CN111704787A - Thermosetting shape memory polymer with intelligent response to friction performance and preparation method and application thereof - Google Patents
Thermosetting shape memory polymer with intelligent response to friction performance and preparation method and application thereof Download PDFInfo
- Publication number
- CN111704787A CN111704787A CN202010640298.8A CN202010640298A CN111704787A CN 111704787 A CN111704787 A CN 111704787A CN 202010640298 A CN202010640298 A CN 202010640298A CN 111704787 A CN111704787 A CN 111704787A
- Authority
- CN
- China
- Prior art keywords
- shape
- thermosetting
- shape memory
- nano
- memory polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a thermosetting shape memory polymer with intelligent response to friction performance, a preparation method and application thereof, belonging to the technical field of micro/nano surface interfaces. The shape memory polymer has a micro/nano surface, the surface shape of the micro/nano surface is a temporary shape before light and/or heat triggering, and the surface friction performance is anisotropic; after light and/or heat triggering, the surface shape is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic; the thermosetting shape memory polymer is made of a thermosetting polymer with dynamic covalent bonds, and the thermosetting polymer contains nano-fillers with photo-thermal conversion performance. The thermosetting shape memory polymer with the intelligent response of friction performance provided by the invention has good cycle performance, the surface shape of the thermosetting shape memory polymer can be repeatedly shaped by virtue of a dynamic covalent bond, and the repeated reciprocating switching between a temporary shape and an initial shape can be realized by virtue of shape memory, so that the reusability of the material is greatly improved.
Description
Technical Field
The invention relates to the technical field of micro/nano surface interfaces, in particular to a thermosetting shape memory polymer with intelligent response to friction performance, and a preparation method and application thereof.
Background
With the continuous development of bionics, the preparation of artificial bionic surfaces by imitating natural organisms is an effective method for preparing special functional surfaces. In recent years, the research and the recognition of the surface interface microstructure with special functions in the nature and the inspiration obtained from the surface interface microstructure are carried out, the bionic construction is carried out by adopting physical and chemical means, the regulation and the control of the friction performance of a micro/nano surface interface are further researched, the anisotropy and the isotropic intelligent response performance of friction are expanded, and the bionic friction surface microstructure becomes a new research hotspot of bionic tribology.
The thermosetting polymer has high mechanical strength and good pressure resistance and heat resistance, however, the thermosetting material is a three-dimensional cross-linked network, has the property of being infusible and insoluble, and cannot be reprocessed and reshaped once being processed and formed. Therefore, thermosetting polymer micro/nano surfaces tend to be single in structure and do not have the function of intelligent response of friction performance.
Disclosure of Invention
In view of the above, the present invention aims to provide a thermosetting shape memory polymer with intelligent response of friction performance, and a preparation method and applications thereof. The micro/nano surface of the thermosetting shape memory polymer provided by the invention has the function of intelligent response of friction performance, and the surface shape and the friction performance of the thermosetting shape memory polymer can realize photo-thermal intelligent regulation and control.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a thermosetting shape memory polymer with intelligent response to friction performance, which has a micro/nano surface, wherein the thermosetting shape memory polymer is made of a thermosetting polymer with a dynamic covalent bond, and the thermosetting polymer contains a nano filler with photo-thermal conversion performance;
the surface shape of the micro/nano surface is a temporary shape before light and/or heat triggering, and the surface friction performance is anisotropic; after light and/or heat triggering, the surface shape is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic;
the temporary shape is an asymmetric array shape formed by a plurality of nano columns; the initial shape is a symmetrical array formed by a plurality of nano-pillars.
Preferably, the light triggering condition is infrared light with the wavelength of 808nm, and the heat triggering temperature is 10-30 ℃ higher than the glass transition temperature of the thermosetting polymer; the light and/or heat triggering time is 5-20 s.
Preferably, the dynamic covalent bond is one or more of a dynamic ester bond, a dynamic disulfide bond, a dynamic imine bond, a dynamic acylhydrazone bond, an olefin metathesis bond, a siloxane-silanol exchange bond and a dynamic vinylamine ester bond.
Preferably, the nanofiller with the photo-thermal conversion performance is one or more of graphene, nano ferroferric oxide, a carbon nano tube and black phosphorus;
the grain diameter of the nano filler is 5 nm-50 mu m;
the mass percentage of the nano filler in the thermosetting polymer is 0.1-5%.
Preferably, the shape of the initial-shaped nano-columns is cylindrical, square or trapezoidal, the height of the nano-columns is 100-300 mu m, and the distance between the nano-columns is 10-100 mu m;
the shape of the temporary-shaped nano-columns is independently one of a cylinder shape, a square shape and a trapezoid shape, the height of the nano-columns is independently 100-300 mu m, and the distance is independently 10-100 mu m.
