CN117567912B - Recyclable polyacrylate emulsion coating and preparation method and application thereof - Google Patents
Recyclable polyacrylate emulsion coating and preparation method and application thereof Download PDFInfo
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- CN117567912B CN117567912B CN202311567305.6A CN202311567305A CN117567912B CN 117567912 B CN117567912 B CN 117567912B CN 202311567305 A CN202311567305 A CN 202311567305A CN 117567912 B CN117567912 B CN 117567912B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 127
- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 56
- -1 acrylic ester compound Chemical class 0.000 claims description 36
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 28
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 28
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 17
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 150000001875 compounds Chemical group 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims description 3
- 239000005871 repellent Substances 0.000 claims description 3
- 239000012781 shape memory material Substances 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000006386 memory function Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000004743 Polypropylene Substances 0.000 description 20
- 229920001155 polypropylene Polymers 0.000 description 20
- 229920000098 polyolefin Polymers 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 238000011084 recovery Methods 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 4
- 230000007334 memory performance Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-M propynoate Chemical compound [O-]C(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-M 0.000 description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent 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
- 239000002699 waste material Substances 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a recyclable polymer material, in particular to a recyclable polyacrylate emulsion coating, a preparation method and application thereof. In the invention, monomer B introduces enamine-ketone dynamic bond into polyacrylate by polymerization, and at 80-120 ℃, an amine cross-linking agent in emulsion and enamine-ketone dynamic bond on a side chain of polyacrylate undergo a bond exchange reaction, and displaced molecular amine volatilizes along with water, so that a cross-linked polyacrylate emulsion coating is finally formed. The coating can be recycled under hot pressing at 100-180 ℃, and the cross-linked network structure and dynamic chemical bond of the coating enable the coating to have excellent shape memory function.
Description
Technical Field
The invention relates to a recyclable polymer material, in particular to a recyclable polyacrylate emulsion coating, a preparation method and application thereof.
Background
Currently, polyolefin materials are mainly prepared by solution polymerization, and the use of solvents results in an increase in VOC content. The most effective solution is to prepare the polyolefin by emulsion polymerization, which makes it possible to use water instead of an organic solvent. Another point is that polypropylene materials are difficult to recycle, and waste polyolefin materials are often disposed of by incineration or burial, which continuously aggravates the problems of environmental pollution and resource waste.
In solving the problem of polyolefin recovery, polyolefin recovery is often achieved by introducing dynamic covalent bonds in the following ways:
(1) Copolymerizing functional olefin monomers, and then reacting with a cross-linking agent to form a dynamic polypropylene network; for example, acrylic compounds containing aldehyde groups or carbonyl groups are copolymerized and then form a Schiff base-based polypropylene network with an amine cross-linking agent; or by adding a cross-linking agent reactive with the functionalized polyolefin, the cross-linking agent bearing exchangeable bonds, such as disulfide bonds. Of course, it is also possible to directly copolymerize the acrylic monomer containing a dynamic bond.
(2) The active functional group grafts modified polyolefin, and then reacts with a cross-linking agent to form a dynamic polypropylene network, wherein a cross-linking point is used as a dynamic bond; for example, by thiol-clicking reaction of cysteamine with polybutadiene and then dynamic imine bond-based reaction with glutaraldehyde, an imine bond-based polyolefin network can be formed.
The two modes are of great significance for preparing dynamic polyolefin, but the preparation process is complex, the preparation process belongs to multicomponent mixing, and the solvent is needed for preparing the coating. Although the two modes provide recyclable polyolefin, the problems of high cost, multiple process steps and the like in preparing the coating exist. In the prior art, the polypropylene emulsion is prepared by copolymerizing diacrylate containing urea bonds or disulfide bonds with other acrylic monomers through emulsion polymerization. The polypropylene latex is a crosslinked polymer, and the self-repairing coating containing dynamic bonds can be directly obtained by volatilizing water, so that the subsequent film forming process is simplified, but the preparation of the disulfide dynamic bond self-repairing polyolefin coating and the research on the self-repairing capability are mainly focused, and the regulation of the mechanical properties of materials and the recovery of the materials are not explored.
