CN102675587A - Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material - Google Patents
Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material Download PDFInfo
- Publication number
- CN102675587A CN102675587A CN201210160087XA CN201210160087A CN102675587A CN 102675587 A CN102675587 A CN 102675587A CN 201210160087X A CN201210160087X A CN 201210160087XA CN 201210160087 A CN201210160087 A CN 201210160087A CN 102675587 A CN102675587 A CN 102675587A
- Authority
- CN
- China
- Prior art keywords
- molecule
- hydroxyls
- environment
- fluorescence radiation
- organic
- 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.)
- Granted
Links
Images
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses the preparation of an environment pH-responsive polyurethane fluorescent light-emitting medical material, belonging to the field of chemical industry. The objective of the invention is to prepare an environment pH-responsive polyurethane fluorescent light-emitting medical material by introducing fluorescent small molecules onto a polyurethane main chain based on excellent stability of macromolecular material. According to the invention, a one-step process and a two-step process are adopted for synthesis: the environment pH-responsive polyurethane fluorescent light-emitting medical material is prepared by using a two-step method, namely, aliphatic diisocyanate or aromatic diisocyanate, polyether glycol, double-hydroxyl organics with carboxyl groups, micromolecular aliphatic ethylene diamine, fluorescent molecules with double hydroxyls and double-hydroxyl organic molecules with secondary amine or tertiary amine groups are polymerized. The environment pH-responsive polyurethane fluorescent light-emitting medical material disclosed by the invention is free from toxicity and good in biocompatibility, has response to pH change and fluorescent performance especially, and is suitable to be used as a hydrophobic drug carrier or a fluorescent probe, etc.
Description
Technical field
The invention belongs to chemical field.
Background technology
Polyurethane material is because there is tangible micro phase separation structure in the uncompatibility of soft or hard section, and wherein soft section provides elasticity; Hard section plays to strengthen and fills and crosslinked action; This heterogeneous polymer has the physical strength height, and blood compatibility is good, performances such as histocompatibility excellence.So polyurethane material has obtained using widely at biomedicine field, like many therapeutic treatments fields such as artificial organ, medical catheter, birth control necessities, controllable sustained-release medicine, medical tamanori, medicine equipment, medical auxilliary materials.
Summary of the invention
The objective of the invention is to utilize macromolecular material to have good stability, fluorescent small molecule is incorporated into the preparation of the environment pH responsiveness urethane fluorescence radiation medical material on the polyurethane backbone.
The present invention adopts single stage method and two-step approach synthetic method:
Adopt two-step approach synthetic environment pH sensitive polyurethane fluorescence radiation medical material, with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic class of two hydroxyls, small molecules aliphatics quadrol, have pair hydroxyl fluorescence molecules, have the organic quasi-molecule polymerization of two hydroxyls of secondary amine or tertiary amine group;
Wherein the polyether Glycols molecular weight is 200 ~ 10000
(1) with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation materials; The organic quasi-molecule of two hydroxyls that has secondary amine or tertiary amine group; Make solvent with N, DMSO 99.8MIN. or N-Methyl pyrrolidone; Make catalyzer with triethylamine; Join in the there-necked flask that has magnet rotor, putting into temperature to flask again is that 70 ~ 85 ° of C oil bath pans reacted 6 hours under the condition of nitrogen protection;
(2) aliphatic diamine that uses 2-6 carbon is as chainextender, and reaction is 6 hours under 70 ~ 85 ° of C conditions;
(3) reduce to the room temperature afterreaction after 12 hours, discharging;
(4) reaction product solution is added drop-wise to sedimentation in the sedimentation solvent ether, can obtains product after the oven dry;
Wherein the weight part of above-mentioned raw materials composition is:
Aliphatic diisocyanate or aromatic diisocyanate 10 ~ 50
Polyether Glycols 10 ~ 50
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has carboxylic group
Have two hydroxyl fluorescence radiation materials 1
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has secondary amine or tertiary amine group
Triethylamine 1.
