CN111269384B - Photochromic shape memory polymer containing spiropyran and preparation method thereof - Google Patents

Photochromic shape memory polymer containing spiropyran and preparation method thereof Download PDF

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CN111269384B
CN111269384B CN202010195264.2A CN202010195264A CN111269384B CN 111269384 B CN111269384 B CN 111269384B CN 202010195264 A CN202010195264 A CN 202010195264A CN 111269384 B CN111269384 B CN 111269384B
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spiropyran
photochromic
diisocyanate
shape memory
prepolymer
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CN111269384A (en
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冷劲松
王晓飞
刘彦菊
何阳
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Harbin Institute of Technology
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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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • 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
    • C08G2280/00—Compositions for creating shape memory
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1475—Heterocyclic containing nitrogen and oxygen as heteroatoms

Abstract

The invention provides a photochromic shape memory polymer containing spiropyran and a preparation method thereof, belonging to the technical field of functional polymer preparation, wherein the preparation method of the photochromic shape memory polymer containing spiropyran comprises the following steps: reacting polyether polyol or polyester polyol with diisocyanate to obtain prepolymer 1 terminated with isocyanate; adding a chain extender into the prepolymer 1 to perform chain extension reaction to obtain a polyurethane polymer; and reacting the polyurethane polymer with spiropyran to obtain the photochromic shape memory polymer containing spiropyran. Compared with the prior art, the photochromic shape memory polymer containing the spiropyran prepared by the invention has both the photochromic shape memory effect and the photochromic effect, namely the photochromic shape memory polymer containing the spiropyran has good shape fixing rate, shape recovery rate and color change rate, and can be widely applied to the fields of information storage, anti-counterfeiting, flexible camouflage robots and the like.

Description

Photochromic shape memory polymer containing spiropyran and preparation method thereof
Technical Field
The invention relates to the technical field of functional polymer preparation, in particular to a spiropyran-containing photochromic polymer and a preparation method thereof.
Background
Shape Memory Polymers (SMPs) are a class of stimuli-responsive smart materials with shape memory effects. When being stimulated by the outside, such as heat, light, electricity, magnetism, chemical solvent and the like, the material can be restored to the initial shape from the temporary shaping state, and is widely applied to the fields of aerospace, biomedicine, sensing braking and the like. Shape memory polymer materials are widely available, and can be classified into a thermotropic type, an electro-type, a photo-type, a magneto-type, and a chemical response type according to the stimulus response. Currently, most studies are made on the SMP of thermal response type, but in some fields of practical application, such as biomedical materials, the application range of shape memory materials is limited because the temperature is too high, which causes irreversible damage to biological tissues, and thus thermal stimulation is not a good inducing mode.
However, most of the existing photoinduced shape memory polymers realize the photoinduced shape memory effect by means of photochemical reaction of cinnamic acid groups or azobenzenes or by adding photothermal effect of photothermal materials such as graphene oxide and gold nanoparticles, and in some special fields such as camouflage robots, the heat generated by the materials is easy to capture by infrared, so that the application range of the photoinduced shape memory polymers is limited.
In view of the above, there is an urgent need to develop new triggering methods to meet the needs of different fields.
Disclosure of Invention
The problem to be solved by the invention is that the thermally responsive shape memory polymers in the prior art limit the application range of shape memory materials.
In order to solve the above problems, the present invention provides a method for preparing a photochromic polymer containing spiropyran, comprising the steps of:
step S1, polyether polyol or polyester polyol reacts with diisocyanate to obtain prepolymer 1 terminated with isocyanate;
step S2, adding a chain extender into the prepolymer 1 to perform chain extension reaction to obtain a polyurethane polymer;
and step S3, reacting the polyurethane polymer with spiropyran to obtain the photochromic shape-memory polymer containing spiropyran.
Alternatively, the molar ratio of the polyether polyol or the polyester polyol to the diisocyanate in step S1 is 1: 2-3.
Optionally, in step S2, adding a molar chain extender into prepolymer 1, and performing a chain extension reaction to obtain the polyurethane polymer, wherein a molar ratio of prepolymer 1 to the chain extender is 1: 0.5-2.
Optionally, in step S2, adding a chain extender to prepolymer 1, and performing a chain extension reaction to obtain the polyurethane polymer, where the polyurethane polymer is a thermoplastic shape memory polyurethane polymer, and a molar ratio of prepolymer 1 to the chain extender is 1: 1-2.
Optionally, step S3 specifically includes: and physically filling the spiropyran with a first weight fraction into the thermoplastic shape memory polyurethane high polymer by using a solution blending method to obtain the spiropyran-containing photochromic thermoplastic polyurethane high polymer.
Optionally, in step S2, adding a chain extender to prepolymer 1, and performing a chain extension reaction to obtain the polyurethane polymer, where the polyurethane polymer is isocyanate-terminated prepolymer 2, and a molar ratio of prepolymer 1 to the chain extender is 1: 0.5-1.
Optionally, step S3 specifically includes: and (3) reacting the isocyanate-terminated prepolymer 2 with a third weight part of the spiropyran to obtain the photochromic shape memory polymer containing the spiropyran.
Optionally, step S3 specifically includes:
step S31, reacting the isocyanate-terminated prepolymer 2 with a second weight part of the spiropyran to obtain isocyanate-terminated prepolymer 3;
step S32, reacting the prepolymer 3 with a cross-linking agent to obtain the spiropyran-containing photoinduced shape memory discolor thermosetting polyurethane high polymer, wherein the molar ratio of the prepolymer 3 to the cross-linking agent is 1: 0.1-0.9.
Alternatively, the diisocyanate in step S1 is toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, methylcyclohexyl diisocyanate, or dicyclohexylmethane diisocyanate.
Alternatively, in step S1, the polyether polyol is polytetrahydrofuran ether glycol.
Optionally, the polyester polyol is poly epsilon-caprolactone diol, polyethylene adipate, polybutylene adipate, polyethylene glycol or polycarbonate diol, and the molecular weight of the polyester polyol is 2000-6000.
Optionally, in step S2, the chain extender is 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, sorbitol, or diethylaminoethanol.
Optionally, in step S32, the cross-linking agent is one or more selected from glycerol, trimethylolpropane, triethylene glycol and pentaerythritol.
Compared with the prior art, the preparation method of the photochromic polymer containing the spiropyran has the advantages that:
the spiropyran is introduced into the shape memory polyurethane matrix to prepare the photochromic shape memory polymer containing spiropyran, and the spiropyran compound not only has photochromic and mechano-photochromic characteristics, but also has a photoinduced plasticizing effect, so that the photochromic shape memory effect can be realized, and the prepared photochromic shape memory polymer containing spiropyran has both the photochromic shape memory effect and the photochromic effect, i.e. the photochromic shape memory polymer containing spiropyran has good shape fixing rate, shape recovery rate and color change rate, and on the other hand, the soft segment is easy to move and recover the shape due to the photoinduced plasticizing effect, and the process does not generate heat and can be widely applied to the fields of information storage, anti-counterfeiting, flexible camouflage robots and the like.
In order to solve the technical problems, the invention also provides a photochromic polymer containing spiropyran, which is prepared by the preparation method of the photochromic polymer containing spiropyran, wherein the content of spiropyran in the photochromic polymer containing spiropyran is 0.1% -20%, and the content of polyurethane hard segment is 20% -40%.
The advantages of the photochromic polymer containing spiropyran in the invention compared with the prior art are the same as the advantages of the preparation method of the photochromic polymer containing spiropyran in the prior art, and are not repeated herein.
