GB2256645A

GB2256645A - Hardenable monomer composition

Info

Publication number: GB2256645A
Application number: GB9212306A
Authority: GB
Inventors: Karoly Discho
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1991-06-14
Filing date: 1992-06-10
Publication date: 1992-12-16
Anticipated expiration: 2012-06-10
Also published as: CH684795A5; FR2677656B1; JP2696039B2; AU654717B2; JPH05239379A; AU1817392A; IT1255669B; DE4218414C2; GB2256645B; AT398966B; ITRM920441A1; FR2677656A1; BE1005805A3; GB9212306D0; CA2071101A1; ES2059235A1; ITRM920441A0; DE4218414A1; ATA121092A; ES2059235B1

Description

2 1 MONOMER COMPOSITIONS L ' This invention relates to hardenable monomer

compositions of the type used to provide flooring or to coat concrete objects.

A common type of composition for use in flooring and in the coating of concrete surfaces comprises a blend of at least one cross-linkable acrylic monomer and at least one coarse filler, usually sand. This type of composition, sometimes referred to in the art as "polymer concrete", is noted for its excellent mechanical properties.

It has now been found that it is possible to prepare compositions of this type with enhanced properties. There is therefore provided, according to the present invention, a hardenable monomer composition adapted to be used in flooring and in the coating of concrete surfaces, comprising (a) binder which comprises (meth)acrylic ester of the Formula I C1-112=C-C-(OR1)jOR2 1 11 R 0 (1) wherein R is hydrogen or methyl; R, is C,.alkylene; n is an integer of from 0-3; and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopentenyl radical; and (b) at least one component selected from the group consisting of (i) carbon blacks with a BET surface area of from 20-460 M2/g, this being present to the extent of from 0.01 -7, preferably 0.01 -3, more preferably 0.1 -0.5, weight 2 % of the acrylic monomer; and (ii) aliphatic and aromatic polyester- and polyetherurethane oligomers of molecular weight 500-2000 and a viscosity of 2,000-100,000 m Pa s at 25C, having at least two ethylenically unsaturated double bonds.

Binders which are useful in the compositions of this invention comprise acrylic monomers which, when mixed with catalysts, harden within a few hours to form polymers. Such acrylic monomers include esters of (meth)acrylic acid, preferably methacrylic acid, and suitable examples have been described in, for example, EP 47120, USP 4,460,625, 4,097,677, 4,299,761, 4,400,413 and GB 2,220,204 the disclosure of which are incorporated herein by reference. Binders suitable for use in this invention comprise monomers of formula I

CH2 = C - C -(OR, OR2 1 11 H U wherein R is hydrogen or methyl, R, is an aikylene group with 2 to 6 C- atoms, n is an integer of from 0 to 3, and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopentenyl radical.

(1) Preference is given to those monomers of formula I in which R is methyl, R, is a branched alkylene group with 3 or 4 C-atoms, n is 1 and R2is the radical of a tetrahydrophthalic acid, which in addition is esterified with an alkanol, preferably aC1-6 alkanol, more preferably methanol or ethanol.

(Meth)acrylic esters according to formula 1 may constitute the entire binder, or they may be mixed with other esters of acrylic or methacrylic acid. This allows the balance of properties of the composition to be adjusted. Examples of such esters are the 1 3 hydroxyalkyl methacrylates, particularly hydroxypropyl methacrylate. Based on the total amount of monomers, the (meth)acrylates of the formula I preferably comprise 20 to 100 percent by weight, more preferably 50-95 percent by weight, and other (meth)acrylate esters preferably comprise up to 80 percent by weight, more preferably 5-50 percent by weight, based on total weight of a binder monomer.