The invention provides a preparation method of the thermosetting shape memory polymer with intelligent response to friction performance, which comprises the following steps:
(1) mixing a reaction raw material with a dynamic covalent bond, a nano filler with a photo-thermal conversion performance and a catalyst, and carrying out thermocuring to obtain a thermosetting shape memory polymer;
(2) performing first hot stamping on the thermosetting shape memory polymer by using an initial shape template to form a micro/nano surface with an initial shape on the surface of the thermosetting shape memory polymer; the temperature of the first hot stamping is 10-30 ℃ higher than the exchange reaction temperature of the dynamic covalent bond;
(3) and heating the thermosetting shape memory polymer with the initial shape to be 20-30 ℃ above the glass transition temperature, performing secondary hot stamping on the micro/nano surface with the initial shape by using a temporary shape template, and cooling to obtain the thermosetting shape memory polymer with intelligent response to friction performance.
Preferably, the catalyst is bicyclic guanidine or dibutyltin dilaurate, and the mass of the catalyst is 1-5% of that of the reaction raw material with the dynamic covalent bond.
Preferably, the load of the first hot stamping is 0.5-5 MPa, and the time is 10 s-120 min.
Preferably, the load of the second hot stamping is 0.5-5 MPa, and the time is 20 s-30 min.
The invention provides application of the thermosetting shape memory polymer with intelligent response to friction performance in the field of intelligent friction control and surface interface adhesion.
The invention provides a thermosetting shape memory polymer with intelligent response to friction performance, which has a micro/nano surface, wherein the surface shape of the thermosetting shape memory polymer is a temporary shape before light and/or heat triggering, and the surface friction performance is anisotropic; after light and/or heat triggering, the surface shape is restored to the original shape from the temporary shape, and the surface friction property is isotropic. The polymer material used in the invention is a polymer with dynamic covalent bonds, and the polymer contains nanofillers with light-heat conversion performance. In the invention, the polymer with dynamic covalent bonds has shape memory effect (the polymer is used as a stationary phase by virtue of the cross-linking of dynamic chemical bonds, the glass transition is used as a reversible phase, the molecular chain of the polymer is easy to move above the glass transition temperature, the polymer can be shaped into a shape under the action of external force, the shape can be fixed after being cooled to low temperature, after being heated to the transition temperature again, the shape can be recovered under the action of the previously stored external force due to the movement of the molecular chain, and the dynamic covalent bonds can generate rapid reversible exchange reaction at high temperature (generally 180 ℃), so that the topological structure of the polymer network is rearranged, and the thermosetting polymer still has the capability of being reprocessed into a temporary shape after being molded into an initial shape; after the polymer with dynamic covalent bonds is formed into an initial shape, the surface friction performance of the polymer is isotropic, after the second hot stamping, the obtained temporary shape has an asymmetric array structure, and shows great difference of friction coefficients during sliding friction in different directions, and the surface friction performance of the polymer is anisotropic. Due to the fact that the nanofiller with the photo-thermal conversion performance is introduced into the thermosetting polymer, after light and/or heat triggering, the surface shape of the polymer is recovered to the original shape from the temporary shape, and the surface friction performance is recovered to the isotropy from the anisotropy. The thermosetting shape memory polymer with the intelligent response of friction performance provided by the invention has good cycle performance, the surface shape of the thermosetting shape memory polymer can be repeatedly shaped by virtue of a dynamic covalent bond, and the repeated reciprocating switching between a temporary shape and an initial shape can be realized by virtue of shape memory, so that the reusability of the material is greatly improved.
The invention provides a preparation method of the thermosetting shape memory polymer with intelligent response to friction performance, which comprises the steps of mixing reaction raw materials with dynamic covalent bonds, nano filler with photo-thermal conversion performance and a catalyst, carrying out thermocuring to obtain the thermosetting shape memory polymer, carrying out first hot stamping on the thermosetting shape memory polymer to obtain a micro-nano surface with an initial shape, carrying out second hot stamping on the thermosetting shape memory polymer with the initial shape to obtain a micro-nano surface with a temporary shape, wherein the polymer is the thermosetting shape memory polymer with intelligent response to friction performance. When the first hot stamping is carried out, because the hot stamping temperature is higher than the exchange reaction temperature of the dynamic covalent bonds, reversible exchange recombination occurs between the dynamic covalent bonds in the polymer after external force is applied to the polymer, so that the topological structure of a polymer network is changed, the internal stress in the polymer is dissipated, and the entropy of a system chain segment is kept unchanged; due to the lack of entropic drive, the resulting micro/nano surface does not return to a flat surface after the external force is removed, and becomes the original shape of the polymer, at which point the frictional properties of the polymer surface are isotropic. In the second hot stamping, the temperature of the polymer is raised to be 20-30 ℃ above the glass transition temperature, and only the polymer molecular chain segment can move and the crosslinking form of the total polymer is unchanged because the temperature is only above the glass transition temperature in the second hot stamping forming, so that the polymer can be formed into a temporary shape; the obtained temporary shape has an asymmetric array structure, and shows great difference of friction coefficients when sliding friction is carried out in different directions, so that the friction performance is changed from isotropy to anisotropy.
