CN102382230B - Trithiocarbonate compound containing ethylene, preparation method and application thereof - Google Patents
Trithiocarbonate compound containing ethylene, preparation method and application thereof Download PDFInfo
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- CN102382230B CN102382230B CN 201110228766 CN201110228766A CN102382230B CN 102382230 B CN102382230 B CN 102382230B CN 201110228766 CN201110228766 CN 201110228766 CN 201110228766 A CN201110228766 A CN 201110228766A CN 102382230 B CN102382230 B CN 102382230B
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Abstract
The invention discloses a trithiocarbonate compound containing ethylene, which is the compound with a structure in the formula I or II, and the ethylene is positioned between the hydrophilic chain segment and the hydrophobic chain segment of the compound. The invention further discloses a preparation method of the trithiocarbonate compound containing the ethylene, under the action of a radical initiator, the compound with the structure in the formula III or VI is firstly reacted with a water-soluble monomer with a chain link A or a chain link C, and is secondarily reacted with a monomer containing a diene double linkage, so the compound with the structure in the formula I or II is obtained; and the preparation method has the characteristics of simple preparation, strong operability, good reproducibility and the like. The invention also discloses the application of the trithiocarbonate compound containing the ethylene in preparing polymer microspheres, so the ethylene is gathered at the surfaces of the polymer microspheres.
Description
Technical field
The present invention relates to the trithiocarbonate compound, its preparation field, be specifically related to a kind of trithiocarbonate compound, its that contains vinyl and its preparation method and application.
Background technology
Studies show that the performance of macromolecular material also is decided by the structure of macromolecular chain to a great extent except being determined by chemical constitution.Preparation has the macromolecular material of accurate molecular chain structure, thereby in the performance of molecular level control material, to the performance that improves macromolecular material and the function that increases macromolecular material, tool is of great significance.Wherein, the chemical reaction that the specific location functional group participates in the macromolecular chain has become a kind of important method (Takemoto K. of design macromolecular material composition and polymer chain structure, Ottenbrite R.M., Kamachi M.Functional Monomers and Polymers, 2
NdEd.Marcel Dekker:New York, 1997; Coessens V., Pintauer T., Matyjaszewski K.Prog Polym Sci, 2001,26,337～377; Braunecker W.A., Matyjaszewski K.Prog Polym Sci, 2007,32,93～146.).
In radical polymerization, trithiocarbonate is the compound that a class has high chain transfer activity, can be used for controlling the structure of polymer chain, is implemented in the target location rhetorical function group of polymer macromolecule chain.In numerous functional groups, the reactive behavior of vinyl is higher, can carry out the chemical reaction of the multiple mechanism such as the chain polymerization that causes such as addition reaction, free radical and coupling reaction, and realize easily the conversion to sulfydryl, epoxide group isoreactivity group, therefore, vinyl (the Gress A. that in the preparation of the design of polymer molecular chain and macromolecular material, receives much concern, Vollkel A., Schlaad H.Macromolecules, 2007,40,7928～7933.; Cherian A.E., Sun F.C., the JAm Chem Soc such as Sheiko S.S., 2007,129,11350～11351.; Paris R., the JPolym Sci Part A:Polym Chem 2005,43,6247～6261. such as De La Fuente J.L.).
When modified by vinyl during in polymer microballoon surperficial, chemical reaction by two keys participations, not only can carry out functional modification to the surface of microballoon, more can be by striding the coupling reaction between the two keys of particle, enhancing improves its application performance in coating and dyeing and printing process by the physical strength of the mould material of polymer microballoon structure.
At present, prepare the method that contains the vinyl polymer microballoon and mainly be limited to homopolymerization or the copolyreaction that the bi-vinyl monomer participates in.,, prepared and contained 1 of vinyl through homopolymerization take divinyl as monomer such as: Korthals etc., 2-polyhutadiene microballoon (Korthals B.B., Morant-Minana M.C., the Macromolecules such as Schmid M., 2010,43,8071～8078.); (Goldmann A., Walther A., the Macromolecules such as Nebhani L. such as Goldmann A S, 2009,42,3707～3714.) and (van Berkel K.Y., the Piekarski A.M. such as Hawker, the Macromolecules such as Kierstead P.H., 2009,42,1425～1427.), cause Vinylstyrene equal polymerization and and the second monomer between copolyreaction, equally also prepared the polymer microballoon that contains vinyl.
Yet the method in the above-mentioned disclosed technical scheme is difficult to regulate vinyl in the distribution of microballoon interior volume.Reason is, vinyl in the polymer microballoon that obtains derives from the residual of a certain vinyl in the bi-vinyl monomers such as divinyl, Vinylstyrene, therefore, vinyl evenly distributes in polymer microballoon, can't make vinyl be enriched in the surface of polymer microballoon.By semi-continuous polymerzation technique, in polymerization reaction late stage, drip the bi-vinyl monomer, vinyl can be controlled at the shell of microballoon, but it is not high finally to rank the ratio of ethene fiduciary point vinyl total amount of microsphere surface.In addition, cause the crosslinked of microballoon interpolymer chain owing to the bi-vinyl monomer participates in polyreaction, the polymkeric substance that causes generation is insoluble also molten, thereby so that during film forming, the difficulty of the polymer chain phase mutual diffusion between microballoon is very large, is difficult to obtain the mould material of continuous structure.These shortcomings have restricted the promotion and application of novel film materials to a great extent.
Summary of the invention
The invention provides a kind of trithiocarbonate compound, its that contains vinyl, have hydrophilic and amphiphilic structure oleophylic, wherein, vinyl ranks between the hydrophilic segment of compound and oleophylic segment.
A kind of trithiocarbonate compound, its that contains vinyl is the compound of formula I structure or formula II structure:
Wherein, y is that 1～5, x is that 10～50, z is that 10～50, n is 4～12, and x, y, z and n are integer;
Wherein,
With
Obtained through polyreaction by water-soluble monomer, consist of the hydrophilic segment of compound;
Obtained through polyreaction by the monomer (such as the bi-vinyl monomer) that contains two olefinic double bonds, because the polymerization activity of two vinyl does not wait, in the polyreaction, active weak vinyl is kept.
The present invention also provides a kind of preparation method who contains the trithiocarbonate compound, its of vinyl, has the characteristics such as preparation is simple, workable, favorable reproducibility.
The described preparation method who contains the trithiocarbonate compound, its of vinyl may further comprise the steps:
Under the effect of radical initiator, the compound of formula III structure carries out the first step reaction with the water-soluble monomer that forms chain link A, carries out the second step reaction with the monomer that contains two olefinic double bonds again, obtains the compound of formula I structure;
N in the formula III formula III has identical implication with n among the formula I,
The water-soluble monomer of described formation chain link A is vinylformic acid, N,N-DMAA, acrylamide or Hydroxyethyl acrylate;
Perhaps, under the effect of radical initiator, the compound of formula IV structure carries out the first step reaction with the water-soluble monomer that forms chain link C, carries out the second step reaction with the monomer that contains two olefinic double bonds again, obtains the compound of formula II structure;
N among the formula IV formula IV has identical implication with n among the formula II,
The water-soluble monomer of described formation chain link C is methacrylic acid, Methacrylamide or hydroxyethyl methylacrylate.
Wherein, the synthetic method of the compound shown in the formula III structure is reported by (Ferguson C J., Hughes R J., the Macromolecules such as Nguyen D., 2005,38,2191～2204.) such as Ferguson; Wherein, the synthetic method of the compound shown in the formula IV structure is reported by (Lai J T., Filla D., Shea R.Macromolecules, 2002,35,6754～6756.) such as Lai.
The described monomer that contains two olefinic double bonds is the compound of structure shown in formula 15, formula 16, formula 17, formula 18, formula 19, formula 20 or the formula 21:
The described monomer that contains two olefinic double bonds can be prepared by existing technology, suc as formula 15,16,19, the monomer that contains two olefinic double bonds of structure shown in 20 and 21 is respectively according to (Aoshima S. such as Aoshima S, Hasegawa O., Higashimura T.Polymer Bulletin, 1985,14,417～423.), (the Ruckenstein E. such as Ruckenstein E, Zhang H M.Polymer Bulletin, 2001,47,113～119.), (the Zhang H M. such as Zhang, Ruckenstein E.Macromolecules, 1999,32,5495～5500.), (the Dong Z M. such as Dong Z M, Liu X H., Lin Y., Li Y S.JPolym Sci Part A:Polym Chem 2008,46,6023～6034.) and (the Ma J. such as Ma J, Cheng C., Sun G R., Wooley K L.Macromolecules, 2008,41,9080～9089.) method of reporting prepares, wherein, " F " in the monomer that contains two olefinic double bonds of structure shown in the formula 21 is the halogeno-group fluorin radical, has arbitrariness in the replacement of phenyl ring.The monomer that contains two olefinic double bonds shown in formula 17 and 18 structures can be selected the commercially available prod, as can be all available from lark prestige Science and Technology Ltd..
In order to obtain better invention effect, the present invention is carried out further preferred:
The reaction conditions of described the first step reaction: reaction medium is organic solvent, and temperature of reaction is 50 ℃～90 ℃, and the reaction times is 10h～25h.
The reaction conditions of described second step reaction: reaction medium is organic solvent, and temperature of reaction is 70 ℃～90 ℃, and the reaction times is 8h～18h.
Described organic solvent is dioxane, dimethyl formamide or 2-butanone.
Described radical initiator is azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline.
The described application of trithiocarbonate compound, its in the preparation polymer microballoon that contains vinyl.
Described application may further comprise the steps:
The trithiocarbonate compound, its that will contain vinyl is added to the water, and forms the solution of the trithiocarbonate compound, its that contains vinyl;
Oil-soluble monomer is joined in the solution of the trithiocarbonate compound, its that contains vinyl, under the condition of nitrogen protection, add initiator at 60 ℃～80 ℃ reaction 5h～10h, obtain the emulsus dispersion liquid of the polymer microballoon of surface enrichment vinyl, in the emulsus dispersion liquid, the diameter of polymer microballoon is 50nm～500nm;
The described trithiocarbonate compound, its that contains vinyl, water, oil-soluble monomer three's mass ratio is 1: 40～200: 8～50.
The present invention contains the amphiphilic structure that the trithiocarbonate compound, its of vinyl has hydrophilic/lipophilic, and vinyl is between the hydrophilic/lipophilic segment.When the preparation polymer microballoon, contain emulsion homopolymerization or the copolyreaction of the trithiocarbonate compound, its control oil-soluble monomer of vinyl, owing to contain in the trithiocarbonate compound, its of vinyl the difference on pair key reactivity ratios in the two keys and oil-soluble monomer (containing the activity of the concentration of trithiocarbonate compound, its medium vinyl of vinyl and polyreaction far below the vinyl in the oil-soluble monomer), the former is kept in letex polymerization, and be defined to water-oil interface, and microballoon interpolymer chain still is linear structure.By regulating the number of trithiocarbonic acid ester molecule medium vinyl, the vinyl concentration on polymer microballoon surface changes thereupon.And when sequentially adding comonomer, the polymer chain that forms microballoon also can form block structure.
Described initiator is ammonium persulphate, Potassium Persulphate or azo dicyano valeric acid.
Described oil-soluble monomer is a kind of or two or more in vinylbenzene, methyl acrylate, ethyl propenoate, n-butyl acrylate, tert-butyl acrylic ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, dodecylacrylate, alpha-methyl styrene, isobornyl acrylate, Vinyl toluene, t-butyl styrene, the Vinylstyrene.
When the preparation polymer microballoon, need not additionally to add emulsifying agent, but also can add anionic emulsifier: sodium lauryl sulphate or Sodium dodecylbenzene sulfonate, nonionic emulsifier: fatty alcohol-polyoxyethylene ether such as the trade mark are the compound of Brij30, Brij35 or Brij56 and above-mentioned anionic emulsifier and nonionic emulsifier.
Compared with prior art, the present invention has following advantage:
The characteristics such as that the preparation method that the present invention contains the trithiocarbonate compound, its of vinyl has is simple, mild condition, workable, favorable reproducibility.
The trithiocarbonate compound, its that the present invention contains vinyl has amphiphilic structure, can be used as emulsifying agent and use in letex polymerization, by linking to each other with polymer chain, has greatly improved the dispersion stabilization of emulsion; Because vinyl is positioned between oleophylic/hydrophilic segment, therefore, its aggregation structure on the polymer microballoon surface belongs to the thermodynamically metastable fixed structure; The method for preparing polymer microballoon adopts letex polymerization, and reaction conditions is gentle, take water as dispersion medium, and environmental friendliness; Owing to the vinyl number in the trithiocarbonate compound, its that contains vinyl is easy to regulate, therefore, the vinyl concentration on polymer microballoon surface also is easy to regulate; Owing to the difference on two key reactivity ratios in two keys and the oil-soluble monomer in the trithiocarbonate compound, its that contains vinyl, the former is kept in letex polymerization, and polymer microballoon interpolymer chain still is linear structure; Contain the trithiocarbonate compound, its controllable poles monomer of vinyl and the polyreaction of non-polar monomer, the suitable monomers scope is wide, and the polarity of the microballoon interpolymer chain that therefore obtains, the composition of polymer chain and sequential structure are easy to regulate; During polyreaction, by adding emulsifying agent and changing the size of the conveniently adjusted microballoon of concentration of emulsifying agent.This method that contains trithiocarbonate compound, its, the polymer microballoon of vinyl and prepare polymer microballoon has a good application prospect.
