CN110016196A - A kind of shape-memory material and preparation method thereof - Google Patents
A kind of shape-memory material and preparation method thereof Download PDFInfo
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- CN110016196A CN110016196A CN201910262406.XA CN201910262406A CN110016196A CN 110016196 A CN110016196 A CN 110016196A CN 201910262406 A CN201910262406 A CN 201910262406A CN 110016196 A CN110016196 A CN 110016196A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000012781 shape memory material Substances 0.000 title claims abstract description 30
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 75
- 229920000636 poly(norbornene) polymer Polymers 0.000 claims abstract description 48
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 43
- 239000005060 rubber Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 24
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims description 17
- 238000004073 vulcanization Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000518 rheometry Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 2
- ZQTYQMYDIHMKQB-UHFFFAOYSA-N exo-norborneol Chemical compound C1CC2C(O)CC1C2 ZQTYQMYDIHMKQB-UHFFFAOYSA-N 0.000 claims 2
- NRVFHZGBTDXOEY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;zinc Chemical group [Zn].CC(=C)C(O)=O NRVFHZGBTDXOEY-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 38
- 239000003431 cross linking reagent Substances 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 description 72
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 14
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical group [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 13
- 238000010382 chemical cross-linking Methods 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 238000007792 addition Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- 238000004220 aggregation Methods 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 229920000554 ionomer Polymers 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006126 semicrystalline polymer Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000668842 Lepidosaphes gloverii Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- -1 peroxide DCP free radical Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 244000132619 red sage Species 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920000431 shape-memory polymer Polymers 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of shape-memory materials and preparation method thereof, belong to polymeric material field.Its technical solution are as follows: it includes main body high molecular material polynorbornene, plasticizer paraffin oil, crosslinking agent cumyl peroxide.Preparation method includes being kneaded polynorbornene and paraffin oil in banburying chamber, and the rear cumyl peroxide that is added is kneaded obtained rubber compound, is vulcanized on vulcanizing press.The invention has the benefit that improving polynorbornene shape fixed rate and recovery rate, increases mechanics of materials intensity, make it have better shape-memory properties.
Description
Technical field
The present invention relates to shape-memory material field more particularly to a kind of polynorbornene memory material and its preparation sides
Method.
Background technique
Shape-memory polymer (SMPs) is a kind of important irritation responsive materials, it can be with deformation occurs and can
Its temporary shapes is fixed, such as heat, electric current, magnetic field, light under environmental stimuli, SMPs, which will be triggered, restores its original shape
Shape, wherein being heated to be most typically and general stimulation mode.Traditional SMPs material can be roughly divided into following four type: object
Manage crosslinking glassy polymers, the glassy polymers of chemical crosslinking, physical crosslinking semi-crystalline polymer, chemical crosslinking
Semi-crystalline polymer, wherein physics and chemical crosslinking network are as stationary phase, the permanent shape of " memory " material, vitrifyingization turn
Temperature (Tg) or fusing point (Tm) are used as reversible phase transition, the fixation for temporary shapes.Nowadays, scholars, which have begun, grinds
SMPs is studied carefully in the potential application of every field, including intelligent clothing, medical applications, biosensor and space industry etc..So far
Until, scholars have developed many different types of SMPs, as PNB, trans-polyisoprene, styrene-butadiene are embedding
Section copolymer, polyurethane, epoxy-based polymerization object etc., shape memory mechanism is also constantly completed.
1984, French CDF Chimie company developed PNB, and is commercialized.PNB and cycloalkane and paraffin oil
With good compatibility, PNB is studied earliest is used as damping material, acoustic material.PNB average molecular weight is about 3 × 106,
Tg is 35 DEG C or so, since it is there are a large amount of physical entanglements, higher than Tg at a temperature of, the sub-chain motion of PNB can be activated,
Show the elasticity of rubber like, provide driving force for shape recovery, thus PNB have as a kind of shape-memory material it is huge
Development potentiality.In research before,
Although the various performances to PNB conduct extensive research, the sub-chain motion energy of PNB how is further increased
Power improves shape fixed rate and recovery rate, increases mechanics of materials intensity, make it have better shape-memory properties is always
One research direction.
Summary of the invention
In order to improve the shape-memory properties of shape-memory material, the present invention provides a kind of shape-memory material and its systems
Preparation Method.
A kind of shape-memory material, shape-memory material contain main body high molecular material polynorbornene, plasticizer paraffin
Oil, crosslinking agent cumyl peroxide.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10-30 parts, cumyl peroxide weight
Part is 1-2.5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are excellent
It is selected as 1 part.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10 parts, and cumyl peroxide parts by weight are excellent
It is selected as 1.5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are excellent
It is selected as 1.5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 30 parts, and cumyl peroxide parts by weight are excellent
It is selected as 1.5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are excellent
It is selected as 2 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are excellent
It is selected as 2.5 parts.
A kind of preparation method preparing above-mentioned shape-memory material, includes the following steps:
(1), first by polynorbornene and paraffin oil in the Haake torque that initial temperature is 125 DEG C, revolving speed is 50r/min
It is kneaded 10min in the banburying chamber of rheometer, rubber compound a is made；
(2), rubber compound a is added and cools to 60 DEG C, in the banburying chamber for the Haake torque rheometer that revolving speed is 30r/min,
Cumyl peroxide is added to be kneaded, rubber compound b is made；
(3), by rubber compound b, film c is made in bottom sheet on a mill, and double roller temperature is 50 DEG C；
(4), film c is parked into 18-24 hours, preferably 20 hours, preferably 22 hours, preferably 23 hours.
(5), film c is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 10min.
The present invention is using polynorbornene as basis material, after paraffin oil is added, introduces cumyl peroxide and then causes
The cross-linking reaction of PNB generates PNB cross-linked network inside system, and system glass transition temperature is effectively reduced, and increases segment fortune
Kinetic force improves shape fixed rate and recovery rate, increases mechanics of materials intensity.
In order to preferably realize foregoing invention purpose, the present invention also provides a kind of shape-memory materials, contain main body height
Molecular material polynorbornene, plasticizer paraffin oil, crosslinking agent cumyl peroxide, assistant crosslinking agent zinc methacrylate.