The present invention adopts two-step approach synthetic method:
With aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, the organic quasi-molecule of two hydroxyls that has carboxylic group, two hydroxyl fluorescence radiation material, aliphatics quadrol, under organic solvent, polymerization;
Second step added NSC 57182 and N-hydroxy-succinamide activated carboxyl group, and the molecule that will have amino group is grafted on the main polymer chain, obtains having environment pH sensitive polyurethane fluorescence radiation medical material;
Wherein the polyether Glycols molecular weight is 200 ~ 10000
(1) with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation materials; With an organic solvent; Use triethylamine to make catalyzer; In having the there-necked flask of magnet rotor, reaction is 6 hours under the condition in nitrogen protection in 70 ~ 85 ° of C oil bath pans;
(2) use aliphatic diamine as chainextender, reaction is 6 hours under 70 ~ 85 ° of C conditions;
(3) reduced to the room temperature afterreaction 12 hours;
Molecule, DCC and the NHS that (4) will have an amino group joins in the solution and at room temperature reacted 24 hours, filters to obtain polymers soln;
(5) drips of solution is added to sedimentation in the ether, oven dry can obtain product;
Wherein the weight part of above-mentioned raw materials composition is:
Aliphatic diisocyanate or aromatic diisocyanate 10 ~ 50
Polyether Glycols 10 ~ 50
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has carboxylic group
Have two hydroxyl fluorescence radiation materials 1
The molecule 10 ~ 50 that has amino group
DCC 10
NHS 10。
The present invention is nontoxic, and good biocompatibility especially can play the response effect and have fluorescence property the variation of pH value, and this product is suitable as hydrophobic drug carrier or fluorescent probe etc.
Description of drawings
Fig. 1 is the building-up process of environment pH sensitive polyurethane material of the present invention;
Fig. 2 is the nmr spectrum of environment pH sensitive polyurethane material of the present invention;
Fig. 3 is the infrared spectrogram of environment pH sensitive polyurethane material of the present invention;
Fig. 4 is the acid base titration buffer curve of environment pH sensitive polyurethane material of the present invention;
Fig. 5 is the fluorescence spectrum figure and the luminous situation of environment pH sensitive polyurethane fluorescence luminescent material of the present invention.
Embodiment
The present invention adopts single stage method and two-step approach synthetic method:
Adopt two-step approach synthetic environment pH sensitive polyurethane fluorescence radiation medical material, with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic class of two hydroxyls, small molecules aliphatics quadrol, have pair hydroxyl fluorescence molecules, have the organic quasi-molecule polymerization of two hydroxyls of secondary amine or tertiary amine group;
Wherein the polyether Glycols molecular weight is 200 ~ 10000
(1) with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation materials; The organic quasi-molecule of two hydroxyls that has secondary amine or tertiary amine group; Make solvent with N, DMSO 99.8MIN. or N-Methyl pyrrolidone; Make catalyzer with triethylamine; Join in the there-necked flask that has magnet rotor, putting into temperature to flask again is that 70 ~ 85 ° of C oil bath pans reacted 6 hours under the condition of nitrogen protection;
(2) aliphatic diamine that uses 2-6 carbon is as chainextender, and reaction is 6 hours under 70 ~ 85 ° of C conditions;
(3) reduce to the room temperature afterreaction after 12 hours, discharging;
(4) reaction product solution is added drop-wise to sedimentation in the sedimentation solvent ether, can obtains product after the oven dry;
Wherein the weight part of above-mentioned raw materials composition is:
Aliphatic diisocyanate or aromatic diisocyanate 10 ~ 50
Polyether Glycols 10 ~ 50
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has carboxylic group
Have two hydroxyl fluorescence radiation materials 1
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has secondary amine or tertiary amine group
Triethylamine 1.
The present invention adopts two-step approach synthetic method:
With aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, the organic quasi-molecule of two hydroxyls that has carboxylic group, two hydroxyl fluorescence radiation material, aliphatics quadrol, under organic solvent, polymerization;
Second step added NSC 57182 and N-hydroxy-succinamide activated carboxyl group, and the molecule that will have amino group is grafted on the main polymer chain, obtains having environment pH sensitive polyurethane fluorescence radiation medical material;
Wherein the polyether Glycols molecular weight is 200 ~ 10000
(1) with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation materials; With an organic solvent; Use triethylamine to make catalyzer; In having the there-necked flask of magnet rotor, reaction is 6 hours under the condition in nitrogen protection in 70 ~ 85 ° of C oil bath pans;
(2) use aliphatic diamine as chainextender, reaction is 6 hours under 70 ~ 85 ° of C conditions;
(3) reduced to the room temperature afterreaction 12 hours;
Molecule, DCC and the NHS that (4) will have an amino group joins in the solution and at room temperature reacted 24 hours, filters to obtain polymers soln;
(5) drips of solution is added to sedimentation in the ether, oven dry can obtain product;
Wherein the weight part of above-mentioned raw materials composition is:
Aliphatic diisocyanate or aromatic diisocyanate 10 ~ 50
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has carboxylic group
Have two hydroxyl fluorescence radiation materials 1
The molecule 10 ~ 50 that has amino group
The invention provides the compound method of two kinds of pH responsiveness urethane fluorescence radiation medical material preparations.
First kind of method for preparing environment pH sensitive polyurethane fluorescence radiation medical material:
(1) with aliphatic diisocyanate (or aromatic diisocyanate), polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation molecules, the organic quasi-molecule of two hydroxyls that has secondary amine or tertiary amine group is in organic solvent; In having the there-necked flask of magnet rotor, under the condition of nitrogen protection, reacted 6 hours in the 70-85 ° of C oil bath pan.
(2) the binary aliphatic amine chainextender is added, under 70-85 ° of C condition, continue reaction 6 hours.
(3) reduced to the room temperature afterreaction 12 hours, discharging.
(4) reaction product solution sedimentation in ether solvent can be obtained product.
So reducing to room temperature in reaction after 12 hours for the molecular weight that improves this product continued to react 12 hours again.In order to improve product gas purity, reaction product is put into vacuum chamber after filtering through sedimentation, and removes the residue ether solvent in 72 hours at the vacuum chamber inner drying.
Aliphatic diisocyanate among the preparation method provided by the invention can be selected hexamethylene diisocyanate, vulcabond methyl acetic acid ester for use.
Polyether Glycols among the preparation method provided by the invention can be selected polyoxyethylene glycol for use.
The two hydroxyls that have carboxylic group among the preparation method provided by the invention can select 2 for use for organic type, two (methylol) propionic acid of 2-.
Having two hydroxyl fluorescence radiation materials and can select red B of algae or fluorescein isothiocyanate (FITC) for use among the preparation method provided by the invention.
There are having among the preparation method provided by the invention two hydroxyls of secondary amine or tertiary amine group can select 1 for use for organic type, two (2-hydroxyethyl) piperazines (HEP) of 4-
Organic amine catalyzer among the preparation method provided by the invention can be selected triethylamine for use.
Organic solvent among the preparation method provided by the invention can be selected DMF, DMSO or N-Methyl pyrrolidone for use.
The optional ether of using of organic ethers among the preparation method provided by the invention.
Second kind of method for preparing environment pH sensitive polyurethane fluorescence radiation medical material:
(1) with aliphatic diisocyanate (or aromatic diisocyanate), polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation molecules; Be dissolved in organic solvent; Join in the there-necked flask that has magnet rotor; In 70-85 ° of C oil bath pan, reaction is 6 hours under the condition of nitrogen protection.
(2) aliphatic diamine is added as chainextender, continue reaction after 6 hours, reduced to the room temperature afterreaction 12 hours in 70-85 ° of C.
(3) will join with organic quasi-molecule, NSC 57182 (DCC) and the N-hydroxy-succinamide (NHS) of amino group in the polymers soln and at room temperature react 24 hours, filter discharging.
So reducing to room temperature in reaction after 12 hours for the molecular weight that improves this product continued to react 12 hours again.In order to improve product gas purity, reaction product is put into vacuum chamber after filtering through sedimentation, and removes the residue ether solvent in 72 hours at the vacuum chamber inner drying.
Aliphatic diisocyanate among the preparation method provided by the invention can be selected hexamethylene diisocyanate, vulcabond methyl acetic acid ester for use.
Polyether Glycols among the preparation method provided by the invention can be selected polyoxyethylene glycol (molecular weight is 2000) for use.
The two hydroxyls that have carboxylic group among the preparation method provided by the invention can select 2 for use for organic type, two (methylol) propionic acid of 2-.
Having two hydroxyl fluorescence radiation materials and can select red B of algae or fluorescein isothiocyanate (FITC) for use among the preparation method provided by the invention.
The amino organic class that has secondary amine or tertiary amine group among the preparation method provided by the invention can be selected 1H-imidazoles-1-propane amine for use.
Activated carboxyl group among the preparation method provided by the invention is selected DCC and NHS activation for use.
Organic amine catalyzer among the preparation method provided by the invention can be selected triethylamine for use.
The optional ether of using of organic ethers among the preparation method provided by the invention.
So-called environment pH Sensitive Polymer Materials is exactly the macromolecular material that produces volume or form change with the variation of extraneous pH value, and this variation is based on the stimulating responsive of molecular level.The pH Sensitive Polymer Materials can be applicable to fixing, the feed separation of drug controllable release system, enzyme, proteinic transmission, molecular imaging etc.Because fluorescent small molecule is unstable in medical diagnosis on disease, simultaneously bad with the substrate material intermiscibility, instrument test result's stability also will be affected.And macromolecular material has good stability, so fluorescent small molecule is incorporated on the polyurethane backbone, can be used as fluorescent probe and is applied to fields such as chemical sensor, optical material, biological detection.
Environment pH sensitive polyurethane fluorescence radiation medical material mainly is by aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, the organic type of material that has two hydroxyls and small molecule chain extender synthetic.Wherein aliphatic diisocyanate and chainextender have constituted hard section of this polyurethane material; Polyether Glycols has constituted soft section of this polyurethane material; Have two hydroxyl fluorescent substances and make this polyurethane material have fluorescence property, the organic quasi-molecule and the organic quasi-molecule that contains amino secondary amine or tertiary amine group that have secondary amine or the tertiary amine group of two hydroxyls simultaneously provide the pH susceptibility of this polyurethane material.
Embodiment 1:
1. the diisocyanates selected for use of instance is hexamethylene diisocyanate (HDI), and gets 50.
2. the polyether-type divalent alcohol selected for use of instance is polyoxyethylene glycol (molecular weight is 2000), and gets 10.
3. organic type of material of two hydroxyls of the band carboxyl selected for use of instance is 2, two (methylol) propionic acid (DMPA) of 2-, and get 20.
4. organic type of material of two hydroxyls that has secondary amine or tertiary amine group that instance is selected for use is 1, two (2 hydroxyethyl) piperazines (HEP) of 4-, and get 20.
5. to select the fluorescence radiation material that two hydroxyls are arranged of band for use be fluorescein isothiocyanate (FITC) to instance.Consumption is 1% of a total reactant weight.
6. the organic amine catalyzer selected for use of instance is a triethylamine, and gets 0.1%.
7. the solvent selected for use of instance is N, dinethylformamide.
8. add above RM and have in the there-necked flask of magnetic force rotor, and to put into temperature to there-necked flask be that the oil bath pan of 70 ° of C reacted 6 hours under nitrogen protection.
9. add small molecules binary amine or di-alcohols chainextender afterwards, the chainextender that instance is selected for use is a quadrol, and gets 1 part, reacts 6 hours.
10. in order to improve the molecular weight of product, continue reaction 12 hours again after reaction system reduced to room temperature.
11. dropwise being added drop-wise to, final product solution carries out sedimentation in the ether solvent.Filter out polymerisate afterwards, put into vacuum chamber and vacuumized 72 hours, obtain purified product.
Embodiment 2:
1. the diisocyanates selected for use of instance is hexamethylene diisocyanate (HDI), and gets 50.
2. the polyether-type divalent alcohol selected for use of instance is polyoxyethylene glycol (molecular weight is 2000), and gets 10.
3. organic type of material of two hydroxyls of the band carboxyl selected for use of instance is 2, two (methylol) propionic acid (DMPA) of 2-, and get 40.
4. to select the fluorescence radiation material that two hydroxyls are arranged of band for use be fluorescein isothiocyanate (FITC) to instance.Consumption is 1 of a total reactant.
5. the organic amine catalyzer selected for use of instance is a triethylamine, and gets 0.1%.
6. the solvent selected for use of instance is N, dinethylformamide.
7. have above RM adding in the there-necked flask of magnetic force rotor, and put into the inherent vacuum condition of oil bath pan that temperature is 70 ° of C to there-necked flask, nitrogen protection was reacted 6 hours down.
8. add small molecules binary amine or di-alcohols chainextender afterwards, the chainextender that instance is selected for use is a quadrol, and gets 1 part, continues reaction 6 hours.
9. in order to improve the molecular weight of product, continue reaction 12 hours again after reducing to room temperature.
10. add N afterwards, N-NSC 57182 (DCC) and N-hydroxy-succinamide (NHS) each 10, the activated carboxyl group continues reaction 2 hours.
11. selecting for use the amino organic class that has secondary amine or tertiary amine group to join in the there-necked flask.This material that instance is selected for use is 1H-imidazoles-1-propane amine.And get 20.
12. at room temperature sustained reaction is 24 hours.
13. dropwise being added drop-wise to, final product solution carries out sedimentation in the ether solvent.Filter out polymerisate afterwards, put into vacuum chamber and vacuumized 72 hours, obtain purified product.
Claims (2)
1. the preparation of an environment pH responsiveness urethane fluorescence radiation medical material is characterized in that: adopt single stage method and two-step approach synthetic method:
Adopt two-step approach synthetic environment pH sensitive polyurethane fluorescence radiation medical material, with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic class of two hydroxyls, small molecules aliphatics quadrol, have pair hydroxyl fluorescence molecules, have the organic quasi-molecule polymerization of two hydroxyls of secondary amine or tertiary amine group;
Wherein the polyether Glycols molecular weight is 200 ~ 10000
(1) with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation materials; The organic quasi-molecule of two hydroxyls that has secondary amine or tertiary amine group; Make solvent with N, DMSO 99.8MIN. or N-Methyl pyrrolidone; Make catalyzer with triethylamine; Join in the there-necked flask that has magnet rotor, putting into temperature to flask again is that 70 ~ 85 ° of C oil bath pans reacted 6 hours under the condition of nitrogen protection;
(2) aliphatic diamine that uses 2-6 carbon is as chainextender, and reaction is 6 hours under 70 ~ 85 ° of C conditions;
(3) reduce to the room temperature afterreaction after 12 hours, discharging;
(4) reaction product solution is added drop-wise to sedimentation in the sedimentation solvent ether, can obtains product after the oven dry;
Wherein the weight part of above-mentioned raw materials composition is:
Aliphatic diisocyanate or aromatic diisocyanate 10 ~ 50
Polyether Glycols 10 ~ 50
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has carboxylic group
Have two hydroxyl fluorescence radiation materials 1
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has secondary amine or tertiary amine group
Triethylamine 1.
2. the preparation of an environment pH responsiveness urethane fluorescence radiation medical material is characterized in that: adopt two-step approach synthetic method:
With aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, the organic quasi-molecule of two hydroxyls that has carboxylic group, two hydroxyl fluorescence radiation material, aliphatics quadrol, under organic solvent, polymerization;
Second step added NSC 57182 and N-hydroxy-succinamide activated carboxyl group, and the molecule that will have amino group is grafted on the main polymer chain, obtains having environment pH sensitive polyurethane fluorescence radiation medical material;
Wherein the polyether Glycols molecular weight is 200 ~ 10000
(1) with aliphatic diisocyanate or aromatic diisocyanate, polyether Glycols, have carboxylic group the organic quasi-molecule of two hydroxyls, have two hydroxyl fluorescence radiation materials; With an organic solvent; Use triethylamine to make catalyzer; In having the there-necked flask of magnet rotor, reaction is 6 hours under the condition in nitrogen protection in 70 ~ 85 ° of C oil bath pans;
(2) use aliphatic diamine as chainextender, reaction is 6 hours under 70 ~ 85 ° of C conditions;
(3) reduced to the room temperature afterreaction 12 hours;
Molecule, DCC and the NHS that (4) will have an amino group joins in the solution and at room temperature reacted 24 hours, filters to obtain polymers soln;
(5) drips of solution is added to sedimentation in the ether, oven dry can obtain product;
Wherein the weight part of above-mentioned raw materials composition is:
Aliphatic diisocyanate or aromatic diisocyanate 10 ~ 50
Polyether Glycols 10 ~ 50
The organic quasi-molecule 10 ~ 50 of two hydroxyls that has carboxylic group
Have two hydroxyl fluorescence radiation materials 1
The molecule 10 ~ 50 that has amino group
DCC 10
NHS 10。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210160087.XA CN102675587B (en) | 2012-05-22 | 2012-05-22 | Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210160087.XA CN102675587B (en) | 2012-05-22 | 2012-05-22 | Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102675587A true CN102675587A (en) | 2012-09-19 |
| CN102675587B CN102675587B (en) | 2014-01-01 |
Family
ID=46808182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210160087.XA Expired - Fee Related CN102675587B (en) | 2012-05-22 | 2012-05-22 | Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102675587B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875772A (en) * | 2012-10-19 | 2013-01-16 | 中国科学院长春应用化学研究所 | Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel |
| CN104164079A (en) * | 2013-08-14 | 2014-11-26 | 长春工业大学 | Preparation method of magnetic fluorescent luminescent pH-sensitive polyurethane material |
| CN109513015A (en) * | 2018-12-11 | 2019-03-26 | 吉林化工学院 | A kind of tumor microenvironment responsiveness self assembly diagnosis and treatment integration reagent and preparation method thereof |
| CN110330623A (en) * | 2019-05-30 | 2019-10-15 | 河北晨阳工贸集团有限公司 | Polyaminoester microball and preparation method thereof with pH responsiveness |
| CN115073701A (en) * | 2022-07-13 | 2022-09-20 | 江苏方正塑业有限公司 | Anionic alizarin-based waterborne polyurethane fluorescent emulsion and preparation method thereof |
| CN115109227A (en) * | 2022-08-14 | 2022-09-27 | 许昌学院 | Novel polyfluoro fluorescent polymer and preparation method thereof |
| CN115215988A (en) * | 2022-08-16 | 2022-10-21 | 重庆科技学院 | Multifunctional polyurethane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080262187A1 (en) * | 2005-12-30 | 2008-10-23 | Albemarle Corporation | Blends of Diamines Having Reduced Color |
| CN101676310A (en) * | 2008-09-16 | 2010-03-24 | 日本油漆株式会社 | Fingerprint resistance photo-curing combination and coating article having a fingerprint resistance coating layer |
-
2012
- 2012-05-22 CN CN201210160087.XA patent/CN102675587B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080262187A1 (en) * | 2005-12-30 | 2008-10-23 | Albemarle Corporation | Blends of Diamines Having Reduced Color |
| CN101676310A (en) * | 2008-09-16 | 2010-03-24 | 日本油漆株式会社 | Fingerprint resistance photo-curing combination and coating article having a fingerprint resistance coating layer |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875772A (en) * | 2012-10-19 | 2013-01-16 | 中国科学院长春应用化学研究所 | Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel |
| CN104164079A (en) * | 2013-08-14 | 2014-11-26 | 长春工业大学 | Preparation method of magnetic fluorescent luminescent pH-sensitive polyurethane material |
| CN109513015A (en) * | 2018-12-11 | 2019-03-26 | 吉林化工学院 | A kind of tumor microenvironment responsiveness self assembly diagnosis and treatment integration reagent and preparation method thereof |
| CN109513015B (en) * | 2018-12-11 | 2021-06-04 | 吉林化工学院 | Tumor microenvironment responsive self-assembled diagnosis and treatment integrated reagent and preparation method thereof |
| CN110330623A (en) * | 2019-05-30 | 2019-10-15 | 河北晨阳工贸集团有限公司 | Polyaminoester microball and preparation method thereof with pH responsiveness |
| CN115073701A (en) * | 2022-07-13 | 2022-09-20 | 江苏方正塑业有限公司 | Anionic alizarin-based waterborne polyurethane fluorescent emulsion and preparation method thereof |
| CN115109227A (en) * | 2022-08-14 | 2022-09-27 | 许昌学院 | Novel polyfluoro fluorescent polymer and preparation method thereof |
| CN115109227B (en) * | 2022-08-14 | 2024-01-30 | 许昌学院 | Novel polyfluoro fluorescent polymer and preparation method thereof |
| CN115215988A (en) * | 2022-08-16 | 2022-10-21 | 重庆科技学院 | Multifunctional polyurethane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102675587B (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102675587B (en) | Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material | |
| KR102139171B1 (en) | Eco-friendly biocompatible thermoplastic polyurethane and method for manufacturing the same and biocompatible article comprising the same | |
| CN100391994C (en) | Preparation method of chitin modified water polyurethane elastic body | |
| Sharifpoor et al. | Synthesis and characterization of degradable polar hydrophobic ionic polyurethane scaffolds for vascular tissue engineering applications | |
| US20030066987A1 (en) | Biodegradable, electrically conducting polymer for tissue engineering applications | |
| US7538163B2 (en) | Modification of thermoplastic polymers | |
| CN103242536A (en) | Method for preparing polypeptide-polylactic acid-polyethyleneglycol dual-graft copolymer | |
| CN111675820B (en) | Surface-grafted curcumin modified degradable polyurethane composite material and preparation method and application thereof | |
| CN101885826A (en) | Biodegradable polyurethane material based on piperazine block D, L-polylactic acid and preparation method thereof | |
| JP2011502182A (en) | Oligofluorinated cross-linked polymer and use thereof | |
| CN113372548B (en) | Vegetable oil-based antifouling polyol and preparation method and application thereof | |
| CN106243352A (en) | A kind of polyphenylene triazole formic acid esters and preparation method and application | |
| JP2023506210A (en) | Unmixed Amphiphilic Thermoplastic Polyurethane, Process for Making Same and Implantable Medical Device Containing Same | |
| CN115215988A (en) | Multifunctional polyurethane and preparation method and application thereof | |
| RU2007137595A (en) | METHOD FOR PRODUCING POLYESTERPOLIOLS WITH FUNCTIONALITY FROM 1.95 TO 3.25 AND HYDROXYL NUMBER FROM 90 TO 33 mg KOH / g AND THEIR APPLICATION | |
| CN104164079A (en) | Preparation method of magnetic fluorescent luminescent pH-sensitive polyurethane material | |
| JP2023535295A (en) | FUNCTIONALIZED THERMOPLASTIC POLYURETHANE, METHOD FOR PRODUCING THE SAME, METHOD FOR PRODUCING MEDICAL HIGH-FUNCTIONAL COMPOSITE MATERIAL USING THE SAME, AND MEDICAL DEVICES CONTAINING THE SAME | |
| CN113912822B (en) | Thermoplastic polyurethane elastomer and preparation method and application thereof | |
| CN103030738A (en) | Lawsone copolymer with antineoplastic activity and preparation method thereof | |
| CN107033337B (en) | A kind of functional poly ester polyurethane alternate copolymer and its preparation and application | |
| KR101260328B1 (en) | Dialkyl aminoalkyl sulfone and their mimics containing self-assembled brush polyether-based polymers for bio-applications, preparation thereof products comprising the polymer | |
| KR101053246B1 (en) | Self-assembled polymer having Purin Mimic at the brush end and its manufacturing method | |
| Nagase et al. | Biocompatible polyamides and polyurethanes containing phospholipid moiety | |
| WO2013176084A1 (en) | Silane coupling agent containing silylalkyl phosphoramidate compound | |
| JP4058676B2 (en) | Functional polyurethane and / or polyurethane urea and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140101 Termination date: 20150522 |
|
| EXPY | Termination of patent right or utility model |