Description of drawings
Fig. 1 is nuclear-magnetism (NMR) the resonance spectrogram of the trithiocarbonate compound, its that contains vinyl that obtains in the embodiment of the invention 1;
Fig. 2 is nuclear-magnetism (NMR) the resonance spectrogram of the trithiocarbonate compound, its that contains vinyl that obtains in the embodiment of the invention 3;
Fig. 3 is nuclear-magnetism (NMR) the resonance spectrogram of the polystyrene microsphere of the surface enrichment vinyl that obtains in the application examples 1 of the present invention;
Fig. 4 is transmission electron microscope (TEM) photo of the polystyrene microsphere of the surface enrichment vinyl that obtains in the application examples 1 of the present invention;
Fig. 5 is the molecular weight distribution curve of the polystyrene microsphere of the surface enrichment vinyl that obtains in the application examples 1 of the present invention;
Fig. 6 is transmission electron microscope (TEM) photo of the polystyrene-b-butyl polyacrylate microballoon of the surface enrichment vinyl that obtains in the application examples 2 of the present invention;
Fig. 7 is transmission electron microscope (TEM) photo of the polystyrene microsphere of the surface enrichment vinyl that obtains in the application examples 3 of the present invention.
Embodiment
Embodiment 1
(1) preparation of 2-(dodecyl trithiocarbonic acid ester group) propionic acid
10 gram sodium hydroxide, 5.4 gram 4-propyl bromides and 10 gram water are at room temperature mixed, join in three mouthfuls of round-bottomed flasks that 500mL is added with stirrer and stir, logical nitrogen is protected reaction system.The 60mL Dodecyl Mercaptan is dropwise joined in three mouthfuls of round-bottomed flasks with syringe, dropwise rear continuation reaction 0.5 hour; Then 200mL acetone is added drop-wise in the flask in 1.5 hours by constant pressure funnel, produces along with the carrying out that drips can observe the adularescent floss, and increase gradually, dropwise rear maintenance reaction 0.5 hour, then carry out ice bath.Temperature of charge drops to after 0 ℃ fully in the question response device, with syringe 15mL dithiocarbonic anhydride is added drop-wise in the flask, at this moment reaction solution yellowing turbid solution.After keeping reacting 0.5 hour, drip 38.42 gram 2 bromopropionic acids, this moment, yellow floss began dissolving, until the yellowing clear solution.Reaction flask is taken out from ice bath, stirring reaction 12 hours at room temperature then, product is viscous liquid.Under the nitrogen protection, slowly pour 100mL 2M (mol/L) hydrochloric acid into, this moment, product was separated out, and was yellow chip solid, collected product, and with pure washing two to three times to remove unnecessary acid, obtain thick product.With normal hexane recrystallization three times of thick product.Collect yellow tabular crystal, be pure 2-(dodecyl trithiocarbonic acid ester group) propionic acid.
(2) contain the preparation of the trithiocarbonate compound, its of vinyl
Be equipped with in 500mL and drop into following reagent in the there-necked flask of reflux condensing tube, nitrogen inlet and charging opening: yellow tabular crystal 1.50 grams of preparation, azo dicyano valeric acid 0.12 gram and vinylformic acid 9.22 grams in dioxane 25 grams, the step (1).Logical high-purity (purity the is 99.99%) nitrogen of said apparatus immersed in 80 ℃ of water-baths after 1 hour, after 8 hours, obtained intermediate product; Continuation adds the monomer that contains two olefinic double bonds 4.82 grams of dioxane 5 grams, azo dicyano valeric acid 0.12 gram, formula 20 structures in the there-necked flask, continues reaction cooling after 12 hours in 80 ℃ of water-baths, and stopped reaction obtains product.Product is poured in the hexanaphthene of 200mL, with Büchner funnel collecting precipitation thing.The throw out that collection is obtained spends the night 40 ℃ of lower vacuum-dryings, obtains containing the trithiocarbonate compound, its of vinyl.Product structure is with nmr analysis, solvent is deuterated dimethyl sulfoxide, the kurtosis of nmr spectrum and characteristic peak and chemical shift as shown in Figure 1, formula 20 for the structure of the structural formula of the monomer that contains two olefinic double bonds, the synthetic trithiocarbonate compound, its that contains vinyl that obtains suc as formula shown in the V:
(1) preparation of 2-(dodecyl trithiocarbonic acid ester group) propionic acid is with embodiment 1.
(2) contain the preparation of the trithiocarbonate compound, its of vinyl
Be equipped with in 250mL and drop into following reagent in the there-necked flask of reflux condensing tube, nitrogen inlet and charging opening: prepare 2-(dodecyl trithiocarbonic acid ester group) propionic acid 0.3 gram, azo dicyano valeric acid 0.025 gram and N in dioxane 5 grams, the step (1), N '-DMAA 4.0 grams.Logical high-purity (purity the is 99.99%) nitrogen of said apparatus immersed in 70 ℃ of water-baths after 1 hour, after 10 hours, obtained intermediate product; Continuation adds the monomer that contains two olefinic double bonds 0.97 gram of dioxane 1 gram, azo dicyano valeric acid 0.025 gram, formula 20 structures in the there-necked flask, continues reaction cooling after 12 hours in 80 ℃ of water-baths, and stopped reaction obtains product.Product is poured in the hexanaphthene of 100mL, with Büchner funnel collecting precipitation thing.The throw out that collection is obtained spends the night 40 ℃ of lower vacuum-dryings, product structure is with nmr analysis, solvent is that deuterium is for water, characterizing the trithiocarbonate compound, its that contains vinyl that obtains through nmr spectrum is the compound of formula VI structure, and the monomer that contains two olefinic double bonds of formula 20 structures is specific as follows with the formula VI structure that the trithiocarbonate compound, its that contains vinyl is determined:
(1) the isobutyric preparation of 2-(dodecyl trithiocarbonic acid ester group)
The mercaptan of 202.4 grams, the methyl tricapryl ammonium chlorides of 16.14 grams and the acetone of 482.06 grams are joined in the there-necked flask with the backflow condensing works, and bath temperature is 10 ℃, and magnetic stirs, logical nitrogen, deoxygenation 20 minutes; Dropwise add the aqueous sodium hydroxide solution (mass concentration is 50%) of 40 grams, added in 20 minutes, continue reaction 15 minutes; Dropwise add the dithiocarbonic anhydride of 76.1 grams and the acetone mixing solutionss of 98.74 grams, after adding in 20 minutes, continue to react 10 minutes; Then the trichloromethane that adds 179.07 grams dropwise adds 200 aqueous sodium hydroxide solutions (mass concentration is 50%) that restrain, and dropwises stirring reaction 12 hours in 0.5 hour; Add 1500 gram deionized waters, then add 109.5 gram concentrated hydrochloric acids (mass concentration is about 37%); Logical nitrogen, vigorous stirring is removed unnecessary acetone; The Büchner funnel suction filtration extracts solid; Add the Virahol dissolved solids, remove by filter insoluble material, dry concentrated aqueous isopropanol is collected the solid matter that obtains; Gained solid normal hexane recrystallization obtains containing the yellow crystals of trithiocarbonic acid ester group, is 2-(dodecyl trithiocarbonic acid ester group) isopropylformic acid.
(2) contain the preparation of the trithiocarbonate compound, its of vinyl
Be equipped with in 500mL and drop into following reagent in the there-necked flask of reflux condensing tube, nitrogen inlet and charging opening: 2-(dodecyl trithiocarbonic acid ester group) isopropylformic acid 1.56 grams of preparation, azo dicyano valeric acid 0.12 gram and methacrylic acid 8.0 grams in dioxane 25 grams, the step (1).Logical high-purity (purity the is 99.99%) nitrogen of said apparatus immersed in 80 ℃ of water-baths after 1 hour, after 8 hours, obtained intermediate product; Continuation adds dioxane 5 grams in there-necked flask, azo dicyano valeric acid 0.12 gram, and the monomer that contains two olefinic double bonds 5.0 grams of formula 21 structures continue reaction cooling after 12 hours in 80 ℃ of water-baths, and stopped reaction obtains product.Product is poured in the hexanaphthene of 200mL, with Büchner funnel collecting precipitation thing.The throw out that collection is obtained spends the night 40 ℃ of lower vacuum-dryings, product structure is with nmr analysis, solvent is deuterated dimethyl sulfoxide, nmr spectrum as shown in Figure 2, the monomer that contains two olefinic double bonds of formula 21 structures and the trithiocarbonate compound, its that contains vinyl that obtains determine that finally formula VII structure is specific as follows:
Application examples 1 (preparation of the polystyrene microsphere of surface enrichment vinyl)
Get the trithiocarbonate compound, its that contains vinyl 0.77 gram that embodiment 1 obtains, be dissolved in the 40 gram water, the solution immigration is equipped with in the 250mL four-hole bottle of reflux condensing tube, nitrogen inlet, stirring arm and thief hole, in four-hole bottle, continues to add vinylbenzene 10 grams.To install and immerse in 70 ℃ of water-baths, logical nitrogen deoxygenation added the aqueous solution 1.0 grams that are dissolved with 0.011 gram Potassium Persulphate, initiated polymerization after 0.5 hour.Sampling in the middle of the reaction process, afterreaction finished in 5 hours, and cooling discharge obtains containing the emulsus dispersion liquid of the polystyrene microsphere of surface enrichment vinyl.Vinyl in the polymerisate is with nmr analysis, and product structure is with nmr analysis, nmr spectrum as shown in Figure 3, the solvent during test is deuterochloroform; Particle is through perosmic anhydride (OsO
4) dyeing, and with perspective Electronic Speculum (TEM) sign, have an X-rayed Electronic Speculum figure as shown in Figure 4, the median size that can get particle after the statistics is 90nm; The molecular weight of polymkeric substance is take gel permeation chromatography as 43000g/mol, and dispersion index is 1.3, and molecular weight distribution curve figure as shown in Figure 5.
Application examples 2 (preparation of the polystyrene of surface enrichment vinyl-b-butyl polyacrylate microballoon)
Get the trithiocarbonate compound, its that contains vinyl 0.77 gram that embodiment 1 obtains, be dissolved in the 35 gram water, the solution immigration is equipped with in the 250mL four-hole bottle of reflux condensing tube, nitrogen inlet, stirring arm and thief hole, in four-hole bottle, continues to add n-butyl acrylate 10 grams.To install and immerse in 70 ℃ of water-baths, logical nitrogen deoxygenation added the aqueous solution 1.0 grams that are dissolved with 0.015 gram Potassium Persulphate, initiated polymerization after 0.5 hour.Sampling in the middle of the reaction process splashes into 5.0 gram vinylbenzene in 1.5 hours backward reactors, obtain containing the emulsus dispersion liquid of the polystyrene of surface enrichment vinyl-b-butyl polyacrylate microballoon.The structure of polymerisate characterizes with nmr analysis and obtains; Molecular weight and distribution thereof are with gel permeation chromatography; Latex particle dyes through perosmic anhydride, and characterizes with TEM, the TEM photo as shown in Figure 6, the median size that can get particle after the statistics is 80nm.
Application examples 3 (preparation of the polystyrene microsphere of surface enrichment vinyl)
Get the trithiocarbonate compound, its that contains vinyl 0.8 gram that embodiment 3 obtains, be dissolved in the 40 gram water, the solution immigration is equipped with in the 250mL four-hole bottle of reflux condensing tube, nitrogen inlet, stirring arm and thief hole, in four-hole bottle, continues to add vinylbenzene 10 grams.To install and immerse in 80 ℃ of water-baths, logical nitrogen deoxygenation added the aqueous solution 1.0 grams that are dissolved with 0.01 gram ammonium persulphate, initiated polymerization after 0.5 hour.Sampling in the middle of the reaction process, afterreaction finished in 5 hours, cooling discharge.The structure of polymerisate characterizes with nmr analysis and obtains; Particle is through OsO
4Dyeing, and characterize with transmission electron microscope, photo as shown in Figure 7, the median size that can get particle after the statistics is 100nm.
