WO2019095116A1 - 可诱导发光的聚氨酯及其制备方法 - Google Patents
可诱导发光的聚氨酯及其制备方法 Download PDFInfo
- Publication number
- WO2019095116A1 WO2019095116A1 PCT/CN2017/110950 CN2017110950W WO2019095116A1 WO 2019095116 A1 WO2019095116 A1 WO 2019095116A1 CN 2017110950 W CN2017110950 W CN 2017110950W WO 2019095116 A1 WO2019095116 A1 WO 2019095116A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- terminated
- group
- hydroxyl
- amino
- polyurethane
- Prior art date
Links
- 0 CC(C)(N(C(CS1)O)*1=C(C)C(O)=*)O Chemical compound CC(C)(N(C(CS1)O)*1=C(C)C(O)=*)O 0.000 description 2
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
-
- 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
Definitions
- the invention relates to the technical field of polyurethane polymer materials, in particular to a polyurethane capable of inducing luminescence and a preparation method of the above-mentioned luminescence-inducing polyurethane.
- Polyurethane is a type of multi-block polymer rich in urethane bonds (—NHCOO—) consisting of a soft segment with a lower softening temperature and a hard segment with a higher softening temperature. Therefore, its molecular structure has good designability.
- the soft segments and hard segments of different structures and different proportions of soft and hard segments can be selected, and polyurethane materials with different properties can be designed and synthesized, which has good processability and is widely used. In the chemical, electronics, construction, automotive, aerospace, textile, medical and other fields.
- the soft segment region is a biodegradable material such as biodegradable polylactic acid (PLA) or polycaprolactone (PCL), the biodegradable polyurethane can be synthesized.
- PLA biodegradable polylactic acid
- PCL polycaprolactone
- biodegradable polyurethane is widely used in artificial heart and auxiliary devices, artificial skin, artificial blood vessels, bone repair materials and the like.
- visualization has attracted wide attention from scholars at home and abroad due to its high sensitivity and rapid response.
- Fluorescent biomaterials are widely used in cell imaging, biosensing, immunology, drug controlled release and tissue engineering, and material ontology visualization. However, there is little research, so the visualization of the bulk of polyurethane materials is imminent.
- the earliest fluorescent visualization material is an organic dye.
- organic dyes are only used for fluorescent markers in vitro due to the potential cytotoxicity of the aromatic ring structure contained therein, and cannot be used in living organisms.
- Quantum dots are also a good fluorescent visualization material, but most of the quantum dots are heavy metal compounds. In addition to the potential nanotoxicity, there are certain heavy metal toxicity.
- Fluorescent protein is a kind of photoprotein expressed by the body itself, and there is no cytotoxicity, but there is a problem of overexpression of fluorescent protein and aggregation of proteins.
- Biodegradable Fluorescent Imaging Polymer is a new fluorescent visualization material that appeared in 2009 with a molecular weight of approximately 1400 Da, which was subsequently introduced into materials such as polylactic acid, but was not easily introduced into organisms due to the uncertainty of BPLP structure.
- Degradable polyurethane structure is a new fluorescent visualization material that appeared in 2009 with a molecular weight of approximately 1400 Da, which was subsequently introduced into materials such as polylactic acid, but was not easily introduced into organisms due to the uncertainty of BPLP structure.
- Degradable polyurethane structure is a new fluorescent visualization material that appeared in 2009 with a molecular weight of approximately 1400 Da, which was subsequently introduced into materials such as polylactic acid, but was not easily introduced into organisms due to the uncertainty of BPLP structure.
- An object of the present invention is to provide a method for preparing a luminescent-inducing polyurethane and a luminescence-inducing urethane according to the above-mentioned drawbacks of the prior art.
- the object of the present invention can be achieved by the following technical measures:
- the present invention provides a luminescence-inducing polyurethane which has a hydroxyl group, a carboxyl group or an amino terminated polymer, a polyisocyanate and a chain extender represented by the formula (II) as a structural unit.
- X 1 represents a hydroxyl group, a carboxyl group or an amino group.
- the polyurethane is obtained by reacting a first polymer represented by the formula (I), a polyisocyanate substance and a chain extender represented by the formula (II).
- X 1 represents a hydroxyl group, a carboxyl group or an amino group
- Y represents a polyester or a polyether component
- X 1 represents a hydroxyl group, a carboxyl group or an amino group.
