CN106009004A - Multiple composite crosslinked acrylic resin emulsion and preparation method thereof - Google Patents
Multiple composite crosslinked acrylic resin emulsion and preparation method thereof Download PDFInfo
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- CN106009004A CN106009004A CN201610629827.8A CN201610629827A CN106009004A CN 106009004 A CN106009004 A CN 106009004A CN 201610629827 A CN201610629827 A CN 201610629827A CN 106009004 A CN106009004 A CN 106009004A
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- emulsion
- acrylic resin
- aqueous solution
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- 239000000839 emulsion Substances 0.000 title claims abstract description 141
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 60
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004945 emulsification Methods 0.000 title description 4
- 239000003999 initiator Substances 0.000 claims abstract description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 72
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 50
- 239000008367 deionised water Substances 0.000 claims abstract description 41
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 41
- 238000010382 chemical cross-linking Methods 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 29
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 239000010985 leather Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 156
- 239000007864 aqueous solution Substances 0.000 claims description 116
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 80
- 235000010265 sodium sulphite Nutrition 0.000 claims description 78
- 150000002500 ions Chemical class 0.000 claims description 41
- 239000000376 reactant Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 20
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 19
- 235000019394 potassium persulphate Nutrition 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 239000012966 redox initiator Substances 0.000 claims description 13
- 230000001960 triggered effect Effects 0.000 claims description 11
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- 239000004141 Sodium laurylsulphate Substances 0.000 description 26
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 25
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 17
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000977 initiatory effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 8
- 238000002242 deionisation method Methods 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 8
- 239000000178 monomer Substances 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 3
- 238000009396 hybridization Methods 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 persulfuric acid Salt Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- KZVVGZKAVZUACK-BJILWQEISA-N rilpivirine hydrochloride Chemical compound Cl.CC1=CC(\C=C\C#N)=CC(C)=C1NC1=CC=NC(NC=2C=CC(=CC=2)C#N)=N1 KZVVGZKAVZUACK-BJILWQEISA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-N sodium;sulfurous acid Chemical compound [Na+].OS(O)=O DWAQJAXMDSEUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/26—Crosslinking, e.g. vulcanising, of macromolecules of latex
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a multiple composite crosslinked acrylic resin emulsion and a preparation method thereof. The emulsion is formed by polymerization reaction of the following components by weight: 240-340 parts of ethyl acrylate, 0-100 parts of butyl acrylate, 7 parts of acrylic acid, 0.6-2.7 parts of an initiator A, 1.75-3.5 parts of a chemical crosslinking agent, 10.5 parts of an emulsifier, 620-650 parts of deionized water, 0.7-3.5 parts of an ionic crosslinking agent, and 0.4 part of an initiator B. Compared with the prior art, chemical crosslinking of the multiple composite crosslinked acrylic resin emulsion is mulfunctional composite crosslinking, can effectively adjust the crosslinking density, and ionic crosslinking is introduced based on chemical crosslinking to form a hybrid emulsion, so that the tensile strength and other performance of the emulsion can be obviously improved, and the problem that leather finishing agents are sticky when heated and fragile when cooled is solved.
Description
Technical field
The invention belongs to acrylic resin paint field, relate to water-borne acrylic resin emulsion and preparation thereof, particularly relate to one many
Repeat to close crosslinked acrylic resin emulsion and preparation method thereof.
Background technology
It is known that the leather finishing agent with acrylic resin as film forming matter, price is the cheapest, has extraordinary sticking together
Power, its film is smooth, flex endurant, and good-extensibility, and physical and chemical stability is preferable, is usually used in middle level or the end of leather
Layer is covered with paint, lacquer, colour wash, etc..But, the temperature sensitive property of polyacrylate itself is strong: film moulds that sense is strong, extensibility is poor at a lower temperature；
And the most tacky, extensibility becomes big, now it is not suitable for primary coat and especially aobvious not for top finishing
Foot.On the other hand, the condensed state structure that linear polymer is formed easily is occurred swelling by the effect of organic solvent or dissolves, even
Come off from the base material covered with paint, lacquer, colour wash, etc..Therefore, the application of acrylic resin, certain modification must be first passed through to overcome drawbacks described above.
The modification of acrylic resin is broadly divided into blending and modifying, cross-linking modified, modification by copolymerization, core-shell emulsion polymerization are modified.Its
In, the cross-linking modified problem that the high temperature for polyacrylate is tackiness and solvent resistant is poor plays good effect.But handing over
The technical field of connection modification there is also some problems: first, easily produces gel in emulsion acrylic resin production process, from
And cause the waste of raw material, such as glytidyl methacrylate (GMA) cross-linking system；Secondly, it is easily caused the resistance to of emulsion film
Cold drastically decline, produce the phenomenon of " embrittlement " the most at normal temperatures, such as the vinyl cross-linking agent of some polyfunctionalities；Finally,
Though some cross-linking system cross-linking effects are good but the material that effect on environment is big, have harm to health can be produced, such as N-methylol
Acrylamide (N-MA) cross-linking system.
Summary of the invention
It is an object of the invention to overcome the shortcoming and defect of prior art, it is provided that a kind of MULTIPLE COMPOSITE crosslinked acrylic resin emulsion
And preparation method thereof, with ethyl acrylate (EA), butyl acrylate (BA), acrylic acid (AA) for polymerization monomer, with persulfuric acid
Salt and sodium sulfite composition oxidation-reduction trigger system, sodium lauryl sulphate and fatty alcohol-polyoxyethylene ether are compound emulsifying agent
Carry out emulsion polymerization, by the modified acrylic acid tree being used for leather finish with synthesis of form that zinc ion crosslinking and chemical crosslinking are compound
Fat liquor.
The present invention is achieved by the following technical solutions: a kind of MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, including following components
Count by weight, formed by reactive polymeric: ethyl acrylate 240-340 part, butyl acrylate 0-100 part, acrylic acid 7
Part, initiator A 0.6-2.7 part, chemical cross-linking agent 1.75-3.5 part, emulsifying agent 10.5 parts, deionized water 620-650 part, from
Sub-cross-linking agent 0.7-3.5 part.
Relative to prior art, the chemical crosslinking of a kind of MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of the present invention is by multifunctional
Degree composite crosslinking, it is possible to effectively regulate crosslink density, and introduce ionomer on the basis of chemical crosslinking, form hybridisation emulsion,
The performances such as the tensile strength that can make described emulsion are significantly improved, and solve the asking of " hot sticky cold crisp " of leather finishing agent
Topic.
Further, the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of be set forth in leather finishing agent also includes initiator B 0.4 part, and it is used
In polymerization reaction late stage holding stage.Phase holding stage is added initiator and can be removed residual monomer after polymerization, makes preparation
The emulsion gel obtained is few, and monomer conversion is high.
Further, described initiator A is persulfate and the redox initiation system of sodium sulfite composition；Described initiator
B is a group in potassium peroxydisulfate/sodium sulfite, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium sulfite
Or several groups of combinations.
Further, described initiator B is the redox initiation system of tert-butyl hydroperoxide/sodium sulfite composition.
Further, described initiator A sulfite hydrogen sodium and persulfate mass ratio are 5.75:1；Tertiary fourth in described initiator B
The mass ratio of base hydrogen peroxide and sodium sulfite is 3:1.
Further, described ion crosslinking agent is nano zine oxide.
Further, described chemical cross-linking agent is the vinyl cross-linking agent of polyfunctionality multiple crosslinking agent two degree of functionality and/or three-functionality-degree
-CX-1 chemical cross-linking agent.
Further, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to include that following components is counted by weight, by instead
Should be polymerized: ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.3 parts, chemistry are handed over
Connection agent part 1.75-3.5 part, emulsifying agent 10.5 parts, deionized water 640 parts, ion crosslinking agent 1.8 parts, initiator B 0.4 part.
Present invention also offers the preparation method of a kind of MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, comprise the following steps:
(1) emulsifying agent is added in deionized water, be warming up to 40-80 DEG C of stirring, make emulsifying agent be completely dissolved in water；
(2) by after ethyl acrylate, butyl acrylate, acrylic acid and chemical cross-linking agent mix homogeneously, it is slowly added dropwise into high-speed stirring
In the emulsifier aqueous solution mixed, drip complete follow-up continuous stirring, obtain pre-emulsion；
(3) take after a small amount of pre-emulsion is warming up to 60-70 DEG C, under agitation, add the aqueous solution of part initiator A, treat
After blue phase occurs in emulsion, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-the most in batches
Emulsion；
(4), after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, in reactant liquor, the water of initiator B point is added for 1-2 time
Solution, is incubated 1-3h；
(5) it is cooled to 30-60 DEG C, adds the water slurry of ion crosslinking agent to the reactant liquor of step (4), protect after dropping
Temperature 10-30min；
(6) with after nertralizer regulation pH to neutrality, discharging is filtered.
Relative to prior art, the preparation method of the multiple composite crosslinking emulsion acrylic resin of the present invention, at the base of chemical crosslinking
Introduce ionomer on plinth and form hybridisation emulsion, improve the performances such as its film tensile strength, and achieve chemical crosslinking and physics friendship
The combination of connection, makes the leather after covering with paint the most tacky and not embrittlement under low temperature；And add initiation at holding stage
Agent can remove the monomer of residual, makes the emulsion gel prepared few, and monomer conversion is high.
Further, described nertralizer is aqueous sodium carbonate or ammonia.
In order to be more fully understood that and implement, describe the present invention below in conjunction with the accompanying drawings in detail.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of the present invention.
Detailed description of the invention
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of the present invention and preparation method thereof is described in detail below in conjunction with embodiment.
The MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of the present invention, it is to include that following components is counted by weight, poly-by reaction
Conjunction forms:
Ethyl acrylate 240-340 part, butyl acrylate 0-100 part, 7 parts of acrylic acid, initiator A 0.6-2.7 part, cause
Agent B 0.4 part, chemical cross-linking agent 1.75-3.5 part, emulsifying agent 10.5 parts, deionized water 620-650 part, ion crosslinking agent 0.7-3.5
Part.Wherein, described initiator A is persulfate and the redox initiation system of sodium sulfite composition；Described initiator B
In potassium peroxydisulfate/sodium sulfite, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium sulfite one group
Or several groups of combinations.Described initiator A is used for the initial polymerization reaction stage, and described initiator B is used for being polymerized later stage holding stage.
Described chemical cross-linking agent is the vinyl cross-linking agent-CX-1ization of polyfunctionality multiple crosslinking agent two degree of functionality and/or three-functionality-degree
Learn cross-linking agent.
Described emulsifying agent is aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate complex emulsifier.
Described ion crosslinking agent is nano zine oxide.
The preparation method of described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion comprises the steps:
(1) emulsifying agent is added in deionized water, be warming up to 40-80 DEG C of stirring, make emulsifying agent be completely dissolved in water；
(2) by after ethyl acrylate, butyl acrylate, acrylic acid and chemical cross-linking agent mix homogeneously, it is slowly added dropwise into high-speed stirring
In the emulsifier aqueous solution mixed, drip complete follow-up continuous stirring, obtain pre-emulsion；
(3) take after a small amount of pre-emulsion is warming up to 60-70 DEG C, under agitation, add the aqueous solution of part initiator A, treat
After blue phase occurs in emulsion, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-the most in batches
Emulsion；
(4), after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, in reactant liquor, the water of initiator B point is added for 1-2 time
Solution, is incubated 1-3h；
(5) it is cooled to 30-60 DEG C, adds the water slurry of ion crosslinking agent to the reactant liquor of step (4), protect after dropping
Temperature 10-30min；
(6) with after nertralizer regulation pH to neutrality, discharging is filtered.
Embodiment 1
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 340 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part, chemical cross-linking agent 2 parts,
Emulsifying agent 10.5 parts, deionized water 650 parts, ion crosslinking agent 2 parts.The solid content of described emulsion is 35-38%.
Persulfate and sodium sulfite in described initiator A are respectively 0.38 part and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.Referring to Fig. 1, it is the infrared spectrogram of MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of the present invention.Wherein, 1740
cm-1For the C=O stretching vibration absworption peak of ester bond on polyacrylate, 2870～2982cm-1For ethyl acrylate and acrylic acid fourth
Ethyl in ester and the C-H stretching vibration absworption peak of butyl.1250cm-1And 1162cm-1It is COOH in acrylic acid respectively
C-O antisymmetry and symmetrical stretching vibration peak.1630cm-1For Zn2+Carboxylate group-COO with deprotonation-The complexation formed
Ionic bond Zn2+[OOC-]- 2The stretching vibration absworption peak of middle C=O.1577cm-1The Weak Absorption peak at place is Zn2+With do not go matter
Oxygen atom in the COOH of sonization produces coordination formation-COOHZn2+Flexible the shaking of the C=O generation in HOOC-structure
Dynamic absworption peak.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 650 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) by after ethyl acrylate 340 parts, 7 parts, 2 parts chemical cross-linking agent LX-1 mix homogeneously of acrylic acid, it is slowly added to
In the aqueous solution of the emulsifying agent to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain pre-emulsion.
Described LX-1 is the vinyl cross-linking agent-CX-1 chemical cross-linking agent of two degrees of functionality and/or three-functionality-degree.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent be by by 2 parts of nano zine oxides by dispersant in 40 parts go from
Sub-water obtains.
(6) with antalkali aqueous sodium carbonate, the pH regulator of reactant liquor is the most neutral, then filter out with 120 eye mesh screens
Expecting i.e. to obtain described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 1, the solid content of described emulsion 1 is 35%.
Relative to prior art, the chemical crosslinking of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion of the present invention is multiple by polyfunctionality
Close crosslinking, it is possible to effectively regulate crosslink density, and on the basis of chemical crosslinking, introduce ionomer, form hybridisation emulsion, energy
The performances such as the tensile strength enough making described emulsion are significantly improved, the problem solving " hot sticky cold crisp " of leather finishing agent.
Embodiment 2
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part,
Chemical cross-linking agent 2 parts, emulsifying agent 10.5 parts, deionized water 640 parts, ion crosslinking agent 2 parts.
Persulfate and sodium sulfite in described initiator A are respectively 1.38 parts and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 640 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts, 2 parts LX-1 mix homogeneously of acrylic acid, slowly
Add in the aqueous solution of the emulsifying agent to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain pre-
Emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent be by by 2 parts of nano zine oxides by dispersant in 40 parts go from
Sub-water obtains.
(6) with antalkali aqueous sodium carbonate, the pH regulator of reactant liquor is the most neutral, then filter out with 120 eye mesh screens
Expecting i.e. to obtain described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 2, the solid content of described emulsion 2 is 40%.
Embodiment 3
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 240 parts, butyl acrylate 100 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4
Part, chemical cross-linking agent 2 parts, emulsifying agent 10.5 parts, deionized water 620 parts, ion crosslinking agent 2 parts.
Persulfate and sodium sulfite in described initiator A are respectively 1.38 parts and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 620 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 240 parts, butyl acrylate 100 parts, 7 parts, 2 parts LX-1 mix homogeneously of acrylic acid, slow
In the aqueous solution of the slow emulsifying agent added to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain
Pre-emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent be by by 2 parts of nano zine oxides by dispersant in 40 parts go from
Sub-water obtains.
(6) with antalkali aqueous sodium carbonate, the pH regulator of reactant liquor is the most neutral, then filter out with 120 eye mesh screens
Expecting i.e. to obtain described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 3, the solid content of described emulsion 3 is 43%.
Embodiment 4
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part,
Chemical cross-linking agent 2 parts, emulsifying agent 10.5 parts, deionized water 640 parts, ion crosslinking agent 0.7 part.
Persulfate and sodium sulfite in described initiator A are respectively 0.38 part and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 640 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts, 2 parts LX-1 mix homogeneously of acrylic acid, slowly
Add in the aqueous solution of the emulsifying agent to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain pre-
Emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent is by being gone in 40 parts by dispersant by 0.7 part of nano zine oxide
Ionized water obtains.
(6) with antalkali ammonia, the pH regulator of reactant liquor is the most neutral, then filter dischargings with 120 eye mesh screens and i.e. obtain institute
Stating MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 4, the solid content of described emulsion 4 is 38%.
Embodiment 5
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part,
Chemical cross-linking agent 2 parts, emulsifying agent 10.5 parts, deionized water 630 parts, ion crosslinking agent 1.8 parts.
Persulfate and sodium sulfite in described initiator A are respectively 0.38 part and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 630 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts, 2 parts LX-1 mix homogeneously of acrylic acid, slowly
Add in the aqueous solution of the emulsifying agent to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain pre-
Emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent is by being gone in 40 parts by dispersant by 1.8 parts of nano zine oxides
Ionized water obtains.
(6) with antalkali ammonia, the pH regulator of reactant liquor is the most neutral, then filter dischargings with 120 eye mesh screens and i.e. obtain institute
Stating MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 5, the solid content of described emulsion 5 is 38%.
Embodiment 6
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part,
Chemical cross-linking agent 2 parts, emulsifying agent 10.5 parts, deionized water 630 parts, ion crosslinking agent 3.5 parts.
Persulfate and sodium sulfite in described initiator A are respectively 0.38 part and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 630 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts, 2 parts LX-1 mix homogeneously of acrylic acid, slowly
Add in the aqueous solution of the emulsifying agent to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain pre-
Emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent is by being gone in 40 parts by dispersant by 3.5 parts of nano zine oxides
Ionized water obtains.
(6) with antalkali aqueous sodium carbonate, the pH regulator of reactant liquor is the most neutral, then filter out with 120 eye mesh screens
Expecting i.e. to obtain described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 6, the solid content of described emulsion 6 is 38%.
Embodiment 7
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part,
Chemical cross-linking agent 1.75 parts, emulsifying agent 10.5 parts, deionized water 630 parts, ion crosslinking agent 2 parts.
Persulfate and sodium sulfite in described initiator A are respectively 0.38 part and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 630 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts, 1.75 parts LX-1 mix homogeneously of acrylic acid, slow
In the aqueous solution of the slow emulsifying agent added to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain
Pre-emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent be by by 2 parts of nano zine oxides by dispersant in 40 parts go from
Sub-water obtains.
(6) with antalkali aqueous sodium carbonate, the pH regulator of reactant liquor is the most neutral, then filter out with 120 eye mesh screens
Expecting i.e. to obtain described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 7, the solid content of described emulsion 7 is 39%.
Embodiment 8
In the present embodiment, described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is to be counted by weight by following components, logical
Cross reactive polymeric to form:
Ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.62 parts, initiator B 0.4 part,
Chemical cross-linking agent 3.5 parts, emulsifying agent 10.5 parts, deionized water 630 parts, ion crosslinking agent 2 parts.
Persulfate and sodium sulfite in described initiator A are respectively 0.38 part and 0.24 part；Described initiator B is uncle
Butylhydroperoxide and the redox initiation system of sodium sulfite composition, described tert-butyl hydroperoxide and sodium sulfite divide
It it is not 0.3 part and 0.1 part.Aliphatic alcohol polyethenoxy base ether in described emulsifying agent and sodium lauryl sulphate be respectively 7 parts and
3.5 part.
The preparation method of the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion in described the present embodiment comprises the steps:
(1) in reactor, it is sequentially added into deionized water 630 parts, 7 parts of aliphatic alcohol polyethenoxy base ether and sodium lauryl sulphate
3.5 parts, it is warming up to 40 DEG C and is stirred, make emulsifying agent aliphatic alcohol polyethenoxy base ether-sodium lauryl sulphate be completely dissolved in water
In.
(2) after ethyl acrylate 290 parts, butyl acrylate 50 parts, 7 parts, 3.5 parts LX-1 mix homogeneously of acrylic acid, slow
In the aqueous solution of the slow emulsifying agent added to the step (1) of high-speed stirred, drip complete follow-up continuous stirring a period of time, obtain
Pre-emulsion.
(3) take 26 parts of pre-emulsions, its temperature is increased to 60 DEG C, add the aqueous solution of part initiator A, treat that emulsion occurs
After blue phase, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining pre-emulsion the most in batches；
Wherein the aqueous solution of initiator A is that potassium peroxydisulfate 1.38 parts, sodium sulfite 0.24 part are dissolved in 80 parts go respectively
In ionized water, concrete, take 1.38g potassium peroxydisulfate, 0.24g sodium sulfite is dissolved separately in the deionized water of 80mL,
Step (3) is first separately added into persulfate aqueous solution and the sodium sulfite aqueous solution of 16mL, is subsequently adding remaining initiation
The aqueous solution of agent A.
(4) after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, at twice by the aqueous solution of initiator B at twice,
In 0.5h adds reactant liquor, it is incubated 1h；
Wherein the aqueous solution of initiator B is for being dissolved in 5 parts by tert-butyl hydroperoxide 0.3 part and sodium sulfite 0.1 part respectively
Deionized water in, concrete, take 0.3g tert-butyl hydroperoxide, 0.1g sodium sulfite is dissolved separately in the deionization of 5mL
In water, step (4) is first separately added into tert-butyl hydroperoxide aqueous solution and the aqueous solution of sodium bisulfite of 2.5mL, every
The aqueous solution of remaining initiator B is added after 0.5h.
(5) reactant liquor is cooled to 40 DEG C, suitably accelerates mixing speed, the water slurry of ion crosslinking agent is added dropwise to reaction
In liquid, it is incubated 0.5h；
Wherein, the water slurry of described ion crosslinking agent be by by 2 parts of nano zine oxides by dispersant in 40 parts go from
Sub-water obtains.
(6) with antalkali aqueous sodium carbonate, the pH regulator of reactant liquor is the most neutral, then filter out with 120 eye mesh screens
Expecting i.e. to obtain described MULTIPLE COMPOSITE crosslinked acrylic resin emulsion 8, the solid content of described emulsion 8 is 39%.
Performance comparison
Performance corresponding to emulsion 1-3 that prepared by embodiment 1-3 is as shown in table 1.As shown in Table 1, along with butyl acrylate
The increase of consumption, the relevant index relating to intensity reduces, and elongation at break then increases.This is due in copolymer, acrylic acid
Butyl ester plays internal plasticization to be caused forming.From intensity and elongation at break data analysis, when ethyl acrylate and butyl acrylate
Usage ratio is emulsion during 29:5, the emulsion 2 in corresponding embodiment 2, has higher intensity and suitable elongation at break.
The performance comparison of table 1 embodiment 1-3 correspondence preparation-obtained emulsion 1-3 of different monomers ratio
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 100% modulus | 0.54MPa | 0.43MPa | 0.30MPa |
| Tensile strength | 4.3MPa | 3.8MPa | 1.5MPa |
| Elongation at break | 1700% | 1950% | 2560% |
| Hardness | 17A | 12A | 8A |
The performance corresponding by preparation-obtained emulsion 4-6 of embodiment 4-6 (is not added with ion crosslinking agent nano oxygen with blank sample 1
Change zinc sample) performance comparison as shown in table 2.As shown in Table 2,100% modulus, tensile strength and hardness are along with ion friendship
Join the increase of agent ZnO consumption and increase, and elongation at break and permanent set reduce therewith.Because on ZnO and strand
COOH group reaction generate Zn2+With COO-, Zn in glued membrane system2+With COO-Interact and form complex ion key,
So that strand crosslinking, so ZnO consumption is the biggest, polymer ions crosslinking degree is the biggest, and its mechanical property improves.But
ZnO consumption increases makes system complex ion key increase, and owing to ionic bond hydrophilic is strong, thus causes glued membrane resistance to water to reduce.Combine
Closing and consider, ZnO consumption is that in embodiment 5, the ion crosslinking agent of addition 1.8 parts is advisable.
