CN108727834A - A kind of human temperature self-healing supramolecular polymer material and preparation method thereof - Google Patents
A kind of human temperature self-healing supramolecular polymer material and preparation method thereof Download PDFInfo
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- CN108727834A CN108727834A CN201810532460.7A CN201810532460A CN108727834A CN 108727834 A CN108727834 A CN 108727834A CN 201810532460 A CN201810532460 A CN 201810532460A CN 108727834 A CN108727834 A CN 108727834A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The present invention is to provide a kind of human temperature self-healing supramolecular polymer materials and preparation method thereof.Human temperature self-healing supramolecular polymer material is made of supermolecule polymer matrix, filler, pigment, and the supermolecule polymer matrix is made of 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure and intermediate segmented polymer.The present invention develops a kind of can widen self-healing flexible material field, the manufacture craft of material is simple, and cost is relatively low with the supermolecule flexible polymer material that can be melted or soften at 30~40 DEG C.Products obtained therefrom has self-healing performance, without adding other substances.The material of gained can adjust melting temperature to meet a variety of demands by changing chemical constitution within the scope of 30~40 DEG C.Material after use recycles after can directly cleaning and melts pouring molding again, effectively avoids the waste of raw material, saves use cost, increases economic efficiency.
Description
Technical field
The present invention relates to a kind of self-repair materials, and the present invention relates to a kind of preparation methods of self-repair material.
Specifically it is a kind of can under human temperature environment spontaneous carry out breakage reparation self-repair material and preparation method thereof.
Background technology
Self-healing (self-healing) refers to material under certain external condition effect, spontaneous to be repaiied to breakage
It is multiple, with restore completely or partially a certain or a variety of property before breakage 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
There are mainly of two types for material, one kind mainly by being realized in material internal dispersion or compound some functional materials, this
A little functional materials are mainly fiber or capsule equipped with chemical substance；It is another kind of mainly to be carried to system by modes such as heating
For energy, crystallization is brought it about, realizes and repairs the effects that surface forms film or generates crosslinking.Preceding one kind material remediation efficiency
Height, speed is fast, but due to its use be damaged filling mode, thus repairing for smaller range and fewer number can only be carried out
It is multiple, if the chemical substance of filling is depleted, the healing that can not be damaged again.The general remediation efficiency of latter approach
Relatively low, repair time is longer, but it can carry out wide range and theory unlimited reparation, and can be carried out at one repeatedly
Effective damage and repair, this be former approach it is incomparable.Thus latter class selfreparing behavior becomes with material
More concerned research hotspot.
The important applied field of self-healing material is to prepare biomimetic material and wearable intelligent device.Latter class reviews one's lessons by oneself compound
Method, which generally requires higher temperature, makes the temperature of damaged part reach phase transformation or softening temperature to make breakage realize melting for both sides
It closes, is repaired to realize.And the phase transformation of traditional material or softening temperature are higher, it is difficult to it is used under human body and biotic environment, because
And limit its development.Therefore a kind of material that can carries out self-healing under body temperature environment is prepared as there is an urgent need to solve
Certainly the problem of.Supermolecule polymer connects polymerized monomer using non-covalent bond effect and is formed with larger molecular weight polymer line
Property or network polymers, while there is certain mechanical strength to ensure its applicability.By the change for changing supermolecule polymer
Structure is learned, mechanical strength and the controllable polymer material of melting temperature can be prepared, largely meet a variety of applications
Demand.Due to the characteristic of supermolecule polymer, prepared self-healing material can by simply melting utilization of turning one's head again,
Cost-effective and environmentally friendly.
Invention content
The purpose of the present invention is to provide a kind of human temperature self-healing oversubscription that can be melted or soften at 30~40 DEG C
Sub- polymer material.The present invention also aims to provide a kind of preparation side of human temperature self-healing supramolecular polymer material
Method.
The human temperature self-healing supramolecular polymer material of the present invention is made of supermolecule polymer matrix, filler, pigment,
The supermolecule polymer matrix is made of 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure and intermediate segmented polymer.
The present invention human temperature self-healing supramolecular polymer material can also include：
1, -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure of the 2- urea groups is arranged according to the position of electron donor D and electron acceptor A
Cloth difference is divided into two kinds of association modes of DADA and AADD, is one or more of such as lower structure,
WhereinRepresent hydrogen bond, R1、R2It is one or two kinds of structures below
1)C1-C10Direct-connected or branched alkyl；
2) include the C of 1-4 Carbamido substituted base1-C10Alkyl, the structure of the urea groups is
Simultaneously.
2,2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure passes through R2It is super that composition is connected into intermediate segment polymer phase
Molecularly Imprinted Polymer material main chain.
3, there is 10-100 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure in the supermolecule polymer matrix
Between segmented polymer segment be connected.
4, the intermediate segmented polymer be such as one or more of lower structure,
1) polyether structure
Wherein R4、R5It is any one in following group with Y,
a)H、
B) C1-C6 linear or branched alkyl groups,
N is 1-6,
O is 10-100；
2) polyolefin structure
Wherein R6、R7、R8、R9It is any one in following group with Y
a)H、
B) C1-C6 linear or branched alkyl groups,
C) C1-C6 linear chain or branched chains alkenyl,
P, q is 10-100.
The preparation method of human temperature self-healing supramolecular polymer material of the present invention is：
(1) as follows in a kind of preparing synthon
1) methylisocytosine is stirred to react 16h for 100 DEG C under protection of argon gas with hexamethylene diisocyanate, has reacted
At n-hexane and high degree of agitation, filtering are added after postcooling to room temperature, are washed with n-hexane, is dried in vacuo and obtains structural formula and beSynthon 1；
2) isopropyl base iso-cytosine is stirred to react for 24 hours for 90 DEG C under protection of argon gas with hexamethylene diisocyanate, instead
It should be cooled to -20 DEG C after the completion, -20 DEG C of n-hexane is added, filter at low temperature washing, vacuum drying obtain structural formula and beSynthon 2；
(2) as follows in a kind of preparing supermolecule polymer
1) hydrogenated polybutadiene diol is dried in vacuo at 100 DEG C, cooling under dry environment, be added synthon 1, chloroform and
Dibutyl tin laurate, 60 DEG C of constant temperature is stirred to react 72h under argon atmosphere, be added after the completion of waiting reacting dry silica gel and
The reaction was continued for dibutyl tin laurate for 24 hours, is cooled to room temperature, and filters to take filtrate concentration, and methanol is added and obtains white precipitate, uses
Methanol washing is dried to obtain supermolecule polymer 1；
2) three-functionality-degree terminal hydroxy group polyethylene glycol oxide/propylene triol is dried in vacuo 1h at 100 DEG C, cold under dry environment
But, synthon 1 or synthon 2, chloroform and dibutyl tin laurate is added, 60 DEG C of constant temperature is stirred to react under argon atmosphere
72h is added dry silica gel and dibutyl tin laurate the reaction was continued for 24 hours, is cooled to room temperature, filters to take after the completion of waiting reacting
Filtrate, concentration are added n-hexane and obtain white precipitate, washed, be dried in vacuo with n-hexane, obtain supermolecule polymer 2；
3) hydrogenated polybutadiene diol is dried in vacuo 1h at 100 DEG C, is cooled down under dry environment, synthon 1, chloroform is added
And dibutyl tin laurate, 60 DEG C of constant temperature is stirred to react 72h under argon atmosphere, and dry silica gel and tin dilaurate two is added
The reaction was continued for butyl tin for 24 hours, is cooled to room temperature, and filters to take filtrate concentration, and methanol is added and obtains white precipitate, is washed with methanol,
Vacuum drying, obtains supermolecule polymer 3；
(3) as follows in a kind of preparing supermolecule polymer matrix
1) polymer 2 is 100 according to mass ratio with white carbon:After 1 ratio mixing, addition chloroform, dissolving are tuned into paste,
Concentration obtains supermolecule polymer sill after pouring into mold drying；
2) polymer 3 is 100 according to mass ratio with carbon black:After 0.05 ratio mixing, chloroform is added, dissolving is tuned into paste
Shape, concentration obtain supermolecule polymer sill after pouring into mold drying；
3) polymer 1, polymer 2 and Ke Site KR312 are 100 according to mass ratio:100：0.:After 25 ratio mixing,
Addition chloroform, dissolving are tuned into paste, concentrate, and supermolecule polymer sill is obtained after pouring into mold drying；
4) polymer 1, polymer 2 and Ranbar Blue P5060/5061 are 170 according to mass ratio:30：1 ratio is mixed
After conjunction, addition chloroform, dissolving are tuned into paste, concentrate, and supermolecule polymer sill is obtained after pouring into mold drying.
For the demand of body temperature self-healing flexible material, can be melted at 30~40 DEG C the present invention provides one kind or
Supermolecule flexible polymer material of softening and preparation method thereof can be used for preparing body temperature self-healing material.