Disclosure of Invention
Based on the above, the invention provides a recyclable polyacrylate emulsion coating, a preparation method and application thereof, and at least one problem in the prior art is solved.
In a first aspect, the present invention provides a method for preparing a recyclable polyacrylate emulsion coating, the method comprising the steps of:
(a) Preparation of polyacrylate emulsion
Mixing the monomer A, the monomer B, an emulsifying agent and water to obtain a pre-emulsion;
mixing an initiator, sodium bicarbonate solution and the pre-emulsion, reacting at 75-85 ℃, then adding an amine cross-linking agent, and filtering to obtain polyacrylate emulsion;
(b) Preparation of polyacrylate emulsion coating
Volatilizing volatile substances in the polyacrylate emulsion at 80-120 ℃ to obtain a recyclable polyacrylate emulsion coating;
Wherein the monomer A contains at least one acrylic ester compound or acrylamide compound, and the monomer B is a compound shown in the following structural formula:
，
Wherein R 1 is selected from H, C C1-C4 alkyl groups, R 2 is selected from C1-C8 alkyl groups, and R 3 is selected from H, C C1-C3 alkyl groups.
In the present invention, monomer B introduces enamine-ketone dynamic bond into polyacrylate by polymerization, and the emulsion volatilizes water at 80-120 ℃ to form a crosslinked film. The key point of forming the crosslinked film from the emulsion is that the amine crosslinking agent in the emulsion system and the enamine-ketone dynamic bond on the side chain of the polyacrylate are subjected to bond exchange reaction. The displaced molecular amine volatilizes with water to finally form a crosslinked polyacrylate emulsion coating. The coating can be recycled under hot pressing at 100-180 ℃, and the cross-linked network structure and dynamic chemical bond of the coating enable the coating to have excellent shape memory function.
In a second aspect, the present invention provides a recyclable polyacrylate emulsion coating resulting from a method of making the recyclable polyacrylate emulsion coating.
In a third aspect, the present invention provides the use of the recyclable polyacrylate emulsion coating in a water repellent material or shape memory material.
Due to the adoption of the technical scheme, the embodiment of the invention has at least the following beneficial effects: the recyclable coating is prepared in an emulsion polymerization mode, does not involve organic solvents, and is environment-friendly; the coating is prepared by a single component, so that the method is simple and efficient; preparing a cross-linked polyolefin network in a manner of enamine-ketone dynamic bond heat exchange, wherein the bond exchange can be carried out at high temperature through the enamine-ketone dynamic bond, so that the polyolefin network can be recycled; the crosslinked network structure of the coating and enamine-ketone dynamic bond enable the coating to have excellent mechanical property and shape memory property.
Drawings
FIG. 1 shows a photograph of the polyacrylic emulsion prepared in example 1 of the present invention after centrifugation 15 min.
Fig. 2 shows stress-strain curves of the acrylic emulsion coatings prepared in examples 1 to 5 of the present invention.
Fig. 3 shows stress-strain curves of the polyolefin emulsion coatings prepared in examples 3, 6 and 7 of the present invention.
FIG. 4 is a schematic view of hot press recovery of the acrylic emulsion-prepared coating layer prepared in example 6 of the present invention.
Fig. 5 shows stress-strain curves of three recoveries of the acrylic emulsion preparation coating prepared in example 6 of the present invention.
FIG. 6 shows the shape memory performance test curves of the acrylic emulsion prepared in example 6 of the present invention.
FIG. 7 is a graph showing the shape memory cycle of the coating layer prepared from the acrylic emulsion prepared in example 6 of the present invention.
Detailed Description
The following is a clear and complete description of the conception and technical effects produced thereby to fully illustrate the objects, aspects, and effects of the present invention.
In a first aspect, the present invention provides a method for preparing a recyclable polyacrylate emulsion coating, the method comprising the steps of:
(a) Preparation of polyacrylate emulsion
Mixing the monomer A, the monomer B, an emulsifying agent and water to obtain a pre-emulsion;
mixing an initiator, sodium bicarbonate solution and the pre-emulsion, reacting at 75-85 ℃, then adding an amine cross-linking agent, and filtering to obtain polyacrylate emulsion;
(b) Preparation of polyacrylate emulsion coating
Volatilizing volatile substances in the polyacrylate emulsion at 80-120 ℃ to obtain a recyclable polyacrylate emulsion coating;
Wherein the monomer A contains at least one acrylic ester compound or acrylamide compound, and the monomer B is a compound shown in the following structural formula:
，
Wherein R 1 is selected from H, C C1-C4 alkyl groups, R 2 is selected from C1-C8 alkyl groups, and R 3 is selected from H, C C1-C3 alkyl groups.
The film forming reaction mechanism is as follows:
Introducing enamine-ketone dynamic bond into polyacrylate by polymerization of monomer B, and performing dynamic exchange reaction between amine cross-linking agent in emulsion and enamine-ketone dynamic bond on polyacrylate side chain at 80-120deg.C, volatilizing displaced molecular amine together with water, and finally forming cross-linked polyacrylate emulsion coating. The coating can be recycled under hot pressing at 100-180 ℃, and the cross-linked network structure and dynamic chemical bond of the coating enable the coating to have excellent shape memory function.
In some preferred embodiments, the monomer B may be obtained by reacting hydroxyethyl alkyl acrylate with propiolic acid to obtain 2- (propiolate) ethyl alkyl acrylate, and then reacting 2- (propiolate) ethyl alkyl acrylate with an amine compound; the amine compound is small molecular amine with the structure of。
In some preferred embodiments, the R 1 is selected from H, -CH 3、-CH2CH3、-C(CH3)3; said R 2 is selected from -CH2CH3、-C(CH3)3、-CH2CH2CH2CH3、-CH2(CH2)4CH3; and said R 3 is selected from H, -CH 3、-CH2CH3、-CH2CH2CH3.
In some preferred embodiments, the monomer a is at least one of methyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate, methylolacrylamide. More preferably, the monomer a is present in a molar ratio of 1 to 2:1-2 methyl methacrylate and butyl acrylate.
In some preferred embodiments, the emulsifier is at least one of OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, ammonium dodecyl polyoxyethylene ether sulfate, polyoxyethylene ether, fatty alcohol polyoxyethylene ether. More preferably, the emulsifier is OP-10 and sodium dodecyl sulfate.
In some preferred embodiments, the initiator is at least one of sodium persulfate, potassium persulfate, ammonium sulfate, ammonium persulfate, sodium bisulfite, azobisisobutyronitrile, benzoyl peroxide.
In some preferred embodiments, the sodium bicarbonate solution is a 5% solids sodium bicarbonate solution.
In some preferred embodiments, the polyacrylate emulsion comprises the following components in weight percent: 10% -60% of monomer A, 3% -10% of monomer B, 4% -11% of amine cross-linking agent, 1% -4% of emulsifying agent, 0.5% -1% of initiator, 1% -5% of sodium bicarbonate solution and the balance of water.
In some preferred embodiments, the amine crosslinker is m-xylylenediamine, 4-diaminodicyclohexylmethane, or a compound represented by one of the following structural formulas:
，
Wherein n is greater than or equal to 1, R 4 is selected from H and-CH 3、-CH2CH3、-C(CH3)3,R5 is selected from H and-CH 3、-CH2CH3、-C(CH3)3.
In some more preferred embodiments, the amine cross-linking agent is m-xylylenediamine.
In some preferred embodiments, the polyacrylate emulsion is poured into a polytetrafluoroethylene mold or sprayed to form a coating, and the coating is placed in an oven at 80-120 ℃ to volatilize volatile components such as moisture and molecular amine.
In a second aspect, the present invention provides a recyclable polyacrylate emulsion coating resulting from a method of making the recyclable polyacrylate emulsion coating.
In a third aspect, the present invention provides the use of the recyclable polyacrylate emulsion coating in a water repellent material or shape memory material.
Some exemplary embodiments are described below.
In the following examples, the preparation scheme for monomer B is as follows:
the specific operation can be as follows: hydroxyethyl methacrylate (13.01 g, 100 mmol), p-toluenesulfonic acid (8.61 g, 100 mmol) and propiolic acid (7 g, 100 mmol) were added to a 250 mL round bottom flask, and then 30 mL chloroform was added to dissolve; after reacting for 18 hours at 60 ℃, washing the mixture for 2-3 times by deionized water and saturated sodium bicarbonate, drying the organic phase, and evaporating the organic phase to obtain a first-step product of ethyl 2- (propiolate) methacrylate; then, ethyl 2- (propiolate) methacrylate (9.11 g, 50 mmol) and diethylamine (3.66 g, 50 mmol) were dissolved with 20 mL dichloromethane respectively, and the diethylamine solution was added dropwise to the ethyl 2- (propiolate) methacrylate solution by means of dropwise addition, and after reacting for 18 hours, the dichloromethane was removed by rotary evaporation to obtain monomer B.
Example 1
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
204.96 mmol methyl methacrylate, 409.92 mmol butyl acrylate (the ratio of methyl methacrylate to butyl acrylate is 1:2), 19.01 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250 r/min for 30min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting for 10-15min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3 mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; centrifuging the prepared emulsion at 4000 r/min for 15: 15min, and observing the change of the emulsion;
The obtained polypropylene emulsion was placed in a polytetrafluoroethylene mold, and the water was volatilized at 100 ℃ to obtain a coating 1.
After the coating 1 was sheared by scissors, the recovered sample was obtained by hot-pressing 1: 1h at 150℃and 10 MPa.
Example 2
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
245.95 mmol methyl methacrylate, 368.93 mmol butyl acrylate (ratio of methyl methacrylate to butyl acrylate is 1:1.5), 19.01 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250 r/min for 30 min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
Adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting 10-15 min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; centrifuging the prepared emulsion at 4000 r/min for 15: 15 min, and observing the change of the emulsion;
The obtained polypropylene emulsion is placed in a polytetrafluoroethylene mould, and the moisture is volatilized at 100 ℃ to obtain a coating 2.
After the coating 2 is sheared by scissors, the recovered sample is obtained by hot pressing for 1h at 150 ℃ and 10 MPa ℃.
Example 3
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
307.44 mmol methyl methacrylate, 307.44 mmol butyl acrylate (ratio of methyl methacrylate to butyl acrylate is 1:1), 19.01 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250 r/min for 30min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting 10-15 min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; the emulsion prepared was centrifuged at 4000 r/min for 15: 15 min and the emulsion was observed for changes.
The obtained polypropylene emulsion is placed in a polytetrafluoroethylene mould, and the moisture is volatilized at 100 ℃ to obtain a coating 3.
The coating 3 was crushed by scissors and hot-pressed at 150℃and 10 MPa for 1 hour to obtain a recovered sample.
Example 4
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
368.93 mmol methyl methacrylate, 245.95 mmol butyl acrylate (the ratio of methyl methacrylate to butyl acrylate is 1.5:1), 19.01 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250r/min for 30 min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
Adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting 10-15 min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; centrifuging the prepared emulsion at 4000 r/min for 15: 15 min, and observing the change of the emulsion;
the obtained polypropylene emulsion was placed in a polytetrafluoroethylene mold, and the water was volatilized at 100 ℃ to obtain a coating layer 4.
After the coating 4 was sheared by scissors, the recovered sample was obtained by hot-pressing at 150℃and 10 MPa under heat and pressure of 1:1 h.
