CN114163812B - A low-temperature and high-wear-resistant nylon material and its preparation method and application - Google Patents
A low-temperature and high-wear-resistant nylon material and its preparation method and application Download PDFInfo
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Abstract
本发明提供一种耐低温高耐磨尼龙材料及其制备方法和应用，所述耐低温高耐磨尼龙材料的制备原料按照重量百分比计，包括如下组分：聚酰胺60‑87％；耐磨母粒12‑38％；润滑剂0.2‑0.8％；抗氧剂0.8‑1.2％。本发明的尼龙材料具有优异的耐低温、高耐磨以及自润滑作用，并且可以保持本色，适用于耐磨滑块、耐磨管道或线缆等。The invention provides a low-temperature-resistant and high-wear-resistant nylon material and its preparation method and application. The raw materials for preparing the low-temperature and high-wear-resistant nylon material include the following components in weight percentage: polyamide 60-87%; wear-resistant Masterbatch 12-38%; lubricant 0.2-0.8%; antioxidant 0.8-1.2%. The nylon material of the present invention has excellent low temperature resistance, high wear resistance and self-lubricating effect, and can maintain its original color, and is suitable for wear-resistant sliders, wear-resistant pipes or cables, etc.
Description
Technical Field
The invention belongs to the technical field of synthesis and processing of high polymer materials, and relates to a low-temperature-resistant high-wear-resistant nylon material, a preparation method and application thereof.
Background
Nylon materials are widely paid attention to as engineering plastics with high mechanical strength, excellent self-lubricating property and oil resistance, and have more application in the aspects of pipeline cables and bearings due to the remarkable performance, and the application in the field is gradually expanded along with the gradual expansion of the wind power industry.
The self-lubricity of the nylon material itself and its low coefficient of friction allow the wear resistance of the material to be adapted to most conduit cable requirements. Among many nylons, short-chain nylons such as PA6 or PA66 nylon have excellent mechanical properties, heat and cold resistance, abrasion resistance and weather resistance, and are widely used for mechanical parts, but nylon is not suitable for manufacturing parts requiring high dimensional accuracy due to its large hygroscopicity and poor dimensional stability. Long carbon chain nylons such as PA11 and PA12 have natural advantages in terms of water absorption and density, and are widely focused on maintaining good dimensional stability and good solvent resistance.
The existing wear-resistant materials are usually polytetrafluoroethylene micropowder, molybdenum disulfide, aramid powder, silicone master batch, graphite, ultra-high molecular weight polyethylene, wollastonite and the like, but many materials belong to inorganic filler or nonpolar materials, and have certain problems in compatibility with nylon, so that the defects in a system are more, the defects of the materials are easily amplified under the action of external force, and the mechanical properties of the materials are easily deteriorated, on the other hand, the system compatibility is poorer, and phenomena such as shark skin, dark lines and the like are easily generated in the processing process, so that the appearance of the materials is deteriorated, and the improvement of the system compatibility is favorable for improving the performance of the nylon materials.
CN112143242a discloses a high-strength wear-resistant nylon composite material, which is prepared from PA66, glass fiber, wear-resistant agent (polytetrafluoroethylene, molybdenum disulfide, etc.), etc., the nylon composite material prepared by the invention has low temperature and wear-resistant properties, but the surface of the prepared material is rough due to the introduction of the glass fiber, thus restricting the application of the material, and meanwhile, the compatibility of the system is reduced due to the added wear-resistant agent fluororesin. CN104788950a discloses a wear-resistant self-lubricating nylon composite material, which uses nylon, carbon fiber, a water repellent, molybdenum disulfide and a compatilizer, wherein the introduction of the carbon fiber and the molybdenum disulfide causes that the material cannot prepare natural color after extrusion, and limits the application of the material.
Therefore, development of a nylon material which is resistant to low temperature and abrasion, has good compatibility and can maintain natural color is desired in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-temperature-resistant high-wear-resistant nylon material, and a preparation method and application thereof. The nylon material has excellent low temperature resistance, high wear resistance and self-lubricating effect, can keep the natural color, and is suitable for various parts requiring special performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
in the invention, the wear-resistant master batch is added to improve the wear resistance of the nylon material; the polyamide belongs to polar materials, and the tail end of the polyamide is provided with amino and carboxyl, which can react with most groups, such as maleic anhydride, epoxy, carboxyl, hydroxyl, esters and the like, which are common in general.