The human temperature self-healing supramolecular polymer material of the present invention, is filled out by supermolecule polymer matrix, organic or inorganic
Material, the raw materials such as pigment composition.The processes such as its preparation process includes the synthesis of matrix resin, is kneaded, pours.Supermolecule polymer base
Body is based on 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure, selects different polymer as intermediate segment, cooperation, which is added, to be had
Machine, inorganic filler prepare the supermolecule flexible polymer material that can be melted or soften at 30~40 DEG C to realize
Self-healing is carried out under body temperature environment.
Supermolecule polymer matrix in the body temperature self-healing flexible polymer material of the present invention is based on Quadrupolar hydrogen bond structure
As end group and select different polymer as intermediate segment.Further, Quadrupolar hydrogen bond system is according to electron donor (D) and electricity
The position arrangement of sub- receptor (A) is different, and there are two kinds of association modes of DADA and AADD for Quadrupolar hydrogen bond.Supermolecule polymer matrix base
In Quadrupolar hydrogen bond structure as end group, and select different polymer as intermediate segment.
Supermolecule polymer matrix resin is compounded with pigment, and pigment content is the 0-5% of entire material content.
- 4 [1H]-pyrimidone Quadrupolar hydrogen bond structure of the 2- urea groups is artificial composite structure, the tree of polymer centre segment
Fat can be natural resin, can also be 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 beneficial effects of the invention are as follows：Develop it is a kind of can be flexible with the supermolecule that can be melted at 30~40 DEG C or soften
Polymer material has widened self-healing flexible material field, and the manufacture craft of material is simple, and cost is relatively low.Products obtained therefrom has
There is self-healing performance, without adding other substances.The material of gained, can be within the scope of 30~40 DEG C by changing chemical constitution
Melting temperature is adjusted to meet a variety of demands.Material after use recycles after can directly cleaning and melts pouring molding again, effectively
The waste of raw material is avoided, use cost is saved, increases economic efficiency.
Specific implementation mode
It illustrates below and the present invention is described in more detail.
Material therefor of the present invention is existing by following pretreatment：
Dry chloroform is evaporated under reduced pressure after overnight by calcium hydride reflux and is obtained.Dry tetrahydrofuran passes through sodium with toluene
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 is obtained with dimethylformamide by being evaporated under reduced pressure after 4A molecular sieve soaked overnights.
2- urea groups -4 [1H]-pyrimidone, which can be reacted by corresponding iso-cytosine with corresponding isocyanates, to be prepared
And it obtains.Iso-cytosine can be prepared by corresponding 'beta '-ketoester and guanidine condensation reaction.
'beta '-ketoester is prepared via a method which
Potassium ethyl malonate generates the intermediate product containing magnesium, Zhi Houjia with anhydrous magnesium chloride in the case where ethyl acetate is solvent
Enter the acyl chlorides of relative acid, carries out addition reaction at room temperature.Hydrogen ion protonation is added later and deacylation acts on obtaining product.
One, the preparation of synthon
Synthon 1
Methylisocytosine (65g) and hexamethylene diisocyanate (HDI, 650g) 100 DEG C of stirrings under protection of argon gas
16h is reacted, white precipitate is obtained after the completion of reaction.1L n-hexanes 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.
Synthon 2
Isopropyl base iso-cytosine (5g) and hexamethylene diisocyanate (HDI, 50g) 90 DEG C of stirrings under protection of argon gas
Reaction for 24 hours, light yellow transparent solution is obtained after the completion of reaction.- 20 DEG C are cooled to, white crystals are precipitated, is added 200mL-20 DEG C
N-hexane, filter at low temperature washing, vacuum drying obtain white powder.
1H NMR(500MHz,CDCl3):δ13.28(1H),11.94(1H),10.20(1H),5.85(1H),3.29(4H),
2.72(1H),1.62,1.56,1.27.
FT-IR:ν(cm-1)3025,2941,2876,2301,1704,1649,1571,1462,1263,1242,752,
790,726.
Two, the preparation of polymer
Polymer 1
(Cray Valley companies of the U.S., linear hydroxyl-terminated hydrogenation are poly- by 22.4g hydrogenated polybutadiene diols 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 long to prevent long-time heating point
Solution), it is cooling under dry environment, 4.3g synthons 1,500mL chloroforms and micro dibutyltin dilaurate catalyst is added,
60 DEG C of constant temperature is stirred to react 72h under argon atmosphere.It waits after the completion of reacting, dry silica gel and micro two fourth of tin dilaurate 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 washs, and vacuum drying obtains the elastomeric material of water white transparency.
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) exist
1h (temperature cannot be excessively high, and the time cannot be long to prevent long-time heating from decomposing) is dried in vacuo at 100 DEG C, it is cold under dry environment
But, 4.36g synthons 1,500mL chloroforms and micro dibutyltin dilaurate catalyst, the constant temperature under argon atmosphere is added
60 DEG C are stirred to react 72h.It waits after the completion of reacting, dry silica gel and micro dibutyl tin laurate 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 the elastomeric material of water white transparency.
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.
Polymer 10
Tm:23.8℃
Polymer 3
(Cray Valley companies of the U.S., linear hydroxyl-terminated hydrogenation are poly- by 22.4g hydrogenated polybutadiene diols 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 long to prevent long-time heating point
Solution), it is cooling under dry environment, 5.0g synthons 1,500mL chloroforms and micro dibutyltin dilaurate catalyst is added,
60 DEG C of constant temperature is stirred to react 72h under argon atmosphere.It waits after the completion of reacting, dry silica gel and micro two fourth of tin dilaurate 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 washs, and vacuum drying obtains the elastomeric material of water white transparency.
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:53.1℃
Three, the preparation of supermolecule polymer matrix
1、
1) component proportion
2 200g of polymer
White carbon 2g
2) preparation method
Dissolving in 2000mL chloroforms is added and is tuned into paste, is concentrated into 500mL, supermolecule is obtained after pouring into mold drying
Polymer-based material.
The material can soften self-healing at 15 DEG C, be melted at 31 DEG C.
2、
1) component proportion
3 200g of polymer
Carbon black 0.1g
2) preparation method
Dissolving in 2000mL chloroforms is added and is tuned into paste, is concentrated into 500mL, supermolecule is obtained after pouring into mold drying
Polymer-based material.
The material can soften self-healing at 25 DEG C, be melted at 53 DEG C.
3、
1) component proportion
1 200g of polymer
2 200g of polymer
Ke Site KR312 (bright red) 0.5g
2) preparation method
It is added in 5000mL chloroforms and dissolves, be concentrated into 1000mL, supermolecule polymer is obtained after pouring into mold drying
Sill.
The material can soften self-healing at 30 DEG C, be melted at 45 DEG C.
4、
1) component proportion
1 170g of polymer
2 30g of polymer
Ranbar Blue P5060/5061 1g
2) preparation method
It is added in 5000mL chloroforms and dissolves, be concentrated into 1000mL, supermolecule polymer is obtained after pouring into mold drying
Sill.
The material can soften self-healing at 40 DEG C, be melted at 55 DEG C.
Claims (7)
1. a kind of human temperature self-healing supramolecular polymer material, it is characterized in that：By supermolecule polymer matrix, filler, pigment
It is made, the supermolecule polymer matrix is by 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure and intermediate segmented polymer
It constitutes.
2. human temperature self-healing supramolecular polymer material according to claim 1, it is characterized in that：The 2- urea groups -4
[1H]-pyrimidone Quadrupolar hydrogen bond structure is divided into DADA and AADD two according to the position arrangement difference of electron donor D and electron acceptor A
Kind association mode is one or more of such as lower structure,
WhereinRepresent hydrogen bond, R1、R2It is one or two kinds of structures below
1)C1-C10Direct-connected or branched alkyl；
2) include the C of 1-4 Carbamido substituted base1-C10Alkyl, the structure of the urea groups isSimultaneously.
3. human temperature self-healing supramolecular polymer material according to claim 2, it is characterized in that：2- urea groups -4 [1H] -
Pyrimidone Quadrupolar hydrogen bond structure passes through R2It is connected into intermediate segment polymer phase and constitutes supramolecular polymer material main chain.
4. human temperature self-healing supramolecular polymer material according to claim 1,2 or 3, it is characterized in that：The oversubscription
There are 10-100 2- urea groups -4 [1H]-pyrimidone Quadrupolar hydrogen bond structure and intermediate segment polymer segment phase in sub- polymeric matrix
Even.
5. human temperature self-healing supramolecular polymer material according to claim 1,2 or 3, it is characterized in that：The centre
Segmented polymer be such as one or more of lower structure,
1) polyether structure
Wherein R4、R5It is any one in following group with Y,
a)H、
B) C1-C6 linear or branched alkyl groups,
N is 1-6,
O is 10-100；
2) polyolefin structure
Wherein R6、R7、R8、R9It is any one in following group with Y
a)H、
B) C1-C6 linear or branched alkyl groups,
C) C1-C6 linear chain or branched chains alkenyl,
P, q is 10-100.
