CN105038165A - Bio-based thermoplastic elastomer with shape memory function and preparation method thereof - Google Patents
Bio-based thermoplastic elastomer with shape memory function and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a bio-based thermoplastic elastomer with shape memory function and a preparation method thereof. The bio-based thermoplastic elastomer with shape memory function is prepared from the following raw materials in parts by mass: 30-80 parts of polylactic acid, 20-70 parts of epoxidized natural rubber, 0.2-2 parts of antioxidant, 0.02-2 parts of boron trifluoride etherate and 0.1-3 parts of crosslinking agent. The preparation method comprises the following steps: uniformly mixing the polylactic acid, antioxidant, boron trifluoride etherate and epoxidized natural rubber at 150-190 DEG C, and adding the crosslinking agent under high-speed shearing actions to vulcanize the rubber in situ, thereby obtaining the bio-based thermoplastic elastomer with shape memory function. The rubber phase and plastic phase of the bio-based thermoplastic elastomer respectively appear a continuous phase structure. The structure endows the material with excellent shape memory function and mechanical properties, so that the shape fixation rate is up to 100%, and the shape recovery rate is up to 90% or above.
Description
Technical field
The present invention relates to a kind of thermoplastic elastomer, particularly relate to a kind of bio-based thermoplastic elastomer with shape memory function and preparation method thereof.With PLA, ENR for basic raw material, by dynamic vulcanization, prepare the material with shape memory function.
Background technology
From the sixties in 20th century, shape-memory material causes the extensive concern in the world with the performance of its uniqueness.Shape memory refers to the goods with original shape, after deformation is fixing, stimulates the process of means that it can be made again to recover the phenomenon of original shape by external conditionss such as heating.Up to the present, the shape-memory material that it is found that mainly contains shape memory alloy, shape memory ceramics, shape-memory polymer etc.Wherein, shape-memory polymer because of its there is lighter in weight, deformation quantity is large, temperature sensor is low, easy machine-shaping and the superior performance such as cheap and come into one's own.Shape-memory material, according to recovery of shape principle, can be divided into thermotropic, electroluminescent type, photic type and chemical co-ordination type etc.And the raw material sources of thermic induction type shape memory polymer material are comparatively wide, it is comparatively easy that deformation adopts temperature to control, and performance range of choice is wider, can meet the service requirements of a lot of occasion, is day by day subject to the attention of Materials science worker.
Polymer in poly lactic acid series is important biological medical polymer material, has good biocompatibility and biodegradability, is widely applied in Fracture internal fixaiion, tissue engineering bracket, surgical sutures, controlled drug delivery systems etc.But its range of application of the drawbacks limit that the fragility of PLA is high, shock resistance is poor, in order to expand the Application Areas of poly(lactic acid), modification need be carried out to it.In addition, polymer in poly lactic acid series has thermoforming memory effect, implement distortion, but finished product response rate is very low more than second-order transition temperature.
Chinese invention patent application CN103642184A discloses dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof, according to the mass fraction, its raw material comprises following component in this invention: poly(lactic acid) 20 ~ 90 parts, rubber 10 ~ 80 parts, 0.1 ~ 1 part, oxidation inhibitor, interface modifier 1 ~ 10 part, linking agent 0.1 ~ 4.8 part, additional crosslinker 0.1 ~ 4.2 part; During preparation, at the temperature of 150 ~ 190 DEG C, poly(lactic acid), oxidation inhibitor, rubber and interface modifier are mixed, under high speed shear, adds linking agent and additional crosslinker carries out dynamic vulcanization to rubber phase, obtain polylactic acid plastic/rubber thermoplastic elastomer prepared by dynamic vulcanization.The polylactic acid plastic/rubber thermoplastic elastomer physical strength of gained of the present invention is high, has excellent impact property, can repeat the features such as processing.But this invention ENR is only as interface modifier, in the mass fraction of recipe ingredient, the highest consumption is 10 parts, and object improves the consistency of PLA and NR.
PLA and ENR is carried out reaction with solution blended process or extrusion by melting and carrys out polydactyl acid by Chinese invention patent application CN102250451A.The method by the epoxy degree of the ratio of controls NR/ENR, ENR, melt extrude temperature, annealing temperature and annealing time etc. and regulate and control degree of crystallinity, the degree of crosslinking of PLA and the situation that is separated, compensate for the weakness of PLA poor toughness, and improve its thermostability, its processing characteristics is improved.But this application just carrys out toughness reinforcing PLA by simple physical blending, does not both relate to the crosslinking reaction of ENR, also do not relate to the reaction of the chemical graft of ENR and PLA, does not more relate to the shape memory function etc. of co-mixing system.
Summary of the invention
The technical problem to be solved in the present invention is that polymer in poly lactic acid series finished product fixed rate is not enough, recovery of shape is slower, the problems such as it is serious that shape recovery rate is low and toughness is poor and Reusability shape-memory properties declines, a kind of shape fixed rate of thermoplastic elastomer is provided to reach 100%, shape recovery rate reaches more than 97%, after 3 times stretch circulation, the shape fixed rate of sample still reaches 100%, shape recovery rate reaches more than 95%, after 5 times stretch circulation, the shape fixed rate of sample still reaches 100%, shape recovery rate reaches more than 90%, and bio-based thermoplastic elastomer with shape memory function of original shape and preparation method thereof can be returned to rapidly in 1 minute.
PLA and ENR of the present invention is renewable resources, PLA and ENR there occurs complicated chemical reaction in melting dynamic vulcanization process, namely ENR there occurs cross-linking chemistry reaction in various degree on the one hand, interface crosslinking is there is with PLA and reacts in another aspect ENR while being cross-linked, thus further increasing the consistency of the two, the toughness of PLA is further enhanced.Meanwhile, boron trifluoride diethyl etherate promotes the carrying out of above-mentioned complex reaction.What is more important, in the present invention, co-mixing system after the two dynamic vulcanization has two-arch tunnel structure, this special construction is different from conventional dynamic vulcanization thermoplastic elastomer (TPV) phase structure, this structure can play toughening effect better to PLA, and gives material more excellent shape memory function.The comprehensive additive effect result of above-mentioned multi-effect, the TPV of PLA/ENR has outstanding tensile strength, shock strength or tear strength, shape fixed rate 100%, first shape recovery rate more than 97%, and turnaround time is short.Medicine, aviation etc. can be widely used in and require higher field.As significant to the intelligence instrument of temperature sensitive response, be particularly useful for the intelligent bandage of intelligent medical apparatus as temperature sensitive response, the fixed rate up to 100% can fix bone, compressing wound etc. fast, accurately and effectively.
The object of the invention is achieved through the following technical solutions:
There is the bio-based thermoplastic elastomer of shape memory function, according to the mass fraction, its composition of raw materials consists of: poly(lactic acid) (PLA) 30 ~ 80 parts, epoxy natural rubber (ENR) 20 ~ 70 parts, 0.2 ~ 2 part, oxidation inhibitor, boron trifluoride diethyl etherate 0.02 ~ 2 part, linking agent 0.1 ~ 3 part; Described linking agent is the perbenzoic acid tertiary butyl, dibenzoyl peroxide, 2,4 ?dichlorobenzoperoxide, dicumyl peroxide, di-t-butyl peroxide, bis-?one or more in (t-butylperoxyisopropyl) benzene;
During preparation, at 150 ~ 190 DEG C, poly(lactic acid), oxidation inhibitor, boron trifluoride diethyl etherate, epoxy natural rubber are mixed, or first by poly(lactic acid), oxidation inhibitor mixing plasticizing, then add epoxy natural rubber, boron trifluoride diethyl etherate, mix; Under high speed shear effect, add linking agent to rubber vulcanization in situ, obtain the bio-based thermoplastic elastomer with shape memory function.
For realizing the object of the invention further, preferably, described poly(lactic acid) for poly-L ?lactic acid, poly-D ?one or more of lactic acid and poly-dl-lactide.
Preferably, described epoxy natural rubber to be epoxidation degree be 10% epoxy natural rubber (ENR ?10), epoxidation degree is the epoxy natural rubber (ENR ?25) of 25%, epoxidation degree is the epoxy natural rubber (ENR ?30) of 30%, epoxidation degree be 50% epoxy natural rubber (ENR ?50) and epoxidation degree be one or more in the epoxy natural rubber (ENR ?75) of 75%.
Preferably, described oxidation inhibitor is one or more in irgasfos 168, antioxidant 1076, antioxidant 1010, antioxidant 2246, oxidation inhibitor 1098, oxidation inhibitor B102, oxidation inhibitor B900 and anti-oxidant DLTP.
Preferably, calculate by mass parts, the consumption of described epoxy natural rubber is 50 ~ 70 parts; The consumption of described poly(lactic acid) be 30 ?50 parts.
