CN110257010B - Preparation method of water-phase free radical polymerization nanocellulose crystal-polyethylene glycol solid-solid phase change material - Google Patents
Preparation method of water-phase free radical polymerization nanocellulose crystal-polyethylene glycol solid-solid phase change material Download PDFInfo
- Publication number
- CN110257010B CN110257010B CN201910583422.9A CN201910583422A CN110257010B CN 110257010 B CN110257010 B CN 110257010B CN 201910583422 A CN201910583422 A CN 201910583422A CN 110257010 B CN110257010 B CN 110257010B
- Authority
- CN
- China
- Prior art keywords
- solid
- phase change
- polyethylene glycol
- change material
- free radical
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
Abstract
The invention provides a preparation method of an aqueous phase free radical polymerization nano-cellulose crystal-polyethylene glycol solid-solid phase change material, and discloses a method for preparing the aqueous phase free radical polymerization nano-cellulose crystal-polyethylene glycol solid-solid phase change material, which comprises the steps of melting and mixing maleic anhydride and polyethylene glycol at a certain temperature, catalyzing to obtain a polymer, mixing and adding carboxylated Cellulose Nanocrystals (CNCs), hydrogen peroxide and sulfate into the polymer, performing ultrasonic dispersion, reacting under the protection of nitrogen, washing with water, centrifuging and drying to obtain the aqueous phase free radical polymerization nano-cellulose crystal-polyethylene glycol solid-solid phase change material. The method for synthesizing the solid-solid phase change material by initiating the synthesis of the solid-solid phase change material by using the hydrogen peroxide mixed solution is simple, generates non-toxic byproducts, is degradable, economical and environment-friendly, and has high phase change energy storage enthalpy and proper phase change temperature and wide application prospect.
Description
Technical Field
The invention relates to a preparation method of a phase-change material, in particular to a preparation method of a water-phase free radical polymerization cellulose-based solid-solid phase-change material, belonging to the field of preparation of high polymer materials.
Background
With the rapid development of society, the demand for energy is increasing. Energy is the basis for human survival and economic development, and at present, the energy crisis is a global focus problem. With the rise of various green energy sources represented by solar energy, how to effectively store various heat energies to solve the energy crisis becomes a hot spot of current research. Thus, there is an urgent need for an efficient energy storage technology.
The phase change material absorbs and releases heat by a change in phase of a substance to store energy, and has a high storage density and a small temperature change during the storage and release of heat. Therefore, phase change materials are the most promising materials in energy storage technology. Phase change materials have many advantages, such as high phase change enthalpy, isothermal storage and release of heat, no energy supply and demand mismatch issues, and the like. Phase change materials can be divided into two broad categories: solid-liquid and solid-solid phase change materials. The organic polymer solid-solid phase change material has no leakage, is easy to chemically modify, and has more advantages relative to proper phase change temperature and high phase change enthalpy. The polymer solid-solid phase transition can be prepared by physical blending or chemical modification. However, physical blending has disadvantages of phase separation, poor durability, and the like. Therefore, chemical modification is an important method for preparing organic polymers with solid-solid phase transition.
PEG has the characteristics of no toxicity, good biocompatibility, biodegradability, easy chemical modification and the like, and is widely applied to the fields of chemistry, medicine and biotechnology. Meanwhile, the phase change energy storage functional polymer has the advantages of large melting heat, high energy storage density, consistent melting behavior, corrosion resistance, melting point suitable for low-temperature application, easiness in chemical modification and the like. However, liquid phase leakage, low thermal stability, is an obstacle in practical energy storage applications.
The nano cellulose crystal is a natural high molecular polymer, has wide sources, is non-toxic, renewable and biodegradable, has large surface area and stable mechanical property, and has a large amount of reactive groups (-OH, -COOH and the like) which are beneficial to chemical modification. The method adopts nano-crystalline cellulose as a phase-change framework material, and grafts PEG on the molecular chain of the nano-crystalline cellulose by a chemical modification method. The chemical bonding mode leads PEG to lose macroscopic fluidity in the phase change process, and stable solid-solid phase change materials are obtained.
