CN104293248A - Modified adhesive - Google Patents
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- CN104293248A CN104293248A CN201410533460.0A CN201410533460A CN104293248A CN 104293248 A CN104293248 A CN 104293248A CN 201410533460 A CN201410533460 A CN 201410533460A CN 104293248 A CN104293248 A CN 104293248A
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Abstract
The invention discloses an adhesive and particularly relates to a modified adhesive. The modified adhesive consists of the following raw materials in parts by weight: 70-95 parts of elastic rubber, 25-35 parts of phthalic anhydride, 7-11 parts of furfuryl alcohol extracted from natural plant, 10-12 parts of triethylene glycol, 15-18 parts of glutaric acid, 8-10 parts of butantriol, 5-7 parts of zinc oxide powder, 3-5 parts of magnesium oxide, 15-25 parts of chloroprene rubber, 2-3 parts of softening oil, 15-20 parts of dimethyl carbonate, 1-3 parts of benzoyl peroxide, 4-8 parts of ethyl acetate, 1-4 parts of an emulsifier, 20-30 parts of flour, 5*10<-5>-9*10<-5> parts of nano sliver, 1-3 parts of a flame retardant, 0.8-2.5 parts of a catalyst, 3-7 parts of a bamboo vinegar aqueous liquid, 6-13 parts of bamboo carbon powder with grain size of 0.01-0.06mm, wherein the bamboo vinegar aqueous liquid is a mixed liquid of bamboo vinegar, a chelating agent and water in a weight ratio of 1 to (0.1-0.2) to (60-100); the bamboo carbon powder is prepared by the steps such as raw material pre-treatment, primary carbon preparation, activation treatment and pelletizing; the elastic rubber comprises first elastic rubber and second elastic rubber mixed in a weight ratio of (1-3) to 1. The adhesive has good antibacterial activity, stability and adhesion property.
Description
Technical field
The present invention relates to a kind of binding agent, particularly relate to a kind of modified binder.
Background technology
Bamboo fibers in the market has following two classes: one is the regenerated fibre produced by bamboo pulp, is commonly referred to bamboo pulp fiber; Two is the fibers directly extracted from bamboo through special process, is called bamboo fiber.Because bamboo fiber has more superior performance in water absorbability, ventilation property, spinning property etc., therefore study spinning property bamboo fiber and there is obvious economic benefit and good social benefit.Although bamboo fiber products itself has certain biocidal property, but still can produce mildew after repeated use, affect perception and use.
It is multi-field that binding agent can be widely used in wood working, building decoration, fabric bonding etc., extensive market, but existing binding agent is mostly unavoidably containing objectionable impurities formaldehyde, and having free formaldehyde after using discharges, and environmental-protecting performance is to be improved.
CN102690618B (2013-12-4) discloses a kind of preparation method of thermosetting acrylic resin binding agent, but this binding agent is mainly used in glass wool, is not suitable for bamboo fiber products.
Summary of the invention
The object of this invention is to provide a kind of biocidal property good, stability and dispersing property good, bond properties is good, the modified binder that is especially suitable for bamboo fiber products.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of modified binder, it is made up of the raw material of following parts by weight:
Phthalic anhydride 25-35 part, the furfuryl alcohol 7-11 part of extracting from natural phant, triethylene glycol 10-12 part, pentanedioic acid 15-18 part, trihydroxybutane 8-10 part, zinc white 5-7 part, magnesium oxide 3-5 part, chloroprene rubber 15-25 part, elastic plastic 70-95 part, softening oil 2-3 part, methylcarbonate 15-20 part, benzoyl peroxide 1-3 part, vinyl acetic monomer 4-8 part, emulsifying agent 1-4 part, flour 20-30 part, nanometer silver 5 × 10
-5-9 × 10
-5part, fire retardant 1-3 part, catalyzer 0.8-2.5 part, 3-7 part bamboo vinegar aqueous solution, 6-13 part particle diameter are the bamboo charcoal powder of 0.01-0.06mm;
The described bamboo vinegar aqueous solution is the mixing solutions of the bamboo vinegar of weight ratio 1:0.1-0.2:60-100, sequestrant and water composition;
Described fire retardant is counted composed of the following components by weight: ammonium low polyphosphate 20 ~ 50 parts, 10 ~ 25 parts, ammonium phosphate, ammonium pyrophosphate 6 ~ 12 parts, 5 ~ 20 parts, ammonium sulfate, boric acid 5 ~ 10 parts, 10 ~ 25 parts, water;
Described bamboo charcoal powder obtains through raw material pre-treatment, primary carbon preparation, activation treatment and granulation step; The concrete preparation method of described bamboo charcoal powder is:
A. raw material pre-treatment: bamboo is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa ~-0.001MPa, then carry out microwave treatment, microwave frequency is 300MHz ~ 950MHz, and microwave treatment time is 1 ~ 3min;
B. primary carbon preparation: the bamboo through raw material pre-treatment gained is experienced successively drying, pre-charing, charing, calcining and cooling, control calcining and be incubated 40-80min with the ramp of 5-15 DEG C/min to 700-750 DEG C, and then be incubated 2-8h with the ramp of 5-15 DEG C/min to 1000-1500 DEG C, then 300-400 DEG C is cooled to the speed of 18-25 DEG C/min, cool to room temperature with the furnace again, obtain primary carbon;
C. then activation treatment: by gained primary carbon and 140-160g/L polymaleic acid and 40-70g/L inferior sodium phosphate mixed solution 1:3-4 mixing submergence 3-5h is in mass ratio neutral by washed with de-ionized water to pH value;
D. granulate;
Described emulsifying agent is one or more in polyoxyethylene octylphenol ether, sulfonated castor oil, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate;
Described elastic plastic comprises the first elastic plastic and the second elastic plastic that mix by weight 1-3:1;
The solids content that described first elastic plastic comprises 10-35 part weight is the Emulsion acrylic resin of 60-75%, 10-15 part aqueous polyurethane, the acrylic resin powder of 5-8 part weight, the solids content of 2-6 part weight are the EVA emulsion of 20-35% and the Chlorinated Polypropylene III of 1-4 part weight;
The preparation method of described Emulsion acrylic resin is: the acrylate monomer mixed solution of preparation 80-110 part weight is stand-by, then the emulsifying agent of 5-7 part weight of several compositions in polyoxyethylene octylphenol ether, sulfonated castor oil, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, the sodium bicarbonate of 0.3-0.7 part weight and deionized water are joined in reactor, add the 1/3 acrylate monomer mixed solution prepared again wherein, be warming up to 50-90 DEG C, fully stir 20-40min; Be warming up to 60-100 DEG C, drip remaining 2/3 acrylate monomer mixed solution and ammonium persulfate solution initiator, time for adding controls, for 1-4h, to ensure that monomer drips prior to initiator solution; Dropwise rear insulation 1-4h, after cooling, regulate ph value of emulsion to about 7;
Described nanometer silver is prepared from according to following steps:
(1) sodium dodecyl sulfate solution, water polyacrylic acid and hydrazine hydrate solution are added in silver nitrate aqueous solution and obtain mixed solution, the mol ratio of described sodium laurylsulfonate and Silver Nitrate is 4-6:1; The mol ratio of described water polyacrylic acid and Silver Nitrate is 0.4-0.6:1; ; The mol ratio of described hydrazine hydrate and Silver Nitrate is 0.2-0.3:1;
(2) in described mixed solution, add crown ether and sodium-metaphosphate, the mol ratio of described crown ether and Silver Nitrate is 3-5:1; The mol ratio of described sodium-metaphosphate and Silver Nitrate is 0.8-1.3:1, and control ph is 8-9, obtains nanometer silver.
The per-cent that the present invention relates to, unless stated otherwise, all refers to mass percent.
Advantage of the present invention is:
1. contriver selects specific activation treatment to coordinate raw material pre-treatment and primary carbon preparation, obtains the bamboo charcoal powder with high bacteriostasis rate and antibacterial value; Meanwhile, bamboo charcoal powder, as the interpolation raw material of binding agent, can further improve again the biocidal property of binding agent, stability, dispersiveness and binding property;
Environmental protection binding agent composition of the present invention environmental protection, while the larger sticking power of imparting bamboo fiber products, can prevent binding agent from coming off, and increases bactericidal properties and the mildew resistance of bamboo fiber products;
2. the combination matching of nanometer silver, furfuryl alcohol, benzoyl peroxide and elastic plastic can improve some performance of binding agent, and makes it have very strong sterilizing ability, stability, dispersing property and bond properties simultaneously;
3. crown ether have hydrophobic external skeletal and hydrophilic can with the inner chamber of metal ion Cheng Jian, stable title complex can be formed with alkalimetal ion.Meanwhile, the present invention is engaged in follow-up reduction reaction and adds sodium-metaphosphate, makes on the one hand free in reaction system or exposed reduction negative ion have higher reactive behavior; Meanwhile, after basic metal and crown ether generation ligand complex, alkali metal cation is coated in inner chamber by crown ether, just pulls open the distance in nanometer silver system between positive and negative charge thus, make nanometer silver can stable dispersion in the aqueous solution, not easily reunite;
4., by each raw material of binding agent and the particular combination of nanometer silver, can not occur to reunite and particle growth in depositing, and can not be oxidized, stability and good dispersity.
As preferably, the sequestrant in the described bamboo vinegar aqueous solution is at least one in ethylenediamine tetraacetic acid (EDTA) or disodium edta.
As preferably, the preparation method of described second elastic plastic is: be that the polyvinyl alcohol water solution of 30-45% and the aqueous polyurethane aqueous solution of 5-10% are heated to 60-80 DEG C by mass concentration, be cooled to 30-50 DEG C and add acrylate 10-15%, then add potassium hydroxide 0.1-0.2% and be warming up to 100-110 DEG C, then the plant phenols 2-4% adding sclerotin albumen 5-8%, rosin fat 6-9%, extract from natural phant; React and be cooled to 45-55 DEG C in 3-5 hour, then add Sodium Benzoate 0.06-0.08%, ditertiary butyl peroxide 0.01-0.02% and vinyl acetic monomer 0.1-0.3%, stir 1-1.5 hour, cooling, obtained described second elastic plastic.
