CN108892768A - One kind can the light-operated plastic polyurethane elastomeric material of self-healing, its preparation and application - Google Patents
One kind can the light-operated plastic polyurethane elastomeric material of self-healing, its preparation and application Download PDFInfo
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- CN108892768A CN108892768A CN201810510455.6A CN201810510455A CN108892768A CN 108892768 A CN108892768 A CN 108892768A CN 201810510455 A CN201810510455 A CN 201810510455A CN 108892768 A CN108892768 A CN 108892768A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
Abstract
The invention discloses a kind of polyurethane elastomer materials and preparation method thereof, by using six aryl bisglyoxaline (HABI) class photochromic molecules and polyalcohol as the crosslinking agent of elastomeric material, construct out the polyurethane elastomer material of double cross-linked network structures, the intelligent deformation polyurethane material that a kind of pair of ultraviolet light has quick response is correspondingly obtained, and the material has self-healing function.Polyurethane elastomer of the invention has the mechanical and physical performances such as good toughness, ductility and fatigue resistance, as a kind of intellectual material, driver, soft robot, bioartificial organs, sensor, manufacturing industry, health care, wearable device and in terms of have potential application market.
Description
Technical field
The invention belongs to flexible intelligents to drive field of material technology, and in particular to one kind can the light-operated plastic polyurethane bullet of self-healing
Elastomer material, preparation method and application.
Background technique
Can the light-operated plastic polyurethane elastomer of self-healing belong to the scope of polymer intelligent drives material, intelligent drives material
It is called actuator or artificial muscle again, environmental stimuli is made a response and own form and size can be changed.Recently as
Deep and production and living demand the continuous growth of research, is just vigorously sending out the research of flexible actuator and stimulate the reaction material
Exhibition, wherein the advantages such as low, easy processing play leading work in intellectual material research and development field to polymer material with its manufacturing cost
With.These materials have innovation health care, wearable device, bioartificial organs, manufacturing industry and flexible robot's technology
Potentiality.
Compared with conventional rigid material, flexible material is easily-deformable, adapts to the setting of the environment and dynamic task of variation, fits
High load capacity is answered, meets human production life safety, allows cheap large-scale production, there is better biological degradability and biology
Compatibility.And to allow material macroscopically responding to certain environmental stimuli, it is microcosmic on, inside necessarily include one or more
A functional molecular；To allow material that can make quick response, while also there is reversible nature, the design of material internal molecular structure is just
It is particularly important.Existing intelligent drives material or complex structural designs increase so that the synthesis of material becomes abnormal difficult
Application cost or blunt or irreversible to extraneous stimulate the reaction, these largely all limit intellectual material reality
The production and living application on border.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides one kind can the light-operated plastic polyurethane of self-healing
Elastomeric material, preparation method and application, its object is to by with six aryl bisglyoxaline (HABI) class photochromic molecules
Crosslinking agent with polyalcohol as elastomeric material constructs out the polyurethane elastomer material of double cross-linked network structures, accordingly
Ground obtains the intelligent deformation polyurethane material that a kind of pair of ultraviolet light has quick response, and the material has self-healing function, by
This solves or irreversible or complex structural designs blunt to extraneous stimulate the reaction existing for the intelligent drives material of the prior art
Etc. technical problems.
To achieve the above object, according to one aspect of the present invention, provide a kind of polyurethane elastomer material, for
Oligomer dihydric alcohol and diisocyanate are raw material, with the six aryl bisglyoxaline class molecular switches and polyalcohol of tetrahydroxy functionalization
What reaction obtained have for crosslinking agent, after the mixing polyurethane elastomer material of double cross-linked network structures, in the network structure
Six aryl bisglyoxalines are dynamic crosslinking point, and polyalcohol is fixed crosslinking points；The molecular weight of the oligomer dihydric alcohol is less than
10000g/mol。
Preferably, six aryl bisglyoxalines of the oligomer dihydric alcohol, diisocyanate, polyalcohol and tetrahydroxy functionalization
Molar ratio be 12.5：(12~14)：(1~5)：(0.5~4).
