CN1730547A - Monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses - Google Patents
Monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses Download PDFInfo
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Abstract
The invention provides a monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses, wherein the emulsion comprises the constituents of epoxy resin, (methyl) acrylic ester, alkenyl carboxyl acid, ethenyl aromatic compound, silicane coupling agent, initiating agent, emulsifying agent, pH regulator, neutralization agent and water. The composite emulsion is prepared through the emulsion polymerization process and by using epoxy propylene acid composite emulsion as the base.
Description
Technical field
The present invention relates to the composite high-molecular material field, particularly a kind of single-component self-cross-linking epoxy acrylic acid composite emulsion and its production and application.
Background technology
Resins, epoxy has good adhesiveproperties, corrosion resistance, electrical insulation capability and chemical-resistant and low-shrinkage, be mainly used in protective system, tackiness agent and prepare composite, but exist quality more crisp, shortcoming such as thermotolerance, shock resistance, resistance to fatigue, resistance to cracking and humidity resistance are relatively poor.Acrylic resin has good weathering resistance, resistance to acids and bases and photostabilization, is mainly used in fields such as coating, fabric treating and tackiness agent, but there is water tolerance in it and shortcoming such as winter hardiness is poor, low temperature becomes fragile, high temperature becomes sticky, and has limited its widespread use.How above-mentioned two kinds of resins are combined, improve the overall performance of filming by having complementary advantages between each component, be that people expect the problem that solves always.
Along with the countries in the world environmental regulation is strict day by day to the restriction of volatile organic compounds in the coating (VOC) content, coatings industry develops towards low pollution, energy-saving direction.Water-borne coatings with water is dispersion medium, and is nontoxic, nonflammable, both helped environmental protection, can reduce production costs again.The epoxy acrylic acid composite emulsion that abroad begins one's study the eighties in last century, this emulsion can be used as the inner-wall paint of containers such as the can, beer, beverage of food grade, and its preparation method can adopt physical blending method and chemical graft process.U.S. Pat 4,247,439 adopt the physical blending method, at first with Resins, epoxy and emulsifier mix, dilute with water obtains epoxy emulsion, epoxy emulsion is mixed with the acrylic resin that contains carboxyl and tertiary amine again, prepares compound aqueous dispersion system of epoxy resin and acrylic resin, this preparation method's technology is simple, but has problem such as consistency difference between package stability difference and component.Compare with the physical blending method, Resins, epoxy and acrylic resin chemical bonding has between the two improved the consistency of two kinds of resins in the chemical graft process.Chemical graft process prepares epoxy acrylic acid composite emulsion and roughly is divided into two classes, and the one, by free radical reaction, the part acrylic acid esters monomer is grafted on the epoxy chain, obtain composite emulsion, as U.S. Pat 2,068,967, US4,212,781, US4,579,888 etc.; The 2nd, utilize epoxide group and carboxyl, amino reactive behavior, by chemical reactions such as esterifications, two kinds of polymers of different nature are combined, form new macromole, as U.S. Pat 4,289,811, US4,963,602 etc.This two classes chemical graft process all is to be that medium carries out grafting with the solvent, and earlier synthetic carboxylic epoxy acrylic resin then with the alkali neutralization, adds the entry dilution and disperses, and removes organic solvent at last, thereby obtains the epoxy acrylic acid composite emulsion system.When using, this composite emulsion adds solidifying agent such as dimethylaminoethyl acrylate methyl amine ester, triethylene tetramine, aminoresin, heating back crosslinking curing film forming, can be used as coil coating, also can be used for fields such as automobile finish, general engineering machinery lacquer, have wide development space.But this two classes chemical graft process all needs to use a large amount of organic solvents in preparation process, and solid part is low in the emulsion of preparation, VOC content is higher, and needs hot setting in the drying process.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of solid part is high, VOC content is low, cost is low, the single-component self-cross-linking epoxy acrylic acid composite emulsion of water-tolerant, strong adhesion.
Another object of the present invention is to provide a kind of preparation method of single-component self-cross-linking epoxy acrylic acid composite emulsion.
A further object of the present invention is to provide the application of a kind of single-component self-cross-linking epoxy acrylic acid composite emulsion as the water-borne coatings base-material.
Purpose of the present invention is achieved through the following technical solutions:
The single-component self-cross-linking epoxy acrylic acid composite emulsion is counted by weight, comprises following component:
2～20 parts of Resins, epoxy
20～40 parts of (methyl) acrylic acid or the like alkyl esters
1～10 part of thiazolinyl carboxylic acid
10～30 parts of vinyl aromatic compounds
1～10 part of silane coupling agent
0.1～1 part of initiator
2～10 parts of emulsifying agents
0.1～1 part of pH value conditioning agent
1～10 part of neutralizing agent
40～100 parts in water
Described Resins, epoxy be bisphenol A epoxide resin (oxirane value be 0.20～0.54mol/100g) and bisphenol F epoxy resin (oxirane value is 0.30～0.58mol/100g).Preferred 5～10 weight parts of the consumption of described Resins, epoxy.
Described (methyl) acrylic acid or the like alkyl ester, the alkyl carbon atoms number is C1～C15, one or more mixtures in preferable methyl methyl acrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid n-octyl, the Isooctyl acrylate monomer.Preferred 33～38 weight parts of consumption of described (methyl) acrylic acid or the like alkyl ester.
Described thiazolinyl carboxylic acid, carbonatoms are C1～C15, one or more mixtures in preferred vinylformic acid, methacrylic acid, the methylene-succinic acid.Preferred 3～6 weight parts of the consumption of described thiazolinyl carboxylic acid.
Described vinyl aromatic compounds can be vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3,4-dimethyl styrene, optimization styrene.Preferred 15～20 weight parts of the consumption of described vinyl aromatic compounds.
Described silane coupling agent can be one or more mixtures in γ-aminopropyl trimethoxy (or ethoxy) base silane, vinyl trimethoxy (or ethoxy, different third oxygen) base silane, vinyl methoxyl group diethoxy (or diisopropyl oxygen) base silane, γ-methacryloxypropyl trimethoxy (or different third oxygen) base silane, the isocynate silane.Preferred 4～8 weight parts of described dosage of silane coupling agent.
Described initiator can be thermal initiator, as vitriolate of tartar, hydrogen persulfate, Sodium Persulfate, ammonium persulphate, isopropyl benzene hydroperoxide; Also can be redox initiator, as hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, Potassium Persulphate-sodium bisulfite, isopropyl benzene hydroperoxide-iron protochloride; Preferred Potassium Persulphate, because Potassium Persulphate solubleness minimum in water reaches 2.0～4.0%, the thermal initiation effect is better.Preferred 0.2～0.6 weight part of the consumption of described initiator.The consumption of initiator can not be too many, and consumption can cause that too much polymericular weight reduces, and polymerization stability descends, thus the impact polymer performance.
Adoptable type emulsifying agent, anionic emulsifier and nonionic emulsifying agent and their mixture thereof of responding of described emulsifying agent.Reactive emulsifier is embedded in the emulsion particle surface by chemical bond, can reduce total consumption of emulsifier mixture, thereby improves the water tolerance and the sticking power of filming.Adjust the consumption of anionic emulsifier and nonionic emulsifying agent, can improve the emulsifying capacity of emulsifier mixture, thereby guarantee that emulsion has good polymerization stability, chemical stability and mechanical stability polymkeric substance.Above-mentioned reactive emulsifier can be selected vinyl alkylphenol-polyethenoxy sulfonate, a-alkene sulfonic acid sodium, allyl ethers hydroxypropyl azochlorosulfonate acid sodium, vinyl alkyl phosphate, alkyl amido sodium vinyl sulfonate, allyl ethers hydroxyl sulfoacid sodium for use.Above-mentioned anionic emulsifier can be selected sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl diphenyl ether disodium sulfonate salt, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, oxyethyl group phenolic ether sodium sulfate etc. for use.Above-mentioned nonionic emulsifying agent can be selected fatty alcohol-polyoxyethylene ether, the poly-ethoxy Vinyl Ether of nonyl phenol, polyoxyethylene octylphenol ether, oxyethyl group propoxy-edge section Fatty Alcohol(C12-C14 and C12-C18), Isosorbide Dinitrate etc. for use.Emulsifying agent preferred weight ratio of the present invention is 1: (1.0～2.0): the mixture of the vinyl alkylphenol-polyethenoxy sulfonate of (1.5～3.0), sodium lauryl sulphate, octylphenol polyethylene ethoxy Vinyl Ether.Preferred 3～5 weight parts of the consumption of described emulsifying agent.
Described pH value conditioning agent can be sodium bicarbonate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, yellow soda ash, salt of wormwood and bicarbonate of ammonia; Preferred sodium bicarbonate.PH value conditioning agent can be reaction system stable p H value polymerization system is provided, and helps polymerization-stable and carries out.Preferred 0.5～0.8 weight part of the consumption of described pH value conditioning agent.
Described neutralizing agent can be ammoniacal liquor, triethylamine, thanomin, dimethylethanolamine or trolamine, preferred ammoniacal liquor.Preferred 4～8 weight parts of the consumption of described neutralizing agent.
The preparation method of above-mentioned single-component self-cross-linking epoxy acrylic acid composite emulsion adopts composite emulsion polymerization technology, comprises the steps:
(1) at first the water of 20～60 weight parts, the emulsifying agent of 1～5 weight part, the pH value conditioning agent of 0.1～0.5 weight part are mixed and violent stirring, be warming up to 60～90 ℃, the mixture of the silane coupling agent of (methyl) alkyl acrylate of adding 2～20 parts by weight of epoxy resin, 5～10 weight parts, the vinyl aromatic compounds of 2～10 weight parts and 0.5～5 weight part, continue to stir after 20～60 minutes, the initiator that adds 0.1～0.6 weight part, react again and be obvious blue light until emulsion in 10～30 minutes, obtain the composite emulsion stratum nucleare;
(2) (methyl) alkyl acrylate of 15～30 weight parts, the thiazolinyl carboxylic acid of 3～5 weight parts, the vinyl aromatic compounds of 8～20 weight parts, the emulsifying agent of 2～5 weight parts, the water of 20～40 weight parts and/or the silane coupling agent of 0.5～5 weight part are mixed and stirring, make the mix monomer pre-emulsion; Then with the initiator solution of described mix monomer pre-emulsion and 0.1～0.4 weight part, in 1～5 hour, splash in the above-mentioned composite emulsion stratum nucleare respectively simultaneously, temperature of reaction maintains 60～90 ℃, continue insulation adds 1～5 weight part after 0.5～1 hour neutralizing agent neutralization, regulating ph value of emulsion is 7.5～8.5, the cold filtration discharging obtains having the single-component self-cross-linking epoxy acrylic acid composite emulsion of the nucleocapsid structure that contains Resins, epoxy stratum nucleare and acrylic resin shell at last.
Adopt composite emulsion polymerization technology, the emulsion particle of the single-component self-cross-linking epoxy acrylic acid composite emulsion that makes is a nucleocapsid structure, and its center partly is that Resins, epoxy, shell partly are acroleic acid resin.The introducing of silane coupling agent has the benefit of following two aspects in this composite emulsion polymerization process: at first, silane coupling agent and acrylic ester monomer carry out copolymerization, have improved the consistency of Resins, epoxy and acroleic acid resin; Secondly, the kind of pH value, polymerization temperature and silane coupling agent by regulating polymerization system, siloxanes hydrolysis, the condensation reaction rate of may command silane coupling agent make Resins, epoxy form the microgel structure, and this microgel structure has improved hardness of film, water tolerance and erosion resistance.
This single-component self-cross-linking epoxy acrylic acid composite emulsion can be used for preparing water-borne coatings, and prepared water-borne coatings can comprise following component: the filler of the single-component self-cross-linking epoxy acrylic acid composite emulsion of 15～35 weight parts, the pigment of 10～30 weight parts, 5～15 weight parts, the auxiliary agent of 1.0～8.0 weight parts, the water of 15～35 weight parts.At first auxiliary agent is dispersed in the water, adds pigment and filler then successively, in dispersion machine high speed dispersed with stirring, stirring velocity is 1000～10000rpm; When pigment and filler in water fineness of dispersion less than 70 μ m after, reduce stirring velocity to 500～5000rpm, add single-component self-cross-linking epoxy acrylic acid composite emulsion and remaining auxiliary agent and fully stir, adjust pH value and viscosity then, obtain water-borne coatings.
The present invention compared with prior art has following advantage and effect:
(1) this epoxy acrylic acid composite emulsion solid part is high, need not additional crosslink agent in use with the coating of this emulsion preparation, and cost is low.
(2) preparation technology of this epoxy acrylic acid composite emulsion is simple.
(3) be the water-borne coatings that base-material makes with the epoxy acrylic acid composite emulsion, dried coating film speed is fast, physical strength is high, water-tolerant, sticking power is good, shelf characteric is stable, and can be widely used in fields such as building, industry, woodenware, paper.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Mixture with 34g methyl methacrylate (MMA), 32g butyl acrylate (BA), 2g vinylformic acid, 10g vinylbenzene (ST) composition, add in the mixed aqueous solution of 0.8g sodium lauryl sulphate (SDS), 1.6g sim alkylphenol Soxylat A 25-7 (OP-10) and 30g water composition, through magnetic agitation 30 minutes, make the mix monomer pre-emulsion.
Thermometer is being housed, in the four-hole bottle of whipping appts and condenser, add 50g water, 1.1g vinyl alkylphenol-polyethenoxy sulfonate (DNS6), 1.4g sim alkylphenol Soxylat A 25-7 (OP-10), with the 0.2g sodium bicarbonate, violent stirring and when being warming up to 78 ℃, add 10g bisphenol A epoxide resin (oxirane value is 0.32mol/100g), 5g vinylbenzene, 2g γ-methacryloxypropyl three isopropoxy silane (C-1757), stir and add 0.12g Potassium Persulphate (KPS) after 20 minutes, the system for the treatment of is reacted to emulsion and is obvious blue light, promptly get the composite emulsion stratum nucleare, in this composite emulsion stratum nucleare, drip above-mentioned mix monomer pre-emulsion and 15 parts of concentration then simultaneously and be 1% potassium persulfate solution, in 4 hours, drip off, finish the polymerization of shell part, continue insulation and add the ammoniacal liquor neutralization after 1 hour, regulating the pH value is 8.0, the cold filtration discharging promptly gets the single-component self-cross-linking epoxy acrylic acid composite emulsion.
Embodiment 2～5
Operation steps and reaction conditions are with embodiment 1, and the each component proportioning sees Table 1, gained epoxy-acrylate emulsion performance such as table 2.
Table 1
| Project name | Monomer composition/part | |||
| Example 2 | Example 3 | Example 4 | Example 5 | |
| Nuclear part ST BA bisphenol A epoxide resin C-1757 DNS6 SDS OP-10 shell partial monosomy forms MMA BA AA ST SDS OP-10 | 5 2 5 2 1.1 1.4 34 32 2 10 0.8 1.6 | 5 2 5 5 1.1 1.4 34 32 2 10 0.8 1.6 | 5 2 5 2 1.1 1.4 34 32 2 10 0.8 1.6 | 5 2 10 2 1.1 1.4 34 32 2 10 0.8 1.6 |
Table 2
| Performance | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Outward appearance polymerization stability viscosity/mPa.s mechanical stability is frozen molten stable ion stability | Oyster white 87 is by by passing through | Oyster white 83 is by by passing through | White 68 is by by passing through | White bad 82 can't pass | White 78 is by by passing through |
Embodiment 6
White water-borne coatings: with 0.15 part of wetting agent, 0.35 part dispersion agent, 0.45 part polyurethane thickener, 0.25 part Mierocrystalline cellulose (2.5%), 0.36 part defoamer, 3 parts of propylene glycol are dispersed in the water, add 25 parts of titanium dioxides then successively, 8 parts of kaolin (3000 order), in dispersion machine under 3000rpm, high speed dispersion to fineness less than 60 μ m after, reduce stirring velocity to 800rpm, add 26 parts of epoxy acrylic acid composite emulsions (embodiment 1), 0.05 part defoamer and 0.3 part 2,2,2-trimethylammonium-1,3-pentanediol first and second butyric esters fully stir, and add pH value and viscosity that 0.3 part of 2-amino-2-methyl-1-propanol is adjusted coating at last.The performance of coating sees Table 3.
Table 3
| Test item | Technical indicator | Example 6 detected results |
| At condition in container | Stir the no lump in back, evenly attitude | Meet the requirements |
| Application property | Brush twice accessible | Meet the requirements |
| Appearance of film | Normally | Meet the requirements |
| Time of drying/h | ≤2 | 1h is dried |
| Sticking power/level | 1 | 0.95 |
| Alkali resistance/48h | No abnormal | The 200h no change |
| Water tolerance/96h | No abnormal | The 200h no change |
Claims (10)
1, a kind of single-component self-cross-linking epoxy acrylic acid composite emulsion is characterized in that: count by weight, comprise following component:
2～20 parts of Resins, epoxy
20～40 parts of (methyl) acrylic acid or the like alkyl esters
1～10 part of thiazolinyl carboxylic acid
10～30 parts of vinyl aromatic compounds
1～10 part of silane coupling agent
0.1～1 part of initiator
2～10 parts of emulsifying agents
0.1～1 part of pH value conditioning agent
1～10 part of neutralizing agent
40～100 parts in water.
2, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1 is characterized in that: described Resins, epoxy is that oxirane value is that bisphenol A epoxide resin and the oxirane value of 0.20～0.54mol/100g is the bisphenol F epoxy resin of 0.30～0.58mol/100g.
3, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1 is characterized in that: described methacrylic alkyl ester is one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid n-octyl, the Isooctyl acrylate monomer.
4, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1 is characterized in that: described thiazolinyl carboxylic acid is one or more mixtures in vinylformic acid, methacrylic acid, the methylene-succinic acid.
5, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1, it is characterized in that: described vinyl aromatic compounds is vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, the 4-dimethyl styrene.
6, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1 is characterized in that: described silane coupling agent is one or more mixtures in γ-aminopropyl trimethoxy or Ethoxysilane, vinyl trimethoxy or ethoxy, isopropoxy silane, vinyl methoxyl group diethoxy or diisopropoxy silane, γ-methacryloxypropyl trimethoxy or isopropoxy silane, the isocynate silane.
7, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1 is characterized in that: described initiator is vitriolate of tartar, hydrogen persulfate, Sodium Persulfate, ammonium persulphate, isopropyl benzene hydroperoxide, hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, Potassium Persulphate-sodium bisulfite or isopropyl benzene hydroperoxide-iron protochloride.
8, single-component self-cross-linking epoxy acrylic acid composite emulsion according to claim 1 is characterized in that: described emulsifying agent is that weight ratio is the mixture of 1: 1.0～2.0: 1.5～3.0 vinyl alkylphenol-polyethenoxy sulfonate, sodium lauryl sulphate, octylphenol polyethylene ethoxy Vinyl Ether.
9,, it is characterized in that comprising the steps: according to the preparation method of each described single-component self-cross-linking epoxy acrylic acid composite emulsion of claim 1～8
(1) at first the water of 20～60 weight parts, the emulsifying agent of 1～5 weight part, the pH value conditioning agent of 0.1～1 weight part are mixed and violent stirring, the mixture that adds the silane coupling agent of the vinyl aromatic compounds of alkyl methacrylate, 1～10 weight part of 2～20 parts by weight of epoxy resin, 0～10 weight part and 0.5～5 weight part simultaneously, be warming up to 60～90 ℃, continue to stir after 20～60 minutes, the initiator that adds 0.1～0.6 weight part, react again and be obvious blue light until emulsion in 10～30 minutes, obtain the composite emulsion stratum nucleare;
(2) alkyl methacrylate of 20～80 weight parts, the thiazolinyl carboxylic acid of 0～5 weight part, the vinyl aromatic compounds of 1～10 weight part, the emulsifying agent of 0～5 weight part, the water of 0～40 weight part and/or the silane coupling agent of 0～5 weight part are mixed and stirring, make the mix monomer pre-emulsion; Then with the initiator solution of described mix monomer pre-emulsion and 0.1～0.4 weight part, in 1～5 hour, splash in the above-mentioned composite emulsion stratum nucleare respectively simultaneously, temperature of reaction maintains 60～90 ℃, continue insulation adds 1～10 weight part after 0.5～1 hour neutralizing agent neutralization, regulating ph value of emulsion is 7.5～8.5, the cold filtration discharging obtains having the single-component self-cross-linking epoxy acrylic acid composite emulsion of the nucleocapsid structure that contains Resins, epoxy stratum nucleare and acrylic resin shell at last.
10, according to the application of each described single-component self-cross-linking epoxy acrylic acid composite emulsion of claim 1～8, it is characterized in that: be used to prepare water-borne coatings, prepared water-borne coatings comprises following component: the filler of the single-component self-cross-linking epoxy acrylic acid composite emulsion of 15～35 weight parts, the pigment of 10～30 weight parts, 5～15 weight parts, the auxiliary agent of 1.0～8.0 weight parts, the water of 15～35 weight parts.
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Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055747A (en) * | 1991-05-06 | 1991-10-30 | 中国林业科学研究院林产化学工业研究所 | Method with the epoxy resin at room temp cross-linking carbonyl bearing polymer emulsion |
| DE4131706C2 (en) * | 1991-09-24 | 1994-10-20 | Basf Lacke & Farben | Process for the preparation of an aqueous coating composition, aqueous coating compositions and their use for coating packaging |
| JPH09124718A (en) * | 1995-10-20 | 1997-05-13 | W R Grace & Co | Production of water-dispersible resin |
| BR0016480A (en) * | 1999-12-10 | 2002-09-10 | Dow Global Technologies Inc | Unique foamable latex / epoxy emulsion, stable in storage and use |
| CN1125854C (en) * | 2001-05-30 | 2003-10-29 | 海洋化工研究院 | Water-thinned epoxy/acrylic amino resin emulsion and water-thinned baking paint with the emulsion as base material |
| CN1288176C (en) * | 2002-09-11 | 2006-12-06 | 江苏日出化工有限公司 | Modified full acrylic ester emulsion |
| CN1229433C (en) * | 2003-12-25 | 2005-11-30 | 中国石化集团巴陵石油化工有限责任公司 | Preparation method of SBS (styrene butadiene styrene) aqueous emulsion |
-
2005
- 2005-08-16 CN CNB2005100365162A patent/CN100387653C/en active Active
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