CN1241197A - 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

graft copolymer composition

field of invention

This invention relates to resins prepared from olefinic monomers and carbon monoxide and their use as adhesives.

Background of the invention

Polymers of carbon monoxide and olefins, generally known as polyketones, are well known in the art. A class of linear alternating copolymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon is of particular interest in polyketone polymers. Polymers of this type are disclosed, for example, in US Patent Nos. 4,880,865 and 4,818,811. Polyketone polymers exhibit a well-balanced set of mechanical properties that make them particularly useful as engineering thermoplastics.

Other materials with suitable properties are also made from combinations of various olefins and carbon monoxide. It contains relatively low molecular weight materials, including oligomers or low molecular weight polymers. In this case, however, monomers other than carbon monoxide and ethylene constitute at least 20% of the total weight of the polymer. Two olefinic monomers, such as ethylene and propylene, are commonly used, with a higher percentage of each (on a weight or mole basis) compared to linear alternating aliphatic polyketones used as engineering thermoplastics. Such monomer mixtures typically include about 50 mole percent CO (based on the total weight of the polymer) and about 50 mole percent olefins (at least about 30 percent by weight of the total olefin content consists of _C3 or higher olefins).

These oligomers or low molecular weight polymers can be used as thermosetting materials. Depending on the composition used and the method of preparation, many polymers will excellently exhibit many of the properties normally associated with thermoplastics over a range of conditions. In these applications, amines are often used as curing agents to cure these materials. Curing can be accomplished in the presence of an acid catalyst. These resins are preferred as thermosets in many applications due to reduced environmental waste, ease of use, and blend of properties.

One application of these thermoset materials is as adhesives. More particularly, they are used as glue for wood composites in the preparation of plywood and particleboard. In this regard, the wood composite industry typically uses binders such as urea-formaldehyde and phenolic resins. However, many wood composites made with these adhesives are losing their important market share. Much of this is due to environmental and safety factors associated with these systems.

Wood glue compositions based on neat olefin/CO resins and amine curing agents have been prepared previously. While these pure gum systems provide good adhesion, their viscosity and pot life are not ideal for many commercial applications. Lowering their viscosity and increasing their pot life expands the range of applications for which olefin/CO resins can be used. In particular, they can be made more suitable for plywood and oriented strand board production under these conditions.

Summary of the invention

In one aspect of the invention, the olefin/CO copolymer is graft copolymerized with vinyl monomers. Grafting can be performed by applying high energy radiation to the olefin/CO copolymer in the presence of a suitable monomer. This graft copolymer is an excellent adhesive especially in wood applications and is cured in the presence of an acid catalyst by reaction with an amine curing agent. Such graft copolymers can be conveniently prepared as low molecular weight polymers.

Another aspect of the invention is the preparation of improved adhesives. These adhesives are especially useful in bonding wood and wood by-products and are prepared from copolymers based on carbon monoxide, ethylenically unsaturated compounds and a curing agent.

In another aspect of the invention, a wood composite material is presented. The wood composite comprises wood parts bonded to each other by a cured adhesive obtained by curing a curable resin composition comprising an ethylenically unsaturated compound Copolymer with carbon monoxide and a curing agent. Detailed description of the invention

Pure olefin/CO copolymer resins combined with amine hardeners can be used effectively as wood glues. In the practice of this invention, olefin/CO resins can be modified by graft copolymerization. It has been found that conversion of such pure olefin/CO copolymers by this method renders the systems suitable for use in aqueous modes, greatly improves shelf life, and reduces viscosity, thereby improving the processability of these systems. Furthermore, the grafted olefin/CO copolymer can greatly reduce the total price of all raw materials of the viscose, since the majority of the viscose can be a very cheap material such as styrene. The graft copolymer is preferably prepared by introducing a vinyl monomer into the oil phase of a dispersion of an olefin/CO copolymer. Grafting can be accomplished by adding a free radical initiator or by high energy radiation. Typically, this is accomplished by a free radical incorporating a hydrogen alpha to the carbonyl group in an olefin/CO copolymer. This forms a large free radical on the olefin/CO copolymer backbone, which then initiates the polymerization of vinyl monomers to form a grafted copolymer.

Copolymers of carbon monoxide and ethylenically unsaturated compounds are known. It is preferred that the copolymer contains 1,4-dicarbonyl groups in its polymer chain, since this arrangement is suitable for certain curing reactions, for example, with polyvalent primary amines as detailed below. Such olefin/CO copolymers can be prepared by known methods by platinum-catalyzed polymerization, the methods used being known from, for example, EP-A-121965, EP-A-181014, EP-A-516238. The polymers prepared in this manner may be linear alternating copolymers of carbon monoxide and ethylenically unsaturated compounds. That is, the polymer chain contains monomer units derived from carbon monoxide (ie, carbonyl groups) alternating with monomer units derived from ethylenically unsaturated compounds. Perfect alternating copolymers of carbon monoxide and ethylenically unsaturated compounds are preferred because these copolymers have a relatively high content of carbonyl groups on the polymer chain compared to random copolymers. This improves the cure quality of resins prepared from these systems, resulting in high quality crosslinks.

The carbon monoxide and ethylenically unsaturated compound copolymer may be based on a hydrocarbon as ethylenically unsaturated compound, but the ethylenically unsaturated compound may also contain a heteroatom, provided it is separated from the double bond by a spacer. For example comonomers such as 10-undecen-1-ol and 10-undecen-acid may be used. Preferred copolymers are based on an ethylenically unsaturated hydrocarbon having up to 10 carbon atoms. Aliphatic alpha-olefins having 3 to 6 carbon atoms are especially suitable in this connection, including those having straight carbon chains such as propylene, 1-butene, 1-pentene and 1-hexene. Propylene is the preferred monomer of this class. Most preferably ethylene and propylene are used in combination with propylene being the main monomer.

The molecular weight of such copolymers prior to grafting can vary over a wide range. A copolymer having a number average molecular weight of 200-20,000 may be used. However, copolymers having a number average molecular weight of 500-5000 are preferred. Molecular weights of 1000-4000 are most preferred. The molecular weight distribution of the polymer should generally be such that it has a Q value equal to 1.1-5, more typically 1.5-3, Q being the quotient of weight average molecular weight and number average molecular weight. The relatively low molecular weight of the copolymers renders the resin systems of the present invention liquid when used at temperatures typical of the processing and use of the copolymers. A frequently used range is 10-80°C, more often 20-60°C. The processing of the copolymers includes, for example, the preparation of the adhesive used in the invention and the use of this adhesive on wood surfaces.

Before grafting, the copolymer comprised approximately 50 mole percent CO and 50 mole percent olefin. A preferred olefin composition comprises 0-70% by weight ethylene and 30-100% by weight propylene. A more preferred olefin mixture is 20-70% by weight ethylene and 80-30% by weight propylene. Most preferred is an olefin mixture of 70% by weight propylene and 30% by weight ethylene.

Grafting can be done in any manner that results in a graft copolymer. This involves exposing a combination of a suitable monomer and copolymer to high energy radiation, such as electron beam radiation, ion radiation, delta radiation or combinations thereof, heating a suitable monomer in the presence of the copolymer, Or react with suitable monomers in the presence of free radical initiators and copolymers. Any other suitable method for grafting copolymerized polymers can be used in the practice of this invention.

The olefin/CO copolymer of the present invention is typically a liquid. Such solutions can generally be prepared from a combination of polymer and graft-forming monomer. It may be necessary to emulsify the solution with a surfactant. Nonionic surfactants are preferably used for this purpose. In many cases, exposure to radiation sufficient to cause graft copolymerization (in the absence of oxygen) will increase the viscosity of the liquid. However, it generally does not cause curing of the polymer. This is useful when applying the materials as glue, as they can be easily placed in an aqueous solution, the applied material becomes tacky, and then cures.

The intensity of radiation sufficient to cause grafting is generally 0.001-20 Mrad/hour, and the total amount of ionizing radiation required for graft copolymerization is generally 0.005-20 Mrad, most preferably 0.1 Mrad.

The polymer to be grafted generally must be free of oxygen during the grafting process. This can be achieved by subjecting the polymer/monomer mixture to vacuum or irradiation in an inert gas such as nitrogen, helium, neon, argon, carbon dioxide, and the like.

The temperature and pressure conditions required for the grafting process of the present invention are not harsh. Generally, any convenient temperature from 0°C to 100°C can be used as the reaction temperature. The reaction can still be carried out at a temperature lower than the lower limit, but the reaction rate will be greatly reduced. Atmospheric pressure is generally used, but a wide range of conditions can be used without appreciably affecting the grafting process.

The reaction time can vary within wide limits. When high radiation doses are used, the reaction can be completed in seconds. The preferred dose of radiation is 0.05-2 Mrad at room temperature. Reaction times of 10 seconds to 24 hours will well provide grafting efficiencies of 5-95%. Grafting efficiency is the ratio of the amount of grafted monomer to the amount of total monomer on a weight basis.

The most preferred method of preparing the graft polymerized copolymers of the present invention is free radical initiation. Suitable monomers for grafting by this method include, for example, monoolefins such as styrene and its derivatives, monoethylenically unsaturated esters such as vinyl acetate, vinyl esters of halogenated acids such as alpha-chlorovinyl acetate , allyl and methallyl compounds such as allyl chloride, esters of alkenyl alcohols such as esters of β-ethylallyl alcohol, etc., haloalkyl acrylates such as α-methyl chloroacrylate, Methyl alpha-cyanoacrylate, fumarate esters such as diethyl fumarate, monoethylenically unsaturated nitriles such as acrylonitrile, amides of the above-mentioned acids such as acrylamide, alkyl ethers such as ethylene methyl ethers, vinyl sulfides such as vinyl β-ethoxyethyl sulfide, diethylenically unsaturated hydrocarbons such as 1,3-butadiene, and mixtures of the above compounds. Preferred monomers are styrene, acrylates, methacrylates, vinyl esters, and vinyl halides. Most preferred is styrene.

Free radical initiators can be water-soluble or oil-soluble. Water-soluble free radical initiators include, for example, potassium persulfate, ammonium peroxodisulfate, potassium peroxodisulfate, sodium persulfate, hydroperoxides and water-soluble azo initiators. Oil-soluble free radical initiators include, for example, benzoyl peroxide, tert-butyl perbenzoate and 2,2'-azobis(isobutylonitrile). Water-soluble initiators are preferably, for example, potassium persulfate or azo initiators. The concentration of free radical initiator is 0.01--0.5g per 100g of total monomer.

Redox initiators comprising an oxidizing agent, such as potassium persulfate or potassium bromate, and a reducing agent, such as sodium sulfite hexahydrate, or tertiary amines, such as triethylamine, can also be used to initiate polymerization, especially at low temperatures.

The method of producing the graft copolymers of the present invention comprises contacting an olefin/CO copolymer with an initiator in the presence of the monomers used to form the grafted portion of the polymer. Preferably, the monomer used to form the graft is introduced into the oil phase of the olefin/CO resin dispersion, and then an initiator is added to the dispersion to complete the grafting process. Minor agitation, such as by stirring or mixing, can be performed.

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. Generally, the dispersion will contain a greater amount of water than the olefin/CO copolymer on a weight basis, however this is readily determined by those skilled in the art, and additional aliquots of copolymer may be added during emulsification to increase The solids content of the final product formed. In viscose applications, a high solids content is desirable, but the viscosity must be controlled low enough to allow easy application of the material. Under these conditions viscose prepared using the graft copolymers of the present invention can achieve solids contents of up to about 60%.

Any surfactant capable of dispersing the olefin/CO resin in water can be used as long as the material does not interfere with the initiation of the graft copolymerization. Preferred surfactants are nonionic and typically include, for example, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol alkylphenyl ethers, polyalkylene glycol fatty acid esters , sorbitan fatty acid ester, alkyl polyglucoside (polyglycoside), fatty acid dialkanolamide and the like. Selection of the amount of surfactant added to form the emulsion is within the purview of one of ordinary skill 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 capable of forming an emulsion of the copolymer and grafted monomers can be used.

Once the graft copolymers of the present invention are prepared, a curing agent and optionally a catalyst are added thereto for further preparation into viscose and binders (commonly referred to as adhesives). Adhesives prepared in this way can then be used to join two or more similar or dissimilar materials together. For example composite materials can consist of wood components, wood chips, different types of veneer panels, metals, different polymers and other materials. Composite materials formed by combining two or more wood components are the most preferred embodiment of the present invention.

The type and form of wood components used to make composites are not critical. Wood can be high or low density and can be of deciduous or coniferous origin. Suitable species are, for example, oak, nutwood, eucalyptus, maple, teak, okoume, mahogany, meranti and pine. Great results can be obtained with beech, spruce and poplar. The wood does not require any pretreatment other than that normally done when using conventional adhesives. It is generally sufficient to obtain, for example, mechanical and/or chemical methods, wood parts of the size and shape required to make certain types of composite materials. Suitable forms of wood, when used, may be planks, veneers, blocks, sheets, chips or pulp. Combinations of two or more types or forms of wood components may also be used, for example to improve the appearance of the composite material.

Wood can be pretreated to increase its durable properties. An example of such pretreatment is treatment with superheated steam at 150°C to 220°C under pressure, followed by heating at ambient pressure 100°C to 220°C. Another pretreatment method is soaking in salts, such as chromium salts, copper salts, mercury salts, arsenic salts, or a combination of these salts.

A number of curing agents can be used in adhesives according to the invention. Suitable curing agents or curing systems are disclosed in EP-A-372602 and may also include, for example, amines, thiols, or acrylonitrile. Preferred curing agents include, for example, hexamethylenediamine (HMDA), hexamethylenediamine carbamate, tetramethylenepentylamine, hexamethylenediaminocinnamaldehyde adduct and hexamethylenediamine Aminodibenzoate. Aromatic and cycloaliphatic amines can also be used, but those with bulky functional groups are less preferred. Primary aliphatic diamines of the structure _H2NR - _NH2 (R represents a divalent aliphatic bridging group having up to 10 carbon atoms in the bridging group) are preferred curing agents. HDMA is the most preferred curing agent.

It is also advantageous to use mixtures of curing agents. In particular, mixtures of a relatively highly reactive curing agent and a relatively low reactive curing agent can be used. For example, linear aliphatic diamines, which are more reactive curing agents, and aromatic or cycloaliphatic primary polyamines, which are less reactive curing agents, can be used in combination. Rapid gelation occurs once cure is initiated in the presence of more reactive curing agents. Curing agents with less activity prolong the curing time of the cyclic carbon skeleton, which will improve the mechanical properties of the composite at high temperatures. The molar ratio of the more reactive curing agent to the less reactive curing agent can vary widely, depending on the requirements of the particular adhesive being used. Such molar ratios can be readily determined by the skilled artisan by routine experimentation. Typical molar ratios are from 2:98 to 98:2.

The degree of crosslinking which takes place during curing is determined in particular by the ratio of the amount of curing agent used relative to the amount of the copolymer of carbon monoxide and ethylenically unsaturated compound. The relative amount of curing agent can vary widely, and a preferred relative amount can be determined by routine experimentation. When multiple primary amines are used as the curing agent, the molar ratio of the carbonyl group in the copolymer to the primary amine group of the curing agent is suitable between 0.25-8.0, more suitable between 0.4-2.0.

Curing of the copolymer can be carried out in the presence of a curing catalyst or in the absence of any curing catalyst. An advantage of using a catalyst is that curing can generally be performed at lower temperatures or in shorter times. When the curing agent is an aliphatic diamine, suitable catalysts are weak acids, especially acids with a pKa measured in water at 20°C of between 2 and 5.5, preferably between 2.5 and 5. A preferred class of acids are organic acids, especially carboxylic acids, since they are at least to some extent soluble in the copolymer to be cured. Monocarboxylic acids are more 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. Another suitable weak acid is phosphoric acid. Acetic acid is the most preferred catalyst.

Small amounts of weak acids can be used. A suitable amount is 0.1 - 15.0% relative to the weight of the copolymer. More preferably the amount of weak acid is 0.2-10.0% by weight. The most preferred amount is 0.5-8.0% by weight based on the same criteria.

The aqueous viscose compositions of the present invention generally exhibit a viscosity that makes them easy to use. The general range is that the viscosity measured with a Brookfield viscometer at room temperature is between 200-5000mPa.s. However, if desired, a diluent may be used in the curable resin composition to facilitate application of the composition to wood parts. Diluents also increase the compatibility of the curing agent and any catalysts with the copolymer. Suitable diluents are, for example, lower alcohols, lower ketones, lower esters such as acetates, and lower ethers. The term "lower" refers to diluents having an average of 5 or fewer carbon atoms per molecule. Examples of preferred diluents are water and lower alcohols, most preferably water. Other suitable diluents are acetone, ethyl acetate, methyl propionate, and ethylene glycol dimethyl ether. When the curable resin composition is applied by eg spraying, the suitable viscosity at the application temperature is 100-2000 mPa.s, preferably 500-1000 mPa.s. Preferably the diluent and copolymer are used in a weight ratio of at least 1:5, especially in the range of 1:2 to 5:1, most especially in the range of 1:1.5 to 2:1.

It is possible to prepare the curable resin composition as a paste which can be conveniently sprayed on the wood surface at a convenient temperature range, for example between 10°C and 50°C. The consistency of the paste can be achieved by adding a relatively small amount of a diluent, such as water, a lower alcohol or a lower ketone, to the binder. Typical amounts of diluents range from 0.2 to 5.0% by weight, especially from 0.3 to 3.0% by weight, more particularly from 0.5 to 1.0% by weight, relative to the weight of the copolymer. Very favorable results can be obtained by mixing a linear alternating copolymer of carbon monoxide and an olefin with water, a surfactant, a free radical initiator and a vinyl polymer, the linear alternating copolymer The weight average molecular weight range is 200-10,000, and then this mixture is stirred for 15 minutes, and then a primary amine, a weak acid used as a curing catalyst, and a 0.2-5.0% by weight relative to the weight of the copolymer are added. Diluent, the resulting mixture is heated between 30°C-100°C, preferably 40°C-80°C. The heating time is determined by the selected temperature, and can be appropriately changed between 5-50 minutes, and can be easily determined through common experiments to select the heating temperature so that the adhesive can reach the desired consistency and quality. The resulting paste can be applied to wood at the temperature used for preparation, but can also be used at ambient temperature.

The adhesive may contain additional components to improve its properties. Examples of suitable additional ingredients are: viscosity modifiers, flame retardants, caulking agents, antioxidants, UV stabilizers and colorants. Example: Clay can be used as a filler, or it can be used to reduce viscosity at high shear rates. A suitable caulk is silica, grain flour or coconut shell flour. Especially desirable additives when the composition prepared according to the present invention is used as a coating material are antioxidants and UV light stabilizers.

The adhesive can be applied to the wood surface using any conventional technique. The adhesive, especially the pastes described above, can be applied to the surface using one such as a brush, roller, applicator knife or doctor blade. It has been shown that, after adding a suitable amount of diluent, the adhesive can likewise be sprayed via a compressed gas-driven nozzle, eg a continuous in-line spray or using a coating sprayer. If desired, when a composite material with a soft hand is to be produced, the adhesive can also be used as a coating on the wood surface on the outer surface of the composite material. It is likewise possible to coat the cured composite material and cure the coating in an additional curing step.

The amount of adhesive relative to the amount of wood can vary widely and is generally determined by the type of composite being prepared, for wood laminates this amount can be defined as per square meter of wood surface coated with adhesive Or the amount per square meter of wood surface required to create a joint between two wood veneers. Generally, 30-400 grams of adhesive is used per square meter at the joint. Preferably 60-120 grams of adhesive is used.

When the wood composite used is a fiberboard or a particleboard, it is more convenient to relate the amount of binder used to the weight of the composite. The amount of binder used generally corresponds to 20-150 g, more typically 30-100 g, of the copolymer of carbon monoxide and ethylenically unsaturated compound from which the binder is made, per kg of fibreboard or particle board. For the specific application of fiberboard, it is desirable to have the binder as a continuous phase, in which case the amount of this binder used per kilogram of composite based on the amount of copolymer from which the binder is made is 150-600 g, especially 200-500 g of copolymers of carbon monoxide and ethylenically unsaturated compounds are used.

Simultaneously or thereafter, the adhesive is applied to the surfaces of the wood parts to be joined such that the adhesive remains between the wood parts and subsequently cured under curing conditions. Temperature and pressure can vary over wide ranges. The temperature is generally determined by the curing agent and the curing catalyst present. When the polybasic primary amine is used as the curing agent, the suitable temperature is above 50°C, such as between 80-200°C, especially 100-160°C. For laminated boards, the general pressure is between 1-30 kg/cm ² , preferably 2.5-25 kg/cm ² . In the use of fiberboard and particleboard, the general pressure is 10-150kg/cm ² , preferably 25-100kg/cm ² .

Different types of wood composites can be produced according to the invention, for example fibreboards, particleboards such as sandwich panels, and laminated panels such as plywood, laminated veneer or timber. These composites have an excellent impact/strength balance and good dimensional stability when wet. Therefore, composite materials can be easily used in the manufacture of doors, veneered floors, sporting goods such as hockey sticks, and electrical appliances such as switching tables and distribution box panels. Fiberboard with binder as continuous phase can be used in building panels.

The invention will be further illustrated in the following non-limiting examples. The viscose formula is as follows: A=100 parts by weight (pbw) of the emulsion of Example 2, 25 parts by weight of 65% HMDA, and 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, and 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, and 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, and 4 parts by weight of 20% acetic acid.

Embodiment 1: (preparation of olefin/CO polymer)

An autoclave containing 80 parts by volume of methanol, 10 parts of water, and 10 parts of acetic acid was heated to 95°C and then filled with 36 bars of propylene, 16 bars of C), 4 bars of ethylene and a solution containing a molar ratio of 1/1.05 /2.1 catalyst solution of palladium acetate, 1,3-bis(di-o-methoxyphenylphosphino)propane and trifluoromethanesulfonic acid. During the reaction, the temperature was kept at 95°C, and the pressure of the reactor was kept constant by continuously feeding a 1/1 ethylene/CO mixture. After 20 hours, the reactor temperature was lowered to room temperature and vented. The solvent was removed under reduced pressure to obtain an olefin/CO alternating copolymer with a number average molecular weight of 1800 and a molar ratio of ethylene/propylene of 28/72. The catalyst yield was 36 kg of oligomer per gram of palladium. Embodiment 2: (preparation of water-containing resin)

Add 76.6 parts by weight (pbw) of the alternating copolymer prepared in Example 1 to the resin reactor equipped with a kind of anchor stirrer, 52 parts by weight of nonionic poly(ethylene glycol) surfactant (available in Shell available from Chemical Corporation under the trade name "23W004") and 108 parts by weight of water. The mixture was stirred at 200 rpm, and an additional equivalent amount of copolymer was added over two hours until the total amount of copolymer in the mixture reached 500 parts by weight. After stirring for a further 3 hours at ambient temperature, 343 parts by weight of water were added over 1 hour to give an emulsion with a solids content of 55%. Embodiment 3A: (preparation of water-containing graft polystyrene olefin/CO resin):

144 parts by weight of water, 163 parts by weight of styrene and 1.45 parts by weight of potassium persulfate were added to the 479 parts by weight of the emulsion prepared in Example 2. The mixture was placed in a bottle, shaken for 15 minutes, and then placed in an oven at 60°C overnight. The obtained product is a grafted polyethylene olefin/CO copolymer emulsion, the weight ratio of olefin/CO copolymer and polystyrene is 60/40, and the solid content of the emulsion is 55% by weight. Example 3B: Graft Copolymerization of Olefin/CO Polymers by Radiation:

A terpolymer of carbon monoxide, ethylene, propylene is prepared in the presence of a catalyst composition formed from palladium acetate, trifluoroacetic acid anion and 1,3-bis(diphenylphosphino)propane. The linear terpolymer has a melting point of 220°C and an intrinsic viscosity number (LVN) of 1.8 measured in m-cresol at 60°C.

10 grams of terpolymer and 2 grams of styrene and 10ppm inhibitor tert-butylcatechol are mixed and placed in a glass container, and in the air with an intensity of 0.26 Mrad/hour cobalt 60δ ray source at room temperature Irradiate for 24 hours. The resulting solid was extracted with hot toluene to remove the homopolystyrene. Solid ^state1HNMR analysis of the extracted product indicated that it contained grafted polystyrene. The grafting efficiency (monomer grafted/total monomer amount) was 78%.

This example shows that polymers based on olefin/CO backbones can be graft-copolymerized by high-energy radiation. Example 3C: (Preparation of Low Molecular Weight Olefin/CO Graft Copolymer: Putative)

150 parts by weight of water and 170 parts by weight of styrene were added to 500 parts by weight of the emulsion prepared in Example 2. The resulting mixture was irradiated with a cobalt 60δ ray source with an intensity of 0.26 Mrad/hour at ambient temperature for 0.5 hour to graft-polymerize styrene to obtain an aqueous emulsion with a solid content of 55%. Example 4: (Preparation of Aqueous Grafted Poly(methyl methacrylate) Olefin/CO Resin)

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 part by weight of potassium persulfate was heated at 60° C. for 6 hours in a resin reactor with stirring. A grafted poly(methyl methacrylate) olefin/CO copolymer emulsion was formed. The ratio of olefin/CO copolymer and 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 an improved version of Plywood Sample Test 6.1.5.3, which was revised in 1995 by the American Plywood Federation as described in PSI-95, Architectural and Industrial Plywood.

The veneer of 0.4 cm (1/6”) Southern Pine was prepared as a three-ply (no cut) cross-ply wood panel by using three different types of aqueous adhesive formulations, respectively Embodiment 2, 3A, and the emulsion that 4 obtains and hexamethylenediamine (HMDA) and acetic acid mix and obtain. Panel is hot-pressed under 200 ℃ and 1.4MPa (200psig).All panel adhesive consumptions are 65 gram solids/ ^m2 per glue line. To evaluate water resistance, cut 2.5×7.6cm ² (1”×3”) samples from the panel, soak in boiling water for 4 hours, and then dry in an oven at 63°C for 23 hours , soaked in water for 4 hours. The performance of the viscose is evaluated according to the number of samples that do not delaminate after two rounds of boiling tests for a given hot pressing time.

The results obtained are listed in Table 1 below. Table 1: Viscose formulation: 200°C hot pressing time

4.5 minutes 6 minutes 10 minutes

(Remaining number of plywood test samples after boiling test) A 0 0 5 3B 0 3 3 3 3C 3 2 3 3 3

This example shows that good wood adhesion can be obtained using a glue prepared according to the invention. Sample A uses a glue comprising an ungrafted copolymerized olefin/CO polymer. Samples B and C are viscose obtained according to the invention. Using ungrafted polymer as the glue, the bonded samples required 10 minutes of hot pressing time to withstand the boiling test. Using an adhesive prepared in accordance with the present invention, a bonded sample required a heat press time of 6 minutes (or less) to withstand the boiling test. Example 6: Preparation and Properties of Particleboard

This example is a modified version of Test 5.4.1 for Plywood Samples, as described in "Standard 0437 Series 93 for OSB and Sandwich Panels," published by the Canadian Standards Association in 1993.

Particleboard was sprayed successively in a drum with a 51% emulsion of a non-volatile wax (15 cpp supplied by Borden) and an aqueous viscose prepared from southern pine shavings 46 x 50 x 1.11 cm ( ¹⁸ "×20"×7/16") random oriented particle board panel. Spraying is done by an atomizing sprayer (concord high-precision sprayer manufactured by Coil Industries). The amount of wax and viscose solids used are respectively 1 and 4% of wood weight. Panels were hot pressed at 200°C for 4.5 minutes, with a pressure of 5.5 MPa (800 psig) for the first 1.5 minutes and a pressure of 2.8 MPa (400 psig) for the rest of the hot pressing process. The results obtained See Table 2 below, modulus of rupture, modulus of elasticity and intrinsic adhesion measured using a Tinius Olsen instrument according to ASTM D 1037. Table 2: Viscose Formulation: Intrinsic Adhesion Modulus of Rupture Elastic Modulus

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 that the intrinsic cohesion is 0.3MPa (50psi), the modulus of rupture is 17.2MPa (2500psi), and the modulus of elasticity is 3.1MPa (450psi). This example shows that the glue made according to the invention has very good wood bonding properties. Particleboards made from viscose obtained according to the invention (D) greatly exceed the standards set by the Canadian Standards Association.

Claims (10)

1, a kind of composition, wherein contain the monomeric alternately aliphatic polymer of the aliphatic olefin of a kind of number-average molecular weight 500-5000 and carbon monoxide and with its grafted polymers of vinyl monomers.

2, the composition of claim 1, wherein said alkene comprises ethene and propylene.

3, a kind of tackiness agent, the aliphatic olefin and the monomeric alternately aliphatic polymer of carbon monoxide that comprise a kind of number-average molecular weight 500-5000, be grafted to the ethene polymers that said aliphatic polymer forms graft copolymer, and the mixed solidifying agent of a kind of and described graft copolymer.

4, the tackiness agent of claim 3, solidifying agent wherein are a kind of Armeens.

5, the tackiness agent of claim 4, wherein in the multipolymer in carbonyl group and the solidifying agent mol ratio of primary amine group be 0.4-2.0.

6, the tackiness agent of claim 3 also comprises a kind of catalyzer, and this catalyzer comprises a kind of organic acid, and in 20 ℃ water, the scope of the pKa that records is 2-5.5, and its amount is a 0.1-10% weight with respect to multipolymer weight.

7, curable resin comprises the composition of the claim 1 in the water, and has the viscosity of about 200-8000mPa.s.

8, the method for a kind of curable resin of preparation, comprise: (a) will have number-average molecular weight and be distributed in the water at alkene/CO multipolymer of about 500-5000, form the dispersion of a kind of alkene/CO multipolymer, (b1) add a kind of initiator and a kind of monomer to said dispersion liquid, form graft copolymer, or (b2) add a kind of initiator and the composition of alkene/CO multipolymer and vinyl monomer is carried out energy-rich radiation expose, form a kind of graft copolymer.

9, the method for claim 8, therein ethylene base monomer is a kind of monoolefine, monoene belongs to unsaturated ester, the vinyl ester of halogenated acid, allylic cpd, methacrylic compound, the ester of alkenyl alcohol, vinylformic acid haloalkyl ester, α-Qing Jibingxisuanwanjizhi, fumarate, monoene belongs to unsaturated nitrile, the acid amides of above-mentioned acid, vinyl alkyl ethers, the vinyl thioether, diolefinic unsaturated hydrocarbons, or their mixture.

10, a kind of method that forms the matrix material of two or more parts, comprise: (a) with composition and a kind of solidifying agent of claim 1, a kind of viscose glue of the mixed formation of a kind of catalyzer, (b) said viscose glue is applied on one or more parts that will engage and (c) with said parts bonding to together.