CN105440972A - Nano-compound biomass waterborne adhesive - Google Patents
Nano-compound biomass waterborne adhesive Download PDFInfo
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- CN105440972A CN105440972A CN201510461431.2A CN201510461431A CN105440972A CN 105440972 A CN105440972 A CN 105440972A CN 201510461431 A CN201510461431 A CN 201510461431A CN 105440972 A CN105440972 A CN 105440972A
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Abstract
The present invention relates to a biomass environmental-friendly waterborne adhesive. The adhesive is prepared by a plurality of raw materials, and comprises an organic silicone modified starch aqueous emulsion, nano-layered clay, and grafting modified soy protein, polyvinyl alcohol and a viscosity increasing component. The waterborne adhesive mainly consists of biomass materials, and is obvious in environmental protection property, and excellent in both the initial adhesiveness and the final adhesiveness. The adhesive can be suitable for bonding plastic base materials and paper with different polarities and wood and paper, is pollution-free and does not mildew, and is stable in high and low temperatures, and can be widely applied to the field of waterborne glue for packaging.
Description
Technical field
The present invention relates to a kind of aqueous binder, particularly relate to a kind of in opposed polarity plastic basis material and paper wood and the preparation method of environment-protection nano composite biomass aqueous binder between timber and paper wood with excellent tack and whole viscosity.
Background technology
Along with protection of the environment, the theory of treasuring resource are rooted in the hearts of the people day by day; the high solids content of sizing agent, solvent-free, the environmental friendliness factor such as water-based, photocuring and the power-saving technology such as low-temperature curing, castoff regenerative utilization are more and more paid attention to, and constantly strengthens up research and development.At flexible packaging industry, the mainly solventless adhesive that European and American developed countries' package compound uses in producing and Aqueous Adhesives.At present, it is solvent-based adhesive that the soft packaging of China more than 95% produces what adopt, uses at most, performance preferably solvent-type double-component adhesive for polyurethane.Because solvent-based adhesive has excellent flexibility, low temperature resistant and boiling resistance, ease for operation and adaptability widely, and the dry complex equipment of domestic Flexible-Packaging Industry is only applicable to solvent-based adhesive at present.In addition, Environment-friendlyadhesive adhesive also also has certain limitation at aspect of performance.Compared with solvent-based adhesive, Aqueous Adhesives has solvent-free release, environmental friendliness, nontoxic, non-combustible, use safety, low cost and other advantages, and solid content up to 50%-60%, can have the advantage that spread is few, cohesive strength is high.Aqueous polyurethane (PU) sizing agent, ACRYLIC EMULSION, EVA copolymer emulsion etc.Meanwhile, in adhesive field, the trend in the whole world adopts biological material preparation while of progressively realizing greenization, and namely a lot of biomass itself have extraordinary binding property, as starch, xylogen liquid, various colloids etc.The domestic and international research to biomass sizing agent at present mainly concentrates on the aspects such as soybean protein, starch, pyrolysis bio-oils and xylogen.Binding property due to biological material itself cannot reach the requirement of industrial application, and obstructed modification mode is used to the binding property improving biological material.As accessed hydrophobic grouping, untiing the three-dimensional aggregate structure etc. of biomass molecule chain.A kind of preparation method of biomass adhesive and biomass adhesive thereof and glued wood disclosed in patent of invention 2011100294798, after cake of camellia oleifera seeds contacts with water with alkali by this invention under polycondensation catalyst exists, react under polycondensation condition with phenol and aldehyde, obtain the biomass binder ingredients that viscosity is 500-5000 centipoise; And for example a kind of disclosed in 2009100843660 take soybean protein isolate as the preparation method of the biomass adhesive of major ingredient; by the amino acid of soybean protein isolate after activation is combined; again by going protecting group, obtaining take soybean protein isolate as the biomass adhesive of major ingredient.The adhesive strength of invention adhesive to timber is high, water-tolerant, and set time is short.
Although biomass tackiness agent is used gradually on cardboard or plank bonding, but at flexible packaging industry, especially gift box packaging field, because involved material category is more, particularly relate to the bonding of a large amount of plastics, paper wood, cloth base material, and require certain open hour, to water-repellancy, anti-mildewly also there is requirement.Obviously, current biomass glue cannot meet above needs.
Summary of the invention
The object of the invention is the defect in order to overcome current biomass glue tack and whole viscosity difference, providing a kind of at opposed polarity plastic basis material and paper wood and the environment-protection nano composite biomass aqueous binder between timber and paper wood with excellent tack and whole viscosity.