Second elastic plastic of the present invention not only environmental protection, water-fast, mildew-resistant, and bonding strength is high, with the first elastic plastic in proportion combination matching in environmental protection binding agent, give environmental protection binding agent of the present invention and there is better bactericidal properties, stability, dispersing property and bond properties.
As preferably, described Emulsion acrylic resin is synthesized as monomer and emulsifying agent, ammonium persulfate initiator, sodium bicarbonate and deionized water by any one or a few in any one or a few in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, dodecylacrylate, octadecyl acrylate and methacrylic acid, vinylformic acid, acrylamide, vinyl cyanide, Methacrylamide, vinylbenzene.
As preferably, described mixed solution is heated to 45-55 DEG C add crown ether and sodium-metaphosphate in described mixed solution before by described step (2).
As preferably, described step (2) adds crown ether and sodium-metaphosphate post-heating to 70-85 DEG C in described mixed solution, Keep agitation 5-8min.
As preferably, described step (2) is carried out under microwave vacuum condition, and be specifically evacuated to vacuum tightness for-0.02MPa ~-0.001MPa, then carry out microwave treatment, microwave frequency is 100MHz ~ 230MHz, and microwave treatment time is 3 ~ 7s.
More preferably, described crown ether is bicyclohexane also-18-hat-6.
As preferably, the described furfuryl alcohol extracted from natural phant is selected from the furfuryl alcohol extracted from the wheat bran or bamboo wood chip of the core slag of corn cob, oat or wheat.
As preferably, the described plant phenols extracted from natural phant is Eugenol or cardanol.
More preferably, described catalyzer is sodium hydroxide.
In sum, the present invention has following beneficial effect:
1, environmental protection binding agent composition of the present invention environmental protection, while the larger sticking power of imparting bamboo fiber products, can prevent binding agent from coming off, and increases bactericidal properties and the mildew resistance of bamboo fiber products;
2, the combination matching of nanometer silver, furfuryl alcohol, benzoyl peroxide and elastic plastic can improve some performance of binding agent, and makes it have very strong sterilizing ability, stability, dispersing property and bond properties simultaneously;
3, by each raw material of binding agent and the particular combination of nanometer silver, can not occur to reunite and particle growth in depositing, and can not be oxidized, stability and good dispersity.
Embodiment
Embodiment one
The preparation of nanometer silver:
(1) sodium dodecyl sulfate solution, water polyacrylic acid and hydrazine hydrate solution are added in silver nitrate aqueous solution and obtain mixed solution, the mol ratio of sodium laurylsulfonate and Silver Nitrate is 4:1; The mol ratio of water polyacrylic acid and Silver Nitrate is 0.4:1; The mol ratio of hydrazine hydrate and Silver Nitrate is 0.2:1;
(2) in mixed solution, add bicyclohexane also-18-hat-6 and sodium-metaphosphate, bicyclohexane also-18-hat-6 is 3:1 with the mol ratio of Silver Nitrate; The mol ratio of sodium-metaphosphate and Silver Nitrate is 0.8:1, and control ph is 8-9, obtains nanometer silver.
The concrete preparation method of bamboo charcoal powder is:
A. raw material pre-treatment: bamboo is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.01MPa, then carry out microwave treatment, microwave frequency is 650MHz, and microwave treatment time is 2min;
B. primary carbon preparation: the bamboo through raw material pre-treatment gained is experienced successively drying, pre-charing, charing, calcining and cooling, controlling calcining with the ramp to 730 of 10 DEG C/min DEG C is incubated 50min, and then be incubated 6h with the ramp to 1300 of 8 DEG C/min DEG C, then 350 DEG C are cooled to the speed of 22 DEG C/min, cool to room temperature with the furnace again, obtain primary carbon;
C. then activation treatment: by gained primary carbon and 140-160g/L polymaleic acid and 60g/L inferior sodium phosphate mixed solution 1:3.5 mixing submergence 4h is in mass ratio neutral by washed with de-ionized water to pH value;
D. granulate.
The preparation method of the second elastic plastic is: be that the polyvinyl alcohol water solution of 30% and the aqueous polyurethane aqueous solution of 5% are heated to 60 DEG C by mass concentration, be cooled to 30 DEG C and add acrylate 10%, then add potassium hydroxide 0.1% and be warming up to 100 DEG C, then add sclerotin albumen 5%, rosin fat 6%, Eugenol 2%; React and be cooled to 45 DEG C in 3 hours, then add Sodium Benzoate 0.06%, ditertiary butyl peroxide 0.01% and vinyl acetic monomer 0.1%, stir 1 hour, cooling, obtained second elastic plastic.
The preparation of Emulsion acrylic resin:
4.63 parts of polyoxyethylene octylphenol ethers (OP-10), 1.67 parts of sodium lauryl sulphate, 0.6 part of sodium bicarbonate are dissolved in 70 parts of deionized waters, then add in reactor, are warming up to about 70 DEG C; Take 1.3 parts of methyl methacrylates, 2.14 parts of vinylbenzene, 50.9 parts of butyl acrylates, 29.08 parts of Isooctyl acrylate monomers, 2.45 parts of butyl methacrylate, 1.8 parts of vinyl cyanide, 0.8 part of vinylformic acid and 1.44 parts of methacrylic acids make mix monomer; 1/3 part of mix monomer is added in reactor, at 85 DEG C of pre-emulsification 30min; Then 0.45 part of initiator ammonium persulfate (APS) joined and make solution in 50 parts of deionized waters and drop to gradually in reactor, drip residual monomer, about 3h dropwises simultaneously, controls mix monomer and drips prior to initiator solution; After dropwising, after insulation 1h, namely can be made into stand-by emulsion;
The preparation of acrylic resin powder: 3 parts of BPO are dissolved in 13.3 parts of methyl methacrylates, 61 parts of vinylbenzene, 21.4 parts of n-butyl acrylates and 4.3 parts of acrylic acid mix monomers; The mix monomer being dissolved with initiator is joined and is dissolved with in 500 parts of deionized waters of 7.5 parts of protective colloids, high-speed stirring, in 30min, be warming up to 85 DEG C simultaneously; Product is collected after insulation reaction 4h; Product is dried after pulverizing, make acrylic resin powder with 200 eye mesh screens filtrations stand-by.
The solids content that first elastic plastic comprises 10 parts of weight is the Emulsion acrylic resin of 60-75%, 10 parts of aqueous polyurethanes, the acrylic resin powder of 5 parts of weight, the solids content of 2 parts of weight are the EVA emulsion of 20% and the Chlorinated Polypropylene III of 1 part of weight.
Fire retardant is counted composed of the following components by weight: ammonium low polyphosphate 20 parts, 10 parts, ammonium phosphate, ammonium pyrophosphate 6 parts, 5 parts, ammonium sulfate, boric acid 5 parts, 25 parts, water.
The composition and ratio of modified binder:
Phthalic anhydride 25 parts, the furfuryl alcohol 7 parts extracted from the core slag of corn cob, triethylene glycol 10 parts, pentanedioic acid 15 parts, trihydroxybutane 8 parts, zinc white 5 parts, 3 parts, magnesium oxide, chloroprene rubber 15 parts, elastic plastic 70 parts, softening oil 2 parts, methylcarbonate 15 parts, benzoyl peroxide 1 part, vinyl acetic monomer 4 parts, emulsifying agent 1 part, 20 parts, flour, nanometer silver 5 × 10
-5, fire retardant 3 parts, sodium hydroxide catalyst 1.5 parts, 5 parts of the bamboo vinegar aqueous solution, 8 parts of particle diameters are the bamboo charcoal powder of 0.01-0.06mm; The bamboo vinegar aqueous solution is the mixing solutions of the bamboo vinegar of weight ratio 1:0.15:80, disodium edta sequestrant and water composition.
Emulsifying agent is polyoxyethylene octylphenol ether;
Elastic plastic comprises the first elastic plastic and the second elastic plastic that mix by weight 1:1.
Embodiment two
The preparation of nanometer silver:
(1) sodium dodecyl sulfate solution, water polyacrylic acid and hydrazine hydrate solution are added in silver nitrate aqueous solution and obtain mixed solution, the mol ratio of sodium laurylsulfonate and Silver Nitrate is 6:1; The mol ratio of water polyacrylic acid and Silver Nitrate is 0.6:1; ; The mol ratio of hydrazine hydrate and Silver Nitrate is 0.3:1;
(2) in mixed solution, add bicyclohexane also-18-hat-6 and sodium-metaphosphate, bicyclohexane also-18-hat-6 is 5:1 with the mol ratio of Silver Nitrate; The mol ratio of sodium-metaphosphate and Silver Nitrate is 1.3:1, and control ph is 8-9, obtains nanometer silver.
The composition and ratio of modified binder:
Phthalic anhydride 35 parts, the furfuryl alcohol 11 parts, triethylene glycol 12 parts, pentanedioic acid 18 parts, trihydroxybutane 10 parts, zinc white 7 parts, 5 parts, magnesium oxide, chloroprene rubber 25 parts, elastic plastic 95 parts, softening oil 3 parts, methylcarbonate 20 parts, benzoyl peroxide 3 parts, vinyl acetic monomer 8 parts, emulsifying agent 4 parts, 30 parts, flour, the nanometer silver 5 × 10 that extract from the wheat bran of oat or wheat
-5-9 × 10
-5, fire retardant 1 part, sodium hydroxide catalyst 2.5 parts, 7 parts of the bamboo vinegar aqueous solution, 13 parts of particle diameters are the bamboo charcoal powder of 0.01-0.06mm; The bamboo vinegar aqueous solution is the mixing solutions of the bamboo vinegar of weight ratio 1:0.2:100, disodium edta sequestrant and water composition;
Described bamboo charcoal powder obtains through raw material pre-treatment, primary carbon preparation, activation treatment and granulation step; The concrete preparation method of bamboo charcoal powder is:
A. raw material pre-treatment: bamboo is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.001MPa, then carry out microwave treatment, microwave frequency is 950MHz, and microwave treatment time is 3min;
B. primary carbon preparation: the bamboo through raw material pre-treatment gained is experienced successively drying, pre-charing, charing, calcining and cooling, controlling calcining with the ramp to 750 of 15 DEG C/min DEG C is incubated 80min, and then be incubated 2-8h with the ramp to 1500 of 15 DEG C/min DEG C, then 400 DEG C are cooled to the speed of 25 DEG C/min, cool to room temperature with the furnace again, obtain primary carbon;
C. then activation treatment: by gained primary carbon and 160g/L polymaleic acid and 70g/L inferior sodium phosphate mixed solution 1:4 mixing submergence 5h is in mass ratio neutral by washed with de-ionized water to pH value;
D. granulate.
Fire retardant is counted composed of the following components by weight: ammonium low polyphosphate 50 parts, 25 parts, ammonium phosphate, ammonium pyrophosphate 12 parts, 20 parts, ammonium sulfate, boric acid 10 parts, 10 parts, water.
Emulsifying agent is sodium lauryl sulphate;
Elastic plastic comprises the first elastic plastic and the second elastic plastic that mix by weight 3:1;
The solids content that first elastic plastic comprises 35 parts of weight is the Emulsion acrylic resin of 75%, 15 parts of aqueous polyurethanes, the acrylic resin powder of 8 parts of weight, the solids content of 6 parts of weight are the EVA emulsion of 35% and the Chlorinated Polypropylene III of 4 parts of weight;
The preparation of Emulsion acrylic resin: 5.28 parts of sulfonated castor oils, 1.84 parts of sodium lauryl sulphate, 0.66 part of sodium bicarbonate are dissolved in 70 parts of deionized waters, then join in reactor, are warming up to about 70 DEG C; Take 6.12 parts of methyl methacrylates, 62.78 parts of butyl acrylates, 11.58 parts of vinylbenzene, 7.35 parts of butyl methacrylate, 0.88 part of vinylformic acid, 1.58 parts of methacrylic acids, 8.7 parts of Isooctyl acrylate monomers make mix monomer; 1/3 part of mix monomer is added in reactor, at 85 DEG C of pre-emulsification 30min; Then joined by 0.5 part of initiator A PS and make solution in 50 parts of deionized waters and drop to gradually in reactor, drip residual monomer, about 3h dropwises simultaneously, controls mix monomer and drips prior to initiator solution; After dropwising, after insulation 1h, namely can be made into stand-by emulsion;
The preparation of acrylic resin powder: 4 parts of BPO are dissolved in 15.96 parts of methyl methacrylates, 65 parts of vinylbenzene, 23.54 parts of n-butyl acrylates, 4.3 parts of acrylic acid mix monomers; The mix monomer being dissolved with initiator is joined and is dissolved with in 600 parts of deionized waters of 8 parts of protective colloids, high-speed stirring, in 30min, be warming up to 85 DEG C simultaneously; Product is collected after insulation reaction 4h; Product is dried after pulverizing, make acrylic resin powder with 200 eye mesh screens filtrations stand-by.The preparation method of the second elastic plastic is: be that the polyvinyl alcohol water solution of 38% and the aqueous polyurethane aqueous solution of 9% are heated to 80 DEG C by mass concentration, be cooled to 50 DEG C and add acrylate 15%, then add potassium hydroxide 0.2% and be warming up to 110 DEG C, then add sclerotin albumen 8%, rosin fat 9%, cardanol 2-4%; React and be cooled to 55 DEG C in 5 hours, then add Sodium Benzoate 0.08%, ditertiary butyl peroxide 0.02% and vinyl acetic monomer 0.3%, stir 1.5 hours, cooling, obtained second elastic plastic.
Embodiment three
The preparation of nanometer silver:
(1) sodium dodecyl sulfate solution, water polyacrylic acid and hydrazine hydrate solution are added in silver nitrate aqueous solution and obtain mixed solution, the mol ratio of sodium laurylsulfonate and Silver Nitrate is 5:1; The mol ratio of water polyacrylic acid and Silver Nitrate is 0.5:1; ; The mol ratio of hydrazine hydrate and Silver Nitrate is 0.25:1;
(2) in mixed solution, add bicyclohexane also-18-hat-6 and sodium-metaphosphate, bicyclohexane also-18-hat-6 is 4:1 with the mol ratio of Silver Nitrate; The mol ratio of sodium-metaphosphate and Silver Nitrate is 1:1, and control ph is 8-9, obtains nanometer silver.
The composition and ratio of modified binder:
Phthalic anhydride 30 parts, the furfuryl alcohol 7-11 part extracted from bamboo wood chip, triethylene glycol 11 parts, pentanedioic acid 16 parts, trihydroxybutane 9 parts, zinc white 6 parts, 4 parts, magnesium oxide, chloroprene rubber 19 parts, elastic plastic 85 parts, softening oil 2.5 parts, methylcarbonate 18 parts, benzoyl peroxide 2 parts, vinyl acetic monomer 7 parts, emulsifying agent 3 parts, 27 parts, flour, nanometer silver 6 × 10
-5, sodium hydroxide catalyst 0.8 part, fire retardant 2 parts, 3 parts of the bamboo vinegar aqueous solution, 6 parts of particle diameters are the bamboo charcoal powder of 0.01-0.06mm; The bamboo vinegar aqueous solution is the mixing solutions of the bamboo vinegar of weight ratio 1:0.1:60, ethylenediamine tetraacetic acid (EDTA) and water composition;
Described bamboo charcoal powder obtains through raw material pre-treatment, primary carbon preparation, activation treatment and granulation step; The concrete preparation method of bamboo charcoal powder is:
A. raw material pre-treatment: bamboo is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa, then carry out microwave treatment, microwave frequency is 300MHz, and microwave treatment time is 1min;
B. primary carbon preparation: the bamboo through raw material pre-treatment gained is experienced successively drying, pre-charing, charing, calcining and cooling, controlling calcining with the ramp to 700 of 5 DEG C/min DEG C is incubated 40min, and then be incubated 2h with the ramp to 1000 of 5 DEG C/min DEG C, then 300 DEG C are cooled to the speed of 18 DEG C/min, cool to room temperature with the furnace again, obtain primary carbon;
C. then activation treatment: by gained primary carbon and 140g/L polymaleic acid and 40g/L inferior sodium phosphate mixed solution 1:3 mixing submergence 3h is in mass ratio neutral by washed with de-ionized water to pH value;
D. granulate.
Fire retardant is counted composed of the following components by weight: ammonium low polyphosphate 30 parts, 15 parts, ammonium phosphate, ammonium pyrophosphate 8 parts, 15 parts, ammonium sulfate, boric acid 8 parts, 18 parts, water.
Emulsifying agent is one or more in polyoxyethylene octylphenol ether, sulfonated castor oil, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate;
Elastic plastic comprises the first elastic plastic and the second elastic plastic that mix by weight 2:1;
The solids content that first elastic plastic comprises 25 parts of weight is the Emulsion acrylic resin of 65%, 12 parts of aqueous polyurethanes, the acrylic resin powder of 7 parts of weight, the solids content of 5 parts of weight are the EVA emulsion of 28% and the Chlorinated Polypropylene III of 3 parts of weight;
The preparation of Emulsion acrylic resin: 4.5 parts of OP-10,1.62 parts of sodium lauryl sulphate, 0.55 part of sodium bicarbonate are dissolved in 70 parts of deionized waters, then join in reactor, are warming up to about 70 DEG C; Take 5.42 parts of methyl methacrylates, 54.79 parts of butyl acrylates, 10.11 parts of vinylbenzene, 6.55 parts of butyl methacrylate, 0.76 part of vinylformic acid, 1.41 parts of methacrylic acids, 7.83 parts of Isooctyl acrylate monomers make mix monomer; 1/3 part of mix monomer is added in reactor, at 85 DEG C of pre-emulsification 30min; Then joined by 0.42 part of initiator A PS and make solution in 50 parts of deionized waters and drop to gradually in reactor, drip residual monomer, about 3h dropwises simultaneously, controls mix monomer and drips prior to initiator solution; After dropwising, after insulation 1h, namely can be made into stand-by emulsion;
The preparation of acrylic resin powder: 2.7 parts of BPO are dissolved in 11.97 parts of methyl methacrylates, 57.95 parts of vinylbenzene, 19.26 parts of n-butyl acrylates, 4.1 parts of acrylic acid mix monomers; The mix monomer being dissolved with initiator is joined and is dissolved with in 420 parts of deionized waters of 6 parts of protective colloids, high-speed stirring, in 30min, be warming up to 85 DEG C simultaneously; Product is collected after insulation reaction 4h; Product is dried after pulverizing, make acrylic resin powder with 200 eye mesh screens filtrations stand-by;
The preparation method of the second elastic plastic is: be that the polyvinyl alcohol water solution of 35% and the aqueous polyurethane aqueous solution of 8% are heated to 69 DEG C by mass concentration, be cooled to 40 DEG C and add acrylate 13%, then add potassium hydroxide 0.15% and be warming up to 105 DEG C, then add sclerotin albumen 6%, rosin fat 8%, Eugenol or cardanol 3%; React and be cooled to 50 DEG C in 4 hours, then add Sodium Benzoate 0.07%, ditertiary butyl peroxide 0.015% and vinyl acetic monomer 0.2%, stir 1.2 hours, cooling, obtained second elastic plastic.
Embodiment four
With embodiment one, before adding crown ether and sodium-metaphosphate unlike nanometer silver preparation process (2) in mixed solution, mixed solution is heated to 45 DEG C; Crown ether and sodium-metaphosphate post-heating to 70 DEG C is added, Keep agitation 5min in mixed solution.Nanometer silver preparation process (2) is carried out under microwave vacuum condition, and be specifically evacuated to vacuum tightness for-0.02MPa, then carry out microwave treatment, microwave frequency is 100MHz, and microwave treatment time is 3s.
Embodiment five
With embodiment two, before adding crown ether and sodium-metaphosphate unlike nanometer silver preparation process (2) in mixed solution, mixed solution is heated to 55 DEG C; Crown ether and sodium-metaphosphate post-heating to 85 DEG C is added, Keep agitation 8min in mixed solution.Nanometer silver preparation process (2) is carried out under microwave vacuum condition, and be specifically evacuated to vacuum tightness for-0.001MPa, then carry out microwave treatment, microwave frequency is 230MHz, and microwave treatment time is 7s.
Embodiment six
With embodiment three, before adding crown ether and sodium-metaphosphate unlike nanometer silver preparation process (2) in mixed solution, mixed solution is heated to 48 DEG C; Crown ether and sodium-metaphosphate post-heating to 78 DEG C is added, Keep agitation 6min in mixed solution.Nanometer silver preparation process (2) is carried out under microwave vacuum condition, and be specifically evacuated to vacuum tightness for-0.01MPa, then carry out microwave treatment, microwave frequency is 180MHz, and microwave treatment time is 5s.
Comparative example one
With embodiment one, unlike the furfuryl alcohol extracted from natural phant 14 parts, triethylene glycol 13 parts, elastic plastic 60 parts, softening oil 4 parts, emulsifying agent 6 parts; Not containing benzoyl peroxide, vinyl acetic monomer;
Elastic plastic comprises the first elastic plastic and the second elastic plastic that mix by weight 4:1.
Comparative example two
With embodiment two, be prepared from according to following steps unlike nanometer silver:
(1) sodium dodecyl sulfate solution and hydrazine hydrate solution are added in silver nitrate aqueous solution and obtain mixed solution, the mol ratio of sodium laurylsulfonate and Silver Nitrate is 3:1; The mol ratio of described hydrazine hydrate and Silver Nitrate is 0.2:1;
(2) in mixed solution, add crown ether and sodium-metaphosphate, the mol ratio of described crown ether and Silver Nitrate is 6:1; The mol ratio of sodium-metaphosphate and Silver Nitrate is 0.8:1, and control ph is 8-9, obtains nanometer silver.
Embodiment 1-6 and comparative example are left standstill, observe the dispersion state of the nanometer silver of sizing agent system after 1 month and 6 months containing nanometer silver respectively, observations is in table 1.
The dispersion state of table 1 containing nanometer silver in the binder system of nanometer silver
The Binder Properties contrast of table 2 embodiment and comparative example
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the amendment not having creative contribution as required after reading this specification sheets, as long as but be all subject to the protection of patent law in right of the present invention.
Claims (10)
1. a modified binder, is characterized in that being made up of the raw material of following parts by weight:
Elastic plastic 70-95 part, phthalic anhydride 25-35 part, the furfuryl alcohol 7-11 part of extracting from natural phant, triethylene glycol 10-12 part, pentanedioic acid 15-18 part, trihydroxybutane 8-10 part, zinc white 5-7 part, magnesium oxide 3-5 part, chloroprene rubber 15-25 part, softening oil 2-3 part, methylcarbonate 15-20 part, benzoyl peroxide 1-3 part, vinyl acetic monomer 4-8 part, emulsifying agent 1-4 part, flour 20-30 part, nanometer silver 5 × 10
-5-9 × 10
-5part, fire retardant 1-3 part, catalyzer 0.8-2.5 part, 3-7 part bamboo vinegar aqueous solution, 6-13 part particle diameter are the bamboo charcoal powder of 0.01-0.06mm;
The described bamboo vinegar aqueous solution is the mixing solutions of the bamboo vinegar of weight ratio 1:0.1-0.2:60-100, sequestrant and water composition;
Described fire retardant is counted composed of the following components by weight: ammonium low polyphosphate 20 ~ 50 parts, 10 ~ 25 parts, ammonium phosphate, ammonium pyrophosphate 6 ~ 12 parts, 5 ~ 20 parts, ammonium sulfate, boric acid 5 ~ 10 parts, 10 ~ 25 parts, water;
Described bamboo charcoal powder obtains through raw material pre-treatment, primary carbon preparation, activation treatment and granulation step;
The concrete preparation method of described bamboo charcoal powder is:
A. raw material pre-treatment: bamboo is sent in microwave vacuum tank, be evacuated to vacuum tightness for-0.02MPa ~-0.001MPa, then carry out microwave treatment, microwave frequency is 300MHz ~ 950MHz, and microwave treatment time is 1 ~ 3min;
B. primary carbon preparation: the bamboo through raw material pre-treatment gained is experienced successively drying, pre-charing, charing, calcining and cooling, control combustion is incubated 40-80min with the ramp of 5-15 DEG C/min to 700-750 DEG C, and then be incubated 2-8h with the ramp of 5-15 DEG C/min to 1000-1500 DEG C, then 300-400 DEG C is cooled to the speed of 18-25 DEG C/min, cool to room temperature with the furnace again, obtain primary carbon;
C. then activation treatment: by gained primary carbon and 140-160g/L polymaleic acid and 40-70g/L inferior sodium phosphate mixed solution 1:3-4 mixing submergence 3-5h is in mass ratio neutral by washed with de-ionized water to pH value;
D. granulate;
Described emulsifying agent is one or more in polyoxyethylene octylphenol ether, sulfonated castor oil, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate; Described elastic plastic comprises the first elastic plastic and the second elastic plastic that mix by weight 1-3:1;
The solids content that described first elastic plastic comprises 10-35 part weight is the Emulsion acrylic resin of 60-75%, 10-15 part aqueous polyurethane, the acrylic resin powder of 5-8 part weight, the solids content of 2-6 part weight are the EVA emulsion of 20-35% and the Chlorinated Polypropylene III of 1-4 part weight;
The preparation method of described Emulsion acrylic resin is: the acrylate monomer mixed solution of preparation 80-110 part weight is stand-by, then the emulsifying agent of 5-7 part weight of several compositions in polyoxyethylene octylphenol ether, sulfonated castor oil, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, the sodium bicarbonate of 0.3-0.7 part weight and deionized water are joined in reactor, add the 1/3 acrylate monomer mixed solution prepared again wherein, be warming up to 50-90 DEG C, fully stir 20-40min; Be warming up to 60-100 DEG C, drip remaining 2/3 acrylate monomer mixed solution and ammonium persulfate solution initiator, time for adding controls, for 1-4h, to ensure that monomer drips prior to initiator solution; Dropwise rear insulation 1-4h, after cooling, regulate ph value of emulsion to about 7;
Described nanometer silver is prepared from according to following steps:
(1) sodium dodecyl sulfate solution, water polyacrylic acid and hydrazine hydrate solution are added in silver nitrate aqueous solution and obtain mixed solution, the mol ratio of described sodium laurylsulfonate and Silver Nitrate is 4-6:1; The mol ratio of described water polyacrylic acid and Silver Nitrate is 0.4-0.6:1; ; The mol ratio of described hydrazine hydrate and Silver Nitrate is 0.2-0.3:1;
(2) in described mixed solution, add crown ether and sodium-metaphosphate, the mol ratio of described crown ether and Silver Nitrate is 3-5:1; The mol ratio of described sodium-metaphosphate and Silver Nitrate is 0.8-1.3:1, and control ph is 8-9, obtains nanometer silver.
2. a kind of modified binder according to claim 1, it is characterized in that: the preparation method of described second elastic plastic is: be that the polyvinyl alcohol water solution of 30-45% and the aqueous polyurethane aqueous solution of 5-10% are heated to 60-80 DEG C by mass concentration, be cooled to 30-50 DEG C and add acrylate 10-15%, then add potassium hydroxide 0.1-0.2% and be warming up to 100-110 DEG C, then the plant phenols 2-4% adding sclerotin albumen 5-8%, rosin fat 6-9%, extract from natural phant; React and be cooled to 45-55 DEG C in 3-5 hour, then add Sodium Benzoate 0.06-0.08%, ditertiary butyl peroxide 0.01-0.02% and vinyl acetic monomer 0.1-0.3%, stir 1-1.5 hour, cooling, obtained described second elastic plastic.
3. a kind of modified binder according to claim 2, is characterized in that: the sequestrant in the described bamboo vinegar aqueous solution is at least one in ethylenediamine tetraacetic acid (EDTA) or disodium edta.
4. a kind of modified binder according to claim 3, is characterized in that: the described furfuryl alcohol extracted from natural phant is selected from the furfuryl alcohol extracted from the wheat bran or bamboo wood chip of the core slag of corn cob, oat or wheat.
5. a kind of modified binder according to claim 4, is characterized in that: described mixed solution is heated to 45-55 DEG C add crown ether and sodium-metaphosphate in described mixed solution before by described step (2).
6. a kind of modified binder according to claim 5, is characterized in that: described step (2) adds crown ether and sodium-metaphosphate post-heating to 70-85 DEG C in described mixed solution, Keep agitation 5-8min.
7. a kind of modified binder according to claim 6, it is characterized in that: described step (2) is carried out under microwave vacuum condition, specifically be evacuated to vacuum tightness for-0.02MPa ~-0.001MPa, carry out microwave treatment again, microwave frequency is 100MHz ~ 230MHz, and microwave treatment time is 3 ~ 7s.
8. a kind of modified binder according to claim 7, is characterized in that: described crown ether is bicyclohexane also-18-hat-6.
9. a kind of modified binder according to claim 8, is characterized in that: the described plant phenols extracted from natural phant is Eugenol or cardanol.
10. a kind of modified binder according to claim 9, is characterized in that: described catalyzer is sodium hydroxide.
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| CN104293248B (en) | 2016-03-30 |
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Effective date of registration: 20230718 Address after: 313000 Wujiatang, Maji Village, Tianhuangping Town, Anji County, Huzhou, Zhejiang Province Patentee after: Anji Bamboo Impression Home Furnishings Co.,Ltd. Address before: 313000 Wujiatang Anji Dengguan Bamboo and Wood Development Co., Ltd., Maji Village, Tianhuangping Town, Anji County, Huzhou, Zhejiang Province Patentee before: ANJI DENGGUAN BAMBOO & WOOD DEVELOP CO.,LTD. |