Preferably, six aryl bisglyoxalines of the oligomer dihydric alcohol, diisocyanate, polyalcohol and tetrahydroxy functionalization
Molar ratio be 12.5：(12~14)：3：1.
It is further preferred that the oligomer dihydric alcohol, diisocyanate, polyalcohol and tetrahydroxy functionalization six aryl
The molar ratio of bisglyoxaline is 12.5：13.7：3：1.
Preferably, the polyalcohol is trihydroxylic alcohol or tetrahydroxylic alcohol.
Preferably, the polyalcohol is glycerol trihydroxylic alcohol or pentaerythrite.
Preferably, six aryl bisglyoxaline class molecular switches of the tetrahydroxy functionalization are using 2-Cl-HABI as molecule master
Body and modify design and obtain, the 2-Cl-HABI have the structure as shown in formula (one)：
Preferably, there are six aryl bisglyoxaline class molecular switches of the tetrahydroxy functionalization such as (two) to formula (ten) to appoint
Structural formula shown in one：
R of the formula (two) into formula (ten) is the alkyl chain containing 2 hydroxyls.
Preferably, R of the formula (two) into formula (ten) is-CH2CHOHCH2OH。
Preferably, the oligomer dihydric alcohol is the polyether-type dihydric alcohol or molecular weight that molecular weight is 400~8000g/mol
For the polyester-type dihydric alcohol of 400~8000g/mol.
Preferably, the diisocyanate is aliphatic diisocyanate or aromatic diisocyanate.
Preferably, the diisocyanate is hexamethylene diisocyanate or methyl diphenylene diisocyanate.
Other side according to the invention provides the preparation method of polyurethane elastomer material described in one kind, packet
Include following steps：
(1) under dark conditions and inert gas shielding, by six aryl bisglyoxaline class molecules of tetrahydroxy functionalization
Organic solution, catalyst, polyalcohol and the oligomer dihydric alcohol after being dried are mixed and stirred for, and obtain mixed solution；
Wherein the molar ratio of six aryl bisglyoxalines of the oligomer dihydric alcohol, diisocyanate, polyalcohol and tetrahydroxy functionalization is
12.5：(12~14)：(1~5)：(0.5~4)；
(2) diisocyanate is mixed with step (1) described mixed solution, is stirred, removed under the conditions of being lower than 35 DEG C molten
Agent obtains the mixed solution of removing solvent；
(3) mixed solution of step (2) the removing solvent is transferred in mold, is made under vacuum-pumping conditions described mixed
Close solution curing molding.
Preferably, step (1) it is described be dried the specific steps are：Oligomer dihydric alcohol is taken out under the conditions of 70-90 DEG C
Vacuum drying 1 to 3 hour.
Preferably, the organic solvent in step (1) described organic solution is anhydrous tetrahydro furan.
Preferably, step (3) is specially：The mixed solution of step (2) the removing solvent is transferred in mold, is being taken out
Under vacuum condition, temperature be 40-80 DEG C reaction 12-48 hours, make the mixed solution curing molding.
Other side according to the invention provides the application of polyurethane elastomer material described in one kind, is used as light
Control plasticity intellectual material or self-healing intellectual material.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect：
(1) polyurethane material proposed by the present invention is a kind of light-operated plastic polyurethane elastomeric material, is networked for double cross
Shape structure, the six aryl bisglyoxaline class molecular switches and polyalcohol of tetrahydroxy functionalization are crosslinking agent, six virtues in network structure
Base bisglyoxaline serves as dynamic crosslinking point, and polyalcohol is fixed crosslinking points.The polyurethane elastomer is when bearing a fixed load, in purple
Material can continuously extend under outer illumination.This process is reversible.Load is removed, due to the presence of fixed crosslinking points, material is returned
Bullet, but initial length cannot be sprung back to, ultraviolet lighting is reused, material further recoils to initial length.
(2) polyurethane elastomer material self-healing effect proposed by the present invention is excellent, and healing time is short, the material after healing
Mechanical performance can match in excellence or beauty initial undamaged material.