Above-mentioned polynorbornene parts by weight are 100 parts, and the paraffin oil parts by weight are 10-30 parts, and the peroxidating two is different
Propyl benzene parts by weight are 0.5-2.5 parts, and the zinc methacrylate parts by weight are 1-9 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate parts by weight are 1 part.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate parts by weight are 1 part.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are
1 part, zinc methacrylate parts by weight are 1 part.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 30 parts, and cumyl peroxide parts by weight are
2 parts, zinc methacrylate parts by weight are 1 part.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate parts by weight are 3 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate preferred weight part is 3 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 30 parts, and cumyl peroxide parts by weight are
2 parts, zinc methacrylate parts by weight are 3 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate parts by weight are 5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate preferred weight part is 5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 30 parts, and cumyl peroxide parts by weight are
2 parts, zinc methacrylate parts by weight are 5 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate parts by weight are 7 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate preferred weight part is 7 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 30 parts, and cumyl peroxide parts by weight are
2 parts, zinc methacrylate parts by weight are 7 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 10 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate parts by weight are 9 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 20 parts, and cumyl peroxide parts by weight are
0.5 part, zinc methacrylate preferred weight part is 9 parts.
Above-mentioned polynorbornene parts by weight are 100 parts, and paraffin oil parts by weight are 30 parts, and cumyl peroxide parts by weight are
2 parts, zinc methacrylate parts by weight are 9 parts.
A method of preparing above-mentioned shape-memory material comprising the steps of:
It (1), is 125 DEG C in initial temperature by polynorbornene, paraffin oil, zinc methacrylate, revolving speed is 50r/min's
Be kneaded 13 minutes in the banburying chamber of Haake torque rheometer, be made rubber compound d wherein institute's zinc methacrylate at 8 minutes
Remaining 50% is added when being added 50%, 10 minutes；
(2), by rubber compound d in the banburying chamber for the Haake torque rheometer that initial temperature is 60 DEG C, revolving speed is 30r/min
After being kneaded 1 minute, cumyl peroxide is added and is kneaded 1min again, rubber compound e is made；
(3), by rubber compound e, film f is made in bottom sheet on a mill, and the double roller temperature of open mill is 50 DEG C；
(4), film f is parked 18-24 hours；It is preferred that 20 hours；It is preferred that 22 hours；It is preferred that 23 hours
(5), film f is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 11min.
Cumyl peroxide can trigger PNB crosslinking, to construct chemical crosslinking net in the huge physical entanglement structure of PNB
Network provides elastic-restoring force for shape recovery, and when DCP is certain number, PNB can achieve higher shape recovery ratio
Metallic salts of unsaturated carboxylate is initially used as the cross-linking aid of peroxide, can improve material cross-linking efficiency and
It can increase crosslink density.In recent years, scholars, which deepen continuously, studies zinc methacrylate ZDMA to nitrile rubber, natural rubber
The reinforcing effect and enhancing mechanism of the materials such as glue, EP rubbers, butadiene-styrene rubber.The present invention using polynorbornene as basis material,
After zinc methacrylate and paraffin oil is added, introduce cumyl peroxide so that cause PNB cross-linking reaction and ZDMA with
The graft reaction of PNB generates poly-ZDMA nanodispersed phase inside system to the stationary phase inside fastening system, paraffin
System glass transition temperature can be effectively reduced in oil, increases sub-chain motion ability, improves shape fixed rate and recovery rate, increases
Add mechanics of materials intensity, especially greatly improves shape fixed rate and shape recovery ratio point.
The beneficial effects of the present invention are: enhancing polynorbornene mechanical property, the shape for improving polynorbornene is fixed
Rate and shape recovery ratio.
Detailed description of the invention
Fig. 1 is the PNB curing curve of the different DCP dosages of embodiment 1,3,5,6 and comparative example 1
Fig. 2 is the PNB crosslink density scanning figure of the different DCP contents of embodiment 1,3,5,6 and comparative example 1
Fig. 3-1, Fig. 3-2, Fig. 3-3 are the synthermal lower difference DCP number crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Stress relaxation curve
Fig. 4-1, Fig. 4-2, Fig. 4-3 are the strain-of the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Time recovery curve
Fig. 5 is the X-ray diffractogram of the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
The shear modulus G that Fig. 6 is the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1 ' with the change of temperature
Change curve
Fig. 7 is the tan δ variation with temperature curve of the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Fig. 8 is the stress-strain diagram of the different number DCP crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Fig. 9 is the storage modulus E of the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Figure 10 is the fissipation factor tan δ figure of the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Figure 11-1 to Figure 11-5 is the shape memory of the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1
Cyclic curve
The shape fixed rate and shape that Figure 12 is the different DCP numbers crosslinking PNB of embodiment 1,3,5,6 and comparative example 1 are extensive
Multiple rate
The cross-linking reaction curve of Figure 13, difference ZDMA number crosslinking PNB
The Tg change curve of Figure 14, difference ZDMA number crosslinking PNB
Figure 15, before not crosslinking reaction, different ZDMA numbers crosslinking PNB XRD diagram
Figure 16, difference ZDMA number is crosslinked the XRD diagram of PNB after crosslinking reaction
Before Figure 17, PNB do not crosslink reaction, the infared spectrum of different ZDMA number crosslinking PNB
After Figure 18, PNB crosslink reaction, the infared spectrum of different ZDMA number crosslinking PNB
The stress relaxation curve of Figure 19, difference ZDMA number crosslinking PNB
The strain recovery curve of Figure 20, difference ZDMA number crosslinking PNB
The stress-strain diagram of Figure 21, difference ZDMA number crosslinking PNB
The stretching cyclic curve t of Figure 22-1 to Figure 22-6 difference ZDMA number crosslinking PNB
The first time that Figure 23 difference ZDMA number is crosslinked PNB stretches the hysteresis loop area of cyclic curve
The strain energy that Figure 24 difference ZDMA number is crosslinked PNB declines percentage Δ W
Figure 25-1 to Figure 25-6 is the memory cycle curve that different ZDMA numbers are crosslinked PNB
Figure 26 difference ZDMA number is crosslinked PNB shape fixed rate and shape recovery ratio.
Specific embodiment
In order to clarify the technical characteristics of the invention, being illustrated below by specific embodiment to this programme.
Embodiment 1
The present embodiment formula are as follows:
PNB:100 parts；DCP:1 parts；Paraffin oil: 20 parts.
Prepare the preparation method of shape-memory material of the invention
(1), first by polynorbornene and paraffin oil in the Haake torque that initial temperature is 125 DEG C, revolving speed is 50r/min
It is kneaded 10min in the banburying chamber of rheometer, rubber compound a is made；
(2), rubber compound a is added and cools to 60 DEG C, in the banburying chamber for the Haake torque rheometer that revolving speed is 30r/min,
Cumyl peroxide is added to be kneaded, rubber compound b is made；
(3), by rubber compound b, film c is made in bottom sheet on a mill, and double roller temperature is 50 DEG C；
(4), film c is parked 20 hours；
(5), film c is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 10min.
Embodiment 2
The present embodiment formula are as follows:
PNB:100 parts；DCP:1.5；Paraffin oil: 10 parts.
The preparation method is the same as that of Example 1
Embodiment 3
The present embodiment formula is
PNB:100 parts；DCP:1.5 parts；Paraffin oil: 20 parts.
The preparation method is the same as that of Example 1
Embodiment 4
The present embodiment formula is
PNB:100 parts；DCP :/1.5；Paraffin oil: 30 parts.
The preparation method is the same as that of Example 1
Embodiment 5
The present embodiment formula are as follows:
PNB:100 parts；DCP:2.0 parts；Paraffin oil: 20 parts.
The preparation method is the same as that of Example 1
Embodiment 6
The present embodiment formula are as follows:
PNB:100 parts；DCP:2.5 parts；Paraffin oil: 20 parts.
The preparation method is the same as that of Example 1
Comparative example 1
This comparative formulation are as follows:
PNB:100 parts；Paraffin oil: 20 parts.
Preparation method:
(1), first by polynorbornene and paraffin oil in the Haake torque that initial temperature is 125 DEG C, revolving speed is 50r/min
It is kneaded 10min in the banburying chamber of rheometer, rubber compound a is made；
(3), by rubber compound a, film c is made in bottom sheet on a mill, and double roller temperature is 50 DEG C；
(4), film c is parked 20 hours；
(5), film c is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 10min.
Comparative example 1 and the obtained shape-memory material performance test results characterization of embodiment 1,3,5,6 are compared as follows:
Experimental raw: PNB, Austrian STARTECH advanced material Co., Ltd；Paraffin oil 2280, Ningbo Chinese sage's chemical industry have
Limit company；DCP-40, Hunan Yixiang Chemical Industrial Co., Ltd..
(1) cross-linking reaction
This experiment uses national standard GB/T16384-1998, the friendship that PNB is measured without rotor vulcameter of ALPHA company, the U.S.
Connection reaction, vulcameter temperature are 170 DEG C, testing time 30min.
(2) differential scanning calorimetric analysis (DSC)
The model DSC204F11 differential scanning calorimeter produced using German NETZSCH company scans temperature range
It is -40 DEG C~150 DEG C, heating rate is 10 DEG C/min.
(3) stress relaxation
DMA-Q800 type Dynamic Mechanical Analyzer, stretch mode are produced using TA company, the U.S..Sample is applied 50%
Strain, slack time 30min, strain recovery time are 20min, and test temperature is 20 DEG C, 35 DEG C, 60 DEG C.
(4) physical mechanical property
The tensile strength and elongation at break of test sample are carried out using national standard GB-T528-1996.Utilize German Zwick
The AI-9000S type electronics tension tester that company produces is tested, tensile speed 100mm/min, and test temperature is 23 DEG C.
(5) dynamic mechanical is tested
Temperature scanning test is carried out using RPA2000 type rubber machining analyzer, temperature range is 60 DEG C -170 DEG C, frequency
For 1Hz.
Temperature scanning test is carried out using German NETZSCH DMA242 type dynamic visco-elasticity analyser, using double cantilever deformation moulds
Formula, frequency 1Hz, temperature range are -50 DEG C -170 DEG C, and heating rate is 3 DEG C/min.
(6) shape-memory properties
Using DMA-Q800 stretch mode.Test temperature is risen to 42 DEG C and stablizes 5min, at this time the initial length of sample
Labeled as ε p.Then applying 50% strain to each sample, the length mark of sample is ε load, -18 DEG C are then cooled to,
External force is removed, constant temperature 5min fixes the temporary shapes of sample, length mark ε.Temperature is finally raised to 42 from -18 DEG C
DEG C, heating rate is 5 DEG C/min, constant temperature 30min, and final specimen length is labeled as ε rec.
Shape fixed rate (Rf) and shape recovery ratio (Rr), such as following formula:
(7) X-ray diffraction (XRD)
Using X-ray diffractometer, test condition are as follows: Cu polar radiations, 2 θ of scanning range=5-40 °, sweep speed be 5 °/
min。
The following are the results and analysis that are obtained by embodiment and comparative experiments
1, cross-linking reaction
The variation of rheometer torque is able to reflect the chemical crosslinking degree inside high molecular material.Fig. 1 is different DCP numbers
It is crosslinked the curing curve of PNB, as seen from the figure, degree is chemically crosslinked with the increase of DCP dosage, in PNB and gradually increases, in PNB
It is middle to form more and more C-C chemical crossbonds.This is because crosslink agent DCP can be formed with the double bond addition in PNB strand
Macromolecular radical is just chemically crosslinked when two PNB macromolecular radicals meet.Therefore the addition of DCP, Ke Yi
Three-dimensional space network structure is formed in the huge line style physical entanglement of PNB, forms thermal stability more on the basis of physical crosslinking
High chemical crosslinking.
2 glass transition temperatures
Fig. 2 is the DSC curve that different DCP numbers are crosslinked PNB, and the Tg of PNB is 35 DEG C or so, as seen from the figure, when PNB with
After 20phr paraffin oil is kneaded, the Tg of PNB is reduced to 11 ° or so, and with the increase of DCP content, PNB crosslinking degree increases, and C-C is handed over
Connection key makes PNB sub-chain motion be obstructed, and the average chain length of network chain becomes smaller between adjacent crosslinking points, and free volume reduces, and Tg gradually rises
It is high.However, the micro DCP of addition can only form slight chemistry inside PNB and hand over since PNB has huge molecular weight
Connection, so sample Tg variation is small.
3 stress relaxations
Fig. 3-1- to 3-3 be at different temperatures difference DCP number crosslinking PNB stress relaxation curve, the test be by
Sample keeps 50% constant strain, observes the attenuation change of its internal stress at any time.When temperature is 20 DEG C, due to close to examination
The Tg of sample, temperature is greater than the limitation of PNB sub-chain motion the presence of chemical crossbond, so at this temperature, sample is answered
Power relaxation degree is almost the same.When temperature is 35 DEG C, 60 DEG C, with the increase of DCP content, PNB crosslinking degree increases, stress
Relaxation rate is accelerated.This is because molecule interchain, which forms cross-bond, constantly forms stable cross-linked network with the increase of cross-bond
The movement of network, molecule segment is limited increase by cross-linked network, cannot arbitrarily be moved, and last internal stress can only decay to and network
Deform corresponding equilibrium stress value.
At a temperature of 20 DEG C, 35 DEG C, 60 DEG C, the PNB sample stress relaxation degree that DCP crosslinking is not added is changed greatly, this
It is because only existing physical entanglement point inside it, without chemical crossbond, with the raising of temperature, strand warm-up movement aggravates,
Warm-up movement and uneven internal stress drive down, and disentanglement, movement, adjustment and rearrangement occur for segment and strand, and internal stress is gradually
Decaying.When DCP is 2.0,2.5phr, stress relaxation degree is almost the same at different temperatures by PNB, this is because strand is handed over
Connection degree is larger, and stable chemical crosslinking network is influenced by temperature smaller.
Fig. 4-1 to Fig. 4-3 be different DCP numbers be crosslinked PNB strain-time recovery curve, be completed by sample it is above-mentioned
After stress relaxation experiment, their strain recovery situations at 20 DEG C, 35 DEG C and 60 DEG C are observed.As seen from the figure, in test temperature
Under, with the raising of crosslinking degree, the enhancing of PNB elastic restoring force, i.e., after removing external force, PNB restores the speed of its original deformation
Rate is accelerated.At 20 DEG C, 35 DEG C and 60 DEG C, the permanent deformation of uncrosslinked PNB increases as temperature increases, and crosslinking is added
The permanent deformation of the PNB of agent reduces with crosslinking degree, this is because the elastic restoring force that crosslinking generates promotes PNB to restore it
Original-shape, while as temperature increases, the locomitivity of segment is stronger, and elastic restoring force is stronger, and uncrosslinked PNB due to
It only exists physical entanglement, and as the temperature rises, strand is easy to happen sliding during the motion, to promote irreversible
Deformation increases.
4, X-ray diffraction
Fig. 5 is the X-ray diffractogram that different DCP numbers are crosslinked PNB, during the test, the thickness base of this five samples
This is consistent, and the crystal diffraction peak of PNB appears near 18 ° as seen from the figure, and with the increase of crosslink agent DCP dosage, PNB is crosslinked journey
The X-ray diffraction peak intensity of the increase of degree, sample gradually decreases, and chemical crossbond limits the movement of molecule segment, hinders PNB
Faint crystallizing power itself.
5 dynamic properties
Fig. 6 is shear modulus G ' variation with temperature curve that different DCP numbers are crosslinked PNB, as seen from the figure, with temperature
It increasing, the G ' value of uncrosslinked PNB reduces, and the DCP being added in PNB is more, and crosslinking degree is higher, and G ' value is bigger, this is because
The line style segment that physical crosslinking is only existed in PNB, as temperature increases, intermolecular force is reduced, and close with being crosslinked in PNB
The raising of degree, the presence of cross-bond can limit the movement of segment, the elastic-restoring force enhancing of PNB.
Fig. 7 is the tan δ variation with temperature curve that different DCP numbers are crosslinked PNB, as seen from the figure the tan δ of uncrosslinked PNB
Highest, and as the temperature rises, tan δ is gradually increased, this is because physical entanglement is only existed in uncrosslinked PNB, in temperature
During raised, the internal friction of sub-chain motion increases, and tan δ increases, and with the raising of crosslinking degree in PNB, is heating up
Cheng Zhong, tan δ are gradually decreased
7 tensile properties
Fig. 8 is the stress-strain diagram that different number DCP are crosslinked PNB, and table 1 is the physical machine that different number DCP are crosslinked PNB
Tool performance, in conjunction with Fig. 8 and table 1 it is found that the PNB that DCP is not added tensile strength with higher, elongation rate of tensile failure, this is because
Under the effect of external force, the strand of PNB is easy to be orientated along external force direction, and stretching induction crystallization occurs.With adding for DCP
Enter, the crosslink density of PNB increases, and there are chemical crossbonds for molecule interchain, limits the movement of strand, unfolds and be orientated, and breaks
It is broken the ability that induction crystallization occurs during stretching for PNB strand, to cause breaking for PNB to be stretched with the increase of DCP
Long rate, tensile strength gradually decrease.
The physical mechanical property of 1 difference number DCP of table crosslinking PNB
8 shape-memory properties
Fig. 9 and Figure 10 be respectively the storage modulus E ' of the different DCP numbers crosslinking PNB tested by DMA and be lost because
Sub- tan δ figure.Glassy modulus is determined by the elastic energy of crystallization and glassy amorphous, higher glassy modulus energy
It is enough that higher shape fixed rate is assigned when material is in cooling and unloading, and elastomeric state modulus is related with the entropic elasticity of material, compared with
High elastomeric state modulus can be improved the shape recovery ratio of material at high temperature.As seen from the figure, this five kinds of samples are in low temperature, tool
There is a higher glassy modulus, when high temperature, as the crosslinking degree of PNB increases, elastomeric state modulus is increased, in Tg ± 30 DEG C range
It is interior, i.e., at -18 DEG C -42 DEG C, it is known that storage modulus E ' illustrates that PNB has the fixation of good shape and shape extensive in decline rapidly
Renaturation energy.
As shown in Figure 10, as the increase of crosslink agent DCP amount, PNB crosslink density increase, molecular chain movement is by more
Limitation, the corresponding temperature value of tan δ peak value are gradually lowered to high-temperature mobile, tan δ value.Tan δ is equal to loss modulus divided by energy storage
There is peak value to move to right may be because crosslink density increases in modulus, and strand is less susceptible to move, under the action of alternation outfield,
The high PNB strand of crosslink density is only in higher temperatures and lower crosslink density PNB molecular chain movement state consistency, therefore peak value goes out
Now move to right.Similarly, due to crosslinking, the locomitivity decline of strand, between segment due to interior friction heat, that is, loss modulus
Decline, therefore peak value reduces.When temperature is higher than 50 DEG C, due to the unique super high molecular weight of PNB, material molecule chain can be transported
It is dynamic, but cannot move completely, there are still hysteresis, and this phenomenon is more significant with the raising of temperature, but cross-bond is again
It will limit the movement of strand, therefore tan δ value gradually decreases, and tan δ value is with being added increasing and reducing for DCP amount.
Figure 11-1 to Figure 11-5 is the memory cycle curve that different DCP numbers are crosslinked PNB, which is by temperature liter
To 42 DEG C (Tg+30 DEG C), apply 50% deformation to sample, and fixes it by the way that temperature is cooled to -18 DEG C (Tg-30 DEG C) and face
When shape, due to the recovery of PNB network segment conformational entropy, PNB is forced to restore its original-shape finally by heating up again.Figure
12 be that the different DCP numbers being calculated by formula (1) and (2) are crosslinked the shape fixed rate and shape recovery ratio of PNB.
As seen from the figure, PNB has good shape fixed rate, and is held at 99% or more, with crosslinking agent
It is added, shape fixed rate has faint promotion, this is because the fixation of shape depends primarily on the glassy modulus of PNB.By Fig. 9
It is found that the glassy modulus of PNB has small increase with the addition of DCP, therefore the shape fixed rate of PNB is influenced smaller.
By reading pertinent literature, it is known that physical entanglement and chemical crosslinking facilitate polymer and remember its permanent shape.By
It is about 3 × 106 in PNB molecular weight, itself can undertake the effect of physical crosslinking, subtract there are a large amount of physical entanglement segments
The irreversible transformation of few PNB, can remember the permanent shape of PNB, therefore the shape fixed rate of uncrosslinked PNB to a certain extent
It can reach 85% or so.The driving force that shape is restored is the elastic strain generated in deformation process, with the increasing of DCP amount in PNB
Adding, crosslink density increases, and the chemical crossbond of generation can provide stronger elastic-restoring force for recovery of shape, therefore with
The shape recovery rate of PNB increases, and when the number of DCP is 1.5phr, the shape recovery ratio of PNB can reach 88.26%.However
When the number of DCP is greater than 1.5phr, the shape recovery rate of PNB is reduced, on the one hand due to the increase of crosslink agent DCP number, in PNB
The chemical crossbond of middle formation increases, and increases the limitation of its sub-chain motion, carrier components calcium carbonate in another aspect DCP
(CaCO3) amount also will increase, and affect the movement of PNB segment in shape recovery process.
In conclusion chemical crosslinking density is gradually increased in PNB with the increase of DCP dosage.At different temperatures, by
In only existing physical entanglement in uncrosslinked PNB, stress relaxation phenomenon is changed greatly, however as crosslinking degree in PNB
Increase, forms stable chemical crosslinking network, stress relaxation degree is almost the same at different temperatures.
The crystal diffraction peak of PNB appears near 18 °, with the increase of crosslink agent DCP dosage, the X-ray diffraction peak of PNB
It gradually decreases by force, chemical crossbond limits the faint crystallizing power of PNB itself, while also limiting strand in external force
Under movement, unfold and be orientated, destroy PNB strand occur during stretching induction crystallization ability.
PNB has good shape fixed rate, and is held at 99% or more.With the increase of DCP amount in PNB,
Crosslink density increases, and the chemical crossbond of generation can provide stronger elastic-restoring force for recovery of shape, therefore with PNB's
Shape recovery rate increases, and when DCP is 1.5phr, shape recovery ratio can reach 88.26%.
The following are the technical solutions of addition ZDMA, in order to clarify the technical characteristics of the invention, below by specific reality
Mode is applied, this programme is illustrated.
Embodiment 7
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:1 parts, paraffin oil: 10 parts, DCP:0.5 parts.
Prepare the preparation method of shape-memory material of the invention
It (1), is 125 DEG C in initial temperature by polynorbornene, paraffin oil, zinc methacrylate, revolving speed is 50r/min's
It is kneaded 13 minutes in the banburying chamber of Haake torque rheometer, rubber compound d is made, and wherein the zinc methacrylate added at 8 minutes
Remaining 50% is added when entering 50%, 10 minutes；
(2), by rubber compound d in the banburying chamber for the Haake torque rheometer that initial temperature is 60 DEG C, revolving speed is 30r/min
After being kneaded 1 minute, DCP is added and is kneaded 1min again, rubber compound e is made；
(3), by rubber compound e, film f is made in bottom sheet on a mill, and the double roller temperature of open mill is 50 DEG C；
(4), film f is parked 20 hours；
(5), film f is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 11min.
Embodiment 8
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:1 parts, paraffin oil: 20 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 9
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:1 parts, paraffin oil: 20 parts, DCP:1 parts.
Preparation method is the same as embodiment 7.
Embodiment 10
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:1 parts, paraffin oil: 20 parts, DCP:2 parts.
Preparation method is the same as embodiment 7.
Embodiment 11
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:3 parts, paraffin oil: 10 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 12
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:3 parts, paraffin oil: 20 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 13
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:3 parts, paraffin oil: 30 parts, DCP:2 parts.
Preparation method is the same as embodiment 7.
Embodiment 14
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:5 parts, paraffin oil: 10 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 15
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:5 parts, paraffin oil: 20 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 16
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:5 parts, paraffin oil: 30 parts, DCP:2 parts.
Preparation method is the same as embodiment 7.
Embodiment 17
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:7 parts, paraffin oil: 10 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 18
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:7 parts, paraffin oil: 20 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 19
The present embodiment formula are as follows:
PNB:100 parts；ZDMA7 parts, paraffin oil: 30 parts, DCP:2 parts.
Preparation method is the same as embodiment 7.
Embodiment 20
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:9 parts, paraffin oil: 10 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 21
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:9 parts, paraffin oil: 10 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 22
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:9 parts, paraffin oil: 20 parts, DCP:0.5 parts.
Preparation method is the same as embodiment 7.
Embodiment 23
The present embodiment formula are as follows:
PNB:100 parts；ZDMA:9 parts, paraffin oil: 30 parts, DCP:2 parts.
Preparation method is the same as embodiment 7.
Comparative example 2
This comparative formulation are as follows:
PNB:100 parts；Paraffin oil: 20 parts；DCP:0.5 parts.
Preparation method:
It (1), is 125 DEG C by polynorbornene, paraffin oil, in initial temperature, revolving speed is the Haake torque rheology of 50r/min
It is kneaded 13 minutes in the banburying chamber of instrument, rubber compound d is made；
(2), by rubber compound d in the banburying chamber for the Haake torque rheometer that initial temperature is 60 DEG C, revolving speed is 30r/min
After being kneaded 1 minute, DCP is added and is kneaded 1min again, rubber compound e is made；
(3), by rubber compound e, film f is made in bottom sheet on a mill, and the double roller temperature of open mill is 50 DEG C；
(4), film f is parked 20 hours；
(5), film f is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 11min.
Comparative example 2 and the obtained shape-memory material performance test results characterization of embodiment 8,12,15,18,22 are compared as follows:
Experimental raw
PNB, Austrian STARTECH Resilient product Co., Ltd；ZDMA, Sartomer, the U.S.；Paraffin oil 2280, rather
Bo Hansheng Chemical Co., Ltd.；DCP is that commercial grade rubber and plastic industry often uses raw material.