The performance comparison of table 2 embodiment 4-6 correspondence preparation-obtained emulsion 4-6 of different ions content of crosslinking agent
| Performance | Blank sample 1 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| 100% modulus | 0.30MPa | 0.32MPa | 0.34MPa | 0.33MPa |
| Tensile strength | 1.72MPa | 1.99MPa | 2.51MPa | 2.55MPa |
| Elongation at break | 2804% | 2464% | 1981% | 1631% |
| Permanent set | 350.17 | 128.33 | 41.73 | 21.67 |
| Hardness | 6A | 8A | 10A | 13A |
Performance and blank sample 2 by the preparation-obtained emulsion of embodiment 7-8 7,8 correspondence (are not added with chemical cross-linking agent LX-1
Sample) performance comparison as shown in table 3.As shown in Table 3, along with the increase of chemical cross-linking agent consumption, emulsion film 100%
Modulus, tensile strength and hardness are all in first increasing the trend reduced afterwards, otherwise permanent set is then, this is because chemical crosslinking
Agent consumption too much causes polymeric system crosslink density excessive, in film forming procedure, cannot fully merge between emulsion particle so that
Glued membrane exists too much defect, thus results in its mechanical property such as 100% modulus, tensile strength and hardness and reduce and elastic variation.
And the increase of crosslink density, the elongation at break of glued membrane reduces, and resistance to water improves, and tolerance to cold reduces.So, chemical cross-linking agent
The consumption of LX-1 is that 1.75-3.5 part is proper.
The performance comparison of the table 3 embodiment 7-8 correspondence preparation-obtained emulsion of different chemical content of crosslinking agent 7,8
| Performance | Blank 2 | Embodiment 7 | Embodiment 8 |
| 100% modulus | 0.25MPa | 0.42MPa | 0.43MPa |
| Tensile strength | 1.56MPa | 2.58MPa | 4.11MPa |
| Elongation at break | 2988% | 2093% | 1792% |
| Permanent set | 165.0 | 20.0 | 18.3 |
| Hardness | 11A | 12A | 13A |
| Embrittlement temperature | -30℃ | -30℃ | -30℃ |
The invention is not limited in above-mentioned embodiment, if to the various changes of the present invention or deformation without departing from the spirit of the present invention
And scope, if within the scope of these are changed and deform claim and the equivalent technologies belonging to the present invention, then the present invention is also intended to
Comprise these to change and deformation.
Claims (10)
1. a MULTIPLE COMPOSITE crosslinked acrylic resin emulsion, it is characterised in that: include that following components is counted by weight, by instead
Should be polymerized: ethyl acrylate 240-340 part, butyl acrylate 0-100 part, 7 parts of acrylic acid, initiator A 0.6-2.7
Part, chemical cross-linking agent 1.75-3.5 part, emulsifying agent 10.5 parts, deionized water 620-650 part, ion crosslinking agent 0.7-3.5
Part.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 1, it is characterised in that: be set forth in leather finishing agent
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion also include initiator B 0.4 part, its be used for polymerization reaction late stage holding stage.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 2, it is characterised in that: described initiator A was
Sulfate and the redox initiation system of sodium sulfite composition；Described initiator B be potassium peroxydisulfate/sodium sulfite,
One group or several groups combination in tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium sulfite.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 3, it is characterised in that: described initiator B is uncle
The redox initiation system of butylhydroperoxide/sodium sulfite composition.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 4, it is characterised in that: the described initiator A Central Asia
Sodium bisulfate and persulfate mass ratio are 5.75:1；Tert-butyl hydroperoxide and sodium sulfite in described initiator B
Mass ratio is 3:1.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 2, it is characterised in that: described ion crosslinking agent is
Nano zine oxide.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 2, it is characterised in that: described chemical cross-linking agent is
Vinyl cross-linking agent-CX-1 the chemical cross-linking agent of two degrees of functionality and/or three-functionality-degree.
MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 5, it is characterised in that: described MULTIPLE COMPOSITE cross-links
Emulsion acrylic resin, it is to include that following components is counted by weight, is formed by reactive polymeric: ethyl acrylate 290
Part, butyl acrylate 50 parts, 7 parts of acrylic acid, initiator A 1.3 parts, chemical cross-linking agent part 1.75-3.5 part, emulsifying
Agent 10.5 parts, deionized water 640 parts, ion crosslinking agent 1.8 parts, initiator B 0.4 part.
9. a preparation method for the MULTIPLE COMPOSITE crosslinked acrylic resin emulsion as described in any claim in claim 2-8, its
It is characterised by:
(1) emulsifying agent is added in deionized water, be warming up to 40-80 DEG C of stirring, make emulsifying agent be completely dissolved in water；
(2) by after ethyl acrylate, butyl acrylate, acrylic acid and chemical cross-linking agent mix homogeneously, it is slowly added dropwise into high-speed stirring
In the emulsifier aqueous solution mixed, drip complete follow-up continuous stirring, obtain pre-emulsion；
(3) take after a small amount of pre-emulsion is warming up to 60-70 DEG C, under agitation, add the aqueous solution of part initiator A, treat
After blue phase occurs in emulsion, maintain temperature 65-68 DEG C；Drip the aqueous solution of remaining initiator A and remaining the most in batches
Pre-emulsion；
(4), after the aqueous solution of to be triggered dose of A and pre-emulsion dropping, in reactant liquor, the water of initiator B point is added for 1-2 time
Solution, is incubated 1-3h；
(5) it is cooled to 30-60 DEG C, adds the water slurry of ion crosslinking agent to the reactant liquor of step (4), protect after dropping
Temperature 10-30min；
(6) with after nertralizer regulation pH to neutrality, discharging is filtered.
The preparation method of MULTIPLE COMPOSITE crosslinked acrylic resin emulsion the most according to claim 9, it is characterised in that: in described
Mediating recipe is aqueous sodium carbonate or ammonia.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109021164A (en) * | 2018-08-16 | 2018-12-18 | 广州市麦吉高分子材料有限公司 | A kind of softness acrylic emulsion leather agent and preparation method thereof |
| CN109135480A (en) * | 2018-08-16 | 2019-01-04 | 广州市麦吉高分子材料有限公司 | A kind of cold-resistant acrylic emulsion leather agent and preparation method thereof |
| CN114349894A (en) * | 2022-01-11 | 2022-04-15 | 北京华腾东光科技发展有限公司 | Vulcanization auxiliary agent and metal oxide modified water-based acrylate emulsion and application thereof |
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| CN102391410A (en) * | 2011-09-10 | 2012-03-28 | 中国十七冶集团有限公司 | Inorganic nano particle modified composite waterproof emulsion and preparation method thereof |
| CN102585072A (en) * | 2012-01-11 | 2012-07-18 | 南京瑞固聚合物有限公司 | Room temperature self-crosslinking acrylic ester emulsion |
| CN103013270A (en) * | 2012-12-13 | 2013-04-03 | 陕西科技大学 | Preparation method of high moisture permeability type polyacrylate nano-composite leather coating agent |
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| CN102304316A (en) * | 2011-07-22 | 2012-01-04 | 陕西科技大学 | Polyacrylate/nanometer ZnO composite finishing agent and preparation method thereof |
| CN102391410A (en) * | 2011-09-10 | 2012-03-28 | 中国十七冶集团有限公司 | Inorganic nano particle modified composite waterproof emulsion and preparation method thereof |
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| CN109135480A (en) * | 2018-08-16 | 2019-01-04 | 广州市麦吉高分子材料有限公司 | A kind of cold-resistant acrylic emulsion leather agent and preparation method thereof |
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