CN1241197A - Graft copolymerized compositions - Google Patents
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- CN1241197A CN1241197A CN 97180866 CN97180866A CN1241197A CN 1241197 A CN1241197 A CN 1241197A CN 97180866 CN97180866 CN 97180866 CN 97180866 A CN97180866 A CN 97180866A CN 1241197 A CN1241197 A CN 1241197A
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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
Invention field
The present invention relates to the resin that makes by olefinic monomer and carbon monoxide with and as the application of tackiness agent.
Background of invention
Being commonly referred to as the carbon monoxide of polyketone and the polymkeric substance of alkene knows in the art.One class preparing linear alternating multipolymer particularly important in polyketane polymers of carbon monoxide and at least a ethylenically unsaturated hydrocarbons.This base polymer is at for example United States Patent (USP) NO.4, and is open in 880,865 and NO.4,818,811.Polyketane polymers shows a series of good isostatic mechanical propertys, and it is particularly useful as the engineered thermoplastic material.
Other the material with applicable performance is equally also made by the combination of different alkene and carbon monoxide.Wherein contain low-molecular-weight relatively material, comprise oligopolymer or low-molecular-weight polymkeric substance.But in this case, the monomer except carbon monoxide and ethene has constituted 20% of total polymer weight at least.Usually use for example ethene and these two kinds of olefinic monomers of propylene, compare every kind of degree (based on weight or mole) with the linear alternated aliphatic polyketone of using as the engineered thermoplastic material higher.This monomeric mixture is general comprises that about 50% mole CO (based on the gross weight of polymkeric substance) and about 50% mole alkene are (at least about 30% weight total olefin composition by C
3Or more high-grade alkene is formed).
These oligopolymer or low-molecular-weight polymkeric substance can use as thermosetting material.According to composition therefor and preparation method, many polymkeric substance will still demonstrate the general many performances relevant with thermoplastics first-class under the condition of certain limit.In these were used, amine commonly used solidified these materials as solidifying agent.Curing can be finished in the presence of acid catalyst.Because of can reduce environmental waste, be easy to use and performance mixed, these resins preferably become thermosetting material in many application.
An application of these thermosetting material is as tackiness agent.More specifically, their viscose glues as Wood composite material in the preparation of glued board and shaving board use.In this, Wood composite material industry is used usually as tackiness agents such as urea-formaldehyde resin and resol.Yet even the demand of the Wood composite material of the high impact properties of maintenance dimensional stability well under the environment of humidity is generally kept under the condition with higher, the Wood composite material that these tackiness agents of many usefulness make is just losing important market share.This is because environment and the safety factor relevant with these systems causes mostly.
Before made wooden sizing composition based on pure alkene/CO resin and amine curing agent.Though these pure colloids are that good binding property is provided, their viscosity and shelf-time are not satisfactory to many commercial applications.Reduce their viscosity and increase its shelf-time and can expand alkene/applicable scope of CO resin.Especially, they can make the production that is more suitable for being used for glued board and oriented wood chipboard under this condition.
Summary of the invention
In one aspect of the invention, alkene/CO multipolymer graft copolymerization of vinyl monomer.Can under the situation that a kind of proper monomer exists,, alkene/CO multipolymer carry out grafting by being applied high-octane radiation.This graft copolymer is fabulous viscose glue in timber is used especially, and solidifies with a kind of amine curing agent reaction in the presence of a kind of acid catalyst.Can prepare this graft copolymer easily as low-molecular weight polymer.
This invention is the improved tackiness agent of preparation on the other hand.These tackiness agents are particularly useful aspect bonding timber and wood by-product, and they are by based on carbon monoxide, the copolymer of alefinically unsaturated compounds and a kind of solidifying agent.
In another aspect of this invention, introduced a kind of Wood composite material.This wood composites comprises by solidified binding agent timber components together adhered to one another, this binding agent obtains by solidifying a kind of curable resin combination, and this resin combination has comprised the multipolymer by alefinically unsaturated compounds and carbon monoxide and a kind of solidifying agent.Detailed Description Of The Invention
Pure alkene/CO copolymer resin and amine curing agent combination can be used as the timber viscose glue effectively.In enforcement of the present invention, alkene/CO resin can improve by graft copolymerization.Found to change by this method this pure alkene/CO multipolymer, the system that makes is suitable for using in moisture mode, has greatly improved staging life, and has reduced viscosity, thereby improved the processibility of these systems.Further, grafting alkene/CO multipolymer can greatly reduce the whole raw-material total price of viscose glue, because the major part of viscose glue can be very cheap material such as vinylbenzene.This graft copolymer preferably prepares by the dispersion oil phase that makes a kind of vinyl monomer enter into a kind of alkene/CO multipolymer.Grafting can be by adding a kind of radical initiator or finishing by high-octane radiation.Usually, this is to finish by the hydrogen on the α position of carbonyl in alkene of a combined with radical/CO multipolymer.Formed a big free radical like this on alkene/CO copolymer skeleton, initiating polymerization of vinyl monomer forms a kind of grafted multipolymer then.
Carbon monoxide and alefinically unsaturated compounds multipolymer are known.Preferred copolymer contains 1 on its polymer chain, 4-dicarbapentaborane group, because this arrangement is suitable for certain curing reaction, for example, with the polynary primary amine reaction of following detailed introduction.This alkene/CO multipolymer can prepare with currently known methods by the catalytic polyreaction of platinum, and used method is from for example EP-A-121965, EP-A-181014, among the EP-A-516238 as can be known.The polymkeric substance that this mode prepares can be the preparing linear alternating multipolymer of carbon monoxide and alefinically unsaturated compounds.Be that polymer chain contains the monomeric unit (being carbonyl group) that comes from carbon monoxide and the monomeric unit that comes from alefinically unsaturated compounds alternately arranged.The perfect alternating copolymer of preferred carbon monoxide and alefinically unsaturated compounds has relative high-load carbonyl group because these multipolymers are compared with random copolymers on polymer chain.Can improve the curing quality by the resin of these system preparations like this, it is crosslinked to produce high quality.
Carbon monoxide and alefinically unsaturated compounds multipolymer can be based on a kind of hydrocarbon as alefinically unsaturated compounds, but alefinically unsaturated compounds also can comprise a kind of heteroatoms, as long as it is separated by a spacer groups with two keys.For example can use the pure and mild 10-hendecene-acid of comonomer such as 10-hendecene-1-.Preferred copolymer is based on having a kind of ethylenically unsaturated hydrocarbons of 10 carbon atoms at the most.Aliphatic alpha-olefin with 3-6 carbon atom comprises those as propylene especially suitable aspect this, 1-butylene, the alkene that normal carbon chain is arranged of 1-amylene and 1-hexene.Propylene is the preferred monomer in this class.Most preferably uniting use ethene and propylene and propylene is main monomer.
The molecular weight of this multipolymer can be in very big range before grafting.Can use to have 200-20 the multipolymer of 000 number-average molecular weight.Yet, the multipolymer that preferably has the number-average molecular weight of 500-5000.The molecular weight of 1000-4000 most preferably.The molecular weight distribution of polymkeric substance generally should make its Q value equal 1.1-5, and more typical is 1.5-3, and the Q value is the merchant of weight-average molecular weight and number-average molecular weight.The relative lower molecular weight of multipolymer makes resin system of the present invention be liquid when using in multipolymer processing with under the general temperature when using.Often the scope of using is 10-80 ℃, and is more frequent at 20-60 ℃.The processing of multipolymer comprises the use at wood surface of the preparation of tackiness agent used in the present invention for example and this tackiness agent.
Before the grafting, multipolymer comprises the alkene of about 50% mole CO and 50% mole.Preferred alkene is formed and is comprised the ethene of 0-70% weight and the propylene of 30-100% weight.Preferred alkene mixture is the ethene of 20-70% weight and the propylene of 80-30% weight.Most preferably alkene mixture is the propylene of 70% weight and the ethene of 30% weight.
Connecing technical ability enough carries out in the mode of any formation graft copolymer.This comprises a kind of suitable monomers and multipolymer mixed and is exposed in the high-octane radiation, electron beam ray for example, ion irradiation, delta ray or its mixed ray, a kind of suitable monomers of heating in the presence of multipolymer, or in the presence of radical initiator and multipolymer, react with suitable monomers.Any other method that is suitable for the graft copolymerization polymkeric substance all can be used for implementing the present invention.