- the first polymer comprises a hydroxyl terminated polylactic acid, a hydroxyl terminated polycaprolactone, a hydroxyl terminated polyglycolide, a hydroxyl terminated lactic acid and ⁇ -caprolactone copolymer, a hydroxyl terminated lactic acid and Glycolic acid copolymer, hydroxyl terminated ⁇ -caprolactone and glycolic acid copolymer, hydroxyl terminated lactic acid, ⁇ -caprolactone and glycolic acid copolymer, carboxyl terminated polylactic acid, carboxyl terminated polyglycolide, carboxyl One or more of a blocked lactic acid and ⁇ -caprolactone copolymer, polytetrahydrofuran, polyethylene glycol, amino terminated polyethylene glycol or a polyol thereof, a polyamine, or a polybasic acid.
- the polyisocyanate material comprises 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 4,4-di One or more of phenylmethane diisocyanate, toluene diisocyanate, benzene dimethylene diisocyanate, triphenylmethane triisocyanate, and L-lysine triisocyanate.
- the ratio of the number of moles of the hydroxyl, carboxyl or amino terminated polymer to the number of moles of polyisocyanate is 1.0: (1.0 to 2.0); the number of moles of chain extender with the hydroxyl, carboxyl or amino terminated polymer
- the ratio of the number of moles is (0.0 to 1.0): 1.0; the total of the number of moles of the hydroxyl group, carboxyl group or amino group-terminated polymer and the number of moles of the chain extender is equal to the number of moles of the polyisocyanate.
- the invention also provides a preparation method of a bulk inducible luminescent polyurethane, characterized in that the method comprises the following steps:
- the isocyanate-terminated prepolymer is prepared by reacting a hydroxyl, carboxyl or amino terminated polymer with a polyisocyanate;
- the isocyanate-terminated prepolymer is reacted with the chain extender represented by the formula (II) to prepare a luminescence-inducing polyurethane;
- X 1 represents a hydroxyl group, a carboxyl group or an amino group.
- the polyisocyanate is used in an amount of from 1.0 to 2.0 times the number of moles of the hydroxyl, carboxyl or amino terminated polymer;
- the chain extender is used in an amount of from 0.0 to 1.0 times the number of moles of the hydroxyl, carboxyl or amino terminated polymer;
- the total number of moles of the hydroxyl group, carboxyl group or amino group-terminated polymer and the number of moles of the chain extender is equal to the number of moles of the polyisocyanate.
- stannous octoate is used as a catalyst, and the amount of stannous octoate is 0.001 to 0.01 times the number of moles of the hydroxyl group, the carboxyl group or the amino group-terminated polymer.
- the polymerization temperature is from 60 ° C to 80 ° C.
- the polymerization temperature is from 0 ° C to 50 ° C; the isocyanate-terminated hard segment prepolymer and the hydroxyl group, carboxyl group or amino group
- the polymerization temperature is from 60 ° C to 90 ° C.
- the bulk-inducible luminescent polyurethane of the present invention comprises a thiazolidine bicyclic repeating unit capable of inducing luminescence, and at the same time, the above-mentioned thiazolidine bicyclic repeating unit has good biocompatibility and can be metabolized by the body.
- FIG. 1 is a schematic view showing the preparation of an inducible luminescent polyurethane according to an embodiment of the present invention.
- Fig. 2 is an FT-IR chart of the luminescence-inducing polyurethane of Example 1 of the present invention.
- Fig. 3 is a 1 H-NMR chart of the luminescence-inducing polyurethane of Example 1 of the present invention.
- Example 4 is a photo-imaging diagram of an inducible luminescent polyurethane solution of Example 1 of the present invention.
- Fig. 5 is a photo-imaging diagram of an inducible luminescent polyurethane film of Example 1 of the present invention.
- Figure 6 is a graph showing the excitation and emission spectra of thiazopyridine dicarboxylic acid and the inductively luminescent polyurethane of Example 1.
- Fig. 7 is a 1 H NMR chart of the luminescence-inducing polyurethane of Example 4 of the present invention.
- Figure 8 is a photo-imaging diagram of an inducible luminescent polyurethane film of Example 4 of the present invention.
- polyhydric alcohol, polyamine, and polybasic acid described in the specification of the present invention are those having a hydroxyl group, an amino group or a carboxyl group of three or more.
