CN101260283B - Method for preparing phenolic aldehyde adhesive based on lignin phenolized liquid and application thereof - Google Patents
Method for preparing phenolic aldehyde adhesive based on lignin phenolized liquid and application thereof Download PDFInfo
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- CN101260283B CN101260283B CN2008100358548A CN200810035854A CN101260283B CN 101260283 B CN101260283 B CN 101260283B CN 2008100358548 A CN2008100358548 A CN 2008100358548A CN 200810035854 A CN200810035854 A CN 200810035854A CN 101260283 B CN101260283 B CN 101260283B
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Abstract
The invention provides a preparation method for phenolic adhesive based on lignin phenolization liquid and application thereof. Under the condition of normal pressure heating or thermalcatalysis, phenol is taken as liquefaction reagent, lignin is added, the temperature is raised to 90 to 150 DEG C, the thermal insulation liquefaction reaction is made to cool to obtain a lignin liquefaction product; basic catalyst and formaldehyde are directly added into the liquefaction liquid, the temperature is raised to 70 to 97 DEG C under normal pressure to react for 1 to 3 hours, the reaction is terminated when the viscosity is measured to meet the preset requirement, and low-free formaldehyde environmental protection type phenolic adhesive based on lignin phenolization liquid is obtained. The adhesive obtained by the invention has lower cost and lower content of free formaldehyde than the prior phenolic resin adhesive. The plywood pressed by using the adhesive obtained by the invention has good bonding performance.
Description
Technical field
The invention belongs to the adhesive technology field, be specifically related to a kind of preparation method and application thereof of adopting the synthetic modified phenolic adhesive of xylogen phenolate liquid.
Background technology
Xylogen is one of three big components (Mierocrystalline cellulose, hemicellulose and xylogen) of plant fiber material, is a kind of macromolecular material that is only second to cellulosic content more than second, and is the unique non-oil resource that renewable compound aromatic base can be provided of nature.Industrial lignin is mainly derived from the waste liquid of paper-making pulping industry thereby has inexpensive, renewable, advantages of environment protection.It is generally acknowledged that chemistry of lignin's structure is the complex compound that phenylpropyl alcohol alkanes structural unit is formed, be joined together to form the unregulated polymer of the natural phenolic of three-dimensional body structure between the structural unit by ehter bond and C-C key.Phenolic hydroxyl group and aldehyde radical are arranged in the lignin molecule, and the certain reaction activity is arranged, can be under certain condition can with plurality of raw materials such as phenol, formaldehyde, the isocyanic ester resins such as forming lignin-base phenolic aldehyde, urea aldehyde and urethane that react, can save consumption of petroleum resources such as phenol simultaneously, reduce the residual volume of formaldehyde.This papermaking wastewater that utilizes, improves for natural resource all has important economic implications and social effect to the pollution of environment, protection environment.
The applied research of xylogen aspect tackiness agent is a lot, but really be successfully applied in the production example seldom.Reason is that molecular structure complexity, the molecular weight of natural lignin is higher, the substituting group steric hindrance on the aromatic ring of xylogen own is bigger, can not effectively react with resol, and hinder the normal polymerization of phenol and formaldehyde.Be improved with unmodified comparison quality as xylogen being carried out the synthetic phenolic glue that obtains of demethylation and methylolation by chemical modification, but the xylogen tackiness agent after the modification still has problems: molecular weight height, viscosity are big, make troubles the homogeneity of influence coating and the flowability of glue to glue-applying technique; Reactive behavior point on the lignin phenol ring is few, and sterically hindered obviously difficult formation is goed deep into firm crosslinked, causes the decline of bonding strength, and wet fastness is inferior; Working life is short or the like, has influenced the application of lignin modification tackiness agent.
The research field of newly opening up in recent years-Thermochemical Liquefaction technology, adopt organism such as phenols or polyhydroxy-alcohol under low-temperature catalyzed condition with the available low molecule liquefied product of high molecular indissoluble infusible lignocellulose raw material (Mierocrystalline cellulose, hemicellulose and xylogen) liquefaction becoming with certain active group, product liquid after the liquefaction can be used as the raw material of producing tackiness agent through processing such as filtrations.It is the liquefy processing method of wooden phenolic glue of feedstock production with the phenolate product of wood powder under catalyst action that Chinese patent 200310124185.9 provides a kind of, under normal pressure or condition of high voltage, with phenol and polarity small molecules is mixed solvent, the liquefied product of preparation timber under catalytic condition is used for the wooden modified phenolic adhesive of preparation liquefaction with liquefier.Chinese patent 200610008469.5 provides a kind of Resorcinol-bamboo lignan liquefied substance-formaldehyde resin gel, the liquefaction raw material that adopts is bamboo wood powder, phenolic material, catalyzer, aldehydes and Resorcinol, the liquefaction reaction of heating generates bamboo lignan liquefied substance, and liquefied product and formaldehyde reaction obtain tackiness agent.It is a kind of by timber liquefied matter synthetic synvaren that Chinese patent 200610012031.4 provides, and earlier wood powder is broken into wood powder, adopts phosphoric acid catalyst to carry out the phenol liquefaction processing, gets timber liquefied matter; Prepare synvaren then.
This shows, can obtain active higher natural low molecular phenolics product by liquefaction technology, and can replace the petroleum-type phenols to prepare modified phenolic adhesive.But timber or bamboo wood liquefied product commercial application still have problems, because the complicacy that natural bamboo and timber are formed, some product that can not be liquefied still in the liquefied product, liquefaction efficiency can not reach 100%, have in the paper of in the above-mentioned patent of enumerating, delivering more and mention with the contriver, liquefied product must just can be used for the preparation of tackiness agent through further filtering separation, has limited the utilization of liquefied product.Therefore, although liquefaction technology at home and abroad is rapidly developed, distance real realization industrial utilization and industrialization are also far away, even carry out the Japan of this technical study the earliest, also still rest on laboratory stage at present.
Summary of the invention
The object of the present invention is to provide a kind of flowability and stability in storage good, the preparation method of the environment-friendly type synvaren that workability is good.
The present invention is according to the more or less freely characteristics that are liquefied of xylogen, with single industrial lignin is the liquefaction raw material, adopt the phenolate technology that aldehydes matter is produced in the fracture of xylogen macromole, acquisition has the pure xylogen liquefied product of high reaction activity, prepare environment-friendly type synvaren on this basis with high performance low-free formaldehyde, tackiness agent with this method preparation greatly reduces the synvaren cost, and have good flowability and a stability in storage, workability utilizes the glued board of this tackiness agent compression moulding to have good glue performance simply and easily.
The preparation method of the synvaren based on xylogen phenolate liquid of the present invention, concrete steps are as follows:
1) xylogen liquefaction
With phenol is liquefied reagent, add xylogen, the mass ratio of phenol and xylogen is 6: 1～5, the heating of employing normal pressure, or (consumption of acid catalyst is 1～6wt%) of phenol and an xylogen total amount, and 90～150 ℃ of heating under agitation condition are to be heated behind preset temperature to add acid catalyst under the condition of normal pressure, insulation liquefaction 0～120 minute obtains the xylogen liquefied product;
2) modified phenolic adhesive is synthetic
After treating the cooling of xylogen liquefied product, (xylogen liquefied product mole number calculates divided by the phenol molecular weight by the total mass of phenol and xylogen in the xylogen liquefied product by 1: 1.5～2.2 mol ratios with xylogen liquefied product and formaldehyde, under the base catalysis condition, react down together), the mol ratio of basic catalyst and xylogen liquefied product is 1: 2～4.5, basic catalyst adds with the aqueous solution form of mass percent 25%～40%, under condition of normal pressure, be warming up to 70～97 ℃, reaction times was controlled at 1～3 hour, measure viscosity with the method for falling the bubble and stop heating when meeting gluing the requirement, add the suitable quantity of water cooling and regulate adhesive solid content, promptly obtain modified phenolic adhesive based on xylogen phenolate liquid.
Described xylogen phenolate liquid base synvaren is water miscible thermosetting resin, solids content: 30～52%; Being coated with 4 glasss of viscosity is 40～100S (25 ℃); PH:10～12; Content of free aldehyde: below 0.1%.
Xylogen liquefaction can be carried out under the non-sour condition of heating among the present invention, also can adopt under the heating acid catalysis condition and carry out.
The xylogen liquefied product need not directly can replace phenol to prepare modified phenolic adhesive through separating treatment among the present invention.
An acidic catalyst that the present invention adopts can be mineral acids such as phosphoric acid, hydrochloric acid or sulfuric acid.
The alkaline catalysts that the present invention adopts can be mineral alkalis such as potassium hydroxide, sodium hydroxide, hydrated barta, magnesium hydroxide or calcium hydroxide.
The present invention is according to the usage quantity of the kind of the used xylogen phenol liquefied reagent different with the liquifying method different choice.
Xylogen among the present invention is alkali lignin, sulfonated lignin, high-boiling alcohol lignin, and the lignin molecule amount is no more than 20000Mw.
The solid content of the formaldehyde that adopts among the present invention is 32～37%, and the adding of formaldehyde can be by feed way repeatedly more than 2 times.
Modified phenolic adhesive by xylogen liquefier preparation of the present invention has good flowability and stability in storage, storage time＞30 day.
Optimized choice of the present invention such as conditions such as catalyzer, temperature, feed way, but obtain the xylogen liquefied product with fine flowability of high-level efficiency utilization by liquefaction.Xylogen after the liquefaction has than higher hydroxy radical content of original xylogen and high reaction activity more, this highly active xylogen liquefied product need not through filtration treatment, can directly replace phenol and formaldehyde reaction to obtain the plain phenolate liquid of novel wooden base synvaren.This tackiness agent has the cost lower than traditional resol, and curing speed is fast, intensity is high, meet construction requirement viscosity and flow leveling, be convenient to construction and store, and have the free formaldehyde content lower than traditional phenolic glue.
Xylogen phenolate liquid base phenolic glue carries out the compacting test of bamboo offset plate among employing the present invention, at 130-140 ℃, 20MPa, 1.0 the glued board MOR of compression moulding, quiet modulus in elasticity in bending all reach standard " bamboo plywood form " (JG/T 156-2004 premium grads index) under the condition of～1.5min/mm, the hot-forming glued board of tackiness agent that adopts the acid catalysis liquefaction technology to prepare can reach the requirement (GB/T 9846.3-2004) of I class glued board.It is raw material that the technology of the present invention has adopted industrial lignin, can make its utilization ratio reach 100%, has improved the utilising efficiency of natural green polymer in material, has advanced the commercial application of natural polymer in the material field.
Embodiment
Following example is used to illustrate the present invention, but is not used for limiting the scope of the invention.
Embodiment 1
In 30.0g phenol, add the 10.0g high-boiling alcohol lignin, be heated to 130 ℃ of insulation reaction 60min, be cooled to below 60 ℃, add 33% alkali lye 18.0g (6.0g potassium hydroxide is dissolved in the water of 12.0mL), add 37% formaldehyde 45.0g again, be warming up to 95 ℃ behind the autoreaction 15min, insulation reaction 30min, be cooled to 70 ℃ again, add 37% formaldehyde 10.0g, be warming up to 94 ℃ of insulations behind the autoreaction 10min, every interval 3～5min, measure its viscosity (viscosity controller is about 3-6S) with the method for falling the bubble, stopped reaction when reaching requirement, and add 20.0mL water, that treats is cooled to below 50 ℃ discharging.
Embodiment 2
53.3g phenol is heated to 45 ℃, add the 26.7g sodium lignosulfonate and the 3.0mL vitriol oil, be rapidly heated to 120 ℃ (10 ℃/min), insulation reaction 20min, be cooled to below 60 ℃, add 30% alkali lye 41.0g (12.5g sodium hydroxide is dissolved in the water of 28.5mL), add 36% formaldehyde 63.0g then, be warming up to 78 ℃ behind the first autoreaction 20min, add 36% formaldehyde 45.0g again, be warming up to 94 ℃ behind the autoreaction 10min, insulation reaction 25min is cooled to 75 ℃ again, the formaldehyde 20.0g of adding 36%, be warming up to 92 ℃ of insulation reaction, every interval 3～5min measures its viscosity (viscosity controller is about 3-8S) with the method for falling the bubble, stop reacting by heating when reaching requirement, add 65.0mL water, that treats is cooled to below 50 ℃ discharging.
Embodiment 3
69.0g phenol is heated to 100 ℃, add 23.0g high-boiling alcohol lignin and 5.0mL concentrated hydrochloric acid, be warming up to 115 ℃, insulation reaction 10min, be cooled to below 55 ℃, add 30% alkali lye 46.7g (14.0g sodium hydroxide is dissolved in the water of 32.7mL), add 37% formaldehyde 63.4g then, be warming up to 80 ℃ behind the first autoreaction 20min, add 37% formaldehyde 49.3g again, be warming up to 94 ℃ behind the autoreaction 15min, insulation reaction 30min is cooled to 75 ℃ again, the formaldehyde 28.2g of adding 37%, be warming up to 92 ℃ of insulation reaction, every interval 3～5min measures its viscosity (viscosity controller is about 3-8S) with the method for falling the bubble, stop reacting by heating when reaching requirement, add 200.0mL water, that treats is cooled to below 50 ℃ discharging.
Embodiment 4
110.4g phenol is heated to 140 ℃, add the 36.8g alkali lignin, be warming up to 140 ℃, insulation reaction 10min, be cooled to below 50-55 ℃, add 30% alkali lye 73.3g (22.1g sodium hydroxide is dissolved in the water of 51.2mL), add 37% formaldehyde 95.8g then, be warming up to 80 ℃ behind the first autoreaction 20min, add 37% formaldehyde 74.5g again, be warming up to 94 ℃ behind the autoreaction 15min, insulation reaction 25min is cooled to 80 ℃ again, the formaldehyde 42.6g of adding 37%, be warming up to 92 ℃ of insulation reaction, every interval 3～5min measures its viscosity (viscosity controller is about 3-8S) with the method for falling the bubble, stop reacting by heating when reaching requirement, add 100.0mL water, that treats is cooled to below 50 ℃ discharging.
Embodiment 5 (pilot scale: 100L oil bath reactor, rotating speed 70r/min)
Add the 3.0kg sodium lignosulfonate at 12.0kg phenol, be heated to 140 ℃, be cooled to 53 ℃ behind the insulation reaction 10min, add 30% alkali lye 7.5kg (2.25kg sodium hydroxide is dissolved in the water of 5.25kg), add 37% formaldehyde 10.0kg again, be warming up to 80 ℃ behind the first autoreaction 20min, add 37% formaldehyde 6.4kg again, be warming up to 94 ℃ behind the autoreaction 15min, insulation reaction 25min is cooled to 80 ℃ again, the formaldehyde 4.0kg of adding 37%, be warming up to 92 ℃ of insulation reaction, every interval 3～5min measures its viscosity (viscosity controller is about 3-8S) with the method for falling the bubble, stop heating when reaching requirement, add 35.0kg water, be cooled to below 50 ℃ discharging.
Adopt above xylogen liquefier base phenolic glue to be diluted with water to applying glue and compacting test that 25wt% carries out the bamboo offset plate, at 130-140 ℃, 20MPa is pressed into glued board under the condition of 1.0～1.5min/mm, and the glue performance of adhesive technology index and glued board is seen attached list.
Subordinate list: the technical indicator of xylogen phenolate liquid base phenolic glue and the glue performance table look-up of glued board
| Sequence number | Solid content | Free aldehyde | Storage time | MOR | Young's modulus | Boiling water boils experiment |
| Example 1 | 50％ | 0.068％ | ＞30 days | 106MPa | 9718MPa | II class plate |
| Example 2 | 44％ | 0.073％ | ＞30 days | 122MPa | 9770MPa | I class plate |
| Example 3 | 32％ | 0.065％ | ＞50 days | 115MPa | 9450MPa | I class plate |
| Example 4 | 47％ | 0.078％ | ＞30 days | 108MPa | 8460MPa | II class plate |
| Example 5 | 30％ | 0.067％ | ＞50 days | 98MPa | 8670MPa | II class plate |
Claims (5)
1. preparation method based on the modified phenolic adhesive of xylogen phenolate liquid is characterized in that concrete steps are as follows:
(1) xylogen liquefaction
With phenol is liquefied reagent, add xylogen, the mass ratio of phenol and xylogen is 6: 1～5, adopt under normal pressure heating or the condition of normal pressure and add acid catalyst, 90～150 ℃ of heating under agitation condition, the consumption of acid catalyst is 1～6wt% of phenol and xylogen total amount, and is to be heated behind preset temperature, insulation liquefaction reaction 0～120 minute obtains the xylogen liquefied product;
(2) modified phenolic adhesive is synthetic
After treating the cooling of xylogen liquefied product, xylogen liquefied product and formaldehyde are reacted under the base catalysis condition by 1: 1.5～2.2 mixed in molar ratio, the mole number of xylogen liquefied product calculates divided by the phenol molecular weight by the total mass of phenol and xylogen in the xylogen liquefied product, the mol ratio of basic catalyst and xylogen liquefied product is 1: 2～4.5, basic catalyst adds with the aqueous solution form of mass percent 25%～40%, under condition of normal pressure, be warming up to 70～97 ℃ and continue reaction 1～3 hour, measure viscosity with the method for falling the bubble and stop heating when meeting gluing the requirement, add the suitable quantity of water cooling and regulate adhesive solid content, promptly obtain modified phenolic adhesive based on xylogen phenolate liquid.
2. preparation method according to claim 1 is characterized in that described xylogen is alkali lignin, sulfonated lignin or high-boiling alcohol lignin, and the lignin molecule amount is no more than 20000Mw.
3. preparation method according to claim 1 is characterized in that described acid catalyst is phosphoric acid, hydrochloric acid or sulfuric acid.
4. preparation method according to claim 1 is characterized in that described basic catalyst is potassium hydroxide, sodium hydroxide, hydrated barta, magnesium hydroxide or calcium hydroxide.
5. preparation method according to claim 1, the solid content that it is characterized in that described formaldehyde is 32～37%, the adding of formaldehyde can be adopted repeatedly feed way.
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| CN102061141B (en) * | 2009-11-11 | 2013-10-16 | 青岛生物能源与过程研究所 | Method for preparing environmentally-friendly adhesive for lignin-based timber |
| CN101942068B (en) * | 2010-08-27 | 2012-09-05 | 安徽格义清洁能源技术有限公司 | Preparation method of lignin phenolic resin |
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| CN102492384A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid |
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| CN102659992B (en) * | 2012-05-11 | 2014-06-25 | 黄山学院 | Phenolic lignin-based modified foaming phenolic resin, foamed plastic and preparation method of phenolic lignin-based modified foaming phenolic resin |
| CN102875753B (en) * | 2012-10-17 | 2014-04-16 | 武汉科技大学 | Lignin modified phenolic resin and using method thereof |
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