AU597503B2

AU597503B2 - Flexible binders and sealants for concrete containing long-chain alkyl methacrylates

Info

Publication number: AU597503B2
Application number: AU19136/88A
Authority: AU
Inventors: Frederick Paul Hinz; Joseph Arthur Lavelle
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1988-07-18
Filing date: 1988-07-18
Publication date: 1990-05-31
Anticipated expiration: 2008-07-18
Also published as: AU1913688A

Description

COMMON WEALTH OF A U s T A PATENTS ACT 1952 COMPLETE SPECIFICATION (Original) FOR OFFICE USE Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: elated Art: S rii C*J

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"Xame of Applicant: 00 Address of Applicant: %'Ndtual Inventor(s): Address for Service: ROHM AND HAAS COMPANY Independence Mall West, Philadelphia, Pennsylvania 19105, UNITED STATES OF AMERICA Joseph Arthur LAVELLE Frederick Paul HINZ DAVIES COLLISON, Patent Attorneys, 1 Little Collins Street, Melbourne, 3000.

Complete specification for the invention entitled: "FLEXIBLE BINDERS AND SEALANTS FOR CONCRETE CONTAINING LONG-CHAIN ALKYL METHACRYLATES0 The following statement is a full description of this including the best method of performing it known to invention, us

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I la- 16 17 18 19 o 9 o 0 20 21 22 23 24 :c *6 27 28 29 30 14 31 32 33 34 36 ^d 37 I 8 t-4 I- j A '1 4 gr7/' 1 This invention relates to improved binders and sealants for concrete containing long chain alkyl methacrylates.

The present invention provides a binder or sealant composition comprising a substantially anhydrous slurry of a non-volatile binder monomer system comprising from 80% to 98% by weight, based on total weight of monomers and of at least one compound selected from the dicyclopentenyloxyalkyl esters of a polymerizable alpha, beta-unsaturated monocarboxylic acid selected from methacrylic acid or acrylic acid, the ester being represented by the formula R 0 H 2C C C 0 4 R' 0 wherein R is CH 3 or H, n is 0 or 1 and R 1 is selected from alkylene groups having 2 to 6 carbon atoms and (ii) 900302.csdat.073.ROHM2.L.1 17 2 11 12 13 14 15 16 c ti S 17 18 19 V a o 20 0 0 21 22 23 24 04B4 25 S 26 27 28 29 S 31 32 33 34 36 oxyalkylene groups having 4 to 6 carbon atoms and having one or more oxygen atoms joining distinct segments of the alkylene chain, each segment having at least 2 carbon atoms, and from 2% to 20% by weight, based on total weight of monomers and of at least one C 1 2

-C

3 0 alkyl methacrylate; a polymerization catalyst selected from 3% to 4% by weight, based on total weight of monomers and in the slurry of a (C 3

-C

18 hydrocarbyl peroxide with 0.1% to 5% by weight, based on total weight of monomers and in the slurry, of an aromatic amine polymerization accelerator; 0.1% to 3% by weight, based on total weight of monomers and in the slurry of a (C 3

-C

18 hydrocarbyl hydroperoxide with 0.0005% to 2% by weight, based on total weight of monomers and in the slurry, of a polyvalent metal salt or complex; mixtures of and 0.005% to 2% by weight, based on total amount of monomers and in the slurry, of a polyvalent metal salt or complex; and mixtures of and 1% to 5% by weight, based on total amount of monomers and in the slurry, of an aromatic amine polymer catalyst.

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4c mixtures of (a yand W eight, based on total amount of onomers, of a polyvalent metal -t or complex; and mixtures-O and about 1% to 5% by weight, based on totaanount of monomers, of an aromatic amine polymer U.S. Patent No. 4,460,625 discloses coating and impregnating compositions for concrete comprising 1) 25 to 75% dicyclopentenyl or dicyclopentenyloxy alkyl acrylate or methacrylate, 2) 25 to 75% hydroxy alkyl methacrylate and 3) polymerization catalyst. The compositions of U.S. Patent No. 4,460,625 has several deficiencies which are eliminated by this invention.

Firstly the high levels of hydroxy alkyl methacrylates in the compositions of the '625 patent reduces the surface cure of the compositions. Secondly, because of the hydrophilic nature of the hydroxy alkyl methacrylates, compositions containing hydroxy alkyl methacrylates are less resistant to aqueous-based chemicals than the compositions of this invention. Further, the compositions of the present invention are less toxic than compositions known in the prior art which contain dicyclopentenyl acrylate or methacrylate.

The compositions of this invention are useful in polymer concrete for sealing or binding a variety of porous surfaces to harden the surface and make it .ri <jt-^ yy t> 17~X7 l~:i I L-~Tn -I 1\, resistant to penetration by liquids such as water, organic .solvents, acids, alkalides and other corrosive and chemically-reactive liquids. Polymer concrete compositions are composite materials formed by polymerizing one or more monomers in the presence of an inert inorganic particulate or granular material. The compositions of this invention are non-toxic and exhibit the properties of flexibility, improved surface cure and improved aqueous-chemical resistance. Examples of poroussurface materials include concrete, stone masonry or brick walls including the facings of the mortar between the bricks and the stones, weathered archeacological artifacts and wall structures, weathered granite and marble walks and sculptures, walls, floors, and ceilings whether formed of plaster, concrete, cement, wood, pressboards, pressed metals such as those formed of iron, aluminium, and steel, and the like.

The diclopentenyloxyalkyl methacrylate and acrylate esters used in this invention as one of the two required components in the binder monomer system are known compounds. These ester-ether compounds and methods for their preparation are disclosed in U.S. Patent No.

1 4,097,677. Preferably, this component of the binder monomer system comprises at least one member selected from the group consisting of dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyisopropyl methacrylate, 4 dicylopentenyloxyisopropyl acrylate, and dicyclopentenyloxyneopentyl methacrylate.

Dicyclopentenyloxyethyl methacrylate is most preferred.

The compositions of the present invention essentially avoid the presence of dicyclopentenyl acrylate or methacrylate due to the objectionable odor and toxicity of these dicyclopentenyl monomers. Also, the compositions of this invention contain less than 25%, preferably 0%, hydroxyl alkyl methacrylate. The compositions of this invention are essentially anhydrous, which is meant to o exclude greater than 1% moisture in the compositions or in the inorganic particulate or aggregate material.

The long-chain alkyl methacrylates useful in the compositions of this invention include C 12

-C

30 alkyl methacrylates such as, for example, lauryl methacrylate, S isodecyl methacrylate and cetyleicosyl methacrylate. The amount of C 1 2

-C

30 alkyl methacrylates useful for this invention ranges from about 2% to about 20% by weight based on total weight of monomers. At less than about 2%

C

12

-C

30 alkyl methacrylates, the cured compositions are brittle and do not have the necessary flexibility to withstand thermal shock and to resist cracking. Levels of

C

12

-C

30 alkyl methacrylates above about 20% tend to lessen the surface cure of the compositions.

By the expression "non-volatile" as applied to the binder monomer system according to the invention, it is intended that the monomers or mixtures thereof must have a vapor pressure/reactivity balance under the conditions of ambient temperature cure such that no more than about by weight of binder monomers is lost by evaporation prior to complete cure or polymerization.

The liquid impregnating composition of the present invention may contain minor amounts of additives such as coloring agents, texturing agents, inhibitors, stabilizers, antioxidants, -thickeners, rheology modifiers, preservatives for wood and other materials subject to biological or environmental degradation) and the like. Depending on the pore size of the substrate, the composition may also contain minor amounts of fillers, and/or small aggregate, subject to the limitation that the average particle size of such materials be substantially Poe less than the size of the largest pores of the substrate.

The aggregate material optionally used herein may be any inert inorganic substance that is resistant to such organic and inorganic acids, salts, and alkalis as may be encountered in common industrial plants. Examples of suitable aggregates include sand, silica flour, crushed rocks or stones of quartz, granite, feldspar, gneiss, basalt, porphyry, and small pebbles thereof. In lieu of or in addition to sand, it is possible to use fractured colored glass marbles, ground glass, energy powder, ground slag, and fine gravel.

6 The composition may be colored by choice of a colored aggregate or by including within the composition a suitable amount of pigment or dye dissolved in the binder monomer system. The amount of such pigment or dye may vary from about 1% to 10% by weight of the total composition.

The addition of the polymerization catalyst, for example, a polyvalent metal salt or complex and organic f' hydroperoxide can be made to the monomer mixture prior to I application. The proportion of metal salt or complex ef added to the composition Lefore application may be from 0.0005 weight percent up to about 2 weight percent, and the amount of hydroperxide may be in the range of 0.1 to 3 weight percent, based on the total weight of the monomers. Similarly, the addition of an organic peroxide with an aromatic amine accelerator, and optionally with a polyvalent metal salt or complex, can be made to the mixture prior to application. The proportion of the organic peroxide to the composition may be in the range of 0.1 to 4 weight percent and the aromatic amine accelerator is used in an effective amount, usually in the range of about 0.1 to 5 weight percent.

The polymerization catalyst components, such as polyvalent metal salt or complex and hydroperoxide, or the aromatic amine accelerator and peroxide, may be packaged. and shipped separately to the site of operations where the 7 _I I I- respective components may be combined and where the composition of the present invention is to be applied, as by pouring or spraying to impregnate or seal a concrete floor, base or pavement. Alternatively, the aromatic amine accelerator and binder monomer system, and the organic peroxide respectively, may be combined in packages for storing and shipping prior to combining them to *4l' provide the composition of the invention shortly before S* applying the composition.

The polyvalent metal salt or complex used in the invention may be any polyvalent metal-containing salt that S catalyzes the oxidative curing of drying oils and, when added to oil-based varnishes and paints, hastens the S' drying or curing thereof. These metal salts or complexes are also known, in the art, as "siccatives" or "driers".

Such substances include the polyvalent metal salts of higher aliphatic acids, such as the butyrate, pentanoate, hezanoate, and especially the salts of higher aliphatic acids having from 8 to 30 carbon atoms or of naphthenic acids that provide solubility in the binder monomer system. Generally, the most useful drier salts for the binder monomer system compositions of the present invention are salts of naphthenic acids or of (C 8 to C 30 aliphatic acids. Examples of the polyvalent metal include calcium, copper I zinc II, manganese II, manganese III lead 1 cobalt

II

iron

III

vanadium

II

and zirconium IV 8

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These salts or complexes accelerate the action of the organic hydroperoxide and promote oxidative curing in the organic peroxide-amine catalyst system. Other examples of the acid component or anion of the drier salt are those of resinic acids, (that is, rosin acids), tall oil fatty acids, linseed oil fatty acids, 2-ethyl-hexanoic acid, lauric acid, palmitic acid, myristic acid, stearic acid, S' oleric acid, linoleic acid, behenic acid, cerotic acid, monotanic acid, and abietic acid. A mixture of drier salts may be used.

SPreferred drier salts are those of cobalt and maganese, such as cobalt octoate, cobalt naphthenate, cobalt acetylacetonate and manganese octoate, manganese

S.

naphthenate, and manganese acetylacetonate.

Aromatic amines may be used in small amounts with the organic peroxides and generally accelerate the action of the peroxide. For example aniline, N,N-dimethylaniline, N,N-diethylaniline, toluidine, N,N-dimethyl p-toluidine, N,N-di(hydroxyethyl)toluidine, and pdimethylaminobenzaldehyde may be added for this purpose in an amount of 0.1 to 5 percent by weight of the binder monomer system.

The organic peroxides and hydroperoxides that may be used include the peroxides and the hydroperoxides derived from hydrocarbons which contain from about 3 to 18 carbon atoms so that they are soluble in the binder monomer 9 system. Suitable organic hydroperoxides include tertiarybutylhydroperoxide, cumene hydroperoxide, methyl ethyl ketone hydroperoxide and diisopropylbenzene hydroperoxide. Suitable peroxides include benzoyl peroxide, tert-butylperbenzoate, 2,2-bis-(tertbutylperoxy)-butarie, bis-(l-hydroxy-cyclohexyl)-butane, bis-(l-hydroxy-cyclohexyl)-peroxide, and tert-butylperoxyisopropyl carbonate.

The compositions of the present invention are especially useful for sealing and repairing industrial flooring, basement flooring, pavement, roads, bridges, and ship decks.

The following examples are presented to illustrate the present invention.

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Example I Binder monomer compositions according to this invention are prepared, formulated with concrete at a level of 13% binder, and compared to a control composition falling outside the scope of this invention. The initiator system used in all examples consisted of 4% by weight(based on binder monomer composition) of active benzoyl peroxide (50% active) and 1.14% by weight (based on binder monomer composition) of cobalt carboxylate. The flexural.modulus of elasticity of the cured concrete formulations was measured and is presented in Table I.

I i _i i II(DI-uaB-- Table I Modulus Of Binder Monomer Composition Elasticity (Psi) Samolp DCPOFMA flMARA Inux ~Y I (Control) 2 t 40. 3 5 .0.0,0 0 6r.

07 *04900 4 9 *0 10 C 00 12 13 14 016 17 96.0 93.0 92.0 90.0 88.0 87.0 84.0 81.0 93.0 92.0 91.3 88.9 88.0 86.5 76.9 92.0 89.0 3.0 4.0 6.0 8.0 9.0 12.0 15.0 L14A CEMl (X 10-6) 1.386 1.044 0.837 0.876 0.577 0.433 0.332 0.197 2.4 1.160 4.0 1.004 4.8 0.800 7.2 0.640 8.0 0.443 9.6 0.520 19.2 0.033 4.0 0.861 8.0 0.245 VCPOEMA a dicyclopentenyloxyethyl methacrylate D4ABA p-dimethylaminobenzaldehyde CEA a cetyleicomyl mothacrylate IDCA a isodecyl methacrylate LMA lauryl methacrylat.

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The results in Table I show that long-chain alkyl methacrylates in binder monomer compositions of this invention improve the flexibility of concrete, without the necessity of hydroxy alkyl methacrylate monomers.

Example I1 Binder monomer compositions were prepared as in Example I containing 3% and 8% by weight lauryl methacrylate. The monomer compositions were formulated into polymer concrete at 13% by weight binder composition.

4 The susceptibility of the polymer concrete formulations to cracking was evaluated by using the partially bonded overlay test. A 6 x 12 x 1 inch concrete o block was used as the substrate for a 1/8 inch thick polymer conciete overlay. Prior to placing the polymer concrete overlay, the center of the block was covered with a 5 x 6 inch x 2 mil thick piece of mylar film. The 4 polymer concrete was troweled over the surface contacting the concrete substrate at each end but covering the mylar in the center. The dimensions of the overlay were 4.25 x x 1/8 inch. The polymer concrete was allowed to cure for 24 hr at 73 degrees F.

After curing, the test sample was placed in a cold box and cooled for 20 hrs. at 12 degrees F. Immediately the block was plunged into hot water at 140 degrees F.

After 30 minutes the sample was removed and inspected for 12 S TVtrrfltWr4~~r~ t-rrr-rr cracks. If none were found, the block was allowed to dry for 4 hrs. and the cycle repeated until cracking was discovered.

The binder monomer compositions of this invention containing lauryl methacrylate were compared to compositions containing equivalent amounts of hydroxy propyl methacrylate (HPMA). The results are presented in Table II.

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*5* t.ItC Table II Sample 18 (comparative) 19 (comparative) 20 21 Binder Monomer Composition (wt. DCPOEMA DMABA LMA HPMA 93.0 4.0 3.0 88.0 4.0 8.0 93.0 4.0 3.0 88.0 4.0 8.0 Cycles to Cracking 1 1 7 >9 Example III Binder~ nonomer compositions were prepared according to this invention containing 3% and 8% lauryl methacrylate and formulated into polymer concrete at a level of 13% binder monomer composition. Samples of the polymer concrete were cast in 2 inch squares having a 1/2 inch thickness. The samples were evaluated for surface cure and compared to a binder composition containing hydroxyl propyl methacrylate. The results are pr esented in Table

III.

#4 I 4 *404 #4 14 t 4 4 4 4 #4.444 4 4404 4* 4. 4 4 444044

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44 4 4 4 44 44 4.

404 '4 0 4 44.

444444 Table III Sample 22 (comparative) 23 24 Binder Monomer Composition (wt. DCPOEMA DMABA LMA HPMA 38.0 4.0 20.0 38.0 93 4.0 3.0 88 4.0 8.0 Surface Cure (minutes) 120 The above results show faster surface cure for samples 23 and 24 which fall within the scope of this invention.

Example IV A binder monomer composition was prepared according to this invention containing by weight 88% DCPOEMA, 4% DMABA and 8% LMA (sample 25). The binder monomer composition was formulated into polymer concrete at a level of 13% by Weight binder composition. For S, comparative purposes, a binder monomer composition was .r prepared according to U.S. Patent No. 25 containing by weight 38% DCPOEMA, 4% DMABA, 20% LMA, and 38.0% HPMA t (sample 26). This composition was formulated into polymer concrete at a level of 13% binder composition. The polymer concrete formulations were S, evaluated for resistance to aqueous-based chemicals by casting 1.25 inch diameter disks of 3/16 inch thickness.

The disks were weighed before and after being submerged for 7 days in aqueous solutions of 10% ethanol, sulfuric acid and sodium hydroxide, respectively. The percent gain in weight due to absorption of the respective solutions is given in Table IV.

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7?able IV Solvent Resistance (%Weight gain) Sample Solvent: Ethanol Sulfuric Acid Sodium Hydroxide 0.16 0.19 0.25 26 (comparative) 0.52 0.25 0.80 C I ~tItI I t 1111 r r 16 II~tt I I 61 S I 64 46

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o 0e *00 The results show that the composition of this invention is more resistance to aqueous chemicals.

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Claims

2. A composition according to claim 1 wherein the ester monomer is selected from dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyisopropyl methacrylate, dicyclopentenyloxyisopropyl acrylate and dicyclopentenyl- oxyneopentenyl methacrylate.
3. A composition according to claim 1 or claim 2 wherein the C 1 2 -C 3 0 alkyl methacrylate is selected from lauryl methacrylate, isodecyl methacrylate or cetyleicosyl methacrylate.
4. A composition substantially as hereinbefore described with reference to the foregoing examples. DATED this 2nd day of March 1990 ROHM AND HAAS COMPANY By its Patent Attorneys: DAVIES COLLISON 900302,csdat.073.ROHM2.L.18 i.;