CN106349457A - Temperature-responsive polyurethane material and preparation method thereof - Google Patents
Temperature-responsive polyurethane material and preparation method thereof Download PDFInfo
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- CN106349457A CN106349457A CN201610864737.7A CN201610864737A CN106349457A CN 106349457 A CN106349457 A CN 106349457A CN 201610864737 A CN201610864737 A CN 201610864737A CN 106349457 A CN106349457 A CN 106349457A
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
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- 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
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- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
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Abstract
The invention discloses a temperature-responsive polyurethane material, and belongs to the field of thermosensitive polymers in smart materials. The polyurethane material consists of structural units shown in a formula (I). The polyurethane material is a random copolymer; the molecular weight of the polyurethane material is 0.85 to 2.45*104 (shown in the description), wherein m is 2, 3, 4 and 5; n is 25 to 100. The invention also discloses a preparation method of the temperature-responsive polyurethane material. The polymer material prepared by the method has the characteristic of temperature sensitiveness and also has excellent biocompatibility and biodegradability.
Description
Technical field
The invention belongs to the temperature sensing polymer field in intellectual material, be related to one kind have good biocompatibility and
MOLECULE DESIGN of temperature-sensing property polymeric material and preparation method thereof and in particular to a kind of temperature-responsive polyurethane material and its
Preparation method, this polymeric material itself is a kind of single polymers, rather than two or more polymer in method of modifying
Mixture, graft, blend.
Background technology
Polyurethane material is the abbreviation of polyurethanes, and English name is polyurethane, and it is a kind of macromolecule
Material.Polyurethane is a kind of emerging high-molecular organic material, is described as " the fifth-largest plastics ", wide because of its remarkable performance
General it is applied to national economy various fields.Products application has been directed to light industry, chemical industry, electronics, weaving, medical treatment, building, building materials, vapour
The various fields such as car, national defence, space flight, aviation.In general, polyurethane is by isocyanate groups and the compound containing reactive hydrogen
(as alcohol, amine, carboxylic acid etc.) is prepared by hydrogen migration additive reaction.According to different molecular chain structures, polyurethane can be divided into line
Property polyurethane polyureas urethane (thermoplasticity), branched and crosslinked polyurethane (thermosetting).Branch can be by polynary with cross-linked polyurethane
The control by rate of charge and the extent of reaction of alcohol and isocyanate-monomer component, carrys out the polyurethane of synthesizing branched type or crosslinking
Material.
At present, the polyurethane material related to Thermo-sensitive also has been reported that, but these materials are often long chain diol as gathered
Ethylene glycol (peg), polypropylene glycol (ppg) etc. are reacted with corresponding isocyanates and are obtained.For example, research worker is by PEG
(peg), poly- (6-caprolactone glycol glycol) (pcl) is respectively polymerized monomer and hexamethylene diisocyanate (hdi) is gathered
Close reaction, prepare a series of block type polyurethane materials, concurrently existing this polyurethane material under certain condition can show temperature
Degree sensitivity.It is soft section that the scientific research personnel of Sichuan University utilizes polycaprolactone glycol (pcl4000), successfully synthesizes containing 4,
4 '-methyl diphenylene diisocyanate (mdi) and the responsive to temperature type polyurethane of 1,4- butanediol (bdo).Urge in Loprazolam
In the presence of agent, haritz sardon et al. successfully utilize PEG glycol (mn=1500), dihydromethyl propionic acid and
Isophorone diisocyanate has synthesized a kind of Thermo-sensitive polyurethane material.The above Thermo-sensitive polyurethane material belongs to block
Type polymeric material, rather than random polymer；In addition, these material temperature-sensing properties mainly rely on polyether structure, poly- second two
Alcohol and polypropylene glycol inherently have certain Thermo-sensitive.
