An artificial rubber material, its preparation and use

Abstract

The application discloses a simulation rubber material and a preparation method and application thereof. The simulation rubber material is prepared from hydrogenated polystyrene-conjugated diene block copolymer with a dendritic random asymmetric long-chain branched structure as a main base material, filling oil, fillers, colorants and the like to form a rubber material. The simulation rubber material has the advantages of meat-like elasticity, high cohesion and tensile strength, constant hardness and strength under changes of medium and low temperature and time, stable use or storage, good oil fixation performance, low oil permeation rate and constant compression deformation resistance, and the comprehensive physical performance is superior to that of a simulation adult health care tool using TPE as a main material.

Description

Technical Field

[0001] This invention relates to a simulated rubber material, specifically a simulated rubber material with highly simulated elasticity, feel, hardness, and strength, made primarily of hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer. It exhibits good oil-binding properties at medium and low temperatures, low oil permeation, and resistance to deformation under pressure. The invention also relates to its preparation method and its application in simulated bonded products, belonging to the field of functional rubber materials technology. Background Technology

[0002] Early typical inflatable sex dolls and sex toys first appeared in Japan. Their texture was already quite close to real skin, but they still felt hard to the touch. Manufacturers attempted to create dolls with skeletons, but the results were not ideal. In the 2000s, the world's first artificial sex toy made of rubber was introduced. Japanese-made dolls were incredibly realistic in appearance and had a feel close to real skin. The article "Hidden Business Opportunities, Modern Marketing (April 2012)" describes China as the world's largest producer of sex toys, accounting for approximately 60% to 80% of the total market. China is a potential major consumer market for adult products, and is expected to enter a period of explosive growth in the consumption of sex toys within 3-5 years, followed by a 15-year period of rapid development.

[0003] Today, the world's adult product manufacturers are mainly located in the Yangtze River Delta and Pearl River Delta regions of China. Their products are sold in adult product stores on the streets and online platforms, and are also exported in large quantities globally, especially to Europe and America. Today's rubber masturbation products, such as fully lifelike inflatable dolls, masturbators, inflatable brothers and sisters, realistic dolls, fake penises, and realistic genitals, are more comfortable and desirable than any previously known artificial devices. They are excellent substitutes for men and women who lack sexual partners. Statistics show that the annual sales of sex products reach 20 billion yuan. Sexual health products have been accepted by over 93% of adults and are growing at a rate of 63.9% annually. With the advent of TPE, a highly oil-filled thermoplastic elastomer material that provides a more "fleshly" feel, it has now replaced 80-90% of silicone sex products that cannot be further softened by oil filling.

[0004] The article "Adult Products, Scientific New Life (Issue 39, 2014)" discussed how adult products are a double-edged sword. In recent years, with changing attitudes towards sex, the use of adult products to achieve therapeutic purposes or obtain physiological and psychological satisfaction has gradually become accepted by some. Statistics reveal that adult product stores are flooded with counterfeit and substandard products, the harm of which is alarming. While existing commercially available male and female sexual partners use thermoplastic elastomers (TPE) instead of silicone, making them more affordable, especially with the commercial application of hydrogenated polystyrene-conjugated diene copolymer elastomers as the main material, hundreds of sizes, appearances, and colors of oil-filled products have been developed. Some products even mimic the weight of an adult. However, after 90 days of storage at room temperature, they exhibit slight cold flow, deformation, and oil seepage. Furthermore, existing TPE products require surface coating with quartz powder, magnesium oxide powder, or calcium powder after production or during storage and transportation to prevent finger sticking. When excessive oil seepage occurs, the product loses its original appearance and even its functionality.

[0005] In the prior art, such as Chinese Patent (CN106243742A, 2016-12-21), a water-based self-lubricating thermoplastic elastomer, its preparation method, and its uses are described. This water-based self-lubricating thermoplastic elastomer is composed of 10-30 parts of thermoplastic elastomer resin, 80-120 parts of filler oil, 5-15 parts of water-based lubricant, 0.2-0.5 parts of processing aid, and 0.05-0.2 parts of antibacterial agent. The material thickens on the surface when it comes into contact with water, producing a delicate and comfortable slippery effect. It does not require the addition of a large amount of lubricant, can be reused multiple times, and has antibacterial effects. It can be widely used in products such as adult toy masturbators. Chinese patents (CN111548595A, 2020-08-18, CN111560152A, 2019-04-13) describe a preparation method and application of a highly antibacterial, far-infrared fluorinated graphene / SEBS composite elastomer, relating to the field of composite materials for adult products. The method involves ball milling 1-10 parts of fluorinated graphene, 5-30 parts of softening oil, 1-10 parts of erucamide, 2-10 parts of perfluorooctanoic acid ammonium, and 1-5 parts of oleamide to obtain a preparative material. Then, 80-100 parts of SEBS elastomer are thoroughly mixed with the preparative material to obtain a fluorinated graphene / SEBS composite compound. The compound is then placed in a fluorination chamber for fluorination treatment. Finally, the fluorinated graphene / SEBS composite elastomer compound is extruded and granulated. The prepared composite material has excellent mechanical properties, lubrication properties, and bactericidal and bacteriostatic functions. It can also generate far-infrared effects at room temperature and can be widely used in products such as adult toy masturbators and dildos.

[0006] For example, Chinese patent (CN214026697U, 2021-08-24) describes the preparation and application of a heating box for male masturbation soft rubber products. Because the product's storage temperature is lower than human body temperature and it lacks the body's temperature sensitivity, this heating box uses a thermoelectric wire to heat the male masturbation soft rubber. Through a heat-reflective coating inside the box, heat can be better radiated throughout the entire heating chamber, facilitating comprehensive and uniform heating of the adult masturbation soft rubber, aiming to reach a normal or slightly higher temperature than human body temperature. However, existing commercially available SEBS or SEPS products with high oil content deform at temperatures above 50°C and melt on the surface at 60°C, losing their functionality.

[0007] Chinese patent (CN109206568B, 2021-09-03) describes a type of SBS containing uniformly distributed butadiene blocks with 1,2-structure, its hydrides, and methods for preparation and application. The preparation process of hydrogenated SBS involves a first-stage polymerization of styrene initiated by an activator. The second-stage polymerization involves dissolving a 1,2-structure modifier in butadiene and uniformly adding it to the polymerization reactor over 16-18 minutes. After addition, the reaction continues for 8-12 minutes. The third-stage polymerization can be carried out using styrene or coupled with a coupling agent. The resulting SBS contains 38-42% uniformly distributed 1,2-addition units in the polybutadiene blocks. The hydrogenated SBS exhibits good compatibility and stability with naphthenic oils or white oils, low oil migration, and high light transmittance, making it widely applicable to transparent elastic materials. However, this technology does not use divinylbenzene as a branching agent in the second-stage reaction, and there is no description of its application in adult sex products. The paper "Preparation Process and Performance Study of SEBS-Based Modified Materials, Qingdao University of Science and Technology, Materials Engineering (Master's Thesis), 2020" introduces styrene-ethylene / butene-styrene thermoplastic elastomer (SEBS), a type of green and environmentally friendly material that aligns with current societal development. Due to its excellent weather resistance, thermal stability, aging resistance, insulation, and ozone oxidation resistance, SEBS is widely used in various fields. However, despite these superior properties, SEBS materials still exhibit several shortcomings under certain specific conditions.

[0008] In summary, existing thermoplastic elastomer-based adult sex toys suffer from several drawbacks, including poor resistance to medium temperatures, easy deformation, melting upon hot air heating, slight cold flow deformation during room temperature storage, and oil seepage leading to adhesion to human skin. However, no reports have yet described composite elastic materials for adult sex toys that, after being filled with oil, possess a realistic human-like feel, high strength, low tensile strength and deformation, are non-leaking, resistant to medium and low temperatures, and do not deform due to cold flow during storage. Summary of the Invention

[0009] As is well known, the necessary conditions for existing adult sex toys, uterine molds, realistic dolls, and phalluses are that they should be elastic, fleshy, and unaffected by changes in hardness and strength due to variations in temperature and time. They should also be stable in all aspects during use or storage. While existing commercially available SEBS or SEPS oil-filled products can meet certain requirements in terms of elasticity, fleshiness, hardness, and strength, they require preheating in colder seasons to reach temperatures above body temperature (37°C) for optimal pleasure. They still cannot withstand medium to high temperatures above 50°C, and prolonged storage can lead to cold flow, oil seepage, poor oil retention, shrinkage, and deformation. Currently, no polymer material has yet fully met the above conditions.

[0010] The first objective of this invention is to provide a simulated rubber material, which is a composite rubber material composed of hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer as the base rubber, and filler oil, filler, colorant, etc. It has fleshy elasticity, high cohesiveness and tensile strength, and its hardness and strength remain unchanged under changes in medium and low temperature and time. It is stable in use or storage, has good oil-fixing properties, low oil leakage rate and no deformation under pressure. Its comprehensive physical properties are superior to existing simulated adult sex toys using TPE as the main material.

[0011] Another objective of this invention is to provide a method for preparing simulated rubber materials that is simple in process and low in cost.

[0012] The third objective of this invention is to provide a method for using simulated rubber materials to prepare simulated masturbation products or simulated dolls and other rubber products. The resulting products have flesh-like elasticity, high cohesion and tensile strength. Their hardness and strength remain unchanged under changes in medium and low temperature and time. They are stable in use or storage, have good oil-fixing properties, low oil leakage rate and no deformation under pressure, and have broad application prospects.

[0013] To achieve the above-mentioned technical objectives, the present invention provides a simulated rubber material comprising a hydrogenated polystyrene-conjugated diene block copolymer and additives;

[0014] The hydrogenated polystyrene-conjugated diene block copolymer has the following structural expression:

[0015] (S t -E o D p ) m -E q D r / Y n

[0016] Among them, E q D r / Y nThe backbone of a random copolymer of hydrogenated conjugated diene and divinylbenzene; S t -E o D p The term "styrene-conjugated diene diblock copolymer" refers to the branched chain of hydrogenated styrene and conjugated diene; S is a styrene unit; E is a hydrogenated 1,4-addition conjugated diene unit; D is a hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit; Y is a divinylbenzene unit; t, o, p, q, and r are the degrees of polymerization of the styrene unit, the hydrogenated 1,4-addition conjugated diene unit in the branched chain, the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit in the branched chain, the hydrogenated 1,4-addition conjugated diene unit in the main chain, and the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit in the main chain, respectively; n is the number of branching nodes introduced by the divinylbenzene unit; and m is the number of branches. The hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer of the present invention exhibits structural differences depending on the selected conjugated diene. If the conjugated diene is a single butadiene, the hydrogenated copolymer dry adhesive is "branch-SEBS"; if the conjugated diene is a single isoprene, the hydrogenated copolymer dry adhesive is "branch-SEPS"; if the conjugated diene is a mixture of butadiene and isoprene, the hydrogenated copolymer dry adhesive is "branch-SEBPS".

[0017] The hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer of the present invention comprises a main chain of hydrogenated asymmetric long-chain branched conjugated diene polymer, which is formed by random copolymerization of conjugated diene monomer and divinylbenzene branching units. The branches are mainly diblock structures, with polystyrene blocks grafted at the ends, and hydrogenated conjugated diene blocks connecting to the main chain. As can be seen from the expression: E q D r / Y n The backbone of the random copolymer of hydrogenated conjugated diene and divinylbenzene, S t -E o D p The branched chain is a diblock copolymer of hydrogenated styrene and conjugated diene; E o For the hydrogenated 1,4-addition conjugated diene unit in the branched chain, D p For conjugated diene units in the branched chain that have undergone hydrogenation 1,2-addition (e.g., butadiene unit) and / or 3,4-addition (e.g., isoprene unit), E q The hydrogenated 1,4-addition conjugated diene unit in the main chain, D r The hydrogenated 1,2-addition and / or 3,4-addition conjugated diene units in the main chain, Y is uniformly distributed in the main chain through random copolymerization, forming grafted S t -E o D p Branched nodes.

[0018] In the hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer of the present invention, due to the introduction of divinylbenzene as a branching unit, a small amount of coupling and cyclization products are inevitably generated during the polymerization process. These coupling and cyclization products are mainly composed of linear molecules coupled with 2 to 3 different asymmetric long-chain branched linear molecules and cyclic molecules coupled with 2 to 3 different asymmetric long-chain branched linear molecules. The number-average molecular weight M of the coupling and cyclized polymers is... n =25×10 4 ~50×10 4 Molecular weight distribution index M w / M n ≤1.16, and the mass fraction of these coupled and cyclized polymers is generally 27-35%.

[0019] As a preferred embodiment, the (S) t -E o D p ) m -E q D r / Y n In this case, t, o, p, q, and r are all positive integers ≥ 1 and are all distinct.

[0020] As a preferred embodiment, the (S) t -E o D p ) m -E q D r / Y n In this case, m and n are both positive integers, m ≥ n, and 1 ≤ n ≤ 2.

[0021] As a preferred embodiment, the mass percentage of the styrene unit to the total mass percentage of the hydrogenated 1,4-addition conjugated diene unit and the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit is 25-35% : 75-65%. It should be noted that, generally, for the anionic polymerization of conjugated dienes, isoprene typically does not undergo 1,2-addition, and its content is negligible; its 1,4- and 3,4-addition unit content is >99.5%.

[0022] As a preferred embodiment, the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene units account for 38% to 68% of the total mass of the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene units and the hydrogenated 1,4-addition conjugated diene units. If the proportion of 1,4-addition units in the conjugated diene units is too high, too many ethylene units will be generated in the molecular chain, and the hydride will have a tendency to crystallize. This phenomenon can be effectively mitigated by controlling the proportion of 1,2-addition and / or 3,4-addition conjugated diene units through branching.

[0023] As a preferred embodiment, the (S) t -E o D p ) m -E q D r / Y n Number-average molecular weight M n =8×10 4 ~20×10 4 .

[0024] As a preferred embodiment, the (S) t -E o D p ) m -E q D r / Y n Molecular weight distribution index M w / M n =1.02~1.05.

[0025] As a preferred embodiment, the (S) t -E o D p ) m -E q D r / Y n The mass of the divinylbenzene unit is 0.7 / 1000 to 1.2 / 1000 of the total mass of the hydrogenated 1,4-addition conjugated diene units and the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene units. It is worth further clarification that: if the DVB dosage is too low, the polymer branching will be too low, failing to achieve the purpose of branching; if the DVB dosage is too high, under the condition of constant NBL dosage, the polymer branching will be too high, the polymer molecular weight will be too high, and the polymer will produce gel or sluggishness.

[0026] As a preferred embodiment, the conjugated diene unit is a butadiene unit and / or an isoprene unit.

[0027] As a preferred embodiment, the (S) t -E o D p ) m -E q D r / Y n The degree of hydrogenation is greater than 98%. The degree of hydrogenation in this invention refers to the degree of hydrogenation of the alkenyl group, not the degree of hydrogenation of the benzene ring.

[0028] The hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer of the present invention not only has good comprehensive physical and mechanical properties, but also exhibits low deformation, excellent compatibility and oil-locking properties with mineral oil and white oil, and is an ideal substitute for existing SEBS and SEPS; it is more suitable for use as a highly oil-filled "jelly-like meaty" soft product, comparable to meaty silicone.

[0029] As a preferred embodiment, the excipients include filler oil, filler, coupling agent, colorant, bactericide, antioxidant, and fragrance.

[0030] As a preferred embodiment, the filler oil is preferably a commercially available, environmentally friendly softening rubber oil, such as a naphthenic white oil, specifically at least one of naphthenic KN4010 and naphthenic KN4006, and / or a paraffinic white oil, specifically at least one of paraffinic 150#, paraffinic 26#, paraffinic 32#, paraffinic 46#, paraffinic 68#, and paraffinic 7#. Most preferably, it is a mixture of naphthenic white oil and paraffinic white oil, with a ratio of naphthenic white oil / paraffinic white oil (weight percentage composition) = (30-60)% / (70-40)%. Generally, paraffinic white oil is beneficial for the compatibility of the polymer's hydrocarbon saturated chains. Naphthenic white oil has a higher viscosity than paraffinic white oil. Products filled with hydrogenated polymers using naphthenic white oil exhibit relatively higher stiffness and reduced cold flow. The combination of the two can achieve better results.

[0031] As a preferred embodiment, the filler is fumed silica. Fumed silica is mainly used for reinforcing, thickening, preventing sedimentation, thixotropic properties, increasing stiffness, preventing sagging, and facilitating coloring of products. Additionally, white filler can be mixed with bright red pigment to create a peach-red color, close to human skin tone. Preferably, the fumed silica produced by the fumed silica process is an oleophilic type, such as at least one of commercially available models like HB-151, HB-620, and HB-132. It is worth further clarification that for soft, highly oil-filled rubber products, the amount of inorganic powder used as filler should not be excessive; otherwise, the product will become too hard.

[0032] As a preferred embodiment, the coupling agent is at least one of KH-550, KH-560, KH-570, silicon-75, and silicon-69. Most preferably, it is at least one of colorless KH-550, KH-560, and KH-570.

[0033] As a preferred embodiment, the colorant is at least one of BASF K3840SQ (Bright Red), 081 Lemon Yellow, 140 / RB Dye Yellow, 272 Dye Orange, and Carbon Black. The choice of colorant depends on the specific needs. For example, if the simulated rubber material is intended to mimic human skin tone, Bright Red (BASF K3840SQ) is preferred for peach yellow, Lemon Yellow for yellow, Dye Orange for orange, and Carbon Black for brown.

[0034] As a preferred embodiment, the bactericide is n-octylisothiazolinone. The preferred bactericide is an oil-soluble antifungal bactericide such as one of the n-octylisothiazolinone (OIT) class, while general water-soluble bactericides are insoluble in filler oils.

[0035] As a preferred embodiment, the antioxidant is at least one of antioxidant 1076 and antioxidant 630. A preferred antioxidant is at least one of well-known non-polluting antioxidants for polyolefins, such as antioxidant 1076 and antioxidant 630.

[0036] As a preferred embodiment, the fragrance is at least one of cosmetic, edible, or plant-based fragrances. The fragrance is any one of commercially available strawberry, lemon, or apple scents, or at least one of commercially available ethyl adipic acid, ethyl succinate, sunflower essence, or rose essence.

[0037] As a preferred embodiment, the simulated rubber material comprises the following components by weight: 25 parts hydrogenated polystyrene-conjugated diene block copolymer; 60-70 parts filler oil; 15-25 parts filler; 0.5-1.5 parts coupling agent; 0.1-0.3 parts colorant; 0.1-0.3 parts bactericide; 0.1-0.3 parts antioxidant; and 0.1-0.3 parts fragrance. This simulated rubber material formulation is mainly used in products such as masturbation dildos and insemination rings.

[0038] As a preferred embodiment, the simulated rubber material comprises the following components in parts by weight: 25 parts hydrogenated polystyrene-conjugated diene block copolymer; 110-130 parts filler oil; 20-30 parts filler; 1.25-1.5 parts coupling agent; 0.3-0.4 parts colorant; 0.3-0.4 parts bactericide; 0.2-0.4 parts antioxidant; and 0.3-0.4 parts fragrance. This simulated rubber material formulation is mainly used in masturbation devices, uterine molds, and simulated dolls.

[0039] The present invention also provides a method for preparing a simulated rubber material, which involves heating and dissolving a hydrogenated polystyrene-conjugated diene block copolymer and auxiliary materials, mixing them evenly, and then cooling and molding them with the aid of a mold to obtain the material.

[0040] As a preferred embodiment, the heating and melting temperature is 80–110°C, and the time is 60–90 min.

[0041] This invention also provides an application of a simulated rubber material for the manufacture of simulated masturbation products or dolls. Specific examples of simulated masturbation products include masturbation sleeves, uterine molds, dolls, and phalluses.

[0042] The hydrogenated dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer of the present invention is prepared by the following method: In an anionic polymerization system, a portion of styrene monomer is first added for a single-stage polymerization, followed by the uniform and continuous addition of a mixture of divinylbenzene and conjugated diene monomers containing a structure modifier for a second-stage polymerization, and then the remaining styrene is added for a third-stage polymerization. After the three-stage polymerization is completed, the polymerization is terminated, yielding a dendritic random asymmetric long-chain branched polystyrene-conjugated diene block copolymer emulsion. This emulsion is then subjected to a hydrogenation reaction to obtain a hydrogenated emulsion. The hydrogenated emulsion is subsequently subjected to coagulation and drying to obtain the final product. In the above method, the anionic polymerization system contains an activator, an initiator, and a solvent. For anionic polymerization systems, activators, initiators, and solvents are all common in the prior art. In the above method, the activator is tetrahydrofuran, and the initiator is alkyllithium, specifically, n-butyllithium; the solvent is cyclohexane and / or hexane, and the amount of solvent is generally such that the mass ratio of the total mass of styrene monomer and conjugated diene monomer to the mass of solvent is (8-15) / 100. In the above method, the amount of activator is 80-160 mg / kg solvent. In the above method, the conditions for the first-stage polymerization are: temperature 50-60℃, time 20-30 min. In the above method, the conditions for the second-stage polymerization are: heating rate controlled within the range of 0.5-1.0℃ / min, maximum temperature not exceeding 73℃, addition time of the mixed monomers of divinylbenzene and conjugated diene containing the structure modifier not less than 20 min, and after addition, reaction at a temperature not exceeding 73℃ for 15-25 min. In the two-stage polymerization process, the optimal operation is to premix DVB and the structure modifier with butadiene monomers and continuously and uniformly add them to the pre-prepared active polystyrene lithium solution from the first-stage polymerization. The continuous addition time is 20-30 minutes, allowing the divinylbenzene and conjugated diene monomers to undergo sufficient random and uniform chain growth and branching. This avoids the aggregation and self-agglomeration that would occur if DVB were added to the polymerization environment all at once, failing to achieve the purpose of dispersed branching. After the mixed monomers are added, the reaction continues for a period of time to form randomly varying asymmetric long-chain branching, ultimately forming different asymmetric long-chain dendritic polymers. In the above method, the three-stage polymerization conditions are: temperature 55-75℃, time 20-30 minutes. In the above method, the structure modifier is at least one of tetrahydrofurfuryl ethyl ether, bis(tetrahydrofurfuryl propane), tetrahydrofurfuryl ethyl ether, and tetrahydrofurfurylamine, and the amount of structure modifier is 120-200 mg / kg solvent. To ensure that the proportion of 1,2-addition and / or 3,4-addition units of conjugated dienes in the polymer before hydrogenation is 38-68%, an appropriate amount of structure modifier needs to be added to the anionic polymerization system.As a preferred technical solution, the hydrogenation catalyst used in the hydrogenation reaction is dicyclopentadiene titanium dichloride or nickel naphthenate / triisobutylaluminum aging solution, wherein the Ni / Al molecular ratio is 3-5:1, and the amount of hydrogenation catalyst added relative to the gel solution is 0.5-0.8 mmol / 100g. The hydrogenation catalyst is measured in molar amounts of nickel naphthenate (or dicyclopentadiene titanium dichloride), and the gel solution is measured by dry weight. Since the traditional dicyclopentadiene titanium dichloride catalyst is inactive for the hydrogenation of polyisoprene, when the conjugated diene contains isoprene, nickel naphthenate / triisobutylaluminum aging solution is preferably used as the catalyst. In the above scheme, the hydrogenation reaction conditions are: pressure 13-18 bar, temperature 70-85℃, and time 120-180 min. By controlling the hydrogenation reaction conditions, the degree of hydrogenation of the hydride can be >98%.

[0043] The present invention provides a method for preparing simulated adult masturbation devices using simulated rubber material: In a container equipped with heating and stirring, filler oil is first placed in a stirrer, then heated to 80-110°C, followed by the addition of hydrogenated polystyrene-conjugated diene block copolymer (Y-SEDS) and stirring until fully dissolved for 60-90 minutes. Then, coupling agent, colorant, bactericide, antioxidant, and fragrance are added sequentially, and finally, white carbon black is added. The mixture is stirred until it flows evenly and has no color difference. The molten rubber composite is then injected into the corresponding mold using an injection pump. After cooling and shaping in a water bath (5-8°C), the mold is opened to obtain the designed simulated adult masturbation device. The cooling and shaping time of the mold is set according to the size of the device and the heat transfer area, preferably not less than 2 minutes.

[0044] The simulated adult masturbation device made of the simulated rubber material of the present invention preferably has a tensile breaking strength ≥1.60MPa, an elongation at break ≥1500%, a permanent deformation ≤10%, and a hardness of C18-30.

[0045] Compared with existing technologies, the beneficial effects of the technical solution of this invention are as follows:

[0046] As is well known, the main rubber material used in existing simulated adult masturbation products and dolls is usually thermoplastic elastomer (TPE), whose molecular structure is a straight-chain polystyrene-conjugated diene hydride, such as SEBS or SEPS. High-oil-filled fleshy masturbation products and dolls have defects such as operating temperature below 55℃ or inability to withstand medium temperature, and cold flow, oil seepage, shrinkage and deformation of finished products after long-term storage.

[0047] This invention is the first to use polystyrene-conjugated diene block copolymer hydropolymer elastomers (Y-SEDS) with different dendritic molecules in simulated adult masturbation products. The resulting high-oil-filled soft flesh-like composite material has excellent elasticity, high cohesiveness, and its hardness and strength remain unchanged under changes in medium and low temperatures and time. It is stable in use or storage, has good oil-fixing properties, low oil seepage rate, and resistance to deformation under pressure. Its overall physical behavior is superior to existing simulated adult masturbation products with TPE as the main material.

[0048] This invention also unexpectedly discovered that the "jelly-like fleshy" soft gel comfort device prepared by the selected branched Y-SEDS can still quickly restore its original shape or state after being subjected to low temperature, compression and expansion, and directional deformation of molecular chains, under conditions of no external heat and external force or other human intervention to restore the original environment. This is due to the high degree of entanglement and encirclement of the molecular chains of the branched Y-SEDS, which is a shortcoming of the human vagina in being unable to shrink or restore its original state after childbirth or surgery.

[0049] The preparation process of the simulated rubber material and its products of the present invention is simple and low-cost, which is conducive to large-scale production. Attached Figure Description

[0050] Figure 1 The image shows the 1H-NMR spectrum of the hydrogenated raw material SIBS in Example 5. Detailed Implementation

[0051] The present invention is illustrated by the following embodiments, which do not constitute a limitation on the scope or implementation of the present invention.

[0052] The mechanical properties of the composite compression adhesive were tested according to the method in GB / T36089-2018;

[0053] Determination of oil penetration rate of high oil-extended composite rubber: The oil-extended composite was hot-pressed into 20×60×2mm samples at 90℃ and immersed in a mixed solution of ethanol / n-octane (by weight) = 7 / 3 at room temperature for 72h. The samples were then removed and dried at room temperature, and the weight loss was measured.

[0054] Immersion weight loss % = [(weight before immersion - weight after immersion) / weight before immersion] × 100.

[0055] Example 1

[0056] Under nitrogen protection, 3500 mL of cyclohexane, 50 mL of styrene, and a small amount of activator (tetrahydrofuran, 100 mg / kg solvent) were added to a 5 L polymerization reactor. Stirring was started, and the solution was heated to 55 °C. Then, 9.0 mL of 0.5 mol / L butyllithium (NBL) was added to initiate polymerization for 25 min. Next, a mixed monomer consisting of 0.17 g of divinylbenzene (DVB), 330 mL of butadiene, and a small amount of regulator (tetrahydrofurfuryl ethyl ether, 150 mg / kg solvent) was continuously added to the polymerization reactor over 25 min, controlling the maximum polymerization temperature not to exceed 70 °C. After the monomers were added, stirring continued for another 18 min. Then, 50 mL of styrene was added to the polymerization reactor, and polymerization was carried out at 70 °C for 25 min to obtain the SBS solution. The number-average molecular weight (Mn) of the coupled cyclized dendrites and highly long-chain branched compounds in the SBS was measured to be 52.86 × 10⁻⁶. 4 and 19.54×10 4 The mass fractions of dendrites and long-chain branched compounds were 33.65% and 65.78%, respectively, and the mass fraction of vinyl units was 43.88%.

[0057] After purging SBS with hydrogen to terminate the reaction, a dicyclopentadiene titanium dichloride catalytic system (0.7 mmol / 100 g solution) was added. The mixture was stirred at 80°C under a hydrogen pressure of 16 bar until the degree of hydrogenation of the polymer was not less than 98%, thus obtaining the Y-SEBS hydrogenated solution. Finally, the solution was condensed with water vapor and dried to obtain the Y-SEBS dry adhesive.

[0058] Example 2

[0059] Under nitrogen protection, 3500 mL of cyclohexane solution, 56 mL of styrene, and an appropriate amount of activator (tetrahydrofuran, 100 mg / kg solvent) were added to a 5 L polymerization reactor. Stirring was started, and when the material temperature reached 55°C, 10.0 mL of 0.5 mol / L NBL was added to initiate polymerization for 25 min. Then, a mixed monomer consisting of 295 mL of isoprene, an appropriate amount of DVB (0.17 g), and a regulator (tetrahydrofurfuryl ethyl ether, 150 mg / kg solvent) was continuously added to the polymerization reactor over 25 min. The maximum polymerization temperature was controlled to not exceed 72°C. After the monomer was added, stirring continued for another 20 min. Then, 56 mL of styrene was added to the polymerization reactor, and polymerization was continued for 25 min, yielding a SIS protoplast with irregularly branched arms and dendritic molecular chains. Samples were taken and the Mn values ​​of the coupled cyclodextrin and long-chain branched compounds were measured to be 48.52 × 10⁻⁶. 4 and 16.85×10 4 The mass fractions of dendritic and long-chain branched compounds were 31.75% and 66.21%, respectively, and the mass fraction of isopropenyl units was 55.83%.

[0060] An appropriate amount of nickel / aluminum aging solution (Ni / Al molecular ratio = 3-5:1, dosage 0.7 mmol / 100g of adhesive solution) was added to the adhesive solution, and hydrogenation was carried out by stirring at a hydrogen pressure of 15 bar and 80°C for 150 min. The degree of hydrogenation of the polymer was measured to be 99.34%. Then, the hydrogenated solution was purified, condensed with water vapor, and dried to obtain the colorless and transparent hydride Y-SEPS.

[0061] Example 3

[0062] The polymerization and hydrogenation process conditions in Example 2 were slightly adjusted. 11 mL of NBL was added to the polymerization, and 58 mL of styrene was added to both the first and third stages of polymerization. The mixed monomers in the two-stage polymerization consisted of 160 mL of butadiene, 170 mL of isoprene, and appropriate amounts of DVB (0.17 g) and regulator (tetrahydrofurfuryl ethyl ether, 150 mg / kg solvent).

[0063] The Mn content of the coupled cyclic dendrites and long-chain branched compounds in the prepared polymeric raw material SIBS was 46.85 × 10⁻⁶. 4 and 13.62×10 4 The mass fractions of dendritic and long-chain branched compounds were 30.56% and 67.43%, respectively, the mass fraction of vinyl units was 48.92%, and the mass fraction of isopropyl units was 50.63%.

[0064] The original gum was then subjected to catalytic hydrogenation, and the resulting colorless polymer (labeled as Y1-SEBPS) had a hydrogenation degree of 98.67%.

[0065] Example 4

[0066] The polymerization and hydrogenation process conditions in Example 2 were slightly adjusted. 12 mL of NBL was added to the polymerization, and 60 mL of styrene was added to both the first and third stages of polymerization. The mixed monomers in the two-stage polymerization consisted of 70 mL of butadiene, 260 mL of isoprene, and appropriate amounts of DVB (0.17 g) and regulator (tetrahydrofurfuryl ethyl ether, 150 mg / kg solvent).

[0067] The Mn content of the coupled cyclic dendrites and long-chain branched compounds in the prepared polymeric raw material SIBS was 44.54 × 10⁻⁶. 4 and 11.32×10 4 The mass fractions of dendritic and long-chain branched compounds were 28.56% and 69.43%, respectively, the mass fraction of vinyl units was 58.89%, and the mass fraction of isopropyl units was 60.87%.

[0068] The final hydrogenated colorless polymer (labeled as Y2-SEBPS) had a hydrogenation degree of 99.28%.

[0069] Example 5

[0070] With only minor adjustments to the polymerization and hydrogenation process conditions in Example 2, 11 mL of NBL was added during polymerization, and 52 mL of styrene was added in both the first and third stages of polymerization. The mixed monomers in the second-stage polymerization consisted of 270 mL of butadiene, 40 mL of isoprene, and appropriate amounts of DVB (0.17 g) and regulators (tetrahydrofurfuryl ethyl ether, 150 mg / kg solvent).

[0071] The Mn content of the coupled cyclic dendrites and long-chain branched compounds in the prepared polymeric raw material SIBS was 42.35 × 10⁻⁶. 4 and 9.87×10 4 The mass fractions of dendritic compounds and long-chain branched compounds were 27.85% and 71.12%, respectively; the mass fraction of vinyl units was 49.05%; and the mass fraction of isopropyl units was 41.96%. The 1H-NMR spectrum of its hydrogenated raw material SIBS is attached. Figure 1 .

[0072] The final hydrogenation-prepared colorless polymer (labeled as Y3-SEBPS) had a degree of hydrogenation of 98.78%.

[0073] Example 6

[0074] Y-SEBS, Y-SEPS, Y1-SEBPS, Y2-SEBPS, Y3-SEBPS prepared from Y-SEDS source examples, and commercially available SEBS (YH-503) and G1650 were respectively prepared with the simulated adult masturbation penis formula described in this invention. The formulas are shown in Table 1, and the performance behavior of the prepared masturbation penises are shown in Table 2.

[0075] Table 1

[0076]

[0077]

[0078] Note: 1) In the formulations of Examples 1#, 2#, 3#, 4#, 5#, 6#, and 7#, the minor ingredients such as KH-560, 1076, OIT, sunflower flavoring, and K3840SQ have mass fractions of 0.85, 0.22, 0.15, 0.18, and 0.17, respectively. 2) YH-503 and G1650 are linear SEBS produced by Sinopec Baling Petrochemical Company Synthetic Rubber Plant and Kraton Company, respectively.

[0079] Table 2 Performance behavior of Jianwei male penis composite melt-pressed sheet

[0080]

[0081] Example 7

[0082] Y-SEBS, Y-SEPS, Y1-SEBPS, Y2-SEBPS, Y3-SEBPS prepared from the Y-SEDS preparation source example, and the commercially available SEPS-4051 and G1651 were respectively prepared with the simulated adult female doll formula described in this invention. The formula is shown in Table 3, and the performance of the prepared simulated adult female doll composite melt-pressed film is shown in Table 4.

[0083] Table 3

[0084] serial number 8# 9# 10# 11# 12# 13# 14# Y-SEBS 25 Y-SEPS 25 Y1-SEBPS 25 Y2-SEBPS 25 Y3-SEBPS 25 SEPS-4051 25 G1651 25 KN4010 47 49 52 54 53 48 50 White oil 46# 67 68 69 71 74 68 70 HB-151 20 22 24 23 24 22 24

[0085] Note: 1) In the formulations of Examples 8#, 9#, 10#, 11#, 12#, 13#, and 14#, the minor ingredients such as KH-550, 630, OIT, rose fragrance, and dye orange have mass fractions of 0.92, 0.24, 0.16, 0.18, and 0.20, respectively.

[0086] 2) SEPS-4051 and G1651 are products manufactured by Sinopec Baling Petrochemical Company's Synthetic Rubber Plant and Kraton Company, respectively.

[0087] Table 4. Performance behavior of meltblown composite material for simulated adult female dolls

[0088]

[0089] As can be seen from Tables 2 and 4, the composite material prepared by the branched elastomer selected in this invention has a much better physical behavior than existing commercially available hydrogenated elastomer-based composite materials (such as 6#, 7#, 13# and 14#).

Claims

1. A simulated rubber material, characterized in that: It includes hydrogenated polystyrene-conjugated diene block copolymer and excipients; the excipients include filler oil, filler, coupling agent, colorant, bactericide, antioxidant and fragrance; The hydrogenated polystyrene-conjugated diene block copolymer has the following structural expression: (S t -E o D p ) m -E q D r / Y n in, E q D r / Y n The backbone of a random copolymer of hydrogenated conjugated diene and divinylbenzene; S t -E o D p The branched chain is a diblock copolymer of hydrogenated styrene and conjugated diene; S represents a styrene unit; E is a hydrogenated 1,4-addition conjugated diene unit; D is a hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit; Y represents a divinylbenzene unit; t, o, p, q, and r represent the degree of polymerization of styrene unit, hydrogenated 1,4-addition conjugated diene unit in the side chain, hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit in the side chain, hydrogenated 1,4-addition conjugated diene unit in the main chain, and hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit in the main chain, respectively. n is the number of branching nodes introduced by the divinylbenzene unit; m is the number of branches; The (S) t -E o D p ) m -E q D r / Y n In this case, t, o, p, q, and r are all positive integers ≥ 1, and are all distinct. Both m and n are positive integers, m ≥ n, 1 ≤ n ≤ 2; The mass percentage composition of the styrene unit and the total mass percentage composition of the hydrogenated 1,4-addition conjugated diene unit and the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit is 25-35%: 75-65%; The hydrogenated 1,2-addition and / or 3,4-addition conjugated diene units account for 38% to 68% of the total mass of the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene units and the hydrogenated 1,4-addition conjugated diene units; The (S) t -E o D p ) m -E q D r / Y n The mass of the divinylbenzene unit is 0.7 / 1000 to 1.2 / 1000 of the total mass of the hydrogenated 1,4-addition conjugated diene unit and the hydrogenated 1,2-addition and / or 3,4-addition conjugated diene unit.

2. The simulated rubber material according to claim 1, characterized in that: The (S) t -E o D p ) m -E q D r / Y n Number-average molecular weight M n =8×10 4 ~20×10 4 ; The (S) t -E o D p ) m -E q D r / Y n Molecular weight distribution index M w / M n =1.02~1.

05.

3. The simulated rubber material according to claim 1, characterized in that: The conjugated diene unit is a butadiene unit and / or an isoprene unit.

4. The simulated rubber material according to claim 1, characterized in that: The (S) t -E o D p ) m -E q D r / Y n The degree of hydrogenation is greater than 98%.

5. The simulated rubber material according to claim 1, characterized in that: The filler oil includes at least one of the following: naphthenic KN4010, naphthenic KN4006, paraffinic 150#, paraffinic 26#, paraffinic 32#, paraffinic 46#, paraffinic 68#, and paraffinic 7#.

6. The simulated rubber material according to claim 1, characterized in that: The filler is fumed silica.

7. The simulated rubber material according to claim 1, characterized in that: The coupling agent is at least one of KH-550, KH-560, KH-570, silicon-75, and silicon-69.

8. The simulated rubber material according to claim 1, characterized in that: The colorant is at least one of BASF K3840SQ Red, 081 Lemon Yellow, 140 / RB Dye Yellow, 272 Dye Orange, and Carbon Black; The bactericide is n-octylisothiazolinone; The antioxidant is at least one of antioxidant 1076 and antioxidant 630; The flavoring is at least one of edible flavoring and plant flavoring.

9. A simulated rubber material according to claim 1, 5, 6, 7 or 8, characterized in that: Includes the following components by weight: 25 parts of hydrogenated polystyrene-conjugated diene block copolymer; 60-70 parts of filler oil; 15-25 parts of filler; 0.5-1.5 parts of coupling agent; Pigment 0.1~0.3 parts; 0.1 to 0.3 parts of bactericide; Antioxidant 0.1~0.3 parts; Spices: 0.1 to 0.3 parts; or, Includes the following components by weight: 25 parts of hydrogenated polystyrene-conjugated diene block copolymer; 110-130 parts of filler oil; 20-30 parts of filler; 1.25~1.5 parts of coupling agent; Pigment 0.3~0.4 parts; 0.3-0.4 parts of bactericide; Antioxidant 0.2~0.4 parts; Spices 0.3 to 0.4 parts.

10. A method for preparing a simulated rubber material according to any one of claims 1 to 9, characterized in that: The hydrogenated polystyrene-conjugated diene block copolymer and its additives are heated, melted, and mixed evenly, and then cooled and shaped using a mold.

11. The method for preparing a simulated rubber material according to claim 10, characterized in that: The heating, dissolving, and mixing temperature is 80~110℃, and the time is 60~90min.

12. The application of the simulated rubber material according to any one of claims 1 to 9, characterized in that: It is used in the preparation of simulated comfort products.

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