Yong Huang et al, using an intermediate chemical grafting method, uses tetrahydrofuran and bisMethyl sulfoxide as solvent to prepare polyethylene glycol solid-solid Phase change material (Yanxinang Li, Ruigang Liu, Yong Huang. Synthesis and Phase Transition of Cellulose-gradient-Poly (ethylene glycol)) with nano-Cellulose base load molecular weight of 1100 and 2000. The results show that: the nano-cellulose can be used as a framework material grafted by an energy storage functional group due to the advantages of large surface area, high crystallinity, fine structure and the like, and the solid-solid phase transition behavior of the composite material can be realized only when the grafting rate of polyethylene glycol is between 50 and 80 percent. But the preparation method is complex and a large amount of toxic byproducts are generated. Yeliz Konuklu et al prepared PEG 1000-based grafted polyethylene glycol solid-solid phase change materials by crosslinking with N, N-dimethylformamide as solvent and toluene 2, 4-diisocyanate as crosslinking agent (
Alkan C,Konuklu Y.Developing a poly(ethylene glycol)/cellulose phase change reactive composite for cooling application[J]Sol. energy. mat. sol. c.,2019,191: 345-349). The results show that: the preparation of the solid-solid phase change material of the cellulose-based supported PEG is successful, but a large amount of hazardous organic solvent is used, and the loss of the phase change enthalpy of the product is serious. Therefore, the invention adopts the carboxylated Cellulose Nanocrystals (CNCs) as the framework material, has large surface area and strong functionality, effectively initiates the bonding of PEG by the aqueous phase free radical polymerization method, has the advantages of environmental protection and simplicity, and has no toxic by-products. The nano-crystalline cellulose-polyethylene glycol solid-solid phase change material can be greatly developed in the technical field of phase change energy storage.
Disclosure of Invention
The invention aims to provide a preparation method of an aqueous phase free radical polymerization nano cellulose crystal-polyethylene glycol solid-solid phase change material, which has the advantages of simple preparation, simple and convenient operation, no pollution and convenient large-scale production.
The technical scheme adopted by the invention is as follows:
a preparation method of an aqueous phase free radical polymerization nano cellulose crystal-polyethylene glycol solid-solid phase change material is characterized by comprising the following steps:
1) mixing maleic anhydride and PEG with proper molecular weight according to a proper molar ratio, fully melting and mixing under the protection of nitrogen at 55-75 ℃, adding a certain amount of catalyst, and reacting for 1-3 hours to obtain a modified PEG polymer;
2) mixing sulfate with hydrogen peroxide with proper concentration according to a proper mass ratio, adding CNCs according to a proper solid-liquid ratio, and performing ultrasonic dispersion for 5-10min to obtain a CNCs suspension;
3) adding the CNCs suspension obtained in the step 2) into the modified PEG polymer obtained in the step 1) according to a proper proportion, raising the temperature to 70-100 ℃, reacting for 6-24h under the protection of nitrogen, stopping the reaction with ethanol, washing with water, centrifuging, and drying to obtain the nano cellulose crystal-polyethylene glycol composite material with solid-solid phase modification performance.
The appropriate molar ratio in step 1) is 1-3: 1, the proper molecular weight of PEG is 800-4000g/mol, the certain amount is 1-3mg, and the catalyst is one of tin isooctanoate, benzenesulfonic acid and p-toluenesulfonic acid.
The appropriate mass ratio in the step 2) is 1: 3-5, sulfate refers to copper sulfate (CuSO)4、CuSO4·5H2O), ferrous sulfate (FeSO)4、FeSO4·7H2O), ferrous ammonium sulfate ((NH)4)2Fe(SO4)2·6H2O), proper concentration is 25% -30%, and proper solid-to-liquid ratio is 1 g; 15-25 mL.
The appropriate proportion in step 3) is 1 mL: 2-5 g.
The invention has the beneficial effects that:
(1) the PEG which is non-toxic, good in biocompatibility and strong in corrosion resistance is used as the phase change energy storage unit, and the PEG has the characteristics of environmental friendliness, low economic cost, high energy storage density and the like;
(2) according to the invention, carboxylic acid nano cellulose crystals (CNCs) are used as a phase change framework, so that the cellulose nano crystal phase change material has good solution dispersibility while being renewable, stable in mechanical property and strong in reactivity, and the defect of preventing agglomeration caused by dissolving nano cellulose crystals by a large amount of traditional organic solvents is overcome;
(3) the method for grafting the PEG by the water-phase free radical polymerization nanocellulose crystal is economic and environment-friendly, the method is simple, and the prepared solid-solid phase change material has the advantages of proper phase change temperature, high phase change enthalpy and strong stability, accords with practical application and is beneficial to large-scale production.
Drawings
FIG. 1 is a graph of Differential Scanning Calorimetry (DSC) measurements of CNCs-PEG1000 polymers prepared at different reaction times (6h, 8h, 10 h).
Detailed Description
The invention is further illustrated below with reference to specific examples. These embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention. In addition, after reading the teaching of the present invention, those skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
1) The molar ratio of the raw materials is 1.3: 1, mixing maleic anhydride and PEG with the molecular weight of 1000g/mol, fully melting and mixing under the protection of nitrogen at 55 ℃, adding 1mg of tin isooctanoate, and reacting for 2.5 hours to obtain a modified PEG polymer;
2) according to the mass ratio of 1: 4 ammonium ferrous sulfate ((NH)4)2Fe(SO4)2·6H2O) and 30% hydrogen peroxide, wherein the solid-liquid ratio is 1 g: adding 20mL of CNCs, and performing ultrasonic dispersion for 5min to obtain a CNCs suspension;
3) mixing the CNCs suspension obtained in the step 2) according to the volume ratio of 1 mL: adding 3g of the mixture into the modified PEG polymer obtained in the step 1), raising the temperature to 80 ℃, reacting for 8 hours under the protection of nitrogen, stopping the reaction by using ethanol, washing, centrifuging, and drying to obtain the nano cellulose crystal-polyethylene glycol composite material a with solid-solid phase modification performance.
Example 2
1) The molar ratio of the raw materials is 2: 1, mixing maleic anhydride and PEG with the molecular weight of 1000g/mol, fully melting and mixing under the protection of nitrogen at 60 ℃, adding 1.5mg of p-toluenesulfonic acid, and reacting for 1.5 hours to obtain a modified PEG polymer;
2) according to the mass ratioIs 1:3 copper sulfate (CuSO)4) Mixing with 25% hydrogen peroxide according to a solid-liquid ratio of 1 g: adding 15mL of CNCs, and performing ultrasonic dispersion for 10min to obtain a CNCs suspension;
3) mixing the CNCs suspension obtained in the step 2) according to the volume ratio of 1 mL: adding 2g of the mixture into the modified PEG polymer obtained in the step 1), raising the temperature to 90 ℃, reacting for 10 hours under the protection of nitrogen, stopping the reaction by using ethanol, washing, centrifuging, and drying to obtain the nano cellulose crystal-polyethylene glycol composite material b with solid-solid phase modification performance.
Example 3
1) The molar ratio of the raw materials is 1: 1, mixing maleic anhydride and PEG with the molecular weight of 1000g/mol, fully melting and mixing under the protection of nitrogen at 75 ℃, adding 3mg of benzenesulfonic acid, and reacting for 3 hours to obtain a modified PEG polymer;
2) according to the mass ratio of 1: 5 ferrous sulfate (FeSO)4) Mixing with 30% hydrogen peroxide according to a solid-liquid ratio of 1 g: adding 25mL of CNCs, and performing ultrasonic dispersion for 7min to obtain a CNCs suspension;
3) mixing the CNCs suspension obtained in the step 2) according to the volume ratio of 1 mL: adding 5g of the modified PEG polymer obtained in the step 1), raising the temperature to 100 ℃, reacting for 6 hours under the protection of nitrogen, stopping the reaction by using ethanol, washing, centrifuging, and drying to obtain the nano cellulose crystal-polyethylene glycol composite material c with solid-solid phase modification performance.
