CN115894739A - Functionalized hydroxyl-terminated polybutadiene and preparation method and application thereof - Google Patents
Functionalized hydroxyl-terminated polybutadiene and preparation method and application thereof Download PDFInfo
- Publication number
- CN115894739A CN115894739A CN202211685426.6A CN202211685426A CN115894739A CN 115894739 A CN115894739 A CN 115894739A CN 202211685426 A CN202211685426 A CN 202211685426A CN 115894739 A CN115894739 A CN 115894739A
- Authority
- CN
- China
- Prior art keywords
- terminated polybutadiene
- hydroxyl
- functionalized
- acetylferrocene
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A functionalized hydroxyl-terminated polybutadiene, a preparation method and application thereof. The invention belongs to the field of piezoelectric materials and preparation thereof. The invention aims to solve the technical problem that the existing HTPB-based polymer material does not have conductive performance. The functional hydroxyl-terminated polybutadiene (m-HTPB) modified by functional acetylferrocene is prepared, and the branched chain modification of a branched chain-1, 4 butadiene molecular chain in the hydroxyl-terminated polybutadiene is realized; the conjugated molecular structure of the functionalized acetylferrocene improves the conductivity of m-HTPB, increases the electric dipole moment of the molecule thereof, enables the molecule to have piezoelectric activity, and provides a specific application case for the functional development of HTPB and the development of a novel sensor.
Description
Technical Field
The invention belongs to the field of piezoelectric materials and preparation thereof, and particularly relates to functionalized hydroxyl-terminated polybutadiene and a preparation method and application thereof.
Background
Hydroxyl-terminated polybutadiene (HTPB) is a liquid rubber that is widely used as a polyol to prepare thermoset Polyurethanes (PU) for elastomers, solid propellant composites, explosives, packaging and gas separation membranes due to its excellent physical properties, such as low viscosity, low glass transition temperature, high mechanical and thermal stability, better thermodynamic and aging properties. However, thermosetting polyurethanes based on HTPB can form inevitable microcracks under external environmental stress, reducing their service life. Therefore, the method for monitoring the microcracks of the HTPB-based PU under stress has important significance for sustainable industrial application.
At present, flexible sensors have been developed and applied in different scenarios based on piezoresistive, capacitive, piezoelectric sensing principles. Typically, flexible sensors are made from crystals, ceramics, and certain polymeric materials. Polymers generally have many advantages over crystalline or inorganic ceramics, such as light weight, high flexibility, and the like. The polymer applied to the flexible sensor needs to have certain conductivity and electron transmission capability or have larger electric dipole moment and piezoelectric activity. Due to the symmetrical-1, 4 butadiene molecular structure, the HTPB has no conductivity and electron transmission capability, and the electric dipole moment is nearly zero. Therefore, the method for modifying hydroxyl-terminated polybutadiene is explored, the sensor function is endowed, and the application range of HTPB in the field of sensors and HTPB-based PU is greatly enriched.
Disclosure of Invention
The invention aims to solve the technical problem that the existing HTPB-based polymer material does not have the conductivity, and provides functionalized hydroxyl-terminated polybutadiene, and a preparation method and application thereof.
One of the purposes of the invention is to provide a preparation method of functionalized hydroxyl-terminated polybutadiene, which comprises the following steps:
s1: dropwise adding formaldehyde into an ethanol solution of p-phenylenediamine, then adjusting the pH value to 4, dropwise adding an ethanol solution of acetylferrocene, carrying out reflux reaction, and separating out a precipitate in anhydrous glacial ethyl ether after the reaction is finished to obtain functionalized acetylferrocene;
s2: adding concentrated hydrochloric acid into the hydroxyl-terminated polybutadiene precursor solution under the stirring condition to react for 0.5-5h, adding sodium carbonate to react under stirring, then adding functionalized acetylferrocene, supplementing sodium carbonate to continue stirring, finally adding anhydrous magnesium sulfate to stand, filtering, and then performing rotary evaporation on the filtrate to obtain the functionalized hydroxyl-terminated polybutadiene.
In a preferred embodiment of the present invention, the molar ratio of formaldehyde to p-phenylenediamine in S1 is 1: (1-5-2.5).
In a preferable embodiment of the present invention, the concentration of the ethanol solution of p-phenylenediamine in S1 is 0.5 to 0.7mol/L.
In a preferred embodiment of the present invention, the pH of S1 is adjusted using concentrated hydrochloric acid.
In a preferable embodiment of the invention, the concentration of the ethanol solution of acetylferrocene in S1 is 0.2-0.3mol/L.
In a preferred embodiment of the present invention, the molar ratio of the acetyl ferrocene in the ethanol solution of acetyl ferrocene in S1 to the p-phenylenediamine in the ethanol solution of p-phenylenediamine is 1: (2-4).
As a preferable scheme of the invention, the temperature of the reflux reaction in S1 is 70-90 ℃ and the time is 10-14h.
As a preferable embodiment of the present invention, the preparation of the hydroxyl-terminated polybutadiene precursor solution in S2 comprises the following steps:
(1) Dissolving butadiene rubber in tetrahydrofuran, dropwise adding a tetrahydrofuran solution of 3-chloroperoxybenzoic acid under the condition of stirring in a water bath at the temperature of 30 ℃, reacting for a certain time, dropwise adding a tetrahydrofuran solution of periodic acid, reacting for 0.5-4h, then adding sodium bicarbonate and 2, 6-di-tert-butyl-4-methylphenol, stirring for a plurality of minutes, cooling and standing;
(2) Adding sodium borohydride, stirring, filtering supernatant, and dripping deionized water until no bubble is generated in the solution to obtain hydroxyl-terminated polybutadiene precursor solution.
In a preferred embodiment of the present invention, the volume ratio of the hydroxyl-terminated polybutadiene precursor solution to the concentrated hydrochloric acid in S2 is 55: (0.2-0.5).
In a preferred embodiment of the present invention, the ratio of the volume of the hydroxyl-terminated polybutadiene precursor liquid in S2 to the mass of the first added sodium carbonate is 55mL: (0.4-0.6) g.
In a preferred embodiment of the present invention, the mass ratio of the sodium carbonate added for the first time to the functionalized acetylferrocene in S2 is 0.48: (0.4-0.5)
As a preferable scheme of the invention, the mass ratio of the sodium carbonate added for the first time to the supplementary sodium carbonate in S2 is 0.48: (0.05-0.15).
In a preferred embodiment of the present invention, the mass ratio of the sodium carbonate added for the first time to the anhydrous magnesium sulfate in S2 is 0.48: (0.2-0.4).
The second purpose of the invention is to provide the functionalized hydroxyl-terminated polybutadiene prepared by the method.
As a preferable scheme of the invention, the cis-1, 4 structure molar content in the functionalized hydroxyl-terminated polybutadiene is up to 98.4%.
The invention also aims to provide application of the functionalized hydroxyl-terminated polybutadiene prepared by the method as a piezoelectric material.
It is a fourth object of the present invention to provide a piezoelectric sensor device using the above functionalized hydroxyl-terminated polybutadiene as a piezoelectric sensing material.
Compared with the prior art, the invention has the advantages that:
the functional hydroxyl-terminated polybutadiene (m-HTPB) modified by functional acetylferrocene is prepared, and the branched chain modification of a branched chain-1, 4 butadiene molecular chain in the hydroxyl-terminated polybutadiene is realized; the conductive performance of m-HTPB is improved and the molecular electric dipole moment of the m-HTPB is increased by functionalizing the conjugated molecular structure of the acetylferrocene, so that the m-HTPB has piezoelectric activity, a specific application case is provided for the functional development of the HTPB and the development of a novel sensor, and the specific advantages are as follows:
(1) The functionalized hydroxyl-terminated polybutadiene prepared by the method can efficiently and accurately control the substitution position of the functionalized acetylferrocene in the hydroxyl-terminated polybutadiene; compared with other molecular chain grafting methods, the method has the advantages of mild reaction conditions, simple process steps, easiness in reaction control, no need of high energy consumption of used equipment, good economy and high yield.
(2) The functionalized hydroxyl-terminated polybutadiene prepared by the invention has high cis-1, 4 structure content in the molecular structure, the cis-1, 4 structure molar content in the functionalized hydroxyl-terminated polybutadiene reaches 98.4 percent, and the hydroxyl value content is high.
(3) Compared with the raw material BR900, the functionalized hydroxyl-terminated polybutadiene prepared by the invention has greatly improved conductivity.
(4) The functional hydroxyl-terminated polybutadiene prepared by the invention has piezoelectric property, solves the problem that the research range of the existing flexible piezoelectric material is limited, and explores the application of the hydroxyl-terminated polybutadiene in the aspect of flexible sensors.
(5) The functionalized hydroxyl-terminated polybutadiene piezoelectric sensing device provided by the invention has the sensitivity of 0.36nAN under the action of 1-3N compressive stress -1 。
Drawings
FIG. 1 is an IR chart of a functionalized hydroxyl-terminated polybutadiene obtained in example 1;
FIG. 2 is a nuclear magnetic carbon spectrum of the functionalized hydroxyl-terminated polybutadiene prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the functionalized hydroxyl-terminated polybutadiene prepared in example 1;
FIG. 4 is a DSC curve of the functionalized hydroxyl-terminated polybutadiene prepared in example 1;
FIG. 5 is a molecular weight distribution (GPC) curve of the functionalized hydroxyl-terminated polybutadiene obtained in example 1;
FIG. 6 is an AC impedance spectrum of the functionalized hydroxyl-terminated polybutadiene prepared in example 1;
FIG. 7 is a graph of force-output current signals of a piezoelectric sensor based on the functionalized hydroxyl-terminated polybutadiene prepared in example 1 in an application example.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
Example 1:
the preparation method of the functionalized hydroxyl-terminated polybutadiene of the embodiment comprises the following steps:
S1：
and (3) acetylferrocene functionalization:
firstly, dissolving 1.6g of p-phenylenediamine in 25mL of absolute ethyl alcohol, dropwise adding 0.6g of formaldehyde under the stirring condition, stirring for 20min after the dropwise adding is finished, and then dropwise adding concentrated hydrochloric acid to adjust the pH value of the solution to be 4 to obtain a p-phenylenediamine/formaldehyde mixed solution;
then, dissolving 1.1g of acetyl ferrocene in 20mL of absolute ethyl alcohol, dropwise adding the acetyl ferrocene into the p-phenylenediamine/formaldehyde mixed solution, carrying out reflux reaction at the temperature of 80 ℃ for 14 hours, and cooling to room temperature;
and finally, refrigerating 200mL of anhydrous diethyl ether in a refrigerator for 12h, placing the refrigerated solution in an ice-water bath, dropwise adding the refluxed solution into the anhydrous diethyl ether, separating out a lower-layer precipitate, washing with diethyl ether for three times, and drying at room temperature to obtain the functionalized acetylferrocene.
S2：
Firstly, preparing hydroxyl-terminated polybutadiene precursor liquid:
firstly, dissolving 5.0g of BR900 cis-butadiene rubber in 100mL of tetrahydrofuran to obtain a cis-butadiene rubber solution, then dissolving 0.9g of 3-chloroperoxybenzoic acid in 10mL of tetrahydrofuran, dropwise adding the tetrahydrofuran solution of the 3-chloroperoxybenzoic acid into the cis-butadiene rubber solution under the condition of stirring in a water bath at 30 ℃, and stirring and refluxing for 1.5 hours;
dissolving 1.5g of periodic acid in 20mL of tetrahydrofuran, dropwise adding the solution into the solution, and refluxing in a water bath at 30 ℃ for 2 hours under the condition of stirring;
sequentially adding 0.9g of sodium bicarbonate and 1.3g of 2, 6-di-tert-butyl-4-methylphenol powder into the reaction solution, continuing reflux reaction for 50min, cooling and standing for 8h;
and then adding 0.9g of sodium borohydride powder, stirring for 2 hours, filtering to remove impurities, and dropwise adding 10 drops of deionized water into the filtrate until no bubbles are generated in the solution to obtain the hydroxyl-terminated polybutadiene precursor solution.
Then, preparing the functionalized hydroxyl-terminated polybutadiene:
taking 55mL of hydroxyl-terminated polybutadiene precursor solution, adding 10 drops (0.4 mL) of concentrated hydrochloric acid under the stirring condition, continuously stirring for 2h, adding 0.48g of sodium carbonate, continuously stirring for 30min, adding 0.45g of functionalized acetylferrocene powder and 0.1g of Na 2 CO 3 Stirring for 1h, adding 0.3g of anhydrous magnesium sulfate, standing for 4h, filtering to remove solid impurities, and performing rotary evaporation on the filtrate to obtain the functionalized hydroxyl-terminated polybutadiene.
The functionalized hydroxyl-terminated polybutadiene prepared in example 1 is detected by infrared spectroscopy, and the detection result is shown in figure 1. FIG. 1 is an infrared spectrum of the functionalized hydroxyl-terminated polybutadiene prepared in example 1, and it can be seen from FIG. 1 that the functionalized hydroxyl-terminated polybutadiene prepared by the method has high cis-1, 4 and hydroxyl structures: 729cm -1 The absorption peak is cis-1, 4 isomer; 3300 to 3500The peak at cm-1 is due to the symmetric tensile vibration of the-OH groups in the functionalized hydroxyl-terminated polybutadiene. 876 and 1510cm in FIG. 1 -1 Absorption peak is tensile vibration of benzene ring, 488cm -1 The characteristic peaks at (A) are attributed to Fe-C and are located at 830, 1389, 1515 and 1560cm -1 The peaks at (A) are associated with the backbone vibration of p-phenylene, cp, C-H vibration out of the plane of the benzene ring, and N-H stretching vibration of the functionalized acetylferrocene, respectively. From the cis-1, 4 isomer (729 cm) -1 ) 1, 2-vinyl structure (910 cm) -1 ) And trans-1, 4 isomer (965 cm) -1 ) Three absorption peaks, the area ratio of which is calculated as 98.4.
The functionalized hydroxyl-terminated polybutadiene prepared in example 1 is dissolved in tetrahydrofuran for nuclear magnetic testing to further determine the molecular structure of the functionalized hydroxyl-terminated polybutadiene, and the nuclear magnetic carbon spectrum detection result is shown in fig. 2. FIG. 2 is nuclear magnetic carbon spectrum of functionalized hydroxyl-terminated polybutadiene prepared in example 1, and it can be seen from FIG. 2 that-CH is contained in the functionalized hydroxyl-terminated polybutadiene prepared by the method 2 The characteristic peak of OH appeared at 62.6ppm and the new single peak appeared at chemical shifts of 20.00 and 69.67ppm was attributed to-CH 3 And the cyclopentadienyl carbon atom, peaks at 139.7 and 201.7 correspond to the carbon atom in p-phenylenediamine and the-CO-in the functionalized acetylferrocene moiety. -CH 3 The appearance of the group indicates that the substitution position of the functionalized acetylferrocene is at two positions in the branch.
The functionalized hydroxyl-terminated polybutadiene prepared in example 1 is dissolved in tetrahydrofuran and used for nuclear magnetic hydrogen spectroscopy to further determine the molecular structure of the functionalized hydroxyl-terminated polybutadiene, and the nuclear magnetic hydrogen spectroscopy detection result is shown in fig. 3. FIG. 3 is nuclear magnetic hydrogen spectrum of functionalized hydroxyl-terminated polybutadiene prepared in example 1, and it can be seen from FIG. 3 that a triplet appears at chemical shifts of 3.56 to 3.59ppm, attributed to the adjacent hydroxyl group (-CH) 2 OH) indicating that there is only one type of hydroxyl group in the functionalized hydroxyl-terminated polybutadiene prepared in example 1. The peak at 5.0ppm in the cis-1,4 isomer corresponds to = CH2, while the = CH proton appears at 5.38ppm. About 5.38ppmThe peak still predominates, indicating that the functionalized hydroxyl-terminated polybutadiene obtained in example 1 retains a high cis-1,4 content. Peaks at 2.41, 3.3, 4.51, 4.77 and 6.55ppm, respectively with-CH 2 The-group, the proton in the benzene ring, the acetyl-m hydrogen on the cyclopentadienyl ring, the acetyl-o hydrogen on the cyclopentadienyl ring and the-NH-of the functionalized acetylferrocene are related, indicating that the functionalized acetylferrocene group is completely reacted with the hydroxyl-terminated polybutadiene.
The functionalized hydroxyl-terminated polybutadiene prepared in example 1 is subjected to Differential Scanning Calorimetry (DSC) test, and the detection result is shown in fig. 4. Fig. 4 is DSC curve of the functionalized hydroxyl-terminated polybutadiene prepared in example 1, and it can be seen from fig. 4 that the presence of the functionalized acetylferrocene branch increases the microstructure regularity of the functionalized hydroxyl-terminated polybutadiene due to the breaking of part of the C = C bond, resulting in the increase of the glass transition temperature and the disappearance of the melting peak.
The functionalized hydroxyl-terminated polybutadiene prepared in example 1 was subjected to gel chromatography to determine the molecular weight, and the detection results are shown in FIG. 5. FIG. 5 is a GPC curve of the functionalized hydroxyl-terminated polybutadiene obtained in example 1, and it can be seen from FIG. 5 that the molecular weight of the functionalized hydroxyl-terminated polybutadiene obtained in example 1 is 3107g/mol.
The functionalized hydroxyl-terminated polybutadiene prepared in example 1 was subjected to an ac impedance test to test its conductivity, and the test results are shown in fig. 6. FIG. 6 is EIS curve of the functionalized hydroxyl-terminated polybutadiene prepared in example 1, and it can be seen from FIG. 6 that the functionalized hydroxyl-terminated polybutadiene prepared in example 1 has an EIS value of 10 -2 Hz to 10 5 In the Hz frequency range, the semi-circle intercept in the high frequency region is 1.55 multiplied by 10 4 。
Application example:
the functionalized hydroxyl-terminated polybutadiene prepared in example 1 is used as an inner layer, and polydimethylsiloxane is used as an outer layer to assemble a piezoelectric sensing device.
Applying periodic vertical compression stress to the assembled piezoelectric sensor, wherein the stress area is 0.5cm 2 Measuring and recording the current of the deviceThe detection result of the output signal is shown in fig. 7. FIG. 7 is a stress response curve of a sensor prepared by using the functionalized hydroxyl-terminated polybutadiene prepared in example 1 as a piezoelectric sensing material, and as can be seen from FIG. 7, the peak value of the output current of the sensor is gradually increased along with the increase of the applied force from 1N to 3N, the current output of the sensor is approximately linear in relation to the applied force within the range of 1-3N, and the sensitivity is 0.36nAN -1 。
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of functionalized hydroxyl-terminated polybutadiene is characterized by comprising the following steps:
s1: dropwise adding formaldehyde into an ethanol solution of p-phenylenediamine, then adjusting the pH value to 4, dropwise adding an ethanol solution of acetylferrocene, carrying out reflux reaction, and separating out a precipitate in anhydrous glacial ethyl ether after the reaction is finished to obtain functionalized acetylferrocene;
s2: adding concentrated hydrochloric acid into the hydroxyl-terminated polybutadiene precursor solution under the stirring condition to react for 0.5-5h, adding sodium carbonate to react under stirring, then adding functionalized acetylferrocene, supplementing sodium carbonate to continue stirring, finally adding anhydrous magnesium sulfate to stand, filtering, and then performing rotary evaporation on the filtrate to obtain the functionalized hydroxyl-terminated polybutadiene.
2. The process of claim 1, wherein the molar ratio of formaldehyde to p-phenylenediamine in S1 is from 1: (1-5-2.5), and the concentration of the ethanol solution of p-phenylenediamine is 0.5-0.7mol/L.
3. The method of claim 1, wherein the pH of S1 is adjusted using concentrated hydrochloric acid.
4. The method of claim 1, wherein the concentration of the ethanol solution of acetylferrocene in S1 is 0.2-0.3mol/L, and the molar ratio of the acetylferrocene to the p-phenylenediamine is 1: (2-4).
5. The method according to claim 1, wherein the temperature of the reflux reaction in S1 is 70-90 ℃ for 10-14h.
6. The method for preparing a hydroxyl-terminated polybutadiene precursor solution as recited in claim 1, wherein the steps of:
1) Dissolving butadiene rubber in tetrahydrofuran, dropwise adding a tetrahydrofuran solution of 3-chloroperoxybenzoic acid under the condition of stirring in a water bath at the temperature of 30 ℃, reacting for a certain time, dropwise adding a tetrahydrofuran solution of periodic acid, reacting for 0.5-4h, then adding sodium bicarbonate and 2, 6-di-tert-butyl-4-methylphenol, stirring for a plurality of minutes, cooling and standing;
2) Adding sodium borohydride, stirring, filtering supernatant, and dripping deionized water until no bubble is generated in the solution to obtain hydroxyl-terminated polybutadiene precursor solution.
7. The method according to claim 1, wherein the mass ratio of the hydroxyl-terminated polybutadiene precursor liquid to the concentrated hydrochloric acid in the S2 and the mass ratio of the first sodium carbonate addition are 55mL: (0.2-0.5) mL: (0.4-0.6) g, wherein the mass ratio of the first added sodium carbonate to the functionalized acetyl ferrocene, the supplemented sodium carbonate and the anhydrous magnesium sulfate is 0.48: (0.4-0.5): (0.05-0.15): (0.2-0.4).
