WO1997014752A2 - Composition polymerisable, procede d'application d'une composition polymerisable et dispositif d'application d'une composition polymerisable - Google Patents

Composition polymerisable, procede d'application d'une composition polymerisable et dispositif d'application d'une composition polymerisable Download PDF

Info

Publication number
WO1997014752A2
WO1997014752A2 PCT/GB1996/002551 GB9602551W WO9714752A2 WO 1997014752 A2 WO1997014752 A2 WO 1997014752A2 GB 9602551 W GB9602551 W GB 9602551W WO 9714752 A2 WO9714752 A2 WO 9714752A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymerisable composition
composition
polymerisable
metal
layer
Prior art date
Application number
PCT/GB1996/002551
Other languages
English (en)
Other versions
WO1997014752A3 (fr
Inventor
Roman Aleksandrovich Veselovsky
Boris Artemovich Lyashenko
Original Assignee
Marubeni Uk Plc
Veselovsky Roman Aleksandrovic
Boris Artemovich Lyashenko
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Marubeni Uk Plc, Veselovsky Roman Aleksandrovic, Boris Artemovich Lyashenko filed Critical Marubeni Uk Plc
Priority to AU73131/96A priority Critical patent/AU7313196A/en
Publication of WO1997014752A2 publication Critical patent/WO1997014752A2/fr
Publication of WO1997014752A3 publication Critical patent/WO1997014752A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
    • B05C3/18—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material only one side of the work coming into contact with the liquid or other fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C7/00—Apparatus specially designed for applying liquid or other fluent material to the inside of hollow work
    • B05C7/04—Apparatus specially designed for applying liquid or other fluent material to the inside of hollow work the liquid or other fluent material flowing or being moved through the work; the work being filled with liquid or other fluent material and emptied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
    • B05C9/08—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation
    • B05C9/10—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation the auxiliary operation being performed before the application
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/281—Polyepoxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/455—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction
    • C04B41/4556—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction coating or impregnating with a product reacting with the substrate, e.g. generating a metal coating by surface reduction of a ceramic substrate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/10—Coatings characterised by the materials used by rubber or plastics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants

Definitions

  • a POLYMERISABLE COMPOSITION A METHOD OF APPLYING A POLYMERISABLE COMPOSITION AND A DEVICE FOR APPLYING A POLYMERISABLE COMPOSITION
  • the present invention relates to a polymerisable composition, a method for applying a polymerisable composition and a device for applying a polymerisable composition and, more particularly, to the use of a polymerisable adhesive composition in the provision of protective coatings on metal objects, the reinforcement of concrete and the production of a particle/chipboard from sawdust or other waste materials.
  • a very common problem is, for example, the rusting and corrosion of metal pipes.
  • a number of materials are known to be useful in protecting the internal surfaces of metal pipes, such as steel pipes, for example, polyvinyl chloride and various pulverulent thermoplastics.
  • a combination of materials varying in composition and state of aggregation, a first polymeric material being applied in powder form as a primer and a second oligomeric material being applied to the layer of primer, has also previously been used to protect the surfaces of metal objects, the primer acting as catalyst for the hardening of the subsequently applied oligomers. See, for example, British Patent No. 2094178.
  • the pipes will almost invariably have defects in the form of holes and variations in the thicknesses of their walls and their internal surfaces will be encrusted with conglomerates varying in shape, dimensions, solidity and chemical composition.
  • Such encrustations include the products of chemical corrosion caused by the action of water and acids present in the soil, products of electro chemical corrosion caused by chemical agents and stray electrical currents in the soil, particularly where pipes are laid parallel to underground electric cables, mechanical impurities in liquid or gaseous conveying media and encrustations due to chemically combined or free water (it is almost impossible to dry the cavities of underground pipes completely).
  • this method does satisfy certain requirements, this method has the disadvantage that polymerisable epoxy compositions cannot usually be applied to surfaces until the surfaces have been carefully cleaned, which is practically impossible in the repair of underground pipes. Furthermore, even though epoxy resins have high adhesive activity when liquid at room temperature, they are not always capable of effectively wetting metal surfaces at the low temperatures found in underground pipes.
  • polymerisable compositions having the high adhesive activity of epoxy resins it is also desirable to be able to wet the surfaces to be coated under varying conditions and to adjust the viscosity of the polymerisable composition within very wide limits so that the polymer composition may be hardened over a wide range of temperatures without heating.
  • the use of simple equipment to apply such polymerisable composition to the underground pipes is also preferable.
  • “Raw” coatings can be applied using the method and device known from German Patent No. 3 147 396.
  • the method disclosed by German Patent No. 3 147 396 comprises a preliminarily cleaning step involving mechanical removal of impurities from the metal surface, supplying (pouring) portions of polymerisable composition into a section of piping which has been isolated for repair, calibrating the thickness of the "raw” coating by means of a scraper and curing the polymerisable material until it hardens to form a protective coating.
  • the device for carrying out this method comprises four main parts, connected in succession on a common support element (rod), including a first control and a first scraper section which is provided with means for applying a layer of polymerisable composition to the metal surface, and a second control and a second scraper section, which serves as the means for calibrating the thickness of the layer of the polymerisable composition.
  • a common support element including a first control and a first scraper section which is provided with means for applying a layer of polymerisable composition to the metal surface, and a second control and a second scraper section, which serves as the means for calibrating the thickness of the layer of the polymerisable composition.
  • Each of the above-mentioned control sections comprises U-shaped resilient brackets which lie along the geometrical axis of the rod and which have ends which are radially bent and secured to the rod.
  • the second control section is disposed on the rod and can move axially in reciprocation.
  • the scraper in the first section has a constant diameter, considerably smaller than the narrowest diameter of the pipe to be repaired, whilst the scraper in the second section comprises an outer cone made of resilient material and firmly secured to the rod and an inner cone made of harder material and secured to the second moveable control section.
  • the viscosity and working life of the above-mentioned previously disclosed polymerisable compositions can be adjusted within very wide limits and the presence therein of isocyanates and surface-active substances (i.e. polyfluorinated alcohol telomer and the block co-polymer of polyorganosiloxane and polyoxyalkylene) enable these compositions to be used for forming anti-corrosive coatings in moist mediums such as that found in underground pipes.
  • isocyanates and surface-active substances i.e. polyfluorinated alcohol telomer and the block co-polymer of polyorganosiloxane and polyoxyalkylene
  • isocyanates may undergo uncontrolled reactions with moisture irrespective of the source of moisture, resulting in the undesirable evolution of carbon dioxide and local foaming of the coating material.
  • Isocyanates can react with oligoesters, which always contain residual quantities of water, and free reactive hydroxyl and carboxyl groups in this way, so that use of isocyanates in oligoester compositions significantly reduces the usefulness of such compositions for underground repair work and makes it practically impossible to obtain continuous anti-corrosive and hematic coatings over the entire surfaces of pipes to be repaired.
  • Wood-chip boards are obtained by pressing wood chips mixed with urea formaldehyde or resol phenol formaldehyde resin at a temperature of 170 - 180°C.
  • the binder makes up 10 - 15% of the weight of the chips.
  • Thermoplastics polyethylene, polyvinyl chloride etc
  • synthetic resins epoxides, polyesters, etc
  • binders for producing pressed articles also require careful drying of the wood filler, and also the consumption of binder in this case is 40 - 60%, which greatly increases the cost of the pressed articles
  • a recently-discovered class of polymerisable compositions based on polyisocyanates can be used in order to reduce the toxicity of the compression-moulded articles and increase their resistance to water.
  • the method of manufacturing wood-chip boards comprises drying the crushed wood, mixing it first with the inorganic binder component and then with the organic component, shaping a mat and hot compression moulding.
  • compositions have a disadvantage in that all their components diffuse into the mass of particles of wood filler, which increases the consumption of the compositions.
  • compression-moulding temperature is above 100°C and requires careful drying of the crushed wood, which increases the energy consumed in the production of wood-chip board.
  • Repeated attempts have been made to use polymer compositions for impregnation of soil, concrete, wood and plaster. There are descriptions of use of compositions based on polyepoxides, unsaturated polyester resins, carbamide and phenol-formaldehyde resins, diisocyanates etc.
  • wet concrete and other materials When wet concrete and other materials are impregnated, the water in the pores prevents the polymer composition penetrating through the concrete.
  • This obstacle is one of the main reasons why wet concrete is impregnated by using water-soluble mixtures of inorganic salts such as "Penetron", which react with the components of the concrete block and are deposited in the pores, when they change into an insoluble state.
  • These mixtures can reduce the porosity of concrete, but polymer compositions are necessary as impregnating liquids for increasing characteristics such as deformability, chemical stability, resistance to abrasion, and strength.
  • One aim of the present invention is, therefore, to provide a significantly improved polymerisable composition having at least one or more of the following properties: high adhesive and cohesive activity, high resistance to aggressive mediums, an adjustable working life despite medium conditions, an adjustable hardening/curing time despite medium conditions, a viscosity which can be adjusted within a wide range of temperatures without heating, the ability to wet surfaces effectively in a wide range of medium conditions (including the ability to wet moist surfaces and surfaces contaminated with impurities which cannot be mechanically removed) and in which uncontrolled chemical reactions are eliminated.
  • Another aim of the present invention is to provide an improved method for adhering materials, an improved method for applying a polymerisable composition to a surface which enhances the polymerisation process with minimum thermal energy consumption and a simple device for applying the polymerisable composition to a surface.
  • An object of one aspect of the invention is to improve the qualitative and quantitative composition by producing a solidifying low-viscosity composition which can additionally physically and chemically activate the surface of the pores in a wet concrete block, so as to ensure that the solidifying composition adheres firmly to the concrete and so as to prevent the components being separated by adsorption during the concrete impregnation process.
  • a polymerisable composition comprising a mixture of an unsaturated oligoester, a cross-linking agent and a complex surface-active agent, wherein the complex surface-active agent comprises at least one of an oxyethylated alkyl phenol ester having the general formula:
  • the surface-active agent in this polymerisable composition ensures effective wetting of the surface to which the composition is applied in a wide range of conditions (including effective wetting of moist and contaminated surfaces) and also improves adhesive strength.
  • the polymerisable composition further comprises at least one accelerator.
  • the accelerator acts to improve cohesive strength.
  • the polymerisable composition further comprises a filler.
  • the filler acts to improve chemical resistance of the cured product.
  • the filler comprises a dispersed material in the form of flakes having thicknesses of 0.1 to 20nm and diameters of 0.1 to 5.0mm.
  • the polymerisable composition further comprises at least one polymerisation initiator.
  • the polymerisable composition of the present invention may be provided as a one-part mixture, in which the polymerisable composition includes the polymerisation initiator, or a two-part mixture, in which the polymerisation initiator is provided separately to the polymerisable composition and then added to the polymerisable composition at the point of use.
  • the polymerisable composition comprises, per 100 parts by weight of mixture of oligoester and cross-linking agent, the following proportions of ingredients (in parts by weight):
  • This polymerisable composition makes use of two types of additive, one to increase the adhesion effect of the polymer used (the complex surface-active agent) and the other to increase the cohesive effect (the accelerator).
  • the oxyethylated alkyl phenol ester and alkyl polybenzyl pyridinium chloride are present in the polymerisable composition in the following quantities (in parts by weight):
  • the oligoester comprises an oligomaleate selected from the group consisting of:
  • the cross-linking agent comprises a monomer selected from the group consisting of styrene, triethylene, glycol dimethacrylate and methyl methacrylate.
  • a device for applying a polymerisable composition to a surface of a metal object comprises means for applying a layer of polymerisable composition to the surface of the metal object, the application means having an enclosed space for at least partially filling with the polymerisable composition in use, and means disposed within the enclosed space for exposing, in use, the surface of the metal object to which the layer of polymerisable composition to be applied.
  • This device provides a very simple means for applying a polymerisable composition to a wide range of objects, including the internal surfaces of underground pipes, in situ.
  • the means for exposing the surface of the metal object under the layer of applied polymerisable composition comprises a first micro-scalper or needle mill. This physically activates the surface of the metal object to improve the strength of adhesion of the cured product to the metal object.
  • a second micro-scalper or needle mill is disposed outside the enclosed space, ahead of the application means. This allows a preliminary cleaning and de-scaling step to be carried out before application of the polymerisable composition, which again adds to improvement of adhesive strength.
  • each micro-scalper or needle mill is connected to a generator of electric pulses for electro-machining the surface of the metal object. Electro-machining of the surface of the metal object creates a free radical status to which a chemically active polymerisable composition may be added, resulting in an adhesive activity of greatly improved strength.
  • each of the micro-scalpers or needle mills comprises a metal brush.
  • the device further comprises means for calibrating the thickness of the layer of applied polymerisable composition.
  • the calibrating means comprises a resilient element for contacting the layer of applied polymerisable composition, the resilient element being secured, in use, to the application means.
  • a method of adhering materials which method comprises physico-chemically reacting a first active surface having a free radical status with a second active surface having a molecular active centre.
  • the first active surface comprises a surface of a metal object and the second active surface comprises a polymerisable composition, the first active surface being activated by electro-machining.
  • the first active surface comprises a concrete surface and the second active surface comprises a polymerisable material, the first active surface being activated by extraction of calcium.
  • the first active surface comprises sawdust or an agricultural waste product and the second active surface comprises a polymerisable binding composition, the first active surface being activated by compression power and subsequent heating processes.
  • the agricultural waste product comprises rice, straw or husks.
  • a method of applying a polymerisable composition to a metal surface comprises distributing the polymerisable composition over a working area of the metal surface and physically activating the working area of the metal surface until residues of solid impurities are fragmented and the surface of the metal under the layer of applied polymerisable composition is exposed.
  • Such a method greatly enhances the strength of adhesion of the final product to the underlying surface.
  • the method further comprises the step of physically cleaning the working area of the metal surfaces by mechanically removing impurities before distributing the polymerisable composition over the working area.
  • the physical activation and/or physical cleaning of the working area of the metal surfaces carried out by micro-scalping.
  • the physical activation and/or physical cleaning of the working area of the metal surfaces is carried out by electro-machining.
  • Electro-machining of the surface of the metal object creates a free radical status to which addition of a chemically active and polymerisable composition will result in an adhesive activity of greatly improved strength.
  • electro-machining is carried out by supplying electric pulses to the working area of the metal surface via a micro-scalper, needle mill or metal brush.
  • the method further comprises the step of calibrating the thickness of the layer of distributed polymerisable composition.
  • the method further comprises the step of curing the layer of polymerisable composition to form a protective coating.
  • a binding material comprising an organic component comprising a polyisocyanate, a hardening agent and an inorganic salt.
  • the non-organic salt is for binding the humidity and strengthening of the end product.
  • Such a binding material may be used for binding sawdust and agricultural waste so that the end product is again stronger, non-toxic and economically safe and does not require an additional protective coating for use in open air. Only a reduced amount of binding material is, again, required and sawdust and agricultural wastes having humidity up to 40% can be used.
  • the present invention further provides a method for mixing a filler with a binder according to the present invention wherein the filler is initially mixed with the hardening agent, subsequently with the inorganic salt and then finally with the organic component.
  • the present invention further comprises a method of producing compression moulded articles comprising moulding a mat of a filler with a binder according to the present invention and hot compression moulding the mat in a temperature range of 60 - 100°C. It is preferred that the filler is not previously subjected to drying.
  • One aspect of the invention relates to the art of moulding compressed articles, more specifically to the qualitative and quantitative composition of polymer binders; a method of applying polymer binders to particles of compressed material and parameters of the industrial process of compressed articles.
  • the invention may most effectively be applied to production of wood-chip boards and pressed articles made from sawdust, waste from hemp, flax, cotton and rice processing and other organic powders and mixtures thereof with inorganic powders.
  • an oligomer is introduced into the polyisocyanate composition, the oligomer comprising a polyester with polyoxyethylene fragments in the chain, applied with a dispersion of calcium hydroxide (lime paste) in water, and a solution of sodium silicate (water glass).
  • a further aspect of the invention relates to the quantitative and qualitative make-up of polymer compositions for impregnating dry or wet concrete.
  • composition for reinforcing concrete comprising phenyl glycidyl ester, having the general formula pyridine and a solidifying epoxide composition comprising epoxide oligomer and an amine curing agent.
  • An epoxide oligomer is a substance containing two or more primary amine groups.
  • Pyridine is the aromatic compound C 6 H 5 N.
  • composition of the aspect of the invention may most effectively be applied to impregnation of concrete constructions or buildings in order to improve their strength, sealing-tightness and protection from corrosion, or for impregnating other kinds of porous materials such as soil, wood, asphalt, splint-slab and plaster boards, loose corrosion on the surface of metal articles and the like.
  • Phenyl glycidyl ester (FGE) and pyridine adsorbed on the surface of the concrete pores, make them water- repellent and provide the conditions whereby water is displaced from the interior of the concrete block and replaced by the polymer composition.
  • ingredients of a preferred composition are taken in the following proportions (in parts by weight):
  • Figure 1 shows a part cross-sectional plan view of a first device for applying a polymerisable composition to a surface, the device shown being located within a portion of a pipe;
  • Figure 2 shows a part cross-sectional front view of a second device for applying a polymerisable composition to a surface, the device shown being located on a curved surface.
  • oligoesters and cross-linking agents which may be used in the polymerisable composition of the present invention are set out in Table 1 below, although any other suitable oligoester or cross-linking agent may be used, including any of the numerous monomers and oligomers currently on the market.
  • the oligomers and cross-linking agents mentioned in Table 1 are relatively inexpensive.
  • the mixtures of the oligomers and cross-linking agents set out in Table 1 can be prepared by standard techniques, for example, metering and agitation and the proportions given in column 3 of Table 1 are, given by way of indication only and any other suitable proportions may be used.
  • Mixture PN-1 is the least expensive to prepare.
  • Mixture PN-609 yields practically non-toxic coatings and is, therefore, preferable for repair of underground pipes carrying drinking water. Other properties of mixture PN-609 are very similar to those of mixtures PN-69 and PN- 10.
  • mixture PN-69 can provide highly resilient coatings and is, therefore, preferred for repair of, for example, ship deck facings.
  • Mixture PN-10 yields the most chemically stable coatings, particularly against acids in crude oil and is, therefore, preferred for repair of pipes carrying such material.
  • compositions of the present invention also comprise a complex surface-active agent and, according to one example of the invention, the complex surface-active agent contains the following components in parts by weight per 100 parts by weight of oligomer:
  • This surface-active agent acts to reduce the free energy of the system, thereby improving wettability of low-energy substrates, so as to ensure efficient coating of moist metal surfaces or metal surfaces within the environment of other liquids and penetration of the polymerisable composition into any defects in the surface to be coated.
  • the surface-active agent also increases the adhesive strength, which is surprising in view of the fact that, in the majority of cases, addition of surfactants to the polymerisable composition results in a decrease of adhesive strength or acts within only a narrow range of surfactant concentrations, this range depending on numerous factors, including adhesive viscosity, cure rate, gluing temperature, etc.
  • peroxide-type or hydro-peroxide-type initiators such as benzyl peroxide, methyl, ethyl, ketone peroxide or isopropyl benzene hydroperoxide.
  • One example of the polymerisable composition of the present invention comprises at least one of these polymerisable initiators in the proportion of 0.1 to 5.0 parts by weight per 100 parts by weight of oligoester, or in any other quantity sufficient to initiate the polymerisation process.
  • the polymerisation initiator can be manufactured and sold separately from the rest of the composition.
  • One example of the polymerisable composition of the present invention comprises at least one of these accelerators, or other suitable accelerators, in the proportion of 0.01 - 2.0 parts by weight per 100 parts by weight of oligomer or in any other quantity sufficient for adjusting the working life of the composition.
  • the polymerisable composition of the present invention may also contain a highly dispersed natural mineral (e.g. basalt) or artificial (e.g.
  • filler material in the form of flakes which preferably have a thickness of 0.1 to 20nm and a diameter of 0.1 to 5.0 mm are preferably provided in the proportion of 5.0 to 100 parts by weight per 100 parts by weight of oligomer and preferably between 80/20 and 50/50 parts by weight of filler to parts by weight of oligomer.
  • filling agents such as basalt flake
  • the addition of filling agents such as basalt flake to the polymerisable compositions of the present invention helps to increase the chemical resistance of the resulting product, an increased proportion of filler material providing an increased chemical resistance.
  • a first package may be prepared containing a mixture of unsaturated oligoesters, a cross-linking agent, one or more suitable accelerators or enhancers and a complex surface-active agent and a second package containing polymerisation initiators.
  • the two packages would then need to be mixed in order to initiate the polymerisation process.
  • Initiators and accelerators were also included within the above-mentioned limits, whereas the quantities of oxyethylated alkyl phenol ester and alkyl polybenzyl pyridinium chloride used fell both within and outside the aforementioned limits.
  • Samples of the polymerisable compositions prepared according to Table 2 were applied in various media (air, under water or under a layer of oil) to the surfaces of specimens of worn steel pipes having defects in small surface areas (not more than 1% of the area of the test piece and not more than 1mm 2 each time) or having impurities in the form of loose layers of rust with interspersed solid oxide conglomerates in various media.
  • the resulting cured coatings were visually evaluated with regard to their continuity and the strength of adherence to the underlying material was determined according to standard techniques.
  • the surface active additives ensured sufficiently strong adhesion to the underlying material and, when used within the specified limits, improved the adhesive strength.
  • the polymerisable compositions of the present invention are particularly useful in repairing and protecting worn, underground water, gas or oil pipes etc. in situ, without continuous uncovering of pipe runs, the polymerisable compositions of the present invention may be used to provide protective, anti-corrosive, chemical resistant, hematic coatings on the internal or external surface of any metal object, for example, metal reservoirs for holding liquids or gases, metal tanks, and metal components of ships' holes, deck coverings and hole platings etc.
  • the device of the present invention may be used to apply a polymerisable composition to the internal or external surface of a metal object, irrespective of the shape of the surface, and certain features of the device greatly enhance the polymerisation process and the adhesive strength of the coating formed.
  • the devices shown in Figures 1 and 2 of the accompanying drawings each comprise a first support element in the form of a shaft 1 secured to a rotary drive (not shown).
  • a rubber vessel or plunger 2 for applying a layer of polymerisable composition to the surface of a metal object is connected to the fist shaft 1 and is provided with an enclosed space for at least partly filling with a polymerisable composition.
  • a calibrating device 3 for calibrating the thickness of the layer of applied polymerisable composition is secured to the rubber vessel 2 and is adapted to make contact with the layer of applied polymerised composition.
  • a micro-scalper or needle mill comprising a metal brush 4, for physically activating the metal surface.
  • the device further comprises a second micro-scalper or needle mill 5 disposed outside the rubber vessel 2, adjacent the rubber vessel 2 and ahead of the normal direction of movement of the rubber vessel 2 for applying the polymerisable composition.
  • the first and, if present, second micro-scalpers or needle mills 4 and 5 are connected to generators 6 and 7 respectively, which generators 6, 7 generate electric pulses for the purpose of electro-machining the surface of the metal object.
  • the device shown in Figure 1 is used for applying coatings to the internal surfaces of pipes.
  • the rubber vessel is formed by two opposed discs 2,3 which are resilient, at least in their peripheral parts, and are disposed in sequence on the first shaft 1.
  • the rear disc in the normal direction of movement also forms a calibrating device 3 behind the normal direction of movement of the rubber vessel for applying a layer of polymerisable composition to the surface of the metal object.
  • the vessel in Figure 1 has a rectangular cross-section and is adapted to fit within the pipe with the long faces of the rubber vessel contacting the internal surfaces of the pipe.
  • Each metal brush 4, 5 in Figure 1 comprises a disc with a plurality of needles extending therefrom.
  • the metal brushes 4, 5 shown in Figure 1 are secured to the same first shaft 1, with the needles extending radially therefrom so as to contact the inner surfaces of the pipe to which the polymerisable composition is to be applied.
  • the first metal brush 4 is located within the rubber vessel and the second metal brush 5 is located outside the rubber vessel on the end of the shaft 1, at a distance from the rubber vessel and ahead of the normal direction of movement of the rubber vessel 2 for applying a layer of polymerisable composition.
  • the device shown in Figure 2 is used for applying a polymerisable composition to the external surface of a metal pipe or to any other open surface, which may be curved.
  • the rubber vessel 2' in Figure 2 also has a rectangular cross-section, but here, the calibrating device 3 is in the form of a resilient ring clamped around the periphery of one long face of the rubber vessel 2'.
  • the first shaft 1 extends through the opposing long face of the rubber vessel 2' and is disposed on bearings (not shown) and a second shaft is provided outside the rubber vessel 2', as explained below.
  • the metal brushes 4, 5 shown in Figure 2 again comprise discs with a plurality of metal needles extending therefrom and the first metal brush 4 in Figure 2 is secured to one end of the first shaft 1 within the rubber vessel 2', with the metal needles extending outwardly from the metal disc along the axis of the shaft 1.
  • the metal needles of the first metal brush 4 are arranged to contact the metal surface to which the polymerisable composition is to be applied and are adapted for face milling of the metal surface.
  • the second metal brush 5 of Figure 2 has the same construction as the first metal brush 4, but is located outside the rubber vessel 2' and is mounted at one end of the second shaft, which is independently connected to the rotary drive (not shown).
  • the devices shown in Figures 1 and 2 may be used to apply a polymerisable composition to the surface of a metal object as follows:
  • the surface of the metal object may first, optionally, be subjected to preliminary cleaning and de-scaling in order to remove impurities, which may be carried out using any suitable means or by using the second metal brush 5 outside the rubber vessel 2' of the device of the present invention.
  • the generator 7 attached to the second metal brush 5 may be used to electro-machine the surface of the metal object so as to burn up any anti-adhesion active impurities and in order to break up only large conglomerates of solid impurities. Preliminary cleaning is particularly advisable for rusty and corroded surfaces of used pipes.
  • the rubber vessel 2 of the device of the present invention is rotated and moved along the surface (or surfaces) of the metal object so as to supply and distribute the polymerisable composition over the desired working area.
  • the surface of the metal object below the layer of applied polymerisable composition is then physically activated using the first metal brush 4 until the original surface under the layer of polymerisable material is exposed.
  • the generator 6 connected to the first metal brush 4 may, again, be switched on to electro-machine the surface of the metal object below the layer of applied polymerisable composition in order to destroy the remaining residues and conglomerates of solid impurities which are resistant to micro-scalping and dispersing the products of final cleaning and de-scaling into the layer of polymerisable material.
  • the dispersed particles of impurities obtained by the physical activation of the underlying surface become additional fillers in the composition of the finished coating and the original surface which is exposed under the layer of polymerisable composition is blocked by the chemically active ingredient of the polymerisable composition, which improves the adhesion of the finished coating to the underlying material.
  • the processing speed of the coating for example, the coating of an inner surface of a pipe with a protective layer using the polymerisable composition and device of the present invention may be conducted at about 10km per hour and can be conducted at a speed of up to 60km per hour.
  • a polymerisable composition according to the present invention having the following components was prepared:
  • the time taken for the composition to harden at 20°C was three hours. Five days after the coating hardened, a dolly was cemented to the coating and the force needed to separate the coating from the carbon steel plate was measured. The adhesive strength was found to be 38 MPa.
  • the inner surface of a corroded metal pipe 300mm in diameter and filled with water, was machined with a metal brush, using electric pulses.
  • the pulse duration was 500 microseconds, the energy was 2 joules and 60% of the inner surface of the pipe was electro-machined.
  • Example 41 After the surface of the pipe had been electromachined, a composition according to Example 41 was applied in a thickness of 0.5mm using a device according to the present invention. After the composition had been applied, the metal surface of the pipe was again machined with electric pulses at a pulse duration of 100 microseconds and an energy of 0.01 joules, 60% of the pipe surface was machined in this way. Five days after application of the covering, the adhesive strength of the coating was found to be 28 MPa.
  • the method of applying a polymerisable composition to the surface of a metal object using a device according to the present invention greatly enhances the adhesive activity of the polymerisable composition so that the resulting protective layer is more securely adhered to the surface of the metal object.
  • the principle used to create this improved adhesive coating is the simultaneous provision of two active surfaces, one in a full free radical status (the surface of the metal object) and the other having molecular active centres (the polymerisable composition of the present invention), the two surfaces being able to react physico-chemically.
  • Electro-machining of the surface of the metal object by the second metal brush 5 outside the rubber vessel 2 activates the surface of the metal object to which the polymerisable composition is to be applied thereby creating a free radical status.
  • a polymerisable composition according to the present invention is then applied to this activated surface of the metal object and electro-machining by the first metal brush 4 within the rubber vessel 2 acts to eliminate the water layer in contact with the surface of the metal object, which is then replaced by the surface-active agent in the polymerisable composition of the present invention to create a diamond-like ultra-hard adhesive surface.
  • the ultra-hard gluing surface then becomes flexible as the accelerator in the polymerisable composition reacts to form multiple layers of polymer-accelerator mix and this allows the hardening time of the polymerisable composition to be adjusted, as desired (usually between 5 minutes and 48 hours depending on application purposes).
  • the method of the present invention involves three different procedures which are effected in parallel: - electro machining to give the surface of the metal object a full free radical status
  • the composition polymerises at the boundary with the metal
  • composition is polymerised throughout the coating under the action of polymerisation initiators in the composition.
  • the principle of the present invention to creating a full free radical status on the surface of the material to which a chemically active adhesive composition is to be applied may be extrapolated to other areas and objects to provide an improved adhesive effect.
  • a free radical status may be created on the surface of a material to be glued depends on the particular material concerned.
  • the free radical status is created by electro-machining, or electro-mechanical brushing of the metallic surface to electrically charge the metallic surface, as described above.
  • the free radical status may be obtained by including a particular additive in the adhesive composition which enables calcium to be extracted from the concrete.
  • Use of the principle of the present invention in the case of concrete is particularly useful in the reinforcement of concrete blocks, for example, in roads, tunnels and structural building elements.
  • composition for reinforcing concrete comprising phenyl glycidyl ester, having the general formula ,
  • An epoxide oligomer is a substance containing two or more primary amine groups.
  • Pyridine is the aromatic compound C 6 H 5 N.
  • Phenyl glycidyl ester (FGE) and pyridine adsorbed on the surface of the concrete pores, make them water- repellent and provide the conditions whereby water is displaced from the interior of the concrete block and replaced by the polymer composition.
  • ingredients of a preferred composition are taken in the following proportions (in parts by weight):
  • the composition is used by applying it to the surface of concrete constructions and buildings. If it is necessary to treat massive buildings, holes are bored in them and the composition is injected through them.
  • the composition is most effectively used for impregnating a layer of corrosion on the reinforcing components of ferroconcrete constructions. In such cases, impregnation prevents further corrosion of the metal, strengthens the already-corroded metal and provides a firm link between the reinforcing components and the concrete body.
  • Rock is impregnated by injecting the composition through blast holes, whereas wooden articles and buildings are impregnated by applying the compositions to their surface.
  • the water in the pores of the concrete block prevents diffusion of the polymer composition throughout the concrete.
  • the water- soluble pyridine and pehnyl glycidyl ether in the composition are adsorbed on the surface of particles of the concrete block and waterproof it and thus provide the conditions for selective adsorption of the composition and expulsion of water from the concrete.
  • the pyridine and phenyl glycidyl ether react with the epoxide oligomer and the amine curing agent, resulting in strong adhesion of the composition to the concrete. Consequently, activation of the concrete surface in the present case is physico-chemical.
  • Diethylene triaminomethyl phenol greatly increases the chemical stability of the impregnated materials and their resistance to solvents
  • the resin is 1,2-epoxypropoxy diphenyl ester of ethylene glycol and the triglycidyl ester of propylene glycol, and the curing agent is polyamino amide.
  • Testpieces were made in order to determine the efficiency with which concrete was impregnated. To this end, a wet mixture of 4 parts sand and 1 part cement was placed in glass tubes. The mixture was compacted at a pressure of 10-15 kg/cm 2 . After 30 days, the mixture in the tube was placed in water for 10 days, after which the excess water was poured off and a layer of composition 5 cm thick was poured on to the end of the testpiece. After 7 days, the testpiece was taken out of the tube and sawn into discs 1 cm thick, which were subjected to compression tests.
  • Concrete cylinders 15 mm in diameter were placed in water for a period not less than 1 month, and were than taken out of the water and the end of each cylinder was wiped with a wet cloth and a layer of composition number 9 was placed on it. After 1 hour, the composition was removed from the surface of the cylinder, using a dry cloth, and the cylinder was placed in a holder. After one day, the holder was placed in a device for supplying water through the cylinder at a pressure up to 8 atmospheres. Water was supplied from the non-impregnated end of the cylinder for five hours. The experiment showed that there was no observable penetration of water through the impregnated end of the cylinder at the end of the stated time.
  • Composition number 12 for impregnating the inner surface was tested on a chamber measuring 6 ⁇ 6 ⁇ 6 metres, a concrete mock-up of the containment zone of damage to an atomic power station.
  • the composition was applied twice with rollers at an interval of 3 hours.
  • a week after application of the composition the chamber was tested for sealing-tightness, by creating a vacuum of 0.01 mPa inside the chamber. Tests showed that after one day, the pressure inside the chamber had not increased by more than 0.005 mPa.
  • Composition number 13 was tested by impregnating moulded concrete decorations in a garden and park complex, with the object of preventing them from further damage. To this end, 15% toluene was added to the composition in order to reduce its viscosity. The composition was applied from a sprayer. The air temperature during the work was 24°C.
  • Example 47 A control sample or blank was treated by the method described and underwent 100 test cycles (moistening, freezing and drying) without deterioration.
  • Example 47
  • Composition number 14 was tested for strengthening damaged brickwork and protecting it from further deterioration.
  • the composition was applied to pieces of damaged brick, using a sprayer, and they were then placed in water for 1 day and then in a freezer at a temperature of -15oC for one day and finally in a drying chamber at 60oC for 1 day.
  • Composition number 15 was tested for use as a material for impregnating the concrete floor of a champagne factory.
  • the mosaic concrete floor quickly lost strength and deteriorated at the places where champagne fell on it.
  • the composition was tested by preparing concrete cubes measuring 10 ⁇ 10 ⁇ 10 cm. The cubes were wetted and impregnated twice with the composition after an interval of 1 day. Three days after the last impregnation, the cubes were placed in a tank containing champagne. Tests during a month showed that the untreated cubes lost 73% of their strength whereas the treated cubes lost only 4.6%.
  • Composition N16 was used to impregnate splint-slab boards in order to increase their resistance to liquid and gaseous media from cattle-breeding establishments.
  • the composition was applied to one surface of the board by a roller, and after impregnation with the composition a second layer containing pigments was applied. Three days after application of the coating, an enclosing rib was formed on the surface of the board and pig's urine was poured inside. Observations during a month showed that the urine did not have any destructive effect on the board, whereas the untreated board was destroyed in two days.
  • Another example where the principle of the present invention may be applied is in the case of applying adhesive to sawdust or other waste materials from agricultural products such as rice, kaoryang husk and straw etc.
  • the adhesive acts as a binding agent to create particle/chipboard.
  • the particle/chipboard can then be used in the manufacture of furniture, shelving and other products.
  • This not only provides the obvious advantage of being able to use woodworking waste/wet waste or agricultural waste in the production of marketable products, but, by following the principle explained above and creating a free radical status to improve adhesive strength, the previously used binding material which was toxic can now be replaced with, for example, non-toxic polymerisable compositions according to the present invention.
  • only 2% polymer is needed for 98% sawdust in weight, which can be wet, whereas previously, a minimum of 15% polymer was needed and the sawdust also had to be completely dry.
  • a binding material comprising an organic component comprising a polyisocyanate, a hardening agent and an inorganic salt.
  • the non-organic salt is for binding the humidity and strengthening of the end product.
  • Such a binding material may be used for binding sawdust and agricultural waste so that the end product is again stronger, non-toxic and economically safe and does not require an additional protective coating for use in open air. Only a reduced amount of binding material is, again, required and sawdust and agricultural wastes having humidity up to 40% can be used.
  • the hardening agent comprises water glass. More preferably the inorganic salt is calcium hydroxide. Most preferably the organic component comprises a polyisocyanate and a polyester containing polyethylene oxide monomeric units.
  • polyisocyanate includes substances selected from:
  • polyester includes products selected from the group of products of a reaction between di- and triethylene glycol, glycerol, trimethylol propane, pentaerythritol, castor oil derivatives and other polyols, and adipic, phthalic, maleinic and other dibasic acids.
  • polyethylene oxide monomeric units relates to a fragment of a molecule containing at least two oxyethylene groups in its composition.
  • the present invention further provides a method for mixing a filler with a binder according to the present invention wherein the filler is initially mixed with the hardening agent, subsequently with the inorganic salt and then finally with the organic component.
  • the present invention further comprises a method of producing compression moulded articles comprising moulding a mat of a filler with a binder according to the present invention and hot compression moulding the mat in a temperature range of 60 - 100°C. It is preferred that the filler is not previously subjected to drying.
  • an oligomer is introduced into the polyisocyanate composition, the oligomer comprising a polyester with polyoxyethylene fragments in the chain, applied with a dispersion of calcium hydroxide (lime paste) in water, and a solution of sodium silicate (water glass).
  • a high rate of solidification of the binder is achieved at a temperature of 60 - 100°C due to interaction between the isocyanate groups of polyisocyanate with one another, with water and with the hydroxyl groups of the polyester.
  • the solidification process is catalysed by anions and cations of calcium and sodium hydroxide.
  • a high degree of dissociation of bases and salts of calcium and sodium is obtained by means of pseudo-crown ethers - oxyethylated fragments of the polyester chain formed during hydrolysis of ester groups in the oligoester - which forms a loose ion pair.
  • This hydrolysis occurs at high speed on contact of the polyester with particles of calcium hydroxide.
  • calcium hydroxide in the system in question is a cross-linking agent which reacts at high speed with the carboxyl groups in the oligomer formed during hydrolysis of ester groups. This is sufficient to ensure that the woodchip board retains its shape even at very low rates of conversion of isocyanate groups, particularly when branched polyesters are used.
  • the described sequence of chemical reactions in the binder fail or practically fail to occur owing to the low rate of hydrolysis of the ester groups in the polyester. This prolongs the working life (suitability for compression moulding of articles) of the sawdust and the binder applied to it.
  • ingredients are present in the following proportions (parts by weight) per 100 parts by weight of polyisocyanate:
  • the wide range of proportions of ingredients of the composition is due to differences in the type of fillers, their moisture content, the selected compression-moulding conditions, and the properties required from the finished articles.
  • the polyester used may comprise products of a reaction between di- and triethylene glycol, glycerol, trimethylol propane, pentaerythritol, castor oil derivatives and adipic, phthalic and maleinic acid.
  • the components of the composition water glass, lime paste, polyester and polyisocyanate are successively applied to the wood filler.
  • applying water glass which reacts with a solution of calcium hydroxide, causes a layer of calcium salt of silic acid to form around the particles of wood filler and prevent the binder components from diffusing throughout the particles of wood binder.
  • sodium hydroxide formed during the reaction diffuses deeply into the particles of filler and plasticises the cellulose, so that it can be shaped when the articles are pressed.
  • the binder solidifies the isocyanate groups react with water, and carbon hydroxide evolved during the reaction inactivates the sodium and calcium hydroxide.
  • Compression-moulding is brought about at a temperature of 60 - 100° and the filler is not dried before pressing.
  • test-pieces The physical and mechanical properties of pressed test-pieces were determined by the following methods: - density - to GOST 15139-69;
  • the fineness of the sawdust was 1 - 4 mm and the moisture content was 20%.
  • the sawdust was mixed with paraffin powder in the proportion 90:10.
  • the resulting crude mixture was compressed to form patterned decorative wall panels.
  • moist oak veneer was stuck to one surface of the moulding.
  • the crude mixture was formed into a mat and compressed at a temperature of 90°C for 5 minutes.
  • the resulting article measured 600 ⁇ 600 ⁇ 5 mm.
  • the resulting article has the following physical and mechanical properties: - density - 860 kg/m 3 ;
  • the fineness of the waste was 2 - 5 mm and the moisture content was 5%.
  • the resulting crude mixture was pressed to form a panel board floor.
  • a patterned prefabricated veneer of oak, beech, hornbeam and birch was applied to one surface of the moulding.
  • an adhesive made by mixing the previously-mentioned binder components was applied to the inner surface of the veneer.
  • the floor panels were pressed at a temperature of 90°C, at a specific pressure of 50 kg/cm 2 and for 10 minutes.
  • the resulting articles had the following physical and mechanical properties. - density - 920 kg/m 3 ;
  • - toxicity depends on choice of the original hemp waste; - maximum strength under static bending - 640 kg/cm 2 ; - elasticity modulus when bent - 68,000 kg/cm 2 .
  • Water glass, silicate liquor ratio 2.8 (0.5 parts by weight) followed in succession by lime paste (0.5 parts by weight), polyethylene glycol adipate triol, molecular weight 2200 (0.3 parts by weight) and polyisocyanates (0.7 parts by weight) were applied to the surface of conifer sawdust (100 parts by weight) using a high-speed agitator.
  • the fineness of the sawdust was 1 - 10 mm.
  • the resulting crude mixture was pressed to form multi-layer panels for building. Compression-moulding was brought about at a temperature of 90°C, specific pressure 50 kg/cm 2 . Duration of pressing - 10 minutes. Thickness of pressed sheet - 200 mm.
  • the pressed sheets had the following physical and mechanical properties: - density - 820 kg/m 3 ; - water penetratability - 0.5 g/m 2 /day; - toxicity - panels permitted for use in residential environment; - breaking strength under compression - 110 kg/cm 2 .
  • a strong liquid foam plastic was poured into the gaps between 3 sheets 20 mm thick. After the foam plastic had hardened, the outer sides of hepanel were impregnated with a mixture of polyol and polyisocyanate to a depth of 1 -2 mm. The total thickness of the 3-ply panel was 100 mm.
  • Water glass with a silicate liquor ratio of 3.0 (0.5 parts by weight) followed in succession by lime paste (0.3 parts by weight), polyethylene glycol adipate triol, molecular weight 2200 (0.3 parts by weight) and polyisocyanate (0.7 parts by weight) were applied to the surface of conifer sawdust (100 parts by weight) using a high-speed agitator.
  • the fineness of the sawdusts was 2 - 4 mm.
  • the resulting crude mixture was pressed in a step-by-step press in order to produce a continuous block, cross-section 25.5 ⁇ 14.5 cm. Compression-moulding was brought about the cyclic feed of the crude mixture to a heated die which was compressed by a punch equipped with a projecting part for forming a cavity in the block. The size of the cavity was 20 ⁇ 8 cm. After the block had been shaped, the cavity was filled with heat-insulating material.
  • the block was pressed at a temperature of 90°C.
  • the force on the punch was 20 t and the speed of shaping the block was 30 m/h.
  • the block had the following physical and mechanical properties: - density - 950 kg/m 3 ; - water permeability - 0.4 g/m 2 /day;
  • polystyrene resin having a very wide range of uses, including, for example:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)

Abstract

L'invention concerne une composition polymérisable comprenant un mélange d'un oligoester insaturé, d'un réticulant et d'un tensioactif complexe, dans laquelle le tensioactif complexe comprend un alkyl phénol ester oxyéthylé dont la formule générale est la suivante: CnH2n+1C6H4O (C2H4O)mH, où n = 8 à 10 et m = 6 à 12 et un chlorure d'aryl polybenzyl pyridinium dont la formule générale est la suivante: (CnH2n+1C6H4CH2(C6H4CH2)mN+C5H5)C1- où n = 6 à 8 et m = 1 à 4. L'invention concerne également un dispositif d'application d'une composition polymérisable sur la surface d'un objet métallique, ledit dispositif étant constitué de moyens d'application d'une couche de la composition polymérisable sur la surface de l'objet métallique, ces moyens présentant un espace clos destiné à contenir la composition polymérisable, ainsi que de moyens d'exposition de la surface de l'objet métallique située sous la couche de composition polymérisable appliquée, ces moyens étant disposés à l'intérieur de l'espace clos des moyens d'application. L'invention concerne en outre un procédé d'adhésion de matériaux et un procédé d'application d'un revêtement protecteur sur une surface métallique. Elle porte aussi sur des compositions visant à renforcer le béton ou permettant la liaison d'une charge, telle que la sciure.
PCT/GB1996/002551 1995-10-20 1996-10-18 Composition polymerisable, procede d'application d'une composition polymerisable et dispositif d'application d'une composition polymerisable WO1997014752A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73131/96A AU7313196A (en) 1995-10-20 1996-10-18 A polymerisable composition, a method of applying a polymerisable composition and a device for applying polymerisable composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
UA95104594 1995-10-20
UA95104594A UA27979C2 (uk) 1995-10-20 1995-10-20 Олігоефірна композиція для захисних покрить, яка полімеризується, спосіб нанесення захисних покрить на поверхні металевих виробів і пристрій для здійснення способу

Publications (2)

Publication Number Publication Date
WO1997014752A2 true WO1997014752A2 (fr) 1997-04-24
WO1997014752A3 WO1997014752A3 (fr) 1997-08-21

Family

ID=21689083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/002551 WO1997014752A2 (fr) 1995-10-20 1996-10-18 Composition polymerisable, procede d'application d'une composition polymerisable et dispositif d'application d'une composition polymerisable

Country Status (3)

Country Link
AU (1) AU7313196A (fr)
UA (1) UA27979C2 (fr)
WO (1) WO1997014752A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001036713A1 (fr) * 1999-11-18 2001-05-25 Champion Technologies Inc. Compositions inhibitrices
WO2004067191A2 (fr) * 2003-01-29 2004-08-12 President And Fellows Of Harward College Alteration des affinites de surface
US11780535B2 (en) 2019-12-18 2023-10-10 Pgs Geophysical As Methods and systems for underwater application of streamer coating on geophysical streamers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU427878A1 (ru) * 1971-03-11 1974-05-15 В. А. Белый , А. М. Красовский Институт механики металлополимерных систем Способ подготовки поверхностей изделий для напесения полимерных покрытий
JPS5562970A (en) * 1978-11-01 1980-05-12 Toyo Tire & Rubber Co Ltd Unsaturated polyester primer for concrete
GB2065263A (en) * 1979-11-22 1981-06-24 Kankyo Kaihatsu Kk Apparatus for reinforcing and repairing a pipe line
US5179143A (en) * 1988-07-26 1993-01-12 Bayer Aktiengesellschaft Process for the preparation of compression molded materials