- the luminescence-inducing polyurethane of the present invention has a hydroxyl group, a carboxyl group or an amino terminated polymer material, a polyisocyanate and a chain extender as structural units. That is, the polyurethane is obtained by reacting a hydroxyl group, a carboxyl group or an amino terminated polymer, a polyisocyanate substance and a chain extender, that is, the polyurethane passes through the first polymer, polyisocyanate substance and formula represented by the formula (I). (L) obtained by the chain extender reaction,
- X 1 represents a hydroxyl group, a carboxyl group or an amino group
- Y represents a polymer
- X 1 represents a hydroxyl group, a carboxyl group or an amino group.
- the hydroxyl, carboxyl or amino terminated polymeric material of the present invention is a diol, diester or diamine having a number average molecular weight of from 500 to 20,000.
- the molecular weight of the hydroxyl group, carboxyl group or amino terminated polymer material of the present invention is 500 or more; preferably, 700 or more; more preferably 1,000 or more.
- the molecular weight of the hydroxyl group, carboxyl group or amino terminated polymer material of the present invention is 20,000 or less; preferably, 1,000 or less.
- Examples of the polymer material which is blocked by a hydroxyl group, a carboxyl group or an amino group include a polyoxyalkylene glycol, a polyoxyalkylene diester, a polyoxyalkylene diamine, a polyester diol, a polyester diester, a polyester diamine, and a poly Ether diol, polyether diester, polyether diamine, polybutadiene diol, polybutadiene diester, polybutadiene diamine, other polyols, polyamines, polybasic acids, and two or more thereof Mixtures, etc.
- hydroxyl, carboxyl or amino terminated polymer material it may include a hydroxyl terminated polylactic acid (HO-PLA-OH), a hydroxyl terminated polycaprolactone (HO-PCL-OH), and a hydroxyl terminated poly(ethylene).
- HO-PLA-OH hydroxyl terminated polylactic acid
- HO-PCL-OH hydroxyl terminated polycaprolactone
- hydroxyl terminated poly(ethylene) hydroxyl terminated poly(ethylene).
- Lactide (HO-PGA-OH), hydroxyl terminated lactic acid and ⁇ -caprolactone copolymer, hydroxyl terminated lactic acid and glycolic acid copolymer, hydroxyl terminated ⁇ -caprolactone and glycolic acid copolymer, hydroxyl terminated Lactic acid, ⁇ -caprolactone and glycolic acid copolymer, carboxyl-terminated polylactic acid (HOOC-PLA-COOH), carboxyl-terminated polyglycolide (HOOC-PGA-COOH), carboxyl-terminated lactic acid and ⁇ -hexane
- PTMG polytetrahydrofuran
- PEG polyethylene glycol
- amino terminated polyethylene glycol (NH 2 -PEG-NH 2 )
- other polyols polyamines or polybasic acidskind.
- the chain extender of the present invention is a thiazolidine bicyclic substance having a thiazole ring and a pyridine ring. The two are connected side by side, and the above-mentioned thiazolidine bicyclic structure is a structure capable of inducing luminescence, and as a chain extender, it is introduced into a polyurethane main chain to obtain a luminescent-inducing polyurethane, thereby realizing visualization of the polyurethane.
- 5-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid (-oxo-2) can be exemplified.
- 3-dihydro-5H-[1,3]thiazolo[3,2-a]pyridine-3,7-dicarboxylic acid, TPA as shown in formula IIa
- 5-oxo-2,3-dihydro-5H -[1,3]thiazolo[3,2-a]pyridine-3,7-diol shown by Formula IIb
- 5-oxo-2,3-dihydro-5H-[1,3]thiazole And [3,2-a]pyridine-3,7-diamine (shown by formula IIc).
- the chain extender of the above thiazolidine bicyclic structure can be synthesized from citric acid and cysteine, has good biocompatibility, and can be metabolized by the body.
- the chain extender may be used singly or in combination of two or more.
- the polyisocyanate of the present invention reacts with a hydroxyl, carboxyl or amino terminated polymeric material and may also react with a chain extender. Further, the polyisocyanate may be used singly or in combination of two or more.
- the polyisocyanate is an aliphatic isocyanate, an aromatic isocyanate or an ester cycloisocyanate.
- examples of the aliphatic isocyanate include 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, and 4,4-dicyclohexylmethane diisocyanate.
