CN1470542A - Modified trimeric cyanamide resin, and its preparing method and use - Google Patents
Modified trimeric cyanamide resin, and its preparing method and use Download PDFInfo
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- CN1470542A CN1470542A CNA021257590A CN02125759A CN1470542A CN 1470542 A CN1470542 A CN 1470542A CN A021257590 A CNA021257590 A CN A021257590A CN 02125759 A CN02125759 A CN 02125759A CN 1470542 A CN1470542 A CN 1470542A
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Abstract
The present invention provides a new-type cross-linking agent modified melamine resin. Said invention also provides the preparation method of said cross-linking agent and the impregnating preparation obtained by utilizing said cross-linking agent. It can be used for treating wood fibre material, specially it can be used for treating real wood material. The modified melamine resin is a product obtained by using formaldehyde and melamine, and making them undergo the processes of condensation and modification with maltodextrin. Said product can be used to make modification treatment of lignin material instead of hexamethoxymethyl melamine.
Description
Technical field
The present invention relates to wood processing field.Relate in particular to the novel crosslinker of the modification that is used for lignin material and woodwork---modified cyanurotriamide resin, relate to the preparation of described linking agent and its at the lignin goods, the purposes during especially the modification of trees solid wood material is handled.
Background of invention
Timber is unique reproducible material in iron and steel, cement, plastics and the timber four big materials, consuming little energy in the course of processing, the pollution that produces is little, and forest has made its status in four big materials more and more outstanding in the important value that shows aspect ecology, the environment in addition.For enlarging resource, simultaneously also owing to ecology and environmental requirement, the processing of cultivation, the especially artificial forest wood of artificial forest (fastgrowing trees) and utilization have become the direction of giving priority to of wood-processing industry.Fastgrowing trees wood is short vegetative period, but material is loose, intensity is low.Therefore, the method for modifying that improve artificial forest wood intensity, improves its defective simultaneously is subjected to various countries more and more and payes attention to.In handling for the modification of this low density and low-intensity material, stowing method, the use in the field of business of densification method are more.Stowing method also is divided into organism filling and inorganics filling, forms according to the steeping fluid that is used for impregnated timber and divides.
In timber, dipping organic monomer or resin prepolymer utilize irradiation or heat, make monomer or performed polymer in timber polymerization or with the timber graft polymerization, generate timber-plastics complex body (WPC), this is the method for the exploitation seventies.Timber size changes little in this method treating processes; After the processing, strength of wood and dimensional stability have been improved; Make timber have corrosion resistant, performance such as fire-retardant.Now, similarly method for modifying wood industrialization at home and abroad, its product can be used for furniture, floor, musical instrument, sports equipment etc.Because use monomer or prepolymer, processing cost is higher; Remaining monomer in workshop and the product, unfavorable to production and environment for use; In addition, also embarrass in, small business accepts.
Similar method, after using aqueous-based polymers (condensation resinoids such as urea-formaldehyde resin, melamine resin, resol) dipping, drying, thermofixation or heating, compression are solidified, this method is developed the forties, impreg (Impreg) and compregnated wood (Compreg) are its representative products, are used for the deck of boat, axle sleeve, lock road, handle of a knife etc.Product has intensity, dimensional stability and water resistance preferably.This class technology and WPC ratio, Yi Weizhong, small business accept, and are hot of research and development always.But for thermofixation person only, because the contraction of resin curing process, the product deformation ratio is more serious, and this is the defective of this method.
U.S. Pat P5,770,319 propose to use the maltodextrin aqueous solution impregnated timber of linking agent (HMMM) precrosslink, dry, curing then.Compare with other known technology, dimensional change is little in this technical finesse process, and the poplar product strength after the processing, dimensional stability are improved, but the burst size of methanal of product is too high, is used for indoor goods, can not reach China's national standard; In addition, this method use linking agent---HMMM cost height influences its competitiveness of product in market.