8. The functionalized hydroxyl-terminated polybutadiene obtained by the process according to any one of claims 1-7, wherein the cis-1, 4 structure has a molar content of up to 98.4%.
9. Use of the functionalized hydroxyl-terminated polybutadiene of claim 8 as a piezoelectric material.
10. A piezoelectric sensor device, characterized in that it uses the functionalized hydroxyl-terminated polybutadiene according to claim 8 as a piezoelectric sensing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211685426.6A CN115894739A (en) | 2022-12-27 | 2022-12-27 | Functionalized hydroxyl-terminated polybutadiene and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211685426.6A CN115894739A (en) | 2022-12-27 | 2022-12-27 | Functionalized hydroxyl-terminated polybutadiene and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115894739A true CN115894739A (en) | 2023-04-04 |
Family
ID=86493843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211685426.6A Pending CN115894739A (en) | 2022-12-27 | 2022-12-27 | Functionalized hydroxyl-terminated polybutadiene and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115894739A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449214A (en) * | 2022-10-12 | 2022-12-09 | 深圳市爱康运动用品有限公司 | Material for paddle and preparation method thereof |
-
2022
- 2022-12-27 CN CN202211685426.6A patent/CN115894739A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449214A (en) * | 2022-10-12 | 2022-12-09 | 深圳市爱康运动用品有限公司 | Material for paddle and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115894739A (en) | Functionalized hydroxyl-terminated polybutadiene and preparation method and application thereof | |
| Coşkun et al. | Synthesis, characterization and investigation of dielectric properties of two-armed graft copolymers prepared with methyl methacrylate and styrene onto PVC using atom transfer radical polymerization | |
| JP2016505677A (en) | Method for preparing biomass polymer emulsion | |
| WO2019095410A1 (en) | Dopo derivative flame retardant, preparation method thereof, and application thereof | |
| CN108341937B (en) | Bio-based polyester containing carbonate structure and preparation method and application thereof | |
| JP2016528327A (en) | Polyorganosiloxane compound, production method and copolycarbonate resin containing the same | |
| Zhang et al. | Synthesis of poly (tetramethyl-m-silphenylenesiloxane), an elastomer of enhanced high-temperature stability | |
| US4853440A (en) | Polymeric stabilizer compounds and process for their preparation | |
| CN112794979A (en) | Preparation method of bionic inspired high-resilience polyurethane elastomer with super-toughness, super-stretching and self-repairing functions | |
| CN114316236B (en) | High-temperature-resistant polycarbonate material and preparation method thereof | |
| Selvaraj et al. | Development of high-performance hybrid sustainable bio-composites from biobased carbon reinforcement and cardanol-benzoxazine matrix | |
| KR20100133681A (en) | Cardanol derivatives, preparation method thereof and cardanol polymer prepared therefrom | |
| Abbasi et al. | Synthesis and characterization of novel ferrocenyl glycidyl ether polymer, ferrocenyl poly (epichlorohydrin) and ferrocenyl poly (glycidyl azide) | |
| CN108395512B (en) | Bio-based polyurethane containing carbonate structure as well as preparation method and application thereof | |
| CN111454662A (en) | Room-temperature-curable organic silicon resin conformal coating and preparation method thereof | |
| Zhang et al. | Preparation of polymer–rare earth complexes based on Schiff-base-containing salicylic aldehyde groups attached to the polymer and their fluorescence emission properties | |
| CN115557848A (en) | Diamine monomer, low CTE (coefficient of thermal expansion) and high-permeability polyimide and preparation method | |
| CN108129632B (en) | Silicon-containing flame-retardant polyol, preparation thereof and flame-retardant polyurethane | |
| JP4295687B2 (en) | Composite and production method thereof | |
| Chen et al. | Synthesis and properties of novel phosphorus‐containing poly (ether ether ketone ketone) s | |
| CN106631751B (en) | More two fluorine monomers of methyl chains of anti-oxidative and preparation method thereof | |
| CN117964907A (en) | Preparation method and application of modified hydroxyl-terminated polybutadiene based on polyaniline derivative | |
| JP3830677B2 (en) | Optically active polythiophene derivative and method for producing the same | |
| Itomi et al. | Helix formation of poly (phenylacetylene) s bearing azide groups through click polymer reaction with optically active acetylenes | |
| JPS63234008A (en) | Copolymer of borane monomers, alpha-olefins and polyalcohols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |