CN114196267A - Flame-retardant microcapsule curd, water-based flame-retardant anticorrosive plastic coating and preparation method thereof - Google Patents
Flame-retardant microcapsule curd, water-based flame-retardant anticorrosive plastic coating and preparation method thereof Download PDFInfo
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- CN114196267A CN114196267A CN202111545601.7A CN202111545601A CN114196267A CN 114196267 A CN114196267 A CN 114196267A CN 202111545601 A CN202111545601 A CN 202111545601A CN 114196267 A CN114196267 A CN 114196267A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 150
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000003094 microcapsule Substances 0.000 title claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000006223 plastic coating Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 81
- 239000011248 coating agent Substances 0.000 claims abstract description 76
- 239000000839 emulsion Substances 0.000 claims abstract description 50
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 150000002978 peroxides Chemical class 0.000 claims abstract description 19
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims abstract description 19
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 18
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 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 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000010008 shearing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 5
- -1 phosphine oxide, phosphite ester Chemical class 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 24
- 229920003023 plastic Polymers 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 21
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 239000002775 capsule Substances 0.000 description 33
- 239000002245 particle Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Fireproofing Substances (AREA)
Abstract
The application relates to the field of water-based coatings, and particularly discloses a flame-retardant microcapsule curd, a water-based flame-retardant anticorrosive plastic coating and a preparation method thereof. The water-based flame-retardant anticorrosive plastic coating comprises: styrene-acrylic emulsion, flame-retardant microcapsule curd, filler, dispersant, film-forming assistant and deionized water. The preparation of the flame-retardant microcapsule curdled milk comprises the following steps: preparing a wall material emulsion: taking deionized water as a dispersing agent, uniformly mixing cyclodextrin, sodium dodecyl benzene sulfonate, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate, preheating, adding peroxide and a catalyst, heating, reacting, and cooling after reaction to obtain a wall material emulsion; coating: adding a flame retardant into the wall material emulsion, and shearing and emulsifying to obtain a microcapsule emulsion; and (3) drying: and drying the microcapsule emulsion until the solid content is 65-70% to obtain the flame-retardant microcapsule curd. The water-based flame-retardant anticorrosive plastic coating has good adhesion to plastics and has good flame retardance and corrosion resistance.
Description
Technical Field
The application relates to the field of coatings, in particular to flame-retardant microcapsule curd, a water-based flame-retardant anticorrosive plastic coating and a preparation method thereof.
Background
The coating generally comprises components such as resin, solvent, filler, additive, auxiliary agent and the like, and when the coating is coated on the surface of a substrate, a continuous coating film can be formed on the surface of the substrate, so that the effects of decoration, protection and the like on the surface of the substrate are achieved. From the viewpoint of the type of solvent, the coating materials can be classified into solvent-type coating materials, which use an organic solvent as a solvent, and water-based coating materials, which use water as a solvent. Obviously, the water-based coating is more environment-friendly than a solvent-based coating, and also represents the development direction of the future coating.
Some application scenes require that the coating has certain flame retardance and corrosion resistance, for example, in the household appliance industry, the shells of electric cookers, electromagnetic oven bases, electric kettle shells, microwave oven door surfaces and the like are made of plastics, and the plastics are required to have good flame retardance and corrosion resistance. If the plastic itself is improved, for example, if a flame retardant is added to the plastic, although the flame retardant effect of the plastic can be improved, the structural strength of the plastic itself is greatly impacted, and the strength requirement is difficult to meet. If the coating with flame retardance and corrosion resistance is coated on the surface of the plastic, the characteristics of the plastic can be kept, and the surface of the plastic can have flame retardance and corrosion resistance.
However, there are difficulties in applying water-based coatings with flame retardancy and corrosion resistance to plastic surfaces, which are reflected in the following aspects: firstly, the water-based paint has high polarity and large surface tension, which makes the water-based paint have poor adhesion to plastics, especially polyolefin plastics with low surface polarity, such as PP; secondly, in order to ensure the flame retardance of the coating, a large amount of flame retardants are often required to be added into the coating, and the existence of the large amount of flame retardants greatly influences the adhesion of the coating, and in addition, the nonpolar characteristic of the surface of the plastic further aggravates the condition of poor adhesion of the coating; thirdly, the resin in the water-based paint is mostly emulsion liquid and exists in micelle, and the compactness after curing is far inferior to that of the resin dissolved in an organic solvent in the solvent-based paint, so that the anticorrosion performance of the coating film of the water-based paint is poor.
In summary, the inventors of the present application believe that there is no ideal flame retardant and corrosion resistant water-based paint for plastic surfaces in the industry, and need to be improved.
Disclosure of Invention
In order to improve the current situation that an ideal water-based paint with flame retardance and corrosion resistance for plastic surfaces is lacked, the application provides a flame-retardant microcapsule curd, a water-based flame-retardant anticorrosive plastic paint and a preparation method thereof.
In a first aspect, the application provides a water-based flame-retardant anticorrosive plastic coating, which adopts the following technical scheme:
the water-based flame-retardant anticorrosive plastic coating comprises the following components in parts by weight: 40-60 parts of styrene-acrylic emulsion, 10-20 parts of flame-retardant microcapsule curd, 15-25 parts of filler, 1.5-2.5 parts of dispersant, 1-5 parts of film-forming assistant and 5-10 parts of deionized water;
wherein,
the preparation raw materials of the flame-retardant microcapsule curd comprise, by weight: 30-50 parts of cyclodextrin, 1-5 parts of sodium dodecyl benzene sulfonate, 10-20 parts of epoxy resin, 5-15 parts of methyl methacrylate, 5-15 parts of acrylic acid, 5-15 parts of butyl methacrylate, 5-15 parts of ethyl acrylate, 5-10 parts of peroxide, 1-1.5 parts of a catalyst and 15-30 parts of a flame retardant; the preparation method of the flame-retardant microcapsule curd comprises the following steps:
preparing a wall material emulsion: taking deionized water as a dispersing agent, uniformly mixing cyclodextrin, sodium dodecyl benzene sulfonate, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate according to parts by weight, preheating, adding peroxide and a catalyst, reacting after heating, and cooling after reacting to obtain a wall material emulsion;
coating: adding a flame retardant into the wall material emulsion according to the parts by weight, and performing shearing emulsification to obtain a microcapsule emulsion;
and (3) drying: and drying the microcapsule emulsion until the solid content is 65-70% to obtain the flame-retardant microcapsule curd.
By adopting the technical scheme, the flame-retardant microcapsule curd prepared by a special method is added into the coating, the flame-retardant microcapsule curd contains numerous tiny microcapsule particles, the microcapsule particles contain capsule walls and capsule cores, the capsule cores are flame retardants, and the microcapsule particles containing the flame retardants are distributed in the coating matrix, so that the flame retardance of the coating can be effectively improved.
The capsule wall is prepared from cyclodextrin, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate. The capsule wall formed by the raw materials after polymerization has good wrapping property, and the flame retardant can be stably maintained in the capsule wall, so that the influence of the flame retardant on a cured coating film is weakened, and the adhesion of the coating is improved. Furthermore, the cyclodextrin contained in the capsule wall has good flame retardance and can be matched with the flame retardant in the capsule core to improve the flame retardance of the coating. Furthermore, the raw materials can form a cross-linked network structure through polymerization reaction, so that the adhesion of the coating on a plastic substrate is improved to a great extent. Moreover, the capsule wall generated by the polymerization reaction has good compactness, and a plurality of microcapsule particles can be dispersed in the styrene-acrylic emulsion, and in the coating curing process, the microcapsule particles can fill the pores in the styrene-acrylic emulsion, so that the compactness of the coating is effectively improved, the adhesive force of the coating can be improved, and the corrosion resistance of the coating can be enhanced.
Experimental data show that the coating is an ideal water-based coating which can be used for the surface of plastic and has flame retardance and corrosion resistance, and the blank in the industry is filled.
Optionally, the preparation raw materials of the flame-retardant microcapsule curd comprise, by weight: 40-45 parts of cyclodextrin, 2-4 parts of sodium dodecyl benzene sulfonate, 16-18 parts of epoxy resin, 10-12 parts of methyl methacrylate, 8-10 parts of acrylic acid, 8-10 parts of butyl methacrylate, 8-10 parts of ethyl acrylate, 8-10 parts of peroxide, 1.2-1.4 parts of a catalyst and 15-30 parts of a flame retardant.