Summary of the invention
Problem at Wooden modifying and manufacture field existence, especially USP 5,770, the production cost height that the HMMM linking agent of record exists in 319, the defective of free formaldehyde content height (reaching about 2%), the invention provides a kind of modified cyanurotriamide resin, it can be used as a kind of novel linking agent and replaces the modification processing that HMMM is used for the lignin material, and the burst size of methanal of the goods that obtain is significantly reduced.
Another object of the present invention provides the preparation method of this linking agent.
The present invention further provides the dipping preparation that utilizes this linking agent to obtain, it can be used for handling lignocellulosic material, especially the trees solid wood material.
The contriver finds that through groping melamine resin and HMMM (hexamethylmethylolmelamine) have similar crosslinked ability, and the consumption of formaldehyde can be regulated in the melamine resin.But melamine resin solution instability, especially undesirable with the stability of the mixed steeping fluid of maltodextrin and storage property, if directly substitute HMMM as linking agent, aspect practicality, be difficult to accept with this melamine resin.
So the present invention proposes a kind of modified cyanurotriamide resin, it is a kind of formaldehyde and trimeric cyanamide condensation and the product after the maltodextrin modification, wherein formaldehyde and trimeric cyanamide be with 3.0 or less than 3.0 mol ratio condensation, and the mass content of maltodextrin is the 5-30% of trimeric cyanamide in the raw material.
The modified cyanurotriamide resin that proposes according to the present invention, the condensation mol ratio of formaldehyde and trimeric cyanamide will influence the crosslinked ability of product, the while also with about the burst size of methanal of timber-work after the processing.So to taking all factors into consideration of crosslinked ability and free formaldehyde content, the present invention requires the mol ratio of formaldehyde and trimeric cyanamide or to be lower than 3.0 3.0, preferably with the mol ratio condensation of 3.0-1.2, preferred molar ratio range is 2.7-1.4.
Why the present invention is referred to as modified cyanurotriamide, be owing to also have the effect of an amount of maltodextrin in the condensation course, thereby helping improving this trimeric cyanamide dried resin reaches with its stability as the steeping fluid of linking agent and the formation of maltodextrin co-blended, experiment shows, can reach two month more than one month its storage period.The DE value (dextrose equivalent value) of maltodextrin used in the present invention is preferably in 5-40, is preferably 10-25.
According to another aspect of the present invention, provide the preparation method of this modified cyanurotriamide resin, formed by formaldehyde and trimeric cyanamide condensation.To achieve the object of the present invention, reaction raw materials comprises formaldehyde, trimeric cyanamide and maltodextrin, wherein, the mol ratio of formaldehyde and trimeric cyanamide is 3.0 or less than 3.0, and the mass content of maltodextrin is the 5-30% of trimeric cyanamide in the raw material, and described raw material carries out condensation under the aqueous conditions of pH8-11.
For improving the solubleness of trimeric cyanamide, under the prerequisite that does not influence material modified intensity, also optionally add an amount of solubilizing agent in the condensation raw material, its addition can be the 0.5-12% of trimeric cyanamide raw material.The present invention does not have special requirement to the selection of this solubilizing agent, as long as can satisfy the conventional solubilizing agent of the needs of solubilising all can use, but preferred solubilizing agent is selected from aprotic solvent for example dimethyl formamide (DMF), methyl-sulphoxide (DMSO) etc., glycol, glycol monoether or tensio-active agent.Glycol wherein or glycol monoether are the glycol or the glycol ethers of the conventional rudimentary carbon that uses, and the indefiniteness example can be ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether (propyl ether, butyl ether etc.), propylene glycol monomethyl ether, propylene-glycol ethyl ether (propyl ether, butyl ether etc.) etc.
Above-mentioned condensation reaction is generally carried out under the aqueous conditions of pH8-11, preferably carries out under the condition of pH9.2-10.5.
Preparation in accordance with the present invention, the condensation terminal point of condensation reaction is judged with any currently known methods, preferably is expressed as 1000%-100% with the water extent of dilution.
Water extent of dilution of the present invention is meant: the resin (for example 2 milliliters) of getting certain volume, at room temperature add entry while stirring, begin to turn white, calculating the adds volume of entry and the ratio of resin volume until resin aqueous solution, multiply by 100%, be the water extent of dilution of this resin.
Reach as previously described, the invention provides the modified cyanurotriamide resin of a kind of HMMM of alternative prior art as the linking agent of Wooden modifying processing, according to another aspect of the present invention, a kind of cross-linked composition that the lignocellulosic material modification is handled that is used for also is provided, its by described modified cyanurotriamide resin and maltodextrin with dry-matter ratio 1: 5-1: 1 mass ratio is formed.Said composition is normally used by a kind of steeping fluid, dip treating for the benefit of, and the viscosity of this steeping fluid is preferably in 40-85 centipoise (20 ℃), and the pH value is at 8-11.In steeping fluid, described modified cyanurotriamide is as linking agent, modified cyanurotriamide resin and maltodextrin with the dry-matter ratio preferably 1: 3-1: 1.
Use steeping fluid of the present invention to handle mode and other common properties-correcting agent of lignocellulosic material, especially above-mentioned USP 5,770, method in 319 is basic identical, with pending material, fully flood in any feasible mode, carry out drying then, make resin solidification, can obtain the goods that need.Substantially the same among the definition of lignocellulosic material of the present invention and the USP 5,770,319, can comprise various logs, sheet material, woodwork, also can comprise various regeneration or synthetical board product, for example fiberboard, glued board etc.The present invention is particularly useful for the modification of trees solid wood and handles, especially the solid wood modification processing of the poplar that intensity of being planted in a large number in China and density are lower, China fir, the livings seeds of paulownia constant speed.
Compared with prior art, the timber-work that utilizes steeping fluid preparation of the present invention to handle, for example poplar goods, mechanical property with peer-level, and its burst size of methanal only is 1/10th of a prior art, and the dipping cost also reduces closely 1/2nd, is more suitable for the use of daily room material.
The specific embodiment of the present invention
Below the beneficial effect further introducing enforcement of the present invention and had by specific embodiment, purpose is to help that the reader is better understands essence of the present invention and spirit, can not constitute the qualification to the scope of the present invention.
Reference examples
According to U.S. Pat P5, the solution 2 preparation steeping fluids in 770,319:
In 2.250 kilograms methyl alcohol, add 2.250 kilograms hexamethoxymethyl melamine, be mixed with solution; 7.149 kilograms of maltodextrins (DE value 14-16%) are dissolved in 14.750 kilograms the water, are mixed with solution.Two solution are mixed, add 107 gram boric acid, as sanitas; Add the right-toluenesulphonic acids of 73 grams, as catalyzer.Stirred 4-5 hour at 20 ℃, because HMMM-CH
2OCH
3With maltodextrin-the OH partial reaction, make the hexamethoxymethyl melamine methanol solution be dissolved in water layer fully, obtain evenly, transparent liquid, stop in order to make the precrosslink reaction, use ammoniacal liquor that pH value of solution is adjusted to 8.This solution can be stored the several months under the condition of pH=8, and maltodextrin and hexamethoxymethyl melamine mass ratio are 3: 1, solution density 1.12 grams per milliliters, viscosity 50 centipoises (20 ℃), solids content 36%.
Embodiment
Embodiment 1
Condensation reaction: in reactor, add 2.300 kilograms of formaldehyde (28.4%), add 0.970 kg of water, under agitation, use 30% aqueous sodium hydroxide solution, pH value of solution is adjusted to 11.Add 1.500 kilograms of trimeric cyanamides, add 220 gram maltodextrins (DE value 14-16%).Under agitation, be warmed up to 90 ℃ in 40-60 minute, keep pH value between 9-10, be reacted to 400% termination of water extent of dilution.
The water extent of dilution is determined: get 2 milliliters of resins, be cooled to 20 ℃, add 20 ℃ water, constantly stir, when resin aqueous solution begins to turn white, with the volume of adding entry and the ratio of unmodified resin volume, multiply by 100%, be this resin water extent of dilution.
The steeping fluid preparation: the pH value of regulating above-mentioned condensation product is cooled to 80 ℃ between the 10-10.5, adds 4.385 kilogram 45% maltodextrin (the DE value 14-16%) aqueous solution, stirs, is cooled to room temperature, keeps the pH value between 10-11.
This steeping fluid solids content 41%, viscosity 70 centipoises (20 ℃), 15 days storage periods.
Embodiment 2
Condensation reaction: in reactor, add 2.300 kilograms of formaldehyde (28.4%), add 0.970 kg of water, stir down, use 30% aqueous sodium hydroxide solution, pH value of solution is adjusted to 10, add ethylene glycol 80 grams, 1.096 kilograms of trimeric cyanamides, add 220 gram maltodextrins (DE value 10-12%), in the stirring, 40-60 minute, be warmed up to 90 ℃, keep the pH value between 9.8-10.2, be reacted to water extent of dilution 600% and stop.
The steeping fluid preparation: the pH value of regulating above-mentioned condensation product is cooled to 80 ℃ between the 9.5-10.0, adds 4.385 kilogram 45% maltodextrin (the DE value 14-16%) aqueous solution, stirs, is cooled to room temperature, keeps the pH value between 9.5-10.0.
This steeping fluid solids content 41%, viscosity 81 centipoises (20 ℃), 45 days storage periods.
Embodiment 3
(the storage effect contrast, basic identical with other condition of embodiment 2, but do not use maltodextrin in the condensation reaction of present embodiment.)
Condensation reaction: in reactor, add 2.300 kilograms of formaldehyde (28.4%), add 0.970 kg of water, stir down, use 30% aqueous sodium hydroxide solution, pH value of solution is adjusted to 9.5, adds the DMF54.8 gram, 1.096 kilograms of trimeric cyanamides, stir, in the 40-60 minute, be warmed up to 90 ℃, keep the pH value between 9.0-9.5, be reacted to water extent of dilution 600% and stop.
The steeping fluid preparation: the pH value of regulating above-mentioned condensation reaction products is cooled to 80 ℃ between the 9.0-9.5, adds 4.385 kilogram 45% maltodextrin (the DE value 14-16%) aqueous solution, stirs, is cooled to room temperature, keeps the pH value between 9.0-9.5.
This steeping fluid solids content 41%, viscosity 60 centipoises (20 ℃), 1 month storage period.
Embodiment 4
Condensation reaction: in reactor, add 2.300 kilograms of formaldehyde (35.2%), add 0.970 kg of water, stir down, use 30% aqueous sodium hydroxide solution, pH value of solution is adjusted to 10.0, add the DMF54.8 gram, 1.096 kilograms of trimeric cyanamides, add 220 gram maltodextrins (DE value 20-25%), in the stirring, 40-60 minute, be warmed up to 90 ℃, keep the pH value between 9.5-10.0, be reacted to water extent of dilution 300% and stop.
The steeping fluid preparation: the pH value of regulating above-mentioned condensation reaction products is cooled to 80 ℃ between the 9.5-10.0, adds 4.385 kilogram 45% maltodextrin (the DE value 14-16%) aqueous solution, stirs, is cooled to room temperature, keeps the pH value between 8-11.
This steeping fluid solids content 41%, viscosity 41 centipoises (20 ℃), 2 months storage periods.
The dipping experiment:
The examination material: poplar, from lumber market, Beijing, gas is done, and water ratio is 8-10%, is of a size of 20 * 20 * 400mm; 50 * 70 * 70mm; 95 * 25 * 950mm.
Take by weighing the quality of poplar examination material.Poplar is tried material place impregnating autoclave, spaced-apart, float for preventing poplar, use weight to press and put.Under vacuum tightness 30-50 mmhg, vacuumize and handled 0.5 hour; Suck the steeping fluid of capacity, kept 0.5 hour; Emptying under the normal atmosphere, keeps after 0.5 hour, takes out sample, removes surface impregnation liquid, and the wet increment of poplar is calculated in weighing.
Dry, curing:
To flood sample and place room temperature, ventilation, seasoning is to water ratio 30%; Sample is placed 70 ℃ of loft drier, dry 12 hours; Then sample is placed 80 ℃ of loft drier, dry 4 hours; Again sample is placed 100 ℃ of loft drier, dry 6 hours; Place 130 ℃ of loft drier, dry 6 hours, make the resin completely solidified.Weigh, calculate the dried increment of poplar.
Physical and mechanical property detects:
According to national standard, formaldehyde discharges limit standard GB-18580-2001 in timberphysics, mechanic property test method standard GB-1927-1943-91 and indoor hardware fitting-wood-based plate and the goods thereof, measures physics, mechanical property and the burst size of methanal of modifying cotton wood material in each experiment respectively.
Measurement result and analysis:
1. poplar and dip treating material mechanical property thereof:
Table 1
Annotate: " contrast material " is meant undressed poplar solid wood material.
| Examination material classification | Density (g/cm 3) | Bending strength (MPa) | Crushing strength parallel to the grain (MPa) | Impelling strength (kJ/m 2) | Hardness (end face) (N) | Hardness (string face) (N) | Hardness (diametric plane) (N) |
| The contrast material | ??0.412 | ??74.6 | ???39.4 | ???63.1 | ????2569 | ????2035 | ????1980 |
| Embodiment 4 | ??0.560 | ??89.3 | ???54.9 | ???35.6 | ????6465 | ????5094 | ????4267 |
| Reference examples | ??0.561 | ??95.1 | ???54.4 | ???38.2 | ????4675 | ????2972 | ????2939 |
| Embodiment 1 | ??0.519 | ??75.1 | ???46.7 | ???26.5 | ????4110 | ????2860 | ????2910 |
| Embodiment 2 | ??0.52 | ??69.3 | ???41.7 | ???24.2 | ????3970 | ????3120 | ????2700 |
2. poplar dip treating plate burst size of methanal and steeping fluid thereof (dried solid) cost
Table 2
| The steeping fluid kind | The dried solid cost of steeping fluid (unit/ton) | Modified Poplar plate burst size of methanal (mg/100g) |
| Reference examples | ????8435 | ??137.36 |
| Embodiment 1 | ????5180 | ??13.36 |
| Embodiment 4 | ????4700 | ??35.04 |
Claims (20)
1, a kind of modified cyanurotriamide resin is characterized in that, is through formaldehyde and trimeric cyanamide condensation and the product after the maltodextrin modification, and wherein the mol ratio of formaldehyde and trimeric cyanamide condensation is 3.0 or less than 3.0.
2, the described modified cyanurotriamide resin of claim 1, wherein, the mass content of maltodextrin is the 5-30% of trimeric cyanamide in the condensation raw material.
3, the described modified cyanurotriamide resin of claim 1, wherein, to be formaldehyde and trimeric cyanamide form with the mol ratio condensation of 3.0-1.2 this resin; Be preferably 2.7-1.4.
4, claim 1,2 or 3 described modified cyanurotriamide resins, wherein, this resin is that condensation forms under the aqueous conditions of pH value 8-11.
5, claim 1 or 2 described modified cyanurotriamide resins, the DE value of maltodextrin that wherein is used for modification is at 5-40; Be preferably 10-25.
6, the purposes of each described modified cyanurotriamide resin in the lignocellulosic material modification is handled among the claim 1-5.
7, the described purposes of claim 6, wherein, described lignocellulosic material is a trees solid wood raw material.
8, the method for preparing modified cyanurotriamide resin, reaction raw materials comprises formaldehyde, trimeric cyanamide and maltodextrin, wherein, the mol ratio of formaldehyde and trimeric cyanamide is 3.0 or less than 3.0, and the mass content of maltodextrin is the 5-30% of trimeric cyanamide in the raw material, and described raw material carries out condensation under the aqueous conditions of pH8-11.
9, the described method of claim 8 wherein, also includes solubilizing agent in the condensation raw material, its addition is the 0.5-12% of trimeric cyanamide raw materials quality.
10, the described method of claim 8, wherein, the condensation terminal point of condensation reaction is expressed as 1000%-100% with the water extent of dilution.
11, the described method of claim 9, wherein, solubilizing agent is selected from: dimethyl formamide, methyl-sulphoxide, glycol, glycol monoether or tensio-active agent.
12, the described method of claim 8, wherein, the DE value of used maltodextrin is 5-40; Be preferably 10-25.
13, each described method among the claim 8-12, wherein, the mol ratio of formaldehyde and trimeric cyanamide is 3.0-1.2; Be preferably 2.7-1.4.
14, each described method among the claim 8-12, wherein, the pH value of condensation reaction system is controlled at 9.2-10.5.
15, a kind of cross-linked composition that the lignocellulosic material modification is handled of can be used for, by each described modified cyanurotriamide resin and maltodextrin among the claim 1-5 with dry-matter ratio 1: 5-1: 1 mass ratio is formed.
16, the described composition of claim 15, wherein, said composition is a steeping fluid, and its viscosity is the 40-85 centipoise down at 20 ℃, and the pH value is at 8-11.
17, the modification processing method of lignocellulosic material uses the composition of claim 15 or 16 to make steeping fluid, and pending material is fully flooded in any feasible mode.
18, the described method of claim 17, wherein, described lignocellulosic material is the trees solid woods.
19, the described method of claim 18, wherein, described lignocellulosic material is the poplar solid wood.
20, utilize the method modification of claim 17 to handle the poplar goods that obtain.
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| CNB021257590A CN1176963C (en) | 2002-08-16 | 2002-08-16 | Modified trimeric cyanamide resin, and its preparing method and use |
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| CN1176963C CN1176963C (en) | 2004-11-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658573A (en) * | 2012-05-08 | 2012-09-12 | 河北爱美森木材加工有限公司 | Fast growing wood steeping liquor, method for preparing fast growing wood steeping liquor and method for steeping wood |
| CN102744754A (en) * | 2011-04-21 | 2012-10-24 | 永港伟方（北京）科技股份有限公司 | Low-grade fast-growing wood modification solution, its preparation method and application |
| CN105128104A (en) * | 2015-08-17 | 2015-12-09 | 安徽中汇木业有限责任公司 | Method for processing fast growing wood into anticorrosive wood |
| CN107177027A (en) * | 2017-06-01 | 2017-09-19 | 东莞市贝辉装饰材料有限公司 | A kind of cyanurotriamide modified resin and its preparation method and application |
-
2002
- 2002-08-16 CN CNB021257590A patent/CN1176963C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744754A (en) * | 2011-04-21 | 2012-10-24 | 永港伟方（北京）科技股份有限公司 | Low-grade fast-growing wood modification solution, its preparation method and application |
| CN102744754B (en) * | 2011-04-21 | 2015-04-01 | 永港伟方（北京）科技股份有限公司 | Low-grade fast-growing wood modification solution, its preparation method and application |
| CN102658573A (en) * | 2012-05-08 | 2012-09-12 | 河北爱美森木材加工有限公司 | Fast growing wood steeping liquor, method for preparing fast growing wood steeping liquor and method for steeping wood |
| CN105128104A (en) * | 2015-08-17 | 2015-12-09 | 安徽中汇木业有限责任公司 | Method for processing fast growing wood into anticorrosive wood |
| CN107177027A (en) * | 2017-06-01 | 2017-09-19 | 东莞市贝辉装饰材料有限公司 | A kind of cyanurotriamide modified resin and its preparation method and application |
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| CN1176963C (en) | 2004-11-24 |
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Assignee: Siyang Shunyang Wood Co., Ltd. Assignor: Lumber Industry Inst., Chinese Forestry Scientific Inst. Contract record no.: 2011320000361 Denomination of invention: Modified trimeric cyanamide resin, and its preparing method and use Granted publication date: 20041124 License type: Common License Open date: 20040128 Record date: 20110322 |
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