CN106832720A - A kind of preparation method of fixed rate high recovery rate shape-memory material high - Google Patents
A kind of preparation method of fixed rate high recovery rate shape-memory material high Download PDFInfo
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- CN106832720A CN106832720A CN201710148465.5A CN201710148465A CN106832720A CN 106832720 A CN106832720 A CN 106832720A CN 201710148465 A CN201710148465 A CN 201710148465A CN 106832720 A CN106832720 A CN 106832720A
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- recovery rate
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- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012781 shape memory material Substances 0.000 title claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000010692 aromatic oil Substances 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- -1 organo montmorillonite Chemical compound 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 claims abstract description 4
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000012644 addition polymerization Methods 0.000 claims abstract description 4
- ZQTYQMYDIHMKQB-UHFFFAOYSA-N exo-norborneol Chemical compound C1CC2C(O)CC1C2 ZQTYQMYDIHMKQB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 235000019241 carbon black Nutrition 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 5
- 238000013016 damping Methods 0.000 abstract description 5
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 9
- 235000010216 calcium carbonate Nutrition 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 230000007334 memory performance Effects 0.000 description 3
- 229920000431 shape-memory polymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 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 provides a kind of preparation method of fixed rate recovery rate shape-memory material high high, belong to memory material technical field, comprise the following steps：（1）, using HAAKE torque rheometers banburying chamber, initial temperature is set as 120 130 DEG C, and rotor speed is 30 40r/min, and first addition polymerization bornylene, environment-friendly aromatic oil mixing, mass fraction ratio are 100 parts of poly- norborneol, and 8 12 parts of environment-friendly aromatic oil is kneaded 45 minutes；Mass parts being separately added into again for 24 parts of carbon blacks, CNT, organo montmorillonite or calcium carbonate, being kneaded 58 minutes, elastomeric compound a is obtained respectively;（2）, elastomeric compound a is stood 8 12 hours after, be molded using flat board moulding press.The present invention can effectively improve the fixed rate and recovery rate of intermingling material；When experiencing multiple shape recovery circulation, remain to keep very excellent shape-memory properties；With frequency, temperature change it is delayed larger, with damping capacity higher.
Description
Technical field
The present invention relates to memory material technical field, more particularly to a kind of fixed rate high recovery rate shape-memory material high
Preparation method.
Background technology
Shape-memory polymer (Shape Memory Polymers, SMPs) be a class Aero-Space, biologic medical,
A kind of new function material that the industries such as weaving, electronics all have wide application prospects, while be also a kind of boost inductor section bar material,
With the characteristic that can change its shape when by the environmental stimuli such as heat, electricity, magnetic, machinery, light, chemistry.
The essence of SME 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）During the above, molecule
Chain has active locomitivity.Under external force effect, the moiety segments in strand are in Impact direction preferential arrangement, strand structure
As changing, the conformational entropy reduction of system, material now forms temporary shapes, with energy higher.When polymer is in
During below Ttrans, strand is frozen, and locomitivity declines to a great extent and Cambium periodicity potential well, in regular hour yardstick
Under, the Molecular connectivity indices after orientation are still remained after removing external force, temporary shapes are fixed.When being warmed up to Ttrans again
During the above, the locomitivity of strand is reactivated, and structure is returned to because warm-up movement is spontaneous without the lower molecule segment of external force effect
As the original shape of entropy maximum rating, i.e. polymer.
Polynorbornene (Polynorbornene) is the head in the world that CdF-Chimie companies developed in success in 1984
Example has the polymer of shape memory function, and this new organic polymer of polynorbornene is used as rubber and obtains extensively
Using.But it is found that it is distinct from traditional high polymer of rubber materials, it is processed in powder form.This height
It is one of the characteristics of it is protruded that the oil absorbency of polymers is excellent, therefore, plasticizer can add to 400 in the formula of polynorbornene
Part or so, the flexibility of its vulcanizate is more much lower than common vulcanizate.Although its oil-filled quantity is very high, in many actual feelings
Under condition, its oil resistivity is still put up a good show.
Polynorbornene belongs to thermotropic shape-memory polymer, influences its shape memory characteristic factor to have a lot, can be with
These main influence factors are summed up as follows:Glass transition region;The stress applied during thermo-mechanical cycle;Thermomechanically
The gentle rate of temperature fall of liter 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
It is high it is oil-filled as elastomeric material in the multiple fields application such as damping damping material, acoustic material.Polynorbornene is found
The first has a macromolecular material of shape-memory properties, but its memory performance rarely seen so far report.
