CN106832720B - A kind of preparation method of the high recovery rate shape-memory material of high fixed rate - Google Patents
A kind of preparation method of the high recovery rate shape-memory material of high fixed rate Download PDFInfo
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- CN106832720B CN106832720B CN201710148465.5A CN201710148465A CN106832720B CN 106832720 B CN106832720 B CN 106832720B CN 201710148465 A CN201710148465 A CN 201710148465A CN 106832720 B CN106832720 B CN 106832720B
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- 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
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- 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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Abstract
The present invention provides a kind of preparation methods of high high recovery rate shape-memory material of fixed rate, belong to memory material technical field, include the following steps: (1), using HAAKE torque rheometer banburying chamber, initial temperature is set as 120-130 DEG C, rotor speed is 30-40r/min, and first addition polymerization bornylene, environment-friendly aromatic oil are kneaded, and mass fraction ratio is 100 parts of poly- norborneol, it 8-12 parts of environment-friendly aromatic oil, is kneaded 4-5 minutes；Being separately added into mass parts again is 2-4 parts of carbon blacks, carbon nanotube, organo montmorillonite or calcium carbonate, is kneaded 5-8 minutes, rubber compound a is made respectively;(2), it after rubber compound a being stood 8-12 hours, is formed using plate moulding press.The present invention can effectively improve the fixed rate and recovery rate of intermingling material；When multiple shape being undergone to restore circulation, it is still able to maintain very excellent shape-memory properties；Larger, the damping capacity with higher with frequency, the lag of temperature change.
Description
Technical field
The present invention relates to memory material technical field more particularly to a kind of high recovery rate shape-memory materials of high fixed rate
Preparation method.
Background technique
Shape-memory polymer (Shape Memory Polymers, SMPs) be it is a kind of aerospace, biologic medical,
Weaving, a kind of new function material that the industries such as electronics all have wide application prospects, while being also a kind of boost inductor profile material,
With the characteristic that can change its shape when by the environmental stimulis such as heat, electricity, magnetic, machinery, light, chemistry.
The essence of shape memory effect is a kind of entropy phenomenon.From molecular level, polymer molecular chain is in not equality of temperature
The greatest differences of locomitivity are shown under degree.When polymer is in Ttrans(shape memory transition temperature) more than when, molecule
Chain has active locomitivity.Under external force, the moiety segments in strand are in Impact direction preferential arrangement, strand structure
As changing, the conformational entropy of system is reduced, and material forms temporary shapes, energy with higher at this time.When polymer is in
When Ttrans or less, strand is frozen, and locomitivity declines to a great extent and Cambium periodicity potential well, in regular hour scale
Under, the Molecular connectivity indices after orientation are still remained after removing external force, temporary shapes are fixed.When being warming up to Ttrans again
When above, the locomitivity of strand is reactivated, and molecule segment is restored to structure since warm-up movement is spontaneous under no external force
As entropy maximum rating, the i.e. original shape of polymer.
Polynorbornene (Polynorbornene) is the head in the world that CdF-Chimie company developed in success in 1984
Example has the polymer of shape memory function, and this novel organic polymer of polynorbornene is used as rubber and obtains extensively
Using.But it is found that its traditional high polymer for being distinct from rubber materials, it is processed in powder form.This height
Excellent one of the feature for being it and protruding of the oil absorbency of polymers, therefore, plasticizer can add to 400 in the formula of polynorbornene
Part or so, the flexibility of vulcanizate is more much lower than common vulcanizate.Although its oil-filled quantity is very high, in many practical feelings
Under condition, oil resistivity is still put up a good show.
Polynorbornene belongs to thermotropic shape-memory polymer, and it is many because being known as to influence its shape memory characteristic, can be with
These main influence factors are summed up as follows: glass transition region;The stress applied during thermo-mechanical cycle;Thermomechanically
Heating and rate of temperature fall in cyclic process;The recovery temperature of thermo-mechanical cycle.
Polynorbornene possesses excellent characteristic, will waste oil and the fresh agent of waste water treating agent, air or by its
Height is oil-filled to be used as rubber material in the multiple fields application such as damping damping material, acoustic material.Polynorbornene is found
The first high molecular material with shape-memory properties, but the report of its memory performance rarely seen so far.
Summary of the invention
It is an object of the invention in view of the above shortcomings of the prior art, provide a kind of high fixed rate, the shape of high recovery rate
The preparation method of shape memory material has many advantages, such as that simple production process is reliable, and material is also equipped with halogen-free flame-retardance.
For achieving the above object, the present invention is realized by following measure: a kind of high high recovery rate shape of fixed rate
The preparation method of shape memory material, wherein include the following steps:
(1), using HAAKE torque rheometer banburying chamber, initial temperature is set as 120-130 DEG C, rotor speed 30-
40r/min, first addition polymerization bornylene, environment-friendly aromatic oil are kneaded, and mass fraction ratio is 100 parts of poly- norborneol, environment-friendly aromatic oil 8-12
Part, it is kneaded 4-5 minutes；Being separately added into mass parts again is 2-4 parts of carbon blacks, carbon nanotube, organo montmorillonite or calcium carbonate, is kneaded 5-
8 minutes, rubber compound a is made respectively;
(2), it after rubber compound a being stood 8-12 hours, is formed using plate moulding press.
Wherein, conditions of vulcanization is pressure 8-10MPa in the step (2), and driving temperature is 58-70 DEG C.
Wherein, the carbon black specific surface is 42m2/g。
Wherein, the environment-friendly aromatic oil is low oil-filled.
Wherein, the calcium carbonate is diameter 0.5um, the club shaped structure of length 1um.
Wherein, the organo montmorillonite is lamellar structure.
The invention has the benefit that material selected by the present invention can effectively improve the fixation of intermingling material after being blended
Rate and recovery rate；When multiple shape being undergone to restore circulation, polynorbornene composite material is still able to maintain very excellent shape note
Recall performance；Using material prepared by preparation method of the present invention with frequency, the lag of temperature change larger, damping and amortization with higher
Energy.
Detailed description of the invention
Fig. 1 is the single deformation TMA shape memory curve that the embodiment of the present invention 1 prepares material.
Fig. 2 is the single deformation TMA shape memory curve that the embodiment of the present invention 2 prepares material.
Fig. 3 is the single deformation TMA shape memory curve that the embodiment of the present invention 3 prepares material.
Fig. 4 is the single deformation TMA shape memory curve that the embodiment of the present invention 4 prepares material.
Fig. 5 is the single deformed shape memory performance that 1-4 of the embodiment of the present invention prepares material.
Fig. 6 is the TMA shape memory curve of deformation twice that the embodiment of the present invention 1 prepares material.
Fig. 7 is the TMA shape memory curve of deformation twice that the embodiment of the present invention 2 prepares material.
Fig. 8 is the TMA shape memory curve of deformation twice that the embodiment of the present invention 3 prepares material.
Fig. 9 is the TMA shape memory curve of deformation twice that the embodiment of the present invention 4 prepares material.
Figure 10 is the deformed shape memory performance twice that 1-4 of the embodiment of the present invention prepares material.
Specific embodiment
The present invention provides a kind of preparation methods of high high recovery rate shape-memory material of fixed rate, include the following steps:
(1), using HAAKE torque rheometer banburying chamber, initial temperature is set as 120-130 DEG C, rotor speed 30-40r/min, first
Addition polymerization bornylene, environment-friendly aromatic oil are kneaded, and mass fraction ratio is 100 parts of poly- norborneol, 8-12 parts of environment-friendly aromatic oil, are kneaded 4-5
Minute；Being separately added into mass parts again is 2-4 parts of carbon blacks, carbon nanotube, organo montmorillonite or calcium carbonate, is kneaded 5-8 minutes, respectively
Rubber compound a is made;
(2), it after rubber compound a being stood 8-12 hours, is formed using plate moulding press.
Wherein, conditions of vulcanization is pressure 8-10MPa in the step (2), and driving temperature is 58-70 DEG C.
Wherein, the carbon black specific surface is 42m2/g。
Wherein, the environment-friendly aromatic oil is low oil-filled.
Wherein, the calcium carbonate is diameter 0.5um, the club shaped structure of length 1um.
Wherein, the organo montmorillonite is lamellar structure.
In order to clarify the technical characteristics of the invention, being illustrated below by specific embodiment to this programme.
Polynorbornene: Austrian STARTECH company；
Calcium carbonate (CaCO3): Zibo Donggao Chemical Co., Ltd.；
Carbon black (CB), N550, Cabot；
Carbon nanotube (CNT), Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences；
Organo montmorillonite (OMMT), commercial grade rubber industry often use raw material；
Environment-friendly aromatic oil (TDAE), commercial grade rubber industry often use raw material.
Embodiment 1:
Using HAAKE torque rheometer banburying chamber, initial temperature is set as 125 DEG C, rotor speed 30r/min, by 100
Gram PNB, 10 grams of TDAE are first placed into banburying chamber, are kneaded 4.5 minutes, and 3 grams of carbon blacks are added, and are kneaded 5.5 minutes.Using compression molding
Machine molding vulcanization, die pressure 10MPa, driving temperature are 68 DEG C, shape recovery ratio can be made, shape recovery ratio all reaches
99% or more intermingling material.Carbon black specific surface is 42m2/g。
Embodiment 2:
Using HAAKE torque rheometer banburying chamber, initial temperature is set as 125 DEG C, rotor speed 30r/min, by 100
Gram PNB, 10 grams of TDAE are first placed into banburying chamber, are kneaded 4.5 minutes, and 3 grams of carbon nanotubes are added, and are kneaded 5.5 minutes.Using plate
Vulcanizer molding vulcanization, die pressure 10MPa, driving temperature are 63 DEG C, shape recovery ratio can be made, shape recovery ratio all reaches
To 99% or more intermingling material.
Embodiment 3:
Using HAAKE torque rheometer banburying chamber, initial temperature is set as 125 DEG C, rotor speed 30r/min, by 100
Gram PNB, 10 grams of TDAE are first placed into banburying chamber, are kneaded 4.5 minutes, and 3 grams of organo montmorillonites are added, and are kneaded 5.5 minutes.Using flat
The molding vulcanization of plate vulcanizer, die pressure 10MPa, driving temperature are 70 DEG C, and shape recovery ratio, shape recovery ratio can be made all
Reach 99% or more intermingling material.
Embodiment 4:
Using HAAKE torque rheometer banburying chamber, initial temperature is set as 125 DEG C, rotor speed 30r/min, by 100
Gram PNB, 10 grams of TDAE are first placed into banburying chamber, are kneaded 4.5 minutes, and 3 grams of calcium carbonate are added, and are kneaded 5.5 minutes.Using plate sulphur
The molding vulcanization of change machine, die pressure 10MPa, driving temperature are 58 DEG C, shape recovery ratio can be made, shape recovery ratio all reaches
99% or more intermingling material.Calcium carbonate is diameter 0.5um, the club shaped structure of length 1um.
1 embodiment of table foaming damping material mechanical property
| 100% stretches/MPa surely | Tensile strength/MPa | Elongation rate of tensile failure/% | |
| Embodiment 1 | 9.94 | 23.05 | 213.86 |
| Embodiment 2 | 15.15 | 20.38 | 156.17 |
| Embodiment 3 | 12.96 | 22.94 | 202.53 |
| Embodiment 4 | 16.19 | 20.19 | 157.97 |
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 (5)
1. a kind of preparation method of the high recovery rate shape-memory material of high fixed rate, which comprises the steps of:
(1), using HAAKE torque rheometer banburying chamber, initial temperature is set as 120-130 DEG C, rotor speed 30-40r/
Min, first addition polymerization bornylene, environment-friendly aromatic oil are kneaded, and mass fraction ratio is 100 parts of poly- norborneol, 8-12 parts of environment-friendly aromatic oil, are mixed
Refining 4-5 minutes；Being separately added into mass parts again is 2-4 parts of carbon blacks, carbon nanotube, organo montmorillonite or calcium carbonate, is kneaded 5-8 points
Rubber compound a is made in clock respectively;
(2), it after rubber compound a being stood 8-12 hours, is formed using plate moulding press, condition is pressure 8-10MPa, driving temperature
It is 58-70 DEG C.
2. the preparation method of the high recovery rate shape-memory material of high fixed rate according to claim 1, which is characterized in that institute
Stating carbon black specific surface is 42m2/g。
3. the preparation method of the high recovery rate shape-memory material of high fixed rate according to claim 1, which is characterized in that institute
It is low oil-filled for stating environment-friendly aromatic oil.
4. the preparation method of the high recovery rate shape-memory material of high fixed rate according to claim 1, which is characterized in that institute
Stating calcium carbonate is diameter 0.5um, the club shaped structure of length 1um.
5. the preparation method of the high recovery rate shape-memory material of high fixed rate according to claim 1, which is characterized in that institute
Stating organo montmorillonite is lamellar structure.
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| CN201710148465.5A CN106832720B (en) | 2017-03-14 | 2017-03-14 | A kind of preparation method of the high recovery rate shape-memory material of high fixed rate |
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| CN106832720B true CN106832720B (en) | 2019-02-22 |
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| JPH01280454A (en) * | 1988-05-07 | 1989-11-10 | Yutaka Yonamine | Lens in eye |
| JP2545039B2 (en) * | 1993-08-20 | 1996-10-16 | 富山県 | Fiber with vibration damping and stretchability and its manufacturing method |
| US7205359B2 (en) * | 2004-02-13 | 2007-04-17 | National Taiwan University Of Science & Technology | Functional norbornenes as initiators for radical polymerization, their polymeric derivatives and a process for producing the same |
| CN101029158A (en) * | 2007-03-05 | 2007-09-05 | 冷劲松 | Particular-filling shape memory composite material and its production |
| CN103992631B (en) * | 2014-05-29 | 2016-09-21 | 理大产学研基地(深圳)有限公司 | Polymeric material with bidirectional shape memory and preparation method thereof |
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