6. human temperature self-healing supramolecular polymer material according to claim 4, it is characterized in that：The intermediate segment is poly-
Close object be such as one or more of lower structure,
1) polyether structure
Wherein R4、R5It is any one in following group with Y,
a)H、
B) C1-C6 linear or branched alkyl groups,
N is 1-6,
O is 10-100；
2) polyolefin structure
Wherein R6、R7、R8、R9It is any one in following group with Y
a)H、
B) C1-C6 linear or branched alkyl groups,
C) C1-C6 linear chain or branched chains alkenyl,
P, q is 10-100.
7. a kind of preparation method of human temperature self-healing supramolecular polymer material, it is characterized in that：
(1) as follows in a kind of preparing synthon
1) methylisocytosine is stirred to react 16h for 100 DEG C under protection of argon gas with hexamethylene diisocyanate, after the completion of reaction
N-hexane and high degree of agitation, filtering are added after being cooled to room temperature, washed with n-hexane, be dried in vacuo and obtain structural formula and beSynthon 1；
2) isopropyl base iso-cytosine is stirred to react for 24 hours for 90 DEG C under protection of argon gas with hexamethylene diisocyanate, has been reacted
It is cooled to -20 DEG C after, -20 DEG C of n-hexane is added, filter at low temperature washing, vacuum drying obtain structural formula and beSynthon 2；
(2) as follows in a kind of preparing supermolecule polymer
1) hydrogenated polybutadiene diol is dried in vacuo at 100 DEG C, cooling under dry environment, and synthon 1, chloroform and February is added
Dilaurylate, 60 DEG C of constant temperature is stirred to react 72h under argon atmosphere, waits that dry silica gel and February are added after the completion of reacting
The reaction was continued for dilaurylate for 24 hours, is cooled to room temperature, and filters to take filtrate concentration, and methanol is added and obtains white precipitate, uses methanol
It washs, be dried to obtain supermolecule polymer 1；
2) three-functionality-degree terminal hydroxy group polyethylene glycol oxide/propylene triol is dried in vacuo 1h at 100 DEG C, cools down, adds under dry environment
Enter synthon 1 or synthon 2, chloroform and dibutyl tin laurate, 60 DEG C of constant temperature is stirred to react 72h under argon atmosphere, waits for
It is added dry silica gel and dibutyl tin laurate after the completion of reaction the reaction was continued for 24 hours, be cooled to room temperature, filter to take filtrate,
Concentration is added n-hexane and obtains white precipitate, washed, is dried in vacuo with n-hexane, obtain supermolecule polymer 2；
3) hydrogenated polybutadiene diol is dried in vacuo 1h at 100 DEG C, is cooled down under dry environment, synthon 1, chloroform and two is added
Dibutyl tin laurate, 60 DEG C of constant temperature is stirred to react 72h under argon atmosphere, and dry silica gel and di lauric dibutyl is added
The reaction was continued for tin for 24 hours, is cooled to room temperature, and filters to take filtrate concentration, and methanol is added and obtains white precipitate, is washed with methanol, vacuum
It is dry, obtain supermolecule polymer 3；
(3) as follows in a kind of preparing supermolecule polymer matrix
1) polymer 2 is 100 according to mass ratio with white carbon:After 1 ratio mixing, addition chloroform, dissolving are tuned into paste, dense
Contracting obtains supermolecule polymer sill after pouring into mold drying；
2) polymer 3 is 100 according to mass ratio with carbon black:After 0.05 ratio mixing, addition chloroform, dissolving are tuned into paste, dense
Contracting obtains supermolecule polymer sill after pouring into mold drying；
3) polymer 1, polymer 2 and Ke Site KR312 are 100 according to mass ratio:100：0.:After 25 ratio mixing, it is added
Chloroform, dissolving are tuned into paste, concentrate, and supermolecule polymer sill is obtained after pouring into mold drying；
4) polymer 1, polymer 2 and Ranbar Blue P5060/5061 are 170 according to mass ratio:30：1 ratio mixing
Afterwards, addition chloroform, dissolving are tuned into paste, concentrate, and supermolecule polymer sill is obtained after pouring into mold drying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810355139 | 2018-04-19 | ||
| CN2018103551396 | 2018-04-19 |
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| Publication Number | Publication Date |
|---|---|
| CN108727834A true CN108727834A (en) | 2018-11-02 |
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Cited By (3)
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| CN110627993A (en) * | 2019-10-22 | 2019-12-31 | 华南理工大学 | Waterborne polyurethane dispersion containing quadruple 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 |
| CN116987278A (en) * | 2023-08-04 | 2023-11-03 | 浙江永通新材料股份有限公司 | Low-temperature self-healing polysiloxane supermolecular elastomer and preparation method thereof |
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