CN104610594A - Low-temperature thermal-shrinkage shape memory material and preparation method thereof - Google Patents
Low-temperature thermal-shrinkage shape memory material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-temperature thermal-shrinkage shape memory material and a preparation method thereof. The low-temperature thermal-shrinkage shape memory material is prepared from a polymer containing unsaturated carbon-carbon double bonds and trans-polyisoprene by blending and crosslinking. The low-temperature thermal-shrinkage shape memory material provided by the invention has the beneficial effects that the tensile strength of the shape memory material reaches up to 18-35MPa (generally the tensile strength of a thermal shrinkage material prepared from polyisoprene is not more than 20MPa, the highest tensile strength of the material provided in CN02136921.6 is 18MPa, and the deformation restoration rate is 80-90%); the elongation at break is 280-650%; the deformation restoration rate is 100-500% (adjustable in the range according to product requirements); and the tensile strength retention rate is kept more than or equal to 75% after thermal ageing at 121 DEG C for 168 hours, the elongation at break retention rate is more than or equal to 85%, and the service life at 90 DEG C is more than 15 years.
Description
Technical field
The present invention relates to a kind of shape memory functional material and preparation method thereof, being specifically related to a kind of pyrocondensation temperature is thermotropic shape-memory material of 60-70 DEG C and preparation method thereof.
Background technology
Shape-memory material refers to have original shape, after deformation is fixing, can changes external conditions, make it recover the polymkeric substance of original shape by methods such as heating.
The outside stimulus condition realizing shape memory effect has the chemical factor such as the physical factors such as heat energy, luminous energy, electric energy and potential of hydrogen, phase in version reaction and chelatropic reaction, according to the difference of outside stimulus condition, shape-memory material is divided into thermic induction type, photic induction type and chemical co-ordination type etc.Thermic induction type shape-memory material has a wide range of applications in medical material, sealing material, thermal control material field.
The memory function of thermic induction type shape-memory material mainly comes from its material internal and there is not exclusively compatible two-phase---keep the stationary phase of shaping article shape and be heated can occur that phase transforms can anti-phase, as crystalline transition or glassy transition.When temperature is elevated to more than second-order transition temperature or Tc, can anti-phase be elastomeric state by solid state transformation, high elastic deformation (alteration of form) can be there is under external force in material, this deformation is fixed when the temperature decreases, again raised temperature is to softening temperature, this deformation disappears, and material recovers is to original shape.
The thermic induction type shape memory functional material that in prior art prepared by differing materials and technique, its use temperature and purposes have bigger difference:
CN 00122353 discloses a kind of manufacture method of pyrocondensation pipe fitting, take polyethylene as main raw material, the use temperature of made heat-shrink tube is greater than 100 DEG C, because its pyrocondensation temperature is high, use temperature scope is restricted, in the material with memory of such as medical use, because material with memory needs to carry out pyrocondensation when the contact with human body, therefore, this material cannot be applied.
Have the technical scheme adopting polyvinyl chloride as material contracting with heat in addition in prior art, polyvinyl chloride take glass transition as phase transition point, and use temperature 80-90 DEG C, still exists the problem of polyethylene material contracting with heat.
The open using trans-polyisoprene of CN 1357572 and the blended pyrocondensation pipe fitting obtained through cobalt-60 radiosterilize of ethylene-vinyl acetate copolymer, its deformation expansion only reaches 150%, and cobalt-60 radiosterilize gamma-ray contamination is serious, although its use temperature is at 60-80 DEG C, have must improve relative to the technical scheme of polyethylene and polyvinyl chloride, but because cobalt-60 radiosterilize gamma-ray contamination is serious, add that cobalt source is expensive, need to supplement for 2 years one, working cost is high, the process of useless source is more expensive, be almost the 6-7 in the source of purchasing doubly, processing bad meeting causes radiating material to leak, the U.S. prohibits, China is also at limit scale, therefore, suitability for industrialized production cannot be realized.
CN 101108909 discloses the shape-memory material that a kind of texturing temperature is less than 50 DEG C, its softening temperature is too low, in the summer in some area of China, air themperature can reach more than 40 DEG C, at this moment shape-memory material cannot use, and its crosslinked irradiation dose is 250kGy, and irradiation efficiency is low, and energy expenditure is larger.
Summary of the invention
In order to overcome the defect too high or too low for temperature of pyrocondensation in prior art, the invention provides the Low Temperature Thermal collapsed shape material with memory that a kind of pyrocondensation temperature is 60-70 DEG C, adopting polymkeric substance containing unsaturated carbon-carbon double bond with using trans-polyisoprene is blended, crosslinked obtain.
Compared with prior art, unsaturated polymer is in radiation field, and can activate and promote TPI structurizing, jointly form cross-linked structure, blend causes melt temperature to reduce.
Preferably: the polymkeric substance containing unsaturated carbon-carbon double bond comprises side chain containing the polymkeric substance of unsaturated double-bond or the main chain polymkeric substance containing unsaturated double-bond.
Compared with prior art, the membership that adds of unsaturated second polymkeric substance causes the irradiation efficiency of material different, particularly in the base of side with the polymkeric substance of carbon-carbon double bond and using trans-polyisoprene mixture, its irradiation efficiency can increase greatly, and larger cross-linked network can be formed, the physicals of this functional materials and shape memory effect are significantly improved.Superpolymer containing double bond in the base of side no matter hot sulfurization or radiation vulcanization, its double bond is easy to open and forms larger cross-linked network, and curing efficiency increases simultaneously, can reach required state of vulcanization within a short period of time, saves hear rate, obtains environmentally friendly functional materials; In cross-linking radiation reaction, polymkeric substance forms free radical C-CH=CH2 through irradiation, and free radical and double bond form a large π key, free radical is relatively stable, increase with the catalytic chance of other macromole, thus yield improves, and namely shows as the energy reached required for identical crosslinking degree and reduces.Side base not double bond containing saturated polymer C stability is more weak, and be easy to take off free radical and form double bond thus termination reaction, yield reduces relatively.The large π key of stable free radical is present on the base of side, and steric effect is little, is easier to attack polymkeric substance thus forms cross-linked network.This polymeric system visible makes using trans-polyisoprene and unsaturated polymer more easily form interpenetrating(polymer)networks, thus shows as dose rate increase, and irradiation efficiency improves.
Preferably: side chain comprises at least one of 3,4-polyisoprene, 1,2-polyhutadiene containing the polymkeric substance of unsaturated double-bond.These two kinds of polymkeric substance due to steric effect little, better effects if.
Preferably: main chain comprises at least one of terpolymer EP rubber, natural rubber, EVA and POE containing the polymkeric substance of unsaturated double-bond.
Preferably: be 5%-70%:30%-95% containing the polymkeric substance of unsaturated double-bond and the mass percent of using trans-polyisoprene.
Preferably: also comprise sensitizing agent and nucleator.
Preferably: sensitizing agent is at least one of TMPTMA, TAIC, TAC, PDMI, nucleator is ZnO or ZnSt
2.
Under sensitizing agent effects of ionizing radiation, the cross-linking process of their participation polymkeric substance becomes a part for structure, strengthens two-phase polymer interface structure, sensitizing agent acting as in system of the present invention simultaneously:
1) promote that TPI is cross-linked, improve Crosslinking G value (yield is the crosslinking degree that identical irradiation dose reaches), reduce required irradiation dose;
2), while promoting to be cross-linked, participation structure, is conducive to the lifting of tensile yield;
3) strengthen the interfacial structure of co-mixing system, in irradiation, two-phase incompatibility polymer interface is cross-linked two phase structure, and then improves tensile strength.
Acting as of nucleator: adjustment TPI state of aggregation (degree of crystallinity improves, and particle diameter reduces) increases the interface of crystal surface and the second polymkeric substance.
