CN106589311B - A kind of Intrinsical selfreparing and recyclable polyether polyols and its preparation method and application - Google Patents

A kind of Intrinsical selfreparing and recyclable polyether polyols and its preparation method and application Download PDF

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CN106589311B
CN106589311B CN201611132325.0A CN201611132325A CN106589311B CN 106589311 B CN106589311 B CN 106589311B CN 201611132325 A CN201611132325 A CN 201611132325A CN 106589311 B CN106589311 B CN 106589311B
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monomer
polyether polyols
parts
glycol
reaction
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CN106589311A (en
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张泽平
容敏智
章明秋
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National Sun Yat Sen University
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Abstract

The invention discloses a kind of Intrinsical selfreparings and recyclable polyether polyols, including raw material as follows by weight: 0.6 ~ 1.8 part of glycol monomer containing fragrant gneissic suite structure, polyester or 2.5 ~ 22.5 parts of polyether Glycols monomer, 0.5 ~ 2.0 part of polyisocynate monomer, 0.6 ~ 2.0 part of diisocyanate monomer, polyalcohol or monomer crosslinked dose 0.1 ~ 0.6 part of multi-thiol；Invention also provides the preparation method and application of above-mentioned polyether polyols, polyether polyols provided by the invention can realize selfreparing and recycling, its selfreparing and principle of PCB recycling are the preferential fracture of the fragrant gneissic suite reversible C-C in center in polymer molecular chain, and it is spread by interfacial molecular chain, infiltration, it tangles, and then the thermal reversion reaction on molecular level occurs, so that macromolecular chain exchange recombination between polymer damage surface or crushed particles, realize selfreparing and solid-state recycling, thus it is conducive to extend the service life of polymer material, energy conservation, reduce the wasting of resources, meet the development trend of global low-carbon economy.

Description

A kind of Intrinsical selfreparing and recyclable polyether polyols and preparation method thereof and Using
Technical field
The invention belongs to intelligent polymer field of material technology, more particularly, to a kind of Intrinsical selfreparing and can return Polyether polyols of receipts and its preparation method and application.
Background technique
Polymer and its composite material have specific strength and specific modulus height, superior fatigue resistance, damping property good, overload peace The advantages that full performance is high, convenient formation, corrosion-resistant, excellent electrical insulation capability overcomes conventional metals and inorganic non-metallic Limitation is widely used in numerous areas.However, polymer material is inevitably in machine-shaping and use process The defects of generating micro-crack, is easy to cause the reduction of stability of material, shortens its length of service, or even cause security risk.Such as What improves the service life and stability of polymer material, realizes high performance and environmental-friendlyization is that polymer material urgently solves One of critical issue certainly.
Intellectual material be derived from bionics, be it is a kind of can perceive and respond external environment variation, by change self structure and Function is allowed to and the extraneous adaptive material system mutually coordinated.Wherein, bionical self-repair material can be with self diagnosis and self-healing material Damage in material, it is ensured that the long-time stability and reliability of material, expanded service life eliminate potential risk, have huge Potential application foreground has become one of material science research hotspot in recent years.Polymer matrix self-repair material, which is broadly divided into, to be buried The selfreparing of plant type and Intrinsical selfreparing two major classes.Heeling-in type selfreparing needs additional renovation agent or catalyst, it is difficult to realize phase With the repetition reparation at position.Intrinsical selfreparing because of the characteristic using reversible keying contained by macromolecular, external condition (such as Heat, light, electricity, pH etc.) it stimulates down, it can be achieved that the self-healing of crackle, theoretically has unlimited number of repair ability.It reports at present Intrinsical selfreparing high molecular material based on dynamic reversible key, because the dynamic of reversible key, is mainly rendered as gel and bullet Elastomer material, intensity is not generally high, and the structural material for being not suitable as carrying uses.
From the point of view of bond energy, carbon-carbon single bond bond energy with higher (376.6kJ/mol) and stability, and monomer The scalability of structure is stronger, is hopeful to be applied to higher-strength structure self-repair material.People utilize DA key in recent years Reciprocal characteristics are prepared for a series of intrinsic self-repair materials, but DA key does not have dynamic reversibility, need to divide at two temperatures Not carry out forward and reverse DA reaction could complete selfreparing, and when inverse DA reacts, material depolymerization cannot keep material bearing capacity And shape, limitation are larger, it is therefore necessary to selfreparing chemistry of the development based on dynamic thermal reversion carbon-carbon single bond.
