CN100406510C - Polyolefin/styrene series elastomer blending shape memory material and preparation method thereof - Google Patents
Polyolefin/styrene series elastomer blending shape memory material and preparation method thereof Download PDFInfo
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- CN100406510C CN100406510C CNB2006100217856A CN200610021785A CN100406510C CN 100406510 C CN100406510 C CN 100406510C CN B2006100217856 A CNB2006100217856 A CN B2006100217856A CN 200610021785 A CN200610021785 A CN 200610021785A CN 100406510 C CN100406510 C CN 100406510C
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Abstract
The present invention discloses shape memory material of co-mixed polyolefin/styrene elastomer. The shape memory material contains polyolefin 20-80 weight portions, styrene elastomer 20-80 weight portions, plasticizer 10-30 weight portions, chemical crosslinking agent 0.1-1 weight portions and co-crosslinking agent 1-10 weight portions. It has tensile strength not lower than 12 MPa, gel rate not higher than 10 wt%, restoring rate at 100 deg.c 80 not lower than wt%, fixing rate at 20 deg.c not lower than 80 wt%, restoring response temperature not lower than 30 deg.c and restoring period not more than 6 sec. The present invention also discloses the preparation process of the shape memory material.
Description
Technical field
The invention belongs to shape-memory polymer intermingling material and preparing technical field thereof, be specifically related to a kind of polyolefine/styrene series elastomer blending shape memory material and preparation method.
Background technology
Shape-memory polymer (SMP) is a kind of new functional macromolecule material, knowing fields such as puppet, entertainment physical culture, articles for daily use and agricultural, the energy at electronic communication, health care, machinofacture, commodity has wide practical use, since the eighties in 20th century, caused people's very big interest, and obtained developing rapidly.Shape memory polymer material mainly is by existing polymer modification or synthetic new SMP are obtained.
The method that existing polymer modification is made it to become SMP comprises physical blending and chemically crosslinked blend.
(the thermal shape memory function of MAH modified PE/PA6 co-mixing system such as Jin He, engineering plastics are used, 2004,32 (2)) adopt the physical blending method, cause the product (MAH-g-PE) and nylon 6 (PA6) blend of maleic anhydride (MAH) grafted polyethylene (PE) with dicumyl peroxide (DCP), prepared physical blending type shape-memory material, and studied of the influence of factors such as recovery temperature, extensibility, deformation set time, answer number of times this material shape memory performance with microlitic structure.Zhang Guangcheng, Liu Tiemin (high density polyethylene(HDPE)/natural rubber Study on Character of Shape Memorizing, Xi'an Petroleum University's journal (natural science edition), 2004,5) adopts the physical blending method, has prepared high density polyethylene(HDPE)/natural rubber (HDPE/NR).This class exists memory performance to weaken with access times repeatedly by the shape-memory material of physical blending method preparation.
(the research of crosslinked with silicane HDPE/TPI blending shape memory material such as Jiang Min, plastics science and technology, 2005,2) selecting HDPE for use is material of main part, blend and the means by crosslinked with silicane have prepared the chemically crosslinked blending shape memory material with it to adopt gutta-percha (TPI), this material shape memory performance excellence, but gel fraction is higher, makes relatively difficulty of recycling of materials and reprocessing.
Summary of the invention
Purpose of the present invention is to provide a kind of polyolefine/styrene series elastomer blending shape memory material (SMPM) at the deficiencies in the prior art.This material can be directly used in injection, spinning, extrudes, compression moulding, produces required shape memory product.
A further object of the invention provides a kind of chemically crosslinked blend method for preparing polyolefine/styrene series elastomer blending shape memory material.
Polyolefine/styrene series elastomer blending shape memory material provided by the invention is characterized in that this material by weight, wherein contains:
20～80 parts of polyolefine
20～80 parts of styrene series elastomers
10～30 parts in softening agent
0.1～1 part of chemical cross-linking agent
1～10 part of additional crosslinker,
And its tensile strength 〉=12Mpa, gel fraction≤10%, response rate (100 ℃) 〉=80%, fixed rate (20 ℃) 〉=80% is replied response temperature 〉=30 ℃, turnaround time≤6s.
Wherein the preferred melt flow rate (MFR) of polyolefine that contains of this material is any in high density polyethylene(HDPE), new LDPE (film grade), linear low density of polyethylene or the polypropylene of 1.5～15g/10min.
Styrene series elastomer optimization styrene-butadiene-styrene block copolymer that this material contains, in the styrene isoprene styrene block copolymer (SIS) any.
The softening agent preferred polyolefm wax that this material contains.
