialdehydes).

These products should be prepared by such technological processes that they do not contain free phenol or cresol in the final state. This group also includes glycidyl ethers of phenolic novolaks.

Glycidyl ethers obtained by the reaction of epichlorohydrin or N-methylepichlorohydrin with aliphatic alcohols and polyols such as butyl glycidyl ether, allyl glycidyl ether, lauryl glycidyl ether, cetylglycidyl ether, ethylene glycol bis-glycidyl ether, 1,4-butylene glycol bisbisetcyl ether, 1,4-butylene glycol bisbisetcyl ether.

Glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, diglycidyl phthalate, diglycidyl ester of hexahydrophthalic acid, tetrahydrophthalic acid and others.

Epoxidated unsaturated carboxylic acid esters, eg epoxidized soybean oil methyl ester.

Epoxidated esters of unsaturated alcohols and carboxylic acids, eg di (2,3-epoxybutyl)

202,378 adipate, di (2,3-epoxybutyl) terephthalate and di (2,3-epoxycyclohexylmethyl) phthalate.

Epoxidated esters of unsaturated alcohols and unsaturated carboxylic acids, such as e.g.

2,3-epoxybutyl-3,4-epoxypentanoet, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexehcarboxylate, and other double bond epoxidation products such as epoxidized ketals and acetals, epoxidized diolefin polymers butadiene and its copolymers with styrene, acrylonitrile, vinyl acetate and the like.

In addition to compounds with three-membered cyclic oxides, cyclic multi-membered oxides such as tetrahydrofuran, ditetrahydrofurfuryl phthalate, 3,3-chloromethylolxacyclohexanone and the like are also suitable.

The unsaturated polyester resins suitable for combination with epoxides are polyols based on polyols, saturated and unsaturated dicarboxylic acids, preferably in a molar ratio of saturated / unsaturated acid of 1: 0.5 to 3. The type of polyols used primarily determines their solubility in reactive monomers, especially in styrene and acrylates. Therefore, the most preferred types are propylene glycol bases which are unrestrictedly soluble.

Unsaturated polyester resins containing aliphatic dicarboxylic acids, most often adipic acid, have excellent plasticizing properties and are advantageous to combine with high-reactive types. However, these types of unsaturated polyester resins and their cured composition are flammable. The flammability reduction is achieved by the use of chemically bonded halogen components, such as Cl and Br, which accelerate the curing of the epoxy component in epoxy resin compositions. Flame retardant resin-incorporated substances can be divided into several groups. These are primarily substances which are involved in the esterification reaction, such as alcohols or acids, and, secondly, reactive monomers carrying a double bond and involved in crosslinking by copolymerization or polymerization. Of the acids, the most important is 1,4,5,6,7,7, -hexaehlorobicyclo (2-2-1) -5-heptene-2,3-dicarboxylic acid resulting from the diene addition of hexachlorocyclopentadiene to maleic anhydride. It has flame retardant effects in unsaturated polyesters and hexachlorocyclopentadiene adduct to tetrahydrophthalic anhydride. Bulk adducts of cyclopentadiene, resp. and 4-chloro-1,2,3,6-tetrahydrophthalic acid, which is formed by the diene addition of chloroprene to maleic anhydride, tetrachlorophthalic acid and tetrabromophthalic acid. 2,3-dihaloalkylsuccinic acid or chlorinated maleic acid is also useful. The halogen carrier may also be an alcoholic component of the polyester, such as dichlorohydrin-2,2,5,5-tetra (oxymethyl) cyclopentanone, 2,2,4,4-tetrachloro-1,5-dihydroxy-3-pentanone or a polyol containing b a (hydroxyethylmercapto) heptachlordiphenyl residue or diol formed by the reaction of tetrachlorohydroquinone with an alpha-olefin.

Among the other aromatic halogenated diols, halogenated biaphenols and isopropylidene-bis (γ-bromophenoxyalkanols) are suitable. Among the aliphatic halogenated components, these include 2-methyl-3,3,3-trichloro-1,2-epoxypropane, 2,2-bis (bromoethyl) -1,3-propanediol, pentaerythro-chlorohydrin or epichlorohydrin.

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The unsaturated polyesters may also contain unsaturated alcohols capable of copolymerization based on vinyl ethers of halogenated phenols. As flame retardants, for example, chlorinated styrenes, in particular 2,5-dichlorostyrene, vinyl trichloroacetate and allyl monomers such as diallyl benzene phosphonate can be used.

Reactive monomers suitable for such compositions are styrene, its methyl and halogen derivatives, and esters of acrylic or methacrylic acid. The acid esters can be prepared from both monovalent alcohols having a carbon number of 1 to 8 and polyhydric alcohols having an OH number of 2 to 4, such as ethylene and propylene glycol, neopentyl glycol, pentaerythritol and the like. Small proportions of non-reactive organic solvents can to control the compatibility of the individual components, such as the addition of ketones, acetic acid esters, etc.

The initiators, i.e. the organic peroxides commonly used in the curing of unsaturated polyester resins, are applicable to a very wide range and are selected according to the desired reaction sequence with mixtures of epoxy and unsaturated polyester resins, including the possible addition of accelerators. Thus, for example, ketone peroxides or curing agents may be used for curing the compositions at temperatures up to 30 ° C. their solutions in non-reactive solvents or plasticizers, such as acetates, phthalates or alkyl esters of phosphoric acid. An exception is diaoyl peroxides, e.g. dibenzoyl peroxide, which is preferably used without the addition of accelerators, optionally in combination with ion-modified target catalysts. amines.

The accelerators, i.e. the organic peroxide activators, are primarily Co-naphthenate or octoate. For casting compositions, it is preferable to use Li salts, e.g. with the addition of ascorbic acid.

In particular, products based on equilibrium mixtures or adducts obtained by the reaction of boric acid or boric oxide with hydrofluoric acid, optionally containing reactive solvents, pigments and fillers, have proved to be ionic hardeners (catalysts). Mostly, complexes of these compounds with various amines are used, the type of amine used affecting the reactivity of the complexes at certain temperatures. Some types practically do not react at room temperature and the curing reaction only occurs at elevated temperature. Of note are, for example, complexes of fluoroboric compounds with less nitrogen, e.g. complexes containing boron and nitrogen in a ratio of 1: 0.1 to 0.8. These substances may be 20 to 30 wt. %, based on the amount of the equilibrium mixture, of monoepoxide compounds selected from the group consisting of glycidyl ethers, glycidyl esters, epoxidized unsaturated fatty acid esters, epichlorohydrin and derivatives thereof. Resin products such as unsaturated polyesters, alkyds and the like can also be used.

The compositions of the invention have a number of advantages over the separate components.

For example, unsaturated polyester compositions cured in volumes of 30 ml and 30 ml will produce a cracked casting due to the high reaction temperature. Epoxy resin cured by an ionic catalyst even with a small excess of this catalyst, containing tetrahydrofuran as a reactive diluent, cures in a foam block or forms a cloudy cast.

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However, the combination of the two constituents can be controlled by the initiation system and the reactivity of the unsaturated polyester resins by initiating the reaction by, for example, an epoxy component and the exothermic reaction gradually initiates the reaction of the unsaturated polyester cured by the initiator. accelerators. The casting is rubbery in the initial phase and gradually becomes a rigid thermoset. By the combination of epoxy and unsaturated polyester resins, the transparency and brightness of the coating layers and castings can be controlled in the compositions, mainly due to unsaturated polyester resins.

The e-catalyst initiator system has a significant effect on the curing process and chemical crosslinking process, i.e. copolymerization of unsaturated polyesters with reactive diluent as well as etherification crosslinking of epoxy groups, including a small proportion of the chemical bonding of the epoxy and unsaturated polyester components. For example, small portions of a target. amines such as dimethylaniline or dimethylparatoluidine slow down the reactivity of the epoxy resin, but increase the activity of the initiator system for the polyester resin, eg the ketemperoxide / Co-accelerator system. By using LiCl as an accelerator instead of Co-salts, the exothermic course of copolymerization of the unsaturated polyester resin is greatly reduced.

The resulting properties of the cured compositions and their type and their miscibility can be controlled to a large extent by the ratio of the two resins. For example, unsaturated polyester resins, when cured in air, give a permanently sticky surface due to air inhibition. However, with a 1: 1 ratio of epoxy to unsaturated polyester resin by weight, a non-tacky surface, but poorly resistant to mechanical failure (low surface hardness) is achieved. By gradually increasing the proportion of epoxy component, the surface hardness of the composition increases. For example, even at epoxy to polyester resin ratios of 5 and 3, surface hardness and boiling water hardness as well as higher are achieved than those of ground and polished unsaturated polyester surfaces with paraffin addition.

Diana-type epoxy resins give cured compositions highly flammable. Combination of these resins with halogenated types of polyester resins can achieve flame retardancy.

Excess polyester component over epoxy can remove surface tack by conventional means, eg by reducing the addition of paraffins or waxy substances that form an airborne insulating layer on the surface or by using non-inhibited polyester resins containing bound allyl ether groups, which is particularly important formulation of paint systems with increased adhesion to substrates.

The combination of these resins gives a wide range of control over both the mechanical properties, flow and adhesion of the compositions to substrates. For example, cured rubber-like compositions to brittle thermosets can be obtained. it is possible to post-harden the formed flexible castings after being removed from the molds into a hard tough mold at elevated temperature.

The unsaturated polyester resins themselves have low adhesion to the glass and are easily peeled when the edges are broken. However, their combinations with epoxy resins have a much higher adhesion, so that coatings cannot be peeled off from the glass surface as described above.

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This implies that by combining epoxy resins with unsaturated polyester resins, a wide range of products can be prepared, ranging from transparent self-leveling binders to compositions pigmented or filled with inorganic or organic fillers of a pulverulent or fibrous nature, respectively. and laminates.

Example 1

Binder for pouring materials:

Dian-type epoxy resin mol. Weight 370

Unsaturated polyester resin of mol. ratio of phthalic anhydride / maleic anhydride 1: 1a of ethylene glycol / propylene glycol by mol. ratio of 2: 1 as a 70% solution in styrene monomer Co-octoate as a solution in toluene of 2 wt. What

Initiator-methylethylcyclohexanone peroxide containing 7 wt. active drawbar

Ion catalyst mass parts by weight parts by weight part of mass parts by weight parts

After the addition of the initiator, the composition becomes slightly opacified and becomes transparent again before gelation begins.

Composition Properties:

Gel time in block 50 g 5 minutes

Gel time of coating, film 500 pm 13 minutes

Paint appearance:

Clear, transparent, high-gloss, hard, non-sticky after 3 hours, stable after 10 hours, even after 10 minutes. 2: 1 acetone / extraction gasoline.

Example 2

The composition of the composition as in Example 1 except that the epoxy resin is first mixed with the initiator and the unsaturated polyester resin with the Co-octoate and the ion catalyst. After 7 days, the two components were combined in a 1: 1 volume ratio. The gelation time of the coating at 1 mm thickness was 3 min. The coating is elastic, high gloss, surface, hardness by pencil

E. 7.

Example 3

The composition of the composition as in Example 1 except that the mixture of epoxy and polyester resin contains only Co-octoate and a solution of the initiator in the ionic catalyst is added prior to application. The stability of the initiator solution is 8 hours.

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Example 4

The components prepared according to Example 2 were mixed in a ratio of 3 wt. parts of unsaturated polyester composition and 5 wt. parts of the epoxy composition. The gel time in the block at 27 ° C was 1 min., The gel time in the 2 mm layer was 2 min. The coating is glossy, transparent. Surface hardness by pencil. 13, after 30 min. exposure to boiling water without turbidity and whitening.

Example 5

Pigmented potting composition pigmented i

Component A: Unsaturated polyester resin based on chlorotetrahydrophthalic acid as a 70% solution in styrene 44 parts by weight.

Co-octoate - 2 wt. Co 1 -FegO 3 - pigm. paste 50% in dibutyl phthalate 2-Epoxy resin type 400 40

Cycloaliphatic type epoxy resins 5

Butylbisglycidylether 5

Component B: Ion catalyst precursor and phenylglycidyl ether in wt. 1: 3 ratio 15

Cyclohexanone Peroxide 6 wt. 0 ₂ 4

Dicumyl peroxide (70%) 1 - ^h Both components A and B are homogenized separately and mixed before application in the mass. ratio of 100: 10 to 20.

Example 6

Leveling putty

Component A: Unsaturated polyester resin to dianol, maleic anhydride and acrylic acid as a 70% solution in monochlorostyrene 13 parts by weight.

% Co-naphthenate solution in styrene / toluene 1: 1 2

Ion catalyst 5

Component B: Epoxy resin mol. wt. 400 50 - Chlorinated paraffin (Cl content 46% by weight) 5 - Powder feldspar 30

Membrane-Fix 13 -Org. ketone peroxide (6 wt.% O ₂ ) 2 -The components A and B are homogenized and mixed in wt. ratio of 2 to 2.5: 10.

Claims (5)

SUBJECT OF THE INVENTION Curing compositions based on epoxy and unsaturated polyester resins, reactive monomers, polymerization initiators, catalysts and optionally accelerators, plasticizers, pigments and fillers, characterized in that for every 100 wt. parts by weight of a mixture of an epoxy resin having a molecular weight of 200 to 600 with an unsaturated polyester resin based on unsaturated and saturated dicarboxylic acids and polyols, in wt. The ratio of 1: 9 to 9: 1 contains 2 to 55 wt. parts of unsaturated monomers selected from the group consisting of styrene, its methyl and halogen derivatives and alkyl esters of acrylic and methacrylic acids having a carbon number of 1 to 8, 0.3 to 15 wt. parts of an organic peroxide type initiator, 1 to 25 wt. % by weight of an ionic polymerization catalyst based on an equilibrium mixture of hydrofluoric acid and boric acid; up to 20 wt.% of the metal cobalt and vanadium organic salts and inorganic lithium salts; parts of plasticizer and up to 100 wt. parts of pigments and / or fillers. 2. The curable composition of claim 1, wherein the unsaturated polyester resin preferably comprises bound halogen, in particular chlorine or bromine. 3. The curable composition of claim 1 wherein the weight ratio of epoxy resin to unsaturated polyester resin is preferably 1: 1 to 2: 1. 4. Curable compositions according to claim 1, characterized in that they contain as the plasticizer chlorinated alkanes, in particular chlorinated paraffin and / or chlorinated diphenyl. 5. The curable composition of claim 1, wherein the ionic polymerization catalyst based on equilibrium mixtures of hydrofluoric acid and boric acid is preferably modified by reaction with glycidyl ether in the composition. ratio of 1: 1 to 1: 3.