In the present invention, sensitizing agent and nucleator produce synergistic effect, by acting in conjunction, and adjustment TPI crystal form, increase the interfacial effect of crystal surface and unsaturated polymer, sensitizing agent participation structure, the interfacial structure of strengthening co-mixing system, promotes that TPI is cross-linked, improve tensile yield, tensile strength, reduce required irradiation dose, improve irradiation efficiency, reduce the generation of side reaction.
Preferably: also comprise oxidation inhibitor, lubricant and weighting agent.
More preferably: oxidation inhibitor comprises the mixture of at least one of anti-aging agent 1010, anti-aging agent 168, at least one of antioxidant MB and antioxidant 4010, anti-aging agent RD.The present invention adopts rubber and plastic double base protection system, in polymeric system of the present invention, contain rubber (TPI) and mould (the second polymkeric substance) two base polymers, rubber-like protection system protects mainly for diene polymer, plastic protection system is mainly protected the second polymkeric substance, hindered phenol, phosphorous acid ester and quinoline, amine antioxidants coupling, produce synergistic effect, not only play its antioxidant, take into account the effectiveness of its textural factor to material irradiation stability, make polymkeric substance after standing harsh heat-resistant experiment, still there is higher physicals, excellent shape memory function and the novel material of performance can be prepared thus.
Preferably: in order to adjust its processing characteristics, also comprise lubricant wax or siloxanes, adding of lubricant ensure that processing technology and Forming Quality.
Preferably, in order to adjust forming stability, also comprise weighting agent Al (OH)
3, Mg (OH)
1, SiO
2, being added in this system except adjustment forming stability (expand, shrink) of weighting agent, also promote the generation of crosslinking structure in irradiation processing, enhancing thermotolerance, anti ageing property and flame retardant resistance, create synergistic effect with sensitizing agent and nucleator.
The pyrocondensation temperature of Low Temperature Thermal collapsed shape material with memory of the present invention is 60-70 DEG C, can recover deformation ratio 100-500%, at 121 DEG C of lasting 168h thermo-oxidative ageings, and stretching strength retentivity more than 75%, extension at break conservation rate more than 85%.
Another object of the present invention is to provide the method preparing above-mentioned Low Temperature Thermal collapsed shape material with memory, and its step comprises:
By containing the polymkeric substance of unsaturated double-bond and using trans-polyisoprene and other auxiliary agents at 0-50
dEG Cunder be uniformly mixed, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 20-350kGy.
The invention has the beneficial effects as follows:
Up to 18-35MPa, (performance of the general material contracting with heat using polyisoprene to make is no more than 20MPa to the tensile strength of shape-memory material of the present invention, in CN02136921.6, the tensile strength of material is up to 18MPa, and deformation recovery is at 80-90%); Elongation at break: 280-650%; Deformation-recovery rate: 100-500% (requiring to adjust within the scope of this according to goods); Thermal ageing 121 DEG C/168 hours back draft strength retention >=75%, extension at break conservation rate >=85%, working life > 15 years at 90 DEG C.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with specific embodiment, embodiment of the present invention is described further in detail.
TMPTMA: trimethylolpropane trimethacrylate, hand in hand Science and Technology Ltd. in Nanjing
Using trans-polyisoprene: Qingdao Cefpirome Culfate material company limited
1,2-polyhutadiene: RB820, JSR Corp.
Anti-aging agent 1010: E.I.Du Pont Company
Anti-aging agent 168: Qingdao Siwei Chemical Co., Ltd.
Antioxidant 4010: Shanxi Xiangyu Chemical Co., Ltd.
3,4-polyisoprene: laboratory is synthesized
Silicon-dioxide: the sub-white carbon black Qingdao Company in sieve ground
Antioxidant MB: Shanghai Kai Yin Chemical Co., Ltd.
Anti-aging agent RD: Guangdong Du Ba novel material Science and Technology Ltd.
POE: polyolefin elastomer, 8450, DOW Chemical
EPDM: polyolefin elastomer, 3745, DOW Chemical
NR: Thailand 10# smoked sheet
EVA:150 Dupont
TAIC: cyanacrylate Shanghai Fang Rui reaches Chemical Company
TAC: cyanacrylate Shanghai Fang Rui reaches Chemical Company
ZnO, ZnSt
2: Shijiazhuang Tai Xin Chemical Co., Ltd.
Wax ... siloxanes: Guangzhou Cheng Hua Chemical Co., Ltd.
α Al, Mg (OH)
2: Taixing, Jinan Fine Chemical Co., Ltd
Remarks: the weathering test condition of the following stated is 121 DEG C/168h.
Comparative example 1:
100 parts of TPI and 3 part TMPTMA, 0.005 part of ZnO, 1 part of anti-aging agent, 1010,1 part of anti-aging agent 168 and 0.5 part of anti-aging agent RD are uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 80kGy.
The performance index of this product are: aging front tensile strength is 28MPa, aging rear trickling; Aging front tensile yield is 468%, aging rear trickling; Response rate is 90%; Heat-drawn wire is 70 DEG C, and gel content is 0.
Embodiment 1:
90 parts of TPI, 10 parts of 1,2-PB, 3 part of TMPTMA, 0.005 part of ZnO, 1 part of anti-aging agent, 1010,1 part of anti-aging agent 168 and 0.5 part of anti-aging agent RD are uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 20kGy.
The performance index of this product are: aging front and back tensile strength is respectively 28MPa and 17MPa; Aging front and back tensile yield is respectively 465% and 380%; Response rate is 100%, and heat-drawn wire is 60 DEG C, and gel content is 12%.
Contrasted from the performance index of embodiment 1 and comparative example 1 product, pure TPI cross-linking radiation is under the dosage of 80kGy, and gel content is 0, aging of product poor performance, and heat-drawn wire is high; Side chain adds in reaction system containing the polymkeric substance of unsaturated double-bond, and improve irradiation efficiency, can reach crosslinked under the dosage of 20kGy, and aging resistance is improved, heat-drawn wire decreases.
Embodiment 1 '
In order to the response situation of this programme under the irradiation dose of proving and comparisom file 1, the irradiation dose of embodiment 1 is adjusted to 80kGy, and other are with embodiment 1.
The performance index of this product of this product are: aging front and back tensile strength is respectively 29MPa and 18MPa; Aging front and back tensile yield is respectively 470% and 395%; Response rate is 100%, and heat-drawn wire is 60 DEG C, and gel content is 56%.
As can be seen here, side chain adds in reaction system containing the polymkeric substance of unsaturated double-bond, compared with pure TPI system, under same irradiation dose, increases the crosslinking degree of TPI.
Comparative example 2:
By 100 parts of TPI and 1 part anti-aging agent, 1010,2 parts of ZnSt
2be uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 260kGy.
The performance index of this product are: aging front tensile strength is 27MPa, aging rear trickling; Aging front tensile yield is 470%, aging rear trickling; Response rate is 100%; Heat-drawn wire is 70 DEG C.
Embodiment 2:
By 100 parts of TPI and 2 part TAC, 1 part of anti-aging agent, 1010,1 part of antioxidant MB, 1 part of anti-aging agent RD and 2 parts of ZnSt
2be uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 200kGy.
The performance index of this product are: aging front and back tensile strength is respectively 27MPa and 20-21MPa; Aging front and back tensile yield is respectively 470% and 400%; Response rate is 100%, and heat-drawn wire is 70 DEG C.
Embodiment 2 ':
By 40 parts of TPI, 60 part of 3,4-polyisoprene and 2 parts of TAC, 1 part of anti-aging agent, 1010,1 part of antioxidant MB, 1 part of anti-aging agent RD and 2 parts of ZnSt
2be uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 120kGy.
