CN102911370B - Amphiphilic ternary polymer brush and nano capsule - Google Patents
Amphiphilic ternary polymer brush and nano capsule Download PDFInfo
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Abstract
The invention discloses an amphiphilic ternary polymer brush and a nano capsule. The amphiphilic ternary polymer brush has the following general formula, wherein A is polymer main chain, B is lipophilic polymer side chain, C is photo-crosslinked polymer side chain, D is hydrophilic polymer side chain, and the side chains B, C and D are randomly grafted onto the main chain A; and the nano capsule is prepared through dispersing the amphiphilic ternary polymer brush into an oil-water two-phase system, and then performing light crosslinking reaction or reaction initiated by light. The amphiphilic ternary polymer brush solves the difficulty that the particle size of the capsule can not be adjusted and controlled effectively by using the conventional segmented copolymers, and the size of the prepared photo-crosslinked nano capsule is easily adjusted and controlled; the nano capsule prepared by the emulsion self-assembly method is simple in operation and easy to use in large-scale preparation; the prepared hollow nano capsule is large in casting quantity; the photo-crosslinked nano capsule provided by the invention is stable, and according to the light crosslinking method, nontoxicity and safety are reliazed, and the environmental protection is realized. The amphiphilic ternary polymer brush has the following general formula: A-g-(B-r-C-r-D).
Description
Technical field
The invention belongs to self-assembly polymeric material field, be specifically related to a kind of amphipathic ternary molecular brush polymer, and the Nano capsule being prepared by this amphipathic ternary molecular brush polymer.
Background technology
Conventionally, Nano capsule is of a size of 1-1000nm, than the little several orders of magnitude of the size of microcapsule (1-2000 μ m).The relative microcapsule of Nano capsule have higher specific surface area, show special nano effect.Because this special nano effect of Nano capsule produces new characteristic, Nano capsule can be applicable to the high-technology fields such as medicament slow release, catalysis, biotechnology, makeup.Because the size of Nano capsule is less, synthetic difficulty is larger.
In recent years, along with the appearance of novel building-up reactions technology, as controllable free-radical polymerisation, point is chemical etc., also emerges recently the technology of a large amount of synthesis of nano capsules.At present, Nano capsule technology of preparing can be divided into non-bonding and chemical bonding mechanism by the interaction force between the polymkeric substance of formation capsule.Non-chemically bonding can be divided into emulsion/suspension polymerization, template polymerization method and self-assembling method; Chemical bonding is dendrimer preparation method.
Emulsion/suspension polymerization is a kind of traditional polymerization process, and technique is simple and practical, but the Nano capsule functionalization preparing is more single, without diversity, and capsule grain diameter wider distribution.
Template polymerization method, by selecting different big or small templates to be prepared capsule, can accurately be controlled the size of capsule and distribute, but usually needing template to carry out aftertreatment, and condition is harsh, and the pattern of capsule is had to larger impact.
Dendrimer preparation method also can accurately control size and the structure of capsule, but the process of synthetic dendrimer is more complicated, wayward, also often will be hydrolyzed and remove core kernel.
Self-assembling method is prepared Nano capsule can be simply by composition, the each several part weight ratio of regulation and control segmented copolymer, and the length of chain etc. is controlled the various functions of capsule.Especially emulsion self-assembling method, take segmented copolymer as emulsifying agent, with oil and water, carries out emulsification, can obtain the capsule of structure homogeneous.Emulsion self-assembling method can just can form stable capsule, and covering amount be large without adding other auxiliary agents, and preparation method's environmental friendliness is pollution-free.But the segmented copolymer difficulty of composite structure complexity is larger at present, condition is comparatively harsh, has limited the diversified capsule of self-assembling method processability.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of amphipathic ternary molecular brush polymer.
The synthetic method of the amphipathic ternary molecular brush polymer that another object of the present invention is to provide above-mentioned.
