CN109265625A - A kind of dedicated acrylic emulsion of lacquer and its preparation method and application - Google Patents
A kind of dedicated acrylic emulsion of lacquer and its preparation method and application Download PDFInfo
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- CN109265625A CN109265625A CN201811114482.8A CN201811114482A CN109265625A CN 109265625 A CN109265625 A CN 109265625A CN 201811114482 A CN201811114482 A CN 201811114482A CN 109265625 A CN109265625 A CN 109265625A
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- acrylic
- lacquer
- acrylic emulsion
- emulsion
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000839 emulsion Substances 0.000 title claims abstract description 101
- 239000004922 lacquer Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 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 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 31
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000006210 lotion Substances 0.000 claims abstract description 23
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000004321 preservation Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 239000000417 fungicide Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 235000013618 yogurt Nutrition 0.000 claims description 3
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 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
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006071 cream Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- -1 polyoxy Ethylene ether ammonium sulfate Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YEQBHMVRNHTCPJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;3-oxobutanoic acid Chemical compound CC(=C)C(O)=O.CC(=O)CC(O)=O YEQBHMVRNHTCPJ-UHFFFAOYSA-N 0.000 description 1
- 208000031639 Chromosome Deletion Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides dedicated acrylic emulsions of a kind of lacquer and its preparation method and application, belong to lacquer technical field.The acrylic emulsion is according to the mass fraction, preparing raw material includes: 6~8 parts of acrylic acid, 4 parts of acrylamide, 160~170 parts of butyl acrylate, 130~150 parts of methyl methacrylate, 130~150 parts of special acrylic monomers, 4~8 parts of reactive emulsifier, 2~4 parts of room-temperature self crosslinking monomer, 3~5 parts of silane coupling agent, 1~2 part of persulfate, 5~6 parts of pH adjusting agent and 500~550 parts of water, and the special acrylic monomers are tert-butyl acrylate.The MFT of acrylic emulsion provided by the invention is 0 DEG C, when for lacquer film forming, without adding coalescing agent, can be formed a film at 0 DEG C, and the lotion is used for lacquer, obtained lacquer is had excellent performance, and standard bonding strength is 1.0~1.3Mpa.
Description
Technical field
The present invention relates to lacquer technical fields more particularly to a kind of dedicated acrylic emulsion of lacquer and preparation method thereof
And application.
Background technique
Lacquer is in recent years all the fashion and widely applied exterior coating product, it is one kind by polymer emulsion, day
The coating that right color sand, function additive, water homogeneous blend are prepared.Since lacquer is typically employed in outdoor, to meet 1 year
Four seasons construction requirement, and exposure that can for a long time by rain drop erosion and sunlight, so filming performance, dry speed to lacquer
The requirement of degree and hardness is very high.Due to lacquer film forming process be exactly in polymer emulsion film forming process, be
The hardness requirement for meeting lacquer, generallys use the high polymer emulsion of glass transition temperature (Tg), the polymer emulsion of Tg high
The hardness of film is high, but polymer emulsion minimum film formation temperature (MFT) is also high when Tg high.Therefore, lacquer wants film formation at low temp must
The MFT of lotion need be reduced.
Generally use the method for lotion China and foreign countries plus coalescing agent in the prior art to realize film formation at low temp, but along with film forming
Phenomena such as addition of auxiliary agent will appear the slow drying speed of paint film and increase volatile organic matter and reduce hardness.Thus, such as
Where without using in the case where coalescing agent, the film formation at low temp of realization lotion or lacquer is that this field technology urgently to be resolved is asked
Topic.
Summary of the invention
The purpose of the present invention is to provide dedicated acrylic emulsion of a kind of lacquer and its preparation method and application, the present invention
The acrylic emulsion of offer is when for lacquer film forming, without adding coalescing agent, can form a film at 0 DEG C.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of dedicated acrylic emulsion of lacquer, the raw material including following mass parts: acrylic acid 6~
8 parts, 4 parts of acrylamide, 160~170 parts of butyl acrylate, 130~150 parts of methyl methacrylate, Specialty Acrylates list
130~150 parts of body, 4~8 parts of reactive emulsifier, 2~4 parts of room-temperature self crosslinking monomer, 3~5 parts of silane coupling agent, persulfuric acid
1~2 part of salt, 5~6 parts of pH adjusting agent and 500~550 parts of water；The special acrylic monomers are tert-butyl acrylate.