What alkene of the present invention/CO multipolymer was general is a kind of liquid.Solution can and form the grafted monomer by polymkeric substance usually and combines and make like this.Might need to come this solution of emulsification with tensio-active agent.Nonionogenic tenside is preferred for this purpose.In many cases, be enough to cause that the radiant exposure (when anaerobic exists) of graft copolymerization will increase the viscosity of liquid.Yet it does not generally cause the curing of polymkeric substance.This is being useful with material during as viscose glue, because can easily they be placed aqueous solution, administration of material becomes sticky, and solidifies then.
Can cause the enough yield of radiation of grafted be generally the 0.001-20 megarad/hour, the total amount of the ionizing radiation that graft copolymerization is required is generally the 0.005--20 millirad, most preferably is 0.1 megarad.
Generally must anaerobic in the grafting process with polymers grafted.This can place vacuum or place a kind of rare gas element to carry out radiation by the mixture with polymer/monomer realizes rare gas element such as nitrogen, helium, neon, argon gas, carbonic acid gas or the like.
The required temperature and pressure condition of grafting process of the present invention is not harsh.General 0 ℃ of-100 ℃ of any temperature easily can be as temperature of reaction.This reaction still can be reacted being lower than under the temperature of lower limit, but speed of response will reduce greatly.Generally use barometric point, but also can use the condition of wide range, and can not influence the grafting process significantly.
Reaction times can change in very wide scope.When using high radiation quantity, reaction can be finished in the several seconds.Preferred radiation quantity is the 0.05-2 megarad during room temperature.10 seconds-24 hours reaction times will provide the grafting efficiency of 5-95% well.Grafting efficiency be based on weight by the ratio of the monomeric amount of grafted with all monomeric amounts.
The most preferred method for preparing graft polymerization multipolymer of the present invention is that free radical causes.The used suitable monomers of grafting for example comprises in this way: monoolefine, for example vinylbenzene and derivative thereof, monoene belongs to unsaturated ester such as vinyl acetate, the vinyl acetate of haloid acid such as α-chlorination vinyl-acetic ester, allyl group and methacrylic compound such as chlorallylene, the ester of the ester of alkenyl alcohol such as β-allyl ethyl alcohol etc., haloalkyl acrylate such as α-Lv Daibingxisuan methyl ester, the alpha-cyanoacrylate methyl ester, fumarate such as DEF, monoene belongs to unsaturated nitrile such as vinyl cyanide, the acid amides of the above-mentioned acid of mentioning such as acrylamide, alkyl oxide such as vinyl methyl ether, vinyl thioether such as vinyl β-ethoxyethyl group thioether, the diolefinic unsaturated hydrocarbons is as 1, the mixture of 3-divinyl and above-mentioned compound.Preferred monomer is a vinylbenzene, acrylate, methacrylic ester, vinyl ester, and vinyl halide.Most preferred is vinylbenzene.
Radical initiator can be water-soluble or oil-soluble.Water miscible radical initiator comprises as Potassium Persulphate, peroxo disulfate acid ammonium, potassium peroxydisulfate, Sodium Persulfate, hydroperoxide and water-soluble azo initiator.Oil-soluble radical initiator comprises for example benzoyl peroxide, the perbenzoic acid tert-butyl ester and 2,2 '-azo two (isobutyl-nitrile).Water soluble starter is for example Potassium Persulphate or azo initiator preferably.The concentration of radical initiator is that per 100 gram total monomers contain 0.01--0.5g.
Comprise that a kind of oxygenant such as Potassium Persulphate or potassium bromate and a kind of reductive agent as six water S-WAT or tertiary amines, as the redox initiator of triethylamine, also can be used for initiated polymerization, be particularly suitable for low temperature.
The method that produces graft copolymer of the present invention comprises alkene/CO multipolymer is contacted with initiator under the situation that the monomer of the grafting part that is used for forming polymkeric substance exists.Preferably will in this dispersion, add initiator then, finish the grafting process by being used to form in the dispersion oil phase that the grafted monomer is incorporated into alkene/CO resin.Can carry out a spot of stirring, stir or mix such as passing through.
Alkene/CO the dispersion that wherein adds grafted monomer preferably mixes by alkene/CO multipolymer and water and a kind of tensio-active agent and forms.Generally by weight, the water yield contained in the dispersion is bigger than the amount of alkene/CO multipolymer, it is definite easily that yet this is those skilled in the art, and extra aliquot multipolymer can add in emulsion process, to increase the solids content of formed the finished product.In the application of viscose glue, highly filled is ideal, but essential viscosity controller is to enough low, so that easily use this material.The viscose glue that uses graft copolymer of the present invention to make under these conditions can reach about at the most 60% solids content.
Any alkene/the tensio-active agent of CO resin dispersion in water can both be able to use be not as long as material disturbs the elicitation procedure of graft copolymerization.Preferred surfactant is a non-ionic type, generally comprise for example polyalkylene glycol, polyalkylene glycol alkyl oxide, polyalkylene glycol alkyl phenyl ether, polyalkylene glycol fatty acid ester, sorbitan fatty acid esters, alkyl poly glucoside (polyglycoxide), lipid acid di alkanolamide or the like.The selection that forms the amount of the tensio-active agent that emulsion added is that those of ordinary skills can grasp.General surfactant comprise forms the 3%-15% of the used alkene/CO multipolymer weight of emulsion, but any amount of multipolymer and grafted monomer formation emulsion all can be able to use.
In case after graft copolymer of the present invention prepares,, can further it be prepared into viscose glue and binding agent (being commonly referred to as tackiness agent) to wherein adding a kind of solidifying agent and optionally adding a kind of catalyzer.Can use the tackiness agent material that two or more are similar or inequality for preparing by this mode to link together then.For example matrix material can be by timber components, wood chip, and different types of crossbanding, metal, different polymkeric substance and other materials are formed.The matrix material that is combined to form by two or more timber components is the most preferred embodiment in the present invention.
The requirement that is used to make the kind of timber components of matrix material and form is not strict.Timber can be high or low density, also can be to come from fallen leaves wood or needlebush.Suitable kind has for example oak, nut wood, Eucalyptus, maple, teak, okoume wood, redwood, meranti and pine.Use beech, dragon spruce and poplar can obtain good result.Timber need not to do any pre-treatment the general processing of being done when using traditional tackiness agent.Generally be enough to by timber components for example machinery and/or that chemical method obtains making the required size and dimension of certain class matrix material.The form that timber is suitable in use can be slab, veneer, wooden unit, thin slice, wood chip or wood pulp.Also can use the combination of timber components kind or form of two or more, for example improve the outward appearance of matrix material with this.
Timber can carry out pre-treatment and increase its endurance quality.A pretreated example like this is to handle with superheated vapour under depressing with 150 ℃-220 ℃ adding, then 100 ℃-220 ℃ of environmental stresss down heating handle.A kind of pretreated method in addition is to soak in salt, chromic salts for example, mantoquita, mercury salt, arsenic salt, or the combination of these salt.
In tackiness agent, can use many solidifying agent according to the present invention.In EP-A-372602, disclose proper curing agents or curing system, also can comprise for example amine, mercaptan, or vinyl cyanide.Preferred solidifying agent comprises for example hexamethylene-diamine (HMDA), hexamethylene-diamine carbamate, tetramethylene amylamine, hexa-methylene diamino cinnamic aldehyde affixture and hexamethyl diamino dibenzoate.Also can use aromatic amine and cycloaliphatic amine, but preferred those do not have the amine of huge functional group.Has structure H
2N-R-NH
2Aliphatics primary diamines (R represents a divalent aliphatic abutment, has 10 carbon atoms at the most in abutment) be preferred solidifying agent.HDMA is most preferred solidifying agent.
Use the mixture of solidifying agent favourable equally.Especially can use the mixture of the relative low solidifying agent of the high relatively solidifying agent of a kind of activity with a kind of activity.For example can use mixing as the aliphatie diamine of the straight chain of the stronger solidifying agent of activity with as poly-primary amine aromatics or cyclic aliphatic of active poor slightly solidifying agent.In the presence of the stronger solidifying agent of activity, Once you begin solidify and just fast gelation can take place.Active poor slightly solidifying agent elongates the time of solidifying the ring-type carbon skeleton, will improve the mechanical property of matrix material under high temperature.According to the demand of the tackiness agent of concrete use, the mol ratio of active stronger solidifying agent and active poor slightly solidifying agent can be in very wide range.This mol ratio can easily be determined by normal experiment by the technician.General mol ratio is 2: 98 to 98: 2.
The crosslinking degree that is taken place when solidifying is especially decided by the amount of the employed solidifying agent ratio with respect to the amount of the multipolymer of carbon monoxide and alefinically unsaturated compounds.The relative content of solidifying agent can be in very wide range, and can determine a preferred relative content by normal experiment.When polynary primary amine used as solidifying agent, the molar ratio of the primary amine group of carbonyl and solidifying agent was suitable between 0.25--8.0 in the multipolymer, and is more suitable between 0.4--2.0.
The curing of multipolymer can be in the presence of a kind of curing catalysts or do not have any curing catalysts in the presence of carry out.Use a kind of advantage of catalyzer to be generally can under lower temperature or in the shorter time, be cured.When solidifying agent is a kind of aliphatie diamine, appropriate catalyst is a weak acid, especially the PKa that in 20 ℃ of following water, measures between 2-5.5, the preferably acid between 2.5-5.A preferred class acid is organic acid, and especially carboxylic acid is treated the solidified multipolymer because they are dissolved at least to a certain extent.Monocarboxylic acid is more preferably because of it generally has better solvability in multipolymer.The example of monocarboxylic acid has acetate, Yan acid, trimethylacetic acid, valeric acid, phenylformic acid and Whitfield's ointment.Another kind of suitable weak acid is phosphoric acid.Acetate is most preferred catalyzer.
Can use a spot of weak acid.Weight appropriate vol with respect to multipolymer is 0.1--15.0%.More preferably the faintly acid amount is a 0.2-10.0% weight.Based on the most preferred consumption of identical standard is 0.5-8.0% weight.
General its wieldy viscosity of sening as an envoy to that shows of moisture sizing composition of the present invention.General scope is that the viscosity that records with the Brookfield viscometer under the room temperature is between 200-5000mPa.s.But, if desired, can in curable resin combination, use a kind of diluent, be beneficial to composition and be applied on the timber components.Thinner also can improve the consistency of solidifying agent and any catalyzer and multipolymer.Suitable diluent has for example lower alcohol, lower ketones, lower member ester such as acetic ester and rudimentary ether.The notion of " rudimentary " refers to per molecule and on average contains 5 or be less than the thinner of 5 carbon atom.The example of preferable absorbent is water and lower alcohol, most preferably water.Other suitable diluent has acetone, vinyl acetic monomer, methyl propionate, and glycol dimethyl ether.When curable resin composition was coated with by the mode that for example sprays, suitable viscosity was 100-2000mPa.s under coating temperature, preferably at 500-1000mPa.s.The weight ratio of preferred used thinner and multipolymer was at least 1: 5, especially 1: 2-5: 1 scope, the most special in 1: 1.5-2: between 1 scope.
Curable resin combination paste might be prepared into, for example wood surface can be sprayed on easily between 10 ℃-50 ℃ in temperature range easily like this.The denseness of this paste can be by adding a kind of thinner of relatively small amount in tackiness agent, for example water, a kind of lower alcohol or a kind of lower ketones realize.The scope of the amount that thinner is general is the 0.2-5.0% weight with respect to the weight of multipolymer, especially 0.3-3.0% weight, based on identical standard 0.5-1.0% weight more particularly.Very favorable result can be by with the linear alternated copolymer of a kind of carbon monoxide and a kind of alkene with water, a kind of tensio-active agent, a kind of radical initiator and a kind of vinyl polymer are mixed obtains, the weight average molecular weight range of this preparing linear alternating multipolymer is 200-10,000, then this mixture was stirred 15 minutes, add a kind of primary amine subsequently, a kind of weak acid that is used as curing catalysts, with a kind of be the thinner of 0.2-5.0% weight with respect to multipolymer weight, resulting mixture is heated preferred 40 ℃-80 ℃ between 30 ℃-100 ℃.The time of heating is determined by selected temperature, and can suitably change between 5-50 minute, can determine to select the temperature of heating by common experiment at an easy rate, so that tackiness agent reaches ideal denseness and quality.Resulting paste can be applied on the timber under the employed in the preparation temperature, but also can use at ambient temperature.
Tackiness agent can comprise the additional ingredients of improving its performance.The example of suitable supplementary component is as viscosity modifier, fire retardant, spackling, antioxidant, UV light stabilizing agent and tinting material.For example: clay can be used as a kind of filler, or comes to reduce viscosity with very high shearing rate with it.A kind of suitable spackling is tripoli, flour or coconut palm shell powder.When composition prepared in accordance with the present invention was used as a kind of coating material, especially the ideal additive was antioxidant and UV light stabilizing agent.
Tackiness agent can use any traditional technology to be applied to wood surface, can use a kind of for example brush, and roller, painting cloth-knife or scraping blade are applied to tackiness agent, paste especially mentioned above on the surface.Show, add a kind of thinner of appropriate amount after, tackiness agent can spray by a kind of nozzle of compressed gas-driven equally, for example: a kind of continuously online spraying method or use a kind of coating atomizer.If needed, in the time will preparing a kind of matrix material with soft feel, tackiness agent can be used as the coating of the wood surface that is positioned at the matrix material outside surface equally.Can be coated with the solidified matrix material equally and solidified coating in additional curing schedule.
The amount of tackiness agent can change in very wide scope with respect to the amount of timber, generally by the type decided of prepared matrix material, can be defined as for this amount of layer of wood plywood between every square metre the wood surface of coating adhesive or every square metre of two-layer thin wood plate and produce the desired amount of wood surface that engages.30-400 gram tackiness agent is used for every square metre in general junction.Preferably use 60-120 gram tackiness agent.
When employed Wood composite material is a kind of fiberboard or a kind of shaving board, can be more easily the amount of adhesive therefor be associated with the weight of matrix material.The amount of the general tackiness agent that uses of every kg of fibers plate or shaving board is equivalent to the 20-150 gram, more generally restrains into the carbon monoxide of this tackiness agent and the multipolymer of alefinically unsaturated compounds for 30-100.Application-specific for fiberboard, it is desirable to tackiness agent is made a kind of external phase, in this case, every kilogram of matrix material uses the amount of this tackiness agent to count the 150-600 gram based on the multipolymer amount of making this tackiness agent, especially uses the multipolymer of 200-500 gram carbon monoxide and alefinically unsaturated compounds.
Simultaneously or thereafter, with the surface of adhesive coated to the timber components that will connect, tackiness agent remains between the timber components like this, is cured under condition of cure subsequently.Temperature and pressure can be in very wide range.Temperature is generally by solidifying agent and the decision of existing curing catalysts.When polynary primary amine was used as solidifying agent, suitable temperature was more than 50 ℃, for example between 80-200 ℃, and especially 100-160 ℃.For the general pressure of laminated wood at 1-30kg/cm
2Between, preferred 2.5-25kg/cm
2In the use of fiberboard and shaving board, general pressure is 10-150kg/cm
2, 25-100kg/cm preferably
2
Can prepare dissimilar Wood composite materials according to the present invention, for example fiberboard, shaving board such as sandwich plate and laminated wood such as glued board, laminated fleshing beam or timber.These matrix materials have outstanding shock resistance/strength balance performance, and have good dimensional stability under the situation of humidity.Therefore, matrix material can be used for the manufacturing of door, veneer floor, sports goods such as hockey lever and electrical appliance such as board and distributor box dashboard easily.Can in building panel, use and have the fiberboard of tackiness agent as external phase.
In following unrestriced example, will further specify the present invention.The viscose glue prescription is as follows: the emulsion of the embodiment 2 of A=100 weight part (pbw), 25 weight fraction 65%HMDA, the acetate of 4 weight parts 20%.The emulsion of the embodiment 3 of B=100 weight part, the HMDA of 21 weight parts 65%, the acetate of 3.3 weight parts 20%.The emulsion of the embodiment 4 of C=100 weight part, the 65%HMDA of 25 weight parts, 20% acetate of 4 weight parts.The emulsion of the embodiment 3 of D=100 weight part, the 65%HMDA of 18.8 weight parts, 20% acetate of 4 weight parts.
The preparation of embodiment 1:(alkene/CO polymkeric substance)
To contain 80 parts of methyl alcohol by volume, 10 parts of water, the autoclave of 10 parts of acetate is heated to 95 ℃, be full of the propylene of 36 crust then, 16 crust C), 4 crust ethene and a kind of acid chloride that mol ratio is 1/1.05/2.1,1, catalyst solutions of 3-two (two-neighbour-p-methoxy-phenyl phosphino-) propane and trifluoromethayl sulfonic acid of containing.Temperature remains on 95 ℃ during reaction, and the mixture of the ethene/CO by continuous adding 1/1 keeps the constant pressure of reactor.After 20 hours, temperature of reactor is reduced to room temperature and venting.Under reduced pressure remove solvent and obtain a kind of alkene/CO alternating copolymer, its number-average molecular weight be 1800 and the mol ratio of ethylene/propene be 28/72, the productive rate of catalyzer is that every gram palladium obtains 36 kilograms oligopolymer.The preparation of embodiment 2:(aqueous resins)
In the resin reaction kettle of being furnished with a kind of anchor shape agitator, add 76.6 weight parts (pbw) as the prepared alternating copolymer of embodiment 1,52 weight part non-ionic types gather (ethylene glycol) tensio-active agent (can buy in shell chemical company, commodity are called " 23W004 ") and 108 weight parts waters.Mixture stirred down at 200 rev/mins, and added the multipolymer of additional equivalent at two hours, reached 500 weight parts up to the total amount of multipolymer in mixture.After further stirring 3 hours at ambient temperature, in 1 hour, add the water of 343 weight parts, obtain solid content and be 55% emulsion.The preparation of the moisture grafted polystyrene alkene of embodiment 3A:(/CO resin):
The water that in the emulsion of 479 weight parts that embodiment 2 prepares, adds 144 weight parts, the Potassium Persulphate of the vinylbenzene of 163 weight parts and 1.45 weight parts.Mixture is placed in the bottle, shakes 15 minutes, is put in the baking oven in 60 ℃ then and spends the night.The product of gained is grafted polyethylene alkene/CO copolymer emulsion, and the weight ratio of alkene/CO multipolymer and polystyrene is 60/40, and the solid content of emulsion is 55% weight.Embodiment 3B: alkene/CO polymkeric substance passes through the radiating graft copolymerization:
By acid chloride, trifluoroacetic acid negatively charged ion and 1, the existence of the catalyst composition that 3-two (diphenylphosphino) propane forms is the terpolymer of preparation carbon monoxide, ethene, propylene down.The fusing point of linear terpolymer is 220 ℃, and to record its intrinsic viscosity (LVN) in 60 ℃ in meta-cresol be 1.8.
10 gram ter-polymers and 2 gram vinylbenzene are mixed mutually with 10ppm stopper tert-butyl catechol and are placed in the Glass Containers, are that 0.26 megarad/hour cobalt 60 delta ray sources were at room temperature shone 24 hours with intensity in air.The gained solid extracts with hot toluene, to remove homopolystyrene.Solid-state
1HNMR analyzes the product extracted and shows that it contains grafted polystyrene.Grafting efficiency (grafted monomer/total monomer amount) is 78%.
This example shows, can be by energy-rich radiation generation graft copolymerization based on the polymkeric substance of alkene/CO skeleton.The preparation of the low-molecular-weight alkene of embodiment 3C:(/CO graft copolymer: infer)
In the emulsion of 500 prepared weight parts of embodiment 2, add the water of 150 weight parts and the vinylbenzene of 170 weight parts.Resulting mixture intensity is that 0.26 megarad/hour cobalt 60 delta ray sources were shone 0.5 hour at ambient temperature, is 55% water miscible liquid with making the styrene-grafted polymerization obtain solid content.The preparation of poly-(methyl methacrylate) alkene of the moisture grafting of example 4:(/CO resin)
Will be in resin reaction kettle according to the emulsion of 90 weight parts of embodiment 2 preparation, the mixture of the Potassium Persulphate of the methyl methacrylate of 29.8 weight parts and 0.1 weight part stirs down 60 ℃ of heating 6 hours.Form poly-(methyl methacrylate) alkene of grafting/CO copolymer emulsion.The ratio of alkene/CO multipolymer and poly-(methyl methacrylate) is 60/40, and the solid content of emulsion is 66% weight.Embodiment 5: preparation plywood panel and performance compare:
This example is the improvement version of glued board sample test 6.1.5.3, and this is tested in nineteen ninety-five and is revised again by U.S. glued board federation, sees content described in " PSI-95, building and industrial glued board ".
