CN115895540A - Adhesive composition and application thereof in preparation of recombined wood - Google Patents
Adhesive composition and application thereof in preparation of recombined wood Download PDFInfo
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Abstract
The invention provides an adhesive composition, which comprises a resin material modifier and an adhesive for wood; the resin material modifier adopts 3-chloro-2-hydroxy-propyl as a blocking group, the sulfur content is 5-60%, and the hydroxyl content is 1-10%. In the adhesive composition system, the polythiol compound is used as a substrate, the 3-chloro-2-hydroxy-propyl group is used as an end capping group, and the mutual restriction of the sulfur content and the hydroxy content is controlled, so that the resin material modifier can realize stable compatibility in a conventional wood colloid system, and simultaneously achieve a good level on the dimensional stability of a reconstituted wood base material, and has excellent aging resistance, the thickness absorption expansion rate is less than or equal to 3.5 percent, and the width absorption expansion rate is less than or equal to 3 percent. The invention also provides an application of the adhesive composition.
Description
Technical Field
The invention belongs to the technical field of wood-based composite materials, and particularly relates to an adhesive composition and application thereof in preparation of recombined wood.
Background
The high-performance recombined wood is a novel high-performance natural polymer composite material which is formed by compounding artificial forest wood serving as a raw material, cells serving as basic units and resin through directional recombination, can overcome the defects of small wood diameter, soft material, low strength, uneven material and the like of the artificial forest wood, has the characteristics of controllable performance, designable structure, adjustable specification and the like, is one of effective ways for large-size small wood and high-quality inferior wood, and is one of the frontiers and hotspots of the research in the field of natural polymer materials at present.
The great challenges faced by reconstituted wood arise from the problems of bond strength and poor dimensional stability and even swelling cracking upon exposure to water after reconstitution.
To address this challenge, the literature reports numerous solutions, such as: CN101357470 improves the uniformity scheme of gum dipping and improves the bonding strength by untwining the veneer, improving the crack uniformity of the wood beam, although the scheme has certain effect under the contrast, the internal bonding strength is still lower and is lower than 2MPa, and the good effect can not be realized; in CN111171770, synergistic silicon modified phenolic resin is adopted, which effectively improves the internal bonding strength and saturated water absorption (internal bonding strength is 3.0-5.0 MPa, saturated water absorption is 12.5-14.9%), and the prior art adopts a modification mode of adding organic salt, which has the defects of poor compatibility or even incompatibility with a phenolic glue system, seriously destroys the stability of the phenolic glue system, causes great passivity in large-scale production and use, and is difficult to apply.
Disclosure of Invention
The invention aims to provide an adhesive composition and application thereof in preparing reconstituted wood.
The invention provides an adhesive composition, which comprises a resin material modifier and an adhesive for wood;
the resin material modifier adopts 3-chloro-2-hydroxy-propyl as an end capping group, and has the sulfur content of 5-60 wt% and the hydroxyl content of 1-10 wt%.
Preferably, the resin material modifier has a structure represented by formula I:
r is a polythiol compound, and n is more than or equal to 1 and less than or equal to 4.
Preferably, R has a structure represented by any one of R-1 to R-22:
preferably, the resin material modifier has a sulfur content of 14 to 40% and a hydroxyl content of 5 to 10%.
Preferably, the adhesive composition has a gel content of 15 to 30%.
Preferably, the adhesive for wood is phenolic resin.
Preferably, the mass ratio of the resin material modifier to the wood adhesive is (0.05-50): 100.
the invention provides an application of the resin material modifier in preparing recombined wood, wherein the resin material modifier is mixed with an adhesive for wood and used as the adhesive to prepare the recombined wood.
Preferably, the preparation of the reconstituted wood comprises the following steps:
and sequentially performing gum dipping, pressing and high-temperature curing on the veneer to obtain the recombined wood.
Preferably, the high-temperature curing adopts the following temperature programming: keeping the temperature of 90-110 ℃ for 0.5-1.5 hours; keeping the temperature of 110-130 ℃ for 1.5-2.5 hours, and keeping the temperature of 130-150 ℃ for 3-5 hours.
