CN112574569B - Multi-temperature response shape memory organic silicon rubber material and preparation method and application thereof - Google Patents
Multi-temperature response shape memory organic silicon rubber material and preparation method and application thereof Download PDFInfo
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention discloses a multi-temperature response deformation organic silicon rubber material and a preparation method and application thereof. Preparation raw materials of the material comprise two or more of polyalkylmethacrylate and polysiloxane; wherein the two or more polyalkylmethacrylates are separately blended with a polysiloxane to form different liquid blends; the liquid blend is prepared by crosslinking and curing. The invention combines the thermoplastic polymer and the organic silicon elastomer, realizes the reinforcement effect of the thermoplastic polymer on the silicon rubber and the shape memory response switch effect, is an organic silicon rubber shape memory material with mechanical property reinforcement and a plurality of stable response temperatures, and simultaneously has excellent hydrophobicity, thermal stability, weather resistance and processability.
Description
Technical Field
The invention belongs to the field of novel intelligent polymer materials, and relates to a shape memory organic silicon rubber material capable of self-reinforcing and having multiple response temperatures, and a preparation method and application thereof.
Background
The shape memory polymer is an intelligent material responding to stimulus, can generate deformation and return to an initial shape after external stimulus, and has wide application in the fields of biological materials, sensors, drivers or textiles and the like. Such as hinges for spatially deployable structures, stents, mirrors and reflectors, deformable surface materials for aircraft folds or variable camber wings, devices in the form of biomedical and biostimulation (e.g., vascular stents with shape memory polymers as drug delivery systems, smart surgical sutures and laser-activated micro-drives), textiles, automotive drives and self-healing systems.
The traditional research on shape memory polymers mainly focuses on materials such as polyurethane, vinyl polymer, epoxy resin, polyester and the like, and although the materials all have excellent mechanical properties, the traditional research still has many defects, and the use of the materials in some environments is seriously influenced. For example, in high temperature environments exceeding 200 ℃ or in severe weather environments, polyurethane, polyester and vinyl polymers all degrade and fail relatively rapidly; in a high-humidity environment, polyurethane absorbs a large amount of water, resulting in unstable shape and reduced performance; vinyl polymers, epoxy resins, polyesters and the like lack sufficient flexibility at room temperature, need to be subjected to shape change at a higher temperature, and do not have good operation performance at room temperature; vinyl polymers, epoxy resins and the like have high processing temperatures and do not have good processing properties at room temperature. In order to meet the above-mentioned requirements of more severe service environment and simple operation and processing properties, a new shape memory material is urgently needed.
The polysiloxane has excellent high temperature resistance, weather resistance, hydrophobicity, room temperature flexibility and processability due to the special organic-inorganic molecular structure, and has good application prospect in the field of shape memory. For this reason, researchers have conducted some quest to incorporate polysiloxanes into shape memory polymers. For example, Zhang et al introduced polydimethylsiloxanes of different lengths as soft segments into polycaprolactone shape memory Polymer (Journal of Polymer Science: Part A: Polymer Chemistry,2011,49,754-. Although the methods achieve the advantages of polysiloxane to a certain extent, the original mechanical properties of the material are greatly damaged, and the actual use requirements cannot be met.
Disclosure of Invention
In a first aspect of the invention there is provided the use of a blend of polyalkylmethacrylate and polysiloxane in a temperature responsive shape memory material. Wherein the blend comprises one, two or more polyalkylmethacrylates, preferably at least two, three, four, five or six
Wherein the temperature responsive shape memory material has one, two or more deformation responsive temperatures, preferably at least two deformation responsive temperatures. Further, the organic silicon rubber material can be subjected to deformation recovery under each deformation response temperature condition, and the final deformation recovery rate is more than 95%, preferably more than 98%.
Wherein the total mass of polyalkylmethacrylate in the blend is 20-50%, such as 25-45%, 30-40% of the total mass of polysiloxane.
Preferably, the form of the temperature-responsive shape memory material is not particularly limited, and may be, for example, an organic silicone rubber material, a fiber material, a film material; preferably an organic silicone rubber material.
According to the technical scheme of the invention, the blend is a liquid blend of polyalkylmethacrylate and polysiloxane, or a polymer material which is further crosslinked and solidified by the liquid blend.
According to the technical scheme of the invention, when the blend contains two or more polyalkyl methacrylates, the alkyl esters can be respectively polymerized with polysiloxane in situ to form different liquid blends and then mixed; for example, polyalkylmethacrylate a and polysiloxane form a liquid blend A, and polyalkylmethacrylate B and polysiloxane form a liquid blend B, and the liquid blend A and the liquid blend B are mixed, wherein the polyalkylmethacrylate a and the polyalkylmethacrylate B contain different alkyl groups, and the liquid blend A and the liquid blend B contain the same or different polysiloxanes.
The parts by weight of each liquid blend may be in the range of from 0.5 to 4 parts, for example from 1 to 3 parts, preferably from 1 to 2.5 parts, respectively, by weight.
Illustratively, when the blend includes liquid blend a and liquid blend B, the weight ratio of a and B may be 1:1, 2:1, 1: 2; when the liquid blend includes liquid blend a, liquid blend B, and liquid blend C, the weight ratio of A, B and C may be 1:1:1, 2:1:1, 1:2:1, 1:1: 2.
According to the technical scheme of the invention, the preparation raw materials of the liquid blend comprise the following components: alkyl methacrylate monomer, polysiloxane and compatibilizer.
According to the technical scheme of the invention, the liquid blend is prepared by dispersing the alkyl methacrylate monomer in polysiloxane solution under the action of a compatibilizer and carrying out in-situ polymerization reaction.
According to the technical scheme of the invention, the compatibilizer is a compatibilizer with the solubility parameter between polyalkylmethacrylate and polydimethylsiloxane (the solubility parameter delta is 7.5-9.5 calories 0.5 Per centimeter 1.5 ) The solvent of (1). Preferably, the compatibilizer is any one or more of toluene, ethylbenzene, cumene, o-xylene, m-xylene, p-xylene, trichloroethane and chloroethane. Further, it is characterized byThe mass-to-volume ratio (g/mL) of the compatibilizer to the polysiloxane is 1 (0.1-10), preferably 1 (0.1-5), for example 1:0.4, 1:0.6, 1: 2. Wherein the amount of compatibilizer increases with increasing viscosity of the polysiloxane.
According to the technical scheme of the invention, the in-situ polymerization reaction is compatibilization in-situ free radical polymerization reaction; preferably, the in situ polymerization reaction is carried out with the aid of a free radical initiator.
According to the technical scheme of the invention, the mass of the alkyl methacrylate monomer is 1-40% of the mass of the polysiloxane, preferably 20-40%, such as 30%, 36%, 37.5% and 40%.
According to the technical scheme of the invention, the polysiloxane comprises a polymer with a structure shown as a formula (I):
in the formula (I), R 1 Selected from hydroxy, C 1-10 Alkyl radical, C 2-10 Any of alkenyl groups; r 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Same or different, independently from each other selected from H, C 1-10 Alkyl radical, C 2-10 Alkenyl radical, C 6-14 Aryl, C substituted by one or more Rs 1-10 Any one or more of alkyl, and Rs is selected from any one or more of halogen and cyano;
m, n and q are the same or different and are independently selected from the number of 0-10000 and are not simultaneously 0.
Preferably, in the formula (I), R 1 Any one selected from methyl, hydroxyl and vinyl; r 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 The same or different, independently selected from any one or more of H, methyl, ethyl, phenyl, vinyl, trifluoropropyl and nitrile ethyl;
m is preferably selected from the group consisting of a number of 100-2000, such as 1000, 200, 400;
n is preferably selected from a number from 10 to 1000, for example 300, 15;
q is preferably selected from the group consisting of 100-2000, e.g. 200, 500, 800.
Preferably, in the formula (I), R 1 Any one selected from methyl, hydroxyl and vinyl; r 2 -R 9 The same or different, and are selected from any one or more of H, methyl, phenyl and vinyl independently.
By way of example, the polymer represented by formula (I) may be any one or a combination of polymers represented by the following formulae (II), (III), (IV):
wherein m, n, q are as defined above.
According to the technical scheme of the invention, the polysiloxane further comprises a filler, the filler can be a reinforcing filler, and the reinforcing filler is preferably at least one of MQ resin and white carbon black. Further, in the polysiloxane, the mass percentage of the filler may be 30 to 60%, preferably 45 to 55%, for example 50%. Further, the viscosity of the polysiloxane is in the range of 500-800000cp, preferably 4000-500000cp, such as 30000cp and 40000 cp.
According to the technical scheme of the invention, the alkyl methacrylate monomer has a structure shown as a formula (V):
in the formula (II), R is C 1-18 Alkyl, preferably C 1-10 The alkyl group is more preferably any of methyl, ethyl, propyl, butyl, hexyl and octylAnd (4) seed preparation.
According to an embodiment of the present invention, the alkyl methacrylate monomer may be selected from at least one of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, and n-octyl methacrylate.
According to the technical scheme of the invention, the free radical initiator is one or two or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, di-tert-butyl peroxide and dicumyl peroxide. Further, the mass of the free radical initiator is 0.1-5% of the mass of the alkyl methacrylate monomer; preferably, the mass of the free radical initiator added is 0.5-2%, for example 0.9%, 1%, 1.5%, 2% of the mass of the alkyl methacrylate monomer.
According to the technical scheme of the invention, the liquid blend can be selected from one of a liquid blend of polymethyl methacrylate and terminal vinyl polysiloxane with a structure of formula (II), a liquid blend of polymethyl methacrylate and terminal hydroxyl polysiloxane with a structure of formula (III), a liquid blend of polyethyl methacrylate and terminal vinyl polysiloxane with a structure of formula (II), a liquid blend of polyethyl methacrylate and terminal hydroxyl polysiloxane with a structure of formula (III), a liquid blend of n-propyl methacrylate and terminal vinyl polysiloxane with a structure of formula (II), a liquid blend of n-propyl methacrylate and terminal hydroxyl polysiloxane with a structure of formula (III), a liquid blend of n-butyl methacrylate and terminal vinyl polysiloxane with a structure of formula (II), a liquid blend of n-butyl methacrylate and terminal hydroxyl polysiloxane with a structure of formula (III), and the like One, two or more.
In a second aspect of the present invention, a multiple temperature-responsive shape memory blend material is provided, which is prepared from raw materials including polysiloxane and two or more alkyl methacrylate monomers. Wherein, the two or more alkyl methacrylate monomers are respectively blended with polysiloxane under the action of a compatibilizer, and are polymerized in situ under the action of an initiator to form different liquid blends, and then are mixed; or, the two or more alkyl methacrylate monomers are directly mixed with polysiloxane under the action of a compatibilizer and are polymerized in situ under the action of an initiator to form a liquid blend; each liquid blend has the meaning and dosage ratios as described above.
Wherein the multiple temperature-responsive shape memory blended material has at least two deformation-responsive temperatures, such as two, three, four, five, or six. For example, the deformation response temperature may comprise at least one of 45-55 deg.C, 60-70 deg.C, 90-100 deg.C, 130-140 deg.C.
Wherein the Young modulus of the multi-temperature response shape memory blending material is more than or equal to 1900kPa, such as more than or equal to 2000kPa, more than or equal to 2100kPa, more than or equal to 2300kPa, more than or equal to 2500kPa, and more than or equal to 2600 kPa.
Wherein the tensile strength of the multi-temperature response shape memory blending material is more than or equal to 3.5MPa, such as more than or equal to 3.8MPa, more than or equal to 4.0MPa, more than or equal to 5MPa, more than or equal to 6MPa, more than or equal to 6.5MPa, and more than or equal to 7 MPa.
Wherein the water contact angle of the multi-temperature response shape memory blend material is 110-120 degrees, such as 113-118 degrees, and exemplary values are 114 degrees, 115 degrees, 116 degrees and 117 degrees.
Wherein the temperature of 5% of the thermal weight loss of the multi-temperature response shape memory blending material is 220-260 ℃, such as 243-253 ℃, exemplary 244 ℃, 245 ℃, 246 ℃, 247 ℃, 248 ℃, 249 ℃, 250 ℃, 251 ℃ and 252 ℃.
Wherein the strength retention rate of the multi-temperature response shape memory blended material after being treated for 48 hours at 200 ℃ is more than 100 percent, such as more than or equal to 102 percent, more than or equal to 103 percent, and exemplary is 104 percent, 105 percent and 106 percent.
According to the technical scheme of the invention, the multi-temperature response shape memory blending material is in the form of an organic silicon rubber material, a fiber material and a film material; preferably an organic silicone rubber material.
According to the technical scheme of the invention, the microstructure of the multi-temperature response shape memory blending material is a sea-island structure which comprises a disperse phase and a continuous phase, wherein the disperse phase is polyalkylmethacrylate particles, and the continuous phase is a polysiloxane network.
According to the technical scheme of the invention, a nano-scale diffusion layer is arranged between the polyalkylmethacrylate particles and the polysiloxane network, and the diffusion layer is a polyalkylmethacrylate chain segment diffusion layer.
According to the technical scheme of the invention, the liquid blend is a dispersion system with macroscopic homogeneous phase and microscopic phase separation.
The third aspect of the present invention provides a method for preparing the multiple temperature response shape memory blend material, which comprises preparing a liquid blend of two or more of polyalkylmethacrylate and polysiloxane, and then crosslinking and curing.
According to the technical scheme of the invention, the preparation of the liquid blend can adopt a one-step method or a two-step method. For example, two or more alkyl methacrylate monomers are dispersed in a polysiloxane solution under the action of a compatibilizer to undergo in-situ polymerization reaction to form a liquid blend, namely a pre-cured blend; or two or more alkyl methacrylate monomers are respectively dispersed in a polysiloxane solution to carry out in-situ polymerization reaction under the action of a compatibilizer to form at least two liquid blends, then the at least two liquid blends are mixed to obtain a pre-cured blend, and the pre-cured blend is crosslinked and cured to obtain the multi-temperature response shape memory blend material.
According to an embodiment of the present invention, the ratio of the two or more alkyl methacrylate monomers is not particularly limited, and the more an alkyl ester monomer is added, the more the corresponding polymer alkyl ester particles are formed, the greater the deformation recovery occurs at the corresponding response temperature.
Preferably, the pre-cured blend is mixed with at least one selected from a cross-linking agent, an inhibitor and a catalyst and then is heated and cured, and the multi-temperature response shape memory blend material is prepared after the curing is completed.
As an embodiment of the present invention, the preparation method comprises the steps of:
(1) preparation of the precured blend: blending at least two liquid blends of polyalkylmethacrylate and polysiloxane in the above proportions;
wherein, the preparation process of each liquid blend comprises the following steps: heating a solution containing polysiloxane and a compatibilizer, adding a free radical initiator and an alkyl methacrylate monomer to perform in-situ polymerization reaction, and performing post-treatment to obtain a liquid blend of polyalkylmethacrylate and polysiloxane;
(2) and (2) mixing the pre-cured blend prepared in the step (1) with at least one selected from a cross-linking agent, an inhibitor and a catalyst, heating and curing, and preparing the multi-temperature response shape memory blend material after complete curing.
As another embodiment of the present invention, the preparation method comprises the steps of:
(1) preparation of the precured blend: heating a solution containing polysiloxane and a compatibilizer, adding a free radical initiator and at least two different alkyl methacrylate monomers to perform in-situ polymerization reaction, and performing post-treatment to obtain a liquid blend of polyalkylmethacrylate and polysiloxane;
(2) and (2) mixing the pre-cured blend prepared in the step (1) with at least one selected from a cross-linking agent, an inhibitor and a catalyst, heating and curing, and preparing the multi-temperature response shape memory blend material after complete curing.
In the preparation method of the invention, the raw material components have the meanings as described above.
According to the invention, the manner of curing in step (2) may be according to R 1 The curing can be any one of hydrosilylation, condensation and free radical.
As an embodiment of the present invention, when R in formula (I) 1 Is C 2-10 And in the alkenyl process, the precured blend, a crosslinking agent, a catalyst and an inhibitor are mixed and then heated and cured by adopting a curing mode of hydrosilylation.
According to the invention, in the curing mode of the hydrosilylation reaction, the cross-linking agent is hydrogen-containing silicone oil, and the hydrogen content in the hydrogen-containing silicone oil is 0.2-1.6%, preferably 0.5-1%, for example 0.8%;
the catalyst is a platinum catalyst;
the inhibitor is a compound containing a terminal alkenyl or alkynyl, and can be any one of 3-methyl-1-butyn-3-ol and divinyltetramethylsilane or a combination thereof.
The mass ratio of the pre-cured blend to the cross-linking agent to the inhibitor to the platinum catalyst is 100 (1-15): 0.01-1, preferably 100 (5-10): 0.05-0.5): 0.1-1;
the curing temperature is 60 ℃ to 200 ℃, for example 100 ℃.
As an embodiment of the present invention, when R in formula (I) 1 And when the hydroxyl is adopted, the pre-cured blend, a cross-linking agent and a catalyst are mixed and then heated and cured by adopting a condensation reaction curing mode.
According to the invention, in the curing mode of the condensation reaction, the cross-linking agent is any one or more of tetraalkoxysilane, trialkoxysilane, multifunctional hydrosilicon compound and polysilazane, such as tetraethoxysilane;
the catalyst is organic tin or organic titanium catalyst, such as butyl tin, stannous octoate;
the mass ratio of the pre-cured blend to the cross-linking agent to the catalyst is 100 (1-50): 0.01-2, preferably 100 (20-50): 0.05-0.5);
the curing temperature is from 25 ℃ to 150 ℃, for example 80 ℃.
As an embodiment of the present invention, when R in formula (I) 1 Is C 1-10 And in the alkyl process, the pre-cured blend and the cross-linking agent are mixed and then heated and cured by adopting a curing mode of free radical reaction.
According to the invention, in the curing mode of the free radical reaction, the cross-linking agent is at least one of dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2, 4-dichlorobenzoyl peroxide and hexane peroxide;
the mass ratio of the pre-cured blend to the cross-linking agent is 100 (0.1-8), preferably 100 (0.1-1);
the curing temperature is 150-250 ℃.
According to the invention, the pre-cured blend obtained in the step (1) can be cured after being placed at a high temperature for a long time, and the performance of the blended polymer material obtained after curing is stable.
According to the invention, the high temperature may be 120-200 ℃, preferably 180 ℃; the time can be 10-120 h, for example 100 h.
The fourth aspect of the invention provides the multi-temperature response shape memory blending material prepared by the method.
The fifth aspect of the invention provides a method for using the above multiple temperature response shape memory blending material, which comprises the steps of firstly deforming the material into a required shape under the action of an external force, and then heating to a temperature above the deformation response temperature for shape fixation. When the material is used, the material does not need to be heated to the temperature above the transition temperature to soften the material and then the shape of the material is fixed, so that the shape operability at room temperature is good.
A sixth aspect of the present invention provides the use of the multiple temperature-responsive shape-changing memory blend material in the fields of biomaterials, sensors, actuators, printing or textiles, such as spatially deployable folding structures (e.g., hinges, elastic members), stents (e.g., variable pipe diameter temperature tube stents), mirrors and reflectors, deformable surface materials for aircraft folds or variable camber wings, biomedical and bio-stimulation devices (e.g., vascular stents, smart surgical sutures), printed substrates (e.g., thermally printable substrates), temperature-responsive switches, textiles, automotive actuators and self-healing systems.
In a seventh aspect, the invention provides any of the above devices, such as printed substrates, space-expandable folded structures, stents, temperature-responsive switches, actuators, comprising the multiple temperature-responsive shape-memory blend material.
The invention has the beneficial effects that:
the invention combines the thermoplastic polymer and the organic silicon elastomer, simultaneously realizes the reinforcement effect of the thermoplastic polymer to the silicon rubber and the shape memory response switching effect, solves the problems of too low mechanical strength of the existing shape memory polymer material based on the organic silicon elastomer and great reduction of mechanical property after the existing shape memory polymer is introduced with polysiloxane, and is the organic silicon rubber shape memory material with mechanical property reinforcement and a plurality of stable response temperatures.
The invention simultaneously reserves the excellent hydrophobicity, thermal stability, weather resistance and processability of the silicon rubber. Is superior to the existing shape memory materials such as polyurethane, epoxy resin, polyester, vinyl polymer, and the like.
The shape memory organic silicon rubber blending material obtained by the invention is different from the traditional temperature response shape memory material, and the material does not need to be heated to the temperature above the transition temperature to soften the material and then is subjected to shape fixation; the material can be deformed into a required shape under the action of external force, and then the shape is fixed by heating to a temperature higher than the response temperature, so that the shape operability at room temperature is good.
The shape memory organic silicon rubber blend material obtained by the invention is different from the reported multi-temperature response material based on crystalline polyester, the response temperature of the blend material is not changed along with the content of the introduced alkyl methacrylate, and the blend material has stable response stability.
The invention provides a simple preparation method of a multi-temperature response material, which can realize the regulation and control of various stable response temperatures and has good controllability.
The invention provides a specific application of shape memory silicone rubber prepared based on the invention, which mainly comprises the following steps: the device comprises a base material capable of repeatedly performing thermal printing, a pipeline support with the temperature of the pipe diameter being variable, a temperature response switch, a folding structure with an expandable space, a driver and the like.
Definition and description of terms:
unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
Where numerical ranges are recited in the specification and claims of this application, and where numerical ranges are defined as "integers," they are to be understood as reciting both endpoints of the range and each integer within the range. For example, "an integer of 0 to 10" should be understood to describe each integer of 0, 1,2, 3, 4, 5, 6,7, 8, 9, and 10. When the numerical range is defined as "a number," it is understood to recite both the endpoints of the range, each integer within the range, and each decimal within the range. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2, 3, 4, 5, 6,7, 8, 9, and 10, but also to recite at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
“C 1-10 Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 1,2, 3, 4, 5, 6,7, 8, 9 or 10 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group, or the like, or isomers thereof. In particular, the groups have 1,2, 3, 4, 5, 6,7, or 8 carbon atoms ("C) 1-8 Alkyl groups) such as methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-octyl.
“C 2-10 Alkenyl "is understood to preferably mean a straight-chain or branched monovalent hydrocarbon radical which comprises one or more double bonds and has 2,3, 4, 5, 6,7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms (" C) 2-3 Alkenyl ") is understood to comprise more than one double bond in the alkenyl radicalIn the case of (2), the double bonds may be separated from each other or conjugated. The alkenyl group is, for example, vinyl, allyl, (E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, m-n-2-enyl, m-n-1-enyl, m-n-E-4-enyl, m-n-2-enyl, m-n-enyl, m-E-4-enyl, m-2-enyl, m-pent-1-enyl, m-2-methyl-enyl, m-2-methylvinyl, m-2-methyl-2-methylvinyl, m-but-2-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, (Z) -1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-enyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl group and 1-isopropylvinyl group.
The term "C 6-14 Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6,7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C 6-14 Aryl group "), in particular a ring having 6 carbon atoms (" C 6 Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C 9 Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C 13 Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C) 14 Aryl), such as anthracenyl.
The term "halogen" is to be understood as fluorine, chlorine, bromine or iodine, preferably fluorine.
The terms "deformation response temperature" and "response temperature" have the same meaning. Specifically, the temperature response refers to the property of the memory material which has undergone a shape change to spontaneously make a corresponding shape change under a temperature change condition (thermal stimulation); the deformation response temperature is the temperature at which the temperature responsive shape memory material is able to respond, the temperature being greater than or equal to the phase transition (e.g., crystalline transition, glass transition, melt transition) temperature of the material, and typically a temperature range not lower than the phase transition temperature. The shape memory effect is a phenomenon that after a solid material with a certain shape is deformed under a certain condition and is heated to a certain temperature, the material is completely restored to the original shape before deformation.
Drawings
FIG. 1 is a schematic photograph showing that the shape of the shape memory silicone rubber blend material in example 1 can be fixed at normal temperature.
FIG. 2 is a photograph of a shape memory silicone rubber blend material repeatedly hot-printed in example 2.
Fig. 3 is a photograph of the shape memory silicone rubber blend material used in the spatially expandable folded structure of example 3.
FIG. 4 is a photograph of the shape memory silicone rubber blend material used in the controlled size conduit stent of example 4.
Fig. 5 is a photograph of the shape-memory silicone rubber blend material for use in an actuator of example 1.
Fig. 6 is a schematic photograph of the shape memory silicone rubber blend material used in the temperature controlled switch in example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The process for preparing the liquid blends of the present invention is described in chinese patent application 2019105338869, which is incorporated herein by reference in its entirety.
The molecular weight of the polysiloxane was determined by gel permeation chromatography using a Waters column pump system (Waters1515) and a differential refractive index detector (Waters2414) with toluene as the mobile phase at 35 deg.C, a flow rate of 1ml/min, and a sample concentration of 5-10 mg/ml. The standard curve was calibrated with monodisperse polystyrene and data acquisition and analysis was performed using the software Millennium.
According to the standard GB/T528-2009, an INSTRON 5565 type microcomputer control universal testing machine is adopted to test the tensile strength, the elongation at break and the Young modulus of the multi-temperature response shape memory silicone rubber.
In the application, the strength retention rate of the shape memory silicone rubber after being treated for 48 hours at 200 ℃ refers to: percentage of tensile strength of the product after treatment at 200 ℃ to tensile strength of the same product without treatment.
The thermal weight loss analysis of the shape memory silicone rubber is tested by adopting a Pyrisl thermal analyzer of Perkin Elmer company in America, the mass of a sample is 5-10mg, the air flow is 20mL/min, the heating rate is 10 ℃/min, and the temperature is increased from 20 ℃ to 800 ℃.
The water contact angle test of the shape memory silicone rubber is carried out by adopting a dataphysics OCA20 contact angle measuring instrument, the volume of a water drop is 3 microliter, and the reading is carried out after the water drop state is stable after 10 seconds.
The method for measuring the shape fixing rate and the recovery rate of the shape memory organic silicon rubber material comprises the following steps: taking the finished products of the straight plate-shaped examples and the comparative examples as test samples, folding the samples (the length, width and height of the samples are 40mm multiplied by 4mm multiplied by 1mm) in half under the action of external force, heating the samples to a temperature above the shape memory transition temperature under the action of keeping the external force, and rapidly cooling the samples to room temperature; after the external force is removed, the deformation angle theta of the external force is recorded 1 Then raising the temperature to be higher than the thermal transition temperature of the shape memory organic silicon rubber material, simultaneously recording the change of the angle along with the time, and recording the change angle theta when the change is stable 2 Shape memory fixation rate (R) f ) And recovery ratio (R) r ) Is calculated by the method R f ＝(180-θ 1 )/180，Rr＝θ 2 /(180-θ 1 )。
Example 1
(1) 50g of a vinyl terminated polysiloxane (commercially available from Silbo rubber products Ltd, Dongguan, Inc., which comprises a polymer having a structure according to formula (II), a viscosity of 40000cp and a molecular weight of 8.36X 10 4 50 wt% of MQ containing resin) was dissolved in 30ml of toluene and heated to 90 ℃ in an oil bath; dropwise adding 20g of methyl methacrylate dissolved with 0.1g of dibenzoyl peroxide at a dropping speed of 10 drops/min, mechanically stirring, controlling the rotating speed at 120rpm, condensing and refluxing, heating to 120 ℃ after dropwise adding, treating for 10h, and vacuumizing to remove the toluene solvent and residual methyl methacrylate to obtain the liquid blend of polymethyl methacrylate and vinyl-terminated polysiloxane.
A liquid blend of polyethylmethacrylate and vinyl terminated polysiloxane was prepared according to the procedure described above with 50g of vinyl terminated polysiloxane, 30ml of toluene, 20g of ethyl methacrylate with 0.1g of dibenzoyl peroxide dissolved therein.
Uniformly mixing the liquid blend of polymethyl methacrylate and vinyl-terminated polysiloxane with the liquid blend of polyethyl methacrylate and vinyl-terminated polysiloxane according to the mass ratio of 1:1 to obtain the shape memory polymer blend before curing.
(2) And (2) uniformly mixing 62.5g of the uncured shape memory polymer blend prepared in the step (1) with 5g of hydrogen-containing silicone oil (the hydrogen content is 0.8 wt%), 0.066g of 3-methyl-1-butyn-3 ol and 0.275g of platinum catalyst, pouring the mixture into a mould, discharging bubbles, heating the mixture in a 100 ℃ oven, and completely curing to obtain the shape memory organic silicon rubber blend material of the embodiment.
The response temperature, the shape fixing temperature and fixing rate, and the sectional recovery temperature and recovery rate of the shape memory silicone rubber blending material prepared in the embodiment are shown in table 1, the mechanical properties are shown in table 3, and the water contact angle and high temperature resistance data are shown in table 4.
A schematic photograph of a material that is shape-fixable at room temperature is shown in fig. 1, and the material is foldable and rollable at room temperature. Fig. 1 shows that the shape memory silicone rubber blend material can be used for shape fixation at normal temperature, and has good flexibility and room temperature operability.
The shape memory silicone rubber blend material can be used as a driver, and a schematic picture of the driver is shown in figure 5.
Example 2
(1) Taking 50g of hydroxyl-terminated polysiloxane (purchased from Jiangxi Shishao silicone factory and comprising a polymer with a structure shown in a formula (III), wherein the viscosity is 30000cp, and the molecular weight is 7.25 multiplied by 10 4 ) Dissolving the mixture in 20ml of toluene, and heating the mixture in an oil bath kettle to 80 ℃; and (2) dropwise adding 18g of n-propyl methacrylate dissolved with 0.27g of di-tert-butyl peroxide at a dropping speed of 5 drops/min, mechanically stirring, controlling the rotating speed at 300rpm, carrying out condensation reflux, further heating to 100 ℃ after dropwise adding, treating for 20h, and vacuumizing to remove the toluene solvent and residual n-propyl methacrylate to obtain the liquid blend of the n-propyl methacrylate and the hydroxyl-terminated polysiloxane.
A liquid blend of poly-n-butyl methacrylate and hydroxyl-terminated polysiloxane was prepared as described above with 50g of hydroxyl-terminated polysiloxane, 20ml of toluene, 18g of n-butyl methacrylate with 0.27g of dibenzoyl peroxide dissolved therein.
Uniformly mixing the liquid blend of the poly-n-propyl methacrylate and the hydroxyl-terminated polysiloxane with the liquid blend of the poly-n-butyl methacrylate and the hydroxyl-terminated polysiloxane according to the mass ratio of 2:1 to obtain the shape memory polymer blend before curing.
(2) And (2) uniformly mixing 68g of the shape memory polymer blend before curing prepared in the step (1), 25g of tetraethoxysilane and 0.15g of butyltin, pouring the mixture into a mold, carrying out bubble removal treatment, heating the mixture in an oven at the temperature of 80 ℃, and completely curing to obtain the shape memory organic silicon rubber blend material of the embodiment.
The response temperature of the shape memory silicone rubber blend material prepared in this example is shown in table 1, the shape fixing temperature and fixing rate, the segment recovery temperature and recovery rate are shown in table 2, the mechanical properties are shown in table 3, and the water contact angle and high temperature resistance data are shown in table 4.
The photograph of the shape memory silicone rubber blended material used for repeatable thermal printing of the word is shown in fig. 2, and fig. 2 shows that the shape memory silicone rubber blended material can be used for repeatable thermal printing and can be used for braille base materials which can be recycled.
The schematic photograph of the shape memory silicone rubber blend material prepared in this example used in a temperature controlled switch is shown in FIG. 6.
Example 3
(1) 50g of the same terminal vinylpolysiloxane as in example 1 were dissolved in 30ml of toluene and heated to 80 ℃ in an oil bath; dropwise adding 15g of n-propyl methacrylate dissolved with 0.1g of dibenzoyl peroxide at a dropping speed of 10 drops/min, mechanically stirring, controlling the rotating speed at 120rpm, carrying out condensation reflux, heating to 100 ℃ after dropwise adding, treating for 10h, and vacuumizing to remove the toluene solvent and residual n-propyl methacrylate to obtain the liquid blend of the n-propyl methacrylate and the vinyl-terminated polysiloxane.
A liquid blend of polyethylmethacrylate and vinyl-terminated polysiloxane was prepared according to the above procedure with 50g of vinyl-terminated polysiloxane, 30ml of toluene, 15g of ethyl methacrylate with 0.1g of dibenzoyl peroxide dissolved therein, a reaction temperature of 90 ℃ and a post-treatment temperature of 120 ℃.
A liquid blend of polymethyl methacrylate and vinyl terminated polysiloxane was prepared according to the above procedure using 50g of vinyl terminated polysiloxane, 30ml of toluene, 15g of methyl methacrylate with 0.1g of dibenzoyl peroxide dissolved therein, a reaction temperature of 100 ℃ and a post-treatment temperature of 130 ℃.
Uniformly mixing the liquid blend of poly (n-propyl methacrylate) and vinyl-terminated polysiloxane, the liquid blend of poly (methyl methacrylate) and vinyl-terminated polysiloxane, and the liquid blend of poly (ethyl methacrylate) and vinyl-terminated polysiloxane according to the mass ratio of 1:1:1 to obtain the shape memory polymer blend before curing.
(2) And (2) uniformly mixing 62.5g of the uncured shape memory polymer blend prepared in the step (1) with 5g of hydrogen-containing silicone oil (the hydrogen content is 0.8 wt%), 0.066g of 3-methyl-1-butyn-3 ol and 0.275g of platinum catalyst, pouring the mixture into a mould, discharging bubbles, heating the mixture in a 100 ℃ oven, and completely curing to obtain the shape memory organic silicon rubber blend material of the embodiment.
The response temperature of the shape memory silicone rubber blend material prepared in this example is shown in table 1, the shape fixing temperature and fixing rate, the segment recovery temperature and recovery rate are shown in table 2, the mechanical properties are shown in table 3, and the water contact angle and high temperature resistance data are shown in table 4.
A photograph of the shape memory silicone rubber blend material prepared in this example for a spatially expandable folded structure is shown in fig. 3. The material may also be used for temperature responsive deployment of aircraft folded materials or antennas.
Example 4
(1) 50g of the same hydroxyl-terminated polysiloxane as in example 2 were dissolved in 20ml of toluene and heated to 80 ℃ in an oil bath; dropwise adding 16g of n-butyl methacrylate dissolved with 0.17g of di-tert-butyl peroxide at a dropping speed of 5 drops/min, mechanically stirring, controlling the rotating speed at 300rpm, carrying out condensation reflux, further heating to 100 ℃ after dropwise adding, treating for 20h, and vacuumizing to remove the toluene solvent and residual n-butyl methacrylate to obtain the liquid blend of poly-n-butyl methacrylate and hydroxyl-terminated polysiloxane.
A liquid blend of poly-n-propyl methacrylate and hydroxyl terminated polysiloxane was prepared as described above with 50g hydroxyl terminated polysiloxane, 20ml toluene, 16g n-propyl methacrylate with 0.17g dibenzoyl peroxide dissolved.
A liquid blend of poly-n-propyl methacrylate and hydroxyl terminated polysiloxane was prepared according to the above procedure with 50g hydroxyl terminated polysiloxane, 20ml toluene, 16g ethyl methacrylate with 0.17g dibenzoyl peroxide dissolved therein, reaction temperature 90 ℃ and post treatment temperature 120 ℃.
Uniformly mixing the liquid blend of poly (n-butyl methacrylate) and hydroxyl-terminated polysiloxane, the liquid blend of poly (n-propyl methacrylate) and hydroxyl-terminated polysiloxane, and the liquid blend of poly (ethyl methacrylate) and hydroxyl-terminated polysiloxane according to the mass ratio of 2:1:1 to obtain the shape memory polymer blend before curing.
(2) And (2) uniformly mixing 68g of the shape memory polymer blend before curing prepared in the step (1), 25g of tetraethoxysilane and 0.15g of butyltin, pouring the mixture into a mould, discharging bubbles, heating the mixture in an oven at the temperature of 80 ℃, and completely curing to obtain the shape memory organic silicon rubber blend material.
The response temperature of the shape memory silicone rubber blend material prepared in this example is shown in table 1, the shape fixing temperature and fixing rate, the segment recovery temperature and recovery rate are shown in table 2, the mechanical properties are shown in table 3, and the water contact angle and high temperature resistance data are shown in table 4.
The picture of the shape memory silicone rubber blend material used for the controllable size pipeline bracket prepared in the embodiment is shown in figure 4, which illustrates that the material can be used in the biomedical field.
Comparative example 1
50g of the same vinyl-terminated polysiloxane as in example 1 was uniformly mixed with 5g of hydrogen-containing silicone oil (hydrogen content: 0.8 wt%), 0.066g of 3-methyl-1-butyn-3 ol and 0.275g of platinum catalyst, poured into a mold, subjected to foam removal treatment, heated in an oven at 100 ℃, and completely cured to obtain a sample of this example.
The response temperature of the sample is shown in Table 1, the shape fixing temperature and fixing rate, the stage recovery temperature and recovery rate are shown in Table 2, the mechanical properties are shown in Table 3, and the water contact angle and high temperature resistance data are shown in Table 4.
Comparative example 2
50g of hydroxyl-terminated polysiloxane identical to that in example 2, 25g of tetraethoxysilane and 0.15g of butyltin are uniformly mixed, poured into a mold, subjected to foam discharging treatment, heated in an oven at 80 ℃, and completely cured to obtain a comparative sample of the example.
The response temperature of the sample is shown in Table 1, the shape fixing temperature and fixing rate, the stage recovery temperature and recovery rate are shown in Table 2, the mechanical properties are shown in Table 3, and the water contact angle and high temperature resistance data are shown in Table 4.
TABLE 1 response temperatures of the examples and comparative examples
| Product(s) | Response temperature (. degree. C.) |
| Example 1 | 95、135 |
| Example 2 | 50、65 |
| Example 3 | 65、95、135 |
| Example 4 | 50、65、95 |
| Comparative example 1 | Is free of |
| Comparative example 2 | Is free of |
TABLE 2 shape fixing temperature and fixing ratio, and stage recovery temperature and recovery ratio of the examples and comparative examples
TABLE 3 mechanical properties of the examples and comparative examples
TABLE 4 Water contact Angle and high temperature resistance of the examples and comparative examples
From the above data and the accompanying drawings, it can be seen that: the data in table 1 show that introducing polyalkylmethacrylate with different phase transition temperatures into the silicone rubber achieves corresponding response temperatures, which correspond to the type of polyalkylmethacrylate one by one and do not change with the introduced content. The data in table 2 show that the shape fixation rate of the shape memory silicone rubber blend material prepared by the present invention becomes greater as the incorporation content of polyalkylmethacrylate increases; at different response temperatures, the material can generate corresponding recovery processes; the larger the content of a certain polyalkyl methacrylate is, the larger the shape recovery degree of the material at the corresponding response temperature is, and the final recovery rate is more than 98 percent when the material is heated to the maximum response temperature. The data in Table 3 show that compared with pure silicone rubber, the introduction of the polyalkylmethacrylate improves the mechanical properties of the original material, increases the tensile strength by 1-2MPa, increases the Young modulus by 500-600KPa, and slightly reduces the elongation at break. The data in Table 4 show that the water contact angle of the shape memory organic silicon rubber blending material prepared by the invention is not obviously changed compared with that of the original silicon rubber, and the excellent hydrophobic property of the original organic silicon rubber is kept; the corresponding temperature is slightly reduced when the thermal weight loss is 5 percent, the strength retention rate of the product after the product is treated at 200 ℃ for 48 hours is more than 100 percent and slightly increased, and the excellent high temperature resistance of the original silicon rubber is maintained.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. Use of a blend of polyalkylmethacrylates and polysiloxanes in a multiple temperature-responsive shape memory material, wherein the blend comprises at least two polyalkylmethacrylates;
the multi-temperature response shape memory material has at least two deformation response temperatures;
the total mass of the polyalkylmethacrylate in the blend accounts for 20-50% of the total mass of the polysiloxane;
the blend is a liquid blend of polyalkylmethacrylate and polysiloxane, or a polymer material which is further cross-linked and solidified by the liquid blend; when the blend contains two or more polyalkylmethacrylates, the polyalkylmethacrylates are separately polymerized in situ in the polysiloxane to form different liquid blends;
the polysiloxane comprises a polymer with a structure shown in a formula (I):
in the formula (I), R 1 Selected from hydroxy, C 1-10 Alkyl radical, C 2-10 Any of alkenyl groups; r 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Same or different, independently from each other selected from H, C 1-10 Alkyl radical, C 2-10 Alkenyl radical, C 6-14 Aryl radicals, substituted by one or more R s Substituted C 1-10 Any one or more of alkyl, R s Any one or more of halogen and cyano;
m, n and q are the same or different and are independently selected from the number of 0-10000 and are not 0 at the same time;
the structure of the alkyl methacrylate monomer is shown as the formula (V):
in the formula (V), R is C 1-10 An alkyl group;
the multi-temperature response shape memory material is prepared by the following method: respectively dispersing two or more alkyl methacrylate monomers in a polysiloxane solution under the action of a compatibilizer to perform in-situ polymerization reaction to form at least two liquid blends, and then mixing the at least two liquid blends to obtain a pre-cured blend; mixing the pre-cured blend with at least one of a cross-linking agent, an inhibitor and a catalyst, and then heating and curing to obtain the multi-temperature response shape memory blend material after complete curing;
the mode of curing is according to R 1 The curing is any one of hydrosilylation reaction, condensation reaction and free radical reaction;
when R in the formula (I) 1 Is C 2-10 In the alkenyl process, a curing mode of hydrosilylation reaction is adopted, and the pre-cured blend is mixed with a cross-linking agent, a catalyst and an inhibitor and then is heated and cured;
when R in the formula (I) 1 When the hydroxyl is adopted, the pre-cured blend, a cross-linking agent and a catalyst are mixed and then heated and cured by adopting a condensation reaction curing mode;
when R in the formula (I) 1 Is C 1-10 When in alkyl, the pre-cured blend and the cross-linking agent are mixed and then heated and cured by adopting a curing mode of free radical reaction; the compatibilizer is a solvent with the solubility parameter between that of the polyalkylmethacrylate and the polydimethylsiloxane;
the microstructure of the multi-temperature response shape memory blending material is a sea-island structure and comprises a disperse phase and a continuous phase, wherein the disperse phase is polyalkylmethacrylate particles, and the continuous phase is a polysiloxane network;
a nano-scale diffusion layer exists between the polyalkylmethacrylate particles and the polysiloxane network, and the diffusion layer is a polyalkylmethacrylate chain segment diffusion layer.
2. Use according to claim 1, wherein the parts by weight of each of the liquid blends are respectively comprised between 0.5 and 4 parts by weight.
3. The use according to claim 1, characterized in that the polysiloxane further comprises a filler, the filler is a reinforcing filler, and the reinforcing filler is at least one of MQ resin and white carbon black.
4. The use of claim 1, wherein the alkyl methacrylate monomer has the structure of formula (V):
in the formula (V), R is any one of methyl, ethyl, propyl, butyl, hexyl and octyl.
5. The use according to claim 4, wherein the alkyl methacrylate monomer is selected from at least one of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate and n-octyl methacrylate.
6. The use according to claim 1, wherein the mass to volume ratio of the polysiloxane to the compatibilizer is 1g (0.1-10) mL, and the mass of the alkyl methacrylate monomer is 1-40% of the mass of the polysiloxane.
7. Use according to claim 1, wherein the in situ polymerization reaction is carried out with the aid of a free radical initiator.
8. Use according to claim 7, wherein the free radical initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide.
9. The use according to claim 1, wherein the polymer represented by formula (I) is any one or a combination of polymers represented by the following formulas (II), (III), (IV):
10. the use according to claim 9, wherein the liquid blend is selected from the group consisting of a liquid blend of polymethyl methacrylate and terminal vinyl polysiloxane having the structure of formula (II), a liquid blend of polymethyl methacrylate and terminal hydroxy polysiloxane having the structure of formula (III), a liquid blend of polyethyl methacrylate and terminal vinyl polysiloxane having the structure of formula (II), a liquid blend of polyethyl methacrylate and terminal hydroxy polysiloxane having the structure of formula (III), a liquid blend of n-propyl methacrylate and terminal vinyl polysiloxane having the structure of formula (II), a liquid blend of n-propyl methacrylate and terminal hydroxy polysiloxane having the structure of formula (III), a liquid blend of n-butyl methacrylate and terminal vinyl polysiloxane having the structure of formula (II), one or more of poly (n-butyl methacrylate) and a liquid blend of a hydroxyl terminated polysiloxane having the structure of formula (III).
11. The multi-temperature response shape memory blending material is characterized in that the preparation raw materials of the material comprise polysiloxane and more than two alkyl methacrylate monomers; wherein, the two or more alkyl methacrylate monomers are respectively blended with polysiloxane under the action of a compatibilizer, and are polymerized in situ under the action of an initiator to form different liquid blends, and then are mixed;
each liquid blend is a liquid blend according to any one of claims 1 to 10;
wherein the multi-temperature response shape memory blend material has at least two deformation response temperatures.
12. The multiple temperature response shape memory blend material of claim 11, wherein the young's modulus of the multiple temperature response shape memory blend material is greater than or equal to 1900 kPa;
the tensile strength of the multi-temperature response shape memory blending material is more than or equal to 3.5 MPa;
the water contact angle of the multi-temperature response shape memory blending material is 110-120 degrees;
the temperature of 5 percent of thermal weight loss of the multi-temperature response shape memory blending material is 220-260 ℃;
the strength retention rate of the multi-temperature response shape memory blend material after being treated for 48 hours at 200 ℃ is more than 100%.
13. The method for preparing a multiple temperature response shape memory blend material according to claim 11 or 12, comprising preparing a liquid blend of polysiloxane and two or more polyalkylmethacrylates, followed by crosslinking and curing;
the preparation of the liquid blend adopts a two-step method: respectively dispersing more than two alkyl methacrylate monomers in a polysiloxane solution under the action of a compatibilizer to perform in-situ polymerization reaction to form at least two liquid blends, and mixing the at least two liquid blends to obtain a pre-cured blend; mixing the pre-cured blend with at least one selected from a cross-linking agent, an inhibitor and a catalyst, and then heating and curing to obtain the multi-temperature response shape memory blend material after complete curing;
the mode of curing is according to R 1 The curing is three reactions of hydrosilylation, condensation and free radicalAny one of the above embodiments;
when R in the formula (I) 1 Is C 2-10 In the alkenyl process, the pre-cured blend, a cross-linking agent, a catalyst and an inhibitor are mixed and then heated and cured by adopting a curing mode of hydrosilylation reaction;
when R in the formula (I) 1 When the hydroxyl is adopted, the pre-cured blend, a cross-linking agent and a catalyst are mixed and then heated and cured by adopting a condensation reaction curing mode;
when R in the formula (I) 1 Is C 1-10 And in the alkyl process, the pre-cured blend and the cross-linking agent are mixed and then heated and cured by adopting a curing mode of free radical reaction.
14. A method for using the multiple temperature response shape memory blending material of claim 11 or 12, characterized in that the material is deformed into a desired shape under the action of external force, and then the temperature is raised to above the deformation response temperature for shape fixation.
15. Use of the multiple temperature-responsive shape-changing memory blend material according to claim 11 or 12 in the fields of biomaterials, sensors, actuators, printing or textiles.
16. A device comprising the multiple temperature-responsive shape-memory blend material of claim 11 or 12, wherein the device is a printed substrate, a spatially-deployable folding structure, a stent, a temperature-responsive switch, or an actuator.
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| CN108456291A (en) * | 2018-01-24 | 2018-08-28 | 成都德科立高分子材料有限公司 | A kind of shape memory type energy-absorbing protection moisture-penetrating composite material and preparation method thereof |
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| CN1048713A (en) * | 1989-06-19 | 1991-01-23 | 日本尤尼卡株式会社 | A kind of shape memory elastic body |
| KR100750220B1 (en) * | 2006-09-28 | 2007-08-17 | 금호타이어 주식회사 | Tire tread rubber composition comprising shape memory resin |
| CN102604298A (en) * | 2010-12-31 | 2012-07-25 | 中国科学院成都有机化学有限公司 | Polydimethylsiloxane (PDMS)-based form memory compound |
| CN106832940A (en) * | 2017-01-24 | 2017-06-13 | 南京天朗制药有限公司 | The moulding shape-memory material of room temperature |
| CN108456291A (en) * | 2018-01-24 | 2018-08-28 | 成都德科立高分子材料有限公司 | A kind of shape memory type energy-absorbing protection moisture-penetrating composite material and preparation method thereof |
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