The described bio-based process for preparation of thermoplastic elastomer with shape memory function: after poly(lactic acid), oxidation inhibitor, epoxy natural rubber are mixed at 150 ~ 190 DEG C, or first by poly(lactic acid), oxidation inhibitor mixing plasticizing, add epoxy natural rubber, boron trifluoride diethyl etherate again, mix; Under high speed shear effect, add linking agent to rubber vulcanization in situ, obtain the bio-based thermoplastic elastomer with shape memory function.
Compared to existing technology, the present invention has the following advantages:
1) the bio-based thermoplastic elastomer prepared by the present invention, PLA and ENR there occurs complicated chemical reaction in melting dynamic vulcanization process, namely ENR there occurs cross-linking chemistry reaction in various degree on the one hand, there is interface crosslinking with PLA and react in another aspect ENR, thus the consistency further increasing the two further increases the toughness of PLA while being cross-linked.Adding of boron trifluoride diethyl etherate, promote the complex reaction that above-mentioned PLA and ENR carries out under complex environment.In this system, plastics phase and crosslinked rubber phase have continuous structure simultaneously, and these are different from the Rubber-Plastics Blends that traditional rubber is dispersed in plastics phase matrix with particulate state.The two-arch tunnel structure of this uniqueness can increase the contact area of PLA phase and ENR phase, is more conducive to Interfacial compatibilization, and when External Force Acting, is conducive to effective transmission of striking energy, thus toughness reinforcing PLA better.In shape memory, time below the second-order transition temperature that temperature is down to PLA, the ENR of distortion can fix by continuous print PLA phase; When temperature rises to more than PLA second-order transition temperature, continuous and crosslinked ENR phase has excellent elastic-restoring force, can promote the reinstatement of PLA phase, thus give this system good shape memory function by good interface in recovery process.
2) the present invention's a kind of bio-based thermoplastic elastomer (TPV) of adopting dynamic vulcanization process to prepare, has good biological functionality and biocompatibility, has better mechanical property and can repeat processing to use.Wherein PLA and ENR derives from nature, is renewable resources.
3) the bio-based thermoplastic elastomers prepared by the present invention has good shape memory function, and can the shape of material be fixed at short notice, fixed rate is 100%, and can reply rapidly after heating, shape recovery rate reaches more than 90%.Present invention reduces the recovery of shape time of shape-memory material in application process, as namely embodiment 3 can reach the response rate of 100% in 19s, in the field that the ask for something such as aviation, medical treatment is meticulous, there is higher using value.
4) the bio-based thermoplastic elastomers with shape memory function adopting the present invention to prepare has outstanding tensile strength, shock strength or tear strength, is several times or the increase by more than 25% of contrast Chinese invention patent application CN102250451A respectively.As: when PLA/ENR mass ratio is 60/40, TPV (embodiment 2) shock strength prepared by the present invention is 47.32kJ/m
2, tensile strength is 26.5MPa, the shock strength of comparative example 2 is 17.38kJ/m
2, tensile strength is 21MPa; When PLA/ENR mass ratio is 30/70, TPV (embodiment 3) tensile strength prepared by the present invention is 7.6MPa, tear strength 44KN/m, and the tensile strength of comparative example 3 is 2MPa, tear strength 21KN/m;
5) the bio-based thermoplastic elastomer prepared by the present invention can use conventional method for processing forming, shaping and processing device carries out forming process, and contour machining equipment is commonly used, and power consumption of polymer processing is low, complete processing is simple, can be shaped to the goods of arbitrary shape according to application target.
6) the bio-based thermoplastic elastomer that prepared by the present invention has the excellent properties of PLA and ENR concurrently; there is excellent toughness and shape memory function, the fields such as medical treatment, aerospace, automotive industry, chemical industry, new forms of energy and environment protection can be widely used in.The present invention suits green, low-carbon (LC), the development trend of environmental protection and requirement.
Accompanying drawing explanation
Surface sweeping Electronic Speculum (SEM) picture of Fig. 1 position embodiment 5 after methylene dichloride etches away (PLA in top layer is etched away, be left crosslinked ENR).
The shape fixed rate situation map that Fig. 2 is embodiment 3, embodiment 5, embodiment 6 stretch at three times.
The shape recovery rate situation map that Fig. 3 is embodiment 3, embodiment 5, embodiment 6 stretch at three times.
