Artificial leather and preparation method therefor, automotive interior, and automotive seat
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2026-01-14
- Publication Date
- 2026-08-13
Smart Images
Figure CN2026072571_13082026_PF_FP_ABST
Abstract
Description
Artificial leather and its preparation methods, automotive interiors, and automotive seats.
[0001] This application is based on and claims priority to Chinese Patent Application No. 202510127510.3, filed on February 5, 2025, and Chinese Patent Application No. 202511058934.5, filed on July 30, 2025, the entire contents of which are incorporated herein by reference. Technical Field
[0002] This invention belongs to the field of artificial leather technology, specifically relating to a polyolefin artificial leather and its preparation method, and automobile seats. Background Technology
[0003] Patent document 202110774131.5 discloses a polyolefin artificial leather substrate and artificial leather containing rubber components, exhibiting excellent resistance to light aging. The artificial leather substrate and artificial leather, from top to bottom, comprise a light-aging-resistant polyolefin layer and a base fabric layer. The light-aging-resistant polyolefin layer contains an appropriate amount of rubber components containing double bonds, forming a cross-linked structure through a suitable method to improve light aging resistance. Simultaneously, a certain amount of ultraviolet absorbers, light stabilizers, and light shielding agents are added. This artificial leather substrate and artificial leather, especially light-colored leather, possess excellent light aging resistance and can be widely used in automotive interiors and other fields. The amount of rubber added in this technical solution is 60-100 parts.
[0004] EPDM has low unsaturation and low polarity. According to the principle of "like dissolves like," polar solvents easily dissolve polar substances, while non-polar solvents dissolve non-polar substances more easily. When EPDM comes into contact with certain solvents, the solvent molecules, being small, diffuse rapidly and preferentially penetrate between EPDM molecules, causing the polymer to swell. After swelling occurs, the polymer may even dissolve. Furthermore, prolonged exposure to ultraviolet light causes EPDM to undergo photo-oxidation, leading to surface cracking, hardening, and even powdering in leather. This is because ultraviolet light can break the unsaturated double bonds in the EPDM molecular chain, initiating free radical reactions and accelerating the aging process.
[0005] Other thermoplastic elastomers, such as TPE, generally have a working temperature not exceeding 80°C, and may soften or deform if exposed to high-temperature environments for a long time; while SEBS has poor low-temperature performance and low elasticity.
[0006] Furthermore, the traditional artificial leather material, polyvinyl chloride (PVC), relies heavily on plasticizers in the process of making artificial leather. Since plasticizers are small molecules with high degrees of freedom, this can cause the PVC surface to become brittle, and this phenomenon is exacerbated at low temperatures. Polyolefin elastomers (TPO) have advantages such as extremely low odor, no reliance on organic solvents in the synthesis process, and aging resistance, but their high crystallinity results in a hard feel and poor low-temperature folding resistance.
[0007] To optimize the feel and improve the softness of artificial leather, existing processes use a foaming process to generate tiny air bubbles in the artificial leather, thereby reducing weight and increasing softness. However, the foaming process has the drawback of insufficient elasticity in artificial leather after long-term use.
[0008] Therefore, overcoming the deficiency of insufficient resilience in artificial leather made of lightweight polyolefins is a technical problem that urgently needs to be solved in this field.
[0009] It should be noted that the information disclosed in this background section is only for understanding the background technology of this application concept, and therefore, the above description is not considered to constitute prior art information. Summary of the Invention
[0010] This disclosure provides at least one polyolefin artificial leather and its preparation method, as well as an automobile seat.
[0011] In a first aspect, embodiments of this disclosure provide a polyolefin artificial leather, comprising: a base fabric layer, a substrate layer, and a coating layer stacked sequentially; the substrate layer comprises the following raw material components in parts by mass: 135-165 parts of island microstructure masterbatch, 0.4-1 parts of crosslinking agent, 0.05-0.2 parts of coupling agent, 0.01-0.2 parts of ultraviolet absorber, 0.01-0.2 parts of light stabilizer, and 0.01-0.2 parts of anti-aging agent; wherein the island microstructure masterbatch comprises polyolefin and rubber with double bonds.
[0012] Secondly, this disclosure also provides a high-elasticity, high-softness layer for artificial leather, wherein the high-elasticity, high-softness layer comprises the following raw material components: modified high-elasticity resin; the modified high-elasticity resin comprises: a high-elasticity polyolefin elastomer, which is obtained by copolymerization of propylene, norbornene, and cashew nut shell; the preparation steps of the high-elasticity polyolefin elastomer are as follows: cashew nut shell is reacted with 1.2 to 1.4 times the amount of cashew nut shell by triisobutylaluminum to obtain pre-protected cashew nut shell; under a nitrogen atmosphere, toluene, modified methylaluminoxane, and 2,6-di-tert-butyl-4-methylphenol are injected into a reactor, and after stirring, the nitrogen is removed, propylene gas is introduced, and the remaining negative pressure space is backfilled with nitrogen to a normal pressure environment, and a catalyst fluorenylaminodimethyltitanium complex / toluene solution is added to catalyze the polymerization reaction; norbornene and pre-protected cashew nut shell are injected into the reactor and polymerized at room temperature, and the reaction is terminated by adding ethanol / hydrochloric acid solution to obtain the high-elasticity polyolefin elastomer.
[0013] The beneficial effects of this invention are that the polyolefin artificial leather and its preparation method, as well as the automotive seat, improve the dispersion performance by improving the amount and process of rubber addition, and protect the double bonds in the rubber in the form of island microstructure masterbatch, so that it can undergo cross-linking reaction with polyolefin to form a cross-linked structure, thereby improving the processing performance. On the one hand, the masterbatch structure can prevent the rubber from hardening and becoming brittle due to long-term exposure to ultraviolet rays. On the other hand, the limitation of rubber content also avoids cracking caused by swelling, effectively improving the anti-aging performance and ensuring that the roughness of the artificial leather does not change after long-term use in high-temperature environments.
[0014] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention are realized and obtained in accordance with the structures particularly pointed out in the description, claims and drawings.
[0015] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description
[0016] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0017] Figure 1 is a schematic diagram of the structure of a polyolefin artificial leather provided in an embodiment of this disclosure;
[0018] Figure 2 is a surface pattern diagram of the polyolefin artificial leather of Example 3 provided in this disclosure;
[0019] Figure 3 is a surface pattern diagram of the polyolefin artificial leather of Example 7 provided in this disclosure;
[0020] Figure 4 is a picture of slight cracking of the polyolefin artificial leather of Example 5 provided in this disclosure;
[0021] Figure 5 is a bending image of the polyolefin artificial leather of Example 8 provided in this disclosure.
[0022] In the picture:
[0023] 1. Base fabric layer; 2. Substrate layer or highly elastic and flexible layer; 3. Coating layer. Detailed Implementation
[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0025] Definitions:
[0026] EPDM: Ethylene Propylene Diene Monomer, is a copolymer of ethylene, propylene and a small amount of non-conjugated diene.
[0027] TPE: Thermoplastic elastomer, abbreviated as TPE or TPR, is an abbreviation for Thermoplastic rubber.
[0028] SEBS: A linear triblock copolymer with polystyrene as the end block and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic block. It is an abbreviation for Styrene Ethylene Butylene Styrene.
[0029] Existing patent 202110774131.5 discloses a polyolefin artificial leather substrate and artificial leather containing rubber components, exhibiting excellent resistance to light aging. The artificial leather substrate and artificial leather, from top to bottom, comprise a light-aging-resistant polyolefin layer and a base fabric layer. The light-aging-resistant polyolefin layer contains an appropriate amount of rubber components containing double bonds, forming a cross-linked structure through a suitable method to improve light aging resistance. Simultaneously, a certain amount of ultraviolet absorbers, light stabilizers, and light shielding agents are added. This artificial leather substrate and artificial leather, especially light-colored leather, possess excellent light aging resistance and can be widely used in automotive interiors and other fields. The rubber component comprises 60-100 parts.
[0030] EPDM (ethylene propylene diene monomer) has low unsaturation and low polarity. According to the principle of "like dissolves like," polar solvents readily dissolve polar substances, while non-polar solvents dissolve non-polar substances more readily. When EPDM comes into contact with certain solvents, the solvent molecules, being small, diffuse rapidly and preferentially penetrate between EPDM molecules, causing polymer swelling. This swelling can even lead to polymer dissolution. Furthermore, prolonged exposure to ultraviolet light causes photo-oxidation of EPDM, resulting in surface cracking, hardening, and even powdering of the leather. This is because ultraviolet light can break the unsaturated double bonds in the EPDM molecular chain, initiating free radical reactions and accelerating the aging process.
[0031] The effects described above are the results obtained by the inventors after practice and careful research. Therefore, the discovery process of the above problems and the solutions proposed in this disclosure below should be considered as contributions made by the inventors to this disclosure.
[0032] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.
[0033] Please refer to Figure 1. As shown in Figure 1, this embodiment of the present disclosure provides a polyolefin artificial leather, comprising: a base fabric layer, a substrate layer, and a coating layer stacked sequentially; the substrate layer comprises the following raw material components in parts by weight: 135-165 parts of island microstructure masterbatch, 0.4-1 parts of crosslinking agent, 0.05-0.2 parts of coupling agent, 0.01-0.2 parts of ultraviolet absorber, 0.01-0.2 parts of light stabilizer, and 0.01-0.2 parts of anti-aging agent; wherein, the island microstructure masterbatch comprises polyolefin and rubber with double bonds.
[0034] In some embodiments, specifically, the island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts of polyolefin and 35-45 parts of EPDM.
[0035] In some embodiments, specifically, the island-shaped regions derived from rubber in the island microstructure masterbatch account for 25-50% of the surface area.
[0036] In some embodiments, specifically, the polyolefin includes any one or more combinations of ethylene and α-olefin copolymers, propylene and α-olefin copolymers.
[0037] In some embodiments, specifically, the island microstructure masterbatch further includes an olefin block copolymer, which is obtained by mixing crystallizable ethylene-octene and amorphous ethylene-octene; and the octene content of the olefin block copolymer is 25-40 mol%.
[0038] In some embodiments, specifically, the island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts polyolefin, 35-45 parts EPDM, and 5-20 parts olefin block copolymer.
[0039] In some embodiments, specifically, the thickness of the substrate layer is 0.15-0.6 mm.
[0040] In some embodiments, specifically, the co-crosslinking agent includes any one or more combinations of monofunctional acrylates, difunctional acrylates, trifunctional acrylates, and polyfunctional acrylates, preferably pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate ethoxylate, pentaerythritol tetraacrylate propoxylate, and trimethylolpropane triacrylate.
[0041] In some embodiments, specifically, the coupling agent comprises one or more of vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and vinyltriisopropoxysilane.
[0042] In some embodiments, specifically, the anti-aging agent includes one or more of antioxidants, heat stabilizers, and free radical scavengers.
[0043] In some embodiments, the light stabilizer specifically includes one or more of the following: salicylic acid derivatives, substituted acrylonitrile derivatives, benzophenone derivatives, benzotriazole derivatives, triazine derivatives, inorganic or organic pigment light shielding agents, and hindered amine derivatives.
[0044] In some embodiments, the ultraviolet absorber specifically includes any one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines.
[0045] In some embodiments, specifically, the base fabric layer includes any one or more combinations of wool fabric, plain weave, polyester fabric, nylon fabric, microfiber base fabric, elastic fabric, and nonwoven fabric.
[0046] In some embodiments, specifically, the coating layer includes any one of polyurethane coatings, acrylic coatings, and silicone coatings; the polyurethane coating includes any one or a combination of acrylic polyurethane, alkyd polyurethane, polyester polyurethane, polyether polyurethane, epoxy polyurethane, and waterborne polyurethane; the acrylic coating includes any one or a combination of acrylic resin and modified acrylic resin; and the silicone coating includes any one or a combination of anionic, cationic, and nonionic silicone coatings.
[0047] This disclosure also provides a method for preparing polyolefin artificial leather as described above, comprising the following steps: Step S1, dispersing polyolefin and rubber by a screw to form island microstructure masterbatch, wherein the screw has an aspect ratio of 20-25, a compression ratio of 2:1, and a processing temperature of 140-180℃; Step S2, after thorough mixing according to the formula, melt extruding and bonding with a base fabric layer, wherein the processing temperature is 120-200℃ and the bonding pressure is 1-10MPa; Step S3, corona treatment, wherein the corona power is 2-10KWh and the linear velocity is 5-30m / min; Step S4, surface coating and embossing to obtain polyolefin artificial leather.
[0048] This disclosure also provides an automotive seat comprising the polyolefin synthetic leather as described above.
[0049] Example 1.1
[0050] Step S1: Polyolefin and rubber are dispersed by a screw to form a sea-island microstructure masterbatch made of 100 parts polyolefin and 35 parts EPDM. The screw has an aspect ratio of 20, a compression ratio of 2:1, and a processing temperature of 150°C.
[0051] Step S2: After fully mixing according to the formula, melt extrusion is applied to the base fabric layer. The processing temperature is 170℃ and the bonding pressure is 8MPa.
[0052] Step S3: Corona treatment, with a corona power of 8 kWh and a linear velocity of 25 m / min.
[0053] Step S4, surface coating and embossing, to obtain polyolefin artificial leather.
[0054] Specifically, the parameter models for steps S2 and S4 are shown in Table 1 below.
[0055] Table 1
[0056] Specifically, by changing some parameters in Example 1.1, the component parameters and performance parameters in Examples 1.1-7, as shown in Tables 2 and 3, are obtained.
[0057] Softness: QB / T5155-2017 "Test Methods for Determination of Softness of Artificial Leather and Synthetic Leather".
[0058] Tensile strength and elongation at break: GB / T1040.3-2006 "Determination of tensile properties of plastics - Part 3: Test conditions for films and sheets".
[0059] Heat aging resistance: The samples were placed in an oven at 110℃±2℃ for 168 hours, and the color change grade was evaluated according to GB / T 250-2008.
[0060] UV aging performance: Irradiation temperature 60℃, UV radiation of 280nm to 400nm 15kwh / ㎡, of which UV radiation of wavelength 280nm to 320nm accounts for at least 3% and not more than 10%, and the color change level is evaluated according to GB / T 250-2008.
[0061] Table 2
[0062] Table 3
[0063] Specifically, comparing the data from Examples 1.1, 1.2, and 1.3 shows that the addition of olefin block copolymer OBC in Examples 1.2 and 1.3 resulted in better pattern retention and better aging performance. The "sea" formed by mixing olefin block copolymer and polyolefin in the island microstructure can further enhance the anti-aging effect.
[0064] Specifically, comparing the data from Examples 1.1, 1.4, and 1.5, it is shown that Example 1.4 has a high EPDM content and good softness, while Example 1.5 has more than 50 parts of EPDM added, resulting in a high swelling rate and poor anti-aging performance.
[0065] Specifically, comparing the data from Examples 1.2, 1.6, and 1.7, it is shown that the OBC in Example 1.7 did not incorporate an island structure, resulting in poor tensile strength.
[0066] Please refer to Figure 2. The polyolefin artificial leather provided in Example 1.3 is a preferred embodiment. In addition to having excellent tensile strength and softness, it also has an extremely high embossing retention rate at extreme temperatures. This is because the rubber in the island microstructure masterbatch provides anti-aging properties, and the rubber in this part of the island microstructure does not exhibit swelling.
[0067] As shown in Figure 3, the polyolefin artificial leather provided in Example 1.7 serves as a comparative example. Because its olefin block copolymer was not added to the island microstructure masterbatch, its tensile strength decreased, and it could not form a combination with the island microstructure masterbatch, which in turn led to a decrease in the retention rate of embossing, and the surface pattern tended to flatten under extreme temperatures.
[0068] In summary, this polyolefin artificial leather and its preparation method, as well as the automotive seat, improve the dispersion performance by improving the amount and process of rubber addition, and protect the double bonds in the rubber in the form of island microstructure masterbatch. On the one hand, the masterbatch structure can prevent the rubber from hardening and becoming brittle due to long-term exposure to ultraviolet rays. On the other hand, the limitation of rubber content also avoids cracking caused by swelling, effectively improving the anti-aging performance and ensuring that the roughness of the artificial leather does not change after long-term use in high-temperature environments.
[0069] Furthermore, the traditional artificial leather material, polyvinyl chloride (PVC), relies heavily on plasticizers in the process of making artificial leather. Since plasticizers are small molecules with high degrees of freedom, this can cause the PVC surface to become brittle, and this phenomenon is exacerbated at low temperatures. Polyolefin elastomers (TPO) have advantages such as extremely low odor, no reliance on organic solvents in the synthesis process, and aging resistance, but their high crystallinity results in a hard feel and poor low-temperature folding resistance.
[0070] To optimize the feel and improve the softness of artificial leather, existing processes use a foaming process to generate tiny air bubbles in the artificial leather, thereby reducing weight and increasing softness. However, the foaming process has the drawback of insufficient elasticity in artificial leather after long-term use.
[0071] Therefore, overcoming the deficiency of insufficient resilience in artificial leather made of lightweight polyolefins is a technical problem that urgently needs to be solved in this field.
[0072] Please refer to Figure 1. In the above embodiments, the substrate layer is replaced with a high-elasticity, high-softness layer. As shown in Figure 1, this disclosure provides a polyolefin artificial leather, comprising a base fabric layer, a high-elasticity, high-softness layer, and a coating layer stacked sequentially. The high-elasticity, high-softness layer comprises the following raw material components by mass: 50-100 parts of polyolefin elastomer, 10-30 parts of low-density polyolefin elastomer, 10-30 parts of modified high-elasticity resin, 0.4-1 part of crosslinking agent, 0.05-0.2 parts of silane coupling agent A, and 0.01-0.2 parts of anti-aging agent.
[0073] In one optional embodiment, the polyolefin elastomer comprises any one or more combinations of ethylene and α-olefin copolymers, propylene and α-olefin copolymers; and the density of the polyolefin elastomer ranges from 0.8 to 1.1 g / cm³. 3 .
[0074] In one optional embodiment, the low-density polyolefin elastomer comprises, by weight, 100 parts of modified polyolefin elastomer, 10-50 parts of inorganic microspheres, and 0.01-1 parts of silane coupling agent B; the density of the low-density polyolefin elastomer is in the range of 0.6-0.9 g / cm³. 3 The inorganic microspheres include any one or more combinations of glass microspheres and ceramic microspheres; the particle size range of the inorganic microspheres is 10-90 μm.
[0075] In one alternative embodiment, the modified polyolefin elastomer is obtained by grafting 4-vinyl-1,2-phthalic acid and maleic anhydride onto a polyolefin elastomer using a melt grafting method.
[0076] In one optional embodiment, the modified high-elasticity resin comprises, by mass parts: 10-100 parts of high-elasticity polyolefin elastomer, 10-100 parts of rubber elastomer, 1-5 parts of silane coupling agent C1, and 0.1-0.5 parts of peroxide crosslinking agent.
[0077] In one optional embodiment, the rubber elastomer includes any one or more combinations of silicone rubber, nitrile rubber, natural rubber, dipropylene diene monomer (DPDM) rubber, ethylene propylene diene monomer (EPDM) rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, cis-butadiene rubber, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer.
[0078] In one alternative embodiment, the high-elasticity polyolefin elastomer is obtained by copolymerization of propylene, norbornene, and cashew phenol, and has a tensile strength ≥10MPa.
[0079] In one alternative embodiment, the silane coupling agent A comprises at least p-chlorophenyltrimethoxysilane.
[0080] In one optional embodiment, the silane coupling agent B and silane coupling agent C comprise any one or more combinations of vinyl silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, epoxy silane coupling agents, and methacryloxy silane coupling agents; the peroxide crosslinking agent comprises any one or more combinations of alkyl peroxides, diacyl peroxides, and ketal peroxides.
[0081] In one optional embodiment, the thickness of the highly elastic and flexible layer is 0.15 to 1.0 mm.
[0082] A method for preparing polyolefin artificial leather includes the following steps:
[0083] Preparation of low-density polyolefin elastomer: In a twin-screw extruder, a twin-cone screw extrusion with an aspect ratio of 25 to 40 is selected. 10 to 50 parts of inorganic microspheres are mixed with 0.01 to 1 part of silane coupling agent B for pretreatment. The mixture is then added to 100 parts of modified polyolefin elastomer through the side feed port to finally obtain low-density polyolefin elastomer.
[0084] Preparation of modified high elasticity resin: 10-100 parts of high elasticity polyolefin elastomer, 10-100 parts of rubber elastomer, 1-5 parts of silane coupling agent C, and 0.1-0.5 parts of peroxide crosslinking agent are blended in a high-speed mixer, heated and plasticized in a twin-screw extruder, and then extruded through a template and pelletized to obtain modified high elasticity resin.
[0085] Preparation of a highly elastic and flexible layer:
[0086] In this process, 10-30 parts of low-density polyolefin elastomer, 10-30 parts of modified high-elasticity resin, 15-20 parts of boric acid, and 99-100 parts by weight of concentrated sulfuric acid are added to a high-speed mixer and mixed. The mixture is then reacted at 165°C for 55-65 minutes, and then the temperature is raised to 180°C and the reaction continues for 25-35 minutes. After that, the mixture is naturally cooled to room temperature, washed with deionized water and filtered until the pH of the filtrate is neutral, and then dried to obtain the initial mixture.
[0087] The primary mixture, 200-500 parts of dimethylformamide, 0.022-0.024 parts of potassium carbonate, and 0.05-0.2 parts of silane coupling agent A are added to a high-speed mixer and mixed. The mixture is then heated to 120°C and kept at that temperature for 23-24 hours. After naturally cooling to room temperature, the mixture is filtered, washed 4-6 times with deionized water, and dried to obtain a secondary mixture.
[0088] The secondary mixture, 50-100 parts of polyolefin elastomer, 0.4-1 part of crosslinking agent, and 0.01-0.2 parts of anti-aging agent are blended in a high-speed mixer, melted in a single-screw extruder, and extruded into a film through a T-die. The film is then rapidly cooled and solidified on a cooling roller to form a smooth, uniform, highly elastic, and highly flexible layer.
[0089] Preparation of polyolefin artificial leather: After cold pressing a high-elasticity and high-softness layer with a base fabric, a coating layer is printed on the surface and cured. The texture is then pressed out by an embossing machine and cooled to set.
[0090] In one optional embodiment, the preparation steps of the modified polyolefin elastomer are as follows: 100 parts of polyolefin elastomer are first added to a torque rheometer for pre-melting for 1 to 3 minutes, and then 1.8 to 3 parts by weight of 4-vinyl-1,2-phthalic acid, 3 to 5 parts of maleic anhydride, and 0.6 to 1 part of dicumyl peroxide are added and mixed evenly. After the reaction is completed, the grafted material is cut into granules while hot and set aside for later use to obtain the modified polyolefin elastomer.
[0091] In one optional embodiment, cashew phenol is placed in an anhydrous oxygen-drying flask, and 1.2 to 1.4 times the amount of cashew phenol is slowly added dropwise at -78°C to carry out a protective reaction. The mixture is stirred for 11 to 13 hours to ensure complete reaction, yielding pre-protected cashew phenol, which is then stored in high-purity nitrogen for later use. First, under a nitrogen atmosphere, toluene, modified methylaluminoxane, and 2,6-di-tert-butyl-4-methylphenol are injected into a reaction vessel and stirred at room temperature for 8 to 12 minutes. The nitrogen is then removed using a vacuum pump, and propylene gas is introduced. The remaining negative pressure space is then filled with nitrogen to bring it to atmospheric pressure. 20 μmol / ml of fluorenylaminodimethylamine catalyst is then added. The polymerization reaction of the titanium complex / toluene solution was carried out at -20℃ for 25-35 min. Norbornene and pre-protected cashew phenol were then simultaneously injected into the reactor, and polymerization was carried out at room temperature for 10-20 min. The reaction was terminated by adding ethanol / hydrochloric acid solution. The resulting polymer was washed with ethanol, filtered, and vacuum dried at 58-62℃ for 6 h to obtain a highly elastic polyolefin elastomer. The addition amounts of propylene were 0.54 mol / L toluene, modified methylaluminoxane was 0.53-0.54 mol / L toluene, and 2,6-di-tert-butyl-4-methylphenol was 6.66-6.67 × 10⁻⁶. -5 The addition amount of the toluene-fluorenylaminodimethyltitanium complex at mol / L was 6.66–6.67 × 10⁻⁶. -4 0.26–0.27 mol / L toluene, 0.13–0.14 mol / L preprotected cashew phenol; wherein, the preparation of ethanol / HCl solution: 250 ml of 99% concentrated hydrochloric acid is added to 5 L of ethanol solution at a rate of 1 drop per second and mixed thoroughly before use.
[0092] A car seat made of the aforementioned polyolefin artificial leather.
[0093] Example 2.1, a method for preparing polyolefin artificial leather, comprising the following steps:
[0094] Preparation of low-density polyolefin elastomer: In a twin-screw extruder, a twin-cone screw extrusion with an aspect ratio of 25–40 is selected. The special conical design ensures sufficient shearing in the meshing region while shortening the residence time in the high-temperature zone, avoiding elastomer cross-linking. Ten parts of inorganic microspheres are mixed with 0.01 parts of silane coupling agent B for pretreatment, and then added to 100 parts of modified polyolefin elastomer through the side feed port to finally obtain the low-density polyolefin elastomer. The polyolefin elastomer selected is... 5136, density is 0.865 g / cm³ 3 The inorganic microspheres are made of glass microspheres with a density of 0.4 g / cm³. 3 With a particle size of 60 μm, silane coupling agent B was selected as KH570, and the density of the resulting low-density polyolefin elastomer was 0.7 g / cm³. 3 ;
[0095] Preparation of modified high-elasticity resin: 10 parts of high-elasticity polyolefin elastomer, 10 parts of rubber elastomer, 1 part of silane coupling agent C, and 0.1 parts of peroxide crosslinking agent are blended in a high-speed mixer, then heated and plasticized in a twin-screw extruder, and then extruded and pelletized through a template to obtain the modified high-elasticity resin; wherein, the rubber elastomer is selected from Sinopec Mitsui 3092PM, the silane coupling agent C is selected from KH570, and the peroxide crosslinking agent is TAIC.
[0096] Preparation of a highly elastic and flexible layer:
[0097] In this process, low-density polyolefin elastomer, modified high-elastic resin, 15 parts of boric acid, and 99 parts of concentrated sulfuric acid are added to a high-speed mixer and mixed. The mixture is then reacted at 165°C for 55 minutes, then heated to 180°C and reacted for another 25 minutes. After that, it is naturally cooled to room temperature, washed with deionized water and filtered until the pH of the filtrate is neutral, and then dried to obtain the initial mixture.
[0098] The primary mixture, 200 parts of dimethylformamide, 0.022 parts of potassium carbonate, and 0.05 parts of silane coupling agent A were added to a high-speed mixer and mixed. The mixture was then heated to 120°C and kept at that temperature for 23 hours. After naturally cooling to room temperature, the mixture was filtered, washed four times with deionized water, and dried to obtain the secondary mixture.
[0099] The secondary mixture, polyolefin elastomer, crosslinking agent, and anti-aging agent are blended in a high-performance mixer, melted in a single-screw extruder, and then extruded through a T-die to form a film. The film is then rapidly cooled and solidified on cooling rollers to form a smooth, uniform, highly elastic, and highly flexible layer. The polyolefin elastomer used is selected from... 5136, TMPTA is selected as the crosslinking agent, and 1010 is selected as the anti-aging agent;
[0100] Preparation of polyolefin artificial leather: After cold pressing a high-elasticity and high-softness layer with a base fabric, a coating layer is printed on the surface and cured. The texture is then pressed out by an embossing machine and cooled and shaped. The base fabric layer is made of polyester knitted leather with a thickness of 0.85mm, and the coating layer is made of water-based polyurethane coating with a thickness of 50μm.
[0101] The preparation steps of the modified polyolefin elastomer are as follows: 100 parts of polyolefin elastomer are first added to a torque rheometer for pre-melting for 2 minutes, and then 1.8 parts by weight of 4-vinyl-1,2-phthalic acid, 3 parts of maleic anhydride, and 0.6 parts of dicumyl peroxide are added and mixed evenly. After the reaction is completed, the grafted material is cut into particles while hot and set aside for later use to obtain the modified polyolefin elastomer with a maleic anhydride grafting rate of 1.76%.
[0102] The preparation steps of the high-elasticity polyolefin elastomer are as follows: Cashew phenol is placed in an anhydrous oxygen-drying flask, and triisobutylaluminum (1.2 times the amount of cashew phenol) is slowly added dropwise at -78℃ for a protective reaction. The mixture is stirred for 11 hours to fully react and obtain pre-protected cashew phenol, which is then stored in high-purity nitrogen for later use. First, under a nitrogen atmosphere, toluene, modified methylaluminoxane, and 2,6-di-tert-butyl-4-methylphenol are injected into a reaction vessel and stirred at room temperature for 8 minutes. The nitrogen is then removed using a vacuum pump, and propylene gas is introduced. The remaining negative pressure space is backfilled with nitrogen to bring it to atmospheric pressure. 20 μmol / ml of catalyst is then added. The polymerization reaction was catalyzed by fluorenylaminodimethyltitanium complex / toluene solution. After reacting at -20℃ for 25 min, norbornene and pre-protected cashew phenol were simultaneously injected into the reactor, and polymerization was carried out at room temperature for 10 min. The reaction was terminated by adding ethanol / hydrochloric acid solution. The resulting polymer was washed with ethanol, filtered, and vacuum dried at 58℃ for 6 h to obtain a highly elastic polyolefin elastomer. The addition amounts of propylene were 0.54 mol / L toluene, modified methylaluminoxane was 0.53 mol / L toluene, and 2,6-di-tert-butyl-4-methylphenol was 6.66 × 10⁻⁶. -5 The addition amount of the toluene-fluorenylaminodimethyltitanium complex at mol / L was 6.66*10 mol / L. -4 0.26 mol / L toluene, 0.26 mol / L norbornene, and 0.13 mol / L preprotected cashew phenol; wherein, the preparation of ethanol / HCl solution: 250 ml of 99% concentrated hydrochloric acid is added to 5 L of ethanol solution at 1 s / drop and mixed evenly for later use; the tensile strength of the high-elasticity polyolefin elastomer is 29.68 MPa.
[0103] Example 2.2, a method for preparing polyolefin artificial leather, includes the following steps:
[0104] Preparation of low-density polyolefin elastomer: A twin-cone screw extruder with an aspect ratio of 25–40 was used. The special conical design ensured sufficient shearing in the meshing region while shortening the residence time in the high-temperature zone, preventing elastomer cross-linking. 30 parts of inorganic microspheres were mixed with 0.06 parts of silane coupling agent B for pretreatment, and then added to 100 parts of modified polyolefin elastomer through a side feed port to finally obtain the low-density polyolefin elastomer. The polyolefin elastomer used was DOW 8137, with a density of 0.861 g / cm³. 3 The inorganic microspheres are made of glass microspheres with a density of 0.4 g / cm³. 3 With a particle size of 60 μm, silane coupling agent B was selected as KH570, and the density of the resulting low-density polyolefin elastomer was 0.7 g / cm³. 3 .
[0105] Preparation of modified high-elasticity resin: 55 parts of high-elasticity polyolefin elastomer, 55 parts of rubber elastomer, 3 parts of silane coupling agent C, and 0.3 parts of peroxide crosslinking agent were blended in a high-speed mixer, then heated and plasticized in a twin-screw extruder, and finally extruded and pelletized through a template to obtain the modified high-elasticity resin; wherein, the rubber elastomer was selected from Sinopec Mitsui 3092PM, the silane coupling agent C was selected from KH570, and the peroxide crosslinking agent was selected from TAIC;
[0106] Preparation of a highly elastic and flexible layer:
[0107] In this process, low-density polyolefin elastomer, modified high-elastic resin, 18 parts of boric acid, and 99.36 parts of concentrated sulfuric acid are added to a high-speed mixer and mixed. The mixture is then reacted at 165°C for 60 minutes, and then heated to 180°C for another 30 minutes. After that, it is naturally cooled to room temperature, washed with deionized water and filtered until the pH of the filtrate is neutral, and then dried to obtain the initial mixture.
[0108] The primary mixture, 300 parts of dimethylformamide, 0.023 parts of potassium carbonate, and silane coupling agent A were added to a high-speed mixer and mixed. The mixture was then heated to 120°C and kept at that temperature for 23.5 hours. After naturally cooling to room temperature, the mixture was filtered, washed five times with deionized water, and dried to obtain the secondary mixture.
[0109] The secondary mixture, polyolefin elastomer, crosslinking agent, and anti-aging agent are blended in a high-speed mixer, melted in a single-screw extruder, and then extruded into a film through a T-die. The film is then rapidly cooled and solidified on a cooling roller to form a smooth, uniform, highly elastic, and highly flexible layer. The polyolefin elastomer used is DOW 8137, the crosslinking agent is TMPTA, and the anti-aging agent is 1010.
[0110] Preparation of polyolefin artificial leather: After cold pressing a high-elasticity and high-softness layer with a base fabric, a coating layer is printed on the surface and cured. The texture is then pressed out by an embossing machine and cooled and shaped. The base fabric layer is made of polyester knitted leather with a thickness of 0.85mm, and the coating layer is made of water-based polyurethane coating with a thickness of 50μm.
[0111] The preparation steps of the modified polyolefin elastomer are as follows: 100 parts of polyolefin elastomer are first added to a torque rheometer for pre-melting for 2 minutes, and then 2.4 parts by weight of 4-vinyl-1,2-phthalic acid, 4 parts of maleic anhydride, and 0.8 parts of dicumyl peroxide are added and mixed evenly. After the reaction is completed, the grafted material is cut into particles while hot and set aside for later use to obtain the modified polyolefin elastomer with a maleic anhydride grafting rate of 1.84%.
[0112] The preparation steps of the high-elasticity polyolefin elastomer are as follows: Cashew phenol is placed in an anhydrous oxygen-drying flask, and triisobutylaluminum (1.3 times the amount of cashew phenol) is slowly added dropwise at -78℃ for a protective reaction. The mixture is stirred for 12 hours to fully react and obtain pre-protected cashew phenol, which is then stored in high-purity nitrogen for later use. First, under a nitrogen atmosphere, toluene, modified methylaluminoxane, and 2,6-di-tert-butyl-4-methylphenol are injected into a reaction vessel and stirred at room temperature for 10 minutes. The nitrogen is then removed using a vacuum pump, and propylene gas is introduced. The remaining negative pressure space is then backfilled with nitrogen to bring it to atmospheric pressure. 20 μmol / ml of catalyst is added. The polymerization reaction was catalyzed by fluorenylaminodimethyltitanium complex / toluene solution. After reacting at -20℃ for 30 min, norbornene and pre-protected cashew phenol were simultaneously injected into the reactor, and polymerization was carried out at room temperature for 15 min. The reaction was terminated by adding ethanol / hydrochloric acid solution. The resulting polymer was washed with ethanol, filtered, and vacuum dried at 60℃ for 6 h to obtain a highly elastic polyolefin elastomer. The addition amounts of propylene were 0.54 mol / L toluene, modified methylaluminoxane was 0.535 mol / L toluene, and 2,6-di-tert-butyl-4-methylphenol was 6.666 × 10⁻⁶. -5 The addition amount of the toluene-fluorenylaminodimethyltitanium complex at mol / L was 6.666*10 mol / L. -4 0.265 mol / L toluene, 0.133 mol / L norbornene, and 0.133 mol / L preprotected cashew phenol; wherein, the preparation of ethanol / HCl solution: 250 ml of 99% concentrated hydrochloric acid is added to 5 L of ethanol solution at 1 s / drop and mixed evenly for later use; the tensile strength of the high-elasticity polyolefin elastomer is 33.56 MPa.
[0113] Example 2.3, a method for preparing polyolefin artificial leather, includes the following steps:
[0114] Preparation of low-density polyolefin elastomer: In a twin-screw extruder, a twin-cone screw extrusion with an aspect ratio of 25–40 is selected. The special conical design ensures sufficient shearing in the meshing region while shortening the residence time in the high-temperature zone, preventing elastomer cross-linking. 50 parts of inorganic microspheres are mixed with 1 part of silane coupling agent B for pretreatment, and then added to 100 parts of modified polyolefin elastomer through a side feed port to finally obtain the low-density polyolefin elastomer. The polyolefin elastomer selected is... 5136, density is 0.865 g / cm³ 3 The inorganic microspheres were ceramic microspheres with a particle size of 40 μm, and the silane coupling agent B was KH570. The density of the resulting low-density polyolefin elastomer was 0.7 g / cm³. 3 ;
[0115] Preparation of modified high-elasticity resin: 100 parts of high-elasticity polyolefin elastomer, 100 parts of rubber elastomer, 5 parts of silane coupling agent C, and 0.5 parts of peroxide crosslinking agent were blended in a high-speed mixer, then heated and plasticized in a twin-screw extruder, and finally extruded and pelletized through a template to obtain the modified high-elasticity resin; wherein, the rubber elastomer was selected from Sinopec Mitsui 3092PM, the silane coupling agent C was selected from KH570, and the peroxide crosslinking agent was selected from TAIC;
[0116] Preparation of a highly elastic and flexible layer:
[0117] In this process, low-density polyolefin elastomer, modified high-elasticity resin, 20 parts of boric acid, and 100 parts by mass of concentrated sulfuric acid are added to a high-speed mixer and mixed. The mixture is then reacted at 165°C for 65 minutes, then heated to 180°C and reacted for another 35 minutes. After that, it is naturally cooled to room temperature, washed with deionized water and filtered until the pH of the filtrate is neutral, and then dried to obtain the initial mixture.
[0118] The primary mixture, 500 parts of dimethylformamide, 0.024 parts of potassium carbonate, and silane coupling agent A were added to a high-speed mixer and mixed. The mixture was then heated to 120°C and kept at that temperature for 24 hours. After naturally cooling to room temperature, the mixture was filtered, washed 6 times with deionized water, and dried to obtain the secondary mixture.
[0119] The secondary mixture, polyolefin elastomer, crosslinking agent, and anti-aging agent are blended in a high-performance mixer, melted in a single-screw extruder, and then extruded through a T-die to form a film. The film is then rapidly cooled and solidified on cooling rollers to form a smooth, uniform, highly elastic, and highly flexible layer. The polyolefin elastomer used is selected from... 5136, TMPTA is selected as the crosslinking agent, and 1010 is selected as the anti-aging agent;
[0120] Preparation of polyolefin artificial leather: After cold pressing a high-elasticity and high-softness layer with a base fabric, a coating layer is printed on the surface and cured. The texture is then pressed out by an embossing machine and cooled and shaped. The base fabric layer is made of polyester knitted leather with a thickness of 0.85mm, and the coating layer is made of water-based polyurethane coating with a thickness of 50μm.
[0121] The preparation steps of the modified polyolefin elastomer are as follows: 100 parts of polyolefin elastomer are first added to a torque rheometer for pre-melting for 3 minutes, and then 3 parts by weight of 4-vinyl-1,2-phthalic acid, 5 parts of maleic anhydride, and 1 part of dicumyl peroxide are added and mixed evenly. After the reaction is completed, the grafted material is cut into particles while hot and set aside for later use to obtain the modified polyolefin elastomer with a maleic anhydride grafting rate of 1.79%.
[0122] The preparation steps of the high-elasticity polyolefin elastomer are as follows: Cashew phenol is placed in an anhydrous oxygen-drying flask, and triisobutylaluminum (1.4 times the amount of cashew phenol) is slowly added dropwise at -78℃ for a protective reaction. The mixture is stirred for 13 hours to ensure complete reaction, yielding pre-protected cashew phenol, which is then stored in high-purity nitrogen for later use. First, under a nitrogen atmosphere, toluene, modified methylaluminoxane, and 2,6-di-tert-butyl-4-methylphenol are injected into a reaction vessel and stirred at room temperature for 12 minutes. The nitrogen is then removed using a vacuum pump, and propylene gas is introduced. The remaining negative pressure space is then backfilled with nitrogen to normal pressure, and 20 μmol / ml of [unspecified substance] is added. The polymerization reaction was catalyzed by a fluorenylaminodimethyltitanium complex / toluene solution. After reacting at -20℃ for 35 min, norbornene and pre-protected cashew phenol were simultaneously injected into the reactor, and polymerization was carried out at room temperature for 20 min. The reaction was terminated by adding ethanol / hydrochloric acid solution. The resulting polymer was washed with ethanol, filtered, and vacuum dried at 62℃ for 6 h to obtain a highly elastic polyolefin elastomer. The addition amounts of propylene, modified methylaluminoxane, and 2,6-di-tert-butyl-4-methylphenol were 0.67 × 10⁻⁶. -5 The addition amount of the toluene-fluorenylaminodimethyltitanium complex at mol / L was 6.67*10 mol / L. -4 0.27 mol / L toluene, 0.27 mol / L norbornene, and 0.14 mol / L preprotected cashew phenol; wherein, the preparation of ethanol / HCl solution: 250 ml of 99% concentrated hydrochloric acid is added to 5 L of ethanol solution at 1 s / drop and mixed evenly for later use; the tensile strength of the high-elasticity polyolefin elastomer is 34.93 MPa.
[0123] Example 2.4 differs from Example 2.1 in that the high-elasticity polyolefin elastomer in the modified high-elasticity resin is DOW 7467, while the other components and steps are the same as in Example 2.1.
[0124] Example 2.5 differs from Example 2.1 in that it does not contain modified high-elasticity resin, while the other components and steps are the same as in Example 2.1.
[0125] Example 2.6 differs from Example 2.1 in that it does not contain low-density polyolefin elastomer, and the anti-aging agent in the high-elasticity and high-softness layer is 1076 combined with 168, wherein the mass ratio of anti-aging agent 1076 to anti-aging agent 168 is 1:1. The remaining components and steps are the same as in Example 2.1.
[0126] Example 2.7 differs from Example 2.1 in that it does not contain low-density polyolefin elastomer, and the crosslinking agent in the high-elasticity and high-softness layer is TMPTMA. The remaining components and steps are the same as in Example 2.1.
[0127] Example 2.8 differs from Example 2.1 in that the polyolefin elastomer used in the high-elasticity, high-softness layer is DOW 9807, while the other components and steps are the same as in Example 2.1.
[0128] Example 2.9 differs from Example 2.1 in that a polyolefin elastomer is used instead of a modified polyolefin elastomer in the low-density polyolefin elastomer, while the other components and steps are the same as in Example 2.1.
[0129] Example 2.10 differs from Example 2.1 in that the silane coupling agent A is KH570, while the other components and steps are the same as in Example 2.1.
[0130] Example 2.11 differs from Example 2.1 in that the modified polyolefin elastomer uses only maleic anhydride-grafted polyolefin elastomer with a maleic anhydride grafting rate of 1.49%. The remaining components and steps are the same as in Example 2.1.
[0131] Example 2.12 differs from Example 2.1 in that the high-elasticity polyolefin elastomer is obtained only by copolymerizing propylene and norbornene, and the tensile strength of the high-elasticity polyolefin elastomer is 12.16 MPa. The remaining components and steps are the same as in Example 2.1.
[0132] Example 2.13 differs from Example 2.1 in that the low-density polyolefin elastomer, modified high-elasticity resin, silane coupling agent A, secondary mixture, polyolefin elastomer, crosslinking agent, and anti-aging agent are directly blended in a high-speed mixer, melted in a single-screw extruder, and extruded into a film through a T-die. Subsequently, it is rapidly cooled and solidified on a cooling roller to form a smooth, uniform, highly elastic, and highly flexible layer. The remaining components and steps are the same as in Example 2.1.
[0133] Specifically, the differences in the weight parts of the raw materials in Examples 2.1 to 2.13 are shown in Table 3 below, and the performance parameters are shown in Table 4 below.
[0134] Table 3. Weight proportions of raw materials for the high-elasticity and high-softness layer
[0135] Specifically, in the polyolefin elastomer artificial leather prepared in Examples 2.1 to 2.13, the hand feel was rated according to ISO 17235 (1 being the hardest and 5 being the softest), the softness was tested according to QB / T 5155-2017 (Method C), with lower softness indicating greater softness, the folding fastness was tested according to ISO 32100, the VOC content (xylene) was tested according to ISO 12219-2:2012 (ND indicates a value less than 30, undetectable), the low temperature impact test was conducted according to ASTM D2137, and the color fastness to artificial light was tested according to GB / T 8427-2019 Textiles Tests, with the test condition being exposure cycle A1.
[0136] Table 4 Performance parameters of artificial leather in Examples 2.1-2.13
[0137] Specifically, as shown in Table 4, the data on softness and VOC content indicate that inorganic microspheres not only provide a lightweight effect in low-density polyolefin elastomers, thereby improving overall softness, but also have hydrophobic properties, enabling them to adsorb non-polar VOCs such as benzene compounds and reduce the impact of humidity on adsorption capacity. These advantages are not found in traditional foamed polyolefin artificial leather.
[0138] As shown in Examples 2.1 to 2.3, under the condition that the proportion of low-density polyolefin elastomer remains unchanged, the increase of modified high-elasticity resin can improve the hand feel of artificial leather, but at the same time the softness will decrease to a certain extent. Therefore, Examples 2 and 2.3 are preferred.
[0139] The difference between Example 2.4 and Example 2.1 is that the high-elasticity polyolefin elastomer in the modified high-elasticity resin is DOW 7467 instead of the high-elasticity polyolefin elastomer obtained by copolymerization of propylene, norbornene, and cashew phenol. As a result, the softness, feel, light aging resistance, and overall resilience of the artificial leather decrease.
[0140] The difference between Example 2.5 and Example 2.1 is that no modified high-elasticity resin is added. As shown in Figure 4, without the addition of modified high-elasticity resin, only low-density polyolefin elastomer will have a lack of mechanical properties due to the reduced density, which will lead to cracking in the folding test; the softness, feel and light aging resistance of the artificial leather will decrease.
[0141] The difference between Example 2.6 and Example 2.1 is that no low-density polyolefin elastomer is added, and the anti-aging agent in the high-elasticity and high-softness layer is 1076 combined with 168, wherein the mass ratio of anti-aging agent 1076 to anti-aging agent 168 is 1:1. The difference between Example 2.7 and Example 2.1 is that no low-density polyolefin elastomer is added, and the crosslinking agent in the high-elasticity and high-softness layer is TMPTMA. Without the addition of low-density polyolefin elastomer, the resilience is insufficient, and under this condition, the addition of modified high-elasticity resin will result in excessively high VOC content due to the lack of inorganic microspheres for adsorption.
[0142] The difference between Example 2.8 and Example 2.1 is that the polyolefin elastomer in the high-elasticity and high-softness layer is DOW 9807, as shown in Figure 5 and Example 2.8. The addition of modified high-elasticity resin and low-density polyolefin elastomer can further reduce the density of artificial leather while ensuring that its mechanical properties and tactile feel are not reduced. Therefore, Example 2.8 is more preferred.
[0143] The difference between Example 2.9 and Example 2.1 is that a polyolefin elastomer is used instead of a modified polyolefin elastomer in the low-density polyolefin elastomer, resulting in a decrease in the softness, feel, light aging resistance, and overall resilience of the artificial leather.
[0144] The difference between Example 2.10 and Example 2.1 is that the silane coupling agent A is KH570, and the light aging resistance of the artificial leather decreases.
[0145] The difference between Example 2.11 and Example 2.1 is that the modified polyolefin elastomer uses only maleic anhydride-grafted polyolefin elastomer, resulting in a decrease in the softness, feel, light aging resistance, and overall resilience of the artificial leather.
[0146] The difference between Example 2.12 and Example 2.1 is that the high-elasticity polyolefin elastomer is obtained by copolymerizing only propylene and norbornene, resulting in a decrease in the softness, feel, light aging resistance, and overall resilience of the artificial leather.
[0147] The difference between Example 2.13 and Example 2.1 is that the low-density polyolefin elastomer, modified high-elasticity resin, silane coupling agent A, secondary mixture, polyolefin elastomer, crosslinking agent, and anti-aging agent are directly blended and extruded in a high-speed mixer to obtain a high-elasticity and high-softness layer. Instead, the low-density polyolefin elastomer and modified high-elasticity resin are premixed before adding silane coupling agent A for secondary mixing, and the remaining raw material components are added at the end. As a result, the light aging resistance of the artificial leather decreases.
[0148] The present invention has the following beneficial effects:
[0149] (1) The polyolefin artificial leather and its preparation method of the present invention, and the automobile seat, by introducing inorganic microspheres to modify and obtain low-density polyolefin elastomers, can destroy the polyolefin crystalline region and form micropores, making the material easier to compress and deform, which macroscopically manifests as improved softness. At the same time, the addition of these inorganic microspheres and modified high-elasticity polyolefin elastomers compensates for the loss of mechanical properties caused by the reduction in density and improves the overall resilience performance.
[0150] (2) The modified polyolefin elastomer of the present invention is obtained by grafting 4-vinyl-1,2-phthalic acid and maleic anhydride onto the polyolefin elastomer using a melt grafting method. By grafting 4-vinyl-1,2-phthalic acid and maleic anhydride, the compatibility between the polyolefin elastomer, the low-density polyolefin elastomer, and the modified high-elasticity resin is increased. The introduction of 4-vinyl-1,2-phthalic acid can preferentially capture free radicals on the polyolefin elastomer, and the chain growth free radicals formed have higher reactivity with maleic anhydride. To a certain extent, it provides a good grafting environment, which increases the number of maleic anhydride molecules finally grafted onto the polyolefin elastomer molecular chain and significantly improves the grafting rate. This allows the low-density polyolefin elastomer obtained to act as an interface modifier, greatly improving the compatibility between the polyolefin elastomer and the modified high-elasticity resin, reducing the interfacial tension between them, and achieving a toughening effect.
[0151] (3) The high-elasticity polyolefin elastomer of the present invention is obtained by copolymerization of propylene, norbornene and cashew phenol. The introduction of a large number of hydroxyl groups into cashew phenol results in strong hydrogen bond interactions between chains. This intermolecular force has a much greater impact on mechanical properties than the increase in branching degree and the decrease in the relative content of rigid norbornene units. Therefore, its tensile strength increases. Furthermore, the introduction of long carbon chains of cashew phenol can make the high-elasticity polyolefin elastomer chain segments more flexible. The formed hydrogen bonds act as physical cross-linking points, resulting in an increase in its elongation at break and an increase in the toughness of the material. The introduction of semi-crystalline syn-PP chains significantly increases the tensile stress of the high-elasticity polyolefin elastomer. The presence of semi-crystalline syn-PP also increases the toughness of the material. This is because the hydrogen bond interaction force in the high-elasticity polyolefin elastomer and the semi-crystalline syn-PP form physical cross-linking points, which hinder the relative slippage of molecular chains under stress, making them more difficult to break.
[0152] (4) In this invention, low-density polyolefin elastomer and modified high-elastic resin are premixed. The phthalic acid on the low-density polyolefin elastomer reacts with the phenol on the modified high-elastic resin to form a 1-hydroxy-9,10-anthraquinone derivative. Then, silane coupling agent A is added for secondary mixing. The chlorobenzene on the silane coupling agent A reacts with the 1-hydroxy-9,10-anthraquinone derivative to form a phenoxyanthraquinone derivative. Under ultraviolet light irradiation, the phenoxyanthraquinone derivative absorbs ultraviolet light and changes from a "trans" quinone structure to an "ana" quinone structure, converting light energy into chemical energy for structural rearrangement, avoiding degradation reactions caused by ultraviolet light, and improving the UV aging resistance of polyolefin artificial leather.
[0153] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.
Claims
1. A microstructured island masterbatch, characterized in that, The island microstructure masterbatch is formed by dispersing polyolefins and rubber. The island microstructure masterbatch also includes an olefin block copolymer, which is obtained by mixing crystallizable ethylene-octene and amorphous ethylene-octene. Furthermore, the octene content of the olefin block copolymer is 25-40 mol%. The island microstructure masterbatch comprises the following raw material components in parts by weight: 100 parts polyolefin, 35-45 parts EPDM, and 5-20 parts olefin block copolymer.
2. The island microstructure masterbatch as described in claim 1, characterized in that, In the island-shaped microstructure masterbatch, the island-shaped regions obtained from rubber account for 25-50% of the surface area.
3. The island microstructure masterbatch as described in claim 1, characterized in that, The polyolefin includes any one or more combinations of ethylene and α-olefin copolymers, propylene and α-olefin copolymers.
4. A method for preparing a microstructured island masterbatch as described in any one of claims 1-3, characterized in that, The process includes the following steps: dispersing polyolefins and rubber using a screw to form island-shaped microstructure masterbatch, wherein the screw has an aspect ratio of 20-25, a compression ratio of 2:1, and a processing temperature of 140-180℃.
5. A type of polyolefin artificial leather, characterized in that, include: A base fabric layer, a substrate layer, and a coating layer are stacked sequentially. The substrate layer comprises the following raw material components in parts by weight: The mixture contains 135-165 parts of island microstructure masterbatch, 0.4-1 parts of crosslinking agent, 0.05-0.2 parts of coupling agent, 0.01-0.2 parts of ultraviolet absorber, 0.01-0.2 parts of light stabilizer, and 0.01-0.2 parts of anti-aging agent.
6. The polyolefin artificial leather as described in claim 5, characterized in that, The thickness of the substrate layer is 0.15-0.6 mm.
7. The polyolefin artificial leather as described in claim 5, characterized in that, The co-crosslinking agent includes any one or more combinations of monofunctional acrylates, difunctional acrylates, trifunctional acrylates and polyfunctional acrylates, preferably pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate ethoxylate, pentaerythritol tetraacrylate propoxylate and trimethylolpropane triacrylate. The coupling agent includes one or more of vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriisopropoxysilane; The anti-aging agent includes one or more of antioxidants, heat stabilizers, and free radical scavengers; The light stabilizer includes one or more of the following: salicylic acid derivatives, substituted acrylonitrile derivatives, benzophenone derivatives, benzotriazole derivatives, triazine derivatives, inorganic or organic pigment light shielding agents, and hindered amine derivatives. The ultraviolet absorber includes any one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines.
8. The polyolefin artificial leather as described in claim 5, characterized in that, The base fabric layer includes any one or more combinations of wool fabric, plain weave, polyester fabric, nylon fabric, microfiber base fabric, elastic fabric and non-woven fabric; The coating layer includes any one of polyurethane coatings, acrylic coatings, and silicone coatings; the polyurethane coating includes any one or a combination of acrylic polyurethane, alkyd polyurethane, polyester polyurethane, polyether polyurethane, epoxy polyurethane, and waterborne polyurethane; the acrylic coating includes any one or a combination of acrylic resin and modified acrylic resin; the silicone coating includes any one or a combination of anionic, cationic, and nonionic silicone coatings.
9. A method for preparing polyolefin artificial leather as described in any one of claims 5-8, characterized in that, Includes the following steps: Step S1: Prepare island microstructure masterbatch; Step S2: After thoroughly mixing according to the formula, melt extrude and bond with the base fabric layer; Step S3, corona treatment; Step S4, surface coating and embossing, to obtain polyolefin artificial leather.
10. A car seat, characterized in that, Including the polyolefin artificial leather as described in any one of claims 5-8.
11. A highly elastic and soft layer for artificial leather, characterized in that, The highly elastic and flexible layer comprises the following raw material components: modified high-elasticity resin; The modified high-elasticity resin includes: a high-elasticity polyolefin elastomer, which is obtained by copolymerization of propylene, norbornene, and cashew nut shell; The preparation steps of the high-elasticity polyolefin elastomer are as follows: Preprotected cashew phenol is obtained by reacting cashew phenol with 1.2 to 1.4 times the amount of cashew phenol by triisobutylaluminum. Under a nitrogen atmosphere, toluene, modified methylaluminoxane and 2,6-di-tert-butyl-4-methylphenol were injected into the reactor. After stirring, the nitrogen was removed and propylene gas was introduced. The remaining negative pressure space was filled with nitrogen to bring it to atmospheric pressure. The catalyst fluorenylaminodimethyltitanium complex / toluene solution was added to catalyze the polymerization reaction. Norbornene and pre-protected cashew phenol were injected into a reactor and polymerized at room temperature. The reaction was terminated by adding ethanol / hydrochloric acid solution to obtain a highly elastic polyolefin elastomer.
12. The high-elasticity, high-softness layer for artificial leather as described in claim 11, characterized in that, In the preparation steps of the high-elasticity polyolefin elastomer: The amount of propylene added was 0.54 mol / L; The amount of modified methylaluminoxane added to toluene is 0.53–0.54 mol / L; The amount of 2,6-di-tert-butyl-4-methylphenol added to toluene is 6.66–6.67 × 10⁻⁵ mol / L; The addition amount of fluorenylaminodimethyltitanium complex in toluene is 6.66–6.67 × 10⁻⁴ mol / L; The amount of norbornene added to toluene is 0.26–0.27 mol / L; The amount of preprotected cashew phenol added to toluene is 0.13–0.14 mol / L.
13. The high-elasticity, high-softness layer for artificial leather as described in claim 11, characterized in that, The modified high-elasticity resin comprises the following raw material components by mass parts: 10-100 parts of high-elasticity polyolefin elastomer; 10-100 parts of rubber elastomer; Silane coupling agent C1 to 5 parts; and, Peroxide crosslinking agent 0.1 to 0.5 parts.
14. The high-elasticity, high-softness layer for artificial leather as described in claim 13, characterized in that, The rubber elastomer includes any one or more combinations of silicone rubber, nitrile rubber, natural rubber, dipropylene propylene rubber, ethylene propylene diene monomer (EPDM) rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, cis-butadiene rubber, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer. The silane coupling agent C includes any one or more combinations of vinyl silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, epoxy silane coupling agents, and methacryloxy silane coupling agents; the peroxide crosslinking agent includes any one or more combinations of alkyl peroxides, diacyl peroxides, and ketal peroxides.
15. The high-elasticity, high-softness layer for artificial leather as described in claim 11, characterized in that, The thickness of the highly elastic and flexible layer is 0.15–1.0 mm.
16. A method for preparing polyolefin artificial leather, characterized in that, Includes the following steps: Preparation of low-density polyolefin elastomer: 10-50 parts of inorganic microspheres are mixed with 0.01-1 parts of silane coupling agent B for pretreatment, and then added to 100 parts of modified polyolefin elastomer to obtain low-density polyolefin elastomer. Preparation of modified high-elasticity resin: 10-100 parts of high-elasticity polyolefin elastomer, 10-100 parts of rubber elastomer, 1-5 parts of silane coupling agent C, and 0.1-0.5 parts of peroxide crosslinking agent are blended, heated and plasticized, and then extruded and pelletized to obtain modified high-elasticity resin. Prepare a highly elastic and flexible layer.
17. The preparation method according to claim 16, characterized in that, The method for preparing the highly elastic and flexible layer includes: A preliminary mixture is obtained by mixing 10-30 parts of low-density polyolefin elastomer, 10-30 parts of modified high-elasticity resin, 15-20 parts of boric acid, and 99-100 parts by weight of concentrated sulfuric acid. The primary mixture, 200-500 parts of dimethylformamide, 0.022-0.024 parts of potassium carbonate, and 0.05-0.2 parts of silane coupling agent A are mixed and then heated to react. After cooling, a secondary mixture is obtained. The secondary mixture, 50-100 parts of polyolefin elastomer, 0.4-1 part of crosslinking agent, and 0.01-0.2 parts of anti-aging agent are blended, melted, extruded into a film, and cooled and cured to form a smooth, uniform, highly elastic and flexible layer. To prepare polyolefin artificial leather, a high-elasticity, high-softness layer is cold-pressed with a base fabric, a coating layer is printed on the surface and cured, a texture is pressed out, and then it is cooled and shaped.
18. The preparation method according to claim 17, characterized in that, The preparation steps of the modified polyolefin elastomer are as follows: 100 parts of polyolefin elastomer were pre-melted, and then 1.8 to 3 parts by weight of 4-vinyl-1,2-phthalic acid, 3 to 5 parts of maleic anhydride, and 0.6 to 1 part of dicumyl peroxide were added and mixed evenly. After the reaction was completed, the grafted material was cut into granules while hot to obtain the modified polyolefin elastomer.
19. The preparation method according to claim 7, characterized in that, The silane coupling agent A comprises at least p-chlorophenyltrimethoxysilane; The silane coupling agent B and silane coupling agent C include any one or more combinations of vinyl silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, epoxy silane coupling agents, and methacryloxy silane coupling agents; the peroxide crosslinking agent includes any one or more combinations of alkyl peroxides, diacyl peroxides, and ketal peroxides.
20. A type of polyolefin artificial leather, characterized in that, include: The base fabric layer, the high-elasticity and high-softness layer as described in any one of claims 11-15, and the coating layer are stacked in sequence.
21. A car seat, characterized in that, The polyolefin artificial leather as described in claim 20 is used.
22. A method for preparing a highly elastic polyolefin elastomer, characterized in that, Preprotected cashew phenol is obtained by reacting cashew phenol with 1.2 to 1.4 times the amount of cashew phenol by triisobutylaluminum. Under a nitrogen atmosphere, toluene, modified methylaluminoxane and 2,6-di-tert-butyl-4-methylphenol were injected into the reactor. After stirring, the nitrogen was removed and propylene gas was introduced. The remaining negative pressure space was filled with nitrogen to bring it to atmospheric pressure. The catalyst fluorenylaminodimethyltitanium complex / toluene solution was added to catalyze the polymerization reaction. Norbornene and pre-protected cashew phenol were injected into a reactor and polymerized at room temperature. The reaction was terminated by adding ethanol / hydrochloric acid solution to obtain a highly elastic polyolefin elastomer.
23. An automotive interior, characterized in that, The polyolefin artificial leather as described in any one of claims 5-8; or the polyolefin artificial leather as described in claim 20.