The catalysts which may be used for crosslinking or hardening of the preparations according to the invention include organic peroxides or hydrogen peroxides of hydrocarbons with 3-18 carbon atoms which are soluble in the monomers, salts or complexes of transition metals and/or aromatic amines as polymerization catalysts. The peroxides or hydrogen peroxides are present in quantities of 0.1 to 5 percent by weight, the salts or complexes of transition metals in quantities of 0.0005 to 2 percent by weight and the aromatic amines in quantities of 0.1 to 5 percent by weight of the total weight of acrylic monomers. Examples of suitable peroxides include benzoyl peroxide, tert. butyl perbenzoate, dilauryl peroxide and 2,2-bis- (te rt. butyl pe ro xy) -butane. Suitable hydrogen peroxides are tert.-butyl hydrogen peroxide, cumene hydrogen peroxide and diisopropylbenzene hydrogen peroxide.

The salts or complexes of transition metals are those which catalyse the oxidative hardening of drying oils and are known as siccatives. They are usually calcium, copper, zinc, magnesium, manganese, lead, cobalt, iron, vanadium or zirconium salts of higher aliphatic (8-30 C) carboxylic acids and naphthenic acids. Cobalt and manganese salts are preferred, such as cobalt octoate, cobalt naphthenate, cobalt acetyiacetonate and the corresponding manganese salts.

The aromatic amines which may optionally be used as polymerization accelerators are well known for this purpose. Examples are aniline, N,Ndimethyl- or N,N-diethylaniline, corresponding toluidines and pdimethylaminobenzaldehyde, these are preferably used in quantities of 0.1 to 6, more preferably 0.1 to 2 percent by weight, based on the weight of the monomer components.

Such a catalyst system preferably consists of a peroxide or hydrogen peroxide, an 4 aromatic amine and a transition metal salt.

The compositions according to the invention preferably contain an essentially dry aggregate, which preferably comprises 40-95 % by weight of the total composition. Any inorganic compound which is inert towards acids, bases and salts may be considered as the aggregate. For example, sand, gravel or coarser aggregate materials of types normally employed in flooring compositions and the like may be employed. For coatings, fine aggregates such as fine sand, possibly mixed with silica fume, may be employed. These various constituents may be added shortly before application of the monomer composition, or may be contained in various packages, which are storage-stable. For example, the aggregate, the various monomers with the optional polymerization accelerators and the polymerization catalyst with the transition metal salt may be delivered in separate packages, which may be mixed together shortly before use. Depending on the catalyst employed, the catalyst system (without accelerator) may also be pre-mixed with the aggregate, or the monomer mixture may be pre-mixed with the aggregate.

In addition to binder (and usually aggregate), the composition of the invention also comprises a third component which is at least one of two other materials, carbon black and oligomer, whose parameters will now be described.

The carbon black has a BET surface area of from 20-400 M2/ g and is present to the extent of from 0.01-7%, preferably 0.01-3.0%, more preferably 0.1-0.5%, by weight of the acrylic binder. Materials such as gas black, lamp black and furnace black may be used.

The carbon black has the effect of reducing the deleterious effect of oxygen, especially at the surface, and pot life and tack-free time are substantially improved without any impairment of the properties of the final polymer. The reactivity of the monomer composition is also improved.

The oligomers used in compositions according to the invention are aliphatic and aromatic polyester- and polyether-urethanes having at least two unsaturated double bonds, -4 71 preferably at least three such bonds, so that they are capable of crosslinking with acrylic binders. Preferred oligomers have molecular weights in the range of 500-2000, preferably 1000-2000, more preferably 1000-1400 and viscosities of 2,000-100,000, more preferably 12,000-100, 000, and most preferably 60,000-75,000 mPa s (at 25C). Such oligomers may be made, for example, by the reaction of carboxyl groups of acrylic acid or methacrylic acid monomer with a polyester- or polyether- urethane. This can be done during or after the preparation of the polyester- or polyether- urethane. Examples of suitable oligomers which are useful in the working of this invention are:

NAME GENOMER Rahn AG T1200 ZOrich GENOMER 11 T1 600 SOURCE NATURE MW aliphatic, triacylate 11 VISCOSITY 1000-1200 70,000 -1600 52,000 GENOMER if aliphatic D1500 B diacrylate EBECRYL UCB aromatic 2,000 30,000 205 Belgium triacrylate EBECRYL aromatic 1,500 4,000 210 diacrylate EBECRYL aliphatic 2,000 14,000 1259 triacrylate EBECRYL aliphatic 1,000 2,000 1290 hexaacrylate When an oligomer is used as component (b), compounds of formula 1 comprise 20-93%, preferably 50-80%, other (meth)acrylates comprise up to 73%, preferably 7-37% and oligomer comprises 7-60%, preferably 13-40% by total weight of acrylic binder and oligomer.

In an especially preferred embodiment, the compositions according to the invention comprise both carbon black and oligomer.

6 These preparations may be used to repair concrete objects or surfaces. In this work, a preparation according to the invention is applied to the surface requiring repair and is allowed to harden at the ambient temperature. However, they may also be used for the impregnation or coating of porous materials, especially concrete, or for filling cracks. These preparations are particularly useful as flooring compositions.

Apart from good water resistance and heat resistance, the polymeric compositions obtained from the hardening of the monomeric compositions according to the invention are especially notable for their increased resistance to impact, their compression strength and flexural strength, and their outstanding adhesive strength.

The invention is further described with reference to the following examples in which the parts and percentages are by weight.

Component I is an ester of tetrahydrophthalic acid monomethyl ester and hydroxypropyl methacrylate. Component 11 is a hydroxypropyl methacrylate. The oligomer is the product GENOMER T 1200 from Rahn AG, ZOrich.

The carbon black used is a furnace black with a BET surface area of 80 m2/g ('Printex" 300 from the company Degussa AG).

The pot life and absence of tackiness of the polymeric concrete mass obtained are determined at room temperature.

Examples 1-7 (Table 1) show the advantages of the use of carbon black in the proportions of the invention.

Examples 8-14 (Table 2) show the advantages of the addition of oligomer according to the invention. The impact resistance (in milliJoules/sq. cm. ) and the flexural and compression strengths (both in Newtons/sq. mm.) are determined by standard methods widely used in the art.

t 7 Examples 15-24 (Table 3) show the advantages of the use of both carbon black and oligomer.

8 T a b 1 e 1 Preparation Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 (for comparison) component 1 10 10 10 10 15 15 15 component 11 5 5 5 5 - - carbon black - 0.02 0.1 1 0.02 0.1 1 cobalt naphthenate 0.15 0.15 0.15 0.15 0.15 0.15 0.15 benzoyl peroxide 0.8 0.8 0.8 0.8 0.8 0.8 0.8 standard sand (1 mm maximum size) ca. 54 ca. 54 ca. 54 ca. 54 ca. 54 ca. 54 ca. 54 quartz sand (0.1-0.3 mm) ca. 26 ca. 26 ca. 26 ca. 26 ca. 26 ca. 26 ca. 26 quartz sand (0.04-0.1 mm) 5 5 5 5 5 5 5 pot life >1 day 50 min 10-1 5min 10 min 50 min 5-10 min 5-8 min absence of > 36 hrs 12-24 hrs 10 hrs 5 hrs 12-24hrs 10 hrs 5-1 Ohrs tackiness v 1 P 11 T a b 1 e 2 Preparation Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 (for comparison) component 1 15 13 11 6 8 6 4 component 11 - - - - 4 3 2 oligomer - 2 4 9 3 6 9 cobalt naphthenate 0.15 0.15 0.15 0.15 0.15 0.15 0.15 benzoyl peroxide 0.8 0.8 0.8 0.8 0.8 0.8 0.8 standard sand (1 mm maximum size) ca. 54 ca. 54 ca. 54 ca. 54 ca. 54 ca. 54 ca. 54 quartz sand (0.1-0.3 mm) ca. 26 ca. 26 ca. 26 ca. 26 ca. 26 ca. 26 ca. 26 quartz sand (0.04-0.1 mm) 5 5 5 5 5 5 5 resistance to impact 80 190 193 250 170 200 240 flexural strength 17 27 29 27 31 34 32 compression strength 46 54 58 68 70 71 70 1 __C? 1 Tab 1 e 3 Preparation Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 component 1 component 11 oligomer carbon black DMAB cobalt naphthenate 0. 15 benzoyl peroxide 0.8 Ti02 sand 7.3 3.7 4 0.02 7.3 7.3 7.3 3.7 3.7 3.7 4 4 4 4 0.1 1 0.02 10 7.8 5.2 10 4 4 0.1 0.5 0.5 4 0.02 0.42 0.15 0.75 6 ca. 82 78.66 4 0.42 0.15 0.75 6 78.66 0.15 0.15 0.15 0.8 0.8 0.8 0.15 0.15 0.8 0.8 0.15 0.15 0.8 0.8 f C) 1 ca. 85 - - pot life 40 min >4 day 20 min <2 min 190min 31 min 5 min 10-1 5min 30 min absence of 1 day ca.6 day 2 day 1-2 hour 90 min 500 min tackiness DMAB = p-dimethylaminobenzaidehyde 9 ' 1 p 1 11 1 -

Claims

1. A hardenable monomer composition adapted to be used in flooring and in the coating of concrete surfaces, comprising (a) binder which comprises (meth)acrylic ester of the Formula 1 C1-12=CC-(ORJ,-OR2 1 11 R 0 (1) wherein R is hydrogen or methyl; R, 'S C2_.alkylene; n is an integer of from 0-3; and R2 is a radical of an aromatic or alicyclic dicarboxylic acid ester or a dicyclopentenyl radical, n being able to be 0 only when R2 is a dicyclopentenyl radical; and (b) at least one component selected from the group consisting of (i) carbon blacks with a BET surface area of from 20-460 M2/g I this being present to the extent of from 0.01-7, preferably 0.01-3, more preferably 0.10.5, weight % of the acrylic monomer; and (ii) aliphatic and aromatic polyester- and polyether- urethane oligomers of molecular weight 500-2000 and a viscosity of 2,000-100,000 mPa s at 25C, having at least two ethylenically unsaturated double bonds.

2. A hardenable monomer compositions according to claim 1, wherein the composition comprises aggregate preferably to the extent of from 40-95% by weight of the total composition.

3. A hardenable monomer composition according to claim 1 or claim 2, wherein R is methyl, R, is a branchedC3-4alkylene, n is 1 and R2 is the radical of a 12 tetrahydrophthalic acid which has been esterified with an alkanol, preferably a Cl-,, alkanol, more preferably methanol or ethanol.

4. A hardenable monomer composition according to any one of the claims 13, wherein component (b) is a carbon black and the binder additionally comprises (meth)acrylic esters other than those of Formula I to the extent of up to 80%, preferably 5-50% by weight of total acrylic monomer.

G.

A hardenable monomer composition according to any one of claims 1-3, wherein component (b) is oligomer and there is present in the composition from 20-93%, preferably 50-80%, of esters of Formula 1, up to 73%, preferably 7-37%, of (meth)acrylic acid esters other than those of Formula 1, and from 7-60%, preferably 13-40%, by weight of oligomer, all by weight of the total weight of binder and oligomer.

A hardenable monomer composition according to claim 4 or claim 5, wherein the (meth)acrylic esters other than those of Formula I are hydroxyalkyl methacrylates.

7. A hardenable monomer composition according to any one of claims 1-3, wherein the composition comprises both carbon black and oligomer.

8. A flooring composition comprising a hardenable monomer composition according to any one of claims 1-7.

9. A coating composition for use on concrete subtrates, comprising a hardenable monomer composition according to any one of claims 1-7.