CN102382230A - 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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- CN102382230A CN102382230A CN2011102287661A CN201110228766A CN102382230A CN 102382230 A CN102382230 A CN 102382230A CN 2011102287661 A CN2011102287661 A CN 2011102287661A CN 201110228766 A CN201110228766 A CN 201110228766A CN 102382230 A CN102382230 A CN 102382230A
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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 trithiocarbonate compound field, be specifically related to a kind of trithiocarbonic acid ester cpds that contains vinyl.
Background technology
Research shows that the performance of macromolecular material also is decided by the structure of macromolecular chain to a great extent except by the chemical constitution decision.Preparation has the macromolecular material of accurate molecular chain structure, thus on molecular level the performance of control material, to performance that improves macromolecular material and the function that increases macromolecular material, have crucial meaning.Wherein, The chemical reaction that the specific location functional group is participated 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 one type of compound with high chain transfer activity, can be used for the structure of controlling polymers 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, the chemical reaction of multiple mechanism such as chain polymerization that can carry out causing such as addition reaction, radical and coupling reaction; And realize easily conversion to sulfydryl, epoxide group isoreactivity group, and 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., JAm Chem Soc such as Sheiko S.S., 2007,129,11350～11351.; Paris R., 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 through two keys participations; Not only can carry out functional modification to the surface of microballoon; More can strengthen the physical strength of the mould material that makes up by polymer microballoon, improve its application performance in coating and printing and dyeing processing through striding the coupling reaction between the two keys of particle.
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 is participated in.For example: Korthals etc. are monomer with the divinyl, through homopolymerization, have prepared and contain 1 of vinyl; 2-polyhutadiene microballoon (Korthals B.B., Morant-Minana M.C., Macromolecules such as Schmid M.; 2010,43,8071～8078.); (Goldmann A., Walther A., Macromolecules such as Nebhani L., 2009 such as Goldmann A S; 42,3707～3714.) and (van Berkel K.Y., Piekarski A.M. such as Hawker; Macromolecules such as Kierstead P.H., 2009,42; 1425～1427.), cause Vinylstyrene equal polymerization and and 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 the distribution of vinyl in the 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 is uniform distribution in polymer microballoon, can't make vinyl be enriched in the surface of polymer microballoon.Through semi-continuous polymerzation technology, in polymerization reaction late stage, drip the bi-vinyl monomer, can vinyl 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; Participate in polyreaction and cause the crosslinked of microballoon interpolymer chain owing to the bi-vinyl monomer, the polymkeric substance that causes generation is insoluble also molten, thereby when making film forming; The difficulty of the polymer chain phase mutual diffusion between microballoon is very big, is difficult to obtain the mould material of continuous structure.These shortcomings have restricted the promotion and application of new membrane material to a great extent.
Summary of the invention
The invention provides a kind of trithiocarbonic acid ester cpds that contains vinyl, have hydrophilic and lipophilic amphiphilic structure, wherein, vinyl ranks between the hydrophilic segment of compound and oleophylic segment.
A kind of trithiocarbonic acid ester cpds that contains vinyl is the compound of formula I structure or formula II structure:
Wherein, y is 1～5, and x is 10～50, and z is 10～50, and n is 4～12, and x, y, z and n are integer;
is the structure shown in formula 1, formula 2, formula 3 or the formula 4:
is the structure shown in formula 12, formula 13 or the formula 14:
Wherein,
and
obtained through polyreaction by water-soluble monomer, constitutes the hydrophilic segment of compound;
obtained through polyreaction by the monomer (like the bi-vinyl monomer) that contains two olefinic double bonds; Because the polymerization activity of two vinyl does not wait; In the polyreaction, active more weak vinyl is able to keep.
The present invention also provides a kind of preparation method who contains the trithiocarbonic acid ester cpds of vinyl, has characteristics such as preparation is simple, workable, favorable reproducibility.
The described preparation method who contains the trithiocarbonic acid ester cpds of vinyl may further comprise the steps:
Under action of free 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 reaction of second step 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, acrylic amide or Hydroxyethyl acrylate;
Perhaps, under action of free 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 reaction of second step 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 methylacrylic acid, USAF RH-1 or Rocryl 400.
Wherein, the compound method of the compound shown in the formula III structure is reported by (Ferguson C J., Hughes R J., Macromolecules such as Nguyen D., 2005,38,2191～2204.) such as Ferguson; Wherein, the compound 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 prepare through existing technology, accordings to (Aoshima S., Hasegawa O., Higashimura T.Polymer Bulletin such as Aoshima S respectively suc as formula the monomer that contains two olefinic double bonds of structure shown in 15,16,19,20 and 21; 1985,14,417～423.), (Ruckenstein E., Zhang H M.Polymer Bulletin such as Ruckenstein E; 2001,47,113～119.), (Zhang H M., Ruckenstein E.Macromolecules such as Zhang; 1999,32,5495～5500.), (Dong Z M., Liu X H. such as Dong Z M; Lin Y., Li Y S.JPolym Sci Part A:Polym Chem 2008,46,6023～6034.) and (Ma J. such as Ma J; Cheng C., Sun G R., Wooley K L.Macromolecules; 2008,41,9080～9089.) institute's reported method 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 for use, as can be all available from lark prestige Science and Technology Ltd..
In order better to be invented effect, the present invention is carried out further preferred:
The reaction conditions of described the first step reaction: reaction medium is an 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 an organic solvent, and temperature of reaction is 70 ℃～90 ℃, and the reaction times is 8h～18h.
Described organic solvent is dioxane, N or 2-butanone.
Described radical initiator is azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline.
The described application of trithiocarbonic acid ester cpds in the preparation polymer microballoon that contains vinyl.
Described application may further comprise the steps:
The trithiocarbonic acid ester cpds that will contain vinyl is added to the water, and forms the solution of the trithiocarbonic acid ester cpds that contains vinyl;
Oil-soluble monomer is joined in the solution of the trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds of vinyl has hydrophilic, and vinyl is between the hydrophilic segment.When the preparation polymer microballoon; Contain the emulsion homopolymerization or the copolyreaction of the trithiocarbonic acid ester cpds control oil-soluble monomer of vinyl; Owing to contain in the trithiocarbonic acid ester cpds of vinyl the difference on pair key reactivity ratios in the two keys and oil-soluble monomer (activity of concentration and polyreaction that contains vinyl in the trithiocarbonic acid ester cpds of vinyl is far below the vinyl in the oil-soluble monomer); The former is able to keep in letex polymerization; And be defined to water-oil interface, and microballoon interpolymer chain still is a linear structure.Through regulating the number of vinyl in the trithiocarbonic acid ester molecule, the vinyl concentration on polymer microballoon surface changes thereupon.And when adding comonomer in proper order, the polymer chain of forming 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 the special butyl ester of vinylbenzene, methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid, TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, dodecylacrylate, alpha-methyl styrene, IBOA, Vinyl toluene, t-butyl styrene, the Vinylstyrene.
When the preparation polymer microballoon; Need not extra interpolation emulsifying agent; But also can add anionic emulsifier: sodium lauryl sulphate or X 2073, nonionic emulsifier: the AEO 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:
Characteristics such as that the preparation method that the present invention contains the trithiocarbonic acid ester cpds of vinyl has is simple, mild condition, workable, favorable reproducibility.
The trithiocarbonic acid ester cpds that the present invention contains vinyl has amphiphilic structure, in letex polymerization, can be used as emulsifying agent and uses, and through linking to each other with polymer chain, has improved the dispersion stabilization of emulsion greatly; Because vinyl is positioned between oleophylic/hydrophilic segment, therefore, its aggregated(particle)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, is dispersion medium with water, environmental friendliness; Owing to the vinyl number in the trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds that contains vinyl, the former is able to keep in letex polymerization, and polymer microballoon interpolymer chain still is a linear structure; Contain the trithiocarbonic acid ester cpds controllable poles property 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, through adding emulsifying agent and changing the size of the conveniently adjusted microballoon of concentration of emulsifying agent.This method that contains trithiocarbonic acid ester cpds, 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 trithiocarbonic acid ester cpds that contains vinyl that obtains in the embodiment of the invention 1;
Fig. 2 is nuclear-magnetism (NMR) the resonance spectrogram of the trithiocarbonic acid ester cpds 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 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 PS-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 500mL and be added with in three mouthfuls of round-bottomed flasks of 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 continued reaction 0.5 hour; Then 200mL acetone is added drop-wise in the flask in 1.5 hours through constant pressure funnel, produces along with the carrying out that drips can observe the adularescent floss, and increase gradually, dropwise the back and keep reaction 0.5 hour, carry out ice bath then.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 thick product with normal hexane recrystallization three times.Collect yellow tabular crystal, be pure 2-(dodecyl trithiocarbonic acid ester group) propionic acid.
(2) contain the preparation of the trithiocarbonic acid ester cpds 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 there-necked flask, in 80 ℃ of water-baths, continue reaction cooling after 12 hours, and stopped reaction obtains product.Product is poured in the hexanaphthene of 200mL, with B collecting precipitation thing.The throw out that collection is obtained obtains containing the trithiocarbonic acid ester cpds of vinyl 40 ℃ of following drying under vacuum overnight.Product structure is with nmr analysis; Solvent is a deuterated dimethyl sulfoxide; The kurtosis and the chemical shift of nmr spectrum and characteristic peak are as shown in Figure 1, formula 20 for the structure of the monomeric structural formula that contains two olefinic double bonds, the synthetic trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds 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 there-necked flask, in 80 ℃ of water-baths, continue reaction cooling after 12 hours, and stopped reaction obtains product.Product is poured in the hexanaphthene of 100mL, with B collecting precipitation thing.The throw out that collection is obtained is 40 ℃ of following drying under vacuum overnight; Product structure is with nmr analysis; Solvent is that deuterium is for water; Characterizing the trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds that contains vinyl is confirmed:
(1) the isobutyric preparation of 2-(dodecyl trithiocarbonic acid ester group)
The mercaptan of 202.4 grams, the methyl trioctylphosphine ammonium chloride of 16.14 grams and the acetone of 482.06 grams are joined in the there-necked flask of taking back the stream 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 solutions of 98.74 grams, after adding in 20 minutes, continue to react 10 minutes; The trichloromethane that adds 179.07 grams dropwise adds the aqueous sodium hydroxide solution (mass concentration is 50%) of 200 grams then, dropwises stirring reaction 12 hours in 0.5 hour; Add 1500 gram deionized waters, add 109.5 gram concentrated hydrochloric acids (mass concentration is about 37%) then; Logical nitrogen, vigorous stirring is removed unnecessary acetone; The B suction filtration extracts solid; Add the Virahol dissolved solids, remove by filter insoluble material, the dry aqueous isopropanol that concentrates is collected the solid matter that obtains; The gained solid is used the 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 trithiocarbonic acid ester cpds 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 methylacrylic 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 B collecting precipitation thing.The throw out that collection is obtained is 40 ℃ of following drying under vacuum overnight; Product structure is with nmr analysis; Solvent is a deuterated dimethyl sulfoxide; Nmr spectrum is as shown in Figure 2, and the monomer that contains two olefinic double bonds of formula 21 structures confirms finally that with the trithiocarbonic acid ester cpds that contains vinyl that obtains formula VII structure is specific as follows:
Application examples 1 (preparation of the polystyrene microsphere of surface enrichment vinyl)
Get the trithiocarbonic acid ester cpds 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, and nmr spectrum is as shown in Figure 3, and the solvent during test is a deuterochloroform; Particle is through perosmic anhydride (OsO
4) dyeing, and with perspective Electronic Speculum (TEM) sign, figure is as shown in Figure 4 for the perspective Electronic Speculum, the median size that can get particle after the statistics is 90nm; The molecular weight of polymkeric substance is 43000g/mol with the gel permeation chromatography, and dispersion index is 1.3, and molecular-weight-distribution figure is as shown in Figure 5.
Application examples 2 (preparation of the PS of surface enrichment vinyl-b-butyl polyacrylate microballoon)
Get the trithiocarbonic acid ester cpds 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 reactor drum after 1.5 hours, obtain containing the emulsus dispersion liquid of the PS-b-butyl polyacrylate microballoon of surface enrichment vinyl.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, and the TEM photo is as shown in Figure 6, and 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 trithiocarbonic acid ester cpds 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 with the transmission electron microscope sign, photo is as shown in Figure 7, the median size that can get particle after the statistics is 100nm.
Claims (10)
1. trithiocarbonic acid ester cpds that contains vinyl is the compound of formula I structure or formula II structure:
Wherein, y is 1～5, and x is 10～50, and z is 10～50, and n is 4～12, and x, y, z and n are integer;
is the structure shown in formula 12, formula 13 or the formula 14:
2. the preparation method who contains the trithiocarbonic acid ester cpds of vinyl according to claim 1 is characterized in that, may further comprise the steps:
Under action of free 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 reaction of second step 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, acrylic amide or Hydroxyethyl acrylate;
Perhaps, under action of free 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 reaction of second step 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 methylacrylic acid, USAF RH-1 or Rocryl 400;
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 trithiocarbonic acid ester cpds of vinyl according to claim 2 is characterized in that, the reaction conditions of described the first step reaction: reaction medium is an organic solvent, and temperature of reaction is 50 ℃～90 ℃, and the reaction times is 10h～25h.
4. the preparation method who contains the trithiocarbonic acid ester cpds of vinyl according to claim 2 is characterized in that, the reaction conditions of described second step reaction: reaction medium is an 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 preparing methods that contain the trithiocarbonic acid ester cpds of vinyl, it is characterized in that described organic solvent is dioxane, N or 2-butanone.
6. the preparation method who contains the trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds 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 trithiocarbonic acid ester cpds that will contain vinyl is added to the water, and forms the solution of the trithiocarbonic acid ester cpds that contains vinyl;
Oil-soluble monomer is joined in the solution of the trithiocarbonic acid ester cpds that contains vinyl, under the condition of nitrogen protection, add initiator, obtain the polymer microballoon of surface enrichment vinyl at 60 ℃～80 ℃ reaction 5h～10h;
The described trithiocarbonic acid ester cpds that contains vinyl, water, oil-soluble monomer three's mass ratio is 1: 40～200: 8～50.
