CN103881633B - Composite adhesive and preparation method thereof and glued board - Google Patents
Composite adhesive and preparation method thereof and glued board Download PDFInfo
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- CN103881633B CN103881633B CN201410158157.7A CN201410158157A CN103881633B CN 103881633 B CN103881633 B CN 103881633B CN 201410158157 A CN201410158157 A CN 201410158157A CN 103881633 B CN103881633 B CN 103881633B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 80
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 239000000843 powder Substances 0.000 claims abstract description 53
- 150000002989 phenols Chemical class 0.000 claims abstract description 33
- 108010064851 Plant Proteins Proteins 0.000 claims abstract description 32
- 235000021118 plant-derived protein Nutrition 0.000 claims abstract description 32
- -1 aldehyde compound Chemical class 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 108010073771 Soybean Proteins Proteins 0.000 claims description 16
- 235000019710 soybean protein Nutrition 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 229920002494 Zein Polymers 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 239000005019 zein Substances 0.000 claims description 5
- 229940093612 zein Drugs 0.000 claims description 5
- 108010068370 Glutens Proteins 0.000 claims description 4
- 235000021312 gluten Nutrition 0.000 claims description 4
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001896 cresols Chemical class 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 67
- 238000000034 method Methods 0.000 abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 235000019256 formaldehyde Nutrition 0.000 abstract description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 14
- 229920001568 phenolic resin Polymers 0.000 abstract description 14
- 239000005011 phenolic resin Substances 0.000 abstract description 14
- 239000002023 wood Substances 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 21
- 238000011056 performance test Methods 0.000 description 18
- 229960004279 formaldehyde Drugs 0.000 description 13
- 229920003987 resole Polymers 0.000 description 13
- 238000004513 sizing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008098 formaldehyde solution Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 241000219000 Populus Species 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 230000017854 proteolysis Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019764 Soybean Meal Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004455 soybean meal Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Veneer Processing And Manufacture Of Plywood (AREA)
Abstract
The invention provides a kind of composite adhesive and preparation method thereof, first plant protein powder, phenolic compound and basic cpd mix by the method, and back flow reaction, obtains the first reaction solution; Then the first reaction solution obtained is mixed with aldehyde compound, continue back flow reaction, obtain the second reaction solution; Finally the second reaction solution obtained is mixed with aminocompound, continue back flow reaction, obtain composite adhesive.The intensity of this composite adhesive and water proof bonding strength are suitable with phenolic resin adhesive, and content of free aldehyde is lower, is applicable to produce various wood working product.In addition, the raw materials cost of this composite adhesive is low, and technique is simple, environmental protection.Present invention also offers a kind of glued board, it uses this composite adhesive to obtain, and has that intensity is high, water-tolerant and an advantage such as burst size of methanal is low, is beneficial to application.
Description
Technical field
The present invention relates to based Wood Adhesives technical field, particularly a kind of composite adhesive and preparation method thereof and glued board.
Background technology
Sizing agent is very fast in RECENT DEVELOPMENTS, and application industry is extremely wide.Wherein, based Wood Adhesives is the sizing agent manufactured for wood adhesion and woodwork.Along with the sustainable development of wood processing industry, the consumption of based Wood Adhesives is in sustainable growth, and kind is also being on the increase.At present, the processing of artificial board mainly uses phenolic resin adhesive, urea-formaldehyde resin adhesive and melamine-formaldehyde resin adhesive to stick agent, namely usually said " three-aldehyde glue ".The cohesive strength of three-aldehyde glue is good, but the artificial board using it to manufacture in use can continuous release formaldehyde, unfavorable to environmental and human health impacts.Therefore, the sizing agent that environmental protection is compared in research and development to have become in industry an important problem.
Protein be formed by connecting by peptide bond by multiple amino acids polypeptide chain, be combined into the molecule with full biological activity again by respective mode by one or more than one polypeptide chain, and, protein contains amino and imino-etc., has certain reactive behavior.Wherein, vegetable-protein also have cheap, source is sufficient, easy handling and environmental sound and the feature such as renewable.Therefore, the exploitation of vegetable-protein sizing agent just progressively becomes study hotspot.Be no lack of in prior art and adopt vegetable-protein to be the report that based Wood Adhesives prepared by raw material, such as, the Chinese patent literature being CN101402842A as publication number discloses a kind of salt-alkali combined modified rubber made from soybean cake stick, in the composition of raw materials of described rubber made from soybean cake stick, the parts by weight of each component are: defatted soyflour 5 ~ 20 parts, 15 ~ 80 parts, water, acid 0.4 ~ 5.0 part, metal chloride 0.001 ~ 0.04 part, alkali lye 1.2 ~ 27.0 parts.Publication number is that the Chinese patent literature of CN101319131 discloses a kind of non-methanal environment-friendly type plant protein modified adhesion agent, and it comprises by weight: the natural phant dregs of rice 30 ~ 50, basic material 5 ~ 12, calcium oxide 5 ~ 10, urea 6 ~ 15, sodium alkyl sulfate 4 ~ 10,10 ~ 20% mass concentration mineral acid 2 ~ 5 and deionized water 90 ~ 120.
Above-mentioned research all with vegetable-proteins such as soybean proteins for raw material, simple degraded is carried out to it and prepares sizing agent, during application, although there is no the release of formaldehyde, compare environmental protection, the intensity of sizing agent and poor water resistance, be difficult to extensively promote in wood-processing industry.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of composite adhesive and preparation method thereof and glued board, composite adhesive provided by the invention has good intensity and water tolerance, and free formaldehyde content is extremely low.
The invention provides a kind of preparation method of composite adhesive, comprise the following steps:
A) plant protein powder, phenolic compound and basic cpd are mixed, back flow reaction, obtains the first reaction solution;
B) the first reaction solution that described step a) obtains is mixed with aldehyde compound, continue back flow reaction, obtain the second reaction solution;
C) the second reaction solution that described step b) obtains is mixed with aminocompound, continue back flow reaction, obtain composite adhesive.
Preferably, in described step a), described plant protein powder be selected from soybean protein powder, gluten powder and Zein powder one or more;
Described phenolic compound be selected from phenol, cresols, Resorcinol and cardanol one or more;
The mass ratio of described plant protein powder and phenolic compound is (1 ~ 10): 10.
Preferably, in described step a), described basic cpd be selected from sodium hydroxide, potassium hydroxide and ammoniacal liquor one or more;
The mass ratio of described basic cpd and phenolic compound is (0.5 ~ 10): 100.
Preferably, in described step a), the temperature of described reaction is 70 DEG C ~ 170 DEG C, and the time of described reaction is 60min ~ 180min.
Preferably, in described step b), described aldehyde compound be selected from formaldehyde, acetaldehyde, furfural and paraformaldehyde one or more;
The mol ratio of described aldehyde compound and phenolic compound is (2 ~ 5): 1.
Preferably, in described step b), the temperature of described reaction is 60 DEG C ~ 90 DEG C, and the time of described reaction is 60min ~ 240min.
Preferably, in described step c), described aminocompound be selected from urea, trimeric cyanamide and Dyhard RU 100 one or more;
The mass ratio of described aminocompound and phenolic compound is (0.5 ~ 10): 10.
Preferably, in described step c), the temperature of described reaction is 50 DEG C ~ 90 DEG C, and the time of described reaction is 60min ~ 240min.
The invention provides a kind of composite adhesive, preparation method by mentioned earlier obtains.
Compared with prior art, first the present invention by the mixing of plant protein powder, phenolic compound and basic cpd, take phenolic compound as solvent, basic cpd is properties-correcting agent, and back flow reaction is by protein degradation; Then the first reaction solution obtained is mixed with aldehyde compound, with described basic cpd for catalyzer, back flow reaction novolak resin; Finally mixed with aminocompound by the second reaction solution obtained, continue back flow reaction, the free aldehyde reaction in described aminocompound and reaction solution, obtains composite adhesive.In whole reaction process, phenolic compound both as solvent and the degradation agents of plant protein powder, again as the synthesis material of resol; Basic cpd both as the properties-correcting agent of plant protein powder, again as resol synthesis catalyzer; The formaldehyde reducing agent that aminocompound synthesizes as resol.Due to the DeR through basic cpd and phenolic compound twice pair of plant protein powder in reaction process, plant protein powder is degraded more abundant, and the building-up process of resol can be participated in, reactant cross-linking density is large, and intensity and the water tolerance of thus obtained composite adhesive improve greatly.Owing to employing plant protein powder and aminocompound in building-up process, cost is lower compared with pure phenolic resin, and free formaldehyde content is lower, environmental protection, is suitable for promoting.
The present invention also provides a kind of glued board, uses composite adhesive mentioned above to obtain.
The advantages such as the glued board that the present invention uses described composite adhesive to prepare has that intensity is high, water tolerance is strong and burst size of methanal is lower, are beneficial to application.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention discloses a kind of preparation method of composite adhesive, comprise the following steps:
A) plant protein powder, phenolic compound and basic cpd are mixed, back flow reaction, obtains the first reaction solution;
B) the first reaction solution that described step a) obtains is mixed with aldehyde compound, continue back flow reaction, obtain the second reaction solution;
C) the second reaction solution that described step b) obtains is mixed with aminocompound, continue back flow reaction, obtain composite adhesive.
The invention discloses the composite adhesive that a kind of plant protein powder and resol are composited, better performances, is suitable for producing various wood working products etc.
First the embodiment of the present invention adds plant protein powder, phenolic compound and basic cpd in reactor, preferably stirs, and to mix, then back flow reaction, obtains the first reaction solution.
The present invention adopts plant protein powder to prepare composite adhesive, relates to bio-based technical field of polymer materials, raw material is easy to get, environmental protection, and cost is lower.Described plant protein powder be preferably in soybean protein powder, gluten powder and Zein powder one or more, be more preferably soybean protein powder, gluten powder or Zein powder, most preferably be soybean protein powder.The source etc. of the present invention to described plant protein powder is not particularly limited, and adopts well known to those skilled in the art.
The present invention adopts phenolic compound to dissolve described plant protein powder, and it is also one of raw material of novolak resin.Described phenolic compound be preferably in phenol, cresols, Resorcinol and cardanol one or more, be more preferably phenol.Wherein, described phenol, preferably in molten state, namely preferably adopts melting phenol.In the present invention, the mass ratio of described plant protein powder and phenolic compound is preferably (1 ~ 10): 10, is more preferably (2 ~ 8): 10.
While plant protein powder is dissolved in phenolic compound, the present invention also adds basic cpd and carries out back flow reaction.Described basic cpd both as the properties-correcting agent of plant protein powder, again as resol synthesis catalyzer.Described basic cpd be preferably in sodium hydroxide, potassium hydroxide and ammoniacal liquor one or more, be more preferably sodium hydroxide or potassium hydroxide.In the present invention, the mass ratio of described basic cpd and phenolic compound is preferably (0.5 ~ 10): 100, is more preferably (1 ~ 8): 100.
Mix described plant protein powder, phenolic compound and basic cpd when reacting, the present invention is not particularly limited order of addition(of ingredients) and speed etc., preferably first add phenolic compound, then add basic cpd, add plant protein powder again, be beneficial to reaction and carry out.The combination of the present invention to above-mentioned material is also not particularly limited, and as adopted the combination of soybean protein powder, phenol and sodium hydroxide, also can adopt the combination etc. of Zein powder, phenol and potassium hydroxide.
In this back flow reaction of the present invention, the temperature of described reaction is preferably 70 DEG C ~ 170 DEG C, is more preferably 80 DEG C ~ 160 DEG C; The time of described reaction is preferably 60min ~ 180min, is more preferably 80min ~ 160min.
This back flow reaction of the present invention is mainly solvent with phenolic compound, basic cpd is properties-correcting agent, is reacted, by protein degradation, obtain the first reaction solution by backflow.
After obtaining the first reaction solution, it mixes with aldehyde compound by the embodiment of the present invention, preferably adds aldehyde compound wherein, continues back flow reaction, obtains the second reaction solution.
The present invention adopts aldehyde compound, with phenolic compound novolak resin under the existence of basic cpd.Described aldehyde compound be preferably in formaldehyde, acetaldehyde, furfural and paraformaldehyde one or more, be more preferably formaldehyde.The present invention preferably adopts formaldehyde solution to react, and described formaldehyde solution is that those skilled in the art commonly use.In the present invention, the mol ratio of described aldehyde compound and phenolic compound is preferably (2 ~ 5): 1, is more preferably (2.5 ~ 4): 1.
In the present invention, this continues in back flow reaction, and control temperature is preferably 60 DEG C ~ 90 DEG C, is more preferably 70 DEG C ~ 80 DEG C; The time of described reaction is preferably 60min ~ 240min, is more preferably 80min ~ 200min.
The present invention this continue back flow reaction mainly with phenolic compound and aldehyde compound be raw material, basic cpd for catalyzer, by backflow react, novolak resin, obtains the second reaction solution.
After obtaining the second reaction solution, it mixes with aminocompound by the embodiment of the present invention, preferably adds aminocompound wherein, continues back flow reaction, obtains composite adhesive.
The present invention adopts aminocompound, with the free aldehyde reaction in the second reaction solution, and continues to degrade to vegetable-protein.Described aminocompound be preferably in urea, trimeric cyanamide and Dyhard RU 100 one or more, be more preferably urea, raw material be easy to get, be beneficial to operation.The mass ratio of described aminocompound and phenolic compound is preferably (0.5 ~ 10): 10, is more preferably (1 ~ 8): 10.
In the present invention, this continues in back flow reaction, and control temperature is preferably 50 DEG C ~ 90 DEG C, is more preferably 70 DEG C ~ 80 DEG C; The time of described reaction is preferably 60min ~ 240min, is more preferably 80min ~ 200min.
After this continuation back flow reaction of the present invention terminates, add appropriate distilled water, to regulate solid content etc., cooling discharge, obtains composite adhesive, namely plant protein powder, resol composite adhesive.
The invention provides a kind of composite adhesive, preparation method by mentioned earlier obtains.
In whole reaction process, phenolic compound both as solvent and the degradation agents of plant protein powder, again as the synthesis material of resol; Basic cpd both as the properties-correcting agent of plant protein powder, again as resol synthesis catalyzer; The formaldehyde reducing agent that aminocompound synthesizes as resol.Due to the DeR through basic cpd and phenolic compound twice pair of plant protein powder in reaction process, plant protein powder is degraded more abundant, and the building-up process of resol can be participated in, reactant cross-linking density is large, and intensity and the water tolerance of thus obtained composite adhesive improve greatly.Owing to employing plant protein powder and aminocompound in building-up process, cost is lower compared with pure phenolic resin, and free formaldehyde content is lower, environmental protection, is suitable for promoting.
In addition, the present invention adopts composite adhesive described in one-step synthesis method, and process operability is strong.
After obtaining composite adhesive, the present invention carries out performance test to it.According to standard GB/T/T14074-2006 " wood adhesive and the resin method of inspection thereof ", the present invention tests the content of free aldehyde of described composite adhesive, free phenol content and viscosity etc.Experiment shows, the free formaldehyde content of composite adhesive provided by the invention is lower.
Present invention also offers a kind of glued board, use composite adhesive mentioned above to obtain.
Glued board is by multiple three layers of wood single-plate sizing agent gummed or the board-like material of multilayer, is one of household common used material.
The kind of the present invention to described timber is not particularly limited, and can adopt poplar and Eucalyptus etc.The present invention is not particularly limited the length and width of described glued board, thickness and number of plies equal-specification, adopts the specification that this area is conventional.
The present invention adopts composite adhesive mentioned above to glue together multiple wood single-plate, and the intensity of obtained glued board is high, water-tolerant, burst size of methanal are lower.The usage quantity of the present invention to described composite adhesive is not particularly limited, if one side resin added can be 60g/m
2~ 80g/m
2(glue dry weight basis).
After obtaining composite adhesive, the present invention uses it to prepare three layers of glued board, concrete grammar is: use the board using poplar board that thickness is 1.3mm ~ 1.7mm to prepare three layers of glued board, in advance board using poplar board being dried to water ratio is 6% ~ 9%, then described composite adhesive is uniformly coated on board using poplar board sandwich layer two sides, one side resin added is 60g/m
2(glue dry weight basis); By the board using poplar board composing plate embryo of gluing, precompressed 5 minutes under the pressure of 1.4MPa, then hot pressing at the temperature of 125 DEG C ~ 135 DEG C, hot pressing time is 70s/mm, obtains three layers of glued board.
After obtaining three layers of glued board, the present invention carries out performance test to it.According to standard GB/T/T9846.5-2004 " glued board the 5th part: normal plywood inspection rule ", the present invention tests the Joint strength of described three layers of glued board.According to standard GB/T 18580-2001 " in indoor decorating and refurnishing materials, wood-based plate and goods thereof Form aldehyde release limitation ", the present invention tests the free formaldehyde release of described three layers of glued board.Experiment display, the glued board that the present invention obtains is boiling 3h in the boiling water of 100 DEG C, bonding strength >=1.5MPa; After poach 4h, bonding strength can at more than 1MPa.The advantage such as show that glued board provided by the invention has that intensity is high, water tolerance is strong and burst size of methanal is lower, is beneficial to application.
In order to understand the present invention further, below in conjunction with embodiment, composite adhesive provided by the invention and preparation method thereof and glued board are specifically described.
The soybean protein powder used in following examples is defatted soybean meal, its protein content >=50%, lipid content < 2%, moisture content < 10%, ash oontent < 6%, purchased from Shandong mental faculties in quescent slate group.
Embodiment 1
100g melting phenol is dropped in four-hole boiling flask, adds 0.5g sodium hydroxide, stir, then 10g soybean protein powder is slowly added, be warming up to 70 DEG C, back flow reaction 180 minutes;
Being cooled to 60 DEG C, adding the formaldehyde solution 145g that concentration is 44%, is under the condition of 60 DEG C in temperature, back flow reaction 240 minutes;
Be cooled to 50 DEG C, add 5g urea, at this temperature back flow reaction 240 minutes, then add appropriate distilled water, cooling discharge, obtain composite adhesive.
According to method mentioned above, carry out performance test to the composite adhesive obtained, result is see table 1, and table 1 is the performance perameter of sizing agent prepared by the embodiment of the present invention and comparative example.
The performance perameter of sizing agent prepared by table 1 embodiment of the present invention and comparative example
As shown in Table 1, the free formaldehyde content of the composite adhesive of the embodiment of the present invention 1 preparation is extremely low.
According to method mentioned above, adopt the composite adhesive obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2, and table 2 is performance perameters of glued board prepared by the embodiment of the present invention and comparative example.
The performance perameter of glued board prepared by table 2 embodiment of the present invention and comparative example
As shown in Table 2, adopt composite adhesive provided by the invention, the glued board that intensity is high, water tolerance better, burst size of methanal is lower can be prepared.
Comparative example 1
100g melting phenol is dropped in four-hole boiling flask, adds 0.5g sodium hydroxide, stir;
Being warming up to 60 DEG C, adding the formaldehyde solution 145g that concentration is 44%, is under the condition of 60 DEG C in temperature, back flow reaction 240 minutes;
Be cooled to 50 DEG C, add 5g urea, at this temperature back flow reaction 240 minutes, then add appropriate distilled water, cooling discharge, obtain phenolic resin adhesive.
According to method mentioned above, carry out performance test to the phenolic resin adhesive obtained, result is see table 1.
According to method mentioned above, adopt the phenolic resin adhesive obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.
Embodiment 2
100g melting phenol is dropped in four-hole boiling flask, adds 10g sodium hydroxide, stir, then 100g soybean protein powder is slowly added, be warming up to 170 DEG C, back flow reaction 60 minutes;
Being cooled to 90 DEG C, adding the formaldehyde solution 362g that concentration is 44%, is under the condition of 90 DEG C in temperature, back flow reaction 60 minutes;
Then adding 100g urea, is under the condition of 90 DEG C in temperature, back flow reaction 60 minutes, then adds appropriate distilled water, cooling discharge, obtains composite adhesive.
According to method mentioned above, carry out performance test to the composite adhesive obtained, result is see table 1.As shown in Table 1, the free formaldehyde content of the composite adhesive of the embodiment of the present invention 2 preparation is extremely low.
According to method mentioned above, adopt the composite adhesive obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.As shown in Table 2, adopt composite adhesive provided by the invention, the glued board that intensity is high, water tolerance better, burst size of methanal is lower can be prepared.
Comparative example 2
100g melting phenol is dropped in four-hole boiling flask, adds 10g sodium hydroxide, stir;
Being warming up to 90 DEG C, adding the formaldehyde solution 362g that concentration is 44%, is under the condition of 90 DEG C in temperature, back flow reaction 60 minutes;
Then adding 100g urea, is under the condition of 90 DEG C in temperature, back flow reaction 60 minutes, then adds appropriate distilled water, cooling discharge, obtains phenolic resin adhesive.
According to method mentioned above, carry out performance test to the phenolic resin adhesive obtained, result is see table 1.
According to method mentioned above, adopt the phenolic resin adhesive obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.
Embodiment 3
100g melting phenol is dropped in four-hole boiling flask, adds 5g potassium hydroxide, stir, then 50g soybean protein powder is slowly added, be warming up to 140 DEG C, back flow reaction 100 minutes;
Being cooled to 80 DEG C, adding the formaldehyde solution 260g that concentration is 44%, is under the condition of 80 DEG C in temperature, back flow reaction 100 minutes;
Then adding 60g urea, is under the condition of 80 DEG C in temperature, back flow reaction 90 minutes, then adds appropriate distilled water, cooling discharge, obtains composite adhesive.
According to method mentioned above, carry out performance test to the composite adhesive obtained, result is see table 1.As shown in Table 1, the free formaldehyde content of the composite adhesive of the embodiment of the present invention 3 preparation is extremely low.
According to method mentioned above, adopt the composite adhesive obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.As shown in Table 2, adopt composite adhesive provided by the invention, the glued board that intensity is high, water tolerance better, burst size of methanal is lower can be prepared.
Comparative example 3
100g melting phenol is dropped in four-hole boiling flask, adds 5g potassium hydroxide, stir;
Being warming up to 80 DEG C, adding the formaldehyde solution 260g that concentration is 44%, is under the condition of 80 DEG C in temperature, back flow reaction 100 minutes;
Then adding 60g urea, is under the condition of 80 DEG C in temperature, back flow reaction 90 minutes, then adds appropriate distilled water, cooling discharge, obtains phenolic resin adhesive.
According to method mentioned above, carry out performance test to the phenolic resin adhesive obtained, result is see table 1.
According to method mentioned above, adopt the phenolic resin adhesive obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.
Comparative example 4
In four-hole bottle, add 200g water and 4g S-WAT, be mixed with sodium sulfite solution, then in described sodium sulfite solution, add 2g organo montmorillonite, stir 30 minutes, be uniformly dispersed, obtain mixed solution;
In described mixed solution, add 30g soybean protein powder, stir 30 minutes, until soybean protein powder is dispersed in water completely, obtain soybean adhesive, its.
According to method mentioned above, carry out performance test to the soybean adhesive, its obtained, result is see table 1.
According to method mentioned above, adopt the soybean adhesive, its obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.
Comparative example 5
Reaction flask is warming up to 50 DEG C, adds the sodium hydroxide solution 250g that preheated 500g phenol, 400g water and concentration are 40%, start stirring 10 minutes;
Then slowly add the formaldehyde solution 690g that concentration is 37%, be warming up to (90 ± 2) DEG C, be incubated 50 minutes at this temperature;
Be cooled to 70 DEG C, then in described reaction flask, slowly add sodium hydroxide solution described in formaldehyde solution described in 179g and 50g, be warming up to (90 ± 2) DEG C after 10 minutes, until viscosity is for being coated with-4 glasss 30 seconds ~ 32 seconds (20 DEG C), be cooled to 40 DEG C immediately, discharging, obtain resol.
80g soft water, 3g sodium carbonate and 35g soybean protein powder are joined in reaction flask, stirs, be warming up to 40 DEG C, insulation reaction 6 hours;
Then be cooled to 30 DEG C, be sequentially added into 1.2g borax and 0.5g Tai-Ace S 150 in mutually described reaction flask, stir, obtain soybean protein additive.
Be 50:50 according to ratio of weight and number, by described resol and soybean protein additives mixed even, obtain sizing agent.
According to method mentioned above, carry out performance test to the sizing agent obtained, result is see table 1.
According to method mentioned above, adopt the sizing agent obtained to prepare three layers of glued board, and carry out performance test to it, result is see table 2.
From above embodiment and comparative example, composite adhesive provided by the invention has good intensity and water tolerance, and product performance are suitable with phenolic resin adhesive, and free formaldehyde content is extremely low.In addition, composite adhesive provided by the invention adopts one-step synthesis method, and technique is simple, cost is lower, workable.
When applying described composite adhesive, the glued board that the present invention obtains is boiling 3h in the boiling water of 100 DEG C, bonding strength >=1.5MPa; After poach 4h, bonding strength can at more than 1MPa.Show that described Strength of Plywood is high, water-tolerant, its burst size of methanal is lower simultaneously.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a preparation method for composite adhesive, comprises the following steps:
A) plant protein powder, phenolic compound and basic cpd are mixed, back flow reaction, obtain the first reaction solution, the mass ratio of described plant protein powder and phenolic compound is (1 ~ 10): 10, the mass ratio of described basic cpd and phenolic compound is (0.5 ~ 10): 100, the temperature of described reaction is 70 DEG C ~ 170 DEG C, and the time of described reaction is 60min ~ 180min;
B) the first reaction solution that described step a) obtains is mixed with aldehyde compound, continue back flow reaction, obtain the second reaction solution;
C) by described step b) the second reaction solution of obtaining mixes with aminocompound, continues back flow reaction, obtain composite adhesive.
2. preparation method according to claim 1, is characterized in that, described step a) in, described plant protein powder be selected from soybean protein powder, gluten powder and Zein powder one or more;
Described phenolic compound be selected from phenol, cresols, Resorcinol and cardanol one or more.
3. preparation method according to claim 1, is characterized in that, described step a) in, described basic cpd be selected from sodium hydroxide, potassium hydroxide and ammoniacal liquor one or more.
4. preparation method according to claim 1, is characterized in that, described step b) in, described aldehyde compound be selected from formaldehyde, acetaldehyde, furfural and paraformaldehyde one or more;
The mol ratio of described aldehyde compound and phenolic compound is (2 ~ 5): 1.
5. preparation method according to claim 1, is characterized in that, described step b) in, the temperature of described reaction is 60 DEG C ~ 90 DEG C, and the time of described reaction is 60min ~ 240min.
6. preparation method according to claim 1, is characterized in that, described step c) in, described aminocompound be selected from urea, trimeric cyanamide and Dyhard RU 100 one or more;
The mass ratio of described aminocompound and phenolic compound is (0.5 ~ 10): 10.
7. preparation method according to claim 1, is characterized in that, described step c) in, the temperature of described reaction is 50 DEG C ~ 90 DEG C, and the time of described reaction is 60min ~ 240min.
8. a composite adhesive, is obtained by the preparation method described in any one of claim 1 to 7.
9. a glued board, uses the composite adhesive described in claim 8 to obtain.
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| CN107312481B (en) * | 2017-08-29 | 2020-11-10 | 阜南县力韦包装材料有限公司 | Modified phenolic resin adhesive |
| CN108214730A (en) * | 2018-02-09 | 2018-06-29 | 广西艾尚嘉家居有限公司 | A kind of production method of environmental protection five-ply board |
| CN109628033A (en) * | 2018-12-29 | 2019-04-16 | 广西六万山林业有限公司 | A kind of environmental protection type veneer board adhesive and the preparation method and application thereof |
| CN109705781A (en) * | 2018-12-29 | 2019-05-03 | 广西六万山林业有限公司 | A kind of Enviorment-protective Phenolic Resin glue and the preparation method and application thereof |
| CN113801616B (en) * | 2020-10-22 | 2023-05-12 | 广州源海新材料科技有限公司 | Modified lignin weather-resistant adhesive |
| CN112592684A (en) * | 2020-11-12 | 2021-04-02 | 来安县昆仑制桶有限公司 | Phenolic adhesive taking biomass as base material and preparation method thereof |
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| CN101319131A (en) * | 2008-07-23 | 2008-12-10 | 上海世鹏聚氨酯科技发展有限公司 | Non-methanal environment-friendly type plant protein modified adhesion agent |
| CN101511960A (en) * | 2006-08-31 | 2009-08-19 | 太尔公司 | Novel hybrid binder with natural compounds for low emission products |
| CN102120926A (en) * | 2010-12-29 | 2011-07-13 | 浙江省农业科学院 | Soybean protein adhesive and preparation method thereof |
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| CN101511960A (en) * | 2006-08-31 | 2009-08-19 | 太尔公司 | Novel hybrid binder with natural compounds for low emission products |
| CN101319131A (en) * | 2008-07-23 | 2008-12-10 | 上海世鹏聚氨酯科技发展有限公司 | Non-methanal environment-friendly type plant protein modified adhesion agent |
| CN102120926A (en) * | 2010-12-29 | 2011-07-13 | 浙江省农业科学院 | Soybean protein adhesive and preparation method thereof |
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Denomination of invention: Composite adhesive and its preparation method and plywood Effective date of registration: 20210908 Granted publication date: 20150923 Pledgee: China Co. truction Bank Corp Ji'nan Zhangqiu sub branch Pledgor: SHANDONG SHENGQUAN NEW MATERIAL Co.,Ltd. Registration number: Y2021980009038 |