CN102268139B - Resin additive and preparation method and application thereof - Google Patents
Resin additive and preparation method and application thereof Download PDFInfo
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- CN102268139B CN102268139B CN 201110141528 CN201110141528A CN102268139B CN 102268139 B CN102268139 B CN 102268139B CN 201110141528 CN201110141528 CN 201110141528 CN 201110141528 A CN201110141528 A CN 201110141528A CN 102268139 B CN102268139 B CN 102268139B
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Abstract
本发明公开了一种树脂添加剂，它是由工业生产过程中产生的含有10%~50%木质素的废料经过磺甲基化改性制成。并且本发明还提供了该树脂添加剂的制备方法及其在改良人造板胶粘剂性能中的应用。本发明所述的树脂添加剂既增加了胶粘剂的粘结能力，又扩大了废物再利用的应用范围，降低了生产成本。The invention discloses a resin additive, which is made from waste materials containing 10% to 50% lignin produced in the industrial production process and modified by sulfomethylation. And the invention also provides the preparation method of the resin additive and its application in improving the performance of the wood-based panel adhesive. The resin additive of the invention not only increases the bonding ability of the adhesive, but also expands the application range of waste recycling, and reduces the production cost.
Description
Technical field
The present invention relates to a kind of resin additive and preparation method thereof and application.
Background technology
China's timber industry in recent years, had become world's Wood-based Panel Production first big country through nearly 30 years fast development, and wood adhesive output is the rank No. 1 in the world.The Wood-based Panel Production scale surpassed 1.15 hundred million M in 2009
3, produce the total value more than one hundred billion per year; The consumption maximum is urea-formaldehyde resin in adhesive of artificial board, resol and melamine formaldehyde resin adhesive, and they also are called wood-based panel industry three big glue.Urea-formaldehyde resin is a kind of aldehyde adhesive that contains by formaldehyde and urea synthesis.The raw material of urea-formaldehyde resin adhesive is easy to get, cost is low, easy to use, excellent property, is widely used in wood working industry.The production of China's urea-formaldehyde resin adhesive in 2010 surpasses 4,500,000 tons (solids content 100%), but has shortcomings such as poor water resistance and residual formaldehyde height.In synvaren, most widely used general with the resol that phenol and formaldehyde condensation polymer form, performances such as the Joint strength of its laminated product is strong, water-fast, heat-resisting, corrosion-resistant are all fine, but resol exists the hot pressing temperature height, time is long and to shortcomings such as veneer water content requirement height, in use be subjected to certain restriction, and because phenol is petroleum chemicals, so the price of synvaren is higher.The melamine-formaldehyde resin adhesive stick has good water tolerance, thermotolerance, hardness height, quick solidifying, (comparing with resol) but price is higher.The raw material of above-mentioned 3 kinds of tackiness agent all derives from non-renewable petroleum products, along with the scarcity of petroleum resources with and price rise steadily, seek and utilize renewable resources to replace petroleum products to become a key issue that needs to be resolved hurrily at present as the raw material of preparation adhesive of artificial board.
Xylogen is the non-oil resource that occurring in nature can provide renewable compound aromatic base, and it is next in number only to Mierocrystalline cellulose, for vegitabilia second enriches organic polymer.According to estimates, every year is produced 6,000,000,000 tons in the whole world approximately.Pulp and paper industry will be isolated 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain the xylogen byproduct about 5,000 ten thousand tons simultaneously; Bio-ethanol industrial development in recent years is rapid, 1 ton of ethanol of every production, to produce 1 ton of residue simultaneously, except the raw material and other impurity of a part without enzymolysis, also contain a certain amount of (50%～10% depends on the difference of pretreatment technology) xylogen in the residue.The application of xylogen in adhesive of artificial board has dual mode, a kind of is that xylogen itself is as tackiness agent, add various auxiliary agents as sulfonated lignin, alkali lignin and directly stick with glue agent as timber, but this type of tackiness agent needs long hot pressing time, higher hot pressing temperature and acidity mostly.Another kind is that xylogen mixes with resol, urea-formaldehyde resin and urethane etc., it is carried out modification, thereby make tackiness agent.
Relevant xylogen Study on making adhesives can trace back to for 19 end of the centurys the earliest; after the 1950's; the patent that xylogen is applied to tackiness agent begins a large amount of appearance; but up to the seventies in 20th century, just begin to carry out production experiment in countries such as Denmark, Switzerland, Finland, after the eighties in 20th century; on the chemical modification that focuses on xylogen of correlative study; along with each pay attention to day by day to environment protection, in recent years, the report that xylogen is used had appearred in environment-friendly adhesive.Though accumulated some technological methods, large-scale industrial production is also rare, only the xylogen waste residue is acted as a fuel and burns or enter the ocean.Up to now, only be utilized effectively less than 20% in the annual industrial lignin that produces in the whole world.
Realization contains the resource reutilization of xylogen waste material, must consider that market is to the factor of four aspects such as characteristic of the greenization of the ratio of performance to price of the demand of product, product, production technique and performance xylogen waste residue material itself.At present, bibliographical information be applied to xylogen Industrial products major part in the tackiness agent be to by separate the plain or refining xylogen of the rugose wood of purifying by sulfonation, methylolation, phenolate, oxidation, demethylation and and chemical modification such as unsaturated aldehyde, be applied to urea-formaldehyde resin, resol, synthetic resins materials such as urethane.Xylogen is used for water reducer mostly through the sulfomethylation modification in the prior art, Scale inhibitors, and coal water slurry dispersing agent yet there are no the residuum feedstocks that report will contain xylogen and directly uses the preparation additive for synthetic resin through the sulfomethylation modification.If it can be developed to high value added product, compare to use and separate the plain or refining xylogen of purification rugose wood, not only can significantly reduce the pollution that when separating purification rugose wood element or refining xylogen environment is produced, can also improve the income of enterprise.
Summary of the invention
First technical problem that the present invention will solve provides a kind of resin additive, and this additive mainly is to utilize the waste material process sulfomethylation modification that contains 10% ~ 50% xylogen that produces in the Industrial processes to make.This resin additive had both increased the viscosifying power of adhesive of artificial board, had enlarged the range of application of refuse reclamation again, had reduced production cost.
Second technical problem that the present invention will solve provides a kind of preferred preparation method of described resin additive.This method is that the waste material that contains xylogen that will produce in the Industrial processes obtains the sulfomethylation product after modification is handled, and makes described resin additive.Technology of the present invention is simple, implements easily, and is respond well.
The 3rd technical problem that the present invention will solve provides the application of described resin additive in improvement adhesive of artificial board performance.
For solving above-mentioned first technical problem, technical scheme provided by the present invention is:
Resin additive provided by the present invention, it is to be made by the waste material process sulfomethylation modification that contains 10% ~ 50% xylogen that produces in the Industrial processes.
" produce in the Industrial processes contain xylogen waste material " of the present invention refers to paper-making pulping waste liquid, biological preparation ethanol waste material, biological sugaring bits etc., the waste material that contains xylogen that the present invention obtains including but not limited to above several Industrial processes.Because xylogen waste residue kind material and pretreatment mode difference (but the hemicellulose in the sour pre-treatment effective elimination fibrous material; Diluted alkaline is handled and is mainly removed most xylogen), the content of lignin difference.Find after deliberation particularly to make described resin additive according to sulfomethylation method provided by the invention as long as the content of xylogen all can pass through the sulfomethylation modification greater than 10% in the waste material.And the content of xylogen is more high in the described waste material, and glue performance is more good.The content of lignin of the waste material after the sugaring of corn cob alkaline process enzyme process is very low, and content of lignin is 6% ~ 7% only, when content of lignin is lower than 10%, owing to introduce a large amount of impurity, and very poor with the consistency of resin, make glue performance become very poor.
For solving above-mentioned second technical problem, technical scheme provided by the present invention is:
Disclose the sulfomethylation method of some xylogen in the prior art, be used for water reducer, Scale inhibitors, coal water slurry dispersing agent mostly through the xylogen of sulfomethylation modification.Resin additive of the present invention can utilize in the prior art disclosed sulfomethylation method that the waste material that contains xylogen is carried out modification, and is applied in the adhesive of artificial board.But in order to reach the better application effect, the invention provides a kind of preferred preparation method of resin additive, this method may further comprise the steps:
(1) waste material that contains 10% ~ 50% xylogen that produces in the Industrial processes is made into the aqueous solution that concentration is 0.1g/ml ~ 0.4g/ml, then with alkali or basic salt adjust pH to 9 ~ 11;
(2) be heated to 70 ℃ ~ 80 ℃, the concentration that adds xylogen quality 20% ~ 60% in the described waste material is 37% formaldehyde, constant temperature backflow stirring reaction 2 ~ 3h;
(3) Na of xylogen quality 30% ~ 70% in the described waste material of adding
2SO
3, with acid or acid-salt adjust pH to 7 ~ 8, in 100 ℃ ~ 140 ℃ reaction 3 ~ 4h, then reaction solution is cooled off;
(4) the reaction soln oven dry that step (3) is made is pulverized, namely.
Further, in step (2) and (3), during adjust pH, described alkali is sodium hydroxide, trolamine or vulkacit H; Described basic salt is yellow soda ash, sodium phosphate or S-WAT; Described acid is sulfuric acid, formic acid, oxalic acid or acetic acid; Described acid-salt is ammonium chloride, zinc chloride or SODIUM PHOSPHATE, MONOBASIC.
Further, in the step (4), after the described reaction soln oven dry, be crushed to more than 100 orders.
For solving above-mentioned the 3rd technical problem, technical scheme provided by the present invention is:
The invention provides the application of described resin additive in improvement adhesive of artificial board performance.Specifically be resin additive of the present invention and adhesive of artificial board to be carried out composite, with the performance of improvement adhesive of artificial board, improve the bonding strength of adhesive of artificial board.
Further, described adhesive of artificial board is urea-formaldehyde resin adhesive, synvaren, melamine formaldehyde resin adhesive or polyurethane adhesive.Ratio of quality and the number of copies when described resin additive and above-mentioned adhesive of artificial board are composite is preferably 5 ~ 45:55 ~ 95.
The invention has the beneficial effects as follows:
1. a certain amount of unmodified xylogen is arranged in the resin additive of the present invention, both contained phenolic hydroxyl group on its structural unit, contain aldehyde radical again, under the pressurized conditions of heating in the making sheet process, the further condensation of xylogen and resin, can produce part new glued construction, cohesive strength is strengthened to some extent; Xylogen is introduced activation functional group after modification, it can reduce the surface tension of resin, makes between plank and the binder molecule closely contact and adsorbs, and has got rid of the gas of adherend surface adsorption simultaneously, reduce the voidage of adhesive interface, thereby improved the bonding strength of glued board; And the inside that can prevent the infiltration that glue is too much causes local starved, saves glue consumption and reduces production costs.
2. the resin additive raw material is for without the industrial residue material that contains 10% ~ 50% xylogen of purifying, a certain amount of Mierocrystalline cellulose is contained in the inside, the free aldehyde of part in the adsorbable resin of Mierocrystalline cellulose can guarantee the stable of colloid, not stratified, and can make the molecule of resin further even, be conducive to storage and the use of Resin adhesive.Though polysaccharide exists as impurity, in the certain limit ratio, be crushed to and have filling effect preferably more than 100 orders, can reduce the stress between bonding interface, improve bonding strength; The xylogen waste material powder that contains after the modification of the present invention has better water tolerance than flour, can prevent that resin adhesive liquid from too immersing to wood-based plate is inner, can significantly improve its wet bonding strength and utilization ratio, and can replace a certain amount of flour, reduces production costs.
3. resin additive is a kind of inert filler, and in building board production process, it can prevent that not only resin from too infiltrating in the timber, has water retention preferably, save the usage quantity of tackiness agent, reduce production costs, and can improve production ageing-resistant performance and the bonding quality of resin.
4. in building board production process, behind a certain amount of modified resin additive of adding, all can improve the bonding strength of adhesive of artificial board in the adhesive of artificial board.The formed compound bonding strength in composite back and initial bonding strength, the addition of resin additive is relevant, and maximum addition can reach 45%, and the tackiness agent after composite has all reached the level of national II class glue.Increase along with described resin additive add-on, tensile strength is obviously strengthened, but descend gradually after surpassing 15%, addition with described resin additive is the mass ratio of 15%(and adhesive of artificial board) time the shearing resistance maximum, the shearing resistance of shearing resistance when not adding resin additive increases by 0.3 ~ 0.5Pa.
5. the artificial board that utilizes the composite back of resin additive of the present invention and adhesive of artificial board to produce all reaches national indoor decorating standard of materials.
Embodiment
The present invention will be further described below in conjunction with specific embodiment, but be not to limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials among the following embodiment if no special instructions, is the routine biochemistry reagent suppliers and buys and obtain.
Embodiment 1 utilizes the waste modified method for preparing resin additive of wheat stalk fermenting alcohol
The preparation mass percentage concentration is 20% the NaOH aqueous solution; Mass percentage concentration is 10% aqueous sulfuric acid, and wherein, the sulfuric acid of use is 98% the vitriol oil;
(1) wheat stalk fermenting alcohol waste material is made into the aqueous solution that concentration is 0.2g/ml, gets 1000ml.Be 20% NaOH aqueous solution adjust pH to 11 with concentration, wherein contain 35% xylogen in the wheat stalk fermenting alcohol waste material;
(2) be heated to 70 ℃, add 23g 37% formaldehyde solution, in 70 ℃ of constant temperature backflow stirring reaction 2h;
(3) add 48g Na
2SO
3, be 10% H with concentration
2SO
4The solution adjust pH is 7, in 100 ℃ of reaction 3h, then reaction solution is cooled off;
(4) the reaction soln oven dry that step (3) is made is crushed to more than 100 orders, is packaged into the product of resin additive.
Embodiment 2 utilizes the corn cob acid system enzyme process waste modified method for preparing resin additive of refining sugar
(1) maize straw acid system enzyme process sugaring waste material is made into the aqueous solution that concentration is 0.4g/ml, gets 1000ml.Be 20%NaOH solution adjust pH to 11 with concentration; Contain 22% xylogen in the wherein said maize straw acid system enzyme process sugaring;
(2) be heated to 80 ℃, add 18g 37% formaldehyde solution, in 80 ℃ of constant temperature backflow stirring reaction 2h;
(3) add 27g Na
2SO
3, be 10% H with concentration
2SO
4The solution adjust pH is 7.5, in 120 ℃ of reaction 3h, then reaction solution is cooled off;
(4) the reaction soln oven dry that step (3) is made is crushed to the above powder of 100 orders, is packaged into the product of resin additive.
Embodiment 3 utilizes the pulping waste liquor modification to prepare the method for resin additive
(1) getting paper-making pulping waste liquid 200g, is 20%NaOH solution adjust pH to 10 with concentration, contains 45% xylogen in the wherein said paper-making pulping waste material;
(2) be heated to 80 ℃, add 54g37% formaldehyde solution, in 80 ℃ of constant temperature backflow stirring reaction 2h;
(3) add 27g Na
2SO
3, be 10% H with concentration
2SO
4The solution adjust pH is 8, in 100 ℃ of reaction 4h, then reaction solution is cooled off;
(4) the reaction soln oven dry that step (3) is made is crushed to the above powder of 100 orders, is packaged into the product of resin additive.
Embodiment 4 modified resin Application of Additives
Below the acid curing agent that uses in the experiment can be one or more the mixture in formic acid, toxilic acid, ammonium sulphite, ammonium chloride, Phenylsulfonic acid or the phosphoric acid.
1. get 90 parts of urea-formaldehyde resin adhesives, add 9 parts of resin additives, 6 parts in flour, (rotating speed is 30 rev/mins, stirs 10 minutes) adds 9 parts of acid curing agents under the condition that stirs, and this moment, pH was 4.6 ~ 4.8.Utilize this tackiness agent at pressure 8.0MPa, after colding pressing 0.5 hour, again at temperature 110 degree, during pressure 1.5MPa, hot pressing 3 minutes, after 3 hours, shearing resistance is 1.4Mpa to the poplar three-layer glued board of production at 63 ℃ of poach, qualification rate is 100%.
2. get 80 parts of urea-formaldehyde resin adhesives, add 20 parts of resin additives, 1 part in flour, (rotating speed is 100 rev/mins, stirs 5 minutes) adds 12 parts of acid curing agents under the condition that stirs, and this moment, pH was 4.6 ~ 4.8.Utilize this tackiness agent at pressure 8.0MPa, after colding pressing 0.5 hour, at temperature 110 degree, during pressure 1.5MPa, hot pressing 3 minutes, after 3 hours, shearing resistance is 0.8Mpa to the poplar three-layer glued board of production at 63 ℃ of poach, qualification rate is 100%.
3. heat-obtaining solidity synvaren is 90 parts, adds 10 parts of resin additives, 6 parts in flour, and stir (rotating speed is 60 rev/mins, stirs 8 minutes) adds 10 parts of acid curing agents, and this moment, pH was 4.6 ~ 4.8.Be 150 when spending in temperature, pressure is 20MPa, and hot pressing time is 7 minutes, insulation 150 degree 4 hours.After 3 hours, shearing resistance is 1.0Mpa to the poplar three-layer glued board of producing at 100 ℃ of poach, and qualification rate is 100%.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give exhaustive to all embodiments.Everyly belong to the row that apparent variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
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| CN102585247B (en) * | 2012-01-12 | 2016-09-28 | 安徽丰原发酵技术工程研究有限公司 | A kind of method utilizing lignocellulose residue from enzymatic hydrolysis to prepare lignosulfonates |
| CN108794715A (en) * | 2018-06-29 | 2018-11-13 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of composite floor board sulfomethylation lignin modification urea-phenolic resin adhesive |
| CN109251700A (en) * | 2018-07-05 | 2019-01-22 | 北京林业大学 | Multi-functional wooden cellulase hydrolysed ferment residue filler, preparation method and applications |
| CN111154437A (en) * | 2019-12-25 | 2020-05-15 | 上海昶法新材料有限公司 | Phenolic resin additive and preparation method thereof |
| CN113563826A (en) * | 2021-07-28 | 2021-10-29 | 上海昶法新材料有限公司 | Adhesive additive for artificial board and preparation method thereof |
| CN113717541A (en) * | 2021-10-09 | 2021-11-30 | 上海昶法新材料有限公司 | Raw material composition, tackifier, preparation method and application of tackifier and blend glue |
| CN115368519A (en) * | 2022-07-11 | 2022-11-22 | 上海昶法新材料有限公司 | Phenolic resin additive and preparation method thereof |
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| DE19503247A1 (en) * | 1995-02-02 | 1996-08-08 | Stuermer Hans Dieter Dipl Chem | Adsorptive material made from cellulose fibers and process for its production |
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| CN101012387A (en) * | 2007-02-01 | 2007-08-08 | 淮北中润生物能源技术开发有限公司 | Technique for manufacturing liquid fuel from highly effective cellulose biomass |
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