CN105860024A - Transparent polyurethane material with adjustable deformation recovery temperature and preparation method thereof - Google Patents
Transparent polyurethane material with adjustable deformation recovery temperature and preparation method thereof Download PDFInfo
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- CN105860024A CN105860024A CN201610282039.6A CN201610282039A CN105860024A CN 105860024 A CN105860024 A CN 105860024A CN 201610282039 A CN201610282039 A CN 201610282039A CN 105860024 A CN105860024 A CN 105860024A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a transparent polyurethane material with an adjustable deformation recovery temperature and a preparation method thereof. The transparent polyurethane material is prepared from at least one resin raw material with a high glass transition temperature, the interior of the prepared polyurethane material is of an amorphous phase structure, and the glass transition temperature of the amorphous phase can be adjusted. The transparent polyurethane material with the adjustable deformation recovery temperature and the preparation method thereof have the advantages that the preparation method is simple, diverse raw materials can be selected, the deformation recovery temperature can be adjusted within a wide range, and the synthesis route is flexible.
Description
Technical field
The present invention relates to a kind of deformation recovery temperature adjustable transparent polyurethane material and preparation thereof
Method.
Background technology
Shape memory high molecule material (SMPs) be a kind of can to its apply certain program make
It remembers a temporary shapes, when to its carry out suitable environmental stimuli (as hot, optical, electrical,
Chemical co-ordination), the intellectual material of original-shape can be returned to.Common has shape memory
Macromolecular material be to thermal stimulus response material, be heated to more than thermal transition temperature
(such as glass transition temperature or crystalline melt temperature), applies certain external force simultaneously and makes it deform
Being a temporary shapes, be cooled to below thermal transition temperature, this temporary shapes is fixed, then
Remove external force；When being reheated to more than thermal transition temperature, it can return to original
Shape.The 1950's, American scientist A.charlesby is accidental in once experiment
The processes for chemically crosslinked polyethylene of stretcher strain is heated, it was found that its shape-memory phenomena.The most often
Temperature is sensed by the macromolecule with SME seen, it can be necessarily
Temperature deformation also can shape and long-term storage under this temperature, a certain specific when being warming up to again
During response temperature, can quickly return to its original shape.Although shape memory high molecule material is opened
The time of sending out is shorter, but due to its have that light weight, inexpensive, deformation quantity be big, shaping easily, shape
Recover to be conveniently adjusted etc. advantage, the most medical treatment, pack, build, toy, automobile, report
The fields such as alert equipment are widely used, now with shape two-way to shape memory high molecule
The research of memory effect, it is expected to open up its potential using value in widely field.
Polyurethane (PU) is to have a large amount of carbamate segment constitutional repeating unit on main chain
Polymer, it is less than the soft segment (also referred to as soft chain segment or soft section) of room temperature by vitrification point
Form higher than rigid chain segment (also referred to as hard segment or the hard section) block of room temperature with vitrification point.From
The thirties in 20th century polyurethane by Germanization scholar O.Bayer invent since, its rely on raw material
The unique advantages such as various, formula flexible, rich choice of products, excellent performance, have been widely used respectively
The each industry of row.The performance that transparent polyurethane material is unique except having conventional urethane, also has preferably
Optical property, be widely used to the field such as optical material, protective materials.From shape memory
Since macromolecular material development, the structure of polyurethane uniqueness becomes research shape memory high score
The important polymer of sub-material, shape memory polyurethane in early days is mainly to its one-way shape memory
Behavior is studied, and the condition that its original-shape recovers is to need to be heated to polyurethane material
On a certain specific temperature.Synthesize the polyurethane with bidirectional shape memory effect at present
Product, but its working mechanism and structural behaviour regulation need to study further.
Summary of the invention
Present invention aim at providing a kind of deformation recovery temperature adjustable transparent polyurethane material
Material and preparation method thereof, a kind of deformation recovery temperature adjustable transparent polyurethane material of the present invention
And preparation method thereof to have preparation method simple, raw material select various, and deformation recovery temperature can
It is adjusted on a large scale, synthetic route feature flexibly.
In order to achieve the above object, the technical scheme is that
A kind of deformation recovery temperature adjustable transparent polyurethane material, has relatively including at least one
The resin raw material of high glass-transition temperature, belongs to nothing inside preparation-obtained polyurethane material
Setting phase structure, the glass transition temperature of wherein said amorphous phase can be adjusted.
The raw material of the described polyurethane material prepared includes having relatively as main material
The hydroxy acrylic acid resin of high glass-transition temperature and auxiliary material；Described auxiliary material uses crystallization
PEPA, have compared with the PPG of lower glass transition temperatures, there is relatively low glass
Change one or more in the Hydroxylated acrylic resin of transition temperature；Wherein said having is higher
Glass transition temperature Tg >=50 DEG C of the hydroxy acrylic acid resin of glass transition temperature, its
Described in the PPG with relatively lower glass transition temperatures or there is relatively reduced TG
Glass transition temperature Tg≤40 DEG C of the Hydroxylated acrylic resin of transition temperature.
The preparation method of a kind of deformation recovery temperature adjustable transparent polyurethane material, including as follows
Step: the resin raw material solvent that first at least one have higher glass transition temperature mixes
Close uniformly, be subsequently adding isocyanates, catalyst, NCO/OH equivalent in whole reaction system
Ratio is 1.2:1, and solid content is 70～about 90wt%；Blending ingredients is poured in aluminium foil weighing plate,
In 80 DEG C of baking ovens, solidify 48h, the most at room temperature place 7 days, keep being coated with thickness after drying
Degree is 0.4～0.5mm.
The consumption of the described resin raw material with higher glass transition temperature is at whole polyurethane
Mass fraction in reaction system is not less than 30%.
Described isocyanates use hexamethylene diisocyanate biruet (HDI biuret),
Hexamethylene diisocyanate trimer (HDI trimer), IPDI three
One or more in aggressiveness (IPDI tripolymer).
Described solvent uses the one in toluene, dimethylbenzene, butanone, butyl acetate.
Described catalyst uses organic tin compound, and the consumption of catalyst is whole poly-for accounting for
The 0.01wt% of the mass fraction in reactive urethane system.
Described organic tin compound use Mono-n-butyltin, Dibutyltin oxide, two
One in dibutyl tin laurate.
The invention has the beneficial effects as follows: a kind of deformation recovery temperature of the present invention is adjustable transparent poly-
It is simple that urethane material and preparation method thereof has preparation method, and raw material select various, and deformation is extensive
Rewarming degree can on a large scale in be adjusted, synthetic route feature flexibly.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but claimed model
Enclose and be not limited to the scope that embodiment is expressed.
Embodiment 1
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
Method: first by Hydroxylated acrylic resin (model: ACR6580, Foshan is with Dehua work), poly-
Caprolactone diol (relative molecular mass 2000) is dissolved in butyl acetate, is subsequently adding six methylenes
(dibutyl tin laurate accounts for whole polyurethane anti-for group diisocyanate tripolymer, catalyst
Answer the 0.01wt% of mass fraction in system), in system, NCO/OH equivalent proportion is 1.2:1, Gu
Content is 86wt%.Blending ingredients is poured in aluminium foil weighing plate, 80 DEG C of baking ovens solidifies 48h,
The most at room temperature place 7 days, keep dried coating thickness to be 0.48mm and get final product.By changing
In variant system, the quality proportioning of Hydroxylated acrylic resin and polycaprolactone glycol, can prepare and have not
With the transparent polyurethane material of glass transition temperature, as shown in table 1, table 1 is embodiment 1-4
Obtaining the performance table of polyurethane, the conclusion of the embodiment 1 drawn from table 1 is: the glass of polyurethane
Change transition temperature adjustable in the range of 47 DEG C～87 DEG C.
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
It is simple that method has preparation method, and raw material select various, and deformation recovery temperature can be on a large scale
Inside it is adjusted, synthetic route feature flexibly.
Embodiment 2
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
Method: first by Hydroxylated acrylic resin (model: ACR6580, Foshan is with Dehua work), poly-
Ethylene glycol (relative molecular mass 3000) is dissolved in toluene, is subsequently adding hexa-methylene two isocyanide
Acid esters tripolymer and isophorone diisocyanate trimer (mass ratio is 1:1), catalyst (two
Butyl tin oxide, accounts for the 0.01wt% of mass fraction in whole polyurethane reaction system), system
Middle NCO/OH equivalent proportion is 1.2:1, and solid content is 80wt%.Blending ingredients is poured into aluminium foil weigh
In dish, 80 DEG C of baking ovens solidify 48h, the most at room temperature places 7 days, keep dried and be coated with
Film thickness is 0.44mm and get final product.By Hydroxylated acrylic resin in change system and polyethylene glycol
Quality proportioning, can prepare the transparent polyurethane material with different glass transition temperature.Such as table
Shown in 1, table 1 obtains the performance table of polyurethane, the embodiment drawn from table 1 for embodiment 1-4
The conclusion of 2 is: the glass transition temperature of polyurethane is adjustable in the range of 25 DEG C～85 DEG C.
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
It is simple that method has preparation method, and raw material select various, and deformation recovery temperature can be on a large scale
Inside it is adjusted, synthetic route feature flexibly.
Embodiment 3
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
Method: first by Hydroxylated acrylic resin (model: Q174, Mitsui KCC),
Polyethylene glycol (relative molecular mass 2000) is dissolved in toluene and butyl acetate (wherein toluene
Be 1:1 with the mass ratio of butyl acetate), be subsequently adding isophorone diisocyanate trimer,
(dibutyl tin laurate accounts for mass fraction in whole polyurethane reaction system to catalyst
0.01wt%), in system, NCO/OH equivalent proportion is 1.2:1, and solid content is 78wt%.Will mixing
Component is poured in aluminium foil weighing plate, solidifies 48h, the most at room temperature place in 80 DEG C of baking ovens
7 days, dried coating thickness is kept to be 0.40mm and get final product.By hydroxyl third in change system
The quality proportioning of olefin(e) acid resin and polyethylene glycol, can prepare and have different glass transition temperature
Transparent polyurethane material, as shown in table 1, table 1 obtains the property of polyurethane for embodiment 1-4
Can table, the conclusion of the embodiment 3 drawn from table 1 is: the glass transition temperature of polyurethane exists
In the range of 42 DEG C～80 DEG C adjustable.
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
It is simple that method has preparation method, and raw material select various, and deformation recovery temperature can be on a large scale
Inside it is adjusted, synthetic route feature flexibly.
Embodiment 4
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
Method: first by Hydroxylated acrylic resin (model: ACR6580, Foshan is with Dehua work), low
The Hydroxylated acrylic resin (model: Q186, Mitsui KCC) of vitrification point
It is dissolved in butanone and butyl acetate (wherein the mass ratio of butanone and butyl acetate is 1:1), so
(Mono-n-butyltin accounts for whole for rear addition hexamethylene diisocyanate biruet, catalyst
Mass fraction 0.01wt% in polyurethane reaction system), in system, NCO/OH equivalent proportion is
1.2:1, solid content is 80wt%.Blending ingredients is poured in aluminium foil weighing plate, 80 DEG C of bakings
Solidifying 48h in case, the most at room temperature place 7 days, keeping dried coating thickness is 0.5mm
Obtain.By the quality proportioning of Hydroxylated acrylic resin and polyethylene glycol in change system, can make
Must have the transparent polyurethane material of different glass transition temperature, as shown in table 1, table 1
Obtain the performance table of polyurethane for embodiment 1-4, the conclusion of the embodiment 4 drawn from table 1 is:
The glass transition temperature of polyurethane is adjustable in the range of 30 DEG C～82 DEG C.
A kind of deformation recovery temperature adjustable transparent polyurethane material of the present embodiment and preparation thereof
It is simple that method has preparation method, and raw material select various, and deformation recovery temperature can be on a large scale
Inside it is adjusted, synthetic route feature flexibly.
Table 1
Claims (8)
1. a deformation recovery temperature adjustable transparent polyurethane material, it is characterized in that: include that at least one has the resin raw material of higher glass transition temperature, belonging to amorphous phase structure inside preparation-obtained polyurethane material, the glass transition temperature of wherein said amorphous phase can be adjusted.
