CN101481438B - Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof - Google Patents

Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof Download PDF

Info

Publication number
CN101481438B
CN101481438B CN2009100255495A CN200910025549A CN101481438B CN 101481438 B CN101481438 B CN 101481438B CN 2009100255495 A CN2009100255495 A CN 2009100255495A CN 200910025549 A CN200910025549 A CN 200910025549A CN 101481438 B CN101481438 B CN 101481438B
Authority
CN
China
Prior art keywords
fluorine
emulsifying agent
monomer
preparation
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2009100255495A
Other languages
Chinese (zh)
Other versions
CN101481438A (en
Inventor
倪沛红
孙桂香
张明祖
朱秀林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN2009100255495A priority Critical patent/CN101481438B/en
Publication of CN101481438A publication Critical patent/CN101481438A/en
Application granted granted Critical
Publication of CN101481438B publication Critical patent/CN101481438B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a fluorine-containing macro-molecule emulsifying agent which is a comb-type random copolymer which consists of hydrophobic fluorine-containing monomers and hydrophilicity monomers; in the invention, conventional radical polymerization is adopted for obtaining the fluorine-containing macro-molecule emulsifying agent, the requirements of reaction conditions and devices are low and the reaction monomers are easily obtained, thus overcoming the disadvantages that methods such as active polymerization, and the like, are carried out under highly-demanding conditions in the prior art, and the cost is high. The reaction of the invention has rapid speed, and the conversion percent is high; at present, the conventional radical polymerization with low cost is still one of thesimplest and most convenient methods in the point of industrialized production and production cost reduction, therefore, the fluorine-containing macro-molecule emulsifying agent is easy for industrial application.

