WO2019033912A1 - Flexible-rigid integrated composite material having shape memory function, preparation method therefor and use thereof - Google Patents

Flexible-rigid integrated composite material having shape memory function, preparation method therefor and use thereof Download PDF

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Publication number
WO2019033912A1
WO2019033912A1 PCT/CN2018/097178 CN2018097178W WO2019033912A1 WO 2019033912 A1 WO2019033912 A1 WO 2019033912A1 CN 2018097178 W CN2018097178 W CN 2018097178W WO 2019033912 A1 WO2019033912 A1 WO 2019033912A1
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Prior art keywords
soft
composite material
shape memory
rubber
layer
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Application number
PCT/CN2018/097178
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French (fr)
Chinese (zh)
Inventor
张继川
张立群
李亮亮
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北京化工大学
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Publication of WO2019033912A1 publication Critical patent/WO2019033912A1/en

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    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the invention relates to the technical field of polymer materials, and further relates to a soft and hard integrated 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 soft and hard integrated 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 soft and hard integrated composite material having a shape memory function.
  • the composite material comprises three layers, which are: a surface decorative layer, a protective layer and a soft lining layer;
  • the protective layer is plastic or 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 soft lining layer is a foamed polyurethane; or the rubber is mixed with an auxiliary agent;
  • the soft lining layer and the protective layer are integrated into each other by heat bonding or co-vulcanization;
  • the surface decorative layer is a coating layer.
  • the soft lining layer and the protective layer are co-vulcanized into a unitary structure.
  • 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.
  • styrene butadiene rubber butadiene rubber
  • ethylene propylene diene monomer silicone rubber
  • fluororubber neoprene rubber
  • nitrile rubber butyl rubber
  • acrylate rubber chlorosulfonated polyethylene.
  • the surface decorative layer is an elastic coating, more preferably a polyurethane 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 coating must meet two conditions: one is insoluble in water, does not hydrolyze, does not degrade at a certain temperature (60-100 ° C), and the other is that it can be repeatedly plasticized with the protective layer and the soft lining.
  • the invention preferably has elasticity. Polyurethane series coatings.
  • 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, it may be preferred to:
  • the protective layer is obtained by mixing raw materials including the following components:
  • the soft lining rubber can preferably be formulated as follows:
  • the soft underlayer is obtained by kneading a raw material comprising the following components:
  • the soft lining layer is made of a foamed rubber
  • a foaming agent is required in the formulation, and the foaming process can adopt the usual process conditions in the art.
  • the following formula is preferably used:
  • the soft underlayer is obtained by kneading a raw material comprising the following components:
  • the composite material has a total thickness of 1 to 10 mm and a soft underlayer thickness of 0.5 to 9 mm.
  • 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 includes: foaming agent AC, foaming agent H, foaming agent DPT
  • Anti-aging agents include: 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;
  • the formulation of the protective layer and the soft lining layer may also add different auxiliaries according to actual conditions, such as: an activator, a toner, a filling reinforcing agent, a plasticizer, a hardening agent, etc., and the amount thereof is also a conventional amount.
  • the technician can determine it according to the actual situation.
  • Another object of the present invention is to provide a method for preparing the soft and hard integrated composite material having the shape memory function.
  • the protective layer and the soft lining layer are integrally bonded by heat bonding or co-vulcanization, and a surface decorative layer is coated on the outer surface of the protective layer to obtain the composite material having a shape memory function.
  • the co-vulcanization pressure is >3.5 MPa
  • the co-vulcanization temperature is 140 to 200 ° C
  • the co-vulcanization time is 5 to 100 minutes.
  • the soft lining layer is a foamed polyurethane which is adhered to the protective layer by a special heat bonding process of polyurethane; the hot splicing process adopts a hot splicing process which is usually used in the prior art.
  • the co-vulcanization process of the protective layer and the soft lining is more suitable for the molding of the open mill, or the extruder is combined with the molding production process.
  • the vulcanization pressure is >3.5Mpa
  • the vulcanization temperature is 140 ⁇ . 200 ° C
  • vulcanization time 5 ⁇ 100 minutes molded into a soft and hard body personalized protective gear or fixtures.
  • the surface modification layer is modified and beautified to obtain a personalized protective gear or fixture of soft and hard structure.
  • the co-vulcanization of the protective layer and the soft lining layer may also be carried out by irradiation vulcanization, and the process conditions are conventional process conditions.
  • a third object of the present invention is to provide a soft and hard integrated composite material having a shape memory function for use in sports protective gears, handicapped aids, and medical instruments.
  • 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 principle of material shape memory, and the temperature rise of 60 ° C or above, the crystallization of materials such as eucommia gum is changed into an amorphous state, and the principle of free shaping can be used to prepare a personalized plastic protection by mixing, vulcanization and the like respectively. With or with disabilities.
  • the prepared protective gear or accessory can adjust the personalized 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
  • 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 60 ° C ⁇ 10 ° C; the mixing temperature of the soft lining is normal temperature plus cooling water circulation cooling.
  • the same amount of protective layer rubber compound and soft lining rubber compound are weighed, and the predetermined shape and thickness sheet are pre-compressed by using the mold respectively;
  • the pre-compression molding temperature of the protective layer is 60 ° C ⁇ 10 °C;
  • the pre-forming temperature of the soft lining is normal temperature.
  • a pre-formed sheet of a protective layer and a soft lining having almost the same shape and thickness was sequentially placed in a mold for a molding co-vulcanization molding reaction, a vulcanization pressure of 10 MPa, a vulcanization temperature of 140 ° C, and a vulcanization time of 200 minutes.
  • a soft and hard integrated shape memory composite material of equal thickness was obtained, the thickness of the protective layer was 3 mm, and the thickness of the soft lining layer was 3 mm.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is 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.
  • volume ratio of 1:9, 1 part by volume of the protective layer rubber compound and 9 parts by volume of the soft lining rubber compound were weighed, and the predetermined shape and thickness sheet were pre-compressed using a mold, respectively;
  • the molding temperature is 70 ° C ⁇ 10 ° C; the pre-compression molding temperature of the soft lining is normal temperature.
  • the protective layer is pre-compressed into a sheet and placed in a mold for a compression vulcanization molding reaction at 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 1 mm.
  • the pre-compressed sheet of the protective layer and the soft lining layer was sequentially placed in another mold to carry out a compression co-vulcanization molding reaction at a vulcanization temperature of 150 ° C and a vulcanization time of 15 minutes.
  • a foamed soft and hard integrated shape memory composite material was obtained, the thickness of the protective layer was 1 mm, and the thickness of the soft lining layer was 9 mm.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is 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 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 volume ratio of 3:7 weigh 3 parts by volume of the protective layer rubber compound and 7 parts by volume of the soft lining rubber compound, and then pre-compress the predetermined shape and thickness sheet with the mold respectively; the pre-stress of the protective layer
  • the molding temperature is 80 ° C ⁇ 10 ° C; the pre-compression molding temperature of the soft lining is normal temperature.
  • a pre-formed sheet of a protective layer and a soft lining having almost the same shape and thickness was sequentially placed in a mold for a molding co-vulcanization molding reaction, a vulcanization pressure of 7 MPa, a vulcanization temperature of 180 ° C, and a vulcanization time of 50 minutes.
  • a soft and hard integrated shape memory composite material of equal thickness was obtained, the thickness of the protective layer was 1.5 mm, and the thickness of the soft lining layer was 3.5 mm.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is 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 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.
  • volume ratio of 4:6 weigh 4 parts by volume of the protective layer rubber compound and 6 parts by volume of the soft lining rubber compound, and then pre-compress the predetermined shape and thickness sheet by using the mold respectively; the pre-stress of the protective layer
  • the molding temperature is 80 ° C ⁇ 10 ° C; the pre-compression molding temperature of the soft lining is normal temperature.
  • a pre-formed sheet of a protective layer and a soft lining having almost the same shape and thickness was sequentially placed in a mold for a molding co-vulcanization molding reaction, a co-vulcanization pressure of 12 MPa, a vulcanization temperature of 200 ° C, and a vulcanization time of 5 minutes.
  • a soft and hard integrated shape memory composite material of equal thickness was obtained, the thickness of the protective layer was 3 mm, and the thickness of the soft lining layer was 4.5 mm.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.
  • the soft lining is specifically formulated as follows:
  • the protective layer formula is mixed Get the protective layer of semi-finished rubber compound and park it for more than 16 hours.
  • the kneading temperature of the protective layer was 80 ° C ⁇ 10 ° C.
  • the protective layer semi-finished product was placed in a mold to carry out a mold co-vulcanization molding reaction at a vulcanization pressure of 10 MPa, a vulcanization temperature of 150 ° C, and a vulcanization time of 30 minutes.
  • the protective layer vulcanized rubber was obtained, and the thickness of the protective layer was 7 mm.
  • the polyether polyol---water---foaming agent---MDI was added to the stirred tank and stirred uniformly. Then, the protective layer vulcanized rubber is put into the polyurethane foaming mold, and then poured into the evenly mixed polyurethane prepolymer. After the foaming is completed, the soft and hard integrated shape memory composite material and the soft lining layer are 3 mm.
  • the resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.

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Abstract

Disclosed in the present invention are a flexible-rigid integrated composite material having shape memory functions, a preparation method therefor and the use thereof. The composite material comprises three layers, which are positioned from outside to inside: a surface decorative layer, a protective layer and a flexible liner layer. The protective layer is a plastic or a vulcanized plastic, and the plastic is softened by heating at 55 °C or higher, and crystallized and hardened when the temperature is lower than 55 °C. The flexible liner layer is a foamed polyurethane, rubber or a foamed rubber, and the flexible liner layer and the protective layer are formed into an integral structure by means of hot-fitting or co-vulcanization. The surface decorative layer is a coating layer. The present invention, according to the material shape memory principle and the principle that Eucommea rubber and the like crystal materials are melted into an amorphous state when the temperature is increased to 60 °C or higher and thus can be freely molded, uses separate mixing and vulcanization processes to prepare a freely shapable personalized protective device or auxiliary device for disabled persons. The prepared protective device or auxiliary device can be adjusted to a personalized device that best fits the shape of the human body according to different body configurations of different groups of people.

Description

一种具有形状记忆功能的软硬一体化复合材料、制备方法及应用Soft and hard integrated composite material with shape memory function, preparation method and application thereof 技术领域Technical field
本发明涉及高分子材料技术领域，进一步地说，是涉及一种具有形状记忆功能的软硬一体化复合材料、制备方法及应用。The invention relates to the technical field of polymer materials, and further relates to a soft and hard integrated composite material having a shape memory function, a preparation method and an application thereof.
背景技术Background technique
高分子材料在体育护具、残疾人辅具以及医疗器械方面有较为广泛的应用。比如，目前国内市场上销售的体育护具主要由高分子材料制成外壳，抵挡外力对人体的伤害，再由EVA、橡胶、聚氨酯等发泡材料做成内衬，耗散能量，保护人体不受伤害。但是这些护具都有两个共同的缺点无法克服：其一，是这些防护材料都是一次性成型，定型后外观形状不可改变，因而不能适应不同人群身体特征不同的特点；这点对于青少年运动员特别重要，因为青少年是人成长最快的阶段，随着青少年不断长高，身体特征也会发生显著改变，因此不得不多次更换护具，从而增加经济负担；其二，这些材料都是石油基化工原料制成，属于不可再生材料，不利于环保，并且由于运动员个体的体质不同，对部分化学成分刺激过敏，还有的可能产生不适。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.
再比如传统的假肢接收腔是由丙烯酸树脂，经过测量、修形和制造三个步骤制备而成。具有许多缺点：1)制造周期较长、工艺繁杂；2)接收腔的制作属于个性化非标准作业，对假肢矫形师的经验和职业素质要求都比较高，所得产品对于残疾人的适应性差异较大；3)原材料都来源于化石资源，属于不可再生资源，显然不属于绿色产品；4)废弃之后，均会增加碳排放，在环保呼声日益高涨的今天，显然不具环保优势；5)接收腔制备一次定型，不能再次更改。因此，残疾人只能选择近似适合于自身残肢形状的接收腔，而不能得到完全适 合于自身残肢形状的接收腔。6)残肢萎缩后，不得不反复制造接收腔，成本昂贵，增加残疾人的经济负担。并且生产过程耗费大量人力、物力。7)在成本方面，接收腔本身价格在3000元左右，再加上假肢关节、支撑杆、假肢等制件，整个假肢的售价往往在2—4万之间，造价昂贵。因此，由于上述原因，加之残障人士往往因为残疾而失去劳动能力，经济能力往往不高，根本无法负担昂贵的假肢费用。由于得不到优质假肢的支撑，残障人士无法获得重返社会工作的机会，生活质量也会变差，从而陷入致残—返贫—买不起假肢—不能重返社会—生活质量变差这样一个恶性循环。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.
同样高分子材料制备的医疗器械，特别是骨科固定以及矫形器材，也面临体育护具和残疾人假肢的诸多缺点，比如不能够标准化制作，制作工艺复杂，产品为石油基原料等。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.
发明内容Summary of the invention
为解决现有技术中出现的问题，本发明提供了一种具有形状记忆功能的软硬一体化复合材料、制备方法及应用。本发明利用杜仲胶等塑胶材料形状记忆的特殊性能，制备出可反复塑形的个性化产品，可广泛应用于体育护具、残疾人辅具以及医疗器械，特别是骨科固定和矫形领域。比如个性化足球护腿板，这样足球运动员，特别是青少年足球运动员，就可以根据自己的腿型不同或者成长带来的腿型变化，很方便的调整护腿板的形状，使之完全贴合腿部，与腿部融为一体，从而最大限度起到防护作用。再比如个性化残疾人假肢接收腔，这样可以根据残疾人自身残肢的形状，由残疾人士亲自操作，制备出适应于残疾人自身残肢外形的个性化接收腔。同样医疗器械也可以标准化生产、个性化操作，满足医生和患者的需求。此外，本发明的复合材料的结晶熔点在60℃左右，并且是热的不良导体，因而不会在软化塑性的操作过程中烫伤人体。本发明利用的天然高分子材料，属于绿色、环保、可再生的材料，且制备过程基本没有三废排放，符合国家节能减排、发展绿色、低碳、循环经济的要求。In order to solve the problems occurring in the prior art, the present invention provides a soft and hard integrated 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.
本发明的目的之一是提供一种具有形状记忆功能的软硬一体化复合材料。One of the objects of the present invention is to provide a soft and hard integrated composite material having a shape memory function.
所述复合材料包括三层，由外及内分别为：表面装饰层、防护层和软衬层；The composite material comprises three layers, which are: a surface decorative layer, a protective layer and a soft lining layer;
所述防护层为塑胶或硫化塑胶；The protective layer is plastic or vulcanized plastic;
所述生胶在55℃以上受热软化，温度低于55℃之后结晶硬化；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;
所述软衬层为发泡聚氨酯；或橡胶与助剂混炼而得；The soft lining layer is a foamed polyurethane; or the rubber is mixed with an auxiliary agent;
所述软衬层与防护层通过热帖合或共硫化成为一体结构；The soft lining layer and the protective layer are integrated into each other by heat bonding or co-vulcanization;
所述表面装饰层为涂料层。The surface decorative layer is a coating layer.
其中，优选：软衬层与防护层共硫化成为一体结构。Among them, it is preferred that the soft lining layer and the protective layer are co-vulcanized into a unitary structure.
所述塑胶为杜仲胶、古塔波胶、巴拉塔胶、桃叶卫矛胶、合成反式-1,4-聚异戊二烯、聚己内酯中的一种或组合；The plastic is one or a combination of gutta percha, gutta-percha, balata, euonymus, synthetic trans-1,4-polyisoprene, polycaprolactone;
所述橡胶为天然橡胶、丁苯橡胶、顺丁橡胶、三元乙丙橡胶、硅橡胶、氟橡胶、氯丁橡胶、丁腈橡胶、丁基橡胶、丙烯酸酯橡胶、氯磺化聚乙烯中的一种或组合；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;
所述表面装饰层为弹性涂料，更优选为聚氨酯类涂料。表面装饰层可以采用通常的涂覆手段，可刷可涂可喷等方式附着在防护层的表面，起到美化、装饰的作用。涂料必须满足两个条件：一是不溶于水，不水解、耐一定温度(60—100℃)不降解，二是可以随着防护层和软衬层反复塑性不破裂，本发明优选具有弹性的聚氨酯系列涂料。The surface decorative layer is an elastic coating, more preferably a polyurethane 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 coating must meet two conditions: one is insoluble in water, does not hydrolyze, does not degrade at a certain temperature (60-100 ° C), and the other is that it can be repeatedly plasticized with the protective layer and the soft lining. The invention preferably has elasticity. Polyurethane series coatings.
防护层的塑胶优选经过硫化的塑胶，硫化方法可采用现有技术通常的硫化工艺，本发明中，可以优选：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, it may be preferred to:
所述防护层是由包括以下组份的原料混炼而得：The protective layer is obtained by mixing raw materials including the following components:
各组分按重量份数计：Each component is in parts by weight:
Figure PCTCN2018097178-appb-000001
Figure PCTCN2018097178-appb-000001
软衬层的橡胶可优选按配方：The soft lining rubber can preferably be formulated as follows:
所述软衬层是由包括以下组份的原料混炼而得：The soft underlayer is obtained by kneading a raw material comprising the following components:
各组分按重量份数计：Each component is in parts by weight:
Figure PCTCN2018097178-appb-000002
Figure PCTCN2018097178-appb-000002
如果软衬层采用发泡橡胶，则在配方中需要添加发泡剂，发泡工艺可以采用本领域通常的工艺条件，本发明中，优选采用以下配方：If the soft lining layer is made of a foamed rubber, a foaming agent is required in the formulation, and the foaming process can adopt the usual process conditions in the art. In the present invention, the following formula is preferably used:
所述软衬层是由包括以下组份的原料混炼而得：The soft underlayer is obtained by kneading a raw material comprising the following components:
各组分按重量份数计：Each component is in parts by weight:
Figure PCTCN2018097178-appb-000003
Figure PCTCN2018097178-appb-000003
所述复合材料总厚度为1～10mm，软衬层厚度0.5～9mm。The composite material has a total thickness of 1 to 10 mm and a soft underlayer thickness of 0.5 to 9 mm.
以上所述的硫化剂、促进剂、发泡剂、防老剂、填料，可采用现有技术中通常的硫化剂、促进剂、发泡剂、防老剂、填料。本发明中，可以优选：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:
硫化剂包括：硫磺、过氧化物(DCP、双25、BPO)Vulcanizing agents include: sulfur, peroxide (DCP, double 25, BPO)
促进剂包括：促TMTD、促M、促CZ、促DM、促TMTM、促TETD、促DPTT、促ZDC、促BZ、促PZ、促D、促CBS、促TBBS、促NOBS、促DZPromoters 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
发泡剂包括：发泡剂AC，发泡剂H，发泡剂DPTThe foaming agent includes: foaming agent AC, foaming agent H, foaming agent DPT
防老剂包括：防264、防AW、防BLE、防RD、防AH、防AP、防A、防D、防4010、防4010NA、防H、防DPD、防CMA、防2264。Anti-aging agents include: 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.
填料优选钛白粉，碳酸钙，白炭黑；The filler is preferably titanium dioxide, calcium carbonate, white carbon black;
防护层和软衬层的配方中还可根据实际情况添加不同的助剂，如：活化剂、调色剂、填充补强剂、增塑剂、增硬剂等，其用量也为常规用量，技术人员可根据实际情况确定。The formulation of the protective layer and the soft lining layer may also add different auxiliaries according to actual conditions, such as: an activator, a toner, a filling reinforcing agent, a plasticizer, a hardening agent, etc., and the amount thereof is also a conventional amount. The technician can determine it according to the actual situation.
本发明的目的之二是提供一种所述的具有形状记忆功能的软硬一体化复合材料的制备方法。Another object of the present invention is to provide a method for preparing the soft and hard integrated composite material having the shape memory function.
包括：include:
所述防护层和软衬层通过热帖合或共硫化成一体结构，防护层外面涂敷表面装饰层，制得所述具有形状记忆功能的复合材料。The protective layer and the soft lining layer are integrally bonded by heat bonding or co-vulcanization, and a surface decorative layer is coated on the outer surface of the protective layer to obtain the composite material having a shape memory function.
其中，among them,
共硫化压力>3.5Mpa，共硫化温度140～200℃，共硫化时间5～100分钟。The co-vulcanization pressure is >3.5 MPa, the co-vulcanization temperature is 140 to 200 ° C, and the co-vulcanization time is 5 to 100 minutes.
软衬层为发泡聚氨酯，是通过聚氨酯特有的热贴合工艺与防护层贴合；热帖合工艺采用现有技术中通常的热帖合工艺。The soft lining layer is a foamed polyurethane which is adhered to the protective layer by a special heat bonding process of polyurethane; the hot splicing process adopts a hot splicing process which is usually used in the prior art.
防护层和软衬层的共硫化工艺比较适合开炼机配合模压，或者挤出机配合模压生产工艺过程。首先要调节二者的正硫化时间趋于一致，然后将二者分别裁剪成设计好的形状和重量，将二者同时放入模具，采取共硫化工艺，硫化压力>3.5Mpa，硫化温度140～200℃，硫化时间5～100分钟，模压制备成为软硬同体个性化护具或夹具等。最后通过表面修饰层进行修饰、美化，得到软硬同体结构的个性化护具或夹具。The co-vulcanization process of the protective layer and the soft lining is more suitable for the molding of the open mill, or the extruder is combined with the molding production process. Firstly, it is necessary to adjust the positive vulcanization time of the two to be consistent, and then cut the two into the designed shape and weight respectively, put the two into the mold at the same time, adopt the co-vulcanization process, the vulcanization pressure is >3.5Mpa, and the vulcanization temperature is 140～. 200 ° C, vulcanization time 5 ~ 100 minutes, molded into a soft and hard body personalized protective gear or fixtures. Finally, the surface modification layer is modified and beautified to obtain a personalized protective gear or fixture of soft and hard structure.
防护层和软衬层的共硫化也可采用辐照硫化，其工艺条件为常规工艺条件。The co-vulcanization of the protective layer and the soft lining layer may also be carried out by irradiation vulcanization, and the process conditions are conventional process conditions.
本发明的目的之三是提供一种所述的具有形状记忆功能的软硬一体化复合材料在体育护具、残疾人辅具以及医疗器械中的应用。A third object of the present invention is to provide a soft and hard integrated composite material having a shape memory function for use in sports protective gears, handicapped aids, and medical instruments.
主要用于体育护具、残疾人辅具以及医疗器械中骨科固定、矫形、夹板等。Mainly used for sports safety, disability aids and orthopedic fixation, orthopedics, splints, etc.
本发明克服了以往体育护具、残疾人辅具一次定型不可更改以及源自不可再生化石基原料，不利于环保的缺点。本发明利用材料形状记忆原理，以及升温60℃以上，杜仲胶等材料结晶融化变为无定形态，可随意塑型的原理，分别采用混炼，硫化等工艺制备出可随意塑型的个性护具或残疾人辅具。所制备的 护具或辅具可以根据不同人群体型的不同，调整出最贴合人体形状的个性化器械器械。本发明体现在：①制作具有普适性，因而模具的制备简单，降低制造成本；②可随意塑型，同一款产品可以适用不同人群，适用面较宽；③随着青少年成长造成的体型变化，可随意塑型，重复使用，为用户节约成本；④原料来自于可再生高分子材料，有利于环保。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 principle of material shape memory, and the temperature rise of 60 ° C or above, the crystallization of materials such as eucommia gum is changed into an amorphous state, and the principle of free shaping can be used to prepare a personalized plastic protection by mixing, vulcanization and the like respectively. With or with disabilities. The prepared protective gear or accessory can adjust the personalized 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.
附图说明DRAWINGS
图1为本发明的具有形状记忆功能的复合材料示意图Figure 1 is a schematic view of a composite material having a shape memory function of the present invention
附图说明：BRIEF DESCRIPTION OF THE DRAWINGS:
1表面装饰层；2防护层；3软衬层。1 surface decorative layer; 2 protective layer; 3 soft lining.
具体实施方式Detailed ways
下面结合实施例，进一步说明本发明。The invention will now be further described in conjunction with the examples.
实施例1Example 1
防护层具体配方为：The specific formula of the protective layer is:
聚己内酯(塑胶)                   100份Polycaprolactone (plastic) 100 parts
DCP                              0.5份DCP 0.5 parts
钛白粉(填料)                     5份Titanium dioxide (filler) 5 parts
软衬层具体配方为：The soft lining is specifically formulated as follows:
Figure PCTCN2018097178-appb-000004
Figure PCTCN2018097178-appb-000004
根据上述防护层配方和软衬层配方，根据传统橡胶开炼、密炼、捏炼或者挤出混炼工艺，按照橡胶—活化剂—填料—软化剂—防老剂—硫化剂的加料顺序，分别对上述两个配方进行混炼，分别得到防护层混料胶半成品和软衬层混炼胶半成品，停放16小时以上待用。防护层的混炼温度为60℃±10℃；软衬层的混炼温度为常温加冷却水循环冷却。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 60 ° C ± 10 ° C; the mixing temperature of the soft lining is normal temperature plus cooling water circulation cooling.
按照50％的比例，称取等量的防护层混炼胶和软衬层混炼胶，先分别使用模具预压成型预定形状和厚度片材；防护层的预压成型温度为60℃±10℃；软衬层的预压成型温度为常温。According to the ratio of 50%, the same amount of protective layer rubber compound and soft lining rubber compound are weighed, and the predetermined shape and thickness sheet are pre-compressed by using the mold respectively; the pre-compression molding temperature of the protective layer is 60 ° C ± 10 °C; The pre-forming temperature of the soft lining is normal temperature.
将形状和厚度几乎一样的防护层和软衬层的预压成型片材，依次放入到模具中进行模压共硫化成型反应，硫化压力10Mpa，硫化温度140℃，硫化时间200分钟。得到等厚度软硬一体化形状记忆复合材料，防护层厚度3mm，软衬层厚度3mm。A pre-formed sheet of a protective layer and a soft lining having almost the same shape and thickness was sequentially placed in a mold for a molding co-vulcanization molding reaction, a vulcanization pressure of 10 MPa, a vulcanization temperature of 140 ° C, and a vulcanization time of 200 minutes. A soft and hard integrated shape memory composite material of equal thickness was obtained, the thickness of the protective layer was 3 mm, and the thickness of the soft lining layer was 3 mm.
将得到的复合材料防护层进行表面处理，如砂纸打磨，使之粗糙，然后喷涂聚氨酯涂料。最终得到三层软硬一体化形状记忆复合材料。The resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.
实施例2Example 2
防护层具体配方为：The specific formula of the protective layer is:
Figure PCTCN2018097178-appb-000005
Figure PCTCN2018097178-appb-000005
软衬层具体配方为：The soft lining is specifically formulated as follows:
Figure PCTCN2018097178-appb-000006
Figure PCTCN2018097178-appb-000006
根据上述防护层配方和软衬层配方，根据传统橡胶开炼、密炼、捏炼或者挤出混炼工艺，按照橡胶—活化剂—填料—软化剂—防老剂—硫化剂的加料顺序，分别对上述两个配方进行混炼，分别得到防护层混料胶半成品和软衬层混炼胶半成品，停放16小时以上待用。防护层的混炼温度为70℃±10℃；软衬层的混炼温度为常温加冷却水循环冷却。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.
按照1：9的体积比例，称取1体积份的防护层混炼胶和9体积份的软衬层混炼胶，先分别使用模具预压成型预定形状和厚度片材；防护层的预压成型温度为70℃±10℃；软衬层的预压成型温度为常温。According to the volume ratio of 1:9, 1 part by volume of the protective layer rubber compound and 9 parts by volume of the soft lining rubber compound were weighed, and the predetermined shape and thickness sheet were pre-compressed using a mold, respectively; The molding temperature is 70 ° C ± 10 ° C; the pre-compression molding temperature of the soft lining is normal temperature.
先将防护层预压成型片材，放入到模具中进行模压硫化成型反应，硫化压力3.5Mpa，硫化温度150℃，硫化时间100分钟。得到防护层硫化胶，厚度1mm。The protective layer is pre-compressed into a sheet and placed in a mold for a compression vulcanization molding reaction at 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 1 mm.
将防护层和软衬层的预压成型片材，依次放入到另外的模具中进行模压共硫化成型反应，硫化温度150℃，硫化时间15分钟。得到发泡软硬一体化形状记忆复合材料，防护层厚度1mm，软衬层厚度9mm。The pre-compressed sheet of the protective layer and the soft lining layer was sequentially placed in another mold to carry out a compression co-vulcanization molding reaction at a vulcanization temperature of 150 ° C and a vulcanization time of 15 minutes. A foamed soft and hard integrated shape memory composite material was obtained, the thickness of the protective layer was 1 mm, and the thickness of the soft lining layer was 9 mm.
将得到的复合材料防护层进行表面处理，如砂纸打磨，使之粗糙，然后喷涂聚氨酯涂料。最终得到三层软硬一体化形状记忆复合材料。The resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.
实施例3Example 3
防护层具体配方为：The specific formula of the protective layer is:
Figure PCTCN2018097178-appb-000007
Figure PCTCN2018097178-appb-000007
软衬层具体配方为：The soft lining is specifically formulated as follows:
Figure PCTCN2018097178-appb-000008
Figure PCTCN2018097178-appb-000008
根据上述防护层配方和软衬层配方，根据传统橡胶开炼、密炼、捏炼或者挤出混炼工艺，按照橡胶—活化剂—填料—软化剂—防老剂—硫化剂的加料顺序，分别对上述两个配方进行混炼，分别得到防护层混料胶半成品和软衬层混炼胶半成品，停放16小时以上待用。防护层的混炼温度为80℃±10℃；软衬层的混炼温度为常温加冷却水循环冷却。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.
按照3：7的体积比例，称取3体积份的防护层混炼胶和7体积份的软衬层混炼胶，先分别使用模具预压成型预定形状和厚度片材；防护层的预压成型温 度为80℃±10℃；软衬层的预压成型温度为常温。According to the volume ratio of 3:7, weigh 3 parts by volume of the protective layer rubber compound and 7 parts by volume of the soft lining rubber compound, and then pre-compress the predetermined shape and thickness sheet with the mold respectively; the pre-stress of the protective layer The molding temperature is 80 ° C ± 10 ° C; the pre-compression molding temperature of the soft lining is normal temperature.
将形状和厚度几乎一样的防护层和软衬层的预压成型片材，依次放入到模具中进行模压共硫化成型反应，硫化压力7Mpa，硫化温度180℃，硫化时间50分钟。得到等厚度软硬一体化形状记忆复合材料，防护层厚度1.5mm，软衬层厚度3.5mm。A pre-formed sheet of a protective layer and a soft lining having almost the same shape and thickness was sequentially placed in a mold for a molding co-vulcanization molding reaction, a vulcanization pressure of 7 MPa, a vulcanization temperature of 180 ° C, and a vulcanization time of 50 minutes. A soft and hard integrated shape memory composite material of equal thickness was obtained, the thickness of the protective layer was 1.5 mm, and the thickness of the soft lining layer was 3.5 mm.
将得到的复合材料防护层进行表面处理，如砂纸打磨，使之粗糙，然后喷涂聚氨酯涂料。最终得到三层软硬一体化形状记忆复合材料。The resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.
实施例4Example 4
防护层具体配方为：The specific formula of the protective layer is:
Figure PCTCN2018097178-appb-000009
Figure PCTCN2018097178-appb-000009
软衬层具体配方为：The soft lining is specifically formulated as follows:
Figure PCTCN2018097178-appb-000010
Figure PCTCN2018097178-appb-000010
根据上述防护层配方和软衬层配方，根据传统橡胶开炼、密炼、捏炼或者挤出混炼工艺，按照橡胶—活化剂—填料—软化剂—防老剂—硫化剂的加料顺序，分别对上述两个配方进行混炼，分别得到防护层混料胶半成品和软衬层混 炼胶半成品，停放16小时以上待用。防护层的混炼温度为80℃±10℃；软衬层的混炼温度为常温加冷却水循环冷却。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.
按照4：6的体积比例，称取4体积份的防护层混炼胶和6体积份的软衬层混炼胶，先分别使用模具预压成型预定形状和厚度片材；防护层的预压成型温度为80℃±10℃；软衬层的预压成型温度为常温。According to the volume ratio of 4:6, weigh 4 parts by volume of the protective layer rubber compound and 6 parts by volume of the soft lining rubber compound, and then pre-compress the predetermined shape and thickness sheet by using the mold respectively; the pre-stress of the protective layer The molding temperature is 80 ° C ± 10 ° C; the pre-compression molding temperature of the soft lining is normal temperature.
将形状和厚度几乎一样的防护层和软衬层的预压成型片材，依次放入到模具中进行模压共硫化成型反应，共硫化压力12Mpa，硫化温度200℃，硫化时间5分钟。得到等厚度软硬一体化形状记忆复合材料，防护层厚度3mm，软衬层厚度4.5mm。A pre-formed sheet of a protective layer and a soft lining having almost the same shape and thickness was sequentially placed in a mold for a molding co-vulcanization molding reaction, a co-vulcanization pressure of 12 MPa, a vulcanization temperature of 200 ° C, and a vulcanization time of 5 minutes. A soft and hard integrated shape memory composite material of equal thickness was obtained, the thickness of the protective layer was 3 mm, and the thickness of the soft lining layer was 4.5 mm.
将得到的复合材料防护层进行表面处理，如砂纸打磨，使之粗糙，然后喷涂聚氨酯涂料。最终得到三层软硬一体化形状记忆复合材料。The resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.
实施例5Example 5
防护层具体配方为：The specific formula of the protective layer is:
聚己内酯/杜仲胶(塑胶)             50/50份Polycaprolactone / gutta percha (plastic) 50/50 parts
防老剂264                         2份Antioxidant 264 2 parts
双25(硫化剂)                      1.5份Double 25 (vulcanizing agent) 1.5 parts
软衬层具体配方为：The soft lining is specifically formulated as follows:
Figure PCTCN2018097178-appb-000011
Figure PCTCN2018097178-appb-000011
根据上述防护层配方以及传统橡胶开炼、密炼、捏炼或者挤出混炼工艺，按照橡胶—活化剂—填料—软化剂—防老剂—硫化剂的加料顺序，对防护层配方进行混炼，得到防护层混料胶半成品，停放16小时以上待用。防护层的混炼温度为80℃±10℃。According to the above protective layer formula and the traditional rubber smelting, mixing, kneading or extrusion mixing process, according to the rubber-activator-filler-softener-anti-aging agent-vulcanizing agent feeding sequence, the protective layer formula is mixed Get the protective layer of semi-finished rubber compound and park it for more than 16 hours. The kneading temperature of the protective layer was 80 ° C ± 10 ° C.
将防护层半成品放入到模具中进行模共硫化成型反应，硫化压力10Mpa， 硫化温度150℃，硫化时间30分钟。得到防护层硫化胶，防护层厚度7mm。The protective layer semi-finished product was placed in a mold to carry out a mold co-vulcanization molding reaction at a vulcanization pressure of 10 MPa, a vulcanization temperature of 150 ° C, and a vulcanization time of 30 minutes. The protective layer vulcanized rubber was obtained, and the thickness of the protective layer was 7 mm.
按照软衬层的配方，依次放入聚醚多元醇---水---匀泡剂---MDI加入到搅拌釜中搅拌均匀。然后将防护层硫化胶放入到聚氨酯发泡模具中，再倒入搅拌均匀的聚氨酯预聚料，待其发泡完毕后，软硬一体化形状记忆复合材料，软衬层3mm。According to the formulation of the soft lining, the polyether polyol---water---foaming agent---MDI was added to the stirred tank and stirred uniformly. Then, the protective layer vulcanized rubber is put into the polyurethane foaming mold, and then poured into the evenly mixed polyurethane prepolymer. After the foaming is completed, the soft and hard integrated shape memory composite material and the soft lining layer are 3 mm.
将得到的复合材料防护层进行表面处理，如砂纸打磨，使之粗糙，然后喷涂聚氨酯涂料。最终得到三层软硬一体化形状记忆复合材料。The resulting composite protective layer is surface treated, such as sanding, roughened, and then sprayed with a polyurethane coating. Finally, a three-layer soft and hard integrated shape memory composite material is obtained.

Claims (10)

  1. 一种具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material with shape memory function, characterized in that:
    所述复合材料包括三层，由外及内分别为：表面装饰层、防护层和软衬层；The composite material comprises three layers, which are: a surface decorative layer, a protective layer and a soft lining layer;
    所述防护层为塑胶或者硫化塑胶；The protective layer is plastic or vulcanized plastic;
    所述塑胶在55℃以上受热软化，温度低于55℃之后结晶硬化；The plastic is softened by heat at 55 ° C or higher, and the crystal is hardened after the temperature is lower than 55 ° C;
    所述软衬层为发泡聚氨酯、橡胶或发泡橡胶；The soft lining layer is foamed polyurethane, rubber or foamed rubber;
    所述软衬层与防护层通过热帖合或共硫化成为一体结构；The soft lining layer and the protective layer are integrated into each other by heat bonding or co-vulcanization;
    所述表面装饰层为涂料层。The surface decorative layer is a coating layer.
  2. 如权利要求1所述的具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material having a shape memory function according to claim 1, wherein:
    所述塑胶为杜仲胶、古塔波胶、巴拉塔胶、桃叶卫矛胶、合成反式-1,4-聚异戊二烯、聚己内酯中的一种或组合；The plastic is one or a combination of gutta percha, gutta-percha, balata, euonymus, synthetic trans-1,4-polyisoprene, polycaprolactone;
    所述橡胶为天然橡胶、丁苯橡胶、顺丁橡胶、三元乙丙橡胶、硅橡胶、氟橡胶、氯丁橡胶、丁腈橡胶、丁基橡胶、丙烯酸酯橡胶、氯磺化聚乙烯中的一种或组合；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;
    所述表面装饰层为弹性涂料。The surface decorative layer is an elastic coating.
  3. 如权利要求2所述的具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material having a shape memory function according to claim 2, wherein:
    所述弹性涂料为聚氨酯类涂料。The elastic coating is a polyurethane coating.
  4. 如权利要求1所述的具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material having a shape memory function according to claim 1, wherein:
    所述防护层是由包括以下组份的原料混炼而得：The protective layer is obtained by mixing raw materials including the following components:
    各组分按重量份数计：Each component is in parts by weight:
    Figure PCTCN2018097178-appb-100001
    Figure PCTCN2018097178-appb-100001
    Figure PCTCN2018097178-appb-100002
    Figure PCTCN2018097178-appb-100002
  5. 如权利要求4所述的具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material having a shape memory function according to claim 4, wherein:
    所述软衬层是由包括以下组份的原料混炼而得：The soft underlayer is obtained by kneading a raw material comprising the following components:
    各组分按重量份数计：Each component is in parts by weight:
    Figure PCTCN2018097178-appb-100003
    Figure PCTCN2018097178-appb-100003
  6. 如权利要求5所述的具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material having a shape memory function according to claim 5, wherein:
    所述软衬层是由包括以下组份的原料混炼而得：The soft underlayer is obtained by kneading a raw material comprising the following components:
    各组分按重量份数计：Each component is in parts by weight:
    Figure PCTCN2018097178-appb-100004
    Figure PCTCN2018097178-appb-100004
  7. 如权利要求1所述的具有形状记忆功能的软硬一体化复合材料，其特征在于：A soft and hard integrated composite material having a shape memory function according to claim 1, wherein:
    所述复合材料总厚度为1～10mm，软衬层厚度0.5～9mm。The composite material has a total thickness of 1 to 10 mm and a soft underlayer thickness of 0.5 to 9 mm.
  8. 一种如权利要求1～7之一所述的具有形状记忆功能的软硬一体化复合材料的制备方法，其特征在于所述方法包括：A method for preparing a soft and hard integrated composite material having a shape memory function according to any one of claims 1 to 7, wherein the method comprises:
    所述防护层和软衬层通过热帖合或共硫化成一体结构，防护层外面涂敷表面装饰层，制得所述具有形状记忆功能的复合材料。The protective layer and the soft lining layer are integrally bonded by heat bonding or co-vulcanization, and a surface decorative layer is coated on the outer surface of the protective layer to obtain the composite material having a shape memory function.
  9. 如权利要求8所述的具有形状记忆功能的软硬一体化复合材料的制备方法，其特征在于：The method for preparing a soft and hard integrated composite material having a shape memory function according to claim 8, wherein:
    共硫化压力>3.5Mpa，共硫化温度140～200℃，共硫化时间5～100分钟。The co-vulcanization pressure is >3.5 MPa, the co-vulcanization temperature is 140 to 200 ° C, and the co-vulcanization time is 5 to 100 minutes.
  10. 如权利要求1～7之一所述的具有形状记忆功能的软硬一体化复合材料在体育护具、残疾人辅具、以及医疗器械中的应用。The soft and hard integrated composite material having a shape memory function according to any one of claims 1 to 7 for use in sportswear, handicapped aids, and medical instruments.
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