CN105524362A - Preparation method for rubber-plastic composition - Google Patents
Preparation method for rubber-plastic composition Download PDFInfo
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- CN105524362A CN105524362A CN201410514226.3A CN201410514226A CN105524362A CN 105524362 A CN105524362 A CN 105524362A CN 201410514226 A CN201410514226 A CN 201410514226A CN 105524362 A CN105524362 A CN 105524362A
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Abstract
The invention discloses a preparation method for a rubber-plastic composition. The method comprises the following steps: (1) subjecting halogenated butyl rubber, low-molecular-weight nylon and an activator to internal mixing and granulating so as to obtain modified rubber; (2) subjecting the modified rubber obtained in the step (1), copolymerized nylon, long-carbon-chain nylon, low-density polyethylene, a vulcanizing agent and a vulcanization accelerator to blending, and carrying out heating, melting, extruding and granulating, wherein the weight-average molecular weight of the low-molecular-weight nylon is 5000 to 25000 Dalton; and the low-density polyethylene has a melt mass flow rate of 0.1 to 10 g/10min and a density of 0.915 to 0.925 g/cm3 which are determined according to GB/T3682-2000. The rubber-plastic composition prepared by using the method provided by the invention has good processibility and blow moldability, well improves the blow-up ratio of the rubber-plastic composition in the film blowing process; meanwhile, the thermoplastic thin film prepared from the rubber-plastic composition provided by the invention has excellent mechanical property and airtightness.
Description
Technical field
The present invention relates to a kind of preparation method of rubber-plastic composition.
Background technology
Thermoplastic elastomers has multiple possible structure, its product had both possessed the snappiness of traditional cross-linking vulcanized rubber, every excellent properties such as ageing-resistant, simultaneously possess again the feature that common plastics is easy to process, processing mode is many, generally can adopt injection moulding, extrude, the processing mode such as blowing produces.
CN101296997A discloses a kind of composition for thermoplastic elastomer, and said composition comprises: at least one halogenation containing isobutylene elastomer; At least one fusing point is the nylon resin of about 170-260 DEG C, and low-molecular weight polymer type nylon softening agent.This composition for thermoplastic elastomer has excellent resistance to air loss, weather resistance and snappiness.But the water absorbability that the film prepared by said composition is stronger because nylon has, cause film easily to occur bubble, and the inflation of nylon is smaller, also seriously limits the blow-up ratio of such composition.
EP0722850A1 discloses a kind of polymer composition for tire, said composition comprises: at least one thermoplastic resin and at least one elastomeric component, described thermoplastic resin is selected from polyamide resin, vibrin etc., and described elastomeric component is selected from divinyl and hydride, olefinic rubber, silicon rubber, halogen-containing rubber etc.EP0969039A1 discloses a kind of composition for thermoplastic elastomer, and said composition comprises containing fusing point the elastomeric component of the nylon resin being 170-230 DEG C, and the iso-butylene of halogenation-p-methylstyrene multipolymer.
EP0722850A1 and EP0969039A1 is all based on binary composition, also namely Iso-butylene-based elastomers and polyamide-based carry out blended, rubber carries out dynamic vulcanization in extruding simultaneously, obtain described composition, such composition is requiring that film thickness is larger, when inflation is smaller, air retaining wall prepared by relative Iso-butylene-based elastomers, has its advantage really.Adding of nylon, not only increase the resistance to air loss of air retaining wall, elastomerics can be made to realize blowfilm shaping simultaneously, the processing mode of conventional rubber before changing.But nylon have excellent bubble-tight while, its relatively limited blowing still makes said composition have some shortcomings part.
CN102066475A discloses a kind of method of Production development vulcanized alloy, described alloy contains at least one isobutylene elastomer and at least one thermoplastic resin, and the method comprises the following steps: described thermoplastic resin and at least one softening agent are mixed to be formed resin concentrates by (a) in the first melt-processed device; B described elastomerics, at least one vulcanizing agent and described resin concentrates are fed to the feed throat of the second melt-processed device by (); C described content in second melt-processed device mixes with formative dynamics vulcanized alloy by () under dynamic vulcanization conditions, its elastomer exists as the disperse phase of the sulfuration in the external phase of thermoplastic resin or partial vulcanization particle.Although the product adopting the method to obtain has good pressuretightness and low-temperature flexibility, the technical process of the method is long, and energy consumption is high.
Summary of the invention
The object of this invention is to provide and overcome the poor defect of rubber-plastic composition of the prior art inflation in blown film process mechanical property that is smaller, thermoplastic film and the preparation method that a kind of rubber-plastic composition is provided.
To achieve these goals, the invention provides a kind of preparation method of rubber-plastic composition, the method comprises:
(1) halogenated butyl rubber and lower molecular weight nylon and activator are carried out banburying and granulation, obtain modified rubber;
(2) modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator that step (1) obtains are carried out blended post-heating melting and extruding pelletization,
Wherein, the weight-average molecular weight of described lower molecular weight nylon is 5000-25000 dalton, described Low Density Polyethylene is 0.1-10g/10min according to the melt mass flow rate that GB/T3682-2000 measures, and the density of described Low Density Polyethylene is 0.915-0.925g/cm
3.
The preparation method of rubber-plastic composition provided by the invention by adding a small amount of Low Density Polyethylene in the dynamic vulcanization system of modified rubber, the modified rubber of dynamic vulcanization is dispersed in nylon mixture better, and make the rubber-plastic composition prepared by the method have good workability and blowing, improve the blow-up ratio of rubber-plastic composition in blown film process well, and make the thermoplastic film adopting rubber-plastic composition provided by the invention to obtain have excellent mechanical property and excellent resistance to air loss; This thermoplastic film is apparent more even simultaneously.In addition, the rubber phase particle diameter of this thermoplastic film is little and particle size distribution range is narrower, makes this thin flexible film better.
Further, the preparation process of rubber-plastic composition provided by the invention is simple, decreases out sweetening process and decreases the thermal ageing degree of rubber-plastic composition Raw.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of rubber-plastic composition, the method comprises:
(1) halogenated butyl rubber, lower molecular weight nylon and activator are carried out banburying and granulation, obtain modified rubber;
(2) modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator that step (1) obtains are carried out blended post-heating melting and extruding pelletization,
Wherein, the weight-average molecular weight of described lower molecular weight nylon is 5000-25000 dalton, described Low Density Polyethylene is 0.1-10g/10min according to the melt mass flow rate that GB/T3682-2000 measures, and the density of described Low Density Polyethylene is 0.915-0.925g/cm
3.
In the present invention, dynamic vulcanization refer to by the rubber that is cross-linked with can not the thermoplastic polymer (such as resin) of sulfuration under shear at high temperature effect, blended and heating and melting, under the effect of linking agent, rubber generation sulfuration.The rubber phase formed after sulfuration is thus dispersed in resin-phase with micron-sized uniform particles.
In the present invention, the performance of melt mass flow rate on rubber-plastic composition of the present invention of described Low Density Polyethylene has significant impact, particularly, when Low Density Polyethylene according to GB/T3682-2000 melt mass flow rate lower than 0.1g/10min or higher than 10g/10min time, the blowing of described rubber-plastic composition or processibility decline.
Under preferable case, described Low Density Polyethylene is 0.2-5g/10min, more preferably 0.3-2g/10min according to the melt mass flow rate that GB/T3682-2000 measures.
In the present invention, the performance of density on rubber-plastic composition of the present invention of described Low Density Polyethylene has significant impact, particularly, when the density of described Low Density Polyethylene is lower than 0.915g/cm
3or higher than 0.925g/cm
3time, the blowing of described rubber-plastic composition or processibility decline.
Under preferable case, the density of described Low Density Polyethylene is 0.920-0.923g/cm
3.
According to the present invention, above-mentioned density that what described Low Density Polyethylene can be well known to those skilled in the art meet and the various Low Density Polyethylenes that melt mass flow rate requires, usually, described Low Density Polyethylene is the low density polyethylene homopolymer of being produced by high pressure method in tubular reactor or tank reactor.Under preferable case, described Low Density Polyethylene is by low density polyethylene homopolymer that high pressure method is produced in tubular reactor.
In the present invention, the mensuration of density measures with reference to GB/T1033-2008 method.The mensuration of melt mass flow rate measures with reference to GB/T3682-2000 method, and condition determination comprises: measuring temperature is 190 DEG C, and load is 2.16kg.
According to the present invention, there is no particular limitation for the consumption of described lower molecular weight nylon, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent, vulcanization accelerator and activator, can change in wider scope, as long as make the rubber-plastic composition obtained have excellent workability and blowing.Usually, the described halogenated butyl rubber of relative 100 weight parts, the consumption of described lower molecular weight nylon is 1-20 weight part, the consumption of described copolymer nylon is 10-80 weight part, the consumption of described long carbon chain nylon is 1-30 weight part, and the consumption of described Low Density Polyethylene is 1-30 weight part, and the consumption of described vulcanizing agent is 0.15-10 weight part, the consumption of described vulcanization accelerator is 0.1-5 weight part, and the consumption of described activator is 0.1-5 weight part; Under preferable case, the isoprene-isobutylene rubber of the halogenation of relative 100 weight parts, the consumption of described lower molecular weight nylon is 5-15 weight part, the consumption of described copolymer nylon is 20-60 weight part, the consumption of described long carbon chain nylon is 10-25 weight part, and the consumption of described Low Density Polyethylene is 10-20 weight part, and the consumption of described vulcanizing agent is 0.8-6 weight part, the consumption of described vulcanization accelerator is 0.5-3 weight part, and the consumption of described activator is 0.5-3 weight part; In most preferred situation, the isoprene-isobutylene rubber of the halogenation of relative 100 weight parts, the consumption of described lower molecular weight nylon is 8-12 weight part, the consumption of described copolymer nylon is 30-50 weight part, the consumption of described long carbon chain nylon is 15-20 weight part, and the consumption of described Low Density Polyethylene is 12-16 weight part, and the consumption of described vulcanizing agent is 2-4 weight part, the consumption of described vulcanization accelerator is 1-2 weight part, and the consumption of described activator is 1-2 weight part.
In the present invention, described halogenated butyl rubber is the halogenated butyl rubber containing reactive halogen.The preferred chlorine of halogen in described halogenated butyl rubber and/or bromine, with the weight of described halogenated butyl rubber for benchmark, the content of the halogen in described halogenated butyl rubber is preferably 1-2.5 % by weight, is more preferably 1.5-2 % by weight.
In the present invention, described halogenated butyl rubber is the rubbery copolymer of iso-butylene and a small amount of isoprene.Wherein, with the total amount of halogenated butyl rubber for benchmark, the content of iso-butylene is 98.0-99.4 % by weight, the content of isoprene is 0.6-2.0 % by weight, under preferable case, the content of iso-butylene is 98.2-98.7 % by weight, and the content of isoprene is 1.3-1.8 % by weight.
According to the present invention, in order to make modified rubber and nylon mixture have better consistency, the mooney viscosity of described halogenated butyl rubber can be 28-60, is preferably 35-55, most preferably is 41-51.Described mooney viscosity can measure according to method disclosed in GB/T1232.1-2000 and obtain, and wherein, warm up time is 1min, and rotation time is 8min, and test temperature is 125 DEG C.
In the preparation of modified rubber, described low-molecular-weight nylon plays the effect of softening agent, adding of it is conducive to the dispersion of modified rubber in following process process, and in order to obtain excellent processing effect, the weight-average molecular weight of described lower molecular weight nylon is preferably 12000-18000 dalton.Described lower molecular weight nylon can be selected from nylon 6, nylon66 fiber, nylon 11, nylon 12 and NYLON610 one or more, be preferably in nylon 6, nylon66 fiber and NYLON610 one or more.
According to the present invention, described copolymer nylon and long-chain-segment nylon can be various copolymer nylon conventional in this area and long-chain-segment nylon, and under preferable case, described copolymer nylon is selected from the multipolymer of nylon 6 with nylon66 fiber and/or the multipolymer of nylon 6 and NYLON610; Described long carbon chain nylon be selected from nylon 1010, Nylon 1012, nylon 11 12 and nylon 1212 one or more.
In order to make the modified rubber that obtains in step (1) and nylon mixture have better consistency, under preferable case, the solution solvent viscosity ratio of described copolymer nylon in the concentrated sulfuric acid solution of 1 % by weight is 2-8 centipoise; The solution solvent viscosity ratio of described long carbon chain nylon in the concentrated sulfuric acid solution of 1 % by weight is 2-8 centipoise, and further in preferred situation, the solution solvent viscosity ratio of described copolymer nylon in the concentrated sulfuric acid solution of 1 % by weight is 3.5-5 centipoise; The solution solvent viscosity ratio of described long carbon chain nylon in the concentrated sulfuric acid solution of 1 % by weight is 3.5-5 centipoise, and in most preferred situation, the solution solvent viscosity ratio of described copolymer nylon in the concentrated sulfuric acid solution of 1 % by weight is 4.2-4.8 centipoise; The solution solvent viscosity ratio of described long carbon chain nylon in the concentrated sulfuric acid solution of 1 % by weight is 4.2-4.8 centipoise.
The condition determination of above-mentioned solution solvent viscosity ratio is: 25 DEG C, and determining instrument is Ubbelohde viscometer, and capillary inner diameter is 1.01-1.05mm.Take the vitriol oil as solvent, nylon is mixed with concentration be 1 % by weight concentrated sulfuric acid solution measure.
According to the present invention, described vulcanizing agent can be the vulcanizing agent for making rubber molecular chain play crosslinking reaction of various routine, such as, can be insoluble sulfur and/or zinc oxide, be preferably insoluble sulfur and zinc oxide.
When described vulcanizing agent is preferably insoluble sulfur and zinc oxide, the halogenated butyl rubber of relative 100 weight parts, the consumption of described insoluble sulfur can be 0.1-2 weight part, is preferably 0.3-1 weight part, is more preferably 0.5-0.8 weight part; The halogenated butyl rubber of relative 100 weight parts, the consumption of described zinc oxide can be 0.05-8 weight part, is preferably 0.5-5 weight part, is more preferably 1.5-3 weight part.Wherein, the nano zine oxide of described zinc oxide to be particularly preferably average particulate diameter be 1-100nm.
Described insoluble sulfur is the allotropic substance of sulphur, and it is insoluble to sulfurous gas and other solvent, is also insoluble to rubber, exists in rubber with dispersion state; After reaching curing temperature, these insoluble sulfurs be dispersed in rubber have one " activation stage ", i.e. chain type unzipping makes vulcanization rate accelerate.Reduce insoluble sulfur consumption, be conducive to the aging resistance improving rubber.
According to the present invention, described vulcanization accelerator can be the existing various curing time that can shorten, reduce curing temperature, reduce vulcanizing agent consumption and improve the material of the mechanical property of rubber, such as, can be that (commodity are called zinc dibutyl dithiocaarbamate: accelerant B Z), thiazole accelerator (such as, the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide (commodity are called TBBS or NS), 2, 2'-dibenzothiazyl disulfide (commodity are called: altax), curing mercaptobenzothiazole (commodity are called: accelerant MBT S) etc.), N, the two thiamide (trade(brand)name: Vulcanization accelerator TMTD) of N '-tetramethyl-two sulphur, 4, 4'-dithio morpholine (trade(brand)name: vulkacit D TDM), one or more in the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide (commodity be called: accelerator TBSI) and vulkacit D (commodity are by name: vulkacit D).
According to the present invention, described activator refers to the activity that can increase vulcanization accelerator, and then reduces the consumption of described vulcanization accelerator or shorten the material of curing time.Add sulphidity and thermotolerance that a small amount of promoting agent can significantly improve described rubber.Activator of the present invention can be existing various activator, such as, can be stearic acid and/or polyoxyethylene glycol.Wherein, the equal molecule of the number of described polyoxyethylene glycol can be 200-8000.
According to the present invention, in step (1), the condition of described banburying comprises: the speed of rotor is 10-100rpm, is preferably 40-80rpm; Banburying temperature is 50-160 DEG C, is preferably 80-150 DEG C; Banburying pressure is 0.1-0.5MPa, is preferably 0.2-0.4MPa; The banburying time is 1-10min, is preferably 3-5min.In the present invention, described pressure refers to the absolute pressure of system.
Described banburying equipment can be mixing facilities conventional in this area, such as Banbury mixer.
Modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator that step (1) obtains are carried out blended post-heating melting and the technique of extruding pelletization can be realized by twin screw extruder.The working conditions of described twin screw extruder comprises: screw speed is 200-600 rev/min, each zone temperatures (comprising feeding section to the section of melt extruding and die temperature) can be respectively 100-180 DEG C, 220-235 DEG C, 225-240 DEG C, 225-240 DEG C, 225-240 DEG C, 220-240 DEG C, the vacuum tightness of forcing machine can be 0.1-0.5MPa, the length-to-diameter ratio of twin screw extruder is 56-60, material is 10-90s in the residence time of twin screw extruder, is preferably 30-45s.The length-to-diameter ratio of described twin screw extruder is the useful length of screw rod and the ratio of outer screw diameter.Described modified rubber is occurrence dynamics sulfuration under the working conditions of above-mentioned twin screw extruder.
In the preparation process of described rubber-plastic composition, in order to obtain more uniform rubber-plastic composition, described melt extrude granulation before, also preferably include and modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator that step (1) obtains carried out just mixed step.Described just mixed method and condition are known to the skilled person, such as, modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator can be joined in existing various mixing equipment and be uniformly mixed, wherein, described mixing equipment can be such as stirrer and/or kneader.The temperature and time be uniformly mixed is conventionally known to one of skill in the art, and such as, the temperature be uniformly mixed can be 25-30 DEG C, and the time be uniformly mixed can be 1-3 minute.
Modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator that step (1) obtains are carried out blended post-heating melting and extruding pelletization, obtains rubber-plastic composition.The rubber and plastic polymkeric substance obtained like this has better blowing and workability.Possible reason is: under the condition of heating, with the mixture of copolymer nylon, long-chain-segment nylon and Low Density Polyethylene for base resin, the modified rubber of dynamic vulcanization can disperse better, forms modified rubber with the structure of the structure disperses on " island " in " sea " of base resin.
According to the present invention, under preferable case, step (1) described banburying is carried out under auxiliary agent exists, and described auxiliary agent is one or more in leveler, stablizer and tackifier.
According to the present invention, described leveler can promote the alternate mixing quickly and evenly of the glue of different relative molecular weight, opposed polarity and different viscosity and the material that can improve the processing characteristics of rubber for existing various can playing.Described leveler can be one or more in the mixture of group aliphatic resin and aromatic resin, group aliphatic resin and the mixture of cycloparaffin series's resin and the mixture of group aliphatic resin, cycloparaffin series's resin and aromatic resin.Such as purchased from the group aliphatic resin of German S.S company and aromatic resin mixture (trade(brand)name 40MS) and group aliphatic resin and cycloparaffin series's resin (trade(brand)name 60NS), the mixture (trade(brand)name M40) of the group aliphatic resin of German KETTLITZ company, cycloparaffin series's resin and aromatic resin.
According to the present invention, described stablizer is the various materials that can prevent ageing of rubber and degraded, such as, can be one or more in epoxy soybean oil, calcium stearate and Magnesium Stearate.
According to the present invention, described tackifier are various materials that can improve product cohesive force, such as, can be one or more in terpine resin, Gum Rosin, petroleum resin and resol.Described resol can be one or more in octyl phenol formaldehyde resin (trade(brand)name HY-203), t-Butylphenol formaldehyde resin (trade(brand)name HY-204) and polynary alkylphenol formaldehyde resin (trade(brand)name HY-2006); Described terpine resin can be one or more in α pinene resin, beta-pinene resin and terpene-styrene resin; Described Gum Rosin can be one or more in pentalyn, ester gum and hydrogenated rosin glyceride; Described petroleum resin can be aliphatics C5 petroleum resin and/or aromatic series C9 petroleum resin.
According to the present invention, in step (1), relative to the halogenated butyl rubber described in 100 weight parts, the consumption of described auxiliary agent is 1-40 weight part.
Under preferable case, described modified rubber is obtained under the existence of leveler, stablizer and tackifier, and relative to the halogenated butyl rubber of 100 weight parts, the consumption of described leveler is 1-10 weight part, is more preferably 2-5 weight part, most preferably is 3-4 weight part; Relative to the halogenated butyl rubber of 100 weight parts, the consumption of described stablizer is 1-20 weight part, is more preferably 5-15 weight part, most preferably is 6-9 weight part; Relative to the halogenated butyl rubber of 100 weight parts, the consumption of described tackifier is 1-10 weight part, is more preferably 2-5 weight part, most preferably is 3-4 weight part.
According to the present invention, be blended in described in step (2) under auxiliary agent exists and carry out, described auxiliary agent is one or more in thermo-stabilizer, compatilizer and softening agent.
According to the present invention, described softening agent is can the various small-molecule substances that change the mechanical property of nylon miscible with nylon.Such as described softening agent can be N-butylbenzenesulfonamide and/or N-ethyl adjacency pair toluol sulfonamide.
According to the present invention, described thermo-stabilizer is can be compatible and can prevent the material of nylon generation thermal destruction with nylon, and such as described thermo-stabilizer can be two or more in hindered phenol type stablizer, phosphite type stablizer, copper halide type stablizer and hindered amine type light stabilizer.
The kind of the present invention to described hindered phenol type stablizer is not particularly limited, such as, four [β-(3 can be selected from, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (being called for short: antioxidant 1010), 1, 3, 5-trimethylammonium-2, 4, 6-(3, 5-di-t-butyl-4-hydroxyphenylmethyl) benzene (being called for short: antioxidant 330), 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide (being called for short: antioxidant 3114), N, N '-bis-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (being called for short: oxidation inhibitor 1098), three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester (be called for short: irgasfos 168) and β-(3, 5-di-tert-butyl-hydroxy phenyl) one or more in the positive octadecanol ester of propionic acid (be called for short: antioxidant 1076), be particularly preferably β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid (be called for short: antioxidant 1076) and/or N, N '-bis-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (being called for short: oxidation inhibitor 1098).
The kind of the present invention to described phosphite type stablizer is also not particularly limited, such as, three (2 can be selected from, 4-di-tert-butyl-phenyl) phosphorous acid ester (being called for short: irgasfos 168), two (2,4-DI-tert-butylphenol compounds) pentaerythritol diphosphites (being called for short: oxidation inhibitor 626) and two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites (is called for short: one or more oxidation inhibitor PEP-36), be particularly preferably three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (168).
The kind of the present invention to described copper halide type stablizer is also not particularly limited, such as, and cuprous iodide.
The kind of the present invention to described hindered amine type light stabilizer is also not particularly limited, such as, succinic acid and (4-hydroxyl-2, 2, 6, the polymkeric substance of 6-tetramethyl--1-piperidine alcohols) (being called for short photostabilizer 622), sebacic acid two-2, 2, 6, 6-tetramethyl piperidine alcohol ester (being called for short: photostabilizer 770) and poly-{ [6-[(1, 1, 3, 3-tetramethyl butyl) amino]]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6,-tetramethyl-4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-] one or more in (be called for short: photostabilizer 944).
According to the present invention, described compatilizer is the consistency improving modified rubber and modified plastics, makes modified rubber be dispersed in material in modified plastics better.Such as described compatilizer can be one or more in maleic anhydride graft terpolymer EP rubber, maleic anhydride grafted polyethylene-octene copolymer and maleic anhydride grafted polyethylene, and described percentage of grafting is 0.5-1.0 % by weight.
According to the present invention, in step (2), relative to the halogenated butyl rubber of 100 weight parts, the consumption of described auxiliary agent is 1-35 weight part.
Under preferable case, relative to the halogenated butyl rubber of 100 weight parts, the consumption of described thermo-stabilizer is 0.1-5 weight part, is more preferably 0.1-3 weight part, most preferably is 0.5-1.5 weight part; Relative to the halogenated butyl rubber of 100 weight parts, the consumption of described compatilizer is 1-20 weight part, is more preferably 5-15 weight part, most preferably is 8-10 weight part; Relative to the halogenated butyl rubber of 100 weight parts, the consumption of described softening agent is 1-10 weight part, is more preferably 2-8 weight part, most preferably is 4-6 weight part.
Below will be described the present invention by embodiment.
In following examples and comparative example, the measuring method of the parameter related to is as follows:
1, the iso-butylene content in brominated butyl rubber and isoprene content adopt the model purchased from Bruker company of Switzerland to be that the nuclear magnetic resonance spectrometer of BRUKER400 carries out hydrogen spectrum and measures, and wherein, solvent is deuterochloroform, and probe temperature is normal temperature;
2, the mensuration of the density of Low Density Polyethylene is with reference to GB/T1033-2008 method.
3, the mensuration of the melt mass flow rate of Low Density Polyethylene is with reference to GB/T3682-2000 method, and condition determination comprises: measuring temperature is 190 DEG C, and load is 2.16kg.
4, the mensuration of the solution solvent viscosity ratio of copolymer nylon and long-chain-segment nylon adopts one point method, condition determination is: 25 DEG C, and determining instrument is Ubbelohde viscometer, and capillary inner diameter is 1.01-1.05mm, take the vitriol oil as solvent, nylon is mixed with concentration be 1 % by weight concentrated sulfuric acid solution measure.
In following examples and comparative example,
Brominated butyl rubber is the model that ExxonMobil company produces is the brominated butyl rubber of 2255, and mooney viscosity (125 DEG C, 1+8) is 46, wherein, iso-butylene content is 98.7 % by weight, and isoprene content is 1.3 % by weight, and the content of bromine is 2 % by weight;
Lower molecular weight nylon is the nylon of the trade mark 6106L that Weihui City Hong Yusu industry company limited produces, and weight-average molecular weight is 15000 dalton; Copolymer nylon is the trade mark that Ube company produces is the nylon (PA6/66 copolymer nylon) of 5033B, and the solution solvent viscosity ratio of this copolymer nylon in the concentrated sulfuric acid solution of 1 % by weight is 4.5 centipoises; Long carbon chain nylon is the 1012H that Weihui City Hong Yusu industry company limited produces, and the solution solvent viscosity ratio of this long carbon chain nylon in the concentrated sulfuric acid solution of 1 % by weight is 4.2 centipoises;
Compatilizer is the maleic anhydride modified terpolymer EP rubber (EPDM) that ExxonMobil company produces, and the trade mark is VA1803;
Low Density Polyethylene-1 is the trade mark that Sinopec Beijing Yanshan Mountain branch office produces is the Low Density Polyethylene of LD100AC, and density is 0.923g/cm
3, melt mass flow rate is 2.0g/10min;
Low Density Polyethylene-2 is the trade mark that Sinopec Beijing Yanshan Mountain branch office produces is the Low Density Polyethylene of LD103, and density is 0.921g/cm
3, melt mass flow rate is 1.0g/10min;
Low Density Polyethylene-3 is the trade mark that Sinopec Beijing Yanshan Mountain branch office produces is the Low Density Polyethylene of LD165, and density is 0.922g/cm
3, melt mass flow rate is 0.3g/10min.
Other auxiliary agents are commercially available conventional products.
Preparation example 1
This preparation example is used for rubber-plastic composition provided by the invention and preparation method thereof.
(1) the leveler 40MS (German S.S company) of the epoxy soybean oil of the stearic acid of the lower molecular weight nylon of the brominated butyl rubber of 100 weight parts, 8 weight parts, 1 weight part, 6 weight parts, 3 weight part tackifier HY-203 (Shanxi chemical research institute), 3 weight parts being put into Banbury mixer carries out just mixed, the speed of rotor is 60rpm, and banburying is carried out at 80 DEG C, banburying pressure is 0.3MPa, the banburying time is 3.5min, then the internal mixing film obtained is carried out granulation in rubber comminutor, obtain modified rubber particle;
(2) by modified rubber particle that step (1) obtains, the zinc oxide of 2 weight parts, the insoluble sulfur of 0.8 weight part, the altax (Tianjin La Bo auxiliary agent company limited) of 2 weight parts, the copolymer nylon of 30 weight parts, the long carbon chain nylon of 15 weight parts, the softening agent N-butylbenzenesulfonamide (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 4 weight parts, the thermo-stabilizer IrganoxB1171 (BASF AG) of 0.5 weight part, the compatilizer VA1803 (ExxonMobil company) of 8 weight parts, the Low Density Polyethylene-1 of 16 weight parts to add in stirrer and stir at 25 DEG C within 1 minute, carry out just mixed after, it is carry out blended heating and melting in the twin screw extruder of 56 that the mixture of gained is sent into length-to-diameter ratio, and extruding pelletization, wherein the working conditions of twin screw extruder comprises: the rotating speed of adjustment screw rod is 300rpm, each zone temperatures controls respectively: 150 DEG C, 225 DEG C, 235 DEG C, 240 DEG C, 240 DEG C and 235 DEG C, the vacuum tightness of forcing machine remains 0.2MPa to 0.5MPa, and material is 45s in the residence time of twin screw extruder, obtains rubber-plastic composition A1.
Preparation example 2
This preparation example is used for rubber-plastic composition provided by the invention and preparation method thereof.
(1) the leveler 40MS (German S.S company) of the epoxy soybean oil of the stearic acid of the lower molecular weight nylon of the brominated butyl rubber of 100 weight parts, 10 weight parts, 2 weight parts, 7.5 weight parts, 3.5 weight part tackifier HY-203 (Shanxi chemical research institute), 3.5 weight parts being put into Banbury mixer carries out just mixed, the speed of rotor is 40rpm, and banburying is carried out at 100 DEG C, banburying pressure is 0.2MPa, the banburying time is 4min, then the internal mixing film obtained is carried out granulation in rubber comminutor, obtain modified rubber particle;
(2) by modified rubber particle that step (1) obtains, the zinc oxide of 3 weight parts, the insoluble sulfur of 0.5 weight part, the altax (Tianjin La Bo auxiliary agent company limited) of 1.0 weight parts, the copolymer nylon of 50 weight parts, the long carbon chain nylon of 20 weight parts, the softening agent N-butylbenzenesulfonamide (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 6 weight parts, the thermo-stabilizer IrganoxB1171 (BASF AG) of 1.5 weight parts, the compatilizer VA1803 (ExxonMobil company) of 10 weight parts, the Low Density Polyethylene-2 of 12 weight parts to add in stirrer and stir at 25 DEG C within 2 minutes, carry out just mixed after, by the mixture of gained send into length-to-diameter ratio be 56 in twin screw extruder, carry out blended heating and melting and extruding pelletization, wherein the working conditions of twin screw extruder comprises: the rotating speed of adjustment screw rod is 600rpm, each zone temperatures controls respectively: 150 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C and 235 DEG C, the vacuum tightness of forcing machine remains 0.2MPa to 0.5MPa, and material is 35s in the residence time of twin screw extruder, obtains rubber-plastic composition A2.