Description

Random copolymerization fluorine-containing macromole emulsifying agent and preparation method thereof
Technical field
The present invention relates to a kind of fluorine-containing macromole emulsifying agent, be specifically related to a kind ofly constitute the random copolymers of comb type, can be used as fluorine-containing macromole emulsifying agent and use by hydrophobicity fluorochemical monomer and hydrophilic monomer.
Background technology
Macromole emulsifying agent is a kind of amphipathic polymkeric substance.Amphipathic nature polyalcohol is defined as: have polymkeric substance hydrophobic and hydrophilic segment or group, hydrophilic segment or group can be ionics, also can be non-ionic types.For amphipathic nature polyalcohol, water is the good solvent of hydrophilic segment or group, is again the precipitation agent of hydrophobic segment.The hydrophobic part self-assembly to reduce they and the contacting of water, forms micella or bilayer structure; And hydrophilic segment stretches in the water.The advantage of macromole emulsifying agent is: as the high-molecular weight component, have the micelle-forming concentration lower than small-molecular emulsifier.Therefore, under the very rare condition of concentration, the surfactivity that they are still remained valid.Compared with low-molecular-weight tensio-active agent, macromole emulsifying agent can use in very wide scope.
Fluorine is the element of electronegativity maximum, because it has many special physicochemical character, therefore, fluorine-containing macromole emulsifying agent is compared with non-fluorine-containing macromole emulsifying agent, has higher surface energy, higher surface activity and stronger hydrophobicity, or the like.Fluoropolymer has premium propertiess such as resist chemical, heat-resisting, stable, hydrophobic, self-lubricating and electrical isolation.Because fluorochemicals is hydrophobic but also oleophobic not only, in solution, have from the character of arranging, make to contain fluoroalkyl and have and be the tendency that pectination is arranged outwardly, thereby the content that contains fluoroalkyl by control in coating just can obtain the not viscosity stabilized coating of low surface energy.Aspect biologic medical, fluorine-containing amphipathic nature polyalcohol has the effect of delivering oxygen and is suitable as the blood substitute, can also be in self-assembly in the solvent optionally, form the various micellas, stabilizing membrane, bimolecular tunic of structure exquisiteness etc.Supramolecular aggregation can be used as control drug release, gene delivery carrier.
In the prior art, mainly concentrate on activity/controllable polymerization technology about the preparation method's of fluorine-containing amphipathic multipolymer report, for example:
(1) people such as Busse k. utilizes the method for active anionic polymerization to synthesize the amphipathic multipolymer of methacrylic tert-butyl acrylate and methacrylic acid-2-(N-methyl perfluoro butyl sulfoamido) ethyl ester [poly (t-BMA-b-FMA)] (referring to Busse k.; Kressler J.Macromolecules, 2002,35,178), yet active anionic polymerization severe reaction conditions, temperature of reaction are very low, difficult realization industrialization control and production;
(2) another kind of synthetic method is to adopt atom transfer radical polymerization (ATRP), has synthesized methacrylic tert-butyl acrylate and perfluoroalkyl methacrylate segmented copolymer (referring to Li.H. as: the method for human ATRP such as domestic Han Zhe literary composition; Wu.P.P.; Han.Z.W.; Polymer, 2002,43,4079); The ATRP method has unique advantage, and but, its weak point is to contain catalyzer in the final product, is difficult to remove, and product is impure.
(3) utilize reversible addition-fracture chain transfer polymerization (RAFT) method to prepare fluorine-containing block polymer (referring to Rixen B.; Severac R.; Boutevin B.; Lacroix-Desmazes P.; Polymer, 2005,46,3579).By RAFT emulsion polymerization prepared methacrylic acid ten difluoro esters (DFMA) and butyl methacrylate (BMA) segmented copolymer (referring to Zhang, Q.H.; Zhan, F.Q.; Shi, Y.; Wang, Q.Y.J.Polym.Sci:Part A:Polym Chem., 2007,45,1585).By the RAFT mini-emulsion polymerization, preparation methacrylic acid-(2,2,3,4,4, the 4-hexafluoro) butyl ester (HFBMA) and butyl methacrylate (BMA) segmented copolymer or methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (OFPMA) and BMA segmented copolymer are (referring to Zhou, X.D.; Ni, P.H.; Yu, Z.Q.; Zhang, F.J.Polym.Sci:Part A:Polym Chem., 2007,45,471-484).By no soap RAFT emulsion polymerization prepared methacrylic acid ten difluoro esters (DFMA) and methacrylic acid amphipathic nature block polymer (referring to Xu, S.; Liu, W.J.Fluorine.Chem, 2008,129,125).Though the RAFT polymerization process has characteristics such as reaction conditions gentleness, the RAFT reagent that is added in polymerization process (sulfur-bearing thing) can remain in the final polymkeric substance, is difficult to remove, and polymer properties is produced certain influence.
Although above-mentioned controlled/living polymerisation process has its special advantages to preparing fluorine-containing amphipathic multipolymer, reaction need be carried out under certain conditions, the purification of reaction product simultaneously also has difficulties; In addition, the Chinese patent of application also discloses the method for preparing fluorinated copolymer before the inventor, is respectively:
(1) patent No. is that 200610038134.8 Chinese patent discloses a kind of fluorinated block copolymer and preparation method thereof, adopted oxygen anion initiated polymerization method, obtain the oligopolymer oxygen anion with polymkeric substance and the highly basic reaction that has terminal hydroxy group, successively react as initiator, obtain amphipathic fluoride block copolymer with methacrylic acid (amino that alkyl replaces) ester and methacrylic acid fluorinated ester;
(2) patent No. is that 200710022726.5 Chinese patent discloses a kind of fluorine-containing amphiphilic macromolecular emulsifying agent and preparation method thereof, adopted oxygen anion initiated polymerization method, obtain the benzyl oxygen anion with phenylcarbinol and highly basic reaction, as initiator, order adds monomers methyl methacrylate, methacrylic acid (amino that alkyl replaces) ethyl ester, through polyreaction, obtain fluorine-containing amphiphilic macromolecular emulsifying agent;
Although above-mentioned oxygen anion polymerization process compared with the reaction conditions gentleness of anionoid polymerization many, can be used for preparing the segmented copolymer of structure exquisiteness, but, for suitability for industrialized production, above-mentioned reaction conditions is still relatively stricter, therefore, be necessary to seek the method that is more suitable for the fluorine-containing macromole emulsifying agent of industrial production, make it all lower polymeric reaction condition and equipment requirements.
Summary of the invention
The purpose of this invention is to provide a kind of fluorine-containing macromole emulsifying agent and preparation method thereof, comprise the fluorine-containing macromole emulsifying agent of anionic, cation fluoride macromole emulsifying agent, the fluorine-containing macromole emulsifying agent of non-ionic type, the fluorine-containing macromole emulsifying agent of both sexes in the interior multiple fluorine-containing macromolecular while to provide, make the reaction conditions gentleness, product is convenient purifies, and suitable industrial production.
For achieving the above object, the technical solution used in the present invention is: a kind of fluorine-containing macromole emulsifying agent, and described fluorine-containing macromole is to be obtained by random copolymerization by hydrophobicity fluorochemical monomer and hydrophilic monomer; Described fluorine-containing macromole emulsifying agent is expressed by following general formula:
Figure G2009100255495D00041
Described hydrophobicity fluorochemical monomer is represented by following general formula:
In the formula, R 1Be selected from hydrogen (H) or methyl (CH 3) in a kind of; R 2Be selected from a kind of in hydrogen (H) or the fluorine (F); N is selected from the arbitrary integer in 2～8, comprises 2,3,5 and 8;
In the optimized technical scheme, described hydrophobicity fluorochemical monomer is selected from: methacrylic acid-(2,2,3,3,4, the 4-hexafluoro) butyl ester (n=2), methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (n=3), methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (n=5) or methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) a kind of in the ester in the last of the ten Heavenly stems (n=8);
Described hydrophilic monomer is represented by following general formula:
Figure G2009100255495D00051
In the formula, R 3Be selected from hydrogen (H), methyl (CH 3) in a kind of;
R 4Be selected from
Figure G2009100255495D00052
Figure G2009100255495D00053
A kind of in hydroxyl or the amino, wherein R 5Be selected from methyl (CH 3) or ethyl (CH 2CH 3) in a kind of, m 〉=1 and m≤7;
R in the optimized technical scheme 3And R 4Selection follow following rule:
(1) works as R 4For
Figure G2009100255495D00054
R in the formula 5Be selected from methyl (CH 3) or ethyl (CH 2CH 3) in a kind of the time, R 3Be methyl (CH 3);
Hydrophilic monomer is expressed as:
Be methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) or methacrylic acid-2-(diethylin) ethyl ester (DEAEMA);
(2) work as R 4For
Figure G2009100255495D00056
The time, R 3Be selected from hydrogen (H) or methyl (CH 3) in a kind of;
Hydrophilic monomer is expressed as:
Figure G2009100255495D00061
Be acrylyl oxy-ethyl-trimethyl salmiac (DAC) or methylacryoyloxyethyl trimethyl ammonium chloride (MADQUAT);
(3) work as R 4For
Figure G2009100255495D00062
The time, R 3Be methyl;
Hydrophilic monomer is expressed as:
That is: methacrylic tert-butyl acrylate (t-BMA); The polymkeric substance of methacrylic tert-butyl acrylate can hydrolysis in methylene dichloride, forms the polymkeric substance (PAA) that contains hydrophilic structure unit methacrylic acid;
(4) work as R 4During for hydroxyl, R 3Be selected from hydrogen (H) or methyl (CH 3) in a kind of;
Hydrophilic monomer is expressed as:
Figure G2009100255495D00064
Promptly show vinylformic acid (AA) or methacrylic acid (MAA);
(5) work as R 4During for amino, R 3Be hydrogen (H);
Hydrophilic monomer is expressed as:
Be acrylamide (AM);
(6) work as R 4For
Figure G2009100255495D00066
M 〉=1 and m≤7 o'clock, R 3Be methyl.
In the technique scheme, the molar ratio of hydrophobicity fluorochemical monomer and hydrophilic monomer is 9: 1～1: 9;
The molecular weight ranges of this fluorine-containing macromole emulsifying agent is 3000～10000gmol -1
In the optimized technical scheme, described hydrophilic monomer is selected from a kind of in the following monomer: cationic hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester, methacrylic acid-2-(diethylin) ethyl ester, acrylyl oxy-ethyl-trimethyl salmiac, the methylacryoyloxyethyl trimethyl ammonium chloride, anionic hydrophilic monomer vinylformic acid, methacrylic acid, non-ionic hydrophilic monomer acrylamide, 2-hydroxyethyl methacrylate, the methacrylic acid macrogol ester, also can be monomer, as the methacrylic tert-butyl acrylate through the possess hydrophilic property that macromolecular reaction generated, a kind of in the glycidyl methacrylate.
A kind of preparation method of random copolymerization fluorine-containing macromole emulsifying agent may further comprise the steps:
(1) adopts the conventional free radical copolymerization process, mol ratio according to hydrophobicity fluorochemical monomer and hydrophilic monomer is 9: 1～1: 9, hydrophobicity fluorochemical monomer and hydrophilic monomer are dissolved in the solvent, add the initiator of all monomer molar amounts 1～10%, mix;
(2) reaction is 2～7 hours, and temperature of reaction is 60～80 ℃, obtains thick product;
(3) except that desolvating, purify, obtain required fluorine-containing macromole emulsifying agent;
Described hydrophobicity fluorochemical monomer is represented by following general formula:
Figure G2009100255495D00071
In the formula, R 1Select hydrogen (H) or methyl (CH 3) in a kind of; R 2Be selected from a kind of in hydrogen (H) or the fluorine (F); N is selected from the arbitrary integer in 2～8, comprises 2,3,5 and 8;
Described hydrophilic monomer is represented by following general formula:
Figure G2009100255495D00081
In the formula, R 3Be selected from hydrogen (H) or methyl (CH 3) in a kind of; R 4Be selected from
Figure G2009100255495D00082
Figure G2009100255495D00083
A kind of in hydroxyl or the amino, wherein R 5Be selected from a kind of in methyl or the ethyl, m 〉=1 and m≤7;
R in the optimized technical scheme 3And R 4Selection follow following rule:
(1) works as R 4For
Figure G2009100255495D00084
R in the formula 5Be selected from methyl (CH 3) or ethyl (CH 2CH 3) in a kind of the time, R 3Be methyl (CH 3);
Hydrophilic monomer is expressed as:
Represent methylidene vinylformic acid-2-(dimethylamino) ethyl ester (DMAEMA) or methacrylic acid-2-(diethylin) ethyl ester (DEAEMA);
(2) work as R 4For The time, R 3Be selected from hydrogen (H) or methyl (CH 3) in a kind of;
Hydrophilic monomer is expressed as:
Figure G2009100255495D00087
Be acrylyl oxy-ethyl-trimethyl salmiac (DAC) or methylacryoyloxyethyl trimethyl ammonium chloride (MADQUAT);
(3) work as R 4For The time, R 3Be methyl;
Hydrophilic monomer is expressed as:
Figure G2009100255495D00092
That is: methacrylic tert-butyl acrylate (t-BMA); The polymkeric substance of methacrylic tert-butyl acrylate can hydrolysis in methylene dichloride, forms the polymkeric substance (PAA) that contains hydrophilic structure unit methacrylic acid;
(4) work as R 4During for hydroxyl, R 3Be selected from hydrogen (H) or methyl (CH 3) in a kind of;
Hydrophilic monomer is expressed as:
Figure G2009100255495D00093
Promptly show vinylformic acid (AA) or methacrylic acid (MAA);
(5) when R4 was amino, R3 was hydrogen (H);
Hydrophilic monomer is expressed as:
Figure G2009100255495D00094
Be acrylamide (AM);
(6) work as R 4For
Figure G2009100255495D00095
M 〉=1 and m≤7 o'clock, R 3Be methyl.
In the technique scheme, can select any radical polymerization initiator, the selection of initiator as well known to those skilled in the art relies on several factors, includes but not limited to temperature, solvent and used monomer.Be used for suitable polymerization starter of the present invention and include but not limited to azo-initiator, peroxide initiator;
In the optimized technical scheme, described initiator is selected from Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN), benzoyl peroxide (BPO) and dilauroyl peroxide (LPO).
In the technique scheme, the described method desolvate and purify of removing of step (3) is: remove with the methods of rotary distillation down at 60～70 ℃ and desolvate, slightly product precipitates in-10 ℃～-20 ℃ normal hexane, with throw out 40～50 ℃ of vacuum-dryings to constant weight.
In the technique scheme, described solvent is selected from dehydrated alcohol or Virahol, and the per-cent that the consumption of solvent is selected to make all preceding monomeric weight of reaction account for whole reaction system weight is 20%.
In the optimized technical scheme, in described monomer and initiator system, 4～8% the positive Dodecyl Mercaptan that adds all monomer weights is as chain-transfer agent, thereby the molecular weight of controlling polymers narrows down molecular weight distribution.
The process that technique scheme prepares fluorine-containing macromole emulsifying agent can be expressed as follows:
Figure G2009100255495D00101
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. because the present invention adopts the conventional radical polymerization to obtain fluorine-containing macromole emulsifying agent, and low to reaction conditions and matching requirements, reaction monomers is easy to get, overcome the shortcoming that method such as living polymerization method in the prior art needs to carry out, cost is higher under strict condition.This speed of response is fast, and the transformation efficiency height considers that from suitability for industrialized production and the angle that reduces production costs conventional radical polymerization is still one of method at present simple and easy to do, the most with low cost, therefore is easy to industrializing implementation.
2. the fluorine-containing cationic emulsifier product of the present invention's acquisition can be used for the stabilization of polymer emulsion, the fluorine-containing chain of the unitary strong-hydrophobicity of methacrylic acid fluorine ester structure has stronger ability of aggregation at aqueous phase, and the micella that forms fluorine carbon-to-carbon hydrogen hydridization with the random copolymers main chain is examined; Be with cationic group to stretch to water in the hydrophilic structure unit, play the electrostatic stabilization effect; The random copolymers main chain is attracted to the emulsion particle surface, and more matter is close to the covering of emulsion particle, makes latex particle stable, finally obtains the positively charged polyalcohol emulsion particle in surface.This type of polymer emulsion can be widely used in yarn fabric arrangement, paper additive, tackiness agent, static inhibitor etc.
3. hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (being DMAEMA) has temperature and pH responsiveness among the present invention, can use in the pH of broad scope;
4. the polymkeric substance of monomer methacrylic tert-butyl acrylate (t-BMA) can the hydrolysis generation contain the polymkeric substance of methacrylic acid structural unit among the present invention in methylene dichloride, thereby changes the hydrophilic structure unit into.
5. vinylformic acid (AA) and methacrylic acid-(2,2,3,3 among the present invention, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) polymerization can generate fluo anion type macromole emulsifying agent, when multipolymer dissolves in water, different with the pH value, the association state is also different, and the viscosity of solubleness and solution also changes.
6. the polymkeric substance of monomer acrylamide (AM) can carry out various modifications among the present invention, generate carboxyl as hydrolysis, utilize the Hofmann DeR to generate amino or the like, thereby can form fluo anion type macromole emulsifying agent or fluorine-containing cationic macromolecules emulsifying agent.
7. the prepared comb type unregulated polymer of the present invention obtains easily, and product especially is suitable as the emulsifying agent of emulsion or mini-emulsion polymerization system, need not to eliminate a small amount of homopolymer that exists in the product, and homopolymer can serve as emulsifying agent and assistant for emulsifying agent uses.
Embodiment
Following embodiment is further described the present invention:
Embodiment one: preparation Poly (DFHMA-co-DMAEMA)
(1) uses activatory alkalescence Al before the preparation of reaction monomers, initiator: methacrylic acid-2-(dimethylamino) ethyl ester and methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DFHMA) uses earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; AIBN is standby to treat with the dehydrated alcohol recrystallization.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DFHMA) 4.41g (0.011mol), hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 15.59g (0.099mol); 0.22g initiator A IBN (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 7h, cooling discharging.
(3) purification of polymkeric substance: with the reaction product in (2) under 60～70 ℃ of conditions, rotary evaporation removes and desolvates, and uses-10 ℃ normal hexane precipitated product then, removes unreacted monomer and homopolymer, be dried to constant weight for 40～50 ℃ at vacuum drying oven at last, obtain lurid viscous substance.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, the result shows that this fluorine-containing macromole emulsifying agent is successfully synthetic.1120～1250cm in the infrared spectrogram -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC result shows that the number-average molecular weight of this fluorine-containing macromole emulsifying agent is 9550gmol -1, molecular weight distributing index (PDI) is 1.56.
In addition, adopt heat to analyze the thermostability that (TGA) investigates this fluorine-containing macromole emulsifying agent.Multipolymer rate of weight loss in the time of 430 ℃ is 80%, than the thermally-stabilised height (401 ℃ of rate of weight loss are 80%) of DMAEMA homopolymer.
The properties of Aqueous Solution of multipolymer characterizes by mensuration surface tension, electrical conductivity of solution, steady-state fluorescence probe method, lower critical solution temperature (LCSTs).Utilize transmission electron microscope (TEM) to observe the accumulation shape of this fluorine-containing macromole emulsifying agent in the aqueous solution.The result shows that this fluorine-containing macromole emulsifying agent has very high surfactivity, can make the minimum 38mNm of reducing to of surface tension of water -1, lower critical solution temperature (LCSTs) is 29 ℃, and can form various self-assembly forms in water.
Embodiment two: preparation Poly (DFHMA-co-DMAEMA)
(1) preparation of reaction monomers, initiator: identical with embodiment one step [1].
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DFHMA) 7.78g (0.019mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 12.22g (0.078mol); 0.19g initiator A IBN (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 7h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, the result shows that this fluorine-containing macromole emulsifying agent is successfully synthetic.1120～1250cm in the infrared spectrogram -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 9490gmol -1, molecular weight distributing index (PDI) is 1.73.
The properties of Aqueous Solution of multipolymer characterizes by mensuration surface tension, electrical conductivity of solution, steady-state fluorescence probe method, lower critical solution temperature (LCSTs).Utilize transmission electron microscope (TEM) to observe the accumulation shape of this fluorine-containing macromole emulsifying agent in the aqueous solution.The result shows that this fluorine-containing macromole emulsifying agent has very high surfactivity, can make the minimum 36mNm of reducing to of surface tension of water -1, lower critical solution temperature (LCSTs) is 17 ℃, and can form various self-assembly forms in water.
Embodiment three: preparation Poly (DFHMA-co-DMAEMA)
(1) preparation of reaction monomers, initiator: the method by embodiment one (1) is carried out.
(2) preparation of polymkeric substance: take by weighing strong-hydrophobicity monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DFHMA) 10.44g (0.026mol); Hydrophilic monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) 9.56g (0.061mol); 0.17g initiator A IBN (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (measuring), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed, logical N by solid content 20% 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 7h, cooling discharging.
(3) purification of polymkeric substance: the method by embodiment one (3) is carried out.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, the result shows that this fluorine-containing macromole emulsifying agent is successfully synthetic.1120～1250cm in the infrared spectrogram -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 7220gmol -1, molecular weight distributing index (PDI) is 1.67.
The properties of Aqueous Solution of multipolymer characterizes by mensuration surface tension, electrical conductivity of solution, steady-state fluorescence probe method, lower critical solution temperature (LCSTs).Utilize transmission electron microscope (TEM) to observe the accumulation shape of this fluorine-containing macromole emulsifying agent in the aqueous solution.The result shows that multipolymer has very high surfactivity, and the minimum surface tension of water that makes is reduced to 32mNm -1, lower critical solution temperature (LCSTs) is 10 ℃, and can form various self-assembly forms in water.
Embodiment four: the preparation of Poly (OFPMA-co-MADQUAT)
(1) preparation of reaction monomers, initiator: use the neutral Al of activatory before methacrylic acid-(2,2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA) uses earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; AIBN is standby to treat with the dehydrated alcohol recrystallization, and methylacryoyloxyethyl trimethyl ammonium chloride (MADQUAT) is standby behind the deposition and purification in acetone.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA) 2.77g (9.23mmol); Hydrophilic monomer methylacryoyloxyethyl trimethyl ammonium chloride (MADQUAT) 17.23g (0.083mol); 0.18g initiator A IBN (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 8h, cooling discharging.
(3) purification of polymkeric substance: adopt the precipitator method to purify.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, and measures structure, molecular weight and the molecular weight distribution of multipolymer respectively, prove to have obtained target product.1120～1250cm in the infrared spectrogram -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 5620gmol -1, molecular weight distributing index (PDI) is 1.57.
Embodiment five: the preparation of Poly (OFPMA-co-DAC)
(1) preparation of reaction monomers, initiator: use the neutral Al of activatory before methacrylic acid-(2,2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA) uses earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; AIBN is standby to treat with the dehydrated alcohol recrystallization, and acrylyl oxy-ethyl-trimethyl salmiac is standby behind the purifying in acetone.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA) 2.94g (9.8mmol); Hydrophilic monomer acrylyl oxy-ethyl-trimethyl salmiac (DAC) 17.06g (0.088mol); 0.28g initiator benzoyl peroxide (BPO) (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 8h, cooling discharging.
(3) purification of polymkeric substance: adopt the precipitator method to purify.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, and measures structure, molecular weight and the molecular weight distribution of multipolymer respectively, prove to have obtained target product.1120～1250cm in the infrared spectra -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 4820gmol -1, molecular weight distributing index (PDI) is 1.69.
Embodiment six: the preparation of Poly (NDFDMA-co-AA)
(1) preparation of reaction monomers, initiator: use activatory alkalescence Al before methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) uses earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; Vinylformic acid is through the underpressure distillation purifying; AIBN is standby to treat with the dehydrated alcohol recrystallization.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) 9.41g (0.017mol); Hydrophilic monomer vinylformic acid (AA) 10.59g (0.147mol); 0.32g initiator A IBN (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) purification of polymkeric substance: adopt the precipitator method to purify.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, and measures structure, molecular weight and the molecular weight distribution of multipolymer respectively, prove to have obtained target product.1120～1250cm in the infrared spectra -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 7500gmol -1, molecular weight distributing index (PDI) is 1.59.
Embodiment seven: the preparation of Poly (NDFDMA-co-HEMA)
(1) preparation of reaction monomers, initiator: use the neutral Al of activatory before methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) and 2-hydroxyethyl methacrylate (HEMA) use earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; AIBN is standby to treat with the dehydrated alcohol recrystallization.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) 6.53g (0.0115mol); Hydrophilic monomer 2-hydroxyethyl methacrylate (HEMA) 13.47g (0.104mol); Initiator benzoyl peroxide (BPO) 0.34g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stir stirring velocity 350rmin -1, be rapidly heated to 70 ℃, and remain on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) purification of polymkeric substance: adopt the precipitator method to purify.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, and measures structure, molecular weight and the molecular weight distribution of multipolymer respectively, prove to have obtained target product.1120～1250cm among the infrared figure -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 8730gmol, and molecular weight distributing index (PDI) is 1.73.
Embodiment eight: preparation and the hydrolysis of Poly (NDFDMA-co-t-BMA)
(1) preparation of reaction monomers, initiator: use the neutral Al of activatory before methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) and methacrylic tert-butyl acrylate use earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; AIBN is standby to treat with the dehydrated alcohol recrystallization.
(2) preparation of polymkeric substance: take by weighing hydrophobic monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) 6.15g (0.011mol); Monomer methacrylic tert-butyl acrylate (t-BMA) 13.85g (0.098mol); Initiator A IBN 0.21g (taking by weighing) by 1.2% of whole monomer molar amounts, measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 4.5h, cooling discharging.
(3) hydrolysis of polymkeric substance: the reaction product in (2) is dissolved in the methylene dichloride, drip trifluoroacetic acid, reacted 24 hours, supernatant liquid is outwelled, to separate out product and be dissolved in the ethanol, in ether, precipitate again, repeated washing 2～3 times, take out and desolvate, obtain the copolymer p oly (NDFDMA-co-MAA) that forms by methacrylic acid 19 fluorine ester structure unit and methacrylic acid structural unit.
(4) purification of polymkeric substance: adopt the precipitator method to purify.
(5) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, and measures structure, molecular weight and the molecular weight distribution of multipolymer respectively, prove to have obtained target product.1120～1250cm among the infrared figure -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 5400gmol -1, molecular weight distributing index (PDI) is 1.62.
Embodiment nine: the preparation of Poly (DFHMA-co-PEGMA)
(1) preparation of reaction monomers, initiator: use the neutral Al of activatory before methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DFHMA) uses earlier 2O 3Post is handled, and underpressure distillation is standby to treat then; AIBN is standby to treat with the dehydrated alcohol recrystallization, methacrylic acid (polyoxyethylene glycol) ester (PEGMA, M n≈ 360) directly use.
(2) preparation of polymkeric substance: methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DFHMA) 2.20g (5.5mmol) hydrophilic monomer methacrylic acid (polyoxyethylene glycol) ester (PEGMA) 17.8g (0.0494mol); 0.11g initiator Diisopropyl azodicarboxylate (AIBN) (taking by weighing) by 1.2% of whole monomer molar amounts; Measure the positive Dodecyl Mercaptan of 1mL, be dissolved in the dehydrated alcohol of 101mL (is 20% to measure by monomer solid content), after stirring, pour in the 250mL four-necked bottle that agitator, reflux condensing tube, thermometer and nitrogen conduit are housed logical N into 2, stirring, stirring velocity 350r/min is rapidly heated to 70 ℃, and remains on this temperature and stirring velocity, reaction 8h, cooling discharging.
(3) purification of polymkeric substance: adopt the precipitator method to purify.
(4) sign of polymkeric substance: with the polymkeric substance after purifying in (3) carry out infrared spectra (FT-IR), proton nmr spectra ( 1H NMR), fluorine spectrum ( 19F NMR), gel permeation chromatography (GPC) analyzes, and measures structure, molecular weight and the molecular weight distribution of multipolymer respectively, prove to have obtained target product.1120～1250cm in the infrared spectra -1Strong absorption peak is CF in the fluorine-containing macromole emulsifying agent 2Absorption peak.GPC shows that the number-average molecular weight of multipolymer is 9820gmol -1, molecular weight distributing index (PDI) is 1.78.

Claims (6)

1. the preparation method of a random copolymerization fluorine-containing macromole emulsifying agent is characterized in that: may further comprise the steps:
(1) adopts the conventional free radical copolymerization process, mol ratio according to hydrophobicity fluorochemical monomer and hydrophilic monomer is 9: 1～1: 9, hydrophobicity fluorochemical monomer and hydrophilic monomer are dropped in the solvent, add the initiator of all monomer molar amounts 1～10%, mix;
(2) reaction is 2～7 hours, and temperature of reaction is 60～80 ℃, obtains thick product;
(3) except that desolvating, purify, obtain required fluorine-containing macromole emulsifying agent;
Described hydrophobicity fluorochemical monomer is represented by following general formula:
Figure FSB00000317820500011
In the formula, R 1Be selected from a kind of in hydrogen or the methyl; R 2Be selected from a kind of in hydrogen or the fluorine; N is selected from the arbitrary integer in 2～8;
Described hydrophilic monomer is represented by following general formula:
Figure FSB00000317820500012
In the formula, R 3Be selected from a kind of in hydrogen or the methyl;
R 4Be selected from
Figure FSB00000317820500013
Figure FSB00000317820500014
Or a kind of in the hydroxyl, wherein R 5Be selected from a kind of in methyl or the ethyl, m 〉=1 and m≤7.
2. preparation method according to claim 1 is characterized in that: described initiator is selected from a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or the dilauroyl peroxide.
3. preparation method according to claim 1, it is characterized in that: the described method of desolvating and purifying of removing of step (3) is: remove 60～70 ℃ of backspin distillations and desolvate, thick product precipitates in-10 ℃～-20 ℃ normal hexane, with throw out 40～50 ℃ of vacuum-dryings to constant weight.
4. preparation method according to claim 1 is characterized in that: described solvent is selected from a kind of in dehydrated alcohol or the Virahol.
5. preparation method according to claim 1 is characterized in that: in monomer and initiator system described in the step (1), 4～8% the positive Dodecyl Mercaptan that adds all monomer weights is as chain-transfer agent.
6. the random copolymerization fluorine-containing macromole emulsifying agent that adopts the described preparation method of claim 1 to prepare, the molecular weight ranges of described fluorine-containing macromole emulsifying agent is 3000～10000gmol -1
CN2009100255495A 2009-02-06 2009-02-06 Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof Expired - Fee Related CN101481438B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100255495A CN101481438B (en) 2009-02-06 2009-02-06 Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100255495A CN101481438B (en) 2009-02-06 2009-02-06 Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof

Publications (2)

Publication Number Publication Date
CN101481438A CN101481438A (en) 2009-07-15
CN101481438B true CN101481438B (en) 2011-03-16

Family

ID=40878738

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100255495A Expired - Fee Related CN101481438B (en) 2009-02-06 2009-02-06 Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof

Country Status (1)

Country Link
CN (1) CN101481438B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106758234B (en) * 2017-01-11 2019-03-29 东华大学 A kind of hydrophilic preparation method for refusing oily automatically cleaning cotton fabric
CN110872363A (en) * 2018-08-31 2020-03-10 浙江大学 Cross-linkable fluorine-containing macromolecular emulsifier, fluorine-containing emulsion containing emulsifier, and preparation and use methods thereof
CN114075315B (en) * 2020-08-19 2024-02-27 南开大学 Environment-friendly fluorine-containing high-molecular surfactant and preparation method thereof
CN115160486B (en) * 2022-07-29 2023-11-03 同济大学 Antibacterial fluorine-containing emulsifier and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072401A1 (en) * 2005-01-05 2006-07-13 Merck Patent Gmbh Fluorosurfactants
CN1817925A (en) * 2006-01-27 2006-08-16 苏州大学 Amphipathic fluoride block copolymer and production thereof
CN1831022A (en) * 2006-02-21 2006-09-13 苏州大学 Fluorine-contg. block copolymers of pH-responsed and its prepn. method
CN101053800A (en) * 2007-05-23 2007-10-17 苏州大学 Fluorine containing cationic macromolecules emulsifying agent and its preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072401A1 (en) * 2005-01-05 2006-07-13 Merck Patent Gmbh Fluorosurfactants
CN1817925A (en) * 2006-01-27 2006-08-16 苏州大学 Amphipathic fluoride block copolymer and production thereof
CN1831022A (en) * 2006-02-21 2006-09-13 苏州大学 Fluorine-contg. block copolymers of pH-responsed and its prepn. method
CN101053800A (en) * 2007-05-23 2007-10-17 苏州大学 Fluorine containing cationic macromolecules emulsifying agent and its preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAODONG ZHOU etc..Latices of Poly(fluoroalkyl mathacrylate)-b-Poly(butyl.Journal of Polymer Science: Part A: Polymer Chemistry.2007,45(3),全文. *

Also Published As

Publication number Publication date
CN101481438A (en) 2009-07-15

Similar Documents

Publication Publication Date Title
Roy et al. RAFT polymerization of methacrylates containing a tryptophan moiety: controlled synthesis of biocompatible fluorescent cationic chiral polymers with smart pH-responsiveness
Chen et al. Synthesis and self-assembly of amphiphilic gradient copolymer via RAFT emulsifier-free emulsion polymerization
CN104650286B (en) The preparation method of high heat-resistant polymethyl methacrylate resin
CN102395607A (en) Branched copolymers, composition and uses
Han et al. Synthesis and characterization of acrylic latex: Effects of fluorine and silicon components on properties of the latex copolymers
CN101481438B (en) Random copolymerization fluorine-containing macromole emulsifying agent and preparation thereof
CN100500716C (en) Random and copolymerized cation macromolecular emulsion and its preparation method
Suchao-In et al. pH-and thermo-multi-responsive fluorescent micelles from block copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization
CN105418826A (en) Preparation of self-emulsifying perfluoropolyether monomer and application of self-emulsifying perfluoropolyether monomer in synthesis of fluorine-containing miniemulsion
CN110052172A (en) A kind of preparation method and correlation block copolymer of the heat-resisting solvent resistant homopore membrane of cross-linking type
CN106519155B (en) The method for preparing high solids content soap-free polymerization object lotion based on semi-continuous charging method
Orekhov et al. Molecular brushes based on copolymers of alkoxy oligo (ethylene glycol) methacrylates and dodecyl (meth) acrylate: features of synthesis by conventional free radical polymerization
CN107922518A (en) With substituent on one-side ends（Methyl）The manufacture method of acrylic polymer
Hemalatha et al. Reactivity ratios of N-vinylpyrrolidone-acrylic acid copolymer
Yang et al. Synthesis and characterization of the fluorinated acrylic latex: Effect of fluorine-containing surfactant on properties of the latex film
CN104761673A (en) Carbomer and preparation method thereof
Patrickios et al. Synthesis and characterization of amphiphilic diblock copolymers of methyl tri (ethylene glycol) vinyl ether and isobutyl vinyl ether
Zhang et al. Synthesis, characterization and properties of a novel fluorinated methacrylate polymer
CN107312138A (en) A kind of preparation method for the response type latex film for possessing Microphase Structure
CN103319668B (en) A kind of preparation method of butyl methacrylate dimethylaminoethyl segmented copolymer
CN100469431C (en) Fluorine containing cationic macromolecules emulsifying agent and its preparation method
Kucharski et al. Copolymerization of hydroxyalkyl methacrylates with acrylamide and methacrylamide I. Determination of reactivity ratios
CN110483707B (en) Vinyl monomer RAFT cation soap-free emulsion polymerization method with good controllability
CN102746475A (en) preparation method and application of trithiocarbonic acid ester compound containing isocyanate group
US20110207881A1 (en) Amphiphilic block copolymer and method for preparing same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee
CP02 Change in the address of a patent holder

Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8

Patentee after: Soochow University

Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199

Patentee before: Soochow University

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110316

Termination date: 20190206