Summary of the invention
It is an object of the invention to according to deficiency in the prior art, provide a kind of Intrinsical selfreparing and recyclable Polyether polyols.
Another object of the present invention is to provide the preparations of above-mentioned Intrinsical selfreparing and recyclable polyether polyols Method.
A further object of the present invention is to provide above-mentioned Intrinsical selfreparings and recyclable polyether polyols to prepare Application in selfreparing and recyclable material.
When polyurethane polymer material provided by the invention generates damage, it need to only be carried out in inert gas or air simple Docking and heating repair process, being automatically repaired for micro-damage can be realized.In addition, polymer can be by hot-forming after crushing The moulding by casting technology of technology or solvent auxiliary realizes the recycling of polymer material.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides a kind of Intrinsical selfreparings and recyclable polyether polyols, including as follows by weight Raw material:
The degree of functionality of the polyisocynate monomer is greater than 3；The polyalcohol or monomer crosslinked dose of multi-thiol of function Degree is greater than 3；
The glycol monomer structural formula containing fragrant gneissic suite structure is shown in formula I:
Wherein, R is derived from alkyl；R1Represent the substituent group on one or more phenyl ring, R1It is derived from hydrogen, alkyl or alkoxy.
The present invention protects the glycol monomer containing fragrant gneissic suite structure in selfreparing and recyclable polymer material simultaneously In application.
Wherein, the glycol monomer provided by the invention containing fragrant gneissic suite structure belongs to tetraphenyl ethane derivative, passes It is used on system as hot iniferter.Repulsion between bulky substituent group makes center C-C key generate distortion, stretch Long and through-bond coupling, enhances the antibonding property of C-C key, as a result bond distance is increased, heated to can produce low activity Or stable free radical.The repair mechanisms of polymer containing fragrant gneissic suite structure are gneissic suite center on polymer molecular chain The preferential fracture of reversible C-C key, and by the diffusion of interfacial molecular chain, infiltration, entanglement, and then the thermal reversion on molecular level occurs Reaction, so that macromolecular chain exchange recombination between polymer damage surface.
The process of polymer selfreparing is carried out using thermal reversion dynamic covalent bond, core is fracture-weight of covalent bond It is new to combine, even if associated polymeric material occurs fragment type and destroys, new covalent bond should be able to be similarly formed between fragment, it is extensive Multiple mechanical property, this actually mean that the reversible reaction based on covalent bond can help polymer material carry out solid-state recycling and It recycles.In actual operation, after the polymer product for having lost use value or having discarded being crushed, using mould Molded or solid-state extrusion forming technique passes through macromolecular between polymer crumb under thermal reversion reaction temperature and certain pressure The exchange of chain recombinates, and the bulk polymer with (or close) original mechanical property is made again.This removal process due to It is carried out under the conditions of all solid state, easy to operate, low energy consumption, very promising.On the other hand, general thermosetting material cannot be molten Solution, and utilize the dissociation of thermal reversion key, then its dissolubility can be assigned, and using solvent auxiliary recycling thermosetting material, more to have Conducive to the original molecular structure of reserved materials.
Fragrant gneissic suite structure with dynamic reversible carbon-carbon bond is introduced into polymer material by the present invention, assigns polymer The selfreparing of material Thermoreversibly and can solid-state or solvent assist recyclability, to extend stability in use and the service life of material.
Preferably, R is derived from the alkyl of C1~10；R1It is derived from the alkoxy of hydrogen, the alkyl of C1~10 or C1~10.
Preferably, the glycol monomer containing fragrant gneissic suite structure is prepared with the following method: by 2.5~7.5 Benzophenone derivates monomer and 0.1~0.5 part of glacial acetic acid of the part containing primary hydroxyl are dissolved in 7.9~47.2 parts of isopropanols, 2~7d of illumination reaction under ultraviolet radiation, the temperature of reaction are 30~40 DEG C, and ultraviolet radiation wavelength is 280~315nm.
Preferably, the preparation of the benzophenone derivates monomer containing primary hydroxyl be under inert gas protection, by 6.0~ The benzophenone derivates monomer of 10.0 parts of phenolic hydroxy groups is mixed with 5.0~10.0 parts of ethylene bromohyrins, adds 5.5~22.1 parts Anhydrous potassium carbonate catalyst is reacted, and the temperature of reaction is 80~100 DEG C, and the reaction time is 12~for 24 hours.
Preferably, the benzophenone derivates monomer of the phenolic hydroxy group be following structural formula one of compound or It is several,
Wherein, R is hydrogen, alkyl or alkoxy.
Preferably, the polyester or polyetherdiol monomer are one or more of the compound of following structural formula,
The polyisocynate monomer is one or more of the compound of following structural formula,
The diisocyanate monomer is one or more of the compound of following structural formula,
Described monomer crosslinked dose of polyalcohol or multi-thiol is one or more of the compound of following structural formula,
Most preferably, the glycol monomer of the structure containing gneissic suite is 1,2- bis- (4- (2- hydroxyl-oxethyl) phenyl)- 1,2- diphenylethane -1,2- glycol, 1,2- bis- (4- (2- hydroxyl-oxethyl) -4- anisyl)-diphenylethane -1 1,2-, 2- glycol or bis- (the pungent oxygen phenyl of 4- (2- hydroxyl-oxethyl)-the 4-) -1,2- diphenylethane -1,2- glycol of 1,2-；
The polyester or polyetherdiol monomer is polytetrahydrofuran diol or polyethylene glycol；
The polyisocynate monomer is that hexamethylene diisocyanate trimer or hexamethylene diisocyanate contract Two ureas；
The diisocyanate monomer is hexamethylene diisocyanate or isophorone diisocyanate；
Described monomer crosslinked dose of polyalcohol or multi-thiol is triethanolamine or trimethylolpropane.
Present invention simultaneously provides the preparation methods of the polyether polyols, the preparation method is that by polyester or polyethers After diol monomer melting, polyisocynate monomer, diisocyanate monomer and the dihydric alcohol list containing fragrant gneissic suite structure is added Precursor reactant, after reacting 18~28h, the reaction was continued for addition polyalcohol or monomer crosslinked dose of multi-thiol, up to described after precipitating Polyether polyols.
The present invention is reacted under ultraviolet lighting with the benzophenone derivates containing primary hydroxyl obtains one kind with dynamic reversible The glycol monomer of the fragrant gneissic suite structure of carbon-carbon bond, then by the glycol monomer and polyethers or polyester-diol monomer, polyisocyanate Cyanate ester monomer, diisocyanate monomer, polyhydroxy or the reaction of more mercapto monomers crosslinking agents, prepare cross-linked polyurethane materials.It should Material has the characteristics that preparation is simple, it can be achieved that selfreparing and solid-state or solvent auxiliary recycling.
Further, after polyurethane material of the present invention generates mechanical damage, can be broken face bonding and 80~ Selfreparing can be realized in heating at 100 DEG C.After polyether polyols are smashed, it is re-prepared as type；Or by polyether polyols Be dissolved in solvent, be re-prepared as type, it can be achieved that above-mentioned material recycling and reusing.
More specifically, above-mentioned self-repair method is to heat the crackle of polyurethane polymer material at 80~100 DEG C to repair Multiple 0.5~3h, realizes selfreparing；
Solid recovery method are as follows: by polyether polyols in inertia or air atmosphere, 80~100 DEG C and 3~5MPa pressures Under power, hot-forming 1~10h is carried out to polymer powder, the bulk with similar primary sample tensile strength can be prepared Material.
Method for recovering solvents are as follows:, will by polyether polyols under 80~100 DEG C of auxiliary with polar solvent (e.g., DMF) Polymer material dissolves and carries out moulding by casting, after solvent volatilization, can prepare with similar primary sample tensile strength Bulk material.
Compared with prior art, the present invention has the following advantages and beneficial effects:
Intrinsical selfreparing provided by the invention and recyclable polyurethane polymer material structure are simple, are readily synthesized system It is standby.And when above-mentioned polyurethane polymer material cracks damage, through Overheating Treatment, it can be repaired, without additional viscous The bonding and overlap joint on surface can be realized in jelly, and repair time is short, repair process material not depolymerization.Above-mentioned polyurethane polymerization simultaneously The solid-state that object has recycles and can dissolve the performance recycled under solvent auxiliary, is by crushing-hot pressing or moulding by casting Can restorer mechanical strength.