The invention also provides application of the thermosetting shape memory polymer with intelligent response to friction performance in the field of intelligent friction control and surface interface adhesion.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a thermosetting shape memory polymer with intelligent response to friction performance according to the present invention;
FIG. 2 is a graph of the thermomechanical properties of a thermoset shape memory polymer of example 1;
FIG. 3 is a shape memory cycle performance curve for the thermoset shape memory polymer of example 1.
Detailed Description
The invention provides a thermosetting shape memory polymer with intelligent response to friction performance, which has a micro/nano surface, wherein the thermosetting shape memory polymer is made of a thermosetting polymer with a dynamic covalent bond, and the thermosetting polymer contains a nano filler with photo-thermal conversion performance;
the surface shape of the micro/nano surface is a temporary shape before light and/or heat triggering, and the surface friction performance is anisotropic; after light and/or heat triggering, the surface shape is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic;
the temporary shape is an asymmetric array shape formed by a plurality of nano columns; the initial shape is a symmetrical array formed by a plurality of nano-pillars.
In the present invention, the dynamic covalent bond is preferably one or more of a dynamic ester bond, a dynamic disulfide bond, a dynamic imine bond, a dynamic acylhydrazone bond, an olefin metathesis bond, a siloxane-silanol exchange bond, and a dynamic vinylamine ester bond. As a specific embodiment of the invention, the raw material for synthesizing the polymer with dynamic covalent bonds comprises epoxy resin and one or more of 4,4' -dithiodiphenylamine, adipic acid, suberic acid, sebacic acid and azelaic acid.
In the invention, the nano filler with the photo-thermal conversion performance is preferably one or more of graphene, nano ferroferric oxide, carbon nano tubes and black phosphorus; the particle size of the nanofiller is preferably 5nm to 50 μm, more preferably 10nm to 5 μm. In the invention, the mass percentage of the nano filler in the thermosetting polymer is preferably 0.1-5%, and more preferably 1-3%; in the present invention, the nanofiller is dispersed between polymer molecular segments.
In the invention, the initial shape is a symmetrical array formed by a plurality of nano columns, the shape of the nano columns in the initial shape is preferably a cylinder, a square or a trapezoid, and the height of the nano columns is preferably 100-300 μm, and more preferably 200 μm; the preferred interval is 10-100 μm, and the more preferred interval is 40-60 μm; the diameter or side length of the nano-column is preferably 10-150 μm, and more preferably 50-100 μm. As a specific example of the present invention, when the initial shape is a micro/nano array shape composed of cylindrical shapes, the cylindrical shapes have a diameter of 20 μm, a height of 200 μm, and a pitch of adjacent cylindrical shapes of 30 μm.
In the invention, the temporary shape is an asymmetric array shape formed by a plurality of nano columns; the shape of the temporary-shaped nano-pillar is preferably a cylinder, a square or a trapezoid, and the height of the nano-pillar is preferably 100-300 μm, and more preferably 200 μm; the distance is preferably 10-100 μm independently, and more preferably 40-60 μm; the diameter or the side length of the nano-column is preferably 10-150 mu m independently, and more preferably 50-100 mu m independently. As a specific example of the present invention, the temporary shape is a micro/nano array shape consisting of a cylindrical shape, the lateral and longitudinal cylinders have the same size, the height is 200 μm, the diameter is 20 μm, but the cylinder pitch is different.
In the invention, the light-triggered infrared light with the wavelength of 808nm, and the heat-triggered temperature is preferably higher than the glass transition temperature of the polymer by 10-30 ℃, and more preferably higher than 20 ℃; the light and/or heat contact time is preferably 5-20 s, and more preferably 10 s. When the trigger condition is thermal trigger, the shape recovery is triggered when the temperature of the polymer is higher than the glass transition temperature, the micro/nano surface shape of the thermosetting shape memory polymer is recovered to the original shape from the temporary shape, and the surface friction property is recovered to the isotropy from the anisotropy. When the triggering condition is light triggering or light-heat triggering, as the nanofiller with light-heat conversion performance is introduced into the polymer, under the action of the nanofiller, light energy is converted into heat, so that the surface shape of the polymer is recovered to the initial shape from the temporary shape, and the surface friction performance is recovered to isotropy from anisotropy.
When the surface shape of the polymer needs to be changed from isotropy to anisotropy, the surface of the thermosetting shape memory polymer with the initial shape is subjected to hot embossing, the surface shape of the thermosetting shape memory polymer is changed into a temporary shape from the initial shape, and the friction performance is changed from isotropy to anisotropy.
The thermosetting shape memory polymer with the intelligent response of friction performance provided by the invention has good cycle performance, the surface shape of the thermosetting shape memory polymer can realize repeated switching between a temporary shape and an initial shape, and the reusability of the material is greatly improved.
The invention provides a preparation method of a thermosetting shape memory polymer with intelligent response to friction performance, which comprises the following steps:
(1) mixing a reaction raw material with a dynamic covalent bond, a nano filler with a photo-thermal conversion performance and a catalyst, and carrying out thermocuring to obtain a thermosetting shape memory polymer;
(2) performing first hot stamping on the thermosetting shape memory polymer by using an initial shape template to form a micro/nano surface with an initial shape on the surface of the thermosetting shape memory polymer; the temperature of the first hot stamping is 10-30 ℃ higher than the exchange reaction temperature of the dynamic covalent bond;
(3) and heating the thermosetting shape memory polymer with the initial shape to be 20-30 ℃ above the glass transition temperature, performing secondary hot stamping on the micro/nano surface with the initial shape by using a temporary shape template, and cooling to obtain the thermosetting shape memory polymer with intelligent response to friction performance.
The invention mixes the reaction raw material with dynamic covalent bond, nano filler with photo-thermal conversion performance and catalyst, and carries out thermocuring to obtain the thermosetting shape memory polymer. In the invention, the dynamic covalent bond is preferably one or more of a dynamic ester bond, a dynamic disulfide bond, a dynamic imine bond, a dynamic acylhydrazone bond, an olefin double decomposition bond, a siloxane-silanol exchange bond and a dynamic vinylamine ester bond; in the invention, the reaction raw material with dynamic covalent bonds is preferably one or more of bisphenol A glycidyl ether epoxy resin, 1, 6-hexamethylene diisocyanate, 4' -dithiodiphenylamine, polyethylene glycol, adipic acid, suberic acid, sebacic acid and azelaic acid. In a specific embodiment of the invention, the reaction raw material with dynamic covalent bond is preferably bisphenol a glycidyl ether epoxy resin E-51 and sebacic acid, and the molar ratio of the bisphenol a glycidyl ether epoxy resin E-51 to the sebacic acid is preferably 1: 1; or the reaction raw materials containing the dynamic covalent bonds are preferably polyethylene glycol and 1, 6-hexamethylene diisocyanate, and the molar ratio of the polyethylene glycol to the 1, 6-hexamethylene diisocyanate is preferably 1: 2-2: 1.
In the present invention, the kind and amount of the nano-filler having the photothermal conversion performance are the same as those described above, and thus, the details are not described herein. In the present invention, the catalyst is preferably bicyclic guanidine (TBD) or dibutyltin dilaurate (DBTDL), and the mass of the catalyst is preferably 1% of the mass of the reaction raw material containing dynamic covalent bonds.
In the invention, the thermosetting raw material further preferably comprises a cross-linking agent, the cross-linking agent is preferably glycerol, and the mass of the cross-linking agent is preferably 5-30% of the mass of the reaction raw material containing the dynamic covalent bond.
The mixing mode of the invention has no special requirement, and the mixing mode known to the person skilled in the art can be used, specifically stirring and mixing.
In the invention, the hot curing method is preferably a direct pouring method, and specifically, the mixed preparation raw materials are directly poured into a polytetrafluoroethylene mold for heating; in the invention, the mixed preparation raw material is in a liquid state, and bubbles of the liquid mixed raw material need to be removed before casting. The invention has no special requirements on the casting mode, and the casting mode known to the skilled person can be used. The present invention has no special requirement on the temperature and time conditions of the thermal curing, and the thermal curing temperature and time which are well known to those skilled in the art can be selected according to the kind of the reaction raw material having dynamic covalent bonds. As a specific embodiment of the invention, when the reaction raw materials with dynamic covalent bonds are bisphenol A glycidyl ether epoxy resin E-51 and sebacic acid, the temperature for thermal curing is 180 ℃ and the time is 12 hours; when the reaction raw materials containing the dynamic covalent bonds are polyethylene glycol and 1, 6-hexamethylene diisocyanate, the thermosetting is divided into two stages, the thermosetting temperature of the first stage is 80 ℃, the thermosetting time is 2 hours, the thermosetting temperature of the second stage is 120 ℃, the thermosetting time is 2 hours, and the heating rate from the first stage to the second stage is preferably 5 ℃/min.