(3) polyurethane elastomer proposed by the present invention has the mechanical-physicals such as good toughness, ductility and fatigue resistance
Performance can be used as being protected in driver, soft robot, bioartificial organs, sensor, manufacturing industry, medical treatment for intellectual material
Strong, wearable device and medical instrument etc. have potential application market.
(4) it is proposed by the present invention can the light-operated plastic polyurethane elastomeric material of self-healing preparation method to the early period of raw material at
Manage it is extremely simple, one step of reaction process complete, be easy to industrial scale production.
Detailed description of the invention
Fig. 1 be embodiment 1 can the light-operated plastic polyurethane elastomer of self-healing when bearing a fixed load, it is UV light-induced can
The optical imagery of repeated deformation；
Fig. 2 be 2 two pieces of embodiment be cut open can the light-operated plastic polyurethane elastomer self-healing of self-healing optical imagery；
Fig. 3 be the polyurethane elastomer material that is prepared of embodiment 2 under visible light, bullet after self-healing in different time
Property body and initial not damaged elastomer stress strain diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The invention proposes a kind of polyurethane elastomer materials, for oligomer dihydric alcohol, diisocyanate, polyalcohol
And six aryl bisglyoxaline (HABI) class molecular switches of tetrahydroxy functionalization are raw material, are joined with six aryl of tetrahydroxy functionalization
Imidazole derivative switch and polyalcohol are crosslinking agent, and that reacts has the polyurethane elastomer material of double cross-linked network structures
Expect, six aryl bisglyoxalines serve as dynamic crosslinking point in the network structure, and polyalcohol is fixed crosslinking points.Oligomer dihydric alcohol, two
The molar ratio of six aryl bisglyoxalines of isocyanates, polyalcohol and tetrahydroxy functionalization is 12.5：(12~14)：(1~5)：
(0.5~4), preferably 12.5：(12~14)：3：1, further preferably 12.5：13.7：3： 1.Four kinds of raw material proportionings are very heavy
It wants, palpus strict control ratio range could form polyurethane elastomer material of the present invention, wherein diisocyanate content
More crucial, content is too low, which can not solidify, and content is too high, then the strength of materials obtained is excessively high, cannot be formed described
Elastomeric material, corresponding light-operated plasticity is just unobvious.
In above-mentioned raw materials, polyalcohol is trihydroxylic alcohol or tetrahydroxylic alcohol, preferably glycerol trihydroxylic alcohol or pentaerythrite.Oligomer is
Refer to that the polymer as composed by less repetitive unit, relative molecular mass are generally less than 10000g/mol, here oligomer
Dihydric alcohol is preferably the polyether-type dihydric alcohol or polyester-type dihydric alcohol that molecular weight is 400~8000g/mol, and further preferred is low
Polymers dihydric alcohol, such as polyethylene glycol PEG or polytetrahydrofuran ether glycol PTMG.Diisocyanate is aliphatic diisocyanate
Or aromatic diisocyanate, preferably hexamethylene diisocyanate HDI or methyl diphenylene diisocyanate MDI.This hair
Bright special six aryl bisglyoxaline (HABI) the class molecular switches for selecting tetrahydroxy functionalization are dynamic crosslinking point crosslinking agent, tetrahydroxy
Six aryl bisglyoxaline class molecular switches of functionalization be modified by molecular bulk of 2-Cl-HABI design obtain it is a series of
Molecule, the 2-Cl-HABI have the structure as shown in formula (one)：
For example, six aryl bisglyoxaline class molecular switches of tetrahydroxy functionalization can have such as any one of (two) to formula (ten)
Shown in structural formula：
R of the formula (two) into formula (ten) is the alkyl chain containing 2 hydroxyls, preferably-CH2CHOHCH2OH.With formula (two) point
For son, when wherein R is-CH2CHOHCH2When OH, the preparation method of formula (two) molecule is：
At (1) 80 DEG C under nitrogen atmosphere, chloro- 4 hydroxy benzaldehyde of 2- and 3- chlorine-1,2-propylene glycol are added to hydroxide
React 12h in the aqueous solution of sodium, after be cooled to room temperature, be added a certain amount of concentrated hydrochloric acid and liquid separation chromatography, the chloro- 4- of 2- is prepared
(bis- propoxyl of 2,3-) benzaldehyde；
The product of the first step, benzil are added in a certain amount of acetic acid solution with ammonium acetate at (2) 90 DEG C and reacted
12h, rear to separate, crystallization and purification obtains 2- chlorine tetrahydroxy triphenylimidazolyl；
(3) at room temperature, the product of second step, potassium ferricyanide solid and potassium hydroxide are added to the organic solution of methylene chloride
Molecule shown in formula (two) structure can be obtained in middle reaction 8h, separating-purifying.
