CN114316174B - High molecular weight linear polyurethane acrylate prepolymer, dielectric elastomer and preparation thereof - Google Patents
High molecular weight linear polyurethane acrylate prepolymer, dielectric elastomer and preparation thereof Download PDFInfo
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Abstract
The invention relates to the field of dielectric elastomer materials, in particular to a high molecular weight linear polyurethane acrylate prepolymer, a dielectric elastomer and a preparation method thereof. The invention provides a preparation method of polyurethane acrylate prepolymer, which comprises the following steps: firstly, diisocyanate, polyalcohol and an organic solvent 1 are stirred and blended to react to prepare polyurethane prepolymer with alternating soft and hard segments, and then the polyurethane prepolymer is dissolved in the organic solvent 2 and an acrylic end capping agent is added to prepare polyurethane acrylate prepolymer; wherein the molar ratio of diisocyanate to polyol is: 1.1 to 2.0; the organic solvent 1 is a weak polar solvent, and the organic solvent 2 is a weak polar or strong polar solvent. According to the invention, the reactive diluent and the photoinitiator are introduced into the linear non-branched and non-crosslinked polyurethane acrylate prepolymer with different tail end structures, so that the polyurethane dielectric elastomer material with good mechanical and dielectric properties can be rapidly prepared.
Description
Technical Field
The invention relates to the field of dielectric elastomer materials, in particular to a high molecular weight linear polyurethane acrylate prepolymer, a dielectric elastomer and a preparation method thereof.
Background
The dielectric elastomer uses electroactive polymer as a matrix, has the characteristics of high speed, high reversibility, high electromechanical conversion efficiency, high energy density and the like, and has wide application prospect in the fields of mechanical drivers, artificial muscles, flexible robots, sensors and the like. The surface of the dielectric elastomer film is coated with a conductive electrode, and Maxwell acting force generated on two sides of the electrode under an external electric field causes the elastomer film to deform, so that the thickness is reduced, and the area is enlarged. According to the theory presented by Pelrine et al, a dielectric elastomer material is able to achieve a large driving strain at low voltages when the dielectric elastomer material has a high dielectric constant, a low elastic modulus, a low dielectric loss, and a high dielectric breakdown strength. Currently common dielectric elastomer materials include Silicone Rubber (SR), acrylate (AAS), polyurethane (PU), and the like, with PU-based dielectric elastomers having higher dielectric constants and weatherability than other polymer-based elastomers. PU is a block polymer with soft segments and hard segments alternately connected, and the two phases have larger thermodynamic difference to cause microphase separation in the material, so that the material has lower crystallinity and larger elasticity; the diversification of the soft and hard segment structures of the PU brings great help to the subsequent structural control, and can endow more special performances to the polyurethane material.
The current methods commonly used to improve the electrical driving performance of PU dielectric elastomer materials generally comprisePhysical modification and chemical synthesis. For the physical modification, one of them is to compound conductive or dielectric filler (silver particles, carbon nanotubes, graphene, carbon black or BaTiO 3 Particles, etc.), the dielectric constant of the PU can be effectively increased, but the elastic modulus of the PU can be obviously increased, and the breakdown strength is reduced. Another physical modification method is to add small molecular diluents (such as azobenzene, diaminonaphthalene, etc.) with dipole structure into the PU matrix; the diluent small molecules with dipoles are added to break the hydrogen bonds inside or among the PU molecular chains, reconstruct the hydrogen bonds between the PU molecular chains and the small molecular diluents, reduce the modulus of the material, increase the polarization degree of the material and improve the dielectric property of the material; however, the method is easy to volatilize and migrate small molecules of the diluent, so that the stability and weather resistance of the material are greatly reduced.
The problem of high modulus and low breakdown strength of polyurethane can be directly and more effectively solved by a chemical synthesis or organic modification molecular chain method. For example, by increasing the length of the soft segment (such as polyethylene glycol) in the PU soft and hard segment structure, the method can effectively reduce the modulus of the PU matrix, but further reduce the dielectric loss (the increase of intramolecular friction dissipation) of the material. In addition, other conventional methods include constructing a PUA network structure having a low degree of crosslinking, or constructing a molecular weight (M) e ) A larger PU network structure; or a grafting to method is adopted to construct a bottle brush structure on a PU main chain, a cyclodextrin (cyclodextrin) host-guest nesting method is adopted to construct a sliding ring structure, and a second phase network is introduced into an elastomer network structure to form an Interpenetrating Polymer Network (IPN) and the like. These methods are effective in reducing crosslink density and intermolecular hydrogen bonding, thereby reducing PU modulus. Based on these methods, the dielectric elastomer structure is further pre-stretched, and the pre-stretching and supporting structure can adjust the stress-strain curve, eliminate the premature electric breakdown and further improve the driving strain of the elastomer. However, these methods all suffer from several common problems that are difficult to solve, including: the preparation has the advantages of higher preparation difficulty, complex steps, higher cost and lower yield, and can reduce the tensile resistance of PU, thereby causingThe drive strain range is narrowed, the relative movement between molecular chains is increased, the dielectric relaxation is obvious, and the like; meanwhile, stress concentration is easy to occur at the interface of the supporting structure and the elastomer, so that the interface is unstable, and the prestretching can lead to stress relaxation of the material, so that the service life of the elastomer is reduced. Therefore, it is highly desirable to find a simple and universal method for rapidly synthesizing and constructing PU dielectric elastomer materials with high electromechanical properties.
Disclosure of Invention
Aiming at the difficulties faced by the molecular structure design of the prior intrinsic PU dielectric elastomer material, polyurethane acrylate (PUA) prepolymer with different tail end structures is prepared by the molecular structure design; further introducing a reactive diluent and a photoinitiator into the obtained prepolymer, and finally preparing a photocurable polyurethane dielectric elastomer material with good mechanical and dielectric properties by optimizing the proportion of the photocurable slurry and the photocuring process; thereby providing feasibility for preparing the dielectric elastomer driver with excellent performance in the later period and widening the application of the dielectric elastomer in the fields of flexible robots and the like.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a preparation method of polyurethane acrylate prepolymer, which comprises the following steps: firstly, diisocyanate, polyalcohol and an organic solvent 1 are stirred and blended to react to prepare polyurethane prepolymer with alternating soft and hard segments, and then the polyurethane prepolymer is dissolved in the organic solvent 2 and an acrylic end capping agent is added to prepare polyurethane acrylate prepolymer; wherein the molar ratio of diisocyanate to polyol is: 1.1 to 2.0; the organic solvent 1 is a weak polar solvent, and the organic solvent 2 is a weak polar or strong polar solvent.
Further, the organic solvent 1 (the solvent selected not to participate in the reaction according to the present invention) is selected from: acetone, tetrahydrofuran, toluene, xylene, or the like.
Further, the organic solvent 2 is selected from: acetone, tetrahydrofuran, toluene, xylene, N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) or Dimethylsulfoxide (DMSO). The solvent may be added in an amount sufficient to completely dissolve the reaction monomer and the product. The reaction of the polyurethane acrylate prepolymer of the invention is carried out in two steps: firstly, preparing polyurethane prepolymer, and precisely regulating and controlling molecular weight by adopting a weak polar solvent; in the second step, a slightly more polar solvent may be used to prepare the urethane acrylate prepolymer.
Further, the acrylic capping reagent is selected from: one of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), glycerol Dimethacrylate (GDMA) or pentaerythritol triacrylate (PETA).
Further, the diisocyanate is selected from the group consisting of: one of p-phenylene diisocyanate (PPDI), toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) or 4,4' -diisocyanate diphenylmethane (MDI).
Further, the polyol is: polyethylene glycol (molecular weight not less than 400 g/mol) or polyvinyl alcohol (PVA).
Further, the preparation method of the polyurethane prepolymer comprises the following steps: firstly, diisocyanate and polyalcohol are dispersed in an organic solvent 1, and polyurethane prepolymer is produced through stirring and blending reaction; the reaction temperature is controlled at room temperature to 100 ℃, the stirring speed is controlled at 60 to 360rpm, and the reaction time is controlled at 2 to 6 hours.
Further, the method for preparing the polyurethane acrylate prepolymer by adding the acrylic end-capping agent comprises the following steps: separating and purifying the obtained polyurethane prepolymer from the organic solvent 1, then dissolving the polyurethane prepolymer in the organic solvent 2, adding an acrylic end capping agent, and stirring and reacting to carry out end capping to obtain polyurethane acrylate prepolymers with different tail end structures and molecular weights; wherein the reaction temperature is controlled at 40-100 ℃, the stirring speed is controlled at 60-360 rpm, and the reaction time is controlled at 2-6 hours.
Furthermore, the polyurethane acrylate prepolymer is required to be subjected to dissolution and regeneration treatment (at least 2 times) to remove unreacted small molecules or byproducts in the reaction, and is preserved for standby in a dark place.
The second technical problem to be solved by the invention is to provide a polyurethane acrylate prepolymer which is prepared by the method.
Further, the polyurethane acrylate prepolymer has a number average molecular weight (Mn) of 7000 to 25000g/mol, preferably 14000 to 25000g/mol.
Further, the urethane acrylate prepolymer is a linear unbranched and non-crosslinked prepolymer.
The third technical problem to be solved by the invention is to provide the application of the polyurethane acrylate prepolymer in preparing dielectric elastomer materials, photosensitive materials, self-repairing materials or sensing materials and the like.
The fourth technical problem to be solved by the present invention is to provide a dielectric elastomer material, the raw materials of which include: the polyurethane acrylic ester prepolymer, reactive diluent and photoinitiator prepared by the method, wherein the proportion of the raw materials is as follows: 50-80 parts of polyurethane acrylate prepolymer, 10-30 parts of reactive diluent and 1-10 parts of photoinitiator.
Further, the elastic modulus (Y) of the resulting dielectric elastomer material is not higher than 1.2MPa without pretensioning or adding other small molecule diluents.
Further, the resulting dielectric elastomer material was found to be at a frequency of 10 3 The dielectric constant (. Epsilon.) at Hz is not lower than 10.
Further, the diluent is selected from: at least one of 1, 6-hexanediol diacrylate, diethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate 400 (molecular weight 400) or polyethylene glycol diacrylate 600 (molecular weight 600).
Further, the photoinitiator is selected from: at least one of 2,4, 6-Trimethylformyldiphenoxyphosphorus (TPO), 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone, 1-hydroxycyclohexylphenyl ketone, 4-bis (diethoxy) benzophenone, 2-methyl-2 (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone or 2-isopropylthioxanthone.
The fifth technical problem to be solved by the present invention is to provide a preparation method of the dielectric elastomer material, which is: firstly, uniformly stirring and blending polyurethane acrylate prepolymer, reactive diluent, photoinitiator and organic solvent 3 to prepare photosensitive polyurethane acrylate slurry; then the obtained slurry is molded into a dielectric elastomer material through photo-curing; wherein the organic solvent 3 is a strong or weak polar solvent.
Further, the preparation method of the photosensitive polyurethane acrylate slurry comprises the following steps: firstly adding a photoinitiator into an organic solvent 3, then uniformly vibrating at room temperature by ultrasonic waves, and dissolving the photoinitiator until the photoinitiator is transparent; adding an active diluent, and uniformly oscillating for 10-30 min by ultrasonic waves to obtain a mixture A; then dissolving polyurethane acrylate prepolymer in polar or weak polar organic solvent 3, and uniformly oscillating by ultrasonic waves for 20-40 min to obtain a mixture B; and finally, uniformly mixing the mixture A and the mixture B, and performing ultrasonic vibration treatment in a water bath for 30-60 min to obtain the photosensitive polyurethane acrylate slurry.
Further, the organic solvent 3 is selected from: acetone, tetrahydrofuran, toluene, xylene, N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) or Dimethylsulfoxide (DMSO).
Further, in the preparation method: spreading the obtained photosensitive polyurethane acrylate slurry into a slurry coating (the thickness is generally 0.05-1.5 mm) by means of blade coating, pouring coating, template pouring or spin coating; and then the dielectric elastomer film is prepared by ultraviolet light with the irradiation wavelength of 330-405 nm for curing for 0.5-30 min.
Further, the dielectric elastomer film obtained is a pale yellow transparent film with a thickness of 50 to 1000. Mu.m.
The invention has the beneficial effects that:
1. the invention prepares the linear non-branched and non-crosslinked polyurethane acrylate prepolymer with the number average molecular weight (Mn) of 7000-25000 g/mol by using a specific solvent and a specific raw material ratio.
2. The photosensitive polyurethane acrylate slurry with high photosensitivity and high forming speed is further prepared by adding the reactive diluent, the photoinitiator and the solvent into the obtained linear non-branched non-crosslinked polyurethane acrylate prepolymer with high molecular weight.
3. The dielectric elastomer formed by photocuring the photosensitive polyurethane acrylate slurry has a linear entanglement network structure with high molecular weight (namely, the polyurethane dielectric elastomer provided by the invention has no cross-linked structure or has less cross-linked structure), and a 'node-shaped' structure formed by curing reaction of a multi-functionality end-capping structure exists in the entanglement network according to the specific selection of monomers, so that the dielectric elastomer with low elastic modulus, good dielectric property and excellent electric driving property is prepared.
Description of the drawings:
FIG. 1 shows the infrared test results of the products obtained in examples 1 to 5, FIG. 1 (a) and FIG. 1 (b) show the infrared test results of the synthesized urethane acrylate prepolymer, and FIG. 1 (c) and FIG. 1 (d) show the infrared results of the cured dielectric elastomer film.
FIG. 2 shows the results of dielectric property tests of the dielectric elastomer films obtained in examples 1 to 5: FIG. 2a shows the dielectric constant results; FIG. 2b is a dielectric loss angle result; fig. 2c is a conductivity result.
FIG. 3 shows the results of electric driving performance tests of the dielectric elastomer films obtained in example 1, example 3 and example 5.
FIG. 4 is a photograph of the prepolymer product obtained in comparative example 1.
FIG. 5 is a graph showing the results of electric driving performance test of the dielectric elastomer film obtained in comparative example 2.
Detailed Description
The invention firstly generates polyurethane prepolymer with alternating soft and hard segments through the reaction of diisocyanate and polyalcohol, and then uses acrylate end capping agents with various functionalities to end cap polyurethane to obtain high molecular weight linear non-branched non-crosslinked polyurethane acrylate prepolymer with different molecular chain lengths and end group structures. Further, the polyurethane dielectric elastomer film with different molecular chain lengths and a 'nodular' structure is prepared by flexibly changing the proportion and the curing process of the photo-curing sizing agent taking polyurethane acrylic ester as a main body, and compared with the common commercial photo-curing polyurethane dielectric elastomer material, the dielectric elastomer material obtained by the invention has better mechanical properties (low modulus and high chain breaking elongation) and dielectric properties.
The following specific examples are provided to further illustrate the technical solution of the present invention and are not intended to limit the present invention, and those skilled in the art may reasonably design the technical solution with reference to the examples, and may also obtain the results of the present invention.
Example 1
The dielectric elastomer material is prepared by the following method:
(1) 28.513g of 4,4' -diisocyanate diphenylmethane (MDI) was weighed into a three-necked flask containing 300ml of acetone and N was replaced 2 Mechanically stirring for three times at room temperature until the system is transparent; 36mL of polyethylene glycol (PEG 400) with molecular weight of 400 after drying treatment is measured, dissolved in 400mL of acetone, and then added into a reaction vessel for reaction, wherein the reaction temperature is set to 50 ℃, the mechanical stirring speed is 180rpm, and the reaction time is 15min;
(2) Taking out the product precipitated in the step (1), dissolving in 600mL of DMF, setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, and reacting for 1h;
(3) Adding 12mL of hydroxyethyl acrylate (HEA), setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, reacting for 2 hours, finally obtaining polyurethane acrylate (PUA) prepolymer, dissolving and regenerating the polyurethane acrylate (PUA) prepolymer by absolute ethyl alcohol for two times, and keeping away from light and heat for later use;
(4) Preparing 76g of polyurethane acrylate prepolymer prepared in the step (3), 19g of reactive diluent, 5g of photoinitiator and solvent into light-curing slurry, wherein the reactive diluent adopts polyethylene glycol diacrylate (PEGDA 600) with the molecular weight of about 600, and the photoinitiator adopts 2,4, 6-Trimethylformyldiphenoxyphosphate (TPO);
(5) After weighing each component according to the step (4), firstly dissolving the photoinitiator in DMF (dimethyl formamide) by an ultrasonic vibration method according to the proportion of 0.1g/mL (w/v) of the photoinitiator to the solvent until the system is uniform and transparent, then adding an active diluent, and uniformly vibrating for 20 minutes by ultrasonic waves to obtain an intermediate mixture A; dissolving polyurethane acrylate prepolymer in DMF according to the ratio of the prepolymer to the solvent of 1.5g/mL (w/v), and uniformly oscillating by ultrasonic waves for 30min to obtain an intermediate mixture B;
(6) Uniformly mixing the intermediate mixture A and the intermediate mixture B, and then carrying out ultrasonic vibration treatment in a water bath for 30min to obtain photo-curing polyurethane acrylate slurry;
(7) Uniformly coating the photo-curing slurry prepared in the step (6) on a glass plate in a blade coating mode to obtain a coating with the thickness of about 0.5mm, and irradiating with an LED ultraviolet lamp with the wavelength of 375nm for a radiation distance of 19.5cm and a curing time of 15min; a polyurethane dielectric elastomer film having a thickness of about 0.150mm was obtained.
The molecular weight of the polyurethane acrylate prepolymer obtained and the mechanical properties of the polyurethane dielectric elastomer film obtained after final curing are shown in Table 1, and the dielectric properties are shown in Table 2.
Example 2
The dielectric elastomer material is prepared by the following method:
(1) 27.449g of 4,4' -diisocyanate diphenylmethane (MDI) was weighed into a three-necked flask containing 300ml of acetone and N was replaced 2 Mechanically stirring for three times at room temperature until the system is transparent; 35mL of the dried polyethylene glycol (PEG 400) with the molecular weight of about 400 is measured and dissolved in 400mL of acetone; then also added into a reaction vessel for reaction: the temperature is set to 50 ℃, the mechanical stirring speed is 240rpm, and the reaction time is 15min;
(2) Taking out the product precipitated in the step (1), dissolving in 600mL of DMF, setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, and reacting for 1h;
(3) Adding 12mL of hydroxyethyl acrylate (HEA), setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, reacting for 2 hours, finally obtaining polyurethane acrylate (PUA) prepolymer, dissolving and regenerating the polyurethane acrylate (PUA) prepolymer by absolute ethyl alcohol for two times, and keeping away from light and heat for later use;
(4) Preparing 76g of polyurethane acrylate prepolymer prepared in the step (3), 19g of reactive diluent, 5g of photoinitiator and solvent into photo-curing slurry, wherein the reactive diluent is PEGDA600, and the photoinitiator is TPO;
(5) After weighing each component according to the step (4), firstly dissolving the photoinitiator in DMF (dimethyl formamide) by an ultrasonic vibration method according to the proportion of 0.1g/mL (w/v) of the photoinitiator to the solvent until the system is uniform and transparent, then adding an active diluent, and uniformly vibrating for 20 minutes by ultrasonic waves to obtain an intermediate mixture A; dissolving polyurethane acrylate prepolymer in DMF according to the ratio of the prepolymer to the solvent of 1.5g/mL (w/v), and uniformly oscillating by ultrasonic waves for 30min to obtain an intermediate mixture B;
(6) Uniformly mixing the intermediate mixture A and the intermediate mixture B, and then carrying out ultrasonic vibration treatment in a water bath for 30min to obtain photo-curing polyurethane acrylate slurry;
(7) Uniformly coating the photo-curing slurry prepared in the step (6) on a glass plate in a blade coating mode to obtain a coating with the thickness of about 0.5mm, and irradiating with an LED ultraviolet lamp with the wavelength of 375nm for a radiation distance of 19.5cm and a curing time of 15min; a polyurethane dielectric elastomer film having an average thickness of about 0.179mm was obtained.
The molecular weight of the polyurethane acrylate prepolymer obtained and the mechanical properties of the polyurethane dielectric elastomer film obtained after final curing are shown in Table 1, and the dielectric properties are shown in Table 2.
Example 3
The dielectric elastomer material is prepared by the following method:
(1) 28.513g of 4,4' -diisocyanate diphenylmethane (MDI) was weighed into a three-necked flask containing 300ml of acetone and N was replaced 2 Mechanically stirring for three times at room temperature until the system is transparent; 35mL of the dried polyethylene glycol (PEG 400) with the molecular weight of about 400 is measured and dissolved in 400mL of acetone; then also added into a reaction vessel for reaction: the temperature is set to 50 ℃, the mechanical stirring speed is 300rpm, and the reaction time is 15min;
(2) Taking out the product precipitated in the step (1), dissolving in 600 mM LDMF, setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, and reacting for 1h;
(3) Adding 12mL of hydroxyethyl acrylate (HEA), setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, reacting for 2 hours, finally obtaining polyurethane acrylate (PUA) prepolymer, dissolving and regenerating the polyurethane acrylate (PUA) prepolymer by absolute ethyl alcohol for two times, and keeping away from light and heat for later use;
(4) Preparing 76g of polyurethane acrylate prepolymer prepared in the step (3), 19g of reactive diluent, 5g of photoinitiator and solvent into light-curing slurry, wherein the reactive diluent adopts polyethylene glycol diacrylate (PEGDA 600) with the molecular weight of about 600, and the photoinitiator adopts 2,4, 6-Trimethylformyldiphenoxyphosphate (TPO);
(5) After weighing each component according to the step (4), firstly dissolving the photoinitiator in DMF (dimethyl formamide) by an ultrasonic vibration method according to the proportion of 0.1g/mL (w/v) of the photoinitiator to the solvent until the system is uniform and transparent, then adding an active diluent, and uniformly vibrating for 20 minutes by ultrasonic waves to obtain an intermediate mixture A; dissolving polyurethane acrylate prepolymer in DMF according to the ratio of the prepolymer to the solvent of 1.5g/mL (w/v), and uniformly oscillating by ultrasonic waves for 30min to obtain an intermediate mixture B;
(6) Uniformly mixing the intermediate mixture A and the intermediate mixture B, and then carrying out ultrasonic vibration treatment in a water bath for 30min to obtain photo-curing polyurethane acrylate slurry;
(7) Uniformly coating the photo-curing slurry prepared in the step (6) on a glass plate in a blade coating mode to obtain a coating with the thickness of about 0.5mm, and irradiating with an LED ultraviolet lamp with the wavelength of 375nm for a radiation distance of 19.5cm and a curing time of 15min; a polyurethane dielectric elastomer film having an average thickness of about 0.196mm was obtained.
The molecular weight of the polyurethane acrylate prepolymer obtained and the mechanical properties of the polyurethane dielectric elastomer film obtained after final curing are shown in Table 1, and the dielectric properties are shown in Table 2.
Example 4
The dielectric elastomer material is prepared by the following method:
(1) 28.245g of 4,4' -diisocyanate diphenylmethane (MDI) was weighed into a three-necked flask containing 300ml of acetone and N was replaced 2 Mechanically stirring for three times at room temperature until the system is transparent; 35mL of the dried polyethylene glycol (PEG 400) with the molecular weight of about 400 is measured and dissolved in 400mL of acetone; then also add into the reaction vesselThe reaction: the temperature is set to 50 ℃, the mechanical stirring speed is 300rpm, and the reaction time is 30min;
(2) Taking out the product precipitated in the step (1), dissolving in 600mL of DMF, setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, and reacting for 1h;
(3) Adding 12mL of hydroxyethyl acrylate (HEA), setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, reacting for 2 hours, finally obtaining polyurethane acrylate (PUA) prepolymer, dissolving and regenerating the polyurethane acrylate (PUA) prepolymer by absolute ethyl alcohol for two times, and keeping away from light and heat for later use;
(4) Preparing 76g of polyurethane acrylate prepolymer prepared in the step (3), 19g of reactive diluent, 5g of photoinitiator and solvent into light-curing slurry, wherein the reactive diluent adopts polyethylene glycol diacrylate (PEGDA 600) with the molecular weight of about 600, and the photoinitiator adopts 2,4, 6-Trimethylformyldiphenoxyphosphate (TPO);
(5) After weighing each component according to the step (4), firstly dissolving the photoinitiator in DMF (dimethyl formamide) by an ultrasonic vibration method according to the proportion of 0.1g/mL (w/v) of the photoinitiator to the solvent until the system is uniform and transparent, then adding an active diluent, and uniformly vibrating for 20 minutes by ultrasonic waves to obtain an intermediate mixture A; dissolving polyurethane acrylate prepolymer in DMF according to the ratio of the prepolymer to the solvent of 1.5g/mL (w/v), and uniformly oscillating by ultrasonic waves for 30min to obtain an intermediate mixture B;
(6) Uniformly mixing the intermediate mixture A and the intermediate mixture B, and then carrying out ultrasonic vibration treatment in a water bath for 30min to obtain photo-curing polyurethane acrylate slurry;
(7) Uniformly coating the photo-curing slurry prepared in the step (6) on a glass plate in a blade coating mode to obtain a coating with the thickness of about 0.5mm, and irradiating with an LED ultraviolet lamp with the wavelength of 375nm for a radiation distance of 19.5cm and a curing time of 15min; a polyurethane dielectric elastomer film having an average thickness of about 0.147mm was obtained.
The molecular weight of the polyurethane acrylate prepolymer obtained and the mechanical properties of the polyurethane dielectric elastomer film obtained after final curing are shown in Table 1, and the dielectric properties are shown in Table 2.
Example 5
The dielectric elastomer material is prepared by the following method:
(1) 28.208g of 4,4' -diisocyanate diphenylmethane (MDI) was weighed into a three-necked flask containing 300ml of acetone and N was replaced 2 Mechanically stirring for three times at room temperature until the system is transparent; 35mL of the dried polyethylene glycol (PEG 400) with the molecular weight of about 400 is measured and dissolved in 400mL of acetone; then also added into a reaction vessel for reaction: the temperature is set to 50 ℃, the mechanical stirring speed is 300rpm, and the reaction time is 15min;
(2) Taking out the product precipitated in the step (1), dissolving in 600mL of DMF, setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, and reacting for 1h;
(3) Adding 8.4mL pentaerythritol triacrylate (PETA), setting the mechanical stirring speed to 300rpm, setting the temperature to 60 ℃, reacting for 2 hours, finally obtaining polyurethane acrylate (PUA) prepolymer, dissolving and regenerating the polyurethane acrylate (PUA) prepolymer by absolute ethyl alcohol for two times, and keeping away from light and heat for later use;
(4) Preparing 76g of polyurethane acrylate prepolymer prepared in the step (3), 19g of reactive diluent, 5g of photoinitiator and solvent into light-curing slurry, wherein the reactive diluent adopts polyethylene glycol diacrylate (PEGDA 600) with the molecular weight of about 600, and the photoinitiator adopts 2,4, 6-Trimethylformyldiphenoxyphosphate (TPO);
(5) After weighing each component according to the step (4), firstly dissolving the photoinitiator in DMF (dimethyl formamide) by an ultrasonic vibration method according to the proportion of 0.1g/mL (w/v) of the photoinitiator to the solvent until the system is uniform and transparent, then adding an active diluent, and uniformly vibrating for 20 minutes by ultrasonic waves to obtain an intermediate mixture A; dissolving polyurethane acrylate prepolymer in DMF according to the ratio of the prepolymer to the solvent of 1.5g/mL (w/v), and uniformly oscillating by ultrasonic waves for 30min to obtain an intermediate mixture B;
(6) Uniformly mixing the intermediate mixture A and the intermediate mixture B, and then carrying out ultrasonic vibration treatment in a water bath for 30min to obtain photo-curing polyurethane acrylate slurry;
(7) Uniformly coating the photo-curing slurry prepared in the step (6) on a glass plate in a blade coating mode to obtain a coating with the thickness of about 0.5mm, and irradiating with an LED ultraviolet lamp with the wavelength of 375nm for a radiation distance of 19.5cm and a curing time of 15min; a polyurethane dielectric elastomer film having an average thickness of about 0.209mm was obtained.
The molecular weight of the polyurethane acrylate prepolymer obtained and the mechanical properties of the polyurethane dielectric elastomer film obtained after final curing are shown in Table 1, and the dielectric properties are shown in Table 2.
Performance test:
the molecular structure and electromechanical properties of the photo-cured polyurethane-based dielectric elastomer films were tested as follows:
the molecular weight and molecular weight distribution of the prepared urethane acrylate prepolymer were measured by gel permeation chromatography (GPC, PL-GPC220, agilent), and the measurement was carried out at room temperature, with a dissolution reagent of DMF, a measurement volume of 200mL, a flow rate of 1mL/min, and final measurement results shown in Table 1. From the results, it can be seen that as the reaction time increases, the monomers are gradually and completely converted, and the molecular weight of the polymer gradually increases until it is maintained within a certain value; wherein the high molecular weight fraction of example 4 (number average molecular weight>10 5 g/mol) content is obviously improved to 54.9%; the invention can flexibly control the molecular chain length of the prepolymer by regulating and controlling the polymerization reaction condition.
Characterization of the molecular structure of polyurethane acrylates using a Fourier transform infrared spectrometer (FTIR, nicolet 6700, USA) with a scanning range of 650-4000cm -1 The resolution of the reflection mode is 2cm -1 The scanning times are 32, the air background is subtracted finally, and the final test result is shown in figure 1; FIG. 1 (a) (b) is an infrared spectrum of a urethane acrylate prepolymer having a peak value of 3292cm -1 And 1539cm -1 Is the stretching vibration of polyurethane heavy-NH, and the vibration peak of C-O-C appears at 1096cm -1 ，1731cm -1 Is the position of C=O stretching vibration and the wave number is 1636cm -1 The appearance of (C) indicates that c=c in the end acrylate has been successfully grafted into the molecular chain. The above results indicate that the target urethane acrylate prepolymer has been successfully synthesized. 1636cm can be seen in FIG. 1 (c) (d) -1 The disappearance of the vibration peak of (2) indicates that the sample has substantially curedAnd (3) forming the finished product.
The mechanical properties of the cured polyurethane dielectric elastomer film are tested, and the mechanical properties of the cured film are tested firstly: the film was cut into 40mm x 5mm rectangular bars, stress strain curves were collected on an AGS-J universal tester, the tensile rate of the test specimen was 50mm/min, and the modulus of elasticity, maximum tensile stress and elongation at break of the test specimen were calculated, and the final test results are shown in table 1. It can be seen that as the molecular weight increases, the maximum tensile stress of the material increases, wherein the maximum tensile stress of the sample can reach 2.98MPa; wherein the elastic modulus of example 4 is highest, the modulus of example 5 is reduced to less than 1MPa due to the introduction of the "nodular structure (the nodular structure is because PETA in example 5 has tri-functional unsaturated carbon-carbon double bond (similar to the" claw-shaped "structure), and the two" claw-shaped "structures are connected to each other to form a closed loop after curing, which is called as the nodular structure in the invention), which is beneficial to increasing the driving strain of the material. The dielectric elastomer films obtained according to the present invention have a maximum elongation at break of up to 430% (the result in Table 1 is an average elongation at break), because the molecular chains of example 4 and example 5 are longer, and the internal entanglement density is higher than that of the other samples, so that the elongation at break is higher.
The polyurethane dielectric elastomer film was cut into a sheet having a certain thickness, and tested by an impedance analyzer (Nococontrol, concept 50, germany) with a voltage of 1V and a frequency in the range of 1Hz to 10 7 Hz, the final test results are shown in fig. 2 (a). Under different frequencies, the polarization types are different, the polarization mode of the polymer under low frequency is mainly interface polarization, and the phase separation degree of the soft section and the hard section has great influence on the dielectric constant under low frequency. As the frequency increases, the relative permittivity of the five samples decreases. When the frequency is higher than 10 3 Hz, the relative dielectric constant tends to stabilize; as can be seen from fig. 2a, the dielectric constant of example 5 is highest because the molecular chain of example 5 contains a "nodular" structure, and a second phase capable of being polarized is formed in the physically entangled network structure, thereby improving the interfacial polarization efficiency of the system. As can be seen from fig. 2 (b), the dielectric loss gradually decreases with increasing frequency; in addition, example 5 at high frequencyThe dielectric loss is slightly larger. As shown in fig. 2 (c), at low frequencies, the presence of a "nodular" structure increases the interfacial polarization efficiency, but sliding and friction between molecular chains also increases the internal loss of material, a phenomenon that is more pronounced at high frequencies.
FIG. 3 shows the results of the electrical driving performance test of the dielectric elastomers obtained in example 1 (PUA 1), example 3 (PUA 3) and example 5 (PUA 5), in which the films were deformed to different degrees with increasing voltage, and the samples in example 5 were found to have the best driving strain effect according to the electric field-driving strain curve, and the driving strain was found to be 13.88% at an electric field strength of 45.41V/. Mu.m; this is due to the fact that the presence of the "nodular" structure increases the hard segment content, resulting in the formation of a phase separated structure, thereby improving the dielectric polarization properties of the material and the driving strain capacity.
TABLE 1 mechanical Properties of polyurethane acrylate prepolymers, dielectric elastomers obtained in examples and comparative examples of the present invention
TABLE 2 dielectric Properties of the polyurethanes, dielectric elastomers obtained in the examples and comparative examples of the present invention
Comparative example 1
The product is prepared by the following method:
(1) 28.140g of MDI was weighed into a three-necked flask and N was replaced 2 Adding 130mL of DMF for three times, and mechanically stirring at room temperature until the DMF is completely dissolved; measuring 35mL of treated PEG400, adding 130mL of DMF to dissolve, adding into a reaction vessel, setting the temperature to 50 ℃, and setting the mechanical stirring speed to 300rpm, wherein the reaction time is 15min;
(2) The prepolymer in the first step starts to generate a large number of bubbles after reacting for 5min, the product generates obvious gelation phenomenon after reacting for 15min, the reaction can not be normally performed, and finally the polyurethane prepolymer product can not be obtained; a photograph of the prepolymer product is shown in FIG. 4.
Comparative example 2
Uniformly spreading commercial photosensitive polyurethane resin (available from Shenzhen plastic photo-curing material Co., ltd., brand H03 TPU) on a glass plate, irradiating with light with a distance of 19.5cm, irradiating with 375nm LED ultraviolet lamp, judging the curing condition by finger touch method, and testing various properties; the electrical driving properties of the commercial photosensitive polyurethane resin are shown in fig. 5. The mechanical properties of the cured polyurethane dielectric elastomer film are shown in Table 1, and the dielectric properties are shown in Table 2.
Compared with the polyurethane dielectric elastomer film provided by the invention, the maximum driving strain of the commercial polyurethane sample under the electric field strength of 31.81V/mu m can only reach 5.38%; the polyurethane dielectric elastomer material obtained by the invention has larger breakdown voltage and more excellent actual dielectric driving performance.
In summary, the invention provides a polyurethane dielectric elastomer film with excellent electromechanical properties and a preparation method thereof, which aims at the existing structural design problem of PU-based dielectric elastomer and the problems of high modulus, low breakdown strength and the like of final materials of the PU-based dielectric elastomer. According to the invention, polyurethane acrylate (PUA) prepolymers with different high molecular weight tail end and molecular chain end telechelic structures are designed by regulating and controlling a molecular chain main chain structure, and then the polyurethane dielectric elastomer film with different molecular chain lengths and a node-shaped structure is prepared by regulating and optimizing the proportion and the process of photo-curing slurry taking the PUA prepolymers as a main body. Compared with the traditional cross linking structure or the letter brush structure and the like, the longer linear entanglement chain structure and the 'knot-shaped' structure provided by the invention effectively reduce the modulus of the polyurethane dielectric elastomer film, and meanwhile, the internal phase separation caused by the structures increases the interfacial polarization efficiency, so that the polyurethane dielectric elastomer film provided by the invention has better dielectric and mechanical properties.
Claims (15)
1. A dielectric elastomeric material, wherein the dielectric elastomeric material comprises: polyurethane acrylic ester prepolymer, reactive diluent and photoinitiator, wherein the proportion of the raw materials is as follows: 50-80 parts of polyurethane acrylate prepolymer, 10-30 parts of reactive diluent and 1-10 parts of photoinitiator;
the polyurethane acrylate prepolymer is prepared by the following method: firstly, diisocyanate, polyalcohol and an organic solvent 1 are stirred and blended to react to prepare polyurethane prepolymer with alternating soft and hard segments, and then the polyurethane prepolymer is dissolved in the organic solvent 2 and an acrylic end capping agent is added to prepare polyurethane acrylate prepolymer; wherein the molar ratio of diisocyanate to polyol is: 1.1 to 2.0; the organic solvent 1 is a weak polar solvent, and the organic solvent 2 is a weak polar or strong polar solvent.
2. A dielectric elastomer material according to claim 1, characterized in that the modulus of elasticity of the resulting dielectric elastomer material is not higher than 1.2MPa.
3. A dielectric elastomer material according to claim 1, characterized in that the resulting dielectric elastomer material has a frequency of 10 3 The dielectric constant at Hz is not lower than 10.
4. A dielectric elastomer material according to claim 1, characterized in that the organic solvent 1 is selected from: acetone, tetrahydrofuran, toluene or xylene;
the organic solvent 2 is selected from: acetone, tetrahydrofuran, toluene, xylene, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
5. A dielectric elastomer material according to claim 1, wherein the acrylic capping agent is selected from the group consisting of: one of hydroxyethyl acrylate, hydroxyethyl methacrylate, glycerol dimethacrylate or pentaerythritol triacrylate;
the diisocyanate is selected from the group consisting of: one of p-phenylene diisocyanate, toluene diisocyanate, isophorone diisocyanate or 4,4' -diisocyanate diphenylmethane;
the polyol is: polyethylene glycol or polyvinyl alcohol.
6. A dielectric elastomer material according to claim 1, characterized in that the polyurethane prepolymer is prepared by the process of: firstly, diisocyanate and polyalcohol are dispersed in an organic solvent 1, and polyurethane prepolymer is produced through stirring and blending reaction; the reaction temperature is controlled at room temperature to 100 ℃, the stirring speed is controlled at 60 to 360rpm, and the reaction time is controlled at 2 to 6 hours.
7. A dielectric elastomer material according to claim 1, wherein the polyurethane acrylate prepolymer is prepared by dissolving polyurethane prepolymer in organic solvent 2 and adding acrylic end-capping agent by the steps of: separating and purifying the polyurethane prepolymer from the organic solvent 1, then dissolving the polyurethane prepolymer in the organic solvent 2, adding an acrylic end-capping agent, and stirring for reacting for end capping to obtain polyurethane acrylate prepolymer; wherein the reaction temperature is controlled to be 40-100 ℃, the stirring speed is controlled to be 60-360 rpm, and the reaction time is controlled to be 2-6 hours.
8. A dielectric elastomer material according to claim 1, wherein the polyurethane acrylate prepolymer has a number average molecular weight of 7000 to 25000g/mol.
9. A dielectric elastomer material according to claim 8, wherein the polyurethane acrylate prepolymer has a number average molecular weight of 14000 to 25000g/mol.
10. A dielectric elastomer material according to claim 1, wherein the urethane acrylate prepolymer is a linear unbranched and uncrosslinked prepolymer.
11. A dielectric elastomer material according to claim 1, wherein the diluent is selected from the group consisting of: at least one of 1, 6-hexanediol diacrylate, diethylene glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate 400 or polyethylene glycol diacrylate 600;
the photoinitiator is selected from the group consisting of: at least one of 2,4, 6-trimethylformyldiphenoxyphosphorus, 2-dimethylamino-2-benzyl-1- (4-piperidinophenyl) -1-butanone, 1-hydroxycyclohexylphenyl ketone, 4-bis (diethoxy) benzophenone, 2-methyl-2 (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone or 2-isopropylthioxanthone.
12. The method of producing a dielectric elastomer material according to any one of claims 1 to 11, characterized in that the method of producing is: firstly, uniformly stirring and blending polyurethane acrylate prepolymer, reactive diluent, photoinitiator and polar or weak polar organic solvent 3 to prepare photosensitive polyurethane acrylate slurry; and then the obtained slurry is molded into the dielectric elastomer material through photo-curing.
13. The method of preparing a dielectric elastomer material according to claim 12, wherein the method of preparing the photosensitive urethane acrylate paste comprises: firstly adding a photoinitiator into an organic solvent 3, then uniformly vibrating at room temperature by ultrasonic waves, and dissolving the photoinitiator until the photoinitiator is transparent; adding an active diluent, and uniformly oscillating for 10-30 min by ultrasonic waves to obtain a mixture A; then dissolving polyurethane acrylate prepolymer in an organic solvent 3, and uniformly oscillating by ultrasonic waves for 20-40 min to obtain a mixture B; finally, uniformly mixing the mixture A and the mixture B, and then carrying out ultrasonic vibration treatment for 30-60 min in a water bath to obtain photosensitive polyurethane acrylate slurry;
the organic solvent 3 is selected from: acetone, tetrahydrofuran, toluene, xylene, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
14. The method for preparing a dielectric elastomer material according to claim 13, wherein the method for forming the dielectric elastomer material by photo-curing the obtained slurry comprises the following steps: spreading the obtained photosensitive polyurethane acrylate slurry into a slurry coating by means of blade coating, flow coating, template pouring or spin coating, and then curing for 0.5-30 min by irradiating ultraviolet light with the wavelength of 330-405 and nm to obtain the dielectric elastomer material.
15. The method for preparing a dielectric elastomer material according to claim 12, wherein the dielectric elastomer material is a yellowish transparent film with a thickness of 50-1000 μm.
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