A difficult problem that is difficult to effectively regulate and control Nano capsule size in order to overcome prior art, a further object of the present invention is to provide a kind of Nano capsule, and this Nano capsule is to be prepared by above-mentioned amphipathic ternary molecular brush polymer.
The 4th object of the present invention is to provide the purposes of above-mentioned Nano capsule.
Object of the present invention is achieved through the following technical solutions:
An amphipathic ternary molecular brush polymer, has general formula as follows:
A-g-(B-r-C-r-D)
Wherein, A is main polymer chain, and B is lipophilicity polymer side chain, and C is the polymer side chain of photo-crosslinking structure, and D is hydrophilic macromolecule side chain, and side chain B, C and D are grafted on main chain A randomly.
Described amphipathic ternary molecular brush polymer, the polymerization degree of main chain is 5-1000, and the polymerization degree of side chain is 5-1000, and side chain graft rate is 5-100%.
The polymkeric substance that forms main chain can be a kind of in poly (glycidyl methacrylate) (PGMA), polyacrylic acid glycidyl ester (PGA), poly hydroxy ethyl acrylate (PHEMA) or polyacrylic acid hydroxyethanoic acid (PHEA);
The polymkeric substance that forms lipophilicity polymer side chain can be a kind of in polystyrene (PS), butyl polyacrylate (PBA), polyacrylonitrile (PAN), the tertiary ester of polyacrylic acid (PtBA), polymethyl acrylate (PMA), polymethylmethacrylate (PMMA), poly(lactic acid) (PLA), polycaprolactone (PCL) or polyvinyl acetate (PVA) (PVAc);
The polymkeric substance that forms the polymer side chain of photo-crosslinking structure can be a kind of in polymethyl acrylic acid cinnamoyl ethyl ester (PCEMA), polyacrylic acid cinnamoyl ethyl ester (PCEA) or poly (glycidyl methacrylate) (PGMA);
The polymkeric substance that forms hydrophilic macromolecule side chain can be a kind of in polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylic acid hydroxyethanoic acid (PHEA), poly hydroxy ethyl acrylate (PHEMA), polyacrylamide (PAM) or polymethyl acrylic acid hydroxypropyl acrylate (PHPMA).
Above-mentioned amphipathic ternary molecular brush polymer can be synthetic by methods such as radical polymerization, controllable free-radical polymerisation or some chemistry, and its synthetic method specifically comprises the following steps:
(1) synthetic main chain, then main chain is carried out to functionalization, obtain trunk polymer;
(2) synthetic side chain is introduced functional group simultaneously or the side chain after synthetic is carried out to functionalization in building-up process, obtains side chain polymer hydrophilic, oleophylic or photo-crosslinking structure;
(3) by a kind of main chain with can mix with the side chain corresponding a kind of hydrophilic, a kind of oleophylic and a kind of photo-crosslinking structure of each Elementary Function group generation chemical reaction of main chain, under catalyzer exists, carry out single step reaction, obtain amphipathic ternary molecular brush polymer;
The described synthetic main chain of step (1) can adopt the polymerization processs such as radical polymerization, controllable free-radical polymerisation, anionoid polymerization;
The described functionalization of step (1) is to introduce nitrine, ethynylene group etc. on each unit of main chain;
The described trunk polymer of step (1) can be P (GMA-N
3), P (GA-N
3), P (HEMA-C ≡ CH) or P (HEA-C ≡ CH) etc.;
The described synthetic side chain of step (2) can adopt the polymerization processs such as radical polymerization, controllable free-radical polymerisation, anionoid polymerization;
Described introducing functional group and the functionalization of step (2) is in the end of side chain, to introduce alkynyl, azido group etc.;
