CN103433988A - Method for performing functional improvement on wood by using polybasic carboxylic acid - Google Patents
Method for performing functional improvement on wood by using polybasic carboxylic acid Download PDFInfo
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- CN103433988A CN103433988A CN2013103791630A CN201310379163A CN103433988A CN 103433988 A CN103433988 A CN 103433988A CN 2013103791630 A CN2013103791630 A CN 2013103791630A CN 201310379163 A CN201310379163 A CN 201310379163A CN 103433988 A CN103433988 A CN 103433988A
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Abstract
The invention provides a method for performing functional improvement on wood by using polybasic carboxylic acid, relates to a method for performing functional improvement on wood, and aims to solve the problems of high cost, complicated process and serious environmental pollution in the existing functional improvement method for wood. The method comprises the following steps: 1, preparing a modifier solution; 2, performing dipping treatment on wood or a base material; and 3, polymerizing the modifier in the wood or base material. For the wood or base material subjected to functional improvement through the method, the dimensional stability is improved by 20-50%, the water absorptivity is lowered by 30-80%, and the compression strength is increased by 20-70%. The method can be used for expansion of the functional improvement technology for wood.
Description
Technical field
The present invention relates to a kind of method of timber being carried out to the function improvement.
Background technology
Timber is the natural biological material, is widely used in the mankind's living space.But there are the characteristics such as anisotropy, hygroscopicity due to wood structure, make its in use easily deform cracking, mycocriny insect pest, therefore, be necessary to use timber to carry out the function improvement to particular place.The chemical functional improvement is to timber, and especially the low-quality fast growing wood, as poplar and Eucalyptus etc., carries out the important channel of higher value application.The wood chemistry function modification method of existing comparative maturity comprises that acetylation processing, the modification of nitrogen hydroxymethyl resin, furfuryl alcohol are processed, dipping hangs down molecule urea aldehyde or phenolic resins etc. in the world.By these chemical modification means, modifying agent can infiltrate through in timber and wood cell wall material generation grafting/cross-linking reaction, perhaps in lumen, polycondensation forms large molecule, thereby realize in timber fixing, improve the dimensional stability of timber, make timber there is the functions such as corrosion resistant is rotten, anti-outdoor ageing.Although these timber Functionalizations can improve some original performance of timber and give its new function, but all there is potential deficiency aspect technology and properties of product, as problems (as patent is 201210194615.3 and 201210306016.6) such as formaldehyde release, the volatilizations of acetic acid residue, therefore most existing capability timber can only be applied to outdoor location.Along with the gradual perfection of environmental protection standard and user discharge the increase of attention rate to chemical functional improved wood product volatile matter, in the urgent need to developing a kind of new environment-friendly and green timber function improving technology and product.
Carboxyl in polybasic carboxylic acid can be under given conditions with timber in hydroxyl generation esterification, and can be fixed in timber, thus the problem of having avoided improved chemical to run off; Polybasic carboxylic acid can derive from natural plants, does not have the problems such as harmful little molecule volatilization with the timber after its modification; Process timber containing materials such as heavy metals, after service life, can equally directly act as a fuel and again utilize with common unseasoned timber.Therefore the polybasic carboxylic acid improved wood has guaranteed the sustainability of raw material, the feature of environmental protection for the treatment of process and the environment friendly of product.
Polybasic carboxylic acid is as a kind of efficient crosslinking agent, the crease-shedding finishing agent that is widely used at first bafta in textile industry, react with two or more cellulosic hydroxies by carboxylic acid and form chemical crosslinking, with wrinkle resistance and the printing and dyeing property that strengthens fabric, keep the mechanical strength (as patent ZL201110171592.4,201210567331.4, ZL96195570.8) of fabric when alkali lye and strong oxidizer washing.In addition, polybasic carboxylic acid is also as the crosslinking agent in wood adhesive or acid-base modifier, effectively control the adhesive solidification time, reduce the burst size of methanal of adhesive, strengthen the chemical reactivity of adhesive and aqueous high molecular, thereby improve the bonding strength of adhesive, prepared adhesive can be widely used in the gummed (ZL03128043.9, ZL200410017054.5,200610018302.7,200610147259.4,200810177621.1,200980125534.4, ZL201110072818.0) of crushed aggregate of plant and timber.
As effective crosslinking agent, polybasic carboxylic acid is also as auxiliary agent and other modified host crystal, as polyalcohol, silicon compound (as sodium metasilicate), chitin, lignin etc. are used from impregnation process timber, purpose is crosslinked Wooden modifying host, form the net macromolecular structure, thereby be fixed on (ZL200880105738.7, WO2012/153183A1, WO2011/042609A1) in timber.Patent (201210479868.5) has also been reported with the crosslinked phosphoric acid of BTCA, urea etc., thereby has been strengthened the resistance leachability of fire retardant in timber.Patent (ZL200710306593.4,201110272901.2, ZL200610027709.6) has been reported in the wood preservation treatment formulations and has been added citric acid, crosslinked fixedly antiseptic ingredient.Existing method is carried out functionality improvement to timber, and not only cost is high, complex process, and polybasic carboxylic acid is serious with other reagent mix use environmental pollution, however have no at present the patent report of independent use polybasic carboxylic acid as Wood modifier function improved wood.
Summary of the invention
The objective of the invention is for solve existing method to timber carry out that the functionality improvement cost is high, complex process, the serious problem of environmental pollution, provide a kind of polybasic carboxylic acid that utilizes timber to be carried out to the method for function improvement.
A kind of method of utilizing polybasic carboxylic acid to carry out the function improvement to timber of the present invention is carried out according to the following steps:
One, the preparation of modifier solution: the polybasic carboxylic acid adding distil water is made into to the polybasic carboxylic acid aqueous solution that mass fraction is 5～30%, add catalyst in the polybasic carboxylic acid aqueous solution, wherein the mass volume ratio of catalyst and the polybasic carboxylic acid aqueous solution is 0～1g: 10mL, mix, obtain modifier solution;
Two, timber or base material impregnation process: adopt the vacuum pressed impregnating equipment, under the vacuum pressed condition, the modifier solution made in step 1 is impregnated in timber or base material;
Three, the polymerization of modifier in timber or base material: timber or the base material elder generation gas under normal temperature and pressure conditions impregnated in step 2 is done 1～10 day, in the dry process of gas every 1～2 day rolling or base material, then by timber or base material heat drying 2 days at 40 ℃, 60 ℃ and 80 ℃ of temperature respectively, last dry solidification 1～4 day under 100～160 ℃ of conditions.
The present invention comprises following beneficial effect:
The invention has the advantages that: the modifier that 1. adopted is the natural polybasic carboxylic acid polymer of environmental protection, and the timber after modification or base material can not cause any harm to environment or human body; 2. the timber after modification or substrate sizes stability, resistance to water and rotproofness and improve a lot, Some Mechanical Properties also has raising in various degree, thereby has widened the range of application of fast-growing or tender constitution timber or base material; 3. use separately polybasic carboxylic acid to carry out functionality improvement to timber, guaranteed sustainability and the low cost of raw material, and treatment process is simple.
The present invention carries out functionality improvement with natural polybasic carboxylic acid polymer to timber or base material, and prepared timber or base material can be used for part (slurry, deck, handrail etc.), outdoor material, bridge, firearms etc. on handle of a knife, kitchen articles, furniture, indoor floor, work top, building part (playing angle, corner, doorframe, threshold, bin etc.), ship.
The functionalization timber that the present invention makes or its impact strength of base material significantly improve, reduce by 75% in the timber impact strength after the 2D resin treatment in patent CN102320069A, and the timber impact strength after the present invention's processing only reduces by 40%, in addition, timber after functionality improvement of the present invention or the dimensional stability of base material improve 20～50%, water imbibition reduces by 30～80%, and compression strength also improves 20～70%.
It is modifier that this patent adopts polybasic carboxylic acid, under the particular modification process conditions, significantly strengthens dimensional stability and the rotten ability of corrosion resistant of timber.This technical method has the medicament green, technique is simple, reaction is efficient, the characteristics of superior performance, is the expansion of timber functionalization improving technology.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: a kind of method of utilizing polybasic carboxylic acid to carry out the function improvement to timber of present embodiment is carried out according to the following steps:
One, the preparation of modifier solution: the polybasic carboxylic acid adding distil water is made into to the polybasic carboxylic acid aqueous solution that mass fraction is 5～30%, add catalyst in the polybasic carboxylic acid aqueous solution, wherein the mass volume ratio of catalyst and the polybasic carboxylic acid aqueous solution is 0～1g: 10mL, mix, obtain modifier solution;
Two, timber or base material impregnation process: adopt the vacuum pressed impregnating equipment, under the vacuum pressed condition, the modifier solution made in step 1 is impregnated in timber or base material;
Three, the polymerization of modifier in timber or base material: timber or the base material elder generation gas under normal temperature and pressure conditions impregnated in step 2 is done 1～10 day, in the dry process of gas every 1～2 day rolling or base material, then by timber or base material heat drying 2 days at 40 ℃, 60 ℃ and 80 ℃ of temperature respectively, last dry solidification 1～4 day under 100～160 ℃ of conditions.
The specific embodiment two: what present embodiment was different from the specific embodiment one is that the timber described in step 2 is fast growing wood or natural tender constitution material, and base material is medium density fibre board (MDF), particieboard and glued board.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is that the polybasic carboxylic acid described in step 1 is oxalic acid, malonic acid, maleic acid, fumaric acid, butanedioic acid, glutaric acid, adipic acid, phthalic acid, malic acid, tartaric acid, citric acid, 1,2, one or more in 3,4-BTCA are according to any mixture than forming.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is that the catalyst described in step 1 is inferior sodium phosphate, magnesium chloride, zinc oxide, stannic chloride, copper sulphate, sodium chloride, iron chloride or aluminum sulfate.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is that the vacuum pressed described in step 2 is treated to independent application of vacuum, independent pressurized treatments or the two alternate treatment, vacuum is-0.1～0MPa, and pressure is 0～0.9MPa.Other is identical with one of specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five is that the drying mode described in step 3 is forced air drying, vacuum drying, heating using microwave, high-energy radiation or multiple drying mode and is used alternatingly.Other is identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to six is that the mass volume ratio of the catalyst described in step 1 and the polybasic carboxylic acid aqueous solution is 0.5g: 10mL.Other is identical with one of specific embodiment one to six.
Verify beneficial effect of the present invention by following examples:
Embodiment mono-: the citric acid adding distil water is mixed with to the aqueous citric acid solution 1000mL that mass fraction is 20%, adds 10g ortho phosphorous acid sodium catalyst, make modifier solution; The poplar sample being soaked in modifier solution, adopting the vacuum pressed impregnating equipment, vacuum be-floods 2 days under the condition of 0.1MPa, the modifier solution made in step 1 is impregnated in timber or base material; Take out sample dry 7 days of gas at normal temperatures and pressures, dry 24h under 40,60,80 ℃ respectively, finally solidify 1 day at 120 ℃ afterwards.
Poplar rate of body weight gain after the present embodiment modification is 25.4%, water absorption decreased 10.4%, and dimensional stability improves 47.2%.
Embodiment bis-: the citric acid adding distil water is mixed with to the aqueous citric acid solution 1000mL that mass fraction is 30%, makes modifier solution; The poplar sample being soaked in modifier solution, adopting the vacuum pressed impregnating equipment, vacuum be-floods 2 days under the condition of 0.1MPa, the modifier solution made in step 1 is impregnated in timber or base material; Take out sample dry 7 days of gas at normal temperatures and pressures, dry 24h under 40,60,80 ℃ respectively, finally solidify 2 days at 120 ℃ afterwards.
Poplar rate of body weight gain after the present embodiment modification is 36.5%, and cubical expansivity is 6.57%, and dimensional stability improves 47%.
Embodiment tri-: the citric acid adding distil water is mixed with to the aqueous citric acid solution 1000mL that mass fraction is 30%, adds 15g ortho phosphorous acid sodium catalyst, make modifier solution; The poplar sample is soaked in modifier solution, adopt the vacuum pressed impregnating equipment, in vacuum, be-condition of 0.1MPa under dipping 1 day, under the condition that is 0.04MPa at pressure afterwards, dipping is 1 day, and the modifier solution made in step 1 is impregnated in timber or base material; Take out sample dry 7 days of gas at normal temperatures and pressures, dry 24h under 40,60,80 ℃ respectively, finally solidify 1 day at 120 ℃ afterwards.
Poplar rate of body weight gain after the present embodiment modification is 34.4%, and cubical expansivity is 6.6%, and dimensional stability improves 54.1%, and concrete modification situation is as table 1.
The situation of change of timberphysics mechanical property after table 1 modification
Embodiment tetra-: 1,2,3,4-BTCA adding distil water is mixed with to the butane tetracarboxylic aqueous acid 1000mL that mass fraction is 20%, adds 10g magnesium chloride catalyst, make modifier solution; The poplar sample being soaked in modifier solution, adopting the vacuum pressed impregnating equipment, vacuum be-floods 2 days under the condition of 0.1MPa, the modifier solution made in step 1 is impregnated in timber or base material; Take out sample dry 7 days of gas at normal temperatures and pressures, dry 24h under 40,60,80 ℃ respectively, finally solidify 1 day at 120 ℃ afterwards.
Poplar rate of body weight gain after the present embodiment modification is 36.4%, and dimensional stability improves 55.3%, and compression strength improves 56.4%.
Embodiment five: the butanedioic acid adding distil water is mixed with to the butanedioic acid aqueous solution 1000mL that mass fraction is 15%, adds the 4.5g ferric chloride catalyst, make modifier solution; The poplar sample is soaked in modifier solution, adopt the vacuum pressed impregnating equipment, vacuum is-condition of 0.1MPa under dipping 1 day, under the condition that is 0.04MPa at pressure afterwards, dipping is 1 day, and the modifier solution made in step 1 is impregnated in timber or base material; Take out sample dry 7 days of gas at normal temperatures and pressures, dry 24h under 40,60,80 ℃ respectively, finally solidify 1 day at 120 ℃ afterwards.
Poplar rate of body weight gain after the present embodiment modification is 20.4%, and dimensional stability improves 45.1%, water absorption decreased 10.1%.
Claims (7)
1. one kind is utilized polybasic carboxylic acid timber to be carried out to the method for function improvement, it is characterized in that described method carries out according to following steps:
One, the preparation of modifier solution: the polybasic carboxylic acid adding distil water is made into to the polybasic carboxylic acid aqueous solution that mass fraction is 5～30%, add catalyst in the polybasic carboxylic acid aqueous solution, wherein the mass volume ratio of catalyst and the polybasic carboxylic acid aqueous solution is 0～1g: 10mL, mix, obtain modifier solution;
Two, timber or base material impregnation process: adopt the vacuum pressed impregnating equipment, under the vacuum pressed condition, the modifier solution made in step 1 is impregnated in timber or base material;
Three, the polymerization of modifier in timber or base material: timber or the base material elder generation gas under normal temperature and pressure conditions impregnated in step 2 is done 1～10 day, in the dry process of gas every 1～2 day rolling or base material, then by timber or base material heat drying 2 days at 40 ℃, 60 ℃ and 80 ℃ of temperature respectively, last dry solidification 1～4 day under 100～160 ℃ of conditions.
2. timber is carried out to the method for function improvement according to a kind of polybasic carboxylic acid that utilizes described in claim 1, it is characterized in that the timber described in step 2 is fast growing wood or natural tender constitution material, base material is medium density fibre board (MDF), particieboard and glued board.
3. timber is carried out to the method for function improvement according to a kind of polybasic carboxylic acid that utilizes described in claim 2, it is characterized in that the polybasic carboxylic acid described in step 1 is oxalic acid, malonic acid, maleic acid, fumaric acid, butanedioic acid, glutaric acid, adipic acid, phthalic acid, malic acid, tartaric acid, citric acid, 1,2, one or more in 3,4-BTCA are according to any mixture than forming.
4. timber is carried out to the method for function improvement according to a kind of polybasic carboxylic acid that utilizes described in claim 3, it is characterized in that the catalyst described in step 1 is inferior sodium phosphate, magnesium chloride, zinc oxide, stannic chloride, copper sulphate, sodium chloride, iron chloride or aluminum sulfate.
5. timber is carried out to the method for function improvement according to a kind of polybasic carboxylic acid that utilizes described in claim 4, it is characterized in that the vacuum pressed described in step 2 is treated to independent application of vacuum, independent pressurized treatments or the two alternate treatment, vacuum is-0.1～0MPa, and pressure is 0～0.9MPa.
6. timber is carried out to the method for function improvement according to a kind of polybasic carboxylic acid that utilizes described in claim 5, it is characterized in that the drying mode described in step 3 is forced air drying, vacuum drying, heating using microwave, high-energy radiation or multiple drying mode and is used alternatingly.
7. timber is carried out to the method for function improvement according to a kind of polybasic carboxylic acid that utilizes described in claim 6, the mass volume ratio that it is characterized in that the catalyst described in step 1 and the polybasic carboxylic acid aqueous solution is 0.5g: 10mL.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107803902A (en) * | 2017-11-07 | 2018-03-16 | 桂林奥尼斯特节能环保科技有限责任公司 | A kind of dedicated modified liquid of timber and preparation method thereof |
| CN109129775A (en) * | 2018-08-28 | 2019-01-04 | 东北林业大学 | Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof |
| CN111975906A (en) * | 2020-08-21 | 2020-11-24 | 西北农林科技大学 | Wood preservation modification treatment method and application thereof |
| CN113386223A (en) * | 2021-07-07 | 2021-09-14 | 中南林业科技大学 | Transparent bamboo material and preparation method and application thereof |
| CN113977724A (en) * | 2021-10-18 | 2022-01-28 | 北京林业大学 | Low-temperature thermal modified wood based on exogenous phosphoric acid catalysis and manufacturing method thereof |
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| JP2002086405A (en) * | 2000-09-12 | 2002-03-26 | National Institute Of Advanced Industrial & Technology | Method for manufacturing wood material having humidity adjusting property and dimensional stability and wood material |
| WO2011042609A1 (en) * | 2009-10-08 | 2011-04-14 | Upm-Kymmene Wood Oy | Impregnation of chemicals into wood |
| CN102320069A (en) * | 2011-09-22 | 2012-01-18 | 东北林业大学 | Brittleness inhibition method of chemical function improved wood |
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2013
- 2013-08-27 CN CN2013103791630A patent/CN103433988A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002086405A (en) * | 2000-09-12 | 2002-03-26 | National Institute Of Advanced Industrial & Technology | Method for manufacturing wood material having humidity adjusting property and dimensional stability and wood material |
| WO2011042609A1 (en) * | 2009-10-08 | 2011-04-14 | Upm-Kymmene Wood Oy | Impregnation of chemicals into wood |
| CN102320069A (en) * | 2011-09-22 | 2012-01-18 | 东北林业大学 | Brittleness inhibition method of chemical function improved wood |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107803902A (en) * | 2017-11-07 | 2018-03-16 | 桂林奥尼斯特节能环保科技有限责任公司 | A kind of dedicated modified liquid of timber and preparation method thereof |
| CN109129775A (en) * | 2018-08-28 | 2019-01-04 | 东北林业大学 | Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof |
| CN111975906A (en) * | 2020-08-21 | 2020-11-24 | 西北农林科技大学 | Wood preservation modification treatment method and application thereof |
| CN113386223A (en) * | 2021-07-07 | 2021-09-14 | 中南林业科技大学 | Transparent bamboo material and preparation method and application thereof |
| CN113977724A (en) * | 2021-10-18 | 2022-01-28 | 北京林业大学 | Low-temperature thermal modified wood based on exogenous phosphoric acid catalysis and manufacturing method thereof |
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Application publication date: 20131211 |