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1083697A (en) * 1965-11-09 1967-09-20 British Ceramic Res Ass Improvements relating to grouting and fixative preparations for tiles
SU858750A1 (ru) * 1979-12-28 1981-08-30 Предприятие П/Я М-5671 Устройство дл зачистки металлических поверхностей
JPS56152819A (en) * 1980-04-30 1981-11-26 Matsushita Electric Works Ltd Unsaturated polyester molding material
US4528154A (en) * 1983-06-15 1985-07-09 Atlantic Richfield Company Preparation of molded lignocellulosic compositions using an emulsifiable polyisocyanate binder and an emulsifiable carboxy functional siloxane internal release agent
CS252558B1 (en) * 1985-03-18 1987-09-17 Jilji Havelka Grooved rotational yarn distributor
US5162401A (en) * 1989-10-30 1992-11-10 Owens-Corning Fiberglas Corporation Unsaturated polyester resin compositions containing compatible compounds
JPH03164201A (ja) * 1989-11-23 1991-07-16 Aisin Takaoka Ltd 籾殻成形体
SU1729652A1 (ru) * 1990-03-11 1992-04-30 Магнитогорский горно-металлургический институт им.Г.И.Носова Устройство дл очистки длинномерных изделий
GB2244781B (en) * 1990-06-08 1993-12-08 Fordbrook Eng Ltd A process for lining a metal pipe
BR9407225A (pt) * 1993-08-12 1996-09-17 Tovarischestvo S Ogranichennoi Método pra limpeza da superfície interna de um tubo e aparelho para execução do mesmo

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU427878A1 (ru) * 1971-03-11 1974-05-15 В. А. Белый , А. М. Красовский Институт механики металлополимерных систем Способ подготовки поверхностей изделий для напесения полимерных покрытий
JPS5562970A (en) * 1978-11-01 1980-05-12 Toyo Tire & Rubber Co Ltd Unsaturated polyester primer for concrete
GB2065263A (en) * 1979-11-22 1981-06-24 Kankyo Kaihatsu Kk Apparatus for reinforcing and repairing a pipe line
US5179143A (en) * 1988-07-26 1993-01-12 Bayer Aktiengesellschaft Process for the preparation of compression molded materials

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 7634 Derwent Publications Ltd., London, GB; Class A32, AN 76-64455X XP002037054 & SU 427 878 A (METAL POLYMER SYSTE) , 21 January 1976 *
DATABASE WPI Section Ch, Week 9134 Derwent Publications Ltd., London, GB; Class A81, AN 91-250016 XP002037057 & JP 03 164 201 A (AISIN TAKAOKA KK) , 16 July 1991 *
DATABASE WPI Section Ch, Week 9314 Derwent Publications Ltd., London, GB; Class M11, AN 93-115633 XP002037055 & SU 1 729 652 A (MAGN MINING METAL INST) , 30 April 1992 *
DATABASE WPI Section PQ, Week 8224 Derwent Publications Ltd., London, GB; Class P24, AN 82-H1847E XP002037056 & SU 858 750 B (TSVETKOV S V) , 30 August 1981 *
PATENT ABSTRACTS OF JAPAN vol. 004, no. 101 (C-019), 19 July 1980 & JP 55 062970 A (TOYO TIRE & RUBBER CO LTD), 12 May 1980, *
PATENT ABSTRACTS OF JAPAN vol. 006, no. 035 (C-093), 3 March 1982 & JP 56 152819 A (MATSUSHITA ELECTRIC WORKS LTD), 26 November 1981, *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001036713A1 (fr) * 1999-11-18 2001-05-25 Champion Technologies Inc. Compositions inhibitrices
WO2004067191A2 (fr) * 2003-01-29 2004-08-12 President And Fellows Of Harward College Alteration des affinites de surface
WO2004067191A3 (fr) * 2003-01-29 2004-12-23 Harvard College Alteration des affinites de surface
US7659053B2 (en) 2003-01-29 2010-02-09 President And Fellows Of Harvard College Methods of alteration of surface affinities using non-chemical force-creating fields
US11780535B2 (en) 2019-12-18 2023-10-10 Pgs Geophysical As Methods and systems for underwater application of streamer coating on geophysical streamers

Also Published As

Publication number Publication date
AU7313196A (en) 1997-05-07
WO1997014752A3 (fr) 1997-08-21
UA27979C2 (uk) 2000-10-16

Similar Documents

Publication Publication Date Title
KR101893791B1 (ko) Sis 및 sbs를 포함하는 프라임 코팅용 아스팔트 콘크리트 조성물 및 이의 시공방법
US2902388A (en) Hydraulic cement-polyurethane compositions useful for coating, sealing, patching, and surfacing
US3432451A (en) Polyolefin-modified polyurethanes and process of making same
CN1187293C (zh) 建筑材料和建筑构件的密封方法
US4559239A (en) Method for repairing cementitious substrate
US2120309A (en) Method of applying noncorrosive surfaces to pipe and the like
KR100631485B1 (ko) 콘크리트 구조물 및 강 구조물의 내구성 증대 및 중성화와염해방지를 위한 속경화 피막 형성 공법
JPS63278584A (ja) パイプの修理若しくは被覆法、その装置および修理若しくは被覆材料
US3723163A (en) Process for sealing a surface and resultant surface
EP1347107A1 (fr) Produit polyvalent, isolant, antivibrations, adhesif et resistant au feu, destine a differents secteurs industriels, notamment a la construction
KR102058680B1 (ko) 방수성을 향상시킨 개질 아스팔트 콘크리트 조성물 및 이의 시공방법
DE19750769C2 (de) Verfahren zum Überdecken von Asbestzementoberflächen
WO1997014752A2 (fr) Composition polymerisable, procede d'application d'une composition polymerisable et dispositif d'application d'une composition polymerisable
WO1993001934A1 (fr) Structure en beton et son procede de fabrication
US4518641A (en) Non-slip surface coatings
KR101009743B1 (ko) 침투형 콘크리트 보강용 보수제
JPH06501504A (ja) 空気乾燥性バインダー
US5996304A (en) Coating composition and method
GB2115312A (en) Non-slip surface coating
RU2291172C1 (ru) Гидроизоляционная мастика
DE19638312C1 (de) Verfahren zur Herstellung eines Dämmsystems, vorzugsweise zur Schall- und Wärmedämmung an Bauwerken
IL190352A (en) A method of forming bricks or tiles made of building material
Neffgen Epoxy resins in the building industry—25 years of experience
US5656674A (en) Method for working up waste materials
DE8320528U1 (de) Korrosionsschutzbeschichtetes rohr mit mechanischer schutzschicht

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN

WR Later publication of a revised version of an international search report
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97515618

Format of ref document f/p: F

NENP Non-entry into the national phase

Ref country code: CA