The described hydrophilic side chain polymer of step (2) can be PEG-C ≡ CH, PEG-N
3, PVA-C ≡ CH, PVA-N
3, PAA-C ≡ CH, PAA-N
3, PHEA-C ≡ CH, PHEMA-N
3, PHEMA-C ≡ CH, PHEMA-N
3, PAM-C ≡ CH, PAM-N
3, PHPMA-C ≡ CH or PHPMA-N
3deng;
The side chain polymer of the described oleophylic of step (2) can be PS-C ≡ CH, PS-N
3, PtBA-C ≡ CH, PtBA-N
3, PBA-C ≡ CH, PBA-N
3, PAN-C ≡ CH, PAN-N
3, PMA-C ≡ CH, PMA-N
3, PMMA-C ≡ CH, PMMA-N
3, PLA-C ≡ CH, PLA-N
3, PCL-C ≡ CH, PCL-N
3, PVAc-C ≡ CH or PVAc-N
3deng;
The side chain polymer of the described photo-crosslinking structure of step (2) can be PCEMA-C ≡ CH, PCEMA-N
3, PCEA-C ≡ CH, PCEA-N
3, PGMA-C ≡ CH or PGMA-N
3deng;
The described catalyzer of step (3) can be a kind of in following combination: copper sulfate and xitix, cuprous bromide and pentamethyl-diethylenetriamine, cuprous bromide and 2,2'-dipyridyl etc.
A Nano capsule, particle diameter is 20-1000nm, is to be prepared by above-mentioned amphipathic ternary molecular brush polymer; Being about to above-mentioned amphipathic ternary molecular brush polymer is scattered in oil and water two-phase system as emulsifying agent, the oleophylic side chain of amphipathic ternary molecular brush polymer is dissolved in oil phase, its hydrophilic side chain is soluble in the aqueous phase, the side chain of its photo-crosslinking structure does not dissolve profit two-phase, the interface that the side chain of photo-crosslinking structure is scattered in oil and water two-phase forms shell or wall, form stable " oil-in-water " or " water-in-oil " emulsion, through illumination, after crosslinked or light trigger initiation reaction, form stable Nano capsule;
Described oil and water two-phase system, oil phase wherein should be able to dissolve side chain polymer but can not dissolve the side chain polymer of photo-crosslinking structure, and oil and water two-phase system can be matched according to amphipathic ternary molecular brush polymer structure; The mixing solutions of described oil and the preferred perhydronaphthalene of water two-phase system and water.
Above-mentioned Nano capsule can be applicable in medicament slow release field, nano-reactor or catalyzer.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention adopts amphipathic ternary molecular brush to construct photo-crosslinking structure nano capsule, solves the difficult difficult problem that effectively regulates and control Nano capsule size of traditional segmented copolymer, and the photo-crosslinking structure nano capsule size of preparation easily regulates and be controlled.
(2) the present invention adopts emulsion self-assembly method to prepare Nano capsule, simple to operate, easily can mass-producing preparation.The hollow Nano capsule of preparation has great covering amount to hydrophobic or oleophobic material, and the size of covering amount depends on the solubleness of coating in oil phase or water, and little with the form relation of capsule.Nano capsule of the present invention Stability Analysis of Structures after photo-crosslinking, light linked method is nontoxic, environmentally friendly.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In following examples, related umber is all mass fractions.
Embodiment 1
Two parent's property ternary molecular brush polymer, are prepared by following steps:
(1) P (GMA-N
3) main chain synthetic
Get 1 part of 2-isobutyl ethyl bromide initiator, 200 parts of glycidyl methacrylate (GMA), 100 parts of phenyl ether, 1 part of CuBr and 1 part of N; N; N'; N'; " pentamethyl-diethylenetriamine (PMDETA); normal temperature carries out ATRP reaction under nitrogen protection obtains the poly (glycidyl methacrylate) (PGMA) that the polymerization degree (DP) is 40 to N.
Get 100 parts of PGMA(DP=40), 100 parts of NaN
3, 500 parts of dimethyl formamide (DMF) and 1 part of AlCl
3, 50 ° of C reactions 24 hours, obtain P (GMA-N
3), as main chain.
Synthesizing of (2) three kinds of side chains
Synthesizing of hydrophilic side chain: get 100 parts of mono methoxy polyethylene glycols (Mn=5000), 20 parts of 2-propynyl acetic acid, 20 parts of DMAPs (DMAP), 20 parts of 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC.HCl) and 200 parts of methylene dichloride, normal-temperature reaction 24 hours, obtains PEG-C ≡ CH(DP=114).
Synthesizing of oleophylic side chain: get 1 part of bromo acid propynyl ester initiator, 100 parts of polystyrene (PS), 100 parts of toluene, 1 part of CuBr and 1 part of PMDETA, 90 ° of C carry out ATRP reaction under nitrogen protection, obtain the PS-C ≡ CH that the polymerization degree (DP) is 30.
Photo-crosslinking structure side chain synthetic: get 1 part of bromo acid propynyl ester initiator, 150 parts of hydroxyethyl methylacrylates (HEMA), 100 parts of methyl alcohol, 1 part of CuCl and 1 part 2; 2'-dipyridyl; under nitrogen protection, 50 ° of C carry out ATRP reaction, obtain the PHEMA-C ≡ CH that the polymerization degree (DP) is 120.
Get 100 parts of PHEMA-C ≡ CH, 200 parts of cinnamyl chlorides and 300 parts of pyridines, carry out acylation reaction under normal temperature, obtain PCEMA-C ≡ CH again.
(3) two parent's property ternary molecular brush PGMA-g-'s (PS-r-PCEMA-r-PEG) is synthetic
Get 10 parts of P (GMA-N
3), 40 parts of PEG-C ≡ CH, 40 parts of PS-C ≡ CH, 20 parts of PCEMA-C ≡ CH, 500 parts of DMF, 1 part of CuSO
4and 5 parts of sodium ascorbates, react at normal temperatures 24 hours, obtain two parent's property ternary molecular brush polymer PGMA-g-(PEG-r-PCEMA-r-PS).
A Nano capsule, adopts emulsion self-assembly method to make, and its preparation method comprises the following steps:
In order accurately to control emulsion nano capsule, first getting 1 part of two parent's property ternary molecular brush polymer PGMA-g-(PS-r-PCEMA-r-PEG) is dissolved in 10 parts of methylene dichloride, under normal temperature mechanical stirring 1000rpm, methylene dichloride is splashed in the mixing solutions of 5 parts of perhydronaphthalenes and 100 parts of water, stir after 30 minutes, be warming up to 50 ° of C, keep 30 minutes, volatilize after methylene dichloride, obtain O/w emulsion.This emulsion is positioned under UV-light to illumination 1 hour, obtains the Nano capsule of rock steady structure, its particle diameter of Dynamic Light Scattering Determination (D
h) be 150nm.
Embodiment 2
Preparation method and raw material form all with embodiment 1, only two main chains of parent's property ternary molecular brush polymer and the polymerization degree of three kinds of side chains of embodiment 1 are regulated, and can make the Nano capsule of different-grain diameter size.The polymerization degree of main chain and three kinds of side chains, Nano capsule size are in Table 1.
Table 1: molecular brush main chain and the impact of the side chain polymerization degree on Nano capsule particle diameter
As can be seen from Table 1, by regulating the polymerization degree of main chain and side chain, can prepare the Nano capsule of different-grain diameter size.
Embodiment 3
Preparation method and raw material form all with embodiment 1, only change the composition of oleophylic side chain of two parent's property ternary molecular brush polymer of embodiment 1, can make the Nano capsule of different-grain diameter size.The composition of oleophylic side chain and Nano capsule size are in Table 2.
Table 2: molecular brush oleophylic side chain forms the impact on Nano capsule particle diameter
As can be seen from Table 2, by changing the composition of oleophylic side chain, can prepare the Nano capsule of different-grain diameter size.
