CN108912665A - A kind of flexible sensor and preparation method of near infrared light selfreparing - Google Patents

A kind of flexible sensor and preparation method of near infrared light selfreparing Download PDF

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Publication number
CN108912665A
CN108912665A CN201810533440.1A CN201810533440A CN108912665A CN 108912665 A CN108912665 A CN 108912665A CN 201810533440 A CN201810533440 A CN 201810533440A CN 108912665 A CN108912665 A CN 108912665A
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polymer
infrared light
near infrared
carbon nanotube
selfreparing
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马宁
李博
张馨月
魏浩
王强
李�瑞
欧阳肖
张智嘉
高闪
王国军
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Harbin Engineering University
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Harbin Engineering University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The present invention is to provide the flexible sensors and preparation method of a kind of near infrared light selfreparing.It is made of supermolecule polymer matrix and carbon nanotube, the supermolecule polymer matrix based on segment among 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure end group and polymer by being formed.The present invention develops a kind of supermolecule flexible polymer material that can be melted or soften under the stimulation of 808nm near infrared light, has widened self-healing flexible material field, the manufacture craft of material is simple, and cost is relatively low.Products obtained therefrom can be used for the more difficult field directly contacted, and being heated by indirect mode makes its spontaneous reparation damage.Replaced material recycles after can directly cleaning dissolves pouring molding again, effectively avoids the waste of raw material, saves use cost, increases economic efficiency.

Description

A kind of flexible sensor and preparation method of near infrared light selfreparing
Technical field
The present invention relates to a kind of flexible sensor, the present invention also relates to be a kind of flexible sensor preparation side Method.The flexible sensor and preparation method of specifically a kind of selfreparing.
Background technique
Flexible sensor refers to using sensor made of flexible material have good flexibility, ductility, even may be used Free bend even folds, and structure type is versatile and flexible, can arbitrarily be arranged according to the requirement of measuring condition, can be very square Just complexity is measured and is detected.Novel flexible sensor is in electronic skin, health care, electronics, electrician, locomotory apparatus The fields such as material, textile, space flight and aviation, environmental monitoring are widely applied.Flexible sensor generally has two parts composition, and one Dividing is flexible substrate, provides support part, and another part is the sensing element responded to a certain or a variety of stimulations.It is flexible Matrix generally has the attributes such as soft, low modulus, easily-deformable.Common flexible material has:Polyvinyl alcohol (PVA), polyester (PET), polyimides (PI), dimethyl silicone polymer (PDMS), paper, textile material etc..Traditional flexible substrate is flexible, Deformation nature is excellent, but material is difficult to self-regeneration after scuffing or breakage, and senser element is caused to fail, increase use at This.Therefore, it is novel can selfreparing flexible sensing device have become a hot topic of research.
Selfreparing (self-healing) refer to material under certain external condition effect, it is spontaneous that breakage is repaired It is multiple, with before restoring breakage completely or partially a certain or a variety of property or (and) performance the phenomenon that, the phenomenon can occur Material be referred to as self-healing material.Self-healing material can be applied to bionical device, intellectual material, packing container, medical equipment, Film shell etc. is easy to the field of damaged and more difficult replacement, thus has obtained extensive concern and research.Traditional selfreparing material Material mostly provides energy to system in a manner of through heating etc., brings it about crystallization, the effects of surface forms film or generates crosslinking It realizes and repairs.Selfreparing flexible sensing device application field is extensive, this is but also in some special applications, it is difficult to directly Heating operation processing is carried out to device, thus develops one kind the flexible sensor of contactless fever can occur as urgent need It solves the problems, such as.
Summary of the invention
The purpose of the present invention is to provide a kind of near infrared lights that can be melted or soften under the excitation of 808nm near infrared light The flexible sensor of selfreparing.The object of the invention is also to provide a kind of preparations of the flexible sensor of near infrared light selfreparing Method.
The flexible sensor of near infrared light selfreparing of the invention is made of supermolecule polymer matrix and carbon nanotube, institute Stating supermolecule polymer matrix is by based on segment among 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure end group and polymer Composition.
The flexible sensor of near infrared light selfreparing of the invention can also include:
1,2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure end group that is based on is such as one or more in flowering structure It is a,
WhereinRepresent hydrogen bond, R1By one or two kinds of structure compositions as described below
1)C1-C10Direct-connected or branched alkyl;
2) comprising the C of 1-4 Carbamido substituted base1-C10Alkyl, the structure of the urea groups is
2, segment is one or more of such as flowering structure among the polymer,
1) polyether structure
Wherein R4、R5It is any one in following group with Y
a)H;
B) C1-C6 linear or branched alkyl group,
N is 1-6,
O is 10-100.
2) polyolefin structure
Wherein R6、R7It is any one in following group with Y
a)H;
B) C1-C6 linear or branched alkyl group;
C) C1-C6 linear chain or branched chain alkenyl,
P is 10-100.
3, it is for the mixture of following two polymer that the supermolecule polymer matrix, which is structure,:
Polymer 1:
Polymer 2:
Mixed proportion is weight ratio 3:1~9:1.
The preparation method of the flexible sensor of near infrared light selfreparing of the invention is:
(1) synthon is prepared
Methylisocytosine is reacted under protection of argon gas with hexamethylene diisocyanate, obtains white precipitate, is cooled to N-hexane stirring is added after room temperature, filtering, with the washed washing of n-hexane, vacuum drying obtains white powder synthon, synthesizes Son structure be
(2) polymer 1 is prepared
Synthon, chloroform and dibutyltin dilaurate catalyst is added after hydrogenated polybutadiene diol vacuum drying, It is reacted under argon atmosphere, to which dry silica gel and dibutyl tin dilaurate are added after the reaction was completed, the reaction was continued, is cooled to room Temperature filters to take filtrate concentration addition methanol and obtains colorless and transparent polymer 1, and the structure of polymer 1 is
(3) polymer 2 is prepared
Three-functionality-degree terminal hydroxy group polyethylene glycol oxide/propylene triol vacuum drying, is added synthon, chloroform and tin dilaurate two Butyl tin catalyst reacts under argon atmosphere, to which the dibutyl tin dilaurate of dry silica gel sum is added after the reaction was completed The reaction was continued, is cooled to room temperature, and filters to take filtrate concentration, and n-hexane is added and obtains colorless and transparent polymer 2, polymer 2 structure is
(4) carbon nanotube is sprayed
Polymer 1 is mixed into addition chloroform with polymer 2 and is tuned into paste, concentration after-pouring is dried to obtain oversubscription into mold Sub- polymeric matrix;Chloroform, ultrasonic disperse, with spray gun even application in supermolecule polymer matrix surface is added in carbon nanotube.
The preparation method of the flexible sensor of near infrared light selfreparing of the invention can also include:
1, polymer 1, polymer 2, carbon nanotube proportion be:
1 180g of polymer
2 20g of polymer
Carbon nanotube chloroformic solution 10mL.
2, polymer 1, polymer 2, carbon nanotube proportion be:
1 170g of polymer
2 30g of polymer
Carbon nanotube chloroformic solution 10mL.
3, polymer 1, polymer 2, carbon nanotube proportion be:
1 150g of polymer
2 50g of polymer
Carbon nanotube chloroformic solution 10mL.
Supermolecule polymer is formed using non-covalent bond effect connection polymerized monomer with larger molecular weight polymer line Property or network polymers, have certain mechanical strength guarantee its applicability.Simultaneously because the dynamic equilibrium of non-covalent bond is special Property, supermolecule polymer may be implemented to carry out self-regeneration damage under a certain or a variety of specified conditions.Carbon nanotube is one The kind higher black-materials of photo-thermal efficiency have stronger absorption to the near infrared light of 808nm and are converted into thermal response.It has simultaneously Excellent conductivity, can be used as conductive coating, have preferable response to mechanical stimulation.By supermolecule polymer and carbon nanotube Material combines, and can prepare the selfreparing flexibility mechanics senser element that can be absorbed 808nm near infrared light and generate heat.