The six aryl bisglyoxaline class molecular switches of tetrahydroxy functionalization of formula (three) to formula (ten) can be according to above-mentioned preparation
The similar thinking of method is prepared.
The present invention provides the preparation methods of the polyurethane elastomer material described in one kind, include the following steps：
(1) under dark conditions and inert nitrogen gas protection, by oligomer dihydric alcohol, the tetrahydroxy after drying process
Organic solution, catalyst and the polyalcohol of six aryl bisglyoxaline class molecules of functionalization are mixed and stirred for, and obtain mixed solution；
Be dried the specific steps are：By oligomer dihydric alcohol vacuum drying 1 to 3 hour under the conditions of 70-90 DEG C.It is described organic
For the organic solvent used in solution for anhydrous tetrahydro furan (THF), the catalyst is dibutyl tin dilaurate (DBTDL).
It is to remove moisture therein to lead to avoid hydrone and di-isocyanate reaction by the purpose that oligomer dihydric alcohol is dried
Cause cannot obtain polyurethane elastomer material of the invention.Inert gas shielding be in order to avoid in air oxygen participate in reaction,
Cause cannot to obtain it is of the invention can the light-operated plastic polyurethane elastomeric material of self-healing.
(2) diisocyanate is mixed with step (1) described mixed solution, is stirred, removed under the conditions of being lower than 35 DEG C molten
Agent obtains the mixed solution of removing solvent；The method of removing solvent can such as reduce solvent boiling point under conditions of vacuumizing
Evaporation of solvent, the temperature that removing solvent is selected is unsuitable excessively high, once because the mixing of diisocyanate addition step (1) is molten
After in liquid, reaction just has begun progress, and temperature is excessively high, reacts too fast, causes to be cured during removing solvent,
Solvent may be contained in final curing materials, or the molded elastomer material that cannot be met the requirements.Control revolving temperature,
After guaranteeing removing solvent, reaction system remains as liquid, convenient for the curing molding in suitable mold in next step.
(3) mixed solution of step (2) the removing solvent is transferred in mold, under vacuum-pumping conditions, temperature is
It is reacted 12-48 hours under the conditions of 40-80 DEG C, makes the mixed solution curing molding.Curing molding is carried out under vacuumized conditions is
In order to avoid oxygen participates in reaction in air, cause cannot to obtain it is of the invention can the light-operated plastic polyurethane elastomer material of self-healing
Material.
The present invention provides one kind can the light-operated plastic polyurethane elastomeric material of self-healing and preparation method thereof, the elastomer material
Material is made by the raw material comprising following components：Oligomer dihydric alcohol, diisocyanate, the six of polyalcohol and tetrahydroxy functionalization
Aryl bisglyoxaline (HABI) class molecular switch.The present invention draws six aryl bisglyoxaline class photochromic molecules of tetrahydroxy functionalization
Enter into polymeric system, the polyurethane material of preparation is double cross-linked structures, six aryl bisglyoxalines of tetrahydroxy functionalization
Class molecular switch and polyalcohol are crosslinking agent, and six aryl bisglyoxalines in network structure serve as dynamic crosslinking point, and polyalcohol is solid
Determine crosslinking points.Here dynamic crosslinking point refers to the molecule for serving as crosslinking points under external condition such as illumination condition inside it
The free radicals of the dissociation of some key and two separation of formation, disconnect and being coupled；And when cancelling illumination, free radical recombines to form friendship
It is coupled the crosslinking points of structure.The fixed crosslinking points, which refer to, not to be occurred to disconnect the crosslinking points being coupled under illumination condition.
The elasticity modulus of double cross-linked network structure polyurethane elastomeric materials changes under ultraviolet lighting, material
Elasticity modulus is constantly reduced with the increase of ultraviolet lighting time, can be used as a kind of controllable plasticity intellectual material of light, such as to purple
The artificial muscle of outer photoresponse.For the polyurethane elastomer when bearing a fixed load, material can be constant under ultraviolet lighting
Ground elongation.This process is reversible.Load is removed, due to the presence of fixed crosslinking points, material rebounds, but initial length cannot be sprung back to
Degree, reuses ultraviolet lighting, material further recoils to initial length.Specifically, under ultraviolet lighting, six aryl bisglyoxalines
C-N key fracture between two imidazole rings of class molecular switch, so that forming two is difficult to the triphenylimidazolyl being stabilized freedom
Base (TPIR), removes ultraviolet lighting, and triphenylimidazolyl free radical (TPIR) forms six aryl bisglyoxalines again.Utilize six aryl
This property of bisglyoxaline class molecular switch, the polyurethane elastomer is when bearing a fixed load, two three under ultraviolet lighting
Phenylimidazole free radical will misplace, and material is caused constantly to extend, and network structure is reset.The deformation quantity of material can be by illumination
Good control, light application time is longer, and deformation quantity is bigger, and this process is reversible.Due to the presence of fixed crosslinking points, material is protected
There is good elasticity, remove load, material is sprung back, but since the dislocation of triphenylimidazolyl free radical is reset, material cannot
Initial length is sprung back to, ultraviolet lighting is reused, original triphenylimidazolyl free radical that dislocation rearrangement occurs can look for just
The triphenylimidazolyl free radical of beginning position, and it is in combination, so material will further spring back to initial length.
In addition, double cross-linked network structure polyurethane elastomeric materials have excellent self-healing capability under visible light,
It can be used as a kind of self-healing intellectual material.The polyurethane elastomer material self-healing effect is excellent, and healing time is short, after healing
The mechanical performance of material can match in excellence or beauty initial undamaged material.Since there is hot dynamic equilibrium between HABIs and TPIRs, therefore
And the material for physical damnification occur is placed under visible light, material self-heal, healing effect is excellent in the short time.It compares
In existing most of self-healing materials, this material healing time is short, does not need the external condition of too many harshness.
Polyurethane elastomer prepared by the present invention has the mechanical-physicals such as good toughness, ductility and fatigue resistance
Can, as a kind of intellectual material, driver, soft robot, bioartificial organs, sensor, manufacturing industry, health care,
Wearable device and medical instrument etc. have potential application market.
Raw material used in the embodiment of the present invention removes six aryl bisglyoxaline class molecules of the tetrahydroxy functionalization voluntarily synthesized
Switch is outer, it is other can market buy, or can be obtained by the method for maturation known in the art.
The following are embodiments：
Embodiment 1
It is that crosslinking agent synthesizes double cross with 2-Cl-4-diol-HABI molecular switch with glycerol using PTMG as oligomer dihydric alcohol
What is joined can the light-operated plastic polyurethane elastic material of self-healing.2-Cl-4-diol-HABI molecular structure is as follows.
Weigh PTMG (1.9g；It 1.9mmol) is put into round-bottomed flask, vacuum drying 1h or so, nitrogen atmosphere at 70 DEG C
It is cooled to room temperature under protection.Glycerol (42mg is weighed again；0.456mmol) be injected into above-mentioned round-bottomed flask, after weigh 2-Cl-4-
diol-HABI(128mg；0.152mmol), it is dissolved with the anhydrous THF of 10ml, is mixed with PTMG, and it is acute that catalyst DBTDL is added
Strong stirring half an hour；It is add to the above mixed solution with the HDI that 1ml syringe extracts 0.33ml；Mixed solution is taken out true
It is three to four times empty, it stirs ten minutes or so, it is rear to rotate, THF is thoroughly removed, mold is poured into.Be put into vacuum oven, at 45 DEG C
It is reacted under vacuum condition for 24 hours, is cooled to room temperature taking-up.Finally obtain the translucent elastic polyurethane of crocus that shape is dumbbell shaped
Body, and carry out UV light-induced tensile deformation test.Load is the counterweight of 100g.Related tension deformation test process such as Fig. 1
It is presented, initial sample has certain length；When adding counterweight, elastic deformation occurs for material, extends a distance；Afterwards to its into
Row ultraviolet radiation, material occur certain plastic deformation, extend again；Illumination and counterweight are gone in recession, and material is certain due to possessing
Elasticity by a distance that bounces back, but cannot recoil to initial length, and gap is several millimeters；Finally, in non-loaded situation
Under ultraviolet lighting is carried out to material again, and material placed under dark surrounds for a period of time, material further restores to first
Beginning length.
Embodiment 2
It is that crosslinking agent synthesizes double cross with 2-Cl-4-diol-HABI molecular switch with glycerol using PTMG as oligomer dihydric alcohol
What is joined can the light-operated plastic polyurethane elastic material of self-healing.
Weigh PTMG (3.8g；It 3.8mmol) is put into round-bottomed flask, vacuum drying 1h or so, nitrogen atmosphere at 70 DEG C
It is cooled to room temperature under protection.Glycerol (112mg is weighed again；1.216mmol) be injected into above-mentioned round-bottomed flask, after weigh 2-Cl-
4-diol-HABI(128mg；0.152mmol), it is dissolved, is mixed with PTMG, and catalyst DBTDL is added with the anhydrous THF of 10ml
It is vigorously stirred half an hour；It is add to the above mixed solution with the HDI that 1ml syringe extracts 0.66ml；Mixed solution is taken out
It vacuum three to four times, stirs ten minutes or so, it is rear to rotate, THF is thoroughly removed, mold is poured into.Vacuum oven is put into, at 45 DEG C
It reacts under vacuum conditions for 24 hours, is cooled to room temperature taking-up.Finally obtain the translucent polyurethane bullet of crocus that shape is dumbbell shaped
Property body, and carry out self-healing related experiment.Self-healing experiment is carried out in room temperature under visible light.Related self-healing experimentation is such as
Fig. 2 is presented, and for that can observe self-healing phenomenon to visual pattern, two pieces are cut with the sample that different colours mark, and splices
Together, rear to place under visible light, it finds after a period of time, notch will not be broken, explanation even if being pullled by manpower
Self-healing has occurred in it；Fig. 3 is the table of material original state and ess-strain after illumination self-healing different time in embodiment 2
Sign is different from the means of optical imagery by another kind to illustrate that material mechanical physical property is restored after self-healing, is prepared
Polyurethane elastomer material under visible light, in different time after self-healing elastomer and initial not damaged elastomer stress
Strain figure, specific recovery extent can be carried out final comparison by Fig. 3 stress strain diagram, it is seen that under light place different time (1h,
6h, 12h) after self-healing sample breaking strain increase with the extension of time, heal 12h after sample breaking strain even
Slightly larger than the breaking strain of initial sample (origin), illustrate that the healing of material is very high, the machinery of self-healing sample
The recovery extent of physical property is also very high.
Embodiment 3
It is that crosslinking agent synthesizes double cross with 2-Cl-4-diol-HABI molecular switch with glycerol using PTMG as oligomer dihydric alcohol
What is joined can the light-operated plastic polyurethane elastic material of self-healing.
Weigh PTMG (3.8g；It 3.8mmol) is put into round-bottomed flask, vacuum drying 1h or so, nitrogen atmosphere at 70 DEG C
It is cooled to room temperature under protection.Glycerol (56mg is weighed again；0.608mmol) be injected into above-mentioned round-bottomed flask, after weigh 2-Cl-4-
diol-HABI(128mg；0.152mmol), it is dissolved with the anhydrous THF of 10ml, is mixed with PTMG, and it is acute that catalyst DBTDL is added
Strong stirring half an hour；It is add to the above mixed solution with the HDI that 1ml syringe extracts 0.66ml；Mixed solution is taken out true
It is three to four times empty, it stirs ten minutes or so, it is rear to rotate, THF is thoroughly removed, mold is poured into.Be put into vacuum oven, at 45 DEG C
It is reacted under vacuum condition for 24 hours, is cooled to room temperature taking-up.Finally obtain the translucent elastic polyurethane of crocus that shape is dumbbell shaped
Body, and carry out corresponding UV light-induced tensile deformation test.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of polyurethane elastomer material, which is characterized in that its be using oligomer dihydric alcohol and diisocyanate as raw material, with
The six aryl bisglyoxaline class molecular switches and polyalcohol of tetrahydroxy functionalization are crosslinking agent, and what reaction obtained after mixing has double cross
Join the polyurethane elastomer material of network structure, six aryl bisglyoxalines are dynamic crosslinking point in the network structure, and polyalcohol is
Fixed crosslinking points；The molecular weight of the oligomer dihydric alcohol is less than 10000g/mol.
2. polyurethane elastomer material as described in claim 1, which is characterized in that the oligomer dihydric alcohol, diisocyanate
The molar ratio of six aryl bisglyoxalines of ester, polyalcohol and tetrahydroxy functionalization is 12.5：(12~14)：(1~5)：(0.5~4).
3. polyurethane elastomer material as described in claim 1, which is characterized in that the polyalcohol is trihydroxylic alcohol or quaternary
Alcohol.
4. polyurethane elastomer material as described in claim 1, which is characterized in that six aryl of the tetrahydroxy functionalization join
To modify design by molecular bulk of 2-Cl-HABI and obtaining, the 2-Cl-HABI has such as formula (one) imidazole derivative switch
Shown in structure：
5. polyurethane elastomer material as claimed in claim 4, which is characterized in that six aryl of the tetrahydroxy functionalization join
Imidazole derivative switch has the structural formula as shown in any one of (two) to formula (ten)：
R of the formula (two) into formula (ten) is the alkyl chain containing 2 hydroxyls.
6. polyurethane elastomer material as described in claim 1, which is characterized in that the oligomer dihydric alcohol is that molecular weight is
The polyether-type dihydric alcohol or molecular weight of 400~8000g/mol is the polyester-type dihydric alcohol of 400~8000g/mol.
7. polyurethane elastomer material as described in claim 1, which is characterized in that the diisocyanate is that aliphatic two is different
Cyanate or aromatic diisocyanate.
8. a kind of preparation method of polyurethane elastomer material as claimed in any one of claims 1 to 7, which is characterized in that
Include the following steps：
(1) under dark conditions and inert gas shielding, by the organic of six aryl bisglyoxaline class molecules of tetrahydroxy functionalization
Solution, catalyst, polyalcohol and the oligomer dihydric alcohol after being dried are mixed and stirred for, and obtain mixed solution；Wherein
The oligomer dihydric alcohol, diisocyanate, polyalcohol and tetrahydroxy functionalization the molar ratios of six aryl bisglyoxalines be 12.5：
(12~14)：(1~5)：(0.5~4)；
(2) diisocyanate is mixed with step (1) described mixed solution, is stirred, removed solvent under the conditions of being lower than 35 DEG C, obtain
To the mixed solution of removing solvent；
(3) mixed solution of step (2) the removing solvent is transferred in mold, makes the mixing molten under vacuum-pumping conditions
Liquid curing molding.
9. preparation method as claimed in claim 7, which is characterized in that step (3) is specially：Step (2) removing is molten
The mixed solution of agent is transferred in mold, under vacuum-pumping conditions, temperature be 40-80 DEG C reaction 12-48 hours, make the mixing
Solution curing molding.
10. a kind of application of the polyurethane elastomer material as described in claim 1 to 6, which is characterized in that be used as light-operated plasticity
Intellectual material or self-healing intellectual material.
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