CN115449261B - Preparation method of coffee flavor printing ink based on recovery of coffee bean waste - Google Patents

Preparation method of coffee flavor printing ink based on recovery of coffee bean waste Download PDF

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CN115449261B
CN115449261B CN202211241253.9A CN202211241253A CN115449261B CN 115449261 B CN115449261 B CN 115449261B CN 202211241253 A CN202211241253 A CN 202211241253A CN 115449261 B CN115449261 B CN 115449261B
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coffee
printing ink
coffee bean
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bean waste
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CN115449261A (en
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陈正宇
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Yangzhou Xianghua New Material Technology Co ltd
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
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Abstract

The invention belongs to the technical field of green chemistry, and relates to a preparation method of coffee flavor printing ink based on coffee bean waste recovery, which comprises the following steps: the coffee bean waste flavor substance is bonded with a multi-component active hydrogen-containing micromolecular compound, the polyurethane prepolymer with coffee flavor is prepared, lignin is finely granulated, and the coffee flavor printing ink consists of three components, namely a component A, a component B and a component C, wherein the components are prepared, mixed and stored independently. According to the invention, furfuryl mercaptan flavor substances in the coffee bean waste are extracted by an organic solvent, the furfuryl mercaptan flavor substances are bonded with a micromolecular compound containing multiple active hydrogen, the coffee flavor substances are combined with a side chain segment directly connected with a main chain segment, and the coffee bean waste after secondary extraction has excellent rigidity and hardness, can be used as a reinforcing agent of printing ink after fine granulation, and is prepared into the printing ink with coffee flavor. After the printing operation is completed, the organic solvent is removed by surface drying and curing, and the coffee Jiao Huxiang is rich.

Description

Preparation method of coffee flavor printing ink based on recovery of coffee bean waste
Technical Field
The invention belongs to the technical field of green chemistry, relates to recycling of coffee bean waste, and particularly relates to a preparation method of coffee flavor printing ink based on recycling of coffee bean waste.
Background
In recent years, the demand and consumption of coffee has been increasing, so that the pressure of processing coffee bean waste has been increasing. According to reports issued by the international coffee organization (International Coffee Organization) 2021, about 1003 ten thousand tons of coffee are consumed worldwide, producing 662 kg of coffee bean waste per ton of coffee beans. From this data, it can be concluded that the global production of coffee bean waste reaches approximately 651 ten thousand tons a year. "coffee giant" starbucks are also known to produce on average about 11.2 kg of coffee bean waste per store per day. The recycling of coffee bean waste is also a academic today, in which the idea of sustainable development is practiced. Coffee bean waste has been reported to be useful as an organic fertilizer. However, the coffee bean waste contains caffeine, tannic acid, polyphenol and other components, and the excessive use can enhance the acidity of the soil and cause damage to the soil ecosystem, so that the coffee bean waste is only used in small and medium ranges in partial crop fields requiring acidic cultivation; it has also been reported that coffee bean waste can be used as an adsorbent. Research shows that the coffee bean waste is rich in plant fiber, and can realize a loose porous structure after carbonization in an anaerobic atmosphere, and can be applied to adsorption materials. However, it should be noted that the absorbent material cannot be used in a humid environment and needs to be replaced periodically and timely, otherwise, the absorbent material is easy to rot and mold, and improper treatment brings negative effects, so that the popularization is not high. Therefore, the coffee bean waste has high yield and low recycling rate, and becomes a troublesome problem for people.
Disclosure of Invention
In order to solve the problem of low recycling efficiency of coffee bean waste, the invention discloses a method for preparing flavor printing ink based on recycling of the coffee bean waste, which not only can effectively utilize the residual aroma substances in the coffee bean waste, but also can be used as a rigid filler of the ink, so that the recycling efficiency of the coffee bean waste is maximized.
A preparation method of coffee flavor printing ink based on coffee bean waste recovery comprises the following steps:
(1) Bonding of coffee bean waste flavor substances and small molecular compounds containing multiple active hydrogen
Weighing 10-150 g of coffee bean waste, adding 40-250 ml of dispersion solvent, stirring at 20-60 ℃ at a stirring speed of 200-1000 r/min; weighing 0.1-16 g of small molecular compound containing multiple active hydrogen, adding 5-30 ml of the same dispersion solvent for dissolution, adding the system in a constant pressure dropping funnel for 5-45 min, and simultaneously adding 0.01-5 mg of homogeneous catalyst; maintaining the system temperature and stirring for 10-60 min, filtering, flushing the filter cake with the same dispersion solvent for multiple times, collecting filtrate, performing reduced pressure distillation until the dispersion solvent is completely removed and the quality is no longer changed, obtaining modified small molecule multi-active hydrogen compound (g-CE), and hermetically preserving for later use;
Vacuum drying the filter cake at 30-60 ℃ for 10-50 min, taking out and crushing for standby;
the dispersion solvent is acetone, butanone, cyclohexanone, ethyl acetate, 1,4 dioxane, N-dimethylformamide, methyl tertiary butyl ether and the like; the small molecule compound containing a polyvalent active hydrogen is a polyhydric alcohol such as 2-hydroxymethyl-2-methyl-1, 3-propanediol, glycerol, 1,2, 4-benzene triol, 1,2, 4-butane triol, etc., or a polybasic amine such as carbamide, 1, 2-propane diamine, 1, 2-phenylenediamine, 1, 2-ethylenediamine, etc.; the homogeneous catalyst is a coordination complex of rhodium, ruthenium or iridium, such as tris (triphenylphosphine) rhodium chloride, tris (triphenylphosphine) ruthenium chlorohydride, tris (triphenylphosphine) iridium hydride, and the like;
preferably, the dispersion solvent is N, N-dimethylformamide, the small molecular compound containing multiple active hydrogen is 1,2, 4-butanetriol, and the homogeneous catalyst is tris (triphenylphosphine) rhodium chloride;
