CN110078883B - Water-based paint resin based on konjac flour, preparation method and composition thereof - Google Patents
Water-based paint resin based on konjac flour, preparation method and composition thereof Download PDFInfo
- Publication number
- CN110078883B CN110078883B CN201910430079.4A CN201910430079A CN110078883B CN 110078883 B CN110078883 B CN 110078883B CN 201910430079 A CN201910430079 A CN 201910430079A CN 110078883 B CN110078883 B CN 110078883B
- Authority
- CN
- China
- Prior art keywords
- water
- acid
- organic
- based paint
- flour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a konjaku flour-based water-based paint resin, a preparation method and a composition thereof. The water-based paint resin is prepared by the following steps: (1) reacting rhizoma Amorphophalli powder with organic acid and/or acid anhydride of the organic acid to obtain rhizoma Amorphophalli powder organic acid ester; (2) reacting an organic matter containing double-end hydroxyl functional groups with isocyanate to obtain a second component; (3) reacting the konjac flour organic acid ester, the second component and the epoxy resin in a catalyst and an inert environment to obtain precursor resin; (4) and removing the organic solvent in the precursor resin, and adding water to obtain the water-based coating resin. The konjaku flour-based water-based paint has good biocompatibility, biosafety and degradability, and can be widely applied to packaging of toys for children, stationery, food and medicines.
Description
Technical Field
The invention relates to the technical field of water-based coating resin and a composition thereof.
Background
The paint is a large class of materials which play roles of decoration, protection and the like on a base material after being coated on the surface of the base material and cured into a film, and consists of film forming substances dispersed (dissolved) in water or an organic solvent. The organic solvent type coating has good solubility and good coating uniformity, but the Volatile Organic Compound (VOC) content of the dispersed coating is high, so that the air pollution can be caused in use, and the severe greenhouse effect of local areas is brought, and the coating belongs to a product which is gradually limited and eliminated; the water-dispersible paint almost does not contain VOC, and belongs to products for promotion and encouragement.
In the common water-based paint in the prior art, such as polyvinyl alcohol paint, water-soluble alkyd resin paint, water-soluble epoxy resin paint and the like, the paint mostly takes artificially synthesized resin as a main film forming substance, has poor biocompatibility, is difficult to degrade, has certain harmfulness to the environment and human body, is difficult to apply to children toys, stationery, food and medicine packages, and simultaneously has complex raw material resin synthesis process and high production cost.
Disclosure of Invention
The invention aims to provide a novel water-based, environment-friendly and easily-degradable coating resin and a composition thereof, which are prepared directly from a biological raw material konjak.
The invention also aims to provide a preparation method of the water-based paint resin.
The invention firstly provides the following technical scheme:
a preparation method of a konjak flour-based water-based paint resin comprises the following steps:
(1) drying the konjac flour until the water content is below 2%, and then reacting the konjac flour with an organic acid and/or an acid anhydride of the organic acid under the action of a catalyst at 110-180 ℃ to obtain konjac flour organic acid ester with the substitution degree of 1.6-2.3;
(2) reacting an organic matter containing double-end hydroxyl functional groups with isocyanate to obtain a second component;
(3) reacting the konjac flour organic acid ester, the second component and the epoxy resin in an inert environment by using a catalyst for the reaction of isocyanate and hydroxyl to obtain precursor resin;
(4) and removing the organic solvent in the precursor resin, and then adding water at the temperature of 30-50 ℃ and stirring to obtain the water-based coating resin.
In the above scheme, the steps (1) and (2) can be performed simultaneously or one step before the other, and the step (1) does not necessarily need to be performed before the step (2).
The rhizoma Amorphophalli powder is preferably solid extract of tuber of rhizoma Amorphophalli with high KGM content such as amorphophallus konjac, white rhizoma Amorphophalli, KELE rhizoma Amorphophalli, and XIUnion rhizoma Amorphophalli, or dry substance obtained by drying and pulverizing its tuber.
The catalyst in the step (1) is preferably one or more of pyridine, NaOH, KOH, perchloric acid and p-toluenesulfonic acid.
The dosage of the catalyst is preferably 1-30% of the mass of the konjac flour.
The mass ratio of the konjac flour to the organic acid and/or the acid anhydride thereof is 1: 1-5.5.
The organic acid is preferably one or more of acetic acid, butyric acid, n-hexanoic acid, caprylic acid, palmitic acid, succinic acid, citric acid.
Correspondingly, the organic acid anhydride is preferably one or more of acetic anhydride, butyric anhydride, n-hexyl anhydride, caprylic anhydride, palmitic anhydride, succinic anhydride and citric anhydride.
The reaction time is determined to achieve the required degree of substitution, and in some embodiments of the present invention, the reaction time is preferably 30 to 100 min.
In the above embodiment, the method for measuring the degree of substitution of the organic acid ester of konjac flour can be referred to the respective publications on the measurement of the degree of substitution of the organic acid ester, such as the following methods: the excess alkali is used to perform saponification reaction with organic acid ester to generate organic acid salt, the excess alkali is neutralized with standard acid, and then compared with blank sample, to calculate the content of organic acid acyl, and then converted into substitution degree.
In a specific embodiment of the above scheme, the organic compound containing a double-terminal hydroxyl functional group in step (2) is one or more selected from dimethylolpropionic acid, dimethylolbutyric acid, dimethylolcyclobutanecarboxylic acid, dihydroxyquinolinecarboxylic acid, and polyethylene glycol.
Wherein the polyethylene glycol is preferably one or more of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000 and polyethylene glycol 3000.
In another embodiment thereof, the isocyanate species is selected from one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI).
In a preferable embodiment of the above scheme, the ratio of the hydroxyl group of the organic substance containing a double-terminal hydroxyl functional group to the content of the substance containing isocyanate group in the step (2) is 0.9-1.1: 2.
In one preferable embodiment of the above scheme, the reaction temperature in the step (2) is 55-75 ℃.
In one preferable embodiment of the above scheme, the preferable reaction time of the reaction in the step (2) is 1-3 h.
In a preferable embodiment of the above embodiment, a ratio of the amount of isocyanate group in the second component to the total amount of hydroxyl group in the konjac powder organic acid ester and the epoxy resin in the step (3) is 0.9 to 1.1: 1.
In one preferable embodiment of the above scheme, the reaction temperature in the step (3) is 60-80 ℃. In one preferable embodiment of the above scheme, the preferable reaction time of the step (3) is 2-4 h.
In one preferable embodiment of the above scheme, the epoxy resin in the step (3) is one or more of bisphenol a type epoxy resins having different epoxy values and hydroxyl values, such as E44, E54, and the like.
In one preferable embodiment of the above scheme, the catalyst in step (3) is an organic tin catalyst, and more preferably, the catalyst is one or more of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate and triethyltin acetate.
The preferable dosage of the catalyst is 0.3-1.5% of the total mass of the konjac flour organic acid ester, the second component and the epoxy resin.
In practice, the catalyst in step (3) may also be other commercial catalysts for catalyzing the reaction of isocyanate with hydroxyl.
In one preferable embodiment of the above scheme, the temperature of the reaction in the step (3) is 60-80 ℃.
In a preferable mode of the above scheme, the reaction time in the step (3) is 2-4 h.
In one embodiment of the above scheme, a diluent may be added to the mixed system before the reaction in step (3).
The diluent is preferably organic solvent such as acetone, butanone, xylene, ethyl acetate, butyl acetate and the like or mixture thereof.
In a preferable mode of the above scheme, the organic solvent removal in the step (4) is performed by a temperature-raising and pressure-reducing distillation method, wherein the temperature is raised to 90-110 ℃, and the pressure is reduced to-0.04 to-0.1 MPa.
In a preferable embodiment of the above scheme, the water added in step (4) is preferably deionized water and/or distilled water, and the water adding time is preferably controlled to be about 20 min.