Claims (9)
1. trithiocarbonate compound, its that contains vinyl is the compound of formula I structure or formula II structure:
Wherein, y is that 1～5, x is that 10～50, z is that 10～50, n is 4～12, and x, y, z and n are integer;
2. the preparation method who contains the trithiocarbonate compound, its of vinyl according to claim 1 is characterized in that, may further comprise the steps:
Under the effect of radical initiator, the compound of formula III structure carries out the first step reaction with the water-soluble monomer that forms chain link A, carries out the second step reaction with the monomer that contains two olefinic double bonds again, obtains the compound of formula I structure;
The water-soluble monomer of described formation chain link A is vinylformic acid, N,N-DMAA, acrylamide or Hydroxyethyl acrylate;
Perhaps, under the effect of radical initiator, the compound of formula IV structure carries out the first step reaction with the water-soluble monomer that forms chain link C, carries out the second step reaction with the monomer that contains two olefinic double bonds again, obtains the compound of formula II structure;
N among the formula IV formula IV has identical implication with n among the formula II,
The water-soluble monomer of described formation chain link C is methacrylic acid, Methacrylamide or hydroxyethyl methylacrylate;
The described monomer that contains two olefinic double bonds is the compound of structure shown in formula 15, formula 16, formula 17, formula 18, formula 19, formula 20 or the formula 21:
3. the preparation method who contains the trithiocarbonate compound, its of vinyl according to claim 2 is characterized in that, the reaction conditions of described the first step reaction: reaction medium is organic solvent, and temperature of reaction is 50 ℃～90 ℃, and the reaction times is 10h～25h.
4. the preparation method who contains the trithiocarbonate compound, its of vinyl according to claim 2 is characterized in that, the reaction conditions of described second step reaction: reaction medium is organic solvent, and temperature of reaction is 70 ℃～90 ℃, and the reaction times is 8h～18h.
5. according to claim 3 or the 4 described preparation methods that contain the trithiocarbonate compound, its of vinyl, it is characterized in that described organic solvent is dioxane, dimethyl formamide or 2-butanone.
6. the preparation method who contains the trithiocarbonate compound, its of vinyl according to claim 2 is characterized in that, described radical initiator is azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline.
7. the application of trithiocarbonate compound, its in the preparation polymer microballoon that contains vinyl according to claim 1.
8. application according to claim 7 is characterized in that, may further comprise the steps:
The trithiocarbonate compound, its that will contain vinyl is added to the water, and forms the solution of the trithiocarbonate compound, its that contains vinyl;
Oil-soluble monomer is joined in the solution of the trithiocarbonate compound, its that contains vinyl, under the condition of nitrogen protection, add initiator at 60 ℃～80 ℃ reaction 5h～10h, obtain the polymer microballoon of surface enrichment vinyl;
The described trithiocarbonate compound, its that contains vinyl, water, oil-soluble monomer three's mass ratio is 1:40～200:8～50;
Described oil-soluble monomer is a kind of or two or more in vinylbenzene, methyl acrylate, ethyl propenoate, n-butyl acrylate, tert-butyl acrylic ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, dodecylacrylate, alpha-methyl styrene, isobornyl acrylate, Vinyl toluene, t-butyl styrene, the Vinylstyrene.
9. application according to claim 8 is characterized in that, described initiator is ammonium persulphate, Potassium Persulphate or azo dicyano valeric acid.
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| CN102746476B (en) * | 2012-06-18 | 2014-04-23 | 浙江理工大学 | Trithiocarbonate compound containing epoxy group, preparation method and application thereof |
| CN102746475B (en) * | 2012-06-18 | 2014-04-23 | 浙江理工大学 | preparation method and application of trithiocarbonic acid ester compound containing isocyanate group |
| CN103044697B (en) * | 2012-12-10 | 2014-12-17 | 浙江理工大学 | Method for preparing microphase structural latex film |
| CN104693385B (en) * | 2015-02-12 | 2017-03-01 | 浙江理工大学 | Trithio ester compounds containing quantitative sulfuric acid ester ethyl sulfone group and its synthetic method and application |
| CN106167993B (en) * | 2016-08-05 | 2018-07-20 | 青岛大学 | A kind of preparation of cationic copper phthalocia- nine pigment and the application process in cotton fabric dyeing process |
| CN108589344A (en) * | 2018-05-18 | 2018-09-28 | 杭州海维特化工科技有限公司 | A kind of rub resistance type structure used for textiles is added lustre to ink and preparation method thereof |
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