CN101830015B - Method for processing polysaccharide material with polymer composition - Google Patents
Method for processing polysaccharide material with polymer composition Download PDFInfo
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- CN101830015B CN101830015B CN2010101316126A CN201010131612A CN101830015B CN 101830015 B CN101830015 B CN 101830015B CN 2010101316126 A CN2010101316126 A CN 2010101316126A CN 201010131612 A CN201010131612 A CN 201010131612A CN 101830015 B CN101830015 B CN 101830015B
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- cellulose material
- acid
- material according
- hydroxyl
- polymeric composition
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- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
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- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000000053 physical method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- 240000001606 Adenanthera pavonina Species 0.000 description 1
- 235000011470 Adenanthera pavonina Nutrition 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The present invention discloses a method for processing a cellulosic material with a polymer composition. The method comprises the following steps of: (1) providing a polymer composition which contains at least one multi-hydroxyl compound and at least one compound containing more than one functional group with reaction activity with hydroxyls; (2) enabling the polymer composition to enter the cellulosic material; and (3) processing the cellulosic material so that the multi-hydroxyl compound and the compound containing more than one functional group with reaction activity with hydroxyls in the polymer composition are polymerized with the cellulosic material to form a water-insoluble composite polymer product. The cellulosic material obtained by using the method has greatly improved physical performance, moisture-proof and heat-resist performance and size stability.
Description
Technical field
The present invention relates to a kind ofly handle the method for cellulose material, relate in particular to a kind of usefulness and contain polyol and handle the method for cellulose material with containing with the respond polymeric composition of active function groups of hydroxyl with polymeric composition.
Background technology
Naturally occurring cellulose material wide material sources, main component has cellulose, hemicellulose etc.The representative of this class natural fiber cellulosic 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 the plain class material of this fibrid.Chemical method mainly is by adding number acid, alkali, aldehyde material, with cellulose material generation chemical reaction, reaching the purpose of material modification.But because the reactivity of these cellulose 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 cellulose material, to improve the various performances of cellulose material.
Summary of the invention
The present invention utilizes existing blank to the cellulose material treatment technology, with polyhydroxy compounds and the polymeric composition that contains the polyfunctional compound composition that responds active with hydroxyl cellulose material is handled, the cellulose material after the processing has significantly raising on intensity, hardness, moisture-proof, heat-resistant stability, dimensional stability.
A first aspect of the present invention provides a kind of method of handling cellulose material, and this method comprises:
1) 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;
2) make described polymeric composition enter cellulose material inside;
3) handle described cellulose 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 cellulose material that responds, form a kind of water-fast composite high-molecular product.
The step 2 of the inventive method) in, preferably will contain at least a polyol and at least a containing to enter cellulose 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 cellulose material inside includes but not limited to injection, flows, migration or diffusion.
In the step 3) of the inventive method, described processing method is generally normal temperature, high temperature or high temperature high pressure process.
High temperature of the present invention 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 invention is a cellulose material, the plain class material of this fibrid includes but not limited to: stalk, timber, rattan material, paper products, bagasse, bamboo product and any above-mentioned mentioned combination of materials.Below we to be example with timber be described further the plain class material of this fibrid, this is a kind of illustrative description, the scope of the processing object that does not limit the present invention and protected.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 handling with method of the present invention.
Be applicable to that the cellulose material that this method 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 invention 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 invention, 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.Of the present inventionly 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.Of the present inventionly 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 inventive method, described containing more than one contained 3 carboxyls at least with respond each molecule of compound of active function groups of hydroxyl.
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 through the composite high-molecular product of the inventive method gained.
Preferably, the present invention's method of handling cellulose material comprises:
1) provides a kind of cellulose 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 cellulose material is immersed in the described polymeric composition, to such an extent as to the hole of the described cellulose 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 cellulose material that responds, form a kind of water-fast composite high-molecular product.
