CN109575697A - A kind of starch-based aqueous coating composition and preparation method thereof - Google Patents
A kind of starch-based aqueous coating composition and preparation method thereof Download PDFInfo
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- CN109575697A CN109575697A CN201811377007.XA CN201811377007A CN109575697A CN 109575697 A CN109575697 A CN 109575697A CN 201811377007 A CN201811377007 A CN 201811377007A CN 109575697 A CN109575697 A CN 109575697A
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- Prior art keywords
- starch
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- hydroxyl
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- 229920002472 Starch Polymers 0.000 title claims abstract description 57
- 239000008107 starch Substances 0.000 title claims abstract description 55
- 235000019698 starch Nutrition 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000008199 coating composition Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 229920000881 Modified starch Polymers 0.000 claims description 8
- 239000004368 Modified starch Substances 0.000 claims description 8
- 235000019426 modified starch Nutrition 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- -1 organic acid esters Chemical class 0.000 claims description 6
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 239000002689 soil Substances 0.000 abstract description 5
- 238000010792 warming Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 229920006334 epoxy coating Polymers 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 240000003183 Manihot esculenta Species 0.000 description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 3
- NGEZPLCPKXKLQQ-VOTSOKGWSA-N (e)-4-(3-methoxyphenyl)but-3-en-2-one Chemical compound COC1=CC=CC(\C=C\C(C)=O)=C1 NGEZPLCPKXKLQQ-VOTSOKGWSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- INJAHHABQHQOMY-UHFFFAOYSA-N 2-(dihydroxymethyl)butanoic acid Chemical compound CCC(C(O)O)C(O)=O INJAHHABQHQOMY-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- IXAWXWACDBWEJF-UHFFFAOYSA-L C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] Chemical compound C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] IXAWXWACDBWEJF-UHFFFAOYSA-L 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 108091022917 Gluconate dehydratase Proteins 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- 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
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/04—Starch derivatives
- C09D103/06—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention provides a kind of starch-based aqueous coating composition and preparation method thereof comprising step: (1) starches hydrophobized modification；(2) isocyanates is reacted with the reactant of the hydroxyl containing both-end；(3) product that step (1) and step (2) respectively obtain is mixed with epoxy resin, 70 ~ 95 DEG C of Yu Wendu are reacted；(4) product of step (3) is subjected to heating treatment and reduced pressure treatment, after distilled water or deionized water mixing is added after cooling down to get starch-based aqueous coating composition.The coating composition of this method preparation can natural degradation do not need to be post-processed in soil, and degradation time is short, and most fast half a year can be completed.
Description
Technical field
The present invention relates to high-molecular organic material technical fields, and in particular to a kind of starch-based aqueous coating composition and its
Preparation method.
Technical background
Coating is major class material the effects of playing decoration, protection to substrate after being coated in substrate surface film-forming,
Generally it is made of in water or organic solvent film forming matter dispersion (dissolution).Tradition is generally contained using the coating of organic solvent dispersion
Have higher volatile organic matter (VOC), and post-processing is difficult, not only results in atmosphere pollution, greenhouse effects, and length
Phase, which exists in the environment, causes compared with major injury human body.
Starch is the main carriers that energy is stored in most of plant cell, is polymerized by gluconate dehydratase, including straight
Two class of chain starch and amylopectin.Starch source is nontoxic in natural products, is easy to degrade, from a wealth of sources, renewable,
It mainly can be from agricultural product such as corn, wheat and potatos.
It is due to major part currently, being that main molecular skeleton prepares the rare report of water paint with starch or derivatives thereof
Starch and its derivative are water-soluble products, it is difficult to be used for coating, therefore exploitation is a harmless pollution-free, is easy to degrade, no
The coating that will cause starch of cumulative environmental pollution or derivatives thereof is particularly significant.
Summary of the invention
The object of the present invention is to provide a kind of starch-based aqueous coating compositions and preparation method thereof, and the method overcome upper
Problem is stated, nontoxic degradable coating composition can be produced using such method, which being capable of natural degradation
It does not need to be post-processed in soil, and degradation time is short, most fast half a year completes.