Experimental data show that the raw materials for preparing the capsule wall have different degrees of influence on the adhesiveness and the flame retardance of the coating, and particularly have larger influence on the adhesiveness of the coating. By adopting the technical scheme, the proportion of the raw materials for preparing the flame-retardant microcapsule curd is optimized, and the coating with better performance can be obtained.
Optionally, the temperature after preheating is 55-65 ℃, the reaction temperature is 95-98 ℃, and the reaction time is 5-6 hours.
Through adopting above-mentioned scheme, set up proper preheating temperature, reaction temperature and reaction time, be favorable to guaranteeing the sufficiency of reaction.
Optionally, the flame retardant is one or more selected from phosphine oxide, phosphite ester, phosphate ester, triphenyl phosphate, red phosphorus, ammonium polyphosphate, melamine phosphate and pentaerythritol.
The flame retardant comprises an organic flame retardant and an inorganic flame retardant, and experiments show that the organic flame retardant or the inorganic flame retardant can be used as the flame retardant of the application.
Optionally, the peroxide is selected from one of ammonium persulfate or potassium persulfate.
Ammonium persulfate and potassium persulfate both have good oxidizability, and are beneficial to the sufficiency of polymerization reaction in the capsule wall preparation process.
Optionally, the catalyst is selected from one of dimethyl azobisisobutyrate or azobisisobutyronitrile.
Aiming at the application, the two catalysts, namely the dimethyl azodiisobutyrate or the azodiisobutyronitrile, have high catalytic activity, and are favorable for ensuring the full implementation of polymerization reaction in the preparation process of the capsule wall.
Optionally, the filler is selected from one or two of talcum powder and titanium dioxide.
The talcum powder has good lubricity and is beneficial to improving the dispersibility of the filler in the coating. The titanium dioxide is soft in texture and is beneficial to improving the toughness of the coating.
In a second aspect, the application provides a preparation method of the above water-based flame-retardant anticorrosive plastic coating, which adopts the following technical scheme:
a preparation method of a water-based flame-retardant anticorrosive plastic coating comprises the following steps:
uniformly mixing deionized water, a dispersing agent and a film-forming auxiliary agent, adding the styrene-acrylic emulsion, uniformly mixing, adding the flame-retardant microcapsule curd, uniformly mixing, adding a filler, and uniformly mixing to obtain the water-based flame-retardant anticorrosive plastic coating.
The coating can be obtained by a mixing mode, traditional processing equipment can be adopted for preparation, and the process is easy to control.
In a third aspect, the application provides a flame-retardant microcapsule curd adopted in the water-based flame-retardant anticorrosive plastic coating.
In a fourth aspect, the application provides a preparation method of the flame-retardant microcapsule curd adopted in the water-based flame-retardant anticorrosive plastic coating.
The flame-retardant microcapsule curd is used as a novel flame-retardant material, so that the flame-retardant property of the coating is well improved, the adhesion and the corrosion resistance of the coating are positively promoted, the flame-retardant microcapsule curd is a flame-retardant material with excellent comprehensive properties, and naturally, the preparation method of the flame-retardant microcapsule curd has important reference significance for the field.
In summary, the present application has the following beneficial effects:
1. the flame-retardant microcapsule curd prepared by a special method is added into the coating, the flame-retardant microcapsule curd comprises countless micro microcapsule particles, the microcapsule particles comprise capsule walls and capsule cores, the capsule cores are flame retardants, and the microcapsule particles containing the flame retardants are distributed in a coating matrix, so that the flame retardance of the coating can be effectively improved; in addition, the cyclodextrin contained in the capsule wall of the flame-retardant microcapsule particle has good flame retardance and can be matched with the flame retardant in the capsule core to improve the flame retardance of the coating;
2. the capsule wall of the flame-retardant microcapsule particle has good wrapping property, and the flame retardant can be stably maintained in the capsule wall, so that the influence of the flame retardant on a cured coating is weakened, and the adhesive force of the coating is improved; moreover, the capsule wall generated by polymerization reaction contains a cross-linked network structure, thereby further improving the adhesion of the coating on the plastic substrate;
3. the capsule wall of the flame-retardant microcapsule particle has good compactness, and a plurality of microcapsule particles can be dispersed in the styrene-acrylic emulsion, and in the coating curing process, the microcapsule particles can fill the pores in the styrene-acrylic emulsion, so that the compactness of a coating film is effectively improved, the adhesive force of the coating film can be further improved, and the corrosion resistance of the coating film can be further enhanced.
