CN113817310A - Shape memory composite material and preparation method and application thereof - Google Patents

Shape memory composite material and preparation method and application thereof Download PDF

Info

Publication number
CN113817310A
CN113817310A CN202110842587.0A CN202110842587A CN113817310A CN 113817310 A CN113817310 A CN 113817310A CN 202110842587 A CN202110842587 A CN 202110842587A CN 113817310 A CN113817310 A CN 113817310A
Authority
CN
China
Prior art keywords
polycaprolactone
pcl
shape memory
phase
composite material
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
Application number
CN202110842587.0A
Other languages
Chinese (zh)
Other versions
CN113817310B (en
Inventor
陈丽娟
牛利
蔡细森
韩冬雪
刘振邦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou University
Original Assignee
Guangzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangzhou University filed Critical Guangzhou University
Priority to CN202110842587.0A priority Critical patent/CN113817310B/en
Publication of CN113817310A publication Critical patent/CN113817310A/en
Application granted granted Critical
Publication of CN113817310B publication Critical patent/CN113817310B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a shape memory composite material and a preparation method and application thereof, wherein the shape memory composite material comprises a stationary phase and a reversible phase, and the stationary phase and the reversible phase are connected to form an interpenetrating polymer network structure; the stationary phase is a material with the functions of memorizing and recovering the original shape; the reversible phase is a material with deformability. The composite material has self-repairing and shape memory functions. The composite material has the characteristic dimension from 1 mu m to 100 mu m, the precision of a printed sample piece is higher, and a more complex geometric 3D sample can be prepared.

Description

Shape memory composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a shape memory composite material and a preparation method and application thereof.
Background
The 3D printing (3D printing) technology, also called additive manufacturing technology, is a kind of rapid prototyping technology, which is a technology for constructing an object by using a bondable material such as powdered metal, plastic or the above composite material and the like through layer-by-layer printing on the basis of a digital model file with the assistance of a computer. It is faster, more flexible and cheaper than conventional manufacturing processes, and especially when producing a relatively small number of parts, and more importantly, it allows the manufacture of very complex models that cannot be manufactured by conventional processes. The printing apparatus includes direct structuring technology (DIW), inkjet printing, Selective Laser Sintering (SLS), digital light processing technology (DLP), Stereolithography (SLA), Fused Deposition Modeling (FDM), and the like. The 3D printing is mainly applied to five fields of transportation, aerospace, industrial equipment, consumer electronics and medical treatment.
Conventional shape memory polymer materials (SMPs) are based on permanently cross-linked covalent network structures using methacrylate-based monomers and cross-linking agents, which have some shape memory but no self-healing capability. Once any damage in the polymeric material due to thermal, mechanical, chemical and/or uv radiation stimulation of these covalent networks is difficult to detect and repair, it can only be discarded, resulting in additional material costs and environmental burdens.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
a shape memory composite material is provided.
The second technical problem to be solved by the invention is:
a preparation method of the composite material for 3D printing is provided.
The third technical problem to be solved by the invention is:
use of the above composite material for 3D printing.
In order to solve the first technical problem, the invention adopts the technical scheme that:
a shape memory composite material:
the device comprises a fixed phase and a reversible phase, wherein the fixed phase and the reversible phase are connected in a crossed mode to form an interpenetrating polymer network structure;
the stationary phase is a material with photocuring capacity and the functions of memorizing and recovering the original shape;
the reversible phase is a material with deformability.
An Interpenetrating Polymer Network (IPN) is a polymer network structure formed by two or more polymer blends that are entangled with each other at the molecular level and cross-linked in a chemically bonded manner.
According to one embodiment of the invention, the stationary phase comprises urethane acrylate.
Polyurethane acrylate (PUA) is a photo-curing material with excellent comprehensive performance, which utilizes polyurethane, the molecule of which contains acrylic acid functional group and urethane bond, the acrylic acid functional group is an oligomer formed by double bond crosslinking reaction under the combined action of illumination and photoinitiator, and the oligomer is a functional group formed by common free radicals in 3D printing; the urethane bond is characterized in that multiple hydrogen bonds can be formed among high polymer molecular chains, so that the polyurethane film has excellent mechanical wear resistance and flexibility and high elongation at break.
According to one embodiment of the present invention, the above-mentioned semicrystalline polycaprolactone is included.
Polycaprolactone (PCL) is a biodegradable high molecular material widely used, and is linear aliphatic polyester obtained by ring-opening polymerization of epsilon-caprolactone (epsilon-CL) in a body or a solution in the presence of a catalyst or an initiator; it is a semi-crystalline polymer, has better thermal stability, regular molecular chains and good flexibility; good biocompatibility, flexibility, biodegradability and permeability, so that the application of the composite material in the field of biological materials is extremely wide.
Hydrogen bonds are formed between hydroxyl on the surface of Polycaprolactone (PCL) and carboxyl of polyurethane acrylate (PUA), so that an Interpenetrating Polymer Network (IPN) composite material with an interpenetrating cross-linked structure can be formed.
The polyurethane acrylate (PUA) is used as a stationary phase and has the functions of memorizing and restoring the original shape, and the Polycaprolactone (PCL) is used as a reversible phase and can change the shape.
In addition, the Polycaprolactone (PCL) linear polymer also endows the 4D printing structure with self-healing capacity, a crystalline region existing in the semi-crystalline Polycaprolactone (PCL) serves as a physical crosslinking site, and a large number of hydroxyl groups in the Polycaprolactone (PCL) and a urethane bond of polyurethane interact through hydrogen bonds to form a reversible dynamic hydrogen bond crosslinked Interpenetrating Polymer Network (IPN).
Adding a "time" dimension in 3D printing is 4D printing.
The shape memory mechanism of the composite material for 3D printing described above is: the shape memory polymer material comprises a fixed phase and a reversible phase, wherein the fixed phase has the functions of memorizing and restoring the original shape; the reversible phase then ensures that the molded product can change shape. Aliphatic polyurethane acrylate is used as a stationary phase, Polycaprolactone (PCL) is used as a reversible phase, when the temperature is raised to be higher than the glass transition temperature (Tg), the microscopic Brownian motion of the molecular chain of the reversible phase Polycaprolactone (PCL) is intensified, the fixed phase polyurethane acrylate (PUA) is still in a curing state, the composite material is deformed by certain external force at the moment, the external force is kept for cooling, and the reversible phase Polycaprolactone (PCL) is cured to obtain a stable new shape, namely a temporary shape. When the temperature is raised to be higher than Tg, the reversible phase Polycaprolactone (PCL) is softened, the fixed phase is kept to be solidified, the molecular chain of the reversible phase Polycaprolactone (PCL) is reactivated through movement, and the reversible phase Polycaprolactone (PCL) gradually reaches a thermodynamic equilibrium state under the action of the recovery stress of the fixed phase polyurethane acrylate (PUA), namely macroscopically shows a recovery state.
The self-repairing mechanism of the composite material for 3D printing is as follows: when heating, above-mentioned a combined material's that is used for 3D to print crystallinity can acutely descend, the hydrogen bond between polyurethane acrylate (PUA) and Polycaprolactone (PCL) will be opened, during the cooling, hydroxyl in Polycaprolactone (PCL) will be through hydrogen bond interact with between polyurethane acrylate (PUA)'s the urethane bond, the mechanical properties of damage structure is under dynamic reversible hydrogen bond effect, room temperature can all realize complete selfreparing to between the melting point Tr temperature of stationary phase, and the higher temperature is Polycaprolactone (PCL) segment motion ability that can reverse phase the stronger, the faster of restoreing.
According to one embodiment of the present invention, the viscosity of the composite material is 1000cps to 3000 cps.
The molecular weight of PCL is high, Mw is about 80000, and the fluidity at 100 ℃ is poor, so that the PCL cannot be well mixed with PUA, and a photo-curing resin with uniform fluidity cannot be obtained.
In order to solve the second technical problem, the invention adopts the technical scheme that:
a method for preparing the composite material for 3D printing comprises the following steps:
mixing the stationary phase, the reversible phase and a photoinitiator, and adding a diluent to obtain a mixed solution;
and (3) placing the mixed solution under an ultraviolet lamp, selecting an ultraviolet light transmission area, and carrying out ultraviolet light initiated polymerization to form the composite material with the interpenetrating polymer network structure.
According to an embodiment of the present invention, the photoinitiator includes diphenyl- (4-phenylsulfide) phenyl sulfonium hexafluoroantimonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
According to one embodiment of the present invention, the diluent comprises 4-Acetoacetylmorpholine (ACMO).
The Polycaprolactone (PCL) molecular chain segment and the polyurethane acrylate (PUA) molecular chain segment are firstly mixed uniformly through physical blending, double bonds in the polyurethane acrylate (PUA) and monomer ACMO are polymerized under ultraviolet light initiated polymerization to form a cross-linked network structure with larger molecular weight, and the self-made polymer Polycaprolactone (PCL) with self-repairing and shape memory characteristics is inserted into the cross-linked network of the polyurethane acrylate (PUA) and the ACMO to form the composite material with an Interpenetrating Polymer Network (IPN) structure.
The preparation process adopts a selective area light curing technology (Liquid Crystal Display): the selective area photocuring technology is developed based on Digital Light Processing (DLP) research. The selective area light curing technology (LCD) technology utilizes a computer to control a selective light-transmitting area of a screen of the selective area light curing technology (LCD), and then radiation light is enabled to transmit the transparent area to expose and cure the composite material, so that the required product can be printed by layer solidification and superposition.
The selective area photocuring technology can realize the rapid manufacturing of a complex three-dimensional structure with the characteristic dimension of 1-100 mu m, the printed sample piece has higher precision, and a more complex geometric 3D sample can be prepared.
The preparation method not only improves the performance of the composite material, but also simplifies the whole preparation process and reduces the production cost. Therefore, the 3D printing technology is combined with a physical blending method, so that the preparation difficulty of a Polycaprolactone (PCL)/polyurethane acrylate (PUA) material is reduced, and the preparation accuracy of the 4D printing shape memory polymer and the geometric complexity of preparing a three-dimensional assembly are improved.
A method for preparing the polycaprolactone comprises the following steps of:
and adding 0.5-6 parts of catalyst and 1.5-10 parts of photoinitiator into 50-200 parts of epsilon-caprolactone, and irradiating for 1.5-5.5 h by using a mercury lamp to obtain the polycaprolactone.
According to one embodiment of the invention, the catalyst comprises oxalic acid.
The prepared Polycaprolactone (PCL) has the advantages that on one hand, the raw material cost is reduced on the basis of raw materials, on the other hand, the prepared molecular weight is only 5000-11000, the molecular weight is moderate, and the Polycaprolactone (PCL) can be compounded with other resins without being dissolved by an organic solvent.
In another aspect, the invention also relates to the application of the shape memory composite material in a sensor and a semiconductor.
In yet another aspect of the present invention, there is also provided a use of the shape memory composite in a 3D medical device.
One of the above technical solutions has at least one of the following advantages or beneficial effects:
(1) polycaprolactone (PCL) is used as reversible phase, and polyurethane acrylate (PUA) is used as stationary phase. When the temperature is raised to be higher than the glass transition temperature (Tg), the micro Brownian motion of the molecular chain of the reversible phase Polycaprolactone (PCL) is intensified, the fixed phase polyurethane acrylate (PUA) is still in a curing state, the composite material is deformed by certain external force at the moment, the external force is kept for cooling the composite material, and the reversible phase Polycaprolactone (PCL) is cured to obtain a stable new shape, namely a temporary shape. When the temperature is raised to be higher than Tg, the reversible phase Polycaprolactone (PCL) is softened, the fixed phase is kept to be solidified, the molecular chain of the reversible phase Polycaprolactone (PCL) is reactivated through movement, and the reversible phase Polycaprolactone (PCL) gradually reaches a thermodynamic equilibrium state under the action of the recovery stress of the fixed phase polyurethane acrylate (PUA), namely macroscopically shows a recovery state. Based on the above, the composite material of the invention has a shape memory function.
(2) With the crystallization district that exists in semicrystalline Polycaprolactone (PCL) act as the physics crosslinking point, through hydrogen bond interaction between the carbamate bond of hydroxyl and polyurethane in Polycaprolactone (PCL), the interpenetrating polymer network structure (IPN) of reversible dynamic hydrogen bond crosslinking has been formed, during the heating, above-mentioned hydrogen bond will be opened, during the cooling, above-mentioned hydrogen bond is the re-crosslinking again, the structure of above-mentioned combined material damage is under the hydrogen bond effect of dynamic reversible, can all realize complete selfreparing between the fusing point Tr temperature of room temperature to the stationary phase, and the higher temperature Polycaprolactone (PCL) segment motion ability that can reverse the phase is stronger, the faster of restoreing.
(3) The selective area photocuring technology is applied to the preparation process, so that the rapid manufacturing of the complex three-dimensional structure with the characteristic dimension of the composite material from 1 mu m to 100 mu m is realized, the printed sample piece has higher precision, and a more complex geometric 3D sample can be prepared.
(4) DMF, CH are also required in the conventional preparation method of Polycaprolactone (PCL)2Cl2The PCL is dissolved by the organic solvent with large polarity, and the Polycaprolactone (PCL) prepared by the invention is dissolved at the temperature of 55-60 DEG CThe Polycaprolactone (PCL) prepared by the method has the advantages that the molecular weight is only 5000-11000, the molecular weight is moderate, and the Polycaprolactone (PCL) can be compounded with other resins without being dissolved by an organic solvent.
(5) The molecular weight of PCL sold in the market is very high, Mw is about 60000-80000, and the flowability is very poor at 100 ℃, so that the PCL and the PUA cannot be well and uniformly mixed, and the PCL with the flowability and the uniform performance cannot be obtained. The Polycaprolactone (PCL) prepared by the invention is used for preparing the composite material, and the composite material with the viscosity of 1000cps to 3000cps can be obtained at 60 ℃.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a pictorial view of a 3D printer used in selective area Light Curing (LCD) technology.
Fig. 2C ═ C (810cm-1) real-time plot of the double bond peak.
FIG. 3 is a graph of double bond conversion for Interpenetrating Polymer Network (IPN) elastomers as Polycaprolactone (PCL) is added.
FIG. 4 stress-strain graph of interpenetrating polymer network structure (IPN) elastomer with Polycaprolactone (PCL).
Fig. 5 is a scratch self-healing test chart of polyurethane acrylate (PUA) -Polycaprolactone (PCL) -30 interpenetrating polymer network structure (IPN) elastomer.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout.
The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, if there are first, second, third, etc. described only for the purpose of distinguishing technical features, it is not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be understood that the orientation or positional relationship referred to in the description of the orientation, such as the upper, lower, left, right, etc., is based on the orientation or positional relationship shown in the drawings, and is only for convenience of description and simplicity of description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that unless otherwise explicitly defined, terms such as arrangement, installation, connection and the like should be broadly understood, and those skilled in the art can reasonably determine the specific meanings of the terms in the present invention in combination with the detailed contents of the technical solutions.
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Firstly, the preparation conditions of Polycaprolactone (PCL) with different molecular weights are explored:
oxalic acid is used as a catalyst, a cationic photoinitiator UV6976 (diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluoroantimonate) is used as a photoinitiator, the ring-opening polymerization of an epsilon-caprolactone monomer is catalyzed and initiated, and poly epsilon-caprolactone (PCL) is prepared from the raw materials. According to the weight, Polycaprolactone (PCL) is prepared by two methods of heating in water bath for 10 hours and irradiating by a mercury lamp (35 min-5.5 hours).
Example 1
S1, weighing two parts of 15.00g of epsilon-caprolactone, adding 2% of oxalic acid and 5% of photoinitiator 6976 into the first part, and reacting for 10 hours under the heating of water bath at 60 ℃, wherein the serial number is Polycaprolactone (PCL) -1; the raw materials are not added into the second part, and the second part is heated in water bath at 60 ℃ for 10h, and the serial number is Polycaprolactone (PCL) -2. Wherein the obtained Polycaprolactone (PCL) -2 is liquid, and it is considered that no Polycaprolactone (PCL) is obtained or that the molecular weight of the obtained Polycaprolactone (PCL) is very small.
S2 subjecting the Polycaprolactone (PCL) -1 obtained above to1H NMR confirmed whether the resulting milky white solid was Polycaprolactone (PCL). And (3) testing results: chemical shift (delta) ═ 3.7 is-CH2-an absorption peak of a hydrogen atom on O-CO-, δ ═ 1.2 is an absorption peak of a hydrogen atom on-C-H-, and the area ratio of the two absorption peaks is 2: 3; delta-CH at 4.252-absorption peak of hydrogen protons on O-; delta 2.6 is-O-CO-CH2-absorption peak of upper hydrogen atom; an overlapped absorption peak is positioned at the position of delta-1.7 and is matched with the structural unit of polycaprolactone.
S3 infrared spectrum characterization of the Polycaprolactone (PCL) -1 obtained above was performed to confirm whether the generated milky white solid was Polycaprolactone (PCL). And (3) testing results: at wavenumber 1727.93cm-1Characteristic absorption peak of C ═ O; at 2944.14-2866.40 cm-1Is represented by-CH2-The stretching vibration absorption peak of (1); at 1468.39-1364.32 cm-1The absorption peak is the C-H in-plane bending vibration absorption peak; at 1291.60-1182.51 cm-1Is a C-C stretching vibration absorption peak; at 3434.47cm-1The absorption peak is O-H stretching vibration absorption peak; at 726.68cm-1The absorption peak is O-H bending vibration absorption peak.
S4, performing DSC representation on the obtained Polycaprolactone (PCL) -1, wherein the test range is room temperature to 80 ℃, and the heating rate is 2 ℃/min. The Polycaprolactone (PCL) -1 absorption peak, melting point, was found to be 59.30.
Example 2
S1 four portions of 15.00g of epsilon-caprolactone are weighed, and oxalic acid and a cationic photoinitiator UV6976 are respectively used as variables, and the time (3.5min-5.5h) is used as a variable.
Wherein: adding 2% oxalic acid into the first part of epsilon-caprolactone, and irradiating for 35min by a mercury lamp, wherein the serial number is Polycaprolactone (PCL) -3;
wherein: adding 2% oxalic acid into the second epsilon-caprolactone, irradiating for 5.5h by using a mercury lamp, and numbering Polycaprolactone (PCL) -4;
wherein: adding 5% of cationic photoinitiator UV6976 into the third epsilon-caprolactone, and irradiating for 1.5h by using a mercury lamp, wherein the serial number is Polycaprolactone (PCL) -5;
wherein: and adding 5% of cationic photoinitiator UV6976 into the fourth part of epsilon-caprolactone, and irradiating for 5.5 hours by using a mercury lamp, wherein the serial number is Polycaprolactone (PCL) -6.
Wherein, when 5% cationic photoinitiator UV6976 is added and the irradiation is carried out for 3.5min under a mercury lamp, the obtained product is still liquid, and Polycaprolactone (PCL) is not obtained or the molecular weight of the obtained Polycaprolactone (PCL) is very small. When the mercury lamp illumination time is increased to 1.5h, the cooling is off-white solid, which is considered as the minimum illumination time of Polycaprolactone (PCL) under the mercury lamp illumination condition.
S2 1H NMR characterization of Polycaprolactone (PCL) -3, Polycaprolactone (PCL) -4, Polycaprolactone (PCL) -5, and Polycaprolactone (PCL) -6 obtained in this example was performed to confirm whether the generated milky white solid was Polycaprolactone (PCL).