In the invention, the polyamide can be used in an amount of 60%, 65%, 70%, 75%, 80%, 85% or 87% in the raw materials for preparing the low-temperature-resistant and high-wear-resistant nylon material.
In the invention, the wear-resistant master batch can be used in the amount of 12%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 35% or 38% in the raw materials for preparing the low-temperature-resistant high-wear-resistant nylon material.
In the invention, the lubricant can be used in an amount of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% in the preparation raw materials of the low-temperature-resistant and high-wear-resistant nylon material.
In the preparation raw materials of the low-temperature-resistant high-wear-resistant nylon material, the dosage of the antioxidant can be 0.8%, 0.9%, 1.0%, 1.1% or 1.2% and the like.
Preferably, the polyamide has an average number of carbon atoms Nc per nitrogen atom of between 6 and 18 (for example 6, 8, 10, 13, 15 or 18, etc.), preferably 9 to 16.
The polyamides used in the present invention may be prepared from diamines and dicarboxylic acids or from aminocarboxylic acids or the corresponding lactams. The resins prepared by lactams have at least 6 carbon atoms per nitrogen atom and in the case of the resins prepared by diamines and dicarboxylic acids the arithmetic average of each carbon atom in the mixed components of diamines and dicarboxylic acids must be at least 6. Polyamides for which the present rule applies are, for example: PA1012 is prepared from decanediamine (10 carbon atoms) and dodecanedioic acid (12 carbon atoms), and PA11 is prepared by polycondensation of aminoundecanoic acid (11 carbon atoms).
Preferably, the polyamide comprises any one or a combination of at least two of PA612, PA614, PA1012, PA11, PA12, PA1212, PA616 or PA 618.
Preferably, the lubricant comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide, or silicone.
Preferably, the antioxidant comprises any one or a combination of at least two of aromatic amines, sterically hindered phenols, phosphites, sulfur-containing synergists, hydroxylamine benzofuranone derivatives or potassium iodide-copper iodide inorganic stabilizers.
Preferably, the wear-resistant master batch is prepared by the following preparation method:
mixing polar functional group modified ultra-high molecular weight polyethylene, multi-active site polymer, modified fluororesin, lubricant and antioxidant, freezing and grinding to obtain the wear-resistant master batch.
Compared with the prior art that the wear-resistant material (polytetrafluoroethylene micropowder, molybdenum disulfide, aramid powder, silicone master batch, graphite and ultra-high molecular weight polyethylene) is directly mixed with polyamide, the wear-resistant master batch prepared by modifying the ultra-high molecular weight polyethylene and the fluororesin and then mixing the polar functional group modified ultra-high molecular weight polyethylene, the multi-active site polymer, the modified fluororesin and the auxiliary agent has better compatibility.
In the invention, the multi-active-site polymer and the modified fluororesin are mutually matched, so that the prepared wear-resistant master batch has better compatibility with polyamide; meanwhile, the ultra-high molecular weight polyethylene is provided with polar functional groups after surface treatment, and the reactivity is considered, so that the dispersion and the dispersion size of the wear-resistant master batch in a system can be better ensured, and the wear resistance of the material can be better exerted; in addition, the polar functional group modified ultra-high molecular weight polyethylene has better low-temperature toughness, and the low-temperature toughness of the nylon material can be realized without adding a toughening agent.
In addition, the wear-resistant master batch provided by the invention ensures that the color of the nylon material is not limited, and the color matching of different colors can be carried out according to practical application in the later period.
Preferably, the polar functional group modified ultra high molecular weight polyethylene is present in an amount of 80-95% (e.g., 80%, 83%, 85%, 88%, 90%, 93%, or 95%, etc.), the multi-active site polymer is present in an amount of 0.1-5% (e.g., 0.1%, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, or 5%, etc.), the modified fluororesin is present in an amount of 5-20% (e.g., 5%, 8%, 10%, 13%, 15%, 18%, or 20%, etc.), the lubricant is present in an amount of 0.6-2.5% (e.g., 0.6%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, or 2.5%, etc.), and the antioxidant is present in an amount of 0.2-0.6% (e.2%, 0.3%, 0.4%, 0.5%, or 0.6%, etc.), based on 100% by weight of the wear resistant master batch.
Preferably, the polar functional groups in the polar functional group-modified ultra-high molecular weight polyethylene include anhydride groups, epoxy groups, halogens, carboxyl groups, amino groups, hydroxyl groups, and derivatives of any one or a combination of at least two of the foregoing groups. These polar functional groups may react with the nylon material.
Preferably, the polar functional group modified ultra high molecular weight polyethylene has a molecular weight of 30 to 500 tens of thousands, for example 30, 50, 80, 100, 200, 300, 400 or 500 tens of thousands, preferably 50 to 200 tens of thousands.
Preferably, the polar functional group-modified ultra-high molecular weight polyethylene has a density of 0.90 to 1.70g/cm 3 For example 0.90g/cm 3 、1.00g/cm 3 、1.10g/cm 3 、1.20g/cm 3 、1.30g/cm 3 、1.40g/cm 3 、1.50g/cm 3 、1.60g/cm 3 Or 1.70g/cm 3 Etc., preferably 0.93-1.50g/cm 3 。
Preferably, the multi-active site polymer comprises any one or a combination of at least two of an ethylene-maleic anhydride copolymer, a branched polymer or a polyethyleneimine.
For example, the ethylene-maleic anhydride copolymer may have the formulaThe branched polymer may have the formula +.>Wherein the hydroxyl group may be replaced with a carboxyl group; the structural formula of the polyethyleneimine can be +.>
Preferably, the ethylene-maleic anhydride copolymer has a copolymerization molar ratio of 1:1 to 1:5 (e.g., 1:1, 1:2, 1:3, 1:4, or 1:5, etc.), wherein the mass ratio of ethylene is < 25%, and the mass ratio of maleic anhydride is > 75%.
Preferably, the molecular weight of the ethylene-maleic anhydride copolymer is 10000-400000, such as 10000, 50000, 100000, 200000, 300000 or 400000, and preferably 10000-150000, and the physical state thereof may be solid powder, granule.
Preferably, the branched polymer may be selected from polyesters of varying degrees of branching, wherein the reactive groups contained therein may be selected from carboxyl, hydroxyl, and epoxy groups and the like, having a melting point of 120-180 ℃, such as 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or the like.
Preferably, the modified fluororesin includes an alkane coupling agent modified fluororesin and/or a titanate coupling agent modified fluororesin.
Preferably, the fluororesin in the modified fluororesin comprises any one or a combination of at least two of FEP, PTFE, ETFE or PVDF.
Preferably, the molecular weight of the fluororesin in the modified fluororesin is 3000 to 15000, for example 3000, 5000, 8000, 10000, 13000 or 15000, etc., preferably 3500 to 12000.
Preferably, the particle size of the fluororesin in the modified fluororesin is 0.02 to 1.2 μm, for example 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1.0 μm or 1.2 μm, etc., preferably 0.05 to 0.8 μm.
The modified fluororesin of the present invention may be prepared by itself or may be purchased. For example, the modified fluororesin may be obtained by directly mixing the fluororesin with an alkane coupling agent modified fluororesin and/or a titanate coupling agent.
Preferably, the lubricant comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide or silicone master batch; a combination of zinc stearate, erucamide and silicone masterbatch is preferred.
Preferably, the zinc stearate is present in an amount of 0.2 to 0.4% (e.g., 0.2%, 0.3%, or 0.4%, etc.), the erucamide is present in an amount of 0.2 to 0.6% (e.g., 0.2%, 0.3%, 0.4%, 0.5%, or 0.6%, etc.), and the silicone masterbatch is present in an amount of 0.2 to 1.5% (e.g., 0.2%, 0.5%, 0.8%, 1%, 1.3%, or 1.5%, etc.), based on 100% by weight of the abrasion resistant masterbatch.