Preferably, the pH adjusting agent is ammonium hydroxide, N, N- dimethylethanolamine or 2-amino-2-methyl-1-propanol.
Preferably, the reactive emulsifier includes allyl alkyl polyoxyethylene ether ammonium sulfate.
Preferably, the room-temperature self crosslinking monomer includes Diacetone Acrylamide or acetoacetate methacrylic acid second
Ester；The silane coupling agent includes vinyltrimethoxysilane or vinyltriethoxysilane.
The present invention also provides the preparation methods of acrylic emulsion described in above-mentioned technical proposal, comprising the following steps:
(1) by reactive emulsifier, acrylic acid, acrylamide, butyl acrylate, methyl methacrylate, extraordinary propylene
Acid ester monomer and water mixing, obtain pre-emulsion；
(2) acrylic acid, methyl methacrylate, room-temperature self crosslinking monomer and silane coupling agent are mixed, obtains shell monomer；
(3) reactive emulsifier, water and persulfate are mixed, obtains reaction bottom material；
(4) pre-emulsion and persulfate that the step (1) obtains are added drop-wise to the reaction bottom material that the step (3) obtains
Middle carry out free radical copolymerization, obtains core lotion；
(5) shell monomer of the step (2) is added drop-wise to progress shell reaction in the core lotion of the step (4), reaction knot
PH adjusting agent is added after beam, obtains the dedicated acrylic emulsion of lacquer；
The temperature of system is controlled at 87~88 DEG C during the step (4) is added dropwise；
The temperature of system is controlled at 84~85 DEG C during the step (5) is added dropwise；
The step (1), (2) and (3) does not have chronological order.
It preferably, further include heat preservation after the step (4) is added dropwise to complete, the temperature of the heat preservation is 87~88 DEG C, heat preservation
Time be 1.0~1.5h.
It preferably, further include heat preservation, the holding temperature before the step (5) is added dropwise to complete rear, addition pH adjusting agent
It is 87~89 DEG C, the time of heat preservation is 1.5h.
Preferably, the quality of reactive emulsifier is the 3/4 of the reactive emulsifier gross mass in the step (1)；
The quality of acrylic acid is the 1/3~1/2 of the acrylic acid gross mass in the step (1)；Methacrylic acid in the step (1)
The quality of methyl esters is the 1/5~1/2 of the acrylic acid gross mass；The quality of water is the water gross mass in the step (1)
1/6~1/5；The quality of persulfate is the 1/5 of the persulfate gross mass in the step (3).
The present invention separately provides preparation method system described in acrylic emulsion or above-mentioned technical proposal described in above-mentioned technical proposal
Application of the standby obtained acrylic emulsion in lacquer coating.
Preferably, the component of the lacquer coating includes: acrylic emulsion, deionized water, cellulose aqueous solution, second two
Alcohol, defoaming agent, fungicide and natural siliceous sand do not include coalescing agent.
The present invention provides a kind of dedicated acrylic emulsions of lacquer, prepare raw material including following mass parts: propylene
Sour 6~8 parts, 4 parts of acrylamide, 160~170 parts of butyl acrylate, 130~162 parts of methyl methacrylate, special acrylic acid
130~150 parts of ester monomer, 4~8 parts of reactive emulsifier, 2~4 parts of room-temperature self crosslinking monomer, 3~5 parts of silane coupling agent, mistake
1~2 part of sulfate, 5~6 parts of pH adjusting agent and 500~550 parts of water；The special acrylic monomers are tert-butyl acrylate.
The present invention uses said components for raw material, and controls the proportion of each raw material, and obtained acrylic emulsion both can guarantee latex particle
Surface hardness be able to achieve the low temperature deformation of latex particle again, to reduce the MFT of acrylic emulsion.Embodiment result table
Bright, the MFT of acrylic emulsion provided by the invention is 0 DEG C, without adding coalescing agent, can be realized 0 DEG C of film forming, and by the cream
Liquid is used for lacquer, and obtained lacquer is had excellent performance, and standard bonding strength is 1.0~1.3Mpa.
The present invention also provides the preparation method of acrylic emulsion described in above-mentioned technical proposal, the present invention passes through control reaction
Condition obtains the core-shell emulsion of soft core hard shell, not only can guarantee the surface hardness of latex particle but also had realized the low temperature shape of latex particle
Become, has obtained the acrylic emulsion of zero MFT.
Specific embodiment
The present invention provides a kind of dedicated acrylic emulsion of lacquer, the raw material including following mass parts: acrylic acid 6~
8 parts, 4 parts of acrylamide, 160~170 parts of butyl acrylate, 130~150 parts of methyl methacrylate, Specialty Acrylates list
130~150 parts of body, 4~8 parts of reactive emulsifier, 2~4 parts of room-temperature self crosslinking monomer, 3~5 parts of silane coupling agent, persulfuric acid
1~2 part of salt, 5~6 parts of pH adjusting agent and 500~550 parts of water；The special acrylic monomers are tert-butyl acrylate.
In parts by mass, the acrylic acid for preparing raw material and including 6~8 parts of acrylic emulsion provided by the invention, preferably 7
~8 parts.The present invention does not have particular/special requirement to the source of the acrylic acid, using the acrylic acid in source known to those skilled in the art
?.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes 4 parts
Acrylamide.The present invention does not have particular/special requirement to the source of the acrylamide, using source known to those skilled in the art
Acrylic acid.
On the basis of the acrylic acid of the mass parts, acrylic emulsion provided by the invention prepare raw material include 160~
170 parts of butyl acrylate, preferably 160~165 parts.The present invention does not have particular/special requirement to the source of the butyl acrylate,
Using the butyl acrylate in source known to those skilled in the art.
On the basis of the acrylic acid of the mass parts, acrylic emulsion provided by the invention prepare raw material include 130~
150 parts of methyl methacrylate, preferably 130~142 parts.The present invention is to the source of the methyl methacrylate without spy
It is different to require, using the methyl methacrylate in source known to those skilled in the art.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes special type third
130~150 parts of olefin(e) acid ester monomer, preferably 140~150 parts.In the present invention, the special acrylic monomers are acrylic acid
The tert-butyl ester.Special acrylic monomers of the present invention can adjust the partial size and hydrophobicity of the acrylic emulsion.The present invention
There is no particular/special requirement to the source of the special acrylic monomers, using the extraordinary propylene in source known to those skilled in the art
Acid ester monomer.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes 4~8 parts
Reactive emulsifier, preferably 5~8 parts.In the present invention, the reactive emulsifier preferably includes allyl alkyl polyoxy
Ethylene ether ammonium sulfate.The present invention does not have particular/special requirement to the source of the reactive emulsifier, ripe using those skilled in the art
Know the reactive emulsifier in source.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes 2~4 parts
Room-temperature self crosslinking monomer, preferably 2~3 parts.In the present invention, the room-temperature self crosslinking monomer preferably includes diacetone acrylamide
Amide or acetoacetoxyethyl methacrylate.The present invention does not have particular/special requirement to the source of the room-temperature self crosslinking monomer,
Using the room-temperature self crosslinking monomer in source known to those skilled in the art.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes 3~5 parts
Silane coupling agent, preferably 4~5 parts.In the present invention, the silane coupling agent preferably includes vinyltrimethoxysilane
Or vinyltriethoxysilane.The present invention does not have particular/special requirement to the source of the silane coupling agent, using art technology
The silane coupling agent in the known source of personnel.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes 1~2 part
Persulfate.In the present invention, the persulfate is preferably potassium peroxydisulfate.The present invention does not have the source of the persulfate
There is particular/special requirement, using the persulfate in source known to those skilled in the art.
On the basis of the acrylic acid of the mass parts, the raw material for preparing of acrylic emulsion provided by the invention includes 5~6 parts
PH adjusting agent；The pH adjusting agent is preferably ammonium hydroxide, N, N- dimethylethanolamine or 2-amino-2-methyl-1-propanol, optimal
It is selected as ammonium hydroxide.The mass concentration of ammonium hydroxide of the present invention is preferably 25~28%.The present invention does not have the source of the pH adjusting agent
There is particular/special requirement, using the pH adjusting agent in source known to those skilled in the art.
On the basis of the acrylic acid of the mass parts, acrylic emulsion provided by the invention prepare raw material include 500~
550 parts of water, preferably 500~540 parts.In the present invention, the water is preferably deionized water, and the present invention is to the deionization
The source of water does not have particular/special requirement, using the deionized water in source known to those skilled in the art.
The present invention uses said components for raw material, and by adjusting the proportion of nucleocapsid amount of monomer and the proportion of each raw material, obtains
To acrylic emulsion not only can guarantee latex particle surface hardness but also realize latex particle low temperature deformation, to reduce third
The MFT of olefin(e) acid lotion, and then when acrylic emulsion of the invention is used for lacquer, it may not need addition coalescing agent, just
Film formation at low temp can be achieved.
The present invention also provides the preparation methods of acrylic emulsion described in above-mentioned technical proposal, comprising the following steps:
(1) by reactive emulsifier, acrylic acid, acrylamide, butyl acrylate, methyl methacrylate, extraordinary propylene
Acid ester monomer and water mixing, obtain pre-emulsion；
(2) acrylic acid, methyl methacrylate, room-temperature self crosslinking monomer and silane coupling agent are mixed, obtains shell monomer；
(3) reactive emulsifier, water and persulfate are mixed, obtains reaction bottom material；
(4) pre-emulsion and persulfate that the step (1) obtains are added drop-wise to the reaction bottom material that the step (3) obtains
Middle carry out free radical copolymerization, obtains core lotion；
(5) shell monomer of the step (2) is added drop-wise to progress shell reaction in the core lotion of the step (4), reaction knot
PH adjusting agent is added after beam, obtains the dedicated acrylic emulsion of lacquer；
The temperature of system is controlled at 87~88 DEG C during being added dropwise in the step (4)；
The temperature of system is controlled at 84~85 DEG C during being added dropwise in the step (5)；
The step (1), (2) and (3) does not have chronological order.
The present invention by reactive emulsifier, acrylic acid, acrylamide, butyl acrylate, methyl methacrylate, special type third
Olefin(e) acid ester monomer and water mixing, obtain pre-emulsion.In the present invention, the mixing is preferably stirred；It is described to be stirred
It is preferred that prevent pre-emulsion to be layered, but there is no particular/special requirement to the rate being stirred using being at the uniform velocity stirred；It is described
The time being stirred is preferably 20~30min.Mixing of the present invention carries out preferably in emulsifying tank, obtains pre-emulsion.?
In the present invention, third described in the quality and above-mentioned technical proposal of the butyl acrylate, acrylamide and special acrylic monomers
The quality of butyl acrylate, acrylamide and special acrylic monomers is corresponding in olefin(e) acid lotion；The reactive emulsifier
Quality be preferably 3/4 of reactive emulsifier quality in acrylic emulsion described in above-mentioned technical proposal；The matter of the acrylic acid
Amount is preferably 1/3~1/2 of acrylic acid quality in acrylic emulsion described in above-mentioned technical proposal；The dosage of the water be preferably on
State 1/6~1/5 of water quality in acrylic emulsion described in technical solution；The quality of the methyl acrylate is preferably above-mentioned technology
The 1/5~1/2 of methyl acrylate quality in acrylic emulsion described in scheme.
The present invention mixes acrylic acid, methyl methacrylate, room-temperature self crosslinking monomer and silane coupling agent, obtains shell list
Body.In the present invention, the mixing is preferably stirred；It is described to be stirred preferably using being at the uniform velocity stirred, to prevent
Shell monomer is layered, but does not have particular/special requirement to the rate being stirred；The time being stirred is preferably 20
~30min.Mixing of the present invention carries out preferably in head tank.In the present invention, the methyl methacrylate, room temperature from
Methyl methacrylate in acrylic emulsion described in the quality and above-mentioned technical proposal of cross-linking monomer and silane coupling agent, room temperature from
The quality of cross-linking monomer and silane coupling agent is corresponding；The quality summation of acrylic acid in the quality and above-mentioned steps of the acrylic acid
The quality of acrylic acid in acrylic emulsion described in corresponding above-mentioned technical proposal.
The present invention mixes reactive emulsifier, water and persulfate, obtains reaction bottom material.Persulfate of the present invention
It is preferred that mixing in form of an aqueous solutions, the concentration of persulfate is preferably 20~40g/L in the persulfate aqueous solution, into one
Step is preferably 30g/L.Mixing of the present invention preferably carries out in a kettle, and the mixing is preferably first by reactive emulsifier
It is mixed with water, obtains reaction kettle bottom material, reaction kettle is then heated to 88 DEG C, persulfate aqueous solution is added into reaction kettle.
It is that reacting initial temperature is provided for the subsequent reaction for obtaining core lotion that the reaction kettle is heated to 88 DEG C by the present invention, control starting
Reaction speed.The present invention does not have particular/special requirement to the mixed mode, can be mixed using well known to those skilled in the art
Uniform mode.In the present invention, the quality of the persulfate is preferably acrylic emulsion described in above-mentioned technical proposal
Middle sulfuric acid salt quality；The quality of the reactive emulsifier is corresponding with the quality summation of reactive emulsifier in the step (1)
The quality of reactive emulsifier in acrylic emulsion described in above-mentioned technical proposal；Water in the quality of the water and the step (1)
Quality summation correspond to the quality of water in acrylic emulsion described in above-mentioned technical proposal.
Step (1), (2) and (3) of the present invention does not have chronological order, i.e., prepares pre-emulsion, shell list in the present invention
Body or the sequencing for preparing for reacting bottom material do not influence the preparation of acrylic emulsion of the present invention.
After obtaining pre-emulsion, shell monomer and reaction bottom material, the pre-emulsion and persulfate are added drop-wise to described by the present invention
Free radical copolymerization is carried out in reaction bottom material, obtains core lotion.In the present invention, the persulfate is preferably with aqueous solution
Form be added dropwise, the concentration of persulfate is preferably 20~40g/L in the persulfate aqueous solution, further preferably 30g/
L.Pre-emulsion of the present invention and persulfate be preferably it is synchronous be added dropwise, the speed of the pre-emulsion dropwise addition is preferably 2.5~
2.7g/min；The rate of addition of the persulfate aqueous solution is preferably 0.014g/min~0.015g/min.In the present invention,
The reaction temperature of system is controlled at 87~88 DEG C during the dropwise addition.In the present invention, it is described be added dropwise to complete after preferably also wrap
Heat preservation is included, the temperature of the heat preservation is preferably 87~88 DEG C, and the time of heat preservation is preferably 1.0~1.5h, heat preservation of the present invention
In temperature and soaking time, guarantee that remaining partial monosomy sufficiently reacts.In the present invention, the quality of the persulfate and institute
The quality summation for stating persulfate in step (3) corresponds to the quality of persulfate in acrylic emulsion described in above-mentioned technical proposal
1/5。
After obtaining core lotion, the shell monomer is added drop-wise to progress shell reaction, reaction in the core lotion by the present invention to be terminated
After add pH adjusting agent, obtain the dedicated acrylic emulsion of lacquer.In the present invention, the mode that shell monomer is added is preferred
To be added dropwise, the speed of the dropwise addition is preferably 2.2~2.8g/min.In the present invention, during the dropwise addition system temperature
Control is at 84~85 DEG C；During the dropwise addition, shell monomer passes through the propylene of free-radical polymerized synthetic kernel shell structure with core lotion
Yogurt micelle.In the present invention, it is described be added dropwise to complete after, be added before pH adjusting agent it is also preferable to include heat preservation, the heat preservation
Temperature is preferably 87~89 DEG C, and the time of heat preservation is preferably 1.5h, in the holding temperature and soaking time, guarantees remaining portion
Monomer is divided sufficiently to react.
Emulsion particle is soft core monocoque in the acrylic emulsion that the present invention obtains, and is had between kernel and shell good
Compatibility and stability not only can guarantee the surface hardness of latex particle in this way but also had been able to achieve the low temperature deformation of latex particle, thus
Reduce the MFT of acrylic emulsion.
It is added before pH adjusting agent, it is also preferable to include cool down to obtained mixed liquor by the present invention；It is described to be cooled to
Temperature preferably at 45 DEG C hereinafter, the present invention does not have particular/special requirement to the mode of the cooling, it is ripe using those skilled in the art
The type of cooling known.The amount that pH adjusting agent is added in the present invention corresponds to pH in acrylic emulsion described in above-mentioned technical proposal and adjusts
The mass parts of agent.After the pH adjusting agent of the dosage is added in the present invention, the pH value of obtained lotion is 7~8, is conducive to improve cream
The stability of liquid.
After pH adjusting agent is added, the present invention is preferably filtered finished emulsion；The present invention does not have the mode of the filtering
There is particular/special requirement, using filter type well known to those skilled in the art.
The present invention separately provides preparation method system described in acrylic emulsion or above-mentioned technical proposal described in above-mentioned technical proposal
Application of the standby obtained acrylic emulsion in lacquer coating.In the present invention, the component of the lacquer coating is preferably wrapped
Include: acrylic emulsion, deionized water, cellulose aqueous solution, ethylene glycol, defoaming agent, fungicide and natural siliceous sand do not include into
Film auxiliary agent.The present invention does not have particular/special requirement to the mode of the application, specifically can be with are as follows: by the acrylic emulsion and go from
Sub- water, cellulose aqueous solution, ethylene glycol, defoaming agent, fungicide and natural siliceous sand mixing, it is common to prepare lacquer coating.This
Invention does not have particular/special requirement to the mixed mode, using hybrid mode well known to those skilled in the art.
Below with reference to embodiment to dedicated acrylic emulsion of lacquer provided by the invention and its preparation method and application into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) emulsifying tank: according to the proportion of table 1, by reactive emulsifier, acrylic acid, acrylamide, butyl acrylate, first
Base methyl acrylate, special acrylic monomers and deionized water, are placed in emulsifying tank, stir 20 minutes, and pre-emulsion is made；
(2) head tank: by acrylic acid, methyl methacrylate, room-temperature self crosslinking monomer and silane coupling agent, it is placed in a high position
In slot, stirs 20 minutes, obtain shell monomer；
(3) reaction kettle: the reactive emulsifier and deionized water of weight under remainder, be heated to temperature be 88 DEG C after, add
The persulfate aqueous solution for entering 1/5 weight obtains reaction bottom material；
(4) potassium peroxydisulfate that the emulsifying tank pre-emulsion and 0.8 weight is added dropwise into mixed liquor at 87~88 DEG C is water-soluble
Liquid is added dropwise 3.0 hours, keeps the temperature 1.0 hours and occurs to obtain core lotion at nuclear reaction；
(5) cooling adjusts temperature of reaction kettle to 84~85 DEG C, and ready head tank shell monomer is added dropwise, and is added dropwise 40 points
Clock after being added dropwise, keeps the temperature 30 minutes 1 hour at 87~89 DEG C, and shelling reaction occurs.Ammonium hydroxide is added after cooling and adjusts pH value
Be 7.0~8.0, can filtering and discharging, obtain the dedicated acrylic emulsion of lacquer.
Solid content through the dedicated acrylic emulsion of lacquer prepared by the preparation method is 46%.
Embodiment 2
According to the proportion of table 1, the preparation method of embodiment 1, acrylic emulsion is prepared, third be prepared through embodiment 2
The solid content of olefin(e) acid lotion is 46%.
1 Examples 1 to 4 of table is raw materials used and dosage
Embodiment 3~4
According to the proportion of table 2, the preparation method of embodiment 1, acrylic emulsion is prepared, is prepared through embodiment 3~4
The solid content of acrylic emulsion is 46%.
2 embodiment 3~4 of table is raw materials used and dosage
Minimum film formation temperature test, test result are carried out according to acrylic emulsion of the GB/T9267-97 to Examples 1 to 4
It is shown in Table 3.
The MFT of the lacquer special emulsion of 3 Examples 1 to 4 of table
| Embodiment | 1 | 2 | 3 | 4 |
| MFT(℃) | 0 | 0 | 0 | 0 |
As can be seen from Table 3, acrylic emulsion provided by the invention is in the case where being not added with any coalescing agent, propylene
The MFT of yogurt liquid is 0 DEG C, illustrates that the lotion can be realized film formation at low temp, i.e., when the lotion is used for lacquer film forming, is not necessarily to
Coalescing agent is added, can realize 0 DEG C of film forming.
Acrylic emulsion described in Examples 1 to 4 is used for lacquer coating, lacquer coating raw material proportion is shown in Table 4.
4 lacquer raw material proportioning of table
The true stone that Examples 1 to 4 is obtained according to JG/T24-2000 " sand textured building coating of synthetic resin emulsion "
The standard state adhesion strength of paint is tested, and test result is shown in Table 5.
The standard state adhesion strength of the lacquer of 5 Examples 1 to 4 of table
| Embodiment | 1 | 2 | 3 | 4 |
| Standard state adhesion strength (MPa) | 1.2 | 1.0 | 1.1 | 1.3 |
As can be seen from Table 5, the acrylic emulsion of Examples 1 to 4 is used to prepare lacquer coating, lacquer has excellent
Different performance, standard state viscosity are 1.0~1.3MPa, meet as defined in JG/T24-2000 >=0.7MPa.
As seen from the above embodiment, acrylic emulsion provided by the invention for lacquer film forming when, without addition at
Film auxiliary agent can form a film at 0 DEG C, and the lotion is used for lacquer, and obtained lacquer is had excellent performance, and standard bonding strength is
1.0~1.3Mpa.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of dedicated acrylic emulsion of lacquer, which is characterized in that the raw material including following mass parts: acrylic acid 6~8
Part, 4 parts of acrylamide, 160~170 parts of butyl acrylate, 130~150 parts of methyl methacrylate, special acrylic monomers
130~150 parts, 4~8 parts of reactive emulsifier, 2~4 parts of room-temperature self crosslinking monomer, 3~5 parts of silane coupling agent, persulfate 1
~2 parts, 5~6 parts of pH adjusting agent and 500~550 parts of water；The special acrylic monomers are tert-butyl acrylate.
2. acrylic emulsion according to claim 1, which is characterized in that the pH adjusting agent is ammonium hydroxide, N, N- dimethyl
Ethanol amine or 2-amino-2-methyl-1-propanol.
3. acrylic emulsion according to claim 1, which is characterized in that the reactive emulsifier includes allyl alkyl
Polyoxyethylene ether ammonium sulfate.
4. acrylic emulsion according to claim 1, which is characterized in that the room-temperature self crosslinking monomer includes diacetone third
Acrylamide or acetoacetoxyethyl methacrylate；The silane coupling agent includes vinyltrimethoxysilane or vinyl
Triethoxysilane.
5. the preparation method of the described in any item acrylic emulsions of Claims 1 to 4, comprising the following steps:
(1) by reactive emulsifier, acrylic acid, acrylamide, butyl acrylate, methyl methacrylate, Specialty Acrylates
Monomer and water mixing, obtain pre-emulsion；
(2) acrylic acid, methyl methacrylate, room-temperature self crosslinking monomer and silane coupling agent are mixed, obtains shell monomer；
(3) reactive emulsifier, water and persulfate are mixed, obtains reaction bottom material；
(4) by pre-emulsion and persulfate that the step (1) obtains be added drop-wise in the reaction bottom material that the step (3) obtains into
Row free radical copolymerization obtains core lotion；
(5) shell monomer of the step (2) is added drop-wise to progress shell reaction in the core lotion of the step (4), after reaction
PH adjusting agent is added, the dedicated acrylic emulsion of lacquer is obtained；
The temperature of system is controlled at 87~88 DEG C during the step (4) is added dropwise；
The temperature of system is controlled at 84~85 DEG C during the step (5) is added dropwise；
The step (1), (2) and (3) does not have chronological order.
6. preparation method according to claim 5, which is characterized in that the step (4) be added dropwise to complete after further include heat preservation,
The temperature of the heat preservation is 87~88 DEG C, and the time of heat preservation is 1.0~1.5h.
7. preparation method according to claim 5, which is characterized in that the step (5) is added dropwise to complete rear, addition pH and adjusts
It further include heat preservation before agent, the holding temperature is 87~89 DEG C, and the time of heat preservation is 1.5h.
8. preparation method according to claim 5, which is characterized in that the quality of reactive emulsifier in the step (1)
It is the 3/4 of the reactive emulsifier gross mass；The quality of acrylic acid is the 1/ of the acrylic acid gross mass in the step (1)
3~1/2；The quality of methyl methacrylate is the 1/5~1/2 of the acrylic acid gross mass in the step (1)；The step
(1) quality of water is the 1/6~1/5 of the water gross mass in；The quality of persulfate is the persulfuric acid in the step (3)
The 1/5 of salt gross mass.
9. the described in any item acrylic emulsions of Claims 1 to 4 or the described in any item preparation method systems of claim 5~8
Application of the standby obtained acrylic emulsion in lacquer coating.
10. application according to claim 9, which is characterized in that the component of the lacquer coating includes: propylene yogurt
Liquid, deionized water, cellulose aqueous solution, ethylene glycol, defoaming agent, fungicide and natural siliceous sand do not include coalescing agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635650A (en) * | 2020-06-04 | 2020-09-08 | 荣新(唐山)涂料有限公司 | Quick-drying type real stone paint and preparation method thereof |
| CN111635163A (en) * | 2020-06-04 | 2020-09-08 | 天津市荣新涂料股份有限公司 | Flexible stone-like veneering sheet and preparation method thereof |
| CN112646445A (en) * | 2020-12-22 | 2021-04-13 | 衡水新光新材料科技有限公司 | Preparation method of real stone paint emulsion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622831A (en) * | 2016-01-28 | 2016-06-01 | 江苏九洲环保技术有限公司 | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion |
| CN107573794A (en) * | 2017-10-23 | 2018-01-12 | 浙江科力森化学有限公司 | A kind of dumb light finishing varnish acrylic emulsion and preparation method thereof |
-
2018
- 2018-09-25 CN CN201811114482.8A patent/CN109265625B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622831A (en) * | 2016-01-28 | 2016-06-01 | 江苏九洲环保技术有限公司 | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion |
| CN107573794A (en) * | 2017-10-23 | 2018-01-12 | 浙江科力森化学有限公司 | A kind of dumb light finishing varnish acrylic emulsion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张心亚等: "苯丙乳液的最低成膜温度及其影响因素分析", 《粘接》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635650A (en) * | 2020-06-04 | 2020-09-08 | 荣新(唐山)涂料有限公司 | Quick-drying type real stone paint and preparation method thereof |
| CN111635163A (en) * | 2020-06-04 | 2020-09-08 | 天津市荣新涂料股份有限公司 | Flexible stone-like veneering sheet and preparation method thereof |
| CN111635163B (en) * | 2020-06-04 | 2022-01-18 | 天津市荣新涂料股份有限公司 | Flexible stone-like veneering sheet and preparation method thereof |
| CN112646445A (en) * | 2020-12-22 | 2021-04-13 | 衡水新光新材料科技有限公司 | Preparation method of real stone paint emulsion |
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Denomination of invention: A special acrylic lotion for stone like paint and its preparation method and application Effective date of registration: 20221227 Granted publication date: 20210226 Pledgee: Bank of Communications Co.,Ltd. Shaoxing Shangyu Sub branch Pledgor: ZHEJIANG KELISEN CHEMICAL Co.,Ltd. Registration number: Y2022330003709 |
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