Detailed description of the invention
Fig. 1 be embodiment 3 prepare selfreparing polyurethane crack forming mechanism photo (a, b, c be respectively original crack, The microphoto of 15min and 30min is handled at 100 DEG C).
Fig. 2 is the nucleus magnetic hydrogen spectrum of 4- ethoxy benzophenone.
Fig. 3 is the infrared spectroscopy of 4- ethoxy benzophenone.
Fig. 4 is the nucleus magnetic hydrogen spectrum of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1,2- diphenylethane -1,2- glycol of 1,2-.
Fig. 5 is the infrared spectroscopy of bis- (4- (2- hydroxyl-oxethyl) the phenyl) -1,2- diphenylethane -1,2- glycol of 1,2-.
Fig. 6 is the nucleus magnetic hydrogen spectrum of 4 ' 4- dihydroxy ethyl benzophenone.
Fig. 7 is the infrared spectroscopy of 4 ' 4- dihydroxy ethyl benzophenone.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
The repairing effect (as shown in Figure 1) of qualitative evaluation material is repaired using micro-crack；In addition, polymer sample rods are made Batten (the l=25mm of rectangle；B=4mm；H=0.5mm overlap joint test) is carried out, lap of splice l ' is 8mm, and at 80~100 DEG C The tensile shear strength of test polymer after lower heat treatment, tensile shear strength calculate as follows:
τ=F/ (bl ')
In formula: F, the peak load of sample failure by shear；B, sample faying surface width；L ', sample faying surface length.
Using the recovery efficiency of mixcrohardness test method evaluation material: polyurethane material prepared by embodiment 3~11 It carries out that polymer is carried out powder under liquid nitrogen quenching after micro- test (load-unload mode) obtains original elasticity modulus Broken, (diameter d is the obtained polymer powder samples that the hot pressing regular hour is recycled at 80~100 DEG C and 3MPa The disc-shaped film of 20mm), and carry out micro-hardness testing.Recovery efficiency is defined as the ratio of recycling sample and original elastic modulus Value:
η=Erecycled/Evirgin
In addition, the test of recovering effect also uses extension test to be characterized, be defined as recycling sample tensile strength or The ratio of person's elongation at break and original sample:
η=σrecycled/σvirginOr η=εrecycled/εvirgin
Equally using extension test evaluation solvent assist recovering effect, by embodiment 3~11 prepare polyurethane material into After row extension test obtains original mechanical strength, then polymer is dissolved in DMF solvent at 80~100 DEG C, led to again Moulding by casting is crossed polyurethane block material is made and carries out extension test, recovery efficiency be defined as recycling sample tensile strength or The ratio of person's elongation at break and original sample.
Embodiment 1
8.0 parts of 4- dihydroxy benaophenonels are added in the 150ml there-necked flask with magnetic agitation, it is molten that 40 parts of DMF are added Then 7.4 parts of ethylene bromohyrins are at the uniform velocity added dropwise in agent stirring and dissolving, 12 parts of Anhydrous potassium carbonates are added after dripping, are warming up to 90 DEG C of nitrogen Atmosphere encloses lower reaction 18h.After reaction, pH=7 is poured into distilled water and adjusted after mixed solution being filtered to remove precipitating, is taken out 4- ethoxy benzophenone white solid can be obtained after filtering and being freeze-dried, molecular structural formula is as follows.The nuclear-magnetism hydrogen of the molecule Spectrum and infrared spectrum are shown in Fig. 2,3.
Embodiment 2
10ml is added to dissolved with the DMF solution of 5.0 parts of 4- ethoxy benzophenone and the DMF solution of 0.2 part of glacial acetic acid In quartz cuvette, 30.0 parts of isopropanols are added, the illumination reaction 6d under the ultraviolet lamp of 315nm.After reaction, it will mix Solution is poured into distilled water and is precipitated, and white powder can be obtained after filtering and being freeze-dried.It is purified using silica gel chromatographic column, eluant, eluent is Petrol ether/ethyl acetate=1:1 (v/v), collects corresponding eluent and decompression boils off solvent and obtains bis- (4- (the 2- '-hydroxyethoxies of 1,2- Base) phenyl) -1,2- diphenylethane -1,2- glycol, molecular structural formula is as follows.The nucleus magnetic hydrogen spectrum and INFRARED SPECTRUM of the molecule Figure is shown in Fig. 4,5.
Embodiment 3
Under argon atmosphere, 5.0 parts of polytetrahydrofuran PTMEG1000 (number-average molecular weight 1000) are added to machinery In the 250ml three-neck flask of stirring, be warming up to 60 DEG C make PTMEG1000 melt after, 100.0 parts of DMF solvents, 1.1 part six are added Methylene diisocyanate tripolymer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyl tin dilaurate are urged Agent is added 1.2 parts by the obtained compound of embodiment 2 (due to the steric hindrance of phenyl ring, fragrant slice after reacting 5h at 60 DEG C Hydroxyl activity on the C-C key of alcohol center is very weak, is not involved in reaction substantially, and what actual participation polymerize is two primary hydroxyls of end Base), it is reacted at room temperature to after for 24 hours, being added 0.25 part of triethanolamine the reaction was continued 12h, precipitating is obtained containing virtue in methanol solvate The cross-linked polyurethane of fragrant gneissic suite structure after the material is scratched or generates micro-crack, is repaired at 100 DEG C in nitrogen or in the air 0.5h, can repair crack.Polymer crush after by 80 DEG C or 100 DEG C it is hot-forming new sample is made again, can be extensive Multiple part mechanical strength.The test of polymer material overlap joint, micro-hardness testing and extension test result be shown in Table respectively 1, table 2, Table 3, table 4.
Embodiment 4
Under argon atmosphere, 10.0 parts of PTMEG2000 (number-average molecular weight 2000) are added to churned mechanically In 250ml three-neck flask, be warming up to 60 DEG C make PTMEG2000 melt after, 100.0 parts of DMF solvents, 1.1 parts of hexa-methylenes are added Diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyltin dilaurate catalyst, 1.2 parts are added by the obtained compound of embodiment 2 after reacting 5h at 60 DEG C, are reacted at room temperature to after for 24 hours, are added 0.25 part three Ethanol amine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure in methanol solvate, which is drawn Wound or after generating micro-crack, repairs 0.5h at 100 DEG C in nitrogen or in the air, can repair crack.Polymer passes through after crushing 80 DEG C or 100 DEG C hot-forming to be made new sample again, can be with recovered part mechanical strength.The test of polymer material overlap joint, The result of micro-hardness testing and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
Embodiment 5
Under argon atmosphere, 15.0 parts of PTMEG3000 (number-average molecular weight 3000) are added to churned mechanically In 250ml three-neck flask, be warming up to 60 DEG C make PTMEG3000 melt after, 100.0 parts of DMF solvents, 1.1 parts of hexa-methylenes are added Diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyltin dilaurate catalyst, 1.2 parts are added by the obtained compound of embodiment 2 after reacting 5h at 60 DEG C, are reacted at room temperature to after for 24 hours, are added 0.25 part three Ethanol amine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure in methanol solvate, which is drawn Wound or after generating micro-crack, repairs 0.5h at 100 DEG C in nitrogen or in the air, can repair crack.Polymer passes through after crushing 80 DEG C or 100 DEG C hot-forming to be made new sample again, can be with recovered part mechanical strength.The test of polymer material overlap joint, The result of micro-hardness testing and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
Embodiment 6
Under argon atmosphere, 10.0 parts of polyethylene glycol PEG2000 (number-average molecular weight 2000) are added to and are stirred with machinery In the 250ml three-neck flask mixed, be warming up to 60 DEG C make PEG2000 melt after, 100.0 parts of DMF solvents, 1.1 part of six methylene are added Group diisocyanate tripolymer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part are dibutyltindilaurate catalyzed Agent is added 1.2 parts by the obtained compound of embodiment 2 after reacting 5h at 60 DEG C, is reacted at room temperature to after for 24 hours, is added 0.25 Part triethanolamine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure, the material in methanol solvate After being scratched or generating micro-crack, 0.5h is repaired at 100 DEG C in nitrogen or in the air, it can repair crack.After polymer crushes By 80 DEG C or 100 DEG C it is hot-forming new sample is made again, can be with recovered part mechanical strength.Polymer material overlap joint is surveyed The result of examination, micro-hardness testing and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
Embodiment 7
Under argon atmosphere, 10.0 parts of polycaprolactone glycol PCL2000 (number-average molecular weight 2000) are added to organic Tool stirring 250ml three-neck flask in, be warming up to 60 DEG C make PCL2000 melt after, 100.0 parts of DMF solvents, 1.1 part six are added Methylene diisocyanate tripolymer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyl tin dilaurate are urged Agent is added 1.2 parts by the obtained compound of embodiment 2 after reacting 5h at 60 DEG C, is reacted at room temperature to after for 24 hours, is added 0.25 part of triethanolamine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure in methanol solvate, should After material is scratched or generates micro-crack, 0.5h is repaired at 100 DEG C in nitrogen or in the air, it can repair crack.Polymer powder It is broken after by 80 DEG C or 100 DEG C it is hot-forming new sample is made again, can be with recovered part mechanical strength.Polymer material is taken The result for connecing test, micro-hardness testing and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
Embodiment 8
Under argon atmosphere, 10.0 parts of polytetrahydrofuran diol PTMEG2000 (number-average molecular weight 2000) are added to band Have in churned mechanically 250ml three-neck flask, be warming up to 60 DEG C make PTMEG1000 melt after, be added 100.0 parts of DMF solvents, 1.1 parts of hexamethylene diisocyanate trimers, 1.7 parts of isophorone diisocyanate monomers and 0.005 part of tin dilaurate two Butyl tin catalyst is added 1.2 parts by the obtained compound of embodiment 2 after reacting 5h at 60 DEG C, is reacted at room temperature to for 24 hours Afterwards, it is added 0.25 part of triethanolamine the reaction was continued 12h, it is poly- to obtain the crosslinking containing fragrant gneissic suite structure for precipitating in methanol solvate Urethane after the material is scratched or generates micro-crack, repairs 0.5h at 100 DEG C in nitrogen or in the air, can repair crack.It is poly- Close object crush after by 80 DEG C or 100 DEG C it is hot-forming new sample is made again, can be with recovered part mechanical strength.Polymer The result of the test of material overlap joint, micro-hardness testing and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
Embodiment 9
Under argon atmosphere, 10.0 parts of polytetrahydrofuran PTMEG2000 (number-average molecular weight 2000) are added to organic Tool stirring 250ml three-neck flask in, be warming up to 60 DEG C make PTMEG2000 melt after, 100.0 parts of DMF solvents, 1.1 parts are added Hexamethylene diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyl tin dilaurate Catalyst reacts the diol monomer 1 that 1.4 parts of structures containing gneissic suite are added after 5h, the bis- (4- (2- hydroxyl-oxethyl)-of 2- at 60 DEG C 4- anisyl) -1,2- diphenylethane -1,2- diol compound, reacts at room temperature to after for 24 hours, 0.25 part of three ethyl alcohol is added Amine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure in methanol solvate, the material be scratched or After generating micro-crack, 0.5h is repaired at 100 DEG C in nitrogen or in the air, it can repair crack.Polymer passes through 80 DEG C after crushing Or 100 DEG C it is hot-forming new sample is made again, can be with recovered part mechanical strength.Polymer material overlap joint is tested, is micro- The result of hardness test and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
The molecular structural formula of the above-mentioned diol monomer containing fragrant gneissic suite structure are as follows:
Embodiment 10
Under argon atmosphere, 10.0 parts of polytetrahydrofuran PTMEG2000 (number-average molecular weight 2000) are added to organic Tool stirring 250ml three-neck flask in, be warming up to 60 DEG C make PTMEG2000 melt after, 100.0 parts of DMF solvents, 1.1 parts are added Hexamethylene diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyl tin dilaurate 1.9 parts of diol monomers 1 containing fragrant gneissic suite structure, bis- (4- (the 2- '-hydroxyethoxies of 2- are added after reacting 5h at 60 DEG C in catalyst Base) the pungent oxygen phenyl of -4-) -1,2- diphenylethane -1,2- diol compound, reacts at room temperature to after for 24 hours, is added 0.25 part three Ethanol amine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure in methanol solvate, which is drawn Wound or after generating micro-crack, repairs 0.5h at 100 DEG C in nitrogen or in the air, can repair crack.Polymer passes through after crushing 80 DEG C or 100 DEG C hot-forming to be made new sample again, can be with recovered part mechanical strength.The test of polymer material overlap joint, The result of micro-hardness testing and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
The molecular structural formula of the above-mentioned diol monomer containing fragrant gneissic suite structure are as follows:
Embodiment 11
Under argon atmosphere, 10 parts of polytetrahydrofuran PTMEG2000 (number-average molecular weight 2000) are added to machinery In the 250ml three-neck flask of stirring, be warming up to 60 DEG C make PTMEG2000 melt after, 100.0 parts of DMF solvents, 1.1 part six are added Methylene diisocyanate biuret, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyl tin dilaurate are urged 1.9 parts of diol monomers 1 containing fragrant gneissic suite structure, bis- (4- (the 2- '-hydroxyethoxies of 2- are added after reacting 5h at 60 DEG C in agent Base) bis- (4- anisyl) ethane -1, the 2- diol compounds of -1,2-, react at room temperature to after for 24 hours, 0.25 part of three ethyl alcohol are added Amine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane containing fragrant gneissic suite structure in methanol solvate, the material be scratched or After generating micro-crack, 0.5h is repaired at 100 DEG C in nitrogen or in the air, it can repair crack.Polymer passes through 80 DEG C after crushing Or 100 DEG C it is hot-forming new sample is made again, can be with recovered part mechanical strength.Polymer material overlap joint is tested, is micro- The result of hardness test and extension test is shown in Table 1, table 2, table 3, table 4 respectively.
The molecular structural formula of the above-mentioned diol monomer containing fragrant gneissic suite structure are as follows:
Comparative example 1
Under argon atmosphere, 5.0 parts of polytetrahydrofuran PTMEG1000 (number-average molecular weight 1000) are added to machinery In the 250ml three-neck flask of stirring, be warming up to 60 DEG C make PTMEG1000 melt after, 100.0 parts of DMF solvents, 1.1 part six are added Methylene diisocyanate biuret, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyl tin dilaurate are urged 0.8 part of 4 ' 4- dihydroxy ethyl benzophenone is added after reacting 5h at 60 DEG C in agent, is reacted at room temperature to after for 24 hours, is added 0.25 part Triethanolamine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane without fragrant gneissic suite structure in methanol solvate, as reality Apply the control sample of example 3.The result of the test of polymer material overlap joint, micro-hardness testing and extension test is shown in Table 1, table respectively 2, table 3, table 4.
The molecular structural formula of above-mentioned 4 ' 4- dihydroxy ethyl benzophenone monomer is as follows, the nucleus magnetic hydrogen spectrum of the molecule and red Outer spectrogram is shown in Fig. 6,7.
Comparative example 2
Under argon atmosphere, 10.0 parts of PTMEG2000 (number-average molecular weight 2000) are added to churned mechanically In 250ml three-neck flask, be warming up to 60 DEG C make PTMEG2000 melt after, 100.0 parts of DMF solvents, 1.1 parts of hexa-methylenes are added Diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyltin dilaurate catalyst, 0.8 part of 4 ' 4- dihydroxy ethyl benzophenone is added after reacting 5h at 60 DEG C, is reacted at room temperature to after for 24 hours, 0.25 part of three second is added Hydramine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane without fragrant gneissic suite structure in methanol solvate, as embodiment 4 control sample.The result of the test of polymer material overlap joint, micro-hardness testing and extension test is shown in Table 1, table 2, table respectively 3, table 4.
Comparative example 3
Under argon atmosphere, 15.0 parts of PTMEG3000 (number-average molecular weight 3000) are added to churned mechanically In 250ml three-neck flask, be warming up to 60 DEG C make PTMEG3000 melt after, 100.0 parts of DMF solvents, 1.1 parts of hexa-methylenes are added Diisocyanate trimer, 1.3 parts of hexamethylene diisocyanate monomers and 0.005 part of dibutyltin dilaurate catalyst, 0.8 part of 4 ' 4- dihydroxy ethyl benzophenone is added after reacting 5h at 60 DEG C, is reacted at room temperature to after for 24 hours, 0.25 part of three second is added Hydramine the reaction was continued 12h, precipitating obtains the cross-linked polyurethane without fragrant gneissic suite structure in methanol solvate, as embodiment 5 control sample.The result of the test of polymer material overlap joint, micro-hardness testing and extension test is shown in Table 1, table 2, table respectively 3, table 4.
The bond effect of 1. polymer material of table overlap joint test compares
The solid-state recovering effect of 2. polymer material micro-hardness testing of table compares
The solid-state recovering effect of 3. polymer material extension test of table compares
The solvent auxiliary recovering effect of 4. polymer material extension test of table compares
Remarks: the material that "-" represents the preparation of comparative example 1,2 and 3 in table 4 can not be completely dissolved.

