CN114507329A - PH response controllable degradable polyurethane and preparation method thereof - Google Patents
PH response controllable degradable polyurethane and preparation method thereof Download PDFInfo
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- CN114507329A CN114507329A CN202111611184.1A CN202111611184A CN114507329A CN 114507329 A CN114507329 A CN 114507329A CN 202111611184 A CN202111611184 A CN 202111611184A CN 114507329 A CN114507329 A CN 114507329A
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
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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
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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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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- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a pH response degradable polyurethane and a preparation method thereof. The pH response controllable degradable polyurethane is obtained by polymerizing and crosslinking a prepolymer and isocyanate, wherein the prepolymer is a double-end hydroxyl compound containing a silicon ether structure and is obtained by reacting polyol and a silane compound; the isocyanate is a diisocyanate trimer having three terminal isocyanate groups (modified so as to be consistent with the following). The polyurethane has the capability of pH response and controllable degradation, and has high degradation rate in an acidic environment and low degradation rate in a neutral environment; the controllable degradation of polyurethane in different solvent environments (such as vinegar environments) can be realized by regulating and controlling the difference of the substituent groups on the silicon atoms of the silane compound.
Description
Technical Field
The invention relates to a pH response degradable polyurethane and a preparation method thereof, belonging to the field of high polymer materials.
Background
Polyurethanes are a class of polymeric materials based on urethane groups. Usually, the polyurethane elastomer is prepared by taking oligomer polyol and polyfunctional isocyanate as main raw materials and adding a chain extender, a cross-linking agent and a small amount of auxiliary agents. From the aspect of molecular structure, the long chain of the polyol forms a soft segment of polyurethane, so that flexibility is provided; the isocyanate and the chain extender form a hard segment of polyurethane to provide rigidity, and the repeated structural unit formed by the alternate arrangement of the hard segment and the soft segment ensures that the polyurethane has the characteristics of good tearing strength, elasticity, toughness, wear resistance and the like, so that the polyurethane can be widely applied to the fields of daily use, industry, national defense, medical treatment and the like. The vigorous development of polyurethane brings great convenience to the production and life of human beings, but simultaneously, the waste is difficult to recycle and degrade, and the problems of environmental pollution and the like are also caused. In the treatment process of the polyurethane waste at the present stage, methods such as land landfill and incineration are often adopted, and the requirements of sustainable development cannot be met. Therefore, the development of a degradable polyurethane is of great importance.
Hydrolysis is an effective means for realizing the degradation of the high molecular material. However, the application background of polyurethane materials often requires considerable stability to aqueous environments. Therefore, the controllable degradation of the polyurethane in a specific water environment has positive significance. The polyurethane material with pH response has wide application prospect in the fields of drug controlled release, biological separation, controllable degradation, regeneration, cyclic utilization and the like. On the one hand, in a neutral water environment, the polymers have good stability; on the other hand, in an acidic aqueous environment, these polymers have rapid degradation capability.
Chinese patent application (CN 108559048B) discloses a pH value sensitive biodegradable polyurethane urea material and a preparation method thereof, wherein the polyurethane urea is prepared by mixing double-end hydroxyl polyether ester and N, N- (2-hydroxyethyl) isonicotinamide, then utilizing diisocyanate containing carbamido to carry out chain extension, and purifying to obtain the pH value sensitive biodegradable polyurethane urea material. The polyurethane urea has biodegradability, absorbability of degradation products and pH sensitivity, can be used as a drug carrier to be applied to the field of sustained and controlled release, but cannot control the degradation rate under the same pH, has high production cost and can not ensure the mechanical property.
The document "High-performance, Bio-based, Degradable polyurethane thermal and its Application in the reaction Recyclable Carbon Fiber Composites" reports a reaction with a biologically based acetal diol: the polyurethane composite material which is prepared by taking 2- (4-hydroxy-3-methoxyphenyl) -1, 3-dioxane-5-alcohol (HMDO) as a raw material and is easy to recycle can realize that PU-HMDO can be completely decomposed within 40min in a low-concentration acidic solution. But can not be degraded in the milder environment such as vinegar and the like, and the preparation process is more complex.
In light of the above-mentioned deficiencies of the prior art, there is a need for a polyurethane material that degrades under milder solvent conditions (such as vinegar environment), has a simple preparation process, and has a controlled pH response.
Disclosure of Invention
The invention aims to provide a pH response degradable polyurethane with controllable response, which has the characteristic of different hydrolysis rates under different pH values; by regulating and controlling different substituents on the prepolymer, controllable hydrolysis under mild solvent conditions (such as a vinegar environment) can be realized.
The pH response degradation-controllable polyurethane provided by the invention is obtained by polymerizing and crosslinking a prepolymer and isocyanate;
the prepolymer is a double-end hydroxyl oligomer with a silicon ether structure;
the isocyanate is hexamethylene diisocyanate Trimer (THDI), toluene diisocyanate trimer or diphenylmethane diisocyanate trimer.
The prepolymer is obtained by reacting polyalcohol with a silane compound;
the molar ratio of the polyol to the silane compound is 1-2: 1-2;
the silane compound contains at least two halogenated groups or alkoxy groups;
preferably, the silane compound has a structural formula shown in formula I or formula II:
in the formulae I and II, R1And R2Independently selected from C1-C4 alkyl or C6-C12 aryl, preferably the aryl is phenyl;
in the formula I, X1And X2Independently selected from chlorine and bromine;
in the formula II, R3And R4Independently selected from alkyl groups of C1-C4, preferably, the aryl group is phenyl;
the silane compound of formula i is preferably any one of the following compounds:
dichlorodimethylsilane, dichlorodiethylsilane, dichlorodiisopropylsilane, dichlorodiphenylsilane, dibromodimethylsilane, dibromodiethylsilane, dibromodiisopropylsilane and dibromodiphenylsilane;
the silane compound represented by the formula II is preferably any one of the following compounds:
dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiisopropylsilane, dimethoxydi-t-butylsilane, dimethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane, diethoxydiisopropylsilane, diethoxydi-t-butylsilane and diethoxydiphenylsilane.
Preferably, the polyol may be polyethylene glycol (PEG), polypropylene glycol (PPG), or Polytetrahydrofuran (PTMEG);
the molecular weight of the polyol is 100-5000, preferably 400-2000;
preferably, the structural formula of the prepolymer is shown as formula III:
in the formula III, n is a number between 9 and 46, such as 22 to 23.
The invention further provides a preparation method of the polyurethane, which comprises the following steps:
mixing the prepolymer with the isocyanate, adding a catalyst, and carrying out polymerization and crosslinking to obtain the isocyanate-terminated polyurethane prepolymer;
the molar ratio of the prepolymer to the isocyanate is 3: 2;
the catalyst is an organic amine catalyst or an organic tin catalyst;
the organic amine catalyst may be triethylenediamine;
the organic tin catalyst can be dibutyltin dilaurate;
preferably, the catalyst is dripped into a reaction system at a dripping speed of 10-30 mg/min.
In the preparation method, the prepolymer is prepared by the following steps:
in the presence of organic alkali, the polyol and the silane compound react to obtain the prepolymer;
the organic base can be at least one of triethylamine, diethylamine and dimethylamine;
the reaction is carried out in an organic solvent, and the organic solvent can be tetrahydrofuran and/or trichloromethane;
the reaction is carried out in a dry inert gas atmosphere, the reaction temperature is 10-30 ℃, and the reaction time is 8-24 hours.
The polyurethane provided by the invention has the characteristic of pH response controllable degradation, and the degradation time is 0-3 months under the conditions that the temperature is 25-80 ℃ and the pH is 2.5-7.4.
According to the pH response degradation-controllable polyurethane provided by the invention, the polyol is used as a main soft segment, the chain segment of the isocyanate is a hard segment, the pH sensitive degradation can be realized, the degradation rate is high under an acidic condition, and the degradation rate is low under a neutral condition.
The degradation with different degradation rates can be realized by regulating and controlling the silanized compounds with different substituents on the prepolymer.
The polyurethane material can realize degradation reaction under mild conditions (such as vinegar environment).
The controllable degradation product of the polyurethane material can be recycled and reused.
The polyurethane material is prepared by a two-step method, the process is simple, and the raw materials are cheap and easy to obtain.
Drawings
FIG. 1 shows the NMR spectrum of a prepolymer prepared in example 1 of the present invention.
FIG. 2 is a schematic diagram of the synthesis process for preparing a controlled degradation polyurethane elastomer in example 1 of the present invention.