Drawings
FIG. 1 is a first flow chart of a process for preparing a photochromic shape memory polymer containing spiropyran according to one embodiment of the present invention;
FIG. 2 is a second flow chart of a process for preparing a photochromic shape memory polymer containing spiropyran according to an embodiment of the present invention;
FIG. 3 is a third flowchart of a process for preparing a photochromic shape-memory polymer containing spiropyran according to example 2 of the present invention;
FIG. 4 is a fourth flowchart of a process for preparing a photochromic shape-memory polymer containing spiropyran according to example 3 of the present invention;
FIG. 5 is a schematic illustration of the photochromic and photo-deformation mechanisms of spiropyrans in an embodiment of the present invention;
FIG. 6 is a first reaction process of preparing a photochromic polymer containing spiropyran according to example 1 of the present invention;
FIG. 7 is a second schematic diagram of the reaction process for preparing the photochromic shape-memory polymer containing spiropyran according to example 2 of the present invention;
FIG. 8 is a schematic diagram of the shape memory process and discoloration of a photochromic shape memory polymer containing spiropyran according to example 2 of the present invention, wherein
Figure BDA0002417372820000041
The soft segment is represented by a soft segment,
Figure BDA0002417372820000042
the hard segment is represented by a hard segment,
Figure BDA0002417372820000043
represents the orthogonal structure of the spiropyran,
Figure BDA0002417372820000044
represents a spiropyran planar structure;
FIG. 9 is a third reaction process of preparing a photochromic polymer containing spiropyran according to example 3 of the present invention.
Detailed Description
Shape Memory Polymers (SMPs) are a class of stimuli-responsive smart materials with shape memory effects. When being stimulated by the outside, such as heat, light, electricity, magnetism, chemical solvent and the like, the material can be restored to the initial shape from the temporary shaping state, and is widely applied to the fields of aerospace, biomedicine, sensing braking and the like. Shape memory polymer materials are widely available, and can be classified into a thermotropic type, an electro-type, a photo-type, a magneto-type, and a chemical response type according to the stimulus response. Currently, most studied are thermally responsive SMPs, i.e., SMP materials that are heated to a certain temperature (the glass transition temperature or melting temperature of the material), deformed by the application of an external force, held and cooled to obtain a temporary shape, and when heated again, the SMP material can return to the original shape. However, in some fields of practical application, such as biomedical materials, thermal stimulation is not a good inducing method because of irreversible damage to biological tissues caused by excessive temperature. There is an urgent need to develop new triggering methods to meet the needs of different fields.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the description of the present invention, it is to be understood that the description of the term "some specific embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
As shown in FIG. 1, the embodiment of the present invention provides a method for preparing a photochromic shape-memory polymer containing spiropyran, comprising the following steps:
step S1, reacting polyether polyol or polyester polyol with diisocyanate to obtain prepolymer 1 terminated by isocyanate;
step S2, adding a chain extender into the prepolymer 1 to perform chain extension reaction to obtain a polyurethane polymer;
and step S3, reacting the polyurethane polymer with spiropyran to obtain the photochromic shape-memory polymer containing spiropyran.
Preferably, the molar ratio of the polyether polyol or the polyester polyol to the diisocyanate in step S1 is 1:2-3, so that the polyether polyol or the polyester polyol can fully react with the diisocyanate to obtain the isocyanate-terminated prepolymer 1, the raw materials can fully react, and waste of the raw materials is avoided.
Preferably, in step S2, 0.5 to 2 moles of chain extender is added to prepolymer 1 to perform chain extension reaction, so as to obtain the polyurethane polymer, wherein the molar ratio of prepolymer 1 to chain extender is 1: 0.5-2. By controlling the proportion of the chain extender, different polyurethane polymers are obtained, and the reaction with spiropyran is facilitated.
Preferably, the diisocyanate in step S1 is toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, methylcyclohexyl diisocyanate, or dicyclohexylmethane diisocyanate.
