CN1408742A - Shape memory polyurethane material produced from trans-polysioprene - Google Patents
Shape memory polyurethane material produced from trans-polysioprene Download PDFInfo
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Abstract
The present invention belongs to the field of shape memory polyurethane material technology and is especially shape memory polyurethane material prepared with trans-polyisoprene as basic material and through chemical modification. The components include hydroxylated trans-polyisoprene, diisocyanate and chain extender. The shape memory polyurethane material after being hot stretched and cooled to fix in shape may be restore its initial shape through heating. It has a shape memory temperature of 40-80 deg.c and deformation restoring rate of 80-100%, which is greater than 85% and may be maintained in the relative deformation up to 100%. The material of the present invention may be used as surgical material, cable casing, building pipe containing union, sealing ring temperature control element.
Description
Technical field
The invention belongs to the shape-memory material technical field, be specifically related to a kind of polyurethane material with shape memory function by trans poly-different diene preparation.
Background technology
Shape-memory polymer is meant to have original shape, after deformation is fixing, can change external conditions by methods such as heating, makes it recover the polymkeric substance of original shape.The outside stimulus condition that realizes the shape memory effect has physical factor and chemical factors such as potential of hydrogen, phase transformation reaction and chelatropic reaction such as heat energy, luminous energy, electric energy. shape-memory polymer thereby be divided into thermic induction type, photic induction type and chemical co-ordination type etc.The thermal shape memory polymkeric substance is in bio-medical material, sealing material, thermal control material field extensive application.
The thermal shape memory polymkeric substance is made up of two kinds of phases: (1) memory stationary phase of original shape and (2) but along with temperature change curing/remollescent anti-phase reversibly.When polymkeric substance is heated to fusing point or second-order transition temperature when above, but the anti-phase effect distortion down of power outside is cooled to the following solid shape of fusing point or second-order transition temperature then, removes external force after strain attitude and at room temperature keeps remaining unchanged for a long period of time; When temperature is elevated to fusing point or second-order transition temperature when above once more, molecular chain issues in the effect of entropy-elasticity is conigenous right curling, and returns to the original form as possible, thereby produces the function of shape memory.Be the recovery process of rubber entropy-elasticity on the memory process nature of shapememory polymer, the resume speed of its memory precision and deformation depends on the size of recovering stress.
Chinese patent 88103742 disclosed shape-memory materials are that employing vulcanization crosslinking using trans-polyisoprene is a basic material.Chinese patent 1357572 is disclosed as the using trans-polyisoprene of thermoplastic tube and the intermingling material of vinyl acetate-ethylene copolymer, is to adopt the moulding process of extruding the back cross-linking radiation to prepare.The effect of crosslinking reaction provides the necessary stationary phase of shape-memory polymer, but causes material shortage toughness simultaneously, in use damages easily.Adopt crosslinking process also to limit the purposes of material, vulcanization crosslinking is fit to compression molding, makes the device of simple shape such as sheet material, packing ring.Cross-linking radiation to by the thickness of irradiated plastics goods and shape certain requirement being arranged, because this has influence on the transmitance of ray, thereby influences crosslinking reaction degree and reaction homogeneity except that will using special electronics or cobalt-60 radiosterilize equipment.
International monopoly WO01/07499 and Chinese patent CN1361799A disclose the preparation method of shape memory polyurethane or polyurethane-urea polymers, and the formulate glass temperature is at the urethane of 20-100 ℃ of scope.The soft segment of polyurethane monomer is to adopt the polysiloxane macromolecule dihydric alcohol, and monomeric cost is higher.
The disclosed shape memory polyurethane of U.S. Pat 5049591 and US513982 utilizes the conventional reagent preparation of polyurethane field, hydrolysis easily.Other has the shape memory polyurethane of bibliographical information, and its soft section monomer is PCDL, polycaprolactone dibasic alcohol, and these compounds belong to polyester polyol, the easy hydrolysis of Zhi Bei urethane thus, degraded easily under biotic condition or humid climate.
