CN103642050A - Dendritic polymer with POSS group and preparation method thereof - Google Patents

Dendritic polymer with POSS group and preparation method thereof Download PDF

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CN103642050A
CN103642050A CN201310538028.6A CN201310538028A CN103642050A CN 103642050 A CN103642050 A CN 103642050A CN 201310538028 A CN201310538028 A CN 201310538028A CN 103642050 A CN103642050 A CN 103642050A
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吴德成
王星
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Institute of Chemistry CAS
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Abstract

The invention relates to a dendritic polymer with POSS group and preparation method thereof. The preparation of the product comprises the following steps: designing a POSS group intermediate R2-POSS-(R1)n-1 (n=6, 8, 10, 12) with asymmetric structure, and then using a chemical synthetic method, and obtaining a dendritic polymer (containing derivatives thereof) containing POSS group and a lot of end functional groups. The product has the advantages of unique structure design and diversified selections, thereby the product has latent application prospects for the aspects of surfactant, biological medicine carrier, catalyst, photon crystallization, optical material, anti-corrosion material, electronic material, information recording material, printing material, battery material, magnetic material, electronic luminescent device, etc.

Description

There is branch-shape polymer of POSS base and preparation method thereof
Technical field
The present invention relates to POSS base, particularly there is branch-shape polymer of POSS base and preparation method thereof.
Background technology
Branch-shape polymer (Dendrimers) is the novel synthetic polymer of a class occurring in recent years, there is complete branching and regular molecular structure, perfect monodispersity, nano level size, a large amount of functional end-groups, numerous features such as inner cavity, good solubility, low viscosity and easy rheology, be specially adapted to the functional modification research of organic polymer material.
A large amount of end group numbers is the most significant feature of branch-shape polymer, and along with the increase of branch-shape polymer algebraically, the number of end group can be by the mode rapid growth of exponential growth.On group endways during ligation characteristic group, the reactive functional groups with very high density be will form, thereby dispersion agent or the coating agent of the highly sensitive supplement of functional mass, highly sensitive multifunctional linking agent, metal or metal oxide are expected to be applied to; And along with the algebraically of branch-shape polymer increases, be subject to the gradually intensive restriction bringing of molecular surface functional group, inside at branch-shape polymer can form a large amount of cavitys, thereby make branch-shape polymer can be used as host molecule, by effect complexing guest molecules such as intermolecular forces, supramolecule reactive force and hydrogen bonds.Therefore, in branch-shape polymer, how setting kind and the number of end group, is the important factor of the characteristic performance of branch-shape polymer, has very important application prospect.
POSS (Polyhedral Oligomeric Silsesquioxanes, polyhedron polyhedral oligomeric silsesquioxane) is quite concerned in recent years a kind of organic-inorganic nano hydridization molecule, and the skeleton symbol of POSS is (RSiO l.5) n, n=6 wherein, 8,10,12, can be abbreviated as T6, T8, T10, T12.It spatially has three-dimensional polyhedral structure, has inorganic cage shape kernel and 6,8,10 or 12 organo-functional group summits (inertia or non-inertia) that Si-O-Si key forms.POSS based polyalcohol is different from SiO 2, organosilicon and other filler, be a kind of Inorganic-Organic Hybrid Material with nano-scale and regular cage structure, there is hybrid structure in (a) molecule; (b) nanometer size effect; (c) structure designability; (d) good solubility; (e) high and (f) feature such as hyperergy of thermostability and structural stability, takes into account processibility, toughness and the low cost of organic materials, retains thermo-oxidative stability that inorganic materials is high and excellent mechanical property simultaneously.
Therefore, POSS based polyalcohol hybrid material becomes the selection of tool potentiality in Molecular Structure Design, and POSS is combined with dendritic macromole, is exactly a kind of important way.6 of POSS, 8,10 or 12 summits or any one summit wherein can grow branching segment by chemical reaction iteration, again through end modified functionalization (dispersing method), or directly connect end containing the wedge shape branch primitive (dendron) (convergence method) of functional groups, make POSS base dendritic macromole.
POSS base branch-shape polymer has merged the advantage of POSS and dendrimer structure and performance, and for example, POSS cage shape kernel can strengthen thermostability and the covering property of dendritic macromole; POSS molecule has 6,8, and 10 or 12 modifiable summits are sterically hindered larger, take it as nucleosynthesis dendrimer, just can reach higher-end base density and spherical symmetric structure when lower algebraically, and branching segment is difficult for occurring to be wound around or to return and sting; And dendritic macromole can not only can effectively be widened the modifiability of POSS functional group by the highly branched molecular structure of generation growth.As a kind of novel nano-hybrid material, POSS base dendritic macromole relies on its unique performance advantage and potential using value to cause vast researcher keen interest.
But up to now, POSS base branch-shape polymer mainly comprises the core as branch-shape polymer based on T6 (hexahedron polyhedral oligomeric silsesquioxane), T8 (octahedra polyhedral oligomeric silsesquioxane), T10 (decahedron polyhedral oligomeric silsesquioxane), T12 (dodecahedron polyhedral oligomeric silsesquioxane) and their derivative thereof, end group number is derivative limited, fails to embody greatly the performance in POSS base branch-shape polymer greater functionality site.The preparation of the branch-shape polymer of constructing based on POSS unit at present, does not also have relevant bibliographical information.
Summary of the invention
One of object of the present invention is to provide the branch-shape polymer (comprising its derivative) of the POSS base of the two-layer above POSS structure of having of compound with regular structure, and functional end-group kind and the number of described branch-shape polymer (comprising its derivative) are various.
Two of object of the present invention is to provide the branch-shape polymer with POSS base that synthesis step is simple, reaction conditions the is gentle preparation method of (comprising its derivative).
The present invention is in order to solve Problems Existing, realize the demand in the branch-shape polymer greater functionality site of POSS base, the structure and the suitable feasible preparation method of selection that design the branch-shape polymer of constructing unique novel two-layer above POSS unit are most important for the functional branch fluidized polymer (comprising its derivative) obtaining.
The present invention is first by the asymmetric POSS base of project organization intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12), then utilize chemical synthesis process, under lower algebraic sheaf, just can obtain the branch-shape polymer with POSS base (comprising its derivative) that contains a large amount of end functional groups, the structure design of this uniqueness and select diversified advantage to make it there is potential application prospect at aspects such as nanocapsule, tensio-active agent, biological medicine carrier, catalysis, electron luminescence devices.
The branch-shape polymer of the POSS of having base of the present invention has one of following structure:
Figure BDA0000407895800000031
In structural formula i-iv (be respectively the branch-shape polymer of hexahedron POSS base, the branch-shape polymer of the branch-shape polymer of octahedra POSS base, decahedron POSS base, the branch-shape polymer of dodecahedron POSS base), A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; C is polyhedral oligomeric silsesquioxane (POSS), fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer or drug molecule; X has a kind of in following structural formula (v-viii);
Figure BDA0000407895800000032
Wherein: B is polyhedral oligomeric silsesquioxane (POSS), fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer or drug molecule.
The described branch-shape polymer with POSS base has two-layer or three layers of POSS structure.
The described branch-shape polymer with POSS base with two-layer POSS structure is that C and the B in structural formula v～viii in structural formula i-iv do not select polyhedral oligomeric silsesquioxane (POSS).
The described branch-shape polymer with POSS base with three layers of POSS structure is that C and the B in structural formula v～viii in structural formula i-iv selects polyhedral oligomeric silsesquioxane (POSS).
For example: when the X in selecting structural formula ii is structural formula vi, the branch-shape polymer that gained has POSS base has following structure:
Figure BDA0000407895800000042
In formula, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; B and C are polyhedral oligomeric silsesquioxane (POSS), fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer or drug molecule independently.If B and C do not select polyhedral oligomeric silsesquioxane (POSS), what obtain so is exactly the POSS base branch-shape polymer with two-layer POSS structure; When B or C selection polyhedral oligomeric silsesquioxane (POSS), what obtain so is exactly the POSS base branch-shape polymer with three layers of POSS structure.
Described polyhedral oligomeric silsesquioxane (POSS) is selected from six ethenyl cage model oligomeric silsesquioxanes, eight ethenyl cage model oligomeric silsesquioxanes, eight (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, eight (diphenylphosphine ethyl) polyhedral oligomeric silsesquioxane, eight azido-polyhedral oligomeric silsesquioxanes, eight sulfydryl POSS, octaphenyl polyhedral oligomeric silsesquioxane, octa-epoxy cage type oligomeric silsesquioxane, eight sulfuryl chlorio polyhedral oligomeric silsesquioxanes, eight carboxyl polyhedral oligomeric silsesquioxanes, ten ethenyl cage model oligomeric silsesquioxanes, ten divinyl polyhedral oligomeric silsesquioxanes, mono-vinyl polyhedral oligomeric silsesquioxane, single (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, single sulfydryl polyhedral oligomeric silsesquioxane, a kind of in single epoxy group(ing) polyhedral oligomeric silsesquioxane and mono carboxylic polyhedral oligomeric silsesquioxane etc.
Described fluorescent mark and derivative thereof are selected from fluorescein isothiocyanate, hydroxyl fluorescein, Tetrachlorofluorescein, tetraethylrhodamine, carboxyl tetramethyl-rhodamine, naphthalene, anthracene, pyrene, indoles, acridine, tonka bean camphor, luxuriant and rich with fragrance ingot, phycoerythrobilin N, piperazine Luoning and Toyomycin A 3deng in a kind of.
Described organic group is selected from hydrogen atom, halogen atom (F, Cl, Br or I), C 1-30a kind of in alkyl, thiazolinyl, alkynyl, alicyclic radical, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, sulfonic group, nitrogen benzide, phenolic hydroxyl group and epoxy group(ing) etc.