further preferably, 80g of coffee bean waste is weighed and 150ml of N, N-dimethylformamide is added, and the mixture is stirred at 30 ℃ with the stirring speed of 450r/min; weighing 12g of 1,2, 4-butanetriol, adding 15ml of the same dispersion solvent for dissolution, adding the system into a constant pressure dropping funnel for 20min, and simultaneously adding 0.03mg of homogeneous catalyst tris (triphenylphosphine) rhodium chloride; maintaining the system temperature and stirring for 20min, filtering, washing filter cake with the same dispersion solvent for multiple times, collecting filtrate, distilling under reduced pressure until the dispersion solvent is completely removed and the quality is unchanged, obtaining modified small molecule multi-active hydrogen compound (g-CE), and hermetically preserving for later use; vacuum drying the filter cake at 50 ℃ for 45min, taking out and crushing for standby;
(2) Preparation of polyurethane prepolymers with coffee flavor
Adding 4-16 mmol of polymeric polyol into a 500ml four-neck flask, wherein the molar mass ratio of polyisocyanate to polymeric polyol is 0.9-1.2:1, g-CE of 0.001-10 g and dispersing solvent of 15-100 ml, and the four-neck flask is provided with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; controlling the stirring speed to be 300-1500 r/min at 25-55 ℃; the maintaining time is 0.5-4 h after 1-5 drops of catalyst; adding 20-100 ml of the same dispersion solvent and 1-3 drops of catalyst into the system, controlling the stirring speed to be 500-2200 r/min at 30-80 ℃ and maintaining for 1-5 h to obtain polyurethane prepolymer for later use;
the polymer polyol is polypropylene glycol, polyether polyol, phthalic anhydride polyester polyol, polyoxypropylene polyol and the like; the polyisocyanate is 2, 2-dimethylglutarimate, 1, 3-butadiene-1, 4-diisocyanate, 4',4 "-triphenylmethane triisocyanate, lysine triisocyanate, 1,2, 3-tris (isocyanatomethylthio) propane, 3, 5-dithio-1, 2,6, 7-heptanetetracyanate, etc.; g-CE is prepared from step (1); the dispersion solvent is xylene, acetone, butanone, cyclohexanone, ethyl acetate, 1,4 dioxane, methyl tertiary butyl ether; the catalyst is triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, diisobutyltin dilaurate, dibutyltin dilaurate, and the like;
The polymeric polyol is phthalic anhydride polyester polyol, the polyisocyanate is 1, 3-butadiene-1, 4-diisocyanate, the dispersion solvent is 1,4 dioxane, and the catalyst is diisobutyltin dilaurate;
further preferably, 8mmol of phthalic anhydride polyester polyol, g-CE with a molar mass ratio of 1, 3-butadiene-1, 4-diisocyanate to phthalic anhydride polyester polyol of 1.1:1,2g, 90ml of 1,4 dioxane are added into a 500ml four-necked flask at one time, and the stirring rate is controlled at 900r/min at 28 ℃; 3 drops of diisobutyltin dilaurate are added dropwise and then maintained for 2 hours; adding 80ml of 1,4 dioxane and 2 drops of diisobutyltin dilaurate into the system, controlling the stirring speed to 1800r/min at 70 ℃ and maintaining for 3 hours to obtain a polyurethane prepolymer for later use;
(3) Fine granulation of lignin
Crushing the crushed filter cake in a ball mill for 1-10 h, wherein the particle size distribution of discharged powder is 0.1-0.5 mu m, 0.5-1 mu m and the mass fraction ratio of 1-1.5 mu m is 0.2-0.4:1:0.3-0.7, and taking out for later use;
wherein the grinding medium is Al 2 O 3 Particles, zrO 2 Particles, mgO particles, etc., preferably Al 2 O 3 Particles;
the size of the grinding medium is 2-10 mm, and the bulk density is 1.2-4.7 g/cm 3 The Mohs hardness is between 8.5 and 9.8, and the crushing process is a Raymond crushing process;
Further preferably, the crushed filter cake is subjected to Raymond crushing process in a ball mill for 8 hours, the particle size distribution of discharged powder is 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m in parts by weight ratio of 0.3:1:0.4, and the powder is taken out for standby; wherein the grinding medium is Al 2 O 3 Particles having a size of 4mm and a bulk density of 2.2g/cm 3 Mohs hardness 9.5;
(4) Preparation of coffee-flavored printing ink
The coffee-flavor printing ink consists of three components, namely a component A, a component B and a component C, wherein the components are prepared and mixed uniformly and stored;
TABLE 1 composition of the components of the printing ink and ranges of the parts by weight
Figure BDA0003884835830000031
Figure BDA0003884835830000041
The component A consists of a polyurethane prepolymer, a preservative and a dispersion solvent A, wherein the polyurethane prepolymer is prepared in the step (2), the preservative is calcium propionate, sodium propionate, ethyl parahydroxybenzoate, p-bromophenol, 3, 5-dibromosalicylanilide, bromo-chloro-5-5' -dimethylhydantoin and the like, and the dispersion solvent A is acetone, butanone, cyclohexanone and ethyl acetate;
the component B consists of a pigment/dye, an anti-settling agent, a defoaming agent, a cross-linking agent and a dispersing solvent B, wherein the pigment/dye is organic, inorganic, metal complex and the like, the anti-settling agent is polyamide wax, polyoxyethylene Zhong Xinfen ether phosphonate and the like, the defoaming agent is polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane and the like, the cross-linking agent is trimethylolpropane-tris (3-aziridinyl propionate), trimethylolpropane-tris [3- (2-methylaziridinyl) propionate ] and the like, the initiator is 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -diimidazole, bis (2-ethylhexyl) peroxydicarbonate, 2-hydroxy-2-methyl-1- [4- (tertiary butyl) phenyl ] -1-propanone and the like, and the dispersing solvent B is acetone, cyclohexanone, 1, 4-dioxane, N-dimethyl formamide and tertiary butyl ether;
Component C is composed of filler, reinforcing agent and brightening agent, the filler is SiO 2 Powder, caCO 3 Powder, tiO 2 Powder and the like, wherein the reinforcing agent is the finely granulated lignin prepared in the step (3), and the whitening agent is 7-diethylamino-4-methyl-2H-1-benzopyran-2-ketone, 3- (4-chlorophenyl) -1- (4-sulfamoyl phenyl) -2-pyrazoline, 1, 4-bis (benzoxazol-2-yl) naphthalene, 1-o-cyanostyryl-4-p-cyanostyryl benzene and the like;
the component A is mixed for 10 to 105 minutes at the stirring speed of 100 to 1000r/min, the component B is mixed for 20 to 100 minutes at the stirring speed of 50 to 200r/min, and the component C is mixed for 40 to 300 minutes at the stirring speed of 10 to 100r/min (the device is provided with a static electricity device when the powder is mixed and stirred); the size of the filler in the component C is 50-800 meshes;
preferably, the preservative of the component A is 3, 5-dibromosalicylanilide, the dispersing solvent is acetone, the pigment/dye of the component B is metal complex, the anti-settling agent I polyamide wax, the antifoaming agent is polydimethylsiloxane, and the crosslinking agent is trimethylolpropane-tris [3- (2-methylazepinyl) propionate]The initiator is bis (2-ethylhexyl) peroxydicarbonate, the dispersing solvent is butanone, and the filler of component C is TiO 2 The powder and the whitening agent are 1, 4-bis (benzoxazol-2-yl) naphthalene; the mass parts of the substances are listed in the following table 2; and mixing component A at stirring rate of 300r/min for 60min, mixing component B at stirring rate of 60r/min for 90min, and mixing component C at stirring rate of 20r/min for 105min; the filler size in component C is 150 mesh;
TABLE 2 composition of the components of the printing ink and parts by weight
Figure BDA0003884835830000051
Purity of the reagents partially involved in the reaction; the manufacturer is as follows:
acetone (chemical purity, national pharmaceutical group chemical agent limited); butanone (chemical purity, national pharmaceutical group chemical agents limited); cyclohexanone (chemical purity, national pharmaceutical group chemical agent limited); ethyl acetate (chemical purity, national pharmaceutical chemicals limited); 1,4 dioxane (chemical purity, national pharmaceutical group chemical reagent limited); n, N-dimethylformamide (chemical purity, national pharmaceutical group chemical reagent limited); methyl tertiary butyl ether (chemical purity, national pharmaceutical groups chemical reagent limited); 2-hydroxymethyl-2-methyl-1, 3-propanediol (chemically pure, jiangsu Wuxi, silver chemical Co., ltd.); glycerol (chemically pure, jiangsu Wuxi Yinling chemical Co., ltd.); 1,2, 4-benzene triol (chemical purity, shanghai chemical reagent general works); 1,2, 4-butanetriol (chemical purity, shanghai chemical reagent works); carbonyl diamide urea (chemical purity, jiangsu Wuxi Yinling chemical Co., ltd.); 1, 2-propanediamine (chemically pure, shanghai chemical reagent general works); 1, 2-phenylenediamine (chemically pure, south kyoo afinib biotechnology limited); 1, 2-ethylenediamine (chemically pure, south kyo aodoforni biotechnology limited); tris (triphenylphosphine) rhodium chloride (chemically pure, ataxia large chemical company limited); tris (triphenylphosphine) ruthenium chlorohydride (chemically pure, atan's major chemicals); tris (triphenylphosphine) iridium hydride (chemical purity, atan's major chemicals); polypropylene glycol (industrial, HUL company, germany); polyether polyols (commercial products, HUL, germany); phthalic anhydride polyester polyol (industrial, HUL company, germany); polyoxypropylene polyols (commercial products, HUL corporation, germany); glycerol (chemically pure, jiangsu Wuxi Yinling chemical Co., ltd.); pentaerythritol (chemically pure, jiangsu Wuxi, silver chemical Co., ltd.); 2, 2-Dimethylpentane diisocyanate (commercial product, PERSOP Co., switzerland); 1, 3-butadiene-1, 4-diiso Cyanate ester (industrial, PERSTOP, switzerland); 4,4' -triphenylmethane triisocyanate (commercial, PERSOP); lysine triisocyanate (industrial, PERSTOP, switzerland); 1,2, 3-tris (isocyanatomethylthio) propane (commercial product, PERSOP Co., switzerland); 3, 5-dithia-1, 2,6, 7-heptanetetracyanate (commercial product, PERSOP Co., switzerland); xylene (analytically pure, ala Ding Shiji limited); n-butanol (analytically pure, ala Ding Shiji limited); triethylamine (analytically pure, ala Ding Shiji limited); 1, 4-diazabicyclo- [ 2.2.2]Octane (analytically pure, ala Ding Shiji limited); diisobutyltin dilaurate (analytically pure, ala Ding Shiji limited); di (dodecylthio) dibutyltin (analytically pure, ala Ding Shiji, inc.); al (Al) 2 O 3 Granules (chemicals, jiangsu Sopp group Co., ltd.); zrO (ZrO) 2 Granules (chemicals, jiangsu Sopp group Co., ltd.); mgO particles (chemicals, jiangsu Sopp group Co., ltd.); calcium propionate (chemically pure, hubei Wan chemical Co., ltd.); sodium propionate (chemically pure, hubei Wan chemical Co., ltd.); ethyl parahydroxybenzoate (chemical purity, shanghai chemical reagent general works); p-bromophenol (chemically pure, shanghai chemical reagent general works); 3, 5-dibromosalicylanilide (chemically pure, shanghai chemical reagent Association); bromo-chloro-5-5' -dimethylhydantoin (chemically pure, shanghai chemical reagent general works); organic pigments/dyes (industrial, shanghai pine chemical Co., ltd.); inorganic pigments/dyes (industrial, shanghai pine chemical Co., ltd.); metal complex pigments/dyes (industrial, shanghai pine chemical Co., ltd.); polyamide wax (industrial, great wall chemical company, inc.); polyoxyethylene Zhong Xinfen ether phosphonate (industrial, great wall chemical company, inc.); polyoxyethylene polyoxypropylene pentaerythritol ether (industrial, great wall chemical agents limited); polyoxypropylene glycerol ether (industrial, great wall chemical agents limited); polyoxypropylene polyoxyethylene glyceryl ether (industrial, great wall chemical reagent limited); polydimethylsiloxane (industrial, great wall chemical company, inc.); trimethylolpropane-tris (3-aziridinyl propionate) (chemically pure, hubei Wanzhen chemical Co., ltd.); Trimethylolpropane-tris [3- (2-methylaziridinyl) propionate]
(chemical purity, hubei Wanzhen chemical Co., ltd.); 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -diimidazole (chemically pure, hubei chemical Co., ltd.); bis (2-ethylhexyl) peroxydicarbonate (chemically pure, hubei Wande chemical Co., ltd.); 2-hydroxy-2-methyl-1- [4- (tert-butyl) phenyl ]]-1-propanone; siO (SiO) 2 Powder (industrial, shanghai pine chemical Co., ltd.); caCO (CaCO) 3 Powder (industrial, shanghai pine chemical Co., ltd.); tiO (titanium dioxide) 2 Powder (industrial, shanghai pine chemical Co., ltd.); 7-diethylamino-4-methyl-2H-1-benzopyran-2-one (chemically pure, hubei Wanzhen chemical Co., ltd.); 3- (4-chlorophenyl) -1- (4-sulfamoylphenyl) -2-pyrazoline (chemically pure, hubei Wan De Chemie Co., ltd.); 1, 4-bis (benzoxazol-2-yl) naphthalene (chemically pure, hubei Wanzhen chemical Co., ltd.); 1-O-Cyanostyryl-4-p-Cyanostyrylbenzene (chemical purity, hubei Wan chemical Co., ltd.);
experimental method
(1) Determination of the solid content of printing ink
Weighing about 2g of the coffee-flavor printing ink prepared by the technical scheme of the invention and the coffee-flavor printing ink purchased in the market, horizontally placing the coffee-flavor printing ink and the coffee-flavor printing ink into a surface dish, keeping the temperature at 60-70 ℃, taking out the surface containing the sample after 6-7 hours, cooling the surface in a dryer, weighing the surface, then placing the surface again into a constant-temperature drying box, taking out the surface again after 30 minutes interval, weighing again, repeating the operation, and requiring the difference value between the two weighing is within 0.01 g. The solids content was calculated according to the following formula:
Figure BDA0003884835830000071
Wherein S is the solid content of printing ink; w (w) 0 -the mass of the dish; w (w) 1 -the total mass of printing ink and the surface dish before drying; w (w) 2 -total mass of printing ink and dish after constant weight.
