CN103881633A - Composite adhesive and preparation method thereof, as well as plywood - Google Patents
Composite adhesive and preparation method thereof, as well as plywood Download PDFInfo
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- CN103881633A CN103881633A CN201410158157.7A CN201410158157A CN103881633A CN 103881633 A CN103881633 A CN 103881633A CN 201410158157 A CN201410158157 A CN 201410158157A CN 103881633 A CN103881633 A CN 103881633A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011120 plywood Substances 0.000 title abstract description 4
- 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 18
- 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
- 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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 71
- 238000000034 method Methods 0.000 abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 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 11
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000010992 reflux Methods 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 22
- 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
- 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
- 239000003292 glue Substances 0.000 description 6
- 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 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
- 230000015572 biosynthetic process Effects 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
- 230000006872 improvement Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing 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
- 150000007513 acids Chemical class 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
- 230000000975 bioactive 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
- 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
- 239000000203 mixture Substances 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 composite adhesive and a preparation method thereof. The method comprises the following steps: firstly mixing plant protein powder, a phenolic compound and an alkaline compound, and performing reaction under refluxing to obtain a first reaction solution; then mixing the obtained first reaction solution with an aldehyde compound, and continuously performing reaction under refluxing to obtain a second reaction solution; finally mixing the obtained second reaction solution with an amino compound and continuously performing reaction under refluxing to obtain the composite adhesive. The strength and the water-resistant bonding strength of the composite adhesive are equivalent to those of a phenolic resin adhesive; furthermore, the content of free aldehydes is lower, and the composite adhesive is suitable for producing various wood processing products. In addition, the composite adhesive has the advantages of low cost of preparation raw materials, simple process and environmental friendliness. The invention further provides a plywood, which is prepared by using the composite adhesive, has the advantages of high strength, good water resistance, low release of formaldehyde and the like, and is conductive to applications.
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 for timber glueds joint and woodwork is manufactured.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, what the processing of artificial board was mainly used is phenolic resin adhesive, urea-formaldehyde resin adhesive and melamine-formaldehyde resin adhesive glutinous agent, namely usually said " three-aldehyde glue ".The cohesive strength of three-aldehyde glue is good, still, in use continuous release formaldehyde of the artificial board that uses its manufacture, unfavorable to environmental and human health impacts.Therefore, the sizing agent of research and development comparison environmental protection has become an important problem in industry.
Protein is the polypeptide chain that is formed by connecting by peptide bond by multiple amino acids, is combined into and has complete bioactive molecule again by one or more than one polypeptide chains by mode separately, 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.In prior art, being no lack of the vegetable-protein of employing is the report that raw material is prepared based Wood Adhesives, such as, the Chinese patent literature that is CN101402842A as publication number discloses the salt-alkali combined modified rubber made from soybean cake stick of a kind of use, in the composition of raw materials of described rubber made from soybean cake stick, the parts by weight of each component are: 5～20 parts of defatted soyflours, 15～80 parts, water, 0.4～5.0 part of acid, 0.001～0.04 part of metal chloride, 1.2～27.0 parts of alkali lye.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 acids 2～5 and deionized water 90～120.
Above-mentioned research, all take vegetable-proteins such as soybean proteins as raw material, is carried out simple degraded to it and is prepared sizing agent, when application, although there is no the release of formaldehyde, relatively 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 preparation method who the invention provides a kind of composite adhesive, comprises 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 described step a) being obtained mixes with aldehyde compound, continues back flow reaction, obtains the second reaction solution;
C) the second reaction solution described step b) being obtained mixes with aminocompound, continues back flow reaction, obtains composite adhesive.
Preferably, in described step a), described plant protein powder is selected from one or more in soybean protein powder, gluten powder and Zein powder;
Described phenolic compound is selected from one or more in phenol, cresols, Resorcinol and cardanol;
The mass ratio of described plant protein powder and phenolic compound is (1～10): 10.
Preferably, in described step a), described basic cpd is selected from one or more in sodium hydroxide, potassium hydroxide and ammoniacal liquor;
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 ℃～170 ℃, and the time of described reaction is 60min～180min.
Preferably, in described step b), described aldehyde compound is selected from one or more in formaldehyde, acetaldehyde, furfural and paraformaldehyde;
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 ℃～90 ℃, and the time of described reaction is 60min～240min.
Preferably, in described step c), described aminocompound is selected from one or more in urea, trimeric cyanamide and Dyhard RU 100;
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 ℃～90 ℃, and the time of described reaction is 60min～240min.
The invention provides a kind of composite adhesive, preparation method by mentioned earlier makes.
Compared with prior art, first the present invention mixes plant protein powder, phenolic compound and basic cpd, and take phenolic compound as solvent, basic cpd is properties-correcting agent, back flow reaction is by protein degradation; Then the first reaction solution obtaining is mixed with aldehyde compound, take described basic cpd as catalyzer, back flow reaction novolak resin; Finally the second reaction solution obtaining is mixed with aminocompound, continue back flow reaction, the free aldehyde reaction in described aminocompound and reaction solution, obtains composite adhesive.In whole reaction process, phenolic compound is both as solvent and the degradation agents of plant protein powder, again as the synthesis material of resol; Basic cpd is both as the properties-correcting agent of plant protein powder, again as the synthetic catalyzer of resol; Aminocompound is as the synthetic formaldehyde reducing agent of resol.Due to twice DeR to plant protein powder of process basic cpd and phenolic compound in reaction process, plant protein powder is degraded more fully, and can participate in the building-up process of resol, reactant cross-linking density is large, and intensity and the water tolerance of thus obtained composite adhesive improve greatly.Owing to having used plant protein powder and aminocompound in building-up process, cost is lower compared with pure phenolic resin, and free formaldehyde content is lower, and environmental protection is suitable for promoting.
The present invention also provides a kind of glued board, uses composite adhesive mentioned above to make.
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 further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The preparation method who the invention discloses a kind of composite adhesive, comprises 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 described step a) being obtained mixes with aldehyde compound, continues back flow reaction, obtains the second reaction solution;
C) the second reaction solution described step b) being obtained mixes with aminocompound, continues back flow reaction, obtains 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, and raw material is easy to get, environmental protection, and cost is lower.Described plant protein powder is preferably one or more in soybean protein powder, gluten powder and Zein powder, and more preferably soybean protein powder, gluten powder or Zein powder, most preferably be soybean protein powder.The source of the present invention to described plant protein powder etc. 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 is preferably one or more in phenol, cresols, Resorcinol and cardanol, more preferably phenol.Wherein, described phenol is preferably molten state, preferably adopts melting phenol.In the present invention, the mass ratio of described plant protein powder and phenolic compound is preferably (1～10): 10, and more preferably (2～8): 10.
When plant protein powder is dissolved in phenolic compound, the present invention also adds basic cpd to carry out back flow reaction.Described basic cpd is both as the properties-correcting agent of plant protein powder, again as the synthetic catalyzer of resol.Described basic cpd is preferably one or more in sodium hydroxide, potassium hydroxide and ammoniacal liquor, 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, and more preferably (1～8): 100.
When mixing described plant protein powder, phenolic compound and basic cpd and 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 present invention is also not particularly limited the combination of above-mentioned material, as adopted the combination of soybean protein powder, phenol and sodium hydroxide, also can adopt the combination of Zein powder, phenol and potassium hydroxide etc.
In this back flow reaction of the present invention, the temperature of described reaction is preferably 70 ℃～170 ℃, more preferably 80 ℃～160 ℃; The time of described reaction is preferably 60min～180min, more preferably 80min～160min.
This back flow reaction of the present invention be mainly take phenolic compound as solvent, basic cpd is properties-correcting agent, reacts by backflow, by protein degradation, obtains the first reaction solution.
Obtain after the first reaction solution, the embodiment of the present invention is mixed it with aldehyde compound, preferably adds wherein aldehyde compound, 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 is preferably one or more in formaldehyde, acetaldehyde, furfural and paraformaldehyde, 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, and more preferably (2.5～4): 1.
In the present invention, this continues in back flow reaction, controls temperature and is preferably 60 ℃～90 ℃, more preferably 70 ℃～80 ℃; The time of described reaction is preferably 60min～240min, more preferably 80min～200min.
The present invention this to continue back flow reaction be mainly take phenolic compound and aldehyde compound as raw material, basic cpd are as catalyzer, react by backflow, novolak resin, obtains the second reaction solution.
Obtain after the second reaction solution, the embodiment of the present invention is mixed it with aminocompound, preferably adds wherein aminocompound, continues back flow reaction, obtains composite adhesive.
The present invention adopts aminocompound, with the free aldehyde reaction in the second reaction solution, and continues vegetable-protein to degrade.Described aminocompound is preferably one or more in urea, trimeric cyanamide and Dyhard RU 100, more preferably urea, and raw material is easy to get, is beneficial to operation.The mass ratio of described aminocompound and phenolic compound is preferably (0.5～10): 10, and more preferably (1～8): 10.
In the present invention, this continues in back flow reaction, controls temperature and is preferably 50 ℃～90 ℃, more preferably 70 ℃～80 ℃; The time of described reaction is preferably 60min～240min, more preferably 80min～200min.
After this continuation back flow reaction of the present invention finishes, 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 makes.
In whole reaction process, phenolic compound is both as solvent and the degradation agents of plant protein powder, again as the synthesis material of resol; Basic cpd is both as the properties-correcting agent of plant protein powder, again as the synthetic catalyzer of resol; Aminocompound is as the synthetic formaldehyde reducing agent of resol.Due to twice DeR to plant protein powder of process basic cpd and phenolic compound in reaction process, plant protein powder is degraded more fully, and can participate in the building-up process of resol, reactant cross-linking density is large, and intensity and the water tolerance of thus obtained composite adhesive improve greatly.Owing to having used plant protein powder and aminocompound in building-up process, cost is lower compared with pure phenolic resin, and free formaldehyde content is lower, and environmental protection is suitable for promoting.
In addition, the present invention adopts single stage method to synthesize described composite adhesive, and technique is workable.
Obtain after 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 ", content of free aldehyde, free phenol content and the viscosity etc. of the present invention to described composite adhesive are tested.Experiment shows, the free formaldehyde content of composite adhesive provided by the invention is lower.
The present invention also provides a kind of glued board, uses composite adhesive mentioned above to make.
Glued board is to glue together by multiple wood single-plates sizing agent three layers or the board-like material of multilayer forming, is one of household common used material.
The present invention is not particularly limited the kind of described timber, can adopt poplar and Eucalyptus etc.Length and width, thickness and the number of plies equal-specification of the present invention to described glued board is not particularly limited, and adopts the conventional specification in this area.
The present invention adopts composite adhesive mentioned above to glue together multiple wood single-plates, and the intensity of the glued board making is high, water-tolerant, burst size of methanal are lower.The present invention is not particularly limited the usage quantity of described composite adhesive, if one side resin added can be 60g/m
2～80g/m
2(glue dry weight basis).
Obtain after composite adhesive, the present invention uses it to prepare three layers of glued board, concrete grammar is: the board using poplar board that used thickness is 1.3mm～1.7mm is prepared 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 to 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 ℃～135 ℃, hot pressing time is 70s/mm, obtains three layers of glued board.
Obtain after 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, formaldehyde discharges limitation ", the present invention tests the free formaldehyde release of described three layers of glued board.Experiment demonstration, the glued board that the present invention obtains is boiling 3h in the boiling water of 100 ℃, bonding strength >=1.5MPa; After poach 4h, bonding strength can be 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 further to understand the present invention, 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 using 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, add 0.5g sodium hydroxide, stir, then 10g soybean protein powder is slowly added, be warming up to 70 ℃, back flow reaction 180 minutes;
Be cooled to 60 ℃, adding concentration is 44% formaldehyde solution 145g, is under the condition of 60 ℃ in temperature, back flow reaction 240 minutes;
Be cooled to 50 ℃, add 5g urea, back flow reaction 240 minutes at this temperature, then add appropriate distilled water, cooling discharge, obtains composite adhesive.
According to method mentioned above, the composite adhesive obtaining is carried out to performance test, result is referring to table 1, and table 1 is the performance perameter of the sizing agent prepared of 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
The free formaldehyde content of the composite adhesive that as shown in Table 1, prepared by the embodiment of the present invention 1 is extremely low.
According to method mentioned above, adopt the composite adhesive that obtains to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2, and table 2 is performance perameters of the glued board prepared of 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, can prepare the glued board that intensity is high, water tolerance better, burst size of methanal is lower.
Comparative example 1
100g melting phenol is dropped in four-hole boiling flask, add 0.5g sodium hydroxide, stir;
Be warming up to 60 ℃, adding concentration is 44% formaldehyde solution 145g, is under the condition of 60 ℃ in temperature, back flow reaction 240 minutes;
Be cooled to 50 ℃, add 5g urea, back flow reaction 240 minutes at this temperature, then add appropriate distilled water, cooling discharge, obtains phenolic resin adhesive.
According to method mentioned above, the phenolic resin adhesive obtaining is carried out to performance test, result is referring to table 1.
According to method mentioned above, adopt the phenolic resin adhesive obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2.
Embodiment 2
100g melting phenol is dropped in four-hole boiling flask, add 10g sodium hydroxide, stir, then 100g soybean protein powder is slowly added, be warming up to 170 ℃, back flow reaction 60 minutes;
Be cooled to 90 ℃, adding concentration is 44% formaldehyde solution 362g, is under the condition of 90 ℃ in temperature, back flow reaction 60 minutes;
Then adding 100g urea, is under the condition of 90 ℃ in temperature, back flow reaction 60 minutes, then add appropriate distilled water, cooling discharge, obtains composite adhesive.
According to method mentioned above, the composite adhesive obtaining is carried out to performance test, result is referring to table 1.The free formaldehyde content of the composite adhesive that as shown in Table 1, prepared by the embodiment of the present invention 2 is extremely low.
According to method mentioned above, adopt the composite adhesive obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2.As shown in Table 2, adopt composite adhesive provided by the invention, can prepare the glued board that intensity is high, water tolerance better, burst size of methanal is lower.
Comparative example 2
100g melting phenol is dropped in four-hole boiling flask, add 10g sodium hydroxide, stir;
Be warming up to 90 ℃, adding concentration is 44% formaldehyde solution 362g, is under the condition of 90 ℃ in temperature, back flow reaction 60 minutes;
Then adding 100g urea, is under the condition of 90 ℃ in temperature, back flow reaction 60 minutes, then add appropriate distilled water, cooling discharge, obtains phenolic resin adhesive.
According to method mentioned above, the phenolic resin adhesive obtaining is carried out to performance test, result is referring to table 1.
According to method mentioned above, adopt the phenolic resin adhesive obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2.
Embodiment 3
100g melting phenol is dropped in four-hole boiling flask, add 5g potassium hydroxide, stir, then 50g soybean protein powder is slowly added, be warming up to 140 ℃, back flow reaction 100 minutes;
Be cooled to 80 ℃, adding concentration is 44% formaldehyde solution 260g, is under the condition of 80 ℃ in temperature, back flow reaction 100 minutes;
Then adding 60g urea, is under the condition of 80 ℃ in temperature, back flow reaction 90 minutes, then add appropriate distilled water, cooling discharge, obtains composite adhesive.
According to method mentioned above, the composite adhesive obtaining is carried out to performance test, result is referring to table 1.The free formaldehyde content of the composite adhesive that as shown in Table 1, prepared by the embodiment of the present invention 3 is extremely low.
According to method mentioned above, adopt the composite adhesive obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2.As shown in Table 2, adopt composite adhesive provided by the invention, can prepare the glued board that intensity is high, water tolerance better, burst size of methanal is lower.
Comparative example 3
100g melting phenol is dropped in four-hole boiling flask, add 5g potassium hydroxide, stir;
Be warming up to 80 ℃, adding concentration is 44% formaldehyde solution 260g, is under the condition of 80 ℃ in temperature, back flow reaction 100 minutes;
Then adding 60g urea, is under the condition of 80 ℃ in temperature, back flow reaction 90 minutes, then add appropriate distilled water, cooling discharge, obtains phenolic resin adhesive.
According to method mentioned above, the phenolic resin adhesive obtaining is carried out to performance test, result is referring to table 1.
According to method mentioned above, adopt the phenolic resin adhesive obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to 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, the soybean adhesive, its obtaining is carried out to performance test, result is referring to table 1.
According to method mentioned above, adopt the soybean adhesive, its obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2.
Comparative example 5
Reaction flask is warming up to 50 ℃, adds the sodium hydroxide solution 250g that preheated 500g phenol, 400g water and concentration are 40%, start and stir 10 minutes;
Then slowly adding concentration is 37% formaldehyde solution 690g, is warming up to (90 ± 2) ℃, at this temperature, is incubated 50 minutes;
Be cooled to 70 ℃, then, to slowly adding described in 179g sodium hydroxide solution described in formaldehyde solution and 50g in described reaction flask, after 10 minutes, be warming up to (90 ± 2) ℃, until viscosity is for being coated with-4 glasss 30 seconds～32 seconds (20 ℃), be cooled to immediately 40 ℃, discharging, obtains resol.
80g soft water, 3g sodium carbonate and 35g soybean protein powder are joined in reaction flask, stir, be warming up to 40 ℃, insulation reaction 6 hours;
Then be cooled to 30 ℃, in mutually described reaction flask, be sequentially added into 1.2g borax and 0.5g Tai-Ace S 150, stir, obtain soybean protein additive.
Be 50:50 according to ratio of weight and number, by even to described resol and soybean protein additives mixed, obtain sizing agent.
According to method mentioned above, the sizing agent obtaining is carried out to performance test, result is referring to table 1.
According to method mentioned above, adopt the sizing agent obtaining to prepare three layers of glued board, and it is carried out to performance test, result is referring to table 2.
From above embodiment and comparative example, composite adhesive provided by the invention has good intensity and water tolerance, and product performance and phenolic resin adhesive are suitable, and free formaldehyde content is extremely low.In addition, composite adhesive provided by the invention adopts single stage method synthetic, and technique is simple, cost is lower, workable.
While applying described composite adhesive, the glued board that the present invention obtains is boiling 3h in the boiling water of 100 ℃, bonding strength >=1.5MPa; After poach 4h, bonding strength can be 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 is just for helping to understand method of the present invention and core concept thereof.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 improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
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, obtains the first reaction solution;
B) the first reaction solution described step a) being obtained mixes with aldehyde compound, continues back flow reaction, obtains the second reaction solution;
C) the second reaction solution described step b) being obtained mixes with aminocompound, continues back flow reaction, obtains composite adhesive.
2. preparation method according to claim 1, is characterized in that, in described step a), described plant protein powder is selected from one or more in soybean protein powder, gluten powder and Zein powder;
Described phenolic compound is selected from one or more in phenol, cresols, Resorcinol and cardanol;
The mass ratio of described plant protein powder and phenolic compound is (1～10): 10.
3. preparation method according to claim 1, is characterized in that, in described step a), described basic cpd is selected from one or more in sodium hydroxide, potassium hydroxide and ammoniacal liquor;
The mass ratio of described basic cpd and phenolic compound is (0.5～10): 100.
4. preparation method according to claim 1, is characterized in that, in described step a), the temperature of described reaction is 70 ℃～170 ℃, and the time of described reaction is 60min～180min.
5. preparation method according to claim 1, is characterized in that, in described step b), described aldehyde compound is selected from one or more in formaldehyde, acetaldehyde, furfural and paraformaldehyde;
The mol ratio of described aldehyde compound and phenolic compound is (2～5): 1.
6. preparation method according to claim 1, is characterized in that, in described step b), the temperature of described reaction is 60 ℃～90 ℃, and the time of described reaction is 60min～240min.
7. preparation method according to claim 1, is characterized in that, in described step c), described aminocompound is selected from one or more in urea, trimeric cyanamide and Dyhard RU 100;
The mass ratio of described aminocompound and phenolic compound is (0.5～10): 10.
8. preparation method according to claim 1, is characterized in that, in described step c), the temperature of described reaction is 50 ℃～90 ℃, and the time of described reaction is 60min～240min.
9. a composite adhesive, is made by the preparation method described in claim 1 to 8 any one.
10. a glued board, right to use requires the composite adhesive described in 9 to make.
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| CN107312481A (en) * | 2017-08-29 | 2017-11-03 | 阜南县力韦包装材料有限公司 | A kind of 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 |
| CN112175558A (en) * | 2020-10-22 | 2021-01-05 | 彭娜 | Modified lignin weather-resistant adhesive and preparation method thereof |
| 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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| CN107312481A (en) * | 2017-08-29 | 2017-11-03 | 阜南县力韦包装材料有限公司 | A kind of modified phenolic resin adhesive |
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| CN112175558B (en) * | 2020-10-22 | 2021-10-22 | 宁波赫革丽高分子科技有限公司 | Modified lignin weather-resistant adhesive and preparation method thereof |
| 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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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 |