CN103788904A - Organic silicon-vinyl acetate-acrylic copolymerized and modified starch-based wood adhesive and preparation process thereof - Google Patents
Organic silicon-vinyl acetate-acrylic copolymerized and modified starch-based wood adhesive and preparation process thereof Download PDFInfo
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- CN103788904A CN103788904A CN201310720410.9A CN201310720410A CN103788904A CN 103788904 A CN103788904 A CN 103788904A CN 201310720410 A CN201310720410 A CN 201310720410A CN 103788904 A CN103788904 A CN 103788904A
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Abstract
The invention relates to an organic silicon-vinyl acetate-acrylic copolymerized and modified starch-based wood adhesive which takes native starch as a main raw material and comprises an oxidative initiators, acid, a cross-linking agent, a plasticizing agent, a defoaming agent and a diluting agent. The organic silicon-vinyl acetate-acrylic copolymerized and modified starch-based wood adhesive is characterized by being prepared from the following raw materials in parts by weight: 180-220 parts of starch, 55-65 parts of vinyl acetate, 25-35 parts of butyl acrylate, 8-12 parts of acrylamide, 7-15 parts of vinyltriethoxysilane, 5-6.5 parts of initiators, 1.2-1.8 parts of the plasticizing agents, 0.15-0.25 part of the defoaming agents and 40-50 parts of the diluting agents. According to the invention, a hydrophobic silicon-oxygen bond is specially introduced, so that the starch not only retains the self property of the starch, but also has macromolecule synthesis characteristic. The starch-based wood adhesive copolymerized and modified through grafting has the advantages of high adhesion, high antibacterial capability and the like, is comparable with a white latex commonly used on the market in property and is non-toxic, environmental friendly, low in cost, excellent in product property and high in market competitiveness.
Description
Technical field
The preparation technology who the present invention relates to a kind of organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives, belongs to field of fine chemical.
Background technology
Urea-formaldehyde resin is the class synthetic adhesive that wood-based plate and timber glued joint usage ratio maximum in goods.Owing to often giving out pungency formaldehyde gas in its use procedure, environment and HUMAN HEALTH are caused to serious threat.By reducing the mol ratio of formaldehyde, adding the formaldehyde-trapping agents such as Resorcinol, trimeric cyanamide is the major measure that current sizing agent industry adopts, but can not tackle the problem at its root.And traditional starch-base adhesive is limited in the industrial production such as textile industry, paper-making industry, Packaging Box, corrugated cardboard use because poor water resistance, Joint strength are low, extremely rare for wood-processing industry.If by hydroxyl is carried out to chemical modification, sealing hydroxyl and other active group of introducing, make the hydroxy number in whole adhesive system drop to appropriate degree and maintain enough active group numbers, not only guaranteed bonding strength but also improved water-fastly, starch is effectively improved by effective modification as a lot of weakness of sizing agent.Utilize novel timber sizing agent that this cheapness, reproducible natural macromolecular material exploitation price, performance, environmental protection aspects can substitute " three-aldehyde glue " completely by significant.
Summary of the invention
The object of the present invention is to provide one to carry out chemical modification to hydroxyl, seal hydroxyl and introduce other active group by oxidation, esterification, grafting, the means such as crosslinked, make the hydroxy number in whole adhesive system drop to appropriate degree and maintain enough active group numbers, not only guaranteed bonding strength but also improved water-fast organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives and preparation technology.
The present invention is achieved through the following technical solutions: ative starch contains a large amount of hydroxyls, the hydrogen bonded power that these hydroxyls produce is that these hydroxyls of close-burning main source while of sizing agent are very easily combined with hydrogen bond form with water, cause splicing face easily by the desorb of water institute, cause water tolerance poor especially, especially not resistance to boiling water.The hydrogen bond forming between these hydroxyls, also easily causes sticking with paste liquid retrogradation, makes tackiness agent short storage period, easily loses flowability.Therefore, can in timber industry, apply in order to make starch adhesive, must carry out chemical modification for hydroxyl, seal hydroxyl and introduce other active group by oxidation, esterification, grafting, the means such as crosslinked, make the hydroxy number in whole adhesive system drop to appropriate degree, and maintain enough active group numbers, not only guarantee bonding strength but also improved water-fast.
The object of the present invention is achieved like this, based on above principle, at ative starch after the pretreatment technology such as acidolysis, oxidation, pre-initiation, adopt vinyl organosilicon alkane, vinyl acetate, butyl acrylate, the monomers such as acrylamide carry out grafting, copolymerization and modification to pretreated starch, form a kind of new multipolymer, introduce especially again hydrophobic siloxane bond, made starch both retain the character of starch self, there is again synthetic high molecular characteristic simultaneously.There is the advantages such as cementability is strong, antibacterial ability is strong by the starch-base timber adhesive of grafting, copolymerization and modification.
A kind of organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives, take ative starch as main raw material, comprise oxidation initiator, acid, linking agent, softening agent, defoamer and thinner, be prepared from by following weight part raw material: 180-220 parts of starch, 55-65 parts of vinyl acetates, 25-35 parts of butyl acrylates, 8-12 parts of acrylamides, vinyltriethoxysilane 7-15 part, 5-6.5 parts of initiators, 1.2-1.8 parts of acid, 1.5-2.5 parts of linking agents, 600-800 parts, water, 1.2-1.8 parts, softening agent, 0.15-0.25 part of defoamer, 40-50 parts of thinners.
Preferred: described starch is tapioca (flour), initiator is ammonium persulphate, and acid is hydrochloric acid, and linking agent is polyvinyl alcohol, and softening agent is glycerine, and defoamer is tributyl phosphate, and thinner is urea.
Be prepared from by following weight part raw material: 200 parts of tapioca (flour)s, 60 parts of vinyl acetates, 10 parts of vinyltriethoxysilanes, 30 parts of butyl acrylates, 10 parts of acrylamides, 5 parts of ammonium persulphates, 1.5 parts of hydrochloric acid, 2 parts of polyvinyl alcohol, 700 parts, water, 1.5 parts of glycerine, 0.2 part of tributyl phosphate, 45 parts, urea.
Its preparation technology of a kind of organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives is as follows:
The first step: acid hydrolysis oxidative stage:
180-220 portions of tapioca (flour)s, the concentration after tapioca (flour) breast is 30 ± 5%; 1.2-1.8 parts of hydrochloric acid, concentration of hydrochloric acid is 0.5 ± 0.1mol/L, ammonium persulphate consumption is the 2.0-2.5% of starch butt quality; Reaction times 1 ± 0.2h; PH=4-5; 50-55 ℃ of temperature of reaction;
Second step: graft copolymerization stage:
65-70 ℃ of temperature of reaction; PH=4-5; Reaction times 3 ± 0.5h: wherein vinyl acetate, butyl acrylate, acrylamide adding procedure time are respectively 1 ± 0.2h; Add 55-65 parts of vinyl acetates, 25-35 parts of butyl acrylates, 8-12 parts of acrylamides, vinyltriethoxysilane 10-15 part; Supplementary initiator ammonium persulfate consumption is 0.5-1% of starch butt quality;
The 3rd step: cross-linking modified stage:
Add 1.5-2.5 parts of linking agent polyvinyl alcohol in the polymerization later stage, reaction 0.5 ± 0.1h;
The 4th step: intensification gelatinization stage
Temperature is 80-90 ℃, insulation 0.5 ± 0.1h;
The 5th step: cooling impregnation stage
Temperature is 50 ± 2 ℃, adds 1.2-1.8 parts of softening agent glycerine, 0.15-0.25 part of defoamer tributyl phosphate, 40-50 parts, thinner urea; Insulation 0.5-1h;
The 6th step packaging final prod.
The present invention prepares aldehyde-free environment-friendly based Wood Adhesives by the multicomponent copolymerized and modified starch of organosilicon-vinegar third, and performance can match in excellence or beauty with conventional " white glue with vinyl " on market.The present invention has avoided the use of formaldehyde, asepsis environment-protecting, with low cost, excellent product performance, there is the stronger market competitiveness, a new thinking of development is provided to again development and the potato starch industrial upgrading of based Wood Adhesives industry, realized the unification of economic benefit and social benefit.
Embodiment
The present invention is by the following examples can the invention will be further described, but scope of the present invention is not limited to following embodiment.
Embodiment 1:
1, raw material consumption (Kg/t product)
Tapioca (flour) 200Kg
Monomer vinyl acetate 60Kg
Butyl acrylate 30Kg
Acrylamide 10Kg
Vinyltriethoxysilane 10Kg
Oxidation initiator ammonium persulfate 5Kg
Hydrochlorate acid 1.5 Kg
Linking agent polyvinyl alcohol 2Kg
Water 700Kg
Softening agent glycerine 1.5 Kg
Defoamer tributyl phosphate 0.2 Kg
Thinner urea 45 Kg
2, processing condition explanation
The first step: acid hydrolysis oxidative stage:
Starch concentration is 30%;
Concentration of hydrochloric acid is 0.5 ± 0.1mol/L, and ammonium persulphate consumption is the 2.0-2.5% of starch butt quality;
Reaction times 1h;
pH=4—5；
50-55 ℃ of temperature of reaction;
Second step: graft copolymerization stage:
65-70 ℃ of temperature of reaction;
pH=4—5；
Reaction times 3h, wherein vinyl acetate, butyl acrylate, acrylamide adding procedure time are respectively 1h; Add vinyl acetate, butyl acrylate, acrylamide, vinyltriethoxysilane; Supplementary initiator ammonium persulfate consumption is 0.5% of starch butt quality;
The 3rd step: cross-linking modified stage:
Add linking agent polyvinyl alcohol etc. in the polymerization later stage, reaction 0.5h;
The 4th step: intensification gelatinization phase temperature is 80-90 ℃, insulation 0.5h;
The 5th step: cooling impregnation phase temperature is 50 ℃, adds softening agent glycerine, defoamer tributyl phosphate, thinner urea etc.; Insulation 0.5-1h;
The 6th step packaging final prod.
The present invention is applicable to the serial timber adhesive products of different occasions, to substitute the product such as " three aldehyde " glue and white glue with vinyl of generally selling on market.Performance index are as shown in the table:
Embodiment
1organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives performance index
| Project name | Index |
| Compression shear dry strength (MPa) | ≥3.5 |
| Water tolerance (MPa) | ≥2.5 |
| Outward appearance | Without granule foreign |
| Viscosity (25 ℃, Pas) | 2.0～5.0 |
| Ash content (%) | ≤2 |
| Storage time (25 ℃, d) | ≥180 |
In other embodiment, each raw material and parameter all can be implemented in technical solution of the present invention.
Claims (4)
1. organosilicon-vinegar third modification by copolymerization Starch Based Wood Adhesives, take ative starch as main raw material, comprise oxidation initiator, acid, linking agent, softening agent, defoamer and thinner, it is characterized in that being prepared from by following weight part raw material: 180-220 parts of starch, 55-65 parts of vinyl acetates, 25-35 parts of butyl acrylates, 8-12 parts of acrylamides, vinyltriethoxysilane 7-15 part, 5-6.5 parts of initiators, 1.2-1.8 parts of acid, 1.5-2.5 parts of linking agents, 600-800 parts, water, 1.2-1.8 parts, softening agent, 0.15-0.25 part of defoamer, 40-50 parts of thinners.
2. a kind of organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives according to claim 1, is characterized in that described starch is tapioca (flour), and initiator is ammonium persulphate, acid is hydrochloric acid, and linking agent is polyvinyl alcohol, and softening agent is glycerine, defoamer is tributyl phosphate, and thinner is urea.
3. a kind of organosilicon-vinegar the third modification by copolymerization Starch Based Wood Adhesives according to claim 2, is characterized in that being prepared from by following weight part raw material: 200 parts of tapioca (flour)s, 60 parts of vinyl acetates, 10 parts of vinyltriethoxysilanes, 30 parts of butyl acrylates, 10 parts of acrylamides, 5 parts of ammonium persulphates, 1.5 parts of hydrochloric acid, 2 parts of polyvinyl alcohol, 700 parts, water, 1.5 parts of glycerine, 0.2 part of tributyl phosphate, 45 parts, urea.
4. organosilicon-vinegar third modification by copolymerization Starch Based Wood Adhesives, is characterized in that its preparation technology is as follows:
The first step: acid hydrolysis oxidative stage:
180-220 portions of tapioca (flour)s, the concentration after tapioca (flour) breast is 30 ± 5%; 1.2-1.8 parts of hydrochloric acid, concentration of hydrochloric acid is 0.5 ± 0.1mol/L, ammonium persulphate consumption is the 2.0-2.5% of starch butt quality; Reaction times 1 ± 0.2h; PH=4-5; 50-55 ℃ of temperature of reaction;
Second step: graft copolymerization stage:
65-70 ℃ of temperature of reaction; PH=4-5; Reaction times 3 ± 0.5h: wherein vinyl acetate, butyl acrylate, acrylamide adding procedure time are respectively 1 ± 0.2h; Add 55-65 parts of vinyl acetates, 25-35 parts of butyl acrylates, 8-12 parts of acrylamides, vinyltriethoxysilane 10-15 part; Supplementary initiator ammonium persulfate consumption is 0.5-1% of starch butt quality;
The 3rd step: cross-linking modified stage:
Add 1.5-2.5 parts of linking agent polyvinyl alcohol in the polymerization later stage, reaction 0.5 ± 0.1h;
The 4th step: intensification gelatinization stage
Temperature is 80-90 ℃, insulation 0.5 ± 0.1h;
The 5th step: cooling impregnation stage
Temperature is 50 ± 2 ℃, adds 1.2-1.8 parts of softening agent glycerine, 0.15-0.25 part of defoamer tributyl phosphate, 40-50 parts, thinner urea; Insulation 0.5-1h;
The 6th step packaging final prod.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104804136A (en) * | 2015-01-30 | 2015-07-29 | 武汉纺织大学 | Synthetic method of degradable adhesive |
| CN107793968A (en) * | 2017-10-25 | 2018-03-13 | 成都纽兰晶茂商贸有限公司 | A kind of preparation method of wood materials environment-friendly type water base adhesive |
| CN107805470A (en) * | 2017-10-25 | 2018-03-16 | 成都纽兰晶茂商贸有限公司 | A kind of wood materials environment-friendly type water base adhesive |
| CN107828356A (en) * | 2017-10-25 | 2018-03-23 | 成都纽兰晶茂商贸有限公司 | A kind of wood furniture starch adhesive |
| CN107892890A (en) * | 2017-12-20 | 2018-04-10 | 杨明超 | A kind of starch-base timber adhesive and preparation method thereof |
| CN108410530A (en) * | 2018-04-08 | 2018-08-17 | 俞小峰 | A kind of preparation method of briquette binder |
| CN109281233A (en) * | 2018-09-12 | 2019-01-29 | 徐晨攀 | A kind of preparation method of degradable wood-plastic board |
| CN111440268A (en) * | 2020-04-14 | 2020-07-24 | 广东佰合新材料科技股份有限公司 | Environment-friendly aqueous composite adhesive and preparation method and application thereof |
| CN111876106A (en) * | 2020-08-12 | 2020-11-03 | 齐鲁工业大学 | Preparation method of binary organic silicon system modified starch-based wood adhesive, product and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804136A (en) * | 2015-01-30 | 2015-07-29 | 武汉纺织大学 | Synthetic method of degradable adhesive |
| CN107793968A (en) * | 2017-10-25 | 2018-03-13 | 成都纽兰晶茂商贸有限公司 | A kind of preparation method of wood materials environment-friendly type water base adhesive |
| CN107805470A (en) * | 2017-10-25 | 2018-03-16 | 成都纽兰晶茂商贸有限公司 | A kind of wood materials environment-friendly type water base adhesive |
| CN107828356A (en) * | 2017-10-25 | 2018-03-23 | 成都纽兰晶茂商贸有限公司 | A kind of wood furniture starch adhesive |
| CN107892890A (en) * | 2017-12-20 | 2018-04-10 | 杨明超 | A kind of starch-base timber adhesive and preparation method thereof |
| CN108410530A (en) * | 2018-04-08 | 2018-08-17 | 俞小峰 | A kind of preparation method of briquette binder |
| CN109281233A (en) * | 2018-09-12 | 2019-01-29 | 徐晨攀 | A kind of preparation method of degradable wood-plastic board |
| CN111440268A (en) * | 2020-04-14 | 2020-07-24 | 广东佰合新材料科技股份有限公司 | Environment-friendly aqueous composite adhesive and preparation method and application thereof |
| CN111440268B (en) * | 2020-04-14 | 2021-03-30 | 广东佰合新材料科技股份有限公司 | Environment-friendly aqueous composite adhesive and preparation method and application thereof |
| CN111876106A (en) * | 2020-08-12 | 2020-11-03 | 齐鲁工业大学 | Preparation method of binary organic silicon system modified starch-based wood adhesive, product and application thereof |
| CN111876106B (en) * | 2020-08-12 | 2021-09-17 | 齐鲁工业大学 | Preparation method of binary organic silicon system modified starch-based wood adhesive, product and application thereof |
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