Chinese patent CN1259155A, international monopoly WO98/52987, WO99/02603, U.S. Pat 5,849,806, US5,486,570, US6,060,560, it is soft section monomer method for producing polyurethanes that European patent EP 0430421, EP0829497 disclose with hydrogenated butadiene polymer hydrocarbon glycol.The chemical structure characteristic of hydrogenated butadiene polymer hydrocarbon glycol is that main chain is saturated, and preparation process is at first to pass through the anionic initiation polymerization by gripping diene monomers altogether, and the reactive polymer that obtains stops with methyl alcohol with ethylene oxide-capped again.The needed reaction conditions of anionoid polymerization is very harsh, preparation process is complicated.Restricted by the anionoid polymerization principle, described its functionality of hydrogenation polydiene diols of above patent is no more than 2.Hydrogenation will change the conformation of polyhutadiene molecular chain, thereby change the crystallization property [Cuillermo A.Cassano etc., Polymer, 1998,39 (22): 5573] of polymkeric substance, and this variation is equally applicable to using trans-polyisoprene.
Summary of the invention
The object of the present invention is to provide a kind of thermal shape memory polyurethane material, it is a kind of elastomerics, and has good water tolerance and higher shape memory response rate.
The thermal shape memory urethane that provided is provided, and its raw material is easy to get, manufacturing cost is relatively low, can be suitable for preparing complex-shaped special-shaped device, makes the thermal shape memory urethane that is provided have purposes widely.
According to the present invention, shape memory polyurethane segmented copolymer by the using trans-polyisoprene preparation is provided, has formed (by weight) by following component: (a) total amount of the above-mentioned 3 kinds of components of hydroxylation using trans-polyisoprene: 80-20% (b) vulcabond: 60-10% (c) chainextender 5-15% (d) satisfies 100%.
Component ratio is preferably: (a) total amount of the above-mentioned 3 kinds of components of hydroxylation using trans-polyisoprene: 70-30% (b) vulcabond: 50-20% (c) chainextender 10-15% (d) satisfies 100%.
Described block polymers of polyurethane is to be formed by hard section (second-order transition temperature is higher than room temperature) and soft section (second-order transition temperature is lower than room temperature) alternating copolymerization.Hard section of described block polymers of polyurethane is the reaction product of vulcabond and chainextender, and it provides the stationary phase of thermal shape memory material, the memory original shape.Soft section of described block polymers of polyurethane is using trans-polyisoprene, but it provides the anti-phase of thermal shape memory material, and when temperature was higher or lower than the using trans-polyisoprene fusing point, softening or curable phase change behavior reversibly took place soft section phase.Therefore described block polymers of polyurethane has shape memory function.
Shape memory polyurethane material of the present invention, its shape memory temperature 40-80 ℃; Have good deformation memory precision, deformation-recovery rate 100-80% is usually greater than 85%; After relaxation cycles repeatedly, deformation-recovery rate remains unchanged substantially.
Shape memory polyurethane of the present invention reaches at 100% o'clock at the relative tensile deformation of original shape, still keeps above-mentioned deformation memory precision.And the shape memory high molecule material of pertinent literature report, their deformation memory performance, pairing tensile deformation only are 13-20%.
Shape memory polyurethane of the present invention, polyvalent alcohol monomer are the hydroxylation using trans-polyisoprenes, and its hydroxy functionality is 1.60-3.0, and preferred hydroxy functionality scope is 1.70-2.50.
Described hydroxylation using trans-polyisoprene belongs to novel polyolefin polyhydric alcohol, the ehter bond or the ester bond that do not contain conventional polyurethanes, polarity is very little, thus Zhi Bei urethane have good resistance to hydrolysis can and the antibiont degradation property, and electrical insulation capability be improved significantly.
Described hydroxylation using trans-polyisoprene is prepared through hydroxylating by the using trans-polyisoprene polymkeric substance, the hydroxylacion method that adopts has following effect and feature simultaneously: (1) gives the using trans-polyisoprene hydroxy-functional, (2) reduce the using trans-polyisoprene molecular weight simultaneously, make resulting hydroxylation using trans-polyisoprene be suitable for preparing urethane, (3) keep the anti-form-1 of using trans-polyisoprene polymkeric substance fully, 4 structures.Within the scope of the present invention, using trans-polyisoprene after the modification, its main chain is undersaturated, anti-form-1,4 structures are greater than 90%, anti-form-1,4 structures by
1The H nmr determination.
The number-average molecular weight of the hydroxylation using trans-polyisoprene of being measured by gel permeation chromatograph (GPC, standard specimen are polystyrene) is between 1.0-8.0 ten thousand, according to sample segment
1H nucleus magnetic resonance (NMR) analytical results, GPC are crossed the highland and have been estimated hydroxylation using trans-polyisoprene molecular weight, and for example the GPC molecular weight 3.2 ten thousand, and the NMR molecular weight is 5100.Therefore, the molecular weight of hydroxylation using trans-polyisoprene provided by the invention is through gauged.
Within the scope of the present invention, the using trans-polyisoprene polymkeric substance that is used for preparing the hydroxylation using trans-polyisoprene is an anti-form-1, and 4 structures comprise synthetic and natural using trans-polyisoprene greater than 85% polyisoprene.Natural trans-polyisoprene comprises gutta-percha (Gutta) (or claiming gutta-percha), Ba Lata glue and Malaysia glue, and raw material sources are abundant.Trans natural rubber has the feature of plastics in fact, and purposes is very narrow.The present invention gives trans natural rubber functionalization, has enlarged the purposes of trans natural rubber.
The hydroxylacion method of using trans-polyisoprene provided by the invention, it comprises that graft copolymerization method, photochemical reaction method, oxidation degradation method and screw rod plasticate-grafting method.According to above-mentioned hydroxylacion method, the scope of the functionality of the hydroxylation using trans-polyisoprene that obtains is at 1.60-3.0.Thus, can be according to concrete purposes, preparation thermoplasticity or thermosetting polyurethane elastomer.And, restricted by the anionoid polymerization principle by gripping the hydroxylation polydiolefin that diene monomers obtains by anionoid polymerization altogether, its functionality is no more than 2.
According to the present invention, described vulcabond can be the diisocyanate compound of functionality at 0.3-10.
According to the present invention, vulcabond can be aliphatics or aromatic diisocyanate, for example 2,4-tolylene diisocyanate (TDI), 4,4-diphenylmethanediisocyanate (MDI), polymeric MDI, 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate (DMMIDI), methylene radical dicyclohexyl vulcabond (H
12MDI), to inferior cresyl vulcabond (p-PDI), to tetramethylxylylene diisocyanate (p-TMXDI), a tetramethylxylylene diisocyanate (m-TMXDI), trans 1,4-cyclohexylidene vulcabond (CHDI), isophorone diisocyanate (IPDI), 1,6-hexyl diisocyanate (DICH), 1,5-is group diisocyanate (NDI) a kind of how, or their mixture.TDI is particularly preferred.
According to the present invention, chainextender can be an aliphatics, aromatic series or silica-based dibasic alcohol, for example 1, the 4-butyleneglycol, ethylene glycol, propylene glycol, Diethylene Glycol, 1, the 4-cyclohexanediol, 1,4-cyclohexyl dimethanol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1,10-certain herbaceous plants with big flowers glycol, 1, the 12-dodecanol, to the toluene glycol, dihydroxyphenyl propane, quinhydrones (beta-hydroxyethyl) ether, Resorcinol (beta-hydroxyethyl) ether, 1,4-two (2-hydroxy ethoxy) benzene, 1,3-two (4-hydroxyl butyl) tetramethyl disiloxane or 1,3-two (6-hydroxy ethoxy) tetramethyl disiloxane a kind of.1, the 4-butyleneglycol is particularly preferred.
According to the present invention, chainextender or diamine, comprise quadrol, propylene diamine, 1,4-butanediamine, diethyl toluene diamine (DETDA), 3,5-diformazan sulfenyl tolylene diamine (DMTDA), 4,4 '-methylene-bis (3-chloro-2,6-Diethyl Aniline) (M-CDEA), 1,3-two (3-aminopropyl) tetramethyl disiloxane or 1,3-two (4-amino butyl) tetramethyl-two silica a kind of.
Shape memory polyurethane of the present invention is a kind of elastomerics.Within the scope of the present invention, the soft section hydrogen bond degree with hard section of shape memory polyurethane is zero, and the degree that is separated height uses electron microscope observation to arrive the hard section of regular ball-type phase, and diameter is between 0.25-0.50 μ m.Good, the easy crystallization of soft section phase integrity of using trans-polyisoprene.Within the scope of the present invention, use wide-angle X diffractometer (WAXD) analysis and obtain, the degree of crystallinity that using trans-polyisoprene is soft section has kept the crystallinity of free using trans-polyisoprene substantially between 32-25%.According to the Polymer Physics principle, for cross-linking type using trans-polyisoprene shape-memory material, the crosslinking reaction of any degree all will reduce the crystallinity of using trans-polyisoprene, thereby can not obtain remembering precision height, deformation-recovery rate to relaxation cycles number of times stable shape memory temperature material.
Can adopt urethane synthesis technique commonly used to prepare shape memory polyurethane of the present invention, promptly adopt solution polymerization or bulk technique, prepare by single stage method or two-step approach, can adopt the urethane cast molding or the injection molding technique metric system commonly used to make shape memory polyurethane device of the present invention.