As a kind of most important intellectual material, temperature sensing polymer refer to external world ambient temperature have can reverse response special
The material of property.Temperature sensing polymer material has been widely used for drug controlled release, bio-separation, enzyme immobilization, immunity point
The biomedical sectors such as analysis.One most important physical parameter of temperature sensing polymer material is exactly lowest critical solution temperature
(lcst) or highest critical solution temperature (ucst), that is, polymer changes with temperature in aqueous and obvious phase reversibly occurs
Temperature during change.In biomedical sector, the practical application of temperature sensing polymer material necessarily involve two most basic
Problem: first, the regulation and control of critical solution temperature (lcst or ucst), that is, control the response temperature of material, such as give material and giving birth to
In reason body temperature, there is temperature-sensing property；Second, the biodegradability of temperature sensing polymer material and biocompatibility, that is, protect
Card material has excellent biodegradability and biocompatibility in actual applications, to tissue no rejection or toxicity.
Due to many, its good bio-compatible closely related with biomedical sector of the practical application of temperature sensitive polymer material
Property with biological degradability be undoubtedly temperature sensitive polymer material inevitable requirement, be also important guarantee safe to the human body.Only temperature
Sensitive polymer material possesses good biocompatibility and biological degradability, and material just can be safer, more to human body itself
Reliable, such temperature sensitive polymer material just has real actual application value and DEVELOPMENT PROSPECT.But it is regrettably, conventional
How based on carbochain type, the backbone structure (- c-c-) of carbon-carbon bond often makes material not possess good life to temperature sensing polymer
The thing compatibility or biological degradability, limit this kind of material in the wider practical application of biomedical sector.For example, the most frequently used
Research widest carbochain type temperature sensing polymer material be first poly- (n- N-isopropylacrylamide), and this polymer
Material has shown rejection to body.For example, the medicament capsule prepared by poly- (n- N-isopropylacrylamide) is to eyes
There is stimulation.In addition, other n- replace the temperature sensing polymers such as (methyl) acrylamide going back in degraded/hydrolytic process
Insalubrious small molecule aminated compoundss can be produced, lead to its application in medical domain greatly to be restricted.
In biomedical sector, give the excellent biological degradability of polymeric material, biocompatibility and temperature simultaneously
Quick characteristic is one of important direction in intellectual material research and development.In order to temperature sensing polymer material is given good life
The thing compatibility and biological degradability, the natural polymer such as shell with biological degradability and biocompatibility is generally gathered by people
Sugar, gelatin, starch, cellulose etc. and there is the carbon chain polymer of temperature-sensing property carry out necessary modification.Modified method bag
Included the technological means such as blending, block and grafting, the material being obtained be actually the mixture of multiple polymers, graft,
Blend.Domestic scholars Zhuo Ren are auspiciousness, Chen Li etc. has done numerous studies work in this regard.Zhuo Renxi select Rhizoma amorphophalli glucomannan and
Poly- (n- N-isopropylacrylamide) is two kinds of components, has synthesized the temperature with enzyme degradable characteristic using ipn technology
Quick property gel；Glucosan and n- N-isopropylacrylamide are then directly carried out glycerol polymerization by Chen Li, find that gel is molten to protein
Liquid has preferable concentrating and separating ability.By above-mentioned method of modifying, can improve or improve temperature sensitive poly- to a certain extent
The biocompatibility of compound material, but bring two insoluble important technological problems: first, because carbochain type is temperature sensitive poly-
The presence of compound, modified material itself does not still possess optimal biocompatibility it is also not possible to complete biodegradable；The
Two, because the introducing of non-Thermo-sensitive natural polymer, the temperature-sensing property of modified material also can be with the increasing of natural polymer content
Plus and reduce, or even thorough disappear.Therefore, by the method for modifying of carbochain type temperature sensitive polymer and natural polymer it is impossible to
When take into account good biocompatibility, biological degradability and temperature-sensing property.In other words, modified polymeric material is not
Excellent biocompatibility, biological degradability, temperature-sensing property can be provided simultaneously with it is impossible to so that these three performances all reach most preferably.
So, design, prepare a kind of both there is good temperature-sensing property, but also with excellent biocompatibility, biological degradability miscellaneous
Chain polymer material, an important technology difficult problem urgently to be resolved hurrily in temperature sensitive polymer developing material field beyond doubt, this is also this
The starting point of invention and purpose.
Content of the invention
The present invention be solve in prior art by the polymeric material prepared of modification can not be provided simultaneously with biocompatibility,
Biological degradability and the technical barrier of temperature-sensing property, there is provided a kind of temperature-responsive polyurethane material and preparation method thereof, this
The polymeric material of invention is single polymer, rather than the mixture of multiple polymers, blend, graft, this polymerization
Thing material is provided simultaneously with excellent biocompatibility, biological degradability and temperature-sensing property.
The present invention is to realize its purpose the technical scheme is that
A kind of temperature-responsive polyurethane material, construction unit shown in formula (i) for this polyurethane material forms, this poly- ammonia
Ester material is random copolymer, and the molecular weight of this polyurethane material is 0.85-2.45 × 104；
Wherein, m=2,3,4,5；N=25-100.
This polyurethane material includes poly- (diethylene glycol-ethyl ester of lysine diisocyanate) material, poly- (2,2'-ethylenedioxybis(ethanol) .-lysine
Ethyl ester diisocyanate) material, poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate) material, poly- (five glycol-ethyl ester of lysine
Diisocyanate) material.
The preparation method of temperature-responsive polyurethane material, with ethyl ester of lysine diisocyanate and diethylene glycol or 2,2'-ethylenedioxybis(ethanol).
Or tetraethylene glycol (TEG) or five glycol are raw material, under stirring, in room temperature reaction 45-50h, obtain product, then use organic solvent
Product is dissolved by (such as methanol), after dialysis, being dried, obtains poly- (diethylene glycol-ethyl ester of lysine diisocyanate) material
Material or poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material or poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate) material
Or poly- (five glycol-ethyl ester of lysine diisocyanate) material.Preferably employ freezer dryer when being dried and 45-50h is dried.
Ethyl ester of lysine diisocyanate is 1 with the mol ratio of diethylene glycol or 2,2'-ethylenedioxybis(ethanol). or tetraethylene glycol (TEG) or five glycol:
(0.95-1.1).
Described dialysis includes, and will be placed in dialyzer with the product after organic solvent (such as methanol) dissolving, plus steams
Distilled water good seal, is subsequently placed in dialysis 20-30h in the container fill distilled water, and bag filter maximum through polymer molecular weight is
2500；Adding in container has magneton, for stirring distilled water, can accelerate speed of dialysing, time-consuming.
During dialysis, change the distilled water in a container every 4-6h.
The invention has the beneficial effects as follows:
The present invention is the difference direct polymerization by ethyl ester of lysine diisocyanate and four kinds of glycol monomers, prepares four
Plant the polyurethane material with temperature-sensing property.Temperature-responsive polyurethane material of the present invention is a kind of single polymers in itself, and
It is not the mixture of two or more polymer, graft, blend in method of modifying, be less block polymer.Meanwhile, originally
Prepared Thermo-sensitive material in invention belongs to miscellaneous chain polymer, contains carbamate groups on its macromolecular main chain,
Contain ester bond in side base again.Therefore, the successful preparation of this novel temperature-sensitive polymeric material can be prevented effectively from method of modifying
Material is still unlikely to degradable or poor biocompatibility problem in itself；It also avoid non-Thermo-sensitive in method of modifying natural
The temperature-sensing property that the introducing of polymer is led to reduces or disappears.In other words, the polymeric material prepared by the present invention is not only
There is good temperature-sensing property, but also taken into account excellent biocompatibility and biological degradability, for it in biomedical neck
The practical application in domain provides important safety guarantee.
Preparation method of the present invention can prepare the polyurethane material with temperature-sensing property, and this polymer molecular weight is 0.85
～2.45 ten thousand, temperature can have excellent reversible response characteristic to external world in the range of 15-35 degree, i.e. its minimum critical temperature
(lcst) it is 15-35 degree, close to room temperature and body temperature.In addition, by the cell of temperature-responsive polyurethane material of the present invention
It is known that after the cultivation of 24 and 48 hours, hela cell survival rate is (in 0.01 100 μ grams per milliliter polyurethane after toxicity is evaluated
Solution) can reach more than 70%, show its good biocompatibility.In a word, this have temperature-sensing property, biocompatibility
Polyurethane, is a kind of up-and-coming " intelligent " material, can be applied in biomedical sector.
