CN102559097A - Preparation method of cassava starch based biomass formaldehyde-free wood adhesive - Google Patents
Preparation method of cassava starch based biomass formaldehyde-free wood adhesive Download PDFInfo
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- CN102559097A CN102559097A CN2011104543361A CN201110454336A CN102559097A CN 102559097 A CN102559097 A CN 102559097A CN 2011104543361 A CN2011104543361 A CN 2011104543361A CN 201110454336 A CN201110454336 A CN 201110454336A CN 102559097 A CN102559097 A CN 102559097A
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Abstract
The invention discloses a preparation method of a cassava starch based biomass formaldehyde-free wood adhesive. The preparation method comprises that cassava starch and polyvinyl alcohol are taken as main raw materials of the formaldehyde-free wood adhesive and then are respectively modified, thus the cassava starch based biomass formaldehyde-free wood adhesive is obtained. The preparation method disclosed by the invention has the beneficial effects that: 1, the technical problem that biological glue has poor water resistance, low bonding strength and low solid content of starch glue is solved, and a production method for preparing the formaldehyde-free wood adhesive by taking the cassava starch as a base material is provided; and 2, artificial panel industry and cassava industry with resource superiority in Guangxi province are promoted to be developed and expanded, labour employment of hundreds of thousands of people in urban and rural areas can be solved, and harmonious development of national economy and society in China is promoted, thus the preparation method disclosed by the invention has wide application prospect.
Description
Technical field
The present invention relates to the technical field of timber sizing agent, specifically is the preparation method of tapioca(flour) based biomass non-formaldehyde wood sizing agent.
Background technology
Since 21 century, tackiness agent demonstrates its powerful life and vigor, and is most important to people's life, and it not only has practicality widely, and createed considerable economic and social benefit.Because lack core technology, the tackiness agent of wood-based plate that China produces is main with " three-aldehyde glue " still, volatilizes obnoxious flavour--formaldehyde makes China's wood-based plate on total quality, be in " low side " level of world's wood-based plate industry " E2 level ".Because high-performance, high-quality tackiness agent belong to high-tech product, though the China market demand is urgent, its technical sophistication, development difficulty is bigger, and global high-end tackiness agent is always by a few developed country's oligopoly.At present, developed countries such as America and Europe carry out the strategic action of " research and development before the competition ", utilize renewable resources to make tackiness agent, attempt to find as early as possible a kind of ability to substitute the no aldehyde type wood adhesive of " three-aldehyde glue ", the environmental protection standard of wood-based plate are reached " E0 level ".Therefore, who can successfully research and develop no aldehyde glue as early as possible, just can make the wood-based plate occupying inter-national market of its production, becomes surging brand.The wood-based plate of China more than 95% do not use this type of tackiness agent at present, and the expert estimates that following 10 years " biomass-based wood adhesive " has breakthrough growth in China, becomes the Chaoyang industry that has bright spot, and the nontoxic glue of novel green will replace three-aldehyde glue.
There are abundant timber and cassava resource in my district, and fast Feng Lin reserved resources is the first in the nation, and the cassava YO is 3,800,000 tons, account for 60% of the whole nation, but both is worth all always with the primary products supply the market for a long time lower.Therefore; Resources advantage in conjunction with Guangxi; With the tapioca(flour) is main material production starch-based bio matter non-formaldehyde wood adhesive; Make it to become and produce the non-formaldehyde wood adhesive raw material, solve the industrialization problem of cassava and timber from the product source, this will bring a kind of new mode of thinking and the change of product structure to cassava and wood industry.Simultaneously, also will promote the exploitation of a series of timber industry derived product, not have aldehyde wood-based panel product etc. such as various E0 levels.Therefore, no aldehyde glue and sheet material thereof will be wood adhesive and artificial board industry development.At present; The domestic report that does not also have starch-based not have aldehyde glue and sheet material industrialization production thereof; It is the good job of benefiting the nation and the people that the development and popularization using environment-friendly does not have aldehyde glue, will promote Guangxi to have the development and the growth of the artificial board industry and the cassava industry of resources advantage, can solve town and country hundreds of thousands of people's labour employment; Promote me to distinguish national economy and social harmonious development, so this project has wide application prospect.
Summary of the invention
The objective of the invention is for a little less than solving xanthan gum poor water resistance, bonding strength, technical problem such as the amylan solid content is low, providing a kind of is the method that base-material prepares the non-formaldehyde wood sizing agent with the tapioca(flour).
The technical scheme that the present invention solves the problems of the technologies described above is following.
The preparation method of tapioca(flour) based biomass non-formaldehyde wood sizing agent is to be the main raw material of non-formaldehyde wood sizing agent with tapioca(flour), Z 150PH; Respectively it is carried out modification then; And synthetic make tapioca(flour) based biomass non-formaldehyde wood sizing agent, the concrete operations step is following:
1. the modification of Z 150PH
Modified polyvinyl alcohol glue is by Z 150PH, water, oxygenant H
2O
2And catalyst Fe SO
47H
2The O hybrid reaction makes; With mass ratio is that 1: 4～1: 6 Z 150PH and water adds after reaction kettle soaks 10～12h; Heating while stirring makes homo(io)thermism between 90～96 ℃; Behind the dissolving 90min, naturally cool to about 60 ℃, adding massfraction then is the catalyst Fe SO of Z 150PH quality 0.4%～0.6%
47H
2O, slowly adding massfraction again is the pure H of Z 150PH quality 3.5%～4.5%
2O
2, maintaining the temperature between 58～65 ℃ and react, reaction naturally cools to room temperature after finishing, and makes modified polyethylene alcohol glue.
2. the modification of tapioca(flour)
The tapioca(flour) modification is by tapioca(flour), linking agent oxalic dialdehyde and catalyst Fe SO
47H
2The O hybrid reaction is produced, and is 40% the glyoxal solution weight by tapioca(flour) with tapioca(flour) and mass concentration: the volume of mass concentration 40% glyoxal solution=mix at 100: 30, and to add massfraction be the FeSO of tapioca(flour) quality 3%
47H
2O is at 1000rmin
-1Speed under stir 30min after, be placed on reacting by heating in the microwave oven, microwave power is set at 500W, temperature of reaction is 60～70 ℃, the reaction times is 45min.
3. tapioca(flour) based biomass aldehyde-free cement is synthetic
Tapioca(flour) based biomass aldehyde-free cement is made by modified polyvinyl alcohol glue, modified tapioca starch, benzene emulsion and initiator ammonium persulfate hybrid reaction; To account for the modified polyvinyl alcohol glue of total quality of material 68～72% and the benzene emulsion uniform mixing of total quality of material 8～10% earlier; Progressively add the modified tapioca starch and the ammonium persulphate that accounts for modified tapioca starch quality 1～2% of shared total quality of material 19～22% more in batches, stir and promptly obtain tapioca(flour) based biomass aldehyde-free cement.
The preparation method of tapioca(flour) based biomass non-formaldehyde wood sizing agent is to be the main raw material of non-formaldehyde wood sizing agent with tapioca(flour), Z 150PH; Respectively it is carried out modification then; And synthetic make tapioca(flour) based biomass non-formaldehyde wood sizing agent, the concrete operations step is following:
1. the modification of Z 150PH
Modified polyvinyl alcohol glue is by Z 150PH, water, oxygenant H
2O
2And catalyst Fe SO
47H
2The O hybrid reaction makes; With mass ratio is that 1: 4～1: 6 Z 150PH and water adds after reaction kettle soaks 10～12h; Heating while stirring makes homo(io)thermism between 90～96 ℃; Behind the dissolving 90min, naturally cool to about 60 ℃, add massfraction then and be 0.4%～0.6% catalyst Fe SO of Z 150PH quality
47H
2O slowly adds massfraction and is 3.5%～4.5% pure H of Z 150PH quality again
2O
2, maintaining the temperature between 58～65 ℃ and react, reaction naturally cools to room temperature after finishing, and makes modified polyethylene alcohol glue;
2. the modification of tapioca(flour)
The tapioca(flour) modification is by tapioca(flour), linking agent oxalic dialdehyde and catalyst Fe SO
47H
2The O hybrid reaction is produced, and is 40% glyoxal solution with tapioca(flour) and mass concentration by tapioca(flour) weight: glyoxal solution (mass concentration 40%) volume=mix at 100: 30, and to add massfraction be the FeSO of tapioca(flour) quality 3%
47H
2O is at 1000rmin
-1Speed under stir 30min after, be placed on reacting by heating in the microwave oven, microwave power is set at 500W, temperature of reaction is 60～70 ℃, the reaction times is 45min.
3. tapioca(flour) based biomass aldehyde-free cement is synthetic
Tapioca(flour) based biomass aldehyde-free cement is made by modified polyvinyl alcohol glue, modified tapioca starch, benzene emulsion and initiator ammonium persulfate hybrid reaction; To account for total quality of material mark earlier and be 68～72% modified polyvinyl alcohol glue and 8～10% benzene emulsion uniform mixing; Progressively add shared total quality of material mark again is 19～22% modified tapioca starch and the ammonium persulphate that accounts for modified tapioca starch quality 1～2% in batches, stirs and promptly obtains tapioca(flour) based biomass aldehyde-free cement.
The method of use of synthetic tapioca(flour) based biomass non-formaldehyde wood adhesive is under condition of the present invention: every square metre of uniform gluing 250～270g; The normal temperature 40min that colds pressing under 5MPa pressure; Be 5MPa at pressure again, temperature is 120 ℃ of following hot pressing certain hours (being generally the 1min/mm thickness of slab).The dry glue intensity maximum of the wood veneer that under such pressing plate condition, prepares has reached 1.91MPa; Wet bonding strength maximum has reached 0.68MPa; Near the requirement of wood veneer national standard II class plate, be 0.40mg/L through the burst size of methanal that detects five layers of (9mm) wood veneer, be lower than E
0The standard of level (0.50mg/L).
Beneficial effect of the present invention is:
1. solved technical problems such as xanthan gum poor water resistance, bonding strength is weak, the amylan solid content is low, providing a kind of is the working method that base-material prepares the non-formaldehyde wood sizing agent with the tapioca(flour).
2. promote development and the growth that Guangxi has the artificial board industry and the cassava industry of resources advantage, can solve town and country hundreds of thousands of people's labour employment, promote me to distinguish national economy and social harmonious development, so this project has wide application prospect.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1
With mass ratio is that 1: 4 Z 150PH and water adds reaction kettle and soaks 12h, and heating while stirring makes homo(io)thermism in 90 ℃, behind the dissolving 90min, naturally cools to about 60 ℃, and adding massfraction then is the catalyst Fe SO of Z 150PH quality 0.6%
47H
2O, slowly adding massfraction again is the pure H of Z 150PH quality 4.5%
2O
2, maintaining the temperature at 60 ℃ and react, reaction naturally cools to room temperature after finishing, and makes modified polyethylene alcohol glue.
Tapioca(flour) and mass concentration 40% glyoxal solution are pressed 100: 30 (g/ml) mixed, and the adding massfraction is the FeSO of tapioca(flour) 3%
47H
2O is earlier at 1000rmin
-1Speed under stir 30min after, be placed on reacting by heating in the microwave oven, microwave power is set at 500W, temperature of reaction is 60 ℃, the reaction times is 45min.
At normal temperatures; To account for the modified polyvinyl alcohol glue of total quality of material 72% and the benzene emulsion uniform mixing of total quality of material 9% earlier; Progressively add modified tapioca starch that accounts for total quality of material 19% and the ammonium persulphate that accounts for modified tapioca starch quality 1.0% more in batches, stir and promptly obtain tapioca(flour) based biomass aldehyde-free cement.
The tackiness agent salient features
| Index name | Unit | Numerical value |
| Outward appearance | Light yellow | |
| The pH value | 6.5～7.5 | |
| Solids content | ％ | 38.2 |
| Burst size of methanal | mg/L | ＜0.4 |
| Viscosity | s | 250 |
| Working life | min | 310 |
| Bonding strength | MPa | 1.91 |
Embodiment 2
With mass ratio is that 1: 5 Z 150PH and water adds reaction kettle and soaks 11h, and heating while stirring makes homo(io)thermism in 93 ℃, behind the dissolving 90min, naturally cools to about 60 ℃, and adding massfraction then is the catalyst Fe SO of Z 150PH quality 0.5%
47H
2O, slowly adding massfraction again is the pure H of Z 150PH quality 4.0%
2O
2, maintaining the temperature at 58 ℃ and react, reaction naturally cools to room temperature after finishing, and makes modified polyethylene alcohol glue.
Tapioca(flour) and mass concentration 40% glyoxal solution are pressed 100: 30 (g/ml) mixed, and the adding massfraction is the FeSO of tapioca(flour) 3%
47H
2O is earlier at 1000rmin
-1Speed under stir 30min after, be placed on reacting by heating in the microwave oven, microwave power is set at 500W, temperature of reaction is 65 ℃, the reaction times is 45min.
At normal temperatures; To account for the modified polyvinyl alcohol glue of total quality of material 68% and the benzene emulsion uniform mixing of total quality of material 10% earlier; Progressively add modified tapioca starch that accounts for total quality of material 22% and the ammonium persulphate that accounts for modified tapioca starch quality 1.5% more in batches, stir and promptly obtain tapioca(flour) based biomass aldehyde-free cement.
The tackiness agent salient features
| Index name | Unit | Numerical value |
| Outward appearance | Light yellow | |
| The pH value | 6.5～7.5 | |
| Solids content | ％ | 38.5 |
| Burst size of methanal | mg/L | ＜0.4 |
| Viscosity | s | 256 |
| Working life | min | 300 |
| Bonding strength | MPa | 1.63 |
Embodiment 3
With mass ratio is that 1: 6 Z 150PH and water adds reaction kettle and soaks 10h, and heating while stirring makes homo(io)thermism in 96 ℃, behind the dissolving 90min, naturally cools to about 60 ℃, and adding massfraction then is the catalyst Fe SO of Z 150PH quality 0.4%
47H
2O, slowly adding massfraction again is the pure H of Z 150PH quality 3.5%
2O
2, maintaining the temperature at 65 ℃ and react, reaction naturally cools to room temperature after finishing, and makes modified polyethylene alcohol glue.
Tapioca(flour) and mass concentration 40% glyoxal solution are pressed 100: 30 (g/ml) mixed, and the adding massfraction is the FeSO of tapioca(flour) 3%
47H
2O is earlier at 1000rmin
-1Speed under stir 30min after, be placed on reacting by heating in the microwave oven, microwave power is set at 500W, temperature of reaction is 70 ℃, the reaction times is 45min.
At normal temperatures; To account for the modified polyvinyl alcohol glue of total quality of material 70% and the benzene emulsion uniform mixing of total quality of material 8% earlier; Progressively add modified tapioca starch that accounts for total quality of material 22% and the ammonium persulphate that accounts for modified tapioca starch quality 2% more in batches, stir and promptly obtain tapioca(flour) based biomass aldehyde-free cement.
The tackiness agent salient features
| Index name | Unit | Numerical value |
| Outward appearance | Light yellow | |
| The pH value | 6.5～7.5 | |
| Solids content | ％ | 37.5 |
| Burst size of methanal | mg/L | ＜0.4 |
| Viscosity | s | 246 |
| Working life | min | 310 |
| Bonding strength | MPa | 1.56 |
Claims (1)
1. the preparation method of tapioca(flour) based biomass non-formaldehyde wood adhesive; It is characterized in that; Method is to be the main raw material of non-formaldehyde wood adhesive with tapioca(flour), Z 150PH; Respectively it is carried out modification then, and synthetic make tapioca(flour) based biomass non-formaldehyde wood adhesive, the concrete operations step is following:
1) modification of Z 150PH
Modified polyvinyl alcohol glue is by Z 150PH, water, oxygenant H
2O
2And catalyst Fe SO
47H
2The O hybrid reaction makes; With mass ratio is that 1: 4～1: 6 Z 150PH and water adds after reaction kettle soaks 10～12h; Heating while stirring makes homo(io)thermism between 90～96 ℃; Behind the dissolving 90min, naturally cool to about 60 ℃, adding massfraction then is the catalyst Fe SO of Z 150PH quality 0.4%～0.6%
47H
2O, slowly adding massfraction again is the pure H of Z 150PH quality 3.5%～4.5%
2O
2, maintaining the temperature between 58～65 ℃ and react, reaction naturally cools to room temperature after finishing, and makes modified polyethylene alcohol glue;
2) modification of tapioca(flour)
The tapioca(flour) modification is by tapioca(flour), linking agent oxalic dialdehyde and catalyst Fe SO
47H
2The O hybrid reaction is produced, and is 40% the glyoxal solution weight by tapioca(flour) with tapioca(flour) and mass concentration: the volume of mass concentration 40% glyoxal solution=mix at 100: 30, and to add massfraction be the FeSO of tapioca(flour) quality 3%
47H
2O is at 1000rmin
-1Speed under stir 30min after, be placed on reacting by heating in the microwave oven, microwave power is set at 500W, temperature of reaction is 60～70 ℃, the reaction times is 45min.
3) tapioca(flour) based biomass aldehyde-free cement is synthetic
Tapioca(flour) based biomass aldehyde-free cement is made by modified polyvinyl alcohol glue, modified tapioca starch, benzene emulsion and initiator ammonium persulfate hybrid reaction; To account for the modified polyvinyl alcohol glue of total quality of material 68～72% and the benzene emulsion uniform mixing of total quality of material 8～10% earlier; Progressively add the modified tapioca starch and the ammonium persulphate that accounts for modified tapioca starch quality 1～2% of shared total quality of material 19～22% more in batches, stir and promptly obtain tapioca(flour) based biomass aldehyde-free cement.
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| CN 201110454336 CN102559097B (en) | 2011-12-30 | 2011-12-30 | Preparation method of cassava starch based biomass formaldehyde-free wood adhesive |
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| CN102559097B CN102559097B (en) | 2013-05-01 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850957A (en) * | 2012-08-30 | 2013-01-02 | 苏州市德莱尔建材科技有限公司 | Preparation method for wood adhesive with starch as raw material |
| CN103665288A (en) * | 2013-12-11 | 2014-03-26 | 广西大学 | Method for preparing wood adhesive using cassava starch hydrolyzed sugar |
| CN105950071A (en) * | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | High-performance glue |
| CN105950072A (en) * | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | Environment-friendly antibacterial glue |
| CN105950070A (en) * | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | Heat-resisting environment-friendly glue |
| CN107459964A (en) * | 2017-09-06 | 2017-12-12 | 陈建峰 | A kind of preparation method of soybean protein water resistance timber adhesive |
| CN114907806A (en) * | 2022-03-30 | 2022-08-16 | 上海中南建筑材料有限公司 | Plant adhesive for artificial board and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| JPS5394348A (en) * | 1977-01-29 | 1978-08-18 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive |
| CN101597414A (en) * | 2009-07-10 | 2009-12-09 | 杨凌瑞丰环保科技有限公司 | Starch base degradable plastic |
| CN102115551A (en) * | 2010-12-31 | 2011-07-06 | 永港伟方（北京）科技股份有限公司 | Starch-based nano biological latex and preparation method thereof |
-
2011
- 2011-12-30 CN CN 201110454336 patent/CN102559097B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5394348A (en) * | 1977-01-29 | 1978-08-18 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive |
| CN101597414A (en) * | 2009-07-10 | 2009-12-09 | 杨凌瑞丰环保科技有限公司 | Starch base degradable plastic |
| CN102115551A (en) * | 2010-12-31 | 2011-07-06 | 永港伟方（北京）科技股份有限公司 | Starch-based nano biological latex and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850957A (en) * | 2012-08-30 | 2013-01-02 | 苏州市德莱尔建材科技有限公司 | Preparation method for wood adhesive with starch as raw material |
| CN102850957B (en) * | 2012-08-30 | 2014-09-10 | 苏州市德莱尔建材科技有限公司 | Preparation method for wood adhesive with starch as raw material |
| CN103665288A (en) * | 2013-12-11 | 2014-03-26 | 广西大学 | Method for preparing wood adhesive using cassava starch hydrolyzed sugar |
| CN103665288B (en) * | 2013-12-11 | 2015-10-28 | 广西大学 | Tapioca (flour) hydrolysis sugar is utilized to prepare the method for wood adhesive |
| CN105950071A (en) * | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | High-performance glue |
| CN105950072A (en) * | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | Environment-friendly antibacterial glue |
| CN105950070A (en) * | 2016-06-17 | 2016-09-21 | 枞阳县新天地高新材料有限公司 | Heat-resisting environment-friendly glue |
| CN107459964A (en) * | 2017-09-06 | 2017-12-12 | 陈建峰 | A kind of preparation method of soybean protein water resistance timber adhesive |
| CN114907806A (en) * | 2022-03-30 | 2022-08-16 | 上海中南建筑材料有限公司 | Plant adhesive for artificial board and preparation method thereof |
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