- examples of the isocyanate include 4,4-diphenylmethane diisocyanate, toluene diisocyanate, benzene dimethylene diisocyanate, and triphenylmethane triisocyanate.
- the luminescence-inducing polyurethane of the present invention is produced by reacting a hydroxyl group, a carboxyl group or an amino terminated polymer, a polyisocyanate, and a chain extender represented by the formula (II) to prepare an luminescence-inducing polyurethane.
- a first polymer represented by the formula (I) is reacted with a polyisocyanate material to prepare an isocyanate group-terminated prepolymer;
- the isocyanate-terminated prepolymer is reacted with a chain extender represented by the formula (II) to prepare a luminescent-inducing polyurethane.
- a polyisocyanate is reacted with a chain extender represented by formula (II) to prepare an isocyanate-terminated hard segment prepolymer; and then, the isocyanate-terminated hard segment prepolymer is The hydroxyl, carboxyl or amino terminated polymer reacts to produce a luminescent-inducing polyurethane.
- the hydroxyl, carboxyl or amino-terminated polymer material is a diol, a diester, a diamine, a polyhydric alcohol, a polybasic acid or a polyamine having a number average molecular weight of 500 to 10,000.
- Molecular number of isocyanate groups of polyisocyanates Is a hydroxyl group, a carboxyl group or an amino terminated polymer having a hydroxyl group, a carboxyl group or an amino group in a molar ratio of 1.0 to 2.0 times; the hydroxyl group, a carboxyl group or an amino group of the chain extender is a hydroxyl group, a carboxyl group or a hydroxyl group of a hydroxyl group, a carboxyl group or an amino group.
- stannous octoate is used as a catalyst, and the amount of stannous octoate is the number of moles of the hydroxyl, carboxyl or amino terminated polymer. 0.001 to 0.01 times, the polymerization temperature is 60 ° C to 80 ° C; in the preparation step of the luminescence-inducing polyurethane, the polymerization temperature is 0 ° C to 50 ° C.
- stannous octoate is used as a catalyst, and the amount of stannous octoate is the number of moles of the hydroxyl, carboxyl or amino terminated polymer. 0.001 to 0.01 times, the polymerization temperature is 60 ° C to 80 ° C; in the preparation step of the luminescence-inducing polyurethane, the polymerization temperature is 60 ° C to 90 ° C.
- an organic solvent may be used in any step, wherein the organic solvent is not particularly limited, and is, for example, a ketone solvent having 3 to 10 carbon atoms (for example, acetone, methyl ethyl ketone, and Methyl isobutyl ketone), an ester solvent having 2 to 10 carbon atoms (for example, ethyl acetate, butyl acetate, and ⁇ -butyrolactone), and an ether solvent having 4 to 10 carbon atoms (for example, tetrahydrofuran) And diethylene glycol dimethyl ether), an amide solvent having 3 to 10 carbon atoms (for example, N,N-dimethylformamide, N,N-dimethylacetamide (hereinafter abbreviated as DMAC), N-methyl-2-pyrrolidone and N-methylcaprolactam), a sulfoxide solvent having 2 to 10 carbon atoms (for example, dimethyl sulfoxide), and
- an amide solvent having 3 to 10 carbon atoms, a sulfoxide solvent having 2 to 10 carbon atoms, and the like are preferable, and the number of carbon atoms is more preferable. It is an amide solvent of 3 to 10, etc. Specifically, it is preferably N,N-dimethylformamide or DMAC.
- the amount of the polyurethane resin to be produced is preferably from 10% by weight to 90% by weight, and more preferably from 20% by weight to 80% by weight.
- a hydroxyl-terminated polylactic acid (HO-PLA-OH) (having a molecular weight of 500 to 20,000 g/mol) is used as a soft segment, 1,6-hexamethylene diisocyanate (HDI).
- HDI 1,6-hexamethylene diisocyanate
- TPA thiazopyridine dicarboxylic acid
- the ratio of the amount is 0.001:1 to 0.011, the polymerization temperature is 60 to 80 ° C, and the polymerization time is 2 to 6 hours.
- the active bifunctional small chain extender thiazopyridine pyridine is added, and the reactant is
- the polymerization temperature is 0 to 50 ° C
- the polymerization time is 1 to 4 hours.
- the excitation wavelength is from 200 nm to 760 nm, so that the polyurethane body can induce luminescence, and the high sensitivity and rapid response of the polyurethane material can be visually detected.
- the above-mentioned inducible luminescent polyurethane material the selected thiazolidine bicyclic substance is synthesized by citric acid and cysteine, has good biocompatibility, and can be metabolized by the body, and adopts soft biocompatibility. Segments can be designed to synthesize materials with good biocompatibility.
- the polyurethane material is a kind of polymer material with inductive luminescence, which not only has the function of supporting the polymer material, but also realizes the high sensitivity and rapid response visual detection of the polyurethane material body.
- HO-PLA-OH with a molecular weight of 8000 g/mol is used as a soft segment
- HDI and TPA are hard segments
- stannous octoate is used as a catalyst to synthesize a polyurethane material.
- the ratio of the molar ratio of stannous octoate to HO-PLA-OH is 0.005:1 with the stannous octoate as the catalyst.
- the temperature was 50 ° C and the polymerization time was 1 to 4 hours.
- HO-PLA-OH with a molecular weight of 8000 g/mol is used as a soft segment
- HDI and TPA are hard segments
- stannous octoate is used as a catalyst to synthesize a polyurethane material.
- HO-PLA-OH with a molecular weight of 8000 g/mol is used as a soft segment
- HDI and TPA are hard segments
- stannous octoate is used as a catalyst to synthesize a polyurethane material.
- the ratio of the molar ratio of stannous octoate to HO-PLA-OH is 0.011 with the stannous octoate as the catalyst.
- the temperature was 30 ° C and the polymerization time was 1 to 4 hours.
- PTMG Polytetrahydrofuran
- HDI and TPA were hard segments
- stannous octoate was used as a catalyst to synthesize a polyurethane material.
- PTMG Polytetrahydrofuran
- HDI and TPA were hard segments
- stannous octoate was used as a catalyst to synthesize a polyurethane material.
- the ratio of the molar ratio of stannous octoate to PTMG is 0.008:1
- the polymerization temperature is 65° C.
- the polymerization time is 2.
- PTMG Polytetrahydrofuran
- HDI and TPA Hard segment, stannous octoate as a catalyst, synthetic polyurethane material.
- TPA is an inducible luminescent thiazopyridine dicarboxylic acid
- the doil has a molecular weight of 8000 Da.
- TPA-PU hydroxyl-terminated polylactic acid
- FT-IR figures FT-IR figures
- TPA-PU is a synthetic inducible emission polyurethane
- FT-IR figures compared doil
- TPA-PU of 3417cm -1, 1620cm -1, 1530cm -
- the characteristic absorption peak of amide appeared at 1 and 519 cm -1 ; in Figure 3, TPA is thiazole pyridine diacid which can induce luminescence, and doil is hydroxy-terminated polylactic acid (HO-PLA-OH) with molecular weight of 8000 Da
- TPA -PU is a synthetic inducible luminescent polyurethane.
- TPA-PU synthesized polyurethane
- Fig. 4 TPA is an inducible luminescent thiazopyridine dicarboxylic acid
- the doil has a molecular weight of 8000 Da.
- Hydroxyl-terminated polylactic acid (HO-PLA-OH) TPA-PU is a synthetic inducible luminescent polyurethane, which is excited by ultraviolet light, and TPA-PU can emit blue light.
- the polyurethane material of Example 4 was successfully synthesized by 1 H NMR, as shown in Figure 7, wherein the soft segment was a hydroxyl terminated polytetrahydrofuran (PTMG) having a molecular weight of 2000 Da, and the PTMG-TPA-PU was a synthetic inducible luminescence.