Polymeric material prepared by the present invention, not only has temperature-sensing property, has had both excellent biocompatibility simultaneously
And biological degradability.Therefore, this new temperature sensing polymer material can be in drug controlled release, bio-separation, immunity
The aspects such as analysis have higher using value and DEVELOPMENT PROSPECT, the especially biocompatibility to Thermo-sensitive material/biology fall
Solution property requires higher biomedical sector.
Brief description
Fig. 1 is poly- (diethylene glycol-ethyl ester of lysine diisocyanate) material infrared spectrogram.
Fig. 2 is poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material infrared spectrogram.
Fig. 3 is poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate) material infrared spectrogram.
Fig. 4 is poly- (five glycol-ethyl ester of lysine diisocyanate) material infrared spectrogram.
Fig. 5 is poly- (diethylene glycol-ethyl ester of lysine diisocyanate) material hydrogen nuclear magnetic resonance spectrogram.
Fig. 6 is poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material hydrogen nuclear magnetic resonance spectrogram.
Fig. 7 is poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate) material hydrogen nuclear magnetic resonance spectrogram.
Fig. 8 is poly- (five glycol-ethyl ester of lysine diisocyanate) material hydrogen nuclear magnetic resonance spectrogram.
Fig. 9 is four kinds of polyurethane material aqueous solution light transmittance variation with temperature curve charts.Wherein, pdild represents poly- (two
Glycol-ethyl ester of lysine diisocyanate) material, ptrld represents poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material,
Pteld represents poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate) material, and ppeld represents poly- (five glycol-ethyl ester of lysine two
Isocyanates) material.
Figure 10 is poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material aqueous solution light transmittance of variable concentrations with temperature
Change curve.
Figure 11 is the Cytotoxic evaluation figure of poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material.
Specific embodiment
Temperature sensing polymer is applied in biomedical sectors such as medicament slow release, Protein Separation and tissue repair.Due to temperature sensitive
The application of polymer is closely related with biomedical sector, and excellent biocompatibility is temperature sensitive polymer material in practical application
In objective requirement, be also important guarantee safe to the human body.In the present invention, we select ethyl ester of lysine diisocyanate
With four kinds of glycol small molecules, that is, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), five glycol are polymerized monomer, and aggregated reaction is directly prepared
Four kinds have excellent temperature-sensing property, have both good biocompatibility polyurethane material again.This Thermo-sensitive material is a kind of miscellaneous
Chain polymer, in 0.85-2.45 ten thousand, molecular weight distribution is 1.3-2.6 to its molecular weight.Below in conjunction with the accompanying drawings and specific embodiment
The present invention is further illustrated.
Embodiment 1, the preparation of poly- (diethylene glycol-ethyl ester of lysine diisocyanate) material
Put into stirring magneton in 50ml single-necked flask, be initially charged 0.835g diethylene glycol liquid, then weighed with 5ml syringe
1.78g l- lysinediisocyanate, opens and is slowly added dropwise in single-necked flask under magneton agitator, stirring, makes two kinds
Liquid is sufficiently mixed in flask.React 48h at room temperature.After stopped reaction, obtain harder colloid.By product
All dissolved with proper amount of methanol, be transferred in dialyzer, plus distilled water good seal, put in the large beaker filling appropriate distilled water
Dialysed.Add magneton in large beaker, and change the distilled water in a large beaker it is ensured that dialysis is abundant every 5h.Thoroughly
After analysis 36h, dialyzer is taken out, the product dialysed in dialyzer is transferred in clean small beaker, done with freezer dryer
Dry two days, after being dried completely, obtain final product.Product is pale yellow transparent colloidal solid, product quality 0.693g, and yield is
26.5%.