Detailed Description
The present application is described in further detail below.
Introduction of raw materials
The sources and model descriptions of some of the raw materials used in the following examples and comparative examples are shown in Table 1.
Table 1 introduction of sources and types of raw materials
Examples
Examples 1 to 1
A flame-retardant microcapsule curd is prepared from the following raw materials: 30kg of cyclodextrin, 5kg of sodium dodecyl benzene sulfonate, 10kg of epoxy resin, 15kg of methyl methacrylate, 5kg of acrylic acid, 15kg of butyl methacrylate, 5kg of ethyl acrylate, 10kg of peroxide, 1kg of catalyst and 30kg of flame retardant; wherein, the peroxide adopts ammonium persulfate, the catalyst adopts dimethyl azodiisobutyrate, and the flame retardant adopts phosphite ester;
the preparation method of the flame-retardant microcapsule curd comprises the following steps:
preparing a wall material emulsion: taking deionized water as a dispersing agent, uniformly mixing cyclodextrin, sodium dodecyl benzene sulfonate, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate according to weight kilogram, preheating to 55 ℃, adding peroxide and a catalyst, heating to 98 ℃, reacting for 5 hours, and cooling to room temperature after reaction to obtain a wall material emulsion;
coating: adding a flame retardant into the wall material emulsion according to the weight kilogram, shearing at the speed of 2000r/min for 10min, and then shearing at the speed of 4500r/min for 60min to obtain microcapsule emulsion;
and (3) drying: and drying the microcapsule emulsion until the solid content is 65% to obtain the flame-retardant microcapsule curd.
Examples 1 to 2
A flame-retardant microcapsule curd is prepared from the following raw materials: 42kg of cyclodextrin, 3kg of sodium dodecyl benzene sulfonate, 17kg of epoxy resin, 11kg of methyl methacrylate, 9kg of acrylic acid, 9kg of butyl methacrylate, 9kg of ethyl acrylate, 9kg of peroxide, 1.3kg of catalyst and 25kg of flame retardant; wherein, the peroxide adopts ammonium persulfate, the catalyst adopts dimethyl azodiisobutyrate, and the flame retardant adopts melamine phosphate;
the preparation method of the flame-retardant microcapsule curd comprises the following steps:
preparing a wall material emulsion: taking deionized water as a dispersing agent, uniformly mixing cyclodextrin, sodium dodecyl benzene sulfonate, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate according to weight kilogram, preheating to 60 ℃, adding peroxide and a catalyst, heating to 97 ℃, reacting for 5.5 hours, and cooling to room temperature after reaction to obtain a wall material emulsion;
coating: adding a flame retardant into the wall material emulsion according to the weight kilogram, shearing at the speed of 2500r/min for 8min, and then shearing at the speed of 4800r/min for 55min to obtain microcapsule emulsion;
and (3) drying: and drying the microcapsule emulsion until the solid content is 68% to obtain the flame-retardant microcapsule curd.
Examples 1 to 3
A flame-retardant microcapsule curd is prepared from the following raw materials: 50kg of cyclodextrin, 1kg of sodium dodecyl benzene sulfonate, 20kg of epoxy resin, 5kg of methyl methacrylate, 15kg of acrylic acid, 5kg of butyl methacrylate, 15kg of ethyl acrylate, 5kg of peroxide, 1.5kg of catalyst and 15kg of flame retardant; wherein, the peroxide adopts potassium persulfate, the catalyst adopts azodiisobutyronitrile, and the flame retardant adopts red phosphorus;
the preparation method of the flame-retardant microcapsule curd comprises the following steps:
preparing a wall material emulsion: taking deionized water as a dispersing agent, uniformly mixing cyclodextrin, sodium dodecyl benzene sulfonate, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate according to weight kilogram, preheating to 65 ℃, adding peroxide and a catalyst, heating to 95 ℃, reacting for 6 hours, and cooling to room temperature after reaction to obtain a wall material emulsion;
coating: adding a flame retardant into the wall material emulsion according to the weight kilogram, shearing at the speed of 3000r/min for 5min, and then shearing at the speed of 5000r/min for 50min to obtain microcapsule emulsion;
and (3) drying: and drying the microcapsule emulsion until the solid content is 70 percent to obtain the flame-retardant microcapsule curd.
Examples 1-4 to 1-5 differ from example 1-2 in that: the preparation raw materials of the flame-retardant microcapsule curd are different in proportion, and the preparation raw materials of the flame-retardant microcapsule curd of examples 1-4 to 1-5 are shown in table 2.
TABLE 2 preparation ratio of raw materials for preparing flame-retardant microcapsule curd of examples 1-4 to 1-5
| Raw materials | Examples 1 to 2 | Examples 1 to 4 | Examples 1 to 5 |
| Cyclodextrin/kg | 42 | 40 | 45 |
| Sodium dodecyl benzene sulfonate/kg | 3 | 4 | 2 |
| Epoxy resin/kg | 17 | 16 | 18 |
| Methyl methacrylate/kg | 11 | 12 | 10 |
| Acrylic acid/kg | 9 | 8 | 10 |
| Butyl methacrylate/kg | 9 | 10 | 8 |
| Ethyl acrylate/kg | 9 | 8 | 10 |
| Peroxide/kg | 9 | 10 | 8 |
| Catalyst/kg | 1.3 | 1.2 | 1.4 |
| Flame retardant/kg | 25 | 30 | 15 |
Example 2-1
The water-based flame-retardant anticorrosive plastic coating comprises the following components in parts by weight in kilograms: 40kg of styrene-acrylic emulsion, 20kg of flame-retardant microcapsule curd, 15kg of filler, 2.5kg of dispersant, 1kg of film-forming assistant and 10kg of deionized water; wherein the flame-retardant microcapsule curd is prepared in example 1-1, and the filler is talcum powder;
the preparation method of the water-based flame-retardant anticorrosive plastic coating comprises the following steps:
uniformly mixing deionized water, a dispersing agent and a film-forming auxiliary agent, adding the styrene-acrylic emulsion, uniformly mixing, adding the flame-retardant microcapsule curd, uniformly mixing, adding a filler, and uniformly mixing to obtain the water-based flame-retardant anticorrosive plastic coating.
Examples 2 to 2
The water-based flame-retardant anticorrosive plastic coating comprises the following components in parts by weight in kilograms: 50kg of styrene-acrylic emulsion, 15kg of flame-retardant microcapsule curd, 20kg of filler, 2kg of dispersing agent, 3kg of film-forming assistant and 7kg of deionized water; wherein the flame-retardant microcapsule curd is prepared by the flame-retardant microcapsule curd prepared in the embodiment 1-2, and the filler is talcum powder and titanium dioxide in a weight ratio of 1: 1;
the preparation method of the water-based flame-retardant anticorrosive plastic coating comprises the following steps:
uniformly mixing deionized water, a dispersing agent and a film-forming auxiliary agent, adding the styrene-acrylic emulsion, uniformly mixing, adding the flame-retardant microcapsule curd, uniformly mixing, adding a filler, and uniformly mixing to obtain the water-based flame-retardant anticorrosive plastic coating.
Examples 2 to 3
The water-based flame-retardant anticorrosive plastic coating comprises the following components in parts by weight in kilograms: 60kg of styrene-acrylic emulsion, 10kg of flame-retardant microcapsule curd, 25kg of filler, 1.5kg of dispersing agent, 5kg of film-forming assistant and 50kg of deionized water; wherein the flame-retardant microcapsule curd is prepared by the flame-retardant microcapsule curd prepared in the embodiment 1-3, and the filler is titanium dioxide;
the preparation method of the water-based flame-retardant anticorrosive plastic coating comprises the following steps:
uniformly mixing deionized water, a dispersing agent and a film-forming auxiliary agent, adding the styrene-acrylic emulsion, uniformly mixing, adding the flame-retardant microcapsule curd, uniformly mixing, adding a filler, and uniformly mixing to obtain the water-based flame-retardant anticorrosive plastic coating.
Examples 2 to 4
The water-based flame-retardant anticorrosive plastic coating is different from the plastic coating in the embodiment 2-2 in that: flame-retardant microcapsule curds prepared in examples 1 to 4 were used.
Examples 2 to 5
The water-based flame-retardant anticorrosive plastic coating is different from the plastic coating in the embodiment 2-2 in that: flame-retardant microcapsule curds prepared in examples 1 to 5 were used.
Comparative example
Comparative example 1
The existing water-based flame-retardant coating is purchased from the market, takes epoxy resin, polyacrylate, phosphorus-nitrogen composite flame retardant, hypophosphite flame retardant, talcum powder, titanium dioxide, dispersing agent, defoaming agent and flatting agent as main raw materials, and indicates that the coating has good glossiness and flame retardance.
Performance detection
The coatings prepared in examples 2-1 to 2-3 and comparative examples 1 to 3 were tested for adhesion, flame retardancy and corrosion resistance. Wherein: the adhesion force test is rated according to the regulation in GB/T9286-1998, the plastic base material adopts non-polar plastic PP, the adhesion force is rated as 0-5 and 5 in total, and the smaller the grade number is, the better the adhesion force is represented; the flame retardance test is carried out according to the regulation in GB/T2406-93, the oxygen index is used as a test index, and the larger the oxygen index is, the better the flame retardance of the surface coating is; the corrosion resistance test is carried out according to the regulation in GB/T1771-2007, and the duration of salt spray resistance is taken as a judgment index. The adhesion, flame retardancy and corrosion resistance test results are shown in table 3.
TABLE 3 adhesion, flame retardancy and Corrosion resistance test results for the coatings
| Sample (I) | Adhesion/grade | Oxygen index/% | Corrosion resistance per hour |
| Example 2-1 | Level 1 | 36.5 | ≥1000h |
| Examples 2 to 2 | Level 0 | 34.2 | ≥1000h |
| Examples 2 to 3 | Level 1 | 32.8 | ≥1000h |
| Examples 2 to 4 | Level 1 | 36.7 | ≥1000h |
| Examples 2 to 5 | Level 0 | 33.8 | ≥1000h |
| Comparative example 1 | Grade 3 | 36.7 | Edge bubble phenomenon appears after 480h |
According to the test data reported in Table 3, the flame retardancy of the coating prepared by the present application is close to that of comparative example 1, and the adhesion and corrosion resistance are significantly better than those of comparative example 1. The technical scheme of the application can greatly improve the adhesion and the corrosion resistance of the coating on the plastic substrate while maintaining the flame retardance of the coating.
In terms of flame retardance, the flame-retardant microcapsule curd prepared by a special method is added into the coating, the flame-retardant microcapsule curd comprises a plurality of tiny microcapsule particles, the microcapsule particles comprise capsule walls and capsule cores, the capsule cores are flame retardants, and the microcapsule particles containing the flame retardants are distributed in the coating matrix, so that the coating can maintain high flame retardance. In addition, the cyclodextrin contained in the capsule wall of the flame-retardant microcapsule particle has good flame retardance, and can be matched with the flame retardant in the capsule core to improve the flame retardance of the coating.
In terms of adhesion, the capsule wall of the flame-retardant microcapsule particle has good wrapping property, a flame retardant can be stably maintained in the capsule wall, the influence of the flame retardant on a cured coating film is weakened, and the adhesion of the coating is improved. Moreover, the capsule wall generated through polymerization reaction contains a cross-linked network structure, so that the adhesion of the coating on the plastic substrate is further improved. Furthermore, a plurality of microcapsule particles can be dispersed in the styrene-acrylic emulsion, and in the coating curing process, the microcapsule particles can fill the pores in the styrene-acrylic emulsion, so that the compactness of the coating film is effectively improved, and the adhesive force of the coating film can be further improved.
In terms of corrosion resistance, the capsule wall of the flame-retardant microcapsule particle has good compactness, and a plurality of microcapsule particles can be dispersed in the styrene-acrylic emulsion, and in the coating curing process, the microcapsule particles can fill the pores in the styrene-acrylic emulsion, so that the compactness of the coating is effectively improved, and the corrosion resistance of the coating is further enhanced.
It can be seen from examples 2-2 and examples 2-4 and 2-5 that the raw materials for preparing the capsule wall have different degrees of influence on the adhesion and flame retardancy of the coating, and particularly have a large influence on the adhesion of the coating. This reflects to some extent the presence of complexation between the raw materials for the capsule wall preparation, and between the capsule wall and the other components of the coating.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The water-based flame-retardant anticorrosive plastic coating is characterized by comprising the following components in parts by weight: 40-60 parts of styrene-acrylic emulsion, 10-20 parts of flame-retardant microcapsule curd, 15-25 parts of filler, 1.5-2.5 parts of dispersant, 1-5 parts of film-forming assistant and 5-10 parts of deionized water;
wherein,
the preparation raw materials of the flame-retardant microcapsule curd comprise, by weight: 30-50 parts of cyclodextrin, 1-5 parts of sodium dodecyl benzene sulfonate, 10-20 parts of epoxy resin, 5-15 parts of methyl methacrylate, 5-15 parts of acrylic acid, 5-15 parts of butyl methacrylate, 5-15 parts of ethyl acrylate, 5-10 parts of peroxide, 1-1.5 parts of a catalyst and 15-30 parts of a flame retardant;
the preparation method of the flame-retardant microcapsule curd comprises the following steps:
preparing a wall material emulsion: taking deionized water as a dispersing agent, uniformly mixing cyclodextrin, sodium dodecyl benzene sulfonate, epoxy resin, methyl methacrylate, acrylic acid, butyl methacrylate and ethyl acrylate according to parts by weight, preheating, adding peroxide and a catalyst, reacting after heating, and cooling after reacting to obtain a wall material emulsion;
coating: adding a flame retardant into the wall material emulsion according to the parts by weight, and performing shearing emulsification to obtain a microcapsule emulsion;
and (3) drying: and drying the microcapsule emulsion until the solid content is 65-70% to obtain the flame-retardant microcapsule curd.
2. The water-based flame-retardant anticorrosive plastic coating according to claim 1, characterized in that: the preparation raw materials of the flame-retardant microcapsule curd comprise, by weight: 40-45 parts of cyclodextrin, 2-4 parts of sodium dodecyl benzene sulfonate, 16-18 parts of epoxy resin, 10-12 parts of methyl methacrylate, 8-10 parts of acrylic acid, 8-10 parts of butyl methacrylate, 8-10 parts of ethyl acrylate, 8-10 parts of peroxide, 1.2-1.4 parts of a catalyst and 15-30 parts of a flame retardant.
3. The water-based flame-retardant anticorrosive plastic coating according to claim 1, characterized in that: the temperature after preheating is 55-65 ℃, the reaction temperature is 95-98 ℃, and the reaction time is 5-6 h.
4. The water-based flame-retardant anticorrosive plastic coating according to claim 1, characterized in that: the flame retardant is selected from one or more of phosphine oxide, phosphite ester, phosphate ester, triphenyl phosphate, red phosphorus, ammonium polyphosphate, melamine phosphate and pentaerythritol.
5. The water-based flame-retardant anticorrosive plastic coating according to claim 1, characterized in that: the peroxide is selected from one of ammonium persulfate or potassium persulfate.
6. The water-based flame-retardant anticorrosive plastic coating according to claim 1, characterized in that: the catalyst is selected from one of dimethyl azodiisobutyrate or azodiisobutyronitrile.
7. The water-based flame-retardant anticorrosive plastic coating according to claim 1, characterized in that: the filler is selected from one or two of talcum powder and titanium dioxide.
8. The preparation method of the water-based flame-retardant anticorrosive plastic coating as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
uniformly mixing deionized water, a dispersing agent and a film-forming auxiliary agent, adding the styrene-acrylic emulsion, uniformly mixing, adding the flame-retardant microcapsule curd, uniformly mixing, adding a filler, and uniformly mixing to obtain the water-based flame-retardant anticorrosive plastic coating.
9. A flame-retardant microcapsule curd adopted in the water-based flame-retardant anticorrosive plastic coating of any one of claims 1 to 7.
10. A preparation method of a flame-retardant microcapsule curd adopted in the water-based flame-retardant anticorrosive plastic coating of any one of claims 1 to 7.
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