Wear-resistant additive for polar polymer as well as preparation method and application of wear-resistant additive

Abstract

The invention relates to the technical field of polymer materials, in particular to a wear-resistant additive for polar polymers as well as a preparation method and application of the wear-resistant additive. The wear-resistant additive for the polar polymer is a graft modifier of high-molecular-weight polysiloxane, the high-molecular-weight polysiloxane is high-molecular-weight polysiloxane nanoparticles with reserved grafting points and side chains being polar groups, and a monomer used for graft modification is a monomer having good compatibility and / or reactivity with the polar polymer. According to the wear-resistant additive for the polar polymer, the monomer with good compatibility with the polar polymer is grafted, the side chain is the polar group, and the wear-resistant additive has good compatibility with the polar polymer, so that the problems of compatibility and dispersity of pure polysiloxane and the polar polymer are solved; therefore, the nanoparticles can be better dispersed in the continuous phase of the polar polymer, and the wear resistance of the polar polymer is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a wear-resistant additive for polar polymers, a preparation method and application thereof. Background Art

[0002] Nylon (polyamide, PA) is a typical polar polymer. This property comes from the fact that its main chain contains repeated amide bonds (-NHCO-), in which the nitrogen atom (N) and oxygen atom (O) have a large difference in electronegativity, resulting in uneven charge distribution within the molecule and the formation of strong polar groups.

[0003] Adding polytetrafluoroethylene (PTFE) to nylon is a common practice to improve its wear resistance. However, PTFE is a non-polar polymer with poor compatibility with nylon. The addition level needs to be increased to 3-10% to significantly improve nylon's wear resistance. Furthermore, the use of fluorinated materials like PTFE has exposed some environmental risks. The C-F bonds are extremely difficult to degrade and can accumulate in the environment and in organisms over long periods of time, polluting water and soil. This has led to growing calls for a global ban on fluorine and an increasingly pronounced trend to restrict the use of fluorinated substances.

[0004] Molybdenum disulfide (MoS2) and graphite can also be used as wear-resistant additives for nylon. MoS2 acts like a crystallizing agent, increasing the crystallinity of nylon and creating a harder and more wear-resistant surface. However, due to its color, MoS2 cannot be used as a wear-resistant additive to manufacture light-colored parts. Graphite, on the other hand, belongs to the hexagonal crystal system, where carbon atoms are bound together by strong covalent bonds within the layers, while the interlayers are connected only by weak van der Waals forces. This structure makes it extremely easy for the layers to slip. When the surface of the material is subjected to friction, the graphite flakes peel off and adhere to the contact surface, providing a continuous lubricating layer and significantly reducing the coefficient of friction. However, graphite is black, and like MoS2, it is not suitable as a wear-resistant additive for light-colored materials.

[0005] Another polar polymer, polyvinyl chloride (PVC), contains a large number of highly electronegative chlorine atoms in its molecular chain, which increases the force between the molecular chains, resulting in increased segment rigidity and reduced molecular spacing. Although this structure improves hardness and strength, it significantly reduces the toughness and ductility of the material. Rigid molecular chains are prone to irreversible slip under the action of external friction forces, and it is difficult to absorb energy through the elastic deformation of the molecular chains, resulting in poor wear resistance of PVC materials. Compared with self-lubricating or high-toughness materials such as polyamide (PA) and polyurethane (PU), PVC has a higher friction coefficient and lacks a friction reduction mechanism (such as molecular chain slip or lattice lubrication), which causes it to wear faster under the same conditions.

[0006] Polysiloxane is often used to reduce the friction coefficient of materials and is suitable for light-colored materials. It can be used as a wear-resistant agent for non-polar polymers such as PE and PP. However, due to its low polarity, it has poor compatibility with polar polymer materials such as nylon and PVC, making it difficult to add it to them as a wear-resistant agent.

[0007] Therefore, there is an urgent need to develop a wear-resistant additive for polar polymers, which has good dispersibility in polar polymers, is suitable for light-colored materials, and has long-lasting wear resistance. Summary of the Invention

[0008] In view of the shortcomings of the prior art described above, the present invention aims to provide a wear-resistant additive for polar polymers, its preparation method, and its use. The wear-resistant additive for polar polymers described in this application addresses the problems of prior art, such as the difficulty in reducing C—F bonds in polytetrafluoroethylene (PTFE), which is environmentally unfriendly; the dark color of other polar polymer wear-resistant additives; and the poor compatibility of conventional polysiloxanes with polar polymers.

[0009] To achieve the above objectives and other related objectives, the present invention is achieved through the following technical solutions.

[0010] The first aspect of the present invention discloses a wear-resistant additive for polar polymers. The wear-resistant additive for polar polymers is a grafted modified product of high molecular weight polysiloxane. The high molecular weight polysiloxane is a high molecular weight polysiloxane nanoparticle with reserved grafting points and polar groups as side chains. The monomer used for the graft modification is a monomer with good compatibility and / or reactivity with the polar polymer.

[0011] Preferably, the raw material components of the wear-resistant additive for polar polymers include: high molecular weight polysiloxane nanoparticles and monomers having good compatibility and / or reactivity with polar polymers.

[0012] Preferably, the particle size of the high molecular weight polysiloxane nanoparticles is 15 to 500 nm, and the viscosity at 25° C. is greater than 2.5 million mPa·s.

[0013] More preferably, the particle size of the high molecular weight polysiloxane nanoparticles is 100 to 500 nm. For example, the particle size of the high molecular weight polysiloxane nanoparticles can be 100 to 150 nm, 150 to 200 nm, 200 to 250 nm, 250 to 300 nm, 300 to 350 nm, 350 to 400 nm, 400 to 450 nm, or 450 to 500 nm. In a specific embodiment, the particle size of the high molecular weight polysiloxane nanoparticles is 150 to 300 nm.

[0014] More preferably, the viscosity of the high molecular weight polysiloxane nanoparticles at 25°C is 5 million to 15 million mPa.s. Furthermore, the viscosity of the high molecular weight polysiloxane nanoparticles at 25°C is 5 million to 10 million mPa.s. For example, the viscosity of the high molecular weight polysiloxane nanoparticles at 25°C is 5 million to 6 million mPa.s, 6 million to 7 million mPa.s, 7 million to 8 million mPa.s, 8 million to 9 million mPa.s, or 9 million to 10 million mPa.s. In a specific embodiment, the viscosity of the high molecular weight polysiloxane nanoparticles at 25°C is 8 million to 10 million mPa.s.

[0015] Preferably, the monomer having good compatibility and / or reactivity with the polar polymer is one or more of unsaturated carboxylic acids, acrylates and acrylamides.

[0016] More preferably, the unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.

[0017] More preferably, the acrylic acid esters are selected from glycidyl acrylate, glycidyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, ethylene urea ethoxylate, ethylene urea ethoxylate methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, ethoxyphenol acrylate, ethoxyphenol methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, trimethylolpropane formal acrylate, trimethylolpropane formal methacrylate, hydroxy-terminated dicaprolactone acrylate, hydroxy-terminated methyl ...methyl acrylate, methyl methacrylate, methyl acrylate, methyl methacrylate, methyl methacrylate, methyl acrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl acrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate, methyl One or more of dicaprolactone acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, ethylene urea ethoxy acrylate, ethylene urea ethoxy methacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, glyceryl diacrylate, glyceryl dimethacrylate, diurea diacrylate, and diurea dimethacrylate.

[0018] More preferably, the acrylamide is selected from one or more of 3-dimethylaminopropyl methacrylamide, 3-dimethylaminopropyl acrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-isopropyl acrylamide, and N-isopropyl methacrylamide.

[0019] Furthermore, the monomer having good compatibility and / or reactivity with the polar polymer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl methacrylamide, diethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, triethylene glycol dimethacrylate, glycerol dimethacrylate, diurethane dimethacrylate, and polyethylene glycol dimethacrylate. The monomer having good compatibility and / or reactivity with the polar polymer has low odor, is safe, readily available, and is highly economical.

[0020] Furthermore, the monomer having good compatibility and / or reactivity with the polar polymer is selected from one or more of methacrylic acid, glycidyl methacrylate, hydroxypropyl methacrylate, 3-dimethylaminopropyl methacrylamide, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, glycerol dimethacrylate, and diurethane dimethacrylate. The monomer having good compatibility and / or reactivity with the polar polymer has a high glass transition temperature and is more likely to form a solid at room temperature.

[0021] Preferably, based on the mass of the high molecular weight polysiloxane nanoparticles, the amount of the monomer having good compatibility and / or reactivity with the polar polymer is 0.1 to 90 wt%. More preferably, the amount of the monomer having good compatibility and / or reactivity with the polar polymer is 1 to 60 wt%. For example, the amount of the monomer having good compatibility and / or reactivity with the polar polymer can be 1 to 3 wt%, 3 to 15 wt%, 15 to 25 wt%, 25 to 35 wt%, 35 to 45 wt%, or 45 to 60 wt%. In a specific embodiment, the amount of the monomer having good compatibility and / or reactivity with the polar polymer is 3 to 35 wt%.

[0022] Preferably, the high molecular weight polysiloxane nanoparticles are obtained by emulsion polymerization of low molecular weight polysiloxane, silane containing an unsaturated group and silane containing a polar group.

[0023] More preferably, the unsaturated group in the silane containing an unsaturated group is a carbon-carbon double bond.

[0024] Furthermore, the carbon-carbon double bond is selected from one or more of vinyl and acryloyloxy groups.

[0025] Furthermore, the carbon-carbon double bond is selected from one or more of vinyl and methacryloyloxy groups.

[0026] Furthermore, the silane containing an unsaturated group is selected from vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-(2-methoxyethoxy)-silane, vinyltriisopropoxysilane, vinylmethylbis(trimethylsiloxy)silane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy) One or more of propyltriisopropoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltriethoxysilane, 3-(acryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxy)propylmethyldiethoxysilane, 3-(acryloyloxy)propylmethyldiisopropoxysilane, (4-vinylphenyl)trimethoxysilane, (4-vinylphenyl)triethoxysilane, (4-vinylphenyl)methyldimethoxysilane, (4-vinylphenyl)methyldiethoxysilane, styreneethyltrimethoxysilane, and styreneethyltriethoxysilane.

[0027] Furthermore, the unsaturated group-containing silane is selected from diethoxysilanes, including one or more of vinylmethyldiethoxysilane and 3-(methacryloyloxy)propylmethyldiethoxysilane. Diethoxysilanes themselves do not crosslink, which facilitates molecular weight growth, and hydrolysis does not produce harmful substances, which is beneficial to the environment and the health of manufacturers. Vinylmethyldiethoxysilane and 3-(methacryloyloxy)propylmethyldiethoxysilane are relatively low-cost and readily available.

[0028] More preferably, the amount of the silane containing an unsaturated group is 0.01 wt% to 30 wt% based on the mass of the low molecular weight polysiloxane. For example, the amount of the silane containing an unsaturated group can be 0.1 to 0.5 wt%, 0.5 to 1 wt%, 1 to 5 wt%, 5 to 10 wt%, 10 to 20 wt%, or 20 to 30 wt%. In a specific embodiment, the amount of the silane containing an unsaturated group is 0.5 to 10 wt%.

[0029] More preferably, the low molecular weight polysiloxane is selected from one or more of dihydroxyl-terminated polysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. In a specific embodiment, the viscosity of the dihydroxyl-terminated polysiloxane at 25°C is less than 5000 mPa·s. More preferably, the viscosity of the dihydroxyl-terminated polysiloxane at 25°C is between 2.0 and 130 mPa·s. In a specific embodiment, the low molecular weight polysiloxane is one or more of dihydroxyl-terminated polysiloxane and / or octamethylcyclotetrasiloxane. Dihydroxyl-terminated polysiloxane and octamethylcyclotetrasiloxane are readily available, highly reactive, and economical. Their low viscosity makes it easy to obtain small-sized, high-molecular-weight polysiloxane nanoparticles.

[0030] More preferably, the polar group-containing silane is selected from one or more of aminosilane, epoxysilane and acyloxysilane.

[0031] Furthermore, the aminosilane is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-n-butyl-3-aminopropylmethyldimethoxysilane, N-n-butyl-3-aminopropylmethyldiethoxysilane, 3-anilinopropyltrimethoxysilane, 3-anilinopropyltriethoxysilane, Silane, 3-anilinopropylmethyldimethoxysilane, 3-anilinopropylmethyldiethoxysilane N,N-diethyl-3-aminopropyltrimethoxysilane, N,N-diethyl-3-aminopropyltriethoxysilane, N,N-diethyl-3-aminopropylmethyldimethoxysilane, N,N-diethyl-3-aminopropylmethyldiethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltriethoxysilane, N,N-diethyl Methyl-3-aminopropylmethyldimethoxysilane, N,N-dimethyl-3-aminopropylmethyldiethoxysilane, 3-(N-cyclohexylamino)propyltrimethoxysilane, 3-(N-cyclohexylamino)propyltriethoxysilane, 3-(N-cyclohexylamino)propylmethyldimethoxysilane, 3-(N-cyclohexylamino)propylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2- One or more of diaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, and diethylenetriaminopropylmethyldiethoxysilane.

[0032] Furthermore, the aminosilane is selected from N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane and 3-ureidopropylmethyldiethoxysilane. The above aminosilane is easily available, economical, environmentally friendly, does not produce cross-linking, and is more effective than monoaminosilane.

[0033] Furthermore, the epoxysilane is selected from one or more of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propyltriethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane, and 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane.

[0034] Furthermore, the epoxysilane is selected from one or more of 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane and 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane. The epoxysilane is readily available, economical, environmentally friendly, and does not produce crosslinking.

[0035] Furthermore, the acyloxysilane is selected from one or more of 3-acetoxypropyltrimethoxysilane, 3-acetoxypropyltriethoxysilane, 3-acetoxypropylmethyldimethoxysilane, and 3-acetoxypropylmethyldiethoxysilane.

[0036] Furthermore, the acyloxysilane is 3-acetoxypropylmethyldiethoxysilane. The above acyloxysilane is readily available, economical, environmentally friendly and does not produce cross-linking.

[0037] More preferably, the amount of the polar group-containing silane is 0.1 to 30.0 wt % based on the mass of the low molecular weight polysiloxane. For example, the amount of the polar group-containing silane can be 0.001 to 0.01 wt %, 0.01 to 0.1 wt %, 0.1 to 5 wt %, 5 to 10 wt %, 10 to 15 wt %, 15 to 20 wt %, 20 to 25 wt %, or 25 to 30 wt %. In a specific embodiment, the amount of the polar group-containing silane is 0.1 to 10 wt %.

[0038] The second aspect of the present invention discloses a method for preparing the wear-resistant additive for polar polymers as described above, the preparation method comprising the following steps: a grafting reaction between high molecular weight polysiloxane nanoparticles with reserved grafting points and polar groups as side chains and a monomer with good compatibility and / or reactivity with the polar polymer.

[0039] Preferably, the high molecular weight polysiloxane nanoparticles are prepared by polymerization of low molecular weight polysiloxane, silane containing an unsaturated group and silane containing a polar group.

[0040] More preferably, the polymerization method of the polymerization reaction is selected from one or more of anionic emulsion polymerization and cationic emulsion polymerization.

[0041] The emulsifier for anionic emulsion polymerization is a negatively charged hydrophilic group, such as sulfonic acid group - SO3 - , carboxylic acid group—COO-, sulfate group—OSO3 - . Furthermore, the emulsifier for the anionic emulsion polymerization is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, dodecyl sulfonic acid, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid, dodecyl-p-toluenesulfonic acid, sodium dodecyl-p-toluenesulfonate or sodium stearate. Most preferably, the emulsifier for the anionic emulsion polymerization is selected from one or more of sodium dodecyl sulfate and dodecylbenzenesulfonic acid. The catalyst can be selected from sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. Dodecylbenzenesulfonic acid, which itself has an emulsifying function, is preferred.

[0042] Cationic emulsion polymerization emulsifiers are selected with positively charged hydrophilic groups, such as quaternary ammonium salts - NR4 + , amine salt—NH3 + . Further, the emulsifier for the cationic emulsion polymerization is selected from hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, and tri(dodecyl)methylammonium hydroxide. More preferably, the tri(dodecyl)methylammonium hydroxide is obtained by exchanging tri(dodecyl)methylammonium chloride with a quaternary amine type I ion exchange resin. Most preferably, the emulsifier for the cationic emulsion polymerization is tri(dodecyl)methylammonium hydroxide.

[0043] More preferably, the polymerization reaction includes a first-stage polymerization and a second-stage polymerization; the first-stage polymerization involves particle size control through shearing and emulsification, and the second-stage polymerization involves chain growth at low temperature. The first-stage shearing-controlled particle size involves dispersing the unsaturated group-containing silane, low molecular weight polysiloxane, polar group-containing silane, and anionic or cationic emulsifier in water, and then shearing and emulsifying to obtain an organosilicon emulsion; the second-stage polymerization involves further polycondensation of the first-stage emulsion to obtain high molecular weight polysiloxane nanoparticles.

[0044] Furthermore, the temperature of the first stage shearing and emulsification is 1-100°C.

[0045] Furthermore, the temperature of the second stage polymerization is 1-15°C. For example, the temperature of the second stage polymerization can be 1-3°C, 3-5°C, 5-7°C, 7-9°C, 9-10°C, 12-14°C, or 14-15°C. In a specific embodiment, the temperature of the second stage polymerization is 5-10°C. The temperature of the second stage polymerization is both energy-saving and sufficient for molecular weight growth.