(1) cross-linking reaction
According to national standard GB/T16384-1998, ALPHA company, the U.S. it is anti-to measure the crosslinking of PNB without rotor vulcameter
It answers, test temperature is 170 DEG C, testing time 30min.
(2) differential scanning calorimetric analysis (DSC)
The differential scanning calorimeter produced using German NETZSCH company, model DSC204F11 scan temperature range
It is -40 DEG C~150 DEG C, heating rate is 10 DEG C/min.
(3) X-ray diffraction (XRD)
Using X-ray diffractometer, test condition are as follows: Cu polar radiations, 2 θ of scanning range=5-40 °, sweep speed be 5 °/
min。
(4) infrared spectroscopy (FTIR)
The VERTEX70 type Fourier Transform Infrared Spectrometer produced using German BRUKER company, ATR mode.
(5) stress relaxation
DMA-Q800 type Dynamic Mechanical Analyzer, stretch mode are produced using TA company, the U.S., test temperature is 42 DEG C, is answered
Become 50%, stress relaxation 30min, strain restores 20min after stress relaxation.
(6) physical mechanical property
According to the tensile strength and elongation at break of national standard GB-T528-1996 test sample.Use German Zwick company
AI-9000S type electronics tension tester is tested, tensile speed 100mm/min, and test temperature is 23 DEG C.
(7) circulation is stretched
It is tested using DMA-Q800 stretch mode, equilibrium temperature is 42 DEG C, strain rate 20%/min, and range of strain is
0-100% is recycled 5 times.
(8) shape-memory properties
Using DMA-Q800 stretch mode.Temperature is risen into 30 DEG C of sample Tg or more and stablizes 5min.The long scale of sample
It is denoted as ε p.Apply 50% strain to each sample, the length mark of sample is ε load, is cooled to 30 DEG C of sample Tg or less, removes
Fall external force, constant temperature 5min, the length mark of sample is ε.Finally, it is raised to Tg+30 DEG C of sample from Tg-30 DEG C of sample, heating rate
For 5 DEG C/min, constant temperature 30min.Sample final lengths are labeled as ε rec.
Shape fixed rate (Rf) and shape recovery ratio (Rr), such as following formula:
The following are the results and analysis that are obtained by embodiment and comparative experiments
1 cross-linking reaction
The variation of rheometer torque value can show that the formation of cross-linked network in high molecular polymer.Figure 13 is different ZDMA
Number is crosslinked the cross-linking reaction curve of PNB, as seen from the figure, with the increase of ZDMA dosage, maximum torque value (Mmax) and minimum
The difference of torque value (Mmin), i.e. Mmax-Mmin increase, and show the addition of ZDMA, can be improved the cross-linking efficiency of PNB and are crosslinked close
Degree.
During cross-linking reaction, it is free that peroxide DCP free radical can generate macromolecular with the double bond addition of PNB
Base forms chemical covalent cross-bond when two PNB free radical groups meet, and DCP can also cause ZDMA polymerization, be formed
The polymerization of poly-ZDMA, ZDMA may prior to the crosslinking of PNB molecule, on the other hand due in PNB main chain there are double bond,
Poly-ZDM can be grafted on PNB main chain by poly-ZDMA free radical with PNB radical reaction.In cross-linking process, PNB's
The formation of chemical crosslink reaction and poly-ZDMA can all consume DCP.
2 glass transition temperatures
Figure 14 is the Tg change curve that different ZDMA numbers are crosslinked PNB.As seen from the figure, the Tg that the PNB of ZDMA is not added is omited
Higher than the sample that 1phr and 3phr ZDMA is added, this is because DCP is all used to cause PNB and chemistry occurs when ZDMA not being added
Crosslinking, when ZDMA is added in PNB, ZDMA can consume a part of DCP to cause ZDMA autohemagglutination, and the chemical crosslinking for limiting PNB is anti-
It answers, and since ZDMA dosage is less, the poly-ZDMA of formation is sporadically distributed in PNB matrix.And with ZDMA dosage
It continues growing, when ZDMA is greater than 3phr, ZDMA forms more and more poly-ZDMA aggregations in PNB, limits PNB
The movement of strand, promotes Tg further to increase.
3, X-ray diffraction
Figure 15 is before not crosslinking reaction, different ZDMA numbers crosslinking PNB XRD diagram.ZDMA is a kind of crystal
Substance, as seen from the figure, when 1phr and 3phr ZDMA is added in PNB, since the amount of ZDMA is less, crystal diffraction peak is unobvious,
Only nearby occurs the crystal diffraction peak of PNB at 18 °, but with the increase of ZDMA amount, when being greater than 3phr ZDMA, at 2 angles θ
There is the diffractive features peak of ZDMA crystal for 9.92 °, 11.0 °, diffractive features peak is more and more sharp, this explanation is in crosslinking
Before, ZDMA does not react, is only dispersed in the form of crystal in PNB matrix.
Figure 16 is the XRD diagram that difference ZDMA number is crosslinked PNB after crosslinking reaction.Compared to Figure 15, in the figure
The characteristic diffraction peak of ZDMA crystal has disappeared, and only nearby the characteristic diffraction peak of PNB occurs at 18 °, illustrates in DCP cross-linking process
In, ZDMA is reacted, and poly-ZDMA aggregation is generated.
4, infrared analysis
Figure 17 is before PNB does not crosslink reaction, and the infared spectrum of different ZDMA number crosslinking PNB may infer that
1660cm-1,830cm-1 are the out-of-plane bending absorption peak peak of-C=C- stretching vibration peak ,=C-H respectively, and 1539cm-1 is insatiable hunger
It, and can also from spectrogram with the characteristic absorption peak of carboxylic metallic salt, the i.e. stretching vibration absworption peak of the COO- of hexa-coordinate
These peak intensities and peak area increase with the increase of the number of ZDMA in PNB out.
After crosslinking reaction by Figure 18 PNB, the infared spectrum of different ZDMA numbers crosslinking PNB it is found that 1660cm-1,
830cm-1 is the absorption peak disappearance of C=C ,=C-H respectively, and 1539cm-1 is replaced to occur that the COO- of 1590cm-1 four-coordination
Stretching vibration absworption peak, illustrate that the microstructure of ZDMA is changed in cross-linking process, in conjunction with X-ray diffraction spectrogram,
It is found that ZDMA is reacted in PNB under DCP initiation.
5, stress relaxation
Figure 19 is the stress relaxation curve that different ZDMA numbers are crosslinked PNB.As seen from the figure, when PNB is sent out under external force
When the shape that changes, with the increase of ZDMA dosage, internal stress can be relaxed to equilibrium valve corresponding with cross-linked network deformation quickly, and flat
The stress value that weighs increases, this is because poly-ZDMA aggregation, and the ionomer on PNB main chain is grafted to by poly-ZDMA
Formation, so that segment is will receive more constraints along the process that external force direction is orientated, make PNB have higher stress transfer
Efficiency.
Figure 20 is the strain recovery curve that different ZDMA numbers are crosslinked PNB, is seen after the completion of above-mentioned stress relaxation test
Examine the case where its strain restores.As seen from the figure, it as the number that ZDMA is added in PNB is more, is generated after external force removes
Overstrain is smaller, this is because poly-ZDMA Micelle-like Nano-structure of Two and poly-ZDMA are grafted on PNB main chain in PNB matrix
The formation of ionomer enhances the cross-linked network of PNB, provides stronger elastic-restoring force for PNB, to promote PNB extensive
The rate of its multiple original deformation is accelerated, and overstrain reduces.
6, mechanical property
Figure 21 is the stress-strain diagram that different ZDMA numbers are crosslinked PNB, and table 2 is the object that different ZDMA numbers are crosslinked PNB
Manage mechanical performance.In conjunction with chart it is found that with ZDMA number in PNB increase, the tensile strength of PNB sample, stress at definite elongation increase
Add.This is because polymerization during cross-linking reaction of ZDMA one side forms poly-ZDMA and is dispersed in PNB matrix, these are received
Rice grain can deform and be orientated under the effect of external force, and the size of these nano particles increases with the increase of external force
Adding, another aspect poly-ZDMA free radical can be grafted on PNB main chain with PNB radical reaction and form ionomer,
These ionic bonds can be preferentially broken under external force, dissipation energy, to improve the tensile strength of PNB.
The physical mechanical property of 2 difference ZDMA number of table crosslinking PNB
7, cyclic curve is stretched
If Figure 22-1 to Figure 22-6 is the stretching cyclic curve that different ZDMA numbers are crosslinked PNB, the fixation of the cyclic curve
Strain is 100%.As seen from the figure, below second of tensile stress strain curve first time, the stress strain curve of third time exists again
It is secondary in the following, with cycle-index increase, this downward trend reduces, and with the increase of ZDMA number, in phase
Under same strain, the stress value of PNB increases.
Figure 23 is the hysteresis loop area for the first time stretching cyclic curve that different ZDMA numbers are crosslinked PNB, and Figure 24 is difference
The strain energy that ZDMA number is crosslinked PNB declines percentage Δ W, and strain energy decline percentage Δ W can be indicated by being stretched to fixation
Stress-softening effect under strain:
W1-is stretched to the strain energy needed when 100% strain for the first time in formula；
After W2-first time stretches recovery, it is stretched to the strain energy needed when 100% strain for the second time.
The area of hysteresis loop is the mechanical work that unit volume ZDMA stretches required consumption in cycle period at one, is passed through
The hysteresis loop area for stretching circulation for the first time is calculated, hysteresis loop area ratio when 1phr ZDMA is added as shown in Figure 11, in PNB
Not to be added the smaller of ZDMA, however when the number that ZDMA is added is greater than 1phr, the area of hysteresis loop with ZDMA amount increasing
Add and increases.This is because the addition of ZDMA facilitates the increase of response lag, due to 1phr in the case where stretching cyclic loading
The amount of ZDMA is less, may sporadicly disperse in PNB matrix, does not form ZDMA aggregation, therefore 1phr ZDMA is added
When, the hysteresis loop area of PNB is smaller.
With the increase of ZDMA number, more and more poly-ZDMA are formed in PNB, in the case where stretching cyclic loading,
ZDMA aggregation is destroyed, and sliding of the PNB chain on ZDMA particle, and is grafted on shape on PNB main chain by poly-ZDMA
At ionic bond weak bond fracture caused by Friction dissipation increase, lag area increase with the increase of ZDMA amount.Herein also
Decline percentage Δ W, the same available and consistent result of hysteresis loop area by calculating strain energy.
8, shape-memory properties
Figure 25-1 to Figure 25-6 is the memory cycle curve that different ZDMA numbers are crosslinked PNB, and Figure 26 is by 1 He of formula
The 2 different ZDMA numbers crosslinking PNB shape fixed rates being calculated and shape recovery ratio.The deformation temperature and shape of the cyclic curve
Shape recovery temperature is 42 DEG C, and shape fixed temperature is -18 DEG C, and shape becomes 50%.When temperature is 42 DEG C, applies external force, make PNB
Deformation is generated, -18 DEG C is then reduced the temperature to, the temporary shapes of PNB is fixed, while storing elastic restoring force, finally rising
During temperature, its original-shape is restored by the conformational entropy of PNB network segment.Shape-memory properties can pass through shape fixed rate
It is characterized with shape recovery ratio.
By Figure 25-1 to Figure 25-6 and Figure 26 it is found that with ZDMA addition, PNB have good shape fixed rate, base
Originally it is held at 99.60% or more.As the number of ZDMA increases, the shape recovery ratio of PNB is increased, this is because compared to not
It is added in the PNB of ZDMA, DCP can trigger ZDMA polymerization, form poly-ZDMA, and poly-ZDM can be grafted to PNB master
Ionomer network is formed on chain, as the progress of the increase of ZDMA number, these reactions will consume more DCP, is promoted
The C-C cross-bond that DCP is formed in PNB tails off, and is chemically crosslinked network compared to ionomer network to shape recovery process
In it is smaller to the movement of segment limitation, while the cross-linked network of PNB can also be enhanced, to improve its shape extensive to store enough elasticity
Multiple rate.And when the number of ZDMA is greater than 3phr, the shape recovery ratio of PNB decreases, this is because ZDMA increases, in PNB
The middle aggregation for forming more poly-ZDMA, in deformation caused by external forces, PNB segment is easy to slide in ZDMA particle, to increase
Add non-reversible deformation.
In summary:
With the increase of ZDMA dosage, the crosslink density of PNB increases, mechanical property enhancing.ZDMA is grafted with PNB segment
While, more and more ZDMA aggregations are formed in PNB, in the case where stretching cyclic loading, ZDMA aggregation is destroyed, and
PNB chain Friction dissipation caused by the sliding on ZDMA particle increases, and lag area increases with the increase of ZDMA amount.
Different ZDMA number crosslinking PNB have good shape fixed rate, are held at 99.60% or more substantially, say
The cross-linked network that bright ZDMA is formed in PNB is more stable, and when ZDMA is 3phr, the shape recovery ratio highest of PNB works as ZDMA
Number when being greater than 3phr, the shape recovery ratio of PNB decreases, this is because ZDMA increases, is formed in PNB more
The aggregation of ZDMA, in deformation caused by external forces, PNB segment is easy to slide in ZDMA particle, to increase non-reversible deformation.
Technical characteristic of the present invention without description can realize that details are not described herein by or using the prior art, certainly,
The above description is not a limitation of the present invention, and the present invention is also not limited to the example above, the ordinary skill of the art
The variations, modifications, additions or substitutions that personnel are made within the essential scope of the present invention also should belong to protection model of the invention
It encloses.
Claims (10)
1. a kind of shape-memory material, which is characterized in that the shape-memory material contains the poly- norborneol of main body high molecular material
Alkene, paraffin oil, cumyl peroxide.
2. shape-memory material according to claim 1, which is characterized in that the polynorbornene parts by weight are 100 parts,
The paraffin oil parts by weight are 10-30 parts, and the cumyl peroxide parts by weight are 1-2.5 parts.
3. shape-memory material according to claim 2, which is characterized in that the polynorbornene parts by weight are 100 parts, institute
Stating paraffin oil parts by weight is 20 parts, and the cumyl peroxide parts by weight are 1.5 parts.
4. any one of -3 shape-memory material according to claim 1, which is characterized in that the preparation of the shape-memory material
Method includes the following steps:
(1), first by polynorbornene and paraffin oil in the Haake torque rheology that initial temperature is 125 DEG C, revolving speed is 50r/min
It is kneaded 10min in the banburying chamber of instrument, rubber compound a is made；
(2), rubber compound a is added and cools to 60 DEG C, in the banburying chamber for the Haake torque rheometer that revolving speed is 30r/min, be added
Cumyl peroxide is kneaded, and rubber compound b is made；
(3), by rubber compound b, film c is made in bottom sheet on a mill, and double roller temperature is 50 DEG C；
(4), film c is parked 18-24 hours；
(5), film c is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 10min.
5. a kind of preparation method of the shape-memory material as described in claim any one of 1-3, which is characterized in that including walking as follows
It is rapid:
(1), first by polynorbornene and paraffin oil in the Haake torque rheology that initial temperature is 125 DEG C, revolving speed is 50r/min
It is kneaded 10min in the banburying chamber of instrument, rubber compound a is made；
(2), rubber compound a is added and cools to 60 DEG C, in the banburying chamber for the Haake torque rheometer that revolving speed is 30r/min, be added
Cumyl peroxide is kneaded, and rubber compound b is made；
(3), by rubber compound b, film c is made in bottom sheet on a mill, and double roller temperature is 50 DEG C；
(4), film c is parked 18-24 hours；
(5), film c is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 10min.
6. a kind of shape-memory material, which is characterized in that the shape-memory material contains the poly- norborneol of main body high molecular material
Alkene, paraffin oil, cumyl peroxide, zinc methacrylate.
7. shape-memory material according to claim 6, which is characterized in that the polynorbornene parts by weight are 100 parts,
The paraffin oil parts by weight are 10-30 parts, and the cumyl peroxide parts by weight are 0.5-2.5 parts, the methacrylic acid
Zinc parts by weight are 1-9 parts.
8. shape-memory material according to claim 7, which is characterized in that the polynorbornene parts by weight are 100 parts,
The paraffin oil parts by weight are 20 parts, and the cumyl peroxide parts by weight are 0.5 part, the zinc methacrylate weight
Part is 3 parts.
9. according to the described in any item shape-memory materials of claim 6-8, which is characterized in that the system of the shape-memory material
Preparation Method comprises the steps of:
It (1), is 125 DEG C in initial temperature by polynorbornene, paraffin oil, zinc methacrylate, revolving speed is the Haake of 50r/min
It is kneaded 13 minutes in the banburying chamber of torque rheometer, rubber compound d is made, and wherein the zinc methacrylate is added in two portions；
(2), rubber compound d is kneaded in the banburying chamber for the Haake torque rheometer that initial temperature is 60 DEG C, revolving speed is 30r/min
After 1 minute, cumyl peroxide is added and is kneaded 1min again, rubber compound e is made；
(3), by rubber compound e, film f is made in bottom sheet on a mill, and the double roller temperature of open mill is 50 DEG C；
(4), film f is parked 18-24 hours；
(5), film f is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 11min.
10. a kind of preparation method such as the described in any item shape-memory materials of claim 6-8, which is characterized in that comprising with
Lower step:
It (1), is 125 DEG C in initial temperature by polynorbornene, paraffin oil, zinc methacrylate, revolving speed is the Haake of 50r/min
It is kneaded 13 minutes in the banburying chamber of torque rheometer, rubber compound d is made, and wherein the zinc methacrylate was added at 8 minutes
Remaining 50% is added when 50%, 10 minutes；
(2), rubber compound d is kneaded in the banburying chamber for the Haake torque rheometer that initial temperature is 60 DEG C, revolving speed is 30r/min
After 1 minute, cumyl peroxide is added and is kneaded 1min again, rubber compound e is made；
(3), by rubber compound e, film f is made in bottom sheet on a mill, and the double roller temperature of open mill is 50 DEG C；
(4), film f is parked 18-24 hours；
(5), film f is vulcanized on vulcanizing press, conditions of vulcanization is 170 DEG C × 11min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022181336A1 (en) * | 2021-02-26 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Film material and laminated material |
| CN116063799A (en) * | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
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| JP2011178939A (en) * | 2010-03-03 | 2011-09-15 | Tokai Rubber Ind Ltd | Norbornene-based polymer molded product |
| CN106832720A (en) * | 2017-03-14 | 2017-06-13 | 青岛科技大学 | A kind of preparation method of fixed rate high recovery rate shape-memory material high |
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| JP2011178939A (en) * | 2010-03-03 | 2011-09-15 | Tokai Rubber Ind Ltd | Norbornene-based polymer molded product |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022181336A1 (en) * | 2021-02-26 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Film material and laminated material |
| CN116063799A (en) * | 2023-01-06 | 2023-05-05 | 华南理工大学 | Ultra-wide melting range two-way shape memory polymer composite material without external force and preparation method thereof |
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| CN110016196B (en) | 2022-01-07 |
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