GB2205104A

GB2205104A - Cold setting compositions

Info

Publication number: GB2205104A
Application number: GB8808845A
Authority: GB
Inventors: Rudolf Semsei; Bela Racz; Belane Karacsonyi; Pal Gittinger
Original assignee: CHEM EPITOEANYAGIPARI
Current assignee: CHEM EPITOEANYAGIPARI
Priority date: 1987-04-16
Filing date: 1988-04-14
Publication date: 1988-11-30
Anticipated expiration: 2008-04-14
Also published as: CS274426B2; AT395979B; DD275469A5; NL8800950A; LU87200A1; GB2205104B; DE3812594A1; BE1002298A3; HU196233B; GB8808845D0; CH675585A5; CS235388A2; ATA85788A

Description

2 2 5 1 C, A Al.

COLD SETTING COMPOSITIONS 2 The invention relates to compositions comprising two-components which are cold setting and applicable in construction, highways, bridges and like installations.

In structural engineering the demand on cementing and sealing joints emerges in several fields and can ba satisfied neither with hot bitumen, or hot bituminous masses nor with solvent or emulsion type products.

The patch-like repair of roof insulation or the sealing of joints or bridges, tunnels and tubbings can be effected Ous With vari product types based on two-component epoxy resin or polyurethane masses comprising coal tar and/or bitumen, which usually contain an organic solvent as well.

They have the disadvantage of being employable in general only to specific purposes, or they contain 40-00 per cent of an organic solvent, thus polluting the environment and having fire-hazard properties.

Organic solvent or aqueous emulsion containing cold curable bituminous products can not be for example utilized for purposes, where drying of the adhesive film is not ensured or volume loss takes place at drying like in case of cementing roofing felts with each other. To repair defects of concrete highways and runways usually tar-epoxy or bitumen- epoxy products are known, since their adhesion to concrete is adequate and exhibit proper elasticity. Because of their high prices the application thereof is confined to special installations, e.g. to the repair of airport runways. Plastic based adhesives and patches such as polysulfide, butyl c@outchouc, polyisobutilene, polyurethane or silicon caoutchouc based products are used for sealing of joints. Their disadvatage;'s the high price, thus the use thereof is restricted.

Disadvantages of the known products are their price on the one hand and their unsuitability for various purposes on the other hand. For example self-spreading of the adhesive in the required 'Layer thickness, eliminating the unevenness of surfaces or correction of the position of materials to be cemented after laying on, i.e. control of the pot-life are unsolved problems. Permanently plastic properties can be attained only by addition of expensive plastics materials, in most cases the use of an organic solvent is unavoidable.

An object of the present invention is to provide a cold usable, permanently plastic product of controllable setting time, which is suitable for manifold uses, is free of water and organic solvent, can be handled simply and causes no damages of the environment and health.

The composition according to the invention is a two-component, cold curable, bitumenous composition free of water and solvent which comprises a 4 - Component A containing 40-60 % by weight bitumen or 2-6 % by weight bitl-- men fied by 70/30-ooi/40 polybutadiene-poly- modi. styrene block copolymer 20-40 % by weight liquid fatty acid (average carbon number C 17C 18 20-40 % by weight filler 0-5 % by weight additive, making the mass thixotropic, and a Component B containing 10-20 % by weight f2Ctice (oil rubber) made of drying veoetable oil and sulfur and comprisino B-20 % by weight sulfur 10-20 % by weight zinc oxide, magnesium oxJLde or alkali earth metal oxide or -hydroxide, or the mixure thereof 0-80 % by weight filler and the mixing ratiD of components A and B being 1 - 3: 3 - 1.