Described chain polymer is selected from polystyrene (PS), poly(lactic acid) (PLA), Poly(D,L-lactide-co-glycolide (PLGA), polyacrylic acid (PAA), polyester (PET), polymethyl acrylic acid monoglyceride (PGMA), polyacrylamide (PAM), polymethyl acrylate (PMA), polyimide (PI), polymethylmethacrylate (PMMA), Vinyl Acetate Copolymer (PVAc), polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), poly-N, a kind of in N-dimethylamino ethyl ester (PDMAEMA) and NIPA (PNIPAM) etc.
That described branch-shape polymer is selected from is polyamide-based, polyacrylamide, polyethers, polyester, polysilanes and a kind of containing in Phosphorus dendrimer etc.
Described drug molecule is selected from a kind of in tamoxifen, mercaptopurine, taxol, Zorubicin, daunorubicin, vinpocetin, podophyllotoxin, l-Asparaginase, harringtonine, Rheumatrex, Rimactazid, atorvastatin and rapamycin etc.
The preparation method of the branch-shape polymer of the POSS of having base of the present invention is:
(1) by polyhedral oligomeric silsesquioxane (POSS) and POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) are dissolved in organic solvent according to the mol ratio of 1:6～1:80, under the condition existing, carry out chemical reaction at the catalyzer of catalytic amount, obtain the branch-shape polymer with POSS base of aforementioned formula i-iv structure;
Described POSS base intermediate R 2-POSS-(R 1) n-1in R 1and R 2a kind of independently selected from the organic groups such as halogen atom (F, Cl, Br or I), thiazolinyl, alkynyl, alicyclic radical, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, sulfonic group, nitrogen benzide, phenolic hydroxyl group and epoxy group(ing), and R 1and R 2can not there is identical organic group.
In described formula i-iv structure, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; C is polyhedral oligomeric silsesquioxane (POSS); B in X structural formula v～viii is described R 2-POSS-(R 1) n-1middle R 1a kind of in the organic group limiting.
It is 1:0.1～1:3 with the mol ratio of catalyzer that the usage quantity of described catalyzer is preferably polyhedral oligomeric silsesquioxane (POSS).
Or
By the first POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) and the second POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) are dissolved in organic solvent according to the mol ratio of 1:6～1:80, under the condition existing, carry out chemical reaction at the catalyzer of catalytic amount, obtain the branch-shape polymer with POSS base of aforementioned formula i-iv structure;
Wherein: the first POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) and the second POSS base intermediate R 2-POSS-(R 1) n-1r in (n=6,8,10,12) 1and R 2a kind of independently selected from the organic groups such as halogen atom (F, Cl, Br or I), thiazolinyl, alkynyl, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, phenolic hydroxyl group and epoxy group(ing), and the first POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) and the second POSS base intermediate R 2-POSS-(R 1) n-1r in (n=6,8,10,12) 1with R 2to select respectively 4 kinds of different organic groups;
In described formula i-iv structure, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30, and C is the second POSS base intermediate R 2-POSS-(R 1) n-1r in (n=6,8,10,12) 1a kind of in the organic group limiting, the B in X structural formula v～viii is the first POSS base intermediate R 2-POSS-(R 1) n-1r in (n=6,8,10,12) 2a kind of in the organic group limiting; Or A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30, C is the second POSS base intermediate R 2-POSS-(R 1) n-1r in (n=6,8,10,12) 2a kind of in the organic group limiting, the B in X structural formula v～viii is the first POSS base intermediate R 2-POSS-(R 1) n-1r in (n=6,8,10,12) 1a kind of in the organic group limiting;
The usage quantity of described catalyzer is preferably the first POSS base intermediate R 2-POSS-(R 1) n-1with the mol ratio of catalyzer be 1:0.1～1:3.
(2) branch-shape polymer with POSS base of aforementioned formula i-iv structure step (1) being obtained carries out further modification, obtains the B branch-shape polymer with POSS base different from C group in formula i-iv structure; The branch-shape polymer with POSS base of the aforementioned formula i-iv structure that step (1) is obtained is dissolved in organic solvent according to the mol ratio of 1:8～1:350 with the molecule with functional group, under the condition existing at the catalyzer of catalytic amount, carry out chemical reaction, obtain the branch-shape polymer with POSS base of aforementioned formula i-iv structure;
In described formula i-iv structure, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; B in C and X structural formula v～viii is a kind of independently selected from polyhedral oligomeric silsesquioxane (POSS), fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer and drug molecule respectively;
When B is selected from organic group, the selected organic group of B in the organic group that it is selected and step (1) can not be selected same organic group simultaneously; When C is selected from organic group, the selected organic group of C in the organic group that it is selected and step (1) can not be selected same organic group simultaneously; B in step (2) is to select different organic groups from the organic group described in C simultaneously;
Functional group in the described molecule with functional group is to be selected from a kind of in halogen atom (F, Cl, Br or I), thiazolinyl, alkynyl, alicyclic radical, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, sulfonic group, nitrogen benzide, phenolic hydroxyl group and epoxy group(ing) etc.; Wherein, described molecule is polyhedral oligomeric silsesquioxane (POSS), fluorescent mark and derivative thereof, chain polymer, branch-shape polymer or drug molecule.
It is 1:0.1～1:3 that the usage quantity of described catalyzer is preferably the branch-shape polymer with POSS base of aforementioned formula i-iv structure and the mol ratio of catalyzer that step (1) obtains.
The branch-shape polymer with POSS base of the aforementioned formula i-iv structure that described step (1) obtains is the branch-shape polymer with the POSS base of two-layer POSS structure.
The branch-shape polymer with POSS base of the aforementioned formula i-iv structure that described step (2) obtains is the branch-shape polymer with the POSS base of two-layer or three layers of POSS structure.
Described catalyzer is selected from DMAP (DMAP), 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI), dicyclohexylcarbodiimide (DCC), triethylamine, acetic acid, the vitriol oil, Diisopropyl azodicarboxylate (AIBN), 2,2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), cuprous bromide (CuBr) and N, N, N', N, ' one or more in N''-five methyl diethylentriamine (PMDETA) etc.
Described organic solvent is selected from one or more in methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), methylene dichloride, trichloromethane, ether, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dioxane, acetone, acetonitrile, normal hexane, hexanaphthene or sherwood oil etc.
Described polyhedral oligomeric silsesquioxane (POSS) is selected from six ethenyl cage model oligomeric silsesquioxanes, eight ethenyl cage model oligomeric silsesquioxanes, eight (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, eight (diphenylphosphine ethyl) polyhedral oligomeric silsesquioxane, eight azido-polyhedral oligomeric silsesquioxanes, eight sulfydryl POSS, octaphenyl polyhedral oligomeric silsesquioxane, octa-epoxy cage type oligomeric silsesquioxane, eight sulfuryl chlorio polyhedral oligomeric silsesquioxanes, eight carboxyl polyhedral oligomeric silsesquioxanes, ten ethenyl cage model oligomeric silsesquioxanes, ten divinyl polyhedral oligomeric silsesquioxanes, mono-vinyl polyhedral oligomeric silsesquioxane, single (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, single sulfydryl polyhedral oligomeric silsesquioxane, a kind of in single epoxy group(ing) polyhedral oligomeric silsesquioxane and mono carboxylic polyhedral oligomeric silsesquioxane etc.
Described POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) have one of following structure:
Figure BDA0000407895800000081
In formula, R 1and R 2a kind of independently selected from the organic groups such as halogen atom (F, Cl, Br or I), thiazolinyl, alkynyl, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, phenolic hydroxyl group and epoxy group(ing), and R 1and R 2can not there is identical organic group.
Described POSS base intermediate R 2-POSS-(R 1) n-1(n=6,8,10,12) can be prepared by following methods:
Polyhedral oligomeric silsesquioxane (POSS) and organic molecule are dissolved in organic solvent according to the mol ratio of 1:0.5～1:3, under the condition existing at the catalyzer of catalytic amount, carry out chemical reaction, obtain having the POSS base intermediate R of single terminal groups modification of formula I～IV structure 2-POSS-(R 1) n-1(n=6,8,10,12).
It is 1:0.1～1:2 with the mol ratio of catalyzer that the usage quantity of described catalyzer is preferably polyhedral oligomeric silsesquioxane (POSS).
Described polyhedral oligomeric silsesquioxane (POSS) is selected from six ethenyl cage model oligomeric silsesquioxanes, eight ethenyl cage model oligomeric silsesquioxanes, eight (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, eight (diphenylphosphine ethyl) polyhedral oligomeric silsesquioxane, eight azido-polyhedral oligomeric silsesquioxanes, eight sulfydryl POSS, octaphenyl polyhedral oligomeric silsesquioxane, octa-epoxy cage type oligomeric silsesquioxane, eight sulfuryl chlorio polyhedral oligomeric silsesquioxanes, eight carboxyl polyhedral oligomeric silsesquioxanes, ten ethenyl cage model oligomeric silsesquioxanes, ten divinyl polyhedral oligomeric silsesquioxanes, mono-vinyl polyhedral oligomeric silsesquioxane, single (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, single sulfydryl polyhedral oligomeric silsesquioxane, a kind of in single epoxy group(ing) polyhedral oligomeric silsesquioxane and mono carboxylic polyhedral oligomeric silsesquioxane etc.
Described catalyzer is selected from DMAP (DMAP), 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI), dicyclohexylcarbodiimide (DCC), triethylamine, acetic acid, the vitriol oil, Diisopropyl azodicarboxylate (AIBN), 2,2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), cuprous bromide (CuBr) and N, N, N', N, ' one or more in N''-five methyl diethylentriamine (PMDETA) etc.
Described organic molecule selected from mercapto acetic acid, thiohydracrylic acid, mercaptoethylamine, aminoethyle alcohol, Mercaptamine, cysteamine, mercaptoethanol, allyl mercaptan, alkynes propylmercaptan, 2 mercaptopropionic acid, 2-MEA, Mercaptobutanol, propargylic acid, propargylamine, metachloroperbenzoic acid, trifluoromethanesulfonic acid, Methanesulfonyl chloride, benzene sulfonyl chloride, propargyl alcohol, carbamyl hydrazine, Succinic anhydried, maleic anhydride, epoxy bromopropane, epoxy chloropropane, alkynes the third bromine, sodiumazide, aminoazobenzene, hydroxyazobenzene, carboxyl nitrogen benzide, acrylate chloride, methacrylic chloride, a kind of in P-hydroxybenzoic acid and hydroxyanilines etc.
Described organic solvent is selected from one or more in methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), methylene dichloride, trichloromethane, ether, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dioxane, acetone, acetonitrile, normal hexane, hexanaphthene or sherwood oil etc.
The branch-shape polymer of the POSS of having base of the present invention can be used as the materials'uses such as preparation table surface-active agent, biological medicine carrier, catalyzer, photonic crystal, optical material, erosion resistant, electronic material, information-recording material, printing material, battery material, magneticsubstance, electron luminescence device.
The present invention, with respect to prior art, has following advantage:
(1) the POSS base intermediate R that prepared by the present invention 2-POSS-(R 1) n-1raw material sources extensive, preparation cost is cheap, the asymmetric intermediate after modification is of a great variety, structure design is versatile and flexible.
(2) what the present invention adopted is all conventional chemical reaction, and synthesis step is simple, reaction conditions is gentle, easy to implement, and has highly selective.
(3) kind of the POSS base branch-shape polymer with two-layer or multilayer POSS structure that prepared by the present invention is various, and the particular functional group of bonding can give the functional of POSS radical derivative excellence.
(4) the POSS base branch-shape polymer that prepared by the present invention and derivative have the surface functional group of accurately controlled structure, size, shape and chemically modified, make it at aspects such as tensio-active agent, biological medicine carrier, catalyzer, photonic crystal, optical material, erosion resistant, electronic material, information-recording material, printing material, battery material, magneticsubstance, electron luminescence devices, have potential application prospect.
Accompanying drawing explanation
POSS base intermediate OH-POSS-(vinyl) in Fig. 1 embodiment of the present invention 35 7's 1h NMR and 13c NMR collection of illustrative plates (CDCl 3, 400MHz).
The FT-IR collection of illustrative plates of the derivative of the POSS base branch-shape polymer with three layers of POSS structure in Fig. 2 embodiment of the present invention 35, wherein A is OH-POSS-(vinyl) 7, B is POSS 9-(vinyl) 56(1 generation), C are POSS 9-(COOH) 56, D is POSS 65-(vinyl) 392(2 generation).
Fig. 3 is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure in the embodiment of the present invention 35 9-(vinyl) 56(1 generation) 1h NMR and 13c NMR collection of illustrative plates (CDCl 3, 400MHz).
Fig. 4 is the derivative POSS of the POSS base branch-shape polymer with three layers of POSS structure in the embodiment of the present invention 35 65-(vinyl) 392(2 generation) 1h NMR and 13c NMR collection of illustrative plates (CDCl 3, 400MHz).
Fig. 5 is the TGA collection of illustrative plates (air atmosphere) of the derivative of the POSS base branch-shape polymer with three layers of POSS structure in the embodiment of the present invention 35, and wherein a is OH-POSS-(vinyl) 7, b is POSS 9-(vinyl) 56(1 generation), c are POSS 9-(COOH) 56, d is POSS 65-(vinyl) 392(2 generation).
Fig. 6 is the gpc chromatogram of the derivative of the POSS base branch-shape polymer with three layers of POSS structure in the embodiment of the present invention 35, and wherein a is OH-POSS-(vinyl) 7, b is POSS 9-(vinyl) 56(1 generation), c are POSS 9-(COOH) 56, d is POSS 65-(vinyl) 392(2 generation).
Fig. 7 is the TEM collection of illustrative plates of the derivative of the POSS base branch-shape polymer with three layers of POSS structure in the embodiment of the present invention 35, and wherein A is POSS 9-(vinyl) 56(1 generation), B is POSS 65-(vinyl) 392(2 generation).
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material are commercially available prod if no special instructions.
Embodiment 1
(1) prepare POSS base intermediate NH 2-POSS-(vinyl) 7
The eight ethenyl cage model oligomeric silsesquioxanes (T8) that U.S. Hybrid company is produced and cysteamine according to the mol ratio of 1:1 in dimethyl formamide, add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 2 hours, after reaction finishes, products therefrom is precipitated in ether, then by silica gel column chromatography, (mixed solvent that tetrahydrofuran (THF) and normal hexane volume ratio be 6:1 of take is eluent, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate NH 2-POSS-(vinyl) 7;
(2) preparation has the branch-shape polymer NH of POSS base 2-POSS 8-(isobutyl-) 49
The NH that step (1) is prepared 2-POSS-(vinyl) 7sH-POSS-(isobutyl-) with the production of U.S. Hybrid company 7according to the mol ratio of 1:20 in tetrahydrofuran (THF), add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 4 hours, after reaction finishes, products therefrom is precipitated in acetone, and the micro-yellow powder obtaining after vacuum-drying is the POSS base branch-shape polymer NH with two-layer POSS structure 2-POSS 8-(isobutyl-) 49.
Gained has the POSS base branch-shape polymer NH of two-layer POSS structure 2-POSS 8-(isobutyl-) 49structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of thioether bond; C is amido; X has aforementioned formula vi structure, and wherein B is isobutyl-.
Embodiment 2
(1) prepare POSS base intermediate COOH-POSS-(vinyl) 7
By eight ethenyl cage model oligomeric silsesquioxanes (T8) and thiohydracrylic acid according to the mol ratio of 1:0.8 in trichloromethane, add 2 of 0.15 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 3 hours, after reaction finishes, products therefrom is precipitated in ether, then by silica gel column chromatography, (mixed solvent that tetrahydrofuran (THF) and normal hexane volume ratio be 1:1 of take is eluent, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate COOH-POSS-(vinyl) 7;
(2) preparation has the branch-shape polymer COOH-POSS of POSS base 8-(cyclopentyl) 49
The COOH-POSS-(vinyl) that step (1) is prepared 7sH-POSS-(cyclopentyl) with the production of U.S. Hybrid company 7according to the mol ratio of 1:7 in tetrahydrofuran (THF), the Diisopropyl azodicarboxylate (AIBN) that adds 0.2 equivalent, be heated to 60 ℃ of stirring reactions 10 hours, after reaction finishes, products therefrom is precipitated in normal hexane, and the micro-yellow powder obtaining after vacuum-drying is the POSS base branch-shape polymer COOH-POSS with two-layer POSS structure 8-(cyclopentyl) 49.
Gained has the POSS base branch-shape polymer COOH-POSS of two-layer POSS structure 8-(cyclopentyl) 49structure as shown in aforementioned formula ii, wherein: A is the straight chain shape alkylidene group that includes thioether bond; C is carboxyl; X has aforementioned formula vi structure, and wherein B is cyclopentyl.
1H?NMR(CDCl 3)δ(ppm)：1.02(t,2H,CH 2)，1.39(t,2H,CH 2)，1.46(m,2H,CH 2)，1.5(t,1H,CH)，1.56(m,2H,CH 2)，1.7(m,2H,CH 2)，2.44(t,2H,CH 2)，2.5(t,2H,CH 2)，2.59(t,2H,CH 2)，2.71(t,2H,CH 2)，11(s,1H,COOH)； 13C?NMR(CDCl 3)δ(ppm)：6.8，12.1，19.9，28.3，30.7，32.3，32.8，33.1，35.5，172.5。
Embodiment 3
(1) prepare POSS base intermediate OH-POSS-(vinyl) 9
By ten ethenyl cage model oligomeric silsesquioxanes (T10) (according to J.Am.Chem.Soc.2013, 135, 12259-12269 synthesize obtain) with mercaptoethanol according to the mol ratio of 1:1.3 in methylene dichloride, add 2 of 0.3 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 3.5 hours, after reaction finishes, products therefrom is precipitated in the mixed solvent of acetone/diethyl ether (volume ratio is 1:1), then by silica gel column chromatography, (mixed solvent that methylene dichloride and normal hexane volume ratio be 1:1 of take is eluent, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate OH-POSS-(vinyl) 9,
(2) preparation has the branch-shape polymer OH-POSS of POSS base 10-(isobutyl-) 63
The OH-POSS-(vinyl) that step (1) is prepared 9with SH-POSS-(isobutyl-) 7according to the mol ratio of 1:30 in trichloromethane, the Diisopropyl azodicarboxylate (AIBN) that adds 0.2 equivalent, be heated to 60 ℃ of stirring reactions after 8 hours, products therefrom is precipitated in methyl alcohol, and the micro-yellow powder obtaining after vacuum-drying is the POSS base branch-shape polymer OH-POSS with two-layer POSS structure 10-(isobutyl-) 63.
Gained has the POSS base branch-shape polymer OH-POSS of two-layer POSS structure 10-(isobutyl-) 63structure as shown in aforementioned formula iii, wherein: A is the alkylidene group that includes the straight chain shape of thioether bond; C is hydroxyl; X has aforementioned formula vi structure, and wherein B is isobutyl-.