For the demand of body temperature self-healing flexible material, this hair provide one kind can 808nm near infrared light excitation under energy Enough supermolecule flexible conductive polymer based composites melted or soften, can be used for preparing selfreparing flexible sensor.This hair Bright middle material prescription is using raw materials such as synthetic resin, carbon nanotubes.
Technical way of the invention is:Near infrared light selfreparing flexible sensor, by supermolecule polymer matrix and Carbon nanotube composition.Its preparation process includes the synthesis of matrix resin, pours, the dispersion and solution in the solution of carbon nanotube The processes such as spraying.Supermolecule polymer matrix is based on 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure, selects different polymer As intermediate segment, the supermolecule flexible polymer material that can be melted or soften under a certain specific temperature is prepared to realize certainly Healing.
It is poly- that the present invention develops a kind of supermolecule flexibility that can be melted or soften under the stimulation of 808nm near infrared light Object material is closed, has widened self-healing flexible material field, the manufacture craft of material is simple, and cost is relatively low.Products obtained therefrom can be used for The more difficult field directly contacted, being heated by indirect mode makes its spontaneous reparation damage.Replaced material can be cleaned directly After recycle and dissolve pouring molding again, effectively avoid the waste of raw material, save use cost, increase economic efficiency.
Specific embodiment
The supermolecule polymer matrix of the flexible sensor of near infrared light selfreparing is based on Quadrupolar hydrogen bond structure as end group And select different polymer as intermediate segment, further, the Quadrupolar hydrogen bond system according to electron donor (D) and electronics by The position arrangement of body (A) is different, and Quadrupolar hydrogen bond is such as one or more in flowering structure there are two kinds of association modes of DADA and AADD It is a,
WhereinRepresent hydrogen bond, R1By one or two kinds of structure compositions as described below
1)C1-C10Direct-connected or branched alkyl;
2) comprising the C of 1-4 Carbamido substituted base1-C10Alkyl, urea groups is shown below structure
Meanwhile Quadrupolar hydrogen bond group passes through R1It is connected with segment among polymer as supermolecule polymer main chain.
There is 10-100 Quadrupolar hydrogen bond group in the supermolecule polymer matrix of the flexible sensor of near infrared light selfreparing It is connected with segment among polymer.
The supermolecule polymer matrix of the flexible sensor of near infrared light selfreparing is based on Quadrupolar hydrogen bond structure as end group, And select different polymer as intermediate segment, and further, the flexible sensor of the near infrared light selfreparing, described in Among polymer segment be such as one or more of flowering structure,
1) polyether structure
Polyether structure is as follows
Wherein R4、R5It is any one in following group with Y
a)H;
B) C1-C6 linear or branched alkyl group.
N is 1-6.
O is 10-100.
2) polyolefin structure
Polyolefin structure is following one of which
Wherein R6、R7It is any one in following group with Y
c)H;
D) C1-C6 linear or branched alkyl group;
E) C1-C6 linear chain or branched chain alkenyl;
P is 10-100.
The supermolecule polymer matrix resin of the flexible sensor of near infrared light selfreparing can be above-mentioned Quadrupolar hydrogen bond oversubscription One in sub- polymer constitutes or multiple compounds.
- 4 [1H]-pyrimidone Quadrupolar hydrogen bond structure of 2- urea groups is artificial composite structure, the tree of segment among polymer Rouge can be natural resin, be also possible to synthetic resin.The solvent of supermolecule polymer matrix preparation process can be alkanes, Or mixtures thereof alkyl halide hydro carbons, alcohols, esters, ethers, ketone, aromatic organic solvent, such as use hexamethylene, trichlorine Methane, ethyl alcohol, ethyl acetate, tetrahydrofuran, butanone, toluene etc..
The carbon nanotube of the flexible sensor of near infrared light selfreparing is near-infrared optical Response material, while having both conduction Property with power/electrical response performance.Carbon nanotube used be commercial single-walled carbon nanotube (SWCNT) or (and) multi-walled carbon nanotube (MWCNT).Carbon nanotube, which is scattered in organic solvent, is sprayed on above-mentioned flexible supermolecule polymer surface, obtains uniform carbon Layer, to prepare the flexible sensor composite material of near infrared light selfreparing.
It illustrates below and the present invention is described in more detail.
Dry chloroform is evaporated under reduced pressure after overnight by calcium hydride reflux and is obtained.Dry tetrahydrofuran and toluene passes through sodium Silk is refluxed overnight rear distillation under pressure with benzophenone and obtains.Dry butanone is evaporated under reduced pressure after being refluxed overnight by natrium carbonicum calcinatum It obtains.Dry ethyl alcohol and dimethylformamide is obtained by being evaporated under reduced pressure after 4A molecular sieve soaked overnight.
(1) preparation of synthon
Methylisocytosine (65g) and hexamethylene diisocyanate (HDI, 650g) 100 DEG C of stirrings under protection of argon gas 16h is reacted, obtains white precipitate after the reaction was completed.1L n-hexane and high degree of agitation 1h, filtering, with just are added after being cooled to room temperature The washed washing of hexane, vacuum drying obtain white powder.
1H NMR(500MHz,CDCl3):δ13.1(1H),11.8(1H),10.1(1H),5.8(1H),3.3(4H),2.1 (3H), 1.6(4H),1.4(4H).
FT-IR:ν(cm-1)2935,2281,1698,1668,1582,1524,1256.
(2) preparation of polymer
Polymer 1
(Cray Valley company of the U.S., linear hydroxyl-terminated hydrogenation are poly- by 22.4g hydrogenated polybutadiene diol HLBH-P3000 Butadiene, 3.2kD) 1h is dried in vacuo at 100 DEG C, and (temperature cannot be excessively high, and the time cannot be too long to prevent long-time heating point Solution), it is cooling under dry environment, 4.3g synthon, 500mL chloroform and micro dibutyltin dilaurate catalyst is added, 72h is stirred to react for 60 DEG C of constant temperature under argon atmosphere.To which dry silica gel and micro two fourth of tin dilaurate after the reaction was completed, is added Ji Xi, the reaction was continued for 24 hours.It is cooled to room temperature, filters to take filtrate, be concentrated into 100mL, methanol is added and obtains white precipitate.Use first Alcohol washing, vacuum drying obtain colorless and transparent elastomeric material.
1H NMR(500MHz,CDCl3):δ5.8,4.1,3.3-3.0,2.9-2.8,2.2,1.6-1.0,0.8.
FT-IR(neat):ν(cm-1)3457,3336,3216,2959,2925,2855,1700,1664,1590,1525, 1461,1379,1252,761.
Tm:65.6℃
Polymer 2
24.8g TEP330N (U.S. Dow chemistry, three-functionality-degree terminal hydroxy group polyethylene glycol oxide/propylene triol, 5.1kD) exists It is dried in vacuo 1h (temperature cannot be excessively high, and the time cannot be too long to prevent long-time heating from decomposing) at 100 DEG C, under dry environment It is cooling, 4.36g synthon, 500mL chloroform and micro dibutyltin dilaurate catalyst, the constant temperature under argon atmosphere is added 60 DEG C are stirred to react 72h.To which dry silica gel and micro dibutyl tin dilaurate after the reaction was completed, is added, the reaction was continued 24h.It is cooled to room temperature, filters to take filtrate, be concentrated into 100mL, n-hexane is added and obtains white precipitate.It is washed with n-hexane, very Sky is dry, obtains colorless and transparent elastomeric material.
1H NMR(500MHz,CDCl3):δ13.1,11.8,10.2,8.0,4.2,3.8-3.1,2.3,1.7-1.0.
FT-IR(neat):ν(cm-1)3341,3216,2971,2931,2869,1722,1700,1667,1588,1527, 1454,1374,1256,1108,1015,931.
Tm:23.8℃
(3) dispersion and spraying of carbon nanotube
0.06g multi-walled carbon nanotube is added in 20mL chloroform, ultrasonic disperse 4h, with spray gun even application in 25*50mm's Supermolecule polymer surface.Spray pressure 0.5MPa, spray gun height 10cm.
Embodiment 1
1 presses following component proportion
1 180g of polymer
2 20g of polymer
Carbon nanotube chloroformic solution 10mL
2 preparation methods
Polymer 1 and polymer 2 are added dissolution in 2000mL chloroform and are tuned into paste after mixing, be concentrated into 500mL, pour to Mould
Supermolecule polymer sill is obtained after drying in tool.After supermolecule polymer matrix is dry, even application carbon is received Mitron chlorine
Imitative solution, the flexible sensor of drying to obtain near infrared light selfreparing.
The material can soften self-healing at 45 DEG C, melt at 60 DEG C.
Embodiment 2
1 presses following component proportion
1 170g of polymer
2 30g of polymer
Carbon nanotube chloroformic solution 10mL
2 preparation methods
Polymer 1 and polymer 2 are added dissolution in 2000mL chloroform and are tuned into paste after mixing, be concentrated into 500mL, pour to Mould
Supermolecule polymer sill is obtained after drying in tool.After supermolecule polymer matrix is dry, even application carbon is received Mitron chlorine
Imitative solution, the flexible sensor of drying to obtain near infrared light selfreparing.
The material can soften self-healing at 40 DEG C, melt at 55 DEG C.
Embodiment 3
1 presses following component proportion
1 150g of polymer
2 50g of polymer
Carbon nanotube chloroformic solution 10mL
2 preparation methods
Polymer 1 and polymer 2 are added dissolution in 2000mL chloroform and are tuned into paste after mixing, be concentrated into 500mL, pour to
Supermolecule polymer sill is obtained after drying in mold.After supermolecule polymer matrix is dry, even application carbon Nanotube
Chloroformic solution, the flexible sensor of drying to obtain near infrared light selfreparing.
The material can soften self-healing at 40 DEG C, melt at 53 DEG C.

Claims (9)

1. a kind of flexible sensor of near infrared light selfreparing, it is characterized in that:By supermolecule polymer matrix and carbon nanotube group At the supermolecule polymer matrix is by based in 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure end group and polymer Between segment form.
2. the flexible sensor of near infrared light selfreparing according to claim 1, it is characterized in that:It is described to be based on 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure end group be such as one or more of flowering structure,
WhereinRepresent hydrogen bond, R1By one or two kinds of structure compositions as described below
1)C1-C10Direct-connected or branched alkyl;
2) comprising the C of 1-4 Carbamido substituted base1-C10Alkyl, the structure of the urea groups is
3. the flexible sensor of near infrared light selfreparing according to claim 1 or 2, it is characterized in that:In the polymer Between segment be one or more of such as flowering structure,
1) polyether structure
Wherein R4、R5It is any one in following group with Y
a)H;
B) C1-C6 linear or branched alkyl group,
N is 1-6,
O is 10-100.
2) polyolefin structure
Wherein R6、R7It is any one in following group with Y
a)H;
B) C1-C6 linear or branched alkyl group;
C) C1-C6 linear chain or branched chain alkenyl,
P is 10-100.
4. the flexible sensor of near infrared light selfreparing according to claim 1 or 2, it is characterized in that:The supermolecule is poly- It is for the mixture of following two polymer that conjunction object matrix, which is structure,:
Polymer 1:
Polymer 2:
Mixed proportion is weight ratio 3:1~9:1.
5. the flexible sensor of near infrared light selfreparing according to claim 3, it is characterized in that:The supermolecule polymer Matrix is that structure is for the mixture of following two polymer:
Polymer 1:
Polymer 2:
Mixed proportion is weight ratio 3:1~9:1.
6. a kind of preparation method of the flexible sensor of near infrared light selfreparing described in claim 1, it is characterized in that:
(1) synthon is prepared
Methylisocytosine is reacted under protection of argon gas with hexamethylene diisocyanate, obtains white precipitate, is cooled to room temperature N-hexane stirring is added afterwards, filtering, with the washed washing of n-hexane, vacuum drying obtains white powder synthon, synthon Structure is
(2) polymer 1 is prepared
Synthon, chloroform and dibutyltin dilaurate catalyst is added after hydrogenated polybutadiene diol vacuum drying, in argon gas It is reacted under atmosphere, to which dry silica gel and dibutyl tin dilaurate are added after the reaction was completed, the reaction was continued, is cooled to room temperature, mistake The concentration of leaching filtrate is added methanol and obtains colorless and transparent polymer 1, and the structure of polymer 1 is
(3) polymer 2 is prepared
Three-functionality-degree terminal hydroxy group polyethylene glycol oxide/propylene triol vacuum drying, is added synthon, chloroform and di lauric dibutyl Tin catalyst reacts under argon atmosphere, and the dibutyl tin dilaurate to which dry silica gel sum is added after the reaction was completed continues Reaction, is cooled to room temperature, and filters to take filtrate concentration, and n-hexane is added and obtains colorless and transparent polymer 2, polymer 2 Structure is
(4) carbon nanotube is sprayed
Polymer 1 is mixed into addition chloroform with polymer 2 and is tuned into paste, it is poly- that concentration after-pouring is dried to obtain supermolecule into mold Close object matrix;Chloroform, ultrasonic disperse, with spray gun even application in supermolecule polymer matrix surface is added in carbon nanotube.
7. the preparation method of the flexible sensor of near infrared light selfreparing according to claim 6, it is characterized in that polymer 1, polymer 2, carbon nanotube proportion be:
1 180g of polymer
2 20g of polymer
Carbon nanotube chloroformic solution 10mL.
8. the preparation method of the flexible sensor of near infrared light selfreparing according to claim 6, it is characterized in that polymer 1, polymer 2, carbon nanotube proportion be:
1 170g of polymer
2 30g of polymer
Carbon nanotube chloroformic solution 10mL.
9. the preparation method of the flexible sensor of near infrared light selfreparing according to claim 6, it is characterized in that polymer 1, polymer 2, carbon nanotube proportion be:
1 150g of polymer
2 50g of polymer
Carbon nanotube chloroformic solution 10mL.
CN201810533440.1A 2018-04-16 2018-05-29 A kind of flexible sensor and preparation method of near infrared light selfreparing Pending CN108912665A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110423337A (en) * 2019-07-08 2019-11-08 浙江大学衢州研究院 A kind of Thermo-sensitive supermolecule polymer and preparation method thereof of multiple hydrogen bonding regulation
CN111286075A (en) * 2019-12-02 2020-06-16 哈尔滨工程大学 Recyclable supramolecular polymer foam material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN104833376A (en) * 2015-04-24 2015-08-12 中国人民大学 Self-repairing sensing chip and preparation method thereof
CN104892871A (en) * 2015-06-16 2015-09-09 厦门大学 Hydrogel with self-repairing function and preparation method of hydrogel
CN106221100A (en) * 2016-07-21 2016-12-14 天津大学 A kind of preparation method of optical drive selfreparing thin film based on ethylene-butylene copolymer
CN107216643A (en) * 2017-08-03 2017-09-29 四川大学 A kind of selfreparing polyurethane nano composite material and its production and use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104833376A (en) * 2015-04-24 2015-08-12 中国人民大学 Self-repairing sensing chip and preparation method thereof
CN104892871A (en) * 2015-06-16 2015-09-09 厦门大学 Hydrogel with self-repairing function and preparation method of hydrogel
CN106221100A (en) * 2016-07-21 2016-12-14 天津大学 A kind of preparation method of optical drive selfreparing thin film based on ethylene-butylene copolymer
CN107216643A (en) * 2017-08-03 2017-09-29 四川大学 A kind of selfreparing polyurethane nano composite material and its production and use

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110423337A (en) * 2019-07-08 2019-11-08 浙江大学衢州研究院 A kind of Thermo-sensitive supermolecule polymer and preparation method thereof of multiple hydrogen bonding regulation
CN110423337B (en) * 2019-07-08 2022-06-07 浙江大学衢州研究院 Temperature-sensitive supramolecular polymer regulated and controlled by multiple hydrogen bonds and preparation method thereof
CN111286075A (en) * 2019-12-02 2020-06-16 哈尔滨工程大学 Recyclable supramolecular polymer foam material and preparation method thereof

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