One-step technology is, under 40-110 ℃ of condition, component (a) is mixed in the A container in proportion with component (c), it in the B container component (b) that is liquid, with volume pump the component in mixture in the A container and the B container is transported in the C container, be expelled to behind the uniform mixing in the die cavity of sulfurizing mould, polyreaction is finished in sulfuration under 150 ℃ of-250 ℃ of conditions, just obtains the shape memory polyurethane device of required type shape after the demoulding.Two-step process is at first prepolymer to be made in the reaction of component (a) and component (b), places the A container, is the component (c) that is liquid in the B container, subsequent step and single stage method basic identical.
In above-mentioned preparation process, generally can add the 0.01-10% antithrombotics of gross weight.This antithrombotics can adopt tartrate.
Solution polymerization is meant to be carried out in organic solvent, and suitable organic solvent comprises toluene, to two dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or their mixture.Within the scope of the present invention, the urethane of solution polymerization can adopt cast molding, or remove the back of desolvating adopt extrude, mold pressing or injection moulding.
Because shape memory polyurethane of the present invention, it can adopt reaction injection moulding, mold pressing, extrude or multiple complete processing such as injection moulding, therefore can make the device of different shape, be suitable as shape memory devices such as Clinical Surgery in irregular shape material, electric wire sleeve pipe, building pipe sleeved, sealing-ring, power-off protection element; Shape memory polyurethane of the present invention, it also can be used as the main component of the shape-memory treating agent of fabric and ready-made clothes and uses.
Clinical Surgery's material comprises the complete fixing or semifixed material of fracture, the various stationary materials of knee joint, spine, neck, wrist, elbow joint or shoulder joint, and facial plasty becomes the shape plate with device or skull.
When using as the building pipe sleeved, with diameter greater than the shape memory pipe box of the diameter of tubing on two building pipes that needs connect, can make pipe box produce recovery of shape by any type of heating, pack tightly building pipe.Because urethane of the present invention has good resistance to hydrolysis energy, is particularly suitable for the connection of plastic water pipe.When using, be to be processed into glove form, be enclosed within on the heart yearn of cable that pack tightly heart yearn after the recovery of shape, shape memory polyurethane of the present invention has the excellent electric insulation performance as cable shoe.
When using as the shape-memory treating agent of fabric and ready-made clothes, it is solution shape or emulsion form urethane.Its effect is that fabric and ready-made clothes are through repeatedly still keeping initial flat very shape after the washing.
The purposes of thermal shape memory polyurethane material of the present invention is not limited to above-mentioned field.
Thermal shape memory urethane of the present invention can also with polyolefine or other urethane and usefulness, the special shape memory devices of processability.
Embodiment
Embodiment 1
The urethane that this example is designed, its composition is that soft section content is about 70%, according to this prescription, hydroxylation using trans-polyisoprene (number-average molecular weight about 12000) is dissolved in the toluene, under continuous condition of stirring, adds 2,4-tolylene diisocyanate (relative molecular weight 174.2), after this keep reaction 20 minutes under 80 ℃, add 1 subsequently, the 4-butyleneglycol carries out chain extension.To synthetic polyurethane solution thus, casting film-forming on the ptfe plastic plate obtains polyurethane film after the drying.
Deformation-recovery rate is that the lax behavior by working sample characterizes: having on the universal testing machine Instron 1121 of heating chamber, at room temperature with sample at 5 minutes internal heating to 65 ℃, rate of extension with 10mm/min is stretched to certain deformation again, stationary fixture then, with the rapid cool to room temperature of temperature, under this temperature, stopped 5 minutes, anchor clamps then come loose, then sample is warmed up to 65 ℃ rapidly once more, record deformation-recovery rate at this moment.With three samples in the batch sample, the test deformation-recovery rate is tried to achieve mean value.
Embodiment 2
The urethane that this example is designed, its composition are that soft section content is about 70%, according to this prescription, hydroxylation using trans-polyisoprene (number-average molecular weight about 5000) are dissolved in the toluene, and subsequent step is identical with example 1.With synthetic polyurethane solution casting film, under heating condition, remove solvent, obtain the urethane print.
Method by embodiment 1 is tested deformation-recovery rate.For observing the shape-memory properties of urethane print after using repeatedly, at same sample, repeat example 1 described process, carry out repeatedly relaxation cycles, obtain the deformation-recovery rate mean value of each relaxation cycles.
Embodiment 3
The designed polyurethane formulations of this example is that soft section content is about 50%, according to this prescription, hydroxylation using trans-polyisoprene (number-average molecular weight about 5000) is dissolved in the toluene, adds dibutyl tin dilaurate (DBTDL) as catalyzer, consumption is 0.06% of a soft section quality.In 90 minutes, add 2,4 toluene diisocyanate (TDI) then, slowly add 1 immediately, the 4-butyleneglycol.To synthetic polyurethane solution thus, casting film-forming on the ptfe plastic plate obtains polyurethane film after the drying.
Method by embodiment 1 is tested deformation-recovery rate.For observing the shape-memory properties of urethane print after using repeatedly, at same sample, repeat example 1 described process, carry out repeatedly relaxation cycles, obtain the deformation-recovery rate mean value of each relaxation cycles.
Embodiment 4
The designed polyurethane formulations of this example is that soft section content is about 50%, according to this prescription, hydroxylation using trans-polyisoprene (number-average molecular weight about 9000) is dissolved in the toluene, adds dibutyl tin dilaurate (DBTDL) as catalyzer, consumption is 0.03% of a soft section quality, 80 ℃ of following condensing refluxes 20 minutes, under whipped state, add 2,4 tolylene diisocyanates then, and then add 1, the 4-butyleneglycol.To synthetic polyurethane solution thus, casting film-forming on the ptfe plastic plate gets the transparent polyurethane film after dry.
Come the deformation-recovery rate of test sample by the method for embodiment 1.
More than the urethane of each examples preparation all can adopt solvent-free mass polymerization-injection molding, but in this research process, lack the polyurethane reaction molding device.
Table 1 is listed the fusing point of deformation-recovery rate, tensile strength and the hydroxylation using trans-polyisoprene of embodiment 1, embodiment 2, embodiment 3, embodiment 4 shape memory polyurethanes.
Table 1
| Urethane | Typing back elongation I?％ | Deformation-recovery rate II?％ | Tensile strength III?(Mpa) | Hydroxylation using trans-polyisoprene fusing point |
| Example 1 | ?100 | ?91 | ?17.0 | ?62℃ |
| Example 2 | ?100 | 87 (once) 86 (secondary) 85 (four times) | ?18.0 | ?42℃ |
| Example 3 | ?100 | 85 (once) 83 (secondary) 81 (four times) | ?10.5 | ?- |
| Example 4 | ?100 | ?85 | ?- | ?60℃ |
I: refer to the deformation ratio after film sample adds thermal stretch, solid shape, promptly with respect to the elongation of original shape.
II: the number of times in the bracket is represented the number of times of relaxation cycles; 4 of example 1 and examples have carried out the single relaxation cycles.
III: at room temperature, on Instron 1121 universal testing machines, press ASTMD-1822 and measure.
Claims (12)
1, a kind of shape memory polyurethane material is characterized in that it being the block polymers of polyurethane that is prepared by using trans-polyisoprene, and by weight percentage, each set of dispense ratio is:
(a) hydroxylation using trans-polyisoprene: 90-15%,
(b) vulcabond: 10-60%,
(c) chainextender: 5-15%,
(d) total amount of above-mentioned 3 kinds of components satisfies 100%.
2, shape memory polyurethane material according to claim 1, the average functionality that it is characterized in that the hydroxyl of hydroxylation using trans-polyisoprene is 1.60-3.0.
3, shape memory polyurethane material according to claim 1, the main chain that it is characterized in that said hydroxylation using trans-polyisoprene is undersaturated, anti-form-1, the ratio of 4 structures is greater than 90%.
4, shape memory polyurethane material according to claim 1 is characterized in that said vulcabond is the diisocyanate compound of functionality at 0.3-10.
5, shape memory polyurethane material according to claim 4 is characterized in that said vulcabond is aliphatics or aromatic diisocyanate.
6, shape memory polyurethane material according to claim 5 is characterized in that said vulcabond is a kind of of TDI, MDI, DMMIDI, H12MDI, p-PDI, p-TMXDI, m-TMXDI, CHDI, IPDI, DICH, NDI or their mixture.
7, shape memory polyurethane material according to claim 1 is characterized in that said chainextender is aliphatics, aromatic series or silica-based dibasic alcohol.
8, shape memory polyurethane material according to claim 7, it is characterized in that said chainextender is 1, the 4-butyleneglycol, ethylene glycol, propylene glycol, Diethylene Glycol, 1, the 4-cyclohexanediol, 1,4-cyclohexyl dimethanol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1,10-certain herbaceous plants with big flowers glycol, 1, the 12-dodecanol, to the toluene glycol, dihydroxyphenyl propane, quinhydrones (beta-hydroxyethyl) ether, Resorcinol (beta-hydroxyethyl) ether, 1,4-two (2-hydroxy ethoxy) benzene, 1,3-two (4-hydroxyl butyl) tetramethyl disiloxane or 1,3-two (6-hydroxy ethoxy) tetramethyl disiloxane a kind of.
9, according to the said shape memory polyurethane material of claim 7, it is characterized in that said chainextender is quadrol, propylene diamine, 1,4-butanediamine, diethyl toluene diamine (DETDA), 3,5-diformazan sulfenyl tolylene diamine (DMTDA), 4,4 '-methylene-bis (3-chloro-2, the 6-Diethyl Aniline) (M-CDEA), 1,3-two (3-aminopropyl) tetramethyl disiloxane or 1,3-two (4-amino butyl) tetramethyl-two silica a kind of.
10, a kind of preparation method of shape memory polyurethane material as claimed in claim 1, it is characterized in that under 40-110 ℃ of condition, component (a) is mixed in the A container in proportion with component (c), it in the B container component (b) that is liquid, with volume pump the component in mixture in the A container and the B container is transported in the C container, be expelled to behind the uniform mixing in the die cavity of sulfurizing mould, polyreaction is finished in sulfuration under 150 ℃ of-250 ℃ of conditions, just obtains the shape memory polyurethane device of required type shape after the demoulding.
11, a kind of preparation method of shape memory polyurethane material as claimed in claim 1 is characterized in that at first prepolymer being made in component (a) and component (b) reaction, places the A container, is the component (c) that is liquid in the B container; With volume pump the component (c) in prepolymer in the A container and the B container is transported in the C container, be expelled to behind the uniform mixing in the die cavity of sulfurizing mould, polyreaction is finished in sulfuration under 150 ℃ of-250 ℃ of conditions, just obtains the shape memory polyurethane device of required type shape after the demoulding.
12,, it is characterized in that also adding the anti-gelation agent of the 0.01-10% of gross weight: tartrate according to claim 10 or 11 described preparation methods.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013000A1 (en) * | 2010-07-28 | 2012-02-02 | 广州市曼博瑞材料科技有限公司 | Method for manufacturing shape memory security label |
| CN102604298A (en) * | 2010-12-31 | 2012-07-25 | 中国科学院成都有机化学有限公司 | Polydimethylsiloxane (PDMS)-based form memory compound |
| CN105601875A (en) * | 2016-01-26 | 2016-05-25 | 浙江大学 | Urethane bond/urea bond exchange based plastic shape memory polymer system and application method thereof |
| CN102604298B (en) * | 2010-12-31 | 2016-12-14 | 中国科学院成都有机化学有限公司 | A kind of shape memory composites based on polydimethylsiloxane |
| CN113667087A (en) * | 2021-08-24 | 2021-11-19 | 中国科学院青岛生物能源与过程研究所 | Hydroxyl-terminated polyisoprene polyurethane synthesized by biological method and preparation method and application thereof |
| CN114716982A (en) * | 2022-05-11 | 2022-07-08 | 青岛科技大学 | Trans-rubber-based phase change energy storage microcapsule material and preparation method thereof |
-
2002
- 2002-09-10 CN CN 02136921 patent/CN1408742A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013000A1 (en) * | 2010-07-28 | 2012-02-02 | 广州市曼博瑞材料科技有限公司 | Method for manufacturing shape memory security label |
| CN102604298A (en) * | 2010-12-31 | 2012-07-25 | 中国科学院成都有机化学有限公司 | Polydimethylsiloxane (PDMS)-based form memory compound |
| CN102604298B (en) * | 2010-12-31 | 2016-12-14 | 中国科学院成都有机化学有限公司 | A kind of shape memory composites based on polydimethylsiloxane |
| CN105601875A (en) * | 2016-01-26 | 2016-05-25 | 浙江大学 | Urethane bond/urea bond exchange based plastic shape memory polymer system and application method thereof |
| CN113667087A (en) * | 2021-08-24 | 2021-11-19 | 中国科学院青岛生物能源与过程研究所 | Hydroxyl-terminated polyisoprene polyurethane synthesized by biological method and preparation method and application thereof |
| CN114716982A (en) * | 2022-05-11 | 2022-07-08 | 青岛科技大学 | Trans-rubber-based phase change energy storage microcapsule material and preparation method thereof |
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