A kind of deformation recovery temperature adjustable transparent polyurethane material the most according to claim 1, it is characterised in that: the raw material of the described polyurethane material prepared includes the hydroxy acrylic acid resin with higher glass transition temperature as main material and auxiliary material；Described auxiliary material use crystalline polyester polyol, the PPG with relatively lower glass transition temperatures, have in the Hydroxylated acrylic resin of relatively lower glass transition temperatures one or more；Glass transition temperature Tg >=50 DEG C of the wherein said hydroxy acrylic acid resin with higher glass transition temperature, the wherein said PPG with relatively lower glass transition temperatures or there are glass transition temperature Tg≤40 DEG C of Hydroxylated acrylic resin of relatively lower glass transition temperatures.
3. the preparation method of one kind according to claim a kind deformation recovery temperature adjustable transparent polyurethane material, it is characterized in that, comprise the steps: that the resin raw material solvent that first at least one have higher glass transition temperature mixes, it is subsequently adding isocyanates, catalyst, in whole reaction system, NCO/OH equivalent proportion is 1.2:1, and solid content is 70～about 90wt%；Blending ingredients is poured in aluminium foil weighing plate, solidifies 48h, the most at room temperature place 7 days, keep dried coating thickness to be 0.4～0.5mm in 80 DEG C of baking ovens.
The preparation method of a kind of deformation recovery temperature the most according to claim 4 adjustable transparent polyurethane material, it is characterised in that there is described in: the consumption of resin raw material of the higher glass transition temperature mass fraction in whole polyurethane reaction system and be not less than 30%.
The preparation method of a kind of deformation recovery temperature the most according to claim 4 adjustable transparent polyurethane material, it is characterised in that: described isocyanates uses one or more in hexamethylene diisocyanate biruet, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer.
The preparation method of a kind of deformation recovery temperature the most according to claim 4 adjustable transparent polyurethane material, it is characterised in that: described solvent uses the one in toluene, dimethylbenzene, butanone, butyl acetate.
The preparation method of a kind of deformation recovery temperature the most according to claim 4 adjustable transparent polyurethane material, it is characterized in that: described catalyst uses organic tin compound, and the consumption of catalyst is the 0.01wt% accounting for the mass fraction in whole polyurethane reaction system.
The preparation method of a kind of deformation recovery temperature the most according to claim 4 adjustable transparent polyurethane material, it is characterised in that: described organic tin compound uses the one in Mono-n-butyltin, Dibutyltin oxide, dibutyl tin laurate.
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| CN201610282039.6A CN105860024A (en) | 2016-04-29 | 2016-04-29 | Transparent polyurethane material with adjustable deformation recovery temperature and preparation method thereof |
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| CN201610282039.6A CN105860024A (en) | 2016-04-29 | 2016-04-29 | Transparent polyurethane material with adjustable deformation recovery temperature and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116239753A (en) * | 2023-02-03 | 2023-06-09 | 上海交通大学 | Two-way shape memory polyurethane and preparation method thereof |
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|---|---|---|---|---|
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN102408539A (en) * | 2011-10-24 | 2012-04-11 | 哈尔滨工业大学 | Shape memory polyurethane and preparation method thereof |
| CN103030957A (en) * | 2012-12-25 | 2013-04-10 | 深圳大学 | Material based on polyhydroxyalkanoate and preparation method and application of material |
| CN105111398A (en) * | 2015-09-07 | 2015-12-02 | 东莞市雄林新材料科技股份有限公司 | TPU (thermoplastic polyurethane) film with shape memory function and preparation method thereof |
-
2016
- 2016-04-29 CN CN201610282039.6A patent/CN105860024A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN102408539A (en) * | 2011-10-24 | 2012-04-11 | 哈尔滨工业大学 | Shape memory polyurethane and preparation method thereof |
| CN103030957A (en) * | 2012-12-25 | 2013-04-10 | 深圳大学 | Material based on polyhydroxyalkanoate and preparation method and application of material |
| CN105111398A (en) * | 2015-09-07 | 2015-12-02 | 东莞市雄林新材料科技股份有限公司 | TPU (thermoplastic polyurethane) film with shape memory function and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116239753A (en) * | 2023-02-03 | 2023-06-09 | 上海交通大学 | Two-way shape memory polyurethane and preparation method thereof |
| CN116239753B (en) * | 2023-02-03 | 2024-05-28 | 上海交通大学 | Two-way shape memory polyurethane and preparation method thereof |
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