CN103709990A - Bio-enzyme modified plant protein base timber adhesive and preparation method thereof - Google Patents
Bio-enzyme modified plant protein base timber adhesive and preparation method thereof Download PDFInfo
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- CN103709990A CN103709990A CN201310660262.6A CN201310660262A CN103709990A CN 103709990 A CN103709990 A CN 103709990A CN 201310660262 A CN201310660262 A CN 201310660262A CN 103709990 A CN103709990 A CN 103709990A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a bio-enzyme modified plant protein base timber adhesive and a preparation method thereof. The preparation method of the plant protein base adhesive is as below: conducting homogenization, pH adjusting, enzymolysis, pH readjusting and anti-corrosion treatment on the components of, by weight, 20-30 parts of biomass containing plant protein, 60-120 parts of water, 0.20-1.50 parts of biological enzyme, 0.3-0.8 part of acid, 0.2-2.0 parts of alkali and 0.24-1.10 parts of a preservative. The adhesive uses renewable material sources, contains no toxic or harmful substance, is green and environment-friendly, has water endurance bonding strength reaching the level of grade II adhesive (indoor), and can be used for manufacturing of various indoor man-made boards. The preparation method of the adhesive reduces the use of chemicals, and has the effects of energy saving and emission reduction; and the adhesive overcomes the problems of harm to the health of producers and users and environment pollution caused by chemicals in ordinary adhesive.
Description
Technical field
The invention belongs to based Wood Adhesives preparing technical field, more specifically relate to a kind of formula of the enzyme modified vegetable-protein base based Wood Adhesives for antificielle plate, asepsis environment-protecting and preparation method thereof.
Background technology
Sizing agent is widely used in human society, and its raw material is mainly petroleum chemicals and natural reproducible resource.Wherein, the environment-friendly type sizing agent that the renewable resources of take is raw material, has agreed with mankind's environmental protection and Sustainable development requirement, is the important directions in sizing agent research.In various renewable resourcess, the biomass that contain vegetable-protein have the features such as activity is high, easy modification, are the preferred raw materials of preparing natural glue.For improving the water resistance of this type of sizing agent, main employing can be carried out modification to it with the chemical reagent of proteins react.Lei Hong etc. choose formaldehyde and Sodium dodecylbenzene sulfonate carries out modification to the soy protein adhesives of alkaline degradation, research thinks that these two kinds of reagent are all conducive to the raising [Lei Hong etc. of sizing agent water resistance, formaldehyde and the SDBS impact on alkaline degradation modified soy protein glue, forestry science and technology exploitation, 2013,27 (2): 81-84]; Kai Gu etc. prepares wood adhesive with polymine, maleic anhydride and sodium hydroxide modified bean powder, and for particle boards to manufacturing, its performance meets the minimum industrial requirements of M-2 level shaving board; Publication number is " the bean powder base based Wood Adhesives of sodium lauryl sulphate and glutaraldehyde modification " that the patent of invention of CN 101565597A is announced, by water, low-temperature defatted bean powder, sodium lauryl sulphate and glutaraldehyde, made, the sizing agent performance after modification improves; Although these researchs have improved the performance of soya-based sizing agent, all consumed a large amount of pharmaceutical chemicalss as properties-correcting agent, the producer and user's health is had to potential hazard.The patent of invention that the patent No. is respectively ZL201010550481.5, ZL201010550477.9, ZL201110117020.3 all provides modified soybean base adhesive formula and preparation method thereof; But all need to add a certain amount of solidifying agent or linking agent to obtain good water resistance.The operation easier that this has increased the producer and user, is unfavorable for applying of sizing agent.
Summary of the invention
The object of the present invention is to provide vegetable-protein base based Wood Adhesives formula of a kind of enzyme modified and preparation method thereof, utilized between small molecules carbohydrate and protein the principle that Maillard reaction can improve product water resistance has occurred, improved the water resistance of sizing agent; These sizing agent raw material sources are renewable, asepsis environment-protecting, and water proof bonding strength can reach the level of II class glue, is suitable for the production of antificielle plate; And preparation method is simple, without hazardous and noxious substances, participate in reaction, reduced the use to chemical reagent, there is the effect of energy-saving and emission-reduction.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified passes through homogeneous, regulates pH, biological enzyme enzymolysis, regulates pH, a rotproofing again for the biomass containing vegetable-protein, obtains vegetable-protein base based Wood Adhesives.
The concrete steps of described method are as follows:
1) will mix in container with water containing the biomass of vegetable-protein in proportion, by clarifixator with the pressure homogeneous of 5-20 MPa 2-5 time;
2) biomass-water mixture after homogeneous is placed in to reactor, controls temperature 20-35 ℃, add acid, reaction 5-15 minute;
3) be warming up to 40-65 ℃, add biological enzyme, reaction 15-50 minute;
4) be cooled to 20-35 ℃, add alkali, reaction 10-40 minute;
5) add sanitas, continue stirring and within 20-60 minute, obtain vegetable-protein base based Wood Adhesives.
In the preparation method of described vegetable-protein base based Wood Adhesives, each proportioning raw materials is: containing biomass 20-30 part of vegetable-protein, water 60-120 part, biological enzyme 0.20-1.50 part, sour 0.3-0.8 part, alkali 0.2-2.0 part, sanitas 0.24-1.10 part.
Described reactor adopts the reactor of temperature controllable and agitator speed, and sizing agent preparation process is started agitator from start to finish; Stirring velocity is 80-120 rev/min; Step 1) container is opened type conventional containers, and clarifixator is high pressure homogenizer.
The described biomass containing vegetable-protein are one or more mixtures in defatted soy flour, Zein powder, peanut powder, granularity 80-300 order.
Described water is distilled water or boiler blow-down water.
Described biological enzyme is one or both mixtures in cellulase, hemicellulose prozyme.
Described acid is one or more mixtures in the hydrochloric acid, acetic acid, citric acid of 30-45wt%; Described alkali is one or more mixtures in the calcium hydroxide, sodium hydroxide, potassium hydroxide of 5-30wt%.
Described sanitas is Sodium Benzoate, Whitfield's ointment, 1, one or more mixtures in 2-benzisothiazole-3-ketone, quaternary ammonium copper.
The vegetable-protein base based Wood Adhesives of the enzyme modified that described preparation method makes.
The vegetable-protein base based Wood Adhesives of producing with composition of raw materials of the present invention and method thereof has following features:
raw material sources are renewable, and the biomass that contain vegetable-protein are worldwide widely cultivated, the danger of powerlessness exhaustion.
produce and use procedure is green, nontoxic, environmental protection, do not use poisonous and hazardous chemical reagent, do not endanger the producer and user's health.
sizing agent self-crosslinkable solidifies, and the small molecules carbohydrate and the protein that in preparation process, produce, in sizing agent solidification process, Maillard reaction occurs, and forms self-crosslinking, can use less or without solidifying agent.
the sizing agent of preparation has good water-fast glue performance, can be used for glueing joint indoor type wood-based plate.
The present invention compared with prior art tool has the following advantages:
1. chemical reagent consumption is few, free from environmental pollution and harm the producer and user healthy;
2. enzyme modified efficiency is high, has the effect of energy-saving and emission-reduction;
3. utilize Maillard reaction to produce self-crosslinking, reduce solidifying agent and use, improved water resistance.
Embodiment
Each proportioning raw materials in the preparation method of the vegetable-protein base based Wood Adhesives of a kind of enzyme modified of the present invention is: containing biomass 20-30 part of vegetable-protein, water 60-120 part, biological enzyme 0.20-1.50 part, sour 0.3-0.8 part, alkali 0.2-2.0 part, sanitas 0.24-1.10 part.
The preparation of this sizing agent is carried out in reactor, and its concrete steps are as follows:
1. in proportion the biomass 20-30 part containing vegetable-protein is mixed in container with water 60-120 part;
2. by clarifixator with the pressure homogeneous of 5-20MPa 2-5 time;
3. biomass-the water mixture after homogeneous is placed in to reactor, controls temperature 20-35 ℃, add sour 0.3-0.8 part, reaction 5-15 minute;
4. be warming up to 40-65 ℃, add biological enzyme 0.20-1.50 part, reaction 15-50 minute;
5. be cooled to 20-35 ℃, add alkali 0.2-2.0 part, reaction 10-40 minute;
6. add sanitas 0.24-1.10 part, continue stirring and within 20-60 minute, obtain this sizing agent.
The present invention further illustrates in conjunction with following specific examples, but the present invention is not limited only to this.
Embodiment 1
By distilled water and defatted soy flour by weight mixing in opened type conventional containers for the ratio of 60:20; Again by high pressure homogenizer with the pressure homogeneous of 5MPa 5 times; By the defatted soy flour-water mixture after high-pressure homogeneous, be placed in temperature and be 35 ℃ and agitator speed and be the reactor of 90 revs/min, add the hydrochloric acid that 0.5 part of concentration is 30wt%, react 5 minutes; Be warming up to 55 ℃, add 0.20 portion of hemicellulase, continue reaction 20 minutes; Be cooled to 20 ℃, add the potassium hydroxide solution that 0.4 part of concentration is 30wt%, continue reaction 30 minutes; Add 0.24 part of Whitfield's ointment, continue to stir 20 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 2
By boiler blow-down water and Zein powder by weight mixing in opened type conventional containers for the ratio of 90:30; Again by high pressure homogenizer with the pressure homogeneous of 10MPa 3 times; By the Zein powder-water mixture after high-pressure homogeneous, be placed in temperature and be 20 ℃ and agitator speed and be the reactor of 120 revs/min, add the acetic acid that 0.3 part of concentration is 45wt%, react 10 minutes; Be warming up to 50 ℃, add 0.60 portion of hemicellulase, continue reaction 20 minutes; Be cooled to 30 ℃, add the potassium hydroxide solution that 0.2 part of concentration is 30wt%, continue reaction 20 minutes; Add 0.34 part of Sodium Benzoate, continue to stir 40 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 3
Sodium Benzoate and Whitfield's ointment is by weight mixing for the ratio of 2:1, standby.By distilled water and peanut powder by weight mixing in opened type conventional containers for the ratio of 75:25; Again by high pressure homogenizer with the pressure homogeneous of 15MPa 3 times; By the peanut powder-water mixture after high-pressure homogeneous, be placed in temperature and be 20 ℃ and agitator speed and be the reactor of 80 revs/min, add the hydrochloric acid that 0.3 part of concentration is 30wt%, react 15 minutes; Be warming up to 65 ℃, first add 0.50 portion of hemicellulase, then add 0.35 part of cellulase, continue reaction 40 minutes; Be cooled to 25 ℃, add the aqua calcis that 1.0 parts of concentration are 5wt%, continue reaction 30 minutes; Add 0.50 part of Sodium Benzoate and salicylic mixture, continue to stir 20 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 4
Defatted soy flour and Zein powder is by weight mixing for the ratio of 1:1, standby.By boiler blow-down water and defatted soy flour with the mixture of Zein powder by weight mixing in opened type conventional containers for the ratio of 120:30; Again by high pressure homogenizer with the pressure homogeneous of 20MPa 2 times; By the defatted soy flour-Zein powder-water mixture after high-pressure homogeneous, be placed in temperature and be 35 ℃ and agitator speed and be the reactor of 90 revs/min, add the hydrochloric acid that 0.8 part of concentration is 30wt%, react 10 minutes; Be warming up to 40 ℃, first add 0.80 portion of hemicellulase, then add 0.70 part of cellulase, continue reaction 50 minutes; Be cooled to 20 ℃, add the aqua calcis that 2.0 parts of concentration are 5wt%, continue reaction 40 minutes; Add 1.10 part 1,2-benzisothiazole-3-ketone, continue to stir 50 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 5
Defatted soy flour and peanut powder is by weight mixing for the ratio of 2:1, standby.By distilled water and defatted soy flour with the mixture of peanut powder by weight mixing in opened type conventional containers for the ratio of 120:30; Again by high pressure homogenizer with the pressure homogeneous of 13MPa 3 times; By the defatted soy flour-peanut powder-water mixture after high-pressure homogeneous, be placed in temperature and be 30 ℃ and agitator speed and be the reactor of 100 revs/min, add the citric acid that 0.8 part of concentration is 35wt%, react 12 minutes; Be warming up to 65 ℃, add 1.20 portions of hemicellulases, continue reaction 40 minutes; Be cooled to 30 ℃, add the aqua calcis that 1.0 parts of concentration are 8wt%, continue reaction 35 minutes; Add 0.80 part of quaternary ammonium copper, continue to stir 60 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 6
The acetic acid that is 30wt% by concentration with the citric acid of 30wt% by volume for the ratio of 1:2 is mixed, standby.By boiler blow-down water and defatted soy flour by weight mixing in opened type conventional containers for the ratio of 75:25; Again by high pressure homogenizer with the pressure homogeneous of 15MPa 4 times; By the defatted soy flour-water mixture after high-pressure homogeneous, be placed in temperature and be 30 ℃ and agitator speed and be the reactor of 120 revs/min, add the mixed solution of 0.5 part of acetic acid and citric acid, react 8 minutes; Be warming up to 60 ℃, add 0.80 portion of hemicellulase, continue reaction 40 minutes; Be cooled to 25 ℃, add the sodium hydroxide solution that 0.6 part of concentration is 20wt%, continue reaction 10 minutes; Add 1.10 parts of quaternary ammonium copper, continue to stir 30 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 7
By 25wt% sodium hydroxide with 25wt% potassium hydroxide solution by volume for the ratio of 1:2 is mixed, standby.By boiler blow-down water and peanut powder by weight mixing in opened type conventional containers for the ratio of 80:20; Again by high pressure homogenizer with the pressure homogeneous of 8MPa 4 times; By the peanut powder-water mixture after high-pressure homogeneous, be placed in temperature and be 20 ℃ and agitator speed and be the reactor of 90 revs/min, add the acetic acid that 0.4 part of concentration is 35wt%, react 10 minutes; Be warming up to 40 ℃, add 0.60 part of cellulase, continue reaction 30 minutes; Be cooled to 35 ℃, add the mixed solution of 0.8 part of sodium hydroxide and potassium hydroxide, continue reaction 30 minutes; Add 0.80 part of Sodium Benzoate, continue to stir 50 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Embodiment 8
1,2-benzisothiazole-3-ketone and quaternary ammonium copper are mixed by weight the ratio that is 1:1, standby.By boiler blow-down water and defatted soy flour by weight mixing in opened type conventional containers for the ratio of 90:30; Again by high pressure homogenizer with the pressure homogeneous of 18MPa 2 times; By the defatted soy flour-water mixture after high-pressure homogeneous, be placed in temperature and be 25 ℃ and agitator speed and be the reactor of 120 revs/min, add the acetic acid that 0.4 part of concentration is 45wt%, react 13 minutes; Be warming up to 50 ℃, first add 0.60 portion of hemicellulase, then add 0.40 part of cellulase, continue reaction 15 minutes; Be cooled to 30 ℃, add the sodium hydroxide solution that 0.8 part of concentration is 15wt%, continue reaction 20 minutes; Add 0.50 part 1,2-benzisothiazole-3-ketone and quaternary ammonium copper mixture, continue to stir 30 minutes a kind of vegetable-protein base based Wood Adhesives of enzyme modified.
Described in the present embodiment 1-8, a kind of vegetable-protein base based Wood Adhesives preparation process of enzyme modified is only used a small amount of chemical reagent (acid, alkali and sanitas), and solidification process does not need to add solidifying agent, is green chemical reaction process; When this sizing agent is used for making glued board, single spreading amount is 130-165g/m
2, can adopt the mode of manual gluing or cylinder gluing to realize; The hot pressing pressure 0.8-1.2MPa of pressing plate, temperature 130-150 ℃, time 0.8-1.5min/mm; Bonding strength all>=0.8MPa, reach the requirement (>=0.7MPa) of II class glued board in GB/T 9846-2004, burst size of methanal≤0.35 mg/L, reaches the E in GB/T 9846-2004
0level (≤0.5 mg/L).The vegetable-protein base based Wood Adhesives of a kind of enzyme modified of the present invention also can be used on other wood-based plates or woodwork beyond glued board.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. the preparation method of the vegetable-protein base based Wood Adhesives of an enzyme modified, it is characterized in that: containing the biomass of vegetable-protein, pass through homogeneous, regulate pH, biological enzyme enzymolysis, regulate pH, rotproofing again, obtain the vegetable-protein base based Wood Adhesives of enzyme modified.
2. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 1, is characterized in that: the concrete steps of described method are as follows:
1) will mix in container with water containing the biomass of vegetable-protein in proportion, by clarifixator with the pressure homogeneous of 5-20 MPa 2-5 time;
2) biomass-water mixture after homogeneous is placed in to reactor, controls temperature 20-35 ℃, add acid, reaction 5-15 minute;
3) be warming up to 40-65 ℃, add biological enzyme, reaction 15-50 minute;
4) be cooled to 20-35 ℃, add alkali, reaction 10-40 minute;
5) add sanitas, continue stirring and within 20-60 minute, obtain vegetable-protein base based Wood Adhesives.
3. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, it is characterized in that: in described preparation method, each proportioning raw materials is: containing biomass 20-30 part of vegetable-protein, water 60-120 part, biological enzyme 0.20-1.50 part, acid 0.3-0.8 part, alkali 0.2-2.0 part, sanitas 0.24-1.10 part.
4. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, is characterized in that: described reactor adopts the reactor of temperature controllable and agitator speed, and sizing agent preparation process is started agitator from start to finish; Stirring velocity is 80-120 rev/min; Step 1) container is opened type conventional containers, and clarifixator is high pressure homogenizer.
5. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, it is characterized in that: the described biomass containing vegetable-protein are one or more mixtures in defatted soy flour, Zein powder, peanut powder, granularity 80-300 order.
6. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, is characterized in that: described water is distilled water or boiler blow-down water.
7. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, is characterized in that: described biological enzyme is one or both mixtures in cellulase, hemicellulose prozyme.
8. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, is characterized in that: one or more mixtures in the hydrochloric acid that described acid is 30-45wt%, acetic acid, citric acid; Described alkali is one or more mixtures in the calcium hydroxide, sodium hydroxide, potassium hydroxide of 5-30wt%.
9. the preparation method of the vegetable-protein base based Wood Adhesives of enzyme modified according to claim 2, is characterized in that: described sanitas is Sodium Benzoate, Whitfield's ointment, 1, one or more mixtures in 2-benzisothiazole-3-ketone, quaternary ammonium copper.
10. the vegetable-protein base based Wood Adhesives of a kind of enzyme modified that preparation method makes as claimed in claim 1.
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| CN104908125A (en) * | 2015-05-29 | 2015-09-16 | 柳州市东汇木业有限公司 | Method for preparing sheet material gap filler |
| CN104908126A (en) * | 2015-05-29 | 2015-09-16 | 柳州市东汇木业有限公司 | Sheet material gap filler |
| CN104946198A (en) * | 2015-07-09 | 2015-09-30 | 福建农林大学 | Method for preparing wood adhesive by fermenting vegetable proteins with microorganisms |
| CN105885771A (en) * | 2015-12-16 | 2016-08-24 | 浙江海洋学院 | Preparation method of compound protein adhesive |
| CN106675515A (en) * | 2016-12-11 | 2017-05-17 | 孙祎 | Preparation method of green nontoxic easy-to-clean label adhesive |
| CN107880809A (en) * | 2017-11-23 | 2018-04-06 | 邓丽珍 | A kind of novel biomass resin |
| CN108977019A (en) * | 2018-05-18 | 2018-12-11 | 刘凡领 | A kind of preparation method of high viscosity high-leveling dumb light paint |
| CN109158252A (en) * | 2018-06-26 | 2019-01-08 | 南宁科天水性科技有限责任公司 | The glue stations and technique of the low sticky based Wood Adhesives of plant proteins |
| CN113684004A (en) * | 2021-09-18 | 2021-11-23 | 武汉轻工大学 | Preparation method of improved wheat protein adhesive |
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| CN104908125A (en) * | 2015-05-29 | 2015-09-16 | 柳州市东汇木业有限公司 | Method for preparing sheet material gap filler |
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| CN104946198A (en) * | 2015-07-09 | 2015-09-30 | 福建农林大学 | Method for preparing wood adhesive by fermenting vegetable proteins with microorganisms |
| CN104946198B (en) * | 2015-07-09 | 2017-03-15 | 福建农林大学 | A kind of method that utilization fermentable vegetable protein prepares based Wood Adhesives |
| CN105885771A (en) * | 2015-12-16 | 2016-08-24 | 浙江海洋学院 | Preparation method of compound protein adhesive |
| CN106675515A (en) * | 2016-12-11 | 2017-05-17 | 孙祎 | Preparation method of green nontoxic easy-to-clean label adhesive |
| CN106675515B (en) * | 2016-12-11 | 2018-12-07 | 深圳市上悦标签有限公司 | A kind of preparation method of green non-poisonous easy cleaning trademark adhesive |
| CN107880809A (en) * | 2017-11-23 | 2018-04-06 | 邓丽珍 | A kind of novel biomass resin |
| CN108977019A (en) * | 2018-05-18 | 2018-12-11 | 刘凡领 | A kind of preparation method of high viscosity high-leveling dumb light paint |
| CN109158252A (en) * | 2018-06-26 | 2019-01-08 | 南宁科天水性科技有限责任公司 | The glue stations and technique of the low sticky based Wood Adhesives of plant proteins |
| CN113684004A (en) * | 2021-09-18 | 2021-11-23 | 武汉轻工大学 | Preparation method of improved wheat protein adhesive |
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