CN111253733B - Modified nylon elastomer and preparation method and application thereof - Google Patents

Modified nylon elastomer and preparation method and application thereof Download PDF

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Publication number
CN111253733B
CN111253733B CN202010263818.8A CN202010263818A CN111253733B CN 111253733 B CN111253733 B CN 111253733B CN 202010263818 A CN202010263818 A CN 202010263818A CN 111253733 B CN111253733 B CN 111253733B
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nylon
elastomer
antioxidant
salt
nylon elastomer
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CN111253733A (en
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邓凯桓
陈如意
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Changsha Wuben New Material Technology Co ltd
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Changsha Wuben New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
    • B29B13/065—Conditioning or physical treatment of the material to be shaped by drying of powder or pellets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/77—Measuring, controlling or regulating of velocity or pressure of moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/78—Measuring, controlling or regulating of temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76498—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76531—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76551—Time
    • B29C2945/76561—Time duration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76595—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76655—Location of control
    • B29C2945/76658—Injection unit
    • B29C2945/76665—Injection unit screw
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76655—Location of control
    • B29C2945/76658—Injection unit
    • B29C2945/76688—Injection unit nozzle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76822—Phase or stage of control
    • B29C2945/76859—Injection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Abstract

A modified nylon elastomer, a preparation method and an application thereof are disclosed, wherein the modified nylon elastomer is mainly prepared from the following components: copolymerized nylon elastomer, white oil, a wear-resisting agent, a hardness regulator, a nylon chain extender, a main antioxidant, an auxiliary antioxidant, an anti-ultraviolet absorber and a lubricant. The preparation method comprises the steps of firstly, uniformly stirring the copolymerized nylon elastomer and the white oil, then adding the rest raw materials, mixing and stirring, adding the mixture into a double-screw blending extruder, blending and extruding, and granulating to obtain the nylon elastomer. The application is that the modified nylon elastomer is injection molded into an elastic pad to replace a TPU elastic pad, a rubber elastic pad or a cast nylon pad, and the modified nylon elastomer is applied to a low-speed heavy-load, low-speed low-load or high-speed heavy-load transmission coupler. The modified nylon elastomer has excellent wear resistance, thermal aging resistance and flexural fatigue resistance, is suitable for various speeds and loads, has long service life, and is safe and environment-friendly. The method is simple, low in cost, high in efficiency, pollution-free and suitable for industrial production.

Description

Modified nylon elastomer and preparation method and application thereof
Technical Field
The invention relates to a nylon elastomer, a preparation method and application thereof, in particular to a modified nylon elastomer, and a preparation method and application thereof.
Background
The main functions of the elastic cushion are damping and buffering, the performance of the elastic cushion is directly influenced by the material used for preparing the elastic cushion, and the key points of ensuring the use safety of machine parts and reducing abrasion are realized. Especially for the plum blossom shaft coupling, the influence of the elastic cushion material on the performance is particularly prominent.
The plum coupling, also called claw coupling, is composed of two metal claw discs and an elastic pad. The elastic pad is arranged between the two metal claws and plays roles in connecting the metal claws, compensating relative displacement of the two shafts, and absorbing shock and buffering. When the elastic pad is damaged or fails in the operation of equipment, the metal claw teeth of the two shaft sleeves can be combined together to intermittently transmit torque, so that the safety control failure of a transmission system is further caused, and the equipment failure occurs, therefore, the elastic pad is a key part of the plum coupling.
The reason for the damage or failure of the elastic pad is that the elastic pad cracks, wears, becomes hard to age and loses elasticity, and depends on the wear resistance, heat aging and flexing fatigue resistance of the elastic pad material. Currently, there are three main categories of resilient pads for couplings:
(1) polyurethane: the clutch is the one with the largest use amount and is mainly used for low-rotating-speed and heavy-load couplings. The prior elastic element is generally formed by casting polyurethane monomer. Polyurethanes have poor elasticity, abrasion resistance, but poor flex fatigue resistance. Because the cohesive energy of polyurethane is high, internal heat can be generated in the process of compression by external force, so that the internal temperature of the elastic cushion is raised, molecular chains are cracked under long-term high temperature, and finally the elasticity is lost, and the elastic cushion is hardened and cracked. Meanwhile, the manual casting process is unstable, so that the product quality is unstable, and the product is easy to crack. Therefore, the service life of the existing polyurethane elastomer element is generally 2 months, the service life is short, the replacement of the elastic pad is very troublesome, particularly, the replacement of the elastic pad of the construction crane coupler is more inconvenient, high-altitude operation is needed, and potential personal safety problems exist for equipment maintenance operators; meanwhile, polyurethane casting also causes great pollution to the surrounding environment.
(2) And (3) nylon pouring: the high-speed high-torque coupling is used.
(3) Rubber: the clutch is used for a low-speed low-torque coupling. The rubber elastic pad is also a traditional plum blossom coupling elastic pad and is characterized by good elasticity, but the rubber elastic pad is easy to age and harden, so the service life is at most 1 year. Meanwhile, the rubber elastic cushion is processed by vulcanization molding, the peripheral environment is also polluted to a certain extent in the vulcanization process, most of molding processes are manual operation, the production period is long, and the efficiency is low.
CN104559071A discloses a preparation method of an anti-fatigue thermoplastic elastomer and a plum coupling element thereof, wherein the anti-fatigue thermoplastic elastomer is prepared from the following raw materials in parts by weight: 100 parts of polyester elastomer, 10-30 parts of thermoplastic elastomer, 2-5 parts of wear-resisting agent, 0.3-0.5 part of hindered phenol antioxidant, 0.2-0.5 part of phosphite antioxidant and 0.5-1.0 part of lubricant. Although the bending fatigue resistance of the plum blossom coupling elastic element prepared from the fatigue-resistant thermoplastic elastomer is improved compared with that of the existing polyurethane elastomer element, the service life is only prolonged by 2-3 times, and the requirement of long service life of the coupling elastic element in large equipment cannot be met.
In conclusion, the existing materials for preparing the elastic pad have poor performances of abrasion resistance, thermal aging resistance, bending resistance and fatigue resistance, and cannot meet the requirement of long service life of the elastic body element of the coupling.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the modified nylon elastomer which has excellent wear resistance, thermal aging resistance and flexural fatigue resistance, is suitable for various speeds and loads, has long service life, and is safe and environment-friendly.
The invention further aims to solve the technical problems of overcoming the defects in the prior art and providing a preparation method and application of the modified nylon elastomer which is simple in process, low in cost, high in efficiency, pollution-free and suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a modified nylon elastomer is mainly prepared from the following components: copolymerized nylon elastomer, white oil, a wear-resisting agent, a hardness regulator, a nylon chain extender, a main antioxidant, an auxiliary antioxidant, an anti-ultraviolet absorber and a lubricant. The white oil is added to wet the copolymerized nylon resin to adhere the powder type additives to the surface of the resin, so that all the additives are uniformly dispersed in the resin. The wear-resisting agent can endow key nylon with excellent lubricity and wear resistance. The hardness regulator can assist the copolymerized nylon elastomer to more conveniently obtain the material with proper hardness required by the elastic cushion of the coupler applicable to different rotating speeds and loads, so that the flexural fatigue resistance is excellent. By adding the nylon chain extender, the molecular weight of the copolymerized nylon elastomer is increased in the blending process, and chain extension and tackifying are realized, so that the wear resistance of the material is improved. When the main antioxidant, the auxiliary antioxidant and the ultraviolet-resistant absorbent are compounded for use, the modified nylon elastomer can be endowed with long-term heat-resistant aging performance. The lubricant provides better self-lubricating property for the modified nylon elastomer, reduces the friction coefficient and endows the modified nylon elastomer with better wear resistance.
Preferably, the modified nylon elastomer comprises the following components in parts by weight: 100 parts of copolymerized nylon elastomer, 0.1-0.4 part of white oil, 3-10 parts of wear-resisting agent, 2-10 parts of hardness regulator, 0.2-1.0 part of nylon chain extender, 0.1-0.6 part of main antioxidant, 0.2-0.6 part of auxiliary antioxidant, 0.3-0.6 part of ultraviolet-resistant absorbent and 0.5-1.5 parts of lubricant. The wear-resistant agent, the nylon chain extender and the lubricant are matched with each other, so that the modified nylon elastomer has better comprehensive wear-resistant performance. The combination of the hardness regulator and the copolymerized nylon elastomer obtains the best hardness material, thereby obtaining excellent flexural fatigue resistance. The heat aging resistance of the modified nylon elastomer is greatly improved by the cooperation of the main antioxidant, the auxiliary antioxidant and the ultraviolet-resistant absorbent, but the heat aging resistance of the modified nylon elastomer is reduced by excessive addition.
More preferably, the modified nylon elastomer comprises the following components in parts by weight: 100 parts of copolymerized nylon elastomer, 0.2-0.3 part of white oil, 4-8 parts of wear-resisting agent, 3-6 parts of hardness regulator, 0.4-0.6 part of nylon chain extender, 0.1-0.6 part of main antioxidant, 0.2-0.6 part of auxiliary antioxidant, 0.3-0.6 part of ultraviolet-resistant absorbent and 0.8-1.2 parts of lubricant.
Preferably, the relative viscosity of the copolymerized nylon elastomer is 3.0-5.0 (more preferably 3.4-4.5), and the Shore hardness is 50-90 (more preferably 55-80).
Preferably, the copolymerized nylon elastomer is one or more of binary copolymerized nylon, ternary copolymerized nylon or quaternary copolymerized nylon. The nylon elastomer is a multi-component copolymerized nylon containing polyether amide and long carbon chain monomers in a molecular chain, and the copolymerized nylon has excellent elasticity, wear resistance and distortion fatigue resistance. In practical application, the hardness of the material can be adjusted by adding different types of copolymerized nylon elastomers, so that the transmission coupling is suitable for transmission couplings with different rotating speeds and different loads.
Preferably, the binary copolymerized nylon is a caprolactam/polyether amide copolymer, a nylon 66 salt/polyether amine copolymer and the like.
Preferably, the terpolymer nylon is one or more of caprolactam/nylon 66 salt/polyether amide copolymer, nylon 66 salt/nylon 1010 salt/11-amino acid copolymer, nylon 66 salt/nylon 1010 salt/12-amino acid copolymer, caprolactam/nylon 66 salt/11-amino acid copolymer, caprolactam/nylon 66 salt/12-amino acid copolymer, caprolactam/nylon 66 salt/nylon 1212 salt copolymer or caprolactam/nylon 66 salt/nylon 1313 salt copolymer.
Preferably, the quadripolymer nylon is caprolactam/nylon 66 salt/11-13 carbon amino acid/polyether amide and the like.
Preferably, the white oil is No. 5 white oil.
Preferably, the anti-wear agent is maleic anhydride grafted ultra-high molecular weight polyethylene and/or high molecular weight polysiloxane. Because the compatibility of the polyethylene resin and the nylon resin is poor, the mechanical property of the resin is reduced when the polyethylene resin and the nylon resin are blended. Therefore, the invention adopts the grafting reaction of the high molecular polyethylene with certain fluidity and the maleic anhydride to obtain the maleic anhydride/polyethylene copolymer which can react with the terminal amino group of the copolymerized nylon so as to increase the compatibility of the polyethylene and the key nylon. The macromolecular polysiloxane is a novel macromolecular material and has very excellent lubricating property and wear resistance.
Preferably, the molecular weight of the maleic anhydride grafted ultrahigh molecular weight polyethylene is 200-350 ten thousand. The maleic anhydride grafted ultrahigh molecular weight polyethylene has excellent wear resistance, the higher the molecular weight of the maleic anhydride grafted ultrahigh molecular weight polyethylene is, the better the wear resistance is, the defects that the traditional low molecular weight lubricant is added too much and the mechanical property of the material is reduced can be overcome, however, if the molecular weight is too high, the processing fluidity is poor, even the fluidity is not good, and the maleic anhydride grafted ultrahigh molecular weight polyethylene is difficult to be melted, blended and extruded with nylon resin.
Preferably, the molecular weight of the high molecular polysiloxane is 4000-10000.
Preferably, the hardness regulator is a sulfonic acid amide and/or nylon acid ester hardness regulator and the like. In practical application, different types of couplings have different hardness requirements on the elastic pad: the Shore hardness of the resin is required to be 45-55 for the elastic cushion of the low-speed and low-load coupler, 50-60 for the elastic cushion of the low-speed and high-load coupler, and 70-80 for the elastic cushion of the high-speed and heavy-load coupler. Although the hardness of the copolymerized nylon elastomer can be adjusted by adjusting the proportion of the elastic component in the macromolecular chain, it is not industrially possible to frequently change the species, and therefore, the hardness of the resin can be adjusted only by the addition of the hardness-adjusting aid.
Preferably, the sulfonic acid amide hardness regulator is one or more of p-toluenesulfonic acid amide, N-ethylsulfonic acid amide, N-butylsulfonic acid amide and the like.
Preferably, the nylon acid ester hardness regulator is diisobutyl nylon acid, dioctyl nylon acid or the like.
Preferably, the nylon chain extender is one or more of ethylene-maleic anhydride copolymer, dimethyl alkyl diamine or 4,4' -methylene bis (2, 6-diethylaniline). Because the molecular weight of the conventional commercial copolymer nylon elastomer is only about 3 ten thousand, the copolymer nylon elastomer needs to be subjected to chain extension and tackifying, so that the relative viscosity of the resin reaches more than 4.0, and the copolymer nylon elastomer has better wear resistance; the nylon chain extender contains amino or carboxyl in the molecule, and can react with the amino or carboxyl of the copolymer of the nylon elastomer during the melt extrusion blending process of the copolymer of the nylon elastomer, thereby increasing the molecular weight of the copolymer of the nylon elastomer, realizing the chain extension and the viscosity increasing, and further improving the wear resistance of the copolymer of the nylon elastomer. The ethylene-maleic anhydride copolymer is preferably Vatelus E60P. The 4,4' -methylene bis (2, 6-diethylaniline) is preferably Bluggeman M1251 or M1253.
Preferably, the primary antioxidant is a hindered phenol antioxidant. The hindered phenol antioxidant belongs to a long-acting antioxidant.
Preferably, the hindered phenol antioxidant is one or more of antioxidant A30, antioxidant HS02, antioxidant H3336 or antioxidant H10.
Preferably, the secondary antioxidant is a phosphate antioxidant. The phosphate antioxidant belongs to a heat stabilizer with excellent hydrolysis resistance.
Preferably, the phosphate antioxidant is one or more of antioxidant 168, antioxidant 626, antioxidant S9228 and the like.
Preferably, the ultraviolet-resistant absorbent is one or more of an ultraviolet absorbent UV320, an ultraviolet absorbent UV380, an ultraviolet absorbent UV670 and the like.
More preferably, the optimal ratio of the primary antioxidant to the secondary antioxidant to the anti-ultraviolet absorber is 1-2: 1: 1-2 (more preferably 1.5:1: 1.5).
Preferably, the lubricant is one or more of silicone, EBS, erucamide or oleamide. The selected lubricant type is internal and external lubricant.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of a modified nylon elastomer comprises the steps of uniformly stirring a copolymer nylon elastomer and white oil, adding a wear-resisting agent, a hardness regulator, a nylon chain extender, a main antioxidant, an auxiliary antioxidant, an ultraviolet-resistant absorbent and a lubricant, mixing and stirring, adding into a double-screw blending extruder, blending and extruding, and granulating to obtain the modified nylon elastomer. The copolymerized nylon elastomer is mixed with the white oil, so that the surface of the copolymerized nylon elastomer can be wetted, and the powder additive can be favorably and uniformly adhered to the surface of resin when the resin is mixed with the powder additive.
Preferably, the stirring speed of the copolymerized nylon elastomer and the white oil is 400-500 rpm, and the time is 1-3 min.
Preferably, the mixing and stirring time is 2-6 min.
Preferably, the temperature of the blending extrusion is 190-230 ℃, the rotating speed is 350-500 rpm, and the vacuum degree is-0.08-0.05 MPa. The melting point of the copolymerized nylon elastomer is 185-200 ℃, the blending extrusion temperature is higher than the melting point of the resin properly, the resin can be fully melted, the melt flow temperature of the maleic anhydride grafted ultra-high molecular weight polyethylene in the wear-resisting agent is about 200-230 ℃, and the melt temperature of the high molecular weight polysiloxane is 210-230 ℃; if the temperature for blending and extruding is too low, the maleic anhydride grafted ultrahigh molecular weight polyethylene and the high molecular weight polysiloxane are incompletely melted, the melt viscosity is high, and the maleic anhydride grafted ultrahigh molecular weight polyethylene and the high molecular weight polysiloxane are difficult to disperse in the copolymerized nylon resin, and if the temperature for blending and extruding is too high, the maleic anhydride grafted ultrahigh molecular weight polyethylene and the high molecular weight polysiloxane are partially degraded and the auxiliary agent is volatilized. Therefore, in order to ensure that all the components are fully melted and blended, the extrusion temperature is controlled to be 190-230 ℃ more suitably.
The technical scheme adopted for further solving the technical problems is as follows: the application of the modified nylon elastomer is characterized in that the modified nylon elastomer is injection-molded into an elastic pad to replace a TPU elastic pad, a rubber elastic pad or a cast nylon pad, and the modified nylon elastomer is applied to a low-speed heavy-load, low-speed low-load or high-speed heavy-load transmission coupler.
Preferably, before injection molding, the modified nylon elastomer is dried for 4-6 hours at 100-120 ℃.
Preferably, in the injection molding process, the heating temperature of the screw is 190-220 ℃, the temperature of the nozzle is 240-260 ℃, the injection speed is 35-65 mm/s (more preferably 45-55 mm/s), the injection pressure is 50-70 bar (more preferably 55-65 bar), and the molding time is 30-80 s. If the heating temperature of the injection molding screw is too low, the viscosity of the resin melt is too low, the fluidity is poor, and the resin cannot be rapidly filled into a mold, so that the product defects are caused; if the injection speed is too high, the temperature of the melt is sharply increased when the melt passes through the nozzle, so that the resin is degraded, and if the injection speed is too low, the resin melt cannot be rapidly filled into a mold; similarly, the injection pressure has a great influence on the melt mold filling speed, the melt mold filling speed is higher when the injection pressure is higher, but the product has more burrs when the injection pressure is too high.
The invention has the following beneficial effects:
(1) the modified nylon elastomer is wear-resistant, the abrasion is as low as 0.17mg, the thermal aging resistance and the flexural fatigue resistance are excellent, the flexural cracking grade is higher than that of a TPU elastic cushion, the Shore hardness can be changed in a large range according to actual requirements, the performance is far better than that of the TPU elastomer, and the modified nylon elastomer is suitable for various speeds and loads;
(2) the longest service life of the plum blossom coupling elastic cushion formed by injection molding of the modified nylon elastomer can reach 42 months, is 14 times of that of a TPU elastic cushion, has an average service life 12 times of that of the TPU elastic cushion, is long in service life, safe and environment-friendly, can replace the TPU elastic cushion, the rubber elastic cushion or a cast nylon cushion, is applied to a low-speed heavy-load, low-speed low-load or high-speed heavy-load transmission coupling, can effectively guarantee long-term normal operation of equipment, reduces equipment maintenance and operation cost, and ensures safe and stable production;
(3) the method has simple process and low cost, and is suitable for industrial production;
(4) compared with the existing TPU pouring process and rubber mould pressing process, the process for injection molding the elastic cushion is simpler, has high production efficiency and does not pollute the environment.
Detailed Description
The present invention will be further described with reference to the following examples.
Copolymerized nylon elastomer used in the examples of the present invention: caprolactam/polyether amide copolymer (short for A, relative viscosity of 3.45, Shore hardness of 65), caprolactam/nylon 66 salt/polyether amide copolymer (short for B, relative viscosity of 3.5, Shore hardness of 70), caprolactam/nylon 66 salt/11-amino acid copolymer (short for C, relative viscosity of 3.8, Shore hardness of 75), caprolactam/nylon 66 salt/11-13 carbon amino acid/polyether amide (short for D, relative viscosity of 3.6, Shore hardness of 70), all purchased from Beijing Heart science and technology Limited; no. 5 white oil used in the examples of the present invention is commercially available; the wear-resistant agents used in the examples of the present invention and the comparative examples: maleic anhydride grafted ultra high molecular weight polyethylene (E, MW 300 ten thousand) available from Takara USA, high molecular weight polysiloxane (F, MW 4500) available from Clariant Germany; the hardness regulator used in the embodiment of the invention is purchased from Suzhou Jinzhou chemical Co., Ltd; the nylon chain extender used in the embodiments of the present invention is available from Rohm and Haas; the antioxidant and the ultraviolet resistant absorbent used in the examples and the comparative examples of the present invention are both purchased from Rohm and Haas; the raw materials or chemical reagents used in the examples and comparative examples of the present invention were obtained by conventional commercial methods unless otherwise specified.
Examples 1 to 8 of modified Nylon elastomer
The raw material components and parts by weight of the modified nylon elastomers of examples 1 to 8 and comparative example 1 are shown in table 1.
TABLE 1 raw material components and parts by weight of modified nylon elastomers in examples 1 to 8 and comparative example 1
Figure DEST_PATH_IMAGE001
Note: in the table, "-" indicates no addition.
Preparation method of modified nylon elastomer, examples 1 to 8
According to the raw material components and parts by weight of the modified nylon elastomer shown in the table 1 in the embodiment 1-8, the copolymerized nylon elastomer and white oil are stirred at the rotating speed of 450rpm for 2min to be uniform, then the wear-resisting agent, the hardness regulator, the nylon chain extender, the main antioxidant, the auxiliary antioxidant, the ultraviolet-resistant absorbent and the lubricant are added, mixed and stirred for 4min, then the mixture is added into a double-screw blending extruder, and the mixture is subjected to blending extrusion and granulation at the rotating speed of 190-230 ℃, the rotating speed of 450rpm and the vacuum degree of-0.06 MPa to respectively obtain the modified nylon elastomers 1-8.
Application examples 1 to 8 of modified nylon elastomer
Respectively injection-molding the modified nylon elastomers 1-8 into plum blossom-shaped elastic pads 1-8 for the coupling, replacing TPU (thermoplastic polyurethane) elastic pads, rubber elastic pads or cast nylon pads, and applying the plum blossom-shaped elastic pads to low-speed heavy-load, low-speed low-load or high-speed heavy-load transmission couplings; before injection molding, drying the modified nylon elastomer 1-8 for 5 hours at 110 ℃; in the injection molding process, the heating temperature of the screw is 190-220 ℃, the temperature of the nozzle is 240-260 ℃, the injection speed is 50mm/s, the injection pressure is 60bar, and the molding time is 50 s.
Comparative example 1
According to the raw material components and the weight parts of the comparative example 1 in the table 1, adding a wear-resistant agent, a main antioxidant, an auxiliary antioxidant, an anti-ultraviolet absorber and a lubricant into TPU, mixing and stirring for 4min, adding into a double-screw blending extruder, blending and extruding at 190-230 ℃, the rotating speed of 450rpm and the vacuum degree of-0.06 MPa, and granulating to obtain the elastomer.
The elastomer obtained was injection-molded into a quincunx elastic pad for a coupling by the method of application example 1 to 8 of the modified nylon elastomer.
In order to examine the performance of the material, the modified nylon elastomers 1-8 and the elastomer obtained in the comparative example 1 are dried and sampled, and the abrasion (GB 3960-2016), the flexural cracking grade (GB/T13934-2006) and the Shore hardness (GB/T531-1999) are tested; then, the quincuncial elastic pads 1 to 8 for the coupling injection molded by the modified nylon elastomers 1 to 8 of the invention and the quincuncial elastic pads for the coupling injection molded by the elastomer obtained in the comparative example 1 were installed on a crane under construction, and the actual service life of the crane was examined by mounting, and the results are shown in table 2.
TABLE 2 comparison table of properties of elastomer obtained in examples 1 to 8 and comparative example 1 and a quincunx elastic pad for injection-molded coupling
Figure 851193DEST_PATH_IMAGE002
As can be seen from Table 2, the abrasion of the modified nylon elastomer 1-8 in the embodiment of the invention is as low as 0.17mg, the flexural cracking grade is higher than that of a TPU elastic cushion, the Shore hardness can be changed in a large range according to actual requirements, and the performance is far better than that of the TPU elastomer; the longest service life of the plum blossom coupling elastic pad injection-molded by the modified nylon elastomer in the embodiments 1-8 of the invention can reach 42 months, which is 14 times that of the TPU elastic pad, and the average service life is 12 times that of the TPU elastic pad.

Claims (6)

1. The modified nylon elastomer is characterized by being prepared from the following components in parts by weight: 100 parts of a copolymerized nylon elastomer, 0.1-0.4 part of white oil, 3-10 parts of a wear-resisting agent, 2-10 parts of a hardness regulator, 0.2-1.0 part of a nylon chain extender, 0.1-0.6 part of a main antioxidant, 0.2-0.6 part of an auxiliary antioxidant, 0.3-0.6 part of an ultraviolet-resistant absorbent and 0.5-1.5 parts of a lubricant;
the relative viscosity of the copolymerized nylon elastomer is 3.0-5.0, and the Shore hardness is 50-90; the copolymerized nylon elastomer is one or more of binary copolymerized nylon, ternary copolymerized nylon or quaternary copolymerized nylon; the binary copolymer nylon is a caprolactam/polyether amide copolymer and/or a nylon 66 salt/polyether amine copolymer; the terpolymer nylon is one or more of caprolactam/nylon 66 salt/polyether amide copolymer, nylon 66 salt/nylon 1010 salt/11-amino acid copolymer, nylon 66 salt/nylon 1010 salt/12-amino acid copolymer, caprolactam/nylon 66 salt/11-amino acid copolymer, caprolactam/nylon 66 salt/12-amino acid copolymer, caprolactam/nylon 66 salt/nylon 1212 salt copolymer or caprolactam/nylon 66 salt/nylon 1313 salt copolymer; the quadripolymer nylon is caprolactam/nylon 66 salt/11-13 carbon amino acid/polyether amide;
the wear-resisting agent is maleic anhydride grafted ultrahigh molecular weight polyethylene and/or high molecular weight polysiloxane; the molecular weight of the maleic anhydride grafted ultrahigh molecular polyethylene is 200-350 ten thousand; the molecular weight of the high-molecular polysiloxane is 4000-10000;
the hardness regulator is a sulfonic acid amide and/or nylon acid ester hardness regulator; the sulfonic acid amide hardness regulator is one or more of p-toluenesulfonic acid amide, N-ethylsulfonic acid amide or N-butylsulfonic acid amide; the nylon acid ester hardness regulator is diisobutyl nylon acid and/or dioctyl nylon acid;
the nylon chain extender is one or more of ethylene-maleic anhydride copolymer, dimethyl alkyl diamine or 4,4' -methylene bis (2, 6-diethylaniline).
2. The modified nylon elastomer of claim 1, wherein:
the main antioxidant is one or more of an antioxidant HS02, an antioxidant H3336 or an antioxidant H10;
the auxiliary antioxidant is one or more of antioxidant 168, antioxidant 626 or antioxidant S9228;
the ultraviolet-resistant absorbent is an ultraviolet absorbent UV320 and/or an ultraviolet absorbent UV 380;
the lubricant is one or more of silicone, EBS, erucamide or oleamide.
3. A method for preparing a modified nylon elastomer according to claim 1 or 2, characterized in that: the modified nylon elastomer is prepared by uniformly stirring the copolymerized nylon elastomer and white oil, adding the wear-resistant agent, the hardness regulator, the nylon chain extender, the main antioxidant, the auxiliary antioxidant, the anti-ultraviolet absorber and the lubricant, mixing and stirring, adding the mixture into a double-screw blending extruder, blending and extruding, and granulating.
4. The process for producing a modified nylon elastomer according to claim 3, characterized in that: the stirring speed of the copolymerized nylon elastomer and the white oil is 400-500 rpm, and the time is 1-3 min; the mixing and stirring time is 2-6 min; the temperature of the blending extrusion is 190-230 ℃, the rotating speed is 350-500 rpm, and the vacuum degree is-0.08-0.05 MPa.
5. Use of the modified nylon elastomer of claim 1 or 2, wherein: the modified nylon elastomer of claim 1 or 2 is injection molded into an elastic pad, and is applied to a low-speed heavy-load, low-speed low-load or high-speed heavy-load transmission coupling instead of a TPU elastic pad, a rubber elastic pad or a cast nylon pad.
6. Use of a modified nylon elastomer according to claim 5, characterized in that: before the injection molding, drying the modified nylon elastomer for 4-6 hours at 100-120 ℃; in the injection molding process, the heating temperature of the screw is 190-220 ℃, the temperature of the nozzle is 240-260 ℃, the injection speed is 35-65 mm/s, the injection pressure is 50-70 bar, and the molding time is 30-80 s.
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