CN110078883A - A kind of water paint resin, preparation method and composition based on konjaku flour - Google Patents
A kind of water paint resin, preparation method and composition based on konjaku flour Download PDFInfo
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- CN110078883A CN110078883A CN201910430079.4A CN201910430079A CN110078883A CN 110078883 A CN110078883 A CN 110078883A CN 201910430079 A CN201910430079 A CN 201910430079A CN 110078883 A CN110078883 A CN 110078883A
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of water paint resin, preparation method and composition based on konjaku flour.The water paint resin is made by following steps: (1) anhydride reaction of konjaku flour and organic acid and/or the organic acid being obtained konjaku flour organic acid esters；(2) organic matter of the hydroxy functional group containing both-end is reacted with isocyanates, obtains the second component；(3) the konjaku flour organic acid esters, the second component, epoxy resin are reacted under catalyst and inert environments, obtains presoma resin；(4) organic solvent in the presoma resin is removed, adds water to get the water paint resin is arrived.Water paint of the gained based on konjaku flour of the invention has good biocompatibility, biological safety, degradability, can be widely applied on toy for children, stationery, food and Key works Drug packing.
Description
Technical field
The present invention relates to the technical fields of water paint resin and combinations thereof.
Background technique
Coating is major class material the effects of playing decoration, protection to substrate after being coated in substrate surface film-forming,
It is made of in water or organic solvent film forming matter dispersion (dissolution).Wherein organic solvent class coating dissolubility is good, coating is uniform
Property it is good, but coating volatile organic matter (VOC) content dispersed is high, will cause atmosphere pollution in use, and bring part
The serious greenhouse effects in area belong to and gradually limit, eliminate the product used；And water-dispersible paint is practically free of VOC, belongs to
It promotes, encourage the product used.
Water paint common in the art such as polyvinyl alcohol coating, water soluble alkyd resin class coating, water solubility
Epoxy coating etc., for these coating mostly using artificial synthetic resin as main film forming substance, biocompatibility is poor, it is difficult to drop
Solution has certain harmfulness to environment and human body, it is difficult to be applied on toy for children, stationery, food and Key works Drug packing object, together
When its material resin synthesis process is complicated, high production cost.
Summary of the invention
It is an object of the invention to propose it is a kind of directly by biological raw material konjaku be prepared it is novel aqueous, environmentally friendly,
Degradable coating resin and combinations thereof, the coating resin and combinations thereof can be widely applied to toy for children, stationery, food and
On Key works Drug packing, environmentally friendly safety.
The present invention also aims to propose the preparation method of above-mentioned water paint resin.
Present invention firstly provides the following technical solutions:
A kind of preparation method of the water paint resin based on konjaku flour comprising following steps:
(1) konjaku flour is dried to water content 2% hereinafter, making with the acid anhydrides of organic acid and/or the organic acid in catalyst thereafter
With, react at 110 ~ 180 DEG C, obtain the konjaku flour organic acid esters that degree of substitution is 1.6 ~ 2.3；
(2) organic matter of the hydroxy functional group containing both-end is reacted with isocyanates, obtains the second component；
(3) by the konjaku flour organic acid esters, the second component, epoxy resin in isocyano and the anti-applications catalyst of hydroxyl and lazy
It is reacted under property environment, obtains presoma resin；
(4) organic solvent in the presoma resin is removed, water, stirring is added at 30 ~ 50 DEG C thereafter, obtains the water
Property coating resin.
Step (1) in above scheme, (2) can carry out respectively simultaneously or one first carries out after one, and step (1) is not required to centainly
It is carried out prior to step (2).
The higher konjaku kinds of KGM content such as the preferred elephant-foot yam of the konjaku flour, white konjaku, formal happy konjaku, western alliance's konjaku
Stem tuber solid extract or the dry matter after its stem tuber drying and crushing.
Catalyst in the step (1) be preferably one of pyridine, NaOH, KOH, perchloric acid, p-methyl benzenesulfonic acid or
It is a variety of.
The dosage of the catalyst is preferably the 1% ~ 30% of konjaku flour quality.
The ratio of the quality of the quality and organic acid and/or its acid anhydrides of the konjaku flour is 1:1 ~ 5.5.
The organic acid be preferably one of acetic acid, butyric acid, n-caproic acid, octanoic acid, palmitinic acid, succinic acid, citric acid or
It is a variety of.
Corresponding, the organic acid anhydride is preferably acetic anhydride, butyric anhydride, n-caproic anhydride, caprylic anhydride, palmitic anhydride, amber
One of acid anhydrides, citric anhydride are a variety of.
The reaction time is subject to the degree of substitution for reaching required, in certain embodiments of the present invention, described anti-
Preferably 30 ~ 100min between seasonable.
In above scheme, the measuring method of konjaku flour organic acid esters degree of substitution can refer to be measured about organic acid esters degree of substitution
Each open source literature, such as measuring method below: being carried out saponification generates organic acid using excessive alkali and organic acid esters
Salt, extra alkali are neutralized with standard acid, thereafter compared with blank sample, thus calculate the content of organic acid acyl group, then change
Calculating is degree of substitution.
In a kind of specific embodiment of above scheme, the hydroxy functional group containing both-end described in the step (2) has
Machine object is in dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxy cyclobutane-carboxylic acid, dihydroxy quinoline carboxylic acid, polyethylene glycol
It is one or more.
Wherein polyethylene glycol is preferably polyethylene glycol 200, polyethylene glycol 400, Macrogol 600, cetomacrogol 1000, gathers
One of ethylene glycol 3000 is a variety of.
In its another specific embodiment, the isocyanate species be selected from toluene di-isocyanate(TDI) (TDI), it is different not
Lovell ketone diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI),
One of hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI) are a variety of.
Above scheme it is a kind of preferably in, the hydroxyl of the organic matter of the hydroxy functional group containing both-end described in the step (2)
The ratio of the amount of the substance of base and isocyano is 0.9 ~ 1.1:2.
Above scheme it is a kind of preferably in, the reaction temperature of the step (2) is 55 ~ 75 DEG C.
Above scheme it is a kind of preferably in, the reaction preferred reaction time of the step (2) is 1 ~ 3h.
Above scheme it is a kind of preferably in, the amount of the substance of the isocyano of the second component described in the step (3)
Ratio with the amount of the total material of hydroxyl in the konjaku flour organic acid esters and epoxy resin is 0.9 ~ 1.1:1.
Above scheme it is a kind of preferably in, the reaction temperature of the step (3) is 60 ~ 80 DEG C.The one of above scheme
During kind is preferred, the preferred reaction time of the step (3) is 2 ~ 4h.
Above scheme it is a kind of preferably in, epoxy resin described in the step (3) is that E44, E54 etc. have different rings
One of oxygen value and the bisphenol A type epoxy resin of hydroxyl value are a variety of.
Above scheme it is a kind of preferably in, catalyst in the step (3) is organic tin catalyst, further excellent
Choosing, the catalyst are dibutyl tin dilaurate, in tin dilaurate dioctyl tin, stannous octoate, triethyl group tin acetate
It is one or more.
Above-mentioned catalyst preferable amount be konjaku flour organic acid esters, the second component and epoxy resin gross mass 0.3% ~
1.5%。
When implementing, catalyst described in step (3) can also be to be other for being catalyzed the quotient that isocyano is reacted with hydroxyl
Product catalyst.
Above scheme it is a kind of preferably in, the temperature reacted in the step (3) is 60 ~ 80 DEG C.
Above scheme it is a kind of preferably in, the time reacted in the step (3) is 2 ~ 4h.
In a kind of specific embodiment of above scheme, it is added in the mixed system before being reacted into step (3) dilute
Release agent.
Wherein the diluent be preferably the organic solvents such as acetone, butanone, dimethylbenzene, ethyl acetate, butyl acetate or its
Mixture.
Above scheme it is a kind of preferably in, in the step (4) organic solvent removal using heating distillation under vacuum,
Middle most 90 ~ 110 DEG C of heating, is decompressed to -0.04 ~ -0.1MPa.
Above scheme it is a kind of preferably in, the water being added in the step (4) is preferably deionized water and/or distillation
Water adds the water time to be preferably controlled in 20min or so.
In a kind of specific embodiment of above scheme, the hydroxy functional group containing both-end described in the step (2) has
Machine object is dihydroxy carboxylic acids type organic, continuously added in step (4) after addition of water with the dihydroxy carboxylic acids type organic etc.
The salt forming agent of the amount of substance.
It is preferably, and the salt forming agent is polynary amine substance, further preferably triethylamine, diethylenetriamine, three
One of ethylene tetramine is a variety of.
After salt forming agent is added, preferably continue to be stirred 20 ~ 40min of system.
Present invention further proposes a kind of water paint resin based on konjaku flour, can pass through any of the above-described kind of skill
Art scheme or its specific, preferred embodiment are prepared.
The invention also provides a kind of water paint resin combination based on konjaku flour is based on konjaku flour containing above-mentioned
Water paint resin.
In the specific implementation, the composition can also contain outside containing the water paint resin based on konjaku flour
There are other water paint usual auxiliaries.
The present invention has the following beneficial effects:
(1) present invention uses konjaku flour as basic raw material, has containing heteroglycan konjak glucomannan (KGM), KGM and inhales
Aqueous, gelation, cohesiveness, low-heat edibility, water paint resin as made from it can be widely applied to food processing, daily
The numerous areas such as chemistry, biological medicine；
(2) it although konjaku flour has the above advantages, is difficult to directly as coating application, the present invention is by carrying out konjaku flour
It is modified, and with other ingredients it is compound after be made a kind of new coating resin, coating resin film forming with higher, soft simultaneously
Toughness, impact resistance, adhesive force and degradability and the feature of environmental protection；
(3) konjaku flour organic acid esters has good hydrophobicity in the present invention, while the residual hydroxy groups that konjaku flour contains can be into one
Step and isocyano etc. react, and obtain the water paint resin using KGM molecule as basic framework, the water paint resin point
Contain hydrophilic radical in son simultaneously, can stablize, be uniformly dispersed in water, makes wholly or substantially to be free of VOC in product, in use
Atmosphere, water body, soil etc. will not be polluted；
(4) it is easy to degrade after the water paint resin film forming that the present invention obtains, natural degradation time in the soil is 3 months
~ 3 years, to environment without accumulative pollution；
(5) the water paint resin good biocompatibility that the present invention obtains, biological safety is good, can be widely applied to children's object for appreciation
In the multiple fields such as tool, stationery, food, medicine, health.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to the following embodiments and the accompanying drawings.Without departing from the idea of the above method of the present invention, common according to this field
The various replacements or change that technological know-how and customary means are made, should be included in the scope of the present invention.
Also, it is understood that the actual use principle of claimed whole raw materials, reagent etc. with it is following
The tie substance specifically enumerated in embodiment or embodiment is identical, following embodiments or embodiment can to the present invention claims
The total material of protection plays role of delegate.
In a kind of specific embodiment of the preparation method of water paint resin based on konjaku flour comprising following step
It is rapid:
Step (1):
Konjaku flour is dried, make its water content control 2% hereinafter, thereafter by it with organic acid and/or its acid anhydrides by certain matter
Amount than uniformly mixing, a certain proportion of catalyst is added, reacts certain time at a certain temperature, obtain degree of substitution be 1.6 ~
Distilled water is added after reaction in 2.3 konjaku flour organic acid esters in the reaction system, filtering, is product after solid drying；
Degree of substitution is surveyed, spare, remaining liq is reusable by concentration, distillation.
Wherein the konjaku flour is from higher evil spirits of KGM content such as elephant-foot yam, white konjaku, formal happy konjaku, western alliance's konjakus
The stem tuber drying of the konjaku of the solid matter or above-mentioned kind that extract in the stem tuber of taro kind, smashed dry matter, preferably make
With the solid matter of extraction.
Wherein the organic acid is preferably acetic acid, butyric acid, n-caproic acid, octanoic acid, palmitinic acid, succinic acid, one in citric acid
Kind is a variety of.
Wherein the acid anhydrides is preferably acetic anhydride, butyric anhydride, n-caproic anhydride, caprylic anhydride, palmitic anhydride, succinic anhydride, lemon
Lemon acid anhydrides it is one or more.
Wherein the mass ratio of konjaku flour and organic acid and/or its acid anhydrides is preferably 1:1 ~ 5.5.
Wherein catalyst is preferably one of pyridine, NaOH, KOH, perchloric acid, p-methyl benzenesulfonic acid or a variety of, meanwhile, this
Field technical staff is it is understood that in the specific implementation, should not select the complex form that can mutually damage catalytic effect, such as
As catalyst after selecting NaOH and/or KOH to combine with perchloric acid.
Wherein the dosage of catalyst is preferably the 1% ~ 30% of konjaku flour quality.
Wherein reaction temperature is 110 ~ 180 DEG C；Reaction time is preferably 30 ~ 100min.
Step (2):
The organic matter of the hydroxyl containing both-end is dissolved, and a certain proportion of isocyanates is added, leads to nitrogen protection, at a certain temperature
React certain time.
Wherein the organic matter of the hydroxyl containing both-end include but is not limited to dihydroxy carboxylic acids substance such as dihydromethyl propionic acid,
Dimethylolpropionic acid, dihydroxy cyclobutane-carboxylic acid, dihydroxy quinoline carboxylic acid etc.；Polyethylene glycol substances such as polyethylene glycol 200 gathers
Ethylene glycol 400, Macrogol 600, cetomacrogol 1000, Macrogol 3000 etc..
Wherein the isocyanate species include but is not limited to toluene di-isocyanate(TDI) (TDI), different not Lovell ketone diisocyanate
Ester (IPDI), methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), hexa-methylene two are different
Cyanate (HDI), lysine diisocyanate (LDI) etc..
Wherein the ratio of the amount of the substance of the hydroxyl and isocyano is preferably 0.9 ~ 1.1:2.
Wherein the reaction temperature is preferably 55 ~ 75 DEG C.
Wherein the reaction time is preferably 1 ~ 3h.
The flow for wherein leading to nitrogen matches in reactor size.
Step (3):
A certain proportion of konjaku flour organic acid esters prepared by step (1) and epoxy resin is added in the reaction product of step (2),
Stirring, dissolution, are added certain diluent when necessary；A certain proportion of catalyst is added, leads to nitrogen protection, at a certain temperature
React certain time.
Wherein isocyano and konjaku flour derivative prepared by step (1) and ring in the reaction product of the step (2)
The ratio of the amount of the substance of the summation of institute's hydroxyl is preferably 0.9 ~ 1.1:1 in oxygen resin.
Wherein the epoxy resin is preferably the bisphenol A type epoxy resin that E44, E54 etc. have different epoxide numbers and hydroxyl value.
Wherein the diluent be preferably the organic solvents such as acetone, butanone, dimethylbenzene, ethyl acetate, butyl acetate or its
Mixture.
Wherein the catalyst is preferably dibutyl tin dilaurate, tin dilaurate dioctyl tin, stannous octoate, triethyl group
The organic tins such as tin acetate are related for being catalyzed the commercial catalyst that isocyano is reacted with hydroxyl.
Wherein the quality of the catalyst is preferably the 0.3% ~ 1.5% of the quality of reaction mass (not including solvent).
Wherein the reaction temperature is preferably 60 ~ 80 DEG C.
Wherein the reaction time is preferably 2 ~ 4h.
Wherein lead to the flow of nitrogen and reactor size matches.
Step (4):
By reaction product heating, the decompression of step (3), organic solvent is distilled；40 DEG C are cooled to, mixing speed is improved, is added dropwise
Distilled water and/or deionized water add the control of water time in 20min or so；As selected dihydroxy carboxylic acids class object in step (2)
Matter then continuously adds the salt forming agent equal with the amount of its substance, continues 20 ~ 40min of stirring after adding to get to based on konjaku flour
Water paint resin.
Wherein temperature is preferably 90 ~ 110 DEG C after the heating；Air pressure is preferably -0.04 ~ -0.1MPa after the decompression.
Step (5):
Other water paint usual auxiliaries are added in the water paint resin obtained to step (4), such as pigment, dispersing agent, defoaming
One of agent, levelling agent, adhesion promoter, delustering agent, thixotropic agent, thickener etc. are a variety of, obtain it is a kind of new based on
The water-base resin coating composition of konjaku flour.
Below by way of some specific embodiments, the present invention is described in further detail.
Embodiment 1
(1) taking 1.5kg purification konjaku flour, (prior by drying, water content is 85%), to add under ice-water bath lower than 2%, KGM content
Enter 0.6kg acetic anhydride, stirs evenly；100 DEG C or so are gradually warming up to, continuously adds 2.25kg acetic anhydride and 60g to toluene sulphur
Acid, it is lasting to stir, 2h is reacted at 100 DEG C, is warming up at 115 DEG C and reacts 1h；Thereafter 40 DEG C or so are cooled to, to reactant
8kg deionized water is added in system, precipitates thereafter, be concentrated, filtering, by the drying of obtained solid component, crushes, obtains product konjaku flour
Organic acid esters, surveying its degree of substitution is 2.02；By the concentration of remaining liq component, distillation, glacial acetic acid, renewable production acetic acid are obtained
Acid anhydride；
(2) 275gIPDI and 84.5g dihydromethyl propionic acid are stirred, is uniformly mixed；Logical nitrogen protection (nitrogen flow 0.1L/
Min), it is warming up to 80 DEG C thereafter, reacts 2.2h；
(3) in the product of step (2) be added 123g epoxy resin E44,140g step (1) products therefrom, 200g butanone,
3.5g dibutyl tin dilaurate, stirs evenly；70 DEG C are warming up to, 2.5h is reacted；
(4) 40 DEG C are cooled to, 600g distilled water and/or deionized water is slowly added dropwise, while quickly stirring, emulsification, in 30 min
Left and right adds to get to the water paint resin based on konjaku flour, and the adhesive force after film forming under standard test condition is 0
Grade (highest in standard), flexibility are 2 grades (highest in standard), and impact resistance is highest in 50cm(standard) more than,
Pencil hardness is HB ~ 1H, and the film is in the soil about by half a year, that is, degradable.
Embodiment 2
(1) taking 1.5kg konjaku dry powder, (prior by drying, content of the water content lower than 2%, KGM is 75%), to add under ice-water bath
Enter 0.9kg butyric anhydride, stirs evenly；130 DEG C or so are gradually warming up to, 2.5 kg butyric anhydrides and 75g perchloric acid is continuously added, holds
Continuous stirring, 0.5h is reacted at 130 DEG C, is warming up to thereafter at 170 DEG C and reacts 1 h；Thereafter 40 DEG C or so are cooled to, to reactant
9kg deionized water is added in system, thereafter precipitating, concentration, filtering, obtains solid component drying, crushing for more, obtain product konjaku flour
Organic acid esters, surveying its degree of substitution is 1.86, and the concentration of remaining liq component, distillation obtain butyric acid, renewable production butyric anhydride；
(2) 200gTDI and 76g dihydromethyl propionic acid are stirred, is uniformly mixed, lead to nitrogen protection (nitrogen flow 0.1 thereafter
L/min), 60 DEG C are warming up to, 2.5h is reacted；
(3) the konjaku flour organic acid of 170 g epoxy resin E54,180g steps (1) preparation is added in the product of step (2)
Ester, 225g butanone, 4g stannous octoate, stir evenly, and are warming up to 75 DEG C thereafter, react 3h；
(4) 40 DEG C are cooled to, 60g triethylamine is added, is stirred to react 15min, 550g distilled water is slowly added dropwise thereafter and/or goes
Ionized water, while quickly stirring, emulsification, add in 30 min or so to get the water paint resin based on konjaku flour described in,
Adhesive force after film forming under standard test condition is 0 grade (highest in standard), and flexibility is highest in 2(standard), it is resistance to
Impact is highest in 50cm(standard) more than, pencil hardness is 1H ~ 3H, and the film was about by eight months in the soil
It is degradable.
Embodiment 3
(1) taking 1.5kg konjaku flour dry powder, (prior by drying, water content is 65%), to add under ice-water bath lower than 2%, KGM content
Enter 1kg palmitinic acid acid anhydrides, stir evenly, be gradually warming up to 120 DEG C or so thereafter, continuously adds 2.5kg palmitinic acid and 100g high
Chloric acid, it is lasting to stir, 1 h is reacted at 120 DEG C, is warming up at 165 DEG C and reacts 0.5h, cools to 40 DEG C or so thereafter, to anti-
Addition 8kg deionized water in system is answered, precipitates thereafter, be concentrated, filtering, by the drying of obtained solid component, crushes, obtains product
Konjaku flour organic acid esters, surveying its degree of substitution is 1.92, the concentration of remaining liq component, distillation, obtains palmitinic acid, renewable production palm fibre
Palmitic acid acid anhydrides；
(2) 250g methyl diphenylene diisocyanate and 74g dimethylolpropionic acid are stirred, is uniformly mixed, lead to nitrogen protection
(nitrogen flow is 0.1 L/min), is warming up to thereafter 70 DEG C, reacts 2.5h；
(3) it is organic that 96.6 g epoxy resin E44, the konjaku flour of 132 g steps (1) preparation are added in the product of step (2)
Acid esters, 200g butanone, 4.2g triethyl group tin acetate, stir evenly, and are warming up to 75 DEG C, react 1.5h；
(4) 40 DEG C are cooled to, thereafter be added 50g triethylamine, be stirred to react 15 min, be slowly added dropwise thereafter 500g distilled water and/
Or deionized water, while quickly stirring, emulsification, it adds in 30min or so to get the water paint tree based on konjaku flour described in
Rouge, the adhesive force after film forming under standard test condition are 0 grade (highest in standard), and flexibility is highest in 2(standard),
Impact resistance is highest in 50cm(standard) more than, pencil hardness is 2H ~ 3H, which was about by 15 months in the soil
It is degradable.
Claims (10)
1. a kind of preparation method of the water paint resin based on konjaku flour, it is characterised in that: the following steps are included:
(1) konjaku flour is dried to water content 2% hereinafter, making with the acid anhydrides of organic acid and/or the organic acid in catalyst thereafter
With, react at 110 ~ 180 DEG C, obtain the konjaku flour organic acid esters that degree of substitution is 1.6 ~ 2.3；
(2) organic matter of the hydroxy functional group containing both-end is reacted with isocyanates, obtains the second component；
(3) by the konjaku flour organic acid esters, the second component, epoxy resin in isocyano and the anti-applications catalyst of hydroxyl and lazy
It is reacted under property environment, obtains presoma resin；
(4) organic solvent in the presoma resin is removed, water, stirring is added at 30 ~ 50 DEG C thereafter, obtains the water
Property coating resin.
2. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly the organic matter of the hydroxy functional group containing both-end described in (2) is dihydroxy carboxylic acids type organic, and water is being added in the step (4)
The salt forming agent with the amount of the substances such as the dihydroxy carboxylic acids type organic is continuously added afterwards, and the preferably described salt forming agent is polynary amine
One of matter, further preferably triethylamine, diethylenetriamine, triethylene tetramine are a variety of.
3. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly organic acid described in (1) is selected from one of acetic acid, butyric acid, n-caproic acid, octanoic acid, palmitinic acid, succinic acid, citric acid or more
Kind, the preferably described konjaku flour is 1:1 ~ 5.5 with the mass ratio of organic acid or/and its acid anhydrides.
4. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly catalyst described in (1) is selected from one of pyridine, NaOH, KOH, perchloric acid, p-methyl benzenesulfonic acid or a variety of, the catalyst
Dosage is preferably the 1 ~ 30% of the konjaku flour quality.
5. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly the organic matter of the hydroxy functional group containing both-end described in (2) is selected from dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxy cyclobutane
One of carboxylic acid, dihydroxy quinoline carboxylic acid, polyethylene glycol are a variety of.
6. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly the ratio of the amount of the substance of the hydroxyl and isocyano of the organic matter of the hydroxy functional group containing both-end described in (2) is 0.9 ~ 1.1:2,
Its reaction temperature is 55 ~ 75 DEG C, and preferred reaction time is 1 ~ 3h.
7. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly the amount of the substance of the isocyano of the second component described in (3) and hydroxyl in the konjaku flour organic acid esters and epoxy resin
The ratio of the amount of total material is 0.9 ~ 1.1:1.
8. the preparation method of the water paint resin according to claim 1 based on konjaku flour, it is characterised in that: the step
Suddenly the reaction temperature of (3) is 60 ~ 80 DEG C, and preferred reaction time is 2 ~ 4h.
9. a kind of water paint resin based on konjaku flour, it is characterised in that: its according to claim 1 ~ 8 in it is any described
Preparation method is prepared.
10. a kind of water-based paint compositions based on konjaku flour, it is characterised in that: it contains as claimed in claim 9 based on evil spirit
The water paint resin of taro powder.
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| 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 |
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