The preferred dicumyl peroxide of the chemical cross-linking agent that this material contains, 2,5-dimethyl-2, any in 5-bis(t-butylperoxy) hexane, two (t-butylperoxy sec.-propyl) benzene.
In preferred maleic anhydride of the additional crosslinker that this material contains or the silane coupling agent any.
A kind of method for preparing polyolefine/styrene series elastomer blending shape memory material provided by the invention is divided into a step blending method and two step blending methods, it is characterized in that a step blending method is with 20～80 parts of polyolefine, 20～80 parts of styrene series elastomers, 10～30 parts in softening agent, 0.1～1 part of chemical cross-linking agent, 1～10 part of additional crosslinker adds Banbury mixer together or adds behind the premix in the common forcing machine together, 150～210 ℃ of temperature, blend got final product in 2～15 minutes; Two step blending methods are earlier with 20～80 parts of styrene series elastomers, 10～30 parts in softening agent, 0.1～0.5 part of chemical cross-linking agent, 1～10 part of additional crosslinker, add Banbury mixer together or add behind the premix in the common forcing machine together, 180～220 ℃ of temperature, blend 2～15 minutes, and then in the gained blend, add 20～80 parts of polyolefine, 0～20 part in softening agent, 0.01～0.5 part of chemical cross-linking agent, 0～9 part of additional crosslinker, and add Banbury mixer together or add in the common forcing machine behind the premix together, 150～210 ℃ of temperature, blend got final product in 2～15 minutes.
Polyolefine/the styrene series elastomer blending shape memory material that makes with aforesaid method can be directly by injection, spinning, extrude, the forming method of common plastics such as compression moulding, it is good to prepare shape-memory properties, along with the increase shape memory rate of replying number of times is constant, and the component that are used for health care, machinofacture, commodity knowledge puppet, entertainment physical culture, clothes, articles for daily use that can recycle.
In order to verify the related physical performance of polyolefine/styrene series elastomer blending shape memory material that the present invention prepares, the present invention detects it according to following testing standard and method, and the total result of detection is as follows:
1. mechanical property
Press the GB/T1042-1992 standard at the test of universal electrical material-testing machine, draw speed 300mm/min.Tensile strength 〉=the 12Mpa of material of the present invention.
2. gel content
Take by weighing 0.5 gram sample, break into the sample bag, place toluene/dimethylbenzene (50/50) mixing solutions of 80 ℃ 10h that refluxes, take out to be placed in 120 ℃ of baking ovens and dries by the fire 6h, taking-up weighing, and calculated for gel rate as follows with 1200 order copper mesh:
The gel fraction of material of the present invention≤10%.
3. response rate
The sheet material of compression moulding is cut into tension specimen with cutting knife, and to draw two stripe pitch with marking pen on batten be the fine rule of 10mm, that is: L
0=10mm.Be loaded on and do the constant temperature stretching on the anchor clamps on press, load 5Kg, stretch ratio are 300% (L
1).Treat its fixedly 12h, be put into the spacing L that measures line-to-line after heating is replied in the hot water then
2Response rate is calculated as follows:
The response rate of material of the present invention (100 ℃) 〉=80%.
4. fixed in shape rate
The fixed in shape rate is an important parameter that influences the shape memory behavior, has characterized the ability that shape-memory material goods when post forming keep its shape.Its size directly have influence on the post forming goods in use depositing and the keeping.
Making two gauge lengths with permanent pen on coupons is L
0Graticule, be fixed in the manual stretcher, by the back cooling rapidly that stretches of 300% stretch ratio: measure the graticule distance L
1After placing 1h, 6h, 24h, 48h, room temperature records distance between bench marks from L
3Then the fixed in shape rate can be expressed as:
The fixed rate of material of the present invention (20 ℃) 〉=80%.
5. answer response temperature
10 ℃/min of rate of heating, sample quality are 5～6mg, aluminium pincers pot with cover, and heated perimeter is 10～180 ℃, nitrogen protection is measured Tg, with this answer response temperature as SMP.
Answer response temperature 〉=30 of material of the present invention ℃.
6. turnaround time
Test sample is made 4 of coiled by a lengthy motion picture bar enclose thread helix shape samples, put into 100 ℃ hot water digital camera shooting motion short-movie, the Movie Maker that is carried by windows XP is put slowly and is read turnaround time again.With this qualitative representation test returns speed.
Turnaround time≤the 6s of material of the present invention.
7. reply number of times and shape memory rate relation
The answer number of times of material of the present invention is greater than after more than 3, and its response rate is almost with to reply number of times irrelevant.
