CN114213614A - Preparation method and application of photocuring polyurethane with self-healing property and shape memory property - Google Patents
Preparation method and application of photocuring polyurethane with self-healing property and shape memory property Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention relates to a preparation method and application of photocuring polyurethane with self-healing property and shape memory property, belonging to the technical field of preparation of photocuring polyurethane. The invention firstly prepares the quaternization dihydroxy ethylene glycol, then respectively prepares a polyurethane soft segment and a polyurethane hard segment, prepares polyurethane emulsion through the reaction between the soft segment and the hard segment, and obtains the polyurethane with self-healing property and shape memory property after photocuring. The method can prepare the photocuring polyurethane with self-healing property and shape memory capability. The polyurethane has excellent performance in the aspects of shape memory capacity and heat-induced self-healing property, and can be applied to the fields of intelligent coatings, self-healing coatings and the like.
Description
Technical Field
The invention relates to a preparation method and application of photocuring polyurethane with self-healing property and shape memory property, belonging to the technical field of preparation of photocuring polyurethane.
Background
The shape memory polymer has shape deformation capacity and recovery capacity under the condition of external stimulation, and can be applied to various fields as an intelligent material, but the shape memory polymer is easy to age, and the service life of a high polymer material is short due to various damages, so that the shape memory polymer has the capacity of self-repairing and is required to be applied more in the aspect of the shape memory polymer.
Currently, more self-healing polymers achieve self-healing capability primarily through functional groups, however, there are fewer studies of self-healing through crystalline side chains. Whereas brush polymers may provide the chain structure required for recombination after damage. When the polymer is physically damaged, the crack can be repaired by external stimuli around the damaged crack.
Polyurethane is used as a common coating raw material, and a long alkane chain side chain is added into the structure, so that the polyurethane can obtain a certain self-healing function. By adding the soft segment and the hard segment in different proportions into the polyurethane, the prepared polyurethane can have a certain shape memory function through the synergistic action between the soft segment and the hard segment. The polyurethane polymer is expanded in the aspects of intelligent coatings and intelligent materials by giving a certain self-healing function and shape memory function to polyurethane.
Disclosure of Invention
The invention aims to overcome the defects, provides a preparation method and application of photocuring polyurethane with self-healing property and shape memory property, and provides feasibility and expansion of the polyurethane in the aspects of self-healing property and shape memory property.
The technical scheme of the invention is a preparation method of photocuring polyurethane with self-healing property and shape memory property, which is characterized by comprising the following steps: firstly, preparing quaternized dihydroxy ethylene glycol, then respectively preparing a polyurethane soft segment and a polyurethane hard segment, preparing polyurethane emulsion through the reaction between the soft segment and the hard segment, and carrying out photocuring to obtain the polyurethane with self-healing property and shape memory property.
Further, the steps are as follows:
(1) preparation of quaternized dihydroxy glycol: mixing alcohol amine and bromoalkane according to a metering ratio, and stirring and reacting at a high temperature to obtain quaternized dihydroxyethylene glycol;
(2) preparation of polyurethane hard segment: mixing the quaternized dihydroxyethylene glycol prepared in the step (1) and diisocyanate in a metering ratio, dropwise adding a catalyst for reaction, and stopping the reaction when the NCO value reaches a theoretical value to obtain a polyurethane hard segment component which is marked as a product 1;
(3) preparing a polyurethane soft segment: adding diisocyanate and glycol according to a metering ratio, dropwise adding a catalyst for reaction to obtain a polyurethane soft segment component, and marking as a product 2;
(4) preparation of polyurethane emulsion: adding the product 1 prepared in the step (2) and the product 2 prepared in the step (3) into a reaction container, and adding a blocking agent and a catalyst for reaction to obtain a polyurethane emulsion;
(5) curing of polyurethane: and (4) adding a photoinitiator into the polyurethane emulsion prepared in the step (4), fully stirring, coating on a carrier, and carrying out UV curing to obtain the UV-cured polyurethane with self-healing property and shape memory property.
Further, the alcohol amine in the step (1) is N-methyldiethanolamine and/or N-ethyldiethanolamine; the bromoalkane is one or more of bromohexadecane, bromooctadecane, bromoeicosane or bromodocosane;
the diisocyanate in the step (2) is one or more of toluene diisocyanate TDI, 4' -diphenylmethane diisocyanate MDI or isophorone diisocyanate IPDI;
the glycol in the step (3) is triethylene glycol and/or tetraethylene glycol.
Further, the catalyst is dibutyltin dilaurate or stannous octoate;
the end-capping reagent is one or more of hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA and pentaerythritol triacrylate PETA.
Further, 0.01-0.03mol of alcohol amine and 0.01-0.03mol of bromoalkane are mixed in the step (1), and the mixture is stirred and reacted for 11-13h at the temperature of 90-110 ℃, so that the quaternized dihydroxyethylene glycol is obtained.
Further, 0.01-0.02mol of quaternized dihydroxy ethylene glycol and 0.02-0.04mol of diisocyanate are added in the step (2), 3-4 drops of catalyst are dripped, and the mixture reacts for 1-3 hours at the temperature of 58-62 ℃; when the NCO value reaches the theoretical value, the reaction is stopped, and the polyurethane hard segment component is obtained and is marked as a product 1.
Further, in the step (3), 0.01-0.02mol of diisocyanate and 0.015-0.03mol of glycol are added, 3-4 drops of catalyst are dripped, and the reaction is carried out for 1-3h at the temperature of 58-62 ℃; when the NCO value reaches the theoretical value, the reaction is stopped, and the polyurethane soft segment component is obtained and is marked as a product 2.
Further, 10.005-0.01 mol of product, 20.001-0.005 mol of product and 0.005-0.02mol of end-capping agent are added in the step (4), 3-4 drops of catalyst are dripped, and the reaction is carried out for 1-3h at the temperature of 58-62 ℃ to obtain the polyurethane emulsion.
Further, in the step (5), adding a photoinitiator with the mass concentration of 0.5% into the polyurethane emulsion prepared in the step (4), and curing for 30-60s on a UV curing machine to obtain the photocured polyurethane with self-healing property and shape memory property.
The polyurethane prepared by the method is applied to intelligent coatings and intelligent materials.
The invention has the beneficial effects that: the method can prepare the photocuring polyurethane with self-healing property and shape memory capability. The polyurethane has excellent performance in the aspects of shape memory capacity and heat-induced self-healing, and can be applied to the aspects of intelligent coatings and intelligent surfaces.
On the one hand, the synergy between the hard segment and the soft segment in the invention ensures that the polyurethane generated by the reaction has certain shape memory capacity. On the other hand, the crystal side chain provided by the bromoalkane in the polyurethane enables alkane chains to mutually permeate and interweave after thermal movement, so that a fracture interface is recombined to play a role in repairing cracks.
Drawings
FIG. 1 is a diagram of the thermally induced shape recovery process of PU 4.
FIG. 2 is a diagram of the thermally induced shape recovery process for PU2, PU3, PU4, PU 5;
1. sample time-temperature profile; 2. sample time-stress curve; 3. sample time-strain curves.
FIG. 3 shows the macroscopic fracture self-healing (a-c) and microscopic fracture self-healing (d-g) plots of PU 4.
FIG. 4 is a graph of tensile stress strain versus time for PU 4.
Detailed Description
(1) preparation of quaternized dihydroxy glycol: 1.19g (0.01mol) of N-Methyldiethanolamine (MDEA) and 3.94g (0.01mol) of bromodocosane are put in a three-neck flask, the temperature is set as 100 ℃, and the mixture is stirred and reacted for 12 hours to obtain quaternized dihydroxy glycol (0.01 mol).
(2) Preparation of polyurethane hard segment: 5.13g (0.01mol) of quaternized dihydroxyethylene glycol and 3.36g (0.02mol) of Hexamethylene Diisocyanate (HDI) were added to a three-necked flask and mixed, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added dropwise and reacted at 60 ℃ for 2 hours, and when the NCO value reached the theoretical value, the reaction was stopped to give a polyurethane hard segment component, which was designated as product 1(0.01 mol).
(3) Preparing a polyurethane soft segment: 2.91g (0.015mol) of tetraethylene glycol (TEG) and 1.68g (0.01mol) of Hexamethylene Diisocyanate (HDI) were added to a three-necked flask, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added dropwise and reacted at 60 ℃ for 2h to obtain a polyurethane soft segment component, which was designated as product 2.
Comparative example 1
(4) Preparation of UV-curing polyurethane: 8.49g (0.01mol) of the product 1 was charged in a three-necked flask, 2.6g (0.02mol) of methyl methacrylate (HEMA) was added thereto, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added dropwise, and the reaction was carried out at 60 ℃ for 2 hours to obtain a polyurethane emulsion.
(5) Curing of polyurethane: and (3) adding 0.25g of 1173 photoinitiator into 5g of polyurethane emulsion, stirring, coating on a sample plate, and curing for 30s on a UV curing machine to obtain the polyurethane PU 0.
Example 1
(4) Preparation of UV-curing polyurethane: 7.64g (0.009mol) of the product 1 and 0.46g (0.001mol) of the product 2 were charged into a three-necked flask, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added, and the mixture was reacted at 60 ℃ for 2 hours, and 2.21g (0.017mol) of hydroxyethyl methacrylate (HEMA) was added and the reaction was continued for 2 hours to obtain a polyurethane emulsion.
(5) Curing of polyurethane: and (3) adding 0.25g of 1173 photoinitiator into 5g of polyurethane emulsion, stirring, coating on a sample plate, and curing for 30-60s on a UV curing machine to obtain the UV-cured polyurethane PU1 with self-healing property and shape memory property.
Example 2
(4) Preparation of UV-curing polyurethane: 6.79g (0.008mol) of the product 1 and 0.92g (0.002mol) of the product 2 were charged into a three-necked flask, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added, and the mixture was reacted at 60 ℃ for 2 hours, and 1.82g (0.014mol) of hydroxyethyl methacrylate (HEMA) was added and the reaction was continued for 2 hours to obtain a polyurethane emulsion.
(5) Curing of polyurethane: and (3) adding 0.25g of 1173 photoinitiator into 5g of polyurethane emulsion, stirring, coating on a sample plate, and curing for 30-60s on a UV curing machine to obtain the UV-cured polyurethane PU2 with self-healing property and shape memory property.
Example 3
(4) Preparation of UV-curing polyurethane: 5.94g (0.007mol) of the product 1 and 1.38g (0.003mol) of the product 2 were put into a three-necked flask, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added, and the mixture was reacted at 60 ℃ for 2 hours, and 1.43g (0.011mol) of hydroxyethyl methacrylate (HEMA) was added and the reaction was continued for 2 hours to obtain a polyurethane emulsion.
Curing of polyurethane: and (3) adding 0.25g of 1173 photoinitiator into 5g of polyurethane emulsion, stirring, coating on a sample plate, and curing for 30-60s on a UV curing machine to obtain the UV-cured polyurethane PU3 with self-healing property and shape memory property.
Example 4
(4) Preparation of UV-curing polyurethane: 5.09g (0.006mol) of the product 1 and 1.84g (0.004mol) of the product 2 were put into a three-necked flask, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added, and the mixture was reacted at 60 ℃ for 2 hours, and 1.04g (0.008mol) of hydroxyethyl methacrylate (HEMA) was added and the reaction was continued for 2 hours to obtain a polyurethane emulsion.
(5) Curing of polyurethane: and (3) adding 0.25g of 1173 photoinitiator into 5g of polyurethane emulsion, stirring, coating on a sample plate, and curing for 30-60s on a UV curing machine to obtain the UV-cured polyurethane PU4 with self-healing property and shape memory property.
Example 5
(4) Preparation of UV-curing polyurethane: 4.25g (0.005mol) of the product 1 and 2.3g (0.005mol) of the product 2 were put into a three-necked flask, 3 to 4 drops of dibutyltin dilaurate (DBTDL) were added, and the mixture was reacted at 60 ℃ for 2 hours, and 0.65g (0.005mol) of hydroxyethyl methacrylate (HEMA) was added and the reaction was continued for 2 hours to obtain a polyurethane emulsion.
(5) Curing of polyurethane: and (3) adding 0.25g of 1173 photoinitiator into 5g of PU5, stirring, coating on a sample plate, and curing for 30-60s on a UV curing machine to obtain the UV-cured polyurethane PU5 with self-healing property and shape memory property.
Application example 1 Heat Induction experiment
The heat induction experiment of PU1-5 prepared in the above examples 1-5 was carried out by the following steps: respectively preparing PU1-5 sample strips, setting the temperature to change in a range of-10 to 60 ℃ in a dynamic mechanical analysis instrument, and measuring the change curves of the stress and the strain.
In the figure of the thermal induced shape recovery process of PU4, as shown in FIG. 1, the temperature was first raised to 60 ℃ and the sample was deformed to 100% strain, then cooled to-10 ℃ and the deformation was substantially fixed, and then reheated to the deformation temperature, and the strain recovery rate was observed to reach 85%, which is a typical thermally induced shape memory behavior. The analysis reason is probably because the polyurethane soft segment and hard segment are related to the synergistic effect, and the soft segment and the hard segment are carried out in proper proportion, so that good fixing and recovery effects can be achieved.
The heat-induced shape recovery process of PU2-5 is shown in FIG. 2.
Application example 2 fracture-self-healing experiment
The PU4 prepared in example 4 above was subjected to a fracture-self-healing experiment; the specific process is as follows: selecting cutting fracture strips, splicing fractures together, heating in an oven at 80 ℃ for 4h, and then stretching the sample through a universal testing machine. The change in microscopic conditions was observed by a hot state polarization microscope.
FIG. 3 is a graph of the macroscopic self-healing (a-c) and the microscopic self-healing (d-g) fractures of PU 4. The broken bars were brought together, heated at 80 ℃ for 4h, and then the sample was stretched to about three times the original length without breaking. From the microscopic image, it can be seen that the self-healing condition of the fracture can only be seen as a shallow trace on the surface, which proves that the self-healing of the sample is successful.
Application example 3 stress-strain test
The PU4 prepared in example 4 was subjected to a stress-strain test; the specific experimental process is as follows: and (4) carrying out a tensile test on the sample strip subjected to fracture repair through a universal testing machine until the sample strip is fractured. The maximum breaking stress and the maximum strain thereof were observed.
FIG. 4 is a graph of tensile stress strain versus time for PU 4. It can be seen that the tensile strength of the initial sample is 3.8MPa and the tensile strain is 51%. After 24h of repair. The tensile strength can reach 3.7MPa, the tensile strain is 46 percent, and the self-healing repair rate exceeds 90 percent. The reason for this analysis may be that under temperature driving, the alkane chains cross-link with each other, thereby recombining the fractured interfaces and playing a self-healing role.
From the application examples, PU2, PU3, PU4 and PU5 all have better shape recovery capability, but in PU2, the strain after temperature recovery is about 35% of the initial strain; in PU3, after the temperature is restored to normal temperature, the strain is only about 50% comparatively, and the strain restoration degree cannot be good; the strain ratio of PU5 at normal temperature can reach about 25%, while the shape recovery capability of PU4 is the best of several groups, the strain can be recovered to below 20% of the original sample, and the comparison shows that PU4 has better shape recovery capability.
Claims (10)
1. A preparation method of photocuring polyurethane with self-healing property and shape memory property is characterized by comprising the following steps: firstly, preparing quaternized dihydroxy ethylene glycol, then respectively preparing a polyurethane soft segment and a polyurethane hard segment, preparing polyurethane emulsion through the reaction between the soft segment and the hard segment, and carrying out photocuring to obtain the polyurethane with self-healing property and shape memory property.
2. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 1, comprising the steps of:
(1) preparation of quaternized dihydroxy glycol: mixing alcohol amine and bromoalkane according to a metering ratio, and stirring and reacting at a high temperature to obtain quaternized dihydroxyethylene glycol;
(2) preparation of polyurethane hard segment: mixing the quaternized dihydroxyethylene glycol prepared in the step (1) and diisocyanate in a metering ratio, dropwise adding a catalyst for reaction, and stopping the reaction when the NCO value reaches a theoretical value to obtain a polyurethane hard segment component which is marked as a product 1;
(3) preparing a polyurethane soft segment: adding diisocyanate and glycol according to a metering ratio, dropwise adding a catalyst for reaction to obtain a polyurethane soft segment component, and marking as a product 2;
(4) preparation of polyurethane emulsion: adding the product 1 prepared in the step (2) and the product 2 prepared in the step (3) into a reaction container, and adding a blocking agent and a catalyst for reaction to obtain a polyurethane emulsion;
(5) curing of polyurethane: and (4) adding a photoinitiator into the polyurethane emulsion prepared in the step (4), fully stirring, coating on a carrier, and carrying out UV curing to obtain the UV-cured polyurethane with self-healing property and shape memory property.
3. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein:
the alcohol amine in the step (1) is N-methyldiethanolamine and/or N-ethyldiethanolamine; the bromoalkane is one or more of bromohexadecane, bromooctadecane, bromoeicosane or bromodocosane;
the diisocyanate in the step (2) is one or more of toluene diisocyanate TDI, 4' -diphenylmethane diisocyanate MDI or isophorone diisocyanate IPDI;
the glycol in the step (3) is triethylene glycol and/or tetraethylene glycol.
4. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein: the catalyst is dibutyltin dilaurate or stannous octoate;
the end-capping reagent is one or more of hydroxyethyl acrylate HEA, hydroxyethyl methacrylate HEMA and pentaerythritol triacrylate PETA.
5. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein: 0.01-0.03mol of alcohol amine and 0.01-0.03mol of alkyl bromide are taken to be mixed in the step (1), and stirred and reacted for 11-13h at the temperature of 90-110 ℃ to obtain the quaternized dihydroxy glycol.
6. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein: in the step (2), 0.01-0.02mol of quaternized dihydroxy ethylene glycol and 0.02-0.04mol of diisocyanate are added, 3-4 drops of catalyst are added dropwise, and the mixture reacts for 1-3 hours at the temperature of 58-62 ℃; when the NCO value reaches the theoretical value, the reaction is stopped, and the polyurethane hard segment component is obtained and is marked as a product 1.
7. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein: adding 0.01-0.02mol of diisocyanate and 0.015-0.03mol of glycol into the mixture obtained in the step (3), dropwise adding 3-4 drops of catalyst, and reacting for 1-3h at 58-62 ℃; when the NCO value reaches the theoretical value, the reaction is stopped, and the polyurethane soft segment component is obtained and is marked as a product 2.
8. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein: adding 10.005-0.01 mol of product, 20.001-0.005 mol of product and 0.005-0.02mol of end-capping agent into the mixture obtained in the step (4), dropwise adding 3-4 drops of catalyst, and reacting at 58-62 ℃ for 1-3h to obtain the polyurethane emulsion.
9. The method for preparing a light-curable polyurethane having self-healing properties and shape memory according to claim 2, wherein: and (5) adding a photoinitiator with the mass concentration of 0.5% into the polyurethane emulsion prepared in the step (4), and curing for 30-60s on a UV curing machine to obtain the photocured polyurethane with self-healing property and shape memory property.
10. Use of the polyurethane prepared by the process according to any one of claims 1 to 9, characterized in that: the nano-silver/nano-silver composite material is applied to intelligent coatings and self-repairing intelligent materials.
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| CN110563906A (en) * | 2019-08-15 | 2019-12-13 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
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| CN110563906A (en) * | 2019-08-15 | 2019-12-13 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
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| Title |
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| 周建萍: "《高分子材料与工程专业实验》", 31 October 2018, 北京航空航天大学出版社 * |
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