The present embodiment reaction equation is as follows, wherein r=ch2ch3,
Embodiment 2, the preparation of poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material
Put into stirring magneton in 50ml single-necked flask, be initially charged 1.37g 2,2'-ethylenedioxybis(ethanol). liquid, then weighed with 5ml syringe
2.04g l- lysinediisocyanate, opens and is slowly added dropwise in single-necked flask under magneton agitator, stirring, makes two kinds
Liquid is sufficiently mixed in flask.React 48h at room temperature.After stopped reaction, obtain hard colloid.Product is used
Proper amount of methanol all dissolves, and is transferred in dialyzer, plus distilled water good seal, puts in the large beaker filling appropriate distilled water
Row dialysis.Add magneton in large beaker, and change the distilled water in a large beaker it is ensured that dialysis is abundant every 5h.Dialysis
After 48h, dialyzer is taken out, the product dialysed is transferred in clean small beaker, is dried with freezer dryer in dialyzer
Two days, after being dried completely, obtain final product.Product is water white transparency colloidal solid, product quality 1.23g, and yield is
36.0%.
The present embodiment reaction equation is as follows, wherein r=-ch2ch3, r1=ch2ch2,
Embodiment 3, the preparation of poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate) material
Put into stirring magneton in 50ml single-necked flask, be initially charged 1.80g tetraethylene glycol (TEG) monomer, then weighed with 5ml syringe
2.04g l- lysinediisocyanate, opens and is slowly added dropwise in single-necked flask under magneton agitator, stirring, makes two kinds
Liquid is sufficiently mixed in flask.React 48h at room temperature.After stopped reaction, obtain hard colloid.Product is used
Proper amount of methanol all dissolves, and is transferred in dialyzer, plus distilled water good seal, puts in the large beaker filling appropriate distilled water
Row dialysis.Add magneton in large beaker, and change the distilled water in a large beaker it is ensured that dialysis is abundant every 5h.Dialysis
After 24h, dialyzer is taken out, the product dialysed is transferred in clean small beaker, is dried with freezer dryer in dialyzer
Two days, after being dried completely, obtain final product.Product is yellow transparent colloidal solid, product quality 1.58g, and yield is
41.2%.
The present embodiment reaction equation is as follows, wherein r=-ch2ch3, r1=ch2ch2,
Embodiment 4, the preparation of poly- (five glycol-ethyl ester of lysine diisocyanate) material
Put into stirring magneton in 50ml single-necked flask, be initially charged 2.66g five glycol monomer, then weighed with 5ml syringe
2.52g l- lysinediisocyanate, opens and is slowly added dropwise in single-necked flask under magneton agitator, stirring, makes two kinds
Liquid is sufficiently mixed in flask.React 48h at room temperature.After stopped reaction, obtain hard colloid.Product is used
Proper amount of methanol all dissolves, and is transferred in dialyzer, plus distilled water good seal, puts in the large beaker filling appropriate distilled water
Row dialysis.Add magneton in large beaker, and change the distilled water in a large beaker it is ensured that dialysis is abundant every 5h.Dialysis
After 24h, dialyzer is taken out, the product dialysed is transferred in clean small beaker, is dried with freezer dryer in dialyzer
Two days, after being dried completely, obtain final product.Product is yellow transparent colloidal solid, product quality 1.54g, and yield is
29.8%.
The present embodiment reaction equation is as follows, wherein r=-ch2ch3, r1=ch2ch2,
In the present invention, we utilize small molecule monomer: natural lysine derivant, a series of glycol are preparing with temperature
The polyurethane material of quick characteristic.We successfully synthesized a series of poly- (diethylene glycol-ethyl ester of lysine diisocyanate),
Poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate), poly- (tetraethylene glycol (TEG)-ethyl ester of lysine diisocyanate), poly- (five glycol-rely
Propylhomoserin ethyl ester diisocyanate) material.These four polyurethane materials all show a reversible lcst phase transformation at 15-35 DEG C,
There is temperature-sensing property, and close to room temperature and human body temperature.The molecular weight of polyurethane be Thermo-sensitive a particular importance because
Element: several polyurethane gained molecular weight (mn) about 1-2 × 10 under not having stannum catalysis4, equal displays temperature response.But, use
Stannum catalysis is lower to be polymerized, then more than 40,000, material does not have temperature-sensing property to gained polyurethane molecular amount.Its reason is probably to cross high score
There is stronger intermolecular interaction (hydrogen bond) between the polymer chain of son amount, lead to water can not dissolve polymeric material.
In the present invention, by mtt method, the cytotoxicity of temperature-responsive polyurethane material is evaluated.As Figure 11
Shown, after the hela cell culture of 24 and 48 hours, the propagation of hela cell in four kinds of variable concentrations polymer solutions
Rate keeps all more than 70%, and in this explanation present invention, temperature-responsive polyurethane material does not have suppression and makees to cell proliferation
With no cytotoxicity.It can be seen that, prepared temperature-responsive polyurethane in the present invention is extremely low to hela cyto-inhibition, its
Biocompatibility is excellent.
Claims (6)
1. a kind of temperature-responsive polyurethane material it is characterised in that: construction unit group shown in formula (i) for this polyurethane material
Become, this polyurethane material is random copolymer, the molecular weight of this polyurethane material is 0.85-2.45 × 104；
Wherein, m=2,3,4,5, n=25-100.
2. a kind of temperature-responsive polyurethane material according to claim 1 it is characterised in that: this polyurethane material includes
Poly- (diethylene glycol-ethyl ester of lysine diisocyanate) material, poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material, poly- (four
Glycol-ethyl ester of lysine diisocyanate) material, poly- (five glycol-ethyl ester of lysine diisocyanate) material.
3. the temperature-responsive polyurethane material described in claim 1 preparation method it is characterised in that: with ethyl ester of lysine two
Isocyanates and diethylene glycol or 2,2'-ethylenedioxybis(ethanol). or tetraethylene glycol (TEG) or five glycol are raw material, under stirring, in room temperature reaction 45-50h, obtain
Then product is dissolved by product with organic solvent, after dialysis, being dried, obtains poly- (diethylene glycol-ethyl ester of lysine
Diisocyanate) material or poly- (2,2'-ethylenedioxybis(ethanol) .-ethyl ester of lysine diisocyanate) material or poly- (tetraethylene glycol (TEG)-ethyl ester of lysine two
Isocyanates) material or poly- (five glycol-ethyl ester of lysine diisocyanate) material.
4. temperature-responsive polyurethane material according to claim 3 preparation method it is characterised in that: ethyl ester of lysine
Diisocyanate is 1:(0.95-1.1 with the mol ratio of diethylene glycol or 2,2'-ethylenedioxybis(ethanol). or tetraethylene glycol (TEG) or five glycol).
5. temperature-responsive polyurethane material according to claim 3 preparation method it is characterised in that: described dialysis bag
Include, the product after being dissolved with organic solvent is placed in dialyzer, plus distilled water good seal, it is subsequently placed in and fill distilled water
Container in dialyse 20-30h.
6. temperature-responsive polyurethane material according to claim 5 preparation method it is characterised in that: during dialysis, often
Change the distilled water in a container every 4-6h.
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| CN112167250A (en) * | 2020-10-13 | 2021-01-05 | 重庆中邦药业（集团）有限公司 | Temperature-sensitive type cyflumetofen capsule sustained release agent and preparation method thereof |
| CN114907540A (en) * | 2022-05-17 | 2022-08-16 | 浙江欧鹿医疗器械有限公司 | Polyurethane high-molecular polymer and preparation method thereof, polyurethane high-molecular polymer hydrogel, kit and application thereof |
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| CN112167250A (en) * | 2020-10-13 | 2021-01-05 | 重庆中邦药业（集团）有限公司 | Temperature-sensitive type cyflumetofen capsule sustained release agent and preparation method thereof |
| CN114907540A (en) * | 2022-05-17 | 2022-08-16 | 浙江欧鹿医疗器械有限公司 | Polyurethane high-molecular polymer and preparation method thereof, polyurethane high-molecular polymer hydrogel, kit and application thereof |
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