MXPA99005626A - Graft copolymerized compositions - Google Patents

Abstract

Relatively low molecular weight olefin/CO polymers are graft copolymerized. The graft copolymers provide the basis for waterborne adhesives that are particularly useful for making wood composites.

Description

COMPOSITIONS COPOLIMIZED BY GRAFT FIELD OF THE INVENTION This invention describes resins made from olefin monomers and carbon monoxide and their use as adhesives. DESCRIPTIVE MEMORY Polymers of carbon monoxide and olefins generally referred to as polyketones are well known in the art. The class of linear alternative polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon are of particular interest among polyketone polymers. This class of polymers is disclosed, for example, in U.S. Patent Nos. 4/880/865 and No. 4/818/811. Polyketone polymers have a well-balanced set of mechanical properties that make them particularly useful as engineering thermoplastics.

Ref, 30274 BACKGROUND OF THE INVENTION Other materials that have useful properties have also been formed from the combination of various olefins and carbon monoxide. Among these are relatively low molecular weight materials comprising oligomers or polymers of low molecular weight. However, in this case, a monomer other than carbon monoxide and ethene comprises at least 20% by weight of the total weight of the polymer. Ordinarily two olefinic monomers are used, for example, ethene and propene with a relatively high percentage of each (by weight or on a molar basis) as compared to the alternative aliphatic polyketones used as engineering thermoplastics. Typically, the monomer mixture will include about 50 mol% (based on the total weight of polymer) of CO and about 50 mol% of olefins (with at least about 30% by weight of the total olefin content). composed of C3 or higher olefins).

These oligomers or low molecular weight polymers can be used as thermostable elements.

Depending on the composition and the preparation method, many will continue to successfully present many properties commonly associated with thermoplastics in a range of conditions. In such applications, these are cured with a curing agent that is generally an amine. Curing can be achieved in the presence of an acid catalyst. These resins are preferred to existing thermosetting elements in a variety of applications due to the reduced environmental damage they cause, the ease of use and the mixture of properties they present.

An application of these thermoset elements is an adhesive. More particularly, they are useful as glues for wood composites in the preparation of plywood and particles or particle boards. At this point, the wood composite industry has generally used adhesives such as urea-formaldehyde resins and phenol-formaldehyde resins. However, many of the wood compounds prepared with them are losing acceptance in important market segments even when the demand remains generally high for a highly impact-resistant wood composite with good dimensional stability in the presence of moisture. Much of this can be attributed to environmental and safety factors associated with the systems.

Wood glue compositions based on pure CO / olefin resins and amine curing agents have been previously prepared. While these pure glue systems provide good adhesion, their viscosity and shelf life are not ideal for many commercial applications. Reducing its viscosity and increasing its container life will extend the range of applications for which CO / olefin resins could be used. In particular, these could be made many more suitable for use in the production of plywood and braided planks oriented in such conditions.

SUMMARY OF THE INVENTION In one aspect of the present invention, the CO / olefin copolymers are copolymerized by grafting with vinyl monomers. The grafting can be done through the application of high energy radiation to olefin / CO copolymers in the presence of a suitable monomer. The grafted polymers are excellent glues, particularly in wood applications, and are cured by reaction with an amine curing agent in the presence of an acid catalyst. The grafted copolymers are advantageously prepared as low molecular weight polymers.

In another aspect of the present invention, better adhesives are prepared. These adhesives are particularly useful for bonding wood and wood by-products and are prepared based on a copolymer of carbon monoxide, olefinically unsaturated compounds, and a curing agent.

In another aspect of the present invention, a wood composite is presented. The composite comprises wood portions adhered to each other by a cured binder which is obtainable by curing a curable resin composition containing a carbon monoxide copolymer with an olefinic unsaturated compound and a curing agent.

DETAILED DESCRIPTION Pure olefin / CO copolymer resins in combination with amine curing agents can be used effectively as wood glues. In the practice of the present invention, the CO / olefin resins are improved through graft copolymerization. It has been discovered that converting the pure olefin / CO copolymer in this form makes the system ready to accept hydraulic applications, considerably lengthens the useful life and reduces the viscosity thereby considerably improving the viability of these systems. In addition, grafting olefin / CO copolymers can greatly reduce the overall cost of raw material in the tails, since a major part of the glue may be an inexpensive material such as styrene. Preferably, the graft copolymer is made by imbibing a vinyl monomer in the oil phase of an olefin / CO copolymer dispersion. Grafting is achieved with the addition of a radical initiator, or through the application of high energy radiation. Generally, this is the result of the abstraction of an alpha hydrogen to a carbonyl group in the olefin / CO copolymer by a radical. This forms a macroradical in the central structure of the olefin / CO copolymer which then initiates the polymerization of vinyl monomers to form a graft copolymer.

The copolymers of carbon monoxide and an olefinically unsaturated compound are known. Preferably, the copolymer contains 1,4-dicarbonyl entities in its polymer chain, because this arrangement accommodates certain curing reactions as, for example, with primary polyamines described in more detail below. Said olefin / CO copolymers can be prepared by catalysed palladium polymerization using the known methods of, for example, EP-A-121965, EP-A-181014 and EP-A-516238. The polymers prepared in this way can be linear alternative copolymers of carbon monoxide and the olefinically unsaturated compound (S). That is, the polymer chains contain the monomer units that originate in the carbon monoxide (ie, the carbonyl groups) and the monomer units that are originally in the olefinically unsaturated compound (s). in an alternative arrangement. Perfectly alternative copolymers of carbon monoxide and olefinically unsaturated compounds are preferred, because they have a higher content of carbonyl groups in the polymer chain relative to the random copolymers. This can contribute to the equal cure of the processed resins of these systems that lead to a high level of crosslinking.

The copolymers of carbon monoxide and olefinically unsaturated compounds can be based on a hydrocarbon as the olefinically unsaturated compound, but the olefinically unsaturated compound can also contain a heteroatom as long as it is separated from the double bond by a spacer group. For example, comonomers such as 10-undecen-l-ol and 10-undecenoic acid can be used. It is preferred that the copolymer be based on an olefinically unsaturated hydrocarbon having up to 10 carbon atoms. The aliphatic alpha-olefins with 3 to 6 carbon atoms are particularly suitable in this capacity and include, for example, those having a straight carbon chain such as, for example, propene, 1-butene, 1-pentene and 1-hexene. Propene is the preferred monomer of this group. What is most preferred to use is a combination of ethene and propene with propene comprising the primary monomer.

The molecular weight of the copolymer before grafting can vary within wide limits. The copolymer with a number average molecular weight in the range of 200 to 20,000 can be used. However, copolymers having number average molecular weights between 500 and 5,000 are preferred. The molecular weights of 1,000 to 4,000 are the most preferred.

The copolymers usually have a molecular weight distribution so that their Q value amounts to 1.1 to 5, more commonly, from 1.5 to 3, with the Q value being the molecular weight ratio. Weight average and number average molecular weight . The relatively low molecular weight of the copolymer allows the resin systems of the present invention to be used in liquid form at the temperatures generally used in processing and working with the copolymer. They are frequently found in the range of 10 to 80 ° C, more frequently, in the range of 20 to 60 ° C. The processing of the copolymer encompasses, for example, the preparation of the binder used in the present invention and the application of the binder on the wood surface.

Before grafting, the copolymer comprises approximately 50 mol% CO and 50 mol% olefin. Preferably, the olefin content comprises between 0% and 70% by weight of ethene and between 30% and 100% by weight of propene. It is more preferred that the olefinic mixture be between 20% and 70% by weight of ethene and 80% to 30% by weight of propene. The most preferred is that the olefinic mixture is 70% by weight of propene and 30% of ethene.

Grafting can be performed with any of the methods used to form grafted copolymers.

This includes exposure of an appropriate monomer and a copolymer mixture to a high energy radiation such as, for example, e-beam radiation, ion radiation, beam radiation thereof, heating a suitable monomer in the presence of the copolymer, or reaction of a suitable monomer in the presence of a radical initiator and copolymer. Any other method for copolymerizing graft polymers will be useful in the practice of the present invention.

The olefin / CO copolymer of the present invention will usually be a liquid. In this way, it is generally possible to prepare a solution of the combination of a polymer and the monomer that will form the graft. It may be necessary to emulsify this solution with a surfactant. For this purpose, nonionic surfactants are preferred. In most cases, exposure to radiation (in the absence of oxygen) that is sufficient to induce graft copolymerization will increase the viscosity of the liquid. However, this will not commonly solidify the polymer. This is useful in the application of materials such as glue, because they can be easily placed in water solutions, applied to the materials that have to be glued, and then cured.

The radiation intensities sufficient to affect the graft are usually 0.001 to 20 Mrads per hour. The total dose of ionizing radiation required for graft copolymerization is usually 0.005 Mrads to 20 Mrads, with 0.1 Mrads being preferred.

The polymer to be grafted should generally be kept free of oxygen during the grafting process. This can be done by subjecting the polymer / monomer mixture to radiation in vacuo or in an inert gas such as, for example, nitrogen, helium, neon, argon, carbon dioxide, and the like.

The conditions of temperature and pressure at which the grafting is performed are not critical to the present invention. Generally, any convenient temperature between 0 ° C and 100 ° C can be used as the reaction temperature. The reaction will continue to occur at temperatures below the lower limit, but reaction rates will decrease considerably. In general, atmospheric pressures are used, but in this case too broad ranges of conditions are possible without significantly affecting the grafting process.

The reaction time can be varied in a wide range. When a high dose of radiation is applied, the reaction can occur in seconds. In the preferred range of radiation doses of between 0.05 Mrad and 2 Mrad at ambient temperatures, reaction times of between 10 seconds and 24 hours will advantageously provide a grafting efficiency of between 5% and 95%. The grafting efficiency is a ratio of the amount of grafted monomer to the amount of monomer available per weight.

Radical initiation is the most preferred method for preparing the graft polymerized copolymers of the present invention. Suitable monomers used in the formation of grafts by this method include, for example, monoolefinic hydrocarbons such as styrene and its derivatives, monoolefinically unsaturated esters such as vinyl acetate, vinyl esters of halogenated acids such as vinyl alpha-co-acetate, allyl and methallyl compounds such as allyl chloride, esters of alkenyl alcohols such as allyl alcohol of beta-ethyl, haloalkyl acrylates such as methyl-chloroacrylate, alkyl-cyanoacrylates, fumarates such as diethyl fumarate, monoolefinically unsaturated nitriles such as acrylonitrile, aforementioned acid amides such as acrylamide, alkyl ethers such as vinyl methyl ether, vinyl sulfides such as beta-ethoxyethyl vinyl sulphides, dioolefinically unsaturated hydrocarbons such as 1,3-butadiene, and mixtures of the aforementioned compounds . The preferred monomers are styrenes, acrylates, methacrylates, vinyl esters, and vinyl halides. The most preferred are the styrenes.

The radical initiators can be either water soluble or oil soluble. Water-soluble radical initiators include, for example, potassium persulfate, ammonium peroxydisulfate, potassium peroxydisulfate, sodium persulfate, hydrogen peroxide, and water soluble azo initiators. Oligible oil radical initiators include, for example, benzoyl peroxide, t-butyl perbenzoate and 2,2'-azobis (isobutyronitrile). Water-soluble initiators such as potassium persulfate or azo initiators are preferred. The concentration of free radical initiators is 0.01 to 0.5 grams per one hundred grams of total monomers.

Redox initiation involving an oxidant, such as, for example, potassium persulfate or potassium bromate, and a reducing agent, such as, for example, sodium metabisulfite, or tertiary amines, such as triethyl amine, can also be used to initiate polymerization, particularly at low temperatures.

The process of producing the graft copolymers of the present invention involves contacting the olefin / CO copolymer with an initiator in the presence of monomer used to form the grafted portion of the polymer. Preferably, this is done by introducing the monomer used to form the graft into the oil phase of an olefin / CO resin dispersion and then adding an initiator to the dispersion. A smaller amount of agitation may be applied, for example, by stirring or mixing.

The olefin / CO dispersion to which the grafted monomer is added is preferably formed by mixing the olefin / CO copolymer with water and a surfactant. Typically, the dispersion will contain more water than olefin / CO copolymer by weight although, as will be readily appreciated by those skilled in the art, copolymer aliquots may be added during emulsification to increase the solids content of the finally formed product. In glue applications, a high solids content is desired as long as the viscosity can be kept low enough to work easily with the material. The solids content up to about 60% can be achieved under these conditions using glues made from the grafted copolymers of the present invention.

Any surfactant able to disperse the olefin / CO resin in the water can be used as long as the material does not interfere with the initiation of the graft copolymerization. Preferably, the surfactants are nonionic and include, for example, polyalkylene glycols in general, and polyalkylene glycol alkyl ethers, polyalkylene glycol alkyl phenyl ethers, polyalkylene glycol fatty acid esters, sorbitan fatty acid esters, alkyl polyglycosides, dialkanole amides, fatty acid, and the like. The selection of the amount of surfactant added to form the emulsion is good within the scope of a person who is ordinarily skilled in the art. Typically, the surfactant will comprise from 3% to 15% by weight of the olefin / CO copolymer used to form the emulsion, but any amount serving for the purpose of introducing both copolymer and graft monomer can be employed. an emulsion Once the graft copolymers of the present invention are prepared, they can also be prepared as glues and adhesives (commonly referred to as binders) through the addition of a curing agent and, optionally, a catalyst. The binders prepared in this way can then be used to join two or more materials of similar or non-similar character. For example, compounds of wood parts, wood chips, wood veneers of different species, metals, various polymers and other materials can be formed, the compounds formed from the union of two or more parts of wood constitute the modality that most Prefer of the present invention.

The species and shape of the wood parts that are used to produce the compounds are not critical. The wood can be a wood of high or low density and can be of deciduous or coniferous origin. Examples of suitable species are oak, chestnut, ash, maple, teak, oku i, mahogany, meranti and pine. Very good results can be obtained with beech, fir and poplar. The wood does not need any pretreatment other than that which can be applied normally when using a conventional binder. In general it is sufficient to give the wooden parts the size and shape desired for the type of compound to be produced, for example, by applying mechanical and / or chemical means. Appropriately, wood can be used in the form of planks, wood veneers, timbers, slivers, chips or pulp. A combination of two or more species or forms of wood parts can be used, for example, to improve the appearance of the compound.

The wood can be subjected to a previous treatment to increase its durability. An example of said pre-treatment is the treatment with super heated steam at 150 to 220 ° C under pressure followed by heating at 100 to 220 ° C at ambient pressure, another pre-treatment is the impregnation with salt, for example, chromium, copper, mercury, arsenic salts or combinations of the same.

Many curing agents can be used in the binder according to the present invention. Suitable curing agents or curing systems are disclosed in EP-A-372602 and these may comprise, for example, an amine, a thiol or acrylonitrile. Preferred curing agents include, for example, hexamethylenediamine (HMDA), hexamethylenediamine carbamate, tetramethylenepentaamine, hexamethylenediaminecinnamaldehyde adduct, and hexamethylenediamineadibenzoate salt. Aromatic amines and cycloaliphatic amines may be used, but those having bulky functional groups are not preferred. Aliphatic primary diamines having the formula H2N-R-NH2, (R denotes a bivalent aliphatic bridging group having up to 10 carbon atoms in the bridge) are the preferred curing agents. HMDA is the most preferred curing agent.

Also, it may be advantageous to employ a mixture of curing agents. In particular, a mixture of a relatively more reactive curing agent and a less reactive curing agent is useful. For example, straight chain aliphatic diamines can be used as the most reactive curing agent in combination with primary aromatic or cycloaliphatic polyamines as the less reactive curing agent. By the presence of the most reactive curing agent, rapid gelling can be achieved once curing has begun. In a prolonged cure, the cyclic carbon backbone of the less reactive curing agent will intensify the mechanical strength of the compound at a high temperature. The molar ratio of the most reactive curing agent / less reactive curing agent can vary within wide limits according to the requirements of the determined use of the binder. This molar ratio can easily be determined by the skilled person by applying routine experiments. Typically, the molar ratio will be from 2:98 to 98: 2.

The degree of crosslinking that occurs during curing depends, among other things, on the amount of curing agent in relation to the amount of the carbon monoxide copolymer and olefinically unsaturated compound. The relative amount of curing agent can vary between wide ranges and a relative relative amount can be established by routine experiments. When a primary Polyamine is used as the curing agent, the molar ratio of the carbonyl groups in the copolymer and the primary amine groups of the curing agent is conveniently in the range of 0.25 to 8.0, and more conveniently, in the range from 0.4 to 2.0.

The curing of the copolymer can be carried out in the presence of a curing catalyst or in the absence of any curing catalyst. The advantages of using a catalyst will generally be that curing can be performed at a lower temperature or for a shorter period of time. When the curing agent is an aliphatic diamine, the suitable catalysts are weak acids, in particular acids having a pKa in the range of 2 to 5.5, preferably in the range of 2.5 to 5, when measured in water at 20 ° C. A preferred class of acids are organic acids, in particular carboxylic acids, because these are at least to some extent soluble in the copolymer to be cured. The monocarboxylic acids are the most preferred due to their generally better solubility in the copolymer. Examples of monocarboxylic acids are acetic acid, nicotinic acid, pivalic acid, valeric acid, benzoic acid and salicylic acid. Other suitable weak acid is phosphoric acid. Acetic acid is the most preferred catalyst.

The weak acid can be used in small amounts. The right amounts are from 0.1 to a . 0% by weight in relation to the weight of the copolymer. It is more preferred to use the weak acid in an amount of 0.2% to 10.0% by weight. What is most preferred is to use 0.5% to 8.0%, on the same basis.

The aqueous glue compositions of the present invention present in customary viscosities which makes it easy to work with them. Typically, these fluctuate between 200 and 5,000 mPa.s at room temperature as measured in a Brookfield viscometer. However, if desired, a diluent may be used in the curable resin composition to facilitate the application of the composition to the wood parts. Also, a diluent can improve the compatibility of the curing agent and any catalyst with the copolymer. Suitable diluents are, for example, lower alcohols, minor ketones, minor esters, such as acetates, and minor ethers. The term "minor" refers to diluents with an average of 5 or fewer carbon atoms per molecule. Preferred diluents are water and minor alcohols, with water being the most preferred diluent. Examples of other diluents are acetone, ethyl acetate, methyl propionate and ethylene glycol dimethyl ether. When the curable resin composition is to be applied, for example, by spraying, the viscosity may conveniently be in the range of 100 to 2,000 mPa.s, preferably in the range of 500 to 1,000 mPa.s, a the application temperature. Preferably, the diluent and the copolymer are used in a weight ratio of at least 1: 5, in particular in the range of 1: 2 to 5: 1, more in particular 1: 1.5 to 2: 1.

It is possible to prepare the curable resin composition in the form of a paste which can be easily spread on the surface of the wood in a suitable temperature range, for example, between 10 and 50 ° C. The consistency of such a paste can be achieved by applying a relatively small amount of a diluent to the binder, such as water, a minor alcohol or a minor ketone. Typical amounts of diluent are in the range of 0.2 to 5.0% by weight relative to the weight of the copolymer, in particular 0.3% to 3.0%, more particularly, 0.5% to 1.0% on the same basis. Very favorable results can be obtained by combining a linear alternative copolymer of carbon monoxide and an α-olefin, the copolymer having a weight average molecular weight in the range of 200 to 10,000, with water, a surfactant, a radical initiator, and a vinyl polymer. The mixture is then stirred for 15 minutes followed by the addition of a primary amine, a weak acid, which can be used as a curing catalyst, and 0.2% to 5.0% by weight of a diluent, relative to the weight of the copolymer , and heating the mixture obtained at a temperature between 30 ° C and 100 ° C, preferably between 40 ° C and 80 ° C. The heating time will depend on the selected temperature and can vary in a convenient way between 5 and 50 minutes. The selection of the heating temperature that will provide optimum binder consistency and quality is readily obtainable based on routine experiments. The paste obtained can be applied to the wood at the temperature applied in its preparation, but it can also be used at room temperature.

The binder may contain additional components that may be added to modify binder properties. Examples of suitable additional components are viscosity modifiers, flame retardants, vacuum fillers, antioxidants, UV stabilizers and colorants. For example, clay can be used as a filler or it can be used to decrease the viscosity at a high shear rate. A suitable vacuum filler is silica, cereal flour, or coconut shell flour. Antioxidants and UV stabilizers are particularly suitable additives when the composition formed according to the invention is used as a coating material.

The binder can be applied to the surface of the wood using any conventional technique. The binder, in particular the paste described hereinabove, can be spread on the surface using, for example, a brush, roller, knife or sheet. It has already been indicated that, after the addition of an adequate amount of diluent, the binder can also be applied by spraying and by a nozzle operated by compressed gas, for example, as in spraying in a continuous line or by using a paint sprayer. . If desired, when a compound having a smooth feel when touched by hand is to be produced, the binder can also be applied as a coating on wooden surfaces which will be located on the external surface of the composite. Also, it is possible to coat the cured compound and cure the coating in an additional curing step.

The amount of binder in relation to the amount of wood can vary between wide limits and will generally depend on the type of compound to be produced. In the case of wood laminates, this amount can be specified per square meter of wood surface covered by the binder or per square meter of joint present between two wooden lamellae. Typically, between 30 and 400 g of the binder per square meter of board are used. Preferably, between 60 and 120 g of binder are used.

When the wood composite is a fiber board or a particulate board, the amount of binder may be more conveniently related to the weight of the compound. Per kilogram of the fiber board or the particulate board, a quantity of binder is usually used which is based on 20 to 150 g, more commonly, on 30 to 100 g the carbon monoxide copolymer with a compound olefinically unsaturated. In the case of special applications to fiber boards, it may be convenient to have the binder present as the continuous phase, in which cases per kilogram of the compound an amount of binder may be used which is based on 150 to 600 g and in particular 200 to 500 g of the carbon monoxide copolymer with an olefinically unsaturated compound.

After, or simultaneously with, the application of the binder on the wooden surface, the wooden parts are brought together, so that the binder resides between the wooden parts, and the curing conditions are subsequently applied. The temperature and pressure can vary between wide limits. Generally, the temperature will depend on the curing agent and the presence of a curing catalyst. When a primary polyamine is used as a curing agent, the temperature will conveniently be above 50 ° C, for example, in the range of 80 ° C to 200 ° C, in particular 100 ° C to 160 ° C. In the case of the laminates, the usual pressures are in the range of 1 to 30 kg / cm2, preferably 2.5 to 25 kg / cm2. In applications to fiber boards and particulate tables, typical pressures are in the range of 10 to 150 kg / cm2, preferably, from 25 to 100 kg / cm2.

Various types of wood compounds can be produced according to the present invention, such as fiber board, particle board, for example, sheet metal board, and laminate, such as plywood and laminated beam or wood. The compounds have excellent impact resistance / resistance balance and in the presence of moisture they have excellent dimensional stability. Accordingly, the compounds can be applied advantageously in the production of doors, parquet flooring, sports articles, such as hockey sticks and electrical appliances, such as control boards and panels for distribution boxes. Fiber boards that have the binder as the continuous phase can be used as building panels.

The invention will be further illustrated by the following non-limiting examples. The glue formulations are as follows: A = 100 parts by weight of the Emulsion of Example 2, 25 parts by weight of 65% HMDA, 4 parts by weight of 20% acetic acid.

B = 100 parts by weight of the Emulsion of Example 3, 21 parts by weight of 65% HMDA, 3.3 parts by weight of 20% acetic acid. C = 100 parts by weight of the Emulsion of Example 4, 25 parts by weight of 65% HMDA, 4 parts by weight of 20% acetic acid. D = 100 parts by weight of the Emulsion of Example 3, 18.8 parts by weight of 65% HMDA, 4 parts by weight of 20% acetic acid.

Example 1 (Preparation of olefin / CO copolymer) An autoclave containing 80 parts by volume of methanol, 10 parts of water, and 10 parts of acetic acid at 95 ° C was heated and then charged with 36 bar of propene, 16 bar of C), 4 bar of ethene and a catalyst solution composed of palladium acetate, l, 3di (di-o-methoxyphenylphosphino) propane, trifluoromethane sulfonic acid in a molar ratio of 1 / 1.05 / 2.1. During the reaction, the temperature was maintained at 95 ° C and the reactor pressure was kept constant by continuous feeding of 1/1 ethene / CO mixture. After 20 hours, the reactor was cooled to room temperature and vented. The solvent was removed under reduced pressure to produce an alternate olefin / CO copolymer with an average number-average molecular weight of 1,800 and a ethanol / propene molar ratio of 28/72. The catalyst productivity was 36 kg of oligomer per g. of Pd.

Example 2 (Preparation of a water resin) A mixture of 76.6 parts by weight of a perfectly alternative copolymer as prepared in Example 1, 52 parts by weight of a poly (ethylene glycol) surfactant was added to a resin kettle equipped with an anchor-shaped stirrer. ionic (commercially available under the trademark "23W004" by Shell Chemical Co.), and 108 parts by weight of water. The mixture was stirred at 200 rpm and additional aliquots of the copolymer were added over a period of 2 hours until the total amount of the copolymer in the mixture was 500 parts by weight. After further stirring at room temperature for 3 hours, 343 parts by weight of water were added over a period of 1 hour to produce an emulsion with a solids content of 55%.

Example 3A (Preparation of olefin resin / hydrocarbon CO grafted with polystyrene) To 479 parts by weight of the emulsion prepared in Example 2 were added 144 parts by weight of water, 163 parts by weight of styrene and 1.45 parts by weight of potassium persulfate. The mixture was placed in a bottle, stirred for 15 minutes and placed in an oven at 60 ° C overnight. The product was an olefin / CO copolymer emulsion grafted with polystyrene. The weight ratio between the olefin / CO copolymer and the polystyrene was 60/40 and the solids content of the emulsion was 55% by weight.

Example 3B graft copolymerization of olefin / CO polymers by irradiation A terpolymer of carbon monoxide, ethylene and propylene was produced in the presence of a catalyst composition formed of palladium acetate, the anion of trifluoroacetic acid and 1,3-bis ( diphenylphosphino) -propane. The melting temperature of the linear terpolymer was 220 ° C and this had a limiting viscosity number (LVN) of 1.8 measured at 60 ° C in m-cresol.

A mixture of 10 g of the terpolymer and 2 g of the inhibited styrene with 10 ppm of t-butylcatechol was placed in a glass jug in the presence of air and irradiated with a d0Co light source at 0.26 Mrad / hour and at room temperature. 24 hours. The resulting solid was extracted with hot toluene to remove the homopolystyrene. The solid state "" H NMR analysis of the extracted product showed that it contained grafted polystyrene The grafting efficiency (grafted monomer / total monomer) was 78%.

This example illustrates that polymers based on a central olefin / CO structure can be copolymerized by grafting through the application of high energy radiation.

Example 3C (preparation of low molecular weight olefin / CO copolymer: hypothetical) To 500 parts by weight of the emulsion prepared in Example 2, 150 parts by weight of water and 170 parts by weight of styrene were added. The irradiation of the resulting mixture with a source of 60Co rays at 0.26 Mrad / h, at room temperature of 0.5 hours will polymerize by grafting the styrene to produce a water emulsion with a solids content of 55%.

Example 4 (Preparation of olefin resin / hydric CO grafted with poly (methyl methacrylate) A mixture of 90 parts by weight of the emulsion prepared according to Example 2, 29.8 parts by weight of methyl methacrylate, and 0.1 parts by weight of potassium persulfate in a resin kettle with stirring at 60 ° C for 6 hours was heated. . An olefin / CO copolymer emulsion grafted with poly (methyl methacrylate) was formed. The weight ratio between the olefin / CO copolymer and the poly (methyl methacrylate) was 60/40 and the solids content of the emulsion was 66% by weight.

Example 5 - Preparation of plywood panels and performance comparison This example is a modified version of the Tertiary Wood Sample Test 6.1.5.3 as described in "PSI-95, Construction and Industrial Ply ood", 1995, reproduced by the American Ply ood Association.

Transversally folded (untyped) wood panels of three layers of 1/4"(0.4 cm) southern pine veneer were prepared using three different water glue formulations prepared by mixing the emulsions obtained in Examples 2, 3 and 4 respectively , with hexamethylenediamine (HMDA) and acetic acid, then the panels were pressed hot at 200 ° C and 1.4 MPa (200 psig) The dose used for all the panels was 65 g solid / m2 per glue line. To evaluate the water resistance, 2.5 x 7.6 cm2 (1"X 3") samples were cut from the panels, soaked in boiling water for 4 hours, dried in an oven at 63 ° C for 23 hours, and they were immersed in water for 4 hours.The tail performance was classified according to the number of samples that do not delaminate after the boiling test of 2 cycles for a determined compression time in heat.

The results are indicated in Table 1 below.

Table 1. Formulation of the tail compression time at 200 ° C 4.5 min 6 min 10 min (number of test samples of plywood passing the boiling test) A 3 of 5 B 3 of 3 3 of 3 C 2 of 3 3 of 3 3 of 3 This example illustrates the superior adhesiveness of the wood that is obtainable by the use of glues made according to the present invention. Sample A used a tail composed of olefin / CO polymer that was not copolymerized by grafting. Samples B and C were tails prepared according to the present invention. The glued samples that used the ungrafted polymer as a glue required 10 minutes of hot compression time to pass the boiling test.

Glued samples using glues made according to the present invention boiled with a hot compression period of 6 minutes (or less).

Example 6 - Preparation and performance of particle tables This example is a modified version of the Sample Test of Tertiary Wood 5.4.1. as described in "0437 Series 93 Standards on OBS and aferboard", 1933, published by the Canadian Standards Association.

Braided table panels randomly oriented 46 x 50 x 1.11 cm3 (18"x 20" x 7/16") of southern pine wood particles were prepared by spraying the particles with a non-volatile wax emulsion at 51 ° C. % (15 cpp provided by Borden) and a water glue, successively in a rotating drum. Spraying was performed with a spray atomizer (Concord High Precision Atomizer made by Coil Industries, Ltd.). The amounts of wax and glue applied were 1% and 4% solid relative to the wood weight, respectively. The panels were hot pressed at 200 ° C for 4.5 minutes and the compression pressure was 5.5 MPa (800 psig) for the first 1.5 minutes and 2.8 MPa (400 psig) for the remainder of the compression cycle. The results are presented in table 2 below. The modulus of rupture, modulus of elasticity and internal union were measured according to ASTM D 1037 using a Tinius Olsen instrument. Table 2 Formulation of - internal union - modulo de - modulo de The tail rupture elasticity Mpa (psi) Mpa (psi) Mpa (psi) A 0.4 (60) 18.8 (2732) 3.0 (430) D 0.7 (106) 26.1 (3792) 3.7 (531) The requirements of the Canadian Standards Association are an Internal Union of 0.3 MPa (50 psi), a Rupture Module of 17.2 MPa (2,500 psi), and an Elasticity Module of 3.1 MPa (450 psi). This example illustrates the excellent adhesive properties to the wood of the glues made according to the present invention. The particle board made with glue according to the invention (D) greatly exceeds the standards established by the Canadian Standards Association.

Claims (10)

1. A composition comprising an aliphatic alternative polymer of olefinically unsaturated olefin monomers and carbon monoxide monomers characterized in that it has a number average molecular weight between 500 and 5,000 and vinyl monomer polymers, grafted therein.

2. The composition according to claim 1, characterized in that said olefins comprise ethene and propene.

3. An adhesive characterized in that it comprises an alternative aliphatic polymer of olefinically unsaturated compounds and carbon monoxide having a number average molecular weight between 500 and 5,000 and vinyl polymers grafted onto said aliphatic polymer to form a graft copolymer, and a mixed curing agent with said grafted copolymer.

4. The adhesive according to claim 3, characterized in that the curing agent is a primary aliphatic amine.

5. The adhesive according to claim 4, characterized in that the molar ratio of the carbonyl groups in the copolymer and the primary amine groups of the curing agent is in the range of 0.4 to 2.0.

6. The adhesive according to claim 4 or 5, characterized in that it further comprises a catalyst comprising an organic acid having a pKa in the range of 2 to 5.5, when measured in water at 20 ° C, and is present in a amount from 0.1% to 10.0% by weight, based on the weight of the copolymer.

7. A curable resin because it comprises the composition according to claim 1, in water and characterized in that it has a viscosity between about 200 and 8,000 mPa.s.

8. A method of making a curable resin because it comprises: (a) dispersion of an alternative aliphatic polymer of olefinically unsaturated compounds and carbon monoxide having a number-average molecular weight between about 500 and 5,000 in water, and (bl) adding an initiator and a monomer to said dispersion for forming a graft copolymer, or (b2) adding a vinyl monomer and exposing the combination of the aliphatic aliphatic polymer of the olefinically unsaturated compounds and carbon monoxide and the vinyl monomer to energy radiation to form a graft copolymer.

9. The method according to claim 8, characterized in that the vinyl monomer is a monoolefinic hydrocarbon, monoolefinically unsaturated ester, vinyl ester of halogenated acids, allyl compound, methallyl compound, alkenyl alcohol esters, halo-alkyl acrylate, alkyl alpha -cyanoacrylate, fumarate, monoolef solely unsaturated nitrile, aforementioned acid amides, vinyl alkyl ether, vinyl sulphides, diolefinically unsaturated hydrocarbon, or mixtures thereof.

10. A method of forming a wood composite of two or more parts comprises: (a) a combination of the composition according to claim 1, with a curing agent and a catalyst to form a glue, (b) application of said glue to one or more parts to be joined, and (c) the union of said parts.