CN102311526A - Composite high-density long-tail-chain-containing bottle brush type polymer chain modified material and preparation method thereof - Google Patents
Composite high-density long-tail-chain-containing bottle brush type polymer chain modified material and preparation method thereof Download PDFInfo
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- CN102311526A CN102311526A CN201110151199A CN201110151199A CN102311526A CN 102311526 A CN102311526 A CN 102311526A CN 201110151199 A CN201110151199 A CN 201110151199A CN 201110151199 A CN201110151199 A CN 201110151199A CN 102311526 A CN102311526 A CN 102311526A
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Abstract
The invention discloses a composite high-density long-tail-chain-containing bottle brush type polymer chain modified material and a preparation method thereof. The material has a structure shown in a formula (1). By using the method disclosed by the invention, the grafting density of the surface of the material is enhanced; through specific selection of monomers, the synergistic effect of two monomers can be realized, so that a new structure constitutes an organic whole, thereby obtaining a more superior modification effect; and excellent blood compatibility is obtained.
Description
Technical field
The invention belongs to the material technology field, relate to a kind of compound high-density particularly and contain the material modified and preparation method of long-tail chain bottle brush type polymer chain.
Technical background
In the practical application of material, often require it to have the superior surface property that material body can not provide.With medical embedded polyurethane material is example, in the use of material, even 10ng/cm
2Fibrinogen absorption or 1ng/cm
2VonWillebrand factor (vWF) absorption will cause hematoblastic comprehensive absorption, thereby form thrombus and embolism at material blood surface in contact.Yet for medical polyurethane material, because the essence of its hydrophobic surface, material itself is difficult to obtain superior biocompatibility.Polyurethane material has limited it in the application aspect the blood contact material for proteic non-specific adsorption.Under this contradiction, investigators have proposed a kind of thinking cleverly: through the method for surface-treated, change raw-material surface property, thereby satisfy under the application-specific condition demand to material property.
The process for modifying surface of having reported has a lot, comprises surface-coated, physical adsorption, grafting modification and plasma surface treatment etc.In numerous modification technologies, the graft polymerization modification can obtain higher grafting density with itself characteristic under the situation of certain or relatively low activated point density.Wherein, ATRP (ATRP) has attracted numerous investigators' interest as a kind of active free radical polymerization.The investigator introduces material surface based on the ultimate principle of ATRP with initiator, successful realization the surperficial initiated polymerization graft reaction of polymerization single polymerization monomer.The surface is caused the ATRP technology and is had the wide in range monomer selection of ATRP, high impurity tolerance and gentle characteristics such as reaction conditions.According to the ultimate principle of ATRP, the s-ATRP method can be at material surface synthetic molecular weight narrowly distributing, and the graft polymerization chain of compound with regular structure simultaneously, as a kind of graft polymerization method, can obtain high relatively grafting density under activated point density one stable condition.
In nearest research, the investigator has successfully realized multiple monomer at macromolecular material, silicon, and the ATRP graft polymerization is caused on the surface of gold and glass, and its modified surface has been carried out performance characterization, has obtained certain modified effect.With the bio-medical material is example, and polyoxyethylene glycol (PEG) type monomer is a kind of functional monomer that is widely used.Because its PEG molecular chain has the wetting ability and the kindliness of height, on the one hand can form hydration PEG chain with water, form stable sterically hinderedly, the obstruction blood ingredient is in the absorption of material surface; On the other hand, hydration PEG chain has lower surface energy in water, and the water miniflow of formation can stop proteinic stagnation, adhere to and distortion.Therefore, it is widely used in the blood compatibility that can improve material; The polymer chain that another kind contains phosphatide group (PC) has attracted the interest of more and more researchers.PC is as the staple of cytolemma, and the investigator pays close attention to the biocompatibility that its bionical performance is used to improve material.Simultaneously, betaine type class PC ampholytic monomer has also obtained using widely with its numerous high-performance.
In the research of having reported, rarely have grafting chain structure and two kinds of synergistic researchs of monomer.
Summary of the invention
The objective of the invention is the angle from molecular designing, selected specific monomer is utilized the synergy between each monomer, and it is material modified to provide a kind of compound high-density that improves the modification performance of modification chain to contain long-tail chain bottle brush type polymer chain.
Second purpose of the present invention provides a kind of compound high-density and contains the material modified preparation method of long-tail chain bottle brush type polymer chain.
Technical scheme of the present invention is summarized as follows:
It is material modified that compound high-density contains long-tail chain bottle brush type polymer chain, has formula (I) structure:
Wherein:
A=(CHR
3CH
2O)
aOr (CHR
4CH
2)
bO;
M=Br, Cl or CH
3
R
1=H or CH
3
R
2=H or CH
3
R
3=H or contain the alkyl of 1-5 carbon atom;
R
4=H or contain the alkyl of 1-5 carbon atom;
N or m=5～10000;
A, b, d or e=2～1000;
g＝1～100000；
Z is material modified for treating, saidly treats material modified be urethane, tetrafluoroethylene, polymeric amide, epoxy resin, Vilaterm, Rohm tech inc, polyethyl acrylate, polyoxymethylene, PVA, poly hydroxybutyric acid, polycaprolactone, Zylox, silicon gel, PS, Vestolen PP 7052, chitosan, POLYACTIC ACID, Sodium bromoacetate homopolymer, SRU ester, silicon, silicon-dioxide, gold, titanium, titanium alloy, titanium chrome alloy, titanium chrome molybdenum or platinum.
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere, the material modified Z that treats that the surface is contained bromine and/or chlorine puts into reactor drum, the ATRP catalyzer is added in the reactor drum and adds sacrifice initiator and/or Cu
2+Compound, the deoxygenation solution of first kind of monomer/solvent of adding, under 0～100 ℃, stirring reaction 0.5～168h, said ATRP catalyzer, sacrifice initiator and/or Cu
2+Compound, first kind of monomeric mol ratio are 1: 1 and/or (0.01～0.2): (5～10000);
(2) will handle the material modified taking-up that obtains through step (1); Use and step (1) same solvent supersound washing 10～60min, after the vacuum-drying, under nitrogen atmosphere; Put into another reactor drum; Add halogenating agent and make material modified surface introduce halogen atom for the second time, the add-on of said halogenating agent and said first kind of monomeric mol ratio are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2), put into another reactor drum, and the ATRP catalyzer added in the reactor drum and adds sacrifice initiator and/or Cu
2+Compound, the deoxygenation solution of second kind of monomer/solvent of adding, under 0～100 ℃, stirring reaction 0.5～168h, said ATRP catalyzer, sacrifice initiator and/or Cu
2+Compound, second kind of monomeric mol ratio are 1: 1 and/or (0.01～0.2): (5～10000), it is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Saidly treat that material modified Z is urethane, tetrafluoroethylene, polymeric amide, epoxy resin, Vilaterm, Rohm tech inc, polyethyl acrylate, polyoxymethylene, PVA, poly hydroxybutyric acid, polycaprolactone, Zylox, silicon gel, PS, Vestolen PP 7052, chitosan, POLYACTIC ACID, Sodium bromoacetate homopolymer, SRU ester, silicon, silicon-dioxide, gold, titanium, titanium alloy, titanium chrome alloy, titanium chrome molybdenum or platinum.
Said ATRP catalyzer is made up of CuX and part, and said CuX is CuBr and/or CuCl; Said part is 2, and at least a in 2-dipyridyl, three (2-methyl amido) ethamine, Tetramethyl Ethylene Diamine, PMDETA, three (2-pyridine) methylamine, the triphenylphosphine, the mol ratio of said CuX and part is 1: 0.1-100.
Said sacrifice initiator is 2-isobutyl ethyl bromide, 2-bromo acid benzyl ester, 2-ethyl bromide, 2-chloro ethyl isobutyrate, 2-chloro benzyl methylpropanoate or 2-chloropropionic acid ethyl ester; Said Cu
2+Compound is CuCl
2Or CuBr
2
Said solvent is methyl alcohol, ethanol, water, fluorine alcohol, THF, N, and dinethylformamide and DMSO 99.8MIN. are at least a.
Said first kind of monomer is hydroxy-end capped polyethylene glycol methacrylate-styrene polymer, 12 carbon glycol methacrylic esters, hydroxy-end capped polyethylene glycol acrylate and/or 12 carbon glycol propenoate.
Said halogenating agent is 2-bromo isobutyl acylbromide, 2-chloro isobutyryl chloride, 2-bromo isobutyryl chloride, 2-bromo PROPIONYL CHLORIDE or 2-chloro propionyl chloride.
Said second kind of monomer is sultaine methacrylic ester, 2-methacryloyl hydroxyethyl Phosphorylcholine, polyethylene glycol methacrylate-styrene polymer, mono methoxy polyethylene glycol methacrylic ester, sultaine propenoate, acryloyl hydroxyethyl Phosphorylcholine, polyethylene glycol acrylate, mono methoxy polyethylene glycol propenoate, acrylic amide, N-NSC 11448, N; N-DMAA, USAF RH-1, N-isopropyl methyl acrylic amide or N, the N-dimethylmethacryl amide.
Advantage of the present invention is:
(1) the present invention utilizes the s-ATRP technology; First kind of end of grafting has the monomer of functional group, and through specific halide reagent and material modified reaction, secondary is introduced halogen atom; And then realize second kind of monomeric graft polymerization, improved the grafting density of material surface;
(2) method of the present invention can realize two monomeric synergies through to monomeric specific selection, makes new structure constitute an organic whole, produces more superior modified effect;
(3) method of the present invention is novel, and wide application all can use in numerous material modifications field.
The present invention is through molecular designing, and utilization s-ATRP technology prepares compound high-density and contains long-tail chain bottle brush type polymer chain structure.The method of utilizing secondary to cause realizes higher grafting density; Utilize two kinds of monomeric synergies simultaneously, obtain better modified effect.
Description of drawings
Fig. 1 contains the material modified synoptic diagram of long-tail chain bottle brush type polymer chain for compound high-density.
Fig. 2 contains the material modified grafting schema of long-tail chain bottle brush type polymer chain for compound high-density.
Fig. 3 contains the material modified infrared analysis figure of long-tail chain bottle brush type polymer chain for compound high-density.
Fig. 4 is the XPS analysis before and after the material modified modification.
Fig. 5 adsorbs test scan Electronic Speculum figure for compound high-density contains the material modified thrombocyte with contrast material of long-tail chain bottle brush type polymer chain.
The practical implementation method
Further set forth the present invention below in conjunction with specific embodiment.Should be understood that this embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.In addition, after the content of reading the present invention's instruction, those skilled in the art can make this moving or modification to the present invention, and this equivalence form falls within claims institute restricted portion of the application equally.
Embodiment 1
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The urethane that bromine is contained on the surface put into reactor drum with the ATRP catalyzer (by 0.1mmolCuBr and 0.2mmol 2; The 2-dipyridyl is formed) add in the reactor drum and add 0.1mmol 2-isobutyl ethyl bromide; The deoxygenation methanol solution that adds the hydroxy-end capped polyethylene glycol methacrylate-styrene polymer of 10mmol 3.8% (w/v), under 0 ℃, stirring reaction 168h;
(2) will handle the material modified taking-up that obtains through step (1), be designated as PU-PEGMAs, with methyl alcohol supersound washing 30min; After the vacuum-drying, under nitrogen atmosphere, put into another reactor drum; Adding 2-bromo isobutyl acylbromide makes material modified surface introduce bromine atoms for the second time; The add-on of 2-bromo isobutyl acylbromide and the mol ratio of first kind of hydroxy-end capped polyethylene glycol methacrylate-styrene polymer of monomer are 1: 1, and the preparation surface is caused ATRP and caused the surface, is designated as PU-(PEGMA-Br) s;
Another reactor drum will be put in the material modified taking-up that (3) will handle obtain through step (2), with the ATRP catalyzer (by 0.1mmolCuBr and 0.2mmol 2; The 2-dipyridyl is formed) add in the reactor drum and add 0.1mmol 2-isobutyl ethyl bromide; Add the deoxygenation methanol solution 10ml that contains 10mmol sultaine methacrylic ester, under 40 ℃, stirring reaction 48h; From solution, take out material modified; Promptly obtaining compound high-density shown in the formula (I), to contain long-tail chain bottle brush polymer chain material modified, is designated as PU-poly (PEG-DMAPSs100), and its synoptic diagram is seen Fig. 1; The grafting schema is seen Fig. 2; Fig. 5 is seen in material modified thrombocyte absorption test with contrast material.
The separation of polymkeric substance and analysis in the polymeric solution system
The polymers soln of step (1) and step (3) is passed through the neutral alumina chromatography column, drench fluid and collect rotary evaporation, through the dialysis tubing dialysis, remove the unreacted small molecules, vacuum-drying obtains polymkeric substance.Through nmr analysis, obtain the molecular weight data of polymkeric substance, thus the textural property of indirect reaction modify and graft chain.Remember that respectively each polymkeric substance is EBIB-PEGMAs and EBIB-DMAPSs.
Analytical results: Fig. 3 is the total reflection infrared spectrum of modified membrane, wherein, because 1530cm
-1The N-H peak at place is no Strength Changes before and after polymerization, and does not receive the influence at other infrared peaks, so choose 1530cm
-1The place for base peak in the collection of illustrative plates-CH
2-carry out normalized Analysis.3430cm
-1Place's broad absorption band is the stretching vibration peak v (H-O) of PEGMA terminal hydroxy group, 1245cm
-1And 1339cm
-1Be the stretching vibration peak of C-Br,, behind the graft polymerization PEGMA, 3430cm occur through film PU and PU-PEGMAs comparative analysis
-1The hydroxyl absorption peak at place; Can reach a conclusion,, successfully realize the graft polymerization of first kind of monomer PEGMA and through polymkeric substance EBIB-PEGMAs is carried out nmr analysis through the s-ATRP grafting method; Its PEGMA if only the polymerization degree be 86, with design theory be worth 1,000 minutes approaching; Comparative film PU-PEGMAs and PU-(PEGMA-Br) s is at 1245cm
-1And 1339cm
-1The C-Br vibration absorption peak appears in the place, explains that secondary bromination achievement is incorporated into the modified membrane surface with initiator B r atom, is that second kind of monomeric s-ATRP graft polymerization created condition.
In conjunction with above-mentioned analysis, the second monomer graft modification film PU-poly (PEG-DMAPSs100) is carried out XPS analysis, confirm the element situation that it is surperficial.It is as shown in Figure 4 that (Fig. 4 A is the mould material that the present invention obtained; Fig. 4 B is the mould material after the specific bromination of first monomer); Compare through film PU-poly (PEG-DMAPSs100) and film PU-(PEGMA-Br) s, the former the S2p peak occurs at 167.8eV, confirms to have the introducing of S element.This shows that second kind of monomer sultaine has been grafted to the end of PEGMA-Br through graft polymerization, realized that the compound high-density of polyurethane film surface grafting contains polyoxyethylene glycol long-tail chain sultaine bottle brush type polymer chain structure Design.Further through the EBIB-DMAPSs polymkeric substance is carried out nmr analysis, the monomeric polymerization degree of its DAMPS is 89, and is consistent with the design theory value.
Select for use the thrombocyte adsorption experiment that modified membrane is done the blood compatibility property testing, among Fig. 5, a; B, c are respectively blank PU film, PU-PEGMA film and PU-poly (PEG-DMAPSs100) film, as can be seen from the figure; The blank film surface adsorption is a large amount of thrombocyte, most of thrombocyte all stretches out pseudopodium; PU-PEGMA film thrombocyte adsorptive capacity makes moderate progress but DeGrain than blank film; Almost do not observed hematoblastic adhesion on modified membrane PU-poly (PEG-DMAPSs100) surface.The compound high-density of grafting contains that long-tail chain bottle brush type polymer chain is material modified to have obtained excellent blood compatibility.
Introduce bromine on the surface of treating material modified urethane: (this also can introduce chlorine with this method for known technology)
1. the preparation of urethane (PU) film
PU/THF (8% w/w) solution is poured in the horizontal positioned petridish, drying at room temperature 3 days, treat the volatilization of most of reagent after, film is taken off vacuum-drying 24h; Desciccator diaphragm is cut into 1cm * 1cm sample, washing with alcohol 24h in shaking table, and vacuum-drying also stores for future use;
2.PU the activation of film
1cm * 1cm polyurethane film is some, 4g hexamethylene diisocyanate (HDI), 60ml anhydrous n-hexane; 0.06ml dibutyl tin laurate (DBTDL) adds in the exsiccant there-necked flask, is warming up to 50 ℃, stirring reaction 2h; Film is taken out, with anhydrous n-hexane supersound washing 5min; To handle film (PU-NCO) adding then and be equipped with in the there-necked flask of zero(ppm) water, 50 ℃ of reactions are spent the night, and isocyano and water are fully reacted, and will handle film and place ethanol to wash 12h, and vacuum-drying is designated as PU-NH
2
3.PU-NH
2Initiationization
With the 59ml anhydrous n-hexane, 0.65ml triethylamine, some dry PU-NH
2Film and rotor add in the 100ml there-necked flask, place low-temp reaction to bathe in mixture, are cooled to-15 ℃; With 0.5ml bromo isobutyl acylbromide (BIBB), the 9.5ml anhydrous n-hexane adds in the constant voltage titration funnel, and 30min is added dropwise to mixture in the there-necked flask; Reaction system is warming up to 25 ℃ then, reaction 5h, and the reaction caudacoria places the ultrasonic 5min of anhydrous n-hexane; Then at ethanol; Wash 12h in the water, vacuum-drying is designated as PU-Br.
Embodiment 2
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The material modified tetrafluoroethylene of treating that the surface is contained chlorine is put into reactor drum, ATRP catalyzer (mol ratio is 1: 0.1 CuCl/ three (2-methyl amido) ethamine) is added in the reactor drum and adds sacrifice initiator 2-bromo acid benzyl ester and CuCl
2, add 12 carbon glycol methacrylic ester/N, the deoxygenation solution of dinethylformamide, under 100 ℃, stirring reaction 0.5h, said ATRP catalyzer, sacrifice initiator, CuCl
2With first kind of monomeric mol ratio be 1: 1: 0.01: 5;
(2) will handle the material modified taking-up that obtains through step (1), use N, dinethylformamide supersound washing 60min; After the vacuum-drying; Under nitrogen atmosphere, put into another reactor drum, add 2-bromo isobutyl acylbromide and make material modified surface introduce bromine atoms for the second time; The add-on of 2-bromo isobutyl acylbromide and the mol ratio of 12 carbon glycol methacrylic esters are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2); Put into another reactor drum, ATRP catalyzer (mol ratio is 1: 0.1 CuCl/ three (2-methyl amido) ethamine) is added in the reactor drum and adds sacrifice initiator 2-bromo acid benzyl ester and CuCl
2, the deoxygenation solution of adding sultaine methacrylic ester/water, under 50 ℃, stirring reaction 0.5h, said ATRP catalyzer, sacrifice initiator, Cu
2+Compound and first kind of monomeric mol ratio are 1: 1: 0.01: 5; It is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Embodiment 3
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The material modified polymeric amide of treating that the surface is contained bromine and chlorine is put into reactor drum, ATRP catalyzer (mol ratio is 1: 100 a CuCl/ Tetramethyl Ethylene Diamine) is added in the reactor drum and adds sacrifice initiator 2-chloro ethyl isobutyrate and CuBr
2, (1: 1 v: deoxygenation solution v), under 40 ℃, stirring reaction 168h, sacrifices initiator, CuBr at said ATRP catalyzer to add first kind of hydroxy-end capped polyethylene glycol acrylate/methanol-water of monomer
2, first kind of monomeric mol ratio be 1: 1: 0.2: 10000;
(2) will handle the material modified taking-up that obtains through step (1); With methanol-water (1: 1 v: v) supersound washing 10min, after the vacuum-drying, under nitrogen atmosphere; Put into another reactor drum; Add 2-chloro isobutyryl chloride and make material modified surface introduce the chlorine atom for the second time, the add-on of 2-chloro isobutyryl chloride and the mol ratio of hydroxy-end capped polyethylene glycol acrylate are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2); Put into another reactor drum, ATRP catalyzer (mol ratio is 1: 100 a CuCl/ Tetramethyl Ethylene Diamine) is added in the reactor drum and adds sacrifice initiator 2-chloro ethyl isobutyrate and CuBr
2, adding 2-methacryloyl hydroxyethyl Phosphorylcholine/methanol-water (1: 1 v: deoxygenation solution v), under 40 ℃, stirring reaction 168h, said ATRP catalyzer, sacrifice initiator, CuBr
2, second kind of monomeric mol ratio be 1: 1: 0.2: 10000; It is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Embodiment 4
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The material modified epoxy resin of treating that the surface is contained chlorine is put into reactor drum; Add in the reactor drum ATRP catalyzer (mol ratio is 1: 1: 1 CuBr, PMDETA and a triphenylphosphine) and adding sacrifice initiator 2-ethyl bromide; The deoxygenation solution that adds first kind of monomer (mol ratio is 1: 1 12 carbon glycol propenoate and a hydroxy-end capped polyethylene glycol methacrylate-styrene polymer)/DMSO 99.8MIN.; Under 80 ℃, stirring reaction 100h, said ATRP catalyzer, sacrifice initiator, first kind of monomeric mol ratio are 1: 1: 100;
