CN111004366A - Tissue organ-imitated polyurethane-based composite material for dummy and preparation method thereof - Google Patents
Tissue organ-imitated polyurethane-based composite material for dummy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of bionic polymer composite materials, and relates to a tissue organ simulating polyurethane-based composite material for a dummy and a preparation method thereof. The composite material is prepared by reacting isocyanate with an alcohol organic matter to generate a prepolymer, blending a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler to prepare a curing agent, and blending the prepolymer and the curing agent and casting. The parameters such as the types, the proportions and the like of the components in the reaction are adjusted, so that the mechanical property of the prepared composite material meets the following requirements: the strength in a tensile test is 0.005-20 MPa, the elongation at break is 0.85-6.8, and the modulus is 0.004-15 MPa; the strength is 0.005 to 20MPa when the deformation rate is 30% in the compression test. The polyurethane-based composite material prepared by the invention is a bionic material with mechanical properties highly similar to human tissues and organs, and can meet the requirements of manufacturing various bionic prostheses which need to simulate the collision, penetration and other tests of the human tissues and organs.
Description
Technical Field
The invention belongs to the technical field of bionic polymer composite materials, and particularly relates to a tissue organ simulating polyurethane-based composite material for a dummy and a preparation method thereof.
Background
The research on the safety performance of human bodies under the extreme environments of automobile collision, target shooting, parachuting, aerospace and the like, such as impact, collision, penetration and the like, is an important subject in the safety field, and the current ubiquitous method is to adopt a dummy to replace a real person to simulate the human bodies to carry out safety tests on different stress occasions. Internationally universal dummy generally uses metal materials such as aluminum alloy, steel and the like to simulate a human body skeleton, uses materials such as rubber, silica gel, plastic and the like to simulate human body soft tissues, and installs sensors at different parts to test human body stress to make damage judgment. Because the market of the dummy is monopolized abroad, the dummy is expensive, and the body type and application occasions can not meet the requirements of domestic tests, the development of the test dummy which is low in price and can meet the requirements of mechanical response has very practical significance.
The human tissue includes tissues such as muscle tissue and skin tissue, and internal organs such as heart, liver, lung, stomach and kidney, and the like, according to literature reports, the tensile modulus of the muscle tissue is 100-200 KPa, the tensile strength is more than 50KPa, the ultimate strain is more than 90%, and the compressive strength is 5-60 KPa when the compressive deformation is 30% (Wangbaozhen. soft tissue dynamic mechanical property research _ Wangbaozhen [ D ] [ fertilizer combination ]: Chinese scientific and technical university, 2010.), and the compressive strength is 1.6-14 MPa when the compressive deformation of organs such as liver, kidney and spleen is 18% -68% (JMechBehavBiomedMater,2013, 17, 22-33). Therefore, there are large differences in the mechanical properties of different tissues and organs in the human body.
At present, some bionic researches on simulating tissues and organs of a human body are developed domestically, mainly relating to the fields of tissue repair, intelligent response and the like, and relatively few patents are used for testing dummy or mechanical simulation. The Chinese patent CN107641271A discloses a collision dummy skin and a preparation process, wherein universal polyvinyl chloride (PVC) and Thermoplastic Polyurethane (TPU) are physically mixed according to a proportion and heated by a double-rotor mixing roll, and the mixture is pressed into a skin material with a certain thickness by a tabletting machine after being mixed. The method can be used for preparing the flat sheet, but cannot simulate the curved surface of the skin combined with the dummy body, cannot be jointed with the dummy body, and the processing technology is more complicated than casting molding. Chinese patent CN207336018U discloses a dummy skin capable of being impacted for many times, wherein the skin outer layer is made of memory sponge and silica gel, and the outer wall of one side of the memory sponge is provided with a water bag mounting groove and a water inlet. Chinese patent CN109438659A discloses a non-yellowing polyurethane material for crash dummy and a preparation method thereof. The patent is mainly aimed at preventing yellowing, and is improved on reactant components, but does not relate to the analysis of mechanical response of a dummy subjected to external force. Chinese patent CN109575321A discloses an electro-responsive interpenetrating polymer hydrogel and a preparation method thereof, which is an interpenetrating polymer network hydrogel formed by a water-soluble polyurethane cross-linked network and an acrylic acid-CO-2-acrylamide-2-methylpropanesulfonic acid-CO-N, N' -methylenebis (acrylamide) cross-linked network to manufacture artificial muscle. The invention in the examples mentions that the tensile strength sum of the two hydrogels is 650kPa and 625kPa, respectively, and the elongation at break is 45% and 58%, respectively, whereas the invention focuses mainly on the electrical response, lacks matching of different soft tissues and their mechanical properties, and is not suitable for the development of total prosthetic materials.
In summary, although some researches have been made on the application fields of various elastic materials in artificial muscles and skins, no materials suitable for the whole dummy and matching the mechanical properties with different tissues and organs of the human body have been systematically developed so far. The existing research lacks the structural design of matching materials for mechanical properties of different tissues and organs in a dummy, and the traditional materials such as rubber, silica gel, plastic and the like can not accurately match the stress condition of each tissue and organ.
The polyurethane is composed of hard segments which are glassy paracrystal or microcrystal and have strong polarity and rigidity, and segments which are weak in polarity, such as polyether segments or polyester segments, which are gathered together to form soft segments. The soft and hard segments are somewhat miscible, but the hard and soft segments form two distinct phase domains exhibiting significant thermodynamic incompatibility resulting in microscopic phase separation and thus distinct domains. The mechanical properties of the composite material such as tensile and compressive strength, modulus, elongation and the like can be changed by adjusting the proportion of the soft segment and the hard segment. The polyurethane-based composite material can change the mechanical property of the polyurethane by adding a plasticizer, a filler and the like before the polyurethane is cured and crosslinked, and can realize high bionics with the mechanical property equivalent to that of human organs and soft tissues by adjusting the parameters such as the types and the proportions of isocyanate, alcohols, a chain extender, a crosslinking agent, a catalyst, the plasticizer and the filler in reactants.
Therefore, the preparation of the polyurethane-based composite material with high bionic human tissue and organ mechanical properties for the dummy has important significance for meeting the application of the bionic dummy which needs to simulate the stress of human tissue and organ under extreme environment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention firstly aims to provide a tissue organ simulating polyurethane-based composite material for a dummy, wherein the polyurethane-based composite material has viscoelasticity, tensile strength, tensile modulus and higher elongation rate which are in accordance with tissues and organs of a human body, and the application of the polyurethane-based composite material in the fields of artificial tissues and organs and bionic dummy is widened.
The second purpose of the invention is to provide the application of the tissue organ imitating polyurethane-based composite material for the dummy.
The third purpose of the invention is to provide a preparation method of a tissue organ-imitated polyurethane-based composite material for a dummy, which is prepared by the steps of reacting isocyanate with an alcohol organic matter to generate a prepolymer, blending a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler to prepare a curing agent, and blending and casting the prepolymer and the curing agent.
In order to achieve the purpose, the invention is realized by the following technical scheme: the invention provides a tissue organ-imitated polyurethane-based composite material for a dummy, which is characterized in that the polyurethane-based composite material is prepared by reacting isocyanate and an alcohol organic matter to generate a prepolymer, blending a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler to prepare a curing agent, and blending the prepolymer and the curing agent and casting the mixture. By adjusting parameters such as the types and the proportions of isocyanate, alcohols, a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler in reactants, the mechanical property of the polyurethane-based composite material is adjustable within the following range: in a tensile test, the strength range is 0.005-20 MPa, the elongation at break range is 0.85-6.8, and the modulus range is 0.004-15 MPa; in the compression test, the strength is 0.005 to 20MPa when the compression deformation rate is 30%.
The polyurethane-based composite material has the capability of highly simulating the mechanical properties of different tissues and organs of a human body.
The invention also provides the application of the tissue organ-imitated polyurethane-based composite material for the dummy, which is characterized in that the material can be used for artificially imitating tissues such as muscle, fat and skin and organs such as liver, lung, pancreas, kidney and heart, and can also be used as a civil, military and aerospace mechanics environment simulation dummy.
The invention also provides a preparation method of the tissue organ-imitated polyurethane-based composite material for the dummy, which is characterized by comprising the following steps of:
s01, reacting isocyanate with an alcohol organic matter to generate a prepolymer;
s02, blending a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler to prepare a curing agent;
and S03, blending the prepolymer and the curing agent, and casting and molding.
And S01 is specifically that the reaction container is connected with a water bath with a preset temperature of 50-90 ℃, a certain amount of isocyanate is added into the reaction container under the nitrogen atmosphere, stirring is started after the isocyanate is in a uniform liquid phase, the dehydrated alcohol organic matter is dropwise added into the reaction container once or continuously according to the quantity ratio of-NCO to-OH substances of 1-3 for reaction, the dropwise adding time is 0-4 hours, and the reaction is carried out for 1-4 hours at the temperature of 50-90 ℃ after the dropwise adding is finished, so that the prepolymer is obtained.
The step S02 is specifically to blend 100 parts of chain extender, 10-50 parts of cross-linking agent, 0-8 parts of catalyst, 0-100 parts of plasticizer and 0-100 parts of filler at room temperature-100 ℃ to prepare the curing agent.
The step S03 is specifically that the prepolymer obtained in the step S01 is preheated to 40-70 ℃, and the temperature of the curing agent obtained in the step S02 is controlled to be 30-70 ℃; in order to prevent micro bubbles from being generated during pouring, the prepolymer and the curing agent are vacuumized for about 30 minutes; the prepolymer and the curing agent are prepared from 20: 100-200: mixing and stirring the components according to the proportion of 100, and controlling the temperature to be 30-100 ℃; stirring for 0.1-20 min, injecting into a mold, controlling the temperature of the mold to be 30-100 ℃, and demolding after 20-360 min; post-vulcanizing at 40-90 ℃ for 0.5-16 hours.
The isocyanate is specifically any one or combination of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The alcohol organic matter is any one or combination of more of polyoxypropylene diol, polyoxypropylene triol, trimethylolpropane, polytetrahydrofuran diol and tetrahydrofuran-propylene oxide copolymerized diol.
The chain extender and the cross-linking agent are any one or combination of more of ethylene glycol, 1, 4-butanediol, trimethylolpropane, polyoxypropylene glycol, polyoxypropylene ether triol, 4 '-diamino-3, 3' -dichlorodiphenylmethane and dimethyl-thio-toluenediamine.
The catalyst is specifically any one or combination of more of N, N-dimethylcyclohexylamine, triethylamine, N' -dimethylpyridine and triethanolamine.
The filler is one or more of glass fiber, medium super carbon black, precipitated calcium carbonate and carbon powder.
The plasticizer is specifically any one or combination of more of dioctyl phthalate, dioctyl terephthalate, dimethoxy ethylene glycol phthalate, tricresyl phosphate, dipropylene glycol phthalate and triethylene glycol dipelargonate.
The invention constructs a multilayer network structure elastomer material by utilizing polyurethane, explores a first-layer network of the elastomer by designing the proportion of a soft segment and a hard segment while maintaining the viscoelasticity of a polyurethane-based composite material, and preliminarily adjusts the mechanical properties of the material, such as tensile and compressive strength, modulus, elongation and the like; then, a second-level network is constructed by controlling the selection and the dosage of the cross-linking agent; and finally, a third-level network is constructed by controlling the addition amounts of the filler and the plasticizer, and finally, the tensile and compressive strength and modulus are adjusted and simultaneously matched with the related mechanical properties of human soft tissues. The invention adopts a three-step method to prepare the polyurethane-based composite material with high bionic human tissue organ mechanical property: 1) isocyanate and alcohol organic matters are adopted to react to generate a prepolymer, the proportion of a soft segment and a hard segment is controlled by selecting different isocyanate and alcohols with different types and molecular weights, and a mechanical network structure is preliminarily designed; 2) selecting proper chain extender, cross-linking agent, catalyst, plasticizer and filler, further controlling the proportion of soft segment, hard segment and cross-linking point, and further designing a mechanical network structure; 3) the prepolymer and the chain extension cross-linking agent are adopted to carry out chain extension cross-linking reaction, and finally the multilayer network type structure elastomer material is formed, so that the corresponding matching of the mechanical properties of different tissues and organs of a human body is realized.
The invention has the beneficial effects that:
(1) the method takes the commonly used reactants in the market as raw materials, selects the low-cost filler and the plasticizer, prepares the required materials by a simple three-step method, has wide raw material sources and simple preparation method, avoids using the raw materials with higher cost, and has high popularization possibility in practical production and application.
(2) The invention realizes the three-layer network structure of the elastomer by the methods of the design of the soft segment and the hard segment, the design of the cross-linking point, the design of the filling material, the plasticization, and the like, controls the mechanical properties (strength, modulus, elongation, and the like) of the composite material, and can be correspondingly matched with the corresponding mechanical properties of different tissues and organs of a human body not only in the tensile property but also in the compressibility.
(3) The composite material has the property of highly simulating the mechanical properties of different tissues and organs of a human body, thereby widening the range of the artificial bionic muscle, fat, skin and other tissues and liver, lung, pancreas, kidney, heart and other organs for the dummy made of the polyurethane-based composite material, and further realizing the important significance of the application of the dummy in the fields of extreme environments such as civil use, military use, aerospace and the like.
Detailed description of the invention
The technical solution of the present invention is further described below with reference to examples, but the practice of the present invention is not limited thereto. The method for testing the mechanical property of the prepared composite material comprises the following steps: the resulting composite was subjected to tensile and compression testing using a U.S. Instron3369 mechanical testing machine. The tensile specimen size was 10mm in width, 4mm in thickness and 80mm in parallel distance, and the test was carried out at a strain rate of 0.1/s. The compressed sample dimensions were 10mm wide, 4mm thick and 10mm long and tested at a strain rate of 0.1/s.
Example 1: preparation of polyurethane-based composite material with simulated liver compression mechanical property
Connecting a reaction container with a water bath at 80 ℃, adding 100 parts of polyoxypropylene diol (average molecular weight 2000), 30-45 parts of polyoxypropylene triol (average molecular weight 3000) and 20-35 parts of toluene diisocyanate (TDI-80) into the reaction container under nitrogen atmosphere, and stirring for reacting for 3 hours to obtain the prepolymer. 100 parts of polyoxypropylene diol (average molecular weight of 3000), 50 parts of dioctyl phthalate and 50 parts of calcium carbonate are added into 25 parts of molten 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) to prepare a hardening agent; mixing and stirring the prepolymer and the cross-linking agent according to the weight ratio of 100-150: 100, and controlling the temperature at 40 ℃; stirring for 5 minutes, injecting into a mold, controlling the temperature of the mold to be 70-90 ℃, and demolding after 60 minutes; and (3) post-vulcanizing at 80-100 ℃ for 8 hours to obtain the polyurethane-based composite material with the simulated liver tensile compression mechanical property.
The prepared composite material has the following mechanical test results: in the tensile test, the tensile modulus is 363KPa, the ultimate strength is 768KPa, and the ultimate elongation is 1.82; in the compression test, the compressive strength was 1.8MPa at a deformation rate of 30%. The mechanical properties are highly similar to those of the liver.
Example 2: preparation of skin-imitated polyurethane-based composite material
Connecting a reaction container with a water bath at 80 ℃, adding 100 parts of polyoxypropylene diol (with an average molecular weight of 1000), 60-85 parts of polyoxypropylene triol (with an average molecular weight of 3000) and 45-70 parts of toluene diisocyanate (TDI-80) into the reaction container under a nitrogen atmosphere, and stirring for reacting for 3 hours to obtain the prepolymer. 100 parts of polyoxypropylene diol (molecular weight is 3000), 20 parts of dioctyl phthalate and 100 parts of calcium carbonate are added into 25 parts of molten 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) to prepare a hardening agent; mixing and stirring the prepolymer and the cross-linking agent according to a weight ratio of 90-120: 100, and controlling the temperature at 40 ℃; stirring for 5 min, injecting into a mold, controlling the temperature of the mold to be 60 ℃ again, and demolding after 60 min; and post-vulcanizing at 70 ℃ for 8 hours to obtain the polyurethane-based composite material with the skin-imitated compression mechanical property.
The prepared composite material has the following mechanical test results: in a tensile test, the tensile modulus is 1.7MPa, the ultimate strength is 7.24MPa, and the ultimate elongation is 3.2; in the compression test, the compressive strength was 2.95MPa at a deformation rate of 30%. The mechanical properties are highly similar to skin.
Example 3: and (3) preparing a muscle-like polyurethane-based composite material.
Connecting a reaction container with a water bath at 80 ℃, adding 100 parts of polyoxypropylene diol (with average molecular weight of 4000), 30-45 parts of polyoxypropylene triol (with average molecular weight of 6000) and 10-30 parts of toluene diisocyanate (TDI-80) into the reaction container under nitrogen atmosphere, and stirring for reacting for 3 hours to obtain the prepolymer. 100 parts of polyoxypropylene diol (with the molecular weight of 4000), 70 parts of dioctyl phthalate and 10 parts of glass fiber (with the size of 400 meshes) are added into 25 parts of molten 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA) to prepare a hardening agent; mixing and stirring the prepolymer and the cross-linking agent according to the weight ratio of 160-240: 100, and controlling the temperature at 40 ℃; stirring for 5 minutes, injecting into a mold, controlling the temperature of the mold to be 70-90 ℃, and demolding after 60 minutes; and (3) post-vulcanizing at 80-100 ℃ for 8 hours to obtain the polyurethane-based composite material with the simulated muscle tensile compression mechanical property.
The prepared composite material has the following mechanical test results: in the tensile test, the tensile modulus is 94KPa, the ultimate strength is 330KPa, and the ultimate elongation is 1.98; in the compression test, the compression strength was 7KPa at a deformation rate of 30%. The mechanical properties are highly similar to those of muscles.
Claims (15)
1. A tissue organ simulating polyurethane-based composite material for a dummy is characterized in that the polyurethane-based composite material is prepared by reacting isocyanate with an alcohol organic matter to generate a prepolymer, blending a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler to prepare a curing agent, and blending and casting the prepolymer and the curing agent.
2. The polyurethane-based composite of claim 1, wherein the composite has properties that mimic highly similar mechanical properties of different tissues and organs of the human body.
3. The polyurethane-based composite material according to claim 1, wherein the mechanical properties of the polyurethane-based composite material are adjustable within the following ranges by adjusting parameters such as the types and proportions of isocyanate, alcohol, chain extender, cross-linking agent, catalyst, plasticizer and filler in the reactants: in a tensile test, the strength range is 0.005-20 MPa, the elongation at break range is 0.85-6.8, and the modulus range is 0.004-15 MPa; in a compression test, when the compression deformation rate is 30%, the strength is 0.005-20 MPa, and the corresponding matching of the mechanical properties of different tissues and organs of a human body is realized.
4. The polyurethane-based composite material according to claim 1, wherein the material is used for artificially simulating tissues such as muscle, fat and skin, and organs such as liver, lung, pancreas, kidney and heart.
5. A polyurethane-based composite material as claimed in claim 1, wherein the material is used to produce a dummy for one-time damage in extreme environments such as civil, military and aerospace applications.
6. A polyurethane-based composite material according to any one of claims 1 to 5, wherein the material is prepared by a method comprising the steps of:
s01, reacting isocyanate with an alcohol organic matter to generate a prepolymer;
s02, blending a chain extender, a cross-linking agent, a catalyst, a plasticizer and a filler to prepare a curing agent;
and S03, blending the prepolymer and the curing agent, and casting and molding.
7. The method of claim 6, wherein the step S01 is performed by connecting a reaction vessel with a water bath having a predetermined temperature of 50 to 90 ℃, adding a certain amount of isocyanate into the reaction vessel under nitrogen atmosphere, stirring after the isocyanate is in a uniform liquid phase, adding the dehydrated alcohol organic substance into the reaction vessel dropwise once or continuously according to the amount ratio of-NCO to-OH substances of 1 to 3, reacting for 0 to 4 hours, reacting at 50 to 90 ℃ for 1 to 4 hours, and discharging the reaction product to obtain the prepolymer.
8. The method for preparing a polyurethane-based composite material as claimed in claim 6, wherein the step S02 is to blend 100 parts of chain extender, 10-50 parts of cross-linking agent, 0-8 parts of catalyst, 0-100 parts of plasticizer and 0-100 parts of filler at room temperature to 100 ℃ to obtain the curing agent.
9. The method for preparing the polyurethane-based composite material as claimed in claim 6, wherein the step S03 is specifically that the prepolymer obtained in the step S01 is preheated to 40-70 ℃, and the temperature of the curing agent obtained in the step S02 is controlled to 30-70 ℃; in order to prevent micro bubbles from being generated during pouring, the prepolymer and the curing agent are vacuumized for about 30 minutes; the prepolymer and the curing agent are prepared from 20: 100-200: mixing and stirring the components according to the proportion of 100, and controlling the temperature to be 30-100 ℃; stirring for 0.1-20 min, injecting into a mold, controlling the temperature of the mold to be 30-100 ℃, and demolding after 20-360 min; post-vulcanizing at 40-90 ℃ for 0.5-16 hours.
10. The isocyanate according to any one of claims 1 to 9, which is any one or a combination of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
11. The organic alcohol compound according to any one of claims 1 to 9, which is one or a combination of two or more selected from the group consisting of polyoxypropylene diol, polyoxypropylene triol, trimethylolpropane, polytetrahydrofuran diol, and tetrahydrofuran-oxypropylene copolyol.
12. The chain extender and the cross-linking agent according to any one of claims 1 to 9, which is any one or a combination of more of ethylene glycol, 1, 4-butanediol, trimethylolpropane, polyoxypropylene glycol, polyoxypropylene ether triol, 4 '-diamino-3, 3' -dichlorodiphenylmethane, and dimethylthiotoluenediamine.
13. The catalyst according to any one of claims 1 to 9, which is one or more selected from the group consisting of N, N-dimethylcyclohexylamine, triethylamine, N' -dimethylpyridine, and triethanolamine.
14. The filler according to any one of claims 1 to 9, which is one or more of glass fiber, medium super black, precipitated calcium carbonate and carbon powder.
15. The plasticizer according to any of claims 1 to 9, which is any one or a combination of dioctyl phthalate, dioctyl terephthalate, dimethoxyethylene terephthalate, tricresyl phosphate, dipropylene glycol phthalate, triethylene glycol dipelargonate.
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