Weather-resistant PUR frosted hose and preparation method thereof

Abstract

The invention belongs to the technical field of PUR protective sleeves, and particularly relates to a weather-resistant PUR frosted hose and a preparation method thereof. The weather-resistant PUR frosted hose is prepared from the following raw materials in parts by weight: 50 to 70 parts of PUR resin, 5 to 15 parts of rubber elastomer, 5 to 10 parts of fluorosilicone modified coated inorganic filler, 1.5 to 2 parts of lubricant and 0.8 to 1 part of antioxidant.

Description

Technical Field

[0001] The present invention belongs to the technical field of PUR protective sleeves, and particularly relates to a weather-resistant PUR matte hose and a preparation method thereof. Background Art

[0002] With the optimization of the automotive structure design, in order to make full use of the interior space of the vehicle, some wire harnesses are usually arranged at the bottom of the vehicle. These wire harnesses may come into contact with the ground during vehicle driving, which is likely to cause wear. At the same time, splashing water droplets, sediment, and dust may cause corrosion or pollution to the wire harnesses, further increasing potential safety hazards.

[0003] Currently, the commonly used wire harness protection hoses include PUR smooth hoses, PVC hoses, and PA / PP corrugated hoses. However, these hoses all have different degrees of defects in actual use. The PUR smooth hose has a too smooth surface, resulting in difficult fixation during installation and easy slippage. In addition, in order to improve the weather resistance, it needs to use polyether-type PUR materials, but the cost of this material is relatively high. The PA / PP corrugated hose has a relatively large hardness and poor flexibility, and is not suitable for complex wiring environments. Although the PVC hose has a relatively low cost, its heat resistance performance is poor and it is difficult to meet the requirements of the vehicle bottom environment.

[0004] To improve the performance of the wire harness protection hose, some products add matte powder to the material to increase the surface friction. However, in the prior art, adding a small amount of matte powder fails to significantly improve the anti-slip performance or enhance the friction effect. But when the addition amount is too large, the matte powder may precipitate, affecting the appearance and service life. At the same time, excessive matte powder may reduce the flexibility and tensile strength of the pipe, having an adverse effect on the mechanical properties. Summary of the Invention

[0005] The purpose of the present invention is to solve the above deficiencies and provide a weather-resistant PUR matte hose and a preparation method thereof.

[0006] A weather-resistant PUR matte hose, the raw materials are in parts by weight and include: 50 - 70 parts of PUR resin, 5 - 15 parts of rubber elastomer, 5 - 10 parts of fluorosilicon-modified coated inorganic filler, 1.5 - 2 parts of lubricant, and 0.8 - 1 part of antioxidant.

[0007] Further, the raw materials are in parts by weight and also include 15 - 20 parts of flame retardant and 1 - 5 parts of masterbatch.

[0008] Further, the PUR resin includes one or more of polyester-type resin and polyether-type resin; the hardness of the PUR resin is 75A - 90A;

[0009] The rubber elastomer includes one or more of ABS, ACS, AES, SBS, and SEBS resins;

[0010] The lubricant includes one or more of paraffin wax, polyethylene wax, stearic acid, hydroxystearic acid, ethylene bisstearamide, butyl stearate, oleamide, barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate, lead stearate, and silicone oil;

[0011] The antioxidant includes one or more of hindered phenol antioxidants, phosphite antioxidants, and hindered amine antioxidants;

[0012] The flame retardant includes one or more of halogen flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, phosphorus-nitrogen flame retardants, and inorganic hydroxides; The masterbatch includes a masterbatch with a PUR carrier.

[0013] Furthermore, the fluorosilicon-modified inorganic filler is prepared by polymerizing a fluorinated acrylate monomer with an inorganic filler modified by a silane coupling agent and an organosilicon core emulsion under the action of an initiator after mixing.

[0014] Furthermore, the inorganic filler includes one or more of white carbon black, glass fiber, light calcium carbonate, heavy calcium carbonate, talc powder, mica, kaolin, silica, titanium dioxide, red mud, fly ash, diatomaceous earth, wollastonite, glass microspheres, barium sulfate, and calcium sulfate;

[0015] The silane coupling agent includes one or more of KH550, KH560, KH570, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane;

[0016] The fluorinated acrylate monomer includes one or more of dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate, and octafluoropentyl methacrylate;

[0017] The initiator includes one or more of benzoyl peroxide, dicumyl peroxide, azobis(fluoronitrile), and perchloroethylene peroxide.

[0018] Furthermore, the organosilicon core emulsion is prepared by reacting a mixture of organosilicon monomers in a solution containing an emulsifier and a catalyst.

[0019] Furthermore, the organosilicon monomer includes one or more of cyclic siloxane monomers, vinyl siloxane, and silane coupling agents;

[0020] The emulsifier includes one or more of fatty alcohol polyoxyethylene ether, polyethylene glycol, polypropylene alcohol, alkyl sulfonate, and cocamidopropyl betaine;

[0021] The catalyst includes one or more of trifluorochlorosilane, p-toluenesulfonic acid, organozinc compounds, dimethyl silicone oil, and titanate.

[0022] A preparation method of a weather-resistant PUR frosted hose, comprising the following process: mixing PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, lubricant, antioxidant, flame retardant and masterbatch raw materials in parts by weight, granulating, and performing pipe extrusion molding to obtain the weather-resistant PUR frosted hose.