The object of the invention is to be achieved through the following technical solutions:
A kind of biomass environment-friendly water-base cement, forms by plurality of raw materials is composite, comprises organic-silicon-modified starch water miscible liquid, nanoscale twins clay, graft modification soybean protein, polyvinyl alcohol, adhesion promoting component.
The massfraction of each component is
Organic-silicon-modified starch water miscible liquid: 30-50 part
Graft modification soybean protein: 20-40 part
Nanoscale twins clay: 2-4 part
Polyvinyl alcohol water solution: 6-12 part
Adhesion promoting component: 1-3 part
Further, the preparation process of described graft modified starch water miscible liquid is:
I: the oxidation of starch: preparation massfraction is the starch water miscible liquid of 35-50%, the mass concentration adding starch water miscible liquid quality 1.5% under stirring is the copper-bath of 1%, be 6% aqueous sodium hydroxide solution adjust ph to 9.5 with massfraction, slowly add the hydrogen peroxide of starch emulsion quality 1.5-2.5% afterwards, constant temperature 50 DEG C reaction 3h, after be 3% with massfraction hydrochloric acid neutralizes pH value for 6.0-6.5, add starch emulsion 1.5% again, massfraction is the sodium sulfite aqueous solution termination reaction of 10%, finally by washing, drying, pulverize and to obtain Sumstar 190 A;
II: starch silicone surface-modifying: Sumstar 190 A being scattered in quality is in the water of its 350%-500%, add the hydrochloric acid soln that massfraction is 3%, its pH value is adjusted to 5, after system temperature being risen to 50 DEG C, dropwise add vinyl three ('beta '-methoxy oxyethyl group) silane that quality is the 15-30% quality of Sumstar 190 A quality, and stir with the speed of 150-200rmp, stationary temperature reacts 2 hours, after be cooled to room temperature, add the anion surfactant of Sumstar 190 quality 1%-3%, under room temperature, 100-150rmp stirs 30min, obtain organic-silicon-modified starch water miscible liquid.
Further, described graft modification soybean protein is with the soybean protein of glycidyl methacrylate graft modification, and its graft(ing) degree is between 38%-54%.
Further, the preparation method of described graft modification soybean protein is: the urea soln adding a certain amount of soybean protein and certain volume in the container with agitator, prolong, thermometer and dropping funnel, pre-treatment 30min in the oil bath of 50-60 DEG C.A certain amount of ammonium persulphate and sodium sulfite solution are added in reaction soln.After 10min, add a certain amount of glycidyl methacrylate, reaction 3h, stopped reaction.Wherein, the ratio of soybean protein and urea is, 1g soybean protein/10-15ml urea soln, the quality of ammonium persulphate is the 5%-10% of soybean protein, strength of solution is 0.1g/ml, the quality of sodium bisulfite is the 2%-4% of soybean protein, and strength of solution is 0.05g/ml, and the ratio of glycidyl methacrylate and soybean protein is 1g soybean protein/0.8-1.5mL glycidyl methacrylate.
Further, described adhesion promoting component is the one in water-based rosin milk, water-based alkene terpene emulsion, water-soluble cellulose derivative solution, wherein, adhesion promoting component is as being water-based rosin milk or water-based alkene terpene emulsion, then for adopting the product of anion surfactant, water-soluble cellulose derivative solution is the derivatived cellulose aqueous solution with hydrophilic radical, preferably, select hydroxyethyl cellulose aqueous solution, concentration of polymer solution is between 5%-10%.
Further, the concentration of described polyvinyl alcohol water solution is between 5%-8%, and the alcoholysis degree of polyvinyl alcohol is lower than 92%.
Further, described nanoscale twins clay is the blend of nanometer lithium algae soil and trisodium phosphate.Wherein, the thickness of nanometer lithium algae soil is 1-2nm, and diameter is 20-30nm, and chemical structure of general formula is [Mg
5.34li
0.66si
8o
20-(OH)
4] Na
0.66, the chemical general formula of trisodium phosphate is Na
4p
2o
7, the massfraction added is 7.68% of nanometer lithium algae soil.
Embodiment
Below will describe illustrative embodiment of the present invention in detail.But these implementation methods are only exemplary object, and the present invention is not limited thereto.
Embodiment 1
A kind of biomass environment-friendly water-base cement, forms by plurality of raw materials is composite, comprises organic-silicon-modified starch water miscible liquid, nanoscale twins clay, graft modification soybean protein, polyvinyl alcohol, adhesion promoting component.
The quality group number of each component is
Organic-silicon-modified starch water miscible liquid: 45 parts
Graft modification soybean protein: 32 parts
Nanoscale twins clay: 3.2 parts
Polyvinyl alcohol water solution: 8.5 parts
Adhesion promoting component: 1.5 parts
The preparation process of described graft modified starch water miscible liquid is:
I: the oxidation of starch: preparation massfraction is the starch water miscible liquid of 42%, the mass concentration adding starch water miscible liquid quality 1.5% under stirring is the copper-bath of 1%, be 6% aqueous sodium hydroxide solution adjust ph to 9.5 with massfraction, slowly add the hydrogen peroxide of starch emulsion quality 2.2% afterwards, constant temperature 50 DEG C reaction 3h, after be 3% with massfraction hydrochloric acid neutralizes pH value for 6.0-6.5, add starch emulsion 1.5% again, massfraction is the sodium sulfite aqueous solution termination reaction of 10%, finally by washing, drying, pulverize and to obtain Sumstar 190 A;
II: starch silicone surface-modifying: Sumstar 190 A being scattered in quality is in its water of 400%, add the hydrochloric acid soln that massfraction is 3%, its pH value is adjusted to 5, after system temperature being risen to 50 DEG C, dropwise add vinyl three ('beta '-methoxy oxyethyl group) silane that quality is 25.6% quality of Sumstar 190 A quality, and stir with the speed of 180rmp, stationary temperature reacts 2 hours, after be cooled to room temperature, add the anion surfactant sodium laurylsulfonate of Sumstar 190 quality 1.5%, under room temperature, 120rmp stirs 30min, obtain organic-silicon-modified starch water miscible liquid.
Further, described graft modification soybean protein is with the soybean protein of glycidyl methacrylate graft modification, and its graft(ing) degree is 46%.
Further, the preparation method of described graft modification soybean protein is: the urea soln adding a certain amount of soybean protein and certain volume in the container with agitator, prolong, thermometer and dropping funnel, pre-treatment 30min in the oil bath of 55 DEG C.A certain amount of ammonium persulphate and sodium sulfite solution are added in reaction soln.After 10min, add a certain amount of glycidyl methacrylate, reaction 3h, stopped reaction.Wherein, the ratio of soybean protein and urea is, 1g soybean protein/12.5ml urea soln, the quality of ammonium persulphate is 7.5% of soybean protein, strength of solution is 0.1g/ml, the quality of sodium bisulfite is 2.5% of soybean protein, and strength of solution is 0.05g/ml, and the ratio of glycidyl methacrylate and soybean protein is 1g soybean protein/1.2mL glycidyl methacrylate.
Described adhesion promoting component is water-based rosin milk, for adopting the product of anion surfactant.
The concentration of described polyvinyl alcohol water solution is 6.5%, and the alcoholysis degree of polyvinyl alcohol is 88%.
Described nanoscale twins clay is the blend of nanometer lithium algae soil and trisodium phosphate.Wherein, the thickness of nanometer lithium algae soil is 1-2nm, and diameter is 20-30nm, and chemical structure of general formula is [Mg
5.34li
0.66si
8o
20-(OH)
4] Na
0.66, the chemical general formula of trisodium phosphate is Na
4p
2o
7, the massfraction added is 7.68% of nanometer lithium algae soil.
Embodiment 2
A kind of biomass environment-friendly water-base cement, forms by plurality of raw materials is composite, comprises organic-silicon-modified starch water miscible liquid, nanoscale twins clay, graft modification soybean protein, polyvinyl alcohol, adhesion promoting component.
The massfraction of each component is
Organic-silicon-modified starch water miscible liquid: 38.5 parts
Graft modification soybean protein: 34.5 parts
Nanoscale twins clay: 2.5 parts
Polyvinyl alcohol water solution: 9 parts
Adhesion promoting component: 2.2 parts
The preparation process of described graft modified starch water miscible liquid is:
I: the oxidation of starch: preparation massfraction is the starch water miscible liquid of 35-50%, the mass concentration adding starch water miscible liquid quality 1.5% under stirring is the copper-bath of 1%, be 6% aqueous sodium hydroxide solution adjust ph to 9.5 with massfraction, slowly add the hydrogen peroxide of starch emulsion quality 2% afterwards, constant temperature 50 DEG C reaction 3h, after be 3% with massfraction hydrochloric acid neutralizes pH value for 6.0-6.5, add starch emulsion 1.5% again, massfraction is the sodium sulfite aqueous solution termination reaction of 10%, finally by washing, drying, pulverize and to obtain Sumstar 190 A;
II: starch silicone surface-modifying: Sumstar 190 A being scattered in quality is in its water of 450%, add the hydrochloric acid soln that massfraction is 3%, its pH value is adjusted to 5, after system temperature being risen to 50 DEG C, dropwise add vinyl three ('beta '-methoxy oxyethyl group) silane that quality is 23.5% quality of Sumstar 190 A quality, and stir with the speed of 150-200rmp, stationary temperature reacts 2 hours, after be cooled to room temperature, add the anion surfactant of Sumstar 190 quality 2%, under room temperature, 140rmp stirs 30min, obtains organic-silicon-modified starch water miscible liquid.
Described graft modification soybean protein is with the soybean protein of glycidyl methacrylate graft modification, and its graft(ing) degree is 41%.
The preparation method of described graft modification soybean protein is: the urea soln adding a certain amount of soybean protein and certain volume in the container with agitator, prolong, thermometer and dropping funnel, pre-treatment 30min in the oil bath of 58 DEG C.A certain amount of ammonium persulphate and sodium sulfite solution are added in reaction soln.After 10min, add a certain amount of glycidyl methacrylate, reaction 3h, stopped reaction.Wherein, the ratio of soybean protein and urea is, 1g soybean protein/12ml urea soln, the quality of ammonium persulphate is 6.5% of soybean protein, strength of solution is 0.1g/ml, the quality of sodium bisulfite is 2.5% of soybean protein, and strength of solution is 0.05g/ml, and the ratio of glycidyl methacrylate and soybean protein is 1g soybean protein/1.1mL glycidyl methacrylate.
Described adhesion promoting component is hydroxyethyl cellulose aqueous solution, and concentration of polymer solution is 6.5%.
The concentration of described polyvinyl alcohol water solution is between 7%, and the alcoholysis degree of polyvinyl alcohol is 88%.
Described nanoscale twins clay is the blend of nanometer lithium algae soil and trisodium phosphate.Wherein, the thickness of nanometer lithium algae soil is 1-2nm, and diameter is 20-30nm, and chemical structure of general formula is [Mg
5.34li
0.66si
8o
20-(OH)
4] Na
0.66, the chemical general formula of trisodium phosphate is Na
4p
2o
7, the massfraction added is 7.68% of nanometer lithium algae soil.
Claims (4)
1. a biomass environment-friendly water-base cement, forms by plurality of raw materials is composite, comprises organic-silicon-modified starch water miscible liquid, nanoscale twins clay, graft modification soybean protein, polyvinyl alcohol, adhesion promoting component;
The mass fraction of each component is
Organic-silicon-modified starch water miscible liquid: 30-50 part
Graft modification soybean protein: 20-40 part
Nanoscale twins clay: 2-4 part
Polyvinyl alcohol water solution: 6-12 part
Adhesion promoting component: 1-3 part
Be further characterized in that: the preparation process of graft modified starch water miscible liquid is:
I: the oxidation of starch: preparation massfraction is the starch water miscible liquid of 35-50%, the mass concentration adding starch water miscible liquid quality 1.5% under stirring is the copper-bath of 1%, be 6% aqueous sodium hydroxide solution adjust ph to 9.5 with massfraction, slowly add the hydrogen peroxide of starch emulsion quality 1.5-2.5% afterwards, constant temperature 50 DEG C reaction 3h, after be 3% with massfraction hydrochloric acid neutralizes pH value for 6.0 ~ 6.5, add starch emulsion 1.5% again, massfraction is the sodium sulfite aqueous solution termination reaction of 10%, finally by washing, dry, pulverize to obtain Sumstar 190 A,
II: starch silicone surface-modifying: Sumstar 190 A being scattered in quality is in the water of its 350%-500%, add the hydrochloric acid soln that massfraction is 3%, its pH value is adjusted to 5, after system temperature being risen to 50 DEG C, dropwise add vinyl three ('beta '-methoxy oxyethyl group) silane that quality is the 15-30% quality of Sumstar 190 A quality, and stir with the speed of 150-200rmp, stationary temperature reacts 2 hours, after be cooled to room temperature, add the anion surfactant of Sumstar 190 quality 1%-3%, under room temperature, 100-150rmp stirs 30min, obtain organic-silicon-modified starch water miscible liquid.Be further characterized in that: described graft modification soybean protein is with the soybean protein of glycidyl methacrylate graft modification, and its graft(ing) degree is between 38%-54%.
2. a kind of biomass environment-friendly water-base cement according to claim 1, is characterized in that: described adhesion promoting component is the one in water-based rosin milk, water-based alkene terpene emulsion, the derivatived cellulose aqueous solution.
3. a kind of biomass environment-friendly water-base cement according to claim 1, is characterized in that: the concentration of described polyvinyl alcohol water solution is between 5%-8%, and the alcoholysis degree of polyvinyl alcohol is lower than 92%.
4. a kind of biomass environment-friendly water-base cement according to claim 1, it is characterized in that: described nanoscale twins clay is the blend of nanometer lithium algae soil and trisodium phosphate, and wherein, the thickness of nanometer lithium algae soil is 1-2nm, diameter is 20-30nm, and chemical structure of general formula is [Mg
5.34li
0.66si
8o
20-(OH)
4] Na
0.66, the chemical general formula of trisodium phosphate is Na
4p
2o
7, the massfraction added is 7.68% of nanometer lithium algae soil.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107057616A (en) * | 2017-04-14 | 2017-08-18 | 湖北工业大学 | The preparation method of composited aluminum and plastic decking adhesive layer resin |
| CN107223483A (en) * | 2017-07-24 | 2017-10-03 | 福建省农业科学院生物技术研究所 | A kind of strawberry disease prevention cultivation matrix and preparation method thereof |
| CN107523307A (en) * | 2017-08-21 | 2017-12-29 | 山西省水利水电科学研究院 | A kind of conditioner for suppressing brackish water irrigated soil polysalt |
| CN107691476A (en) * | 2017-09-15 | 2018-02-16 | 四川兆和种业有限公司 | A kind of sterilization processing agent of wheat seed |
| CN107787837A (en) * | 2017-10-23 | 2018-03-13 | 河北省农林科学院石家庄果树研究所 | A kind of test tube seedling of pear tree somatic embryo, which increases, plants culture medium |
| CN107974220A (en) * | 2017-12-12 | 2018-05-01 | 徐发昌 | A kind of environmentally protective resin binder and preparation method thereof |
| CN110205080A (en) * | 2019-06-17 | 2019-09-06 | 湖南工业大学 | A kind of biomass combined environment-friendly water-based adhesive |
| CN111087949A (en) * | 2019-12-12 | 2020-05-01 | 广州国色生物科技有限公司 | Water-resistant high-viscosity wood adhesive |
| CN111875333A (en) * | 2020-08-11 | 2020-11-03 | 湖州五好建材有限公司 | Gypsum board with superstrong sound insulation effect |
| CN111875334A (en) * | 2020-08-11 | 2020-11-03 | 湖州五好建材有限公司 | Gypsum board with super-strong fire resistance |
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|---|---|---|---|---|
| CN107057616A (en) * | 2017-04-14 | 2017-08-18 | 湖北工业大学 | The preparation method of composited aluminum and plastic decking adhesive layer resin |
| CN107057616B (en) * | 2017-04-14 | 2019-02-12 | 湖北工业大学 | The preparation method of composited aluminum and plastic decking adhesive layer resin |
| CN107223483A (en) * | 2017-07-24 | 2017-10-03 | 福建省农业科学院生物技术研究所 | A kind of strawberry disease prevention cultivation matrix and preparation method thereof |
| CN107523307A (en) * | 2017-08-21 | 2017-12-29 | 山西省水利水电科学研究院 | A kind of conditioner for suppressing brackish water irrigated soil polysalt |
| CN107691476A (en) * | 2017-09-15 | 2018-02-16 | 四川兆和种业有限公司 | A kind of sterilization processing agent of wheat seed |
| CN107787837A (en) * | 2017-10-23 | 2018-03-13 | 河北省农林科学院石家庄果树研究所 | A kind of test tube seedling of pear tree somatic embryo, which increases, plants culture medium |
| CN107974220A (en) * | 2017-12-12 | 2018-05-01 | 徐发昌 | A kind of environmentally protective resin binder and preparation method thereof |
| CN110205080A (en) * | 2019-06-17 | 2019-09-06 | 湖南工业大学 | A kind of biomass combined environment-friendly water-based adhesive |
| CN111087949A (en) * | 2019-12-12 | 2020-05-01 | 广州国色生物科技有限公司 | Water-resistant high-viscosity wood adhesive |
| CN111875333A (en) * | 2020-08-11 | 2020-11-03 | 湖州五好建材有限公司 | Gypsum board with superstrong sound insulation effect |
| CN111875334A (en) * | 2020-08-11 | 2020-11-03 | 湖州五好建材有限公司 | Gypsum board with super-strong fire resistance |
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