The present invention compared with prior art has following advantage:
1, the polyolefine/styrene series elastomer blending shape memory material gel fraction of the present invention's preparation is lower, has only percentum generally speaking, so its processing characteristics is good, can match in excellence or beauty with polyolefine, and also can process repeatedly, helps reclaiming.
2, the polyolefine/styrene series elastomer blending shape memory material of the present invention preparation response rate height not only, recovery rate is fast, and when replying number of times greater than after more than 3, its response rate is almost irrelevant with the answer number of times, thereby can reclaim processing repeatedly and do not influence its memory performance, having solved memory performance that prior art exists can weaken with access times repeatedly, influences the problem of recycling of materials and reprocessing.
3, not only memory performance is good for the polyolefine/styrene series elastomer blending shape memory material of the present invention's preparation, and good mechanical properties.
4, preparation method's technology of the present invention is simple, does not need special processing equipment, is easy to apply.
5, the cost of material of the present invention's use is inexpensive, thereby has broad application prospects in fields such as health care, machinofacture, commodity knowledge puppet, entertainment physical culture, clothes, articles for daily use and agricultural, the energy.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for that the present invention is further described; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection domain of the present invention.
The code name that uses in following examples is:
HDPE=high density polyethylene(HDPE) LDPE=new LDPE (film grade) LLDPE=linear low density of polyethylene
SBS=styrene-butadiene-styrene block copolymer PP=polypropylene
The SIS=styrene isoprene styrene block copolymer (SIS)
SEBS=hydrogenation of ethylene-butadiene block copolymer DCP=dicumyl peroxide
AD=2,5-dimethyl-2,5-bis(t-butylperoxy) hexane
SMPM=polyolefine/styrene series elastomer blending shape memory material
Embodiment 1
First with 60 parts of SEBS, 20 parts of polyethylene waxs, 0.2 part of DCP, 5 parts of maleic anhydrides add in the common Banbury mixer together, are warming up to 200 ℃ of melt temperatures, blend 5 minutes; Then in the blend of the SEBS of gained, the HDPE that to add 40 parts of melt flow rate (MFR)s again be 2～4g/10min, 0.2 part of DCP, 3 parts of maleic anhydrides continue after 8 minutes, promptly to obtain SMPM in 200 ℃ of following blend of melt temperature in common Banbury mixer.Melt flow rate (MFR) is 1.5～15g/10min
This SMPM recovery of shape rate is 85～87%, and fixed rate 85～87%, tensile strength are 18～20MPa, and turnaround time, 2～3s replied 33～35 ℃ of response temperatures, gel fraction 3～5%.
Embodiment 2
First with 30 parts of SIS, 9 parts of oxidized polyethlene wax, 0.3 part of AD, 4 parts of maleic anhydrides add in the common Banbury mixer together, are warming up to 180 ℃ of melt temperatures, blend pelletizing in 5 minutes; To blend and 70 parts of LDPE that melt flow rate (MFR) is 5～7g/10min of the SIS of pelletizing, 1 part of oxidized polyethlene wax, 0.3 part of AD then, in high-speed mixer premix evenly after, add in the twin screw extruder,, promptly obtain SMPM 185 ℃ of following blend of melt temperature 2 minutes.
This SMPM recovery of shape rate is 88～90%, and fixed rate 85～87%, tensile strength are 14～16MPa, and turnaround time, 3～5s replied 63～65 ℃ of response temperatures, gel fraction 5～7%.
Embodiment 3
With 70 parts of SEBS, 30 parts of melt flow rate (MFR)s are the PP of 9～10g/10min, 30 parts of Poly Propylene Waxes, 0.2 part DCP, 3 parts of silane coupling agents add together in the high-speed mixer premix evenly after, add in the twin screw extruder, 165 ℃ of melt temperatures, blend 6 minutes promptly obtains SMPM.
This SMPM recovery of shape rate is 85～90%, and fixed rate 88～89%, tensile strength are 18～20MPa, and turnaround time, 2～4s replied 33～35 ℃ of response temperatures, gel fraction 1～3%.
Embodiment 4
First with 50 parts of SBS, 19.5 parts of polyethylene waxs, 0.2 part of AD, 10 parts of silane coupling agents add in the common Banbury mixer together, are warming up to 210 ℃ of melt temperatures, blend pelletizing in 10 minutes; To blend and 50 parts of HDPE that melt flow rate (MFR) is 2～4g/10min of the SBS of pelletizing, 0.5 part of polyethylene wax, 0.3 part of AD then, in high-speed mixer premix evenly after, add in the single screw extrusion machine,, promptly obtain SMPM 210 ℃ of following blend of melt temperature 7 minutes.
This SMPM recovery of shape rate is 88～90%, and fixed rate 87～90%, tensile strength are 18～21MPa, and turnaround time, 3～5s replied 44～47 ℃ of response temperatures, gel fraction 4～6%.
Embodiment 5
With 60 parts of SBS, 40 parts of melt flow rate (MFR)s are the PP of 1.5～2.5g/10min, 30 parts of Poly Propylene Waxes, 0.1 part two (t-butylperoxy sec.-propyl) benzene, 2 parts of maleic anhydrides add in the common Banbury mixer together, 200 ℃ of melt temperatures, blend 15 minutes promptly obtains SMPM.
This SMPM recovery of shape rate is 85～87%, and fixed rate 88～91%, tensile strength are 24～27MPa, and turnaround time, 3～5s replied 40～45 ℃ of response temperatures, gel fraction 1～3%.
Embodiment 6
First with 30 parts of SIS, 29 parts of polyethylene waxs, 0.5 part of two (t-butylperoxy sec.-propyl) benzene, 2 parts of silane coupling agents add in the common Banbury mixer together, are warming up to 180 ℃ of melt temperatures, blend pelletizing in 8 minutes; To blend and 70 parts of HDPE that melt flow rate (MFR) is 7～9g/10min of the SIS of pelletizing then, 1 part of polyethylene wax, 0.3 part two (t-butylperoxy sec.-propyl) benzene, in high-speed mixer premix evenly after, add in the single screw extrusion machine, 195 ℃ of following blend of melt temperature 4 minutes, promptly obtain SMPM.
This SMPM recovery of shape rate is 80～85%, and fixed rate 90～96%, tensile strength are 25～28MPa, and turnaround time, 4～6s replied 65～67 ℃ of response temperatures, gel fraction 5～7%.
Embodiment 7
With 80 parts of SIS, 20 parts of melt flow rate (MFR)s are the PP of 10～11g/10min, 20 parts of oxidized polyethlene wax, 0.2 part AD, 6 parts of silane coupling agents add together in the high-speed mixer premix evenly after, add in the single screw extrusion machine, 210 ℃ of following blend of melt temperature 7 minutes, promptly obtain SMPM.
This SMPM recovery of shape rate is 90～95%, and fixed rate 82～84%, tensile strength are 18～20MPa, and turnaround time, 1～2s replied 30～35 ℃ of response temperatures, gel fraction 1～3%.
Embodiment 8
With 40 parts of SEBS, 60 parts of melt flow rate (MFR)s are the LDPE of 13～15g/10min, 10 parts of oxidized polyethlene wax, 0.6 part DCP, 5 parts of maleic anhydrides add together in the high-speed mixer premix evenly after, add in the twin screw extruder, 200 ℃ of following blend of melt temperature 3 minutes, promptly obtain SMPM.
This SMPM recovery of shape rate is 92～95%, and fixed rate 80～83%, tensile strength are 16～19MPa, and turnaround time, 2～3s replied 45～47 ℃ of response temperatures, gel fraction 5～7%.
Embodiment 9
First with 40 parts of SBS, 8 parts of oxidized polyethlene wax, 0.4 part of two (t-butylperoxy sec.-propyl) benzene, 5 parts of silane coupling agents add in the common Banbury mixer together, are warming up to 160 ℃ of melt temperatures, blend pelletizing in 8 minutes; To blend and 60 parts of LDPE that melt flow rate (MFR) is 8～10g/10min of the SBS of pelletizing then, 10 parts of oxidized polyethlene wax, 0.4 part two (t-butylperoxy sec.-propyl) benzene, in high-speed mixer premix evenly after, add in the twin screw extruder, 180 ℃ of following blend of melt temperature 6 minutes, promptly obtain SMPM.
This SMPM recovery of shape rate is 85～90%, and fixed rate 80～83%, tensile strength are 17～20MPa, and turnaround time, 3～4s replied 45～47 ℃ of response temperatures, gel fraction 6～8%.
Embodiment 10
With 20 parts of SEBS, 80 parts of melt flow rate (MFR)s are the LLDPE of 3～4g/10min, 15 parts of polyethylene waxs, 0.9 part AD, 4 parts of silane coupling agents add together in the high-speed mixer premix evenly after, add in the twin screw extruder, 190 ℃ of following blend of melt temperature 10 minutes, promptly obtain SMPM.
This SMPM recovery of shape rate is 82～85%, and fixed rate 88～90%, tensile strength are 16～20MPa, and turnaround time, 4～6s replied 60～63 ℃ of response temperatures, gel fraction 8～10%.
Claims (10)
1. polyolefine/styrene series elastomer blending shape memory material is characterized in that this material by weight, wherein contains:
20～80 parts of polyolefine
20～80 parts of styrene series elastomers
10～30 parts in softening agent
0.1～1 part of chemical cross-linking agent
1～10 part of additional crosslinker,
And its tensile strength 〉=12Mpa, gel fraction≤10% at 100 ℃ of following response rate 〉=80%, at 20 ℃ of following fixed rate 〉=80%, is replied response temperature 〉=30 ℃, turnaround time≤6s.
2. polyolefine/styrene series elastomer blending shape memory material according to claim 1 is characterized in that polyolefine that this material contains is selected from any in high density polyethylene(HDPE), new LDPE (film grade), linear low density of polyethylene or the polypropylene that melt flow rate (MFR) is 1.5～15g/10min.
3. polyolefine/styrene series elastomer blending shape memory material according to claim 1 and 2 is characterized in that styrene series elastomer that this material contains is selected from any in styrene-butadiene-styrene block copolymer, the styrene isoprene styrene block copolymer (SIS).
4. polyolefine/styrene series elastomer blending shape memory material according to claim 1 and 2 is characterized in that the softening agent that this material contains is selected from polyolefin-wax.
5. polyolefine/styrene series elastomer blending shape memory material according to claim 3 is characterized in that the softening agent that this material contains is selected from polyolefin-wax.
6. polyolefine/styrene series elastomer blending shape memory material according to claim 1 and 2, it is characterized in that the chemical cross-linking agent that this material contains is selected from dicumyl peroxide, 2,5-dimethyl-2, any in 5-bis(t-butylperoxy) hexane, two (t-butylperoxy sec.-propyl) benzene.
7. polyolefine/styrene series elastomer blending shape memory material according to claim 5, it is characterized in that the chemical cross-linking agent that this material contains is selected from dicumyl peroxide, 2,5-dimethyl-2, any in 5-bis(t-butylperoxy) hexane, two (t-butylperoxy sec.-propyl) benzene.
8. polyolefine/styrene series elastomer blending shape memory material according to claim 1 is characterized in that additional crosslinker that this material contains is selected from any in maleic anhydride or the silane coupling agent.
9. polyolefine/styrene series elastomer blending shape memory material according to claim 7 is characterized in that additional crosslinker that this material contains is selected from any in maleic anhydride or the silane coupling agent.
10. the method for preparing polyolefine/styrene series elastomer blending shape memory material, it is characterized in that this method is with 20～80 parts of polyolefine, 20～80 parts of styrene series elastomers, 10～30 parts in softening agent, 0.1～1 part of chemical cross-linking agent, 1～10 part of additional crosslinker, add Banbury mixer together or add in the common forcing machine behind the premix together, 150～210 ℃ of temperature, blend got final product in 2～15 minutes, or earlier with 20～80 parts of styrene series elastomers, 10～30 parts in softening agent, 0.1～0.5 part of chemical cross-linking agent, 1～10 part of additional crosslinker, add Banbury mixer together or add behind the premix in the common forcing machine together, 180～220 ℃ of temperature, blend 2～15 minutes, and then in the gained blend, add 20～80 parts of polyolefine, 0～20 part in softening agent, 0.01～0.5 part of chemical cross-linking agent, 0～9 part of additional crosslinker, and add Banbury mixer together or add behind the premix in the common forcing machine together, 150～210 ℃ of temperature, blend got final product in 2～15 minutes.
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| US9963584B2 (en) * | 2013-12-27 | 2018-05-08 | Zeon Corporation | Block copolymer composition, production method therefor, and film |
| CN106317579B (en) * | 2016-09-13 | 2019-12-03 | 复旦大学 | It is a kind of can be with the polymer-function material of 3D printing |
| CN106589738A (en) * | 2016-12-15 | 2017-04-26 | 叶静 | Fast-self-repairing shape memory polymer material |
| CN107033304A (en) * | 2017-05-09 | 2017-08-11 | 东南大学 | With can self-repair function shape memory inlay section thermal plastic high polymer material |
| CN111484659B (en) * | 2019-01-29 | 2022-05-10 | 合肥杰事杰新材料股份有限公司 | Shape memory polyolefin composite material and preparation method thereof |
| CN112721371A (en) * | 2020-12-25 | 2021-04-30 | 江阴中达软塑新材料股份有限公司 | Shape memory biaxially oriented polypropylene heat-seal film and preparation method thereof |
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