HU195528B - Process for producing foam product of polyester resin base - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to: a) a vinyl monomeric solution of 100 parts by weight, preferably of unsaturated polyester resin, with 0.5 to 5 parts by weight of a sulphonyl hydrazide blowing agent, 0.01 to 1 part by weight; mixed with a metal ion-containing activator, 0.5-3 parts by weight of surfactant, 0-150 parts by weight of reinforcing material, 0-150 parts by weight of filler, and immediately before foaming add 0.2-3 parts by weight of 100% active ingredient of organic peroxide or hydroperoxide and 0.05 to 1 part by weight of hydrogen peroxide, then the mixture is foamed at room temperature; or b) 20 to 80% of the polyester resin solution of 100 parts by weight of polyester resin, preferably unsaturated, from 0.5 to 5 parts by weight of the total polyester resin solution; 0.01 to 1 part by weight of wood mixed with a mion-containing activator, 0.5-3 parts by weight of surfactant, 0 50 parts by weight of crisping material, 0-150 parts by weight of the filler, and added to the remaining portion of the polyester resin solution - from 0.2 to 3 parts by weight - 100% active ingredient per whole polyester resin solution , an organic peroxide or hydroperoxide compound, and 0.5-1 parts by weight of hydrogen peroxide, the two resin mixtures are combined immediately before foaming and then foamed at room temperature. -1-

Description

The present invention relates to a process for preparing a hard foam product based on a polyester resin, preferably an unsaturated polyester resin.

A number of patents have been found in the literature which disclose the composition of various foamable and curable unsaturated polyester resin based compositions and methods of making the foamed product. These processes accomplish foaming and curing either as a sequential process or as a seam process. Various compounds are used as leachate filters, some of which are gaseous! in addition to the process, you are also involved in the hardening reaction.

According to British Patent No. 1,044,611, the hot foam (130-190 ° C) is the propellant and also the initiator of polynization in various azo or bidrazo compounds.

The foaming of a sulfonyl hydrazide compound is disclosed in U.S. Patent No. 4,327,196, which, in addition to sulfonyl hydrazide, utilizes an organic peroxide compound, as well as a primary and secondary activator, to carry out the foaming and curing process.

British Patent 2,031,900 employs a carbon dioxide generating compound to foam a crosslinking polyester resin.

German Patent Publication No. 3 201 345 discloses a process in which a combination of a hydrazide compound, a cobalt compound and a perborate or percarbonate compound is used to foam unsaturated polyester resins.

In U.S. Patent No. 3,920,590, the foaming of an unsaturated polyester resin with a peroxide catalyst and cobalt octate is performed with hydroxysulfonyl hydrazide.

Peroxide catalysts are either organic peroxide or inorganic peroxide.

In some cases, the practical applicability of the known methods is hindered by the need for special treatment of the blowing agent (refrigerated storage, use of personal protective equipment, etc.), while in other cases the storage of the blowing agent composition is inadequate. In some cases, a lack of aesthetically effective volume growth, or gas and root formation may not be adequately controlled, and therefore a pore-free, non-cracking foam structure with sufficient reliability cannot be produced.

It is an object of the present invention to provide a process for controlling the foaming and curing reactions well and to provide a uniform, fine pore distribution foam structure.

The present invention is based on the discovery that effective gas release and well controlled curing can be achieved by using a composition consisting of an organic pcroxide ring and a hydrogen peroxide combination using a sulfonyl hydrazide blowing agent. The organic-inorganic peroxide compound composition plays a dual role in the presence of a metal ion-containing activator, on the one hand, causing the breakdown of the sulfonyl hydrazide at room temperature, and, on the other hand, curing the polyester resin solution.

However, the organic and inorganic peroxide catalysts can best exert this beneficial effect in the presence of a siloxane block polymeric surfactant.

Particularly surprising is the unexpected effect that the triple system of hydrogen peroxide, organic peroxide and siloxane block polymer in the presence of the hydrazide blowing agent results in a substantially larger volume increase than when using only the organic peroxide compound.