1H NMR characterization test results: chemical shift (delta) ═ 3.7 is-CH2-an absorption peak of a hydrogen atom on O-CO-, δ ═ 1.2 is an absorption peak of a hydrogen atom on-C-H-, and the area ratio of the two absorption peaks is 2: 3; delta-CH at 4.252-absorption peak of hydrogen protons on O-; delta 2.6 is-O-CO-CH2-absorption peak of upper hydrogen atom; an overlapped absorption peak is positioned at the position of delta-1.7 and is matched with the structural unit of polycaprolactone.
S3 is performed to characterize the infrared spectrum of Polycaprolactone (PCL) -3, Polycaprolactone (PCL) -4, Polycaprolactone (PCL) -5, and Polycaprolactone (PCL) -6 obtained in this example, and further confirm that the generated milky white solid is Polycaprolactone (PCL).
Infrared spectrum characterization test result at wave number of 1727.93cm-1Characteristic absorption peak of C ═ O; at 2944.14-2866.40 cm-1Is represented by-CH2-The stretching vibration absorption peak of (1); at 1468.39-1364.32 cm-1The absorption peak is the C-H in-plane bending vibration absorption peak; at 1291.60-1182.51 cm-1Is a C-C stretching vibration absorption peak; at 3434.47cm-1The absorption peak is O-H stretching vibration absorption peak; at 726.68cm-1The absorption peak is O-H bending vibration absorption peak;
s4 DSC representation is carried out on the Polycaprolactone (PCL) -3, the Polycaprolactone (PCL) -4, the Polycaprolactone (PCL) -5 and the Polycaprolactone (PCL) -6 obtained in the embodiment, the test range is room temperature to 80 ℃, and the heating rate is 2 ℃/min. The peak absorbance of Polycaprolactone (PCL) -3, melting point 56.21, and the peak absorbance of Polycaprolactone (PCL) -4, melting point 58.12 were determined. The melting point, which is the absorption peak of Polycaprolactone (PCL) -5, was 58.31. The melting point, which is the absorption peak of Polycaprolactone (PCL) -6, was 55.78.
Example 3
S1 four parts of 15.00g of epsilon-caprolactone are weighed, and Polycaprolactone (PCL) is prepared by using water bath heating, mercury lamp irradiation and mercury lamp irradiation time (3.5h-5.5h) as variables under the same conditions of 2% of oxalic acid and 5% of cationic photoinitiator UV 6976.
Wherein, 2 percent of oxalic acid and 5 percent of cationic photoinitiator UV6976 are added into the first part of epsilon-caprolactone, and then the mixture is heated in water bath at 60 ℃ for 10 hours, and Polycaprolactone (PCL) -7 is numbered;
adding 2% of oxalic acid and 5% of cationic photoinitiator UV6976 into the second part of epsilon-caprolactone, and irradiating for 3.5h under a mercury lamp to code Polycaprolactone (PCL) -8;
adding 2% of oxalic acid and 5% of cationic photoinitiator UV6976 into the third epsilon-caprolactone, and irradiating for 5h under a mercury lamp to code Polycaprolactone (PCL) -9;
adding 2% of oxalic acid and 5% of cationic photoinitiator UV6976 into the fourth part of epsilon-caprolactone, and irradiating for 5.5h under a mercury lamp to code Polycaprolactone (PCL) -10;
s2 preparation of Polycaprolactone (PCL) -7, 8, 9 and 101H NMR characterization confirmed the resulting milky white solid to be Polycaprolactone (PCL).
1H NMR characterization test results: chemical shift (delta) ═ 3.7 is-CH2-an absorption peak of a hydrogen atom on O-CO-, δ ═ 1.2 is an absorption peak of a hydrogen atom on-C-H-, and the area ratio of the two absorption peaks is 2: 3; delta-CH at 4.252-absorption peak of hydrogen protons on O-; delta 2.6 is-O-CO-CH2-absorption peak of upper hydrogen atom; an overlapped absorption peak is positioned at the position of delta-1.7 and is matched with the structural unit of polycaprolactone.
S3 is performed to characterize the infrared spectrum of Polycaprolactone (PCL) -7, Polycaprolactone (PCL) -8, Polycaprolactone (PCL) -9, and Polycaprolactone (PCL) -10 obtained in this example, and further confirm that the generated milky white solid is Polycaprolactone (PCL).
Infrared spectrum characterization test result at wave number of 1727.93cm-1Characteristic absorption peak of C ═ O; at 2944.14-2866.40 cm-1Is represented by-CH2-a stretching vibration absorption peak; at 1468.39-1364.32 cm-1The absorption peak is the C-H in-plane bending vibration absorption peak; at 1291.60-1182.51 cm-1Is a C-C stretching vibration absorption peak; at 3434.47cm-1The absorption peak is O-H stretching vibration absorption peak; at 726.68cm-1The absorption peak is O-H bending vibration absorption peak;
s4 DSC representation is carried out on the Polycaprolactone (PCL) -7, the Polycaprolactone (PCL) -8, the Polycaprolactone (PCL) -9 and the Polycaprolactone (PCL) -10 obtained in the embodiment, the test range is room temperature to 80 ℃, and the heating rate is 2 ℃/min. The melting point of the absorption peak of Polycaprolactone (PCL) -7 was found to be 50.31, the melting point of Polycaprolactone (PCL) -8 was found to be 59.34, the melting point of Polycaprolactone (PCL) -9 was found to be 51.25, and the melting point of Polycaprolactone (PCL) -10 was found to be 55.06.
Example 4
The peaks of the Polycaprolactone (PCL) -1 and the Polycaprolactone (PCL) -8 are narrower, and the purity is higher when the peak of a DSC curve is narrower, which indicates that the purity of the prepared PCL is high; in addition, the absorption peak is the highest melting point, which shows that the Polycaprolactone (PCL) obtained under the two preparation conditions of 2% oxalic acid, 60 ℃ water bath heating for 10 hours, 2% oxalic acid, 5% cationic photoinitiator UV6976 and mercury lamp irradiation for 3.5 hours has the best performance and higher molecular weight.
The higher the melting point, i.e., the higher the glass transition temperature, and if the melting point is low, the glass will soften and deform at room temperature, so that the application is not necessary for practical use or the application range is very limited, and the glass can be applied only in a low-temperature environment.
Example 5
Polycaprolactone (PCL) -1 and Polycaprolactone (PCL) -8 were further tested.
S1 GPC test of Polycaprolactone (PCL) -1 and Polycaprolactone (PCL) -8, the test results are shown in Table 1, the molecular weight of the Polycaprolactone (PCL) -8 polymerized is obviously greater than that of Polycaprolactone (PCL) -1, the molecular weight of the synthesized Polycaprolactone (PCL) is 6420, and meanwhile, the dispersity is smaller, namely, the molecular weight distribution is concentrated, and the PDI value is 1.663.
S2, XRD characterization is performed on the Polycaprolactone (PCL) -8 obtained in this example and the commercially available Polycaprolactone (PCL) with molecular weight Mw 60000, and the test results show that, by comparison, the absorption peak positions and peak shapes of the characteristic peaks in the XRD spectra of the lab-made Polycaprolactone (PCL) -8 and the commercially available Polycaprolactone (PCL) are substantially consistent, and the characteristic peaks of crystal diffraction are found at positions 2 θ 21.5 ± 0.1 °, 22 ± 0.1 ° and 23.8 ± 0.1 °, which correspond to (110), (111) and (200)3 crystal planes in the polycaprolactone crystal respectively.
Secondly, exploring the preparation conditions of the composite material for 3D printing:
photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone) and TPO (2,4, 6-trimethylbenzoyl-diphenylphosphine oxide) were now mixed in a mass part of 1: 1. The polyurethane acrylate, the diluent ACMO (4-acryloyl morpholine) and the synthesized optimal Polycaprolactone (PCL) (0-50%) are debugged according to a certain proportion.
Example 6
S1 is weighed as polyurethane acrylate, ACMO, a photoinitiator 1173+ TPO (1:1), the different dosages of Polycaprolactone (PCL) -8 (the mass percentage concentration is 0-50%) are taken as variables, the materials are weighed and then placed into a beaker to be magnetically stirred and mixed, the materials are poured into a polytetrafluoroethylene mold, the materials are subjected to photocuring under crawler-type ultraviolet light, and after cooling, the materials are irradiated for 5min to be post-cured, so that the composite material of the polycaprolactone/polyurethane acrylate interpenetrating polymer network structure (IPN) elastomer is obtained, and the components are prepared as shown in Table 2.
S2, when the doping amount of Polycaprolactone (PCL) is 10%, real-time infrared characterization is carried out on the polyurethane acrylate (PUA) -Polycaprolactone (PCL) interpenetrating polymer network structure (IPN) elastomer, photocuring is completed within about 16S, and the test result is shown in figure 3.
S3 is shown in fig. 3: the conversion rate of C ═ C double bonds is calculated by doping Polycaprolactone (PCL) from 0-30% of real-time infrared, the conversion rate can reach over 90%, and the highest conversion rate is up to 98.4%, which shows that the prepared composite material has good photo (ultraviolet) curing capability.
S4 is shown in fig. 4: stretching the Polycaprolactone (PCL) -8 from a 0-50% gradient. In order to observe the physical and mechanical properties of the gradient change of the Polycaprolactone (PCL), along with the increase of the content of the Polycaprolactone (PCL), the elongation at break of the polyurethane acrylate (PUA) -Polycaprolactone (PCL) interpenetrating polymer network structure (IPN) elastomer is gradually increased to reach 614%, but the tensile strength is gradually weakened and is only about 9.2MPa at most.
S5 is shown in fig. 4: and (3) carrying out a stress-strain test on the gradient change of the Polycaprolactone (PCL) -8 from 0 to 50 percent, wherein the strain value gradually shows a descending trend under the same strain along with the increase of the content of the Polycaprolactone (PCL).
S6 is shown in fig. 5: when the content of Polycaprolactone (PCL) -8 is 30%, the Interpenetrating Polymer Network (IPN) elastomer scratch self-healing test is carried out, wherein a reversible dynamic hydrogen bond crosslinked interpenetrating polymer network structure is formed through the interaction of hydrogen bonds between hydroxyl groups in the PCL and a urethane bond of polyurethane, so that the polyurethane acrylate (PUA) -Polycaprolactone (PCL) Interpenetrating Polymer Network (IPN) elastomer has the self-healing performance.
And (3) performance testing:
TABLE 1 molecular weight distribution and Dispersion of Polycaprolactone (PCL) made by the laboratory
Figure RE-GDA0003373082950000151
Table 23D printed resin formulation table
Figure RE-GDA0003373082950000152
TABLE 3 Selective area photocuring (LCD)3D Printer parameters
Figure RE-GDA0003373082950000153
Figure RE-GDA0003373082950000161
In the composite material system, the photosensitive polymer is a high molecular substance formed by double bond opening polymerization, so that the double bond conversion rate is used as a reference standard of the polymerization degree of the photopolymerization of the polyurethane acrylate (PUA) and the Polycaprolactone (PCL) in the light (ultraviolet) polymerization process.
Referring to fig. 1, fig. 1 is a schematic diagram of a 3D printer for selective area photo-curing (LCD) technology used in the present invention, wherein the parameters of the printer are shown in table 3.
As shown in fig. 2, C ═ C (810 cm) was monitored by real-time infrared-1) The absorption peak of the double bond was varied with time to calculate the conversion. Fig. 3 is a double bond conversion rate curve of the urethane acrylate (PUA) -Polycaprolactone (PCL) interpenetrating polymer network structure (IPN) elastomer when the doped amount of the Polycaprolactone (PCL) is 10%, and it can be seen from the graph that the photo-curing is completed in about 16 s.
As shown in fig. 3, the conversion rate of the doped Polycaprolactone (PCL) in the composite material from 0-30% of C ═ C double bonds can reach over 90%, and the highest conversion rate is as high as 98.4%, which indicates that the prepared composite material has good photocuring capability.
As shown in fig. 4, as the stress-strain curve of the Interpenetrating Polymer Network (IPN) elastomer increases with the Polycaprolactone (PCL), the stress-strain curves of the elastomers have substantially the same trend, and as the content of the Polycaprolactone (PCL) increases, the strain value gradually decreases under the same strain, which may be caused by the two-phase separation state of the urethane acrylate (PUA) and the Polycaprolactone (PCL), and the larger the phase separation degree is, the lower the interaction force between the two-phase interfaces of the urethane acrylate (PUA) and the Polycaprolactone (PCL) is, so that the tensile strength of the elastomer is reduced.
As shown in fig. 5, fig. 5 shows the scratch self-healing test of Interpenetrating Polymer Network (IPN) elastomer when the doping amount of Polycaprolactone (PCL) is 30%. Fig. 5(a) shows the elastomer scratched, and the scratched elastomer was placed in an oven at 70 ℃ and heated for 3min, and then taken out, and the scratch was found to disappear completely, as shown in fig. 5 (b). A large number of hydroxyl groups in Polycaprolactone (PCL) and urethane bonds of polyurethane interact through hydrogen bonds, and an Interpenetrating Polymer Network (IPN) of reversible dynamic hydrogen bond crosslinking is formed. During heating, the crystallinity of Polycaprolactone (PCL) can violently descend in the combined material, hydrogen bond between polyurethane and Polycaprolactone (PCL) will be opened, during the cooling, hydroxyl in Polycaprolactone (PCL) will again with through hydrogen bond interact between the urethane bond of polyurethane, the mechanical properties of damage structure is under the effect of dynamic reversible hydrogen bond, can all realize complete selfreparing between room temperature to the melting point Tr (169.3) temperature of stationary phase, and the higher temperature is, the stronger the motion ability of Polycaprolactone (PCL) chain segment of reversible phase is, the faster the restoration. Meanwhile, the scratch self-healing performance of the product is good.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention as described in the specification of the present invention or directly or indirectly applied to the related technical fields are included in the scope of the present invention.

Claims (10)

1. A shape memory composite characterized by:
the device comprises a fixed phase and a reversible phase, wherein the fixed phase and the reversible phase are connected in a crossed mode to form an interpenetrating polymer network structure;
the stationary phase is a material with photocuring capacity and the functions of memorizing and recovering the original shape;
the reversible phase is a material with deformability.
2. A shape memory composite according to claim 1, wherein: the stationary phase comprises a urethane acrylate.
3. A shape memory composite according to claim 1, wherein: the reversible phase comprises semi-crystalline polycaprolactone.
4. A shape memory composite according to claim 1, wherein: the viscosity of the composite material is 1000cps to 3000 cps.
5. A method of preparing a shape memory composite as claimed in any one of claims 1 to 4, wherein: the method comprises the following steps:
mixing the stationary phase, the reversible phase and a photoinitiator, and adding a diluent to obtain a mixed solution;
and (3) placing the mixed solution under an ultraviolet lamp, selecting an ultraviolet light transmission area, and carrying out ultraviolet light initiated polymerization to form the composite material with the interpenetrating polymer network structure.
6. The method of claim 5, wherein: the photoinitiator comprises diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
7. The method of claim 5, wherein: the diluent comprises 4-acetoacetylyl morpholine.
8. A process for preparing the polycaprolactone of claim 3, wherein: counted by mass parts, the method comprises the following steps:
and adding 0.5-6 parts of catalyst and 1.5-10 parts of photoinitiator into 50-200 parts of epsilon-caprolactone, and irradiating for 1.5-5.5 h by using a mercury lamp to obtain the polycaprolactone.
9. Use of a shape memory composite according to any one of claims 1 to 4 in sensors and semiconductors.
10. Use of a shape memory composite according to any one of claims 1 to 4 in a 3D printed medical device.
CN202110842587.0A 2021-07-26 2021-07-26 Shape memory composite material and preparation method and application thereof Active CN113817310B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110842587.0A CN113817310B (en) 2021-07-26 2021-07-26 Shape memory composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110842587.0A CN113817310B (en) 2021-07-26 2021-07-26 Shape memory composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113817310A true CN113817310A (en) 2021-12-21
CN113817310B CN113817310B (en) 2023-03-24

Family

ID=78923937

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110842587.0A Active CN113817310B (en) 2021-07-26 2021-07-26 Shape memory composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113817310B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040024143A1 (en) * 2002-04-18 2004-02-05 Mnemoscience Gmbh Interpenetrating networks
CN1721450A (en) * 2004-07-15 2006-01-18 中国科学院成都有机化学有限公司 Shape memory polymer with secondary transition temperature and method for preparing same
US20090092807A1 (en) * 2007-10-09 2009-04-09 The Hong Kong Polytechnic University Two-way shape memory composite polymer and methods of making
CN101466787A (en) * 2006-04-12 2009-06-24 Gkss研究中心盖斯特哈赫特有限公司 Shape memory polymer with polyester and polyacrylate segments and process for its production and programming
CN102181066A (en) * 2011-01-18 2011-09-14 嘉兴学院 Preparation method of thermo-sensitive waterproof moisture-permeable film based on shape-memory polyurethane semi-interpenetrating network
CN102480014A (en) * 2011-05-11 2012-05-30 深圳光启高等理工研究院 Shape memory metamaterial and preparation method thereof
CN106379011A (en) * 2016-09-05 2017-02-08 四川大学 Preparation method of novel polymer-based multilayer shape memory material
CN110483699A (en) * 2019-09-27 2019-11-22 常州大学 A kind of multiple response shape memory polyurethane acrylate copolymer and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040024143A1 (en) * 2002-04-18 2004-02-05 Mnemoscience Gmbh Interpenetrating networks
CN1721450A (en) * 2004-07-15 2006-01-18 中国科学院成都有机化学有限公司 Shape memory polymer with secondary transition temperature and method for preparing same
CN101466787A (en) * 2006-04-12 2009-06-24 Gkss研究中心盖斯特哈赫特有限公司 Shape memory polymer with polyester and polyacrylate segments and process for its production and programming
US20090092807A1 (en) * 2007-10-09 2009-04-09 The Hong Kong Polytechnic University Two-way shape memory composite polymer and methods of making
CN102181066A (en) * 2011-01-18 2011-09-14 嘉兴学院 Preparation method of thermo-sensitive waterproof moisture-permeable film based on shape-memory polyurethane semi-interpenetrating network
CN102480014A (en) * 2011-05-11 2012-05-30 深圳光启高等理工研究院 Shape memory metamaterial and preparation method thereof
CN106379011A (en) * 2016-09-05 2017-02-08 四川大学 Preparation method of novel polymer-based multilayer shape memory material
CN110483699A (en) * 2019-09-27 2019-11-22 常州大学 A kind of multiple response shape memory polyurethane acrylate copolymer and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KHASRAGHI, SS，等: "Bio-based UV curable polyurethane acrylate: Morphology and shape memory behaviors", 《EUROPEAN POLYMER JOURNAL》 *
任文惠，等: "形状记忆聚氨酯丙烯酸酯的制备及性能", 《高分子材料科学与工程》 *

Also Published As

Publication number Publication date
CN113817310B (en) 2023-03-24

Similar Documents

Publication Publication Date Title
Liu et al. Chemically cross-linked polycyclooctene: synthesis, characterization, and shape memory behavior
Peng et al. 3D printing mechanically robust and transparent polyurethane elastomers for stretchable electronic sensors
Zhao et al. 4D printing of shape memory polyurethane via stereolithography
Wu et al. High-performance soybean-oil-based epoxy acrylate resins:“Green” synthesis and application in UV-curable coatings
CN111349257B (en) Method for constructing 3D shape memory material through optical programming, obtained product and application
Parameswaranpillai et al. Shape memory properties of Epoxy/PPO–PEO–PPO triblock copolymer blends with tunable thermal transitions and mechanical characteristics
US20120077946A1 (en) Cationically polymerizable resin composition and cured object obtained therefrom
Yue et al. Recyclable, reconfigurable, thermadapt shape memory polythiourethane networks with multiple dynamic bonds for recycling of carbon fiber-reinforced composites
Zhang et al. Mechanically robust, stretchable, recyclable, and biodegradable ionogels reinforced by polylactide stereocomplex nanocrystals
CN113817310B (en) Shape memory composite material and preparation method and application thereof
Hu et al. Synthesis of photocurable cellulose acetate butyrate resin for continuous liquid interface production of three-dimensional objects with excellent mechanical and chemical-resistant properties
Fei et al. Progress in photocurable 3D printing of photosensitive polyurethane: a review
Jiang et al. 4D printing of single-network shape memory polyurethanes with two-way actuation properties
Mauriello et al. 3D/4D printing of polyurethanes by vat photopolymerization
Wang et al. 4D printing of triple-shape memory cyanate composites based on interpenetrating polymer network structures
Jiang et al. A high-fidelity preparation method for liquid crystal elastomer actuators
Fang et al. Light and Shape‐Memory Polymers: Characterization, Preparation, Stimulation, and Application
US20190055392A1 (en) Particle-based multi-network polymers
Shan et al. Epoxy acrylate-based shape memory polymer via 3D printing.
Liao et al. A realizable green strategy to negative polyurethane photoresists through the application of a silicone resin photoinitiator
CN107474266B (en) A kind of thermosetting polymer and application with region plasticity
Jiang et al. The structural variety of shape-memory polymers
Huang et al. Application of Bis [2-(3, 4-epoxycyclohexyl) ethyl] octamethyltetrasiloxane in the Preparation of a Photosensitive Resin for Stereolithography 3D Printing
CN113248654B (en) Dynamic ester exchange glass body high polymer material and preparation method thereof
Nakagawa et al. Linking microscopic structural changes and macroscopic mechanical responses in a near-ideal bottlebrush elastomer under uniaxial deformation

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