[0046] Furthermore, the time of the second stage polymerization is 2 to 300 hours. Further, the time of the second stage polymerization is 2 to 300 hours. For example, the time of the second stage polymerization can be 2 to 12 hours, 12 to 24 hours, 24 to 48 hours, 48 ​​to 96 hours, 96 to 120 hours, 120 to 150 hours, 150 to 200 hours, 200 to 250 hours, or 250 to 300 hours. In a specific embodiment, the time of the second stage polymerization is 24 to 150 hours. The time of the second stage polymerization meets the actual needs of production efficiency, energy saving, and degree of polymerization.

[0047] Furthermore, the shearing and emulsification treatment is performed until the particle size of the organosilicon emulsion is 15 to 500 nm. More preferably, the particle size of the organosilicon emulsion is 100 to 500 nm. For example, the particle size of the organosilicon emulsion may be 100 to 150 nm, 150 to 200 nm, 200 to 250 nm, 250 to 300 nm, 300 to 350 nm, 350 to 400 nm, 400 to 450 nm, or 450 to 500 nm. In a specific embodiment, the particle size of the organosilicon emulsion is 150 to 300 nm.

[0048] Furthermore, the shear treatment equipment includes one or more of a high-pressure homogenizer, a colloid mill, a high-shear emulsifier, and an ultrasonic emulsifier;

[0049] Preferably, the grafting reaction is a free radical reaction, and the initiation method is selected from one or more of high-energy ray source irradiation, persulfate initiator, oxidation-reduction initiation system, azo initiator, and thermal initiation.

[0050] More preferably, the initiation method is an oxidation-reduction initiation system, which has better economy, effectiveness, safety and degree of reaction completion.

[0051] More preferably, the amount of the initiator is 0.001-30 wt% of the mass of the monomer having good compatibility and / or reactivity with the polar polymer. For example, the amount of the initiator can be 0.001-0.01 wt%, 0.01-0.1 wt%, 0.1-5 wt%, 5-10 wt%, 10-15 wt%, 15-20 wt%, 20-25 wt%, or 25-30 wt%. In a specific embodiment, the amount of the initiator is 0.1-10 wt%.

[0052] More preferably, the high-energy ray source irradiation is selected from one or more of a cobalt source, X-rays, ultraviolet rays, and a high-energy electron accelerator. In a specific embodiment, the high-energy ray source irradiation is a cobalt source irradiation.

[0053] Furthermore, the irradiation dose range of the high-energy ray source is 0.1 to 30 Mrad. For example, the irradiation dose range of the high-energy ray source is 0.1 to 1 Mrad, 1 to 5 Mrad, 5 to 10 Mrad, 10 to 15 Mrad, 15 to 20 Mrad, 20 to 25 Mrad, or 25 to 30 Mrad. In a specific embodiment, the irradiation dose range of the high-energy ray source is 1 to 10 Mrad.

[0054] More preferably, the persulfate initiator is selected from one or more of potassium persulfate, sodium persulfate, and ammonium persulfate.

[0055] More preferably, the persulfate initiator is added in an amount of 0.001 to 30 wt % based on the mass of the monomer having good compatibility and / or reactivity with the polar polymer. For example, the persulfate initiator may be added in an amount of 0.001 to 0.01 wt %, 0.01 to 0.1 wt %, 0.1 to 5 wt %, 5 to 10 wt %, 10 to 15 wt %, 15 to 20 wt %, 20 to 25 wt %, or 25 to 30 wt %. In a specific embodiment, the persulfate initiator is added in an amount of 0.1 to 10 wt %.

[0056] More preferably, the azo initiator is selected from one or more of azobisisobutylnitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, and azobisisopropylimidazoline.

[0057] More preferably, the amount of the water-soluble azo initiator added is 0.001 wt% to 30 wt% based on the weight of the monomer having good compatibility and / or reactivity with the polar polymer. For example, the amount of the water-soluble azo initiator added can be 0.001 to 0.01 wt%, 0.01 to 0.1 wt%, 0.1 to 5 wt%, 5 to 10 wt%, 10 to 15 wt%, 15 to 20 wt%, 20 to 25 wt%, or 25 to 30 wt%. In a specific embodiment, the amount of the water-soluble azo initiator added is 0.1 to 10 wt%.

[0058] More preferably, the initiator of the redox initiation system is selected from one or more of ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-ferrous sulfate, hydrogen peroxide-ferrous sulfate, ammonium persulfate-ferrous chloride, hydrogen peroxide-ferrous chloride, potassium persulfate-silver nitrate, persulfate-thiol, tert-butyl hydroperoxide-rongalite, isopropyl benzene hydroperoxide-rongalite, diisopropyl benzene hydroperoxide-rongalite, and isopropyl benzene hydroperoxide-FF6M.

[0059] Furthermore, the initiator of the redox initiation system is selected from cumene hydroperoxide-rongalite, ammonium persulfate-sodium bisulfite, tert-butyl hydroperoxide-rongalite, and cumene hydroperoxide-FF6M. FF6M is a sodium salt of an organic sulfinic acid derivative produced by Bruggemann, Germany.

[0060] More preferably, the amount of the initiator added to the redox initiation system is 0.001 wt% to 30 wt% based on the weight of the monomer having good compatibility and / or reactivity with the polar polymer. For example, the amount of the initiator added to the redox initiation system can be 0.001 to 0.01 wt%, 0.01 to 0.1 wt%, 0.1 to 0.5 wt%, 0.5 to 2 wt%, 2 to 5 wt%, 5 to 15 wt%, 15 to 25 wt%, or 25 to 30 wt%. In a specific embodiment, the amount of the initiator added to the redox initiation system is 0.5 to 5 wt%.

[0061] More preferably, the thermal initiation temperature is 30°C to 100°C.

[0062] Furthermore, the thermal initiation temperature is 50° C. to 95° C. For example, the thermal initiation temperature can be 50° C. to 55° C., 55° C. to 60° C., 60° C. to 65° C., 65° C. to 70° C., 70° C. to 75° C., 75° C. to 80° C., 80° C. to 85° C., 85° C. to 90° C., or 90° C. to 95° C. In a specific embodiment, the thermal initiation temperature is 65° C. to 85° C.

[0063] More preferably, before the grafting reaction, the step of dispersing the high molecular weight polysiloxane nanoparticles in a medium and deoxygenating the medium is further included. The deoxygenation eliminates oxygen inhibition and improves polymerization efficiency. In a specific embodiment, the medium is water.

[0064] More preferably, when the monomer having good compatibility and / or reactivity with the polar polymer includes a polymerization inhibitor, the grafting reaction further includes a step of removing the polymerization inhibitor from the monomer having good compatibility and / or reactivity with the polar polymer.

[0065] More preferably, the grafting reaction further comprises the step of adding a chain transfer agent. Further, the chain transfer agent is selected from one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolate, thioglycerol, thiophenol, thiosalicylic acid, etc.

[0066] More preferably, the grafting reaction further includes the steps of solid-liquid separation and drying.

[0067] Furthermore, the drying method is selected from one or more of freeze drying, spray drying, flash drying, fluidized bed drying, microwave drying, and vacuum drying.

[0068] More preferably, after the grafting reaction and before the solid-liquid separation, a flocculation step is further included, wherein the flocculant used in the flocculation is one or more selected from calcium chloride, calcium acetate, magnesium sulfate, and aluminum sulfate. The flocculation reduces the loss of the product during the filtration process.

[0069] The third aspect of the present invention further discloses the use of the aforementioned anti-wear additive for polar polymers in improving the wear resistance of polar polymers.

[0070] The fourth aspect of the present invention further discloses a wear-resistant polar polymer composition, wherein the raw materials of the wear-resistant polar polymer composition include any one of the above-mentioned wear-resistant additives for polar polymers and a polar polymer.

[0071] Preferably, the raw materials further include an antioxidant, which can prevent the polar polymer from being oxidatively degraded and yellowing during processing.

[0072] More preferably, the antioxidant comprises one or both of a primary antioxidant and a secondary antioxidant. In a specific embodiment, the primary antioxidant is selected from Irganox 1098. In a specific embodiment, the secondary antioxidant is selected from one or more of Irgafos 168.

[0073] More preferably, the antioxidant is added in an amount of 0.1 to 0.8 wt % based on the mass of the polar polymer.

[0074] Preferably, the content of the wear-resistant additive for polar polymers is 0.1-30.0 wt%, based on the total mass of the wear-resistant additive for polar polymers and the polar polymers. For example, the content of the wear-resistant additive can be 0.001-0.01 wt%, 0.01-0.1 wt%, 0.1-0.5 wt%, 0.5-2 wt%, 2-5 wt%, 5-15 wt%, 15-25 wt%, or 25-30 wt%. In a specific embodiment, the content of the wear-resistant additive is 0.5-5 wt%.

[0075] Preferably, the polar polymer is selected from one or more of nylon, polyvinyl chloride, polyurethane, and polycarbonate.

[0076] The fifth aspect of the present application also discloses a method for preparing the wear-resistant polar polymer composition as described above, which comprises the following steps: adding the wear-resistant additive for polar polymer as described above into the polar polymer in a molten state and dispersing the same.

[0077] Preferably, the anti-wear additive for polar polymers is added into the polar polymer in a molten state through a twin-screw extruder and / or an internal mixer and dispersed.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] The wear-resistant additive for polar polymers disclosed in the present application has good compatibility with polar polymers because it is grafted with monomers that are compatible with polar polymers and has polar groups as side chains. This changes the compatibility and dispersibility issues between pure polysiloxane and polar polymers, allowing nanoparticles to be better dispersed in the continuous phase of the polar polymer, significantly improving the wear resistance of the polar polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 Shown is a photograph of the appearance of the wear-resistant disc taking the average value of Application Examples 1 to 4 of this application.

[0081] Figure 2 Shown is a photograph of the appearance of the wear-resistant disc taking the average value of Application Examples 7 to 10 of this application. DETAILED DESCRIPTION

[0082] The following describes the implementation of the present invention through specific embodiments. People skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0083] Before further describing the specific embodiments of the present invention, it should be understood that the scope of the present invention is not limited to the specific embodiments described below. It should also be understood that the terminology used in the examples is intended to describe specific embodiments and is not intended to limit the scope of the present invention. The experimental procedures in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the respective manufacturers.

[0084] When the embodiments provide numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the understanding of the prior art by those skilled in the art and the description of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention may also be used to implement the present invention.

[0085] In this application, the applicant addresses the technical issues of prior art fluorine-free wear-resistant additives for polar polymers, which result in darker colors and poor compatibility between conventional polysiloxanes and polar polymers. The applicant provides a wear-resistant additive for polar polymers, as well as its preparation method and use. The wear-resistant additive for polar polymers described in this application is easy to use, significantly improves compatibility and dispersibility in polar polymers, easily forms nanoscale dispersions in polar polymers, and can significantly improve the wear resistance of polar polymers with relatively low addition amounts.

[0086] Specifically, embodiments of the present invention provide a specific wear-resistant additive for polar polymers and a method for preparing the same. The wear-resistant additive for polar polymers is a grafted modified product of a high molecular weight polysiloxane, wherein the high molecular weight polysiloxane is a high molecular weight polysiloxane nanoparticle with reserved grafting points and polar groups as side chains. The monomer used for the grafting modification is a monomer that has good compatibility and / or reactivity with the polar polymer. In other words, the raw material components of the wear-resistant additive for polar polymers include: high molecular weight polysiloxane nanoparticles and a monomer that has good compatibility and / or reactivity with the polar polymer.

[0087] In the present application, during grafting, the reaction is a free radical reaction type.

[0088] In a more specific embodiment, when the amount of the grafted monomer is greater than 30 wt % based on the mass of the high molecular weight polysiloxane nanoparticles, a chain transfer agent may be used. The chain transfer agent is selected from one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolate, thioglycerol, thiophenol, thiosalicylic acid, and the like. The amount used may be selected based on the specific circumstances of the free radical polymerization reaction. For example, based on the mass of the high molecular weight polysiloxane nanoparticles, the amount of the grafted monomer may be 0.1 to 5 wt %, such as 0.1 to 1 wt %, 1 to 2 wt %, 2 to 3 wt %, 3 to 4 wt %, or 4 to 5 wt %.

[0089] In the present application, the high molecular weight polysiloxane is a nanoscale high molecular weight polysiloxane.

[0090] In one specific embodiment, the present application obtains high molecular weight polysiloxane nanoparticles through emulsion polymerization. In a more specific embodiment, the raw materials for the emulsion polymerization include: a low molecular weight polysiloxane, a silane containing an unsaturated group, a silane containing a polar group, and an emulsifier. In a more specific embodiment, the specific method for preparing the high molecular weight polysiloxane nanoparticles includes: 1) dispersing the raw materials for the emulsion polymerization in deionized water, completing a first stage of shearing and emulsification, and shearing the silicone emulsion to a predetermined particle size of 5 to 500 nm; 2) conducting a second stage of polymerization, further polycondensing at low temperature, and then neutralizing to terminate the polymerization reaction to obtain the high molecular weight polysiloxane nanoparticles.

[0091] In a more specific embodiment, the particle size of the final product in step 2) is determined by step 1); since the second stage polymerization is a condensation dehydration reaction of the terminal hydroxyl groups, to a certain extent, the particle size of the final product in step 2) is slightly smaller than that in step 1), but the change is not large.

[0092] In a more specific embodiment, the dispersion time in step 1) is 10 to 120 minutes. Preferably, the dispersion time is 20 to 60 minutes. For example, the dispersion time can be 20 to 30 minutes, 30 to 40 minutes, 40 to 50 minutes, or 50 to 60 minutes. Taking into account the dispersion effect and energy saving, the dispersion time in a specific embodiment is 30 minutes. It should be noted that the dispersion time can be adjusted according to the actual dispersion equipment and its power, as long as the effect of uniformly dispersing the raw materials for emulsion polymerization can be achieved, such as when the rotation speed is faster, the dispersion time is shorter; when the rotation speed is slower, the dispersion time is longer.

[0093] In a more specific embodiment, the low molecular weight polysiloxane in step 1) is selected from one or more of bihydroxyl-terminated polysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Preferably, the viscosity of the bihydroxyl-terminated polysiloxane at 25° C. is less than 5000 mPa.s. More preferably, the viscosity of the bihydroxyl-terminated polysiloxane at 25° C. is 2.0 to 130 mPa.s, such as 2.0 to 30 mPa.s, 30 to 40 mPa.s, 40 to 50 mPa.s, 50 to 60 mPa.s, 60 to 70 mPa.s, 70 to 80 mPa.s, 80 to 90 mPa.s, 90 to 100 mPa.s, 100 to 110 mPa.s, 110 to 120 mPa.s, or 120 to 130 mPa.s. Considering the availability, reactivity, and economy, as well as the low viscosity and easy acquisition of small particle size, in a specific embodiment, the low molecular weight polysiloxane is one or more of dihydroxyl-terminated polysiloxane and octamethylcyclotetrasiloxane. It should be noted that the dihydroxyl-terminated polysiloxane can be obtained by hydrolysis and ring-opening polymerization of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and thus used as the raw material for dihydroxyl-terminated polysiloxane.

[0094] In a more specific embodiment, the silane unsaturated group containing an unsaturated group in step 1) is selected from one or more of vinyl and acryloxy groups.

[0095] Furthermore, the silane containing an unsaturated group is selected from vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-(2-methoxyethoxy)-silane, vinyltriisopropoxysilane, vinylmethylbis(trimethylsiloxy)silane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propyl The present invention can be used in combination with one or more of triisopropoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltriethoxysilane, 3-(acryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxy)propylmethyldiethoxysilane, 3-(acryloyloxy)propylmethyldiisopropoxysilane, (4-vinylphenyl)trimethoxysilane, (4-vinylphenyl)triethoxysilane, (4-vinylphenyl)methyldimethoxysilane, (4-vinylphenyl)methyldiethoxysilane, styreneethyltrimethoxysilane, and styreneethyltriethoxysilane. Considering that trialkoxysilanes can produce crosslinking, which is not conducive to the growth of molecular weight; and that methoxysilanes can produce methanol upon hydrolysis, which is not conducive to the environment and the health of producers, ethoxysilanes are preferred; and considering cost and availability, one or a mixture of two of vinylmethyldiethoxysilane and 3-(methacryloyloxy)propylmethyldiethoxysilane is preferred.

[0096] In a more specific embodiment, in step 1), the amount of the silane containing an unsaturated group is 0.01 wt% to 30 wt% based on the mass of the low molecular weight polysiloxane. For example, the amount of the silane containing an unsaturated group can be 0.1 to 0.5 wt%, 0.5 to 1 wt%, 1 to 5 wt%, 5 to 10 wt%, 10 to 20 wt%, or 20 to 30 wt%. In a specific embodiment, the amount of the silane containing an unsaturated group is 0.5 to 10 wt%.

[0097] In a more specific embodiment, the solid content of the silicone emulsion in step 1) is 10-65 wt%, preferably 20-50%, such as 20-25 wt%, 25-30 wt%, 30-35 wt%, 35-40 wt%, 40-42 wt%, 42-44 wt%, 44-46 wt%, 46-48 wt%, 48-50 wt%.

[0098] In a more specific embodiment, the temperature of the second stage polymerization in step 1) is 1-25°C. Furthermore, the temperature of the second stage polymerization is 1-15°C. For example, the temperature of the second stage polymerization can be 1-3°C, 3-5°C, 5-7°C, 7-9°C, 9-10°C, 12-14°C, or 14-15°C. Taking into account energy saving and the degree of molecular weight growth, in a specific embodiment, the temperature of the second stage polymerization is 5-10°C.

[0099] In a more specific embodiment, the time of the second stage polymerization in step 1) is 2 to 300 hours. Further, the time of the second stage polymerization is 2 to 300 hours. For example, the time of the second stage polymerization can be 2 to 12 hours, 12 to 24 hours, 24 to 48 hours, 48 ​​to 96 hours, 96 to 120 hours, 120 to 150 hours, 150 to 200 hours, 200 to 250 hours, or 250 to 300 hours. Taking into account the actual needs of production efficiency, energy conservation, and degree of polymerization, in a specific embodiment, the time of the second stage polymerization is 24 to 150 hours.

[0100] In a more specific embodiment, the shear treatment in step 1) is performed until the average particle size of the silicone emulsion is 15 to 500 nm, such as 15 to 100 nm, 100 to 150 nm, 150 to 200 nm, 200 to 250 nm, 250 to 300 nm, 300 to 350 nm, 350 to 400 nm, 400 to 450 nm, or 450 to 500 nm. Furthermore, the shear treatment equipment includes one or more of a high-pressure homogenizer, a colloid mill, a high-shear emulsifier, and an ultrasonic emulsifier. Most preferably, the average particle size is 200 to 300 nm.

[0101] The high molecular weight polysiloxane with nano-scale particle size in the present application has a smaller particle size than that of micron-scale particles, and has a higher degree of spatial dispersion after the polar polymer is evenly dispersed, thereby achieving better wear resistance.

[0102] In a more specific embodiment, the emulsifier in step 1) is an anionic emulsifier or a cationic emulsifier.

[0103] The emulsifier for anionic emulsion polymerization is a negatively charged hydrophilic group, such as sulfonic acid group - SO3 - , carboxylic acid group—COO - , sulfate group—OSO3 -. Furthermore, the emulsifier for the anionic emulsion polymerization is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfonate, dodecyl sulfonic acid, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid, dodecyl-p-toluenesulfonic acid, sodium dodecyl-p-toluenesulfonate or sodium stearate. Most preferably, the emulsifier for the anionic emulsion polymerization is selected from one or more of sodium dodecyl sulfate and dodecylbenzenesulfonic acid. The catalyst can be selected from sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. Dodecylbenzenesulfonic acid, which itself has an emulsifying function, is preferred.

[0104] Cationic emulsion polymerization emulsifiers are selected with positively charged hydrophilic groups, such as quaternary ammonium salts - NR4 + , amine salt—NH3 + . Further, the emulsifier for the cationic emulsion polymerization is selected from hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, and tri(dodecyl)methylammonium hydroxide. More preferably, the tri(dodecyl)methylammonium hydroxide is obtained by exchanging tri(dodecyl)methylammonium chloride with a quaternary amine type I ion exchange resin. Most preferably, the emulsifier for the cationic emulsion polymerization is tri(dodecyl)methylammonium hydroxide.

[0105] In step 1), the first stage is to obtain the particle size of polysiloxane nanoparticles by shearing and emulsification. The size can be adjusted by the amount of emulsifier, shear strength and frequency, such as the amount of emulsifier is large, the particle size is small; the pressure of the high-pressure homogenizer is high, the particle size is small.

[0106] In step 2), the pH of the neutralization system is in the range of 3 to 7, more preferably 4 to 7, such as 4 to 4.2, 4.2 to 4.4, 4.4 to 4.6, 4.6 to 4.8, 4.8 to 5.0, 5.0 to 5.2, 5.2 to 5.4, 5.4 to 5.6, 5.6 to 5.8, 5.8 to 6, 6 to 6.2, 6.2 to 6.4, 6.4 to 6.6, 6.6 to 6.8, and 6.8 to 7. The most preferred pH is 4 to 6. Furthermore, during neutralization, one or more of sodium carbonate, sodium bicarbonate, and acetic acid may be used depending on the pH.

[0107] Specifically, the preparation method comprises the following steps: grafting reaction of high molecular weight polysiloxane nanoparticles with reserved grafting points and polar side chains and monomers with good compatibility and / or reactivity with polar polymers.

[0108] In a specific embodiment, the grafting reaction is initiated by a method selected from the group consisting of high-energy ray source irradiation, persulfate initiator, oxidation-reduction initiation system, azo initiator, and thermal initiation.

[0109] Preferably, the high-energy ray source is selected from one of a cobalt source, X-rays, ultraviolet rays, and a high-energy electron accelerator, more preferably selected from a cobalt source; the irradiation dose range is 0.1 Mrad to 30 Mrad, more preferably 1 Mrad to 10 Mrad.

[0110] Preferably, the persulfate initiator is selected from a combination of one or more of potassium persulfate, sodium persulfate, and ammonium persulfate, and the added amount of the persulfate initiator is 0.001 wt% to 30 wt% of the weight of the group having good compatibility and / or reactivity with the polar polymer, and in a specific embodiment, it is 0.1 wt% to 10 wt%.

[0111] Preferably, the azo initiator is selected from azobisisobutylnitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline, and a combination of one or more thereof. The water-soluble azo initiator is 0.001 wt% to 30 wt% of the weight of the group having good compatibility and / or reactivity with the polar polymer. More preferably, the amount of the azo initiator added is 0.1 wt% to 10 wt%.

[0112] Preferably, the water-soluble redox initiator is selected from one or more combinations of ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-ferrous sulfate, hydrogen peroxide-ferrous sulfate, ammonium persulfate-ferrous chloride, hydrogen peroxide-ferrous chloride, potassium persulfate-silver nitrate, persulfate-thiol, tert-butyl hydroperoxide-rongalite, isopropylbenzene hydroperoxide-rongalite, and diisopropylbenzene hydroperoxide-rongalite; more preferably, it is selected from isopropylbenzene hydroperoxide-rongalite, ammonium persulfate-sodium bisulfite, tert-butyl hydroperoxide-rongalite, and isopropylbenzene hydroperoxide-Bruggolite FF6M; and the redox initiator is 0.001 wt% to 30 wt% of the weight of the group having good compatibility and / or reactivity with the polar polymer. For example, the amount of the initiator added to the oxidation-reduction initiation system can be 0.001-0.01 wt%, 0.01-0.1 wt%, 0.1-0.5 wt%, 0.5-2 wt%, 2-5 wt%, 5-15 wt%, 15-25 wt%, or 25-30 wt% of the total monomer amount. In a specific embodiment, the amount of the initiator added to the oxidation-reduction initiation system is 0.5 wt% to 5.0 wt% of the total monomer amount.

[0113] Preferably, the thermal initiation temperature is 30° C. to 100° C., preferably 50° C. to 95° C. For example, the thermal initiation temperature may be 50° C. to 55° C., 55° C. to 60° C., 60° C. to 65° C., 65° C. to 70° C., 70° C. to 75° C., 75° C. to 80° C., 80° C. to 85° C., 85° C. to 90° C., or 90° C. to 95° C. In a specific embodiment, the thermal initiation temperature is 60° C. to 90° C.

[0114] The technical solutions and technical effects of the present invention are further described and explained through the following specific embodiments and implementation effects.

[0115] In the following embodiments of the present application:

[0116] The average particle size was obtained using a BeNano 90 nanometer particle size analyzer from Dandong Better Instrument Co., Ltd.

[0117] The viscosity was measured at 25°C using a rotational viscometer.

[0118] In the embodiment of the present application, the wear and wear reduction are calculated by the following formula:

[0119] The wear calculation formula is: (initial weight of the disc - weight of the disc after wear) / initial weight of the disc;

[0120] The calculation formula for wear reduction is: (blank sample wear – non-blank sample wear) / blank sample wear;

[0121] Abrasion testing equipment: TABER 5135;

[0122] Abrasion test conditions: 750g weight, CALLBRADE H-18 grinding wheel, total 10 minutes

[0123] Measuring balance: METTLER TOLEDO MS304TS, accurate to 0.0001 g.

[0124] Example 1

[0125] In this embodiment, a specific wear-resistant additive for polar polymers and a preparation method thereof are provided. The preparation method comprises the following steps:

[0126] 1) Preparation of high molecular weight polysiloxane nanoparticles with reserved grafting points and polar side chains: 1310 g viscosity 35

[0127] A mixture of a bihydroxylated polysiloxane (1000 mPa.s at 25°C), 45 g of 3-(methacryloyloxy)propylmethyldiethoxysilane, and 45 g of 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane was added to a mixture of 24 g of sodium lauryl sulfate, 21 g of dodecylbenzenesulfonic acid, and 1800 g of deionized water. The mixture was stirred at high speed for 30 minutes and passed through a high-pressure homogenizer three times at 70 MPa to obtain a 243 nm organosilicone emulsion containing methacryloxy and epoxy groups. The organosilicone content was 45 wt% based on the total mass of the emulsion. The mixture was then placed in a low-temperature environment at 10°C for 100 hours to complete anionic emulsion polymerization. The polymerization reaction was terminated by neutralization with sodium carbonate to a pH of 6.3, yielding an emulsion of high-molecular-weight polysiloxane nanoparticles. The viscosity of the high-molecular-weight polysiloxane nanoparticles was measured to be 8.21 million mPa.s at 25°C.

[0128] 2) Grafting reaction of monomers having good compatibility and / or reactivity with polar polymers: 2500 g of the above-mentioned emulsion having a pH of 6.3 and a content of 45 wt% of high molecular weight polysiloxane nanoparticles was diluted with 1500 g of deionized water, and then 0.05 g of ferrous sulfate and 0.14 g of ethylenediaminetetraacetic acid were added. The mixture was stirred and heated to 75° C., and then a mixture of 140 g of ethylene glycol dimethacrylate, 40 g of glycidyl methacrylate, and 9.1 g of cumene hydroperoxide, and a mixture of 6.3 g of Rongalite and 480 g of deionized water were added dropwise. The additions were completed over 5 hours to complete the grafting. The amount of the monomers having good compatibility and / or reactivity with polar polymers was 30 wt% based on the mass of the high molecular weight polysiloxane nanoparticles.

[0129] 3) Solid-liquid separation: Calcium chloride was added to the above product to form flocculation, and water was removed by filter pressing. Deionized water was then added, and the dilution, flocculation, and filter pressing were repeated three times.

[0130] 4) Dilute to 40% solid content, and prepare into a wear-resistant additive for polar polymers through a spray dryer. The wear-resistant additive for polar polymers prepared in this example is wear-resistant agent #1.

[0131] Example 2

[0132] In this embodiment, a specific wear-resistant additive for polar polymers and a preparation method thereof are provided. The preparation method comprises the following steps:

[0133] 1) Preparation of high molecular weight polysiloxane nanoparticles with reserved grafting points and polar side chains: 1000 g viscosity 50

[0134] mPa.s (25°C), a mixture of a bihydroxylated polysiloxane, 398 g of octamethylcyclotetrasiloxane, 60 g of 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, and 42 g of vinylmethyldiethoxysilane was added to a mixture of 19 g of sodium lauryl sulfate, 20 g of dodecylbenzenesulfonic acid, and 1800 g of deionized water. The mixture was stirred at high speed for 30 minutes and passed through a high-pressure homogenizer at 70 MPa three times to obtain a silicone emulsion having a particle size of 235 nm and containing vinyl and epoxy groups. The silicone content was 45 wt% based on the total mass of the emulsion. The mixture was first kept warm and stirred at 70°C for 24 hours, and then placed in a low-temperature environment of 10-15°C for 150 hours to complete anionic emulsion polymerization.

[0135] The polymerization reaction was terminated by neutralizing the mixture to pH 6.6 with sodium bicarbonate to obtain an emulsion of high molecular weight polysiloxane nanoparticles. The viscosity of the high molecular weight polysiloxane nanoparticles was tested to be 8.01 million mPa·s (25° C.).

[0136] 2) Grafting reaction of monomers having good compatibility and / or reactivity with polar polymers: 2650 g of the above-mentioned emulsion having a pH of 6.6 and containing 45 wt% of high molecular weight polysiloxane nanoparticles was diluted with 1350 g of deionized water, and then 0.062 g of ferrous sulfate and 0.15 g of ethylenediaminetetraacetic acid were added. The mixture was stirred and heated to 72° C., and a mixture of 280 g of glycerol dimethacrylate, 19 g of methacrylic acid, and 8.2 g of cumene hydroperoxide, preheated to 60° C., was then added dropwise. Simultaneously, a mixture of 6.8 g of Bruggolite FF6M (Brüggemann reducing agent) and 500 g of deionized water was added dropwise. The addition took 4.5 hours to complete the grafting. The amount of the monomers having good compatibility and / or reactivity with polar polymers was 25 wt% based on the weight of the high molecular weight polysiloxane nanoparticles.

[0137] 3) Solid-liquid separation: Calcium acetate was added to the above product to form flocculation, and water was removed by filter pressing. Deionized water was then added, and the dilution, flocculation, and filter pressing were repeated three times.

[0138] 4) Dilute to 40% solid content, and prepare into solid powder by spray drying to form a wear-resistant additive for polar polymers. The wear-resistant additive for polar polymers prepared in this example is wear-resistant agent #2.

[0139] Example 3

[0140] In this embodiment, a specific wear-resistant additive for polar polymers and a preparation method thereof are provided. The preparation method comprises the following steps:

[0141] 1) Preparation of high molecular weight polysiloxane nanoparticles with reserved grafting points and polar side chains: 1100 g 60 mPa.s

[0142] A mixture of a bihydroxy-terminated polysiloxane (25° C.), 319 g of octamethylcyclotetrasiloxane, 25 g of vinylmethyldiethoxysilane, and 45 g of N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane was added to a mixture of 80 g of an 80% by mass solution of tridodecylmethylammonium chloride in isopropanol and 2100 g of deionized water, stirred at high speed for 90 minutes, and passed through a high-pressure homogenizer at 70 MPa three times to obtain a 241 nm vinyl- and amino-containing organosilicon emulsion having a particle size of 241 nm and an organosilicon content of 41 wt % based on the total mass of the emulsion. The emulsion was treated with 150 g of a macroporous quaternary amine type I ion exchange resin IRA-900 (DuPont product) to convert the tridodecylmethylammonium chloride into tridodecylmethylammonium hydroxide. The mixture was reacted at 63° C. for 20 hours and then placed in a low-temperature environment at 3° C. for 136 hours to complete cationic emulsion polymerization. The polymerization reaction was terminated by neutralizing with acetic acid to pH 5.8 to obtain an emulsion of high molecular weight polysiloxane nanoparticles. The viscosity of the high molecular weight polysiloxane nanoparticles was tested to be 8.09 million mPa.s (25°C).

[0143] 2) Grafting reaction of monomers having good compatibility and / or reactivity with polar polymers: 2000 g of the above-mentioned emulsion having a pH of 5.8 and containing 41 wt% of high molecular weight polysiloxane nanoparticles was diluted with 700 g of deionized water, and then 0.05 g of ferrous sulfate and 0.16 g of ethylenediaminetetraacetic acid were added. The mixture was stirred and heated to 75° C., and a mixture of 200 g of triethylene glycol dimethacrylate, 22 g of 3-dimethylaminopropyl methacrylamide, and 7.5 g of tert-butyl hydroperoxide was added dropwise. Simultaneously, a mixture of 6.15 g of Rongalite and 230 g of deionized water was added dropwise. The additions were completed over 3.5 hours to complete the grafting. The amount of the monomers having good compatibility and / or reactivity with polar polymers was 27 wt% based on the mass of the high molecular weight polysiloxane nanoparticles.

[0144] 3) Solid-liquid separation: magnesium sulfate was added to the above product to form flocculation, and water was removed by filter pressing. Deionized water was then added, and the dilution, flocculation, and filter pressing were repeated three times.

[0145] 4) The obtained filter cake is prepared into a solid powder by flash drying to prepare a wear-resistant additive for polar polymers. The wear-resistant additive for polar polymers prepared in this example is wear-resistant agent #3.

[0146] Example 4

[0147] In this embodiment, a specific wear-resistant additive for polar polymers and a preparation method thereof are provided. The preparation method comprises the following steps:

[0148] 1) Preparation of high molecular weight polysiloxane nanoparticles with reserved grafting points and polar side chains: 1428 g viscosity 60

[0149] mPa.s (25 ° C) double-terminal hydroxyl polysiloxane, 36 g 3-(methacryloyloxy)propylmethyldiethoxysilane, 36 g 3-ureapropylmethyldiethoxysilane were added to a mixture of 75 g of 80% by mass tridodecylmethylammonium chloride isopropanol solution and 2150 g deionized water, stirred at high speed for 60 minutes, and passed through 70

[0150] MPa high-pressure homogenizer three times to obtain a 255nm organosilicon emulsion containing methacryloxy and ureapropyl groups, wherein the organosilicon content is 40wt% based on the total mass of the emulsion. The emulsion is treated with 160g of macroporous quaternary ammonium type I ion exchange resin IRA-900 (DuPont product) to convert tridodecylmethylammonium chloride into tridodecylmethylammonium hydroxide, and then placed in a low-temperature environment of 4°C for 120 hours to complete cationic emulsion polymerization. The polymerization reaction is terminated by neutralization with acetic acid to a pH of 6.8 to obtain an emulsion of high-molecular-weight polysiloxane nanoparticles. The viscosity of the high-molecular-weight polysiloxane nanoparticles is 8.12 million mPa·s.

[0151] (25℃).

[0152] 2) Grafting reaction of monomers having good compatibility and / or reactivity with polar polymers: 2300 g of the above-mentioned emulsion having a pH of 6.8 and containing 40 wt% of high molecular weight polysiloxane nanoparticles was diluted with 600 g of deionized water, and then 0.06 g of ferrous sulfate and 0.19 g of ethylenediaminetetraacetic acid were added. The mixture was stirred and heated to 80° C., and a mixture of 180 g of diurea alkyl dimethacrylate, 23 g of hydroxypropyl methacrylate, and 5.6 g of diisopropylbenzene hydroperoxide, preheated to 50° C., was dropwise added. Simultaneously, a mixture of 4.48 g of Rongalite and 250 g of deionized water was dropwise added. The addition was completed over 4.5 hours to complete the grafting. The amount of the monomers having good compatibility and / or reactivity with polar polymers was 22 wt% based on the mass of the high molecular weight polysiloxane nanoparticles.

[0153] 3) Solid-liquid separation: Aluminum sulfate was added to the above product to form flocculation, and water was removed by filter pressing. Deionized water was then added, and the dilution, flocculation, and filter pressing were repeated three times.

[0154] 4) Dilute to 40% solid content, and prepare into solid powder by spray drying to form a wear-resistant additive for polar polymers. The wear-resistant additive for polar polymers prepared in this example is wear-resistant agent #4.

[0155] Application Examples 1-4

[0156] The anti-wear agent #1, anti-wear agent #2, anti-wear agent #3 and anti-wear agent #4 prepared in Examples 1 to 4 were added to the polar polymer and mixed with an antioxidant respectively, melt-granulated by a twin-screw extruder, and then injection-molded wear-resistant samples for wear resistance testing. As Application Examples 1 to 4, the amounts of the anti-wear agents #1 to 4 and the antioxidants are shown in Table 1.

[0157] The twin-screw extruder has a length-to-diameter ratio of 48, a rotation speed of 600 rpm, and temperatures in each zone (from the feed port to the die) ℃: =81, 180, 190, 190, 195, 195, 195, 195, 190, 180.

[0158] The polar polymer is nylon 6, brand YH800 (produced by Yueyang Baling Petrochemical).

[0159] The antioxidants include: Irganox 1098: N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, BASF; and an auxiliary antioxidant, Irgafos 168: tris(2,4-di-tert-butyl)phenyl phosphite, BASF. The amounts of the primary antioxidant and the auxiliary antioxidant are shown in Table 1.

[0160] The temperatures of the injection molding sections of the wear-resistant test discs were as follows: 245, 245, 258, 245, 233°C = die opening.

[0161] The wear resistance test was carried out using a rotary abrader, the rotary abrader equipment brand: TABER5135, the test conditions: #18 grinding wheel, 750g weight, 10 minutes, each group of 12 discs were weighed before and after grinding, the wear was calculated, the maximum and minimum values ​​were removed, and the average value of the remaining 10 discs was taken.

[0162] Application Example 5

[0163] The difference between Application Example 5 and Application Examples 1 to 4 is that the wear-resistant agents are replaced with equal amounts of polytetrafluoroethylene powder (JTW-9957, Quzhou Wannengda, melting point: 327° C.).

[0164] Application Example 6

[0165] The difference between Application Example 6 and Application Examples 1 to 4 is that no anti-wear agent is added, and only the polar polymer is contained, and the amount of antioxidant is the same as that of Application Examples 1 to 4. The disc obtained in Application Example 6 is a nylon blank sample.

[0166] The test results of application examples 1 to 6 are shown in Table 1 below. The wear and wear reduction in Table 1 are calculated using the above formula.

[0167] Table 1

[0168] Weight ratio Application Example 1 Application Example 2 Application Example 3 Application Example 4 Application Example 5 Application Example 6 Nylon 6YH800 96.60 96.60 96.60 96.60 96.60 99.60 Anti-wear agent #1 3.00 0.00 0.00 0.00 0.00 0.00 Anti-wear agent #2 0.00 3.00 0.00 0.00 0.00 0.00 Anti-wear agent #3 0.00 0.00 3.00 0.00 0.00 0.00 Anti-wear agent #4 0.00 0.00 0.00 3.00 0.00 0.00 polytetrafluoroethylene 0.00 0.00 0.00 0.00 3.00 0.00 Antioxidant 1098 0.20 0.20 0.20 0.20 0.20 0.20 Antioxidant 168 0.20 0.20 0.20 0.20 0.20 0.20 total 100 100 100 100 100 100 Wear% 0.0251 0.0211 0.0198 0.0234 0.0241 0.0650 Reduced wear 61.38％ 67.54％ 69.54％ 64.00％ 62.92％

[0169] Test effect data description:

[0170] a) The wear of the polar polymers in Examples 1-4 using anti-wear agent #1-4 was significantly reduced. Compared with the nylon blank samples without anti-wear agent, under the same test conditions, the wear was reduced by 61.38% to 69.54%, reaching the wear resistance level of PTFE with the same proportion of added PTFE, while ensuring that the formula does not contain fluorine.

[0171] b) The samples of application examples 1-4 are all light white. Figure 1 It can be seen that the wear-resistant agent prepared by the present invention is suitable for light-colored applications.

[0172] Application Examples 7-10

[0173] The difference between Examples 7-10 and Application Examples 1-4 is that the polar polymer is a common wear-resistant PVC. Based on the total mass of the wear-resistant PVC, the composition comprises 46 wt% PVC paste resin (Xinjiang Tianye TPM-31), 20 wt% PVC blending resin (Shanghai Chlor-Alkali Chemical SB100), 26 wt% dioctyl phthalate, 4 wt% epoxidized soybean oil, 2.0 wt% calcium zinc stabilizer, and 2.0 wt% calcium carbonate. The calcium zinc stabilizer is a white powder with a melting range of 75-95°C. The amounts of wear-resistant agents #1-4 are shown in Table 2.

[0174] Application Example 11

[0175] The difference between Application Example 11 and Application Examples 7 to 10 is that the wear-resistant agent is replaced with an equal amount of polytetrafluoroethylene powder.

[0176] Application Example 12

[0177] The difference between Application Example 12 and Application Examples 7 to 10 is that no anti-wear agent is added, and only polar polymer is contained. The disc obtained in Application Example 12 is a PVC blank sample.

[0178] The test results of application examples 7 to 11 are shown in Table 2 below. The wear and wear reduction in Table 2 are calculated using the above formula.

[0179] It should be noted that the above application examples are only used as examples to prove that the wear-resistant additives described in this application have good compatibility with polar polymers (including nylon and PVC) and significantly improve their wear resistance. The scope of protection of the present invention is not limited to the specific embodiments described below.

[0180] In practical applications, based on the prior art and the disclosure of this invention by those skilled in the art, materials similar to or equivalent to those described in the embodiments of the present invention may also be used to implement the present invention. For example, in the embodiments of this application, the components and amounts of nylon and PVC can be adjusted based on actual application requirements. For example, the components and amounts of PVC paste resin, PVC blended resin, and calcium-zinc stabilizer can be adjusted based on actual injection molding and application requirements.

[0181] Table 2

[0182] Weight ratio Application Example 7 Application Example 8 Application Example 9 Application Example 10 Application Example 11 Application Example 12 Wear-resistant PVC 98.50 98.50 98.50 98.50 98.50 100.00 Anti-wear agent #1 1.50 0.00 0.00 0.00 0.00 0.00 Anti-wear agent #2 0.00 1.50 0.00 0.00 0.00 0.00 Anti-wear agent #3 0.00 0.00 1.50 0.00 0.00 0.00 Anti-wear agent #4 0.00 0.00 0.00 1.50 0.00 0.00 polytetrafluoroethylene 0.00 0.00 0.00 0.00 1.50 0.00 total 100 100 100 100 100 100 Wear% 5.1200 6.1900 4.8800 5.9800 9.4300 130.0000 Reduced wear 96.06％ 95.24％ 96.25％ 95.40％ 92.75％

[0183] Test effect data description:

[0184] c) The wear of the polar polymers in Application Examples 7-10 using anti-wear agents #1-4 was significantly reduced. Compared with the PVC blank samples without anti-wear agents, under the same test conditions, the wear was reduced by 95.24% to 96.25%, slightly higher than the 92.75% of PTFE, and the formulation was fluorine-free.

[0185] d) The samples of application examples 7 to 10 are all light white. Figure 2 It can be seen that the wear-resistant agent prepared by the present invention is suitable for light-colored applications.

[0186] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A wear-resistant additive for polar polymers, characterized in that The wear-resistant additive for polar polymers is a grafted modified product of high molecular weight polysiloxane, wherein the high molecular weight polysiloxane is a high molecular weight polysiloxane nanoparticle with reserved grafting points and polar groups as side chains, and the monomer used for the grafting modification is a monomer with good compatibility and / or reactivity with the polar polymer.

2. The wear-resistant additive for polar polymers according to claim 1, characterized in that The raw material components of the wear-resistant additive for polar polymers include: high molecular weight polysiloxane nanoparticles and monomers with good compatibility and / or reactivity with polar polymers; and / or, the high molecular weight polysiloxane nanoparticles have an average particle size of 15 to 500 nm and a viscosity of greater than 2.5 million mPa.s at 25° C.; and / or, the monomers having good compatibility and / or reactivity with the polar polymer are unsaturated carboxylic acids, acrylates and acrylamides; and / or, the high molecular weight polysiloxane nanoparticles are obtained by emulsion polymerization of low molecular weight polysiloxane, silane containing an unsaturated group, and silane containing a polar group; and / or, based on the mass of the high molecular weight polysiloxane nanoparticles, the amount of the monomer having good compatibility and / or reactivity with the polar polymer is 0.1 to 90 wt %; And / or, the high molecular weight polysiloxane nanoparticles are prepared by polymerization of low molecular weight polysiloxane, silane containing an unsaturated group and silane containing a polar group.

3. The wear-resistant additive for polar polymers according to claim 2, characterized in that The unsaturated group in the silane containing an unsaturated group is selected from one or more of vinyl and acryloyloxy groups; and / or, based on the mass of the low molecular weight polysiloxane, the amount of the silane containing an unsaturated group is 0.01 wt% to 30 wt%; And / or, the silane containing a polar group is selected from one or more of aminosilane, epoxysilane and acyloxysilane; and / or, based on the mass of the low molecular weight polysiloxane, the amount of the polar group-containing silane is 0.1 wt% to 30.0 wt%; And / or, the low molecular weight polysiloxane is selected from one or more of dihydroxy-terminated polysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; and / or the monomer having good compatibility and / or reactivity with the polar polymer is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl methacrylamide, 3-dimethylaminopropyl acrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, ethylene urea ethoxy acrylate, ethylene urea ethoxy methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate, methyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, ethoxyphenol acrylate, ethoxyphenol methacrylate, tetrahydrofuran acrylate, tetrahydrofuran acrylate, One or more of methyl acrylate, trimethylolpropane formal acrylate, trimethylolpropane formal methacrylate, hydroxy-terminated dicaprolactone acrylate, hydroxy-terminated dicaprolactone methacrylate, methoxy polyethylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, ethylene urea ethoxy acrylate, ethylene urea ethoxy methacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, glyceryl diacrylate, glyceryl dimethacrylate, diureaalkyl diacrylate, and diureaalkyl dimethacrylate; and / or, based on the mass of the high molecular weight polysiloxane nanoparticles, the amount of the monomer having good compatibility and / or reactivity with the polar polymer is 3.0 to 35.0 wt %; And / or, the polymerization reaction includes a first stage and a second stage polymerization; the first stage is to control the particle size by emulsification and shearing, and the second stage polymerization is chain growth at low temperature; And / or, the polymerization reaction is one selected from anionic emulsion polymerization and cationic emulsion polymerization.

4. The wear-resistant additive for polar polymers according to claim 3, characterized in that The unsaturated group is selected from one or more of vinyl and methacryloyloxy groups; and / or, the silane containing an unsaturated group is selected from vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-(2-methoxyethoxy)-silane, vinyltriisopropoxysilane, vinylmethylbis(trimethylsiloxy)silane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(methacryloyloxy)propylmethyldiethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propyl one or more of 3-(acryloyloxy)propyltriisopropoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, 3-(acryloyloxy)propyltriethoxysilane, 3-(acryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxy)propylmethyldiethoxysilane, 3-(acryloyloxy)propylmethyldiisopropoxysilane, (4-vinylphenyl)trimethoxysilane, (4-vinylphenyl)triethoxysilane, (4-vinylphenyl)methyldimethoxysilane, (4-vinylphenyl)methyldiethoxysilane, styreneethyltrimethoxysilane, and styreneethyltriethoxysilane; And / or, the silane containing a polar group is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-n-butyl-3-aminopropylmethyldimethoxysilane, N-n-butyl-3-aminopropylmethyldiethoxysilane, 3-anilinopropyltrimethoxysilane, 3-anilinopropyltriethoxysilane, 3-anilinopropylmethyldimethoxysilane, 3-anilinopropylmethyldiethoxysilane N,N-diethyl-3-aminopropyltrimethoxysilane, N, N-Diethyl-3-aminopropyltriethoxysilane, N,N-diethyl-3-aminopropylmethyldimethoxysilane, N,N-diethyl-3-aminopropylmethyldiethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltriethoxysilane, N,N-dimethyl-3-aminopropylmethyldimethoxysilane, N,N-dimethyl-3-aminopropylmethyldiethoxysilane, 3-(N-cyclohexylamino)propyltrimethoxysilane, 3-(N-cyclohexylamino)propyltriethoxysilane, 3-(N-cyclohexylamino)propylmethyldimethoxysilane, 3-(N-cyclohexylamino)propylmethyldiethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-ureapropylmethyldimethoxysilane, 3-ureapropylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, diethylenetriaminopropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane one or more of alkyl, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propyltriethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-acetoxypropyltriethoxysilane, 3-acetoxypropylmethyldimethoxysilane, and 3-acetoxypropylmethyldiethoxysilane; and / or, the temperature of the shearing and emulsification in the first stage is 1 to 100° C.; and / or, the temperature of the second stage polymerization is 1 to 25°C; And / or, the second stage polymerization time is 2 to 300 hours.

5. A method for preparing the wear-resistant additive for polar polymers according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: carrying out grafting reaction between high molecular weight polysiloxane nanoparticles with reserved grafting points and polar group side chains and monomers with good compatibility and / or reactivity with polar polymers.

6. The preparation method according to claim 5, characterized in that And / or, the grafting reaction is a free radical reaction, and its initiation mode is selected from one or more of high-energy ray source irradiation, persulfate initiator, oxidation-reduction initiation system, azo initiator, and thermal initiation.

7. The preparation method according to claim 6, characterized in that The high-energy ray source is selected from one or more of a cobalt source, X-rays, ultraviolet rays, and a high-energy electron accelerator; And / or, the irradiation dose of the high-energy ray source is selected in the range of 0.1 to 30 Mrad; And / or, the persulfate initiator is selected from one or more of potassium persulfate, sodium persulfate, and ammonium persulfate; and / or, based on the mass of the monomer having good compatibility and / or reactivity with the polar polymer, the amount of the persulfate initiator added is 0.001 to 30 wt %; And / or, the azo initiator is selected from one or more of azobisisobutylnitrile, azobisisoheptonitrile, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, and azobisisopropylimidazoline; and / or, based on the mass of the monomer having good compatibility and / or reactivity with the polar polymer, the amount of the water-soluble azo initiator added is 0.001 to 30 wt%; and / or, the initiator of the redox initiation system is selected from one or more of ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, ammonium persulfate-ferrous sulfate, hydrogen peroxide-ferrous sulfate, ammonium persulfate-ferrous chloride, hydrogen peroxide-ferrous chloride, potassium persulfate-silver nitrate, persulfate-thiol, tert-butyl hydroperoxide-rongalite, cumene hydroperoxide-rongalite, diisopropylbenzene hydroperoxide-rongalite, and cumene hydroperoxide-Bruggolite FF6M; and / or, based on the mass of the monomer having good compatibility and / or reactivity with the polar polymer, the amount of the initiator added to the redox initiation system is 0.001 to 30 wt %; and / or, the temperature of the thermal initiation is 30° C. to 100° C.; and / or, the amount of the initiator is 0.001 to 30 wt% of the mass of the monomer having good compatibility and / or reactivity with the polar polymer; And / or, before the grafting reaction, the method further comprises the steps of dispersing high molecular weight polysiloxane nanoparticles in a medium and deoxygenating the medium; And / or, when the monomer having good compatibility and / or reactivity with the polar polymer includes a polymerization inhibitor, before the grafting reaction, The step of removing the polymerization inhibitor in the monomer having good compatibility and / or reactivity with the polar polymer is also included; And / or, the grafting reaction further comprises the step of adding a chain transfer agent; And / or, the grafting reaction further includes the steps of solid-liquid separation and drying; And / or, after the grafting reaction, a flocculation step is further included before solid-liquid separation.

8. The preparation method according to claim 7, characterized in that The drying method is selected from one or more of freeze drying, spray drying, flash drying, fluidized bed drying, microwave drying, and vacuum drying; and / or, the chain transfer agent is selected from one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolate, thioglycerol, thiophenol, thiosalicylic acid, etc.; And / or, the flocculant used in the flocculation is one or more selected from calcium chloride, calcium acetate, magnesium sulfate, and aluminum sulfate.

9. Use of the anti-wear additive for polar polymers according to any one of claims 1 to 4 in improving the wear resistance of polar polymers.

10. A wear-resistant polar polymer composition, characterized in that The raw materials of the wear-resistant polar polymer composition include the wear-resistant additive for polar polymers according to any one of claims 1 to 4 and a polar polymer; preferably, the content of the wear-resistant additive for polar polymers is 0.1 wt% to 30.0 wt% based on the total mass of the wear-resistant additive for polar polymers and the polar polymer; Preferably, the raw material further comprises an antioxidant; preferably, the antioxidant comprises a primary antioxidant and an auxiliary antioxidant, the primary antioxidant is selected from antioxidant 1098, and the auxiliary antioxidant is selected from antioxidant 168; Preferably, the antioxidant is added in an amount of 0.1 to 0.8 wt % based on the mass of the polar polymer.

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