[0023] Further, the preparation method of the fluorosilicon-modified coated inorganic filler comprises the following process:

[0024] Surface-modify the inorganic filler with a silane coupling agent, wash with water, dry, and pulverize to obtain a modified inorganic filler;

[0025] Mix the organosilicon monomers and add them to an aqueous solution containing an emulsifier and a catalyst for reaction to obtain an organosilicon core emulsion;

[0026] Add the modified inorganic filler to the organosilicon core emulsion, stir, adjust the pH, add a fluorinated acrylate monomer and an initiator for polymerization reaction. After the reaction is completed, demulsify, wash and filter the powder, and dry to obtain the fluorosilicon-modified coated inorganic filler.

[0027] Further, mix the cyclic siloxane monomer, vinyl siloxane and silane coupling agent and add them to a solution containing an emulsifier and a catalyst, and react at 80 °C to 90 °C for 8 h to 10 h to obtain the organosilicon core emulsion.

[0028] Further, add the modified inorganic filler to the organosilicon core emulsion, stir for 4 h to 5 h, adjust the pH to neutral, add a fluorinated acrylate monomer and an initiator, and perform a polymerization reaction at 60 °C to 75 °C for 6 h to 8 h. After the reaction is completed, demulsify, wash and filter the powder, and dry to obtain the fluorosilicon-modified coated inorganic filler.

[0029] The beneficial effects of the present invention:

[0030] A weather-resistant PUR frosted hose provided by the present invention uses PUR resin as the main chain material, which can provide excellent strength, toughness, and anti-aging performance. It is particularly outstanding in terms of flexibility and wear resistance. During the use of the hose, the molecular structure of the PUR resin can effectively resist the damage of the external environment to it, ensuring that the hose can still maintain good physical properties after long-term use; the addition of a rubber elastomer further enhances the elasticity and impact resistance of the hose, enabling the hose to withstand greater external impacts in the working environment without being easily damaged. The compatibility of the rubber elastomer and the PUR resin optimizes the overall mechanical properties of the hose and improves its durability under high stress; the addition of fluorosilicon-modified coated inorganic fillers significantly improves the corrosion resistance, weather resistance, and anti-pollution ability of the hose. The fluorosilicon-modified inorganic fillers can not only enhance the binding force between the fillers and the resin, improve their interfacial properties, but also effectively improve the stability and service life of the hose in harsh environments. The introduction of fluorosilicon compounds gives the filler surface an extremely low surface energy, thereby improving the hydrolysis resistance, chemical corrosion resistance, and oil resistance of the hose, and adapting to a wider range of use conditions; the reasonable ratio of lubricants and antioxidants further ensures the stability of the hose under extreme conditions such as high temperature and strong light. The lubricant reduces the friction between the resin and the fillers, reduces wear, and improves the anti-wear ability of the hose, while the antioxidant can effectively delay the oxidation process of the material and reduce the aging phenomenon caused by factors such as high temperature and oxygen, ensuring the reliability of the hose during long-term use. Detailed implementation manners

[0031] The following further specifically describes a weather-resistant PUR frosted hose and its preparation method according to the present invention in conjunction with embodiments. For the sake of simplicity of description, this document cannot list all the alternative technical features and implementation manners included in the present invention. Therefore, those skilled in the art should be aware that any technical feature and implementation manner in this embodiment do not limit the protection scope of the present invention, and this protection scope includes any alternative technical features and implementation manners that those skilled in the art can obtain without creative labor. Specifically, any implementation manner obtained by replacing any technical feature in the present invention or combining any two or more technical features provided by the present invention should be within the protection scope of the present invention.

[0032] This embodiment provides a weather-resistant PUR frosted hose. The raw materials are in parts by weight and include: 50-70 parts of PUR resin, 5-15 parts of rubber elastomer, 5-10 parts of fluorosilicon-modified coated inorganic filler, 1.5-2 parts of lubricant, and 0.8-1 part of antioxidant.

[0033] In some embodiments, the raw materials are in parts by weight and further include 15-20 parts of flame retardant and 1-5 parts of color masterbatch.

[0034] In some embodiments, the PUR resin includes one or more of polyester resins and polyether resins; the hardness of the PUR resin is 75A to 90A;

[0035] The rubber elastomer includes one or more of ABS, ACS, AES, SBS, and SEBS resins;

[0036] The lubricant includes one or more of paraffin wax, polyethylene wax, stearic acid, hydroxystearic acid, ethylene bisstearamide, butyl stearate, oleamide, barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate, lead stearate, and silicone oil;

[0037] The antioxidant includes one or more of hindered phenol antioxidants, phosphite antioxidants, and hindered amine antioxidants;

[0038] The flame retardant includes one or more of halogen flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, phosphorus-nitrogen flame retardants, and inorganic hydroxides; the masterbatch includes a masterbatch with a PUR carrier.

[0039] In some embodiments, the fluorosilicone-modified inorganic filler is prepared by polymerizing a monomer mixture of an inorganic filler modified with a silane coupling agent and an organosilicon core emulsion with a fluoroacrylate monomer under the action of an initiator.

[0040] In some embodiments, the inorganic filler includes one or more of fumed silica, glass fiber, light calcium carbonate, heavy calcium carbonate, talc powder, mica, kaolin, silica, titanium dioxide, red mud, fly ash, diatomaceous earth, wollastonite, glass beads, barium sulfate, and calcium sulfate;

[0041] The silane coupling agent includes one or more of KH550, KH560, KH570, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane;

[0042] The fluoroacrylate monomer includes one or more of dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate, and octafluoropentyl methacrylate;

[0043] The initiator includes one or more of benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, and perchloroethylene peroxide;

[0044] In some embodiments, the organosilicon core emulsion is prepared by mixing organosilicon monomers and adding them to a solution containing an emulsifier and a catalyst for reaction.

[0045] In some embodiments, the organosilicon monomer includes one or more of cyclic siloxane monomers, vinylsiloxanes, and silane coupling agents;

[0046] The emulsifier includes one or more of fatty alcohol polyoxyethylene ether, polyethylene glycol, polypropylene alcohol, sodium alkyl sulfonate, and cocamidopropyl betaine;

[0047] The catalyst includes one or more of trifluorochlorosilane, p-toluenesulfonic acid, organozinc compound, dimethyl silicone oil, and titanate.

[0048] This embodiment provides a preparation method of a weather-resistant PUR matte hose, which includes the following process: mixing PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, lubricant, antioxidant, flame retardant, and masterbatch raw materials according to parts by weight, granulating, and then performing pipe extrusion molding to obtain the weather-resistant PUR matte hose.

[0049] In some embodiments, the preparation method of the fluorosilicon-modified coated inorganic filler includes the following process:

[0050] Surface-modify the inorganic filler with a silane coupling agent, wash with water, dry, and pulverize to obtain a modified inorganic filler;

[0051] Mix the organosilicon monomers and add them to an aqueous solution containing an emulsifier and a catalyst for reaction to obtain an organosilicon core emulsion;

[0052] Add the modified inorganic filler to the organosilicon core emulsion, stir, adjust the pH, add a fluorinated acrylate monomer and an initiator for polymerization reaction. After the reaction is completed, demulsify, wash and filter the powder, and dry to obtain the fluorosilicon-modified coated inorganic filler.

[0053] In some embodiments, mix the cyclic siloxane monomer, vinyl siloxane, and silane coupling agent, add them to a solution containing an emulsifier and a catalyst, and react at 80°C to 90°C for 8h to 10h to obtain an organosilicon core emulsion.

[0054] In some embodiments, add the modified inorganic filler to the organosilicon core emulsion, stir for 4h to 5h, adjust the pH to neutral, add a fluorinated acrylate monomer and an initiator, and perform a polymerization reaction at 60°C to 75°C for 6h to 8h. After the reaction is completed, demulsify, wash and filter the powder, and dry to obtain the fluorosilicon-modified coated inorganic filler.

[0055] In the above embodiments, the preparation process of the fluorosilicon-modified coated inorganic filler involves multiple key chemical reaction stages, and each stage is based on specific chemical reaction principles, thereby realizing the functionalization and surface modification of the inorganic filler.

[0056] First, the inorganic filler is surface-modified with a silane coupling agent. In this process, functional groups such as alkoxy or amino groups in the silane coupling agent molecule undergo a condensation reaction with the hydroxyl groups (-OH) on the surface of the inorganic filler (Si-OH + R-Si(OR')3 → Si-O-Si-R), generating stable silicon-oxygen bonds (Si-O-Si). This chemical reaction effectively transforms the surface of the filler from hydrophilic to organophilic, while introducing chemical active sites that can interact with subsequent organic reaction groups. For example, using silane coupling agents such as KH550 and KH570 can provide higher surface binding ability for subsequent polymerization reactions, thus significantly improving the interfacial compatibility between the filler and the organic matrix.

[0057] Secondly, in the preparation stage of the organosilicon core emulsion, cyclic siloxane monomers (such as octamethylcyclotetrasiloxane) and vinyl siloxane undergo ring-opening polymerization reactions under the combined action of an emulsifier and a catalyst. The catalyst (such as p-toluenesulfonic acid or trifluorochlorosilane) promotes the ring-opening reaction of cyclic siloxanes by providing an acidic environment or activating the cleavage and regeneration of silicon-oxygen bonds (Si-O-Si), enabling the formation of linear or cross-linked polysiloxane molecular chains (Si-O-Si backbone structure). The emulsifier (such as fatty alcohol polyoxyethylene ether or alkyl sulfonate) forms a stable emulsion system by reducing the surface tension at the water-organosilicon interface during this process, ensuring uniform dispersion of organosilicon during the polymerization. The finally formed organosilicon core emulsion has a uniform particle size and surface activity, providing a reaction platform for the next step of coating the inorganic filler.

[0058] Finally, in the fluorosilicon-modified coating reaction stage, the modified inorganic filler is added to the organosilicon core emulsion, and the filler is uniformly dispersed in the emulsion through physical adsorption and chemical bonding. After adjusting the pH to neutral, a fluorinated acrylate monomer (such as dodecafluoroheptyl methacrylate) and a radical initiator (such as benzoyl peroxide) are added. At this time, the radical initiator decomposes upon heating to generate free radicals, which can activate the double bonds (C=C) in the fluorinated acrylate monomer molecules, thus forming a polymer chain structure through radical polymerization reactions. Meanwhile, chemical cross-linking reactions during the polymerization enable grafting reactions between the fluorinated acrylate and the polysiloxane groups in the organosilicon core emulsion, ultimately forming a modified layer containing a fluorosilicon structure on the surface of the filler.

[0059] After the reaction, through post-treatment steps such as demulsification, washing, and drying, the coated particles in the emulsion are separated from the aqueous phase, and unreacted monomers and by-products are further removed. The demulsification process mainly releases solid particles by destroying the interfacial stability of the emulsion; washing and drying ensure the purity and stability of the final product.

[0060] The core of the entire preparation process lies in the synergistic effect of the surface chemical modification of inorganic fillers, and through the combination of emulsion polymerization and free radical polymerization, a functionalized fluorosilicon modified layer is achieved. In this layer structure, the silicon-oxygen bond provides high mechanical strength and chemical stability, while fluorinated groups (such as -CF2- or -CF3) endow the filler with extremely low surface energy and excellent hydrophobicity and chemical corrosion resistance, making the modified filler show significant advantages in enhancing matrix compatibility and improving material properties.

[0061] Example

[0062] Example 1

[0063] Example 1 provides a weather-resistant PUR frosted hose, and the raw materials include: 50 kg of PUR resin, 5 kg of ABS elastomer, 5 kg of fluorosilicon-modified coated inorganic filler, 1.5 kg of calcium stearate, and 0.8 kg of antioxidant; among them, the inorganic filler is talc powder; the antioxidant is a compound antioxidant of type 1010 and type 1076 with a mass ratio of 1:1.

[0064] Example 1 also provides a preparation method of a weather-resistant PUR frosted hose, including the steps of: weighing PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, lubricant, and antioxidant by weight, mixing them evenly and granulating, and then performing pipe extrusion molding to obtain a weather-resistant PUR frosted hose.

[0065] Example 1 also provides a preparation method of a fluorosilicon-modified coated inorganic filler, including the following steps:

[0066] After drying the inorganic powder, surface modification is carried out with an ethanol aqueous solution of silane coupling agent KH550, then washed with water, vacuum dried, and pulverized to obtain a modified inorganic filler;

[0067] Octamethylcyclotetrasiloxane, vinyl siloxane, and silane coupling agent KH550 are mixed and then added to an aqueous solution containing emulsifier fatty alcohol polyoxyethylene ether and catalyst p-toluenesulfonic acid and stirred for 4 h to obtain an organosilicon core emulsion;

[0068] The modified inorganic filler is added to the organosilicon core emulsion, the pH is adjusted to neutral, dodecafluoroheptyl methacrylate and benzoyl peroxide are added, and a polymerization reaction is carried out at 60 °C for 8 h. After the reaction is completed, demulsification, washing and filtration, and drying are carried out to obtain a fluorosilicon-modified coated inorganic filler.

[0069] Example 2

[0070] Example 2 provides a weather-resistant PUR matte hose, and the raw materials include: 70 kg of PUR resin, 15 kg of SBS elastomer, 10 kg of fluorosilicon-modified coated inorganic filler, 2 kg of stearic acid, and 1 kg of antioxidant; wherein, the inorganic filler is silica; the antioxidant is a compound antioxidant of type 1010 and type 1076 with a mass ratio of 1:1.

[0071] Example 2 also provides a preparation method of a weather-resistant PUR matte hose, including the steps of: weighing PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, lubricant and antioxidant by weight, mixing them evenly and granulating, and then performing pipe extrusion molding to obtain a weather-resistant PUR matte hose.

[0072] Example 2 also provides a preparation method of a fluorosilicon-modified coated inorganic filler, including the following steps:

[0073] After drying the inorganic powder, surface modification is carried out with an ethanol aqueous solution of silane coupling agent vinyltriethoxysilane, then water washing, vacuum drying and pulverizing are carried out to obtain a modified inorganic filler;

[0074] Octamethylcyclotetrasiloxane, vinyl siloxane and silane coupling agent vinyltriethoxysilane are mixed and then added to an aqueous solution dissolved with emulsifier sodium alkyl sulfonate and catalyst dimethyl silicone oil and stirred for 5 h to obtain an organosilicon core emulsion;

[0075] The modified inorganic filler is added to the organosilicon core emulsion and the pH is adjusted to neutral, methyl methacrylate hexafluorobutyl ester and dichloroethylene peroxide are added, and a polymerization reaction is carried out at 75 °C for 6 h. After the reaction is completed, demulsification, water washing, filtration and drying are carried out to obtain a fluorosilicon-modified coated inorganic filler.

[0076] Example 3

[0077] Example 3 provides a weather-resistant PUR matte hose, and the raw materials include: 60 kg of PUR resin, 10 kg of SEBS elastomer, 8 kg of fluorosilicon-modified coated inorganic filler, 2 kg of oleic acid amide, and 1 kg of antioxidant; wherein, the inorganic filler is calcium sulfate; the antioxidant is a compound antioxidant of type 1010 and type 1076 with a mass ratio of 1:1.

[0078] Example 3 also provides a preparation method of a weather-resistant PUR matte hose, including the steps of: weighing PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, lubricant and antioxidant by weight, mixing them evenly and granulating, and then performing pipe extrusion molding to obtain a weather-resistant PUR matte hose.

[0079] Example 3 also provides a preparation method of a fluorosilicon-modified coated inorganic filler, including the following steps:

[0080] After drying the inorganic powder, it was surface-modified with an ethanol aqueous solution of the silane coupling agent vinyltris(β-methoxyethoxy)silane, then washed with water, dried under vacuum, and pulverized to obtain the modified inorganic filler;

[0081] Octamethylcyclotetrasiloxane, vinylsiloxane, and the silane coupling agent vinyltris(β-methoxyethoxy)silane were mixed and then added to an aqueous solution containing the emulsifier polyvinyl alcohol and the catalyst trichlorosilane fluoride, and stirred for 4.5 h to obtain an organosilicon core emulsion;

[0082] The modified inorganic filler was added to the organosilicon core emulsion and the pH was adjusted to neutral. Octafluoropentyl methacrylate and azobisisobutyronitrile were added, and a polymerization reaction was carried out at 70 °C for 7 h. After the reaction, demulsification, washing, filtration, and drying were carried out to obtain the fluorosilicon-modified coated inorganic filler.

[0083] Example 4

[0084] Example 4 provides a weather-resistant PUR frosted hose, and the raw materials include: 60 kg of PUR resin, 10 kg of AES elastomer, 8 kg of fluorosilicon-modified coated inorganic filler, 2 kg of paraffin, and 1 kg of antioxidant; among them, the inorganic filler is kaolin; the antioxidant is a compound antioxidant with a mass ratio of 1:1 of type 1010 and type 1076.

[0085] Example 4 also provides a preparation method of a weather-resistant PUR frosted hose, including the steps of: weighing the PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, lubricant, and antioxidant by weight, mixing them evenly and granulating, and then carrying out pipe extrusion molding to obtain the weather-resistant PUR frosted hose.

[0086] Example 4 also provides a preparation method of a fluorosilicon-modified coated inorganic filler, including the following steps:

[0087] After drying the inorganic powder, it was surface-modified with an ethanol aqueous solution of the silane coupling agent vinyltrimethoxysilane, then washed with water, dried under vacuum, and pulverized to obtain the modified inorganic filler;

[0088] Octamethylcyclotetrasiloxane, vinylsiloxane, and the silane coupling agent vinyltrimethoxysilane were mixed and then added to an aqueous solution containing the emulsifier polyethylene glycol and the catalyst titanate, and stirred for 4.5 h to obtain an organosilicon core emulsion;

[0089] The modified inorganic filler was added to the organosilicon core emulsion and the pH was adjusted to neutral. Dodecafluoroheptyl methacrylate and diisopropylbenzene peroxide were added, and a polymerization reaction was carried out at 70 °C for 7 h. After the reaction, demulsification, washing, filtration, and drying were carried out to obtain the fluorosilicon-modified coated inorganic filler.

[0090] Example 5

[0091] The difference between the weather-resistant PUR matte hose provided in Example 5 and that in Example 4 lies in that the rubber elastomer is ACS, the inorganic filler is light calcium carbonate, and the lubricant is silicone oil.

[0092] The preparation method of the weather-resistant PUR matte hose provided in Example 5 and the preparation method of the fluorosilicon-modified coated inorganic filler are the same as those in Example 4.

[0093] Example 6

[0094] The difference between the weather-resistant PUR matte hose provided in Example 6 and that in Example 4 lies in that the rubber elastomer is ABS, the inorganic filler is glass fiber, and the lubricant is vinyl bisstearamide.

[0095] The preparation method of the weather-resistant PUR matte hose provided in Example 6 is the same as that in Example 4; the preparation method of the fluorosilicon-modified coated inorganic filler is the same as that in Example 1.

[0096] Example 7

[0097] The difference between the weather-resistant PUR matte hose provided in Example 7 and that in Example 4 lies in that the raw materials further include 15 kg of flame retardant ADP and 1 kg of masterbatch.

[0098] The preparation method of the weather-resistant PUR matte hose provided in Example 7 includes the steps of: weighing PUR resin, rubber elastomer, fluorosilicon-modified coated inorganic filler, flame retardant, masterbatch, lubricant and antioxidant by weight, mixing them evenly and granulating, and then performing pipe extrusion molding to obtain the weather-resistant PUR matte hose.

[0099] The fluorosilicon-modified coated inorganic filler provided in Example 7 is the same as that in Example 2.

[0100] Example 8

[0101] The difference between the weather-resistant PUR matte hose provided in Example 8 and that in Example 7 lies in that the raw materials include 20 kg of flame retardant ADP and 5 kg of masterbatch.

[0102] The preparation method of the weather-resistant PUR matte hose provided in Example 8 is the same as that in Example 7; the preparation method of the fluorosilicon-modified coated inorganic filler is the same as that in Example 3.

[0103] Comparative Example

[0104] Comparative Example 1

[0105] The difference between the PUR hose and its preparation method provided in Comparative Example 1 and those in Example 1 lies in that the fluorosilicon-modified coated inorganic filler is equally replaced with inorganic filler talc powder.

[0106] Comparative Example 2

[0107] Comparative Example 2 provides a PUR hose and its preparation method, which is different from Example 1 in that the fluorosilicon-modified coated inorganic filler is replaced with an ABS elastomer in equal amounts.

[0108] Comparative Example 3

[0109] Comparative Example 3 provides a PUR hose and its preparation method, which is different from Example 1 in that the SBS elastomer is replaced with a fluorosilicon-modified coated inorganic filler in equal amounts.

[0110] Comparative Example 4

[0111] Comparative Example 4 provides a PUR protective tube and its preparation method, which is different from Example 1 in that the ABS elastomer is replaced with a PUR resin in equal amounts.

[0112] Comparative Example 5

[0113] Comparative Example 5 provides a PUR hose, and the difference from Example 1 is that the fluorosilicon-modified coated inorganic filler is replaced with a modified inorganic filler in equal amounts, specifically as follows:

[0114] Comparative Example 5 provides a PUR hose, and the raw materials include: 50 kg of PUR resin, 5 kg of ABS elastomer, 5 kg of modified inorganic filler, 1.5 kg of calcium stearate, and 0.8 kg of antioxidant; among them, the inorganic filler is talc powder; the antioxidant is a compound antioxidant with a mass ratio of 1:1 of type 1010 and type 1076.

[0115] Comparative Example 5 also provides a preparation method of a PUR hose, including the steps of: weighing the PUR resin, rubber elastomer, modified inorganic filler, lubricant, and antioxidant by weight, mixing them evenly and granulating, and then performing tube extrusion molding to obtain a PUR hose.

[0116] Comparative Example 5 also provides a preparation method of a modified inorganic filler, including the following steps:

[0117] After drying the inorganic powder, surface modification is carried out with an ethanol aqueous solution of silane coupling agent KH550, then water washing, vacuum drying, and pulverization are carried out to obtain the modified inorganic filler.

[0118] Comparative Example 6

[0119] Comparative Example 6 provides a PUR hose and its preparation method, which is the same as that of Example 1, and the difference is that the preparation method of the fluorosilicon-modified coated inorganic filler is different.

[0120] Comparative Example 6 provides a preparation method of a fluorosilicon-modified coated inorganic filler, specifically including the following steps:

[0121] Octamethylcyclotetrasiloxane, vinyl siloxane, and silane coupling agent KH550 were mixed and then added to an aqueous solution containing emulsifier fatty alcohol polyoxyethylene ether and catalyst p-toluenesulfonic acid, and stirred for 4 h to obtain an organosilicon core emulsion;

[0122] Inorganic filler was added to the organosilicon core emulsion and the pH was adjusted to neutral. Dodecafluoroheptyl methacrylate and benzoyl peroxide were added, and polymerization reaction was carried out at 60 °C for 8 h. After the reaction was completed, demulsification was carried out, followed by washing, filtration, and drying to obtain fluorosilicon-modified coated inorganic filler.

[0123] Performance testing

[0124] The PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 were subjected to mechanical property and wear resistance tests. The specific test methods are as follows:

[0125] Referring to the requirements of Section 6.3.3 of MBN_LV_312-3_2017-09, testing was carried out on finished products and performed according to the following method conditions: Test conditions: specimen length: 100 mm; test rate: 100 mm / min; clamp distance: 50 mm; Observe the extruded pipe surface of each formulation and record whether the frosting is good or not.

[0126] Wear resistance detection was carried out according to Section 5.12.4.2 of ISO 6722-1:2011. Product pretreatment conditions: 23 °C ± 5 °C, 45-75% RH, 16 h; Test conditions: test frequency: (55 ± 5) cycles / min; test load: 7 N, grinding needle diameter: 0.45 mm ± 0.01 mm; wear length: 20 mm ± 1 mm; grinding needle length: 15.5 mm ± 1 mm; grinding needle replacement frequency: 1 time / pcs; mandrel specification: Φ9 mm.

[0127] The test results of the mechanical properties and wear resistance of the PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 are shown in Table 1 in detail.

[0128] Table 1 Mechanical properties and wear resistance of PUR protection hoses provided in Examples 1-5 and Comparative Examples 1-6

[0129]

[0130]

[0131] Surface roughness testing

[0132] The PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 were subjected to surface roughness testing. The specific test methods and conditions are as follows:

[0133] (1) Contact measurement method

[0134] Instrument: Stylus surface roughness tester (such as Taylor Hobson, Mitutoyo, etc.).

[0135] Steps:

[0136] Prepare the sample: Clean the surface and remove oil stains and dust.

[0137] Calibrate the instrument: Use a standard block to calibrate the roughness tester to ensure accurate measurement of the instrument.

[0138] Set parameters: Input the measurement length, sampling length (such as 0.8 mm) and evaluation length (such as 4 mm).

[0139] Scan the surface: The stylus moves at a constant speed (such as 0.5 mm / s) to collect surface height data.

[0140] Calculate the results: The built-in algorithm of the instrument calculates roughness parameters such as Ra, Rz, Rq, etc. based on the collected data.

[0141] (2) Non-contact measurement method

[0142] Instrument: Laser interferometer, white light interferometer or confocal microscope.

[0143] Steps:

[0144] Optical system calibration: Adjust the optical path and focal length of the instrument.

[0145] Sample installation: Place the surface to be measured on the sample stage of the instrument to ensure stability.

[0146] Measure the surface: Scan the surface with laser or white light to collect height data.

[0147] Analyze the data: Use software to generate a three-dimensional surface profile and calculate roughness parameters.

[0148] Test parameters

[0149] The following key parameters usually need to be set during surface roughness testing:

[0150] Sampling length: The length of a single segment of data sampling, typical values are 0.08 mm, 0.25 mm, 0.8 mm, etc.

[0151] Evaluation length: The total measurement length including multiple sampling lengths, usually 4 times or 5 times the sampling length.

[0152] Stylus radius (contact type): The radius of the front end of the stylus, generally 2 μm or 5 μm.

[0153] Measurement speed: The stylus or optical scanning speed, typical value is 0.5 mm / s.

[0154] The surface roughness data of the PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 are shown in Table 2 below.

[0155] Table 2 Surface roughness of the PUR pipes provided in Examples 1-8 and Comparative Examples 1-6

[0156]

[0157] Weather resistance test

[0158] The PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 were respectively subjected to performance tests of anti-ultraviolet aging, hydrolysis resistance, high and low temperature resistance, chemical corrosion resistance, and antioxidant performance.

[0159] (1) Anti-ultraviolet aging performance test

[0160] Test method: Ultraviolet light aging test (QUV test).

[0161] Test conditions: Use an ultraviolet aging test chamber (such as a QUV-340 device), select a UV-A lamp tube (wavelength 340 nm), the radiation intensity is 0.89 W / m 2 , the test temperature is 60 °C, and the cycle period is 4 hours of light + 4 hours of condensation.

[0162] Test content:

[0163] Test the tensile strength and retention rate after 100 hours, 200 hours, and 500 hours of light exposure.

[0164] Test results: The test results of anti-ultraviolet aging of the PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 are shown in Table 3.

[0165] Table 3 Anti-ultraviolet aging performance test (UV-A, 340 nm, 60 °C)

[0166]

[0167] (2) Hydrolysis resistance performance test

[0168] Test method: Damp heat aging test

[0169] Test conditions: Place the PUR pipe sample in a damp heat environment chamber (such as 85 °C, 85% relative humidity) for aging for 7 days, 14 days, and 28 days, and regularly sample to test the change of mechanical properties.

[0170] Test content:

[0171] Measure the tensile strength and elongation at break before and after aging.

[0172] Test results: The test results of hydrolysis resistance of the PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 are shown in Table 4.

[0173] Table 4 Hydrolysis Resistance Performance Test (85°C / 85% Humidity)

[0174]

[0175]

[0176] (3) High and Low Temperature Resistance Performance Test

[0177] Test Method: High and Low Temperature Cycling Test

[0178] Test Conditions:

[0179] Place the PUR pipe sample in a high and low temperature cycling test chamber, set the temperature range from -40°C to 80°C, the cycle period is 2 hours (1 hour at high temperature + 1 hour at low temperature), and test for 20 cycles.

[0180] After each cycle ends, restore the sample to room temperature and then conduct a bending test.

[0181] Test Contents:

[0182] Test the bendability of the hose and record the breaking strength of the sample.

[0183] Test Results: The high and low temperature resistance test results of the PUR pipes provided in Examples 1 - 8 and Comparative Examples 1 - 6 are shown in Table 5.

[0184] Table 5 High and Low Temperature Resistance Performance Test (-40°C to 80°C, 20 Cycles)

[0185]

[0186] (4) Chemical Corrosion Resistance Performance Test

[0187] Test Method: Chemical Immersion Test

[0188] Test Conditions:

[0189] Immerse the PUR pipe samples in 10% sulfuric acid solution, 10% sodium hydroxide solution, and diesel oil solution respectively, the test temperature is 25°C, and the immersion time is 72 hours.

[0190] Test Contents:

[0191] Measure the tensile strength and elongation at break before and after immersion.

[0192] Observe whether there are phenomena such as swelling, blistering, and decomposition on the surface of the hose.

[0193] Test Results: The chemical corrosion resistance test results of the PUR pipes provided in Examples 1 - 8 and Comparative Examples 1 - 6 are shown in Table 6.

[0194] Table 6 Chemical Resistance Performance Test (10% Sulfuric Acid, 10% Sodium Hydroxide, Diesel, 72 hours)

[0195]

[0196] (5) Antioxidant Performance Test

[0197] Test Method: Oxidation Induction Time (OIT) Test

[0198] Test Conditions:

[0199] Use a differential scanning calorimeter (DSC) for testing. Heat the test sample to 200°C under nitrogen protection, then switch to an oxygen atmosphere, and record the time from stability to thermal oxidative decomposition of the sample.

[0200] Test Content:

[0201] Measure the oxidation induction time (OIT). The longer the OIT, the better the antioxidant performance of the material.

[0202] Test Results: The antioxidant test results of the PUR pipes provided in Examples 1-8 and Comparative Examples 1-6 are shown in Table 7.

[0203] Table 7 Antioxidant Performance Test (OIT Test, 200°C, Oxygen Atmosphere)

[0204]

[0205] As can be seen from Tables 1-7 above, the test results of the weather-resistant PUR matte hoses are respectively involved in mechanical properties, surface roughness, weather resistance (including anti-ultraviolet aging, hydrolysis resistance, high and low temperature adaptability, chemical corrosion resistance) and antioxidant performance. Generally speaking, these data comprehensively demonstrate the differences and advantages of the products of different examples and comparative examples in key performance.

[0206] As can be seen from Table 1, the hoses of Examples 1-8 perform excellently in terms of tensile strength, elongation rate and wear resistance, and are significantly better than the products of the comparative examples. This indicates that the addition of the fluorosilicon-modified coated inorganic filler significantly improves the mechanical strength, flexibility and wear resistance of the hose. In particular, the performance of Examples 7 and 8 is the most prominent, with a tensile strength of more than 250 N and a wear resistance of more than 13,000 times, reflecting the best material ratio and process optimization effect.

[0207] As can be seen from Table 2, the test results of the surface roughness in Table 2 show that the matte surface texture of Examples 1-8 is more significant, and parameters such as Ra and Rz are much higher than those of the comparative examples, further verifying the improvement effect of the fluorosilicon-modified coated inorganic filler on the surface performance. At the same time, the synergistic effect of the high surface roughness and wear resistance makes the hose more slip-resistant and durable during installation and use.

[0208] The weather resistance tests of Tables 3 to 6 show that the products of the examples are superior to the comparative examples in terms of anti-ultraviolet aging, hydrolysis resistance, high and low temperature adaptability, and chemical corrosion resistance, and the performance improves with the increase in the content of fluorosilicon-modified coated inorganic fillers. In particular, for Examples 7 and 8, the tensile strength retention rate is as high as over 85% after 500 hours of aging, and the hydrolysis resistance elongation at break retention rate reaches 91%, showing excellent environmental adaptability and stability. In addition, in the high and low temperature cycle test, there are no cracks in the products of the examples, while cracks and even fractures generally exist in the comparative examples, further demonstrating the durability advantage of the materials.

[0209] The test results of the antioxidant performance in Table 7 show that the oxidation induction time (OIT) of the examples is significantly longer than that of the comparative examples. In particular, for Example 8, it reaches 60 minutes, indicating that the reasonable ratio of the added antioxidant and lubricant effectively delays the thermal oxidative decomposition and ensures the long-term stability of the material in a high temperature environment.

[0210] Generally speaking, in the examples, through the fluorosilicon-modified coated inorganic fillers and the optimized ratio of PUR resin and additives, multiple improvements in mechanical properties, surface quality, and weather resistance are achieved, providing a practical technical path for the development of high-performance weather-resistant PUR frosted hoses.

[0211] For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here, and the obvious changes or modifications derived therefrom are still within the protection scope of the claims of this invention.

Claims

1. A weather-resistant PUR frosted hose, characterized in that: The raw materials include, by weight, 50-70 parts of PUR resin, 5-15 parts of rubber elastomer, 5-10 parts of fluorine-silicon modified coated inorganic filler, 1.5-2 parts of lubricant and 0.8-1 part of antioxidant.

2. A PUR protective hose according to claim 1, characterized in that: The raw materials also include 15 to 20 parts of flame retardant and 1 to 5 parts of masterbatch in parts by weight.

3. A weather-resistant PUR frosted hose according to claim 2, characterized in that: The PUR resin includes one or more of polyester resin and polyether resin; the hardness of the PUR resin is 75A to 90A; The rubber elastic body includes one or more of ABS, ACS, AES, SBS and SEBS resins; The lubricant includes one or more of paraffin, polyethylene wax, stearic acid, hydroxystearic acid, vinyl bisstearamide, butyl stearate, oleamide, barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate, lead stearate, and silicone oil; The antioxidant includes one or more of a hindered phenol antioxidant, a phosphite antioxidant and a hindered amine antioxidant; The flame retardant includes one or more of halogen flame retardant, phosphorus flame retardant, nitrogen flame retardant, phosphorus nitrogen flame retardant and inorganic hydroxide; the masterbatch includes masterbatch with PUR carrier.

4. The weather-resistant PUR frosted hose according to claim 1, characterized in that: The fluorine-silicon modified inorganic filler is prepared by mixing an inorganic filler modified by a silane coupling agent with an organic silicon core emulsion and then polymerizing the mixture with a fluorine-containing acrylate monomer under the action of an initiator.

5. A weather-resistant PUR frosted hose according to claim 4, characterized in that: The inorganic filler includes one or more of white carbon black, glass fiber, light calcium carbonate, heavy calcium carbonate, talc, mica, kaolin, silicon dioxide, titanium dioxide, red mud, fly ash, diatomaceous earth, wollastonite, glass microspheres, barium sulfate and calcium sulfate; The silane coupling agent includes one or more of KH550, KH560, KH570, vinyl triethoxy silane, vinyl trimethoxy silane, and vinyl tri (β-methoxyethoxy) silane; The fluorine-containing acrylate monomer includes one or more of dodecafluoroheptyl methacrylate, hexafluorobutyl methacrylate, and octafluoropentyl methacrylate; The initiator includes one or more of benzoyl peroxide, dicumyl peroxide, azobisfluorocapronitrile and dichloroethylene peroxide.

6. A weather-resistant PUR frosted hose according to claim 4, characterized in that: The organosilicon core emulsion is prepared by mixing organosilicon monomers and adding them to a solution containing an emulsifier and a catalyst for reaction; The organic silicon monomer includes one or more of cyclic siloxane monomer, vinyl siloxane and silane coupling agent; The emulsifier includes one or more of fatty alcohol polyoxyethylene ether, polyethylene glycol, polypropylene alcohol, sodium alkyl sulfonate, and cocamidopropyl betaine; The catalyst comprises one or more of trifluorochlorosilane, p-toluenesulfonic acid, an organic zinc compound, dimethyl silicone oil and titanate.

7. A method for preparing the weather-resistant PUR frosted hose according to any one of claims 2 to 6, characterized in that: The process includes the following steps: uniformly mixing PUR resin, rubber elastomer, fluorine-silicon modified coated inorganic filler, lubricant, antioxidant, flame retardant and masterbatch raw materials according to weight proportions, granulating the mixture, and extruding the mixture into a tube to obtain the weather-resistant PUR frosted hose.

8. The method for preparing a weather-resistant PUR frosted hose according to claim 7, characterized in that: The preparation method of the fluorine-silicon modified coated inorganic filler, The process includes: The inorganic filler is surface-modified by using a silane coupling agent, washed with water, dried, and crushed to obtain a modified inorganic filler; The organic silicon monomers are mixed and added into an aqueous solution containing an emulsifier and a catalyst for reaction to obtain an organic silicon core emulsion; The modified inorganic filler is added to the organic silicon core emulsion and stirred, the pH is adjusted, and a fluorinated acrylate monomer and an initiator are added to carry out a polymerization reaction. After the reaction is completed, the emulsion is broken, and the powder is washed, filtered, and dried to obtain the fluorinated silicon modified coated inorganic filler.

9. A method for preparing a weather-resistant PUR frosted hose according to claim 8, characterized in that: The cyclic siloxane monomer, vinyl siloxane and silane coupling agent are mixed and added into a solution containing an emulsifier and a catalyst, and reacted at 80° C. to 90° C. for 8 h to 10 h to obtain the organic silicone core emulsion.

10. A method for preparing a weather-resistant PUR frosted hose according to claim 8, characterized in that: The modified inorganic filler is added to the silicone core emulsion and stirred for 4h to 5h, the pH is adjusted to neutral, fluorinated acrylate monomer and initiator are added, and polymerization reaction is carried out at 60°C to 75°C for 6h to 8h. After the reaction is completed, the emulsion is broken, the powder is washed with water, filtered, and dried to obtain the fluorosilicone modified coated inorganic filler.

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