In one embodiment of the above embodiment, the organic material having a double hydroxyl group at the terminal in the step (2) is a dihydroxy carboxylic acid organic material, and the salt forming agent is added in an amount corresponding to the amount of the dihydroxy carboxylic acid organic material after the addition of water in the step (4).
Preferably, the salt forming agent is a polyamine substance, and more preferably one or more of triethylamine, diethylenetriamine and triethylenetetramine.
After the salt forming agent is added, the mixed system is preferably continuously stirred for 20-40 min.
The present invention further provides a konjac flour-based water-based paint resin, which can be produced by any one of the above-described embodiments or specific, preferred embodiments thereof.
The invention also provides a konjak powder-based water-based paint resin composition which contains the konjak powder-based water-based paint resin.
In particular, the composition may further contain other conventional additives for aqueous coating materials in addition to the konjac flour-based aqueous coating resin.
The invention has the following beneficial effects:
(1) the invention uses the konjac flour as a basic raw material, which contains heteropolysaccharide Konjac Glucomannan (KGM), wherein the KGM has water absorbability, gel property, cohesiveness and low-heat edibility, and the water-based coating resin prepared by the konjac flour can be widely applied to the fields of food processing, daily chemistry, biological medicine and the like;
(2) although the konjac flour has the advantages, the konjac flour is difficult to be directly applied as a coating, and the konjac flour is modified and compounded with other components to prepare a novel coating resin which simultaneously has high film forming property, flexibility, impact resistance, adhesive force, degradability and environmental friendliness;
(3) the konjac flour organic acid ester has good hydrophobicity, residual hydroxyl contained in konjac flour can further react with isocyanic acid radical and the like to obtain the water-based coating resin taking KGM molecules as a basic framework, hydrophilic groups are contained in the water-based coating resin molecules at the same time, and the water-based coating resin can be stably and uniformly dispersed in water, so that the product is completely or basically free of VOC (volatile organic compounds), and the pollution to the atmosphere, water bodies, land and the like can be avoided in use;
(4) the water-based paint resin obtained by the invention is easy to degrade after being formed into a film, the natural degradation time of the water-based paint resin in soil is 3 months-3 years, and the water-based paint resin has no accumulated pollution to the environment;
(5) the water-based paint resin obtained by the invention has good biocompatibility and biological safety, and can be widely applied to the fields of toys for children, stationery, food, medicine, sanitation and the like.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the embodiments described below. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Meanwhile, it is understood that the actual use principles of all the materials, reagents and the like claimed in the present invention are the same as those specifically listed in the following embodiments or examples, which can represent all the materials claimed in the present invention.
In a specific embodiment of a method for preparing a konjac flour-based water-based paint resin, the method comprises the following steps:
step (1):
drying the konjac flour to control the water content of the konjac flour to be below 2%, uniformly mixing the konjac flour with an organic acid and/or an acid anhydride thereof according to a certain mass ratio, adding a certain proportion of a catalyst, reacting for a certain time at a certain temperature to obtain an organic acid ester of the konjac flour with the substitution degree of 1.6-2.3, after the reaction is finished, adding distilled water into a reaction system, filtering, and drying the solid to obtain a product; measuring the degree of substitution, reserving for use, concentrating and distilling the residual liquid, and recycling.
Wherein the rhizoma Amorphophalli powder is solid substance extracted from tuber of rhizoma Amorphophalli with high KGM content such as amorphophallus konjac, white rhizoma Amorphophalli, YULE rhizoma Amorphophalli, and western union rhizoma Amorphophalli, or dried and pulverized dry substance of rhizoma Amorphophalli tuber.
Wherein the organic acid is preferably one or more of acetic acid, butyric acid, n-hexanoic acid, caprylic acid, palmitic acid, succinic acid, citric acid.
Wherein the acid anhydride is preferably one or more of acetic anhydride, butyric anhydride, n-hexyl anhydride, caprylic anhydride, palmitic anhydride, succinic anhydride, citric anhydride.
The mass ratio of the konjac flour to the organic acid and/or the acid anhydride thereof is preferably 1: 1-5.5.
The catalyst is preferably one or more of pyridine, NaOH, KOH, perchloric acid and p-toluenesulfonic acid, and those skilled in the art can understand that in practice, a complex form which can mutually damage the catalytic effect should not be selected, for example, NaOH and/or KOH and perchloric acid are combined to be used as the catalyst.
The dosage of the catalyst is preferably 1-30% of the mass of the konjac flour.
Wherein the reaction temperature is 110-180 ℃; the reaction time is preferably 30-100 min.
Step (2):
dissolving organic matter containing double-end hydroxyl, adding isocyanate in certain proportion, introducing nitrogen for protection, and reacting at certain temperature for certain time.
Wherein the organic compounds containing double terminal hydroxyl groups include, but are not limited to, dihydroxy carboxylic acids such as dimethylol propionic acid, dimethylol butyric acid, dimethylol cyclobutane carboxylic acid, dihydroxy quinoline carboxylic acid, etc.; polyethylene glycol such as polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 3000, etc.
Wherein the isocyanate species include, but are not limited to, Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), and the like.
The ratio of the hydroxyl to the isocyanate is preferably 0.9-1.1: 2.
Wherein the reaction temperature is preferably 55-75 ℃.
Wherein the reaction time is preferably 1-3 h.
Wherein the flow of the introduced nitrogen is matched with the size of the reactor.
And (3):
adding the reaction product obtained in the step (2) into the konjac flour organic acid ester and the epoxy resin prepared in the step (1) in a certain proportion, stirring and dissolving, and adding a certain diluent if necessary; adding a certain proportion of catalyst, introducing nitrogen for protection, and reacting for a certain time at a certain temperature.
Wherein the ratio of the content of isocyanate group in the reaction product of the step (2) to the total content of hydroxyl group in the konjac flour derivative and the epoxy resin prepared in the step (1) is preferably 0.9-1.1: 1.
Wherein the epoxy resin is preferably bisphenol A type epoxy resin having different epoxy values and hydroxyl values such as E44, E54, etc.
The diluent is preferably organic solvent such as acetone, butanone, xylene, ethyl acetate, butyl acetate and the like or mixture thereof.
The catalyst is preferably organic tin such as dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate and triethyltin acetate or related commercial catalysts for catalyzing the reaction of isocyanic acid radical and hydroxyl radical.
Wherein the mass of the catalyst is preferably 0.3-1.5% of the mass of the reaction materials (excluding the solvent).
Wherein the reaction temperature is preferably 60-80 ℃.
Wherein the reaction time is preferably 2-4 h.
Wherein the flow of the introduced nitrogen is matched with the size of the reactor.
And (4):
heating and decompressing the reaction product obtained in the step (3), and distilling off the organic solvent; cooling to 40 deg.C, increasing stirring speed, and adding distilled water and/or deionized water dropwise for about 20 min; and (3) if the dihydroxy carboxylic acid substances are selected in the step (2), continuously adding a salt forming agent with the same amount as the substances, and continuously stirring for 20-40 min after the salt forming agent is added, so as to obtain the konjac flour-based water-based paint resin.
Wherein the temperature after the temperature rise is preferably 90-110 ℃; the air pressure after decompression is preferably-0.04 to-0.1 MPa.
And (5):
and (3) adding other common additives of the water-based paint, such as one or more of pigments, dispersing agents, defoaming agents, flatting agents, adhesion promoters, flatting agents, thixotropic agents, thickening agents and the like, into the water-based paint resin obtained in the step (4) to obtain a novel water-based resin paint composition based on the konjac powder.
The present invention is further illustrated by the following specific examples.
Example 1
(1) Taking 1.5kg of refined konjac flour (dried in advance, the water content is lower than 2%, and the KGM content is 85%), adding 0.6kg of acetic anhydride in ice-water bath, and stirring uniformly; gradually heating to about 100 ℃, continuously adding 2.25kg of acetic anhydride and 60g of p-toluenesulfonic acid, continuously stirring, reacting for 2 hours at 100 ℃, and heating to 115 ℃ for reacting for 1 hour; then cooling to about 40 ℃, adding 8kg of deionized water into the reactant system, then precipitating, concentrating, filtering, drying and crushing the obtained solid component to obtain a product of the konjac flour organic acid ester, wherein the measured substitution degree is 2.02; concentrating and distilling the residual liquid components to obtain glacial acetic acid, and reproducing acetic anhydride;
(2) 275g of IPDI and 84.5g of dimethylolpropionic acid were stirred and mixed uniformly; introducing nitrogen for protection (the nitrogen flow is 0.1L/min), then heating to 80 ℃ and reacting for 2.2 h;
(3) adding 123g of epoxy resin E44, 140g of the product obtained in the step (1), 200g of butanone and 3.5g of dibutyltin dilaurate into the product obtained in the step (2), and uniformly stirring; heating to 70 ℃ and reacting for 2.5 h;
(4) and (2) cooling to 40 ℃, slowly dripping 600g of distilled water and/or deionized water, simultaneously quickly stirring and emulsifying, and finishing adding within about 30min to obtain the konjac flour-based water-based paint resin, wherein the adhesion force under standard test conditions after film forming is 0 (highest in standard), the flexibility is 2 (highest in standard), the impact resistance is more than 50cm (highest in standard), the pencil hardness is HB-1H, and the film can be degraded in soil after about half a year.
Example 2
(1) Taking 1.5kg of konjac dry powder (dried in advance, the water content is lower than 2 percent, and the KGM content is 75 percent), adding 0.9kg of butyric anhydride in ice-water bath, and stirring uniformly; gradually heating to about 130 ℃, continuously adding 2.5kg of butyric anhydride and 75g of perchloric acid, continuously stirring, reacting for 0.5h at 130 ℃, and then heating to 170 ℃ for reacting for 1 h; then cooling to about 40 ℃, adding 9kg of deionized water into the reaction system, then precipitating, concentrating, filtering, drying and crushing more obtained solid components to obtain a product of konjac powder organic acid ester, actually measuring the substitution degree of the konjac powder organic acid ester to be 1.86, concentrating and distilling the rest liquid components to obtain butyric acid, and reproducing butyric anhydride;
(2) stirring and uniformly mixing 200g of TDI and 76g of dimethylolpropionic acid, introducing nitrogen for protection (the nitrogen flow is 0.1L/min), heating to 60 ℃, and reacting for 2.5 hours;
(3) adding 170 g of epoxy resin E54, 180g of konjac flour organic acid ester prepared in the step (1), 225g of butanone and 4g of stannous octoate into the product obtained in the step (2), uniformly stirring, and then heating to 75 ℃ for reaction for 3 hours;
(4) and (3) cooling to 40 ℃, adding 60g of triethylamine, stirring for reacting for 15min, slowly adding 550g of distilled water and/or deionized water dropwise, simultaneously stirring and emulsifying quickly, and finishing adding for about 30min to obtain the konjac flour-based water-based paint resin, wherein the adhesion under standard test conditions after film formation is 0 (highest in standard), the flexibility is 2 (highest in standard), the impact resistance is more than 50cm (highest in standard), the pencil hardness is 1H-3H, and the film can be degraded after about eight months in soil.
Example 3
(1) Taking 1.5kg of konjac flour dry powder (dried in advance, the water content is lower than 2 percent, and the KGM content is 65 percent), adding 1kg of palmitic acid anhydride under an ice-water bath, uniformly stirring, gradually heating to about 120 ℃, continuously adding 2.5kg of palmitic acid and 100g of perchloric acid, continuously stirring, reacting for 1h at 120 ℃, heating to 165 ℃ for 0.5h, cooling to about 40 ℃, adding 8kg of deionized water into a reaction system, precipitating, concentrating, filtering, drying and crushing the obtained solid component to obtain a konjac flour organic acid ester product, actually measuring the substitution degree of the konjac flour organic acid ester to be 1.92, concentrating and distilling the residual liquid component to obtain palmitic acid, and reproducing the palmitic acid anhydride;
(2) stirring 250g of diphenylmethane diisocyanate and 74g of dimethylolbutyric acid, uniformly mixing, introducing nitrogen for protection (the nitrogen flow is 0.1L/min), and then heating to 70 ℃ for reaction for 2.5 hours;
(3) adding 96.6 g of epoxy resin E44, 132 g of konjac flour organic acid ester prepared in the step (1), 200g of butanone and 4.2g of triethyl tin acetate into the product obtained in the step (2), uniformly stirring, heating to 75 ℃, and reacting for 1.5 h;
(4) and (3) cooling to 40 ℃, adding 50g of triethylamine, stirring for reacting for 15min, slowly dropwise adding 500g of distilled water and/or deionized water, simultaneously stirring and emulsifying quickly, and finishing adding for about 30min to obtain the konjac flour-based water-based paint resin, wherein the adhesion under standard test conditions after film formation is 0 (highest in standard), the flexibility is 2 (highest in standard), the impact resistance is more than 50cm (highest in standard), the pencil hardness is 2H-3H, and the film can be degraded in soil after about 15 months.
Claims (8)
1. A preparation method of a water-based paint resin based on konjac flour is characterized by comprising the following steps: the method comprises the following steps:
(1) drying the konjac flour until the water content is below 2%, wherein the KGM content is 75-85%, then reacting the konjac flour with an organic acid and/or an acid anhydride of the organic acid in the presence of a catalyst, wherein the organic acid is selected from acetic acid and butyric acid, the mass ratio of the konjac flour to the organic acid or/and the acid anhydride of the organic acid is 1: 1-5.5, the amount of the catalyst is 1-30% of the mass of the konjac flour, and the reaction is carried out at 110-180 ℃ to obtain an organic acid ester of the konjac flour with the substitution degree of 1.6-2.3;
(2) reacting an organic matter containing double-end hydroxyl functional groups with isocyanate, wherein the ratio of the amount of hydroxyl of the organic matter containing double-end hydroxyl functional groups to the amount of isocyanate is 0.9-1.1: 2, obtaining a second component;
(3) reacting the konjac flour organic acid ester, a second component and epoxy resin in an inert environment in the presence of a catalyst for the reaction of isocyanate and hydroxyl, wherein the ratio of the amount of the isocyanate in the second component to the total amount of hydroxyl in the konjac flour organic acid ester and the epoxy resin is 0.9-1.1: 1, so as to obtain a precursor resin;
(4) and removing the organic solvent in the precursor resin, and then adding water at the temperature of 30-50 ℃ and stirring to obtain the water-based coating resin.
2. The method for preparing the konjaku flour-based water-based paint resin according to claim 1, wherein: and (3) the organic matter containing double-end hydroxyl functional groups in the step (2) is a dihydroxy carboxylic acid organic matter, a salt forming agent in an amount equal to that of the dihydroxy carboxylic acid organic matter is continuously added after water is added in the step (4), and the salt forming agent is one or more of triethylamine, diethylenetriamine and triethylenetetramine.
3. The method for preparing the konjaku flour-based water-based paint resin according to claim 1, wherein: the catalyst in the step (1) is one or more selected from pyridine, NaOH, KOH, perchloric acid and p-toluenesulfonic acid.
4. The method for preparing the konjaku flour-based water-based paint resin according to claim 1, wherein: the organic matter containing double-end hydroxyl functional groups in the step (2) is selected from one or more of dimethylol propionic acid, dimethylol butyric acid, dimethylol cyclobutane carboxylic acid, dihydroxy quinoline carboxylic acid and polyethylene glycol.
5. The method for preparing the konjaku flour-based water-based paint resin according to claim 1, wherein: the reaction temperature in the step (2) is 55-75 ℃, and the reaction time is 1-3 h.
6. The method for preparing the konjaku flour-based water-based paint resin according to claim 1, wherein: the reaction temperature of the step (3) is 60-80 ℃, and the reaction time is 2-4 h.
7. A water-based paint resin based on konjaku flour is characterized in that: the compound is prepared by the preparation method of any one of claims 1 to 6.
8. A water-based paint composition based on konjak powder is characterized in that: which contains the konjaku flour-based water-based paint resin according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430079.4A CN110078883B (en) | 2019-05-22 | 2019-05-22 | Water-based paint resin based on konjac flour, preparation method and composition thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430079.4A CN110078883B (en) | 2019-05-22 | 2019-05-22 | Water-based paint resin based on konjac flour, preparation method and composition thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110078883A CN110078883A (en) | 2019-08-02 |
| CN110078883B true CN110078883B (en) | 2021-08-03 |
Family
ID=67421258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910430079.4A Active CN110078883B (en) | 2019-05-22 | 2019-05-22 | Water-based paint resin based on konjac flour, preparation method and composition thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078883B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126317A (en) * | 2020-09-28 | 2020-12-25 | 山东七维新材料有限公司 | Low-temperature-resistant novel water-based epoxy coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013117611A1 (en) * | 2012-02-07 | 2013-08-15 | Chemetall Gmbh | Method for coating metallic surfaces of substrates, and objects coated according to said method |
| CN103554393A (en) * | 2013-10-18 | 2014-02-05 | 华中农业大学 | Method for preparing natural polymer matrix light-cured resin |
| CN105925165A (en) * | 2016-04-29 | 2016-09-07 | 李强 | Polymer waterborne polyurethane coating and preparation method thereof |
| CN107400494A (en) * | 2016-05-19 | 2017-11-28 | 长沙市汇华胶粘剂科技有限公司 | A kind of wheat stalk-konjaku flour composite adhesive and preparation method thereof |
| CN108912807A (en) * | 2018-08-16 | 2018-11-30 | 南京林业大学 | A method of improving aqueous polyurethane coating wearability |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031492A1 (en) * | 1994-05-11 | 1995-11-23 | Bayer Aktiengesellschaft | Paper finishing aid |
| CN1159342C (en) * | 2001-08-27 | 2004-07-28 | 武汉大学 | Semi-interpenetrating network polymer of castor oil type polyurethane and benzoic konjak polyglucosiduronate and its prepn and application |
| SE0300801D0 (en) * | 2003-03-21 | 2003-03-21 | Paul Gatenholm | Polymeric film or coating comprising hemicellulose |
| US20090177226A1 (en) * | 2005-05-05 | 2009-07-09 | Jon Reinprecht | Bioabsorbable Surgical Compositions |
| CN102020790B (en) * | 2010-11-11 | 2013-03-06 | 昆明理工大学 | Natural polymer film material with adjustable degradation rate and preparation method |
| CN102505183A (en) * | 2011-10-31 | 2012-06-20 | 昆明理工大学 | Konjac glucomannan contained filament fiber material and preparation method thereof |
| CN107586510B (en) * | 2017-10-27 | 2020-06-26 | 西华大学 | Preparation method of corrosion-resistant polyurethane modified epoxy resin emulsion |
| CN107964237A (en) * | 2017-12-26 | 2018-04-27 | 芜湖市长江起重设备制造有限公司 | A kind of preparation method of modified glass-fiber polycarbafil type aqueous polyurethane anti-static material |
| CN108086045A (en) * | 2017-12-26 | 2018-05-29 | 芜湖市长江起重设备制造有限公司 | A kind of preparation method of wear-resisting and waterproof waterborne polyurethane resin coating coating paper |
| CN109575697B (en) * | 2018-11-19 | 2020-12-18 | 西华大学 | Starch-based water-based paint composition and preparation method thereof |
-
2019
- 2019-05-22 CN CN201910430079.4A patent/CN110078883B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013117611A1 (en) * | 2012-02-07 | 2013-08-15 | Chemetall Gmbh | Method for coating metallic surfaces of substrates, and objects coated according to said method |
| CN103554393A (en) * | 2013-10-18 | 2014-02-05 | 华中农业大学 | Method for preparing natural polymer matrix light-cured resin |
| CN105925165A (en) * | 2016-04-29 | 2016-09-07 | 李强 | Polymer waterborne polyurethane coating and preparation method thereof |
| CN107400494A (en) * | 2016-05-19 | 2017-11-28 | 长沙市汇华胶粘剂科技有限公司 | A kind of wheat stalk-konjaku flour composite adhesive and preparation method thereof |
| CN108912807A (en) * | 2018-08-16 | 2018-11-30 | 南京林业大学 | A method of improving aqueous polyurethane coating wearability |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110078883A (en) | 2019-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107236109B (en) | Citric acid chitosan modified waterborne polyurethane and preparation method thereof | |
| JPS62256817A (en) | Production of aqueous dispersion of polyurethane-polyurea, dispersion obtained and use thereof as coating composition | |
| CN107163217B (en) | Preparation method of nano-diamond modified waterborne polyurethane | |
| CN107129565B (en) | Preparation process of waterborne polyurethane emulsion | |
| CN109575697B (en) | Starch-based water-based paint composition and preparation method thereof | |
| CN107082860A (en) | Self-emulsifying waterborne polyurethane curing agent and preparation method thereof | |
| CN109957091B (en) | Polyurethane polymer suitable for adjusting viscosity of aqueous high-solvent system and composition containing polyurethane polymer | |
| CN110078883B (en) | Water-based paint resin based on konjac flour, preparation method and composition thereof | |
| CN106700021A (en) | Chitosan modified cationic waterborne polyurethane resin and preparation method and application thereof | |
| CN110835398A (en) | Preparation method of rosin-based waterborne polyurethane emulsion | |
| CN104151073A (en) | Preparation method of coated sustained-release fertilizer | |
| CN107828049A (en) | A kind of watersoluble closed polyisocyanate curing agent of aziridine type and preparation method thereof | |
| CN109942770A (en) | A kind of water paint emulsion compositions and preparation method thereof | |
| DE19947563A1 (en) | Transesterification polyols for polyurethane prepolymers with specifically adjustable viscosity | |
| CN108753134B (en) | Water-based metallic paint and preparation method thereof | |
| CN107118326B (en) | Method for preparing waterborne polyurethane film forming material from mixture of glucose and castor oil | |
| CN116200117A (en) | Bio-based automobile exterior decorative paint and preparation method and application method thereof | |
| CN112300375B (en) | Preparation method of waterborne light-cured epoxy acrylic resin | |
| CN112062923B (en) | Waterborne polyurethane-urea dispersion for nail polish and preparation method thereof | |
| CN101981146B (en) | Aqueous coating composition comprising an autoxidisable amide group containing resin | |
| CN102816527A (en) | Super-scratch-resistant self volatilizing and curing paint | |
| CN103275667B (en) | Active methylene group modified waterborne polyurethane adhesive | |
| CN102757726B (en) | Water-based ultraviolet (UV) curing paint and preparation method thereof based on natural polyhydroxy carbohydrate | |
| DE1645563A1 (en) | Process for the production of coatings | |
| CN110092883A (en) | Corrosion-resistant aqueous supermolecule polyurethane resin of one kind and the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221222 Address after: No. 28 Pugong Road, Fengxian Chemical Industry Zone, Shanghai 201400 Patentee after: SHANGHAI HONGHU CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 610039, No. 999, Jin Zhou road, Jinniu District, Sichuan, Chengdu Patentee before: XIHUA University |
|
| TR01 | Transfer of patent right |