Embodiment 4
Preparation method and raw material form all with embodiment 1, only change the composition of hydrophilic side chain of two parent's property ternary molecular brush polymer of embodiment 1, can make the Nano capsule of different-grain diameter size.The composition of hydrophilic side chain and Nano capsule size are in Table 3.
Table 3: molecular brush hydrophilic side chain forms the impact on Nano capsule particle diameter
As can be seen from Table 3, by changing the composition of hydrophilic side chain, can prepare the Nano capsule of different-grain diameter size.
Embodiment 5
Two parent's property ternary molecular brush polymer, are prepared by following steps:
(1) P (GMA-N
3) main chain synthetic
Get 1 part of 2-isobutyl ethyl bromide initiator, 200 parts of GMA, 100 parts of phenyl ether, 1 part of CuBr and 1 part of PMDETA, under nitrogen protection, normal temperature carries out ATRP reaction, the PGMA that the preparation polymerization degree (DP) is 100.
Get 100 parts of PGMA(DP=100), 100 parts of NaN
3, 500 parts of DMF and 1 part of AlCl
3, 50 ° of C reactions 24 hours, make P (GMA-N
3), as main chain.
Synthesizing of (2) three kinds of side chains
Synthesizing of hydrophilic side chain: get 100 parts of mono methoxy polyethylene glycols (Mn=2000), 20 parts of 2-propynyl acetic acid, 20 parts of DMAP, 20 parts of EDC.HCl and 200 parts of methylene dichloride, normal-temperature reaction 24 hours, makes PEG-C ≡ CH.
Synthesizing of oleophylic side chain: get 1 part of bromo acid propynyl ester initiator, 300 parts of PS, 100 parts of toluene, 1 part of CuBr and 1 part of PMDETA, 90 ° of C carry out ATRP reaction under nitrogen protection, obtain the PS-C ≡ CH that the polymerization degree (DP) is 120.
Synthesizing of photo-crosslinking structure side chain: get 1 part of bromo acid propynyl ester initiator, 300 parts of PGMA, 300 parts of toluene, 1 part of CuBr and 1 part of PMDETA, 50 ° of C carry out ATRP reaction under nitrogen protection, make the PGMA-C ≡ CH that the polymerization degree (DP) is 150.
(3) two parent's property ternary molecular brush polymer PGMA-g-'s (PS-r-PGMA-r-PEG) is synthetic
By 10 parts of P (GMA-N
3), 40 parts of PEG-C ≡ CH, 40 parts of PS-C ≡ CH, 20 parts of PGMA-C ≡ CH, 500 parts of DMF, 1 part of CuSO
4and 5 parts of sodium ascorbates, react at normal temperatures 24 hours, make two parent's property ternary molecular brush polymer PGMA-g-(PEG-r-PGMA-r-PS).
A Nano capsule, adopts emulsion self-assembly method to make, and its preparation method comprises the following steps:
1 part of synthetic PGMA-g-(PS-r-PGMA-r-PEG) is dissolved in 10 parts of methylene dichloride, under normal temperature mechanical stirring 1000rpm, methylene dichloride is splashed in the mixing solutions of 10 parts of perhydronaphthalenes and 100 parts of water, stir after 30 minutes, be warming up to 50 ° of C, keep 30 minutes, volatilize after methylene dichloride, be prepared into O/w emulsion, add 1 part of light trigger dimethoxybenzoin, PGMA is carried out to photo-crosslinking, obtain the Nano capsule of rock steady structure, DLS measures its particle diameter (D
h) be 250nm.
Embodiment 6
Two parent's property ternary molecular brush polymer, are prepared by following steps:
(1) P (HEMA-C ≡ CH) main chain is synthetic
Get 1 part of 2-isobutyl ethyl bromide initiator, 500 parts of HEMA, 100 parts of methyl alcohol, 1 part of CuCl and 1 part of BiPy, under nitrogen protection, normal temperature carries out ATRP reaction, makes the PHEMA that the polymerization degree (DP) is 200.
