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WO2019033911A1 - Matériau composite à fonction de mémoire de forme, procédé de fabrication et applications - Google Patents

Matériau composite à fonction de mémoire de forme, procédé de fabrication et applications Download PDF

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Publication number
WO2019033911A1
WO2019033911A1 PCT/CN2018/097176 CN2018097176W WO2019033911A1 WO 2019033911 A1 WO2019033911 A1 WO 2019033911A1 CN 2018097176 W CN2018097176 W CN 2018097176W WO 2019033911 A1 WO2019033911 A1 WO 2019033911A1
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Prior art keywords
rubber
layer
protective layer
composite material
shape memory
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Ceased
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PCT/CN2018/097176
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English (en)
Chinese (zh)
Inventor
张继川
张立群
李亮亮
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Definitions

  • the invention relates to the technical field of polymer materials, and further relates to a composite material having a shape memory function, a preparation method and an application thereof.
  • Polymer materials have a wide range of applications in sports protective gear, handicapped aids and medical devices.
  • the sports protective gears currently sold in the domestic market are mainly made of polymer materials to protect the human body from external forces, and then made of linings made of foam materials such as EVA, rubber, polyurethane, etc., dissipating energy and protecting the human body. Getting hurt.
  • these protective gears have two common shortcomings that cannot be overcome: First, these protective materials are all formed at one time, and the shape of the appearance after stereotypes cannot be changed, so that they cannot adapt to the different physical characteristics of different groups of people; this is for young athletes. It is especially important because adolescents are the fastest growing stage of adolescents.
  • the traditional prosthetic receiving cavity is made of acrylic resin, which is measured, modified and manufactured in three steps. It has many shortcomings: 1) long manufacturing cycle and complicated process; 2) the production of the receiving cavity is a personalized non-standard operation, the experience and professional quality requirements of the prosthetic orthopaedic division are relatively high, and the adaptability of the obtained product to the disabled 3) Raw materials are all derived from fossil resources, which are non-renewable resources and obviously do not belong to green products; 4) After abandonment, they will increase carbon emissions. In today's increasingly popular environmental protection, it is obviously not environmentally friendly; 5) receiving The chamber is prepared once and cannot be changed again.
  • a person with a disability can only select a receiving cavity that is approximately suitable for the shape of his or her residual limb, and cannot obtain a receiving cavity that is completely suitable for the shape of his own residual limb.
  • the present invention provides a composite material having a shape memory function, a preparation method and an application thereof.
  • the invention utilizes the special properties of the shape memory of plastic materials such as gutta percha, and prepares a personalized product which can be repeatedly shaped, and can be widely applied to sports safety tools, handicapped aids and medical instruments, especially in the field of orthopedic fixation and orthopedics.
  • personalized football leggings so that football players, especially young football players, can easily adjust the shape of the leg shield according to the leg shape changes caused by different leg types or growth, so that it fits perfectly with the leg. It is integrated with the legs to maximize protection.
  • the personalized disabled limb receiving cavity is the personalized disabled limb receiving cavity, so that the disabled person can personally operate according to the shape of the disabled person's own residual limb, and prepare a personalized receiving cavity adapted to the shape of the disabled person's own residual limb.
  • medical devices can be standardized and produced in a personalized way to meet the needs of doctors and patients.
  • the composite material of the present invention has a crystalline melting point of about 60 ° C and is a poor conductor of heat, so that it does not burn the human body during the softening and plasticizing operation.
  • the natural polymer material utilized by the invention belongs to green, environmentally friendly and renewable materials, and the preparation process basically has no three waste discharges, and meets the requirements of national energy conservation and emission reduction, development of green, low carbon and circular economy.
  • One of the objects of the present invention is to provide a composite material having a shape memory function.
  • the composite material comprises four layers, which are: a surface decorative layer, a protective layer, an adhesive layer and a soft lining layer;
  • the protective layer is plastic and vulcanized plastic
  • the raw rubber is softened by heat at 55 ° C or higher, and the crystal is hardened after the temperature is lower than 55 ° C;
  • the plastic is preferably gutta percha, Gutapo, Balata, Peach, and synthetic trans-1,4-poly One or a combination of pentadiene and polycaprolactone;
  • the soft lining is a foamed plastic, rubber or foamed rubber
  • the foamed plastic can be made of all the foamed plastics of the prior art, and the foamed plastic can be prepared according to the usual foaming process, and a commercially available foamed plastic can also be directly purchased.
  • the foamed plastic may preferably be one or a combination of a polyethylene foaming material, a polypropylene foaming material, a polystyrene foaming material, an EVA foaming material, a polyvinyl chloride foaming material, and a polyurethane foaming material.
  • the rubber is preferably natural rubber, styrene butadiene rubber, butadiene rubber, ethylene propylene diene monomer, silicone rubber, fluororubber, neoprene rubber, nitrile rubber, butyl rubber, acrylate rubber, chlorosulfonated polyethylene.
  • styrene butadiene rubber butadiene rubber
  • ethylene propylene diene monomer silicone rubber
  • fluororubber neoprene rubber
  • nitrile rubber butyl rubber
  • acrylate rubber chlorosulfonated polyethylene
  • the foamed rubber is preferably natural rubber, styrene butadiene rubber, butadiene rubber, ethylene propylene diene monomer, silicone rubber, fluororubber, neoprene rubber, nitrile rubber, butyl rubber, acrylate rubber, chlorosulfonated
  • One or a combination of polyethylenes is a foamed rubber prepared from a raw material; the foamed rubber may be prepared by using the above-mentioned rubber as a raw material in accordance with a usual foaming process, or a commercially available foamed rubber may be directly purchased.
  • the soft lining layer and the protective layer are connected by an adhesive layer;
  • the adhesive layer is a rubber series, a urethane glue series and an epoxy resin series adhesive.
  • the adhesive In order to meet the requirements of individualized re-formability, the adhesive must meet three conditions: First, excellent bonding performance, must adhere to the characteristics of 1.1 and 1.2 materials without cracking; second, insoluble in water, not hydrolyzed, resistant A certain temperature (60-100 ° C) does not degrade; third, it can be repeated with the protective layer and soft lining without plasticity (deformation). Such as: tire glue, yellow plastic, 401 glue, universal glue, brother good, 502 glue, etc. can meet the requirements.
  • the surface decorative layer is an elastic coating; preferably a polyurethane series coating.
  • the surface decorative layer can be attached to the surface of the protective layer by brushing or spraying, and can beautify and decorate.
  • the material In order to meet the requirements of individualized and re-shapeable, if the method of spraying and tracing is adopted, the material must meet two conditions: one is insoluble in water, does not hydrolyze, is resistant to certain temperature (60-100 ° C), and is not degradable.
  • the protective layer and the soft lining are not plastically broken, if the bonding method is adopted, the third condition is also satisfied, that is, the bonding property is excellent, and the protective layer must be bonded without cracking.
  • the adhesive decorative material is made of a protective layer and a soft lining material, so as to satisfy the fact that the decorative layer does not rupture with the main material.
  • the plastic of the protective layer is preferably a vulcanized plastic, and the vulcanization method may be a conventional vulcanization process of the prior art.
  • the following formula may be preferably used:
  • the protective layer is obtained by mixing raw materials including the following components:
  • the soft lining rubber can preferably be formulated as follows:
  • An accelerator may also be added.
  • the amount of the accelerator may be a conventional amount in the art. If the soft lining layer is made of a foamed rubber, a foaming agent may be added in the formulation, and the foaming process may employ the usual process conditions in the art. Among them, the following formula is preferably used:
  • a vulcanizing agent, an accelerator, a foaming agent, an antioxidant, and a filler which are conventionally used in the prior art can be used.
  • a vulcanizing agent, an accelerator, a foaming agent, an antioxidant, and a filler which are conventionally used in the prior art can be used.
  • Vulcanizing agents include: sulfur, peroxide (DCP, double 25, BPO);
  • Promoters include: promoting TMTD, promoting M, promoting CZ, promoting DM, promoting TMTM, promoting TETD, promoting DPTT, promoting ZDC, promoting BZ, promoting PZ, promoting D, promoting CBS, promoting TBBS, promoting NOBS, promoting DZ
  • the foaming agent comprises: a foaming agent AC, a foaming agent H, a foaming agent DPT;
  • Anti-aging agent includes: anti-264, anti-AW, anti-BLE, anti-RD, anti-AH, anti-AP, anti-A, anti-D, anti-4010, anti-4010NA, anti-H, anti-DPD, anti-CMA, anti-2264;
  • the filler is preferably titanium dioxide, calcium carbonate, white carbon black;
  • auxiliaries in the field such as an activator, a toner, a filling reinforcing agent, a plasticizer, a hardening agent, etc., may be added according to actual conditions. Also for routine use, the technician can determine according to the actual situation.
  • the composite material preferably has a total thickness of from 1 to 10 mm and a soft underlayer thickness of from 0.5 to 9 mm.
  • Another object of the present invention is to provide a method for preparing a composite material having a shape memory function.
  • the method includes:
  • the protective layer is kneaded or vulcanized, and after the soft lining layer is foamed, kneaded or vulcanized, the protective layer and the soft lining layer are bonded together through the adhesive layer;
  • a surface decorative layer is coated on the outer surface of the protective layer outside the protective layer to obtain the composite material having a shape memory function.
  • a third object of the present invention is to provide a composite material having a shape memory function for use in sports protectors, handicapped aids, and medical devices.
  • the invention overcomes the shortcomings that the physical protective gear and the handicapped aid of the prior art can not be changed once and can be derived from non-renewable fossil-based raw materials, which is not conducive to environmental protection.
  • the invention utilizes the material shape memory principle, and the temperature rise of 60 ° C or above, the crystallization of the material such as eucommia gum is changed into an amorphous state, and the principle of free shaping can be adopted, and the individual shaping and vulcanization processes are used to prepare the personalized protection. With or with disabilities.
  • the prepared protective gear or accessory can adjust the personalized instrument device that fits the shape of the human body according to different groups of people.
  • the invention is embodied in: 1 production has universality, so the preparation of the mold is simple, and the manufacturing cost is reduced; 2 can be freely molded, the same product can be applied to different groups of people, and the application surface is wider; 3 the body shape change with the growth of the adolescents , can be freely molded, reused, to save costs for users; 4 raw materials from renewable polymer materials, is conducive to environmental protection.
  • Figure 1 is a schematic view of a composite material having a shape memory function of the present invention
  • Soft pad is purchased EVA foam sheet, thickness 9mm
  • Adhesive is a universal adhesive
  • the coating is polyurethane elastic coating
  • the protective layer formula according to the traditional rubber opening, mixing, kneading or extrusion mixing process, according to the feeding sequence of the plastic-titanium white powder---vulcanizing agent, the protective layer formula is mixed, and the protective layer is mixed.
  • the refining temperature is 60 °C ⁇ 10 °C, and the semi-finished product of the protective layer is obtained, and it is reserved for more than 16 hours.
  • the protective layer rubber compound was placed in a mold to carry out a compression vulcanization molding reaction at a vulcanization pressure of 10 MPa, a vulcanization temperature of 140 ° C, and a vulcanization time of 200 minutes.
  • a protective sheet of a predetermined shape and a thickness of 1 mm was obtained.
  • the purchased 9 mm thick EVA foam sheet was cut into the same shape as the protective layer.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, four layers of soft and hard integrated shape memory composite materials were obtained.
  • Soft pad is purchased polyurethane foam sheet, thickness 5mm
  • Adhesive is a tire sealant
  • the coating is polyurethane elastic coating
  • the protective layer formula is mixed. Refining, get the protective layer of mixed rubber semi-finished products, parked for more than 16 hours for use.
  • the kneading temperature of the protective layer was 70 ° C ⁇ 10 ° C.
  • the protective layer rubber compound was placed in a mold to carry out a compression vulcanization molding reaction, a vulcanization pressure of 3.5 MPa, a vulcanization temperature of 150 ° C, and a vulcanization time of 100 minutes.
  • a protective sheet of a predetermined shape and a thickness of 3 mm was obtained.
  • the purchased 5 mm polyurethane foam sheet was cut into the same shape as the pre-formed protective layer.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, four layers of soft and hard integrated shape memory composite materials were obtained.
  • Soft pad is purchased polyethylene foam sheet, thickness 3mm
  • Adhesive is 502 glue
  • the coating is polyurethane elastic coating
  • the protective layer formula is mixed. Refining, get the protective layer of mixed rubber semi-finished products, parked for more than 16 hours for use.
  • the kneading temperature of the protective layer was 80 ° C ⁇ 10 ° C.
  • the protective layer rubber compound was placed in a mold to carry out a compression vulcanization molding reaction at a vulcanization pressure of 5 MPa, a vulcanization temperature of 160 ° C, and a vulcanization time of 60 minutes.
  • a protective sheet of a predetermined shape and a thickness of 5 mm was obtained.
  • the purchased 3 mm polyethylene foam sheet was cut into the same shape as the pre-formed protective layer.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, four layers of soft and hard integrated shape memory composite materials were obtained.
  • Soft padding is a natural rubber foam piece purchased with a thickness of 1.5mm
  • Adhesive is yellow glue
  • the coating is polyurethane elastic coating
  • the protective layer formula is mixed. Refining, get the protective layer of mixed rubber semi-finished products, parked for more than 16 hours for use.
  • the kneading temperature of the protective layer is 90 ° C ⁇ 10 ° C.
  • the protective layer rubber compound was placed in a mold to carry out a compression vulcanization molding reaction, a vulcanization pressure of 15 MPa, a vulcanization temperature of 170 ° C, and a vulcanization time of 20 minutes.
  • a protective sheet of a predetermined shape and a thickness of 8 mm was obtained.
  • the purchased 1.5 mm natural rubber foam sheet was cut into the same shape as the pre-formed protective layer.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, four layers of soft and hard integrated shape memory composite materials were obtained.
  • the soft lining is specifically formulated as follows:
  • the coating is polyurethane elastic coating
  • the above protective layer formula and soft lining formula according to the traditional rubber smelting, mixing, kneading or extrusion mixing process, according to the rubber-activator-filler-softener-anti-aging agent-vulcanizing agent feeding sequence, respectively
  • the above two formulations were mixed to obtain a protective layer of mixed rubber semi-finished products and soft lining mixed rubber semi-finished products, which were reserved for more than 16 hours.
  • the mixing temperature of the protective layer is 80 ° C ⁇ 10 ° C; the mixing temperature of the soft lining is normal temperature plus cooling water circulation cooling.
  • the kneaded protective layer rubber compound and the soft lining rubber compound were respectively placed in a mold to carry out a compression vulcanization molding reaction, and the vulcanization pressure was 12 MPa, the vulcanization temperature was 200 ° C, and the vulcanization time was 5 minutes.
  • the protective layer was respectively obtained with a thickness of 9.5 mm; a soft lining layer having a thickness of 0.5 mm.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, four layers of soft and hard integrated shape memory composite materials were obtained.
  • the soft lining is specifically formulated as follows:
  • the above protective layer formula and soft lining formula according to the traditional rubber smelting, mixing, kneading or extrusion mixing process, according to the rubber-activator-filler-softener-anti-aging agent-vulcanizing agent feeding sequence, respectively
  • the above two formulations were mixed to obtain a protective layer of mixed rubber semi-finished products and soft lining mixed rubber semi-finished products, which were reserved for more than 16 hours.
  • the kneading temperature of the protective layer is 70 ° C ⁇ 10 ° C; the mixing temperature of the soft lining is normal temperature plus cooling water circulation cooling.
  • the protective layer rubber compound is first placed in a mold for a compression vulcanization molding reaction, a vulcanization pressure of 3.5 MPa, a vulcanization temperature of 150 ° C, and a vulcanization time of 100 minutes.
  • a protective layer of vulcanizate was obtained with a thickness of 4 mm.
  • the soft lining rubber compound was then placed in another mold for a foam vulcanization molding reaction at a vulcanization temperature of 150 ° C and a vulcanization time of 15 minutes.
  • a soft lining foam vulcanizate was obtained with a thickness of 4 mm.
  • the surface of the protective layer and the soft lining are sanded and roughened, and then the two are bonded together using 401 glue.
  • a composite material having shape memory properties is obtained.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, four layers of soft and hard integrated shape memory composite materials were obtained.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Vascular Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Laminated Bodies (AREA)
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Abstract

L'invention concerne un matériau composite présentant une fonction de mémoire de forme, un procédé de fabrication et des applications. Le matériau composite comprend quatre couches, respectivement dans une séquence vers l'intérieur : une couche décorative de surface, une couche protectrice, une couche adhésive et une couche de revêtement souple. La couche protectrice est constituée de matière plastique ou de matière plastique vulcanisée. Le plastique se ramollit lorsqu'il est chauffé à une température supérieure ou égale à 55 °C et cristallise et durcit lorsque la température est inférieure à 55 °C. La couche de revêtement souple est constituée de plastique expansé, de caoutchouc ou de caoutchouc expansé. La couche de revêtement souple et la couche protectrice sont reliées par la couche adhésive. La couche décorative de surface est une couche de revêtement. La présente invention utilise le principe de la mémoire de forme de matériau et le principe selon lequel, lors d'un chauffage à une température supérieure ou égale à 60 °C, des cristaux de matière tels que de gomme d'Eucommia ulmoides sont fondus en un état amorphe et peuvent être moulés librement, un mélange séparé est employé, et un traitement de vulcanisation permet la fabrication d'un dispositif de protection personnalisé librement façonnable ou d'un dispositif d'assistance pour des personnes handicapées. Un instrument personnalisé qui s'adapte mieux à la forme du corps humain peut être personnalisé à partir du dispositif de protection ou du dispositif d'assistance fabriqué sur la base de différentes formes corporelles de différents groupes de personnes.
PCT/CN2018/097176 2017-08-18 2018-07-26 Matériau composite à fonction de mémoire de forme, procédé de fabrication et applications Ceased WO2019033911A1 (fr)

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CN110372922B (zh) * 2019-07-22 2021-06-01 北京化工大学 一种具有三重形状记忆效应的聚合物材料及其制备与应用
CN116444726A (zh) * 2022-01-10 2023-07-18 北京化工大学 一种高硬度形状记忆复合材料及其制法和应用
CN116726337A (zh) * 2023-07-05 2023-09-12 中日友好医院(中日友好临床医学研究所) 个性化记忆型无创通气面罩
CN120623588B (zh) * 2025-08-08 2025-11-18 山东玲珑轮胎股份有限公司 一种轮胎胎侧用橡胶复合材料及其制备方法

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