(2) will handle the material modified taking-up that obtains through step (1); With DMSO 99.8MIN. supersound washing 20min; After the vacuum-drying; Under nitrogen atmosphere, put into another reactor drum, add 2-bromo isobutyryl chloride and make material modified surface introduce bromine atoms for the second time; The mol ratio of the add-on of 2-bromo isobutyryl chloride and said first kind of monomer (mol ratio is 1: 1 12 carbon glycol propenoate and a hydroxy-end capped polyethylene glycol methacrylate-styrene polymer) is 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2); Put into another reactor drum; Add in the reactor drum ATRP catalyzer (mol ratio is 1: 1: 1 CuBr, PMDETA and a triphenylphosphine) and adding sacrifice initiator 2-ethyl bromide; The deoxygenation solution that adds polyethylene glycol methacrylate-styrene polymer/DMSO 99.8MIN.; Under 100 ℃, stirring reaction 100h, said ATRP catalyzer, sacrifice initiator, second kind of monomeric mol ratio are 1: 1: 100; It is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Embodiment 5
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The Rohm tech inc that bromine is contained on the surface is put into reactor drum ATRP catalyzer (0.1mmolCuBr and 0.2mmol three (2-pyridine) methylamine) is added reactor drum and adds 0.1mmol 2-chloro benzyl methylpropanoate; The THF deoxygenation solution that adds the hydroxy-end capped polyethylene glycol methacrylate-styrene polymer of 10mmol 3.8% (w/v); Under 0 ℃, stirring reaction 168h;
(2) will handle the material modified taking-up that obtains through step (1); With THF supersound washing 10min, after the vacuum-drying, under nitrogen atmosphere; Put into another reactor drum; Add 2-chloro propionyl chloride and make material modified surface introduce the chlorine atom for the second time, the add-on of 2-chloro propionyl chloride and the mol ratio of hydroxy-end capped polyethylene glycol methacrylate-styrene polymer are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2); Put into another reactor drum; Add in the reactor drum ATRP catalyzer (mol ratio is 1: 1 CuBr, a PMDETA) and adding sacrifice initiator 2-ethyl bromide; Add mono methoxy polyethylene glycol methacrylic ester/alcoholic acid deoxygenation solution; Under 40 ℃, stirring reaction 100h, said ATRP catalyzer, sacrifice initiator, second kind of monomeric mol ratio are 1: 1: 100; It is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Embodiment 6
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The POLYACTIC ACID that bromine is contained on the surface is put into reactor drum ATRP catalyzer (0.1mmolCuBr and 0.2mmol three (2-pyridine) methylamine) is added reactor drum and adds 0.1mmol 2-chloropropionic acid ethyl ester; The deoxygenation ethanolic soln that adds the hydroxy-end capped polyethylene glycol methacrylate-styrene polymer of 10mmol 3.8% (w/v); Under 0 ℃, stirring reaction 168h;
(2) will handle the material modified taking-up that obtains through step (1); With ethanol supersound washing 10min, after the vacuum-drying, under nitrogen atmosphere; Put into another reactor drum; Add 2-bromo PROPIONYL CHLORIDE and make material modified surface introduce bromine atoms for the second time, the add-on of 2-bromo PROPIONYL CHLORIDE and the mol ratio of hydroxy-end capped polyethylene glycol methacrylate-styrene polymer are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2); Put into another reactor drum; Add in the reactor drum ATRP catalyzer (mol ratio is 1: 1 CuBr, a PMDETA) and adding sacrifice initiator 2-ethyl bromide; Add N, the deoxygenation solution of N-dimethylmethacryl amide/THF is under 40 ℃; Stirring reaction 100h, said ATRP catalyzer, sacrifice initiator, second kind of monomeric mol ratio are 1: 1: 100; It is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Embodiment 7
Compound high-density contains the material modified preparation method of long-tail chain bottle brush type polymer chain, comprises the steps:
(1) under nitrogen atmosphere; The gold that bromine is contained on the surface is put into reactor drum ATRP catalyzer (0.1mmolCuBr and 0.2mmol three (2-pyridine) methylamine) is added reactor drum and adds 0.1mmol 2-chloropropionic acid ethyl ester; The fluorine alcohol deoxygenation solution that adds the hydroxy-end capped polyethylene glycol methacrylate-styrene polymer of 10mmol 3.8% (w/v); Under 25 ℃, stirring reaction 72h;
(2) will handle the material modified taking-up that obtains through step (1); With fluorine alcohol supersound washing 10min, after the vacuum-drying, under nitrogen atmosphere; Put into another reactor drum; Add 2-bromo PROPIONYL CHLORIDE and make material modified surface introduce bromine atoms for the second time, the add-on of 2-bromo PROPIONYL CHLORIDE and the mol ratio of hydroxy-end capped polyethylene glycol methacrylate-styrene polymer are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2); Put into another reactor drum; Add in the reactor drum ATRP catalyzer (mol ratio is 1: 1 CuBr, a PMDETA) and adding sacrifice initiator 2-ethyl bromide; Add N-isopropyl methyl acrylic amide/N, the deoxygenation solution of dinethylformamide is under 100 ℃; Stirring reaction 100h, said ATRP catalyzer, sacrifice initiator, second kind of monomeric mol ratio are 1: 1: 100; It is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
Can also use Vilaterm, polyethyl acrylate, polyoxymethylene, PVA, poly hydroxybutyric acid, polycaprolactone, Zylox, silicon gel, PS, Vestolen PP 7052, chitosan, Sodium bromoacetate homopolymer, SRU ester, silicon-dioxide, titanium, titanium alloy, titanium chrome alloy, titanium chrome molybdenum or platinum to substitute the gold of present embodiment, also can preparing corresponding compound high-density, to contain long-tail chain bottle brush type polymer chain material modified.
Can also use sultaine propenoate, acryloyl hydroxyethyl Phosphorylcholine, polyethylene glycol acrylate, mono methoxy polyethylene glycol propenoate, acrylic amide, N-NSC 11448, N; N-DMAA or USAF RH-1 substitute the N-isopropyl methyl acrylic amide of present embodiment, and also can preparing corresponding compound high-density, to contain long-tail chain bottle brush type polymer chain material modified.
Claims (9)
1. it is material modified that compound high-density contains long-tail chain bottle brush type polymer chain, (I) structure that it is characterized in that having formula:
Wherein:
A=(CHR
3CH
2O)
aOr (CHR
4CH
2)
bO;
M=Br, Cl or CH
3
R
1=H or CH
3
R
2=H or CH
3
R
3=H or contain the alkyl of 1-5 carbon atom;
R
4=H or contain the alkyl of 1-5 carbon atom;
N or m=5～10000;
A, b, d or e=2～1000;
g＝1～100000；
Z is material modified for treating, saidly treats material modified be urethane, tetrafluoroethylene, polymeric amide, epoxy resin, Vilaterm, Rohm tech inc, polyethyl acrylate, polyoxymethylene, PVA, poly hydroxybutyric acid, polycaprolactone, Zylox, silicon gel, PS, Vestolen PP 7052, chitosan, POLYACTIC ACID, Sodium bromoacetate homopolymer, SRU ester, silicon, silicon-dioxide, gold, titanium, titanium alloy, titanium chrome alloy, titanium chrome molybdenum or platinum.
2. the compound high-density of claim 1 contains the material modified preparation method of long-tail chain bottle brush type polymer chain, it is characterized in that comprising the steps:
(1) under nitrogen atmosphere, the material modified Z that treats that the surface is contained bromine and/or chlorine puts into reactor drum, the ATRP catalyzer is added in the reactor drum and adds sacrifice initiator and/or Cu
2+Compound, the deoxygenation solution of first kind of monomer/solvent of adding, under 0～100 ℃, stirring reaction 0.5～168h, said ATRP catalyzer, sacrifice initiator and/or Cu
2+Compound, first kind of monomeric mol ratio are 1: 1 and/or (0.01～0.2): (5～10000);
(2) will handle the material modified taking-up that obtains through step (1); Use and step (1) same solvent supersound washing 10～60min, after the vacuum-drying, under nitrogen atmosphere; Put into another reactor drum; Add halogenating agent and make material modified surface introduce halogen atom for the second time, the add-on of said halogenating agent and said first kind of monomeric mol ratio are 1: 1, and the preparation surface is caused ATRP and caused the surface;
(3) will handle the material modified taking-up that obtains through step (2), put into another reactor drum, and the ATRP catalyzer added in the reactor drum and adds sacrifice initiator and/or Cu
2+Compound, the deoxygenation solution of second kind of monomer/solvent of adding, under 0～100 ℃, stirring reaction 0.5～168h, said ATRP catalyzer, sacrifice initiator and/or Cu
2+Compound, second kind of monomeric mol ratio are 1: 1 and/or (0.01～0.2): (5～10000), it is material modified that compound high-density shown in the acquisition formula (I) contains long-tail chain bottle brush polymer chain.
3. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain, it is characterized in that saidly treating that material modified Z is urethane, tetrafluoroethylene, polymeric amide, epoxy resin, Vilaterm, Rohm tech inc, polyethyl acrylate, polyoxymethylene, PVA, poly hydroxybutyric acid, polycaprolactone, Zylox, silicon gel, PS, Vestolen PP 7052, chitosan, POLYACTIC ACID, Sodium bromoacetate homopolymer, SRU ester, silicon, silicon-dioxide, gold, titanium, titanium alloy, titanium chrome alloy, titanium chrome molybdenum or platinum.
4. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain, it is characterized in that said ATRP catalyzer is made up of CuX and part, and said CuX is CuBr and/or CuCl; Said part is 2, and at least a in 2-dipyridyl, three (2-methyl amido) ethamine, Tetramethyl Ethylene Diamine, PMDETA, three (2-pyridine) methylamine, the triphenylphosphine, the mol ratio of said CuX and part is 1: 0.1-100.
5. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain, it is characterized in that said sacrifice initiator is 2-isobutyl ethyl bromide, 2-bromo acid benzyl ester, 2-ethyl bromide, 2-chloro ethyl isobutyrate, 2-chloro benzyl methylpropanoate or 2-chloropropionic acid ethyl ester; Said Cu
2+Compound is CuCl
2Or CuBr
2
6. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain; It is characterized in that said solvent is methyl alcohol, ethanol, water, fluorine alcohol, THF, N, dinethylformamide and DMSO 99.8MIN. are at least a.
7. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain; It is characterized in that said first kind of monomer is hydroxy-end capped polyethylene glycol methacrylate-styrene polymer, 12 carbon glycol methacrylic esters, hydroxy-end capped polyethylene glycol acrylate and/or 12 carbon glycol propenoate.
8. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain, it is characterized in that said halogenating agent is 2-bromo isobutyl acylbromide, 2-chloro isobutyryl chloride, 2-bromo isobutyryl chloride, 2-bromo PROPIONYL CHLORIDE or 2-chloro propionyl chloride.
9. compound high-density according to claim 2 contains the material modified preparation method of long-tail chain bottle brush type polymer chain; It is characterized in that said second kind of monomer is sultaine methacrylic ester, 2-methacryloyl hydroxyethyl Phosphorylcholine, polyethylene glycol methacrylate-styrene polymer, mono methoxy polyethylene glycol methacrylic ester, sultaine propenoate, acryloyl hydroxyethyl Phosphorylcholine, polyethylene glycol acrylate, mono methoxy polyethylene glycol propenoate, acrylic amide, N-NSC 11448, N; N-DMAA, USAF RH-1, N-isopropyl methyl acrylic amide or N, the N-dimethylmethacryl amide.
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| CN104069743A (en) * | 2014-05-20 | 2014-10-01 | 江苏朗生生命科技有限公司 | Preparation method of polylactic acid hemodialysis membrane with zwitterionic surface |
| JP2016098287A (en) * | 2014-11-20 | 2016-05-30 | 花王株式会社 | Hydrophilic treatment agent |
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| CN108586668A (en) * | 2018-04-11 | 2018-09-28 | 天津大学 | High-toughness polypropylene and polylactic acid ion graft copolymer and preparation method thereof |
| CN108586668B (en) * | 2018-04-11 | 2020-07-21 | 天津大学 | High-toughness polypropylene and polylactic acid ion graft copolymer and preparation method thereof |
| EP3816205A4 (en) * | 2018-06-28 | 2022-03-09 | South China University of Technology | Hyaluronic acid-based zwitterionic polymer brush, preparation method thereof, and application thereof |
| CN113036087A (en) * | 2021-02-26 | 2021-06-25 | 中山大学 | Ultrahigh-sulfur-content two-dimensional molecular brush and preparation method and application thereof |
| CN113036087B (en) * | 2021-02-26 | 2022-04-26 | 中山大学 | Ultrahigh-sulfur-content two-dimensional molecular brush and preparation method and application thereof |
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