Example 4
1) The molar ratio of the components is 3: 1, mixing maleic anhydride and PEG with the molecular weight of 4000g/mol, fully melting and mixing under the protection of nitrogen at 70 ℃, adding 2mg of tin isooctanoate, and reacting for 2 hours to obtain a modified PEG polymer;
2) according to the mass ratio of 1:3 ferrous sulfate (FeSO)4·7H2O) and 30% hydrogen peroxide, wherein the solid-liquid ratio is 1 g: adding 15mL of CNCs, and performing ultrasonic dispersion for 6min to obtain a CNCs suspension;
3) mixing the CNCs suspension obtained in the step 2) according to the volume ratio of 1 mL: adding 2g of the mixture into the modified PEG polymer obtained in the step 1), raising the temperature to 70 ℃, reacting for 24 hours under the protection of nitrogen, stopping the reaction by using ethanol, washing, centrifuging and drying to obtain the nano cellulose crystal-polyethylene glycol composite material d with solid-solid phase modification performance.
Example 5
1) The molar ratio of the raw materials is 1: 1, mixing maleic anhydride and PEG with the molecular weight of 800g/mol, fully melting and mixing under the protection of nitrogen at 75 ℃, adding 1mg of p-toluenesulfonic acid, and reacting for 1h to obtain a modified PEG polymer;
2) according to the mass ratio of 1:3 copper sulfate (CuSO)4·5H2O) and 25% hydrogen peroxide, and mixing the mixture according to the solid-liquid ratio of 1 g: adding 15mL of CNCs, and performing ultrasonic dispersion for 5min to obtain a CNCs suspension;
3) mixing the CNCs suspension obtained in the step 2) according to the volume ratio of 1 mL: adding 5g of the mixture into the modified PEG polymer obtained in the step 1), raising the temperature to 100 ℃, reacting for 12h under the protection of nitrogen, stopping the reaction by using ethanol, washing, centrifuging, and drying to obtain the nano cellulose crystal-polyethylene glycol composite material e with solid-solid phase modification performance.
The phase transition performance of the nano-crystalline cellulose-polyethylene glycol solid-solid phase change material obtained by the invention is tested by a Differential Scanning Calorimeter (DSC), and the test result of the Differential Scanning Calorimeter (DSC) shows that the nano-crystalline cellulose-polyethylene glycol solid-solid phase change material prepared by the invention has proper phase transition temperature and certain phase transition enthalpy, which is shown in figure 1.
The nano-crystalline cellulose-polyethylene glycol solid-solid phase change material prepared by the method has excellent phase change temperature and phase change enthalpy, and has wide application prospect in the aspects of latent heat energy storage technology and the like.
Claims (4)
1. A preparation method of an aqueous phase free radical polymerization nano cellulose crystal-polyethylene glycol solid-solid phase change material is characterized by comprising the following steps:
1) mixing maleic anhydride and PEG in proper molar ratio, fully melting and mixing under the protection of nitrogen at 55-75 ℃, adding a certain amount of catalyst, and reacting for 1-3h to obtain a modified PEG polymer;
2) mixing sulfate and hydrogen peroxide with proper concentration, adding CNCs with proper solid-liquid ratio, and performing ultrasonic dispersion for 5-10min to obtain CNCs suspension; the mass ratio of the sulfate to the hydrogen peroxide is 1: 3-5, wherein the sulfate refers to one of copper sulfate, copper sulfate pentahydrate, ferrous sulfate heptahydrate and ferrous ammonium sulfate hexahydrate;
3) adding the CNCs suspension obtained in the step 2) into the modified PEG polymer obtained in the step 1) according to a proper proportion, raising the temperature to 70-100 ℃, reacting for 6-24h under the protection of nitrogen, stopping the reaction with ethanol, washing with water, centrifuging, and drying to obtain the nano cellulose crystal-polyethylene glycol composite material with solid-solid phase modification performance.
2. The preparation method of the aqueous phase free radical polymerization nano cellulose crystal-polyethylene glycol solid-solid phase change material according to claim 1, characterized in that: the appropriate molar ratio in step 1) is 1-3: PEG has a molecular weight of: 800-4000g/mol, the certain amount is 1-3mg, and the catalyst is one of tin isooctanoate, benzenesulfonic acid and p-toluenesulfonic acid.
3. The preparation method of the aqueous phase free radical polymerization nano cellulose crystal-polyethylene glycol solid-solid phase change material according to claim 1, characterized in that: in the step 2), the proper concentration of the hydrogen peroxide is 25-30%, and the proper solid-to-liquid ratio is 1 g: 15-25 mL.
4. The preparation method of the aqueous phase free radical polymerization nano cellulose crystal-polyethylene glycol solid-solid phase change material according to claim 1, characterized in that: the appropriate proportion in step 3) is 1 mL: 2-5 g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910583422.9A CN110257010B (en) | 2019-07-01 | 2019-07-01 | Preparation method of water-phase free radical polymerization nanocellulose crystal-polyethylene glycol solid-solid phase change material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910583422.9A CN110257010B (en) | 2019-07-01 | 2019-07-01 | Preparation method of water-phase free radical polymerization nanocellulose crystal-polyethylene glycol solid-solid phase change material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110257010A CN110257010A (en) | 2019-09-20 |
| CN110257010B true CN110257010B (en) | 2020-12-18 |
Family
ID=67923455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910583422.9A Active CN110257010B (en) | 2019-07-01 | 2019-07-01 | Preparation method of water-phase free radical polymerization nanocellulose crystal-polyethylene glycol solid-solid phase change material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110257010B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279927A (en) * | 2020-11-04 | 2021-01-29 | 暨南大学 | Carboxyl nano-cellulose, preparation method and application thereof |
| CN112770487B (en) * | 2020-12-31 | 2022-01-28 | 深圳市捷安纳米复合材料有限公司 | Flexible composite circuit board with virus killing function and manufacturing process thereof |
| CN113637459B (en) * | 2021-07-13 | 2022-07-12 | 中南大学 | Preparation method of composite mineral microsphere-based phase-change heat storage material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710012A (en) * | 2005-06-29 | 2005-12-21 | 中国科学院广州化学研究所 | Nano cellulose solid-solid phase transition material and its preparing method |
| CN101519581A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院化学研究所 | Phase change energy storage material and preparation method thereof |
| CN101967697A (en) * | 2010-10-20 | 2011-02-09 | 东华大学 | Method for preparing biodegradable solid-solid phase transition nano fibers or fiber membranes |
| CN102276843A (en) * | 2011-06-14 | 2011-12-14 | 东华大学 | Method for preparing solvent-free solid-solid phase change energy storage material |
| CN107620212A (en) * | 2017-09-18 | 2018-01-23 | 武汉纺织大学 | The preparation method of phase transformation nanofiber |
| CN108360080A (en) * | 2018-02-12 | 2018-08-03 | 天津工业大学 | A kind of cellulose-acrylate base solid-solid phase transition material and preparation method thereof |
-
2019
- 2019-07-01 CN CN201910583422.9A patent/CN110257010B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710012A (en) * | 2005-06-29 | 2005-12-21 | 中国科学院广州化学研究所 | Nano cellulose solid-solid phase transition material and its preparing method |
| CN101519581A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院化学研究所 | Phase change energy storage material and preparation method thereof |
| CN101967697A (en) * | 2010-10-20 | 2011-02-09 | 东华大学 | Method for preparing biodegradable solid-solid phase transition nano fibers or fiber membranes |
| CN102276843A (en) * | 2011-06-14 | 2011-12-14 | 东华大学 | Method for preparing solvent-free solid-solid phase change energy storage material |
| CN107620212A (en) * | 2017-09-18 | 2018-01-23 | 武汉纺织大学 | The preparation method of phase transformation nanofiber |
| CN108360080A (en) * | 2018-02-12 | 2018-08-03 | 天津工业大学 | A kind of cellulose-acrylate base solid-solid phase transition material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Characterization of Carboxylated Cellulose Nanocrytals Isolated;Roya Koshani et al.;《Journal of Agricultural and Food Chemistry》;20180705;第7693-7695页 * |
| Free radical graft copolymerization of nanofibrillated cellulose with;Kuisma Littunena et al.;《Carbohydrate Polymers》;20101225;第1039–1047页 * |
| H202-Induced Graft Polymerization of Acrylic Acid on;A. HEBEISH et al.;《Journal of Applied Polymer Science》;19811231;第3245-3251页 * |
| Network formation of nanofibrillated cellulose in solution blended poly(methyl;Kuisma Littunen et al.;《Carbohydrate Polymers》;20120818;第183–190页 * |
| Synthesis and Characterization of Storage Energy Materials;Xiao Ping YUAN et al.;《Chinese Chemical Letters》;20061231;第17卷(第8期);第1129-1132页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110257010A (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110257010B (en) | Preparation method of water-phase free radical polymerization nanocellulose crystal-polyethylene glycol solid-solid phase change material | |
| Gao et al. | Fabrication of lignin based renewable dynamic networks and its applications as self-healing, antifungal and conductive adhesives | |
| Wu et al. | Preparation and characterization of side-chain liquid crystal polymer/paraffin composites as form-stable phase change materials | |
| Cao et al. | Phase change materials based on comb-like polynorbornenes and octadecylamine-functionalized graphene oxide nanosheets for thermal energy storage | |
| CN103484064B (en) | A kind of thermoplastic cellulose base solid-solid phase transition material and preparation method thereof | |
| CN102838085B (en) | High-capacity high-molecular polymer hydrogen storing material and preparation method thereof | |
| Mu et al. | Synthesis and thermal properties of poly (styrene-co-acrylonitrile)-graft-polyethylene glycol copolymers as novel solid–solid phase change materials for thermal energy storage | |
| CN106432656B (en) | Preparation method based on the poly- porphyrin of semi-rigid monolithic three dimensional | |
| CN102977292B (en) | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface | |
| CN110804301A (en) | Polyethylene glycol/hydroxypropyl cellulose carbon nanotube composite solid-solid phase change material and preparation method thereof | |
| Mu et al. | A novel solid-solid phase change material based on poly (styrene-co-acrylonitrile) grafting with palmitic acid copolymers | |
| CN104211863A (en) | Preparation method and application of free nitroxide radical polymer brush polymerization inhibitor | |
| Zhang et al. | Grafting polymers from cellulose nanocrystals via surface‐initiated atom transfer radical polymerization | |
| CN105037724A (en) | Hyperbranched polyimide containing alkynyl group, and preparation method and application thereof | |
| CN105482078A (en) | Rosin-based epoxy resin curing agent and its preparation method and use | |
| Ge et al. | Thermal properties and shape stabilization of epoxidized methoxy polyethylene glycol composite PCMs tailored by polydopamine-functionalized graphene oxide | |
| CN110835402B (en) | Low-viscosity bio-based epoxy resin based on vanillin and preparation method thereof | |
| CN102336998A (en) | Functional epoxy-modified polyethylene material | |
| CN104003926A (en) | Alkyl ammonium salt-based side chain type magnetic monomer and polymer as well as preparation method and application thereof | |
| CN110628033B (en) | Polyimide grafted polyethylene glycol composite solid-solid phase change material and preparation method thereof | |
| CN110817857B (en) | Modified graphene and n-octadecane phase change composite material and preparation method thereof | |
| CN110903606A (en) | Plant oil-based composite material and preparation method thereof | |
| CN110305634A (en) | A kind of preparation method of carbon ball base composite phase-change material | |
| CN101148501B (en) | Method for preparing polyhydroxy fatty acid ester with high thermal stability | |
| CN102504092A (en) | High molecular solid-to-solid phase transition energy storage material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |