DE1187013B - Molding compounds containing unsaturated polyesters made from certain dialcohols - Google Patents

Description

Molding compounds, the unsaturated polyester from certain dialcohols In general, molding compounds contain unsaturated polyesters and polyesters which can be polymerized onto them contain monomeric vinyl or / and allyl compounds and catalysts. viscose, sticky liquids.

With these masses impregnated fiber products have the disadvantage that they have to be hardened immediately after manufacture because the Molding compound emerges from the fiber material and then no uniform layered body more can be obtained. Even by mixing the molding compounds with granular ones molding compounds produced or powdery fillers can only be stored for a limited time, because they harden gradually even at room temperature. Plus, they're sticky and can therefore only be processed with difficulty.

It is already known, non-tacky, filler-containing polyester molding compounds with unsaturated polyesters with a high softening temperature. To this Admittedly, non-sticky and durable molding compounds can be obtained, but it is one in the selection of fillers and the polymerizable, monomeric, unsaturated compounds severely restricted in type and amount. With solutions such polyester impregnated in monomeric vinyl or / and allyl compounds In addition, fiber mats or fabrics are neither tack-free nor storable.

According to another known method of making tack-free The fillers are molded with such solutions of unsaturated polyester in molding compounds monomeric, polymerizable. unsaturated compounds mixed up beforehand were thickened by the addition of metal oxides. Admittedly, these are non-sticky products preserved, but these only remain processable for a relatively short time, because the gradual progress of the thickening process gradually changes after the flowability of the mass worsened during pressing, so that after some Time no more uniform pressed parts can be produced.

It is also already known for the production of dry and storable, molding compounds containing fillers, »crystalline« polyesters from fumaric acid and symmetrical, to use dihydric, aliphatic alcohols. However, these polyesters have the disadvantage. that their copolymers with vinyl and / or allyl compounds are not good mechanical properties and, above all, too low for many purposes Have water and temperature resistance. In addition, the viscosities of Solutions of such polyesters in mono- meren. polymerizable. unsaturated Connections at higher temperatures so low that they are hot-pressed from them manufactured mixtures containing fillers, the fillers are easily filtered out, which in turn results in non-uniform compacts.

Resin-containing impregnation solutions are from the German Auslegeschrift 1060 137 known for the production of cellulosic laminates, characterized in that are that they are polymerizable polyesters mainly from a. B-unsaturated dicarboxylic acids and predominantly bisoxalkylated, exclusively alkyl-substituted in the alkylidene radical Dihydroxydiarylalkanes, water-soluble melamine-formaldehyde condensation products, Water and a water-soluble ketone as solvents and optionally additionally contain certain vinyl monomers. Cellulosic laminates impregnated with such solutions are indeed tack-free according to the information in the interpretative document. As a result of the need In addition to an unsaturated polyester resin, there are also considerable amounts of a melamine-formaldehyde resin However, to use the method there is very complex and technically difficult to handle.

It also leads to hardening products with opposite without additional Use of a melamine-formaldehyde resin made different products Properties. It's surprising. that you can do without the addition of a melamine-formaldehyde resin using selected dihydroxy compounds according to the present invention for the production of polyester resins tack-free, perfectly storable, thermosetting Molding compounds received.

The invention now relates to thermosetting molding compounds which contain unsaturated polyesters, unsaturated organic monomeric compounds which can be polymerized onto them, inorganic or organic fillers and organic peroxides and, if appropriate, inhibitors. The molding compounds are characterized in that they contain polyester with an acid number of less than 50, which in the usual way by esterifying an ethylene-1,2-dicarboxylic acid or a mixture of an ethylene-1,2-dicarboxylic acid with other saturated or unsaturated dicarboxylic acids or their anhydrides, chlorides or esters with a dihydric alcohol of the general formula where Ri is an H atom or a CH3 group and R2 is H or Cl atoms, but Ri is different from R2, or with mixtures of these alcohols, optionally together with other polyhydric, saturated or unsaturated alcohols and optionally with the addition of small amounts monohydric alcohols.

As dihydric alcohols that are used for the preparation of the invention Can serve polyester to be used, the following derivatives of 4,4'-Diß-hydroxyäthoxydiphenylmethans in question: 3,3'-dichloro-4, 4'-di-p-hydroxyethoxydiphenylmethane, 3,3'-dimethyl-4, 4'-di-ß-hydroxyäthoxydiphenylmethan and 3,3'-dimethyl-4, 4'-di-ß-hydroxyäthoxy-5, 5'-dichlorodiphenylmethane.

It is true that bis (- hydroxyäthy!) - ether of 4,4'-dihydroxydiphenylmethane or of 3,3 ', 5,5'-tetrachloro-4,4'-dihydroxydiphenylmethane similar polyesters obtained; However, their melting points are so high that they with monomeric vinyl or / and allyl compounds with the addition of polymerization catalysts cannot be processed into homogeneous mixtures, because the necessary, Polymerization takes place prematurely at relatively high temperatures. on the other hand The polyesters from such dihydroxyalkoxydiphenylalkanes possess the substituted Contain methylene groups, e.g. B. 2,2-bis (3,5-dichloro-4β-hydroxyethoxyphenyl) propane or 3,3'-dichloro-4,4'-di-ß-hydroxypropoxydiphenylmethane, at low acid numbers low crystalline sation tendency and unsatisfactory crystallinity, so that from it only under special conditions non-sticky mixtures or mixtures containing fillers Have molding compounds produced. It is therefore surprising that the above-mentioned Dihydroxy compounds for the production of high-quality, tack-free, hardenable mixtures in such an excellent way.

For comparison, in addition to the crystallization behavior at room temperature, the following table shows the minimum temperatures at which polyesters, whose acid numbers are between 14 and 20, dissolve in styrene from equivalent amounts of fumaric acid and the particular compound listed. It should be borne in mind that the temperature at which customary molding compositions composed of unsaturated polyesters and vinyl monomers begin to gel is 100 to a maximum of 110.degree ', 5,5'-tetrachloro-4,4'-dihydroxydiphenylmethane requires a processing temperature which is far above this limit, the polyester from 3,3', 5,5'-tetrachlorodihydroxydiphenylpropane tends to crystallize only in very small amounts , while, in contrast, the polyesters from the bis-ß-hydroxyethyl ether according to the invention require only low processing temperatures with likewise good crystallinity and tendency to crystallize and are therefore outstandingly suitable for the production of free-flowing molding compounds. Solved in 100 parts crystallization behavior at 20 ° C Styrene 150 parts of polyester from bis * hydroxyethyl ether of 3,3 ', 5,5'-Tetrachlor4, 4'-dihydroxydiphenyl-> 146 ° C crystallizes quickly and practically completely methane constantly 3,3 ', 5,5'-tetrachloro-4,4'-dihydroxydiphenyl- <50 ° C only after 5 days to a small extent propane crystalline 3,3'-Dimethyl4,4'-dihydroxydiphenylmethane 61 ° C largely crystallizes, but slowly 3,3'-dichloro-4,4'-dihydroxydiphenylmethane 78 ° C crystallizes quickly and practically completely constant 3,3'-Dimethyl-5,5'-dichloro-4,4'-dihydroxy- 106 ° C crystallizes quickly and practically completely diphenylmethane constantly Another invention relates to a process for the production of flame-retardant molded parts by curing molding compositions which contain halogen-containing unsaturated polyesters-produced with 2,2'- [isopropenyl-bis- (2,6-dihalogen-p-phenyleneoxy)] - dipropanol as Dialcohol component, polymerizable monomeric compounds as well as peroxides as catalysts and optionally customary accelerators, which is characterized in that molding compositions containing polyesters are cured with a dialcohol of the general structural formula wherein R denotes hydrogen atoms or low molecular weight alkyl groups and X represents hydrogen atoms or bromine atoms, the amount of bromine-containing polyester being such that the finished molded parts have a bromine content of at least 10 percent by weight.

Although those according to this prior invention for the preparation of the unsaturated Polyesters used dialcohols in their constitution are those to be used according to the invention They are similar to dialcohols, but cannot be compared with them, since the ones made from them Unsaturated polyesters produced by dialcohols differ because of their low tendency to crystallize with polymerizable vinyl compounds and filler not to tack-free molding compounds let process, while the dialcohols according to the invention surprisingly Easily crystallizing unsaturated polyesters provide, which are therefore polymerizable with Vinyl compounds and fillers result in high-quality, tack-free molding compounds.

In addition to the polyesters used according to the invention, others can also be used Polyesters are used, which are additionally saturated or unsaturated, preferably Contain built-in dihydric alcohols. Their amount depends on the type of used Dependent on dialcohols and should generally be about 30 mole percent. based on the Do not exceed the total amount of hydroxyl groups to be esterified. As examples for such polyhydric alcohols the following may be mentioned: ethylene glycol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol. 1,3-butanediol, 1-butene-3, 4-diol. Tetrachloroxylylene glycol, Glycerine and trimethylol propane.

The main ethylene-1,2-dicarboxylic acid used is fumaric acid Consideration. But it can also be maleic acid or a derivative derived from this acid, z. B. maleic anhydride, maleic acid dichloride or a maleic acid dialkyl ester, be used.

In addition to the ethylene-1,2-dicarboxylic acids mentioned, others can also be used saturated or unsaturated dicarboxylic acids, for example succinic acid, adipic acid, Phthalic acid, terephthalic acid, hexachlorendomethylenetetrahydrophthalic acid or itaconic acid, used to manufacture the polyester.

However, their amount should also not be more than about 30 mol percent. based on the total amount of carboxyl groups to be esterified, so that the degree of crystallinity of the products is not reduced too much.

If necessary, it can be advantageous in the production of the Polyester the reaction mixture as a chain terminator small amounts of monohydric alcohols to add. Hydroxyethy are particularly suitable! ether of the invention to be used bis (hydroxyethyl) bisphenol ethers are based on the phenols, z. B. the ß-hydroxyethyl ether of 2-methylphenol, 2-chlorophenol or 2-methyl-6-chlorophenol. The crystallizability and the other good properties of the polyester are not significantly affected by this.

The bis or. Monohydroxyäthyläther of Dihydroxydiarylmethane resp. Phenols are known in a manner such. B. by reacting the phenols with ethylene oxide or ethylene chlorohydrin, readily available.

Alcohols and carboxylic acids are used to produce the polyester advantageously used in approximately equivalent amounts; optionally can also a certain excess of one of the two components can be selected. The esterification takes place as usual, if appropriate at elevated temperature, until an acid number is below 50 is reached. You can use an inert gas stream, a circulating agent or use reduced pressure to accelerate the reaction.

The reaction products generally solidify on rapid cooling to amorphous, glass-like masses. If you contrast the polyester in the warmth with solvents, e.g. B. xylene, toluene, styrene or diallyl phthalate, mixed, they are obtained in crystalline form on cooling the solutions. Also through slow cooling of the melt or by subsequent tempering, the Polyester easily converted into the crystalline state when the softening temperature of the amorphous resins is below the melting temperature of the crystalline polyester. In order to avoid gelatinization, it is advisable to add polymerization inhibitors to the polyesters, for example hydroquinone, 2,6-di-tert. butyl-p-cresol or 3, 6-dipropylpyrocatechol, in a small amount, preferably about 0.005 to about 0.1%.

As polymerizable vinyl or / and allyl compounds, For the production of the PreB masses, in addition to styrene, it is also advisable to use unsaturated ones Compounds are used whose boiling points are above about 100 ° C, such as Vinyl toluene, divinylbenzene, diallyl adipate, diallyl phthalate, partially polymerized diallyl phthalate, Triallyl cyanurate and triallyl phosphate. The weight ratio of the unsaturated Connections to the unsaturated polyesters can vary within wide limits and generally said to be between about 1: 1 and about 1: 4.

As fillers, inorganic or organic, fibrous or granular materials of various kinds and mixtures thereof are used. Fiber products, for example made of glass.

Asbestos, jute, sisal, synthetic polyamides or polyacrylonitrile, can be in any form, e.g. B. as strands, mats or fabrics, use.

Examples of granular or powdery fillers are Kaolin, chalk, dolomite, glass powder, mica, silica, asbestos, antimony trioxide, Apatite and wood flour. Color pigments such as iron oxides also belong to this group or titanium dioxide.

The weight ratio of the fillers to the mixture of unsaturated Polyesters and polymerizable, unsaturated compounds can be used within wide limits fluctuate without affecting the water and heat resistance of the non-tacky materials obtained Masses produced by curing moldings is influenced significantly. In general, it is advantageous to use a weight ratio of from about 1: 5 to about 3: 1 to be applied.

As optionally to be added to the curable mixtures according to the invention Curing catalysts are basically all used to polymerize mixtures unsaturated polyester and unsaturated compounds that can be polymerized onto it commonly used polymerization catalysts in question.

Because the hardening at elevated temperatures at which the mixtures-apart of their filler content - present as homogeneous solutions - is made to to arrive at uniform polymerization products, however, are such hardening catalysts, which only initiate the polymerization at these temperatures are to be preferred.

Particularly suitable for this purpose are, for. B. named: Benzoyl peroxide, tert-butyl perbenzoate, tert. Butylcumyl peroxide, di-tert. butyl peroxide and dicumyl peroxide.

The curing catalysts can anyway! individually as well as with each other mixed are added to the curable mixtures according to the invention. Your crowd depends, among other things, on the processing temperature and the desired hardening time dependent and can be up to 10% of the weight of the resin mixture.

The mixing of the individual components of the curable according to the invention Masses can be made in any way and in any order, however, it is convenient to add the polymerization inhibitors to the polyester prior to mixing to be added with the remaining ingredients.

If fiber products are used as fillers, it generally is expediently, first the catalyst at an elevated temperature in the liquefied To dissolve the polyester mixture and then pour the mixture, soak, spray, To apply dipping or rocketing to the fiber material, if necessary under the following Squeezing off an excess between rollers.

Granular fillers or filler powder can, for. B. in heated Kneading tools or on heated roller mills with the other ingredients thoroughly be mixed.

The filler-containing prepregs, any additional Admixtures such as dyes, lubricants for press tools, etc., in the usual May contain amounts, represent at normal or slightly elevated temperature, d. H. at temperatures up to about 40%, dry, completely tack-free products that are still easy to process even after several months of storage. they draw is particularly characterized by the fact that the viscosity of the polymer content increases with increasing Temperature decreases only relatively little, so that even at high press temperatures uniform products are obtained. The masses can under shaping in the Warmth, d. H. at temperatures between about 100 and about 180 ° C, under an excess pressure from about 0.1 to 20 kg / cm2, slightly to possibly also flame retardant Moldings with high water and heat resistance and excellent mechanical properties Properties to be cured.

The parts mentioned in the following examples are parts by weight.

Example I a) Production of the polyester on which no protection here It is claimed in a reaction vessel with a stirrer and a descending cooler and nitrogen supply are 4620 parts of bis (3-methyl-4-A-hydroxyethoxy-5-chlorophenyl) methane melting point 112 ° C and 1400 parts of fumaric acid with passing nitrogen first heated to 160 ° Ct then to 180 ° C until the acid number of the unsaturated Polyester has dropped to 24. This gives about 340 parts of distillate. After this Cooling to 160 ° C. 1.4 parts of hydroquinone and 1.4 parts of quinone are added. b) The molding compound according to the invention 120 parts of the product thus obtained are at 140 ° C mixed with 80 parts of diallyl phthalate. The solution solidifies when it cools to a solid crystal mass, which can be liquefied again by heating.

750 parts of the polyester mixed with hydroquinone quinone Melted on a heated two-roll mill at about 100 ° C. Then adding a mixture of 200 parts of diallyl phthalate and 100 parts of styrene as well a mixture of 800 parts of mica flour. 250 parts of asbestos flour, 200 parts of antimony trioxide and 30 parts of zinc stearate alternately in small amounts. Last will be 30 Parts of a 50% tert. Butyl perbenzoate paste incorporated into the mass. the Mixture can be used as a cohesive coat that becomes dry and firm when it cools, be lifted off the roller mill. The mass is crushed using a hammer mill to a non-sticky and free-flowing granulate with a grain size of 2 to 4 mm. This still has after six weeks of storage in a closed container at 40 ° C unchanged pourability and good processing properties.

The powder becomes standard rods and in a tool according to DIN 53470 Standard flat bars pressed. The temperature is 165 ° C. and the pressing time is 8 Minutes. The pressed bodies have those in the table listed after the examples specified properties. A test piece that is heated at 980 ° C for 30 seconds Glow rod has been ignited, goes out immediately after removal of the ignition source.

Example 2 464 parts of bis (3-chloro-4 -, - hydroxyethoxyphenyl) methane from melting point 113 to 114 ° C, 151 parts of fumaric acid and 0.14 parts of hydroquinone are esterified according to the information in Example I at 160 to 190 ° C until an acid number of 17 is reached. Dissolve in the esterification product at 145.degree 0.14 parts quinone, at 130 ° C 383 parts Styrene and at 80 ° C 28.7 Parts of a 50% solution of tert. Butyl perbenzoate in dimethyl phthalate.

The catalyzed polyester solution solidifies on cooling to room temperature to a crumbly crystal mass. 72 g of this crumbly polyester blend will be distributed on a 20 cm glass fiber mat (the weight of which is 600 gXm2) and covered with an equal fiberglass mat.

A glass plate is placed over it and heated under a load from 10 g / cm2 to 80 ° C for about 30 minutes. During this process, the polyester mixture liquefies and soaks the mats without hardening. A non-tacky, impregnated one is obtained Mat placed in a press tool at 140 ° C and at a pressure of 10 kg / cm inside 3 minutes can be cured. The end product has those listed in the table Properties.

Example 3 416 parts of bis (3-methyl-4-t3-hydroxyethoxy-5-chlorophenyl) methane, 45 parts of l-methyl-2-p-hydroxyethoxy-3-chlorobenzene and 139.5 parts of fumaric acid are used heated at 160 to 200 ° C while distilling off the condensation water for so long until the acid number of the polyester has dropped to 18. At around 160 ° C, 0, 14 parts of hydroquinone and 0.14 part of quinone dissolved in the reaction product.

Then the 150 ° C hot polyester is poured onto an enamel sheet, where it solidifies into a solid, glass-like mass that is in a laboratory mill can be comminuted to a granulate with a grain size of about 1 mm.-By tempering for several days at 90 to 100 ° C. the product can be converted into the crystalline state.

480 parts of the ground polyester are at about 95 ° C in 320 parts Dissolved styrene and treated with 24 parts of a 50% solution of tert. Butyl perbenzoate mixed.

450 g of the warm polyester solution thus obtained are poured onto a 150 g heavy and 50-50 50 cm large glass fiber mat poured. The resin is applied immediately put a second, identical mat. This is covered with a film and then the resin rolled out. After the resin mixture has cooled and is crystallized, which is the case after a few minutes, the film can be peeled off again.

The resin-impregnated mat obtained in this way is dry and tack-free ; it is fully polymerized as described in Example 2. The end product owns then the properties given in the table.

Example 4 75 parts of the obtained according to the instructions of Example 3, Only polyester mixed and granulated with hydroquinone and quinone, 20 parts Diallyl phthalate, 10 parts of styrene, 100 parts of mica flour, 25 parts of asbestos flour and 3 parts of zinc stearate are uniform in a kneader heated to 95 ° C Processed paste. Then 3 parts of 50% tert. Butyl perbenzoate solution within of 5 minutes distributed in the mass. The mixture is removed from the kneading tool and solidifies to a hard product, which is granules with a grain size of 2 to 4 mm is ground. A powder of the same consistency as in the example is obtained I was described.

The product is pressed according to the instructions in Example I and has then the properties given in the table.

Example 5 411 parts of bis (3-methyl-4-3-hydroxyethoxy-5-chlorophenyl) methane. 21 parts of ethylene glycol, 151 parts of fumaric acid and 0.12 part of hydroquinone are used Esterified 160 to 185 ° C until an acid number of 14 is reached. The reaction product is hot with 0.13 parts of quinone, 359 parts of styrene and 26. 9 parts of 50% piger tert. Butyl perbenzoate solution mixed.

The polyester solution obtained in this way solidifies to a at room temperature Crystal mass. As described in Example 2, these become tack-free and storable. Resin-impregnated fiberglass mats are produced, which can be heated at 140 ° C and under pressure of 10 kglcm2 can polymerize within 5 minutes. The properties the compacts are given in the table.

Properties of the polymerisation products containing fillers Polymerization product according to the example 12345 Flexural strength 507z) 20311) 21041) 5732) 20331) after 5 weeks of immersion in water at 100 ° C Water absorption (percent by weight) ........... 2, 17 2, 09 1. 26 I, 95 2, 10 Weight loss (%) ........................ Q3) 0.933) 0. 623) 04) 1.493) Flexural strength (kg (CM2) when wet ... 17481) 20211) 14001) ') Measured in the Dynstat. 3) Specimen size: 70-30-2 mm.

2) According to DIN 53452. 4) Test piece size -30-15 4 mm.

Claims (1)

Claim: Thermosetting molding compounds which contain unsaturated polyesters, unsaturated organic monomeric compounds which can be polymerized onto them, inorganic or organic fillers and organic peroxides and optionally inhibitors, characterized in that they contain unsaturated polyesters with an acid number of less than 50, which are conventionally by esterification of an ethylene-1,2-dicarboxylic acid or a mixture of a withylene-1,2-dicarboxylic acid with other saturated or unsaturated dicarboxylic acids or their anhydrides, chlorides or esters with a dihydric alcohol of the general formula where Ri is an H atom or a CH3 group and Ra is H or Cl atoms, but Ri is different from R2, or with mixtures of these alcohols, optionally together with other polyhydric, saturated or unsaturated alcohols and optionally with the addition of small amounts monohydric alcohols. Documents considered: German Auslegeschrift No. 1,060,137; Belgian patent specification No. 571 437.