1H?NMR(CDCl 3)δ(ppm)：0.54(s,2H,CH 2)，0.58(t,2H,CH 2)，0.91(d,9H,CH 3)，1.39(t,2H,CH 2)，1.7(m,2H,CH 2)，1.8(m,2H,CH 2)，2.44(t,2H,CH 2)，2.5(t,2H,CH 2)； 13C?NMR(CDCl 3)δ(ppm)：10，12.1，15.9，25.2，26.4，35.3，36.1，36.4。
Embodiment 4
(1) prepare POSS base intermediate OH-POSS-(vinyl) 7
By eight ethenyl cage model oligomeric silsesquioxanes (T8) and trifluoromethanesulfonic acid according to the mol ratio of 1:1 in anhydrous methylene chloride, the acetic acid that adds 0.1 equivalent, react 3 hours by being extracted 3 times by saturated sodium carbonate solution, after system is concentrated, add a large amount of acetone solns, after 4 hours, by silica gel column chromatography, (mixed solvent that methylene dichloride and normal hexane volume ratio be 1:2 of take is eluent to stirring at room, silica gel (200-300 order)) purify, after vacuum-drying, can obtain white product and be POSS base intermediate OH-POSS-(vinyl) 7;
(2) preparation has the branch-shape polymer POSS of POSS base 9-(vinyl) 56
The OH-POSS-(vinyl) that step (1) is prepared 7with POSS-(COOH) 8according to the mol ratio of 10:1 in anhydrous tetrahydro furan, add the DMAP (DMAP) of 0.2 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by trichloromethane/water, collect after organic phase, products therefrom is precipitated in normal hexane, and after vacuum-drying, available white powder is the POSS base branch-shape polymer POSS with two-layer POSS structure 9-(vinyl) 56.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 9-(vinyl) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is vinyl.
Embodiment 5
(1) prepare POSS base intermediate COOH-POSS-(vinyl) 5
The six ethenyl cage model oligomeric silsesquioxanes (T6) that U.S. Hybrid company is produced and trifluoromethanesulfonic acid according to the mol ratio of 1:1.2 in anhydrous methylene chloride, the acetic acid that adds 0.1 equivalent, react 3 hours by being extracted 3 times by saturated sodium carbonate solution, after system is concentrated, add a large amount of dioxane solution, after 5 hours, by silica gel column chromatography (mixed solvent that tetrahydrofuran (THF) and normal hexane volume ratio be 1:4 of take is eluent, silica gel (200-300 order)), purify to obtain OH-POSS-(vinyl) to stirring at room 5; Then by OH-POSS-(vinyl) 5with Succinic anhydried according to the mol ratio of 1:1.2 in methyl alcohol, stirring at room reaction, after 4 hours, precipitates products therefrom purification in ether, can obtain micro-yellow product and be POSS base intermediate COOH-POSS-(vinyl) after vacuum-drying 5;
(2) preparation has the branch-shape polymer POSS of POSS base 9-(vinyl) 40
By eight ethenyl cage model oligomeric silsesquioxanes (T8) and trifluoromethanesulfonic acid according to the mol ratio of 1:10 in methylene dichloride, the acetic acid that adds 0.1 equivalent, react 3 hours by being extracted 3 times by saturated sodium carbonate solution, after system is concentrated, add a large amount of acetone solns, after 4 hours, by silica gel column chromatography (mixed solvent that tetrahydrofuran (THF) and normal hexane volume ratio be 3:1 of take is eluent, silica gel (200-300 order)), purify to obtain POSS-(OH) to stirring at room 8, then by products therefrom POSS-(OH) 8the COOH-POSS-(vinyl) obtaining with step (1) 5according to the mol ratio of 1:10 in tetrahydrofuran (THF), add the DMAP (DMAP) of 0.2 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by trichloromethane/water, collect after organic phase, products therefrom is precipitated in hexanaphthene, and the white powder obtaining after vacuum-drying is the POSS base branch-shape polymer POSS with two-layer POSS structure 9-(vinyl) 40.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 9-(vinyl) 40structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is vinyl.
Embodiment 6
(1) prepare POSS base intermediate alkynyl-POSS-(vinyl) 7
The OH-POSS-(vinyl) that embodiment 4 steps (1) are prepared 7with propargylic acid according to the mol ratio of 1:1 in anhydrous methylene chloride, add the DMAP (DMAP) of 0.1 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.1 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by methylene dichloride/water, can obtain white product and be POSS base intermediate alkynyl-POSS-(vinyl) after vacuum-drying 7;
(2) preparation has the branch-shape polymer POSS of POSS base 9-(vinyl) 56
Alkynyl-POSS-(vinyl) that step (1) is prepared 7pOSS-(N with the production of U.S. Hybrid company 3) 8according to the mol ratio of 1:10 in anhydrous dimethyl formamide, add the CuBr of 0.2 equivalent and the N of 0.2 equivalent, N, N', N, ' N''-five methyl diethylentriamine (PMDETA), stirring at room carries out after cycloaddition reaction that (mixed solvent that methylene dichloride and normal hexane volume ratio be 3:1 of take is eluent by silica gel column chromatography for 12 hours, silica gel (200-300 order)) purify, the white powder obtaining after vacuum-drying is the POSS base branch-shape polymer POSS with two-layer POSS structure 9-(vinyl) 56.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 9-(vinyl) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the ring-type of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is vinyl.
1H?NMR(CDCl 3)δ(ppm)：1.02(t,2H,CH 2)，1.5(m,2H,CH 2)，1.6(m,2H,CH 2)，2.1(m,2H,CH 2)，2.4(m,2H,CH 2)，2.55(t,2H,CH 2)，2.7(m,2H,CH 2)，4.13(t,2H,CH 2)，4.36(m,1H,CH)，5.8(m,1H,CH)，6.2(m,2H,CH 2)； 13C?NMR(CDCl 3)δ(ppm)：11.2，13.3，28.7，34.7，38.4，56.8，58.9，67.8，69，124.9，138,173.1。
Embodiment 7
(1) prepare POSS base intermediate epoxy group(ing)-POSS-(vinyl) 7
The OH-POSS-(vinyl) that embodiment 4 steps (1) are prepared 7with epoxy bromopropane according to the mol ratio of 1:1 in N,N-DIMETHYLACETAMIDE, the potassium tert.-butoxide that adds 1 equivalent, stirring at room is reacted 6 hours by being extracted by methylene dichloride/water, then by silica gel column chromatography, (mixed solvent that methylene dichloride and hexanaphthene volume ratio be 1:1 of take is eluent, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate epoxy group(ing)-POSS-(vinyl) 7;
(2) preparation has the branch-shape polymer POSS of POSS base 17-(vinyl) 112
Epoxy group(ing)-POSS-(vinyl) that step (1) is prepared 7with POSS-(NH 3cl) 8according to the mol ratio of 1:2.2 in the mixing solutions of tetrahydrofuran (THF)/methyl alcohol (volume ratio is 1:1), the triethylamine that adds 2.5 equivalents, stirring at room is carried out after ring-opening reaction for 8 hours, products therefrom is precipitated in normal hexane, and the white powder obtaining after vacuum-drying is the POSS base branch-shape polymer POSS with two-layer POSS structure 17-(vinyl) 112.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 17-(vinyl) 112structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is vinyl.
Embodiment 8
(1) prepare POSS base intermediate OH-POSS-(vinyl) 11
By ten divinyl polyhedral oligomeric silsesquioxanes (T12) (according to J.Am.Chem.Soc.2013, 135, 12259-12269 synthesize obtain) with mercaptoethanol according to the mol ratio of 1:1.3 in methylene dichloride, add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 3.5 hours, after reaction finishes, products therefrom is precipitated in ether, then by silica gel column chromatography, (mixed solvent that methylene dichloride and normal hexane volume ratio be 2:1 of take is eluent, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate OH-POSS-(vinyl) 11,
(2) preparation has the branch-shape polymer POSS of POSS base 9-(vinyl) 88
The OH-POSS-(vinyl) that step (1) is prepared 11pOSS-(methylsulfonyl) with the production of U.S. Hybrid company 8according to the mol ratio of 1:12 in anhydrous methylene chloride, the triethylamine that adds 1.1 equivalents, stirring at room reaction is the white powder obtaining after products therefrom vacuum-drying the POSS base branch-shape polymer POSS with two-layer POSS structure by being extracted by trichloromethane/water in 2 hours 9-(vinyl) 88.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 9-(vinyl) 88structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T12); X has aforementioned formula viii structure, and wherein B is vinyl.
Embodiment 9
(1) prepare POSS base intermediate NH 2-POSS-(vinyl) 9
By ten ethenyl cage model oligomeric silsesquioxanes (T10) and cysteamine according to the mol ratio of 1:1 in tetrahydrofuran (THF)/methanol mixed solution, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 3 hours, after reaction finishes, products therefrom is precipitated in ether, then by silica gel column chromatography, (take methyl alcohol and methylene chloride volume is eluent than the mixed solvent that is 1:10, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate NH 2-POSS-(vinyl) 9;
(2) preparation has the branch-shape polymer POSS of POSS base 9-(vinyl) 72
The NH that step (1) is prepared 2-POSS (vinyl) 9pOSS-(chloropropyl) with the production of U.S. Hybrid company 8according to the mol ratio of 1:10 in tetrahydrofuran (THF), the solution of potassium carbonate that adds 1 equivalent, be heated to 50 ℃ of stirring reactions 12 hours by being extracted by trichloromethane/water, then by products therefrom, by silica gel column chromatography, (mixed solvent that tetrahydrofuran (THF) and normal hexane volume ratio be 1:1 of take is eluent, silica gel (200-300 order)) purify, the white powder obtaining after vacuum-drying is the POSS base branch-shape polymer POSS with two-layer POSS structure 9-(vinyl) 72.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 9-(vinyl) 72structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T10); X has aforementioned formula vii structure, and wherein B is vinyl.
1H?NMR(CDCl 3)δ(ppm)：1.02(t,2H,CH 2)，1.39(t,2H,CH 2)，1.5(m,2H,CH 2)，2.0(s,1H,NH)，2.5(m,6H,CH 2)，2.92(t,2H,CH 2)，5.3(s,H,CH)，5.4(m,2H,CH 2)； 13C?NMR(CDCl 3)δ(ppm)：12.8，15.2，29.8，32.5，43.5，51.5，124.9，138.0。
Embodiment 10
(1) prepare POSS base intermediate NH 2-POSS-(vinyl) 5
By six ethenyl cage model oligomeric silsesquioxanes (T6) and cysteamine according to the mol ratio of 1:1 in the mixing solutions of methylene chloride/methanol (volume ratio is 1:1), add 2 of 0.15 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 2.5 hours, after reaction finishes, products therefrom is precipitated in ether, then by silica gel column chromatography, (mixed solvent that tetrahydrofuran (THF) and sherwood oil volume ratio be 3:1 of take is eluent, silica gel (200-300 order)) purify, after vacuum-drying, can obtain micro-yellow product and be POSS base intermediate NH 2-POSS-(vinyl) 5;
(2) preparation has the branch-shape polymer POSS of POSS base 9-(vinyl) 80
By eight ethenyl cage model oligomeric silsesquioxanes (T8) and metachloroperbenzoic acid (m-CPBA) according to the mol ratio of 1:10 in anhydrous methylene chloride, the vitriol oil that adds 0.1 equivalent, stirring at room reaction can obtain POSS-(epoxy group(ing)) by being extracted by methylene dichloride/water after purification is dry in 10 hours 8; Then by products therefrom POSS-(epoxy group(ing)) 8the NH preparing with step (1) 2-POSS-(vinyl) 5according to the mol ratio of 1:8 in the mixing solutions of tetrahydrofuran (THF)/methyl alcohol (volume ratio is 1:1), stirring at room reaction is after 7 hours, products therefrom is precipitated in ether, and the white powder obtaining after vacuum-drying is the POSS base branch-shape polymer POSS with two-layer POSS structure 9-(vinyl) 80.
Gained has the POSS base branch-shape polymer POSS of two-layer POSS structure 9-(vinyl) 80structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is vinyl.
Embodiment 11
Preparation has the derivative PEG-POSS of the branch-shape polymer of POSS base 8-(isobutyl-) 49
By the POSS base branch-shape polymer NH with two-layer POSS structure preparing in embodiment 1 2-POSS 8-(isobutyl-) 49with COOH-PEG (M n=1000) according to the mol ratio of 1:1.2 in anhydrous tetrahydro furan, add the DMAP (DMAP) of 0.1 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out amidate action for 12 hours by being extracted by trichloromethane/water, then the dialysis tubing that is 1500 by products therefrom by molecular weight cut-off dialysis three days, the white powder obtaining after vacuum-drying is the derivative PEG-POSS of the POSS base branch-shape polymer with two-layer POSS structure 8-(isobutyl-) 49.
Gained has the derivative PEG-POSS of the POSS base branch-shape polymer of two-layer POSS structure 8-(isobutyl-) 49structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is PEG; X has aforementioned formula vi structure, and wherein B is isobutyl-.
Embodiment 12
Preparation has the derivative PNIPAM-POSS of the branch-shape polymer of POSS base 8-(cyclopentyl) 49
Synthetic route is as follows:
Figure BDA0000407895800000171
By the POSS base branch-shape polymer COOH-POSS with two-layer POSS structure preparing in embodiment 2 8-(cyclopentyl) 49nIPA (the NH modifying with commercially available monoamine base 2-PNIPAM) (M n=2000) according to the mol ratio of 1:1.3 in anhydrous methylene chloride, the dicyclohexylcarbodiimide (DCC) that adds DMAP (DMAP) and 1.3 equivalents of 0.15 equivalent, stirring at room is carried out amidate action for 12 hours by being extracted by trichloromethane/water, then the dialysis tubing that is 2000 by products therefrom by molecular weight cut-off dialysis three days, the white powder obtaining after vacuum-drying is the derivative PNIPAM-POSS of the POSS base branch-shape polymer with two-layer POSS structure 8-(cyclopentyl) 49.
Gained has the derivative PNIPAM-POSS of the POSS base branch-shape polymer of two-layer POSS structure 8-(cyclopentyl) 49structure as shown in aforementioned formula ii, wherein: A is the straight chain shape alkylidene group that includes thioether bond; C is NIPA; X has aforementioned formula vi structure, and wherein B is cyclopentyl.
1H?NMR(CDCl 3)δ(ppm)：1.00(d,6H,CH 3)，1.02(t,2H,CH 2)，1.06(t,2H,CH 2)，1.39(t,2H,CH 2)，1.46(m,2H,CH 2)，1.5(t,1H,CH)，1.56(m,2H,CH 2)，1.7(m,2H,CH 2)，2.27(t,H,CH)，2.44(t,2H,CH 2)，2.5(t,2H,CH 2)，2.59(t,2H,CH 2)，2.71(t,2H,CH 2)，3.81(s,1H,CH)，8.03(s,1H,NH)； 13C?NMR(CDCl 3)δ(ppm)：6.8，10.0，12.1，19.9，23.2，28.3，30.0，30.7，32.3，32.8，33.1，35.5，44.7，137.0，172.5。
Embodiment 13
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(COOH) 56
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 4 9-(vinyl) 56with thiohydracrylic acid according to the mol ratio of 1:80 in trichloromethane, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 6 hours, after reaction finishes, products therefrom is precipitated in sherwood oil, and the micro-yellow powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(COOH) 56.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(COOH) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is carboxyl.
Embodiment 14
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(NH 3cl) 40
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 5 9-(vinyl) 40with Mercaptamine according to the mol ratio of 1:50 in the mixed solvent of tetrahydrofuran (THF)/methyl alcohol (volume ratio is 1:1), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 4.5 hours, after reaction finishes, the dialysis tubing that is 800 by molecular weight cut-off by products therefrom dialysis two days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(NH 3cl) 40.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(NH 3cl) 40structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is NH 3cl.
Embodiment 15
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(PEG) 56
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 6 9-(vinyl) 56polyoxyethylene glycol (SH-PEG) (M with commercially available single sulfydryl modification n=550) according to the mol ratio of 1:100 in methylene dichloride, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 8 hours, after reaction finishes, the dialysis tubing that is 1000 by molecular weight cut-off by products therefrom dialysis four days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(PEG) 56.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(PEG) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the ring-type of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is polyoxyethylene glycol.
1H?NMR(CDCl 3)δ(ppm)：1.02(t,2H,CH 2)，1.5(m,2H,CH 2)，1.6(m,2H,CH 2)，2.1(m,2H,CH 2)，2.4(m,2H,CH 2)，2.55(t,2H,CH 2)，2.7(m,2H,CH 2)，3.58(m,2H,CH 2)，3.77(s,3H,CH 3)，4.13(t,2H,CH 2)，4.36(m,1H,CH)，5.8(m,1H,CH)，6.2(m,2H,CH 2)； 13C?NMR(CDCl 3)δ(ppm)：11.2，13.3，28.7，34.7，38.4，56.8，58.9，59.3，67.8，69，71.6，124.9，138，173.1。
Embodiment 16
Preparation has the derivative PDMAEMA-POSS of the branch-shape polymer of POSS base 10-(isobutyl-) 63
Synthetic route is as follows:
Figure BDA0000407895800000201
By the POSS base branch-shape polymer OH-POSS with two-layer POSS structure preparing in embodiment 3 10-(isobutyl-) 63poly-N with mono carboxylic modification, N-dimethylamino ethyl ester (COOH-PDMAEMA) (Mn=800) according to the mol ratio of 1:1.15 in anhydrous tetrahydro furan, add the DMAP (DMAP) of 0.1 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by methylene dichloride/water, the dialysis tubing that is 1000 by molecular weight cut-off by products therefrom dialysis two days, the white powder obtaining after vacuum-drying is the derivative PDMAEMA-POSS of the POSS base branch-shape polymer with two-layer POSS structure 10-(isobutyl-) 63.
Gained has the derivative PDMAEMA-POSS of the POSS base branch-shape polymer of two-layer POSS structure 10-(isobutyl-) 63structure as shown in aforementioned formula iii, wherein: A is the alkylidene group that includes the straight chain shape of thioether bond; C is poly-N, N-dimethylamino ethyl ester; X has aforementioned formula vi structure, and wherein B is isobutyl-.
1H?NMR(CDCl 3)δ(ppm)：0.54(s,2H,CH 2)，0.58(t,2H,CH 2)，0.84(s,3H,CH 3)，0.89(d,9H,CH 3)，0.91(d,6H,CH 3)，1.14(s,2H,CH 2)，1.39(t,2H,CH 2)，1.52(m,2H,CH 2)，1.7(m,2H,CH 2)，1.8(m,2H,CH 2)，1.81(m,1H,CH)，2.44(t,2H,CH 2)，2.5(t,2H,CH 2)，4.13(s,2H,CH 2)； 13C?NMR(CDCl 3)δ(ppm)：10，12.1，15.9，18.2，19.1，22.9，24.3,25.2,26.4,34.0,35.3,36.1，36.4，38.7，62.7，177.0。
Embodiment 17
Preparation has the derivative POSS of the branch-shape polymer of POSS base 17-(PAA) 112
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 7 17-(vinyl) 112polyacrylic acid (SH-PAA) (M with commercially available single sulfydryl modification n=1200) according to the mol ratio of 1:180 in methylene dichloride, add 2 of 0.25 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 11 hours, after reaction finishes, the dialysis tubing that is 2000 by molecular weight cut-off by products therefrom dialysis four days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 17-(PAA) 112.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 17-(PAA) 112structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is polyacrylic acid.
Embodiment 18
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(PNIPAM) 88
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 8 9-(vinyl) 88nIPA (SH-PNIPAM) (M with commercially available single sulfydryl modification n=2000) according to the mol ratio of 1:80 in tetrahydrofuran (THF), add 2 of 0.15 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 7.5 hours, after reaction finishes, the dialysis tubing that is 3000 by molecular weight cut-off by products therefrom dialysis three days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(PNIPAM) 88.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(PNIPAM) 88structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T12); X has aforementioned formula viii structure, and wherein B is NIPA.
Embodiment 19
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(PLGA) 72
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 9 9-(vinyl) 72poly(D,L-lactide-co-glycolide (SH-PLGA) (M with commercially available single sulfydryl modification n=6000) according to the mol ratio of 1:120 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 3 hours, after reaction finishes, the dialysis tubing that is 8000 by molecular weight cut-off by products therefrom dialysis five days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(PLGA) 72.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(PLGA) 72structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T10); X has aforementioned formula vii structure, and wherein B is Poly(D,L-lactide-co-glycolide.
Embodiment 20
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(COOH) 72
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 9 9-(vinyl) 72with Thiovanic acid according to the mol ratio of 1:90 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 1 hour, after reaction finishes, products therefrom is precipitated in ether, and the white powder that obtains tool after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(COOH) 72.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(COOH) 72structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T10); X has aforementioned formula vii structure, and wherein B is carboxyl.
Embodiment 21
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(OH) 40
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 5 9-(vinyl) 40with mercaptoethanol according to the mol ratio of 1:60 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 1.5 hours, after reaction finishes, products therefrom is precipitated in sherwood oil, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(OH) 40.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(OH) 40structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is hydroxyl.
Embodiment 22
Preparation has the derivative POSS of the branch-shape polymer of POSS base 17-(PS) 112
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 7 17-(vinyl) 112polystyrene (SH-PS) (M with commercially available single sulfydryl modification n=3500) according to the mol ratio of 1:180 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 6 hours, after reaction finishes, products therefrom is precipitated in the mixed solvent of ether/normal hexane (volume ratio is 1:1), the dialysis tubing that is then 5000 by molecular weight cut-off dialysis four days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 17-(PS) 112.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 17-(PS) 112structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is polystyrene.
Embodiment 23
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(PLA) 88
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 8 9-(vinyl) 88poly(lactic acid) (SH-PLA) (M with commercially available single sulfydryl modification n=5000) according to the mol ratio of 1:70 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 11 hours, after reaction finishes, products therefrom is precipitated in the mixed solvent of ether/normal hexane (volume ratio is 1:1), the dialysis tubing that is then 10000 by molecular weight cut-off dialysis five days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(PLA) 88.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(PLA) 88structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T12); X has aforementioned formula viii structure, and wherein B is poly(lactic acid).
Embodiment 24
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(PMMA) 80
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 10 9-(vinyl) 80polymethylmethacrylate (SH-PMMA) (M with commercially available single sulfydryl modification n=400) according to the mol ratio of 1:120 in tetrahydrofuran (THF), add 2 of 0.15 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 3 hours, after reaction finishes, products therefrom is precipitated in ether, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(PMMA) 80.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(PMMA) 80structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is polymethylmethacrylate.
Embodiment 25
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(DOX) 56
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 4 9-(vinyl) 56with the Zorubicin biomacromolecule (SH-DOX) of commercially available single sulfydryl modification according to the mol ratio of 1:160 in trichloromethane, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 6 hours, after reaction finishes, products therefrom is precipitated in ether, then the dialysis tubing that is 3000 by molecular weight cut-off dialysis three days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(DOX) 56.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(DOX) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is Zorubicin.
Embodiment 26
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(Calan) 40
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 5 9-(vinyl) 40with the vinpocetin medicine macromole (SH-Calan) of commercially available single sulfydryl modification according to the mol ratio of 1:60 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 4.5 hours, after reaction finishes, products therefrom is precipitated in sherwood oil, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(Calan) 40.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(Calan) 40structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is vinpocetin.
Embodiment 27
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(INH) 56
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 6 9-(vinyl) 56with vazadrine medicine macromole (SH-INH) of commercially available single sulfydryl modification according to the mol ratio of 1:80 in tetrahydrofuran (THF), add 2 of 0.3 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 5 hours, after reaction finishes, products therefrom is precipitated in hexanaphthene, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(INH) 56.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(INH) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the ring-type of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is vazadrine.
1H?NMR(CDCl 3)δ(ppm)：1.02(t,2H,CH 2)，1.5(m,2H,CH 2)，1.6(m,2H,CH 2)，2.1(m,2H,CH 2)，2.4(m,2H,CH 2)，2.55(t,2H,CH 2)，2.7(m,2H,CH 2)，4.13(t,2H,CH 2)，4.36(m,1H,CH)，5.8(m,1H,CH)，6.2(m,2H,CH 2)，7.81(m,2H,p-H)，8.89(m,2H,o-H)； 13C?NMR(CDCl 3)δ(ppm)：11.2，13.3，28.7，34.7，38.4，56.8，58.9，67.8，69.1，121.7，124.9，138，140.8，149.7，167.2，173.1。
Embodiment 28
Preparation has the derivative POSS of the branch-shape polymer of POSS base 17-(PTX) 112
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 7 17-(vinyl) 112with the taxol drug macromole (SH-PTX) of commercially available single sulfydryl modification according to the mol ratio of 1:180 in methylene dichloride, add 2 of 0.25 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 11 hours, after reaction finishes, products therefrom is precipitated in sherwood oil, then the dialysis tubing that is 2000 by molecular weight cut-off dialysis four days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 17-(PTX) 112.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 17-(PTX) 112structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is taxol.
Embodiment 29
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(RFP) 80
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 10 9-(vinyl) 80with the rifampicin medicine macromole (SH-RFP) of commercially available single sulfydryl modification according to the mol ratio of 1:130 in tetrahydrofuran (THF), add 2 of 0.3 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 5.5 hours, after reaction finishes, products therefrom is precipitated in the mixed solvent of ether/hexanaphthene (volume ratio is 1:1), the dialysis tubing that is 2000 by molecular weight cut-off dialysis four days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(RFP) 80.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(RFP) 80structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is Rifampin.
Embodiment 30
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(PerCP) 56
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 4 9-(vinyl) 56with many dinoflagellates phyllochlorin macromole (SH-PerCP) of commercially available single sulfydryl modification according to the mol ratio of 1:130 in trichloromethane, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 6 hours, after reaction finishes, products therefrom is precipitated in ether, then the dialysis tubing that is 3000 by molecular weight cut-off dialysis two days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(PerCP) 56.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(PerCP) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is many dinoflagellates phyllochlorin.
Embodiment 31
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(6-TAMRA) 40
By the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure preparing in embodiment 21 9-(OH) 40with commercially available 6-carboxyl tetramethyl-rhodamine (6-TAMRA) according to the mol ratio of 1:80 in anhydrous tetrahydro furan, add the DMAP (DMAP) of 0.1 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by methylene dichloride/water, then the dialysis tubing that is 4000 by products therefrom by molecular weight cut-off dialysis two days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(6-TAMRA) 40.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(6-TAMRA) 40structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is 6-carboxyl tetramethyl-rhodamine.
Embodiment 32
Preparation has the derivative POSS of the branch-shape polymer of POSS base 17-(TRITC) 112
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 7 17-(vinyl) 112with the TRITC (SH-TRITC) of commercially available single sulfydryl modification according to the mol ratio of 1:160 in methylene dichloride, add 2 of 0.35 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 11 hours, after reaction finishes, products therefrom is precipitated in ether, then the dialysis tubing that is 5000 by molecular weight cut-off dialysis four days, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 17-(TRITC) 112.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 17-(TRITC) 112structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is TRITC.
Embodiment 33
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(NAP) 72
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 9 9-(vinyl) 72with the naphthalene molecule (SH-NAP) of commercially available single sulfydryl modification according to the mol ratio of 1:100 in tetrahydrofuran (THF), add 2 of 0.1 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 1.5 hours, after reaction finishes, products therefrom is precipitated in ether, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(NAP) 72.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(NAP) 72structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of amido linkage; C is cage-type silsesquioxane (T10); X has aforementioned formula vii structure, and wherein B is naphthalene.
Embodiment 34
Preparation has the derivative POSS of the branch-shape polymer of POSS base 9-(nitrogen benzide) 56
By the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure preparing in embodiment 13 9-(COOH) 56with 4-aminoazobenzene according to the mol ratio of 1:100 in anhydrous methylene chloride, add the DMAP (DMAP) of 0.2 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by ethyl acetate/water, after collecting organic phase, in normal hexane, precipitate, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 9-(nitrogen benzide) 56.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 9-(nitrogen benzide) 56structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is nitrogen benzide.
Embodiment 35
Preparation has the derivative POSS of the branch-shape polymer of POSS base 65-(vinyl) 392
Synthetic route is as follows:
Figure BDA0000407895800000291
Figure BDA0000407895800000301
By the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure preparing in embodiment 13 9-(COOH) 56with OH-POSS-(vinyl) 7according to the mol ratio of 1:120 in anhydrous methylene chloride, add the DMAP (DMAP) of 0.2 equivalent and 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) of 1.2 equivalents, stirring at room is carried out esterification for 12 hours by being extracted by ethyl acetate/water, after collecting organic phase, in normal hexane, precipitate, the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with three layers of POSS structure 65-(vinyl) 392; The OH-POSS-of POSS base intermediate (vinyl) wherein 7's 1h NMR and 13c NMR collection of illustrative plates (CDCl 3, 400MHz) as shown in Figure 1; Have three layers of POSS structure POSS base branch-shape polymer derivative FT-IR collection of illustrative plates as shown in Figure 2, wherein A is OH-POSS-(vinyl) 7, B is POSS 9-(vinyl) 56(1 generation), C are POSS 9-(COOH) 56, D is POSS 65-(vinyl) 392(2 generation); The derivative POSS with the POSS base branch-shape polymer of two-layer POSS structure 9-(vinyl) 56(1 generation) 1h NMR and 13c NMR collection of illustrative plates (CDCl 3, 400MHz) as shown in Figure 3; The derivative POSS with the POSS base branch-shape polymer of three layers of POSS structure 65-(vinyl) 392(2 generation) 1h NMR and 13c NMR collection of illustrative plates (CDCl 3, 400MHz) as shown in Figure 4; Have three layers of POSS structure POSS base branch-shape polymer derivative TGA collection of illustrative plates (air atmosphere) as shown in Figure 5, wherein a is OH-POSS-(vinyl) 7, b is POSS 9-(vinyl) 56(1 generation), c are POSS 9-(COOH) 56, d is POSS 65-(vinyl) 392(2 generation); Have three layers of POSS structure POSS base branch-shape polymer derivative gpc chromatogram as shown in Figure 6, wherein a is OH-POSS-(vinyl) 7, b is POSS 9-(vinyl) 56(1 generation), c are POSS 9-(COOH) 56, d is POSS 65-(vinyl) 392(2 generation); Have three layers of POSS structure POSS base branch-shape polymer derivative TEM collection of illustrative plates as shown in Figure 7, wherein A is POSS 9-(vinyl) 56(1 generation), B is POSS 65-(vinyl) 392(2 generation).
Embodiment 36
Preparation has the derivative POSS of the branch-shape polymer of POSS base 60-(vinyl) 392
Synthetic route is as follows:
Figure BDA0000407895800000321
Figure BDA0000407895800000331
(1) preparation has the branch-shape polymer G1POSS of POSS base 4-(vinyl) 28
By the POSS base intermediate epoxy group(ing)-POSS-(vinyl) obtaining in embodiment 7 7with butanediamine according to the mol ratio of 4.4:1 in methyl alcohol, add the triethylamine of 0.1 equivalent, stirring at room reaction, after 12 hours, precipitates products therefrom in ether, can obtain the branch-shape polymer POSS that white powder is POSS base after vacuum-drying 4-(vinyl) 28;
(2) preparation has the derivative POSS of the branch-shape polymer of POSS base 60-(vinyl) 392
The POSS that step (1) is prepared 4-(vinyl) 28with cysteamine according to the mol ratio of 1:40 in methyl alcohol, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 5 hours, after reaction finishes, products therefrom is precipitated in ether/normal hexane mixed solvent, and the dialysis tubing that is 500 by molecular weight cut-off dialysis two days, can obtain white powder and be POSS after vacuum-drying 4-(NH 2) 28, and then with epoxy group(ing)-POSS-(vinyl) 7according to the mol ratio of 1:80, in methyl alcohol, stirring at room reaction, after 12 hours, precipitates products therefrom in ether, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure 60-(vinyl) 392.
Gained has the derivative POSS of the POSS base branch-shape polymer of two-layer POSS structure 60-(vinyl) 392structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is dendritic macromole; X has aforementioned formula vi structure, and wherein B is vinyl.
Embodiment 37
Preparation has the derivative POSS of the branch-shape polymer of POSS base 65-(vinyl) 280
By the derivative POSS of the POSS base branch-shape polymer with two-layer POSS structure preparing in embodiment 14 9-(NH 3cl) 40with COOH-POSS-(vinyl) 7according to the mol ratio of 1:50 in anhydrous tetrahydro furan, the DMAP (DMAP), the triethylamine of 0.2 equivalent and the 1-of 1.3 equivalents (3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCI) that add 0.1 equivalent, stirring at room is carried out esterification for 15 hours by being extracted by methylene dichloride/water, collect after organic phase, products therefrom is precipitated in normal hexane, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with three layers of POSS structure 65-(vinyl) 280.
Gained has the derivative POSS of the POSS base branch-shape polymer of three layers of POSS structure 65-(vinyl) 392structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ester bond; C is cage-type silsesquioxane (T6); X has aforementioned formula v structure, and wherein B is ethenyl cage model sesquialter siloxane.
Embodiment 38
(1) preparation has the branch-shape polymer PEG2000-POSS of POSS base 4-(vinyl) 28
By the POSS base intermediate epoxy group(ing)-POSS-(vinyl) obtaining in embodiment 7 7with commercially available NH 2-PEG-NH 2(M n=2000) according to the mol ratio of 6:1 in methyl alcohol, the triethylamine that adds 0.1 equivalent, stirring at room reaction is after 12 hours, products therefrom is precipitated in ether, then the dialysis tubing that is 2000 by molecular weight cut-off dialysis four days, can obtain white powder and be POSS base branch-shape polymer NH after vacuum-drying 2-PEG-NH 2-POSS 4-(vinyl) 28;
(2) preparation has the derivative PEG2000-POSS of the branch-shape polymer of POSS base 60-(vinyl) 392
The NH that step (1) is prepared 2-PEG-NH 2-POSS 4-(vinyl) 28with cysteamine according to the mol ratio of 1:40 in methyl alcohol, add 2 of 0.2 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 5 hours, after reaction finishes, products therefrom is precipitated in the mixed solvent of ether/normal hexane (volume ratio is 1:1), and the dialysis tubing that is then 500 by molecular weight cut-off dialysis two days, can obtain white powder and be POSS after vacuum-drying 4-(NH 2) 28, and then with epoxy group(ing)-POSS-(vinyl) 7according to the mol ratio of 1:80, in methyl alcohol, stirring at room reaction precipitated after 12 hours in ether, and the white powder obtaining after vacuum-drying is the derivative PEG2000-POSS of the POSS base branch-shape polymer with two-layer POSS structure 60-(vinyl) 392.
Gained has the derivative PEG2000-POSS of the POSS base branch-shape polymer of two-layer POSS structure 60-(vinyl) 392structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is PEG; X has aforementioned formula vi structure, and wherein B is vinyl.
Embodiment 39
Preparation has the derivative POSS of the branch-shape polymer of POSS base 241-(vinyl) 1568
By the POSS base branch-shape polymer POSS with two-layer POSS structure preparing in embodiment 7 17-(vinyl) 112with Mercaptamine according to the mol ratio of 1:200 in ethanol, add 2 of 0.3 equivalent, 2-dimethoxy-2-phenyl methyl phenyl ketone (DMPA), ultraviolet radiation reacts for 10 hours, after reaction finishes, products therefrom is precipitated in the mixed solvent of ether/normal hexane (volume ratio is 1:1), and the dialysis tubing that is then 500 by molecular weight cut-off dialysis three days, can obtain white powder and be POSS after vacuum-drying 17-(NH 3cl) 112, and then with embodiment 7 in POSS base intermediate epoxy group(ing)-POSS-(vinyl) of obtaining 7according to the mol ratio of 1:350, in methyl alcohol, add the triethylamine of 2 equivalents, stirring at room reaction precipitated after 12 hours in ether, and the white powder obtaining after vacuum-drying is the derivative POSS of the POSS base branch-shape polymer with three layers of POSS structure 241-(vinyl) 1568.
Gained has the derivative POSS of the POSS base branch-shape polymer of three layers of POSS structure 241-(vinyl) 1568structure as shown in aforementioned formula ii, wherein: A is the alkylidene group that includes the straight chain shape of ehter bond; C is cage-type silsesquioxane (T8); X has aforementioned formula vi structure, and wherein B is ethenyl cage model sesquialter siloxane.

Claims (12)

1. a branch-shape polymer with POSS base, is characterized in that, the described branch-shape polymer with POSS base has one of following structure:
In structural formula i-iv, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; C is polyhedral oligomeric silsesquioxane, fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer or drug molecule; X has a kind of in following structural formula;
Figure FDA0000407895790000021
Wherein: B is polyhedral oligomeric silsesquioxane, fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer or drug molecule;
Described fluorescent mark and derivative thereof are selected from fluorescein isothiocyanate, hydroxyl fluorescein, Tetrachlorofluorescein, tetraethylrhodamine, carboxyl tetramethyl-rhodamine, naphthalene, anthracene, pyrene, indoles, acridine, tonka bean camphor, luxuriant and rich with fragrance ingot, phycoerythrobilin N, piperazine Luoning and Toyomycin A 3in a kind of;
Described organic group is selected from hydrogen atom, halogen atom, C 1-30a kind of in alkyl, thiazolinyl, alkynyl, alicyclic radical, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, sulfonic group, nitrogen benzide, phenolic hydroxyl group and epoxy group(ing); Described halogen atom is F, Cl, Br or I;
Described chain polymer is selected from polystyrene, poly(lactic acid), Poly(D,L-lactide-co-glycolide, polyacrylic acid, polyester, polymethyl acrylic acid monoglyceride, polyacrylamide, polymethyl acrylate, polyimide, polymethylmethacrylate, Vinyl Acetate Copolymer, polyvinyl alcohol, polyoxyethylene glycol, poly-N, a kind of in N-dimethylamino ethyl ester and NIPA;
Described branch-shape polymer is selected from polymeric amide, polyacrylamide, polyethers, polyester, polysilane and a kind of containing in Phosphorus dendrimer.
2. the branch-shape polymer with POSS base according to claim 1, is characterized in that: the described branch-shape polymer with POSS base has two-layer or three layers of POSS structure;
The described branch-shape polymer with POSS base with two-layer POSS structure is that C in structural formula i-iv and the B in structural formula v～viii do not select polyhedral oligomeric silsesquioxane;
The described branch-shape polymer with POSS base with three layers of POSS structure is that C and the B in structural formula v～viii in structural formula i-iv selects polyhedral oligomeric silsesquioxane.
3. the branch-shape polymer with POSS base according to claim 1 and 2, it is characterized in that: described polyhedral oligomeric silsesquioxane is selected from six ethenyl cage model oligomeric silsesquioxanes, eight ethenyl cage model oligomeric silsesquioxanes, eight (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, eight (diphenylphosphine ethyl) polyhedral oligomeric silsesquioxane, eight azido-polyhedral oligomeric silsesquioxanes, eight sulfydryl POSS, octaphenyl polyhedral oligomeric silsesquioxane, octa-epoxy cage type oligomeric silsesquioxane, eight sulfuryl chlorio polyhedral oligomeric silsesquioxanes, eight carboxyl polyhedral oligomeric silsesquioxanes, ten ethenyl cage model oligomeric silsesquioxanes, ten divinyl polyhedral oligomeric silsesquioxanes, mono-vinyl polyhedral oligomeric silsesquioxane, single (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, single sulfydryl polyhedral oligomeric silsesquioxane, a kind of in single epoxy group(ing) polyhedral oligomeric silsesquioxane and mono carboxylic polyhedral oligomeric silsesquioxane.
4. the branch-shape polymer with POSS base according to claim 1 and 2, is characterized in that: described drug molecule is selected from a kind of in tamoxifen, mercaptopurine, taxol, Zorubicin, daunorubicin, vinpocetin, podophyllotoxin, l-Asparaginase, harringtonine, Rheumatrex, Rimactazid, atorvastatin and rapamycin.
5. a preparation method for the branch-shape polymer with POSS base described in claim 1～4 any one, is characterized in that:
(1) by polyhedral oligomeric silsesquioxane and POSS base intermediate R 2-POSS-(R 1) n-1according to the mol ratio of 1:6～1:80, be dissolved in organic solvent, under the condition existing at the catalyzer of catalytic amount, carry out chemical reaction, obtain the branch-shape polymer with POSS base of the formula i-iv structure in claim 1;
Described POSS base intermediate R 2-POSS-(R 1) n-1in n=6,8,10,12; R 1and R 2a kind of independently selected from halogen atom, thiazolinyl, alkynyl, alicyclic radical, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, sulfonic group, nitrogen benzide, phenolic hydroxyl group and epoxy group(ing) organic group, and R 1and R 2can not there is identical organic group; Described halogen atom is F, Cl, Br or I;
In described formula i-iv structure, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; C is polyhedral oligomeric silsesquioxane; B in X structural formula v～viii is described R 2-POSS-(R 1) n-1middle R 1a kind of in the organic group limiting;
Or
By the first POSS base intermediate R 2-POSS-(R 1) n-1with the second POSS base intermediate R 2-POSS-(R 1) n-1according to the mol ratio of 1:6～1:80, be dissolved in organic solvent, under the condition existing at the catalyzer of catalytic amount, carry out chemical reaction, obtain the branch-shape polymer with POSS base of the formula i-iv structure in claim 1;
Wherein: the first POSS base intermediate R 2-POSS-(R 1) n-1with the second POSS base intermediate R 2-POSS-(R 1) n-1in n=6,8,10,12; R 1and R 2a kind of independently selected from halogen atom, thiazolinyl, alkynyl, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, phenolic hydroxyl group and epoxy group(ing) organic group, and the first POSS base intermediate R 2-POSS-(R 1) n-1with the second POSS base intermediate R 2-POSS-(R 1) n-1in R 1with R 2to select respectively 4 kinds of different organic groups; Described halogen atom is F, Cl, Br or I; In described formula i-iv structure, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30, and C is the second POSS base intermediate R 2-POSS-(R 1) n-1in R 1a kind of in the organic group limiting, the B in X structural formula v～viii is the first POSS base intermediate R 2-POSS-(R 1) n-1in R 2a kind of in the organic group limiting; Or A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30, C is the second POSS base intermediate R 2-POSS-(R 1) n-1in R 2a kind of in the organic group limiting, the B in X structural formula v～viii is the first POSS base intermediate R 2-POSS-(R 1) n-1in R 1a kind of in the organic group limiting;
(2) branch-shape polymer with POSS base of the formula i-iv structure in the claim 1 step (1) being obtained is dissolved in organic solvent according to the mol ratio of 1:8～1:350 with the molecule with functional group, under the condition existing at the catalyzer of catalytic amount, carry out chemical reaction, obtain the branch-shape polymer with POSS base of the formula i-iv structure in claim 1;
In described formula i-iv structure, A is the alkylidene group that includes straight chain shape, a chain or ring-type that the carbonatoms of ehter bond, ester bond, ammonia ester bond or amido linkage is 1～30; B in C and X structural formula v～viii is a kind of independently selected from polyhedral oligomeric silsesquioxane, fluorescent mark and derivative thereof, organic group, chain polymer, branch-shape polymer and drug molecule respectively; When B is selected from organic group, the selected organic group of B in the organic group that it is selected and step (1) can not be selected same organic group simultaneously; When C is selected from organic group, the selected organic group of C in the organic group that it is selected and step (1) can not be selected same organic group simultaneously; B in step (2) is to select different organic groups from the organic group described in C simultaneously;
Functional group in the described molecule with functional group is to be selected from a kind of in halogen atom, thiazolinyl, alkynyl, alicyclic radical, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, sulfonic group, nitrogen benzide, phenolic hydroxyl group and epoxy group(ing); Described halogen atom is F, Cl, Br or I; Molecule in the described molecule with functional group is polyhedral oligomeric silsesquioxane, fluorescent mark and derivative thereof, chain polymer, branch-shape polymer or drug molecule.
6. preparation method according to claim 5, is characterized in that: the branch-shape polymer with POSS base of the formula i-iv structure in the claim 1 that described step (1) obtains is the branch-shape polymer with the POSS base of two-layer POSS structure;
The branch-shape polymer with POSS base of the formula i-iv structure in the claim 1 that described step (2) obtains is the branch-shape polymer with the POSS base of two-layer or three layers of POSS structure.
7. preparation method according to claim 5, is characterized in that: described by polyhedral oligomeric silsesquioxane and POSS base intermediate R 2-POSS-(R 1) n-1according to the mol ratio of 1:6～1:80, be dissolved in organic solvent and carry out chemical reaction, wherein the usage quantity of catalyzer is that the mol ratio of polyhedral oligomeric silsesquioxane and catalyzer is 1:0.1～1:3;
Described by the first POSS base intermediate R 2-POSS-(R 1) n-1with the second POSS base intermediate R 2-POSS-(R 1) n-1according to the mol ratio of 1:6～1:80, be dissolved in organic solvent and carry out chemical reaction, wherein the usage quantity of catalyzer is the first POSS base intermediate R 2-POSS-(R 1) n-1with the mol ratio of catalyzer be 1:0.1～1:3;
The branch-shape polymer with POSS base of the formula i-iv structure in the described claim 1 that step (1) is obtained and the molecule with functional group are dissolved in and in organic solvent, carry out chemical reaction according to the mol ratio of 1:8～1:350, and wherein the usage quantity of catalyzer is that the branch-shape polymer with POSS base of formula i-iv structure and the mol ratio of catalyzer in the claim 1 that obtains of step (1) are 1:0.1～1:3.
8. according to the preparation method described in claim 5 or 7, it is characterized in that: described POSS base intermediate R 2-POSS-(R 1) n-1there is one of following structure:
Figure FDA0000407895790000061
Wherein: n=6,8,10,12; R 1and R 2a kind of independently selected from halogen atom, thiazolinyl, alkynyl, azido-, sulfydryl, amido, carboxyl, aldehyde radical, hydroxyl, phenolic hydroxyl group and epoxy group(ing) organic group, and R 1and R 2can not there is identical organic group; Described halogen atom is F, Cl, Br or I;
Described POSS base intermediate R 2-POSS-(R 1) n-1to be prepared by following methods:
Polyhedral oligomeric silsesquioxane and organic molecule are dissolved in organic solvent according to the mol ratio of 1:0.5～1:3, under the condition existing at the catalyzer of catalytic amount, carry out chemical reaction, obtain having the POSS base intermediate R of single terminal groups modification of formula I～IV structure 2-POSS-(R 1) n-1;
Described organic molecule selected from mercapto acetic acid, thiohydracrylic acid, mercaptoethylamine, aminoethyle alcohol, Mercaptamine, cysteamine, mercaptoethanol, allyl mercaptan, alkynes propylmercaptan, 2 mercaptopropionic acid, 2-MEA, Mercaptobutanol, propargylic acid, propargylamine, metachloroperbenzoic acid, trifluoromethanesulfonic acid, Methanesulfonyl chloride, benzene sulfonyl chloride, propargyl alcohol, carbamyl hydrazine, Succinic anhydried, maleic anhydride, epoxy bromopropane, epoxy chloropropane, alkynes the third bromine, sodiumazide, aminoazobenzene, hydroxyazobenzene, carboxyl nitrogen benzide, acrylate chloride, methacrylic chloride, a kind of in P-hydroxybenzoic acid and hydroxyanilines.
9. preparation method according to claim 8, is characterized in that: the usage quantity of described catalyzer is that the mol ratio of polyhedral oligomeric silsesquioxane and catalyzer is 1:0.1～1:2.
10. according to claim 5, 7, preparation method described in 8 or 9, it is characterized in that: described polyhedral oligomeric silsesquioxane is selected from six ethenyl cage model oligomeric silsesquioxanes, eight ethenyl cage model oligomeric silsesquioxanes, eight (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, eight (diphenylphosphine ethyl) polyhedral oligomeric silsesquioxane, eight azido-polyhedral oligomeric silsesquioxanes, eight sulfydryl POSS, octaphenyl polyhedral oligomeric silsesquioxane, octa-epoxy cage type oligomeric silsesquioxane, eight sulfuryl chlorio polyhedral oligomeric silsesquioxanes, eight carboxyl polyhedral oligomeric silsesquioxanes, ten ethenyl cage model oligomeric silsesquioxanes, ten divinyl polyhedral oligomeric silsesquioxanes, mono-vinyl polyhedral oligomeric silsesquioxane, single (3-aminopropyl hydrochloride) polyhedral oligomeric silsesquioxane, single sulfydryl polyhedral oligomeric silsesquioxane, a kind of in single epoxy group(ing) polyhedral oligomeric silsesquioxane and mono carboxylic polyhedral oligomeric silsesquioxane.
11. according to the preparation method described in claim 5,7,8 or 9, it is characterized in that: described catalyzer is selected from DMAP, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, dicyclohexylcarbodiimide, triethylamine, acetic acid, the vitriol oil, Diisopropyl azodicarboxylate, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, cuprous bromide and N, N, N', N, ' one or more in N''-five methyl diethylentriamine.
12. according to the preparation method described in claim 5,7 or 8, it is characterized in that: described organic solvent is selected from one or more in methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), methylene dichloride, trichloromethane, ether, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dioxane, acetone, acetonitrile, normal hexane, hexanaphthene or sherwood oil.
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