- PTMG-TPA-PU has the function of inducing luminescence by photoexcitation of different wavelengths, as shown in Fig. 8, where A: blue light is excited by blue light, and B: blue light is excited by green light. , C: Green light stimulates red light.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Claims (11)
- 根据权利要求1所述的可诱导发光的聚氨酯,其特征在于,羟基、羧基或氨基封端的聚合物包括聚氧化烯二醇、聚氧化烯二酯、聚氧化烯二胺、聚酯二醇、聚酯二酯、聚酯二胺、聚醚二醇、聚醚二酯、聚醚二胺、聚丁二烯二醇、聚丁二烯二酯、聚丁二烯二胺、多元醇、多元胺或多元酸中的一种或多种。
- 根据权利要求1所述的可诱导发光的聚氨酯,其特征在于,所述第一聚合物包括羟基封端聚乳酸,羟基封端聚已内酯,羟基封端聚乙交酯,羟基封端的乳酸和ε-己内酯共聚物,羟基封端的乳酸和羟基乙酸共聚物,羟基封端的ε-己内酯和羟基乙酸共聚物,羟基封端的乳酸、ε-己内酯和羟基乙酸共聚物,羧基封端的聚乳酸,羧基封端的聚乙交酯,羧基封端的乳酸和ε-己内酯共聚物,聚四氢呋喃,聚乙二醇或氨基封端的聚乙二醇、多元醇、多元胺或多元酸中的一种或多种。
- 根据权利要求1所述的可诱导发光的聚氨酯,其特征在于,所述多异氰酸酯物质包括1,6-六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯、4,4-二环已基甲烷二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、三苯甲烷三异氰酸酯或L-赖氨酸三异氰酸酯中的一种或多种。
- 根据权利要求6所述的可诱导发光的聚氨酯的制备方法,其特征在于, 多异氰酸酯的异氰酸酯基摩尔数是羟基、羧基或氨基封端的聚合物的羟基、羧基或氨基摩尔数的1.0~2.0倍;扩链剂的羟基、羧基或氨基摩尔数是羟基、羧基或氨基封端的聚合物的羟基、羧基或氨基摩尔数的0.0~1.0倍;羟基、羧基或氨基封端的聚合物的羟基、羧基或氨基摩尔数和扩链剂的羟基、羧基或氨基摩尔数的合计值与多异氰酸酯的异氰酸酯基摩尔数相等。
- 根据权利要求8所述的可诱导发光的聚氨酯的制备方法,其特征在于,在步骤a中,以辛酸亚锡为催化剂,辛酸亚锡的用量是羟基、羧基或氨基封端的聚合物的摩尔数的0.001~0.01倍,聚合温度为60℃~80℃;在步骤b中,聚合温度为0℃~50℃。
- 根据权利要求9所述的可诱导发光的聚氨酯的制备方法,其特征在于,在步骤a’中,以辛酸亚锡为催化剂,辛酸亚锡的用量是羟基、羧基或氨基封端的聚合物的摩尔数的0.001~0.01倍,聚合温度为60℃~80℃;在步骤b’中,聚合温度为60℃~90℃。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2017/110950 WO2019095116A1 (zh) | 2017-11-14 | 2017-11-14 | 可诱导发光的聚氨酯及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2017/110950 WO2019095116A1 (zh) | 2017-11-14 | 2017-11-14 | 可诱导发光的聚氨酯及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019095116A1 true WO2019095116A1 (zh) | 2019-05-23 |
Family
ID=66538350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2017/110950 WO2019095116A1 (zh) | 2017-11-14 | 2017-11-14 | 可诱导发光的聚氨酯及其制备方法 |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2019095116A1 (zh) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB886967A (en) * | 1959-01-22 | 1962-01-10 | Ciba Ltd | Process for the production of coloured polyurethane plastics |
CN102876322A (zh) * | 2012-10-24 | 2013-01-16 | 上海理工大学 | 一种稀土聚氨酯类高分子复合发光材料及其制备方法 |
CN105017288A (zh) * | 2015-07-01 | 2015-11-04 | 西安交通大学 | 一种蓝色荧光化合物及其制备方法 |
CN105377929A (zh) * | 2013-06-11 | 2016-03-02 | 巴斯夫欧洲公司 | 用于荧光聚合物的非迁移性光活性二醇 |
CN105418642A (zh) * | 2015-11-03 | 2016-03-23 | 西安交通大学 | 一种含噻唑吡啶酮结构的甲基丙烯酸酯荧光单体及其制备方法 |
WO2016164437A1 (en) * | 2015-04-06 | 2016-10-13 | The Penn State Research Foundation | Luminescent compositions and applications thereof |
CN106596479A (zh) * | 2016-11-29 | 2017-04-26 | 福州大学 | 一种用于游离氯检测的荧光传感器 |
CN106832175A (zh) * | 2017-02-17 | 2017-06-13 | 华南理工大学 | 一种基于咔唑衍生物的双羟基荧光扩链剂及其制备与应用 |
-
2017
- 2017-11-14 WO PCT/CN2017/110950 patent/WO2019095116A1/zh active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB886967A (en) * | 1959-01-22 | 1962-01-10 | Ciba Ltd | Process for the production of coloured polyurethane plastics |
CN102876322A (zh) * | 2012-10-24 | 2013-01-16 | 上海理工大学 | 一种稀土聚氨酯类高分子复合发光材料及其制备方法 |
