CN112300360A - Preparation of amphiphilic dendritic copolymer - Google Patents
Preparation of amphiphilic dendritic copolymer Download PDFInfo
- Publication number
- CN112300360A CN112300360A CN202011213044.4A CN202011213044A CN112300360A CN 112300360 A CN112300360 A CN 112300360A CN 202011213044 A CN202011213044 A CN 202011213044A CN 112300360 A CN112300360 A CN 112300360A
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- amphiphilic dendritic
- parts
- dendritic block
- amphiphilic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001577 copolymer Polymers 0.000 title abstract description 3
- 229920001400 block copolymer Polymers 0.000 claims abstract description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- OFXSXYCSPVKZPF-UHFFFAOYSA-N methoxyperoxymethane Chemical compound COOOC OFXSXYCSPVKZPF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 4
- -1 ether diol Chemical class 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 4
- 239000002539 nanocarrier Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000000693 micelle Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002246 antineoplastic agent Substances 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 238000002512 chemotherapy Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KLWPJMFMVPTNCC-UHFFFAOYSA-N Camptothecin Natural products CCC1(O)C(=O)OCC2=C1C=C3C4Nc5ccccc5C=C4CN3C2=O KLWPJMFMVPTNCC-UHFFFAOYSA-N 0.000 description 1
- 206010048610 Cardiotoxicity Diseases 0.000 description 1
- 208000005422 Foreign-Body reaction Diseases 0.000 description 1
- 229930012538 Paclitaxel Natural products 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- VSJKWCGYPAHWDS-FQEVSTJZSA-N camptothecin Chemical compound C1=CC=C2C=C(CN3C4=CC5=C(C3=O)COC(=O)[C@]5(O)CC)C4=NC2=C1 VSJKWCGYPAHWDS-FQEVSTJZSA-N 0.000 description 1
- 229940127093 camptothecin Drugs 0.000 description 1
- 231100000259 cardiotoxicity Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940044683 chemotherapy drug Drugs 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- VSJKWCGYPAHWDS-UHFFFAOYSA-N dl-camptothecin Natural products C1=CC=C2C=C(CN3C4=CC5=C(C3=O)COC(=O)C5(O)CC)C4=NC2=C1 VSJKWCGYPAHWDS-UHFFFAOYSA-N 0.000 description 1
- 229960004679 doxorubicin Drugs 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002757 inflammatory effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000036457 multidrug resistance Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 229960001592 paclitaxel Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 description 1
- 238000011287 therapeutic dose Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of an amphiphilic dendritic block copolymer with good biocompatibility. The amphiphilic dendritic block copolymer is prepared by polymerizing polytetrahydrofuran ether diol, trimethylolpropane and isophorone diisocyanate to prepare a prepolymer block functionalized by isocyanate groups, and then adding hydrophilic polyethylene glycol monomethoxy ether for reaction. And dissolving the copolymer and the hydrophobic drug in a solution to form a mixed solution, and dialyzing away from light to prepare the nano micelle with the particle size of 27-35 nm. The preparation method is simple, efficient and controllable, develops and provides a novel nano carrier with good biocompatibility, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of biomedical high molecular polymer materials, and particularly relates to a structure and a preparation method of an amphiphilic dendritic block copolymer.
Background
The most effective anticancer drugs such as paclitaxel, doxorubicin, camptothecin, etc. are important components of cancer chemotherapy. Nevertheless, they have a series of significant drawbacks in chemotherapy such as severe cardiotoxicity and multidrug resistance. The delivery of chemotherapeutic drugs to treat cancer by selecting precise polymeric nanocarriers has been a continuing scientific challenge. Therefore, the development of the multifunctional properties of nanocarriers in the biomedical field remains an urgent task. Recent literature suggests that multifunctional nanoparticles may be a very promising tool for cancer therapy. These nanosystems form precise biological channels in the human body that not only allow diagnostic images to be acquired, but also deliver therapeutic doses of drugs to the patient in a well-defined and efficient manner. To date, a large number of polymers have been reported for the development of polymeric nanocarriers for loading poorly soluble drugs. The polyurethane material has good biocompatibility, and the chemically modified hydrophilic surface of the polyurethane material can reduce protein adsorption and platelet adhesion, so that the polyurethane material is a biological medicine carrier with great potential.