The performance index of this product of this product are: aging front and back tensile strength is respectively 25MPa and 19-20MPa; Aging front and back tensile yield is respectively 526% and 450%; Response rate is 100%, and heat-drawn wire is 60 DEG C.
Contrasted from the performance index of comparative example 2 and embodiment 2 product, rubber and plastic double base protection system adds with sensitizing agent, acts synergistically, improve the crosslinking degree of TPI cross-linking radiation system, thus improve ageing-resistant performance crosslinked generation of TPI system.
Contrasted from the performance index of comparative example 2, embodiment 2 and embodiment 2 ' product, side chain, containing under unsaturated double-bond polymkeric substance and sensitizing agent and the acting in conjunction of rubber and plastic double base protection system, improves TPI interfacial effect, adds crosslinking degree, improve ageing-resistant performance, reduce heat-drawn wire.
Comparative example 3:
At mill 120 DEG C, add using trans-polyisoprene 70 parts, after plasticating, add ethylene-vinyl acetate copolymer (30/10) 20 part successively, antioxidant 1010 1 part, Zinic stearas 1 part, 3 parts, zinc oxide, 5 parts, calcium carbonate, even post-tensioning of plasticating is in blocks, pelletizing after cooling, through twin screw extruder extruding pelletization, single screw extrusion machine is extruded into pipe, pipe irradiates through Co 60, and irradiation dose is 130KGy.Pipe after irradiation is expanded to 100% of former pipe diameter at the temperature of 80 DEG C, cooling and shaping.
The performance index of this product are: aging front and back tensile strength is respectively 11-19MPa and 10-18MPa; Aging front and back tensile yield is respectively 350-850% and 300-800%; Heat-drawn wire is 80 DEG C.
Embodiment 3:
By 60 parts of TPI, 40 parts of EVA, 4 parts of TAIC, 1 part of ZnSt, 1 part of antioxidant 4010,1 part of anti-aging agent, 1010,0.5 part of antioxidant MB is uniformly mixed at 0-50 DEG C, and hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 100kGy.
The performance index of this product are: aging front and back tensile strength is respectively 30-32MPa and 20-23MPa; Aging front and back tensile yield is respectively 280-650% and 250-600%; Heat-drawn wire is 62 DEG C.
Contrasted from the performance index of comparative example 3 and embodiment 3 product, main chain is containing acting synergistically with sensitizing agent and preventing aging system adding of unsaturated double-bond polymkeric substance, increase the interfacial effect of crystal form and unsaturated polymer, promote that TPI is cross-linked, when not adding weighting agent and coupling agent, ageing-resistant performance and tensile strength still have significantly to be improved.
And adopt cobalt-60 radiosterilize in comparative example 3, electron rays irradiation is adopted in embodiment 3, the irradiation source environmental protection of embodiment 3, and the synergistic effect that sensitizing agent and main chain produce containing unsaturated double-bond polymkeric substance, the transmission of irradiation ray to system is high, the dosage reached required for identical crosslinking degree obtains and reduces, and improves irradiation efficiency, has saved the energy.
Comparative example 4:
At mixing facilities 120 DEG C, add anti-form-1,4-polyisoprene 40 parts, adds 50 parts, ethylene-propylene rubber(EPR) successively after plasticating, White Carbon black 7 parts, other auxiliary agents 3 parts, even post-tensioning of plasticating is in blocks, and pelletizing after cooling, uses twin screw extruder granulation, single screw extrusion machine is extruded into pipe, then uses 20Mrad (being equivalent to 200kGy) irradiation dose irradiation.Pipe embryo after irradiation is expanded and is put in place at the temperature of 100 DEG C, cooling and shaping.The complete shrinkage temperature of this Low Temperature Thermal shrink sleeve is 50 DEG C.
Embodiment 4:
90 parts of TPI, 10 parts of EPDM and 3 part TAIC, 1 part of anti-aging agent, 1010,1 part of anti-aging agent, 168,0.5 part of anti-aging agent RD and 5 parts of silicon-dioxide are uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 150kGy.
The performance index of this product are: aging front and back tensile strength is respectively 25-28MPa and 19-21MPa; Aging front and back tensile yield is respectively 530-550% and 450-480%; Heat-drawn wire is 65 DEG C.
Contrasted from the performance index of comparative example 4 and embodiment 4 product, sensitizing agent and unsaturated polymer add generation synergistic effect, when EPDM add-on is only 10 parts, improve the crosslinking degree of TPI under same irradiation dose, improve irradiation efficiency, and improve heat-drawn wire.
Comparative example 5:
At mixing facilities 120 DEG C, add anti-form-1,4-polyisoprene 35 parts, adds natural rubber 55 parts successively after plasticating, White Carbon black 5 parts, other auxiliary agents 5 parts, even post-tensioning of plasticating is in blocks, and pelletizing after cooling, uses twin screw extruder granulation, single screw extrusion machine is extruded into pipe, then uses 25Mrad (being equivalent to 250kGy) irradiation dose irradiation.Pipe embryo after irradiation is expanded and is put in place at the temperature of 100 DEG C, cooling and shaping.The complete shrinkage temperature of this Low Temperature Thermal shrink sleeve is only 45 DEG C.
Embodiment 5:
70 parts of TPI, 25 parts of natural rubbers and 3 parts of TMPTMA, 1 part of ZnO, 1 part of antioxidant 4010,2 parts of anti-aging agent, 1010,1.5 parts of anti-aging agent RDs are uniformly mixed at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixing 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 100kGy.
The performance index of this product are: aging front and back tensile strength is respectively 30MPa and 22-24MPa; Aging front and back tensile yield is respectively 510% and 480%; Heat-drawn wire is 60 DEG C.
Contrasted from the performance index of comparative example 5 and embodiment 5 product, sensitizing agent and unsaturated polymer add generation synergistic effect, when natural rubber add-on is only 25 parts, improve the crosslinking degree of TPI under same irradiation dose, improve irradiation efficiency, and improve heat-drawn wire.
Claims (11)
1. a Low Temperature Thermal collapsed shape material with memory, is characterized in that: employing contains the polymkeric substance of unsaturated carbon-carbon double bond and using trans-polyisoprene is blended, it is obtained to be cross-linked.
2. Low Temperature Thermal collapsed shape material with memory as claimed in claim 1, is characterized in that: the polymkeric substance containing unsaturated carbon-carbon double bond comprises side chain containing the polymkeric substance of unsaturated double-bond or the main chain polymkeric substance containing unsaturated double-bond.
3. Low Temperature Thermal collapsed shape material with memory as claimed in claim 2, is characterized in that: side chain comprises at least one of 3,4-polyisoprene, 1,2-polyhutadiene containing the polymkeric substance of unsaturated double-bond.
4. Low Temperature Thermal collapsed shape material with memory as claimed in claim 2, is characterized in that: main chain comprises at least one of terpolymer EP rubber, natural rubber, EVA and POE containing the polymkeric substance of unsaturated double-bond.
5. Low Temperature Thermal collapsed shape material with memory as claimed in claim 1, is characterized in that: be 5%-70%:30%-95% containing the polymkeric substance of unsaturated double-bond and the mass percent of using trans-polyisoprene.
6. Low Temperature Thermal collapsed shape material with memory as claimed in claim 1, is characterized in that: also comprise sensitizing agent and nucleator.
7. Low Temperature Thermal collapsed shape material with memory as claimed in claim 6, it is characterized in that: sensitizing agent is at least one of TMPTMA, TAIC, TAC, PDMI, nucleator is ZnO or ZnSt
2.
8. Low Temperature Thermal collapsed shape material with memory as claimed in claims 6 or 7, is characterized in that: also comprise oxidation inhibitor, lubricant and weighting agent.
9. Low Temperature Thermal collapsed shape material with memory as claimed in claims 6 or 7, is characterized in that: oxidation inhibitor comprises the mixture of at least one of anti-aging agent 1010, anti-aging agent 168, at least one of antioxidant MB and antioxidant 4010, anti-aging agent RD.
10. Low Temperature Thermal collapsed shape material with memory as claimed in claim 1, it is characterized in that: the pyrocondensation temperature of Low Temperature Thermal collapsed shape material with memory is 60-70 DEG C, deformation ratio 100-500% can be recovered, at 121 DEG C of lasting 168h thermo-oxidative ageings, stretching strength retentivity more than 75%, extension at break conservation rate more than 85%.
As described in 11. preparations are as arbitrary in claim 1-10, the method for Low Temperature Thermal collapsed shape material with memory, is characterized in that, comprise the steps:
Be uniformly mixed containing polymkeric substance and the using trans-polyisoprene of unsaturated double-bond and other auxiliary agents at 0-50 DEG C, hybrid frequency 100-1800 turns/min, mixes 2-15min; After being extruded by mixture, through injection moulding, molding or blow molding, then through electron rays irradiation, irradiation dose is 20-350kGy.
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| CN107298775A (en) * | 2017-08-10 | 2017-10-27 | 青岛科技大学 | It is a kind of that there is composite material of shape memory of two kinds of deformation temperatures and preparation method thereof |
| WO2019033911A1 (en) * | 2017-08-18 | 2019-02-21 | 北京化工大学 | Composite material having shape memory function, manufacturing method, and applications |
| CN113072722A (en) * | 2021-03-03 | 2021-07-06 | 中国科学院化学研究所 | Preparation method of radiation cross-linked trans-1, 4-polyisoprene material and trans-1, 4-polyisoprene material |
| CN113265088A (en) * | 2021-05-18 | 2021-08-17 | 浙江理工大学 | Preparation method of ethylene-vinyl acetate copolymer porous shape memory material |
| CN115819874A (en) * | 2022-12-09 | 2023-03-21 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Sports shoe sole foaming composite material and preparation method thereof and sports shoe sole |
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| CN107298775A (en) * | 2017-08-10 | 2017-10-27 | 青岛科技大学 | It is a kind of that there is composite material of shape memory of two kinds of deformation temperatures and preparation method thereof |
| CN107298775B (en) * | 2017-08-10 | 2021-09-03 | 青岛科技大学 | Shape memory composite material with two deformation temperatures and preparation method thereof |
| WO2019033911A1 (en) * | 2017-08-18 | 2019-02-21 | 北京化工大学 | Composite material having shape memory function, manufacturing method, and applications |
| CN113072722A (en) * | 2021-03-03 | 2021-07-06 | 中国科学院化学研究所 | Preparation method of radiation cross-linked trans-1, 4-polyisoprene material and trans-1, 4-polyisoprene material |
| CN113265088A (en) * | 2021-05-18 | 2021-08-17 | 浙江理工大学 | Preparation method of ethylene-vinyl acetate copolymer porous shape memory material |
| CN113265088B (en) * | 2021-05-18 | 2022-07-01 | 浙江理工大学 | Preparation method of ethylene-vinyl acetate copolymer porous shape memory material |
| CN115819874A (en) * | 2022-12-09 | 2023-03-21 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Sports shoe sole foaming composite material and preparation method thereof and sports shoe sole |
| CN115819874B (en) * | 2022-12-09 | 2024-05-14 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Foam composite material for soles of sports shoes, preparation method of foam composite material and soles of sports shoes |
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Inventor after: Li Haixia Inventor after: Wang Shaorong Inventor after: Chen Zhanxun Inventor after: Zhang Shuhua Inventor after: Sun Yingying Inventor after: Xie Huanhuan Inventor before: Li Haixia Inventor before: Wang Shaorong Inventor before: Chen Zhanxun Inventor before: Zhang Lihua |
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