Preferably, in step S1, the polyether polyol is polytetrahydrofuran ether glycol, and in some embodiments, the polytetrahydrofuran ether glycol may be one of PTMEG-2000, PTMEG-3000, PTMEG-4000 or PTMEG-6000, which are readily available.
Preferably, the polyester polyol is poly epsilon-caprolactone diol, polyethylene adipate, polybutylene adipate, polyethylene glycol or polycarbonate diol, the molecular weight of the polyester polyol is 2000-6000, and the raw materials are easy to obtain.
Preferably, in step S2, the chain extender is 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, sorbitol, or diethylaminoethanol. The use of the chain extender enables the molecular chain to be diffused and extended, thereby realizing the curing and forming of the resin.
Preferably, in step S32, the cross-linking agent is one or more selected from glycerol, trimethylolpropane, triethylene glycol and pentaerythritol. The use of the cross-linking agent makes the molecular chains of the matrix more easily form a network structure. In some specific embodiments, the combination of the chain extender and the cross-linking agent can obtain a polyurethane material with excellent comprehensive performance.
Compared with the prior art, the preparation method of the photochromic polymer containing spiropyran has the advantages that:
according to the embodiment of the invention, the spiropyran is introduced into the shape memory polyurethane matrix to prepare the photochromic shape memory polymer containing the spiropyran, and the spiropyran compound not only has photochromic and mechanochromic characteristics, but also has a photoplasticizing effect, so that the photochromic shape memory effect can be realized. Namely, when molecules of the spiropyran compound structure are excited by ultraviolet irradiation, heterolytic cleavage occurs on C-O bonds in the molecular structure, so that isomerization and rearrangement occur on the molecular structure and the configuration of electrons, and the structure is changed into an open-loop structure from an initial shape. Two ring systems of molecules in the spiropyran compound structure can be changed into a plane from an orthogonal state, and the whole spiropyran molecule can form a large conjugated system, so that the material can be shrunk macroscopically, and the color of the spiropyran compound is darkened and red. And under the action of visible light or heat, the spiropyran compound undergoes a ring-closure reaction to return to an original shape, as shown in fig. 5. Therefore, the photochromic polyurethane containing spiropyran prepared by the embodiment has both the photochromic effect and the photochromic effect, namely, the photochromic polymer containing spiropyran has good shape fixing rate, shape recovery rate and discoloration rate, and on the other hand, the soft segment is easy to move and recover the shape due to the photoinduced plasticizing effect, so that the photochromic polyurethane containing spiropyran can be widely applied to the fields of information storage, anti-counterfeiting, flexible camouflage robots and the like.
The method can be widely applied to the fields of information storage, anti-counterfeiting, flexible camouflage robots and the like.
In some preferred embodiments:
in step S2, a chain extender is added to the prepolymer 1 to perform a chain extension reaction, so as to obtain a polyurethane polymer, where the polyurethane polymer is a thermoplastic shape memory polyurethane polymer, and a molar ratio of the prepolymer 1 to the chain extender is 1: 1-2;
in step S3: and physically filling a first weight fraction of the spiropyran into the thermoplastic shape memory polyurethane high polymer by using a solution blending method to obtain the spiropyran-containing photochromic shape memory polyurethane, wherein the first weight fraction is (0.1% -20%) wt.
In the embodiment, the spiropyran is introduced into the thermoplastic shape memory polyurethane matrix by adopting a physical filling method to obtain the spiropyran-containing photochromic shape memory polyurethane, and the method is simple, easy to implement and quick in reaction.
In some preferred embodiments:
in step S2, a chain extender is added to prepolymer 1 to perform a chain extension reaction, so as to obtain a polyurethane polymer, where the polyurethane polymer is isocyanate-terminated prepolymer 2, and the mole number of prepolymer 1 and the chain extender is 1: 0.5-1.
