CN105482430A - Method for preparing polyethylene glycol (PEG) phase transition material through sol-gel method - Google Patents
Method for preparing polyethylene glycol (PEG) phase transition material through sol-gel method Download PDFInfo
- Publication number
- CN105482430A CN105482430A CN201510838982.6A CN201510838982A CN105482430A CN 105482430 A CN105482430 A CN 105482430A CN 201510838982 A CN201510838982 A CN 201510838982A CN 105482430 A CN105482430 A CN 105482430A
- Authority
- CN
- China
- Prior art keywords
- peg
- certain amount
- phase transition
- warming
- sol
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a polyethylene glycol (PEG) phase transition material and a preparation method thereof. The composite phase transition material contains phosphor, nitrogen and silicon. The composite PEG phase transition material containing phosphor, nitrogen and silicon is prepared from graphite oxide, cyanuric chloride, an organic phosphoryl chloride compound, amino siloxane and PEG as raw materials through a sol-gel method. The phase transition material PEG in the same skeletal material can improve high temperature resistance and a seepage prevention capability. The use amount of the PEG is variable. The prepared skeletal material can be added into a polymer so that material flame retardation performances are improved.
Description
Technical field
The present invention relates to a kind of method utilizing sol-gel method to prepare high thermal stability PEG phase change material, belong to phase change material field.
Background technology
So-called phase change material is exactly that material can absorb energy, otherwise then releases energy when the fusing point of envrionment temperature higher than material.The energy of a large amount of form can be undertaken storing thus being reused by latent heat phase-changing energy storage material, heat energy of such as sun power, Geothermal energy and industrial waste etc.Polyoxyethylene glycol (PEG) has suitable transformation temperature because of it, without surfusion, nontoxic, high latent heat, and the advantage such as good chemical stability, thus becomes the focus instantly studied.
But PEG easily reveals in phase transition process, the shortcoming such as low and inflammableness of the capacity of heat transmission makes it be restricted in actual applications.The superfine capillary attraction of aerosil hole, employing chemical graft and the sol-gel method of utilizing of Zheng has prepared PEG/SiO2 composite phase-change material (South China Science & Engineering University, 2013) respectively; ChongyunWang etc. adopt the expanded graphite of three kinds of Different Pore Structures, gac, ordered mesoporous carbon material is prepared into composite phase-change material with PEG respectively, selection for porous material proposes experimental foundation (SolarEnergyMaterialsandSolarCells, 2012,105:21-26).But select inorganic materials can reduce the latent heat of phase change material as skeletal support material, affect the energy-storage property of material.Phase change material also can utilize organic polymer material as body material, but organic materials inflammableness in actual applications limits it in many-sided use.Therefore, the flame retardant properties improving material seems particularly important.Now fire-retardant at preparation collection, heat conduction, energy storage still lacks cost-effective method in the PEG matrix material aspect of one.
Silica-based fire retardant is acknowledged as desirable halogen-free flame retardants (PolymerDegradationandStability, 2009,94:465-495), and siloxanes can form polyfunctional material as support of the catalyst, porous material and fire retardant (AngewandteChemieInternationalEdition, 2006,45:3216-3251).Therefore, if having siloxanes in flame-retardant composition contained by material, then this material is expected to the matrix material (simultaneously possessing the thermotolerance of inorganic materials and the compatibility of organic materials) becoming applicable stored energy application.
Summary of the invention
The invention provides a kind of high thermal stability PEG phase change composite material.Wherein skeleton structure type is as follows: (wherein G represents oxidized graphite flake Rotating fields)
In formula, R is Cl, NH
2, or be the group that can react with amino as phosphoryl chloride, carboxyl, isocyanic ester, polyethylene polyamine, polymeric amide, polyetheramine, phenolic aldehyde amine, epoxy group(ing), sulfonic group etc.;
R ' is phenyl or chlorine; R 〞 is oxygen or sulphur.
The present invention also provides a kind of high thermal stability PEG phase change composite material preparation method, specifically comprises the steps:
(1) take GO as raw material, add N, dinethylformamide (DMF), dropwise thionyl chloride is added while stirring under normal temperature, then 50 ~ 80 DEG C are warming up to, centrifugal removing thionyl chloride after 12 ~ 24h, then wash repeatedly with trichloromethane dried in advance, last 50 ~ 80 DEG C of oven dry obtain intermediate I;
(2) Cynuric Chloride (CAC) is scattered in the acetone and deionized water of refrigeration, abundant stirring, keep solution temperature between 0 ~ 5 DEG C, drip ammoniacal liquor (time for adding controls in 20 ~ 40min), filter after reaction 30 ~ 60min, obtain product 2-amino-4,6-bis-chloro-1,3,5-triazine (ADCT) i.e. intermediate II;
(3) a certain amount of intermediate I and intermediate II are scattered in DMF solution, and after adding triethylamine, mix and blend 24 ~ 30h at 70 ~ 90 DEG C, finally obtains intermediate III with the deionized water centrifuge washing of ethanol and refrigeration;
(4) in intermediate III, add the acetone through refrigeration, deionized water, utilize separating funnel to drip ammoniacal liquor, be warming up to 70 ~ 90 DEG C of reaction 1 ~ 2h after dropwising, last 70 ~ 90 DEG C of oven dry obtain intermediate IV;
(5) a certain amount of triethylamine and diphenylphosphoryl dichloro to join in there-necked flask and pass to nitrogen protection.Intermediate IV is scattered in a certain amount of trichloromethane, dropwise joins in there-necked flask.Add a certain amount of aminopropyl triethoxysilane (KH550) after mix and blend 24 ~ 36h under room temperature, stir after 2 ~ 5h and be warming up to 50 ~ 60 DEG C, remix stirs 3 ~ 5h, finally centrifugally obtains intermediate V;
(6) a certain amount of polyoxyethylene glycol (2000 ~ 4000) (PEG) is dissolved in a certain amount of deionized water, stirred at ambient temperature 2 ~ 3h.Intermediate V is scattered in a certain amount of dehydrated alcohol, and is slowly added drop-wise in the aqueous solution of PEG after ultrasonic 1 ~ 5min, adds a certain amount of 28%NH under normal temperature after mix and blend 24 ~ 36h
3h
2o, stirs 24 ~ 36h after being warming up to 50 ~ 60 DEG C again, utilize in this process sol-gel method achieve by coated for PEG enter framework material vesicular structure in, final mixture proceeds to beaker, and 60 ~ 70 DEG C are dried to constant weight and obtain compound PEG phase change material.
Advantage of the present invention:
(1) PEG can realize improving heat-resisting ability, leak-preventing ability in same framework material simultaneously;
(2) obtained framework material can add in macromolecular material the flame retardant properties improving material;
(3) add-on of PEG can be flexible and changeable.
As seen from Figure 1,3438cm
-1near be the stretching vibration peak of O-H, 2960cm
-1and 2850cm
-1near be respectively-CH
3-and-CH
2-antisymmetric stretching vibration absorption peak and symmetrical stretching vibration absorption peak, 1630cm
-1and 1440cm
-1near be respectively-CH
3-and-CH
2-formation vibration absorption peak, 1261cm
-1near be the stretching vibration absorption peak of P=O, 1029cm
-1near be the stretching vibration absorption peak of P-O-C, 924cm
-1near be the absorption peak of P-N, 694cm
-1near be the stretching vibration absorption peak of P-C, 1110cm
-1near be the stretching vibration absorption peak of Si-O-Si, 806cm
-1near be the formation vibration absorption peak of triazine ring skeleton.The characteristic IR absorbance peaks of framework material is there is in this molecular structure of above-mentioned data declaration.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of the framework material of the embodiment of the present invention 2.
Embodiment
The present invention can further illustrate in conjunction with the embodiments
Embodiment 1
Take the GO0.20g prepared in advance and be placed in 250ml there-necked flask, add the DMF (DMF) of 1ml wherein, open and slowly stir, slowly drip 50ml thionyl chloride (SOCl with constant pressure funnel to above-mentioned system
2), be then warming up to 70 DEG C of reaction 24h, the reaction product intermediate I obtained;
Take 4.00gCAC be placed in condition of ice bath under 250ml flask, slowly add successively through refrigeration 50ml acetone and 50ml deionized water, after magnetic agitation, form uniform suspension, in the process keep 0 DEG C.Be that the ammoniacal liquor of 1mol/L is slowly added drop-wise in above-mentioned suspension under the help of dropping funnel again by 100ml concentration, keep 0 ~ 5 DEG C to react 30min.After filtration, washing and 50 DEG C of dryings obtain product A DCT and intermediate II;
Intermediate I and intermediate II, under the existence of 50mlDMF and 669ul triethylamine, are heated to 85 DEG C of stirring reaction 30h and obtain intermediate III;
In intermediate III, add the 35ml acetone through refrigeration, 40ml deionized water, then slowly dripping 60ml concentration is the ammoniacal liquor of 1mol/L, and be warming up to 85 DEG C of reaction 1h after dropwising, last 85 DEG C of oven dry obtain intermediate IV;
200ul triethylamine and 10ml trichloromethane to join in 250ml there-necked flask and pass to nitrogen protection, then add 200ul diphenylphosphoryl dichloro.Intermediate IV is scattered in 50ml trichloromethane, dropwise slowly joins in there-necked flask.Add 670ulKH550 and 400ul triethylamine after mix and blend 24h under room temperature, stir after 2h and be warming up to 50 DEG C, close nitrogen, remix stirs 3h, finally centrifugally obtains intermediate V;
0.10gPEG2000 is dissolved in 20ml deionized water, stirred at ambient temperature 2h.Intermediate V is scattered in 20ml dehydrated alcohol, and be slowly added drop-wise in the aqueous solution of PEG after ultrasonic 1min, add the ammoniacal liquor of 1ml28% under normal temperature after mix and blend 24h, after being warming up to 60 DEG C, stir 24h again, final mixture proceeds to beaker, and 60 DEG C are dried to constant weight and obtain PEG matrix material.The enthalpy change value of gained matrix material is 88.12J/g.
Embodiment 2
Intermediate V is prepared according to the method in embodiment 1 and consumption;
0.15gPEG2000 is dissolved in 20ml deionized water, stirred at ambient temperature 2h.Intermediate V is scattered in 20ml dehydrated alcohol, and be slowly added drop-wise in the aqueous solution of PEG after ultrasonic 1min, add the ammoniacal liquor of 1ml28% under normal temperature after mix and blend 24h, after being warming up to 60 DEG C, stir 24h again, final mixture proceeds to beaker, and 60 DEG C are dried to constant weight and obtain PEG matrix material.The enthalpy change value of gained matrix material is 102.1J/g.
Embodiment 3
Intermediate V is prepared according to the method in embodiment 1 and consumption;
0.20gPEG2000 is dissolved in 20ml deionized water, stirred at ambient temperature 2h.Intermediate V is scattered in 20ml dehydrated alcohol, and be slowly added drop-wise in the aqueous solution of PEG after ultrasonic 1min, add the ammoniacal liquor of 1ml28% under normal temperature after mix and blend 24h, after being warming up to 60 DEG C, stir 24h again, final mixture proceeds to beaker, and 60 DEG C are dried to constant weight and obtain PEG matrix material.The enthalpy change value of gained matrix material is 63.19J/g.
Claims (2)
1. the method utilizing sol-gel method to prepare polyoxyethylene glycol (PEG) phase change material, it is characterized in that, utilize the hydrolytic process of KH550, be coated to by PEG in the pore structure of framework material simultaneously and go, wherein framework material structure is as follows: (wherein G represents oxidized graphite flake Rotating fields)
In formula, R is Cl, NH
2, or be the group that can react with amino as phosphoryl chloride, carboxyl, isocyanic ester, polyethylene polyamine, polymeric amide, polyetheramine, phenolic aldehyde amine, epoxy group(ing), sulfonic group etc.;
R ' is phenyl or chlorine; R 〞 is oxygen or sulphur.
2. a kind of method utilizing sol-gel method to prepare PEG phase change material as claimed in claim 1, is characterized in that, the steps include:
(1) take GO as raw material, add N, dinethylformamide (DMF), dropwise thionyl chloride is added while stirring under normal temperature, then 50 ~ 80 DEG C are warming up to, centrifugal removing thionyl chloride after 12 ~ 24h, then wash repeatedly with trichloromethane dried in advance, last 50 ~ 80 DEG C of oven dry obtain intermediate I;
(2) Cynuric Chloride (CAC) is scattered in the acetone and deionized water of refrigeration, abundant stirring, keep solution temperature between 0 ~ 5 DEG C, drip ammoniacal liquor (time for adding controls in 20 ~ 40min), filter after reaction 30 ~ 60min, obtain product 2-amino-4,6-bis-chloro-1,3,5-triazine (ADCT) i.e. intermediate II;
(3) a certain amount of intermediate I and intermediate II are scattered in DMF solution, and after adding triethylamine, mix and blend 24 ~ 30h at 70 ~ 90 DEG C, finally obtains intermediate III with the deionized water centrifuge washing of ethanol and refrigeration;
(4) in intermediate III, add the acetone through refrigeration, deionized water, utilize separating funnel to drip ammoniacal liquor, be warming up to 70 ~ 90 DEG C of reaction 1 ~ 2h after dropwising, last 70 ~ 90 DEG C of oven dry obtain intermediate IV;
(5) a certain amount of triethylamine and diphenylphosphoryl dichloro to join in there-necked flask and pass to nitrogen protection; Intermediate IV is scattered in a certain amount of trichloromethane, dropwise joins in there-necked flask; Add a certain amount of aminopropyl triethoxysilane (KH550) after mix and blend 24 ~ 36h under room temperature, stir after 2 ~ 5h and be warming up to 50 ~ 60 DEG C, remix stirs 3 ~ 5h, finally centrifugally obtains intermediate V;
(6) a certain amount of polyoxyethylene glycol (2000 ~ 20000) (PEG) is dissolved in a certain amount of deionized water, stirred at ambient temperature 2 ~ 3h; Intermediate V is scattered in a certain amount of dehydrated alcohol, and be slowly added drop-wise in the aqueous solution of PEG after ultrasonic 1 ~ 5min, a certain amount of ammoniacal liquor is added after mix and blend 24 ~ 36h under normal temperature, 24 ~ 36h is stirred again after being warming up to 50 ~ 60 DEG C, utilize in this process sol-gel method achieve by coated for PEG enter framework material vesicular structure in, final mixture proceeds to beaker, and 60 ~ 70 DEG C are dried to constant weight and obtain compound PEG phase change material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510838982.6A CN105482430B (en) | 2015-11-27 | 2015-11-27 | A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510838982.6A CN105482430B (en) | 2015-11-27 | 2015-11-27 | A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105482430A true CN105482430A (en) | 2016-04-13 |
CN105482430B CN105482430B (en) | 2017-10-03 |
Family
ID=55669718
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510838982.6A Expired - Fee Related CN105482430B (en) | 2015-11-27 | 2015-11-27 | A kind of method that utilization sol-gal process prepares polyethylene glycol phase-change material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105482430B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107987320A (en) * | 2017-12-29 | 2018-05-04 | 青岛合家兴工贸有限公司 | A kind of aza synergistic expanding fire retardant of phosphorus and preparation method thereof |
CN114940889A (en) * | 2022-05-25 | 2022-08-26 | 大连理工大学 | Composite phase change energy storage material with temperature-sensitive conductive characteristic and preparation method and application thereof |
CN116515120A (en) * | 2023-06-07 | 2023-08-01 | 中石油(上海)新材料研究院有限公司 | Polyamide elastomer containing triazine ring and preparation method thereof |
CN117511514A (en) * | 2024-01-04 | 2024-02-06 | 西南石油大学 | Flame-retardant polyvinyl alcohol aerogel phase-change material and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1793277A (en) * | 2006-01-06 | 2006-06-28 | 华南理工大学 | Process for preparing compound forming phase changing material of polyethyldiol/silicon dioxide |
CN102391441A (en) * | 2011-09-23 | 2012-03-28 | 大连工业大学 | Preparation method of solid-solid phase-change material immobilized by chemical cross-linking method |
CN103623709A (en) * | 2013-11-11 | 2014-03-12 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
-
2015
- 2015-11-27 CN CN201510838982.6A patent/CN105482430B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1793277A (en) * | 2006-01-06 | 2006-06-28 | 华南理工大学 | Process for preparing compound forming phase changing material of polyethyldiol/silicon dioxide |
CN102391441A (en) * | 2011-09-23 | 2012-03-28 | 大连工业大学 | Preparation method of solid-solid phase-change material immobilized by chemical cross-linking method |
CN103623709A (en) * | 2013-11-11 | 2014-03-12 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
CHONGYUN WANG ET AL.: "Shape-stabilized phase change materials based on polyethylene glycol/porous carbon composite:The influence of the pore structure of the carbon materials", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107987320A (en) * | 2017-12-29 | 2018-05-04 | 青岛合家兴工贸有限公司 | A kind of aza synergistic expanding fire retardant of phosphorus and preparation method thereof |
CN107987320B (en) * | 2017-12-29 | 2019-08-09 | 青岛合家兴工贸有限公司 | A kind of aza synergistic expanding fire retardant of phosphorus and preparation method thereof |
CN114940889A (en) * | 2022-05-25 | 2022-08-26 | 大连理工大学 | Composite phase change energy storage material with temperature-sensitive conductive characteristic and preparation method and application thereof |
CN116515120A (en) * | 2023-06-07 | 2023-08-01 | 中石油(上海)新材料研究院有限公司 | Polyamide elastomer containing triazine ring and preparation method thereof |
CN116515120B (en) * | 2023-06-07 | 2024-01-26 | 中石油(上海)新材料研究院有限公司 | Polyamide elastomer containing triazine ring and preparation method thereof |
CN117511514A (en) * | 2024-01-04 | 2024-02-06 | 西南石油大学 | Flame-retardant polyvinyl alcohol aerogel phase-change material and preparation method thereof |
CN117511514B (en) * | 2024-01-04 | 2024-04-30 | 西南石油大学 | Flame-retardant polyvinyl alcohol aerogel phase-change material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN105482430B (en) | 2017-10-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105482430A (en) | Method for preparing polyethylene glycol (PEG) phase transition material through sol-gel method | |
Du et al. | Preparation and characterization of flame-retardant nanoencapsulated phase change materials with poly (methylmethacrylate) shells for thermal energy storage | |
CN103374333B (en) | Composite phase change material | |
CN107057026A (en) | A kind of polyurethane phase-change material for regulating and controlling polyethylene glycol containing functionalization graphene and preparation method thereof | |
CN102321452B (en) | Method for preparing cross-linked solid-solid phase change energy storage material | |
CN110564093B (en) | Adjustable fluorescent ion gel with multiple stimulus responsiveness | |
CN103980863B (en) | A kind of side chain liquid crystalline polymer composite shape-setting phase-change material and preparation method thereof | |
CN102408897A (en) | Expansible fire retardant having double-layer core-shell structure, and preparation method and application thereof | |
CN108865078A (en) | Phase-change material, yarn, fabric and wearing product for fabric based on microporous barrier | |
CN104650929A (en) | Halogen-free flame-retardant temperature controlled microcapsules and preparation method thereof | |
CN101280024B (en) | Cationic polysaccharide derivates and preparation thereof | |
CN102888062B (en) | Heat exchange heterogeneous composite film and preparation method thereof | |
CN103012297A (en) | Cyanate ester and polymer containing s-triazine structure and preparation methods of cyanate ester and polymer | |
CN104629692A (en) | Preparation method of inorganic-organic composite phase-change energy storage material for buildings | |
CN104371659A (en) | Attapulgite-base composite phase-change heat storage material and preparation method thereof | |
CN104910852A (en) | Preparation method of nano TiO2 modified carbonate polyurethane adhesive | |
CN105153206B (en) | Two HMeQ[6] microporous supermolecular frame materials as well as preparation and application thereof | |
CN103483284A (en) | Aluminium dihydrogen phosphate melamine salt and preparation method thereof | |
CN105505108A (en) | Waterborne fireproof coating and preparation method thereof | |
CN104130586B (en) | Grafted by super branched polymer SBS application in waterproof roll | |
CN105905929B (en) | The method that lithium carbonate is prepared from the carbonate type bittern of plateau | |
CN105648578A (en) | Solid-solid phase-change composite fiber with skin-core structure and online cross-linked core layer and preparation method of solid-solid phase-change composite fiber | |
CN114958310B (en) | Phase-change cooling-anti-icing material and preparation method thereof | |
CN102974235B (en) | Preparation method of thermoplastic polyimide microporous film | |
CN104371665B (en) | One kind is without flexible spacer side chain liquid crystalline polymer composite shape-setting phase-change material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171003 Termination date: 20211127 |