Preferably, the antioxidant comprises any one or a combination of at least two of an aromatic amine, a sterically hindered phenol, a phosphite, a sulphur-containing synergist or a hydroxylamine benzofuranone derivative.
Preferably, the mixing is performed by a torque rheometer.
Preferably, the temperature of the mixing is 250-270 ℃, e.g. 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃, etc., for a period of 5-15min, e.g. 5min, 10min or 15min, etc.
Preferably, the freezing is performed in a liquid nitrogen environment for a period of time ranging from 5 to 10 minutes, such as 5 minutes, 10 minutes, 15 minutes, etc.
Preferably, the wear resistant master batch has a length of 2-5 μm, e.g. 2 μm, 3 μm, 4 μm or 5 μm etc.
Preferably, the preparation raw materials of the low-temperature-resistant high-wear-resistant nylon material further comprise a plasticizer.
Preferably, the plasticizer is present in an amount of 0.1 to 10%, such as 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., based on 100% by weight of the low temperature resistant, high abrasion resistant nylon material.
Preferably, the plasticizer comprises an ester of p-hydroxybenzoic acid having 2 to 20 (e.g., 2, 3, 5, 8, 10, 13, 15, 18, or 20, etc.) carbon atoms and/or an amide of aryl sulfonic acid having 2 to 12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, etc.) carbon atoms; preferably any one or a combination of at least two of P-benzenesulfonamide, N-butylbenzenesulfonamide, methyl P-hydroxybenzoate, N-methylbenzenesulfonamide, ethyl hydroxybenzoate, octyl P-hydroxybenzoate, isocetyl P-hydroxybenzoate, N-octylamide toluene sulfonic acid, N-butylamide benzene sulfonic acid or 2-ethylhexyl benzenesulfonamide.
Preferably, the preparation raw materials of the low-temperature-resistant high-wear-resistant nylon material also comprise other auxiliary agents.
Preferably, the content of the other auxiliary agent is 0.1-5%, for example 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5% based on 100% by weight of the low temperature resistant and high abrasion resistant nylon material.
Preferably, the other auxiliary agent comprises any one or a combination of at least two of an ultraviolet stabilizer, a nucleating agent, a flame retardant, a pigment, a leveling agent, a heat conducting agent or a conductive performance additive.
In a second aspect, the invention provides a preparation method of the low-temperature-resistant high-wear-resistant nylon material in the first aspect, which comprises the following steps:
mixing the polyamide, the wear-resistant master batch, the lubricant, the antioxidant, the optional plasticizer and the optional other auxiliary agents according to the formula, extruding and granulating, cooling, granulating and drying to obtain the low-temperature-resistant high-wear-resistant nylon material.
Preferably, the extrusion granulation is performed by a twin screw extruder.
Preferably, the twin screw extruder has an extrusion temperature of 240℃to 260℃such as 240℃245℃250℃255℃260℃or the like and an extrusion speed of 25 to 35kg/h such as 25kg/h, 30kg/h or 35kg/h or the like.
Preferably, the melt temperature of the extrusion process is from 250℃to 270℃such as 250℃255℃260℃265℃270℃or the like, and the vacuum is from-0.05 MPa to-0.08 MPa such as-0.05 MPa, -0.06MPa, -0.07MPa or-0.08 MPa or the like.
In a third aspect, the invention provides an application of the low-temperature-resistant high-wear-resistant nylon material in a wear-resistant sliding block, a wear-resistant pipeline or a cable. The low temperature resistant and high wear resistant nylon material of the first aspect can be used for extrusion or injection molding.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) In the invention, the addition of the wear-resistant master batch improves the wear resistance (friction coefficient: 0.15-0.27) of the nylon material, and the wear-resistant master batch has better compatibility with polyamide;
(2) In the invention, the multi-active-site polymer and the modified fluororesin are mutually matched, so that the prepared wear-resistant master batch has better compatibility with polyamide; meanwhile, the ultra-high molecular weight polyethylene is provided with polar functional groups after surface treatment, and the reactivity is considered, so that the dispersion of the wear-resistant master batch in the system can be better ensured, and the wear resistance of the material can be better exerted; in addition, the polar functional group modified ultra-high molecular weight polyethylene has better low-temperature toughness, and the nylon material can be realized without adding a toughening agent (-30 ℃ simple beam notch impact strength: 7.2-25.4 KJ/m) 2 )。
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw material brands and supplier information used in the preparation examples and examples of the present invention are as follows:
the preparation method of the modified fluororesin used in the preparation example of the invention comprises the following steps: the fluorine resins (F201 and AT-3000) were mixed with a silane coupling agent (KH 550) in a mass ratio of 100:0.8, respectively, to obtain a modified fluorine resin A and a modified fluorine resin B.
Preparation example 1
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
88.4% of polar group modified ultra-high molecular weight polyethylene, 0.4% of ethylene-maleic anhydride copolymer, 10% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 0.4% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch A with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the ethylene-maleic anhydride copolymer is marked as E60P; the brand of the modified fluororesin is modified fluororesin A; the phosphite antioxidant is Irganox 168.
Preparation example 2
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
93.7% of polar group modified ultra-high molecular weight polyethylene, 0.3% of polyethylenimine, 5% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 0.2% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch B with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the brand of the polyethyleneimine is P1050; the brand of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irganox 168.
Preparation example 3
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
79% of polar group modified ultra-high molecular weight polyethylene, 0.4% of hyperbranched polyester, 18.6% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 1.2% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch C with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the brand of the hyperbranched polyester is Hyper C181; the brand of the modified fluororesin is modified fluororesin A; the phosphite antioxidant is Irganox 168.
Preparation example 4
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
93.7% of polar group modified ultra-high molecular weight polyethylene, 0.3% of hyperbranched polyester, 5% of modified fluororesin, 0.2% of zinc stearate, 0.2% of erucamide, 0.2% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ for 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch D with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the brand of the hyperbranched polyester is Hyper C181; the brand of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irganox 168.
Preparation example 5
In the preparation example, a wear-resistant master batch is provided, and the wear-resistant master batch is prepared by the following preparation method:
79.5% of polar group modified ultra-high molecular weight polyethylene, 1.5% of ethylene-maleic anhydride copolymer, 17.8% of modified fluororesin, 0.2% of zinc stearate, 0.4% of erucic acid amide, 0.2% of silicone master batch and 0.4% of phosphite antioxidant are mixed by a torque rheometer, the mixing temperature is 250 ℃ and the time is 5min, and after the mixing is completed, the mixture is frozen for 10min in a liquid nitrogen environment and ground, so that the wear-resistant master batch E with the length of 2-5 mu m is obtained.
Wherein the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the ethylene-maleic anhydride copolymer is identified by the trademark E400; the brand of the modified fluororesin is modified fluororesin B; the phosphite antioxidant is Irganox 168.
Preparation example 6
The present preparation example differs from preparation example 1 only in that the polar group-modified ultra-high molecular weight polyethylene was replaced with an unmodified ultra-high molecular weight polyethylene (brand G015T), and the other conditions were the same as those of preparation example 1, to obtain master batch F.
Preparation example 7
The preparation example differs from preparation example 1 only in that the ethylene-maleic anhydride copolymer was not included in the preparation raw material, and the other conditions were the same as those of preparation example 1, to obtain a master batch G.
Preparation example 8
The present preparation example differs from preparation example 1 only in that the modified fluororesin was replaced with an unmodified fluororesin (trade name: F201), and the other conditions were the same as those of preparation example 1, to obtain a master batch H.
Example 1
The embodiment provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
wherein the polyamide is PA12 resin; the wear-resistant master batch is wear-resistant master batch A; the lubricant is zinc stearate; antioxidants were 1098 (0.4%), 168 (0.2%) and DSTDP (0.2%).
The preparation method comprises the following steps:
mixing polyamide, wear-resistant master batch, lubricant and antioxidant in a formula amount for 5min by a high-speed mixer, granulating by a double-screw extruder, wherein the extrusion temperature is 250 ℃, the extrusion speed is 30kg/h, the melt temperature is 255 ℃, and the vacuum degree is-0.08 MPa, so as to obtain the low-temperature-resistant high-wear-resistant nylon material natural-color particles.
Example 2
The difference between this example and example 1 is only that the abrasion resistant master batch A was replaced with the abrasion resistant master batch B, the addition was adjusted to 35%, the polyamide ratio was adjusted to 64%, and the preparation method was the same.
Example 3
The embodiment provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
wherein the polyamide is PA612 resin; the wear-resistant master batch is a wear-resistant master batch C; the lubricant is zinc stearate; antioxidants were 1098 (0.4%), 168 (0.2%) and DSTDP (0.2%).
The preparation method comprises the following steps:
mixing polyamide, wear-resistant master batch, lubricant and antioxidant in the formula amount for 5min by a high-speed mixer, granulating by a double-screw extruder, wherein the extrusion temperature is 260 ℃, the extrusion speed is 30kg/h, the melt temperature is 265 ℃, and the vacuum degree is-0.08 MPa, so as to obtain the low-temperature-resistant high-wear-resistant nylon material natural-color particles.
Example 4
The difference between this example and example 1 is only that the abrasion resistant master batch A was replaced with the abrasion resistant master batch E, the addition was adjusted to 28%, the polyamide ratio was adjusted to 71%, and the preparation method was the same.
Example 5
The difference between this example and example 1 is only that the abrasion resistant master batch A was replaced with the abrasion resistant master batch D, the addition was adjusted to 19%, the polyamide ratio was adjusted to 80%, and the preparation method was the same.
Example 6
The difference between this example and example 3 is that the abrasion resistant master batch C was replaced with the abrasion resistant master batch B, the addition was adjusted to 16%, the polyamide ratio was adjusted to 83%, and the preparation method was the same.
Comparative example 1
This comparative example differs from example 1 only in that the wear-resistant master batch a was replaced with an equal amount of master batch F, with the other conditions being the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that the abrasion resistant master batch a was replaced with an equal amount of master batch G, with the other conditions being the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that the abrasion resistant master batch a was replaced with an equal amount of master batch H, with the other conditions being the same as in example 1.
Comparative example 4
This comparative example differs from example 1 only in that the weight percentage of the abrasion resistant masterbatch A is 8%, the weight percentage of the polyamide is 91.1% and the other conditions are the same as in example 1.
Comparative example 5
The embodiment provides a low-temperature-resistant high-wear-resistant nylon material, which is prepared from the following raw materials in percentage by weight:
wherein the polyamide is PA12 resin; the brand of the polar group modified ultra-high molecular weight polyethylene is LY1040; the ethylene-maleic anhydride copolymer is E60P, and the modified fluororesin is modified fluororesin A; the lubricant is zinc stearate (0.23%), erucamide (0.03%), silicone master batch (0.05%); antioxidants were 1098 (0.4%), 168 (0.25%) and DSTDP (0.2%).
The preparation method comprises the following steps:
mixing polyamide, polar functional group modified ultra-high molecular weight polyethylene, ethylene-maleic anhydride copolymer, modified fluororesin, lubricant and antioxidant in a formula amount for 5min by a high-speed mixer, granulating by a double-screw extruder, wherein the extrusion temperature is 250 ℃, the extrusion speed is 30kg/h, the melt temperature is 255 ℃, and the vacuum degree is-0.08 MPa, so as to obtain the low-temperature-resistant high-wear-resistant nylon material natural-color particles.
The nylon materials of examples 1-6 and comparative examples 1-5 were tested for performance as follows:
(1) Coefficient of friction: testing according to GB/T3960 standard;
(2) Notched impact strength of simply supported beams: testing according to ISO179 standard;
(3) Gloss level: the test was performed according to the method of ASTM D523.
The results of the performance test are shown in Table 1.
TABLE 1
As can be seen from Table 1, the low temperature resistant and high abrasion resistant nylon materials prepared in examples 1 to 6 of the present invention are excellent in low temperature impact properties, all being more than 6KJ/m 2 The modified fluororesin and the ultrahigh molecular weight polyethylene have better compatibility, are intuitively embodied on the glossiness and the low-temperature toughness of the material, and simultaneously, have certain improvement on the performances of the material in all aspects through premixing treatment.
The applicant states that the low temperature resistant and high abrasion resistant nylon material of the present invention and the preparation method and application thereof are described by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (38)
1. The low-temperature-resistant high-wear-resistant nylon material is characterized by comprising the following raw materials in percentage by weight:
60-87% of polyamide;
12-38% of wear-resistant master batch;
0.2-0.8% of lubricant;
0.8-1.2% of antioxidant;
the wear-resistant master batch is prepared by the following preparation method:
mixing polar functional group modified ultra-high molecular weight polyethylene, multi-active site polymer, modified fluororesin, lubricant and antioxidant, freezing and grinding to obtain the wear-resistant master batch;
the weight of the wear-resistant master batch is 100%, the content of the polar functional group modified ultra-high molecular weight polyethylene is 80-95%, the content of the multi-active site polymer is 0.1-5%, the content of the modified fluororesin is 5-20%, the content of the lubricant is 0.6-2.5%, and the content of the antioxidant is 0.2-0.6%;
the polar functional group in the polar functional group modified ultra-high molecular weight polyethylene comprises any one or a combination of at least two of an anhydride group, an epoxy group, a carboxyl group, an amino group and a hydroxyl group;
the multi-active site polymer comprises any one or a combination of at least two of ethylene-maleic anhydride copolymer, branched polymer or polyethyleneimine;
the branched polymer is selected from polyesters with different branching degrees, wherein active groups contained in the branched polymer are selected from carboxyl, hydroxyl or epoxy, and the melting point of the branched polymer is 120-180 ℃;
the modified fluororesin comprises silane coupling agent modified fluororesin and/or titanate coupling agent modified fluororesin.
2. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said polyamide has an average number of carbon atoms Nc per nitrogen atom comprised between 6 and 18.
3. The low temperature and high abrasion resistant nylon material according to claim 2, wherein said polyamide has an average number of carbon atoms Nc per nitrogen atom of between 9 and 16.
4. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said polyamide comprises any one or a combination of at least two of PA612, PA614, PA1012, PA11, PA12, PA1212, PA616 or PA 618.
5. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the lubricant in the raw materials for preparing the low temperature and high abrasion resistant nylon material comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide or silicone.
6. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the antioxidant in the raw material for preparing the low temperature and high abrasion resistant nylon material comprises any one or a combination of at least two of aromatic amine, sterically hindered phenol, phosphite, sulfur-containing synergist or potassium iodide-copper iodide inorganic stabilizer.
7. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the polar functional group modified ultra-high molecular weight polyethylene has a molecular weight of 30 to 500 tens of thousands.
8. The low temperature resistant and high abrasion resistant nylon material according to claim 7, wherein the polar functional group modified ultra-high molecular weight polyethylene has a molecular weight of 50 to 200 tens of thousands.
9. The nylon material of claim 1, wherein the polar functional group modified ultra-high molecular weight polyethylene has a density of 0.90-1.70g/cm 3 。
10. The nylon material of claim 9, wherein the polar functional group modified ultra-high molecular weight polyethylene has a density of 0.93-1.50g/cm 3 。
11. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the copolymerization mole ratio of the ethylene-maleic anhydride copolymer is 1:1-1:5, wherein the mass ratio of ethylene is < 25%, and the mass ratio of maleic anhydride is > 75%.
12. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said ethylene-maleic anhydride copolymer has a molecular weight of 10000 to 400000.
13. The low temperature and high abrasion resistant nylon material according to claim 12, wherein said ethylene-maleic anhydride copolymer has a molecular weight of 10000 to 150000.
14. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the fluororesin in the modified fluororesin comprises any one of FEP, PTFE, ETFE or PVDF or a combination of at least two thereof.
15. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the molecular weight of the fluororesin in the modified fluororesin is 3000 to 15000.
16. The low temperature and high abrasion resistant nylon material according to claim 15, wherein the molecular weight of the fluororesin in the modified fluororesin is 3500 to 12000.
17. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the particle size of the fluororesin in the modified fluororesin is 0.02 to 1.2 μm.
18. The low temperature resistant and high abrasion resistant nylon material according to claim 17, wherein the particle size of the fluororesin in the modified fluororesin is 0.05 to 0.8 μm.
19. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the lubricant in the abrasion resistant master batch preparation raw material comprises any one or a combination of at least two of zinc stearate, titanate, stearic acid, erucamide, oleamide or silicone master batch.
20. The low temperature and high abrasion resistant nylon material according to claim 19, wherein the lubricant in the abrasion resistant master batch preparation raw material comprises a combination of zinc stearate, erucamide and silicone master batch.
21. The nylon material of claim 20, wherein the zinc stearate is 0.2-0.4%, the erucamide is 0.2-0.6%, and the silicone masterbatch is 0.2-1.5% by weight of the wear-resistant masterbatch is 100%.
22. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the antioxidant in the abrasion resistant masterbatch preparation raw material comprises any one or a combination of at least two of aromatic amine, sterically hindered phenol, phosphite or sulfur-containing synergist.
23. The low temperature and high abrasion resistant nylon material according to claim 1, wherein said mixing is performed by a torque rheometer.
24. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the temperature of the mixing is 250-270 ℃ for 5-15min.
25. The low temperature and high abrasion resistant nylon material according to claim 1, wherein the freezing is performed in a liquid nitrogen environment for 5-10 min.
26. The low temperature resistant and high abrasion resistant nylon material according to claim 1, wherein the length of the abrasion resistant master batch is 2-5 μm.
27. The low temperature-resistant and high wear-resistant nylon material according to claim 1, wherein the low temperature-resistant and high wear-resistant nylon material further comprises a plasticizer.
28. The nylon material of claim 27, wherein the plasticizer is present in an amount of 0.1 to 10% based on 100% by weight of the nylon material.
29. The low temperature and high abrasion resistant nylon material according to claim 27, wherein said plasticizer comprises an ester of p-hydroxybenzoic acid having 2 to 20 carbon atoms and/or an amide of aryl sulfonic acid having 2 to 12 carbon atoms.
30. The low temperature and high abrasion resistant nylon material according to claim 29, wherein said plasticizer comprises any one or a combination of at least two of P-benzenesulfonamide, N-butylbenzenesulfonamide, methyl parahydroxybenzoate, N-methylbenzenesulfonamide, ethyl parahydroxybenzoate, octyl parahydroxybenzoate, isohexadecyl parahydroxybenzoate, N-octylamide toluene sulfonic acid, N-butylbenzenesulfonamide, or 2-ethylhexyl benzenesulfonamide.
31. The low-temperature-resistant and high-wear-resistant nylon material according to claim 1, wherein the preparation raw materials of the low-temperature-resistant and high-wear-resistant nylon material further comprise other auxiliary agents.
32. The nylon material of claim 31, wherein the other auxiliary agent is present in an amount of 0.1-5% based on 100% by weight of the nylon material.
33. The low temperature and high abrasion resistant nylon material according to claim 31, wherein said other auxiliary agents comprise any one or a combination of at least two of ultraviolet stabilizers, nucleating agents, flame retardants, pigments, leveling agents, heat conductive agents or conductive performance additives.
34. The method for preparing a low temperature resistant and high abrasion resistant nylon material according to any one of claims 1 to 33, wherein said method comprises the steps of:
and mixing the polyamide, the wear-resistant master batch, the lubricant, the antioxidant, the optional plasticizer and the optional other auxiliary agents according to the formula amount, extruding and granulating to obtain the low-temperature-resistant high-wear-resistant nylon material.
35. The method of claim 34, wherein the extrusion pelletization is performed by a twin screw extruder.
36. The process of claim 35, wherein the twin screw extruder has an extrusion temperature of 240 ℃ to 260 ℃ and an extrusion speed of 25 to 35 kg/h.
37. The method according to claim 34, wherein the melt temperature during extrusion is 250 ℃ to 270 ℃ and the vacuum degree is-0.05 MPa to-0.08 MPa.
38. Use of a low temperature resistant high wear resistant nylon material according to any one of claims 1-33 in a wear resistant slider, a wear resistant pipe or a cable.
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