Embodiment
For understanding the present invention better, below in conjunction with drawings and Examples, the present invention will be further described, but it should be noted that, embodiment does not form the restriction to application claims protection domain.Poly(lactic acid) all in 75 degree of loft drier dry 6 hours before use in embodiment and comparative example.
Embodiment 1
Choosing poly(lactic acid) is matrix resin, specifically selects poly-dl-lactide (PDLLA, Zhejiang Hisun Biomaterials Co., Ltd).First on a mill until by ENR ?10 to plasticate.Secondly by poly(lactic acid) (80g), irgasfos 168 (0.2g), join temperature 150 DEG C, rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?10 (20g), boron trifluoride diethyl etherate (0.5g), adds the perbenzoic acid tertiary butyl (0.1g) after mixing 3min and carries out dynamic vulcanization, discharging after 5min.Being the particle of fine uniform with crusher by sample broke, is then standard batten with the injection molding of singe screw injection moulding machine.The injection temperature of singe screw injection moulding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, and screw speed is 90r/min.
Embodiment 2
Choosing poly(lactic acid) is matrix resin, poly-dl-lactide (PDLLA, Zhejiang Hisun Biomaterials Co., Ltd), ENR ?30.First on a mill until by ENR ?30 to plasticate.Secondly by poly(lactic acid) (60g), antioxidant 1010 (0.8g), join temperature 170 DEG C, rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?30 (40g), boron trifluoride diethyl etherate (0.4g), mixing 3min after add 2,4 ?dichlorobenzoperoxide (1.0g) carry out dynamic vulcanization, discharging after 5min.Being the particle of fine uniform with crusher by sample broke, is then standard batten with the injection molding of singe screw injection moulding machine.The injection temperature of singe screw injection moulding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, and screw speed is 90r/min.
Embodiment 3
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?30.First on a mill until by ENR ?30 to plasticate.By poly(lactic acid) (30g), oxidation inhibitor B102 (1.8g), join temperature 150 DEG C, rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?30 (70g), boron trifluoride diethyl etherate (1.0g), mixing 3min after add Er ?(t-butylperoxyisopropyl) benzene (1.8g) carry out dynamic vulcanization, discharging after 5min.Be the particle of fine uniform with crusher by sample broke, gained blend heats on compression molding instrument, pressurization, Heating temperature 160 DEG C, and institute's plus-pressure is: 25MPa, and hot pressing was colded pressing 4 minutes after 10 minutes, and obtained thickness is the film of 1mm.
Embodiment 4
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?25.First on a mill until by ENR ?25 to plasticate.Secondly by poly(lactic acid) (70g), antioxidant 1076 (0.4g), join temperature 160 DEG C, rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?25 (30g), boron trifluoride diethyl etherate (0.5g), adds benzoyl peroxide (2.0g) after mixing 3min and carries out dynamic vulcanization, discharging after 5min.Being the particle of fine uniform with crusher by sample broke, is then standard batten with the injection molding of singe screw injection moulding machine.The injection temperature of singe screw injection moulding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, and screw speed is 90r/min.
Embodiment 5
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?50.First on a mill until by ENR ?50 to plasticate.Secondly by poly(lactic acid) (50g), antioxidant 2246 (1.2g), join temperature 180 DEG C, rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?50 (50g), boron trifluoride diethyl etherate (0.6g), adds dicumyl peroxide (2.5g) after mixing 3min and carries out dynamic vulcanization, discharging after 5min.Be the particle of fine uniform with crusher by sample broke, gained blend heats on compression molding instrument, pressurization, Heating temperature 160 DEG C, and institute's plus-pressure is: 25MPa, and hot pressing was colded pressing 4 minutes after 10 minutes, and obtained thickness is the film of 1mm.
Embodiment 6
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?75.First on a mill until by ENR ?75 to plasticate.By poly(lactic acid) (40g), oxidation inhibitor 1098 (2.0g), join temperature 190 DEG C, rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?75 (60g), boron trifluoride diethyl etherate (0.5g), adds di-t-butyl peroxide (3.0g) after mixing 3min and carries out dynamic vulcanization, discharging after 5min.Be the particle of fine uniform with crusher by sample broke, gained blend heats on compression molding instrument, pressurization, Heating temperature 160 DEG C, and institute's plus-pressure is: 25MPa, and hot pressing was colded pressing 4 minutes after 10 minutes, and obtained thickness is the film of 1mm.
Comparative example 1 (adopting Chinese invention patent application CN102250451A)
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?10.First on a mill until by ENR ?10 to plasticate.Secondly by poly(lactic acid) (80g), irgasfos 168 (0.2g), joins temperature 150 DEG C, and rotor speed is in the torque rheometer of 60r/min, adds ENR10 (20g) after 3min, discharging after mixing 5min.Being the particle of fine uniform with crusher by sample broke, is then standard batten with the injection molding of singe screw injection moulding machine.The injection temperature of singe screw injection moulding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, and screw speed is 90r/min.
Comparative example 2 (adopting Chinese invention patent application CN102250451A)
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?30.First on a mill until by ENR ?30 to plasticate.Secondly by poly(lactic acid) (60g), antioxidant 1010 (0.8g), joins temperature 170 DEG C, and rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?30 (40g), discharging after mixing 5min.Being the particle of fine uniform with crusher by sample broke, is then standard batten with the injection molding of singe screw injection moulding machine.The injection temperature of singe screw injection moulding machine is: feeding section 165 DEG C, 170 DEG C, compression section, homogenizing zone 170 DEG C, machine head port mould part 175 DEG C, and screw speed is 90r/min.
Comparative example 3 (adopting Chinese invention patent application CN102250451A)
Choosing poly(lactic acid) is matrix resin, Zhejiang Hisun Biomaterials Co., Ltd, poly-dl-lactide (PDLLA), ENR ?30.First on a mill until by ENR ?30 to plasticate.By poly(lactic acid) (30g), oxidation inhibitor B102 (1.8g), joins temperature 150 DEG C, and rotor speed is in the torque rheometer of 60r/min, add after 3min ENR ?30 (70g), mixing 5min after discharging.Be the particle of fine uniform with crusher by sample broke, gained blend heats on compression molding instrument, pressurization, Heating temperature 160 DEG C, and institute's plus-pressure is: 25MPa, and hot pressing was colded pressing 4 minutes after 10 minutes, and obtained thickness is the film of 1mm.
Embodiment 1 ?6 and comparative example 1 ?3 performance be shown in Table 1.The test procedure of shape fixed rate and shape recovery rate is as follows:
1. in the middle of dumbbell shape sample, draw two lines, spacing 20mm, is labeled as L
0.
2. sample is heated to heat-drawn wire 60 DEG C, continues 10min.
3. tension specimen is to 100% deformation.
4. under stretched state, temperature drops to room temperature, and continue 5min, now two distance between centers of tracks are L
1
5. unloaded by sample, now distance between centers of tracks is L
2
6. sample reheats temperature 60 C, and after 5min, distance between centers of tracks is L
3
The test procedure being returned to net shape required time is as follows:
1, sample is heated 10min at about 80 DEG C, then bend to volution with glass stick.
2, sample is cooled to room temperature, solid shape rapidly.
3, be placed on by sample in the water-bath of 60 DEG C, record is returned to net shape required time.
Table 1
As can be seen from Table 1, according to comparative example 1 and embodiment 1, comparative example 2 and embodiment 2, comparative example 3 and embodiment 3 (identical rubber and plastic ratio), the TPV mechanical property prepared by the present invention is better than simple physical blending system all greatly.The shock strength of embodiment 2 has brought up to 2.7 times of comparative example 2.The tensile strength of embodiment 3, tear strength are 1.9 times, 2.10 times of comparative example 2 respectively.The shock strength of embodiment 1, tensile strength, elongation at break are 1.18 times, 1.05 times, 2.9 times of comparative example 1 respectively.
Shape recovery rate, the reply speed of TPV co-mixing system prepared by the embodiment of the present invention are all good than the system of simple blend, if shape recovery rate is higher than 90%, recovers shape required time and are significantly shorter than contrast Chinese invention patent application CN102250451A.
Fig. 1 is the electron scanning micrograph of embodiment 5 after methylene dichloride etching, and methylene dichloride can dissolve PLA phase, and remaining is crosslinked ENR phase.Can find out, the PLA etched away presents external phase structure with residual ENR, namely “ Hai ?sea " structure.This from common rubber phase with particulate state be dispersed in “ Hai in plastics external phase ?island " TPV of structure has the different of essence, this two-arch tunnel structure makes material have more excellent shape memory function and mechanical property.
Shape fixed rate after Fig. 2 and Fig. 3 is embodiment 3, embodiment 5, embodiment stretch for 6 three times and shape recovery rate.After three times stretch, the shape fixed rate of sample is still 100%, and shape recovery rate, all more than 95%, shows excellent shape fixed rate and response rate.
Bio-based thermoplastic elastomer provided by the invention is with the excellent properties of polylactic acid plastic and vegetable rubber, there is good shape memory function, its fixed rate can reach 100%, shape memory response rate reaches more than 97% first, after 3 times stretch circulation, the shape fixed rate of sample still reaches 100%, shape recovery rate reaches more than 95%, after 5 times stretch circulation, the shape fixed rate of sample still reaches 100%, shape recovery rate reaches more than 90%, and in 1 minute, can return to original shape rapidly.The intelligence instrument of these characteristics to temperature sensitive response is significant.Boron trifluoride diethyl etherate promotes that the chemical graft of PLA and ENR reacts in the present invention and can effectively improve two-phase interface consistency and cohesiveness simultaneously, effectively can maintain the Reusability performance of excellent shape-memory properties.Material of the present invention can be widely used in the fields such as medical treatment, aerospace, automotive industry, agriculture production, chemical industry, new forms of energy and environment protection.PLA/ENR shape-memory material of the present invention is particularly useful for the intelligent bandage of intelligent medical apparatus as temperature sensitive response, and it can fix bone, compressing wound etc. fast, accurately and effectively up to the fixed rate of 100%.The present invention also suits green, low-carbon (LC), the development trend of environmental protection and requirement.
Claims (6)
1. there is the bio-based thermoplastic elastomer of shape memory function, it is characterized in that, according to the mass fraction, its composition of raw materials consists of: poly(lactic acid) 30 ~ 80 parts, epoxy natural rubber 20 ~ 70 parts, 0.2 ~ 2 part, oxidation inhibitor, boron trifluoride diethyl etherate 0.02 ~ 2 part, linking agent 0.1 ~ 3 part; Described linking agent is the perbenzoic acid tertiary butyl, dibenzoyl peroxide, 2,4 ?dichlorobenzoperoxide, dicumyl peroxide, di-t-butyl peroxide, bis-?one or more in (t-butylperoxyisopropyl) benzene;
During preparation, at 150 ~ 190 DEG C, poly(lactic acid), oxidation inhibitor, boron trifluoride diethyl etherate, epoxy natural rubber are mixed, or first by poly(lactic acid), oxidation inhibitor mixing plasticizing, then add epoxy natural rubber, boron trifluoride diethyl etherate, mix; Under high speed shear effect, add linking agent to rubber vulcanization in situ, obtain the bio-based thermoplastic elastomer with shape memory function.
2. the bio-based thermoplastic elastomer with shape memory function according to claim 1, is characterized in that: described poly(lactic acid) for poly-L ?lactic acid, poly-D ?one or more of lactic acid and poly-dl-lactide.
3. there is the bio-based thermoplastic elastomer of shape memory function according to claim 1, it is characterized in that: described epoxy natural rubber to be epoxidation degree be 10% epoxy natural rubber, epoxidation degree is the epoxy natural rubber of 25%, epoxidation degree is the epoxy natural rubber of 30%, epoxidation degree be 50% epoxy natural rubber and epoxidation degree be one or more in the epoxy natural rubber of 75%.
4. the bio-based thermoplastic elastomer with shape memory function according to claim 1, is characterized in that: described oxidation inhibitor is one or more in irgasfos 168, antioxidant 1076, antioxidant 1010, antioxidant 2246, oxidation inhibitor 1098, oxidation inhibitor B102, oxidation inhibitor B900 and anti-oxidant DLTP.
5. the bio-based thermoplastic elastomer with shape memory function according to claim 1, is characterized in that: calculate by mass parts, the consumption of described epoxy natural rubber is 50 ~ 70 parts; The consumption of described poly(lactic acid) be 30 ?50 parts.
6. utilize the bio-based process for preparation of thermoplastic elastomer with shape memory function described in any one of claim 1 ?5, it is characterized in that: after poly(lactic acid), oxidation inhibitor, epoxy natural rubber are mixed at 150 ~ 190 DEG C, or first by poly(lactic acid), oxidation inhibitor mixing plasticizing, add epoxy natural rubber, boron trifluoride diethyl etherate again, mix; Under high speed shear effect, add linking agent to rubber vulcanization in situ, obtain the bio-based thermoplastic elastomer with shape memory function.
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