The invention provides an adhesive composition, which comprises a resin material modifier and an adhesive for wood; the resin material modifier adopts 3-chloro-2-hydroxy-propyl as an end capping group, the sulfur content is 5-60%, and the hydroxyl content is 1-10%. In the adhesive composition system, the polythiol compound is used as a substrate, the 3-chloro-2-hydroxy-propyl group is used as an end capping group, and the mutual restriction of the sulfur content and the hydroxy content is controlled, so that the resin material modifier can realize stable compatibility in a conventional wood colloid system, and simultaneously achieve a good level on the dimensional stability of a reconstituted wood base material, and has excellent aging resistance, the thickness absorption expansion rate is less than or equal to 3.5 percent, and the width absorption expansion rate is less than or equal to 3 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The substrate applicability is strong, and the compatibility is better when the resin modifier is added into a conventional wood adhesive system;
(2) The composition containing the modifier has excellent mechanical property and size stability in the application of the reconstituted wood.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a fluorescent microscope photograph of the impregnated veneers of example 1, example 2, example 5 and comparative example 1 of the present invention;
FIG. 2 is a liquid phase diagram of a resin material modifier with 3-chloro-2-hydroxy-propyl group as an end capping group in example 1;
FIG. 3 is a Raman spectrum of the starting material 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol;
FIG. 4 is a Raman spectrum of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane.
Detailed Description
The invention provides an adhesive composition, which comprises a resin material modifier and an adhesive for wood;
the resin material modifier adopts 3-chloro-2-hydroxy-propyl as an end capping group, the sulfur content is 5-60%, and the hydroxyl content is 1-10%.
In the present invention, the resin material modifier has a structure represented by formula I:
r is a polythiol compound, n is more than or equal to 1 and less than or equal to 4, such as n is 1,2,3 or 4. Preferably, R has a structure represented by any one of R-1 to R-22:
in the present invention, the sulfur content in the resin material modifier is preferably 5 to 60%, more preferably 10 to 55%, such as 5%,10%,15%,20%,25%,30%,35%,40%,45%,50%,55%,60%, and is preferably a value in the range having any of the above values as the upper or lower limit; the content of hydroxyl groups in the resin material modifier is preferably 1 to 10%, more preferably 3 to 8%, such as 1%,2%,3%,4%,5%,6%,7%,8%,9%,10%, and preferably a value in the range of any of the above values as the upper or lower limit.
In the present invention, the resin material modifier is preferably prepared according to the following steps:
and (2) uniformly stirring the polythiol monomer and methanol, adding epoxy chloropropane, uniformly stirring, dropwise adding an alkaline catalyst, reacting, determining the reaction end point by using the content of high performance liquid chromatography, and removing the solvent by using a rotary evaporator to obtain the resin material modifier, wherein the reaction end point is determined by using the content of the polythiol monomer less than 3%.
In the present invention, the molar ratio of the polythiol monomer to epichlorohydrin is preferably 1: (1 to 4), such as 1, 1.
In the present invention, the reaction temperature is preferably-15 to 65 ℃, more preferably 0 to 45 ℃, such as-15 ℃, -10 ℃, -5 ℃,0 ℃,5 ℃,10 ℃,15 ℃,20 ℃,25 ℃,30 ℃,35 ℃,40 ℃,45 ℃,50 ℃,55 ℃,60 ℃,65 ℃, and is preferably a range value taking any of the above values as an upper limit or a lower limit; the reaction time is preferably 2 to 24 hours, more preferably 6 to 20 hours, and most preferably 10 to 15 hours.
In the invention, the wood adhesive is a common wood adhesive in the field, the resin material modifier in the invention has strong substrate applicability, and has better compatibility when added into a conventional wood adhesive system, so the invention does not make special limitation on the type of the wood adhesive, and concretely, in the embodiment of the invention, the phenolic resin adhesive can be used.
In the present invention, the mass ratio of the resin material modifier to the wood adhesive is preferably (0.05 to 50): 100, more preferably (1 to 40): 100, such as 0..05:100,1:100,5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100 is preferably a range value having any of the above numerical values as an upper limit or a lower limit. When the content of the resin material modifier is low, the grid structure formed in the system is few, the effect on the stability of the reconstituted wood base material is not obvious, and when the content of the resin material modifier is too high, the risk of the stability deterioration of an adhesive system can occur, so that passivity is caused in large-scale production, and the effect of improving the dimensional stability is not obvious.
In the present invention, the adhesive composition preferably has a gel content of 10 to 30%, more preferably 20%.
The invention also provides an application of the resin material modifier in preparing reconstituted wood, and the resin material modifier is mixed with an adhesive for wood to be used as the adhesive for preparing the reconstituted wood.
Specifically, the veneers are dipped in the adhesive, and then are sequentially pressed and cured at high temperature to obtain the reconstituted wood.
In the present invention, the types and the amounts of the resin material modifier and the wood adhesive are the same as those of the resin material modifier and the wood adhesive, and the description of the present invention is omitted here.
In the present invention, the impregnation and pressing are processes for preparing recombined wood commonly used in the art, and the present invention is not described herein again.
In the invention, the high-temperature curing preferably adopts temperature programming, specifically, the temperature is firstly kept at 90-110 ℃ for 0.5-1.5 hours; then keeping the temperature of 110-130 ℃ for 1.5-2.5 hours, and finally keeping the temperature of 130-150 ℃ for 3-5 hours, more preferably keeping the temperature of 100 ℃ for 1 hour; then keeping the temperature of 120 ℃ for 2 hours, finally keeping the temperature of 140 ℃ for 4 hours, keeping the temperature of the core layer at 120 ℃ for 2 hours, then cooling, and opening the die to obtain the recombined wood.
The invention provides an adhesive composition, which comprises a resin material modifier and an adhesive for wood; the resin material modifier adopts 3-chloro-2-hydroxy-propyl as a blocking group, the sulfur content is 5-60%, and the hydroxyl content is 1-10%. In the adhesive composition system, a polythiol compound is used as a substrate, 3-chloro-2-hydroxy-propyl is used as a blocking group, and the mutual restriction of sulfur content and hydroxy content is controlled, so that the resin material modifier can realize stable compatibility in a conventional wood colloid system, and meanwhile, the dimensional stability of a reconstituted wood base material reaches a better level, the aging resistance is excellent, the thickness absorption expansion rate is less than or equal to 3.5%, and the width absorption expansion rate is less than or equal to 3%.
Compared with the prior art, the invention has the following beneficial effects:
(1) The substrate applicability is strong, and the compatibility is better when the resin modifier is added into a conventional wood adhesive system;
(2) The composition containing the modifier has excellent mechanical property and size stability in the application of the reconstituted wood.
In order to further illustrate the present invention, an adhesive composition and its application in the preparation of reconstituted wood are described in detail in the following examples, which should not be construed as limiting the scope of the present invention.
The phenolic adhesives used in the wood industry in the following examples and comparative examples are all phenolic adhesives used in the wood industry in the same manufacturer in a uniform batch.
Example 1
Preparation of biomass recombination agent 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane:
weighing 130.5g of 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol and 460g of solvent methanol, uniformly stirring, adding 166.7g of epoxy chloropropane, continuously uniformly stirring, adding 6g of 2% sodium hydroxide aqueous solution while stirring, controlling the system to react at 0 ℃ for 20 hours, determining the reaction end point by using the content of high performance liquid chromatography, and removing the solvent by using a rotary evaporator to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane when the content of the 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol is less than 3%.
The preparation steps of the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry are as follows:
(a) Adding 6g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 18g of water into the step (b) to dilute the mixed solution to a glue content of 26.4 percent, so as to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle, and keeping the single plate in vacuum for 0.5h under-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1 hour;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 2
The biomass reforming agent 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane was prepared according to the same method as in example 1.
The preparation steps of the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry are as follows:
(a) Adding 2g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 22g of water into the step (b), and diluting the mixed solution to a glue content of 22.4% to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive into a reaction kettle, keeping the veneer below the liquid level completely, and maintaining the veneer for soaking for 24h until the veneer is completely soaked;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and the temperature is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 3
The biomass reforming agent 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane was prepared according to the same method as in example 1.
The preparation steps of the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry are as follows:
(a) Adding 1g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 23g of water into the step (b), and diluting the mixed solution to a glue content of 21.4% to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle, and keeping the single plate in vacuum for 0.5h under-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1 hour;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a hot pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 4
The preparation method of the biomass reforming agent 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane is the same as that of the example 1.
The preparation steps of the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry are as follows:
(a) Adding 0.5g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) Adding 23.5g of water into the step (b), and diluting the mixed solution to a gel content of 20.9% to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of veneer into a 10L reaction kettle, and keeping the mixture for 0.5h under vacuum of-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1 hour;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 5
Preparation of biomass recombination agent 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -3-propane-1-thiol
Weighing 130.5g of 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol and 460g of solvent methanol, uniformly stirring, adding 111.1g of epoxy chloropropane, continuously uniformly stirring, adding 4.8g of 2% sodium hydroxide aqueous solution while stirring, controlling the system to react at 15 ℃, controlling the reaction time to be 20 hours, determining the reaction end point by using the content of high performance liquid chromatography, and removing the solvent by using a rotary evaporator to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane when the content of the 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol is less than 3%.
The preparation steps of the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry are as follows:
(a) Adding 2g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 22g of water into the step (b) to dilute the mixed solution until the gel content is 22.4%, so as to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle, and keeping the single plate in vacuum for 0.5h under-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1h;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 6
Biomass recombinants 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -3-propane-1-thiol was prepared as in example 3.
The preparation steps of the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified adhesive for wood industry are as follows:
(a) Adding 1g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 23g of water into the step (b) to dilute the mixed solution until the gel content is 21.4%, so as to obtain the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle, and keeping the single plate in vacuum for 0.5h under-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified wood industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1 hour;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a hot pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 7
Preparation of biomass recombination agent 2,2' -bis (2- (3-chloro-2-hydroxy-propylthio) ethyl sulfide
154.3g of thiodiglycol and 460g of solvent methanol are weighed, after uniform stirring, 203.5g of epichlorohydrin is added, after continuous uniform stirring, 7.2g of 2% sodium hydroxide aqueous solution is added while stirring, the system is controlled to react at 0 ℃, the reaction time is 20 hours, the reaction end point is determined by the content of high performance liquid chromatography, when the content of thiodiglycol is less than 3%, the end point is determined, and a rotary evaporator is adopted to remove the solvent, thus obtaining the 2,2' -bis (2- (3-chloro-2-hydroxy-propylthio) ethyl sulfide.
The preparation steps of the 2,2' -bis (2- (3-chloro-2-hydroxy-propylthio) ethyl sulfide modified adhesive for wood industry are as follows:
(a) Adding 4g of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 20g of water into the step (b), and diluting the mixed solution to obtain the adhesive with the glue content of 24.4 percent, so that the 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane modified for wood industry is obtained.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle, and keeping the single plate in vacuum for 0.5h under-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1h;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Example 8
Preparation of biomass recombinant 3,3 '-thiobis (1- (2- (3-chloro-2-hydroxy-propyl) thioethyl) -2,2' -bis (3-chloro-2-hydroxy-propyl) thiopropyl sulfide:
183.4g of 3,3 '-thiobis (1- (2-mercaptoethyl) thiopropane) -2,2' -dithiol and 408g of solvent methanol are weighed, uniformly stirred, 222.1g of epoxy chloropropane is added, the mixture is continuously and uniformly stirred, 8.1g of 2% sodium hydroxide aqueous solution is added while stirring, the reaction temperature of the system is controlled to be 0 ℃, the reaction time is 20 hours, the reaction end point is determined by the content of high performance liquid chromatography, when the content of the 3,3 '-thiobis (1- (2-mercaptoethyl) thiopropane) -2,2' -dithiol is less than 3%, the reaction end point is determined, and a rotary evaporator is adopted to remove the solvent to obtain the 3,3 '-thiobis (1- (2- (3-chloro-2-hydroxy-propyl) thioethyl) -2,2' -bis (3-chloro-2-hydroxy-propyl) thiopropyl sulfide.
The preparation steps of the 3,3 '-thiobis (1- (2- (3-chloro-2-hydroxy-propyl) thioethyl) -2,2' -bis (3-chloro-2-hydroxy-propyl) thiopropyl sulfide modified phenolic adhesive for wood industry are as follows:
(a) Dissolving 2g of 3,3 '-thiobis (1- (2- (3-chloro-2-hydroxy-propyl) thioethyl) -2,2' -bis (3-chloro-2-hydroxy-propyl) thiopropyl sulfide in 36g of ethanol, uniformly dissolving, and adding into a reaction kettle;
(b) Adding 40g of phenolic adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 22g of water into the step (b) to dilute the mixed solution to a gel content of 22.4% so as to obtain the 3,3 '-thiobis (1- (2- (3-chloro-2-hydroxy-propyl) thioethyl) -2,2' -bis (3-chloro-2-hydroxy-propyl) thiopropyl sulfide modified phenolic aldehyde adhesive for wood industry.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle, and keeping the single plate in vacuum for 0.5h under-0.4 MPa;
(b) Adding 10Kg of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1h;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a hot pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Comparative example 1
The preparation method of the phenolic adhesive for the wood industry comprises the following steps:
adding 40g of the phenolic adhesive for the wood industry and 60g of water into a reaction kettle, mixing and diluting until the glue content is 22.4%, and obtaining the phenolic adhesive for the wood industry.
The recombination wood comprises the following steps:
(a) Adding 1.2Kg of veneer into a 10L reaction kettle, and keeping the mixture for 0.5h under vacuum of-0.4 MPa;
(b) Adding 10Kg of industrial phenolic glue with the solid content of 22.4 percent into a reaction kettle, and carrying out positive pressure impregnation for 1 hour under 0.6 MPa;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Comparative example 2
The preparation method of the phenolic adhesive for the wood industry comprises the following steps:
adding 40g of the phenolic adhesive for the wood industry and 60g of water into a reaction kettle, mixing and diluting until the glue content is 22.4%, and obtaining the phenolic adhesive for the wood industry.
The recombination wood comprises the following steps:
(a) Adding 1.2Kg of single plate into a 10L reaction kettle;
(b) Adding 10Kg of industrial phenolic glue with the solid content of 22.4% into a reaction kettle, and keeping the complete immersion for 24 hours until the veneer is completely soaked;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a hot pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Comparative example 3
Preparation of a biomass recombination agent, namely tri (3-chloro-2-hydroxy-propyl) trifunctional polyether polybasic thioether:
weighing 130.5g of trifunctional polyether polythiol and 460g of solvent methanol, uniformly stirring, adding 59.12g of epoxy chloropropane, continuously uniformly stirring, adding 3.8g of 2% sodium hydroxide aqueous solution while stirring, controlling the system to react at 0 ℃, the reaction time to be 20 hours, determining the reaction end point by using the content of gas chromatography, and removing the solvent by using a rotary evaporator to obtain the tris (3-chloro-2-hydroxy-propyl) trifunctional polyether polythioether (the content of hydroxyl is 10.7%, and the content of sulfur is 9.48%) when the content of the epoxy chloropropane is less than 3.5%.
The preparation steps of the tri (3-chloro-2-hydroxy-propyl) trifunctional polyether polybasic thioether modified adhesive for wood industry are as follows:
(a) Adding 6g of tri (3-chloro-2-hydroxy-propyl) trifunctional polyether polybasic thioether and 36g of ethanol into a reaction kettle, and mixing for 30min;
(b) Adding 40g of adhesive for wood industry into the step (a) and mixing for 30min;
(c) And (c) adding 18g of water into the step (b) to dilute the mixed solution, so as to obtain the tri (3-chloro-2-hydroxy-propyl) trifunctional polyether polybasic thioether modified wood industrial adhesive.
The preparation method of the restructured wood comprises the following steps:
(a) Adding 1.2Kg of veneer into a 10L reaction kettle, and keeping the mixture for 0.5h under vacuum of-0.4 MPa;
(b) Adding 10Kg of tri (3-chloro-2-hydroxy-propyl) trifunctional polyether polybasic thioether modified wood industrial adhesive into a reaction kettle, and carrying out positive pressure impregnation at 0.6MPa for 1h;
(c) Taking out the wood in the reaction kettle, carrying out extrusion-glue draining-extrusion for 4-5min in total, and then airing for 24h;
(d) Curing the gum-dipped veneers by a cold pressing process to prepare the recombined wood, wherein the temperature adopts temperature programming and curing, and the temperature is 100-1h, 120-2h and 140 ℃, and the temperature of a test core layer reaches 120 ℃ and is kept for 2h.
Respectively detecting the performances of the recombined wood prepared by the thiol modified adhesive for wood industry provided by the examples 1-8 and the comparative examples 1-3; wherein, the internal bonding strength is detected by adopting a 3365 universal tensile machine of the American Instron company; evaluation of 28h cycle cracking: adopting American society for I-type plywood performance evaluation standards, boiling at 100 ℃ for 4h, drying in a 63 ℃ oven for 20h, boiling at 100 ℃ for 4h, observing the cracking of sample blocks, and determining that the sample blocks are qualified if no cracking exists; the anti-aging performance is detected by irradiation of a BD/ZN-P ultraviolet lamp of the Chinese Boda science and technology Limited company; the results of the performance tests are shown in table 1.
Table 1 performance data for reconstituted wood prepared with thiol-modified wood industrial adhesives provided in examples 1-8 and comparative example 1
As can be seen from table 1, the reconstituted wood prepared by modifying the adhesive for wood industry with the reconstituted agent provided in embodiments 1 to 8 of the present invention has excellent mechanical properties and better aging resistance.
In order to further analyze the characteristic of excellent performance of the recombined wood prepared by the recombined agent modified wood glue, a German Zeiss Axio Scope A1 fluorescence microscope is adopted to detect and track the distribution state of the phenol glue in the lower dipping glue single plate of different embodiments, and the result is shown in figure 1.
In FIG. 1, the graphs a, b, c and d are fluorescence analysis comparisons of the impregnated veneers of example 1, example 2, example 5 and comparative example 1 in sequence. As can be seen from fig. 1, the phenolic glue modified by the resin material modifier is distributed more uniformly in the veneer (the bright fluorescent dots are phenolic glue).
Fig. 2 is a liquid column chromatography spectrum of the resin material modifier in example 1, by liquid column chromatography, methanol-acid water 32:68 gradient separation, and determining that the peak of the resin material modifier product with 3-chloro-2-hydroxy-propyl as the end capping group is concentrated at 14.4-15.13 min, and the normalization content is 72-78%.
FIG. 3 is a Raman spectrum of a starting material 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol, and FIG. 4 is a Raman spectrum of 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane. From the Raman spectrum analysis of FIGS. 3 and 4, the peak of thiol group at 2556.74cm-1 of resin material modifier 2, 3-bis (2- (3-chloro-2-hydroxy-propylthio) ethylthio) -1- (3-chloro-2-hydroxy-propyl) thiopropane completely disappeared, indicating that the thiol group in the product was completely reacted.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. An adhesive composition comprising a resin material modifier and an adhesive for wood;
the resin material modifier adopts 3-chloro-2-hydroxy-propyl as an end capping group, and has the sulfur content of 5-60 wt% and the hydroxyl content of 1-10 wt%.
2. The adhesive composition of claim 1, wherein the resin material modifier has a structure represented by formula I:
r is polythiol compound, n is more than or equal to 1 and less than or equal to 4.
3. The adhesive composition of claim 2, wherein R has a structure represented by any one of R-1 to R-22:
4. the adhesive composition of claim 1, wherein the resin material modifier has a sulfur content of 14 to 40% and a hydroxyl content of 5 to 10%.
5. The adhesive composition of claim 1, wherein the adhesive composition has a gel content of 15 to 30%.
6. The adhesive composition of claim 1, wherein the wood adhesive is a phenolic resin.
7. The adhesive composition of claim 6, wherein the mass ratio of the resin material modifier to the wood adhesive is (0.05-50): 100.
8. use of the resin material modifier as defined in claim 1 in the preparation of reconstituted wood by mixing the resin material modifier with an adhesive for wood as the adhesive.
9. Use according to claim 8, wherein the preparation of the reconstituted wood comprises the steps of:
and sequentially carrying out gum dipping, pressing and high-temperature curing on the veneer to obtain the recombined wood.
10. Use according to claim 8, wherein the high temperature curing employs the following temperature program: keeping the temperature at 90-110 ℃ for 0.5-1.5 hours; keeping the temperature of 110-130 ℃ for 1.5-2.5 hours, and keeping the temperature of 130-150 ℃ for 3-5 hours.
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