CN1865322A - Method for preparing solid-solid phase conversion material using polyglycol and terylene graft copolymerization technology - Google Patents
Method for preparing solid-solid phase conversion material using polyglycol and terylene graft copolymerization technology Download PDFInfo
- Publication number
- CN1865322A CN1865322A CN 200610040067 CN200610040067A CN1865322A CN 1865322 A CN1865322 A CN 1865322A CN 200610040067 CN200610040067 CN 200610040067 CN 200610040067 A CN200610040067 A CN 200610040067A CN 1865322 A CN1865322 A CN 1865322A
- Authority
- CN
- China
- Prior art keywords
- terylene
- polyoxyethylene glycol
- solid
- graft copolymerization
- solid phase
- 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Graft Or Block Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a polietilenglicol and solid-phase material transition method of polyester grafted copolymerization, which is characterized by the following: adapting carbowax, polyester fiber, crosslinking phthalandione and catalyst concentrated sulfuric acid as raw material; forming carbowax or polyester fiber grafted copolymerization solid-phase material transition material through macromolecular grafting polymerization reaction and connecting polietilenglicol and polyester fiber. The invention displays stable property, which is easy to control.
Description
Technical field
The present invention relates to a kind of method of utilizing polyoxyethylene glycol and terylene graft copolymerization to prepare solid-solid phase change material.
Background technology
The major advantage of polymer solid-solid phase change material is not occur liquid state before and after the phase transformation; When solid-solid phase change material changes mutually, high tens of times of the thermal capacitance of ratio of specific heats water; Utilize the characteristic of phase change material simultaneously, can be used for the regulation and control of temperature at the transformation temperature approximately constant.At present similarly solid-solid phase change material polyoxyethylene glycol/cellulose acetate, polyoxyethylene glycol/chitosan are synthetic, but polyoxyethylene glycol and chitosan solid-solid phase change material are not suitable for as battery heat absorption pond, polyoxyethylene glycol and cellulose acetate solid-solid phase change material production cost height, the catalyzer and the linking agent that adopt cost an arm and a leg, speed of response is too fast wayward, easily form the build molecule, big for environment pollution, linking agent is difficult to buy and preserve on market.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide method that a kind of polyoxyethylene glycol and terylene graft copolymerization prepare solid-solid phase change material by macromolecular grafted copolyreaction, select cheap starting material, suitable cross-linking system, by chemical bond polyoxyethylene glycol and terylene are coupled together, form polyoxyethylene glycol/terylene graft copolymerization solid-solid phase change material.
The present invention realizes with following technical scheme: a kind of polyoxyethylene glycol and terylene graft copolymerization prepare the method for solid-solid phase change material, it is characterized in that with polyoxyethylene glycol, terylene, linking agent phthalic acid, the catalyzer vitriol oil be raw material, by macromolecular grafted copolyreaction, by chemical bond polyoxyethylene glycol and terylene are coupled together, form polyoxyethylene glycol/terylene graft copolymerization solid-solid phase change material, the two ends of peg molecule are bound by on the inflexible terylene molecular chain by chemical bond or Intermolecular Forces in this material.Terylene only is inert support in material.Under the polyoxyethylene glycol melting temperature, the energy shortage of molecular heat vibration to be destroying this chemical bond, and peg molecule can not break away from constraint and can't free shift, so polyoxyethylene glycol can not become liquid state.But the bound peg molecule in two ends is still rotatable and vibration, can form amorphous state and crystalline state with the lifting of temperature and solid solid transformation occur.
Concrete processing step is as follows:
(1) terylene solution+linking agent+catalyzer is added in the reactor stirring and refluxing pre-reaction 20min under 40 ℃ of conditions;
(2) add polyglycol solution, keep 2-3h at 100 ℃ under the magnetic agitation, fully reaction;
(3) suction filtration;
(4) solids is placed the room temperature deionized water soak 24-36h;
(5) after the filtration, solids is placed the dry moisture of removing of a conventional oven, place vacuum drying oven dry 24h under 100 ℃ at last, promptly get the polyoxyethylene glycol and the terylene solid-solid phase change material of graft copolymerization.
Wherein, the quality proportioning of polyoxyethylene glycol and terylene is 95: 5, and the quantity of the contained carboxylate radical of linking agent Tetra hydro Phthalic anhydride is 1.1 times of hydroxyl in polyoxyethylene glycol and the terylene, and the consumption of the catalyzer vitriol oil is 0.2% of a Tetra hydro Phthalic anhydride consumption.
Above-mentioned terylene solution is the molecular weight solution that to be 15000 POLYESTER YARNS and dimethyl sulfoxide (DMSO) be made into 1/20 mass ratio.
Above-mentioned polyglycol solution is the molecular weight solution that to be 10000 polyoxyethylene glycol and dimethyl sulfoxide (DMSO) be made into 1/3 mass ratio.
The above-mentioned vitriol oil is a catalyzer, is 98% the analytical pure vitriol oil, and consumption is 0.2% of a Tetra hydro Phthalic anhydride consumption.
Above-mentioned polyoxyethylene glycol, POLYESTER YARNS, dimethyl sulfoxide (DMSO), Tetra hydro Phthalic anhydride are technical grade product.The invention has the beneficial effects as follows:
Chemical graft copolymerization synthetic polyoxyethylene glycol and terylene graft copolymerization solid-solid phase change material be than the good stability of physical blending, and long service life is because polyoxyethylene glycol is connected by chemical bond with terylene rather than by connections such as secondary or physical bond hydrogen bonds; Transportation, low-cost starting material polyoxyethylene glycol, textile industry have been selected on market, to be easy to buy and have preserved with POLYESTER YARNS, Tetra hydro Phthalic anhydride, the vitriol oil etc., so polyoxyethylene glycol/terylene solid solid transformation lower cost for material.Selected suitable cheap graft copolymerization linking agent, the catalyzer of reactive behavior; The terylene of simultaneously same quality also lacks than cellulose acetate, the contained hydroxyl of chitosan, so the terylene chemically reactive is little; Select for use the temperature of graft reaction lower than other cross-linking system, so the polyoxyethylene glycol and the terylene solid-solid phase change material that generate are particulate state rather than gel, so under all identical situation of other condition, the restraining function of the suffered cross-link bond of polyoxyethylene glycol is little, easier crystallization and dissolving, polyoxyethylene glycol/terylene solid solid transformation material phase transformation enthalpy is big; Cross-linking system does not adopt that severe toxicity is expensive, the toluene-2,4-diisocyanate that is difficult to preserve is as linking agent, and is most important to environment protection and workman's personal safe protection; Processing step and the plant and instrument implemented are simple, implement the production less investment.
Embodiment
Further illustrate the solution of the present invention and effect below in conjunction with embodiment.
At first be that 10000 polyoxyethylene glycol, molecular weight are 15000 POLYESTER YARNS, linking agent Tetra hydro Phthalic anhydride drying with molecular weight, then with dried polyoxyethylene glycol 9.5Kg, 0.5Kg terylene respectively with 28.5Kg and 10Kg dimethyl sulfoxide (DMSO) wiring solution-forming.In terylene solution, add the Tetra hydro Phthalic anhydride of 160.0g and the vitriol oil of 0.32g catalyzer 98%, mixed solution is pre-reaction 20min under the stirring and refluxing condition, the polyglycol solution that adds 9.5Kg at last, under magnetic agitation, mix the back and keep 2.5h at 100 ℃, allow it fully react, in reaction process, utilize density difference in time to remove and anhydrate.The reaction back mixture that reacts completely becomes the particulate state Off-white solid, behind the washing suction filtration 3～4 times, place the room temperature deionized water to soak more than the 24h milky white granules shape solid, remove free polyoxyethylene glycol and remaining dimethyl sulfoxide (DMSO), Tetra hydro Phthalic anhydride, catalyzer etc., place the baking oven finish-drying to remove moisture again, place vacuum drying oven dry 24h under 100 ℃ at last, promptly obtain the polyoxyethylene glycol and the terylene solid-solid phase change material of the graft copolymerization of milky white granules shape.
This stability of material is good, long service life.
The technical process of present embodiment is as follows: raw material drying dissolving → terylene solution+linking agent+catalyzer → backflow → reflux solution+polyglycol solution → crosslinking reaction → cooling washing → suction filtration → immersion → drying → milky white granules shape solid-solid phase change material → vacuum-drying → performance test.
Claims (5)
1, a kind of polyoxyethylene glycol and terylene graft copolymerization prepare the method for solid-solid phase change material, it is characterized in that with polyoxyethylene glycol, terylene, linking agent phthalic acid, the catalyzer vitriol oil be raw material, by macromolecular grafted copolyreaction, by chemical bond polyoxyethylene glycol and terylene are coupled together, form polyoxyethylene glycol/terylene graft copolymerization solid-solid phase change material
Specifically may further comprise the steps:
(1) terylene solution+linking agent+catalyzer is added in the reactor stirring and refluxing pre-reaction 20min under 40 ℃ of conditions;
(2) add polyglycol solution, keep 2-3h at 100 ℃ under the magnetic agitation, fully reaction;
(3) suction filtration;
(4) solids is placed the room temperature deionized water soak 24-36h;
(5) after the filtration, solids is placed the dry moisture of removing of a conventional oven, place vacuum drying oven dry 24h under 100 ℃ at last, promptly get the polyoxyethylene glycol and the terylene solid-solid phase change material of graft copolymerization;
Wherein, the quality proportioning of polyoxyethylene glycol and terylene is 95: 5, and the quantity of the contained carboxylate radical of linking agent Tetra hydro Phthalic anhydride is 1.1 times of hydroxyl in polyoxyethylene glycol and the terylene, and the consumption of the vitriol oil is 0.2% of a Tetra hydro Phthalic anhydride consumption.
2, the method for preparing solid-solid phase change material according to described a kind of polyoxyethylene glycol of claim 1 and terylene graft copolymerization is characterized in that described terylene solution is the molecular weight solution that to be 15000 POLYESTER YARNS and dimethyl sulfoxide (DMSO) be made into 1/20 mass ratio.
3, the method for preparing solid-solid phase change material according to described a kind of polyoxyethylene glycol of claim 1 and terylene graft copolymerization is characterized in that described polyglycol solution is the molecular weight solution that to be 10000 polyoxyethylene glycol and dimethyl sulfoxide (DMSO) be made into 1/3 mass ratio.
4, preparing the method for solid-solid phase change material according to described a kind of polyoxyethylene glycol of claim 1 and terylene graft copolymerization, it is characterized in that the described vitriol oil is a catalyzer, is 98% the analytical pure vitriol oil, and consumption is 0.2% of a Tetra hydro Phthalic anhydride consumption.
5, prepare the method for solid-solid phase change material according to described a kind of polyoxyethylene glycol of claim 1 and terylene graft copolymerization, it is characterized in that described polyoxyethylene glycol, POLYESTER YARNS, dimethyl sulfoxide (DMSO), Tetra hydro Phthalic anhydride are technical grade product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100400673A CN100436510C (en) | 2006-04-25 | 2006-04-25 | Method for preparing solid-solid phase conversion material using polyglycol and terylene graft copolymerization technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100400673A CN100436510C (en) | 2006-04-25 | 2006-04-25 | Method for preparing solid-solid phase conversion material using polyglycol and terylene graft copolymerization technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1865322A true CN1865322A (en) | 2006-11-22 |
| CN100436510C CN100436510C (en) | 2008-11-26 |
Family
ID=37424478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100400673A Expired - Fee Related CN100436510C (en) | 2006-04-25 | 2006-04-25 | Method for preparing solid-solid phase conversion material using polyglycol and terylene graft copolymerization technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100436510C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851336A (en) * | 2010-06-13 | 2010-10-06 | 大连工业大学 | Method for preparing shape-stabilized phase change material by using acrylic fiber waste silks |
| CN101386683B (en) * | 2008-10-07 | 2011-02-02 | 徐州工业职业技术学院 | Method for improving phase transition behavior of polyethyleneglycol/terylene solid-to-solid transition material using different molecular weight polyethyleneglycol eutectic |
| CN102978739A (en) * | 2012-12-25 | 2013-03-20 | 四川大学 | Preparation method of polyethylene glycol/polyvinyl alcohol phase change energy storage fiber by in situ crosslinking |
| CN103540294A (en) * | 2013-10-15 | 2014-01-29 | 徐州工业职业技术学院 | Method used for preparing solid-solid phase change material by polyethylene glycol/terylene physical blending |
| CN104831439A (en) * | 2015-05-11 | 2015-08-12 | 陆宝夫 | Mixed cotton blended yarn and preparation method and application thereof |
| CN108642599A (en) * | 2018-04-24 | 2018-10-12 | 苏州龙杰特种纤维股份有限公司 | Phase change fiber and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6454026A (en) * | 1987-08-24 | 1989-03-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of modified polyester |
| CN1079109C (en) * | 1999-09-08 | 2002-02-13 | 中国科学院广州化学研究所 | Reticular solid-solid phase change material and its preparing process |
| CN1079420C (en) * | 1999-09-21 | 2002-02-20 | 中国科学院广州化学研究所 | Pectinate solid-solid phase change material and its preparing process |
-
2006
- 2006-04-25 CN CNB2006100400673A patent/CN100436510C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386683B (en) * | 2008-10-07 | 2011-02-02 | 徐州工业职业技术学院 | Method for improving phase transition behavior of polyethyleneglycol/terylene solid-to-solid transition material using different molecular weight polyethyleneglycol eutectic |
| CN101851336A (en) * | 2010-06-13 | 2010-10-06 | 大连工业大学 | Method for preparing shape-stabilized phase change material by using acrylic fiber waste silks |
| CN102978739A (en) * | 2012-12-25 | 2013-03-20 | 四川大学 | Preparation method of polyethylene glycol/polyvinyl alcohol phase change energy storage fiber by in situ crosslinking |
| CN102978739B (en) * | 2012-12-25 | 2014-05-14 | 四川大学 | Preparation method of polyethylene glycol/polyvinyl alcohol phase change energy storage fiber by in situ crosslinking |
| CN103540294A (en) * | 2013-10-15 | 2014-01-29 | 徐州工业职业技术学院 | Method used for preparing solid-solid phase change material by polyethylene glycol/terylene physical blending |
| CN103540294B (en) * | 2013-10-15 | 2016-04-06 | 徐州工业职业技术学院 | Polyoxyethylene glycol/terylene physical blending prepares the method for solid-solid phase change material |
| CN104831439A (en) * | 2015-05-11 | 2015-08-12 | 陆宝夫 | Mixed cotton blended yarn and preparation method and application thereof |
| CN108642599A (en) * | 2018-04-24 | 2018-10-12 | 苏州龙杰特种纤维股份有限公司 | Phase change fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100436510C (en) | 2008-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100436510C (en) | Method for preparing solid-solid phase conversion material using polyglycol and terylene graft copolymerization technology | |
| CN101437871B (en) | Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom | |
| KR20090006223A (en) | Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom | |
| CN103145918B (en) | Preparation method of cellulose-g-resin acid grafted copolymer | |
| Li et al. | Synthesis and characterization of lactic acid esterified starch by an in-situ solid phase method | |
| CN111909364B (en) | Preparation method of silver-series antibacterial masterbatch | |
| CN112500530A (en) | Calcium carbonate/bagasse cellulose-based super absorbent resin and preparation method thereof | |
| CN101508786A (en) | Method for dissolution of bacteria cellulose | |
| CN101386683B (en) | Method for improving phase transition behavior of polyethyleneglycol/terylene solid-to-solid transition material using different molecular weight polyethyleneglycol eutectic | |
| CN111500037B (en) | High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof | |
| CN103572605A (en) | Mixed size prepared from waste PET (polyethylene terephthalate) and used for filament spinning and preparation method of mixed size | |
| Fukuoka et al. | Bioprocessing of glycerol into glyceric acid for use in bioplastic monomer | |
| CN115594972B (en) | Method for improving processability of polybenzimidazole resin solution | |
| CN101693743B (en) | Process for preparing cellulose derivatives containing double-bond lateral group | |
| CN101613479A (en) | The method of dissolution of bacteria cellulose | |
| Xu et al. | Synthesis of adipic acid dihydrazide-decorated coco peat powder-based superabsorbent for controlled release of soil nutrients | |
| CN1318583A (en) | Chitin/cellulose intermingling material and its preparation and use | |
| CN112358627B (en) | Method for promoting starch dissolution by ionic liquid, sol system and application | |
| CN113930039B (en) | Bamboo-plastic composite board material for container bottom plate | |
| CN113512299A (en) | Preparation method of lignin/chitosan/montmorillonite composite material | |
| CN1286856C (en) | Process for preparing poly saccuinimide crosslinking modified chitin material | |
| CN111286027A (en) | Production method of polyphenylene sulfide with low covalent bonding chlorine | |
| CN114854180B (en) | Thermoplastic cellulose/PBAT composite film and preparation method thereof | |
| CN113025012B (en) | PBAT (poly (butylene adipate-co-terephthalate)) bio-based polyester composite material filled with modified fibers and preparation method thereof | |
| CN108003363A (en) | A kind of preparation method of NTAA modified celluloses film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081126 |