Example 5
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
409.92mmol of methyl methacrylate, 204.96 mmol butyl acrylate (the ratio of methyl methacrylate to butyl acrylate is 2:1), 19.01 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250 r/min for 30 min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
Adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting 10-15 min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; centrifuging the prepared emulsion at 4000 r/min for 15: 15 min, and observing the change of the emulsion;
The obtained polypropylene emulsion is placed in a polytetrafluoroethylene mould, and the moisture is volatilized at 100 ℃ to obtain a coating 5.
The coating 5 was crushed by scissors and hot-pressed at 150℃and 10 MPa for 1 hour to obtain a recovered sample.
Example 6
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
297.93 mmol methyl methacrylate, 297.93 mmol butyl acrylate, 38.03 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250 r/min for 30 min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
Adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting 10-15 min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; centrifuging the prepared emulsion at 4000 r/min for 15: 15 min, and observing the change of the emulsion;
The obtained polypropylene emulsion was placed in a polytetrafluoroethylene mold, and the water was volatilized at 100 ℃ to obtain a coating 6.
After the coating 6 is sheared by scissors, the recovered sample is obtained by hot pressing for 1h at 150 ℃ and 10 MPa ℃.
Example 7
The recyclable polyacrylate emulsion coating is prepared according to the following steps:
288.42 mmol methyl methacrylate, 288.42 mmol butyl acrylate, 57.05 mmol monomer B, deionized water, 2.1 g emulsifier OP-10 and 2.1 g sodium dodecyl sulfate are added into a round bottom flask, and stirred at 250 r/min for 30 min to obtain a pre-emulsion;
Dissolving 0.6 g potassium persulfate in 30 mL deionized water to obtain a potassium persulfate solution; dissolving 0.5g sodium bicarbonate in 10 mL deionized water to obtain sodium bicarbonate solution;
Adding 20 mL of pre-emulsion into a three-neck round bottom flask, heating to 80 ℃, adding 6 mL of potassium persulfate solution and 10mL of sodium bicarbonate solution, and reacting 10-15 min (emulsion bluing); adding the rest pre-emulsion and the initiator solution, and finishing the addition in a period of 2 h; finally, adding 3mL of initiator solution, then reacting 2 h, cooling to room temperature, and adding m-xylylenediamine to obtain polypropylene emulsion; centrifuging the prepared emulsion at 4000 r/min for 15: 15 min, and observing the change of the emulsion;
The obtained polypropylene emulsion was placed in a polytetrafluoroethylene mold, and the water was volatilized at 100℃to obtain a coating 7.
The coating 7 was crushed by scissors and hot-pressed at 150℃and 10 MPa for 1 hour to obtain a recovered sample.
FIG. 1 shows photographs of the polyacrylic emulsion prepared in example 1 and photographs after centrifugation 15 min. As can be seen from FIG. 1, the prepared polyacrylate emulsion has no obvious precipitation after being centrifuged at 4000 r/min for 15: 15min, which indicates that the prepared polyacrylate emulsion has good stability.
Fig. 2 shows stress-strain curves of the acrylic emulsion coatings prepared in examples 1 to 5. The Young's modulus of the coatings of examples 1-5 increased with increasing ratio of methyl methacrylate to butyl acrylate in monomer A, with increasing and decreasing tensile break length, indicating that increasing the methyl methacrylate content of the monomer increases the stiffness of the polymer when methyl methacrylate and butyl acrylate are 1:1, the coating exhibits the best flexibility. It can be seen that by adjusting the hard and soft acrylic monomers, a coating material of suitable flexibility can be obtained.
Fig. 3 shows stress-strain curves of the polyolefin emulsion coatings prepared in examples 3, 6 and 7. Examples 3, 6 and 7 increased the amount of monomer B, which resulted in an increase in the young's modulus of the coating, with a subsequent decrease in elongation at break, indicating that the coating was most flexible at 6% of monomer B. It can be seen that varying the monomer B content can adjust the mechanical properties of the material.
FIG. 4 is a schematic view of hot press recovery of the acrylic emulsion-prepared coating prepared in example 6. As can be seen from fig. 4, the coating appearance before and after recovery was unchanged.
Fig. 5 shows stress-strain curves of three recoveries of the acrylic emulsion preparation coating prepared in example 6. As can be seen from FIG. 5, the mechanical properties of the prepared coating before and after recovery are not greatly changed, which indicates that the material has excellent recoverable function.
FIG. 6 shows the shape memory performance test curves of the acrylic emulsion prepared in example 6. As can be seen in fig. 6, 55 s is required for the coating to recover from the zero-time shape to the original shape at 70 ℃.
The shape memory performance of the coating was tested in a tensile mode using a DMA Q800 dynamic mechanical analyzer, with a controlled load of 0.2N, a cycling temperature of 20-120 ℃, and a test of 4 cycles, with the shape retention and shape recovery of the 2 nd cycle evaluating the shape memory performance. FIG. 7 is a graph showing the shape memory cycle of the coating layer prepared from the acrylic emulsion prepared in example 6 of the present invention. As can be seen from fig. 7, the shape fixation rate is 88% and the shape recovery rate is 91%, which indicates that the coating material prepared according to the present invention has good shape memory properties.
The present invention is not limited to the above embodiments, but is merely preferred embodiments of the present invention, and the present invention should be considered as being within the scope of the present invention as long as the technical effects of the present invention are achieved by the same or equivalent means. Various modifications and variations are possible in the technical solution and/or in the embodiments within the scope of the invention.
Claims (8)
1. A method for preparing a recyclable polyacrylate emulsion coating, comprising the following steps:
(a) Preparation of polyacrylate emulsion
Mixing the monomer A, the monomer B, an emulsifying agent and water to obtain a pre-emulsion;
mixing an initiator, sodium bicarbonate solution and the pre-emulsion, reacting at 75-85 ℃, then adding an amine cross-linking agent, and filtering to obtain polyacrylate emulsion;
(b) Preparation of polyacrylate emulsion coating
Volatilizing volatile substances in the polyacrylate emulsion at 80-120 ℃ to obtain a recyclable polyacrylate emulsion coating;
Wherein the monomer A contains at least one acrylic ester compound or acrylamide compound, and the monomer B is a compound shown in the following structural formula:
，
wherein R 1 is selected from H, C C1-C4 alkyl, R 2 is selected from C1-C8 alkyl, and R 3 is selected from H, C C1-C3 alkyl;
The polyacrylate emulsion comprises the following components in percentage by weight: 10% -60% of monomer A, 3% -10% of monomer B, 4% -11% of amine cross-linking agent, 1% -4% of emulsifying agent, 0.5% -1% of initiator, 1% -5% of sodium bicarbonate solution and the balance of water.
2. The method of claim 1, wherein R 1 is selected from H, -CH 3、-CH2CH3、-C(CH3)3; said R 2 is selected from -CH2CH3、-C(CH3)3、-CH2CH2CH2CH3、-CH2(CH2)4CH3; and said R 3 is selected from H, -CH 3、-CH2CH3、-CH2CH2CH3.
3. The method according to claim 1, wherein the monomer a is at least one of methyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate, and methylolacrylamide.
4. The method of claim 1, wherein the emulsifier is at least one of OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, ammonium dodecyl polyoxyethylene ether sulfate, polyoxyethylene ether, fatty alcohol polyoxyethylene ether.
5. The method of claim 1, wherein the initiator is at least one of sodium persulfate, potassium persulfate, ammonium sulfate, ammonium persulfate, sodium bisulfite, azobisisobutyronitrile, benzoyl peroxide.
6. The method of claim 1, wherein the amine cross-linking agent is m-xylylenediamine, 4-diaminodicyclohexylmethane, or a compound represented by one of the following structural formulas:
，
Wherein n is greater than or equal to 1, R 4 is selected from H and-CH 3、-CH2CH3、-C(CH3)3,R5 is selected from H and-CH 3、-CH2CH3、-C(CH3)3.
7. A recyclable polyacrylate emulsion coating, characterized in that it is obtained by a method for preparing a recyclable polyacrylate emulsion coating according to any one of claims 1-6.
8. Use of a recyclable polyacrylate emulsion coating according to claim 7 in a water repellent material or shape memory material.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59225447A (en) * | 1983-06-06 | 1984-12-18 | Mitsubishi Electric Corp | Floating point numeral arithmetic device |
| CA2016022A1 (en) * | 1989-05-30 | 1990-11-30 | Exxon Chemical Patents Inc. | Branched amido-amine dispersant additives |
| CN101660276A (en) * | 2009-09-21 | 2010-03-03 | 江西科技师范学院 | Aqueous silicon-acrylate textile adhesive coating and preparation method thereof |
| CN101704981A (en) * | 2009-11-26 | 2010-05-12 | 浙江新力化工有限公司 | Cationic polyacrylate emulsion and preparation method thereof |
| CN103772625A (en) * | 2014-01-17 | 2014-05-07 | 广州市东雄化工有限公司 | Freezing-resistant acrylate suspended thickening emulsion and preparation method thereof |
| CN103922947A (en) * | 2014-04-21 | 2014-07-16 | 江西师范大学 | Novel method for synthesizing N, N-disubstituted enamine ketone compound |
| WO2018063095A1 (en) * | 2016-09-29 | 2018-04-05 | Nipsea Technologies Pte Ltd | Crosslinking agent for polymer emulsions |
| CN109912742A (en) * | 2019-01-24 | 2019-06-21 | 南阳星港涂料有限公司 | A kind of room-temperature self crosslinking fluorin modified crylic acid lotion of core-shell structure and preparation method thereof |
| CN115926454A (en) * | 2023-01-09 | 2023-04-07 | 中南大学 | Remodelable and degradable dynamic covalent polymer cross-linked network and preparation method thereof |
-
2023
- 2023-11-22 CN CN202311567305.6A patent/CN117567912B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59225447A (en) * | 1983-06-06 | 1984-12-18 | Mitsubishi Electric Corp | Floating point numeral arithmetic device |
| CA2016022A1 (en) * | 1989-05-30 | 1990-11-30 | Exxon Chemical Patents Inc. | Branched amido-amine dispersant additives |
| CN101660276A (en) * | 2009-09-21 | 2010-03-03 | 江西科技师范学院 | Aqueous silicon-acrylate textile adhesive coating and preparation method thereof |
| CN101704981A (en) * | 2009-11-26 | 2010-05-12 | 浙江新力化工有限公司 | Cationic polyacrylate emulsion and preparation method thereof |
| CN103772625A (en) * | 2014-01-17 | 2014-05-07 | 广州市东雄化工有限公司 | Freezing-resistant acrylate suspended thickening emulsion and preparation method thereof |
| CN103922947A (en) * | 2014-04-21 | 2014-07-16 | 江西师范大学 | Novel method for synthesizing N, N-disubstituted enamine ketone compound |
| WO2018063095A1 (en) * | 2016-09-29 | 2018-04-05 | Nipsea Technologies Pte Ltd | Crosslinking agent for polymer emulsions |
| CN109912742A (en) * | 2019-01-24 | 2019-06-21 | 南阳星港涂料有限公司 | A kind of room-temperature self crosslinking fluorin modified crylic acid lotion of core-shell structure and preparation method thereof |
| CN115926454A (en) * | 2023-01-09 | 2023-04-07 | 中南大学 | Remodelable and degradable dynamic covalent polymer cross-linked network and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Self-healing dynamic bond-based robust polyurethane acrylate hybrid polymers;Wu Xueqi;et al.;《New Journal of Chemistry》;20220531;第46卷(第28期);第13415-13421页 * |
| 烯胺酮的合成及其在有机合成中的应用;李明等;《有机化学》;20060930;第26卷(第9期);第1192-1207页 * |
| 烯胺酮的合成及衍生化研究;高勇;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20181215;B014-46 * |
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