In the development of biomedical nanomaterials, biocompatibility, a property of living tissue to respond to inactive materials, remains a major challenge. A biologically inert material is a material that does not release toxic or inflammatory substances, nor does it trigger the interaction of substances with biological tissue. The introduction of such materials to the surface does not induce foreign body reactions. To construct a biologically inert surface, polyethylene glycol-based materials are most commonly incorporated.
The invention discloses a structure and a preparation method of an amphiphilic dendritic block copolymer. By adopting a block copolymerization synthesis mode, in a prepolymer stage, active hydrogen of trimethylolpropane and polytetrahydrofuran ether and isocyanate groups are subjected to addition copolymerization reaction, and a dendritic hydrophobic structure is formed due to the existence of multi-branched chains of the trimethylolpropane; and then polyethylene glycol monomethoxy ether is introduced as a hydrophilic structure to form a unique amphiphilic dendritic block copolymer.
Disclosure of Invention
The invention aims to construct an amphiphilic dendritic block copolymer which can stably exist under normal physiological environment. Therefore, the invention provides preparation and application of the amphiphilic dendritic block copolymer.
The technical scheme of the invention is as follows:
1. in order to overcome the above-mentioned drawbacks and deficiencies of the prior art, it is a primary object of the present invention to provide an amphiphilic dendritic block copolymer.
An amphiphilic dendritic block copolymer comprising a hydrophilic segment and a hydrophobic segment, having the structure shown in the following formula:
wherein: n' is 5 to 20, and n is 20 to 50.
2. A preparation method of the amphiphilic dendritic block copolymer comprises the following steps:
(1) preparation of the isocyanate group functionalized block: adding isophorone diisocyanate, polytetrahydrofuran ether diol, trimethylolpropane and dibutyltin dilaurate in a certain proportion into a three-neck flask, stirring, reacting at 70-85 ℃, and reacting for 4 hours to obtain the isocyanate group functionalized block prepolymer.
(2) Preparation of amphiphilic dendritic block copolymers: and (2) adding weighed polyethylene glycol monomethoxy ether into the isocyanate group functionalized block prepolymer prepared in the step (1), accurately controlling the reaction temperature to be 70-85 ℃, controlling the rotating speed to be 300-500 revolutions per minute, taking out after the temperature is reduced to room temperature after the reaction is carried out for 3 hours, precipitating a reactant by using n-pentane at the temperature of-15 ℃, then carrying out vacuum drying at the temperature of 35 ℃ for 24 hours, and drying to obtain the amphiphilic dendritic block copolymer.
3. The preparation method according to step 2, further comprising:
the formula of the reactants in the step (1) in parts by mole is as follows:
| raw materials | Number of moles |
| Isophorone |
2 to 4 portions of |
| Polytetrahydrofuran ether |
2 to 3 parts of |
| Trimethylolpropane | 0.05 to 0.1 portion |
| Dibutyl tin dilaurate | 0.03 to 0.1 portion |
| Acetone (II) | 50 to 60 portions of |
The formula of the reactants in the step (2) in parts by mole is as follows:
| raw materials | Number of moles |
| Performed polymer | 1 part of |
| Polyethylene |
2 portions of |
| Acetone (II) | 50 to 60 portions of |
Drawings
FIG. 1 is a synthetic route for the amphiphilic dendritic block copolymer of example 1.
FIG. 2 shows the nuclear magnetic hydrogen spectrum of the amphiphilic dendritic block copolymer of example 1 with deuterated chloroform (CDCl) as solvent3)。
FIG. 3 is an IR spectrum of the amphiphilic dendritic block copolymer of example 1.
Detailed Description
The following examples are provided to illustrate embodiments of the present invention, but are not intended to limit the present invention.
The reagents in the following examples are commercially available.
Example 1:
(1) synthesis of isocyanate-functionalized Block prepolymers
A100 mL dry three-neck flask is taken, added with polytetrahydrofuran ether dihydric alcohol (2g, 2mmol), trimethylolpropane (13.4mg, 0.1mmol), isophorone diisocyanate (0.67g, 3mmol), dibutyltin dilaurate (0.1g, 0.16mmol) and 50mL acetone in sequence, heated in a water bath at a constant temperature of 80 ℃, stirred at a speed of 300 revolutions per minute, and reacted for 5 hours to obtain the isocyanate group functionalized prepolymer.
(2) Synthesis of amphiphilic dendritic Block copolymer
Adding polyethylene glycol monomethoxy ether (2g, 1mmol) and 30mL of acetone into the isocyanate group functionalized block prepolymer synthesized in the step (1), heating in a water bath at the constant temperature of 80 ℃, controlling the stirring speed at 300 r/min, reacting for 3h, cooling to room temperature, taking out, slowly dripping into n-pentane at the temperature of-15 ℃ at the room temperature for precipitation, and drying in vacuum for 24h at the temperature of 35 ℃ to obtain the amphiphilic dendritic block copolymer.
Example 2:
(1) synthesis of isocyanate-functionalized Block prepolymers
A100 mL dry three-neck flask is taken, added with polytetrahydrofuran ether dihydric alcohol (2g, 2mmol), trimethylolpropane (26.8mg, 0.2mmol), isophorone diisocyanate (0.67g, 3mmol), dibutyltin dilaurate (0.1g, 0.16mmol) and 50mL acetone in sequence, heated in a water bath at a constant temperature of 80 ℃, stirred at a speed of 300 revolutions per minute, and reacted for 5 hours to obtain the isocyanate group functionalized prepolymer.
(2) Synthesis of amphiphilic dendritic Block copolymer
Adding polyethylene glycol monomethoxy ether (2g, 1mmol) and 30mL of acetone into the isocyanate group functionalized block prepolymer synthesized in the step (1), heating in a water bath at the constant temperature of 80 ℃, controlling the stirring speed at 300 r/min, reacting for 3h, cooling to room temperature, taking out, slowly dripping into n-pentane at the temperature of-15 ℃ at the room temperature for precipitation, and drying in vacuum for 24h at the temperature of 35 ℃ to obtain the amphiphilic dendritic block copolymer.
Example 3:
(1) synthesis of isocyanate-functionalized Block prepolymers
A100 mL dry three-neck flask is taken, added with polytetrahydrofuran ether dihydric alcohol (2g, 2mmol), trimethylolpropane (40.2mg, 0.3mmol), isophorone diisocyanate (0.67g, 3mmol), dibutyltin dilaurate (0.1g, 0.16mmol) and 50mL acetone in sequence, heated in a water bath at a constant temperature of 80 ℃, stirred at a speed of 300 revolutions per minute, and reacted for 5 hours to obtain the isocyanate group functionalized prepolymer.
(2) Synthesis of amphiphilic dendritic Block copolymer
Adding polyethylene glycol monomethoxy ether (2g, 1mmol) and 30mL of acetone into the isocyanate group functionalized block prepolymer synthesized in the step (1), heating in a water bath at the constant temperature of 80 ℃, controlling the stirring speed at 300 r/min, reacting for 3h, cooling to room temperature, taking out, slowly dripping into n-pentane at the temperature of-15 ℃ at the room temperature for precipitation, and drying in vacuum for 24h at the temperature of 35 ℃ to obtain the amphiphilic dendritic block copolymer.
Claims (6)
1. An amphiphilic dendritic block copolymer characterized by: the amphiphilic dendritic block copolymer comprises a hydrophobic block and a hydrophilic block, and has the following structural formula:
wherein: n' is 5-20, n is 20-50;
r is at least one of isophorone diisocyanate, toluene-2, 4-diisocyanate and hexamethylene diisocyanate.
2. A method for preparing the amphiphilic dendritic block copolymer of claim 1, characterized in that it comprises the steps of:
(1) preparation of the isocyanate group functionalized block: adding isophorone diisocyanate, polytetrahydrofuran ether diol, trimethylolpropane and dibutyltin dilaurate in a certain proportion into a three-neck flask, stirring, heating for reaction, and reacting for a period of time to obtain the isocyanate group functionalized block prepolymer.
(2) Preparation of amphiphilic dendritic block copolymers: and (2) adding weighed polyethylene glycol monomethoxy ether into the isocyanate group functionalized block prepolymer prepared in the step (1), stirring and heating the mixture in a solvent for reaction, cooling the mixture, taking the mixture out, precipitating a product by using a solvent with lower polarity, drying the product in vacuum for 24 hours, and drying the product to obtain the amphiphilic dendritic block copolymer.
3. The method of preparing an amphiphilic dendritic block copolymer according to claim 2, characterized in that:
the formula of the reactants in the step (1) in parts by mole is as follows:
2-4 parts of isophorone diisocyanate
2-3 parts of polytetrahydrofuran ether dihydric alcohol
0.05 to 0.1 portion of trimethylolpropane
0.03-0.1 part of dibutyltin dilaurate
40-60 parts of acetone
The formula of the reactants in the step (2) in parts by mole is as follows:
prepolymer 1 part
2 parts of polyethylene glycol monomethoxy ether
40-60 parts of acetone.