Another type of the comiposition of the instant invention comprises a Component A containing 40-60 % by weight bitumen 20-40 % by weight liquid fatty acid having C 17- C 18 carbon atoms or naphtenic acid 5-10 by weight solid sulfur factice with 17-19 % by weight total sulfur content, made from j - i pre-treated r20e Oil and sulfur, and a Component B containing 10-20 % by weight zinc oxide, magnesium oxide, calcium oxide or -hydroxide, or chlorinated lime or their mixture 10-90 % by weight filler 1-20 % by weight ground rubber the mixing of components A and B being The bitumen is modified with 2-8 % by weight thermoplastic s4tyrene- butadiene copolymer of type SBR or SBS. Such products are Europrene 161A and 161B (Enichem, Italy), Cardflex 1101, 1184, 1186 /Shell Co./, Finaprene 411, Claprene /Shell/). Their moleCU12r weight is between 120 and 280 000. Pine oil fatty acid with iodine numbet 84-92 can be used 2S liqUi fatty acid. Other usatle -ty acids are tallow fatty a-cid, technical fatty liquid f@ 4L L a C 4 id W4 - L.th iodine number 20, saponification numbe.- 1653-210, sunflower fatty acid, rape oil, P21M Oil, coconut oil or linseed oil fatty acid. The inert filler may be sand, or quartz flour, andesite, basalt, rock flour, talc of 0-1 mm -pal-ticle size, kaolin, bentonite or clay, micrD I silica powder, aluminium hydrate, ground corundum, asbestos fibres, mineral wool, artificial fibres, viscose fibres or mixture thereof. The drying or 5emi-drying oil - suitable to f8Ctice preparation is sunflower-, rape-, cottonseed-, pumpkin seed,-, sesame-, hempseed-, olive- , fish-, soybean-, malze-, linseed- or castGr oil, which exhibit 2 iodine number ci 80 to 200, but also drying vegetable oil varnish is suitable. Quality and material composition of the inert filler can be the aforesaid, the use of quartz powder or fire sand with 0-1 mm particle size is preferred. Ratio of components A and B may be varied between the given limit values, however, the mixing ratio 2:1 is preferable for cementing (adhesive) purposes and 1:1 for sealing of joints.

On preparing the composition of the invention the thermoplastic SBS copolymer is gradually added to the bitumen at a temperature above its softening pcint - preferably between 160 and 180 0 C - under stirring. The liquid cle-ic acid is added thereafter to the homogen-1 zed mixture again under stirring, SUIL-Isequently, finally the the filler is added to the warm mixture Llatter is left to cool to 30-40 0 C, and the so obtained comporient A is stored separately until its processing.- In a separate stelp sulfur containing f2Ctice is cooked from drying oil and sulfur. Total sulfur content of the factice should be about 6-10 '-. by weight on the total mass. After coolino z'Lnc oxide is based added or magnesium oxide or alkali-earth metal9xides and the mixture is blended until homogenity, finally the filler is added to the thus obtained component B. Alternatively on producing the component A to the bitumen at 160-170 0 C the solid or semi-solid factice is added then the oleiC 2Cid and in a separ2te 7 - Q step the zinc oxide, magnesium oxide or alk2li-earth metal oxides or chlorinated lime resp. This mixture is blended with the fillers and ground rubber.

An important precondition of utilization of the instant composition is the full and complete mixing 0 f components A and B, to which a mixing time of 5-10 minutes is usually suffici2nt. The pot-life of the fluid, mortar-like mass is 2 to 2.5 hours depending on the temperature, however, pot-life can be extended or substantially to shortened when aliphatic carboxylic acid is added component A in a mtximum quantity of 5 per cent calcula ed on JL k 10 minutes and 24 hours. During the e contro.lled between I - open period (pot life) the mortar-like mass is not thickening, spreads well and after certain time setting Starts suddenly, the M2SS cures in 10-15 minutes, but its permanently plastic condition remains. Setting of the CompoSiti on takes place in ccld state, at normal tempera ture, preferably at about 20 0 C and presumably consists of three proceedings:

In the saponification process between the metal oxi.de employed and the free fatty acid a bond is formed, the duration of which can be controlled. The lenoth of time may by shortened on using of aliphatic carboxylic acid, whereas on addition of factice the bond can be in hibited and the setting time lenothened. Parallel to the setting bond partly or fully cross-links are formed as well, 8 1 c.L between the f@ctice, metal oxide. unsaturated fatty acid and possibly the Unsaturated linkages of the added polymer. In the surface layer of the cured mass which 15 in contact with air and lioht, the unsaponified residues of the semi-saturated vegetable oil and the unsaturated fatty acid cure in relatively s hort time upon oxygen uptake and the applied M25S "dries through". This can be established from the fact that stickiness of the mass ceases and softening point rises slowly.

The product according to the invention has the advantace that the laver thickness can be varled. ra."It. start O-C setting can be eliminated, -Le mass is 11sprea-ding" on the surf ace to be covered. BeczuEs of the ad, uEtability of the setting time, PCS-L'LiC-. Cf the Materials _L Lo be adhered -LCOether can be corrected even after lay on, in aodi tion the material to be cemented is not d@,-,aoed b heat or chemical action. After setting the mass ren2ins pezni2r,ently plastic, takes over the Motions of the covered surface without formation of cracks. The mass at; eres well to the dry substrate, subsequently the laer becomes wate.-- proof, no water uptake occurs and the mass cures even under water. In practical use cementing sealing of joints and other operations can be carried out by simple means, without fire-hazard, accident risk and health hazard, no special skill is required. The products according to the invention can be used to fill the joints of concre"t.e pavement, roof insulation elements, to ce,,.)ent M S1 f1cors and roofing felts. Their use is economic, since the active ingredient content of the cori position can be put together of e2sily available components, character of the product can be varied by v2ryina the ratio of compo nents A and B. Further details are illustr2ted in the following examples:

EX2Mp1e 1 Composition suitable for joint scaling is prepared from the following components:

Component A 38 % by weight Bitumen B-90 (softening pCint 46 0 C, e penetration 71-100) 2 % by weight Pt,,-ene-butad-ene copo'vmer L - 1 161A), average molecular weight 280,000 % by weight oleic acid (oleine) % by weight sand of 0-1 mm particle size Com.ponent B 9 by weight sunflower oil 1 % by weight sulfur % by weight zinc oxide (zinc white) % by weight sand of 0-1 mm particle size.

In component B partly or fully coal tar or fluid gasoline pyrolisis tar can be employed instead of vecetable oil.

On preparing component A bitumien is heated in a heatable equipment with Stirrer to 150 0 C and the r_ ccpolymer added under vigorous stirring during a period h - id:he cf 45-60 minutes. Next the ole-ic ac. is added to homogenous mixturean stirred vigorously for some minutes, than the fine Sand is slowly added to the mixture under further stirring. This is continued under water- cooling until temperature of the mixture falls to 35-40 0 C. Thereafter the black, liquid product is filled in containers_-n producing component B at first factice is prepared from drying vegetable oil and sulfur. The vegetable oil is heated to 130-140 0 C, the powdered or lamellar sulfur is then added, the mixture is stirred at this temperature for 3-4 hours until complete incorporation of the sulfur. The ottained factice is a deep brown, liquid, transparent in intensive light, free cf sed.iment and turbidity. After cooling the zinc oxide is added to the fluid factice and mixed to a ho-mcgenous paste. Subsequently the fine washed sand is added, and 2 product similar to wet sand in colour Find appearance is obtained, which can be packed in sacks. The thus obtained com-ponentS A and B are mixed in a ratio of 1:1 for joint sealing purposes. Complete compounding can be achieved in 5-10 minutes. The pot-life of the so produced fluid and self-spreading composition is 2- to 2.5 hours depending on temperature, during this time no thickening occurs, it flows and spreads well. After this setting starts particularly at temperatures above 20 0 C and in 10-15 minutes curing takes place in the seal or in the "Pot".

4 11 Example 2

Elastic composition suitable to cold cementing can be produced by mixing components A and B of Example 1 in a ratio of 2:1. This mixture suitable for cementing has a lower viscosity and shorter setting time.

Example 3

Rapid setting type of joint sealing compositions described in Examples 1 and 2 are prepared with the difference that 0.05-0.5 % by weight concentrated acetic acid is added to component A. The acetic ' acid can also added on the site cf application at room temperature. By this solution the setting time can be adjusted and varied between wide limits independent of the temiperature.

Example 4

Hard setting, non-elastic smoothing mass is produced from following components:

Component A:

% by weight % by weight 40 % by weight bitumen B-30 (softening point 60 OC, penetration 20-45) fluid C 17- C 18 vegetable fatty acid quartz sand of 1-3 mm particle size Component B:

1 % by weight sulfur 9 by Weight drying vegetable oil varnish by weight powdered lime hydrate (hydrated lime powder.) 12 - % by weight quartz of 0-1 mm particle size.

The two components are blended in mass ratio 1:1. Rapid setting mixture is obtained. Coal tar pitch or blown gasoline pyrolysis tar pitch of 60 0 C soften- ing point can be used partly or fully instead of bitumen.

Example 5

Smoothing mass dyeable with oxide dye- stuffs can be prepared from the following components:

Component % by weight liquid distilled fatty acid petroleum tar (iodine number 100) % by weight crushed, sized gravel of 1-3 mm particle size Component E:

9 % by weight rape oil 1 % by weight sulfur 10 % by weight MgO (calcinated magnesium) 80 % by weight dolomit or limestone of 0-1 mm particle size.

The two components are blended in 1:1 mass ratio. For dyeing 5-10 percent iron oxide red or oxide green dyestuff is added to the smoothing mass until the desired colour is attained.

Example 6

For joint sealing and adhering vertical surfaces component B according to Example 1 is mixed in a ratio of 1:1 or 1:2 with component A of following composition:

Q 13 - Component A:

38.0 % by weight bitumen B-90 2.0 % by weight 60/40 polybutadiene-polystvrene 19.5 % by weight 40.5 % by weight copolymer pine oil fatty acid micro silica powder (92 % SiO 2 content, formed as waste at the production of ferrosilicium, which is in 50 per cent composed from particles below 6 micron) On producing the component A modified bitumen is homogenized in warm state with the micro silica powder, and the pine oil. fatty acid added. Subsequent procedure are carried out similarly as in Example 1.

Example 7

Product suitable to cementing and pouring Mass is prepared from the following components:

Component A:

% by weight bitumen B-50 '-. by weight oleic acid (C 17- C is) % by weight factice with 19 % sulfur content, made of pre-treated rape oil Component B: Ca (OH) 2 zinc oxide rubber ground from tyre, particle size 1 mm max.) qU2rtz sand (particle size 1 mm max.

1 % by weight 9 % by weight 10 % by weight % by weight 14 - Bitumen is mixed at 160-170 0 C with the hard factice, cooled and the oleic acid is added.

Component B is made by mixing zinc oxide, ground rubber and quartz sand.

Example 8

Product suitable as pouring mass is made from the following components:

Component A:

% by weight bitumen B-90 % by weight % by weight oleic acid (C 17-Cl,) or naphtenic acid medium hard factice with 19 % sulfur content from rape oil Component B:

% by weight chlorinated lime (25-30 % active % by weight chlorine content ground rubber flour (according to Example 7 % by weight quartz sand The composition is prepared according to the method described in Example 7.

Example 9

Cementing and pouring mass is prepared from the following components:

Component A according to Example 8 and Component B:

by weight 5 by weight 20 % by weight zinc oxide magnesium oxide around rubber 1 1 % by weight quartz sand The composition is prepared according to Example 7.

Claims

1. Cold setting composition comprisJLng two-components, w h e r e i n Component A contains 40-60 % by weight bitumen or with 2-6 % by weight polystyrene-polybutadiene polymer modified bitumen 20-40 % by weight 20140 % by weight % by weight 10-20 % by weight 60-80 % by weight liquid fatty acid, filler, and component B contains liquid f ECtice of 5-10 % by weig L cj h t sulfur content made from drying or semi-drying vegetable oil. and sulfur, zinc or magnesiumi, oxide, alkali-earth oxide or -hydroxide, chlorinated lime or the MiXture thereof, filler, preferably quartz or sand of 0-3 mm particle size or 0-20 % by-weight groud rubber and the ratio of components A and B is 1-3:3-1.

2. Composition according to Claim 1, w h e r e i n bitumen and fatty acid is replaced by fatty acid goudron (distillation residue).

3. Composition according to Claim 1, w he r e i n liquid fatty acid is oleic acid or oleine, pine oil fatty acid or mixed liquid vegetable fatty acid.

11 j 1-3: 3-1.

- 17. -

4. Composition according to Claim 1, w h e r e i n the drying or semi-drying oil is sun- flower-, rape-, hempseed-, olive-, fish-, linseedor soybean oil or varnish comprising any of the said oils.

5. Composition according to Claim 1, w h e r e i n lime hydrate powder is used as alkali earth oxide.

6. Cold setting composition comprising two components, wh e r e i n Component A contains:

40-60 by weight bitumen 20-40 by weight liquid fatty acid having C 17-C is carbon atoms or naphtenic acid - 10 % by weight solid sulfur factice with 17-19 by weight total sulfur content, made from pre-treated rape oil and sulfur, and Component B contains:

10-20 % by weight zinc oxide, magnesium oxide, calcium oxide or hydroxide, or chlorinated lime or their mixture 10-90 % by weight filler 1-20 % by weight ground rubber the mixing of components A and B being 1

7. A corniposition as clained in any one of claims 1 to 5, wherein the vegetable oil in comPonent B is partly or completely replaced by tar.

8. A composition subs tanti ally as hereinbefore described in any one of Examples 1 to 9.

9. A method of sealing a structure which comprises applying to the structure a 1:3 to 3:1 mixture of components A and B as defined in any one of claims 1 to 8.

i Published 1988 at The Patent Office, State House, 66.71 High Holborn, London WC1R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mar3r Cray, Kent. Con. 1/87.