In step S3, reacting the isocyanate terminated prepolymer 2 with a third weight fraction of the spiropyran to obtain a spiropyran-containing photochromic thermoplastic polyurethane high polymer, wherein the third weight fraction is (15% -20%) wt.
In the embodiment, the spiropyran is introduced into the thermoplastic shape memory polyurethane matrix by adopting a chemical grafting method, so that the spiropyran-containing photochromic thermoplastic polyurethane high polymer with stable structure and excellent performance is obtained.
In some preferred embodiments:
step S31, reacting the isocyanate-terminated prepolymer 2 with a second weight fraction of the spiropyran to obtain isocyanate-terminated prepolymer 3, wherein the second weight fraction is (0.1% -10%) wt;
step S32, reacting the prepolymer 3 with a cross-linking agent to obtain the spiropyran-containing photoinduced shape memory allochroic thermosetting polyurethane high polymer, wherein the molar ratio of the prepolymer 3 to the cross-linking agent is 1: 0.1-0.9.
In the embodiment, the spiropyran is introduced into the thermosetting shape memory polyurethane matrix by adopting a chemical grafting method to obtain the spiropyran-containing photoinduced shape memory discoloring thermosetting polyurethane high polymer which has stable structure and excellent performance.
In some toolsIn the embodiment, when the spiropyran is physically filled or chemically grafted into the shape memory polyurethane matrix, the crystallinity of the polyurethane is affected, and the shape memory performance of the material is further affected. Meanwhile, as the crystallinity of the shape memory polyurethane hinders the molecular motion of the spiropyran, the C-O bond in the spiropyran molecule is heterocracked and is changed from an orthogonal structure to a planar structure in the photoisomerization process, and the photochromic effect is influenced by the hindering effect of the crystallization of the matrix material. Therefore, in the embodiment of the present invention, by controlling the molar ratio of the isocyanate to the hydroxyl in the spiropyran, linear polyurethane polymers or three-dimensionally crosslinked polyurethane polymers with different spiropyran contents and different hard segment contents can be obtained. And with the increase of the content of the spiropyran, the proportion of the hard segment is increased, which is beneficial to the improvement of the shape fixing rate of the material and the improvement of the photochromic rate, but simultaneously can weaken the shape recovery rate and the recovery rate of the material, therefore, the proportion of the soft segment and the hard segment needs to be kept within a certain controllable range, and the shape fixing rate, the shape recovery rate and the photochromic rate are taken into consideration. In the implementation of the invention, when the content of the spiropyran is 2-10 percent by weight and the method of chemically grafting polyurethane is adopted, better performance can be realized, so that the shape fixing rate is as high as (90-100)%, the shape recovery rate is (90-100)%, and the photochromic rate is (0.1-5) s/cm2。
The other embodiment of the invention provides a photochromic shape memory polymer containing spiropyran, which is prepared by the preparation method of the photochromic shape memory polymer containing spiropyran, and the content of spiropyran in the photochromic shape memory polymer containing spiropyran is 0.1% -20%, and the content of polyurethane hard segment is 20% -40%.
The advantages of the photochromic polymer containing spiropyran over the prior art are the same as the advantages of the preparation method of the photochromic polymer containing spiropyran over the prior art, and are not repeated herein.