4. The method of preparing an amphiphilic dendritic block copolymer according to claim 2, characterized in that: the heating reaction in the step (1) is heating to 70-85 ℃, the reaction time is 4-6 h, and the solvent is at least one of acetone and toluene.
5. The method of preparing an amphiphilic dendritic block copolymer according to claim 2, characterized in that: the reaction time in the step (2) is 3-5h, and the temperature range of vacuum drying is 25-35 ℃.
6. The method of preparing an amphiphilic dendritic block copolymer according to claim 2, characterized in that: the precipitant in the step (2) is at least one of n-pentane and n-hexane. The temperature range of the precipitant is-15 to-20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011213044.4A CN112300360A (en) | 2020-11-03 | 2020-11-03 | Preparation of amphiphilic dendritic copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011213044.4A CN112300360A (en) | 2020-11-03 | 2020-11-03 | Preparation of amphiphilic dendritic copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112300360A true CN112300360A (en) | 2021-02-02 |
Family
ID=74324744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011213044.4A Pending CN112300360A (en) | 2020-11-03 | 2020-11-03 | Preparation of amphiphilic dendritic copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112300360A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403730A (en) * | 2022-10-13 | 2022-11-29 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
-
2020
- 2020-11-03 CN CN202011213044.4A patent/CN112300360A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403730A (en) * | 2022-10-13 | 2022-11-29 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
| CN115403730B (en) * | 2022-10-13 | 2023-06-27 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172819B (en) | Biodegradable polyurethane with amino on side chain and preparation method and application thereof | |
| Jagur-Grodzinski | Biomedical application of functional polymers | |
| Feng et al. | Construction of functional aliphatic polycarbonates for biomedical applications | |
| CN101503501B (en) | Biodegradable nontoxic amphipathic multi-block polyurethane material and preparation thereof | |
| US8445016B2 (en) | Grafted polymers and uses thereof | |
| US10982058B2 (en) | Polycarbonate containing compounds and methods related thereto | |
| CN102335435B (en) | Multifunctional polyurethane medicament carrier as well as preparation method and application thereof | |
| Bahadur et al. | Regulating the anticancer drug release rate by controlling the composition of waterborne polyurethane | |
| EP1498147B1 (en) | Absorbable biocompatible block copolymer | |
| US20020155092A1 (en) | Phosphate based biodegradable polymers | |
| Sawdon et al. | Polymeric micelles for acyclovir drug delivery | |
| CN110938200B (en) | Preparation method of amine polyester containing dimethyl pyridine on side chain | |
| US8728453B2 (en) | Combinatorial polymeric compositions for drug delivery | |
| CN107200825B (en) | Synthesis of amphiphilic triblock antibacterial peptide containing epsilon-polylysine and preparation method and application of assembly of amphiphilic triblock antibacterial peptide | |
| CN112300360A (en) | Preparation of amphiphilic dendritic copolymer | |
| CN101565497B (en) | Amphiphilic block copolymer, nano-particles thereof and method for preparing same | |
| CN105968370B (en) | The polyethylene glycol polycaprolactone triblock polymer and its preparation method and application of triple disulfide bond connections | |
| CN100365043C (en) | Synthesis of ABA polypeptide -b- polytetrahydrofuran-b-polypeptide triblock copolymer | |
| CN101880381A (en) | Segmented copolymer modified by polyethylene glycol 1000 vitamin E succinic acid ester, preparation method and applications thereof | |
| Davaran et al. | Synthesis and hydrolysis of polyurethanes containing ibuprofen pendent groups | |
| Chang et al. | Ring-opening polymerization of ε-caprolactone initiated by the antitumor agent doxifluridine | |
| CN102898635A (en) | Amphipathic high polymer material and method for preparing same | |
| Guidotti et al. | Micro/nanoparticles fabricated with triblock PLLA-based copolymers containing PEG-like subunit for controlled drug release: Effect of chemical structure and molecular architecture on drug release profile | |
| US20050106120A1 (en) | Polyester containing active drugs and having amino acids in the main chain & comma; and its preparation method | |
| CN110483740B (en) | Polymer, pH-sensitive nano-vesicle, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210202 |
|
| WD01 | Invention patent application deemed withdrawn after publication |