9. application according to claim 8 is characterized in that, described initiator is ammonium persulphate, Potassium Persulphate or azo dicyano valeric acid.
10. application according to claim 8; It is characterized in that described oil-soluble monomer is a kind of or two or more in the special butyl ester of vinylbenzene, methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid, TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, dodecylacrylate, alpha-methyl styrene, IBOA, Vinyl toluene, t-butyl styrene, the Vinylstyrene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746476A (en) * | 2012-06-18 | 2012-10-24 | 浙江理工大学 | Trithiocarbonate compound containing epoxy group, preparation method and application thereof |
| CN102746475A (en) * | 2012-06-18 | 2012-10-24 | 浙江理工大学 | preparation method and application of trithiocarbonic acid ester compound containing isocyanate group |
| CN103044697A (en) * | 2012-12-10 | 2013-04-17 | 浙江理工大学 | Method for preparing microphase structural latex film |
| CN104693385A (en) * | 2015-02-12 | 2015-06-10 | 浙江理工大学 | Trithio ester compounds containing quantitative sulfate ethyl sulfone group, and synthesis method and application thereof |
| CN106167993A (en) * | 2016-08-05 | 2016-11-30 | 青岛大学 | The preparation of a kind 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63105013A (en) * | 1986-10-22 | 1988-05-10 | 日本油脂株式会社 | Carbonate resin |
| US20030232895A1 (en) * | 2002-04-22 | 2003-12-18 | Hossein Omidian | Hydrogels having enhanced elasticity and mechanical strength properties |
| JP3490436B2 (en) * | 1991-11-05 | 2004-01-26 | ボシュ・アンド・ロム・インコーポレイテッド | Novel UV-curable crosslinker useful in copolymerization |
| CN1527809A (en) * | 2001-05-22 | 2004-09-08 | �����ɷ� | Process for the preparation of 7-substituted 3-alkyl-3H-isobenzofuran-1-one derivatives |
| CN101559343A (en) * | 2009-04-16 | 2009-10-21 | 同济大学 | Method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique |
| CN101665513A (en) * | 2009-09-30 | 2010-03-10 | 中国科学技术大学苏州研究院 | Flame-retardant polystyrene/layered inorganic nanocomposite and preparation method thereof |
-
2011
- 2011-08-10 CN CN 201110228766 patent/CN102382230B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63105013A (en) * | 1986-10-22 | 1988-05-10 | 日本油脂株式会社 | Carbonate resin |
| JP3490436B2 (en) * | 1991-11-05 | 2004-01-26 | ボシュ・アンド・ロム・インコーポレイテッド | Novel UV-curable crosslinker useful in copolymerization |
| CN1527809A (en) * | 2001-05-22 | 2004-09-08 | �����ɷ� | Process for the preparation of 7-substituted 3-alkyl-3H-isobenzofuran-1-one derivatives |
| US20030232895A1 (en) * | 2002-04-22 | 2003-12-18 | Hossein Omidian | Hydrogels having enhanced elasticity and mechanical strength properties |
| CN101559343A (en) * | 2009-04-16 | 2009-10-21 | 同济大学 | Method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique |
| CN101665513A (en) * | 2009-09-30 | 2010-03-10 | 中国科学技术大学苏州研究院 | Flame-retardant polystyrene/layered inorganic nanocomposite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 冉蓉等: "三硫代碳酸酯引发的苯乙烯活性自由基光聚合", 《高分子材料科学与工程》, no. 06, 28 November 2006 (2006-11-28) * |
| 周晓静等: "三种硫代酯的合成和表征", 《苏州科技学院学报(自然科学版)》, no. 02, 15 June 2009 (2009-06-15) * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746476A (en) * | 2012-06-18 | 2012-10-24 | 浙江理工大学 | Trithiocarbonate compound containing epoxy group, preparation method and application thereof |
| CN102746475A (en) * | 2012-06-18 | 2012-10-24 | 浙江理工大学 | preparation method and application of trithiocarbonic acid ester compound containing isocyanate group |
| 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 |
| CN103044697A (en) * | 2012-12-10 | 2013-04-17 | 浙江理工大学 | Method for preparing microphase structural latex film |
| CN103044697B (en) * | 2012-12-10 | 2014-12-17 | 浙江理工大学 | Method for preparing microphase structural latex film |
| CN104693385A (en) * | 2015-02-12 | 2015-06-10 | 浙江理工大学 | Trithio ester compounds containing quantitative sulfate ethyl sulfone group, and synthesis method and application thereof |
| 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 |
| CN106167993A (en) * | 2016-08-05 | 2016-11-30 | 青岛大学 | The preparation of a kind 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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