CN105377929A (zh) * | 2013-06-11 | 2016-03-02 | 巴斯夫欧洲公司 | 用于荧光聚合物的非迁移性光活性二醇 |
WO2016164437A1 (en) * | 2015-04-06 | 2016-10-13 | The Penn State Research Foundation | Luminescent compositions and applications thereof |
CN105017288A (zh) * | 2015-07-01 | 2015-11-04 | 西安交通大学 | 一种蓝色荧光化合物及其制备方法 |
CN105418642A (zh) * | 2015-11-03 | 2016-03-23 | 西安交通大学 | 一种含噻唑吡啶酮结构的甲基丙烯酸酯荧光单体及其制备方法 |
CN106596479A (zh) * | 2016-11-29 | 2017-04-26 | 福州大学 | 一种用于游离氯检测的荧光传感器 |
CN106832175A (zh) * | 2017-02-17 | 2017-06-13 | 华南理工大学 | 一种基于咔唑衍生物的双羟基荧光扩链剂及其制备与应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Marcos-Fernández et al. | Synthesis and characterization of biodegradable non-toxic poly (ester-urethane-urea) s based on poly (ε-caprolactone) and amino acid derivatives | |
US6784273B1 (en) | Biomedical polyurethane, its preparation and use | |
US9611354B2 (en) | Biodegradable photoluminescent polymers | |
Caracciolo et al. | Effect of the hard segment chemistry and structure on the thermal and mechanical properties of novel biomedical segmented poly (esterurethanes) | |
CN104520345B (zh) | 高强度聚氨异丁烯聚氨甲酸酯 | |
US9034361B2 (en) | Hydroswellable, segmented, aliphatic polyurethanes and polyurethane ureas | |
US8551519B2 (en) | Bioabsorbable surgical articales or components thereof | |
JP6587318B2 (ja) | 超分子生分解性ポリマー | |
CN101885826B (zh) | 基于哌嗪嵌段d,l-聚乳酸的生物可降解聚氨酯材料及制备方法 | |
ES2974903T3 (es) | Poliuretanos termoplásticos biodegradables y/o bioabsorbibles | |
CN107987248B (zh) | 可诱导发光的聚氨酯及其制备方法 | |
Noordzij et al. | The aza-Michael reaction: towards semi-crystalline polymers from renewable itaconic acid and diamines | |
US20060205910A1 (en) | Polyureaurethane material and method of producing a polyureaurethane material | |
WO2019095116A1 (zh) | 可诱导发光的聚氨酯及其制备方法 | |
EP3545040B1 (en) | Polyurethane, method of preparation, and article comprising the polyurethane | |
CN114133507B (zh) | 一种生物基可降解聚氨酯的一锅制备法 | |
Covolan et al. | Polyurethane based materials for the production of biomedical materials | |
CN105073025A (zh) | 由具有两个或更多个羧酸基团的单醇和二醇聚合引发剂制备的聚内酯聚合物 | |
JP4135076B2 (ja) | ポリアルキレンエーテル鎖含有ジオ−ル化合物、その製造法及びポリウレタン樹脂 | |
US20190276583A1 (en) | Modification of Segmented Polyurethane Properties by Copolymerizing with Pendant Functionalized Diols | |
JP2011213866A (ja) | 鎖伸長剤およびその製造方法、および、熱可塑性ポリウレタン樹脂 | |
JP4228274B2 (ja) | ポリアルキレンエーテル鎖含有ジオ−ル化合物、その製造法及びポリウレタン樹脂 | |
US20230272148A1 (en) | Thermoplastic poly(urethane-urea) polyadducts | |
US11116211B2 (en) | Modification of segmented polyurethane properties by copolymerizing with pendant functionalized diols | |
JP2003335837A (ja) | ポリエステルウレタン |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17931890 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17931890 Country of ref document: EP Kind code of ref document: A1 |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 22/09/2020) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17931890 Country of ref document: EP Kind code of ref document: A1 |