After the thermosetting shape memory polymer is obtained, carrying out first hot stamping on the thermosetting shape memory polymer by using an initial shape template, and forming a micro/nano surface with an initial shape on the surface of the thermosetting shape memory polymer; the temperature of the first hot stamping is 10-30 ℃ higher than the exchange reaction temperature of the dynamic covalent bond, and preferably 20 ℃. In the invention, the material of the initial shape template is preferably silicon, and the surface shape of the initial shape template is matched with the inner and outer initial shapes of the micro/nano surface of the thermosetting shape memory polymer; the invention does not require any particular source for the template, and templates of sources well known to those skilled in the art may be used. In the invention, the load of the first hot stamping is preferably 0.5-5 MPa, and more preferably 1-3 MPa; the time is preferably 10s to 120min, and more preferably 10 to 60 min. In the invention, the exchange reaction temperature of the dynamic ester bond is 180-200 ℃, the exchange reaction temperature of the dynamic disulfide bond is 180-200 ℃, the exchange reaction temperature of the dynamic imine bond is 160-210 ℃, the exchange reaction temperature of the dynamic acylhydrazone bond is 150-200 ℃, the exchange reaction temperature of the olefin double decomposition bond is 120-180 ℃, the exchange reaction temperature of the siloxane-silanol exchange bond is 100-180 ℃, and the exchange reaction temperature of the dynamic vinylamine ester bond is 130-200 ℃. When the first hot stamping is carried out, because the hot stamping temperature is higher than the exchange reaction temperature of the dynamic covalent bonds, reversible exchange recombination occurs between the dynamic covalent bonds in the polymer after external force is applied to the polymer, so that the topological structure of a polymer network is changed, the internal stress in the polymer is dissipated, and the entropy of a system chain segment is kept unchanged; due to the lack of entropic drive, the resulting micro/nano surface does not return to a flat surface after the external force is removed, and becomes the original shape of the polymer, at which point the frictional properties of the polymer surface are isotropic.
The thermosetting shape memory polymer with the initial shape is heated to a temperature 20-30 ℃ above the glass transition temperature, the temporary shape template is used for carrying out secondary hot stamping on the thermosetting shape memory polymer with the initial shape, and the thermosetting shape memory polymer with intelligent response of friction performance is obtained after cooling. In the invention, the material of the temporary shape template is preferably silicon, and the surface shape of the temporary shape template is matched with the inner and outer temporary shapes of the micro/nano surface of the thermosetting shape memory polymer; the invention does not require any particular source for the template, and templates of sources well known to those skilled in the art may be used. In the invention, the micro/nano surface of the thermosetting shape memory polymer with the initial shape is heated to 20-30 ℃ above the glass transition temperature, the invention also preferably carries out heat preservation after heating, and the heat preservation time is preferably 10 min. In the invention, the load of the second hot stamping is preferably 0.5-5 MPa, and more preferably 2-4 MPa; the time is preferably 20s to 30min, and more preferably 5 to 10 min.
The invention has no special requirements on the cooling method, and the cooling method known by the technicians in the field can be used, in particular to natural cooling.
In the invention, the flow diagram of the preparation method of the thermosetting shape memory polymer with intelligent response of friction performance is shown in fig. 1, wherein in fig. 1, T is the hot stamping temperature, Tp is the exchange reaction temperature of dynamic covalent bonds, and Tg is the glass transition temperature.
The invention also provides application of the thermosetting shape memory polymer with intelligent response to friction performance in the field of intelligent friction control and surface interface adhesion.
The present invention provides a thermosetting shape memory polymer with intelligent response to friction performance, its preparation method and application, which are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) The photo-thermal response shape memory polymer composite material is prepared by adopting a direct pouring method: uniformly mixing bisphenol A glycidyl ether epoxy resin E-51(5mmol), sebacic acid (5mmol), nano ferroferric oxide (the particle diameter is 20nm, the mass is 2% of the sum of the mass of the bisphenol A glycidyl ether epoxy resin and the weight of the sebacic acid), and a catalyst TBD (the mass is 1% of the sum of the mass of the bisphenol A glycidyl ether epoxy resin and the weight of the sebacic acid), pouring the mixture into a tetrafluoro mold after removing air bubbles, performing heat curing at 180 ℃ for 12 hours, and demolding to obtain the thermosetting shape memory polymer.
(2) The method comprises the steps of carrying out first hot stamping (hot stamping temperature is 180 ℃ and load is 1MPa) on a shape memory polymer at 20 ℃ above the dynamic covalent bond exchange reaction temperature by using a silicon template with a cylindrical surface (the diameter of a cylinder is 20 microns, the depth of the cylinder is 200 microns and the distance of the cylinder is 30 microns), keeping the temperature for 30min, then cooling to normal temperature, removing the load to obtain a thermosetting shape memory polymer micro/nano surface with an initial shape, testing the friction force in each direction in a reciprocating mode by using a 14-FW friction tester, wherein the friction force in each direction is the same in numerical value when the surface slides, and the surface friction performance is isotropic.
(3) Heating the micro/nano surface of the thermosetting shape memory polymer with the initial shape to 80 ℃ and keeping for 10min, carrying out second hot embossing on the surface by using a silicon template (the array is 180 mu m high and the intervals are different) with an asymmetric array on the surface, carrying out load of 2MPa and keeping for 10min, cooling to obtain the thermosetting shape memory polymer with the friction performance intelligent response of the temporary shape, testing the friction force in each direction in a reciprocating mode by a 14-FW friction tester, wherein the friction force in the radial direction and the friction force in the latitudinal direction are greatly different when the surface slides, and the surface friction performance is shown to be anisotropic.
And thermally triggering the thermosetting shape memory polymer with the friction performance intelligent response of the temporary shape, wherein the heating temperature is 100 ℃, the time is 10s, the micro/nano surface of the polymer after thermal triggering has the shape memory performance, the surface shape of the polymer is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic.
The thermo-mechanical property curve of the thermosetting shape memory polymer is shown in fig. 2, the peak of the loss factor is the glass transition temperature, the rubber-state modulus of the storage modulus curve reflects the crosslinking degree, and the sharp drop of the storage modulus indicates that the molecular chain of the material is softened near the glass transition temperature, the mobility is strong, and the material is shaped by external force easily.
The process of step (3) and thermal triggering is repeated for the thermosetting shape memory polymer micro/nano surface which returns to the original shape, the shape memory cycle performance curve is shown in fig. 3, and as can be seen from fig. 3, the shape fixing rate and the recovery rate of the polymer micro/nano surface are more than 99% within 11 cycles.
Example 2
(1) The photo-thermal response shape memory polymer composite material is prepared by adopting a direct pouring method, bisphenol A glycidyl ether epoxy resin E-51(1mmol), sebacic acid (1mmol), graphene (3-5 layers, the mass of the graphene is 2% of the sum of the mass of the bisphenol A glycidyl ether epoxy resin and the mass of the sebacic acid), and a catalyst TBD (the mass of the catalyst TBD is 1% of the sum of the mass of the bisphenol A glycidyl ether epoxy resin and the mass of the sebacic acid) are uniformly mixed, bubbles are removed, the mixture is poured into a tetrafluoro mold, the mixture is subjected to heat curing at 180 ℃ for 12 hours, and the thermosetting shape memory polymer is obtained after demolding.
(2) The method comprises the steps of carrying out first hot stamping (hot stamping temperature is 190 ℃ and load is 1MPa) on a shape memory polymer at 30 ℃ above the dynamic covalent bond exchange reaction temperature by using a silicon template with a cylindrical surface (cylinder diameter is 40 mu m, depth is 200 mu m and spacing is 30 mu m), keeping for 30min, then cooling to normal temperature, removing the load to obtain a thermosetting shape memory polymer micro/nano surface with an initial shape, testing the friction force in each direction in a reciprocating mode by using a 14-FW friction tester, wherein the friction force in each direction is the same in numerical value when the surface slides, and the surface friction performance is isotropic.
(3) Heating the micro/nano surface of the thermosetting shape memory polymer with the initial shape to 80 ℃ and keeping for 10min, carrying out second hot embossing on the surface by using an asymmetric array silicon template (the array is 180 mu m high and the spacing is unequal), keeping for 10min under the load of 2MPa, cooling to obtain the thermosetting shape memory polymer with intelligent response of friction performance, testing the friction force in each direction in a reciprocating manner by using a 14-FW friction tester, wherein the friction force in the radial direction and the friction force in the latitudinal direction have larger difference when the surface slides, and the surface friction performance is shown as anisotropy.
And thermally triggering the thermosetting shape memory polymer with the friction performance intelligent response of the temporary shape, wherein the heating temperature is 80 ℃, the time is 10s, the micro/nano surface of the polymer after thermal triggering has the shape memory performance, the surface shape is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic.
Example 3
(1) The photo-thermal response shape memory polymer composite material is prepared by adopting a direct pouring method, uniformly mixing polyethylene glycol (5mol), 1, 6-hexamethylene diisocyanate (10mol), a cross-linking agent glycerol (10% of the mass of the sum of 1, 6-hexamethylene diisocyanate), a catalyst dibutyltin dilaurate (1% of the mass of the sum of 1, 6-hexamethylene diisocyanate) and graphene (1% of the mass of the sum of 1, 6-hexamethylene diisocyanate), pouring the mixture in a tetrafluoro mold, carrying out thermal curing at 80 ℃ for 2 hours, carrying out thermal curing at 120 ℃ for 2 hours, and demolding to obtain the thermosetting shape memory polymer.
(2) The method comprises the steps of carrying out first hot stamping (hot stamping temperature is 180 ℃) on a shape memory polymer at the temperature of 20 ℃ above the dynamic covalent bond exchange reaction temperature by using a template with cubic (the length and width of the cube is 20 mu m, the depth of the cube is 200 mu m, and the distance between the cubic and the depth of the cube is 30 mu m) deep grooves, keeping the temperature for 30min, then cooling to normal temperature, removing load, obtaining a thermosetting shape memory polymer micro/nano surface with an initial shape, testing the friction force in each direction in a reciprocating mode by using a 14-FW friction tester, wherein the friction force in each direction is the same in numerical value when the surface slides, and the surface friction performance is shown to be the.
(3) Heating the micro/nano surface of the thermosetting shape memory polymer with the initial shape to 60 ℃ and keeping for 10min, carrying out second hot embossing on the surface by using an asymmetric array silicon template (the array is 180 mu m high and the spacing is unequal), keeping for 10min under the load of 3MPa, cooling to obtain the thermosetting shape memory polymer with intelligent response of friction performance, testing the friction force in each direction in a reciprocating manner by using a 14-FW friction tester, wherein the friction force in the radial direction and the friction force in the latitudinal direction have larger difference when the surface slides, and the surface friction performance is shown as anisotropy.
The thermosetting shape memory polymer with the temporary shape and intelligent response to the friction performance is subjected to light triggering, infrared light with the wavelength of 808nm lasts for 10s, the micro/nano surface of the polymer subjected to light triggering has the shape memory performance, the surface shape is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A thermoset shape memory polymer with intelligent response to friction performance has a micro/nano surface,
the thermosetting shape memory polymer is made of a thermosetting polymer with dynamic covalent bonds, and the thermosetting polymer contains nano-filler with light-heat conversion performance;
the surface shape of the micro/nano surface is a temporary shape before light and/or heat triggering, and the surface friction performance is anisotropic; after light and/or heat triggering, the surface shape is recovered to the original shape from the temporary shape, and the surface friction performance is isotropic;
the temporary shape is an asymmetric array shape formed by a plurality of nano columns; the initial shape is a symmetrical array formed by a plurality of nano-pillars.
2. The thermosetting shape memory polymer with intelligent response to friction performance, according to claim 1, is characterized in that the condition of light trigger is infrared light with wavelength of 808nm, and the temperature of heat trigger is 10-30 ℃ higher than the glass transition temperature of the thermosetting polymer; the light and/or heat triggering time is 5-20 s.
3. The tribological smart responsive thermoset shape memory polymer of claim 1, wherein the dynamic covalent bond is one or more of a dynamic ester bond, a dynamic disulfide bond, a dynamic imine bond, a dynamic acylhydrazone bond, an olefin metathesis bond, a siloxane-silanol exchange bond, and a dynamic vinylamine bond.
4. The thermosetting shape memory polymer with intelligent response to friction performance of claim 1, wherein the nano filler with photo-thermal conversion performance is one or more of graphene, nano ferroferric oxide, carbon nano tube and black phosphorus;
the grain diameter of the nano filler is 5 nm-50 mu m;
the mass percentage of the nano filler in the thermosetting polymer is 0.1-5%.
5. A tribological smart responsive thermoset shape memory polymer according to claim 1, wherein the initial shape of the nanopillars is cylindrical, square or trapezoidal, the nanopillars having a height of 100 to 300 μ ι η and a pitch of 10 to 100 μ ι η;
the shape of the temporary-shaped nano-columns is independently one of a cylinder shape, a square shape and a trapezoid shape, the height of the nano-columns is independently 100-300 mu m, and the distance is independently 10-100 mu m.
6. A method for preparing a thermosetting shape memory polymer with intelligent response to friction performance according to any one of claims 1 to 5, comprising the following steps:
(1) mixing a reaction raw material with a dynamic covalent bond, a nano filler with a photo-thermal conversion performance and a catalyst, and carrying out thermocuring to obtain a thermosetting shape memory polymer;
(2) performing first hot stamping on the thermosetting shape memory polymer by using an initial shape template to form a micro/nano surface with an initial shape on the surface of the thermosetting shape memory polymer; the temperature of the first hot stamping is 10-30 ℃ higher than the exchange reaction temperature of the dynamic covalent bond;
(3) and heating the thermosetting shape memory polymer with the initial shape to be 20-30 ℃ above the glass transition temperature, performing secondary hot stamping on the micro/nano surface with the initial shape by using a temporary shape template, and cooling to obtain the thermosetting shape memory polymer with intelligent response to friction performance.
7. The preparation method according to claim 6, wherein the catalyst is bicyclic guanidine or dibutyltin dilaurate, and the mass of the catalyst is 1-5% of the mass of the reaction raw material having the dynamic covalent bond.
8. The manufacturing method according to claim 6, wherein the first hot embossing load is 0.5 to 5MPa and the time is 10s to 120 min.
9. The preparation method according to claim 6, wherein the load of the second hot stamping is 0.5-5 MPa, and the time is 20 s-30 min.
10. The application of the thermosetting shape memory polymer with intelligent response to friction performance according to any one of claims 1 to 5 or the thermosetting shape memory polymer with intelligent response to friction performance prepared by the preparation method according to any one of claims 6 to 9 in the field of intelligent friction control and surface interface adhesion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010640298.8A CN111704787B (en) | 2020-07-06 | 2020-07-06 | Thermosetting shape memory polymer with intelligent response to friction performance and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010640298.8A CN111704787B (en) | 2020-07-06 | 2020-07-06 | Thermosetting shape memory polymer with intelligent response to friction performance and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111704787A true CN111704787A (en) | 2020-09-25 |
| CN111704787B CN111704787B (en) | 2021-03-09 |
Family
ID=72545879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010640298.8A Active CN111704787B (en) | 2020-07-06 | 2020-07-06 | Thermosetting shape memory polymer with intelligent response to friction performance and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111704787B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480452A (en) * | 2020-11-27 | 2021-03-12 | 中国科学院兰州化学物理研究所 | Method for modifying polymer surface by anisotropic texture/metal ion implantation |
| CN113337082A (en) * | 2021-07-15 | 2021-09-03 | 中国科学院兰州化学物理研究所 | Shape memory biphenyl type epoxy resin composite material capable of realizing near-infrared response and programming and preparation method and application thereof |
| CN113801569A (en) * | 2021-09-17 | 2021-12-17 | 西北工业大学 | Regulation and control lubricating coating, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090087348A1 (en) * | 2007-02-16 | 2009-04-02 | Richard Otto Claus | Sensor applications |
| CN108342002A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of dynamic aggregation object and its application with hybrid cross-linked network |
| CN109265716A (en) * | 2018-08-01 | 2019-01-25 | 清华大学 | The processing method and thermosetting polymer composite material of thermoset macromolecule material |
| CN111215044A (en) * | 2020-02-06 | 2020-06-02 | 浙江理工大学 | Ga based on flexible substrate2O3Nano-column photocatalytic material and preparation method thereof |
-
2020
- 2020-07-06 CN CN202010640298.8A patent/CN111704787B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090087348A1 (en) * | 2007-02-16 | 2009-04-02 | Richard Otto Claus | Sensor applications |
| CN108342002A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of dynamic aggregation object and its application with hybrid cross-linked network |
| CN109265716A (en) * | 2018-08-01 | 2019-01-25 | 清华大学 | The processing method and thermosetting polymer composite material of thermoset macromolecule material |
| CN111215044A (en) * | 2020-02-06 | 2020-06-02 | 浙江理工大学 | Ga based on flexible substrate2O3Nano-column photocatalytic material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480452A (en) * | 2020-11-27 | 2021-03-12 | 中国科学院兰州化学物理研究所 | Method for modifying polymer surface by anisotropic texture/metal ion implantation |
| CN112480452B (en) * | 2020-11-27 | 2021-08-24 | 中国科学院兰州化学物理研究所 | Method for modifying polymer surface by anisotropic texture/metal ion implantation |
| CN113337082A (en) * | 2021-07-15 | 2021-09-03 | 中国科学院兰州化学物理研究所 | Shape memory biphenyl type epoxy resin composite material capable of realizing near-infrared response and programming and preparation method and application thereof |
| CN113801569A (en) * | 2021-09-17 | 2021-12-17 | 西北工业大学 | Regulation and control lubricating coating, preparation method and application |
| CN113801569B (en) * | 2021-09-17 | 2022-05-31 | 西北工业大学 | Regulation and control lubricating coating, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111704787B (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111704787B (en) | Thermosetting shape memory polymer with intelligent response to friction performance and preparation method and application thereof | |
| Xie et al. | Photo-cross-linking: a powerful and versatile strategy to develop shape-memory polymers | |
| US20200339730A1 (en) | Processable, Tunable Thiol-ene Crosslinked Polyurethane Shape Memory Polymers | |
| CN100482614C (en) | Collidal forming process for preparing high strength light ceramic material | |
| CN109280336B (en) | Multiple-drive type shape memory composite material and preparation method thereof | |
| CN1014221B (en) | Method and apparatus for moulding using the solid flowable polymer as medium | |
| CN109910208A (en) | A kind of core model and preparation method thereof and composite material shape tube forming method | |
| CN105601875A (en) | Urethane bond/urea bond exchange based plastic shape memory polymer system and application method thereof | |
| CN105884969A (en) | Intelligent aerogel with dual responses and adjustable response behaviors and preparation method thereof | |
| JP6271130B2 (en) | Manufacturing method of composite material | |
| CN107814940A (en) | A kind of preparation method of shape-memory polymer and its application in 4D printings | |
| CN101847786A (en) | Reflecting surface of deployable antenna based on shape memory polymer and manufacturing method of skeleton structure thereof | |
| CN112778566A (en) | Preparation method of high-power foamed polypropylene board | |
| CN111359554B (en) | Large-particle-size polyurethane phase change microcapsule and preparation method thereof | |
| CN107365401A (en) | A kind of near-infrared response backbone chain type liquid crystal elastomer and preparation method thereof | |
| CN113276440A (en) | Preparation method and unfolding and recycling method of thin-wall column shell structure | |
| CN103897337A (en) | Nano graphite flake reinforced shape-memory composite material and preparation method thereof | |
| CN109575334A (en) | A kind of shape memory epoxy resin prepreg and preparation method thereof | |
| CN102774008A (en) | Method of fabricating shape memory polymer-based three-dimensional devices | |
| CN101015973A (en) | Aeration steel shape memory composite film | |
| CN108003330B (en) | High-performance shape memory biodegradable material | |
| CN106977875A (en) | A kind of low-temperature catalyzed solidification aldol resin system and preparation method thereof | |
| Al-Humairi et al. | Future prospects: shape memory features in shape memory polymers and their corresponding composites | |
| CN111808259A (en) | 3D printing silicone rubber and preparation method and application thereof | |
| CN110315751A (en) | Based on the restructural micro-nano structure of liquid-gas phase transition material and manufacture, control method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |