AU7170800A

AU7170800A - Improved phenolic resin

Info

Publication number: AU7170800A
Application number: AU71708/00A
Authority: AU
Inventors: Franck Weber
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-11-30
Filing date: 2000-11-20
Publication date: 2001-05-31
Also published as: PL344174A1; CZ20004398A3; TR200402778T4; PL201241B1; DE60012853D1; FR2801602A1; DE60012853T2; EP1106670A1; CZ299117B6; ZA200006722B; FR2801602B1; EP1106670B1; ES2223435T3

Description

U.

(i P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

TO BE COMPLETED BY APPLICANT Name of Applicant: Actual Inventor: Address for Service: Invention Title: A. WEBER FRANCK WEBER CALLINAN LAWRIE, 711 High Street, Kew, Victoria 3101, Australia IMPROVED PHENOLIC RESIN The following statement is a full description of this invention, including the best method of performing it known to me:- 17/1 l/00,mcl 1688.cs.doc,l la-

DESCRIPTION

A subject-matter of the present invention is a product based on phenolic resin exhibiting improved characteristics of flexibility similar to expanded polyurethanes, that is to say not exhibiting total adhesive bonding failure, even seven days after its application.

The invention relates in particular to the field of soil consolidation in mining operations and in civil engineering.

The characteristics of these consolidation products are evaluated by flexural tests on test specimens with a square cross section adhesively bonded to one another by a polymerized product with a thickness of 3 mm. The adhesive bonding values and the displacement are measured over time and the results are made use of in a curve by comparison with the characteristics of products regarded as supple, such as polyurethanes.

The appearance of this curve is a bell-shaped •c curve, which allows the flexibility to be thoroughly characterized. Such a curve, represented below, shows, on the abscissa, the displacement of the flexural jaw and, on the ordinate, the force applied or the adhesive bonding strength calculated.

0* 4-) (mm) cn Displacements (ITm) 2 Currently, in the context of mining operations and in particular the mining of coal, recourse is commonly had to organic products, among which appear in particular phenolic resins, in the formulation of products for consolidating or rendering leaktight. Most of these products certainly make it possible to satisfy their essential objective but all exhibit the disadvantage either of insufficient adhesive bonding, or of being brittle after polymerization, or of being inflammable, or exhibit reaction temperatures which may be higher than the self-ignition temperatures of coal.

Thus, twin-component products, resol and catalyst based on sulphonic acids, to which linear polyesters and a resorcinol/formaldehyde condensate are added, are known from FR-A-2 774 384 or corresponding EP-A-0 934 994, which products are non-flammable and with a low reaction temperature. These products, which polymerize at a temperature below 100 0 C, certainly make it possible to gain with regard to flexibility but, however, exhibit, after polymerization, the disadvantage of rapidly yielding to a flexural load by o*oo total failure, beyond a certain polymerization time.

This total failure is clearly apparent in the curve i, represented above, regarding a product according to the state of the art.

In fact, all the products based on phenolic resin known to date, although being supple and flexible immediately after their polymerization and retaining stability over time, reveal, by the mechanical measurement of the deflection, that the desired characteristic as regards flexibility, i.e. a bellr....shaped curve, is not retained.

Furthermore, a twin-component product acting as base in the chemistry of phenolics, which is a phenol/formaldehyde resin to which trichlorotrifluoroethane is added as swelling agent, is known by FR-A-2 484 529. Such a product makes it possible to obtain a non-flammable phenolic foam but one which does not exhibit any lasting characteristic of flexibility.

3 An aim of the present invention is to overcome these disadvantages by providing a product based on phenolic resin which is intended for soil consolidation, this product being employed by injection and exhibiting improved characteristics of flexibility similar to expanded polyurethanes, the flexural test of which shows a bell-shaped curve without total adhesive bonding failure, even after a period of several days.

The corresponding flexibility curve 3 is represented above and may be compared with that, 2, of a polyurethane.

To this end, the product, which is a twincomponent product comprising a resin based on a resol and a catalyst based on sulphonic acid, is characterized in that it comprises, as additives, a surfactant or a combination of surfactants, resorcinol, a novolak resin or a sulphonated novolak resin and/or a dispersion of precrosslinked resol, these additives being invariably added to the resin component or to the catalyst component.

These various additives make possible, by oo reaction with the sulphonic acid of the catalyst and with the resol of the resin, the formation of groups capable of forming a three-dimensional network with the resol of the resin.

According to one characteristic of the invention, the surfactant or surfactants are added in a large amount to the resin part and/or to the catalyst part. The result of this is that, during polymerization 30 as a thin layer, the product in accordance with the invention exhibits excellent adhesion to the substrate, a high wettability index and flexibility characteristics which are maintained over a long period of time.

The types of surfactants which can be used are the types generally known in industry and more particularly nonionic surfactants. To this end, among nonionic surfactants, the most effective are polyethoxylated fatty alcohols, taken alone or in 4 combination with one another or with products such as polyols, polyesters, and the like. These surfactants can be added without distinction to the resin part or to the catalyst part, according to the desired characteristics.

The resol used in the resin part can be either a resol resulting solely from condensation of formaldehyde with phenol in a basic medium or can be a resol resulting from condensation between substituted phenols, such as alkylphenols, cresols or xylenol, and formaldehyde or its derivatives.

According to another characteristic of the invention, the resin component can be provided with an additive, such as an organosilane intended to promote the adhesion, in particular to any inorganic substrate, or such as a furfuryl alcohol, which makes it possible to increase, if necessary, the reactivity of the mixture, so that the final mixture of adhesive bonding product can be perfectly suited to the conditions of application.

It is also possible to obtain expansion of the "e product by mechanical foaming, by addition of air or of gas, or by chemical foaming, by addition to the resin component of a porogenic agent which gives off a gas by reaction with an acid medium, such as, for example, sodium bicarbonate. The cellular complex thus formed is stabilized by the surfactant or surfactants present in the resin component or in the catalyst component.

The product based on phenolic resin in accordance with the invention exhibits the following composition: Resol from 10% to 50%, preferably Sulphonic acid from 10% to 50%, preferably Surfactant from 5% to 40%, preferably Novolak, sulphonated novolak or dispersion of resol in an excess of sulphonic acid from 5% to 40%, preferably 17.5% Resorcinol from 1% to 15%, preferably 5 As a preferential example, the product according to the invention will be provided in the form of a twin-component product comprising: a resin part which is composed of Resol Surfactants a catalyst part which is composed of Sulphonic acid and preferably phenolsulphonic acid Sulphonated novolak obtained by sulphonation of a novolak resin or by polycondensation of phenolsulphonic acid and of formaldehyde or of paraformaldehyde Resorcinol In an alternative form, the product can also be provided in the form of a twin-component product comprising: a resin part which is composed of Resol Surfactants o a catalyst part which is composed of Sulphonic acid and preferably phenolsulphonic acid Crosslinked sulphonic acid/resol mixture dispersible in the medium Resorcinol The resin and catalyst components can be employed in a ratio of between 1:4 and 4:1 and 30 preferably in a ratio of 1/1.

The product which is a subject-matter of the present invention is intended to be used more particularly in the field of mining operations and civil engineering for the consolidation of soil or of coal and for rendering leaktight to air and to gas, in particular by injection.

In addition, the product in accordance with the invention exhibits a low reaction temperature, a good 6 adhesive bonding capability and a non-flammability which is particularly advantageous as regards safety.

Of course, the invention is not limited to the embodiment disclosed. Modifications remain possible, in particular from the viewpoint of the composition of the components of the product or by substitution of technical or chemical equivalents, without for all that departing from the field of protection of the invention.

Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof oooo oo* ooooo*

Claims

1. Twin-component product based on phenolic resin, comprising a resin based on a resol and a catalyst based on sulphonic acid, intended for injection for soil consolidation, exhibiting improved characteristics of flexibility similar to expanded polyurethanes, the flexural test of which shows a bell-shaped curve without total adhesive bonding failure, even after a period of several days, characterized in that it comprises, as additives, a surfactant or a combination of surfactants, resorcinol, a novolak resin or a sulphonated novolak resin and/or a dispersion of precrosslinked resol, these additives being invariably added to the resin component or to the catalyst component.

2. Product according to Claim 1, characterized in that the surfactant or surfactants are added in a large amount to the resin part and/or to the catalyst part.

3. Product according to Claim 2, characterized in that the surfactants are nonionic surfactants.

4. Product according to either one of Claims 2 and 3, characterized in that the surfactants are polyethoxylated fatty alcohols, taken alone or in combination with one another or with products such as polyols, polyesters, and the like.

5. Product according to Claim 1, characterized in that the resol used in the resin part is either a resol resulting solely from condensation of formaldehyde with S 30 phenol in a basic medium or a resol resulting from condensation between substituted phenols, such as alkylphenols, cresols or xylenol, and formaldehyde or its derivatives.

6. Product according to Claim 1, characterized in that the resin component is provided with an additive, such as an organosilane or such as a furfuryl alcohol.

7. Product according to Claim 1, characterized in that the resin component has a porogenic agent, such as sodium bicarbonate, added thereto. 8

8. Product according to any one of Claims 1 to 7, characterized in that it exhibits the following composition: Resol from 10% to 50%, preferably Sulphonic acid from 10% to 50%, preferably Surfactant from 5% to 40%, preferably Novolak, sulphonated novolak or dispersion of resol in an excess of sulphonic acid from 5% to 40%, preferably 17.5% Resorcinol from 1% to 15%, preferably

9. Product according to any one of Claims 1 to 7, characterized in that it is provided in the form of a twin-component product comprising: a resin part which is composed of Resol Surfactants a catalyst part which is composed of Sulphonic acid and preferably phenolsulphonic acid Sulphonated novolak obtained by ~sulphonation of a novolak resin or by polycondensation of phenolsulphonic acid and of formaldehyde or of Sparaformaldehyde Resorcinol Product according to any one of Claims 1 to 7, characterized in that it is provided in the form of a twin-component product comprising: a resin part which is composed of Resol Surfactants a catalyst part which is composed of Sulphonic acid and preferably phenolsulphonic acid Crosslinked sulphonic acid/resol mixture dispersible in the medium Resorcinol -9-

11. Product according to either one of Claims 9 and 10, characterized in that the resin and catalyst components are employed in a ratio of between 1:4 and 4:1 and preferably in a ratio of 1/1. DATED this 17 th day of November, 2000 A. WEBER By their Patent Attorneys: CALLINAN LAWRIE e) 17/1 1/00,mcl 1688. sped. doc, 9