FIG. 3 is a graph showing the controlled degradation effect of the polyurethane elastomers prepared in examples 1 to 3 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of pH-controlled degradable polyurethane elastomer
(1) The raw materials used in this example consisted of, by mass:
(2) the preparation method comprises the following specific steps:
1) at room temperature, dropwise adding dichlorodimethylsilane into a round-bottom flask filled with a mixed solution of PEG1000, TEA and THF, introducing nitrogen for protection, stirring for 8 hours, filtering the mixed solution through filter paper, removing solids, taking filtered filtrate, performing rotary evaporation on the filtrate through a rotary evaporator to obtain a retained product, and vacuumizing for 2 hours to obtain a prepolymer; wherein, the molar ratio of PEG1000 to dichlorodimethylsilane is 1: 2.
the structural formula of the prepolymer prepared in the embodiment is shown as formula III-1, n is 22-23, and the nuclear magnetic resonance hydrogen spectrum is shown in figure 1, so that the target product is obtained.
2) Mixing the prepolymer obtained in the step 1) with THDI (hexamethylene diisocyanate trimer) according to a molar ratio of 3: 2, mixing and stirring for 10min, then dripping a catalyst DBTDL, stirring, pouring into a mold, and placing in a vacuum oven at 80 ℃ for reaction for 2h to obtain the controllable degradable polyurethane elastomer.
The reaction equation of step 2) is shown in FIG. 2.
Example 2 preparation of pH-controllable degradable polyurethane elastomer
(1) The raw materials used in this example consisted of, by mass:
(2) the preparation method comprises the following specific steps:
1) dropwise adding dichlorodiethylsilane into a round-bottom flask filled with a mixed solution of PEG1000, TEA and THF at 25 ℃, introducing nitrogen for protection, stirring for 12 hours, filtering the mixed solution through filter paper, removing solids, taking filtered filtrate, and performing rotary evaporation on the filtrate through a rotary evaporator to obtain a retention product, and vacuumizing for 2 hours to obtain a prepolymer, wherein the molar ratio of PEG1000 to dichlorodiethylsilane is 1: 2.
the structural formula of the prepolymer prepared in the embodiment is shown as formula III-2, and n is 22-23.
2) Mixing the prepolymer obtained in the step 1) with THDI (hexamethylene diisocyanate trimer) according to a molar ratio of 3: 2, mixing and stirring for 10min, then dripping a catalyst DBTDL, stirring, pouring into a mould, placing in a vacuum oven at 80 ℃ for reaction for 3h, and obtaining the controllable degradable polyurethane elastomer.
Example 3 preparation of pH-controllable degradable polyurethane elastomer
(1) The raw materials used in this example consisted of, by mass:
(2) the preparation method comprises the following specific steps:
1) at 25 ℃, dropwise adding dichlorodiisopropylsilane into a round-bottom flask filled with a mixed solution of PEG1000, TEA and THF, introducing nitrogen for protection, stirring for 12 hours, filtering the mixed solution through filter paper, removing solids, taking filtered filtrate, performing rotary evaporation on the filtrate through a rotary evaporator to obtain a retention product, and vacuumizing for 2 hours to obtain a prepolymer, wherein the molar ratio of PEG1000 to dichlorodipropylsilane is 1: 2.
the structural formula of the prepolymer prepared in the embodiment is shown as formula III-3, and n is 22-23.
2) Mixing the prepolymer obtained in the step 1) with THDI (hexamethylene diisocyanate trimer) according to a molar ratio of 3: 2, mixing and stirring for 10min, then dripping a catalyst DBTDL, stirring, pouring into a mould, placing in a vacuum oven at 80 ℃ for reaction for 3h, and obtaining the controllable degradable polyurethane elastomer.
Examples 4 to 5,
The procedure of example 1 was followed, except that: and replacing dichlorodimethylsilane with dichlorodi-tert-butylsilane and dichlorodiphenylsilane by 6-12 parts by mass, wherein the reaction time is 12 hours and 14 hours respectively, and the mass of added THDI is 0.62g and 0.60g respectively.
The structural formulas of the prepolymers prepared in examples 4 and 5 are respectively shown in formulas III-4 and III-5:
example 6 preparation of pH-controllable degradable polyurethane elastomer
(1) The raw materials used in this example consisted of, by mass:
(2) the preparation method comprises the following specific steps:
1) at 25 ℃, diethoxydimethylsilane was added dropwise to a reaction flask containing a mixed solution of PEG1000, THF and TEA, and stirred for 12 hours under nitrogen protection. And filtering the reacted mixed solution through filter paper, removing solids, taking filtered filtrate, performing rotary evaporation on the filtrate through a rotary evaporator to obtain a retention product, and vacuumizing for 2 hours to obtain a prepolymer, wherein the structural formula of the prepolymer prepared in the embodiment is shown in formula III-1, and n is 22-23.
2) Mixing the prepolymer obtained in the step 1) with THDI (hexamethylene diisocyanate trimer) according to a molar ratio of 3: 2, mixing and stirring for 8min, then dripping a catalyst DBTDL, stirring, pouring into a mold, and placing in a vacuum oven at 80 ℃ for reaction for 2h to obtain the controllable degradable polyurethane elastomer.
Examples 7 to 10,
The same procedure as in example 6, except that: and replacing diethoxydimethylsilane with diethoxydiethylsilane, diethoxydiisopropylsilane, diethoxydi-tert-butylsilane and diethoxydiphenylsilane, wherein the mass is 6-11 parts, the reaction time is 12-24 hours, 4.00g of the prepared prepolymer is taken, and the mass of the added THDI is 0.60-0.66 g.
The following analytical methods were used in all examples unless otherwise indicated.
Degradation performance: mixing 1X 1cm3The polyurethane material with controllable degradation in pH response is soaked in 10mL of vinegar and a phosphate buffer (pH 7.4) respectively, the temperature is maintained at 60 ℃, the system is kept closed, the degradation state of the membrane material is observed, the absorbance of the solution is tested by an ultraviolet spectrophotometer, and when the absorbance is not increased any more, the degradation of the polyurethane elastomer is considered to be completed, and the degradation service life is determined.
The degradation effect of the controllably degradable polyurethane prepared in example 3 of the present invention at a temperature of 60 ℃ under different pH conditions is shown in fig. 3, wherein the first row shows the degradation effect in a vinegar (pH 2.5-3) environment for different time periods, and the second row shows the degradation effect in a PBS (pH 7.4) environment for different time periods.
The degradation performance of the controllable degradation polyurethane prepared by the embodiment of the invention in different pH environments with the same substituent at the temperature of 60 ℃ is shown in Table 1.
Table 1 degradation times of polyurethane elastomers prepared in example 3 in different pH environments
As can be seen from the data in Table 1, the polyurethane prepared by the invention has different hydrolysis rates under different pH values, has a fast degradation rate under an acidic condition and a slow degradation rate under a neutral condition, and has the characteristic of pH response controllable degradation.
The degradation performance of the controllably degradable polyurethane prepared by the embodiment of the invention in the same pH environment at the temperature of 60 ℃ is shown in Table 2.
TABLE 2 degradation times of polyurethane elastomers prepared in examples 1-10 in different pH environments
| Example number | Acetic acid solution (pH 2.6) | PBS buffer solution (pH 7.4) |
| Example 1 | 0 to 30 minutes | 30 to 90 minutes |
| Example 2 | 30 to 90 |
1 to 3 hours |
| Example 3 | 1 to 5 |
1 to 2 months |
| Example 4 | 1 to 3 days | 3-5 months |
| Example 5 | 1 to 5 days | 3-6 months |
| Example 6 | 0 to 40 |
20 to 100 minutes |
| Example 7 | 20 to 120 |
1 to 5 hours |
| Example 8 | 1 to 5 |
1 to 3 months |
| Example 9 | 1 to 3 days | 4-6 months |
| Example 10 | 3 to 10 days | 4-8 months |
As can be seen from the data in table 2, the substituent on the prepolymer affects the degradation rate of the polyurethane, and in general, the degradation rate when the substituent is aryl is less than the degradation rate when the substituent is alkyl; when both are alkyl substituents, the degradation rate of an alkyl group of carbon atom chain length is less than the degradation rate of an alkyl group of carbon atom chain length. Therefore, the regulation and control of different degradation rates of polyurethane can be realized by regulating and controlling the substituent groups on the prepolymer.
The invention also adopts other isocyanate (toluene diisocyanate Tripolymer (THDI) and diphenylmethane diisocyanate tripolymer) and the prepolymers to obtain various polyurethane elastomers through polymerization and crosslinking according to the method, and the network density of the formed polyurethane is different due to different isocyanate.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A pH response controllable degradable polyurethane is obtained by polymerizing and crosslinking a prepolymer and isocyanate;
the prepolymer is a double-end hydroxyl oligomer containing a silicon ether structure.
2. The polyurethane of claim 1, wherein: the isocyanate is hexamethylene diisocyanate trimer, toluene diisocyanate trimer or diphenylmethane diisocyanate trimer.
3. Polyurethane according to claim 1 or 2, characterized in that: the prepolymer is obtained by reacting polyalcohol with a silane compound;
the molar ratio of the polyol to the silane compound is 1-2: 1-2;
the silane compound contains at least two halo groups or alkoxy groups.
4. A polyurethane according to claim 3, characterized in that: the structural formula of the silane compound is shown as a formula I or a formula II:
in the formulae I and II, R1And R1Independently selected from alkyl of C1-C4 or aryl of C6-C12;
in the formula I, X1And X2Independently selected from chlorine and bromine;
in the formula II, R3And R4Independently selected from alkyl of C1-C4 or aryl of C6-C12.
5. Polyurethane according to claim 3 or 4, characterized in that: the polyalcohol is polyethylene glycol, polypropylene glycol or polytetrahydrofuran;
the molecular weight of the polyol is 100-5000.
6. A process for the preparation of the polyurethane according to any one of claims 1 to 5, comprising the steps of:
mixing the prepolymer with the isocyanate, adding a catalyst, and carrying out polymerization and crosslinking to obtain the isocyanate-terminated polyurethane prepolymer;
the catalyst is an organic amine catalyst or an organic tin catalyst.
7. The method of claim 6, wherein: the prepolymer was prepared as follows:
and reacting the polyol with the silane compound in the presence of organic base to obtain the prepolymer.
8. The method of claim 7, wherein: the organic base is at least one of triethylamine, diethylamine and dimethylamine;
the reaction is carried out in an organic solvent, wherein the organic solvent is tetrahydrofuran and/or trichloromethane;
the reaction is carried out in a dry inert gas atmosphere, the reaction temperature is 10-30 ℃, and the reaction time is 8-24 hours.
9. Use of a polyurethane according to any one of claims 1 to 5 as a material for controlled degradation in response to pH.
10. Use according to claim 9, characterized in that: the degradation time of the polyurethane is 0-3 months under the following conditions:
the temperature is 25-80 ℃, and the pH is 2.5-7.4.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169641A (en) * | 1990-03-08 | 1992-12-08 | Rhone-Poulenc Chimie | Hydrolytically degradable polyester/silicon co-crosslinked matrices |
| US6121404A (en) * | 1998-07-06 | 2000-09-19 | Dow Corning Corporation | β-diketo functional organosilicon compounds |
| CN102112118A (en) * | 2008-04-25 | 2011-06-29 | 北卡罗来纳-查佩尔山大学 | Degradable compounds and methods of use thereof, particularly with particle replication in non-wetting templates |
| US20200332054A1 (en) * | 2016-12-15 | 2020-10-22 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Degradable silyl-containing thermosetting networks |
| WO2021204874A1 (en) * | 2020-04-07 | 2021-10-14 | Polyu Gmbh | Isocyanate-free chain extension and crosslinking by means of functional silanes |
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2021
- 2021-12-27 CN CN202111611184.1A patent/CN114507329A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169641A (en) * | 1990-03-08 | 1992-12-08 | Rhone-Poulenc Chimie | Hydrolytically degradable polyester/silicon co-crosslinked matrices |
| US6121404A (en) * | 1998-07-06 | 2000-09-19 | Dow Corning Corporation | β-diketo functional organosilicon compounds |
| CN102112118A (en) * | 2008-04-25 | 2011-06-29 | 北卡罗来纳-查佩尔山大学 | Degradable compounds and methods of use thereof, particularly with particle replication in non-wetting templates |
| US20200332054A1 (en) * | 2016-12-15 | 2020-10-22 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Degradable silyl-containing thermosetting networks |
| WO2021204874A1 (en) * | 2020-04-07 | 2021-10-14 | Polyu Gmbh | Isocyanate-free chain extension and crosslinking by means of functional silanes |
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| Title |
|---|
| PATHIRAJA A. GUNATILLAKE，当: "Advancements in the Development of Biostable Polyurethanes" * |
| SHOUPENG ZHANG，等: "Controllable Degradation of Polyurethane Thermosets with Silaketal Linkages in Response to Weak Acid" * |
| 刘英，等: "聚醚改性三硅氧烷的生物降解性能研究" * |
| 宋海香，等: "聚醚硅氧烷二元醇改性水性聚氨酯的合成及性能" * |
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