Example 1
As shown in fig. 2 and fig. 6, this embodiment provides a method for preparing a photochromic polymer containing spiropyran, comprising the following steps:
step S1, adding 10-30g polytetrahydrofuran ether glycol (PTMEG) and 10-30g N, N-methylene formamide (DMF) in sequence into a dry three-neck flask, then connecting the experimental device, introducing nitrogen and condensed water, and adjusting the rotating speed of a stirrer to 250 r/min. Slowly dripping 5-20g of diphenylmethane-4, 4-diisocyanate (MDI) within 5min, stirring for 15min, adding 5% dibutyltin dilaurate (DBTDL), heating an oil bath to 50-80 ℃, and continuously reacting for 1-2h to obtain prepolymer 1 terminated by isocyanate, namely PTMEG-MDI; wherein the polytetrahydrofuran ether glycol (PTMEG) can be polytetrahydrofuran ether glycol (PTMEG-2000), polytetrahydrofuran ether glycol (PTMEG-3000), polytetrahydrofuran ether glycol (PTMEG-4000) or polytetrahydrofuran ether glycol (PTMEG-6000);
step S2, adding 5-10g of chain extender 1, 4-butanediol into PTMEG-MDI, stirring for 15min, adding 1-5 drops of catalyst dibutyltin dilaurate (DBTDL), continuing to react for 1-3h to obtain linear polyurethane, pouring the linear polyurethane into a polytetrahydrofuran mould, putting the mould into a vacuum oven at 60-80 ℃, preserving the temperature for 24h, volatilizing N, N-methylene formamide (DMF) solvent, and naming the mould as SMTPU, wherein the hard segment content is 20-40%
And step S3, dissolving SMTPU in N, N-methylene formamide (DMF), adding spiropyran with the mass fraction of 0.1-20 wt%, stirring for dissolving, coating the film in a polytetrafluoroethylene mold, putting the polytetrafluoroethylene mold in a vacuum oven, keeping the temperature for 24 hours at 60 ℃, and volatilizing the solvent of the N, N-methylene formamide (DMF) to obtain the spiropyran-containing thermoplastic polyether polyurethane film 1 with the shape memory and photochromic functions.
Example 2
The present embodiment is different from embodiment 1 in that:
in step S1, diphenylmethane-4, 4-diisocyanate (MDI) may be replaced with Toluene Diisocyanate (TDI), hexamethylene 1, 6-diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), naphthalene 1, 5-diisocyanate (NDI), methylcyclohexyl diisocyanate (HTDI), or dicyclohexylmethane diisocyanate (HMDI);
in step S2, 1, 4-butanediol may be replaced with 1, 6-hexanediol, diethylene glycol, neopentyl glycol, sorbitol or diethylaminoethanol;
wherein, the catalyst dibutyltin dilaurate (DBTDL) can be replaced by stannous octoate, lead octoate, cobalt octoate, iron octoate, organic bismuth or organic tin.
Example 3
This example is different from example 1 in that in step S1, polytetrahydrofuran ether glycol (PTMEG) may be replaced by polyester polyol, and the polyester polyol is poly-epsilon-caprolactone glycol, polyethylene adipate, polybutylene adipate, polyethylene glycol or polycarbonate glycol, and the molecular weight of the polyester polyol is 2000-6000, and the raw materials are easily available.
Example 4
As shown in fig. 3 and 7, this example provides a method for preparing a photochromic shape-memory polymer containing spiropyran, which includes the following steps:
and step S1, sequentially adding 10-30g of PTMEG and 10-30g of DMF (dimethyl formamide) into a dry three-neck flask, then connecting the experimental device, introducing nitrogen and condensed water, and adjusting the rotating speed of the stirrer to 250 r/min. Slowly dripping 5-20g of MDI within 5min, stirring for 15min, adding 5% of DBTDL, heating the oil bath to 50-80 ℃, and continuing to react for 1-2h to obtain prepolymer 1 terminated by isocyanate, which is named PTMEG-MDI;
step S2, adding 2-4.9g of chain extender 1, 4-butanediol into PTMEG-MDI, stirring for 15min, adding a few drops of DBTDL, and continuing to react for 1-3h to obtain prepolymer 2 terminated by isocyanate, namely PTMEG-MDI-BD;
and step S3, dissolving 3-5g of spiropyran in DMF, uniformly mixing, adding the mixture into PTMEG-MDI-BD, stirring for 15min, adding a few drops of DBTDL, continuously reacting for 1-3h, pouring the mixture into a polytetrahydrofuran mold, putting the mold into a vacuum oven for 60-80 ℃, preserving the temperature for 24h, and volatilizing the DMF solvent to obtain the spiropyran chemically grafted thermoplastic polyether polyurethane film 3 with the photochromic and shape memory function, wherein the hard segment content is 20-40%.
As shown in FIG. 8, the photochromic shape-memory polymer containing spiropyran prepared in this example was heated to the glass transition temperatureAfter the conditions are stimulated and the mixture is cooled and fixed, the colorless initial shape is changed into a colorless temporary shape, and after the mixture is excited by ultraviolet irradiation, C-O bonds in a molecular structure are heterocleaved, so that the isomerization and rearrangement of the molecular structure and the configuration of electrons are caused, and the colorless temporary shape is changed into an open-loop structure. Two ring systems of molecules in the spiropyran-containing photoinduced shape memory discoloring polymer are changed into planes from orthogonal, the whole spiropyran molecule can form a large conjugated system, macroscopically, the material is shrunk to be changed into a dark red temporary shape, and under the action of visible light or heat, the spiropyran generates a ring-closing reaction and is restored to a colorless initial shape, so that the spiropyran-containing photoinduced shape memory discoloring polyurethane prepared by the embodiment has both the photoinduced shape memory effect and the photochromic effect, namely the spiropyran-containing photoinduced shape memory discoloring polymer has good shape fixing rate, shape recovery rate and discoloring rate, the shape fixing rate is (90-100)%, the shape recovery rate is (90-100)%, and the photochromic rate is (0.1-5) s/cm2The method can be widely applied to the fields of information storage, anti-counterfeiting, flexible camouflage robots and the like.
Example 5
This embodiment is different from embodiment 4 in that:
in step S1, MDI may be replaced with Toluene Diisocyanate (TDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), naphthalene-1, 5-diisocyanate (NDI), methylcyclohexyl diisocyanate (HTDI), or dicyclohexylmethane diisocyanate (HMDI);
in step S2, 1, 4-butanediol may be replaced with 1, 6-hexanediol, diethylene glycol, neopentyl glycol, sorbitol or diethylaminoethanol;
wherein DBTDL can be replaced by stannous octoate, lead octoate, cobalt octoate, iron octoate, organic bismuth or organic tin.
Example 6
This example is different from example 4 in that PTMEG can be replaced by polyester polyol in step S1, and the polyester polyol is poly-epsilon-caprolactone diol, polyethylene adipate, polybutylene adipate, polyethylene glycol or polycarbonate diol, and the molecular weight of the polyester polyol is 2000-6000, and the raw materials are easily available.
Example 7
As shown in fig. 4 and 9, this embodiment provides a method for preparing a photochromic polymer containing spiropyran, comprising the following steps:
and step S1, sequentially adding 10-30g of PTMEG-2000 and 10-30g of DMF (dimethyl formamide) into a dry three-neck flask, then connecting the experimental device, introducing nitrogen and condensed water, and adjusting the rotating speed of the stirrer to be 250 r/min. Slowly dripping 5-20g of MDI within 5min, stirring for 15min, adding 5% of DBTDL, heating the oil bath to 50-80 ℃, and continuing to react for 1-2h to obtain prepolymer 1 terminated by isocyanate, which is named PTMEG-MDI;
step S2, adding 0.5-1.9g of chain extender 1, 4-butanediol into PTMEG-MDI, stirring for 15min, adding a few drops of DBTDL, and continuing to react for 1-2h to obtain prepolymer 2 terminated by isocyanate, namely PTMEG-MDI-BD;
step S31, dissolving 0.1-2.9g of spiropyran in DMF, uniformly mixing, adding the mixture into PTMEG-MDI-BD, stirring for 15min, adding a few drops of DBTDL, and continuously reacting for 1-3h to obtain prepolymer 3 terminated by isocyanate, namely PTMEG-MDI-BD-SP;
step S32, adding 0.1-0.9g of trimethylolpropane into PTMEG-MDI-BD-SP, stirring for 15min, adding a few drops of DBTDL, pouring into a polytetrahydrofuran mold, putting into a vacuum oven at 60-80 ℃, preserving heat for 24h, crosslinking and curing polyurethane, and volatilizing DMF solvent to obtain the spiropyran chemically grafted thermosetting polyether polyurethane film 5 with the light induced shape memory and the light induced discoloration, wherein the hard segment content is 20-40%.
Example 8
This embodiment differs from embodiment 7 in that:
in step S1, MDI may be replaced with Toluene Diisocyanate (TDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), naphthalene-1, 5-diisocyanate (NDI), methylcyclohexyl diisocyanate (HTDI), or dicyclohexylmethane diisocyanate (HMDI);
in step S2, 1, 4-butanediol may be replaced with 1, 6-hexanediol, diethylene glycol, neopentyl glycol, sorbitol or diethylaminoethanol;
wherein DBTDL can be replaced by stannous octoate, lead octoate, cobalt octoate, iron octoate, organic bismuth or organic tin;
in step S32, trimethylolpropane may be substituted with glycerol, triethylene glycol or pentaerythritol.
Example 9
This embodiment differs from embodiment 7 in that: in step S1, PTMEG may be replaced by polyester polyol, and the polyester polyol is poly-epsilon-caprolactone diol, polyethylene adipate, polybutylene adipate, polyethylene glycol or polycarbonate diol, and the molecular weight of the polyester polyol is 2000-6000, and the raw materials are easily available.
Although the present disclosure has been described with reference to the above embodiments, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to fall within the scope of the present disclosure.

Claims (4)

1. A preparation method of a photochromic polymer containing spiropyran is characterized by comprising the following steps:
step S1, dissolving polyether polyol in DMF, and then reacting with diisocyanate to obtain prepolymer 1 terminated by isocyanate; the molar ratio of the polyether polyol to the diisocyanate is 1: 2-3; the polyether polyol is polytetrahydrofuran ether glycol 2000, polytetrahydrofuran ether glycol 3000, polytetrahydrofuran ether glycol 4000 or polytetrahydrofuran ether glycol 6000;
step S2, adding a chain extender into the prepolymer 1 to carry out chain extension reaction to obtain a polyurethane polymer; the polyurethane polymer is isocyanate terminated prepolymer 2, wherein the molar ratio of prepolymer 1 to the chain extender is 1: 0.5 to 1;
step S3, reacting the polyurethane polymer with spiropyran to obtainA spiropyran-containing photochromic shape memory polymer comprising: reacting the isocyanate-terminated prepolymer 2 with the spiropyran with the weight fraction of (2% -10%) to obtain isocyanate-terminated prepolymer 3, wherein the spiropyran has a structure
Figure FDF0000016808520000011
And reacting the prepolymer 3 with a cross-linking agent to obtain the spiropyran-containing photoinduced shape memory allochroic thermosetting polyurethane high polymer, wherein the molar ratio of the prepolymer 3 to the cross-linking agent is 1: 0.1-0.9, and the content of the hard segment of the polyurethane in the photochromic polymer containing the spiropyran is 20-40%.
2. The method for preparing a photochromic shape memory polymer containing spiropyran according to claim 1, wherein said diisocyanate in step S1 is toluene diisocyanate, diphenylmethane-4, 4，Diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, methylcyclohexyl diisocyanate or dicyclohexylmethane diisocyanate.
3. The method of preparing a spiropyran-containing photochromic polymer according to claim 1, wherein in step S2, said chain extender is 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, neopentyl glycol, sorbitol, or diethylaminoethanol.
4. The method for preparing a photochromic shape memory polymer containing spiropyran according to claim 1, characterized in that said cross-linking agent is one or more selected from the group consisting of glycerol, trimethylolpropane, triethylene glycol or pentaerythritol.
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