In reaching above-mentioned purpose, the present invention provides following technical schemes:
In fact, the present invention relates to a kind of starch-based aqueous coating compositions and preparation method thereof comprising step:
(1) starch is subjected to hydrophobic modification, obtains modified starch；
(2) isocyanates is reacted with the reactant of the hydroxyl containing both-end, obtains reaction product A；
(3) modified starch, reaction product A and epoxy resin are mixed, is reacted thereafter, is obtained in 70~95 DEG C of temperature
Reaction product B, wherein the ratio of the amount of the substance of modified starch institute's hydroxyl and epoxy resin institute hydroxyl is 0.5~1.5:
1；The amount of the substance of contained isocyano is n in reaction product A1, the summation of institute's hydroxyl in modified starch and epoxy resin
The amount of substance is n2, the n1With n2Meet relationship: n1: n2=1:1；
(4) reaction product B is subjected to heating treatment and reduced pressure treatment, after distilled water or deionized water are added after cooling down
Mixing to get.
The present invention is handled by the hydrophobic modification to starch, can pass through hydroxyl and isocyano, epoxy resin
It is reacted, forms the water-based paint compositions with starch or derivatives thereof for basic molecular skeleton.The water-based paint compositions
Containing a large amount of hydrophilic radicals, can not be directly dispersing in by organic solvent in water and form stable dispersion, thus without VOC or
The ratio of contained VOC is extremely low, can effectively control atmosphere pollution.
As another specific embodiment, the step (1) is to mix after drying starch with organic acid or its acid anhydrides, thereafter
The first catalyst is added, 15~300min is reacted under the conditions of temperature is 150~220 DEG C, starch organic acid esters is obtained, exists thereafter
Distilled water is added in reaction system, using filter, drying.
As another specific embodiment, the starch is 1:1~5.5 with the mass ratio of organic acid or its acid anhydrides.
Han Shui Liang≤2% as another specific embodiment, after the starch drying.
As another specific embodiment, the degree of substitution of the starch organic acid esters is 2~2.8.
As another specific embodiment, the step (2) is the both-end hydroxylated material dissolution that will contain hydrophilic radical, and is added
Isocyanates reacts 1.5~3.5h by nitrogen protection under conditions of 65~90 DEG C of temperature.
As another specific embodiment, the both-end hydroxylic species and isocyanates are according to the substance of hydroxyl and isocyano
The ratio of amount is that 1:2 is reacted.
As another specific embodiment, in the step (4), heating treatment is that temperature is warming up to 110~130 DEG C, institute
Stating reduced pressure treatment is by air pressure drop down to -0.04~-0.1MPa.
As another specific embodiment, in the step (4), cooling is that temperature is reduced to 40~45 DEG C.
The invention further relates to coating compositions obtained by a kind of preparation method as described in claim 1~9 is any.
Compared with prior art, the present invention program have the utility model has the advantages that
(1) the water-fast product having enhanced antibacterial action of coating composition of the method for the present invention preparation, raw material is natural, nontoxic, hardly
Containing volatile organic matter (VOC), to human health；
(2) coating composition of the method for the present invention preparation can natural degradation, the degradation time in soil is 0.5~4 year,
Most fast half a year completes, and high-efficiency environment friendly is conducive to the sustainable development of environmental resource；
(3) coating composition of the method for the present invention preparation with starch or derivatives thereof for basic molecular skeleton, match by each ingredient
Than reasonable, for the efficient using opening up a new way of starch, be conducive to the exploitation of agricultural product high added value, increase peasant's receipts
Enter；
(4) preparation method of the invention can recycle organic acid or its acid anhydrides, economize on resources, reduce and be produced into
This；
(5) preparation method environment-friendly high-efficiency of the invention, easy to operate, gained coating composition is particularly suitable for toy for children
The coating of external coating, food and medicament packaging container, is widely used.
Specific embodiment
The present invention is described in further detail below by specific embodiment and comparative example, but those skilled in the art
Member will be understood that the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not infused in embodiment
Bright actual conditions person, carries out according to conventional conditions or manufacturer's recommended conditions.Production firm is not specified in agents useful for same or instrument
Person is the conventional products that can be obtained by commercially available purchase.
It should be noted that the " comprising " in the technical program mean its in addition to the ingredient, can also include other at
Point, the " comprising ", may be replaced by enclosed " for " or " by ... form ".
In the step of the technical program (1), starch, organic acid or its acid anhydrides, the first catalyst are logical in the market sell
Product, specifically, the starch includes but is not limited to from one in cornstarch, tapioca, potato starch, wheaten starch
Kind is a variety of；The organic acid includes but is not limited to one of acetic acid, butyric acid, palmitinic acid or a variety of；The acid anhydrides include but
It is not limited to one of acetic anhydride, butyric anhydride, palmitic anhydride or a variety of；First catalyst include but is not limited to pyridine,
One of NaOH, KOH, perchloric acid, p-methyl benzenesulfonic acid are a variety of.
In addition, the degree of substitution of starch organic acid esters can be used measuring method disclosed in existing literature and be surveyed in step (1)
Amount, specific measuring principle are to carry out the salt that saponification generates organic acid with excessive alkali and starch ester, and extra alkali is used
Standard acid neutralizes.By compared with blank sample, calculating the content of the organic acid acyl group in starch, then it is converted into degree of substitution.
In the step of the technical program (2), both-end hydroxylated material and isocyanates containing hydrophilic radical are logical in the market
The product sold, specifically, the both-end hydroxylated material containing hydrophilic radical includes but is not limited to dihydromethyl propionic acid, dihydroxymethyl
Butyric acid, polyethylene glycol 200, polyethylene glycol 400, Macrogol 600；The isocyanate species include but is not limited to that toluene two is different
Cyanate (TDI), different not Lovell ketone diisocyanate (IPDI), methyl diphenylene diisocyanate (MDI).
Preferably, in order to further increase the preparation efficiency that hydrophilic radical introduces reactant, the flow of nitrogen is 0.1~
10L/min。
In the step of the technical program (3), epoxy resin is to lead to the product sold in the market, specifically, the epoxy resin
It can be selected from Sinopec E44 model bisphenol A type epoxy resin, Sinopec E51 model bisphenol A type epoxy resin.Preferably,
In order to further increase reaction effect and rate, the second catalyst can also be added in step (3) reaction process, described second urges
Agent includes but is not limited to dibutyl tin dilaurate, tin dilaurate dioctyl tin, stannous octoate, triethyl group tin acetate.As
It is another preferred, in order to further adjust the viscosity of reaction mass system, improves processing performance, may be used also in step (3) reaction process
Diluent is added, the catalyst is organic tin catalyst, specifically, can be selected from dibutyl tin dilaurate, two laurels
One of sour dioctyl tin, stannous octoate, triethyl group tin acetate are a variety of, wherein the ratio of catalyst be reaction mass (no
Including solvent) gross mass 0.3%~1.5%.
In addition, the substance containing hydrophilic radical of selection is dihydromethyl propionic acid or dihydroxymethyl fourth in above-mentioned steps (2)
Acid, then also need to be added salt forming agent in above-mentioned steps (4), the salt forming agent is polynary amine substance, specifically can be selected from triethylamine,
Diethylenetriamine, triethylene tetramine.
Embodiment 1
A kind of starch-based aqueous coating composition and preparation method thereof comprising step:
(1) taking 1kg purification potato starch, (in advance by drying, 0.5kg is added under ice-water bath lower than 2%) in water content
Acetic anhydride stirs evenly；90 DEG C or so are gradually warming up to, 1.8kg acetic anhydride and 50g p-methyl benzenesulfonic acid is continuously added, persistently stirs
It mixes, reacts 2h at 90 DEG C, be warming up at 120 DEG C and react 1h；Thereafter 40 DEG C or so are cooled to, 8kg is added in reaction mass and goes
Ionized water, using, by solid component drying, crushing, acetic acid product starch is obtained after filter, surveying its degree of substitution is 2.21；Liquid
Component concentration, distillation, obtain glacial acetic acid, renewable production acetic anhydride；
(2) 222g IPDI and 67.5g dihydromethyl propionic acid are stirred, is uniformly mixed；Logical nitrogen protection, nitrogen flow are
0.1L/min；80 DEG C are warming up to, 2.2h is reacted, obtains reaction product A；
(3) acetic acid that 96.6g epoxy resin E44,114g step (1) preparation is added in the reaction product A of step (2) forms sediment
Powder, 200g butanone and 2.8g dibutyl tin dilaurate, stir evenly, and are warming up to 90 DEG C thereafter, react 2.5h, must react production
Object B；
(4) reaction product B is cooled to 40 DEG C, 500g distilled water or deionized water is slowly added dropwise, while quickly stirring,
30min or so is added, and obtains the starch epoxy coating.
Embodiment 2
A kind of starch-based aqueous coating composition and preparation method thereof comprising step:
(1) taking 1kg refining cassava starch, (in advance by drying, 0.8kg fourth is added lower than 2%) in water content under ice-water bath
Acid anhydrides stirs evenly；110 DEG C or so are gradually warming up to, 2.2kg butyric anhydride and 65g perchloric acid are continuously added, it is lasting to stir,
2h is reacted at 110 DEG C, is warming up at 130 DEG C and reacts 1.5h；40 DEG C or so are cooled to, 8kg deionized water is added in reaction mass,
Using, by solid component drying, crushing, product butyric acid starch is obtained after filter, surveying its degree of substitution is 2.16；Liquid component is dense
Contracting, distillation, obtain butyric acid, renewable production butyric anhydride；
(2) 174.5g TDI and 67.5g dihydromethyl propionic acid are stirred, is uniformly mixed；Logical nitrogen protection, nitrogen flow are
0.1L/min；70 DEG C are warming up to, 2.5h is reacted, obtains reaction product A；
(3) butyric acid that 152g epoxy resin E51,161g step (1) preparation is added in the reaction product A of step (2) forms sediment
Powder, 200g butanone and 3.5g stannous octoate, stir evenly；85 DEG C are warming up to, 3h is reacted, obtains reaction product B；
(4) reaction product B is cooled to 40 DEG C, 50g triethylamine is added, is stirred to react 15min；500g is slowly added dropwise later
Distilled water or deionized water, while quickly stirring, add in 30min or so, obtain the starch epoxy coating.
Embodiment 3
A kind of starch-based aqueous coating composition and preparation method thereof comprising step:
(1) taking 1kg refined wheat starch, (in advance by drying, 1kg palm is added lower than 2%) in water content under ice-water bath
Acid anhydrides stirs evenly；130 DEG C or so are gradually warming up to, 2.5kg palmitinic acid and 100g perchloric acid are continuously added, it is lasting to stir,
2h is reacted at 130 DEG C, is warming up at 155 DEG C and reacts 2.5h；40 DEG C or so are cooled to, 8kg deionization is added in reaction mass
Water, using, by solid component drying, crushing, product palmitinic acid acid-starch is obtained after filter, surveying its degree of substitution is 2.32；Liquid
Component concentration, distillation, obtain palmitinic acid, renewable production palmitic anhydride；
(2) 250g methyl diphenylene diisocyanate and 74g dimethylolpropionic acid are stirred, is uniformly mixed；Logical nitrogen is protected
Shield, nitrogen flow 0.1L/min；80 DEG C are warming up to, 2.5h is reacted, obtains reaction product A；
(3) palmitinic acid of 96.6g epoxy resin E44,132g step (1) preparation is added in the reaction product A of step (2)
Acid-starch, 200g butanone and 4.2g triethyl group tin acetate, stir evenly；90 DEG C are warming up to, 3.5h is reacted, obtains reaction product B；
(4) reaction product B is cooled to 40 DEG C, 50g diethylenetriamine is added, is stirred to react 15min；It is slowly added dropwise later
500g distilled water or deionized water, while quickly stirring, add in 30min or so, obtain the starch epoxy coating.
Embodiment 4
A kind of starch-based aqueous coating composition and preparation method thereof comprising step:
(1) taking 1kg purification potato starch, (in advance by drying, 0.5kg is added under ice-water bath lower than 2%) in water content
Butyric anhydride stirs evenly；150 DEG C or so are gradually warming up to, 1.8kg butyric anhydride and 50g KOH are continuously added, it is lasting to stir,
2h is reacted at 150 DEG C, is warming up at 220 DEG C and reacts 0.25h；Thereafter 40 DEG C or so are cooled to, in reaction mass be added 7kg go from
Sub- water, using, by solid component drying, crushing, product butyric acid starch is obtained after filter, surveying its degree of substitution is 2.21；Liquid group
Divide concentration, distillation, obtains butyric acid, renewable production butyric anhydride；
(2) 296g IPDI and 88.7g dihydromethyl propionic acid are stirred, is uniformly mixed；Logical nitrogen protection, nitrogen flow are
10L/min；65 DEG C are warming up to, 3.5h is reacted, obtains reaction product A；
(3) acetic acid that 120g epoxy resin E44,164g step (1) preparation is added in the reaction product A of step (2) forms sediment
Powder, 216g ethyl acetate and 3.4g stannous octoate, stir evenly, and are warming up to 70 DEG C thereafter, react 3.2h, obtain reaction product B；
(4) reaction product B is warming up to 110 DEG C, air pressure drop reacts 20min, cool to 40 thereafter down to -0.04MPa
DEG C, 500g distilled water or deionized water is slowly added dropwise, while quickly stirring, is added in 30min or so, obtain the starch epoxy
Cold coating.
Embodiment 5
A kind of starch-based aqueous coating composition and preparation method thereof comprising step:
(1) taking 1kg refining cassava starch, (in advance by drying, 0.5kg second is added lower than 2%) in water content under ice-water bath
Acid anhydrides stirs evenly；100 DEG C or so are gradually warming up to, 1.6kg acetic anhydride and 50g pyridine are continuously added, it is lasting to stir, 100
2h is reacted at DEG C, is warming up at 150 DEG C and is reacted 5h；Thereafter 40 DEG C or so are cooled to, 8kg deionized water is added in reaction mass,
Using, by solid component drying, crushing, acetic acid product starch is obtained after filter, surveying its degree of substitution is 2.8；Liquid component is dense
Contracting, distillation, obtain glacial acetic acid, renewable production acetic anhydride；
(2) 268g IPDI and 68.7g dimethylolpropionic acid are stirred, is uniformly mixed；Logical nitrogen protection, nitrogen flow are
0.5L/min；90 DEG C are warming up to, 3.5h is reacted, obtains reaction product A；
(3) acetic acid that 106g epoxy resin E44,154g step (1) preparation is added in the reaction product A of step (2) forms sediment
Powder, 158g dimethylbenzene and 2.5g dibutyl tin dilaurate, stir evenly, and are warming up to 95 DEG C thereafter, react 2.3h, must react
Product B；
(4) reaction product B is warming up to 130 DEG C, air pressure drop reacts 20min, cool to 40 thereafter down to -0.1MPa
DEG C, 500g distilled water or deionized water is slowly added dropwise, while quickly stirring, is added in 30min or so, obtain the starch epoxy
Cold coating.
Performance test: starch epoxy coating obtained in Examples 1 to 5 is tested for the property, as follows:
1. basic soil buries method surveys degree of degradation
Product after reacting processing is directly imbedded in soil, every 90 days weighing weight, until degradable, record
Under every 90 days degradation amounts and final degradation time.
Examples 1 to 5 natural degradation situation, such as table 1:
Table 1
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of starch-based aqueous coating composition, which is characterized in that itself comprising steps of
(1) starch is subjected to hydrophobic modification, obtains modified starch；
(2) isocyanates is reacted with the reactant of the hydroxyl containing both-end, obtains reaction product A；
(3) modified starch, reaction product A and epoxy resin are mixed, is reacted thereafter, is reacted in 70 ~ 95 DEG C of temperature
Product B, wherein the ratio of the amount of the substance of modified starch institute's hydroxyl and epoxy resin institute hydroxyl is 0.5 ~ 1.5:1；Reaction
The amount of the substance of contained isocyano is n in product A1, the substance of the summation of institute's hydroxyl in modified starch and epoxy resin
Amount is n2, the n1With n2Meet relationship: n1: n2=1:1；
(4) reaction product B is subjected to heating treatment and reduced pressure treatment, after distilled water is added after cooling down or deionized water is mixed
Close to get.
2. preparation method as described in claim 1, which is characterized in that the step (1) be after starch is dried with organic acid
Or the mixing of its acid anhydrides, the first catalyst is added thereafter, 15 ~ 300min is reacted under the conditions of temperature is 150 ~ 220 DEG C, obtains starch
Distilled water is added thereafter in organic acid esters in the reaction system, using filter, drying.
3. preparation method as claimed in claim 2, which is characterized in that the mass ratio of the starch and organic acid or its acid anhydrides is
1:1~5.5。
4. preparation method as claimed in claim 2, which is characterized in that Han Shui Liang≤2% after the starch drying.
5. preparation method as claimed in claim 2, which is characterized in that the degree of substitution of the starch organic acid esters is 2 ~ 2.8.
6. preparation method as described in claim 1, which is characterized in that the step (2) is the both-end hydroxyl that will contain hydrophilic radical
The dissolution of substratess matter, and isocyanates is added, 1.5 ~ 3.5h is reacted under conditions of 65 ~ 90 DEG C of temperature by nitrogen protection.
7. preparation method as claimed in claim 6, which is characterized in that the both-end hydroxylic species and isocyanates according to hydroxyl with
The ratio of the amount of the substance of isocyano is that 1:2 is reacted.
8. preparation method as described in claim 1, which is characterized in that in the step (4), heating treatment is that temperature heats up
To 110 ~ 130 DEG C, reduced pressure treatment is by air pressure drop down to -0.04 ~ -0.1MPa.
9. preparation method as described in claim 1, which is characterized in that in the step (4), cooling is that temperature is reduced to 40
~45℃。
10. coating composition obtained by a kind of preparation method as described in claim 1 ~ 9 is any.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078883A (en) * | 2019-05-22 | 2019-08-02 | 西华大学 | A kind of water paint resin, preparation method and composition based on konjaku flour |
| CN110437678A (en) * | 2019-08-07 | 2019-11-12 | 西华大学 | A kind of energy-saving environment-friendly aqueous coating and preparation method thereof |
| CN114213952A (en) * | 2021-12-28 | 2022-03-22 | 广东美涂士建材股份有限公司 | Environment-friendly water-based paint and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070275258A1 (en) * | 2003-01-22 | 2007-11-29 | Kansai Paint Co., Ltd. | Curable starch composition, modified starch, preparation method and articles |
| US20090047532A1 (en) * | 2005-10-06 | 2009-02-19 | Nissan Motor Co., Ltd. The University Of Tokyo | Material for Room Temperature Curable Solvent-Borne Overcoating Material,Coating Material Using Same and Coating Film |
| CN101418119A (en) * | 2008-12-02 | 2009-04-29 | 江苏大学 | Method for preparing oxidative crosslinked starch modified waterborne polyurethane hybridization material |
| CN101717488A (en) * | 2009-12-03 | 2010-06-02 | 上海维凯化学品有限公司 | Epoxy resin modified water-based polyurethane emulsion and preparation method thereof |
| US20130224482A1 (en) * | 2012-02-27 | 2013-08-29 | Hercules Incorporated | Diluents for crosslinker-containing adhesive compositions |
| CN108707414A (en) * | 2018-05-18 | 2018-10-26 | 安徽朗凯奇建材有限公司 | A kind of epoxy resin modification polyurethane water-proof paint and preparation method thereof |
-
2018
- 2018-11-19 CN CN201811377007.XA patent/CN109575697B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070275258A1 (en) * | 2003-01-22 | 2007-11-29 | Kansai Paint Co., Ltd. | Curable starch composition, modified starch, preparation method and articles |
| US20090047532A1 (en) * | 2005-10-06 | 2009-02-19 | Nissan Motor Co., Ltd. The University Of Tokyo | Material for Room Temperature Curable Solvent-Borne Overcoating Material,Coating Material Using Same and Coating Film |
| CN101418119A (en) * | 2008-12-02 | 2009-04-29 | 江苏大学 | Method for preparing oxidative crosslinked starch modified waterborne polyurethane hybridization material |
| CN101717488A (en) * | 2009-12-03 | 2010-06-02 | 上海维凯化学品有限公司 | Epoxy resin modified water-based polyurethane emulsion and preparation method thereof |
| US20130224482A1 (en) * | 2012-02-27 | 2013-08-29 | Hercules Incorporated | Diluents for crosslinker-containing adhesive compositions |
| CN108707414A (en) * | 2018-05-18 | 2018-10-26 | 安徽朗凯奇建材有限公司 | A kind of epoxy resin modification polyurethane water-proof paint and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵青山等: ""醋酸淀粉合成的工艺研究"", 《山西食品工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078883A (en) * | 2019-05-22 | 2019-08-02 | 西华大学 | A kind of water paint resin, preparation method and composition based on konjaku flour |
| CN110437678A (en) * | 2019-08-07 | 2019-11-12 | 西华大学 | A kind of energy-saving environment-friendly aqueous coating and preparation method thereof |
| CN110437678B (en) * | 2019-08-07 | 2021-04-27 | 西华大学 | Energy-saving environment-friendly water-based paint and preparation method thereof |
| CN114213952A (en) * | 2021-12-28 | 2022-03-22 | 广东美涂士建材股份有限公司 | Environment-friendly water-based paint and preparation method thereof |
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