The content of the invention
It is an object of the invention to be directed to above-mentioned the deficiencies in the prior art, there is provided a kind of fixed rate high, the shape of recovery rate high
The preparation method of shape memory material, with simple production process reliability, the advantages of 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 fixed rate high recovery rate shape high
The preparation method of shape memory material, wherein, comprise the following steps：
（1）, using HAAKE torque rheometers banburying chamber, initial temperature is set as 120-130 DEG C, and rotor speed is 30-40r/
Min, first addition polymerization bornylene, environment-friendly aromatic oil mixing, mass fraction ratio are 100 parts of poly- norborneol, environment-friendly aromatic oil 8-12 parts, are mixed
Refining 4-5 minutes；Mass parts are separately added into again for 2-4 parts of carbon black, CNT, organo montmorillonite or calcium carbonate, 5-8 points of mixing
Clock, is obtained elastomeric compound a respectively;
（2）, by elastomeric compound a stand 8-12 hours after, be molded using flat board moulding press.
Wherein, the step（2）Middle conditions of vulcanization is pressure 8-10MPa, and actuation 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.
Beneficial effects of the present invention are：The fixation of intermingling material can be effectively improved after material blending selected by the present invention
Rate and recovery rate；When experiencing multiple shape recovery circulation, the shape that polynorbornene composite remains to keep very excellent is remembered
Recall performance；Using preparation method of the present invention prepare material with frequency, temperature change it is delayed larger, with damping and amortization higher
Energy.
Brief description of the drawings
Fig. 1 is the single deformation TMA shape memory curves that the embodiment of the present invention 1 prepares material.
Fig. 2 is the single deformation TMA shape memory curves that the embodiment of the present invention 2 prepares material.
Fig. 3 is the single deformation TMA shape memory curves that the embodiment of the present invention 3 prepares material.
Fig. 4 is the single deformation TMA shape memory curves that the embodiment of the present invention 4 prepares material.
Fig. 5 is the single deformed shape memory performance that embodiment of the present invention 1-4 prepares material.
Fig. 6 is the TMA shape memory curves of deformation twice that the embodiment of the present invention 1 prepares material.
Fig. 7 is the TMA shape memory curves of deformation twice that the embodiment of the present invention 2 prepares material.
Fig. 8 is the TMA shape memory curves of deformation twice that the embodiment of the present invention 3 prepares material.
Fig. 9 is the TMA shape memory curves of deformation twice that the embodiment of the present invention 4 prepares material.
Figure 10 is the deformed shape memory performance twice that embodiment of the present invention 1-4 prepares material.
Specific embodiment
The invention provides a kind of preparation method of fixed rate recovery rate shape-memory material high high, comprise the following steps：
（1）, using HAAKE torque rheometers banburying chamber, initial temperature is set as 120-130 DEG C, and rotor speed is 30-40r/min, first
Addition polymerization bornylene, environment-friendly aromatic oil mixing, mass fraction ratio are 100 parts of poly- norborneol, environment-friendly aromatic oil 8-12 parts, knead 4-5
Minute；Mass parts are separately added into again for 2-4 parts of carbon black, CNT, organo montmorillonite or calcium carbonate, are kneaded 5-8 minutes, respectively
Elastomeric compound a is obtained;
（2）, by elastomeric compound a stand 8-12 hours after, be molded using flat board moulding press.
Wherein, the step（2）Middle conditions of vulcanization is pressure 8-10MPa, and actuation 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.
For the technical characterstic for illustrating this programme can be understood, below by specific embodiment, this programme is illustrated.
Polynorbornene：Austrian STARTECH companies；
Calcium carbonate（CaCO3）：Zibo Donggao Chemical Co., Ltd.；
Carbon black (CB), N550, Cabot；
CNT（CNT）, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences；
Organo montmorillonite（OMMT）, commercial grade rubber industry often uses raw material；
Environment-friendly aromatic oil（TDAE）, commercial grade rubber industry often uses raw material.
Embodiment 1：
Using HAAKE torque rheometers banburying chamber, initial temperature is set as 125 DEG C, and rotor speed is 30r/min, by 100 grams
PNB, 10 grams of TDAE are first placed into banburying chamber, knead 4.5 minutes, add 3 grams of carbon blacks, knead 5.5 minutes.Using vulcanizing press
Molding vulcanization, die pressure is 10MPa, and actuation temperature is 68 DEG C, shape recovery ratio, shape recovery ratio can be obtained and all reaches 99%
Intermingling material above.Carbon black specific surface is 42m2/g。
Embodiment 2：
Using HAAKE torque rheometers banburying chamber, initial temperature is set as 125 DEG C, and rotor speed is 30r/min, by 100 grams
PNB, 10 grams of TDAE are first placed into banburying chamber, knead 4.5 minutes, add 3 grams of CNTs, knead 5.5 minutes.Using flat board sulphur
The molding vulcanization of change machine, die pressure is 10MPa, and actuation temperature is 63 DEG C, shape recovery ratio, shape recovery ratio can be obtained and all reaches
More than 99% intermingling material.
Embodiment 3：
Using HAAKE torque rheometers banburying chamber, initial temperature is set as 125 DEG C, and rotor speed is 30r/min, by 100 grams
PNB, 10 grams of TDAE are first placed into banburying chamber, knead 4.5 minutes, add 3 grams of organo montmorillonites, knead 5.5 minutes.Using flat board
Vulcanizer molding vulcanization, die pressure is 10MPa, and actuation temperature is 70 DEG C, shape recovery ratio, shape recovery ratio can be obtained and all reaches
To more than 99% intermingling material.
Embodiment 4：
Using HAAKE torque rheometers banburying chamber, initial temperature is set as 125 DEG C, and rotor speed is 30r/min, by 100 grams
PNB, 10 grams of TDAE are first placed into banburying chamber, knead 4.5 minutes, add 3 grams of calcium carbonate, knead 5.5 minutes.Using compression molding
Machine molding vulcanization, die pressure is 10MPa, and actuation temperature is 58 DEG C, shape recovery ratio, shape recovery ratio can be obtained and all reaches
More than 99% intermingling material.Calcium carbonate is diameter 0.5um, the club shaped structure of length 1um.
The embodiment of table 1 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 be realized by or using prior art, will not be repeated here, certainly, above-mentioned
Illustrate it is not limitation of the present invention, the present invention is also not limited to the example above, those skilled in the art
Change, remodeling, addition or the replacement made in essential scope of the invention, should also belong to protection scope of the present invention.
Claims (6)
1. the preparation method of a kind of fixed rate high recovery rate shape-memory material high, it is characterised in that comprise the following steps：
（1）, using HAAKE torque rheometers banburying chamber, initial temperature is set as 120-130 DEG C, and rotor speed is 30-40r/
Min, first addition polymerization bornylene, environment-friendly aromatic oil mixing, mass fraction ratio are 100 parts of poly- norborneol, environment-friendly aromatic oil 8-12 parts, are mixed
Refining 4-5 minutes；Mass parts are separately added into again for 2-4 parts of carbon black, CNT, organo montmorillonite or calcium carbonate, 5-8 points of mixing
Clock, is obtained elastomeric compound a respectively;
（2）, by elastomeric compound a stand 8-12 hours after, be molded using flat board moulding press.
2. the preparation method of fixed rate high according to claim 1 recovery rate shape-memory material high, it is characterised in that institute
State step（2）Middle conditions of vulcanization is pressure 8-10MPa, and actuation temperature is 58-70 DEG C.
3. the preparation method of fixed rate high according to claim 1 recovery rate shape-memory material high, it is characterised in that institute
Carbon black specific surface is stated for 42m2/g。
4. the preparation method of fixed rate high according to claim 1 recovery rate shape-memory material high, it is characterised in that institute
It is low oil-filled to state environment-friendly aromatic oil.
5. the preparation method of fixed rate high according to claim 1 recovery rate shape-memory material high, it is characterised in that institute
Calcium carbonate is stated for diameter 0.5um, the club shaped structure of length 1um.
6. the preparation method of fixed rate high according to claim 1 recovery rate shape-memory material high, it is characterised in that institute
Organo montmorillonite is stated for lamellar structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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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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| Publication Number | Publication Date |
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| CN106832720A true CN106832720A (en) | 2017-06-13 |
| CN106832720B CN106832720B (en) | 2019-02-22 |
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| CN201710148465.5A Expired - Fee Related 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016196A (en) * | 2019-04-02 | 2019-07-16 | 青岛科技大学 | A kind of shape-memory material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01280454A (en) * | 1988-05-07 | 1989-11-10 | Yutaka Yonamine | Lens in eye |
| JPH0770823A (en) * | 1993-08-20 | 1995-03-14 | Toyama Pref Gov | Fiber having damping and elastic performances and its production |
| US20050182220A1 (en) * | 2004-02-13 | 2005-08-18 | Der-Jang Liaw | Novel 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 |
| CN103992631A (en) * | 2014-05-29 | 2014-08-20 | 理大产学研基地(深圳)有限公司 | Polymer material with two-way shape memory and preparation method thereof |
-
2017
- 2017-03-14 CN CN201710148465.5A patent/CN106832720B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01280454A (en) * | 1988-05-07 | 1989-11-10 | Yutaka Yonamine | Lens in eye |
| JPH0770823A (en) * | 1993-08-20 | 1995-03-14 | Toyama Pref Gov | Fiber having damping and elastic performances and its production |
| US20050182220A1 (en) * | 2004-02-13 | 2005-08-18 | Der-Jang Liaw | Novel 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 |
| CN103992631A (en) * | 2014-05-29 | 2014-08-20 | 理大产学研基地(深圳)有限公司 | Polymer material with two-way shape memory and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016196A (en) * | 2019-04-02 | 2019-07-16 | 青岛科技大学 | A kind of shape-memory material and preparation method thereof |
| CN110016196B (en) * | 2019-04-02 | 2022-01-07 | 青岛科技大学 | Shape memory material and preparation method thereof |
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| CN106832720B (en) | 2019-02-22 |
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