(2) Determination of thermal and freeze-thaw stability of printing inks
Diluting the printing ink sample with the acetone until the solid content is about 20%, placing the printing ink sample in a temperature control oven at 60 ℃, and observing and recording the state change of the printing ink sample after 24 hours.
The printing ink sample was placed in a refrigerator at-20℃for 18 hours, after which the sample was removed and melted at room temperature (about 25 ℃) for 6 hours. After repeating the operation 5 times, the state change of the printing ink sample was observed and recorded.
(3) Characterization of the IR spectrum of polyurethane prepolymers
The functional groups of the polyurethane prepolymers were tested using a fourier transform infrared (FI-IR) analytical tester (ATAVAR model 360, nicolet corporation, usa). During testing, the scanning wavelength is 500-4000 nm, and the average resolution is 2cm -1 The scanning is not less than 32 times.
Advantageous effects
In general, reports of modification of a main chain segment of polyurethane are common in modes of crosslinking modification, copolymerization modification and the like, furfuryl mercaptan flavor substances in coffee bean waste are extracted by an organic solvent and bonded with a small molecular compound containing multiple active hydrogen, and the modified small molecular multiple active hydrogen compound is utilized to combine the coffee flavor substances with a side chain segment directly connected with the main chain segment by utilizing the characteristic that the modified small molecular multiple active hydrogen compound has more competitive power to isocyanate groups than that of a polymerized polyol in the polymerization process of a polyurethane monomer, so that the polyurethane prepolymer prepared by the technical scheme retains Jiao Huxiang unique to coffee. In addition, the coffee bean waste material after secondary extraction has excellent rigidity and hardness, and can be used as a reinforcing agent of printing ink after being finely granulated. The finally prepared printing ink with coffee flavor shows rich coffee Jiao Huxiang after the organic solvent in the printing ink is removed by surface drying and solidification after the printing operation is finished, and the printing effect is not obviously different from that of the printing ink sold in the common market, so that the utilization rate of the waste coffee beans can be maximized.
Drawings
FIG. 1. IR spectrum of functional groups of polyurethane prepolymer.
Detailed Description
The invention will now be described in detail with reference to specific examples which will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.
Example 1
Weighing 80g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; 150ml of N, N-dimethylformamide is added into the system, the temperature is regulated to 30 ℃, and the stirring speed is controlled to be 450r/min; 12g of 1,2, 4-butanetriol is weighed, dissolved by 15ml of N, N-dimethylformamide, and the system is added under a constant pressure dropping funnel for 20min, and meanwhile, 0.03mg of tris (triphenylphosphine) rhodium chloride is added; maintaining the system temperature and stirring speed for 20min; filtering the reaction substances, flushing a filter cake with N, N-dimethylformamide for 4 times, collecting filtrate, performing reduced pressure distillation until the N, N-dimethylformamide is completely removed and the quality is not changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and performing airtight preservation for later use; placing the filter cake under a vacuum drying oven at 50 ℃ for 45min, taking out and crushing for standby;
To a 500ml four-necked flask equipped with a condenser, thermometer, constant pressure dropping funnel, mechanical stirring paddle, 8mmol of phthalic anhydride polyester polyol, 8.8mmol of 1, 3-butadiene-1, 4-diisocyanate, 2g of g-CE, 90ml of 1,4 dioxane were added all at once; regulating the temperature to 28 ℃ and controlling the stirring speed to 900r/min; 3 drops of diisobutyltin dilaurate are added dropwise and then maintained for 2 hours; adding 80ml of 1,4 dioxane and 2 drops of diisobutyltin dilaurate into the system, adjusting the temperature to 70 ℃, controlling the stirring speed to 1800r/min, and maintaining for 3 hours to obtain a polyurethane prepolymer for later use;
weighing the crushed filter cake, and selecting Al 2 O 3 The particle material has a size of 4mm and a bulk density of 2.2g/cm 3 Grinding medium with Mohs hardness of 9.5, and Raymond pulverizing process in ball mill for 8h, and controllingThe powder material is prepared and discharged, wherein the grain size distribution and the proportion of the powder material are 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m, and the mass part ratio is 0.3 part to 1 part of 0.4 part, and the powder material is taken out for standby;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio listed in the table 3, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 60min under the stirring speed of 300r/min, the component B is mixed for 90min under the stirring speed of 60r/min, and the component C is mixed for 105min under the stirring speed of 20 r/min;
TABLE 3 composition of the components of the printing ink and the mass portion ratio
Figure BDA0003884835830000091
Example 2
Weighing 10g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; adding 40ml of N, N-dimethylformamide into the system, regulating the temperature to 20 ℃, and controlling the stirring speed to be 200r/min; weighing 0.1g of 1,2, 4-butanetriol, dissolving with 5ml of N, N-dimethylformamide, adding the system under a constant pressure dropping funnel for 5min, and simultaneously adding 0.01mg of tris (triphenylphosphine) rhodium chloride; maintaining the system temperature and the stirring speed for 10min; filtering the reaction substances, flushing a filter cake with N, N-dimethylformamide for 3 times, collecting filtrate, performing reduced pressure distillation until the N, N-dimethylformamide is completely removed and the quality is not changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and performing airtight preservation for later use; placing the filter cake under a vacuum drying oven at 30deg.C for 10min, taking out, and pulverizing;
to a 500ml four-necked flask equipped with a condenser, thermometer, constant pressure dropping funnel, mechanical stirring paddle, 4mmol of phthalic anhydride polyester polyol, 3.6mmol of 1, 3-butadiene-1, 4-diisocyanate, 0.001g of g-CE, 15ml of 1,4 dioxane were added all at once; regulating the temperature to 25 ℃ and controlling the stirring speed to 300r/min; 1 drop of diisobutyltin dilaurate is added dropwise and then maintained for 0.5h; adding 20ml of 1,4 dioxane and 1 drop of diisobutyltin dilaurate into the system, adjusting the temperature to 30 ℃, controlling the stirring speed to 500r/min, and maintaining for 1h to obtain a polyurethane prepolymer for later use;
Weighing the crushed filter cake, and selecting Al 2 O 3 The particle material has a size of 2mm and a bulk density of 1.2g/cm 3 Grinding medium with Mohs hardness of 8.5, raymond pulverizing process in a ball mill for 1h, controlling the particle size distribution and proportion of discharged powder to be 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m in 0.2 part by weight to 1 part by weight to 0.3 part by weight, and taking out for standby;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio listed in the table 4, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 10min under the stirring speed of 100r/min, the component B is mixed for 20min under the stirring speed of 50r/min, and the component C is mixed for 40min under the stirring speed of 10 r/min;
TABLE 4 composition and mass fraction ratio of the components of the printing ink
Figure BDA0003884835830000101
Figure BDA0003884835830000111
Example 3
Weighing 150g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; 250ml of N, N-dimethylformamide is added into the system, the temperature is regulated to 60 ℃, and the stirring speed is controlled to 1000r/min; weighing 16g of 1,2, 4-butanetriol, dissolving with 30ml of N, N-dimethylformamide, adding the system under a constant pressure dropping funnel for 45min, and simultaneously adding 5mg of tris (triphenylphosphine) rhodium chloride; maintaining the system temperature and stirring speed for 60min; filtering the reaction substances, flushing a filter cake with N, N-dimethylformamide for 7 times, collecting filtrate, performing reduced pressure distillation until the N, N-dimethylformamide is completely removed and the quality is not changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and performing airtight preservation for later use; placing the filter cake under a vacuum drying oven at 60 ℃ for 50min, taking out and crushing for standby;
16mmol of phthalic anhydride polyester polyol, 19.2mmol of 1, 3-butadiene-1, 4-diisocyanate, 10g of g-CE and 100ml of 1,4 dioxane were added into a 500ml four-necked flask with a condenser, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; regulating the temperature to 55 ℃ and controlling the stirring speed to 1500r/min; dropwise adding 5 drops of diisobutyltin dilaurate, and maintaining for 4 hours; adding 100ml of 1,4 dioxane and 3 drops of diisobutyltin dilaurate into the system, adjusting the temperature to 80 ℃, controlling the stirring speed to 2200r/min, and maintaining for 5 hours to obtain a polyurethane prepolymer for later use;
weighing the crushed filter cake, and selecting Al 2 O 3 The particle material has a size of 10mm and a bulk density of 4.7g/cm 3 Grinding medium with Mohs hardness of 9.8, raymond pulverizing process in a ball mill for 10 hours, controlling the particle size distribution and proportion of discharged powder to be 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m in 0.4 part by weight to 1 part by weight to 0.7 part by weight, and taking out for standby;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio shown in the table 5, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 105min under the stirring speed of 1000r/min, the component B is mixed for 100min under the stirring speed of 200r/min, and the component C is mixed for 300min under the stirring speed of 100 r/min;
TABLE 5 composition of the components of the printing ink and the mass portion ratio
Figure BDA0003884835830000121
Example 4
Weighing 20g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; 45ml of acetone is added into the system, the temperature is regulated to 40 ℃, and the stirring speed is controlled to 600r/min; 10g of 2-hydroxymethyl-2-methyl-1, 3-propanediol was weighed, dissolved in 12ml of acetone, and the system was added under a constant pressure dropping funnel for 25min, and 1.2mg of tris (triphenylphosphine) ruthenium chloride was added at the same time; maintaining the system temperature and stirring speed for 50min; filtering the reaction substances, flushing a filter cake with acetone for 5 times, collecting filtrate, performing reduced pressure distillation until the acetone is completely removed and the quality is not changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and hermetically preserving for later use; placing the filter cake under a vacuum drying oven at 40 ℃ for 30min, taking out and crushing for standby;
to a 500ml four-necked flask equipped with a condenser, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle, 7mmol of polypropylene glycol, 7.7mmol of 2, 2-dimethylglutarimate, 4g of g-CE and 33ml of xylene were added all at once; regulating the temperature to 32 ℃ and controlling the stirring speed to be 800r/min; 2 drops of triethylamine are added dropwise and then maintained for 1h; 70ml of dimethylbenzene and 2 drops of triethylamine are added into the system, the temperature is regulated to 40 ℃, the stirring speed is controlled to 1600r/min, and the reaction time is maintained for 2 hours, so as to obtain polyurethane prepolymer for standby;
Weighing the crushed filter cake, and selecting ZrO 2 The particle material has a size of 5mm and a bulk density of 1.8g/cm 3 Grinding medium with Mohs hardness of 8.6, raymond pulverizing process in a ball mill for 2 hours, controlling the particle size distribution and proportion of discharged powder to be 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m in 0.3 part by weight to 1 part by weight to 0.4 part by weight, and taking out for standby;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio listed in the table 6, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 40min under the stirring speed of 200r/min, the component B is mixed for 30min under the stirring speed of 70r/min, and the component C is mixed for 125min under the stirring speed of 90 r/min;
TABLE 6 composition and mass fraction ratio of the components of the printing ink
Figure BDA0003884835830000131
Example 5
Weighing 110g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; 90ml butanone is added into the system, the temperature is regulated to 22 ℃, and the stirring speed is controlled to 700r/min; 14g of carbamide is weighed, dissolved in 28ml of butanone, and the system is added under a constant pressure dropping funnel for 43min, and 1.5mg of tris (triphenylphosphine) iridium hydride is added; maintaining the system temperature and stirring speed for 44min; filtering the reaction substances, flushing a filter cake with butanone for 4 times, collecting filtrate, performing reduced pressure distillation until the butanone is completely removed and the quality is no longer changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and hermetically preserving for later use; placing the filter cake under a vacuum drying oven at 52 ℃ for 46min, taking out and crushing for standby;
15mmol of polyoxypropylene polyol, 15mmol of 4,4' -triphenylmethane triisocyanate, 7g of g-CE and 60ml of cyclohexanone are added into a 500ml four-necked flask which is provided with a condenser, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; regulating the temperature to 48 ℃ and controlling the stirring speed to 400r/min; dropwise adding 4 drops of 1, 4-diazabicyclo- [2, 2] -octane, and maintaining for 3 hours; adding 90ml of cyclohexanone and 1 drop of 1, 4-diazabicyclo- [2, 2] -octane into the system, adjusting the temperature to 38 ℃, controlling the stirring rate to 1900r/min, and maintaining for 4 hours to obtain a polyurethane prepolymer for later use;
weighing the crushed filter cake, and selecting MgO particle material with a size of 6mm and a bulk density of 3.4g/cm 3 Grinding medium with Mohs hardness of 9.0, raymond pulverizing process in a ball mill for 6 hours, controlling the particle size distribution and proportion of discharged powder to be 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m to be 0.3 part by weight to 1 part by weight to 0.6 part, and taking out for standby;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio shown in the table 7, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 30min at the stirring speed of 900r/min, the component B is mixed for 80min at the stirring speed of 80r/min, and the component C is mixed for 85min at the stirring speed of 550 r/min;
TABLE 7 composition and mass fraction ratio of the components of the printing ink
Figure BDA0003884835830000141
Figure BDA0003884835830000151
Example 6
Weighing 77g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; adding 65ml of 1,4 dioxane into the system, adjusting the temperature to 48 ℃, and controlling the stirring speed to 800r/min; 9g of 1, 2-phenylenediamine is weighed, after 22ml of 1,4 dioxane is used for dissolution, the system is added under a constant pressure dropping funnel for 37min, and 2.6mg of tris (triphenylphosphine) iridium hydride is added; maintaining the system temperature and stirring speed for 42min; filtering the reaction substances, flushing a filter cake with 1,4 dioxane for 3 times, collecting filtrate, performing reduced pressure distillation until the 1,4 dioxane is completely removed and the quality is no longer changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and hermetically preserving for later use; placing the filter cake under a vacuum drying oven at 32 ℃ for 50min, taking out and crushing for standby;
to a 500ml four-necked flask equipped with a condenser, thermometer, constant pressure dropping funnel, mechanical stirring paddle were added 7mmol of pentaerythritol, 6.3mmol of 1,2, 3-tris (isocyanatomethylthio) propane, 3g of g-CE, 95ml of methyl t-butyl ether at one time; regulating the temperature to 45 ℃ and controlling the stirring speed to be 350r/min; dropwise adding 5 drops of dibutyltin di (dodecyl sulfide) and maintaining for 1h; adding 90ml of methyl tertiary butyl ether and 1 drop of dibutyl tin di (dodecyl sulfide) into the system, adjusting the temperature to 45 ℃, controlling the stirring speed to 500r/min, and maintaining for 5 hours to obtain a polyurethane prepolymer for later use;
Weighing the crushed filter cake, and selecting ZrO 2 The particle material has a size of 8mm and a bulk density of 1.8g/cm 3 Grinding medium with Mohs hardness of 9.0, raymond pulverizing process in ball mill for 5h, and controlling particle size distribution of discharged powderThe mixture is taken out for standby after being mixed with the mass part ratio of 0.2 to 1 part to 0.7 part of 0.1 to 0.5 mu m, 0.5 to 1 mu m and 1 to 1.5 mu m;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio shown in the table 8, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 20min at the stirring speed of 400r/min, the component B is mixed for 80min at the stirring speed of 150r/min, and the component C is mixed for 120min at the stirring speed of 30 r/min;
TABLE 8 composition of the components of the printing ink and the mass portion ratio
Figure BDA0003884835830000161
Example 7
Weighing 51g of coffee bean waste, and placing the coffee bean waste into a 500ml four-necked flask with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; 72ml of methyl tertiary butyl ether is added into the system, the temperature is regulated to 25 ℃, and the stirring speed is controlled to 880r/min; 9g of 2-hydroxymethyl-2-methyl-1, 3-propanediol was weighed, dissolved in 11ml of methyl tertiary butyl ether, and the system was added under a constant pressure dropping funnel for 33 minutes, and 0.004mg of tris (triphenylphosphine) rhodium chloride was added; maintaining the system temperature and the stirring speed for 11min; filtering the reaction substances, flushing a filter cake with methyl tertiary butyl ether for 6 times, collecting filtrate, and then performing reduced pressure distillation until the methyl tertiary butyl ether is completely removed and the quality is not changed, thus obtaining modified small molecule multi-active hydrogen compounds (g-CE), and hermetically preserving for later use; placing the filter cake under a vacuum drying oven at 56 ℃ for 22min, taking out and crushing for standby;
13mmol of pentaerythritol, 15.6mmol of 3, 5-dithio-1, 2,6, 7-heptane tetraisocyanate, 6g of g-CE and 40ml of 1,4 dioxane are added into a 500ml four-necked flask which is provided with a condenser, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; regulating the temperature to 26 ℃ and controlling the stirring speed to 700r/min; after 4 drops of diisobutyltin dilaurate are added dropwise, the mixture is maintained for 1h; adding 60ml of 1,4 dioxane and 1 drop of diisobutyltin dilaurate into the system, adjusting the temperature to 70 ℃, controlling the stirring speed to 500r/min, and maintaining for 4 hours to obtain a polyurethane prepolymer for later use;
weighing the crushed filter cake, and selecting MgO particle material with a size of 7mm and a bulk density of 4.3g/cm 3 Grinding medium with Mohs hardness of 9.6, raymond pulverizing process in a ball mill for 9h, controlling the particle size distribution and proportion of discharged powder to be 0.1-0.5 mu m, 0.5-1 mu m and 1-1.5 mu m in 0.3 part by weight to 1 part by weight to 0.6 part by weight, and taking out for standby;
the coffee-flavor printing ink is composed of three components, wherein the three components are prepared separately according to the substances and the mass parts ratio shown in the table 9, are mixed for corresponding time under corresponding stirring rates and are stored respectively; wherein, the component A is mixed for 22min under the stirring speed of 250r/min, the component B is mixed for 70min under the stirring speed of 70r/min, and the component C is mixed for 140min under the stirring speed of 90 r/min;
TABLE 9 composition and mass fraction ratio of the components of the printing ink
Figure BDA0003884835830000171
Comparative example
8mmol of phthalic anhydride polyester polyol, 8.8mmol of 1, 3-butadiene-1, 4-diisocyanate and 90ml of 1, 4-dioxane are added into a 500ml four-necked flask which is provided with a condenser, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; regulating the temperature to 28 ℃ and controlling the stirring speed to 900r/min; 3 drops of diisobutyltin dilaurate are added dropwise and then maintained for 2 hours; adding 80ml of 1,4 dioxane and 2 drops of diisobutyltin dilaurate into the system, adjusting the temperature to 70 ℃, controlling the stirring speed to 1800r/min, and maintaining for 3 hours to obtain a polyurethane prepolymer for later use;
the printing ink of the comparative example consists of three components which are independently prepared according to the substances and the mass parts ratio shown in the table 10, are respectively mixed for corresponding time under corresponding stirring rates and are respectively stored; wherein, the component A is mixed for 60min under the stirring speed of 300r/min, the component B is mixed for 90min under the stirring speed of 60r/min, and the component C is mixed for 105min under the stirring speed of 20 r/min;
TABLE 10 composition of the components of the printing ink and the mass portion ratio
Figure BDA0003884835830000181
The solid content, apparent morphology, storage stability, thermal stability, freeze-thaw stability, apparent viscosity, particle size, surface tension and other test results of the emulsion were measured separately for some of the coffee flavored printing inks prepared in the examples and for the printing inks prepared in the comparative examples, as shown in table 11.
TABLE 11 comparison of physical Properties of examples and comparative printing inks
Figure BDA0003884835830000182
Figure BDA0003884835830000191
(note: indicate no change)
From the analysis in Table 11 and as follows: (1) The actual solids content of all printing inks is similar, ranging from 34.3 to 37.2%. The coffee flavor printing ink obtained under the conditions of different formulas and preparation parameters is different from the comparative printing ink in the solid content, although the addition amount of the aromatic substances extracted from the coffee bean waste and the modified aromatic substances containing the multi-active hydrogen micromolecular compound and lignin is different, the solid content difference of the prepared printing ink is not obvious, so that the influence of the addition amount of the coffee bean waste on the solid content of the printing ink is small, the influence is negligible, and the coffee flavor printing ink and the subsequent mixed batch are easy to industrially produce in multiple batches. (2) All the printing inks show good homogeneous transparency, which indicates that the preparation of the coffee-flavored printing ink has a good process width range, and meanwhile, the addition amount of the coffee bean waste in the technical scheme provided by the invention can not influence the homogeneous stability of the printing ink. (3) The coffee flavor printing ink is similar to the printing ink of the comparative example, and can show good storage stability, thermal stability and freeze thawing stability, so that the addition of the coffee bean waste in the technical scheme provided by the invention can not influence the stability of the printing ink, and the industrial production and long-term storage of the coffee flavor printing ink are facilitated.
FIG. 1 is an infrared spectrum of functional groups of a polyurethane prepolymer in some examples, the polyurethane prepolymer having a coffee flavor has an infrared absorption peak position substantially similar to that of a normal polyurethane prepolymer, and no significant difference is found due to the fact that the absorption peak of-SH of furfuryl mercaptan compound of coffee flavor is 2680cm -1 About 2600cm from the N-H generated shrinkage vibration peak -1 The interval positions are approximately coincident, and the shoulder peak with a certain shape is shown; meanwhile, the-O-characteristic absorption peak of the coffee flavor substance furfuryl mercaptan compound is 1125cm -1 About, the absorption peak value is similar to that of-O-in polyether polyol; notably, at 1125cm of example 3 -1 The characteristic absorption peak was more remarkable in the vicinity, mainly because the amount of furfuryl mercaptan compound added in example 3 was the upper limit, and a small amount of-O-in the free form formed stronger bending vibration.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (13)

1. The preparation method of the coffee flavor printing ink based on coffee bean waste recycling is characterized by comprising the following steps of:
(1) Bonding of coffee bean waste flavor substances and small molecular compounds containing multiple active hydrogen
Weighing 10-150 g of coffee bean waste, adding 40-250 mL of dispersing solvent, stirring at 20-60 ℃ at the stirring speed of 200-1000 r/min, and extracting furfuryl mercaptan flavor substances in the coffee bean waste by the dispersing solvent; weighing 0.1-16 g of small molecular compound containing multiple active hydrogen, adding 5-30 mL of the same dispersion solvent for dissolution, adding the system in a constant pressure dropping funnel for 5-45 min, and simultaneously adding 0.01-5 mg of homogeneous catalyst; maintaining the system temperature and stirring for 10-60 min, filtering, flushing a filter cake with the same dispersion solvent for multiple times, collecting filtrate, and then performing reduced pressure distillation until the dispersion solvent is completely removed and the quality is no longer changed, thus obtaining a modified small molecule multi-active hydrogen compound g-CE, and hermetically preserving for later use; wherein the small molecular compound containing multiple active hydrogen is one of 2-hydroxymethyl-2-methyl-1, 3-propanediol, glycerol, 1,2, 4-benzene triol, 1,2, 4-butane triol, carbamide, 1, 2-propylene diamine, 1, 2-phenylenediamine or 1, 2-ethylenediamine; the homogeneous catalyst is a coordination complex of rhodium, ruthenium or iridium;
Vacuum drying the filter cake at 30-60 ℃ for 10-50 min, taking out and crushing for standby;
(2) Preparation of polyurethane prepolymers with coffee flavor
Adding 4-16 mmol of polymeric polyol and polyisocyanate into a 500mL four-neck flask, wherein the molar mass ratio of the polyisocyanate to the polymeric polyol is 0.9-1.2:1, g-CE of 0.001-10 g and dispersing solvent of 15-100 mL, and the four-neck flask is provided with a condenser tube, a thermometer, a constant pressure dropping funnel and a mechanical stirring paddle; controlling the stirring speed to be 300-1500 r/min at 25-55 ℃; the maintaining time is 0.5-4 h after 1-5 drops of catalyst; adding 20-100 mL of the same dispersion solvent and 1-3 drops of catalyst into the system, controlling the stirring speed to be 500-2200 r/min at 30-80 ℃ and maintaining for 1-5 h to obtain a polyurethane prepolymer for later use;
(3) Fine granulation of lignin
Crushing the crushed filter cake in a ball mill for 1-10 h, wherein the particle size distribution of discharged powder is 0.1-0.5 mu m, 0.5-1 mu m and the mass fraction ratio of 1-1.5 mu m is 0.2-0.4:1:0.3-0.7, and taking out for later use;
(4) Preparation of coffee-flavored printing ink
The coffee-flavor printing ink consists of three components, namely a component A, a component B and a component C, wherein the components are prepared and mixed uniformly and stored; wherein the component A consists of 40-80 parts of polyurethane prepolymer, 0.01-0.08 part of preservative and 20-70 parts of dispersing solvent A; the component B consists of 30-70 parts of pigment/dye, 1-5 parts of anti-settling agent, 0.001-0.02 part of defoaming agent, 0.002-0.6 part of cross-linking agent, 0.002-0.09 part of initiator and 40-60 parts of dispersing solvent B; the component C consists of 10-50 parts of filler, 30-70 parts of reinforcing agent and 5-20 parts of whitening agent, wherein the reinforcing agent is the fine granular lignin prepared in the step (3).
2. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (1), the dispersing solvent is acetone, butanone, cyclohexanone, ethyl acetate, 1,4 dioxane, N-dimethylformamide or methyl tertiary butyl ether.
3. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (1), the dispersion solvent is N, N-dimethylformamide.
4. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (1), the small molecular compound containing multiple active hydrogen is 1,2, 4-butanetriol.
5. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (1), the homogeneous catalyst is tris (triphenylphosphine) rhodium chloride, tris (triphenylphosphine) ruthenium chlorohydride, and tris (triphenylphosphine) iridium hydride.
6. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (1), the homogeneous catalyst is tris (triphenylphosphine) rhodium chloride.
7. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in step (2), the polymeric polyol is a polypropylene glycol, a polyether polyol, a phthalic anhydride polyester polyol, or a polyoxypropylene polyol; the polyisocyanate is 2, 2-dimethylglutaric isocyanate, 1, 3-butadiene-1, 4-diisocyanate, 4',4 "-triphenylmethane triisocyanate, lysine triisocyanate, 1,2, 3-tris (isocyanatomethylthio) propane or 3, 5-dithio-1, 2,6, 7-heptanetetracyanate; the dispersion solvent is xylene, acetone, butanone, cyclohexanone, ethyl acetate, 1,4 dioxane or methyl tertiary butyl ether; the catalyst is triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, diisobutyltin dilaurate or dibutyltin dilaurate.
8. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (2), the polymeric polyol is phthalic anhydride polyester polyol, the polyisocyanate is 1, 3-butadiene-1, 4-diisocyanate, the dispersing solvent is 1,4 dioxane, and the catalyst is diisobutyltin dilaurate.
9. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in step (3), the grinding medium is Al 2 O 3 Particles, zrO 2 Particles or MgO particles; the size of the grinding medium is 2-10 mm, and the bulk density is 1.2-4.7 g/cm 3 The Mohs hardness is between 8.5 and 9.8, and the crushing process is a Raymond crushing process.
10. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 9, characterized in that: in step (3), the grinding medium is Al 2 O 3 And (3) particles.
11. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (3)The crushed filter cake is subjected to Raymond crushing process in a ball mill for 8 hours, the particle size distribution of discharged powder is 0.1-0.5 mu m, the mass fraction ratio of 0.5-1 mu m and 1-1.5 mu m is 0.3:1:0.4, and the powder is taken out for standby; wherein the grinding medium is Al 2 O 3 Particles having a size of 4mm and a bulk density of 2.2g/cm 3 Mohs hardness 9.5.
12. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (4), the component A consists of a polyurethane prepolymer, a preservative and a dispersing solvent A, wherein the polyurethane prepolymer is prepared in the step (2), the preservative is calcium propionate, sodium propionate, ethyl p-hydroxybenzoate, p-bromophenol, 3, 5-dibromosalicylanilide or bromo-chloro-5-5' -dimethylhydantoin, and the dispersing solvent A is acetone, butanone, cyclohexanone or ethyl acetate;
Component B is composed of a pigment/dye which is an organic, inorganic or metal complex, an anti-settling agent which is a polyamide wax or a polyoxyethylene Zhong Xinfen ether phosphonate, an antifoaming agent which is polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether or polydimethylsiloxane, an initiator which is trimethylolpropane-tris (3-aziridinyl propionate) or trimethylolpropane-tris [3- (2-methylaziridinyl) propionate ], and a dispersing solvent B which is 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -diimidazole, bis (2-ethylhexyl) peroxydicarbonate or 2-hydroxy-2-methyl-1- [4- (tert-butyl) phenyl ] -1-propanone, and a dispersing solvent B which is acetone, cyclohexanone, 1, 4-dioxane, N-dimethylformamide or tert-butyl ether;
component C is composed of filler, reinforcing agent and brightening agent, the filler is SiO 2 Powder, caCO 3 Powder or TiO 2 The brightening agent is 7-diethylamino-4-methyl-2H-1-benzopyran-2-ketone, 3- (4-chlorphenyl) -1- (4-sulfamoyl phenyl) -2-pyrazoline, 1, 4-di (benzoxazol-2-yl) naphthalene or 1-o-cyanostyryl-4-p-cyanostyrene And (3) phenyl.
13. The method for preparing coffee flavored printing ink based on coffee bean waste recycling according to claim 1, characterized in that: in the step (4), the component A is mixed for 10-105 min at the stirring speed of 100-1000 r/min, the component B is mixed for 20-100 min at the stirring speed of 50-200 r/min, and the component C is mixed for 40-300 min at the stirring speed of 10-100 r/min, wherein the size of the filler is 50-800 meshes.
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