Get 100 parts of PHEMA(DP=60), 200 parts of 2-propynyl acetic acid, 50 parts of DMAP, 50 parts of EDC.HCl and 500 parts of DMF, normal-temperature reaction 24 hours, make P (HEMA-C ≡ CH), as main chain.
Synthesizing of (2) three kinds of side chains
Synthesizing of hydrophilic side chain: get 100 parts of mono methoxy polyethylene glycols (Mn=2000), 50 parts of 2-bromine isobutyl bromides, 50 parts of triethylamines and 200 parts of methylene dichloride, normal-temperature reaction 24 hours, then add 50 parts of NaN
3, make PEG-N
3.
Synthesizing of oleophylic side chain: get 1 part of bromo acid propynyl ester initiator, 500 parts of PS, 100 parts of toluene, 1 part of CuBr and 1 part of PMDETA, 90 ° of C carry out ATRP reaction 6 hours under nitrogen protection, add 50 parts of NaN
3, make the PS-N that the polymerization degree (DP) is 200
3.
Synthesizing of photo-crosslinking structure side chain: get 1 part of bromo acid propynyl ester initiator, 100 parts of HEA, 100 parts of methyl alcohol, 1 part of CuBr and 1 part of BiPy, 50 ° of C carry out ATRP reaction 2 hours under nitrogen protection, add 50 parts of NaN
3, make the PHEA-N that the polymerization degree (DP) is 50
3.Again by 100 parts of PHEA-N
3, 200 parts of cinnamyl chlorides and 300 parts of pyridines, carry out acylation reaction under normal temperature, make PCEA-N
3.
(3) two parent's property ternary molecular brush polymer PHEMA-g-'s (PEG-r-PCEA-r-PS) is synthetic
By 10 parts of P (HEMA-C ≡ CH), 30 parts of PEG-N
3, 40 parts of PS-N
3, 20 parts of PCEA-N
3, 500 parts of DMF, 1 part of CuSO
4and 5 parts of sodium ascorbates, react at normal temperatures preparation two parent's property ternary molecular brush polymer PHEMA-g-(PEG-r-PCEA-r-PS) 24 hours.
A Nano capsule, adopts emulsion self-assembly method to make, and its preparation method comprises the following steps:
1 part of synthetic PHEMA-g-(PEG-r-PCEA-r-PS) is dissolved in to 10 parts of methylene dichloride, under normal temperature mechanical stirring 1000rpm, methylene dichloride is splashed in the mixing solutions of 100 parts of cyclohexanes and 3 parts of water, stir after 30 minutes, be warming up to 50 ° of C, keep 30 minutes, volatilize after methylene dichloride, be prepared into water-in-oil emulsion.Emulsion is positioned under UV-light to illumination 1 hour, obtains the Nano capsule of rock steady structure, DLS measures its particle diameter (D
h) be 350nm.
Embodiment 7
Preparation method and raw material form all with embodiment 6, only two main chains of parent's property ternary molecular brush polymer and the polymerization degree of three kinds of side chains of embodiment 6 are regulated, and can make the Nano capsule of different-grain diameter size.The polymerization degree of main chain and three kinds of side chains, Nano capsule size are in Table 4.
Table 4: molecular brush main chain and the impact of the side chain polymerization degree on Nano capsule particle diameter
As can be seen from Table 4, by regulating the polymerization degree of main chain and side chain, can prepare the Nano capsule of different-grain diameter size.
Embodiment 8
Preparation method and raw material form all with embodiment 6, only change the composition of oleophylic side chain of two parent's property ternary molecular brush polymer of embodiment 6, can make the Nano capsule of different-grain diameter size.The composition of oleophylic side chain and Nano capsule size are in Table 5.
Table 5: molecular brush oleophylic side chain forms the impact on Nano capsule particle diameter
As can be seen from Table 5, by changing the composition of oleophylic side chain, can prepare the Nano capsule of different-grain diameter size.
Embodiment 9
Preparation method and raw material form all with embodiment 6, only change the composition of hydrophilic side chain of two parent's property ternary molecular brush polymer of embodiment 6, can make the Nano capsule of different-grain diameter size.The composition of hydrophilic side chain and Nano capsule size are in Table 6.
Table 6: molecular brush hydrophilic side chain forms the impact on Nano capsule particle diameter
As can be seen from Table 6, by changing the composition of hydrophilic side chain, can prepare the Nano capsule of different-grain diameter size.
Embodiment 10
Preparation method and raw material form all with embodiment 6, the percentage of grafting of side chain that only changes two parent's property ternary molecular brush polymer of embodiment 6 be the relative molecular fraction of each side chain than forming, can make the Nano capsule of different-grain diameter size.The percentage of grafting of side chain and Nano capsule size are in Table 7.
Table 7: molecular brush hydrophilic side chain forms the impact on Nano capsule particle diameter
As can be seen from Table 7, by changing the molecular fraction ratio of the percentage of grafting of side chain, form, can prepare the Nano capsule of different-grain diameter size.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an amphipathic ternary molecular brush polymer, is characterized in that having general formula as follows:
A-g-(B-r-C-r-D)
Wherein, A is main polymer chain, and B is lipophilicity polymer side chain, and C is the polymer side chain of photo-crosslinking structure, and D is hydrophilic macromolecule side chain, and side chain B, C and D are grafted on main chain A randomly;
The polymkeric substance that forms main chain is a kind of in poly (glycidyl methacrylate), polyacrylic acid glycidyl ester, poly hydroxy ethyl acrylate or polyacrylic acid hydroxyethanoic acid;
The polymkeric substance that forms lipophilicity polymer side chain is a kind of in polystyrene, butyl polyacrylate, polyacrylonitrile, polymethyl acrylate, polymethylmethacrylate, poly(lactic acid), polycaprolactone or polyvinyl acetate (PVA);
The polymkeric substance that forms the polymer side chain of photo-crosslinking structure is a kind of in polymethyl acrylic acid cinnamoyl ethyl ester, polyacrylic acid cinnamoyl ethyl ester or poly (glycidyl methacrylate);
The polymkeric substance that forms hydrophilic macromolecule side chain is a kind of in polyoxyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylic acid hydroxyethanoic acid, poly hydroxy ethyl acrylate, polyacrylamide or polymethyl acrylic acid hydroxypropyl acrylate;
The synthetic method of described amphipathic ternary molecular brush polymer, comprises the following steps:
(1) synthetic main chain, then main chain is carried out to functionalization, obtain trunk polymer;
(2) synthetic side chain is introduced functional group simultaneously or the side chain after synthetic is carried out to functionalization in building-up process, obtains side chain polymer hydrophilic, oleophylic or photo-crosslinking structure;
(3) a kind of main chain is mixed with corresponding a kind of side chain hydrophilic, a kind of oleophylic and a kind of photo-crosslinking structure, under catalyzer exists, carry out single step reaction, obtain amphipathic ternary molecular brush polymer;
The described functionalization of step (1) is to introduce nitrine, ethynylene group on each unit of main chain;
Described introducing functional group and the functionalization of step (2) is in the end of side chain, to introduce alkynyl, azido group;
The described catalyzer of step (3) can be a kind of in following combination: copper sulfate and xitix, cuprous bromide and pentamethyl-diethylenetriamine, cuprous bromide and 2,2'-dipyridyl.
2. amphipathic ternary molecular brush polymer according to claim 1, is characterized in that: described amphipathic ternary molecular brush polymer, and the polymerization degree of main chain is 5-1000, and the polymerization degree of side chain is 5-1000, and side chain graft rate is 5-100%.
3. the synthetic method of the amphipathic ternary molecular brush polymer described in claim 1 or 2, is characterized in that comprising the following steps:
(1) synthetic main chain, then main chain is carried out to functionalization, obtain trunk polymer;
(2) synthetic side chain is introduced functional group simultaneously or the side chain after synthetic is carried out to functionalization in building-up process, obtains side chain polymer hydrophilic, oleophylic or photo-crosslinking structure;
(3) a kind of main chain is mixed with corresponding a kind of side chain hydrophilic, a kind of oleophylic and a kind of photo-crosslinking structure, under catalyzer exists, carry out single step reaction, obtain amphipathic ternary molecular brush polymer;
The described functionalization of step (1) is to introduce nitrine, ethynylene group on each unit of main chain;
Described introducing functional group and the functionalization of step (2) is in the end of side chain, to introduce alkynyl, azido group;
The described catalyzer of step (3) can be a kind of in following combination: copper sulfate and xitix, cuprous bromide and pentamethyl-diethylenetriamine, cuprous bromide and 2,2'-dipyridyl.
4. the synthetic method of amphipathic ternary molecular brush polymer according to claim 3, is characterized in that: the described trunk polymer of step (1) is P (GMA-N
3), P (GA-N
3), P (HEMA-C ≡ CH) or P (HEA-C ≡ CH).
5. the synthetic method of amphipathic ternary molecular brush polymer according to claim 3, is characterized in that: the described hydrophilic side chain polymer of step (2) is PEG-C ≡ CH, PEG-N
3, PVA-C ≡ CH, PVA-N
3, PAA-C ≡ CH, PAA-N
3, PHEA-C ≡ CH, PHEMA-N
3, PHEMA-C ≡ CH, PAM-C ≡ CH, PAM-N
3, PHPMA-C ≡ CH or PHPMA-N
3.
6. the synthetic method of amphipathic ternary molecular brush polymer according to claim 3, is characterized in that: the side chain polymer of the described oleophylic of step (2) can be PS-C ≡ CH, PS-N
3, PtBA-C ≡ CH, PtBA-N
3, PBA-C ≡ CH, PBA-N
3, PAN-C ≡ CH, PAN-N
3, PMA-C ≡ CH, PMA-N
3, PMMA-C ≡ CH, PMMA-N
3, PLA-C ≡ CH, PLA-N
3, PCL-C ≡ CH, PCL-N
3, PVAc-C ≡ CH or PVAc-N
3.
7. the synthetic method of amphipathic ternary molecular brush polymer according to claim 3, is characterized in that: the side chain polymer of the described photo-crosslinking structure of step (2) is PCEMA-C ≡ CH, PCEMA-N
3, PCEA-C ≡ CH, PCEA-N
3, PGMA-C ≡ CH or PGMA-N
3.
8. a Nano capsule, is characterized in that: particle diameter is 20-1000nm, is to be prepared by following steps by the amphipathic ternary molecular brush polymer described in claim 1 or 2:
Amphipathic ternary molecular brush polymer described in claim 1 or 2 is scattered in oil and water two-phase system, through illumination, after crosslinked or light trigger initiation reaction, forms Nano capsule.
9. Nano capsule according to claim 8, is characterized in that: described oil and water two-phase system are the mixing solutions of perhydronaphthalene and water.
10. the application of the Nano capsule described in claim 8 or 9 in medicament slow release field, nano-reactor or catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210407079.0A CN102911370B (en) | 2012-10-23 | 2012-10-23 | Amphiphilic ternary polymer brush and nano capsule |
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| CN101891870A (en) * | 2010-06-30 | 2010-11-24 | 华南理工大学 | Amphiphilic copolymer brush with pH responsiveness, preparation method thereof and use thereof |
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| CN101891870A (en) * | 2010-06-30 | 2010-11-24 | 华南理工大学 | Amphiphilic copolymer brush with pH responsiveness, preparation method thereof and use thereof |
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