DE1109886B - Process for the production of transparent, flame-retardant moldings with tack-free surfaces or of tack-free drying coatings - Google Patents

Description

Process for the production of transparent, flame-retardant moldings with tack-free surface or tack-free drying coatings It is known Moldings and coatings by polymerizing unsaturated, linear polyesters or low molecular weight, spatially branched, unsaturated polyesters with monomers to produce polymerizable vinyl and / or allyl compounds. Used one here polyester, which is halogen-free, unsaturated by polycondensation and saturated dicarboxylic acids, such as. B. maleic, fumaric, itaconic, phthalic acid inter alia, can be obtained with dihydric alcohols in a known manner, so the polymerization products made from them do not have adequate flame retardancy.

However, polymerization products with improved flame retardancy can be obtained produce when these halogen-containing components are incorporated by, for example the polyester resins before curing with halogen-containing additives, such as. B. chlorinated paraffins, Trichloroethyl phosphate and other suitable compounds. Here the added halogen compound is indeed dissolved in the liquid polyester resin, however, it is not involved in the polymerization and thus acts as a foreign body.

The tolerance is often only limited. They also have chlorinated paraffins in polymerization products obtained in this way a plasticizing effect, whereby the mechanical properties and the heat resistance of the molded body impaired It is also possible to produce polymerization products with improved flame retardancy to produce, if one in the condensation of the polyester or the low molecular weight, spatially branched, unsaturated polyesters containing halogenated dicarboxylic acids, such as B. chloromaleic acid, tetrachlorophthalic acid, hexachlorendomethylenetetrahydrophthalic acid (HET acid) or chlorine-containing ethers containing OH groups, such as. B. Pentachlorophenyl monoglycerol ether, used. But you can also use both the dicarboxylic acid and the glycol component at the same time modify in the designated manner to a higher halogen content of the polyester.

The use of chlorinated monomers, such as. B. nuclear chlorinated Styrenes are known.

When using HET acid or when combining tetrachlorophthalic acid with pentachlorophenyl monoglycerin ether, a chlorine content of 25 up to 30O / o, based on the mixture of polyester and monomers, obtained highly viscous resins, which are more or less yellow in color.

In the polycondensation polyester is obtained that is already at high temperatures around 130 "C are so viscous that it is difficult to mix the monomers prepares. Another disadvantage of these polyester resins is their inefficiency.

It is also known to use polyester resins with a relatively high chlorine content, z. B. based on HET acid, by condensing organic phosphorus compounds, z. B. phosphoric acid to give improved flame retardancy. Made from it Moldings are indeed transparent, but have thin layers, e.g. B. in corrugated sheets, not yet sufficient flame retardancy. In addition, there are the disadvantages mentioned above.

Polymerization products from unsaturated polyester resins containing chlorine and / or low molecular weight, spatially branched, unsaturated poly mixed ester resins alone, even with a chlorine content of 30 to 40%, are not sufficient Flame retardancy, especially not in thin glass fiber laminates. It is known, to incorporate antimony trioxide into the polymerizable mixture before it hardens, However, this only gives opaque moldings with good flame retardancy can be.

It is also known to use chlorine-containing, unsaturated polyester resins Antimony salts of aliphatic or aromatic oxycarboxylic acids, e.g. B. Antimonyl derivatives the tartaric acid. Moldings produced from this have a certain Transparency that only depends on the similar refractive index to that finely divided in the polymer Salts based.

Of a real solubility of these salts in the polymerizable Mixing can of course be out of the question.

It is also known that triphenylstibine is thermoplastic, transparent Resins, e.g. polystyrene, polymethyl methacrylate, vinyl chloride - vinyl acetate copolymers, but also oxidatively hardening alkyd resins of the glycerol-phthalic acid type in connection add chlorinated paraffins and homogenize the mixtures on heated rollers. These are evidently not resins which harden by polymerisation.

It has now been found that transparent, flame-retardant moldings which also have a tack-free surface, or tack-free drying coatings can be produced by using known mixtures of halogen-containing, linear, unsaturated polyesters and / or halogen-containing, low molecular weight, spatially branched mixed esters polymerizable monomeric vinyl and / or allyl compounds, which are polymerization catalysts known per se and, if appropriate, accelerators, and also organic compounds of trivalent or sivalent antimony of the general formula where R '= aryl, aralkyl or halogen, R "and R"' = aryl or aralkyl, X = halogen, are added, triple or more unsaturated alkoxysilanes, the double bonds of which are predominantly in the alkoxy groups, are added before curing.

The organic antimony compounds are both in the liquid polymerizable mixture as well as by customary polymerization catalysts and, if appropriate, accelerators or moldings hardened in a known manner Clearly soluble coatings.

When adding, for example, triphenylstibine to unsaturated polyester resins is the usual amounts of organic peroxides and, if necessary, accelerators initiated polymerization is delayed to a not inconsiderable extent. This delay occurs particularly when curing at room temperature, but can penetrate the purpose of increased amounts of peroxide are compensated.

If instead of organic compounds of the trivalent antimony compounds of the valuable antimony as additives to the polymerizable ones described Mixtures are used, then there is only a slight delay in curing Dimensions on. As already mentioned, this delay can also occur if necessary Adding increased amounts of organic peroxides can be compensated for.

In the case of the moldings or coatings to be produced according to the invention not only is flame retardant achieved, but also when air is admitted Obtain tack-free hardening surfaces.

The halogen-containing, unsaturated, linear polyesters to be used can in a known manner, for example from tetrachlorophthalic anhydride, maleic anhydride and propylene glycol.

The halogen-containing, low molecular weight, spatially branched, Unsaturated polyesters are, for example, by polycondensation of 1 Moles of a saturated or unsaturated one Alcohol with a functionality of more than 2 and a number of moles of saturated and / or corresponding to this functionality unsaturated, optionally halogen-containing dicarboxylic acids or their anhydrides and the same number of moles of saturated and / or unsaturated, optionally halogen-containing monohydric alcohols prepared in a known manner.

The halogen-containing, low molecular weight, spatially branched, unsaturated ones Poly mixed esters are expediently in the monomeric polymerizable vinyl and / or Allyl compounds dissolved and after the addition of the organic compounds to be used according to the invention Hardened silicon compounds as well as compounds of trivalent or sivalent antimony.

The unsaturated alkoxy silanes to be used according to the invention are by known processes from suitable halosilanes, for example vinyltrichlorosilane, Methyltrichlorosilane, ethyltrichlorosilane, also made of silicon tetrachloride and dimers Halosilanes, and unsaturated monohydric alcohols, for example allyl alcohol, Endomethylenetetrahydrobenzyl alcohol "B-Oxyäthylallyläther, with elimination of hydrochloric acid manufactured.

As polymerizable monomeric vinyl and / or allyl compounds z. B. styrene, vinyl toluene, n-vinyl butyl ether, acrylic and methacrylic acid esters, diallyladipate, Triallyl cyanurate and other known allyl esters of saturated and unsaturated acids, as trivalent or sivalent organic antimony compounds, for example triphenylstibine, Methyldiphenylstibine, diphenylchlorostibine, triphenylstibine dichloride, diphenylstibine trichloride and the corresponding bromides can be used.

The organic antimony compounds become the polymerizable ones Mixture in amounts of 2 to 10%, preferably in amounts of 3 to 50 / o, added.

The polymerization of the mixture according to the invention becomes more common with the aid Polymerization catalysts, such as. B. diacyl peroxides, peracid esters and hydroperoxides, but also carried out, for example, with aralkylene oxides.

The polymerization can be completed with or, depending on the choice of components without the application of pressure and at low temperatures, for example at temperatures from 18 to 25 "C, or at elevated temperatures, for example at temperatures from 80 to 150 "C. If the work is carried out under pressure, for example Pressures of 1 to 10kg / cm2 are possible.

The mixtures polymerizable according to the invention can be used together with transparent carrier materials, such as fiberglass products, and / or optionally soluble dyes, are processed to moldings.

It may be useful to use the halogen-containing, low molecular weight, spatially branched, unsaturated polyesters or their solutions in polymerizable monomeric vinyl and / or allyl compounds, as already mentioned, together with to use the halogen-containing, linear unsaturated polyester resins in order to achieve the To lower the viscosity of the polyester resins and to process them with, for example To facilitate fiber optic products.

The process is illustrated by the following examples: Example 1 In 95 g of a polyester resin composition, which consists of a mixture of 700/0 of a linear polyester, the off 1.5 moles of tetrachlorophthalic anhydride, 1 mole of maleic anhydride and 2.7 mol of 1,2-propylene glycol in the usual manner with the addition of 0.1% hydroquinone was prepared as a stabilizer, and 300 / o styrene, stabilized at 0.01 0 / o tert. Butylcatechol, consists of 5 g of vinyltrioxyallylsilane and 4 g of commercially available Triphenylstibine stirred in and the clear solution with 8 g of commercially available 500/0 but Benzoyl peroxide paste and 0.4 g of dimethylaniline were added.

A paint spread made with it is at ordinary temperature Dust dry after 1/2 hour and hardens within several hours a transparent, tack-free, hard, flame-retardant film.

The hardening can be accelerated by heating.

Example 2 In 100 g of the polyester mixture described in Example 1 8 g of vinyltrioxyallylsilane and 5 g of triphenylstibine dichloride are produced with styrene from triphenylstibine by introducing chlorine at room temperature, dissolved and 3 g commercial 500/0 but benzoyl peroxide paste added. With the resin mixture is a commercially available alkali-free glass fiber mat soaked, this in a cellulose film laid out in a corrugated sheet and at 80 to 100 "C within 20 to 30 minutes hardened. The result is a transparent, glass fiber reinforced corrugated sheet, which at Ignition goes out by itself after removing the flame.

Example 3 In a mixture of 50 g of those described in Example 1 Polyester-styrene mixture and 50 g of a mixture consisting of 35 g of a spatially branched Poly mixed ester consisting of 1 mole of pentaerythritol, 2 moles of maleic anhydride, 2 moles of tetrachlorophthalic anhydride and 4.1 mol of n-heptanol is built up, and 15 g of monostyrene, stabilized as above, exists, 5 g of vinyltrioxyallylsilane and 4 g of triphenylstibine are dissolved and the Mixture with 8 g of commercially available 500/0 but benzoyl peroxide paste and 0.6 g of dimethylaniline offset and painted on glass or sheet metal plates. The spread gels inside less minutes and is dust-dry within 1 hour at normal temperature. It hardens slowly at ordinary temperature.

Full curing can be achieved by heating to 100 to 120 "C within 1/2 to 1 hour can be achieved.

The result is a clear, light, flame-retardant, hard paint film.

Example 4 In 40 g of the polyester resin composition described in Example 1 2 g of triphenylstibine are dissolved, 2.5 g of vinyltrioxyallylsilane and 5 g of styrene oxide added and the mixture spread on glass or sheet metal plates.

The spread is dust-dry within 1 hour and hardens in the course of the process a few more hours to a clear, tack-free, flame-retardant paint film.

Claims (4)

PATENT CLAIMS: 1. Process for the production of transparent, flame-retardant moldings with tack-free surfaces or of tack-free drying coatings by polymerizing mixtures of halogen-containing, unsaturated polyesters and monomeric vinyl and / or allyl compounds in the presence of polymerization catalysts and, if necessary, accelerators and organic compounds of the 3- or Swertigen Antimons of the general formula wherein R '= aryl, aralkyl radical or halogen atom, R "and R"' = aryl or aralkyl radical, X = halogen atom, characterized in that, in addition to the vinyl and / or allyl compounds, triply or more highly unsaturated alkoxysilanes are used as monomeric compounds . 2. Embodiment according to claim 1, characterized in that the organic compounds of the trivalent or sivalent antimony in amounts of 2 to 10 0 /, containing polymerization mixtures are fully polymerized. 3. Embodiment according to claims 1 and 2, characterized in that that the mixtures are polymerized to completion at temperatures between 18 and 25 "C. 4. Embodiment according to claims 1 and 2, characterized in that that the mixtures are polymerized to completion at temperatures between 80 and 150 "C. Documents considered: French patent specification No. 1157 208; Belgian patent specification No. 562 579.