CN103305167A - Method for preparing phenolic resin adhesives by using organic method lignin instead of phenol - Google Patents
Method for preparing phenolic resin adhesives by using organic method lignin instead of phenol Download PDFInfo
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- CN103305167A CN103305167A CN2013102468632A CN201310246863A CN103305167A CN 103305167 A CN103305167 A CN 103305167A CN 2013102468632 A CN2013102468632 A CN 2013102468632A CN 201310246863 A CN201310246863 A CN 201310246863A CN 103305167 A CN103305167 A CN 103305167A
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Abstract
The invention provides a method for preparing phenolic resin adhesives by using organic method lignin instead of phenol, relating to methods for preparing phenolic resin adhesives and aiming to solve the technical problem that non-renewable petrochemical raw materials with higher toxicity are used in quantity in the existing preparation processes of phenolic resin adhesives. The method comprises the steps of: I. preparing and combining filtrates; II. preparing powdery organic method lignin; and III. preparing the phenolic resin adhesives. The method has the beneficial effects that the prepared phenolic resin adhesives have the low-toxicity advantages of low free phenol, low formaldehyde residues and low formaldehyde volatility, thus providing extensive prospects for expanding preparation of environment-friendly phenolic resin adhesives and high value-added utilization of the organic method lignin. The method is applied to the field of preparation of the phenolic resin adhesives.
Description
Technical field
The present invention relates to prepare the method for synvaren.
Background technology
Xylogen (lignin), its character heterogeneity, chemical structure is complicated, separation and acquisition technique is loaded down with trivial details, condensation reaction easily occurs, thereby seriously restricting the development and utilization of xylogen.In the paper-making pulping production process, isolate several hundred million tons Mierocrystalline cellulose take vegetable fibre as raw material, yet but produce a large amount of xylogen by-products, approximately 5,000 ten thousand ton/years, form mainly with pollutent " black liquor " directly enters in the natural water, and portion of product is concentrated afterfire, and the xylogen that can be utilized effectively is lower than 20%, wherein, xylogen that can recycling still less.Thereby this has not only caused the waste of organic resource, and serious pollution environment.If xylogen can be used as industrial chemicals and by recycling, can reduce the quantity discharged of carbonic acid gas, thereby minimizing is conducive to environment protection to the contribution of Greenhouse effect.Along with people deepen continuously to the theory of ecological industry and Green Chemistry, the development and utilization of this renewable resources of xylogen will be opened up brand-new research field and direction for macromolecular material, will have good economic benefit and social benefit.
Xylogen is as one of main ingredient of plant, have unique advantages such as biodegradable, pollution-free, recyclability, output are large, many active groups are arranged in the molecular structure, its chemical reactivity mainly is directly proportional with the content of phenolic hydroxyl group, alcoholic extract hydroxyl group and phenolic hydroxyl group ortho para reactive hydrogen in the structural unit, can be used as industrial chemicals and be widely used, being called as has the green non-pollution of development potentiality type raw material most.Canada, the U.S. etc. have developed various novel environmental protection or oligosaprobic Organosolv Pulping.This method is to utilize the good easy volatile of organic solvent and solvability, realizes the xylogen in the dissolving plant, so that xylogen separates with Mierocrystalline cellulose, the xylogen organic solution that extracts can adopt the recovery organic solvents such as distillation method; Realized closed-cycle operation, whole production process does not have waste water, or only has a small amount of waste water, is a kind of green pulp technology with significant development prospect " zero pollutes "; Domestic investigator extracts xylogen to organic solvent method and explores and study, and has obtained certain achievement.Organic solvent method is as the novel method of lignin extraction, mainly be utilize that organic solvent has the excellent dissolution performance and easily volatile matter from characteristics, thereby reach the high efficiency extraction separating lignin.In the sepn process of organic solvent method lignin extraction, wood material heats in organic solution, and the xylogen macromole of cracking under the acid catalyst effect, so that alpha-aromatic ehter bond and aryl glyceryl-beta-aromatic ether bond rupture and dissolve, the fracture of ehter bond makes the new phenolic hydroxyl group of generation in the xylogen, so that the organosolv lignin solubility property further strengthens, xylogen dissolves in the organic solution and separates with Mierocrystalline cellulose.Organic solvent method destroys less to the two chemical structure, so that organic method xylogen can keep original natural polymer chemically reactive, thereby provide the new way with good prospect for deep development and the recycling of xylogen.
Meanwhile, in the industrial production in modern times, phenol is a large amount of larger petrochemical materials of non-renewable toxicity that use in the resol building-up process.Therefore, the industrial chemicals of seeking a kind of alternative phenol of environment-friendly type is the focus of the common concern of investigator.Owing to containing a large amount of phenol structures in the xylogen, the renewable nontoxic Liginon Resource of development and utilization makes it part and even replacing whole phenol, is used for the preparation of xylogen-resol etc., can effectively reduce the usage quantity of phenol, thereby realize the development and utilization of Liginon Resource.
For these reasons, use organic solvent by this invention and extract and prepare organic method xylogen for the preparation of synvaren, so that Liginon Resource obtains more extensive, more effective high value added utilization.
Summary of the invention
The present invention will solve a large amount of technical problems of using the larger petrochemical material of non-renewable toxicity in the preparation process of existing synvaren, thereby provides organic method xylogen to substitute the method that phenol prepares synvaren.
The method that the alternative phenol of the organic method xylogen of the first of the present invention prepares synvaren is to carry out according to the following steps:
One, it is 1g with plant fiber material and organic solvent by mass volume ratio: 2～5mL mixing, put into stainless steel cauldron, under the temperature rise rate of 10～20 ℃/min, be heated to 160～200 ℃ and be incubated 1～2h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30～60min under the speed of 4000～5000r/min, organosolv lignin solution and fibre stuff are separated, then use reaction solvent washing the fibre slurry 3 times, keep washings, organosolv lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 20～40min, the organosolv lignin Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40～60 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add the formaldehyde of 5～10kg and the water of 2.5～5kg, and minute 3 batches of organic method xylogen and sodium hydroxide that the adding step 2 obtains, reaction under temperature is 60～100 ℃, 3 elementary reaction times are respectively 60～100min, 60～80min and 40～70min, after reaction is finished, obtain hydroxymethylated lignin; Wherein, it is 10～20kg that organic method xylogen adds total amount, and in (1～3): (1～2): 1 ratio is divided 3 batches of inputs; It is 0.2～0.5kg that sodium hydroxide adds total amount, and in (2～6): (1～3): 1 ratio is divided 3 batches of inputs;
Four, the hydroxymethylated lignin that step 3 is obtained after stirring 5～10min under the normal temperature, namely gets organic method xylogen phenolic aldehyde composite adhesive with after resol mixes; Wherein, the mass ratio of hydroxymethylated lignin and resol (1～3): (1～2).
The method that the alternative phenol of the organic method xylogen of the second of the present invention prepares synvaren is to carry out according to the following steps:
One, it is 1g with plant fiber material and organic solvent by mass volume ratio: 2～5mL mixing, put into stainless steel cauldron, under the temperature rise rate of 10～20 ℃/min, be heated to 160～200 ℃ and be incubated 1～2h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30～60min under the speed of 4000～5000r/min, organosolv lignin solution and fibre stuff are separated, then use reaction solvent washing the fibre slurry 3 times, keep washings, organosolv lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 20～40min, the organosolv lignin Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40～60 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, organic method xylogen that the step 2 of 8～10kg is obtained, the phenol of 3～8kg mixes, then add first sodium hydroxide and first formaldehyde, after mixing, under agitation condition, be warming up to 80～90 ℃, keep reaction 50min, then add second batch sodium hydroxide and second batch formaldehyde, at 60～90min sodium hydroxide is added, continuing to keep temperature is 80～90 ℃, and then the 3rd batch of sodium hydroxide of temperature-resistant lower adding and the 3rd batch of formaldehyde, and sodium hydroxide needs to add at 50～70min, the urea that adds again 1～4kg, adding at 30～40min, is 80～85 ℃ of lower reactions in temperature, when material state reach sticky after, with its cooling, namely get organic method xylogen phenolic aldehyde copolymerized adhesive rapidly; Wherein, it is 10～20kg that formaldehyde adds total amount, and in (1～3): (1～2): 1 ratio is divided 3 batches of addings; It is 2～5kg that sodium hydroxide adds total amount, and in (1～2): (1～3): the ratio of (2～4) is divided 3 batches of addings.
The present invention includes following beneficial effect:
1, the raw material that is suitable for of the present invention is all fibres cellulosic biomass raw material, comprises various softwoods, pourous wood, agricultural crop straw etc.;
2, the present invention is owing to having adopted organic method xylogen Substitute For Partial and even whole phenol, and whole preparation process has advantages of economic environmental protection; Owing to adopting organic method xylogen to substitute the preparation that phenol is used for synvaren, greatly reduced the usage quantity of the larger petrochemical material-phenol of toxicity non-renewable in the resol building-up process, this not only makes production resol cost greatly reduce, can also by the performance that makes to improve resol of organic method xylogen, obtain the synvaren that bonding strength is higher, formaldehyde release is lower, performance is more stable;
3, the synvaren of the present invention preparation has the low toxicity advantage of low free-phenol, low residues of formaldehyde and the volatilization of low formaldehyde, for the preparation of expanding the Enviorment-protective Phenolic Resin tackiness agent and the high value added utilization of organic method xylogen have been opened bright prospects.
Embodiment
Embodiment one: the method that the alternative phenol of organic method xylogen of present embodiment prepares synvaren is carried out according to the following steps:
One, it is 1g with plant fiber material and organic solvent by mass volume ratio: 2～5mL mixing, put into stainless steel cauldron, under the temperature rise rate of 10～20 ℃/min, be heated to 160～200 ℃ and be incubated 1～2h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30～60min under the speed of 4000～5000r/min, organosolv lignin solution and fibre stuff are separated, then use reaction solvent washing the fibre slurry 3 times, keep washings, organosolv lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 20～40min, the organosolv lignin Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40～60 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add the formaldehyde of 5～10kg and the water of 2.5～5kg, and minute 3 batches of organic method xylogen and sodium hydroxide that the adding step 2 obtains, reaction under temperature is 60～100 ℃, 3 elementary reaction times are respectively 60～100min, 60～80min and 40～70min, after reaction is finished, obtain hydroxymethylated lignin; Wherein, it is 10～20kg that organic method xylogen adds total amount, and in (1～3): (1～2): 1 ratio is divided 3 batches of inputs; It is 0.2～0.5kg that sodium hydroxide adds total amount, and in (2～6): (1～3): 1 ratio is divided 3 batches of inputs;
Four, the hydroxymethylated lignin that step 3 is obtained after stirring 5～10min under the normal temperature, namely gets organic method xylogen phenolic aldehyde composite adhesive with after resol mixes; Wherein, the mass ratio of hydroxymethylated lignin and resol (1～3): (1～2).
Present embodiment comprises following beneficial effect:
1, the applicable raw material of present embodiment is all fibres cellulosic biomass raw material, comprises various softwoods, pourous wood, agricultural crop straw etc.;
2, present embodiment is owing to having adopted organic method xylogen Substitute For Partial and even whole phenol, and whole preparation process has advantages of economic environmental protection; Owing to adopting organic method xylogen to substitute the preparation that phenol is used for synvaren, greatly reduced the usage quantity of the larger petrochemical material-phenol of toxicity non-renewable in the resol building-up process, this not only makes production resol cost greatly reduce, can also by the performance that makes to improve resol of organic method xylogen, obtain xylogen-phenolic composite adhesive that bonding strength is higher, formaldehyde release is lower, performance is more stable;
3, the xylogen-phenolic composite adhesive of present embodiment preparation has the low toxicity advantage of low free-phenol, low residues of formaldehyde and the volatilization of low formaldehyde, for the preparation of expanding the Enviorment-protective Phenolic Resin tackiness agent and the high value added utilization of organic method xylogen have been opened bright prospects.
Embodiment two: what present embodiment and embodiment one were different is: organic solvent is ethyl acetate, acetone, formic acid, acetic acid, ethanol, BDO, ethylene glycol or butyleneglycol in the step 1.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: be heated to 180 ℃ and be incubated 1h in the step 1 under the temperature rise rate of 15 ℃/min.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: in the step 1 under the speed of 4500r/min centrifugal 30min.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is: 3 elementary reaction times are respectively 80min, 70min and 60min in the step 3.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is: organic method xylogen divides 3 batches of inputs in 3: 2: 1 ratio in the step 3.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is: sodium hydroxide divides 3 batches of inputs in 6: 3: 1 ratio in the step 3.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is: the mass ratio 1: 1 of hydroxymethylated lignin and resol in the step 4.Other is identical with one of embodiment one to seven.
Embodiment nine: the method that the alternative phenol of organic method xylogen of present embodiment prepares synvaren is carried out according to the following steps:
One, it is 1g with plant fiber material and organic solvent by mass volume ratio: 2～5mL mixing, put into stainless steel cauldron, under the temperature rise rate of 10～20 ℃/min, be heated to 160～200 ℃ and be incubated 1～2h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30～60min under the speed of 4000～5000r/min, organosolv lignin solution and fibre stuff are separated, then use reaction solvent washing the fibre slurry 3 times, keep washings, organosolv lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 20～40min, the organosolv lignin Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40～60 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, organic method xylogen that the step 2 of 8～10kg is obtained, the phenol of 3～8kg mixes, then add first sodium hydroxide and first formaldehyde, after mixing, under agitation condition, be warming up to 80～90 ℃, keep reaction 50min, then add second batch sodium hydroxide and second batch formaldehyde, at 60～90min sodium hydroxide is added, continuing to keep temperature is 80～90 ℃, and then the 3rd batch of sodium hydroxide of temperature-resistant lower adding and the 3rd batch of formaldehyde, and sodium hydroxide needs to add at 50～70min, the urea that adds again 1～4kg, adding at 30～40min, is 80～85 ℃ of lower reactions in temperature, when material state reach sticky after, with its cooling, namely get organic method xylogen phenolic aldehyde copolymerized adhesive rapidly; Wherein, it is 10～20kg that formaldehyde adds total amount, and in (1～3): (1～2): 1 ratio is divided 3 batches of addings; It is 2～5kg that sodium hydroxide adds total amount, and in (1～2): (1～3): the ratio of (2～4) is divided 3 batches of addings.
Embodiment ten: what present embodiment and embodiment nine were different is: formaldehyde divides 3 batches of addings in 1.2: 1: 1 ratio in the step 3.Other is with identical with embodiment nine.
Embodiment 11: what present embodiment was different from embodiment nine or ten is: sodium hydroxide divides 3 batches of addings in 1: 1: 2.85 ratio in the step 3.Other is with identical with embodiment nine or ten.
By following verification experimental verification beneficial effect of the present invention:
Test one: the method that the alternative phenol of organic method xylogen of this test prepares synvaren is to realize according to the following steps:
One, be 1g with plant fiber material and butyleneglycol by mass volume ratio: the 4mL mixing, put into stainless steel cauldron, under the temperature rise rate of 15 ℃/min, be heated to 180 ℃ and be incubated 1h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30min under the speed of 4500r/min, butyleneglycol lignin liquor and fibre stuff are separated, then use butyleneglycol washing the fibre slurry 3 times, keep washings, butyleneglycol lignin liquor and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 30min, butyleneglycol xylogen Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40 ℃ of lower dryings until the quality constant weight obtains pulverous butyleneglycol method xylogen;
Three, in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add the formaldehyde of 5kg and the water of 2kg, and minute 3 batches of butyleneglycol method xylogen and sodium hydroxide that the adding step 2 obtains, reaction under temperature is 80 ℃, 3 elementary reaction times are respectively 80min, 70min and 60min, after reaction is finished, obtain hydroxymethylated lignin; Wherein, it is 15kg that butyleneglycol method xylogen adds total amount, divides 3 batches of inputs in 3: 2: 1 ratio; It is 0.45kg that sodium hydroxide adds total amount, divides 3 batches of inputs in 6: 3: 1 ratio;
Four, the hydroxymethylated lignin that step 3 is obtained after stirring 10min under the normal temperature, namely gets butyleneglycol method xylogen phenolic aldehyde composite adhesive with after resol mixes; Wherein, the mass ratio 1: 1 of hydroxymethylated lignin and resol.
Test two: the method that the alternative phenol of organic method xylogen of this test prepares synvaren is to realize according to the following steps:
One, be 1g with plant fiber material and butyleneglycol by mass volume ratio: the 4mL mixing, put into stainless steel cauldron, under the temperature rise rate of 15 ℃/min, be heated to 180 ℃ and be incubated 1h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30min under the speed of 4500r/min, butyleneglycol lignin liquor and fibre stuff are separated, then use butyleneglycol washing the fibre slurry 3 times, keep washings, butyleneglycol lignin liquor and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 30min, butyleneglycol xylogen Precipitation, pass through again negative pressure leaching, filter cake is washed with distilled water to without butyleneglycol residual, then filter cake is placed in the vacuum drying oven 40 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, the acetone method xylogen that the step 2 of 7.5kg is obtained, 7.5kg phenol mix, then add first sodium hydroxide and first formaldehyde, after mixing, under agitation condition, be warming up to 90 ℃, keep reaction 50min, then add second batch sodium hydroxide and second batch formaldehyde, at 70min sodium hydroxide is added, continuing to keep temperature is 90 ℃, and then the 3rd batch of sodium hydroxide of temperature-resistant lower adding and the 3rd batch of formaldehyde, and sodium hydroxide needs to add at 60min, the urea that adds again 2.02kg, adding at 30min, is 85 ℃ of lower reactions in temperature, when material state reach sticky after, with its cooling, namely get acetone method xylogen phenolic aldehyde copolymerized adhesive rapidly; Wherein, it is 10.57kg that formaldehyde adds total amount, divides 3 batches of addings in 1.2: 1: 1 ratio; It is 3.28kg that sodium hydroxide adds total amount, divides 3 batches of addings in 1: 1: 2.85 ratio.
Test three: the method that the alternative phenol of organic method xylogen of this test prepares synvaren is to realize according to the following steps:
One, be 1g with plant fiber material and acetic acid by mass volume ratio: the 4mL mixing, put into stainless steel cauldron, under the temperature rise rate of 15 ℃/min, be heated to 180 ℃ and be incubated 1h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30min under the speed of 4500r/min, acetic acid lignin solution and fibre stuff are separated, then use acetic acid washing the fibre slurry 3 times, keep washings, acetic acid lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 30min, the acetic acid lignin Precipitation, pass through again negative pressure leaching, filter cake is washed with distilled water to without acetic acid residual, then filter cake is placed in the vacuum drying oven 40 ℃ of lower dryings until the quality constant weight obtains pulverous Acetic xylogen;
Three, in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add the formaldehyde of 5kg and the water of 2kg, and minute 3 batches of Acetic xylogen and sodium hydroxide that the adding step 2 obtains, reaction under temperature is 80 ℃, 3 elementary reaction times are respectively 80min, 70min and 60min, after reaction is finished, obtain hydroxymethylated lignin; Wherein, it is 15kg that the Acetic xylogen adds total amount, divides 3 batches of inputs in 3: 2: 1 ratio; It is 0.3kg that sodium hydroxide adds total amount, divides 3 batches of inputs in 6: 3: 1 ratio;
Four, the hydroxymethylated lignin that step 3 is obtained after stirring 10min under the normal temperature, namely gets Acetic xylogen phenolic aldehyde composite adhesive with after resol mixes; Wherein, the mass ratio 1: 1 of hydroxymethylated lignin and resol.
Test four: the method that the alternative phenol of organic method xylogen of this test prepares synvaren is to realize according to the following steps:
One, be 1g with plant fiber material and acetic acid by mass volume ratio: the 4mL mixing, put into stainless steel cauldron, under the temperature rise rate of 15 ℃/min, be heated to 180 ℃ and be incubated 1h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30min under the speed of 4500r/min, acetic acid lignin solution and fibre stuff are separated, then use acetic acid washing the fibre slurry 3 times, keep washings, acetic acid lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 30min, the acetic acid lignin Precipitation, pass through again negative pressure leaching, filter cake is washed with distilled water to without acetic acid residual, then filter cake is placed in the vacuum drying oven 40 ℃ of lower dryings until the quality constant weight obtains pulverous Acetic xylogen;
Three, the acetone method xylogen that the step 2 of 7.5kg is obtained, 7.5kg phenol mix, then add first sodium hydroxide and first formaldehyde, after mixing, under agitation condition, be warming up to 90 ℃, keep reaction 50min, then add second batch sodium hydroxide and second batch formaldehyde, at 70min sodium hydroxide is added, continuing to keep temperature is 90 ℃, and then the 3rd batch of sodium hydroxide of temperature-resistant lower adding and the 3rd batch of formaldehyde, and sodium hydroxide needs to add at 60min, the urea that adds again 2.02kg, adding at 30min, is 85 ℃ of lower reactions in temperature, when material state reach sticky after, with its cooling, namely get acetone method xylogen phenolic aldehyde copolymerized adhesive rapidly; Wherein, it is 10.57kg that formaldehyde adds total amount, divides 3 batches of addings in 1.2: 1: 1 ratio; It is 3.28kg that sodium hydroxide adds total amount, divides 3 batches of addings in 1: 1: 2.85 ratio.
Test five: the method that the alternative phenol of organic method xylogen of this test prepares synvaren is to realize according to the following steps:
One, be 1g with plant fiber material and acetone by mass volume ratio: the 4mL mixing, put into stainless steel cauldron, under the temperature rise rate of 15 ℃/min, be heated to 180 ℃ and be incubated 1h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30min under the speed of 4500r/min, acetone lignin liquor and fibre stuff are separated, then use the washing with acetone fibre stuff 3 times, keep washings, acetone lignin liquor and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 30min, acetone xylogen Precipitation, pass through again negative pressure leaching, filter cake is washed with distilled water to without acetone residual, then filter cake is placed in the vacuum drying oven 40 ℃ of lower dryings until the quality constant weight obtains pulverous acetone method xylogen;
Three, in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add the formaldehyde of 5kg and the water of 2kg, and minute 3 batches of acetone method xylogen and sodium hydroxide that the adding step 2 obtains, reaction under temperature is 80 ℃, 3 elementary reaction times are respectively 80min, 70min and 60min, after reaction is finished, obtain hydroxymethylated lignin; Wherein, it is 15kg that the acetone method xylogen adds total amount, divides 3 batches of inputs in 3: 2: 1 ratio; It is 0.3kg that sodium hydroxide adds total amount, divides 3 batches of inputs in 6: 3: 1 ratio;
Four, the hydroxymethylated lignin that step 3 is obtained after stirring 10min under the normal temperature, namely gets acetone method xylogen phenolic aldehyde composite adhesive with after resol mixes; Wherein, the mass ratio 1: 1 of hydroxymethylated lignin and resol.
This test has adopted organic method xylogen to substitute phenol, and whole preparation process has advantages of economic environmental protection; Owing to adopting organic method xylogen to substitute the preparation that phenol is used for synvaren, greatly reduced the usage quantity of the larger petrochemical material-phenol of toxicity non-renewable in the resol building-up process, this not only makes production resol cost greatly reduce, can also by the performance that makes to improve resol of organic method xylogen, obtain the synvaren that bonding strength is higher, formaldehyde release is lower, performance is more stable;
Test six: the method that the alternative phenol of organic method xylogen of this test prepares synvaren is to realize according to the following steps:
One, be 1g with plant fiber material and acetone by mass volume ratio: the 4mL mixing, put into stainless steel cauldron, under the temperature rise rate of 15 ℃/min, be heated to 180 ℃ and be incubated 1h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30min under the speed of 4500r/min, acetone lignin liquor and fibre stuff are separated, then use the washing with acetone fibre stuff 3 times, keep washings, acetone lignin liquor and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 30min, acetone xylogen Precipitation, pass through again negative pressure leaching, filter cake is washed with distilled water to without acetone residual, then filter cake is placed in the vacuum drying oven 40 ℃ of lower dryings until the quality constant weight obtains pulverous acetone method xylogen;
Three, the acetone method xylogen that the step 2 of 7.5kg is obtained, 7.5kg phenol mix, then add first sodium hydroxide and first formaldehyde, after mixing, under agitation condition, be warming up to 90 ℃, keep reaction 50min, then add second batch sodium hydroxide and second batch formaldehyde, at 70min sodium hydroxide is added, continuing to keep temperature is 90 ℃, and then the 3rd batch of sodium hydroxide of temperature-resistant lower adding and the 3rd batch of formaldehyde, and sodium hydroxide needs to add at 60min, the urea that adds again 2.02kg, adding at 30min, is 85 ℃ of lower reactions in temperature, when material state reach sticky after, with its cooling, namely get acetone method xylogen phenolic aldehyde copolymerized adhesive rapidly; Wherein, it is 10.57kg that formaldehyde adds total amount, divides 3 batches of addings in 1.2: 1: 1 ratio; It is 3.28kg that sodium hydroxide adds total amount, divides 3 batches of addings in 1: 1: 2.85 ratio.
The synvaren of this test preparation has the low toxicity advantage of low free-phenol, low residues of formaldehyde and the volatilization of low formaldehyde, for the preparation of expanding the Enviorment-protective Phenolic Resin tackiness agent and the high value added utilization of organic method xylogen have been opened bright prospects.
Claims (10)
1. organic method xylogen substitutes the method that phenol prepares synvaren, it is characterized in that organic method xylogen substitutes the method that phenol prepares synvaren and carries out according to the following steps:
One, it is 1g with plant fiber material and organic solvent by mass volume ratio: 2～5mL mixing, put into stainless steel cauldron, under the temperature rise rate of 10～20 ℃/min, be heated to 160～200 ℃ and be incubated 1～2h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30～60min under the speed of 4000～5000r/min, organosolv lignin solution and fibre stuff are separated, then use reaction solvent washing the fibre slurry 3 times, keep washings, organosolv lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 20～40min, the organosolv lignin Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40～60 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, add the formaldehyde of 5～10kg and the water of 2.5～5kg, and minute 3 batches of organic method xylogen and sodium hydroxide that the adding step 2 obtains, reaction under temperature is 60～100 ℃, 3 elementary reaction times are respectively 60～100min, 60～80min and 40～70min, after reaction is finished, obtain hydroxymethylated lignin; Wherein, it is 10～20kg that organic method xylogen adds total amount, and in (1～3): (1～2): 1 ratio is divided 3 batches of inputs; It is 0.2～0.5kg that sodium hydroxide adds total amount, and in (2～6): (1～3): 1 ratio is divided 3 batches of inputs;
Four, the hydroxymethylated lignin that step 3 is obtained after stirring 5～10min under the normal temperature, namely gets organic method xylogen phenolic aldehyde composite adhesive with after resol mixes; Wherein, the mass ratio of hydroxymethylated lignin and resol (1～3): (1～2).
2. organic method xylogen according to claim 1 substitutes the method that phenol prepares synvaren, it is characterized in that organic solvent is ethyl acetate, acetone, formic acid, acetic acid, ethanol, BDO, ethylene glycol or butyleneglycol in the step 1.
3. organic method xylogen according to claim 1 substitutes the method that phenol prepares synvaren, it is characterized in that being heated under the temperature rise rate of 15 ℃/min in the step 1 180 ℃ and be incubated 1h.
4. organic method xylogen according to claim 1 substitutes the method that phenol prepares synvaren, it is characterized in that in the step 1 centrifugal 30min under the speed of 4500r/min.
5. organic method xylogen according to claim 1 substitutes the method that phenol prepares synvaren, it is characterized in that organic method xylogen divides 3 batches of inputs in 3: 2: 1 ratio in the step 3.
6. organic method xylogen according to claim 1 substitutes the method that phenol prepares synvaren, it is characterized in that sodium hydroxide divides 3 batches of inputs in 6: 3: 1 ratio in the step 3.
7. organic method xylogen according to claim 1 substitutes the method that phenol prepares synvaren, it is characterized in that the mass ratio 1: 1 of hydroxymethylated lignin and resol in the step 4.
8. organic method xylogen substitutes the method that phenol prepares synvaren, it is characterized in that organic method xylogen substitutes the method that phenol prepares synvaren and carries out according to the following steps:
One, it is 1g with plant fiber material and organic solvent by mass volume ratio: 2～5mL mixing, put into stainless steel cauldron, under the temperature rise rate of 10～20 ℃/min, be heated to 160～200 ℃ and be incubated 1～2h, water of condensation cool to room temperature after insulation finishes, by taking out reaction residual after the relief valve pressure release, with reaction residual centrifugal 30～60min under the speed of 4000～5000r/min, organosolv lignin solution and fibre stuff are separated, then use reaction solvent washing the fibre slurry 3 times, keep washings, organosolv lignin solution and washings are merged, obtain merging filtrate;
Two, after adding the long-pending water of triploid in the merging filtrate that obtains to step 1 under the room temperature, static 20～40min, the organosolv lignin Precipitation, pass through again negative pressure leaching, it is residual that filter cake is washed with distilled water to organic solvent-free, then filter cake is placed in the vacuum drying oven 40～60 ℃ of lower dryings until the quality constant weight obtains pulverous organic method xylogen;
Three, organic method xylogen that the step 2 of 8～10kg is obtained, the phenol of 3～8kg mixes, then add first sodium hydroxide and first formaldehyde, after mixing, under agitation condition, be warming up to 80～90 ℃, keep reaction 50min, then add second batch sodium hydroxide and second batch formaldehyde, at 60～90min sodium hydroxide is added, continuing to keep temperature is 80～90 ℃, and then the 3rd batch of sodium hydroxide of temperature-resistant lower adding and the 3rd batch of formaldehyde, and sodium hydroxide needs to add at 50～70min, the urea that adds again 1～4kg, adding at 30～40min, is 80～85 ℃ of lower reactions in temperature, when material state reach sticky after, with its cooling, namely get organic method xylogen phenolic aldehyde copolymerized adhesive rapidly; Wherein, it is 10～20kg that formaldehyde adds total amount, and in (1～3): (1～2): 1 ratio is divided 3 batches of addings; It is 2～5kg that sodium hydroxide adds total amount, and in (1～2): (1～3): the ratio of (2～4) is divided 3 batches of addings.
9. organic method xylogen according to claim 8 substitutes the method that phenol prepares synvaren, it is characterized in that formaldehyde divides 3 batches of addings in 1.2: 1: 1 ratio in the step 3.
10. organic method xylogen according to claim 8 substitutes the method that phenol prepares synvaren, it is characterized in that sodium hydroxide divides 3 batches of addings in 1: 1: 2.85 ratio in the step 3.
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