CN201895347U - Composite wood - Google Patents

Abstract

The utility model discloses a composite wood which is characterized in that the composite wood is provided with pores and macromolecules are deposited in at least one part of the pores. The composite wood belongs to a composite macromolecular product of which the physical properties, the dampness/heat resisting performances and dimensional stability are greatly improved.

Description

A kind of composite wood

Technical field

The utility model relates to a kind of composite wood.

Background technology

Naturally occurring polysaccharide material wide material sources, main component has cellulose, hemicellulose, starch, shitosan etc.The representative of this class natural polysaccharide material has timber, bamboo, wooden rattan, stalk etc.Although these natural materials have purposes separately, often at intensity, hardness, moisture-proof, heat-resistant stability, performance is not enough to some extent on the dimensional stability.The method of this class material of conventional process comprises physical method and chemical method.Physical method mainly is that applying pressure is strengthened this class polysaccharide material.Chemical method mainly is by adding number acid, alkali, aldehyde material, with polysaccharide material generation chemical reaction, reaching the purpose of material modification.But because the reactivity of these polysaccharide materials is limited, so modified effect is limited.And have a large amount of holes not to be filled in the material, also limited the performance performance of material.

Polyhydroxy compounds and containing and the hydroxyl active polyfunctional compound that responds can polymerization reaction take place as carboxylic acid, fat, isocyanates, aldehyde etc., generates macromolecule.The purity requirement height of this two classes monomer of this family macromolecule reaction pair, avoiding side reaction, and hydroxyl and be controlled near 1: 1 with the hydroxyl active functional group's mol ratio that responds.Further, it is very abundant that these reaction requirements are carried out, and general the requirement reaches more than 98%, to reach enough big molecular weight, will remove accessory substances such as water, alcohol in the course of reaction.At present, this family macromolecule reaction is not widely used in the processing of polysaccharide material, to improve the various performances of polysaccharide material.

The utility model content

The utility model provides a kind of composite wood of improvement, this composite wood is by with the polyhydroxy compounds with contain and the hydroxyl processing polysaccharide material with polymer composition gained that active polyfunctional compound forms that responds, and the polysaccharide material after the processing has on intensity, hardness, moisture-proof, heat-resistant stability, dimensional stability significantly and improves.

The utility model provides a kind of composite wood, it is characterized in that, described composite wood contains hole, and deposits macromolecule to the small part hole.

Described composite wood is prepared from by following method, and this method comprises:

1) provides a kind of polysaccharide material;

2) provide a kind of polymeric composition, said composition contain at least a polyol and at least a contain more than one with the respond compound of active function groups of hydroxyl;

3) make described polymeric composition enter polysaccharide material inside;

4) handle described polysaccharide material, make polyol in the described polymeric composition, contain and the hydroxyl polymerization reaction take place between the compound of active function groups and the polysaccharide material that responds, form a kind of water-fast composite wood.

Above-mentioned steps 3) in, preferably will contain at least a polyol and at least a containing to enter polysaccharide material inside with the respond method of described polymeric composition by vacuum-high-pressure impregnation of compound of active function groups of hydroxyl more than one; Modes such as the mode that described polymeric composition enters polysaccharide material inside includes but not limited to injection, flows, migration or diffusion.

Above-mentioned steps 4) in, described processing method is generally normal temperature, high temperature or high temperature high pressure process.

High temperature described in the utility model refers to that temperature is higher than 180 ℃; A high end finger 10-25 atmospheric pressure of the present invention.

Be applicable to that processing object of the present utility model is a polysaccharide material, this class polysaccharide material includes but not limited to: stalk, timber, rattan material, paper products, bagasse, bamboo product and any above-mentioned mentioned combination of materials.Said method is particularly useful for processing and is rich in cellulosic polysaccharide material, and this class polysaccharide material comprises the solid material of any fibre-bearing element or hemicellulose.Below we are that example is described further this class polysaccharide material with timber, this is a kind of illustrative description, does not limit the scope of the processing object that the utility model protects.Comprise any geometry as processed object timber, suitable timber includes but not limited to: cork, hardwood, fast growing wood; Described cork includes but not limited to: pine, maple, China fir, poplar and beech, and described hardwood includes but not limited to birch, Eucalyptus and Bai La; And any above-mentioned mentioned combination of materials.Wherein pine includes but not limited to: Korean pine, larch, masson pine, pine, Lapland pine, needle pine, pinus yunnanensis, Bald pine, maritime pine and any above-mentioned mentioned combination of materials.Timber itself can be wood chip, plank, wood-fibred, untreated timber, half-dried timber, beam, floor, wooden decoration materials etc.Timber itself can pass through processing methods such as polishing, boiling, bleaching or etching before processing.

Be applicable to that the polysaccharide material that the utility model is handled generally all contains hole, contains the part hole at least.This class space is followed in the arboreal growth process and is formed.These spaces can be coupled together by conduit.In general, cork is more prone to form large-sized conduit and more a high proportion of hole.Hole also can increase by known chemistry or mechanical means, as etching and indentation.The linear dimension scope of these holes is from the nanometer to the micron.

The polyol that is applicable to polymeric composition of the present utility model can comprise any organic molecule more than a hydroxyl, oligomer and high polymer.Illustrate the polyol that some typically are applicable to this method below, as any derivative of ethylene glycol, propane diols, glycerine, polysaccharide, polyvinyl alcohol, pentaerythrite, diethanol amine, triethanolamine, polyhydroxy amino acid, poly-hydroxy acrylic acid and above compound.Contain the polyol that surpasses 2 hydroxyls, this compounds is generally for another component of composition---and contain and the respond compound of active function groups of hydroxyl, stronger reactivity is arranged.By way of example, such polyol can have 2 to 4000 hydroxyls, preferred 2 to 2000 hydroxyls, and more preferably 3 to 1000 hydroxyls do not wait, and and contain with the respond compound of active function groups of hydroxyl very strong reactivity is arranged.

In being applicable to this class polyol of the present utility model, polysaccharide is a kind of important material standed for.This class polysaccharide comprises any derivative of cellulose, glucan, curdlan, pyrenomycetes glucose, schizophan, dextran, starch, xylan, dextrin, Propiram, guar gum, inulin, chitin, shitosan, alginate and above compound.Described starch comprises any derivative of amylose, amylopectin and above compound.Wherein water miscible polysaccharide---dextrin wide material sources are a kind of raw materials with industrial applications potentiality.This class dextrin comprises any derivative of dried dextrin, maltodextrin, cyclodextrin, corn dextrin and above compound.The DE value of described maltodextrin and derivative thereof is between 1-30%.

In the polymeric composition more than one with the respond compound of active function groups of hydroxyl, contain at least 2 active function groups that react with hydroxyl.These functional groups comprise: the combination of NCO, ester group, carboxyl, anhydride group, amide groups, alcoholic extract hydroxyl group, phenolic hydroxyl group, aldehyde carbonyl and any above-mentioned mentioned functional group.Owing to can react with hydroxyl, this compounds can react with the polyol of above introducing, and generates new covalent bond, and end product is water insoluble.Polybasic carboxylic acid be this class contain contain at least 2 with the respond representative of compound of active function groups of hydroxyl.Described in the utility modelly comprise containing of carboxyl and respond the compound of active function groups when containing carboxyl with hydroxyl more than one, its diacid of can selecting oneself, glutaric acid, succinic acid, malonic acid, oxalic acid, 3,4-dicarboxyl adipic acid, glutamic acid, aspartic acid, maleic acid, fumaric acid, the 2-mesaconic acid, the 2-methyl-maleic acid, 2-vinyl succinic acid, citric acid, D-type tartaric acid, L-type tartaric acid, DL type tartaric acid, glucaric acid, polyacrylic acid, polymethylacrylic acid, ethylenediamine tetra-acetic acid, saturated fatty acid, unrighted acid, phthalic acid, M-phthalic acid, any derivative of terephthalic acid (TPA) and above compound.Described in the utility modelly comprise containing more than one of carboxyl and respond the compound of active function groups when containing acid anhydrides with hydroxyl, it can be selected from: any derivative of maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride and above compound.

According to the utility model, described containing more than one contained 3 carboxyls at least with respond each molecule of compound of active function groups of hydroxyl.

Composite wood of the present utility model can further pass through any combined treatment of constant temperature and humidity, the heating of circulation humidification, high temperature and high pressure steam, natural air drying and the above method.

Preferably, the method for processing polysaccharide material comprises:

1) provides a kind of polysaccharide material that contains hole;

2) provide a kind of polymeric composition, said composition contain at least a polyol and at least a contain more than one with the respond compound of active function groups of hydroxyl;

3) described polysaccharide material is immersed in the described polymeric composition, to such an extent as to the hole of the described polysaccharide material of part is filled by this polymeric composition at least in part;

4) polyol in the described polymeric composition, contain and the hydroxyl polymerization reaction take place between the compound of active function groups and the polysaccharide material that responds, form a kind of water-fast composite wood.

Described impregnation steps comprises: described polysaccharide material is vacuumized processing earlier; Polysaccharide material after this processing is contacted with polymeric composition; By continuous pressurization polymeric composition is constantly moved in the hole in polysaccharide material at last.

Be that example illustrates this application of class polyol in polymeric composition below with the maltodextrin.With starch is raw material, and through the control hydrolysis, the DE value is called maltodextrin at the product below 20%, with the dextrin product of difference starch through the pyrolytic reaction generation.The DE value is the percentage that reduced sugar (with glucose meter) accounts for the syrup dry.Different polymerization degree, and various stereomeric maltodextrin may be used in this polymeric composition.For example the maltodextrin of DE value 1-30 can be as the component of the polyol in the polymeric composition.Wherein, a kind of maltodextrin can use separately, also can mix with multiple different maltodextrin and use, perhaps mix and use with other water miscible carbohydrate, as other dextrin, the carbohydrate after the modification, and this family macromolecule compound of polyvinyl alcohol.

Atom or atomic group that term in the utility model " derivative " is often referred in the parent compound molecule are replaced formed compound by other atoms or atomic group.

" maltodextrin " described in this explanation and " polysaccharide " are meant any derivative that comprises maltodextrin and polysaccharide.These method of modifying, for example, acetylation, sulfonated, dehydration, alkoxylate or any other chemical modification, finally each derived molecules comprises two hydroxyls at least.

In addition at polyol or contain with hydroxyl and respond in the structure of compound of active function groups, can comprise unsaturated bond, described unsaturated bond can cause by heat initiation, free radical initiation, redox initiation or high energy, causes crosslinked or polymerisation.Wherein carbon-carbon double bond is to be applied to unsaturated bonds maximum in this polymeric composition.Fumaric acid for example, maleic acid, the carboxyl of polybasic unsaturated fatty acid and the hydroxyl of maltodextrin react, and generate polyester.These unsaturated bonds of the polyester that generates can be at free radical, and heat can further take place crosslinked or polymerization under the initiations such as high energy.Polyol or contain with the respond unsaturated bond of compound of active function groups of hydroxyl and cause and crosslinkedly also can before being impregnated into timber, finish, generate oligomer or macromolecule, enter polysaccharide material inside by dipping afterwards, the hydroxyl with maltodextrin reacts again, generates polyester.The initator of free radical for example, AIBA (azo diisobutyl amidine hydrochloride), benzoyl peroxide (BPO) and persulfate.It is crosslinked that metal or oxidant also can add the redox of catalyzed ethylene base in the polymeric composition.The high energy initiation comprises ultraviolet, electron beam, gamma-rays and ultrasonic wave etc.

Polyol and the mixture that contains at least 2 active function groups compounds that react with hydroxyl have been formed the main body of polymeric composition, and this polymeric composition may further include water or organic solvent.In such mixture, with hydroxyl respond the ratio of the hydroxyl integral molar quantity in the total mole of active function groups and this polymeric composition minimum be 1: 12.The scope of mol ratio can be 1: 12 to 35: 1.In the effective polymeric composition, polyol and the ratio that contains at least 2 active function groups compounds that react with hydroxyl are in above-mentioned scope, and the water-fast product of generation q.s, to reach treatment effect to polysaccharide material.In a typical polymeric composition, the hydroxyl of polyol can have 2 to 4000 hydroxyls, preferred 2 to 2000 hydroxyls, more preferably 3-1000 hydroxyl, the scope of the active function groups of the active function groups compound that reacts with hydroxyl is at 2-5.

In the example below, maltodextrin and citric acid are two kinds of components in the polymeric composition, and the scope of the mol ratio of citric acid and maltodextrin can be 2: 1 to 30: 1.In above proportion, the mol ratio of hydroxyl and carboxyl is higher than 1: 12 minimum ratio.In this example, the carboxyl of citric acid can also react with the hydroxyl of polysaccharose substance, and is further crosslinked.These firm covalent bonds will further improve final treatment effect, such as the hardness that improves this polysaccharide material, intensity, moisture-proof, heat-resistant stability, dimensional stability etc.Effectively the general viscosity of polymeric composition is lower, and greatly about the 20-800 centipoise, this can guarantee that polymeric composition can effectively infiltrate the hole of polysaccharide material.

In polymeric composition, can also add dyestuff, metal inorganic salt, metal organic salt, repellent agent, spices, anti-ultraviolet reagent, nano particle, insect-proof agent, timber preservative or fire retardant.These additives are by being impregnated into polysaccharide material inside, because polyol and generate water-fast product with the respond compound crosslink of active function groups of hydroxyl finally is fixed on polysaccharide material inside.

Following example will illustrate how to handle polysaccharide material with above-mentioned polymeric composition.A plank that contains the space is put into reactor, by reduced pressure treatment, this timber is contacted with polymeric composition earlier, because prior reduced pressure treatment, polymeric composition will move by flowing, and modes such as diffusion enter into the hole of timber.This polymeric composition can further further effectively pass through to flow by the gradient pressing mode, migration, and modes such as diffusion enter into the hole of timber.Such as, in the reactor due to the timber, be decompressed to vacuum 70%, inject polymeric composition then, be pressurized to 10-25 atmospheric final pressure then gradually.By this processing procedure, timber will effectively be immersed polymeric composition.If this polymeric composition is made up of water-soluble prescription, then selecting water for use is primary solvent, and may add the part organic solvent and improve the solubility of some component in water.These organic solvents can comprise: methyl alcohol, ethanol, isopropyl alcohol, n-butanol, acetone, glycerine, glycerin ether, glyceride etc.This processing procedure can be in room temperature, and perhaps heating condition is handled down.Modes such as the timber after the processing can be air-dry by normal temperature, and it is air-dry to reduce pressure are carried out preliminarily dried.Can effectively shorten the required time of this processing method by drying under reduced pressure.

By said process, be immersed in the polyol in the polymeric composition in the timber and will react mutually with the respond compound of active function groups of hydroxyl, generate water-fast product.In order to promote such reaction to carry out, the wood handled well can be handled in the scope of room temperature to 150 ℃.Polyol in the timber with respond the compound of active function groups because the prescription of reaction and reaction condition different needed a few minutes to finish reaction by several days with hydroxyl.Timber can pass through the combined treatment of constant temperature and humidity, the heating of circulation humidification, high temperature and high pressure steam, natural air drying and above any method afterwards, reaches with external environment humidity to keep balance or eliminate the some or all of stress of material internal.For example, under 180 ℃ high-pressure water vapors were handled, specific Wooden modifying product can be eliminated inner most of or whole stress in a few minutes.Another advantage of this processing method is, polyol and do not need extra processing with the hydroxyl accessory substance that the compound of active function groups will react mutually that responds, and traditional esterification, perhaps ester exchange reaction etc. then needs water that reaction is generated or alcohol to remove system just to reach fully fully, and suppresses back reaction.

Polyol and if unsaturated bond is arranged in polymeric composition with the respond compound of active function groups of hydroxyl, in polymeric composition, add the new monomer that contains vinyl again, oligomer or macromolecule, this will cause further polymerization or cross-linking reaction, improve high molecular molecular weight.Such polymerization or cross-linking reaction can be by free radicals, heat, initiations such as high energy.For example maltodextrin and itaconic acid are as the main body of polymeric composition, in said composition, add the part styrene monomer, after being impregnated in the polysaccharide material, maltodextrin and itaconic acid reaction generate polyester, unsaturated double-bond in the polyester is in the presence of radical initiator, intermolecular polymerization or crosslinked takes place, and can with styrene monomer generation combined polymerization, generate copolymerized macromolecule.

Preferably, in the composite wood that the utility model provides, the macromolecule major part that described polymeric composition polymerization produces is deposited in the hole of described composite wood.

Described composite wood preferably further passes through any combined treatment of constant temperature and humidity, the heating of circulation humidification, high temperature and high pressure steam, natural air drying and the above method, keeps balance or eliminates the some or all of stress of material internal thereby reach with external environment humidity.

The physical property of the composite wood that the utility model provides, moisture-proof, heat resistance, dimensional stability all have lifting significantly.

Description of drawings

Fig. 1 is the China fir plank before handling;

Fig. 2 is treated China fir plank.

The specific embodiment

Embodiment 1:

With reference to Fig. 1, Fig. 1 is the China fir plank before handling, and white circle is wherein represented the natural space of timber.

With the 432g maltodextrin, 192g citric acid, 9g boric acid are dissolved in the 1.16kg water, and agitating solution is up to the solution clear.(unit: China fir plank mm) places autoclave with 3 100 * 60 * 20, at first be evacuated to 90% vacuum, kept this vacuum time 30 minutes, then above-mentioned solution is injected autoclave, treat that the solution adding finishes, and improves pressure to 18 atmospheric pressure gradually.Kept pressure 5 hours, the normal pressure that reduces pressure gradually then detaches solution from reactor.Be decompressed to 80% vacuum about 20 minutes, then under normal pressure 95 ℃ of dry planks 24 hours.After the drying, in autoclave, handled this wooden unit 10 minutes, return to normal temperature and pressure then, obtain composite wood of the present utility model with 180 ℃ high-pressure water vapor, as shown in Figure 2, the space that black circles representative is wherein filled by macromolecule.The correction data of the timber before and after handling is as follows.

Claims (1)

1. a composite wood is characterized in that, described composite wood contains hole, and deposits macromolecule to the small part hole.

Images