CN1948416A - New technology of perparing formaldehyde less wood adhesion agent using vegetable raw material rich in protein - Google Patents
New technology of perparing formaldehyde less wood adhesion agent using vegetable raw material rich in protein Download PDFInfo
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- CN1948416A CN1948416A CN 200610124835 CN200610124835A CN1948416A CN 1948416 A CN1948416 A CN 1948416A CN 200610124835 CN200610124835 CN 200610124835 CN 200610124835 A CN200610124835 A CN 200610124835A CN 1948416 A CN1948416 A CN 1948416A
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Abstract
This invention relates to a new craft of making non formaldehyde wood adhesive with vegetality materials rich in protein, and its preparation is that (1) The protein from vegetality materials is dissolved and mechanically mixed with powder. (2)The mixture is conducted with homogeneous treatment by collid mill. (3) Adding compounding agent for allround regulation.(4)The ultimate product is obtained after the homogeneous treatment on protein. Its merits are as follows, simple craft, convenient operation, with completely no dependence of formaldehyde, carbolic acid, isocyanate, epoxy resin or other synthesis resins, only with a little no environmental pollution chemical engineering compounding agents making breakthrough of water tolerance of plant.
Description
Technical field
The present invention relates to the novel process that a kind of vegetable raw material with rich in proteins prepares formaldehyde-free wood adhesive.
Background technology
Along with world economy by industrialization society to the ecology social development, timber industry faces significant problems such as timber resource shortage, environment protection, this has just brought new opportunities and challenges for wood adhesive.Therefore how to utilize the wood adhesive of renewable resources research and development environmental protection to become the focus that countries in the world timber industry circle is paid close attention to gradually.
Though the leading glue kind of wood adhesive remains urea-formaldehyde resin, resol and trimeric cyanamide formal at present, but because since the nineties in 20th century, global oil is supplied with unbalance problem and is on the rise, the cost of material of adhesive made of synthetic resin climbs up and up and adds volatility obnoxious flavour in the adhesive made of synthetic resin such as free formaldehyde and free-phenol to reasons such as the harm of HUMAN HEALTH more and more receive publicity, and countries in the world are constantly strengthened the dynamics of low formaldehyde, formaldehyde-free wood adhesive research and development.Wherein again being that the wood adhesive of basic raw material exploitation environmental protection is main focus with biomass.At present, domestic and international research and development to the protein-based wood adhesive heat up once again.Albumin glue is one of the most ancient glue kind, and environmental sound and reproducible plant albumin glue adhesive are subject to people's attention day by day and favor.And along with the progress of science and technology, be on the increase in the plant protein material that can be utilized source.
Plant product with rich in proteins is that raw material making wood adhesive has two big bottleneck problems: the first, and the bonding strength of vegetable-protein glue is relative with water resisting property relatively poor; It two is, a little less than the antibiont degradation capability of vegetable-protein glue glue.Hindered the popularization of vegetable-protein base timber adhesive in modern timber processing thus.
Summary of the invention
The purpose of this invention is to provide the novel process that a kind of vegetable raw material with rich in proteins prepares formaldehyde-free wood adhesive, it solves the high base strength that the sex change of plant storage characteristics sphaeroprotein needs, and nearly neutral environment stable with vegetable protein glue and requirement for anticorrosion is difficult to unified contradiction.Adopt the composite and comprehensive anticorrosive measure of efficient industrial preservative to make the shelf time of vegetable protein glue extend to the length that possesses the commodity circulation system of entering.
The present invention is achieved like this, its step of preparation process is: (1) at room temperature, with the highly basic of protein component 0～7.5% in the vegetable raw material that is equivalent to rich in proteins be equivalent to the nitrogenous polar material of protein component 0～30% in the vegetable raw material of rich in proteins, be dissolved in the water of 0.5～1.75 times of the vegetable raw material dry weight that is equivalent to rich in proteins, the vegetable raw material powder with the rich in proteins of certain fineness carries out mechanically mixing and physical chemistry sex change again.(2) the final liquid-solid ratio that keeps the skin wet in the vegetable raw material through the rich in proteins of sex change is 2.55～7.55: 1, again mixture is carried out preliminary homogenization treatment by modern high new installations such as colloidal mills; (3) in vegetable protein glue, add a little auxiliary such as sanitas, buffer reagent, water-fast reinforcer, urease inhibitor and carry out comprehensively regulating by preliminary homogenization treatment; (4) will obtain the finished product by ultimate homogenization treatment equipment by the vegetable protein glue of conditioning.
The vegetable raw material of indication rich in proteins comprises that various leguminous plants seeds such as de-fatted soybean dregs, the defatted peanut dregs of rice, the degreasing wild soybean dregs of rice, Xiao Mai paddy ?albumen, zein, cassava crude protein extract the crude protein that produces behind grouts behind the grease and cereal, the starch plants separate tissue starch among the present invention;
The vegetable raw material of indication rich in proteins needs to pulverize before sex change among the present invention, at least by 40 mesh sieves;
Highly basic among the present invention refers to strong aqua, caustic soda, Ke Xingjia, soda ash etc., its consumption be rich in proteins the vegetable raw material dry weight 0～4.5%, optimum parameters is with 1.25～3.25%;
The nitrogenous polar material of indication refers to urea, thiocarbamide or Guanidinium hydrochloride among the present invention, its consumption be rich in proteins the vegetable raw material dry weight 0～30%, optimum parameters is with 8～12%;
The indication denaturation temperature is a room temperature among the present invention, is-25 ℃-+35 ℃ through the denaturation temperature interval of optimizing;
The low liquor ratio in indication sex change stage is a denaturant solution weight and the dry weight ratio of the vegetable raw material of rich in proteins among the present invention, and span 0.50～1.75, optimum parameters are 1.25～1.50;
The final liquid-solid ratio of the vegetable raw material of denaturant solution and rich in proteins is a span 2.75～7.0 in the vegetable-protein base timber adhesive of the present invention: 1, and optimum parameters is 2.85～6.15: 1;
Among the present invention the denaturation process of the vegetable raw material of indication rich in proteins be with denaturing agent to plant store the sphaeroprotein internal diffusion fully after, effect 1～24hr., optimum parameters is 8～12hr.;
The preliminary homogenization treatment of indication vegetable-protein base timber adhesive is that the denatured plant protein collagen material of adjusting solid content is handled to utilize various grinding plant such as colloidal mill, disk mill, ultrasonic disintegrator etc. among the present invention, but to be selection preferably by colloidal mill;
The new and effective industrial preservative of indication is a class high-efficiency low-toxicity, the sanitas soft to environment among the present invention, and they can both adapt to strong basicity, contain the environment of free ammonia, and can tolerate higher temperature (＜200 ℃).Comparatively suitable type has BIT series and MIT series etc., and the most suitable is BIT (1, the 2-benzisothiazole-3-ketone), and effective dose is 0.02%～0.12% (w/w, bean gum quality), and MIT0.03%～0.15% is composite.
Among the present invention the indication buffer reagent be meant can in and vegetable-protein glue strong basicity, and make vegetable-protein glue keep nearly neutral one class material, comprise mineral acid, organic acid, acidic oxidation starch etc., the most feasible is to adopt inorganic acid, vegetable-protein glue terminal point pH through overregulating is 5.0～7.5 feasible, preferably is controlled at 6.85～7.0;
The water-fast reinforcer of indication is the various environmental friendliness industrial chemicals or the natural products that can promote to form between the protein and peptide chain covalent cross-linking among the present invention, the general vegatable tannin that uses, usage quantity be in the vegetable-protein glue protein wt 0～0.01%, optimum parameters be in the vegetable-protein glue protein wt 0.005～0.006%.
The ultimate homogenization treatment equipment of indication mainly is various types of colloidal mills or clarifixator among the present invention, with the clarifixator of big flow for well.
Advantage of the present invention is: (1) adopts the plant storage sphaeroprotein sex change technology of low sex change dosage and high density and the process modification that homogenization treatment is carried out respectively.Realized not relying on fully under the prerequisite of formaldehyde, phenol, isocyanic ester, Resins, epoxy or other synthetic resins, only utilize a small amount of non-harmful auxiliary chemicals to realize the water-proof breakthrough of plant, prepared vegetable-protein glue has passed through the mechanics index of physics requirement of GB II class plate with glue GB (heat-resisting water); (2) find the important value in vegetable-protein glue is anticorrosion such as new and effective industrial preservative BIT, MIT, and the serial correlative factor that improves results of use such as BIT, MIT.Filter out vegetable-protein glue sanitas combination with remarkable role in synergy.
Embodiment
Embodiment one: raw material comprises low-temperature defatted dehulled soybean meal, conjugated protein denaturing agent, BIT, MIT, Weibull.
Low-temperature defatted dehulled soybean meal is a crude protein content more than 42.5%, the dregs of beans that does not go mouldy.Pulverize and cross 40 mesh sieves with beater disintegrating machine;
The conjugated protein denaturing agent is made up of for 125 parts 3 parts in caustic soda, 10 parts in urea, water;
In the low temperature soy meal powder of 100 kilograms of mistake 40 mesh sieves, add the agent of 138 kilograms of alkali urea complex denaturations, mix with the mixing screw brute force, the diffusion sex change is after 12 hours, keep the skin wet 175 kilograms, mixture is crossed in the mixing vessel that imports belt stirrer behind the colloidal mill, sulphuric acid soln with 30% is carefully regulated the potential of hydrogen of bean gum to pH6.85, add 0.24 kilogram of BIT sanitas, 1.25 kilograms of the 14%MIT aqueous solution, 0.15 kilogram of pyrocatechol is after stirring, after colloidal mill once, obtain about 408 kilograms of novel soybean base timber adhesives;
Embodiment two: raw material comprises low-temperature defatted peanut meal, the agent of alkali urea complex denaturation, BIT, MIT, Sodium Benzoate, pyrocatechol.
Raw material is a crude protein content more than 45%, the low-temperature defatted peanut meal that does not go mouldy.Pulverize and cross 40 mesh sieves with beater disintegrating machine;
The agent of alkali urea complex denaturation is made up of for 130 parts 2.75 parts in caustic soda, 8 parts in urea, water;
In the peanut meal powder of 100 kilograms of mistake 40 mesh sieves, add the agent of 140 kilograms of alkali urea complex denaturations, mix with the mixing screw brute force, the diffusion sex change is after 8 hours, keep the skin wet 180 kilograms, mixture is crossed in the mixing vessel that imports belt stirrer behind the colloidal mill, sulphuric acid soln with 30% is regulated the potential of hydrogen of bean gum to pH6.85, add 0.34 kilogram of BIT sanitas, 0.75 kilogram of the 14%MIT aqueous solution, molecular weight are 0.025 kilogram in 9000 Weibull, after stirring, (20-25MPa 1t/h), obtains about 420 kilograms of novel peanut meal base timber adhesives to cross clarifixator;
Embodiment three: raw material comprises soybean protein isolate, the agent of alkali urea complex denaturation, BIT, MIT, sulfuric acid, Weibull.
Raw material is the soybean protein isolate of crude protein content more than 85%.Pulverize and cross 100 mesh sieves with beater disintegrating machine;
The agent of alkali urea complex denaturation is made up of for 250 parts 3.5 parts in caustic soda, 6 parts in urea, water;
In the soybean isolate protein powder of 100 kilograms of mistake 20 mesh sieves, add the agent of 260 kilograms of alkali urea complex denaturations, mix with the mixing screw brute force, the diffusion sex change is after 3 hours, keep the skin wet 340 kilograms, mixture is crossed in the mixing vessel that imports belt stirrer behind the colloidal mill, sulphuric acid soln with 30% is regulated the potential of hydrogen of bean gum to pH7.0, add 0.45 kilogram of BIT sanitas, 0.45 kilogram of the 14%MIT aqueous solution, molecular weight is 0.05 kilogram in 9000 a Weibull, after stirring, crosses clarifixator (20-25MPa, 1t/h), obtain about 700 kilograms of novel soybean protein-based wood adhesives;
Embodiment four: raw material comprises cassava protein isolate, the agent of thiocarbamide Guanidinium hydrochloride complex denaturation, BIT, MIT, Weibull.
The cassava protein isolate is a crude protein content more than 75%, the product that does not go mouldy.Pulverize and cross 120 mesh sieves with beater disintegrating machine;
The agent of thiocarbamide Guanidinium hydrochloride complex denaturation is made up of for 225 parts 7 parts of thiocarbamides, 3 parts of Guanidinium hydrochlorides, water;
Cassava protein isolate to 100 kilograms of mistake 80 mesh sieves is in the crude protein powder, add the agent of 235 kilograms of thiocarbamide Guanidinium hydrochloride complex denaturations, mix with the mixing screw brute force, the diffusion sex change is after 10 hours, keep the skin wet 225 kilograms, mixture is crossed in the mixing vessel that imports belt stirrer behind the colloidal mill, add 0.25 kilogram of sanitas BIT, 0.75 kilogram of 14%MIT, molecular weight is 0.10 kilogram of 9000 single lemon acid, after stirring, crosses clarifixator (20-25MPa, 1t/h), obtain about 560 kilograms of novel soybean base timber adhesives;
Embodiment five: raw material comprises Xiao Mai paddy ?protein powder, alkali, the agent of thiocarbamide complex denaturation, BIT, MIT, citric acid, Resorcinol.
Xiao Mai paddy ?protein powder is a crude protein content more than 65%, the product that does not go mouldy.Pulverize and cross 40 mesh sieves with beater disintegrating machine;
Alkali, the agent of thiocarbamide complex denaturation are made up of for 186 parts 6 parts of soda ash, 8 parts of thiocarbamides, water;
In the Xiao Mai paddy ?of 100 kilograms of mistake 40 mesh sieves protein powder, add the agent of 200 kilograms of alkali thiocarbamide complex denaturations, mix with the mixing screw brute force, the diffusion sex change is after 12 hours, keep the skin wet 200 kilograms, mixture is crossed in the mixing vessel that imports belt stirrer behind the colloidal mill, the potential of hydrogen of regulating bean gum with 25% citric acid solution arrives pH6.95, add 0.35 kilogram of sanitas BIT, 0.70 kilogram of 14%MIT, 0.125 kilogram of Resorcinol.After stirring, (20-25MPa 1t/h), obtains about 500 kilograms of Xiao Mai paddy ?protein-based wood adhesives to cross clarifixator.
Claims (10)
1, a kind of vegetable raw material with rich in proteins prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that step of preparation process is: (1) at room temperature, with the highly basic of protein component 0～7.5% in the vegetable raw material that is equivalent to rich in proteins be equivalent to the nitrogenous polar material of protein component 0～30% in the vegetable raw material of rich in proteins, be dissolved in the water of 0.5～1.75 times of the vegetable raw material dry weight that is equivalent to rich in proteins, the vegetable raw material powder with the rich in proteins of certain fineness carries out mechanically mixing and physical chemistry sex change again; (2) the final liquid-solid ratio that keeps the skin wet in the vegetable raw material through the rich in proteins of sex change is 2.55～7.55: 1, again mixture is carried out preliminary homogenization treatment by modern high new installations such as colloidal mills; (3) in vegetable protein glue, add a little auxiliary such as sanitas, buffer reagent, water-fast reinforcer, urease inhibitor and carry out comprehensively regulating by preliminary homogenization treatment; (4) will obtain the finished product by ultimate homogenization treatment equipment by the vegetable protein glue of conditioning.
2, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, and the vegetable raw material that it is characterized in that rich in proteins comprises that various leguminous plants seeds such as de-fatted soybean dregs, the defatted peanut dregs of rice, the degreasing wild soybean dregs of rice, Xiao Mai paddy ?albumen, zein, cassava crude protein extract the crude protein that produces behind grouts behind the grease and cereal, the starch plants separate tissue starch;
3, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that highly basic refers to strong aqua, caustic soda, Ke Xingjia, soda ash etc., its consumption be rich in proteins the vegetable raw material dry weight 0～4.5%, optimum parameters is with 1.25～3.25%;
4, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that the nitrogen polar material refers to urea, thiocarbamide or Guanidinium hydrochloride, its consumption be rich in proteins the vegetable raw material dry weight 0～27%, optimum parameters is with 8～12%;
5, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that denaturation temperature is a room temperature, is-25 ℃-+35 ℃ through the denaturation temperature interval of optimizing;
6, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, the low liquor ratio that it is characterized in that the sex change stage is a denaturant solution weight and the dry weight ratio of the vegetable raw material of rich in proteins, span 0.50～1.75, optimum parameters are 1.25～1.50;
7, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, the final liquid-solid ratio that it is characterized in that the vegetable raw material of denaturant solution and rich in proteins in the vegetable-protein base timber adhesive is a span 2.75～7.0: 1, and optimum parameters is 2.85～6.15: 1;
8, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that the preliminary homogenization treatment of vegetable-protein base timber adhesive is that the denatured plant protein collagen material of adjusting solid content is handled to utilize various grinding plant such as colloidal mill, disk mill, ultrasonic disintegrator etc., but to be selection preferably by colloidal mill;
9, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that buffer reagent be meant can in and vegetable-protein glue strong basicity, and make vegetable-protein glue keep nearly neutral one class material, comprise mineral acid, organic acid, acidic oxidation starch etc., the most feasible is to adopt inorganic acid, vegetable-protein glue terminal point pH through overregulating is 5.0～7.5 feasible, preferably is controlled at 6.85～7.0;
10, a kind of vegetable raw material with rich in proteins according to claim 1 prepares the novel process of formaldehyde-free wood adhesive, it is characterized in that water-fast reinforcer is the various environmental friendliness industrial chemicals or the natural products that can promote to form between the protein and peptide chain covalent cross-linking, the general vegatable tannin that uses, usage quantity be in the vegetable-protein glue protein wt 0～0.01%, optimum parameters be in the vegetable-protein glue protein wt 0.005～0.006%.
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| CN 200610124835 CN1948416A (en) | 2006-10-20 | 2006-10-20 | New technology of perparing formaldehyde less wood adhesion agent using vegetable raw material rich in protein |
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| CN 200610124835 CN1948416A (en) | 2006-10-20 | 2006-10-20 | New technology of perparing formaldehyde less wood adhesion agent using vegetable raw material rich in protein |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009086752A1 (en) * | 2008-01-04 | 2009-07-16 | Guang Yang | A new lumber adhesive and the preparation thereof |
| CN101955748A (en) * | 2010-11-04 | 2011-01-26 | 漳州市圣木林业科技有限公司 | Formaldehyde-free corn protein powder wood adhesive and preparation method thereof |
| CN101402843B (en) * | 2008-11-18 | 2011-02-09 | 福建农林大学 | Metallic ion and active compound combined modified plant albumin glue adhesive and method of producing the same |
| CN102086371A (en) * | 2010-11-19 | 2011-06-08 | 南京林业大学 | Method for preparing antiseptic soy protein adhesive |
| CN101412899B (en) * | 2008-02-18 | 2011-06-22 | 河南新鼎科技发展有限公司 | Completely degradable plant protein wood adhesive and preparation thereof |
| CN101412898B (en) * | 2007-10-18 | 2011-08-24 | 中国科学院宁波材料技术与工程研究所 | Novel non-formaldehyde wood adhesive and preparation thereof |
| CN102295902A (en) * | 2011-06-24 | 2011-12-28 | 浙江农林大学 | Manufacturing method of oil-tea camellia meal protein adhesive |
| CN102504757A (en) * | 2011-11-29 | 2012-06-20 | 南开大学 | Biological environment-friendly adhesion agent and preparation method thereof |
| CN105969304A (en) * | 2016-05-31 | 2016-09-28 | 北京林业大学 | Soybean aldehyde-free adhesive and preparation method thereof |
| CN108203577A (en) * | 2017-12-24 | 2018-06-26 | 北京林业大学 | A kind of high reaction activity dregs of beans albumen and preparation method thereof |
| CN109796773A (en) * | 2019-01-23 | 2019-05-24 | 福建农林大学 | A kind of vegetable protein adhesive and the method for preparing wood-based plate |
| CN111019597A (en) * | 2019-12-02 | 2020-04-17 | 福建农林大学 | Vegetable protein-based adhesive and preparation method and application thereof |
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2006
- 2006-10-20 CN CN 200610124835 patent/CN1948416A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412898B (en) * | 2007-10-18 | 2011-08-24 | 中国科学院宁波材料技术与工程研究所 | Novel non-formaldehyde wood adhesive and preparation thereof |
| WO2009086752A1 (en) * | 2008-01-04 | 2009-07-16 | Guang Yang | A new lumber adhesive and the preparation thereof |
| CN101412899B (en) * | 2008-02-18 | 2011-06-22 | 河南新鼎科技发展有限公司 | Completely degradable plant protein wood adhesive and preparation thereof |
| CN101402843B (en) * | 2008-11-18 | 2011-02-09 | 福建农林大学 | Metallic ion and active compound combined modified plant albumin glue adhesive and method of producing the same |
| CN101955748A (en) * | 2010-11-04 | 2011-01-26 | 漳州市圣木林业科技有限公司 | Formaldehyde-free corn protein powder wood adhesive and preparation method thereof |
| CN102086371A (en) * | 2010-11-19 | 2011-06-08 | 南京林业大学 | Method for preparing antiseptic soy protein adhesive |
| CN102086371B (en) * | 2010-11-19 | 2013-04-24 | 南京林业大学 | Method for preparing antiseptic soy protein adhesive |
| CN102295902B (en) * | 2011-06-24 | 2012-09-05 | 浙江农林大学 | Manufacturing method of oil-tea camellia meal protein adhesive |
| CN102295902A (en) * | 2011-06-24 | 2011-12-28 | 浙江农林大学 | Manufacturing method of oil-tea camellia meal protein adhesive |
| CN102504757A (en) * | 2011-11-29 | 2012-06-20 | 南开大学 | Biological environment-friendly adhesion agent and preparation method thereof |
| CN102504757B (en) * | 2011-11-29 | 2013-05-01 | 南开大学 | Biological environment-friendly adhesion agent and preparation method thereof |
| CN105969304A (en) * | 2016-05-31 | 2016-09-28 | 北京林业大学 | Soybean aldehyde-free adhesive and preparation method thereof |
| CN105969304B (en) * | 2016-05-31 | 2018-12-18 | 北京林业大学 | A kind of aldehyde-free cement and preparation method thereof |
| CN108203577A (en) * | 2017-12-24 | 2018-06-26 | 北京林业大学 | A kind of high reaction activity dregs of beans albumen and preparation method thereof |
| CN109796773A (en) * | 2019-01-23 | 2019-05-24 | 福建农林大学 | A kind of vegetable protein adhesive and the method for preparing wood-based plate |
| CN111019597A (en) * | 2019-12-02 | 2020-04-17 | 福建农林大学 | Vegetable protein-based adhesive and preparation method and application thereof |
| CN111019597B (en) * | 2019-12-02 | 2020-11-13 | 福建农林大学 | Vegetable protein-based adhesive and preparation method and application thereof |
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