DE2209149A1 - PROCESS FOR MANUFACTURING MOLDED BODIES SUBSTANTLY FROM MINERAL BUILDING MATERIALS - Google Patents

Description

Process for the production of shaped bodies consisting essentially of mineral building materials

The main patent relates to mixtures for coating formed from mineral building materials or asphalt

Surfaces.

Mixtures of the kind in embossing consist of the following

Components:

1) a (meth) acrylic ester with 1 to 4 carbon atoms in the alcohol residue and / or styrene, or a predominant part (more than 50 wt .- ^) from one of the (meth) acrylic acid esters mentioned and / or styrene and the remainder of one or several other unsaturated compounds copolymerizing with these monomers, if appropriate from one which is soluble or swellable in the monomers or monomer mixtures mentioned Polymer or copolymer,

2) an adduct, originated from

a) a di- or triisocyanate,

b) a polyalcohol, the hydroxyl content of which is 1 to 10 % , or a mixture of such polyalcohols,

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c) a hydroxy ester of acrylic or methacrylic acid or a mixture such hydroxyester,

J5) an accelerator causing the polymerization or accelerator system.

With regard to the proportions in which components 1 to 3 are contained in the mixture according to the main patent, it applies that

component l), based on the total amount of components 1 and 2, between 55 to 95 wt -.%, and

component 2), again based on the total amount of the components 1 + 2, 45 to 5 wt -.% constitutes,

component J>), again based on the total amount of the components 1 + 2, 0.1 to 10 wt -% by..

Comonomers which may be present in the mixture according to the invention in addition to the specified (meth) acrylic ester and / or styrene are higher esters of acrylic and methacrylic acid (C number in the alcohol residue> 4), acrylic and methacrylic acid nitrile, vinyl acetate and monomers with two or more CC double bonds in the molecule mentioned by way of example. That comonomers with two or more CC double bonds in the molecule only in small proportions of z. B. 0.05 to 5 % may also be used, is familiar to the polymerization expert familiar with crosslinking reactions. - The use of << - methylstyrene deserves special mention, namely in amounts of 0.5 to 20 wt .- #,

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based on the plastic component 1 + 2, since such an additive surprisingly the polymerization, even at higher temperatures of z. B. 130 ⁰ C, can run evenly.

It has proven advantageous in the preparation of mixtures according to the main patent, one in the monomers mentioned or a mixture of monomers which is soluble or swellable Use polymer or copolymer, e.g. B. finely divided Polymethacrylate or polystyrene. Such additives increase on the one hand the viscosity of the in the invention Mixtures contained proportion, so that a segregation of the synthetic resin mortar is prevented during the hardening time, and, on the other hand, reduce the shrinkage associated with the polymerization of unsaturated compounds.

As is known, only a few of the di- and triisocyanates have achieved industrial importance. Among these, the 2,4- and 2,6-isomers of tolylene diisocyanate and the dimer of the 2,4-compound play a special role. In addition, the aliphatic hexamethylene diisocyanate and the aromatic compounds, vie have diphenylmethane diisocyanate 4,4-, naphthylene-1,5-diisocyanate and triphenylmethane-4,4 ^l, 4 ^t! -triisocyanate is mentioned as a technically important product * It deserves to be emphasized that both the monomeric di- or triisocyanates and the commercially available prepolymers of these compounds, i.e. polyisocyanates, can be used to prepare the adducts.

As particularly advantageous for the preparation of the mixtures According to the main patent, adducts have been found which have arisen from such diisocyanates whose isocyanate groups are different Have reactivities. Among these, the commercially available isophrone diisocyanate (J-Isoeyanato-

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methyl-3.5.5-trimethylcyclohexyl isocyanate) special mention. It is known that the isocyanate group separated from a ring C atom by a methylene group is an eight to has ten times as high reactivity as the second isocyanate group located directly on a ring carbon atom.

The addition of alcohols to isocyanates is known. The desired viscoplastic behavior of the coating produced according to the main patent from the mixture according to the invention is achieved if a polyalcohol, the hydroxyl content of which is comparatively low, is attached to part, advantageously to approximately half of the free isocyanate groups. While when using alcohols with a high hydroxyl content, e.g. B. with the addition of ethylene glycol (OH group content 5 ^ * 8 %), glycerine (OH group content 55.4 %), trimethyl propane (OH group content 38%) or butanol (OH group content 22.9 %) * If hard to brittle coatings are obtained under otherwise identical conditions, long-chain polyalcohols with a hydroxyl content of 1 to 10 % result in viscoplastic products. The addition of such long-chain polyester and polyether alcohols to diisocyanates is known from the art of polyurethane plastics. By using a mixture of polyester and polyether alcohols whose average hydroxyl group content z. B. makes up 2% , one obtains mixtures according to the invention which harden to form particularly tough-elastic products.

To the remaining, generally half of the -N = C * = O groups which make up the diisocyanate used, z. B. Ethylene glycol mono- (meth-) acrylate, propanediol-1,2-mono- (meth-) acrylate and butanediol-1,4-mono- (meth-) acrylate added are, however, all esters of acrylic and methacrylic acid containing a free OH group for the production of the polyurethane contained in the mixture according to the invention is suitable. - As far as tri- or polyisocyanates, If appropriate, in addition to diisocyanates, are used to produce the polyurethane, the proportions of polyol and

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To choose hydroxy esters such that at least 1/5 of the free -N = C = O groups and at most 2/3 of these groups a polyol and an unsaturated hydroxy ester are added to the remaining isocyanate groups.

As a rule, the adduct, which is involved in the structure of the mixtures according to the main patent, is produced in such a way that in a first process stage the polyalcohol is added on and after this addition reaction has ended or has subsided the hydroxy ester is added. This sequence of additions has the advantage that the isocyanate-alcohol adduct initially formed is a stable connection that can be stored without any special precautionary measures, while the reverse is the case Sequence a tendency to polymerize adduct is obtained, which only under certain conditions, eg. B. can be stored after adding an inhibitor and / or with cooling. - That’s the case, especially when using it a large proportion of the monomers or monomer mixtures representing component ^ 1, proven to be useful, to allow the polyurethane formation to take place only in a part of this monomer or monomer mixture and the resultant Then dilute the solution of the polyurethane formed with the remaining monomers or monomer mixture.

It is known from the production of the polyurethanes that the addition are often catalytically accelerated by alcohols or other compounds containing free OH groups got to. As catalysts for the addition, for example, organometallic compounds or tert. Amines in use. Since, as will be explained later, tert. Amines can be a component of the accelerator system that drives the polymerization of the mixture according to the invention triggers, this can just tert. Amines also act as addition catalysts works. In other cases, especially when using diisocyanates with different reactivities of the -N = C = O groups, it is necessary to add the

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called hydroxyesters in the second reaction stage, if one is not ready, unusually long reaction times from Z. B. several days to accept to run in the presence of known accelerators.

The hardening of the synthetic resin mortar according to the invention takes place under the action of radical accelerators, of which peroxidic compounds and azodiisobutyric acid nitriles are the best known. In combination with tert. Amines are peroxides known rapid accelerators, which are used with advantage in the present case.

It has now been found that mixtures according to the main patent not only for the production of thin layers, which in turn are under firmly adhered to concrete or asphalt road surfaces, taxiways or floors of factory buildings, can be used, but that the same mixtures for the production of moldings of any thickness, which in the consist essentially of mineral building materials, are suitable. It must be described as surprising that in the For the purposes of the present invention, it is possible to even produce concrete girders of severalfcen irr volume, which with regard to their mechanical strength outperform concrete bodies of the conventional type. It was unforeseeable that the mass forming such a shaped body sets quickly and completely without being in such Bodies develop tensions that reduce their strength. The setting time of a molding produced according to the invention, z. B. a concrete beam, which must be waited until the carrier can be demolded, is significant shorter than the setting time of a concrete molding produced in the previous way.

It deserves to be emphasized that the mechanical strength of molded articles according to the present invention, in particular their flexural strength, tensile strength and

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Elongation at break through the introduction of reinforcing iron, reinforcement mats made of metal, glass or plastic can be increased. The application of the mixtures according to the main patent to a core material of z. B. Foamed plastic creates heatsinking bodies, which are formed by an intimate connection of the hard surface layer mark with the core material.

Examples of moldings that can be produced according to the invention are, in addition to the concrete beams already mentioned, pipes, structural elements, Passade parts, pillars for bridges and railings as well as tombstones, window sills and the like.

Examples of mineral building materials from which the invention Shaped bodies essentially consist of: sand, gravel, chippings, S -hotter, pumice, tuff, slag, Ashes, brick and slate chippings. These building materials can be used in the production of moldings according to the present Invention of heavy spar, light spar, chalk, quartz powder and color pigments are added.

It has already been pointed out that the use of a polymer which is soluble or swellable in the monomer or monomer mixture used can also be used in order to reduce the shrinkage associated with the polymerization of unsaturated compounds. In cases in which this slight shrinkage also has to be reduced further, the organic phase functioning as a binder is varied in such a way that, at the same time as the polymerization of the unsaturated components, the known formation of a polyurethane from a di-, tri- or polyisocyanate is achieved and a polyalcohol of the type already identified (1 to 10 % hydroxyl groups) can run off, the proportion of the so

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resulting polyurethane, based on the total weight of the (meth) acrylate component 1, between 5 and 45 wt -.% makes. The procedure here is to add an isocyanate and the amount of a polyol or a mixture of several polyols necessary to form the polyurethane to the mixture already characterized. When the mixture is hardened by polymerization and polyaddition taking place next to one another, depending on the amount of the additional, modifying polyurethane component, only an extremely small or no volume contraction of the mass takes place during hardening.

The following examples illustrate the invention without the To restrict protection of the requested patent to precisely these embodiments.

example 1
12.0 kg of a copolymer consisting of

70 parts by weight of methyl methacrylate 25 parts by weight of isobutyl acrylate 5 parts by weight of ethyl acrylate

will be in
68.0 kg of a monomer mixture consisting of

95 Oew. Tl. Methyl methacrylate and 5 ow. Tl. 1,4 - butanediol methacrylate

solved.

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After dissolving the copolyraeren

19iO kg of an adduct added to the following Way was made:

A mixture of 416.48 parts by weight of J5-isocyanatomethyl-p, 5,5-trimethylcyclohexyl isocyanate and 1200 parts by weight of methyl methacrylate is mixed with 90.12 parts by weight of 1,4 - butanediol and 4.0 parts by weight of methyl methacrylate. Dibutyltin dilaurate is added with stirring. The reaction product is added after cooling to about 30 ⁰ C and 260.28 wt. Tl. 2 hydroxyethyl methacrylate with stirring.

1.0 kg of dimethyl - ρ - toluidine

100.0 kg of this reaction mixture are with

1.5 kg dichlorobenzoyl peroxide 50% in dibutyl phthalate 900.0 kg and mineral additives consisting of:

450.0 parts by weight, grain size up to 2 mm

90.0 parts by weight, grain size 3 to 7 mm

560.0 parts by weight, grain size 7 to 15 mm

mixed to a homogeneous mass, which in a corresponding form within J5 hours to a component hardened from plastic-bound mortar.

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Example 2
10.0 kg of a copolymer consisting of

βθ part by weight of methyl methacrylate 4θ part by weight of isobutyl acrylate

will be in
64.0 kg of a monomer mixture consisting of

95 parts by weight of methyl methacrylate, 5 parts by weight of ethylene glycol dimethacrylate

solved.

After dissolving the copolymer will be

10.0 kg of an adduct which was prepared according to Example 1 were added.

The following are also added:

14.0 kg of a branched polyether with a hydroxyl content of 9 * 5 %

2.0 kg diethanoi - ρ - toluidine 100.0 kg of this reaction resin are with

20.0 kg of a prepolymer based on diphenylmethane - 4,4 - diisocyanate,

and

- 11 -

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8.0 kg of methyl methacrylate and

2.0 kg dibenzoyl peroxide 50, ^ - ig in dibutyl phthalate as well

1900.0 kg mixed mineral additives consisting of

855.0 kg fillers grain size up to 2 mm

265.0 kg of sand, grain size 3 to 7 mm

355.0 kg gravel grain size 7 to 15 mm

445.0 kg gravel grain size 15 to 30 mm

mixed homogeneously and compacted in a mold using vibrating tables.

The synthetic resin mortar produced in this way hardens in the form within 3-4 hours.

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Claims (2)

"12" 2209U9 Patent claims Claim 1: Process for the production of shaped bodies consisting essentially of mineral building materials, characterized in that finely divided building materials are mixed with a mixture consisting of 1) a (meth) acrylic ester with 1 to 4 carbon atoms in the alcohol residue and / or styrene, or a predominant part (more than 50% by weight ) of one of the mentioned (meth) acrylic acid esters and / or styrene and for the remainder of one or more other unsaturated compounds copolymerizing with these monomers, optionally from a polymer or copolymer which is soluble or swellable in the monomers or monomer mixtures mentioned, 2) an adduct, originated from a) a di- or triisocyanate, b) a polyalcohol, the hydroxyl content of which is 1 to 10 % , or a mixture of such polyalcohols, c) iron hydroxy ester of acrylic or methacrylic acid or a mixture such hydroxyester, 309836/0655 ²¹⁴⁸⁷¹ j) an accelerator or accelerator system causing the polymerization, Component I) _-, based on the total amount of components 1 and 2, between 55 to 95 wt -.%, and component 2), again based on the total amount of the components 1 + 2, 45 to 5 wt. -fo constitutes, component 3), in turn, j based on the total amount of the components 1 + 2, 0.1 to 10 wt -.% amounts, be mixed largely homogeneously, the mixture obtained is introduced into a mold and through it Polymerization of the unsaturated compounds is hardened. Claim 2 Process according to Claim 1, characterized in that the adduct (2) has arisen from a diisocyanate whose Isocyanate groups have different reactivities. claim p Process according to Claims 1 and 2, characterized in that an adduct (2) is used which is formed by attachment of a polyalcohol and an unsaturated hydroxy ester of ^ -Isocyanatomethyl- ^ S.S-trimethylcyclohexyl isocyanate is. - 14 3 0 9 8 3 6/0655 ²¹⁴⁸⁷¹ 2209H9 Claim 4; Process according to claims 1 to ^, characterized in that a di-, tri or polyisocyanate and an amount of a polyalcohol with 1 to 10 % hydroxyl groups or a mixture of several such alcohols equimolar to the free isocyanate groups is added to the mixture functioning as a binder, the di -, tri- or polyisooyanate, together with the assigned amount of polyol, from 5 to% by weight , based on the total weight of components 1. Claim 5? Process according to Claims 1 to 4, characterized in that the mixture acting as a binder is of-methylstyrene in amounts of 0.5 to 20 wt .- ^, based on the Total amount of components 1 + 2, is added. 309836/0655 '" ^{Λ 2l4871}