Claims (10)

1. a kind of Intrinsical selfreparing and recyclable polyether polyols, which is characterized in that including as follows by weight Raw material:
The degree of functionality of the polyisocynate monomer is 3 or more；The polyalcohol or monomer crosslinked dose of multi-thiol of degree of functionality It is 3 or more；
The glycol monomer structural formula containing fragrant gneissic suite structure is shown in formula I:
Wherein, R is derived from alkylidene；R1Represent the substituent group on one or more phenyl ring, R1It is derived from hydrogen, alkyl or alkoxy.
2. polyether polyols according to claim 1, which is characterized in that R is derived from the alkylidene of C1~10；R1Be derived from hydrogen, The alkyl of C1~10 or the alkoxy of C1~10.
3. polyether polyols according to claim 1, which is characterized in that the binary containing fragrant gneissic suite structure Alcohol monomer is prepared with the following method: by 2.5~7.5 parts of benzophenone derivates monomers containing primary hydroxyl and 0.1~0.5 part Glacial acetic acid is dissolved in 7.9~47.2 parts of isopropanols, 2~7d of illumination reaction under ultraviolet radiation, and the temperature of reaction is 30~40 DEG C, ultraviolet radiation wavelength is 280~315nm.
4. polyether polyols according to claim 3, which is characterized in that the benzophenone derivates monomer containing primary hydroxyl Preparation be under inert gas protection, by the benzophenone derivates monomer and 5.0~10.0 of 6.0~10.0 parts of phenolic hydroxy groups Part ethylene bromohyrin mixing, adds 5.5~22.1 parts of Anhydrous potassium carbonate catalyst and is reacted, and the temperature of reaction is 80~100 DEG C, the reaction time be 12~for 24 hours.
5. polyether polyols as claimed in claim 4, which is characterized in that the benzophenone derivates monomer of the phenolic hydroxy group For one or more of the compound of following structural formula,
Wherein, R is hydrogen, alkyl or alkoxy.
6. polyether polyols according to claim 1, which is characterized in that the polyester or polyetherdiol monomer is such as One or more of the compound of flowering structure formula,
The polyisocynate monomer is one or more of the compound of following structural formula,
The diisocyanate monomer is one or more of the compound of following structural formula,
Described monomer crosslinked dose of polyalcohol or multi-thiol is one or more of the compound of following structural formula,
7. polyether polyols according to any one of claims 1 to 6, which is characterized in that described containing fragrant gneissic suite structure Glycol monomer be bis- (4- (2- hydroxyl-oxethyl) phenyl) -1,2- diphenylethane -1, the 2- glycol of 1,2-, 1,2- bis- (4- (2- hydroxyl-oxethyl) -4- anisyl) -1,2- diphenylethane -1,2- glycol or the bis- (4- (2- hydroxyl-oxethyl)-of 1,2- The pungent oxygen phenyl of 4-) -1,2- diphenylethane -1,2- glycol；
The polyester or polyetherdiol monomer is polytetrahydrofuran diol or polyethylene glycol；
The polyisocynate monomer is hexamethylene diisocyanate trimer or hexamethylene diisocyanate biruet；
The diisocyanate monomer is hexamethylene diisocyanate or isophorone diisocyanate；
Described monomer crosslinked dose of polyalcohol or multi-thiol is triethanolamine or trimethylolpropane.
8. a kind of preparation method of polyether polyols described in claim 1, which is characterized in that by polyester or polyetherdiol list After body melting, polyisocynate monomer, diisocyanate monomer and the glycol monomer reaction containing fragrant gneissic suite structure is added, After reacting 18~28h, the reaction was continued for addition polyalcohol or monomer crosslinked dose of multi-thiol, up to the polyurethane polyureas after precipitating Close object.
9. application of the polyether polyols described in claim 1 in preparation selfreparing and recyclable polymer material.
10. application according to claim 9, which is characterized in that the self-repair method is that will generate gathering for mechanical damage The fracture face bonding of urethane polymers simultaneously heats at 80~100 DEG C；Recyclable method is directly to smash polyether polyols Afterwards, it is re-prepared as type；Or polyether polyols are dissolved in solvent, then be re-prepared as type.
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