Described impregnation steps comprises: described cellulose material is vacuumized processing earlier; Cellulose material after this processing is contacted with polymeric composition; By continuous pressurization polymeric composition is constantly moved in the hole in cellulose 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 among the present invention " 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 cellulosic material inside by dipping afterwards, 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 cellulose 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 cellulose substances, and is further crosslinked.These firm covalent bonds will further improve final treatment effect, such as the hardness that improves this cellulose 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 the effectively hole of infiltrated fiber cellulosic material of polymeric composition.
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 cellulose material inside, because polyol and generate water-fast product with the respond compound crosslink of active function groups of hydroxyl finally is fixed on cellulose material inside.
Following example will illustrate how to handle cellulose 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 cellulose 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.
A second aspect of the present invention provides the composite high-molecular that obtains according to the inventive method product, and described composite high-molecular product contains hole, and the macromolecule that the polymeric composition polymerization produces can partly be deposited in the hole at least.
Preferably, the macromolecule major part of described polymeric composition polymerization generation is deposited in the hole of described composite high-molecular product.
Described composite high-molecular product 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.
Physical property, moisture-proof, heat resistance, the dimensional stability of the cellulose material that obtains by the inventive method all has significantly and promotes.
The specific embodiment
Embodiment 1:
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 the composite high-molecular product with 180 ℃ high-pressure water vapor.The correction data of the timber before and after handling is as follows:
Embodiment 2:
With the 300g water soluble starch, the 25g citric acid, 48g tartaric acid, the 48g maleic acid, the 20g triethanolamine, 5g zinc bromide, 2g ammonium phosphate are dissolved in the 1.16kg water, and the ammoniacal liquor with 30% is regulated pH value to 6, and agitating solution is up to the solution clear.(unit: paulownia plank mm) places autoclave with 3 100 * 60 * 20, at first be evacuated to 85% vacuum, kept this vacuum time 30 minutes, then above-mentioned solution is injected autoclave, treat that the solution adding finishes, and improves pressure to 22 atmospheric pressure gradually.Kept pressure 3 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 110 ℃ of dry planks 24 hours.After the drying, in autoclave, handled this wooden unit 10 minutes, return to normal temperature and pressure then, obtain the composite high-molecular product with 180 ℃ high-pressure water vapor.The correction data of the timber before and after handling is as follows:
Embodiment 3:
With the poly-hydroxy acrylic acid of 250g, 20g 4-hydroxyl threonine, 227g glucaric acid, 15g terephthalic acid (TPA), the 15g maleic anhydride, 10g boric acid, 2.5g zinc acetate, 2g ammonium phosphate is dissolved in the 1.23kg water, and the ammoniacal liquor with 30% is regulated pH value to 6, and agitating solution is up to the solution clear.(unit: bamboo chip mm) places autoclave, at first is evacuated to 90% vacuum, keeps this vacuum time 30 minutes, then above-mentioned solution is injected autoclave, treats that solution adds to finish, and improves pressure to 20 atmospheric pressure gradually with 3 200 * 25 * 5.Kept pressure 3.5 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 110 ℃ of dry planks 24 hours.After the drying,, obtain the composite high-molecular product climatic chamber inner equilibrium 48 hours.The correction data of the bamboo chip before and after handling is as follows:
Embodiment 4:
With 70ml ethylene glycol, the 70ml propane diols, the 60ml glycerine, 25g gathers hydroxy acrylic acid, the 100g trimethylol melamine, 25g glutaraldehyde, 20g '-diphenylmethane diisocyanate, 10g diethyl terephthalate, 100ml DMF is dissolved in the 1.2kg water, and agitating solution is up to the solution clear.(unit: pine plank mm) places autoclave with 3 100 * 60 * 20, at first be evacuated to 85% vacuum, kept this vacuum time 30 minutes, then above-mentioned solution is injected autoclave, treat that the solution adding finishes, and improves pressure to 15 atmospheric pressure gradually.Kept pressure 3 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 110 ℃ of dry planks 24 hours.After the drying, in autoclave, handled this wooden unit 10 minutes, return to normal temperature and pressure then, obtain the composite high-molecular product with 180 ℃ high-pressure water vapor.The correction data of the timber before and after handling is as follows:
Embodiment 5:
With the 432g maltodextrin, the 50g succinic acid, the 10g citraconic acid, 200g 2,3, and 4,5 tetracarboxylic caproic acids, 9g boric acid are dissolved in the 1.16kg water, and agitating solution is up to the solution clear.(unit: maize straw compression blocks mm) places autoclave, then above-mentioned solution is injected autoclave, treats that solution adds to finish, and improves pressure to 10 atmospheric pressure gradually with 1 100 * 100 * 100.Kept pressure 2 hours, the normal pressure that reduces pressure gradually then detaches solution from reactor.The maize straw compression blocks after 80 ℃ of dryings should be handled 24 hours under normal pressure obtains the composite high-molecular product then.The correction data of the material before and after handling is as follows:
Embodiment 6:
With the 200g cyclodextrin, the 100g shitosan, 50g polyvinyl alcohol 5000, the 192g citric acid, the direct dyes that 9g boric acid, 4g are mixed colours is dissolved in the 1.1kg water, and the ammoniacal liquor with 30% is regulated pH value to 5.5, and agitating solution is up to the solution clear.(unit: pine 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 the composite high-molecular product with 180 ℃ high-pressure water vapor.The wood color homogeneous, and similar with the red sandalwood color.The correction data of the timber before and after handling is as follows:
Claims (35)
1. method of handling cellulose material, this method comprises:
1) 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;
2) make described polymeric composition enter cellulose material inside;
3) handle described cellulose 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 cellulose material that responds, form a kind of water-fast composite high-molecular product.
2. the method for processing cellulose material according to claim 1 is characterized in that step 2) in the method for described polymeric composition by vacuum-high-pressure impregnation entered cellulose material inside.
3. according to the method for the processing cellulose material of claim 1 or 2, it is characterized in that step 2) described in enter to injection, flow, migration or diffusion.
4. the method for processing cellulose material according to claim 1 is characterized in that, is treated to normal temperature, high temperature or high temperature high pressure process described in the step 3).
5. the method for processing cellulose material according to claim 1 is characterized in that, described cellulose material contains hole.
6. the method for processing cellulose material according to claim 1 is characterized in that, described cellulose material is selected from one or more in the following material: stalk, timber, rattan material, paper products, bagasse and bamboo product.
7. the method for processing cellulose material according to claim 6 is characterized in that, described timber is selected from one or more of following material: cork, hardwood and fast growing wood.
8. the method for processing cellulose material according to claim 7 is characterized in that, described cork is selected from one or more of following material: pine, maple, China fir, poplar and beech.
9. the method for processing cellulose material according to claim 7 is characterized in that, described hardwood is selected from one or more of following material: birch, Eucalyptus and Bai La.
10. the method for processing cellulose material according to claim 8, it is characterized in that described pine is selected from one or more of following material: Korean pine, larch, masson pine, pine, Lapland pine, needle pine, pinus yunnanensis, Bald pine and maritime pine.
11. the method for processing cellulose material according to claim 1 is characterized in that, each molecule of described polyol contains 2-4000 hydroxyl.
12. the method for processing cellulose material according to claim 11 is characterized in that, each molecule of described polyol contains 2-2000 hydroxyl.
13. the method for processing cellulose material according to claim 1, it is characterized in that, in the described polymeric composition, polyol is selected from one or more in the following compound: ethylene glycol, propane diols, glycerine, polysaccharide, polyvinyl alcohol, pentaerythrite, diethanol amine, triethanolamine, polyhydroxy amino acid and poly-hydroxy acrylic acid.
14. the method for processing cellulose material according to claim 13 is characterized in that, in the described polymeric composition, polyol is selected from polysaccharide.
15. the method for processing cellulose material according to claim 14, it is characterized in that described polysaccharide is selected from one or more in the following compound: cellulose, glucan, curdlan, pyrenomycetes glucose, schizophan, dextran, starch, xylan, dextrin, Propiram, guar gum, inulin, chitin, shitosan and alginate.
16. the method for processing cellulose material according to claim 15 is characterized in that, described starch is selected from one or more in the following compound: amylose and amylopectin.
17. the method for processing cellulose material according to claim 15 is characterized in that, described dextrin is selected from one or more in the following compound: dried dextrin, maltodextrin, cyclodextrin and corn dextrin.
18. the method for processing cellulose material according to claim 17 is characterized in that, the DE value of described maltodextrin and derivative thereof is between 1-30%.
19. the method for processing cellulose material according to claim 1, it is characterized in that described containing more than one comprises at least 2 following functional groups with the respond compound of active function groups of hydroxyl: 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.
20. the method for processing cellulose material according to claim 19, it is characterized in that, describedly comprise containing of carboxyl and be selected from down group: adipic acid with the respond compound of active function groups of hydroxyl more than one, 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 and terephthalic acid (TPA).
21. the method for processing cellulose material according to claim 19, it is characterized in that, describedly comprise containing of anhydride group and be selected from down group: maleic anhydride, succinic anhydride, glutaric anhydride and phthalic anhydride with the respond compound of active function groups of hydroxyl more than one.
22. the method for processing cellulose material according to claim 1 is characterized in that, described containing more than one contained 3 carboxyls at least with respond each molecule of compound of active function groups of hydroxyl.
23. the method for processing cellulose material according to claim 1, it is characterized in that, in the described polymeric composition, contain more than one and be at least 1: 12 with the respond ratio of the integral molar quantity in composition of the hydroxyl in the integral molar quantity of carboxyl in composition and the polyol in the compound of active function groups of hydroxyl.
24. the method for processing cellulose material according to claim 23, it is characterized in that, in the described polymeric composition, containing more than one is 1: 12 to 35: 1 with the respond ratio of the integral molar quantity in composition of the hydroxyl in the integral molar quantity of carboxyl in composition and the polyol in the compound of active function groups of hydroxyl.
25. the method for processing cellulose material according to claim 1 is characterized in that, described polyol and contain to respond with hydroxyl more than and have at least a kind of compound to contain at least one unsaturated bond in the compound of active function groups.
26. the method for processing cellulose material according to claim 25 is characterized in that, described unsaturated bond can cause by heat initiation, free radical initiation, redox initiation or high energy, causes crosslinked or polymerisation.
27. the method for processing cellulose material according to claim 26 is characterized in that, described crosslinked or polymerisation took place before described polymeric composition adds cellulose material inside.
28. the method according to claim 25 or 26 arbitrary described processing cellulose materials is characterized in that, described unsaturated bond is two keys.
29. the method for processing cellulose material according to claim 1, it is characterized in that polymeric composition also contains one or more in dyestuff, metal inorganic salt, metal organic salt, repellent agent, anti-ultraviolet reagent, insect-proof agent, timber preservative, fire retardant, water, the organic solvent.
30. the method for processing cellulose material according to claim 1, it is characterized in that c) the composite high-molecular product described in the step 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.
31. the method for processing cellulose material according to claim 1, this method comprises:
1) provides a kind of cellulose 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 cellulose material is immersed in the described polymeric composition, to such an extent as to the hole of the described cellulose 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 cellulose material that responds, form a kind of water-fast composite high-molecular product.
32. the composite high-molecular product that the method for processing cellulose material according to claim 31 obtains is characterized in that, described dipping comprises: described cellulose material is vacuumized processing earlier; Cellulose material after this processing is contacted with polymeric composition; By continuous pressurization polymeric composition is constantly moved in the hole in cellulose material at last.
33. the composite high-molecular product that the method for processing cellulose material according to claim 1 obtains, it is characterized in that, described composite high-molecular product contains hole, and the macromolecule that the polymeric composition polymerization produces can partly be deposited in the hole at least.
34. composite high-molecular product according to claim 33 is characterized in that, the macromolecule major part that described polymeric composition polymerization produces is deposited in the hole of described composite high-molecular product.
35. according to claim 32 or 34 arbitrary described composite high-molecular products, it is characterized in that described composite high-molecular product 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.
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| CN2010101316126A CN101830015B (en) | 2010-03-24 | 2010-03-24 | Method for processing polysaccharide material with polymer composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102975248A (en) * | 2012-11-24 | 2013-03-20 | 姚高 | Impregnant composite for treating cellulose material |
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