By using three kinds of different types of moisture viscose prescriptions that the facing of 0.4cm (1/6 ") southern pine is prepared into three layers of (non-incision) orthogonal layers wood panel; three kinds of different types of moisture viscose glue prescriptions are respectively by embodiment 2; emulsion that 3A and 4 obtains and hexamethylene-diamine (HMDA) and acetate are mixed to be obtained.Panel is 200 ℃ and 1.4MPa (200psig) hot pressing down.All panel viscose glue consumptions are 65 gram solid/m
2Every adhesive line.In order to estimate water resistance, from panel, downcut 2.5 * 7.6cm
2The sample of (1 " * 3 ") soaked 4 hours in boiling water, then in baking oven in 63 ℃ of dryings 23 hours, in water, soaked 4 hours.The performance of viscose glue is made evaluation according to the sample number that delamination does not take place after the two rounds boiling test of given hot pressing time.
Resulting result lists at following table 1.Table 1: viscose glue prescription: 200 ℃ of hot pressing times
4.5 minutes 6 minutes 10 minutes
Surplus (the glued board specimen is at the remaining number in boiling test back) A 005 surplus the 3B 03 surplus in the of 33 surplus the 3C 3 surplus in the of 23 surplus in the of 333
This example shows that the viscose glue that uses the present invention to prepare can acquire good wood bonding, and sample A has used a kind of viscose glue that comprises the alkene/CO polymkeric substance of not graft copolymerization.Sample B and C are the viscose glues that obtains according to invention.Use polymers grafted as viscose glue, the hot pressing time that the sample that bonding is good needs 10 minutes stands the boiling test.Use viscose glue prepared in accordance with the present invention, the sample that bonding is good will stand boiling test () the hot pressing time or still less that needs 6 minutes.Embodiment 6: the preparation of shaving board and performance
This example is the improvement version of glued board sample test 5.4.1, sees content described in " OSB and sandwich plate 0437 serial 93 standards " delivered by Canadian standard federation in 1993.
Successively in a rotary drum, spray the emulsion of wax (a kind of 15cpp that provides by Borden) of a kind of 51% non-volatility and a kind of moisture viscose glue by southern pine wood shavings preparation 46 * 50 * 1.11cm to shaving board
3(18 " * 20 " * 7/16 ") random orienting shaving board panel.Finish spraying by a kind of Dey-Dose (by the concord high precision atomizer of Coil industrial manufacturing).The consumption solid content of used wax and viscose glue is respectively 1 and 4% of a timber weight.Panel is 5.5MPa (800psig) 200 ℃ of following hot pressing 4.5 minutes at 1.5 minutes pressure that begin, and the pressure of remaining hot pressing is 2.8MPa (400psig).Resultingly the results are shown in the following Table 2, use Tinius Olsen instrument to measure rupture modulus according to ASTM D 1037, Young's modulus and inherent bounding force.Table 2: viscose glue prescription: inherent bounding force rupture modulus Young's 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 requirement of Canadian standard federation is that inherent cohesive force is 0.3MPa (50psi), and rupture modulus is 17.2MPa (2500psi), and Young's modulus is 3.1MPa (450psi).This example shows that the viscose glue that makes according to the present invention has good wood bonding performance.The shaving board that the viscose glue that obtains according to the present invention (D) makes substantially exceeds the standard of being formulated by Canadian standard federation.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180866 CN1241197A (en) | 1996-12-23 | 1997-12-18 | Graft copolymerized compositions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/034,140 | 1996-12-23 | ||
| US60/034,141 | 1996-12-23 | ||
| CN 97180866 CN1241197A (en) | 1996-12-23 | 1997-12-18 | Graft copolymerized compositions |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382436A (en) * | 2016-12-14 | 2019-10-25 | 阿科玛法国公司 | Air void control composition for the monomer polymerization containing carbonyl |
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1997
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382436A (en) * | 2016-12-14 | 2019-10-25 | 阿科玛法国公司 | Air void control composition for the monomer polymerization containing carbonyl |
| CN110382436B (en) * | 2016-12-14 | 2022-10-28 | 阿科玛法国公司 | Air void controlling compositions for polymerization of carbonyl containing monomers |
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