WO2019033911A1 - Composite material having shape memory function, manufacturing method, and applications - Google Patents

Abstract

Disclosed are a composite material having a shape memory function, a manufacturing method, and applications. The composite material comprises four layers, respectively in an inward sequence: a surface decorative layer, a protective layer, an adhesive layer, and a soft lining layer. The protective layer is a plastic or vulcanized plastic. The plastic softens when heated to 55 °C or more and crystalizes and hardens when the temperature is lower than 55 °C. The soft lining layer is a foamed plastic, rubber, or foamed rubber. The soft lining layer and the protective layer are connected by the adhesive layer. The surface decorative layer is a coating layer. The present invention utilizes the principle of material shape memory and the principle that, when warmed to 60 °C or more, material crystals such as Eucommia ulmoides gum are molten into an amorphous state and can be molded freely, separated mixing is employed, and a vulcanization process allows the manufacturing of a freely shapeable personalized protective gear or assistive device for persons with disabilities. A personalized instrument that best fit the shape of the human body can be tuned from the manufactured protective gear or assistive device on the basis of different body shapes of different groups of people.

Description

Composite material with shape memory function, preparation method and application thereof Technical field

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.

Background technique

Polymer materials have a wide range of applications in sports protective gear, handicapped aids and medical devices. For example, 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. However, 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. As adolescents continue to grow and their physical characteristics change significantly, they have to change their protective gear several times, thus increasing their financial burden. Second, these materials are all oil. Made of chemical raw materials, it is a non-renewable material, which is not conducive to environmental protection. Because of the different physical fitness of athletes, they are allergic to some chemical components, and some may cause discomfort.

For example, 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. Therefore, 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. 6) After the limbs are atrophied, it is necessary to repeatedly manufacture the receiving cavity, which is expensive and increases the economic burden of the disabled. And the production process consumes a lot of manpower and material resources. 7) In terms of cost, the price of the receiving cavity itself is about 3,000 yuan, plus the prosthetic joints, support rods, prostheses and other parts, the price of the entire prosthesis is often between 20,000 and 40,000, and the cost is expensive. Therefore, due to the above reasons, people with disabilities often lose their ability to work because of their disability, and their economic ability is often not high enough to afford expensive prosthetic costs. Without the support of high-quality prosthetics, people with disabilities can't get the opportunity to re-enter the work, the quality of life will also be worse, and thus become disabled - returning to poverty - can not afford a prosthetic - can not re-return to society - the quality of life is worse Vicious circle.

Medical devices made of the same polymer materials, especially orthopedic fixation and orthopedic devices, also face many shortcomings of sports protective gear and disabled prostheses, such as the inability to standardize production, complicated production processes, and petroleum-based raw materials.

Summary of the invention

In order to solve the problems occurring in the prior art, 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. For example, 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. Another example 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. Similarly, medical devices can be standardized and produced in a personalized way to meet the needs of doctors and patients. Further, 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. One or a combination.

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. 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. 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. As 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. Preferably, 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. In the present invention, the following formula may be preferably used:

The protective layer is obtained by mixing raw materials including the following components:

Each component is in parts by weight:

The soft lining rubber can preferably be formulated as follows:

Each component is in parts by weight:

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:

Each component is in parts by weight:

As the vulcanizing agent, the accelerator, the foaming agent, the antioxidant, and the filler described above, a vulcanizing agent, an accelerator, a foaming agent, an antioxidant, and a filler which are conventionally used in the prior art can be used. In the present invention, it is preferred to:

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;

In the formulation of the protective layer and the soft lining layer, other conventional 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.

Mainly used for sports equipment, disabled assistive devices, orthopedic fixation, orthopedics, splints and other medical equipment.

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.

DRAWINGS

Figure 1 is a schematic view of a composite material having a shape memory function of the present invention

BRIEF DESCRIPTION OF THE DRAWINGS:

1 surface decorative layer; 2 protective layer; 3 soft lining; 4-adhesive layer.

Detailed ways

The invention will now be further described in conjunction with the examples.

Example 1

The specific formula of the protective layer is:

Polycaprolactone (plastic) 100 parts

DCP 0.5 parts

Titanium dioxide (filler) 10 parts

Soft pad is purchased EVA foam sheet, thickness 9mm

Adhesive is a universal adhesive

The coating is polyurethane elastic coating

According to the above 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. Then, 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.

Use a universal glue to bond the two together.

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.

Example 2

The specific formula of the protective layer is:

Soft pad is purchased polyurethane foam sheet, thickness 5mm

Adhesive is a tire sealant

The coating is polyurethane elastic coating

According to the above protective layer formula, according to the traditional rubber opening, mixing, kneading or extrusion mixing process, according to the rubber-activator-filler-softener-antioxidant-vulcanizing agent feeding sequence, 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. Then, 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.

Use a tire seal glue to bond the two together.

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.

Example 3

The specific formula of the protective layer is:

Soft pad is purchased polyethylene foam sheet, thickness 3mm

Adhesive is 502 glue

The coating is polyurethane elastic coating

According to the above protective layer formula, according to the traditional rubber opening, mixing, kneading or extrusion mixing process, according to the rubber-activator-filler-softener-antioxidant-vulcanizing agent feeding sequence, 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. Then, 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.

Use 502 glue to bond the two together.

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.

Example 4

The specific formula of the protective layer is:

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

According to the above protective layer formula, according to the traditional rubber opening, mixing, kneading or extrusion mixing process, according to the rubber-activator-filler-softener-antioxidant-vulcanizing agent feeding sequence, 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. Then, 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.

Use yellow glue to bond the two together.

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.

Example 5

The specific formula of the protective layer is:

The soft lining is specifically formulated as follows:

Adhesive is good glue for brothers

The coating is polyurethane elastic coating

According to 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.

Grind the surface of the protective layer and the soft lining with sandpaper to make it rough, and then use the glue to glue the two together. 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.

Example 6

The specific formula of the protective layer is:

The soft lining is specifically formulated as follows:

According to 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.

Claims (9)

A composite material having a shape memory function, characterized in that: 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 or vulcanized plastic; The plastic is softened by heat at 55 ° C or higher, and the crystal is hardened after the temperature is lower than 55 ° C; The soft lining is a foamed plastic, rubber or foamed rubber; The soft lining layer and the protective layer are connected by an adhesive layer; The surface decorative layer is a coating layer. A composite material having a shape memory function according to claim 1, wherein: The plastic is one or a combination of gutta percha, gutta-percha, balata, euonymus, synthetic trans-1,4-polyisoprene, polycaprolactone; The rubber is natural rubber, styrene butadiene rubber, butadiene rubber, ethylene propylene diene monomer, silicone rubber, fluororubber, neoprene rubber, nitrile rubber, butyl rubber, acrylate rubber, chlorosulfonated polyethylene. One or a combination; The foaming rubber is natural rubber, styrene butadiene rubber, butadiene rubber, ethylene propylene diene monomer, silicone rubber, fluororubber, neoprene rubber, nitrile rubber, butyl rubber, acrylate rubber, chlorosulfonated poly One or a combination of ethylene as a raw material prepared foamed rubber; The foamed plastic is 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 adhesive layer is a rubber series, a polyurethane glue series and an epoxy resin series adhesive. A composite material having a shape memory function according to claim 2, wherein: The surface decorative layer is a polyurethane series coating. A composite material having a shape memory function according to claim 1, wherein: The protective layer is obtained by mixing raw materials including the following components: Each component is in parts by weight:

A composite material having a shape memory function according to claim 1, wherein: The soft underlayer is obtained by kneading a raw material comprising the following components: Each component is in parts by weight:

A composite material having a shape memory function according to claim 5, wherein: The soft underlayer is obtained by kneading a raw material comprising the following components: Each component is in parts by weight:

A composite material having a shape memory function according to claim 1, wherein: The composite material has a total thickness of 1 to 10 mm and a soft underlayer thickness of 0.5 to 9 mm. A method for preparing a composite material having a shape memory function according to any one of claims 1 to 7, wherein the method comprises: The protective layer is kneaded and vulcanized, and after the soft lining is kneaded and vulcanized or foamed, the protective layer and the soft lining layer are bonded together through the adhesive layer; Wherein the vulcanization pressure is >3.5 MPa, the vulcanization temperature is 140 to 200 ° C, and the vulcanization time is 5 to 100 minutes; 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. The composite material having shape memory function according to any one of claims 1 to 7 for use in sportswear, handicapped aids and medical instruments.

Images