CN100556974C - A kind of aqueous adhesive without aldehyde and preparation method thereof - Google Patents
A kind of aqueous adhesive without aldehyde and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of tackiness agent and preparation method thereof.A kind of aqueous adhesive without aldehyde is characterized in that it is that the macromolecule resin aqueous solution of 5-70%, the natural polymer aqueous solution, mineral filler and the auxiliary agent raw material that mass concentration is 15-40% mix by mass concentration; The shared macromolecule resin of macromolecule resin and natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 20-80%, the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 19.99-79.99%, and the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01-5%; Wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 5-95%, natural polymer 5-95%.The present invention has that high adhesion energy, with low cost, technology are simple, the characteristics of environmental protection.Be mainly used in the bonding of article such as timber, paper.
Description
Technical field
The present invention relates to a kind of tackiness agent and preparation method thereof, belong to the natural macromolecular material field, also belong to the fine polymer chemical field.
Background technology
At occurring in nature, the binding property of material and material extensively is familiar with, and protein is to serve as the adhesive material that this class works.As in the ocean, the proteic binding property of bivalves is extremely strong, even on wet surface, also can form very strong adhesive effect, this proteinoid is called as the ocean binding proteins.Therefore, structure by studying this proteinoid and the relation between the performance, utilizing the bionic function expectation to obtain with protein is the aqueous adhesive without aldehyde of main component.Occurring in nature, many-sided advantage such as vegetable-protein is renewable because of having, be easy to get, environmental friendliness, so the development and utilization vegetable-protein has profound significance.Soy-protein is one of widely used vegetable-protein, is soybean extract oil byproduct afterwards, and major part is used for foodstuffs industry, also is applied in material fields such as tackiness agent, degradative plasticss.Zein powder also is a class vegetable-protein, and has the price cheaper than soybean protein, therefore its development and utilization is had more wide prospect.Starch is the product of photosynthesis of plant, is one of the abundantest natural polymer child resource of nature.The bond properties of vegetable-protein and starch obtains understanding very early and uses, but because it is used for tackiness agent, has that intensity is not high, water resistance is strong, an easy shortcoming such as moldy metamorphism, so practical application has obtained very big restriction.Because distinctive inexpensive, renewable, the advantages of environment protection of natural polymer, and because of growing tension, crude oil price continuous rise and the problem of environmental pollution of petroleum resources, based on the research of the natural macromolecular material of renewable resources with use and extensively paid attention to.Research to vegetable-protein and Starch Adhesive becomes the research focus, and main thought is to prepare vegetable-protein or the Starch Adhesive with higher using value by the method modification of physics and chemistry at present.Soybean protein or starch and synthetic macromolecule blend are prepared tackiness agent, and as starch and polyurethane binder is compound, the hydroxyl of starch has certain influence (Int.J.Adhes.Adhes., 2003,23,393-399 to the performance of polyurethane binder; Chinese patent: 200510016573).Utilize starch and synthetic macromolecule to prepare the nontoxic polymeric gel mixture (Chinese patent: 200510033797) of starch conversion composite high-molecular.Adopting low-cost defatted soyflour is raw material, by directed sex change technology of albumen and modification technique, produce non-toxic additive and have no irritating odor, cohesive strength and the similar environmental-protection type adhesive of high quality and at a reasonable price (Chinese patent: 200410002616) of aldehyde adhesive stick.Carry out blend by soybean protein and water-based are strengthened resin, obtain all wood adhesive (United States Patent (USP)s: US0089418A1) preferably of bond strength and water resistance.These tackiness agents are improved in intensity and aspect of performance, but still there are some difficulties in practical application, and, set time not high as initial bonding strength, long, perishable shortcoming such as mouldy was difficult to really be applied to reality.By regulating group and the polymer type on vegetable-protein and the starch chain, add some auxiliary agents simultaneously and improve performance, in the hope of its acquisition is applied even more extensively.
Summary of the invention
The object of the present invention is to provide aqueous adhesive without aldehyde of a kind of high adhesion energy, with low cost, environmental protection and preparation method thereof.
To achieve these goals, the technical solution adopted in the present invention is as follows: a kind of aqueous adhesive without aldehyde is characterized in that it is that the macromolecule resin aqueous solution of 5-70%, the natural polymer aqueous solution, mineral filler and the auxiliary agent raw material that mass concentration is 15-40% mix by mass concentration; The shared macromolecule resin of macromolecule resin and natural polymer, natural polymer, mineral filler and auxiliary agent raw material (being the solid dry material) total mass per-cent is: 20-80%, the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 19.99-79.99%, and the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01-5%; Wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 5-95%, natural polymer 5-95%;
Described natural polymer is any one or any two kinds or any mixture more than two kinds in vegetable-protein thing, modified vegetable protein thing, starch, the treated starch, any two kinds or any when mixing more than two kinds, is any proportioning; Perhaps natural polymer is vegetable-protein thing and starch-mixed modifier (being undertaken by existing alkaline modification, esterification modification, etherification modified or oxidation modification), shared vegetable-protein thing of starch and starch quality per-cent are: 1-70, and shared vegetable-protein thing of vegetable-protein thing and starch quality per-cent are: 30-99;
Described mineral filler is any one or any two kinds or any mixture more than two kinds in ground barium sulfate, silica powder, talcum powder, the wollastonite powder, any two kinds or any when mixing more than two kinds, is any proportioning; Described auxiliary agent is any one or any two kinds or any mixture more than two kinds in defoamer, efficient sterilizing mould inhibitor, the water-based anti-settling agent, any two kinds or any when mixing more than two kinds, is any proportioning.
Described macromolecule resin is the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring, or the mixture of any one or any two kinds or three kinds in the polyamide resin of quaternary ammonium salt tetra-atomic ring and acrylic resin, urethane resin, the vinyl acetate resin, the mass percent that its polyamide resin accounts for whole macromolecule resin is: 50-100 is any proportioning between acrylic resin, urethane resin, the vinyl acetate resin.
Described vegetable-protein thing is the mixture of a kind of in soybean protein, the zein or two kinds, two kinds when mixing, is any proportioning.Described starch is W-Gum, wheat starch, potato starch (comprising yam starch, tapioca (flour), sweet potato starch etc.) or legume starch various natural plant starch such as (comprising pea starch, green starch etc.).
Described soybean protein is any one or any two kinds or any mixture more than two kinds in soybean protein isolate, soybean apolipoprotein, the soybean residue, any two kinds or any when mixing more than two kinds, is any proportioning.
The described polyamide resin that contains the quaternary ammonium salt tetra-atomic ring adopts following step preparation: 1). by organic dibasic acid and the binary primary amine condensation reaction that contains secondary amine, organic dibasic acid is 1 with the mol ratio that contains secondary amine: 0.8-1.5, temperature of reaction is 110-185 ℃, reaction times is 0.5-5 hour, adds water after reaction finishes and regulates the mass percent of solid content at 5-70%; 2). add epoxy chloropropane again, the molar weight of epoxy chloropropane is the 0.8-1.4% that contains the binary primary amine consumption of secondary amine, earlier after reacting 0.2-2 hour under the 15-30 ℃ of condition, be warmed up to 55-75 ℃ of condition again and reacted 1-3 hour, add after reaction finishes dilute sulphuric acid be acidified to the pH value 3～6 and the mass percent of regulating solid content be 5-70%.
Described organic dibasic acid is hexanodioic acid, Succinic Acid, suberic acid etc.; The described binary primary amine that contains secondary amine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc.
Described acrylic resin, urethane resin, vinyl acetate resin are commercial commodity.
A kind of preparation method of aqueous adhesive without aldehyde is characterized in that it comprises the steps:
1) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent is: 20-80%, choosing mass concentration is the macromolecule resin aqueous solution of 5-70%, the natural polymer aqueous solution that mass concentration is 15-40%, wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 5-95%, natural polymer 5-95%, and standby;
Described natural polymer is any one or any two kinds or any mixture more than two kinds in vegetable-protein thing, modified vegetable protein thing, starch, the treated starch, any two kinds or any when mixing more than two kinds, is any proportioning; Perhaps natural polymer is vegetable-protein thing and starch-mixed modifier (being undertaken by existing alkaline modification, esterification modification, etherification modified or oxidation modification), shared vegetable-protein thing of starch and starch quality per-cent are: 1-70, and shared vegetable-protein thing of vegetable-protein thing and starch quality per-cent are: 30-99;
2) by the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 19.99-79.99%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01-5%, choose mineral filler, auxiliary agent, standby;
3) mass concentration is that to add mass concentration in the macromolecule resin aqueous solution of 5-70% be the natural polymer aqueous solution, the mineral filler of 15-40%, adds auxiliary agent again and stirs and promptly get product.
Can be according to using and the performance requriements mass concentration is regulated the pH value as the NaOH solution of 0.01-40% and is 5-11.
The solid content of being controlled whole aqueous adhesive without aldehyde by mineral filler is 10-60wt%.
When natural polymer is that (promptly get rid of natural polymer only is the modifier that contains the vegetable-protein thing: starch, treated starch, starch and treated starch, one of four kinds of vegetable-protein thing and starch) time, be called and contain the modified vegetable protein thing, its aqueous solution is called and contains the modified vegetable protein thing aqueous solution.
When natural polymer was the modifier of vegetable-protein thing and starch, the natural polymer aqueous solution that get this moment was called and contains the modified vegetable protein thing aqueous solution; Promptly contain the modifier that the modified vegetable protein thing is vegetable-protein thing and starch (by existing alkaline modification, esterification modification, etherification modified or oxidation modification).Employing contains adhesiveproperties the best of the aqueous adhesive without aldehyde that the modified vegetable protein thing aqueous solution obtains.
Contain the preparation of the modified vegetable protein thing aqueous solution: with vegetable-protein thing and starch by the shared mass percent of starch be earlier: 1-70, the shared mass percent of vegetable-protein thing are: the 30-99 blend is scattered in (add-on of water is 15-40% for the mass concentration that control contains the modified vegetable protein thing) in the water, again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification, the mass percent that the consumption of alkali accounts for vegetable-protein thing, starch and NaOH alkali total mass is 4-10, mass concentration be 15-40% contain the modified vegetable protein thing aqueous solution.
The present invention adopts natural polymer { vegetable-protein or vegetable-protein modifier (thereby the polarity of utilizing chemical modification to change some group changes the consistency of itself and macromolecule resin), the perhaps mixture of starch, starch conversion thing and modified vegetable protein }, with macromolecule resin { synthetic contains polyamide resin and other macromolecule resins of quaternary ammonium salt tetra-atomic ring } blend, owing to formed cross-linked network structure, thereby bond strength and water resistance are improved, have high adhesion energy (better use properties).Simultaneously, add mineral filler and can regulate solid content, improve performance, reduce cost etc., more help being applied to reality, add auxiliary agent and can improve in the tackiness agent use and the performance after using.The present invention is compound with natural polymer and macromolecule resin by blend method, and the preparation method is simple.The used natural polymer of the present invention, raw materials cost is cheap, and biodegradable; Adopt water as solvent, technology is simple, environmental protection, does not use formaldehyde etc. can eliminate the harm of aldehyde material to human body fully, can satisfy modern society people's demand better, meets the era development requirement; Therefore, the present invention has high adhesion energy (comprising hygrometric state cementability and dry state cementability), with low cost, advantages of environment protection.
The present invention has following beneficial effect: high adherence energy, with low cost, environmental protection, technology are simple.Product of the present invention is mainly used in the bonding of article such as timber, paper.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, contains the preparation of the polyamide resin of quaternary ammonium salt tetra-atomic ring: hexanodioic acid is mixed with diethylenetriamine, the mol ratio of hexanodioic acid and diethylenetriamine is 1: 1, be heated to then under the 150-180 ℃ of condition and reacted 3 hours, polycondensation obtains polyamide resin, the cooling thin up promptly gets the precursor solution that contains quaternary ammonium salt tetra-atomic ring polyamide resin, and solid content (mass percent) is 25%.Again with precursor solution and epichlorohydrin reaction, the molar weight of epoxy chloropropane is the 0.8-1.4 of diethylenetriamine consumption, room temperature reaction 30 minutes, reacted 1 hour down at 60 ℃ again, obtain having the polyamide resin of quaternary ammonium salt tetra-atomic ring, add sulfuric acid acidation and help its preservation to the pH value between 4-5, solid content (mass percent) is 10-50%, and the polyamide resin aqueous solution that obtains containing the quaternary ammonium salt tetra-atomic ring is stand-by.Described hexanodioic acid can change Succinic Acid, suberic acid etc. into; Described diethylenetriamine can change triethylene tetramine, tetraethylene pentamine etc. into, below identical.Polyamide resin also can adopt existing product.
2, the preparation of tackiness agent:
1); the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier soybean protein (Yunmeng egg-white food company limited of Hubei Province Du Pont) and starch [yam starch (Shanghai chemical reagents corporation of Chinese Medicine group)] are scattered in (add-on of water is 15% for the mass concentration that control contains the modified vegetable protein thing) in the water by mass ratio blend in 80: 20; again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification; the consumption of alkali accounts for soybean protein; the mass percent of starch and NaOH alkali total mass is 10, obtain mass concentration and be 15% contain the modified vegetable protein thing aqueous solution.
2) be that 15% contain the modified vegetable protein thing aqueous solution and mass concentration are that 15% the polyamide resin aqueous solution and mass concentration are 15% water-borne acrylic resin aqueous solution blend, by mass concentration, add ground barium sulfate again and regulate solid content, mix the back vigorous stirring, add 0.1% auxiliary agent again, described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N), and stirring promptly gets aqueous adhesive without aldehyde.Contain the modified vegetable protein thing (modifier that refers to vegetable-protein thing and starch in the aqueous adhesive without aldehyde, be soybean protein, starch and NaOH alkali) (the albumen thing does not comprise starch, starch belongs to polyose), the mass percent of polyamide resin, water-borne acrylic resin, ground barium sulfate, the shared tackiness agent gross dry weight of each raw material of auxiliary agent is: contain modified vegetable protein thing 20%, polyamide resin 20%, water-borne acrylic resin 20%, ground barium sulfate 39.9%, auxiliary agent 0.1%.To not have the aldehyde aqueous binder then and be applied on two planks, the bond area that makes it is on the test panel of 12.5mm * 25mm, and is as follows.Keep promptly getting in 5 minutes under 120 ℃ and 1.4MPa testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 8.96.Mechanical property thinks carefully newly in Shenzhen with reference to ASTM D906 on the CMR6503 instrument of testing tool company and records that rate of extension is 1mm/min, and is as follows.
Embodiment 2:
Substantially the same manner as Example 1, difference is: step 2 1), be to carry out modification at 70: 30 by soybean protein and starch quality ratio, mass concentration be 15% contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 0.2% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, water-borne acrylic resin, ground barium sulfate, the shared tackiness agent gross dry weight of each raw material of auxiliary agent is: contain modified vegetable protein thing 30%, polyamide resin 30%, water-borne acrylic resin 10%, ground barium sulfate 29.8%, auxiliary agent 0.2% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 9.32.
Embodiment 3:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1); the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier Zein powder (the grand together biotechnology feed corporation,Ltd in Binzhou) and starch [yam starch (Shanghai chemical reagents corporation of Chinese Medicine group)] are scattered in (add-on of water is 20% for the mass concentration that control contains the modified vegetable protein thing) in the water by mass ratio blend in 80: 20; again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification; the consumption of alkali accounts for Zein powder; the mass percent of starch and NaOH alkali total mass is 5, mass concentration be 20% contain the modified vegetable protein thing aqueous solution.
2) be that 20% contain the modified vegetable protein thing aqueous solution and mass concentration are that 15% the polyamide resin aqueous solution and mass concentration are 15% polyurethane resin water solution blending, by mass concentration, add ground barium sulfate again and regulate solid content, mix the back vigorous stirring, add 0.3% auxiliary agent again, described auxiliary agent is 4 for the efficient sterilizing mould inhibitor, 4-dimethyl oxazoline alkanes (lot identification mark Canguard327), stirring promptly gets aqueous adhesive without aldehyde.The mass percent that contains modified vegetable protein thing (modifier that refers to vegetable-protein thing and starch, i.e. Zein powder, starch and NaOH alkali), polyamide resin, urethane resin, ground barium sulfate, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 30%, polyamide resin 20%, urethane resin 20%, ground barium sulfate 29.7%, auxiliary agent 0.3%.Keep promptly getting in 5 minutes under 115 ℃ and 1.6MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 7.68.
Embodiment 4:
Substantially the same manner as Example 3, difference is: step 2 1), be to carry out modification at 70: 30 by Zein powder and starch quality ratio, mass concentration be 20% contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 0.2% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, urethane resin, ground barium sulfate, the shared tackiness agent gross dry weight of each raw material of auxiliary agent is: contain modified vegetable protein thing 30%, polyamide resin 30%, urethane resin 10%, ground barium sulfate 29.8%, auxiliary agent 0.2% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 10.57.
Embodiment 5:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1); the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier soybean protein (Yunmeng egg-white food company limited of Hubei Province Du Pont) and starch [W-Gum (Shanghai chemical reagents corporation of Chinese Medicine group)] are scattered in (add-on of water is 40% for the mass concentration that control contains the modified vegetable protein thing) in the water by mass ratio blend in 99: 1; again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification; the consumption of alkali accounts for soybean protein; the mass percent of starch and NaOH alkali total mass is 4, mass concentration be 40% contain the modified vegetable protein thing aqueous solution.
2) be that 40% contain the modified vegetable protein thing aqueous solution and mass concentration are that 25% the polyamide resin aqueous solution and mass concentration are 15% vinyl acetate resin aqueous solution blend, by mass concentration, add silica powder again and regulate solid content, mix the back vigorous stirring, add 0.4% auxiliary agent again, described auxiliary agent is for the water-based anti-settling agent is an ion-exchanged sodium bentonite class, and stirring promptly gets aqueous adhesive without aldehyde.The mass percent that contains modified vegetable protein thing (modifier that refers to vegetable-protein thing and starch, i.e. soybean protein, starch and NaOH alkali), polyamide resin, vinyl acetate resin, silica powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 25%, polyamide resin 25%, vinyl acetate resin 20%, silica powder 29.6%%, auxiliary agent 0.4%.Keep promptly getting in 4 minutes under 130 ℃ and 1.5MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 8.91.
Embodiment 6:
Substantially the same manner as Example 5, difference is: step 2 1), be to carry out modification at 20: 80 by soybean protein and starch quality ratio, mass concentration be 40% contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 0.25% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, urethane resin, the shared tackiness agent gross dry weight of each raw material of silica powder is: contain modified vegetable protein thing 40%, polyamide resin 30%, urethane resin 10%, silica powder 20% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 7.32.
From embodiment 1-6 as can be known, the present invention adds polymer resin such as polymeric amide to be had preferably the bonding effect of vegetable-protein and strengthens, and illustrates that its raising to performance played reasonable effect.
Embodiment 7:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier Zein powder (the grand together biotechnology feed corporation,Ltd in Binzhou) and starch [pea starch starch (Shanghai chemical reagents corporation of Chinese Medicine group)] are scattered in the water by mass ratio blend in 90: 10; again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification; the mass percent that the consumption of alkali accounts for Zein powder, starch and NaOH alkali total mass is 8, mass concentration be 20% contain the modified vegetable protein thing aqueous solution.
2) be that 20% contain the modified vegetable protein thing aqueous solution and mass concentration are that 40% the polyamide resin aqueous solution and mass concentration are 30% water-borne acrylic resin aqueous solution blend, by mass concentration, add silica powder again and regulate solid content, mix the back vigorous stirring, add 0.4% auxiliary agent again, described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N), and stirring promptly gets aqueous adhesive without aldehyde.The mass percent that contains modified vegetable protein thing (modifier that refers to vegetable-protein thing and starch, i.e. Zein powder, starch and NaOH alkali), polyamide resin, water-borne acrylic resin, silica powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 25%, polyamide resin 25%, water-borne acrylic resin 20%, silica powder 29.6%%, auxiliary agent 0.4%.Keep promptly getting in 8 minutes under 110 ℃ and 1.7MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 9.25.
Embodiment 8:
Substantially the same manner as Example 7, difference is: step 2 1), be to carry out modification at 50: 50 by Zein powder and starch quality ratio, must contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 0.4% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, water-borne acrylic resin, the shared tackiness agent gross dry weight of each raw material of silica powder is: contain modified vegetable protein thing 25%, polyamide resin 20%, water-borne acrylic resin 25%, silica powder 30% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 7.32.
Embodiment 9:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier soybean protein (Yunmeng egg-white food company limited of Hubei Province Du Pont) and esterification starch (sky, Jiangsu scholar's power starch company limited) are scattered in the water by mass ratio blend in 90: 10, must mass concentration be 20% contain the modified vegetable protein thing aqueous solution.Also can adopt existing modified vegetable protein thing, be prepared into mass concentration and be 20% contain the modified vegetable protein thing aqueous solution, standby.
2) be that 20% contain the modified vegetable protein thing aqueous solution and mass concentration are that 15% the polyamide resin aqueous solution and mass concentration are 15% polyurethane resin water solution blending, by mass concentration, add wollastonite powder again and regulate solid content, mix the back vigorous stirring, add 0.4% auxiliary agent again, described auxiliary agent is 4 for the efficient sterilizing mould inhibitor, 4-dimethyl oxazoline alkanes (lot identification mark Canguard327), stirring promptly gets aqueous adhesive without aldehyde.The mass percent that contains modified vegetable protein thing [referring to soybean protein and esterification starch], polyamide resin, urethane resin, wollastonite powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 25%, polyamide resin 25%, urethane resin 20%, wollastonite powder 29.6%, auxiliary agent 0.4%.Keep promptly getting in 6 minutes under 120 ℃ and 1.9MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 9.25.
Embodiment 10:
Substantially the same manner as Example 9, difference is: step 2 1), be to carry out modification at 60: 40 by soybean protein and starch quality ratio, must contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 0.5% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, urethane resin, the shared tackiness agent gross dry weight of each raw material of wollastonite powder is: contain modified vegetable protein thing 20%, polyamide resin 30%, urethane resin 25%, wollastonite powder 24.5%%, auxiliary agent 0.5% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 7.32.
Embodiment 11:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier Zein powder (the grand together biotechnology feed corporation,Ltd in Binzhou) and Sumstar 190 (no Sillim Yongfeng starch company limited) are scattered in the water by mass ratio blend in 90: 10, must mass concentration be 20% contain the modified vegetable protein thing aqueous solution.Also can adopt existing modified vegetable protein thing (the albumen thing does not comprise starch, and starch belongs to polyose), be prepared into mass concentration and be 20% contain the modified vegetable protein thing aqueous solution, standby.
2) be that 20% contain the modified vegetable protein thing aqueous solution and mass concentration are that 25% the polyamide resin aqueous solution and mass concentration are 20% vinyl acetate resin aqueous solution blend, by mass concentration, add talcum powder again and regulate solid content, mix the back vigorous stirring, add 0.4% auxiliary agent again, described auxiliary agent is for the water-based anti-settling agent is an ion-exchanged sodium bentonite class, and stirring promptly to get does not have the aldehyde aqueous binder.The mass percent that contains modified vegetable protein thing [referring to Zein powder and Sumstar 190], polyamide resin, vinyl acetate resin, talcum powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the tackiness agent is: contain modified vegetable protein thing 25%, polyamide resin 25%, vinyl acetate resin 20%, talcum powder 29.6%%, auxiliary agent 0.4%.Keep promptly getting in 7 minutes under 120 ℃ and 2.0MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 9.25.
Embodiment 12:
Substantially the same manner as Example 11, difference is: step 2 1), be to carry out modification at 60: 40 by Zein powder and starch quality ratio, must contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 0.5% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, vinyl acetate resin, talcum powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent is: contain modified vegetable protein thing 20%, polyamide resin 30%, vinyl acetate resin 25%, talcum powder 24.5%%, auxiliary agent 0.5% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 7.32.
Embodiment 13:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier soybean protein (Yunmeng egg-white food company limited of Hubei Province Du Pont) and Sumstar 190 (no Sillim Yongfeng starch company limited) are scattered in the water by mass ratio blend in 95: 5, must mass concentration be 40% contain the modified vegetable protein thing aqueous solution.Also can adopt existing modified vegetable protein thing (the albumen thing does not comprise starch, and starch belongs to polyose), be prepared into mass concentration and be 40% contain the modified vegetable protein thing aqueous solution, standby.
2) be that 40% contain the modified vegetable protein thing aqueous solution and mass concentration are that 40% the polyamide resin aqueous solution and mass concentration are that 30% vinyl acetate resin and mass concentration are 25% polyurethane resin water solution blending, by mass concentration, add talcum powder again and regulate solid content, mix the back vigorous stirring, add 3% auxiliary agent again, described auxiliary agent is for the water-based anti-settling agent is an ion-exchanged sodium bentonite class, and stirring promptly gets aqueous adhesive without aldehyde.The mass percent that contains modified vegetable protein thing [referring to soybean protein and Sumstar 190], polyamide resin, vinyl acetate resin, urethane resin, talcum powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 20%, polyamide resin 20%, vinyl acetate resin 20%, urethane resin 10%, talcum powder 27%, auxiliary agent 3%.Keep promptly getting in 4 minutes under 125 ℃ and 2.5MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 10.12.
Embodiment 14:
Substantially the same manner as Example 13, difference is: step 2 1), be to carry out modification at 75: 25 by soybean protein and starch quality ratio, must contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 2% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, vinyl acetate resin, urethane resin, talcum powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent is: contain modified vegetable protein thing 20%, polyamide resin 20%, vinyl acetate resin 25%, urethane resin 15%, talcum powder 18%, auxiliary agent 2% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 8.59.
Embodiment 15:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier Zein powder (the grand together biotechnology feed corporation,Ltd in Binzhou) and Sumstar 190 (no Sillim Yongfeng starch company limited) are scattered in the water by mass ratio blend in 80: 20, must mass concentration be 20% contain the modified vegetable protein thing aqueous solution.Also can adopt existing modified vegetable protein thing (the albumen thing does not comprise starch, and starch belongs to polyose), be prepared into mass concentration and be 20% contain the modified vegetable protein thing aqueous solution, standby.
2) be that 20% contain the modified vegetable protein thing aqueous solution and mass concentration are that 50% the polyamide resin aqueous solution and mass concentration are that 30% the urethane resin aqueous solution and mass concentration are 25% water-borne acrylic resin blend, by mass concentration, add talcum powder again and regulate solid content, mix the back vigorous stirring, add 4% auxiliary agent again, described auxiliary agent is for the water-based anti-settling agent is an ion-exchanged sodium bentonite class, and stirring promptly gets aqueous adhesive without aldehyde.The mass percent that contains modified vegetable protein thing [referring to Zein powder and Sumstar 190], polyamide resin, urethane resin, water-borne acrylic resin, talcum powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 20%, polyamide resin 20%, urethane resin 20%, water-borne acrylic resin 10%, talcum powder 26%, auxiliary agent 4%.Keep promptly getting in 8 minutes under 120 ℃ and 2.3MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 10.51.
Embodiment 16:
Substantially the same manner as Example 5, difference is: step 2 1), be to carry out modification at 70: 30 by Zein powder and starch quality ratio, must contain the modified vegetable protein thing aqueous solution; Step 2 2) in add 5% auxiliary agent, the mass percent that contains modified vegetable protein thing, polyamide resin, vinyl acetate, water-borne acrylic resin, talcum powder, the shared tackiness agent gross dry weight of each raw material of auxiliary agent is: contain modified vegetable protein thing 25%, polyamide resin 25%, urethane resin 20%, water-borne acrylic resin 10%, talcum powder 15%, auxiliary agent 5% preparation tackiness agent.The mechanical property shearing resistance (Mpa) of the sheet material of preparation is 8.95.
Embodiment 17:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier soybean protein (Yunmeng egg-white food company limited of Hubei Province Du Pont) and esterification starch (sky, Jiangsu scholar's power starch company limited) are scattered in the water by mass ratio blend in 50: 50, again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification, the mass percent that the consumption of alkali accounts for soybean protein, esterification starch and NaOH alkali total mass is 4, mass concentration be 30% contain the modified vegetable protein thing aqueous solution.Also can adopt existing modified vegetable protein thing (the albumen thing does not comprise starch, and starch belongs to polyose), be prepared into mass concentration and be 30% contain the modified vegetable protein thing aqueous solution, standby.
2), by mass concentration is that 30% contain the modified vegetable protein thing aqueous solution and mass concentration are that 30% the polyamide resin aqueous solution and mass concentration are 25% polyurethane resin water solution blending, add ground barium sulfate again and regulate solid content, mix the back vigorous stirring, add 2% auxiliary agent again, described auxiliary agent is an ion-exchanged sodium bentonite class 0.5% for the water-based anti-settling agent, defoamer is polysiloxane-based (lot identification mark byk-066N) 0.5%, the efficient sterilizing mould inhibitor is 4,4-dimethyl oxazoline alkanes (lot identification mark Canguard327) 1%, stir, according to using and performance requriements is 7 with 0.01% NaOH solution adjusting pH value, promptly get aqueous adhesive without aldehyde.The mass percent that contains modified soy protein thing (referring to soybean protein and esterification starch), polyamide resin, urethane resin, ground barium sulfate, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 25%, polyamide resin 25%, urethane resin 25%, ground barium sulfate 23%, auxiliary agent 2%.Keep promptly getting in 5 minutes under 110 ℃ and 1.5MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 8.25.
Embodiment 18:
A kind of preparation method of aqueous adhesive without aldehyde, it comprises the steps:
1, it is substantially the same manner as Example 1 to contain the preparation of polyamide resin of quaternary ammonium salt tetra-atomic ring.
2, the preparation of tackiness agent:
1), the preparation of the natural polymer aqueous solution (containing the modified vegetable protein thing aqueous solution): earlier Zein powder (the grand together biotechnology feed corporation,Ltd in Binzhou) and etherification starch (Qingdao perseverance auspicious safe foodstuff additive trade Co., Ltd) are scattered in the water by mass ratio blend in 90: 10, again with mass concentration be 10% NaOH alkaline aqueous solution with it blend it is carried out modification, the mass percent that the consumption of alkali accounts for Zein powder, etherification starch and NaOH alkali total mass is 4, mass concentration be 25% contain the modified vegetable protein thing aqueous solution.Also can adopt existing modified vegetable protein thing, be prepared into mass concentration and be 25% contain the modified vegetable protein thing aqueous solution, standby.
2), by mass concentration is that 25% contain the modified vegetable protein thing aqueous solution and mass concentration are that 40% the polyamide resin aqueous solution and mass concentration are 30% vinyl acetate resin aqueous solution blend, add ground barium sulfate again and regulate solid content, mix the back vigorous stirring, add 3% auxiliary agent again, described auxiliary agent is an ion-exchanged sodium bentonite class 1% for the water-based anti-settling agent, defoamer is polysiloxane-based (lot identification mark byk-066N) 1%, the efficient sterilizing mould inhibitor is 4,4-dimethyl oxazoline alkanes (lot identification mark Canguard 327) 1%, stir, according to use and performance requriements to regulate the pH value with mass concentration master 25% NaOH solution be 6, promptly get aqueous adhesive without aldehyde.The mass percent that contains modified soy protein thing (referring to Zein powder and etherification starch), polyamide resin, vinyl acetate resin, ground barium sulfate, the shared tackiness agent gross dry weight of each raw material of auxiliary agent in the aqueous adhesive without aldehyde is: contain modified vegetable protein thing 30%, polyamide resin 30%, vinyl acetate resin 20%, ground barium sulfate 17%, auxiliary agent 3%.Keep promptly getting in 7 minutes under 120 ℃ and 1.9MPa then testing sheet material, the mechanical property shearing resistance (Mpa) of the sheet material of preparation is 9.13.
Embodiment 19:
A kind of aqueous adhesive without aldehyde preparation method, it comprises the steps:
1) by the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring: the mass ratio of urethane resin is to choose polyamide resin and the urethane resin (for existing material) that contains the quaternary ammonium salt tetra-atomic ring at 1: 1, is mixed with mass concentration and is 5% the macromolecule resin aqueous solution (polyamide resin: urethane resin is a macromolecule resin);
2) natural polymer is selected existing vegetable-protein thing for use, is mixed with mass concentration and is 15% the natural polymer aqueous solution, and is standby;
3) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 80%, choose mass concentration and be 5% the macromolecule resin aqueous solution, mass concentration and be 15% the natural polymer aqueous solution, the mass percent that its macromolecule resin, natural polymer respectively account for macromolecule resin and natural polymer is: macromolecule resin 5%, natural polymer 95%; By the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 19.99%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01%, choose mineral filler, auxiliary agent, standby;
Described mineral filler is a ground barium sulfate; Described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N);
4) mass concentration is that to add mass concentration in 5% the macromolecule resin aqueous solution be 15% the natural polymer aqueous solution, mineral filler, adds auxiliary agent again and stirs and promptly get product.
Embodiment 20:
A kind of aqueous adhesive without aldehyde preparation method, it comprises the steps:
1) by the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring: the mass ratio of urethane resin is to choose polyamide resin and the urethane resin (for existing material) that contains the quaternary ammonium salt tetra-atomic ring at 1: 1, is mixed with mass concentration and is 30% the macromolecule resin aqueous solution (polyamide resin and acrylic resin are macromolecule resin);
2) natural polymer is selected existing vegetable-protein thing and starch for use, and the shared mass percent of vegetable-protein thing is: 99%, and the shared mass percent of starch is: 1%, be mixed with mass concentration and be 20% the natural polymer aqueous solution, standby;
3) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 20%, choose mass concentration and be 30% the macromolecule resin aqueous solution, mass concentration and be 20% the natural polymer aqueous solution, wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 50%, natural polymer 50%; By the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 78%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 2%, choose mineral filler, auxiliary agent, standby;
Described mineral filler is a ground barium sulfate; Described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N);
4) mass concentration is that to add mass concentration in 30% the macromolecule resin aqueous solution be 20% the natural polymer aqueous solution, mineral filler, adds auxiliary agent again and stirs and promptly get product.
Embodiment 21:
A kind of aqueous adhesive without aldehyde preparation method, it comprises the steps:
1) by the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring: the mass ratio of urethane resin is to choose polyamide resin and the urethane resin (for existing material) that contains the quaternary ammonium salt tetra-atomic ring at 1: 1, is mixed with mass concentration and is 70% the macromolecule resin aqueous solution (polyamide resin and vinyl acetate resin are macromolecule resin);
2) natural polymer is selected existing modified vegetable protein thing and starch for use, and the shared mass percent of modified vegetable protein thing is: 30%, and the shared mass percent of starch is: 70%, be mixed with mass concentration and be 40% the natural polymer aqueous solution, standby;
3) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 20%, choose mass concentration and be 70% the macromolecule resin aqueous solution, mass concentration and be 40% the natural polymer aqueous solution, wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 95%, natural polymer 5%; By the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 79.99%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01%, choose mineral filler, auxiliary agent, standby;
Described mineral filler is a ground barium sulfate; Described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N);
4) mass concentration is that to add mass concentration in 70% the macromolecule resin aqueous solution be 40% the natural polymer aqueous solution, mineral filler, adds auxiliary agent again and stirs and promptly get product.
Embodiment 22:
A kind of aqueous adhesive without aldehyde preparation method, it comprises the steps:
1) by the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring: the mass ratio of urethane resin is to choose polyamide resin and the urethane resin (for existing material) that contains the quaternary ammonium salt tetra-atomic ring at 1: 1, is mixed with mass concentration and is 30% the macromolecule resin aqueous solution (polyamide resin and urethane resin are macromolecule resin);
2) natural polymer is selected existing modified vegetable protein thing and treated starch for use, the shared mass percent of modified vegetable protein thing is: 70%, the shared mass percent of treated starch is: 30%, be mixed with mass concentration and be 20% the natural polymer aqueous solution, and standby;
3) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 39%, choose mass concentration and be 30% the macromolecule resin aqueous solution, mass concentration and be 20% the natural polymer aqueous solution, wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 60%, natural polymer 40%, and standby; By the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 60%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 1%, choose mineral filler, auxiliary agent, standby;
Described mineral filler is a ground barium sulfate; Described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N);
4) mass concentration is that to add mass concentration in 30% the macromolecule resin aqueous solution be 20% the natural polymer aqueous solution, mineral filler, adds auxiliary agent again and stirs and promptly get product.
Embodiment 23:
A kind of aqueous adhesive without aldehyde preparation method, it comprises the steps:
1) chooses the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring (for existing material), be mixed with mass concentration and be 30% the macromolecule resin aqueous solution;
2) natural polymer is selected existing starch for use, is mixed with mass concentration and is 20% the natural polymer aqueous solution, and is standby;
3) press the shared macromolecule resin of macromolecule resin and natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 39%, choose mass concentration and be 30% the macromolecule resin aqueous solution, mass concentration is 20% the natural polymer aqueous solution, macromolecule resin wherein, the mass percent that natural polymer respectively accounts for macromolecule resin and natural polymer is: macromolecule resin 60%, natural polymer 40%, choose mass concentration and be 30% the macromolecule resin aqueous solution, mass concentration is 20% the natural polymer aqueous solution, and is standby; By the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 60%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 1%, choose mineral filler, auxiliary agent, standby;
Described mineral filler is a ground barium sulfate; Described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N);
4) mass concentration is that to add mass concentration in 30% the macromolecule resin aqueous solution be 20% the natural polymer aqueous solution, mineral filler, adds auxiliary agent again and stirs and promptly get product.
Embodiment 24:
A kind of aqueous adhesive without aldehyde preparation method, it comprises the steps:
1) by the polyamide resin that contains the quaternary ammonium salt tetra-atomic ring: the mass ratio of urethane resin is to choose polyamide resin and the urethane resin (for existing material) that contains the quaternary ammonium salt tetra-atomic ring at 1: 1, is mixed with mass concentration and is 30% the macromolecule resin aqueous solution (polyamide resin and urethane resin are macromolecule resin);
2) natural polymer is selected existing treated starch for use, is mixed with mass concentration and is 20% the natural polymer aqueous solution, and is standby;
3) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 39%, choose mass concentration and be 30% the macromolecule resin aqueous solution, mass concentration and be 20% the natural polymer aqueous solution, wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 60%, natural polymer 40%, and standby; By the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 60%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 1%, choose mineral filler, auxiliary agent, standby;
Described mineral filler is a ground barium sulfate; Described auxiliary agent is that defoamer is polysiloxane-based (lot identification mark byk-066N);
4) mass concentration is that to add mass concentration in 30% the macromolecule resin aqueous solution be 20% the natural polymer aqueous solution, mineral filler, adds auxiliary agent again and stirs and promptly get product.
Claims (2)
1. an aqueous adhesive without aldehyde is characterized in that it is that the macromolecule resin aqueous solution of 5-70%, the natural polymer aqueous solution, mineral filler and the auxiliary agent raw material that mass concentration is 15-40% mix by mass concentration; The shared macromolecule resin of macromolecule resin and natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 20-80%, the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 19.99-79.99%, and the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01-5%; Wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 5-95%, natural polymer 5-95%;
Described natural polymer is any one or any two kinds or any mixture more than two kinds in vegetable-protein thing, modified vegetable protein thing, starch, the treated starch, any two kinds or any when mixing more than two kinds, is any proportioning; Perhaps natural polymer is vegetable-protein thing and starch-mixed modifier, and shared vegetable-protein thing of starch and starch quality per-cent are: 1-70, and shared vegetable-protein thing of vegetable-protein thing and starch quality per-cent are: 30-99;
Described mineral filler is any one or any two kinds or any mixture more than two kinds in ground barium sulfate, silica powder, talcum powder, the wollastonite powder, any two kinds or any when mixing more than two kinds, is any proportioning; Described auxiliary agent is any one or any two kinds or any mixture more than two kinds in defoamer, efficient sterilizing mould inhibitor, the water-based anti-settling agent, any two kinds or any when mixing more than two kinds, is any proportioning;
Described macromolecule resin is the mixture of any one or any two kinds or three kinds in the polyamide resin of quaternary ammonium salt tetra-atomic ring and acrylic resin, urethane resin, the vinyl acetate resin, the mass percent that the polyamide resin of its quaternary ammonium salt tetra-atomic ring accounts for whole macromolecule resin is: 50-100 is any proportioning between acrylic resin, urethane resin, the vinyl acetate resin;
Described vegetable-protein thing is the mixture of a kind of in soybean protein, the zein or two kinds, two kinds when mixing, is any proportioning.
2. the preparation method of a kind of aqueous adhesive without aldehyde as claimed in claim 1 is characterized in that it comprises the steps:
1) by macromolecule resin and the shared macromolecule resin of natural polymer, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent is: 20-80%, choosing mass concentration is the macromolecule resin aqueous solution of 5-70%, the natural polymer aqueous solution that mass concentration is 15-40%, wherein macromolecule resin, natural polymer respectively account for the mass percent of macromolecule resin and natural polymer and are: macromolecule resin 5-95%, natural polymer 5-95%, and standby;
Described natural polymer is any one or any two kinds or any mixture more than two kinds in vegetable-protein thing, modified vegetable protein thing, starch, the treated starch, any two kinds or any when mixing more than two kinds, is any proportioning; Perhaps natural polymer is vegetable-protein thing and starch-mixed modifier, and shared vegetable-protein thing of starch and starch quality per-cent are: 1-70, and shared vegetable-protein thing of vegetable-protein thing and starch quality per-cent are: 30-99;
2) by the shared macromolecule resin of mineral filler, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent be: 19.99-79.99%, the shared macromolecule resin of auxiliary agent, natural polymer, mineral filler and auxiliary agent raw material total mass per-cent are: 0.01-5%, choose mineral filler, auxiliary agent, standby;
3) mass concentration is that to add mass concentration in the macromolecule resin aqueous solution of 5-70% be the natural polymer aqueous solution, the mineral filler of 15-40%, adds auxiliary agent again and stirs and promptly get product.
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| CN101629019B (en) * | 2009-01-21 | 2011-09-07 | 郑州佰沃生物质材料有限公司 | Basic biomass synthetic resin and preparation method and application thereof |
| CN102367367B (en) * | 2011-08-31 | 2013-02-13 | 华南理工大学 | Preparation method for environment-friendly starch-based binder |
| CN103333654B (en) * | 2013-05-31 | 2014-11-26 | 安徽祈艾特电子科技有限公司 | Adhesive used for waterproof carton, and preparation method thereof |
| CN103571431B (en) * | 2013-11-01 | 2016-01-20 | 上海置辰环保科技有限公司 | A kind of binding agent and preparation method thereof |
| CN103849349B (en) * | 2014-03-14 | 2016-03-09 | 江南大学 | A kind of aqueous adhesive and preparation method thereof |
| CN106147647A (en) * | 2015-04-21 | 2016-11-23 | 浙江新木材料科技有限公司 | A kind of tencel adhesive |
| CN106147646A (en) * | 2015-04-21 | 2016-11-23 | 浙江新木材料科技有限公司 | A kind of viscose stick |
| CN107955573A (en) * | 2017-12-05 | 2018-04-24 | 江南大学 | A kind of preparation method of modified soy protein adhesive |
| CN110561885A (en) * | 2019-08-30 | 2019-12-13 | 李魁 | Preparation method of high-barrier flexible aluminized film |
| CN111890482B (en) * | 2020-08-18 | 2021-05-07 | 宁夏福宁木业有限公司 | Formaldehyde-free environment-friendly plywood and manufacturing method thereof |
| CN113234409B (en) * | 2021-04-29 | 2022-06-03 | 北新集团建材股份有限公司 | Composite adhesive and application thereof |
| CN114262603A (en) * | 2022-01-20 | 2022-04-01 | 佛山市卓仕高新型材料有限公司 | Environment-friendly waterproof adhesive and preparation method thereof |
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| 大豆蛋白胶黏剂制备过程中的黏度变化及其黏合性研究. 张军涛等.中国油脂，第30卷第7期. 2005 * |
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