The present invention relates to a process for preparing foam products based on polyester resin, preferably unsaturated polyester resin, using an aliphatic, aromatic or cycloaliphatic sulfonylhydrazide blowing agent, a metal ion-containing activator and a peroxide catalyst.

According to the invention, the process is carried out by:

a) 100 parts by weight of a vinyl monomer solution of polyester resin, preferably unsaturated, with 0.5 to 5 parts by weight of a sulfonyl hydrazide blowing agent, 0.01 to 1 part by weight of metal ion activator, 0.5 to 3 parts by weight of surfactant, preferably from 0 to 50 parts by weight 0-350 parts by weight of filler, immediately before foaming, add 0.2-3 parts by weight of an organic peroxide or hydroxy peroxide compound containing 100% of the active ingredient and 0.05 to 1 part by weight of hydrogen peroxide, and then the mixture is foamed at room temperature. , obsession

b) 20 to 80% by weight of 100 parts by weight of a solution of polyester resin, preferably unsaturated, in vinyl monomer

- mixed with 0.5 to 5 parts by weight of sulfonyl hydrazide blowing agent, 0.01 to 1 part by weight of metal ion activator, 0.5 to 3 parts by weight of siloxane block polymeric surfactant, 0 to 150 parts by weight of filler, 0 to 50 parts by weight based on total resin, and to the remainder of the polyester resin solution, add 0.2-3 parts by weight of the total resin to 100-3% organic peroxide or bridged peroxide compound, as well as 0.05 to 1 part by weight of hydrogen peroxide, the two resin mixtures combine immediately before foaming and foam at room temperature.

In a preferred embodiment of the process according to the invention, for 100 parts by weight of a polyester resin solution, 1 to 3 parts by weight of a sulfonyl hydrazide, 0.02 to 0.06 parts by weight of a metal activator, 1-2 parts by weight surfactant, preferably siloxane block polymer, 1.5 parts by weight of an organic peroxide or hydroperoxide compound (100% active ingredient) and 0.1-0.4 parts by weight hydrogen peroxide are added.

Suitably the siloxane block polymer surfactant is a block polymer consisting of poly (dimethylsiloxane) and polypropylene oxide.

The composition to be foamed according to the invention is preferably processed by spraying. The spraying may be carried out using spraying equipment designed for polyester processing. In the manufacture of a fiberglass reinforced foam product, a spray device combined with a glass fiber cutter is used.

The main advantages of the process according to the invention are as follows:

- the foaming begins immediately after mixing the components;

- gelation occurs at room temperature within a few minutes;

- the volume increase m, the foaming and curing time can be well controlled by varying the proportion of the components, the volume increase being greater than that of known systems;

- the foam formed is a hard foam of high strength and high modulus of elasticity, known as structural foam.

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If the foaming process is carried out in the absence of any of the components used in the present invention, only a slight increase in volume is observed and the density of the foam formed is higher.

As a solution of the polyester resin, a vinyl monomeric solution of a low molecular weight unsaturated polyester (oligoester) can be used. The polyester resin is prepared by polycondensation of saturated and unsaturated divalent acids and divalent glycols.

The vinyl monomer may be styrene and / or methyl methacrylate and / or vinyl acetate.

Further, as the unsaturated polyester resin, vinyl esterified epoxidized bisphenol derivatives in the form of a vinyl monomeric solution may also be used.

The organic peroxide or hydroperoxide used in the process may be cyclohexanone peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide.

The hydrogen peroxide is conveniently used in the form of a 30% aqueous solution.

Preferably, metal ionic activators include cobalt salts such as cobalt naphthenate, cobalt octoate or other metal compounds commonly used to cure polyester.

The sulfonyl hydrazide compound used as the blowing agent is characterized by the formula RSO ₂ NHNH ₂ , wherein R is C ₁ -C 18 alkyl. a cycloalkyl or aryl group, preferably a benzyl or naphthyl group, or substituted derivatives thereof.

The surfactant used is a copolymer of polydimethylsiloxane and polyethylene oxide or polypropylene oxide having an average molecular weight of 10,000 to 20,000.

In the process according to the invention, various fillers, preferably colloidal silica, aluminum trihydrate, calcium carbonate, microspherical fillers, and various reinforcing agents may be used. Preferably, the reinforcing material is an organic or inorganic fibrous material, such as fiberglass, polymer fiber, or graphite.

The following examples illustrate the process of the invention.

Example 1 A polyester prepared from moles of maleic anhydride, 1 mole of phthalic anhydride, 1 mole of ethylene glycol and 1 mole of 1,2-propylene glycol is dissolved in styrene in a weight ratio of 65 to 35. 50 g of the resulting polyester resin solution are dissolved in 1.2 g of benzenesulfonyl hydrazide, 0.04 g of metal cobalt cobalt octoate solution and 1 g of polydimethylsiloxane and polypropylene oxide. stationary block copolymer surfactant (solution A).

A further 50 g of the above polyester resin solution are mixed with 0.45 g of a 30% aqueous hydrogen peroxide solution and 2 g of a 50% solution of methyl ethyl ketone peroxide ("U" solution).

Solutions A and B are thoroughly mixed and then poured into a container. Foaming begins immediately, after 20 seconds at room temperature gelling occurs and after 10 minutes the foam hardens. The foam is non-cracked, has a uniform pore structure, an average cell size of 0.02 mm, and a foam density of 0.55 g / cm ³ .

For comparison, the density of the non-foamed polyester resin of the composition given in the example is 12.5 g / cm ³ .

A: Vessel growth relative to solid polyester resin 127%.

Example 2

100 g of the polyester resin solution of Example 1 are dissolved in 1 g of p-toluenesulfonyl hydrazide, 0.06 g of metal cobalt solution of cobalt naphthenate and 0.7 g of the surfactant of Example 1. After thorough mixing, 0.5 g of 30% aqueous hydrogen peroxide solution and 2.5 g of 50% by weight cyclohexanone peroxide solution are added and mixed vigorously. Then pour into a flat bowl. There is a large volume increase and the foam cures in 8 minutes. A fine, uniform pore structure with a density of 0.49 g / cm ^{3 is} formed. The increase in volume relative to the solid polyethylene resin is 155%.

Example 3 (Comparative)

Example 2 is repeated. with the change, bog), no cyclohexanone hydrogen peroxide and a siloxane block polymeric surfactant are added this time.

In this case, gas evolution is absent and the resulting product has a density of 1.05 g / cm ³ , which is hardly different from that of the non-foamed polyester resin.

The increase in volume relative to the solid polyester resin is 100%, but after 24 hours the bean will cure.

Example 4 (Comparative)

Example 2 is repeated, except that hydrogen peroxide and surfactant are not added this time. The gas evolution in this case is insignificant.

The product obtained had a density of 1.1 g / cm ³ . The volume increase in this case is very small, only 13.6%. The foam hardens only after 20 hours.

Example 5 (Comparative)

Example 2 is repeated, except that no surfactant is added this time. Density of cured foam: 0.68 g / cin ³ .

The volume increase relative to the solid polyester resin is only 84%, compared to 1.55% as obtained in Example 2.

Example 6

Example 1 is repeated with the difference that this time 3 g of surfactant is used instead of 1 g when preparing the A side.

The density of the hard foam is 0.479 g / cm ³ .

Volume increase: 165%.

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Example 7

Example 1 is repeated except that 0.15 g of a 30% solution of H ₂ O ₂ and 2.5 g of p-toluenesulfonyl hydrazide are used.

The density of the hard foam is 0.42 g / cm ³ .

Volume increase: 180%.

Example 8

Example 2 is repeated, but using the same amount of t-butylsulfonylhydrazide instead of p-toluenesulfonylhydrazide and the same amount of cumene hydroperoxide instead of cyclohexanone peroxide. The foam thus obtained has a uniform pore structure and a density of 0.60 g / cm ³ . Volume increase: 150%.

Example 9 Polyester prepared from moles of maleic anhydride, 0.15 moles sebacic acid, 0.85 moles phthalic anhydride, 1.4 moles ethylene glycol and 0.6 moles dimethylene glycol dissolved in styrene 60:40 ratio.

To 100 g of the above polyester resin solution are added 0.02 g of a metal cobalt cobalt octoate solution and 2 g of benzenesulfonyl hydrazide and 0.5 g of the surfactant of Example 1. After dissolution, 20 g of power plant fly ash is mixed homogeneously. To the mass were added 2.5 g of 30% aqueous hydrogen peroxide solution and 3 g of 50% methyl ethyl ketone peroxide solution, and the mixture was thoroughly mixed. It's 15 minutes. material hardens. Foam density: 0.77 g / cm ³ .

- Example 10

Example 1 is repeated with the exception that each component is used in three hundred times, that is, solutions 15 and 15 kg of the polyester resin solution are made into solutions A and B, the two solutions being filled into the containers of the spray equipment. 4.5 kg of cut glass fiber are added during spraying. The glass-containing foam cures after 30 seconds and gels 15 minutes. Λ fine cellular foam has an average cell size of 0.02 mm and a density of 0.9 g / cm ³ . Volume increase: 125%.

Example 11

The dimethacrylate ester of a bisphenol A epoxy resin having a molecular weight of 500-600 molar is dissolved in styrene in a 55:45 weight ratio.

Dissolve 1.5 g of benzenesulfonyl hydrazide in 100 g of vinyl ester resin solution. 4 g of cobalt octoate solution (metal cobalt content: 0.04 g) and 3 g of the surfactant of Example 1. Then, 1 g of 30% aqueous hydrogen peroxide solution and 2 g of 50% cumene hydroperoxide solution are added.

After mixing, pour the material into a flat bowl. Volume expansion begins immediately and gelling occurs within 80 seconds. The foam density after curing was 0.65 g / cm ³ . Volume increase: 140%.

Claims (3)

A process for the preparation of a hard foam product based on a polyester resin, preferably an unsaturated polyester resin, using an aliphatic, aromatic or cycloaliphatic sulfonyl hydrazide foaming agent, a metal ion-containing activator and a peroxide compound, a) 100 parts by weight of a vinyl monomer solution of polyester resin, preferably unsaturated, with 0.5 to 5 parts by weight of sulphoryl hydrazide blowing agent, 0.01 to 1 part by weight of metal ion-containing activator, 0.5 to 3 parts by weight of surfactant, 0 to 50 parts by weight of filler and then, prior to foaming, mix 0.2 to 3 parts by weight of an organic peroxide or organic hydroperoxide compound and 0.05 to 1 part by weight of hydrogen peroxide, then foam at room temperature, or b) 20 to 80% by weight of a vinyl monomeric side of 100 parts by weight of a polyester resin, preferably unsaturated, 0.5 to 5 parts by weight of a sulfonyl hydrazide blowing agent 0.01 to 1 part by weight of a metal ion activator, 0.5 to 3 parts by weight of a surfactant; -50 parts by weight of a reinforcing agent, 0-150 parts by weight of a filler, and 0.2 to 3 parts by weight of an organic peroxide or an organic hydroperoxide compound, based on the total polyester resin solution, is added to the remaining portion of the polyester resin solution; 0.05 to 1 part by weight of hydrogen peroxide, the two resin mixtures were combined immediately before foaming and then foamed at room temperature. 2. The process according to claim 1, wherein the resin solution comprises from 1 to 3 parts by weight of a sulfonyl hydrazidool, from 0.02 to 0.06 parts by weight of a metal ionic activator, from 0.5 to 1.5 parts by weight of a 100% organic active ingredient. peroxide or hydroperoxide compound, 0.1-0.4 wt. hydrogen peroxide, 1-2 parts by weight of a surfactant. 3. The process according to claim 1, wherein the surfactant is a siloxane block pobomer.