Preparation example 3
This preparation example is used for rubber-plastic composition provided by the invention and preparation method thereof.
(1) by the leveler 40MS (German S.S company) of the epoxy soybean oil of the stearic acid of the lower molecular weight nylon of the brominated butyl rubber of 100 weight parts, 12 weight parts, 1.5 weight parts, 8 weight parts, 4 weight part tackifier HY-203 (Shanxi chemical research institute), 4 weight parts, put into Banbury mixer and carry out just mixed, the speed of rotor is 80rpm, and banburying is carried out at 150 DEG C, banburying pressure is 0.4MPa, the banburying time is 5min, then the internal mixing film obtained is carried out granulation in rubber comminutor, obtain modified rubber particle;
(2) by modified rubber particle that step (1) obtains, the zinc oxide of 3 weight parts, the insoluble sulfur of 0.65 weight part, the copolymer nylon of altax (Tianjin La Bo auxiliary agent company limited) 40 weight parts of 1.5 weight parts, the long carbon chain nylon of 17 weight parts, the softening agent N-butylbenzenesulfonamide (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 5 weight parts, the thermo-stabilizer IrganoxB1171 (BASF AG) of 1 weight part, the compatilizer VA1803 (ExxonMobil company) of 9 weight parts, the Low Density Polyethylene-3 of 14 weight parts to add in stirrer and stir at 25 DEG C within 2 minutes, carry out just mixed after, it is carry out blended heating and melting and extruding pelletization in the twin screw extruder of 56 that the mixture of gained is sent into length-to-diameter ratio, wherein the working conditions of twin screw extruder comprises: the rotating speed of adjustment screw rod is 400rpm, each zone temperatures controls respectively: 160 DEG C, 225 DEG C, 235 DEG C, 240 DEG C, 240 DEG C and 235 DEG C, the vacuum tightness of forcing machine remains 0.2MPa to 0.5MPa, and material is 42s in the residence time of twin screw extruder, obtains rubber-plastic composition A3.
Preparation example 4
This preparation example is used for rubber-plastic composition provided by the invention and preparation method thereof.
(1) the leveler 40MS (German S.S company) of the epoxy soybean oil of the stearic acid of the lower molecular weight nylon of the brominated butyl rubber of 100 weight parts, 10 weight parts, 2 weight parts, 7.5 weight parts, 3.5 weight part tackifier HY-203 (Shanxi chemical research institute), 3.5 weight parts being put into Banbury mixer carries out just mixed, the speed of rotor is 60rpm, and banburying is carried out at 80 DEG C, banburying pressure is 0.3MPa, the banburying time is 3.5min, then the internal mixing film obtained is sent in rubber comminutor and carry out granulation, obtain modified rubber particle;
(2) by modified rubber particle that step (1) obtains, the zinc oxide of 4 weight parts, the insoluble sulfur of 0.5 weight part, the copolymer nylon of altax (Tianjin La Bo auxiliary agent company limited) 50 weight parts of 1.0 weight parts, the long carbon chain nylon of 1 weight part, the softening agent N-butylbenzenesulfonamide (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 6 weight parts, the thermo-stabilizer IrganoxB1171 (BASF AG) of 1.5 weight parts, the compatilizer VA1803 (ExxonMobil company) of 10 weight parts, the Low Density Polyethylene of 12 weight parts carry out just mixed after, blended heating and melting is carried out and extruding pelletization in twin screw extruder, wherein the working conditions of twin screw extruder comprises: the rotating speed of adjustment screw rod is 500rpm, each zone temperatures controls respectively: 180 DEG C, 225 DEG C, 230 DEG C, 225 DEG C, 225 DEG C and 235 DEG C, the vacuum tightness of each section remains 0.2MPa to 0.5MPa, and material is 38s in the residence time of twin screw extruder, obtains rubber-plastic composition A4.
Preparation comparative example 1
This comparative example is for illustration of reference rubber-plastic composition and preparation method thereof.
Rubber-plastic composition is prepared according to the method for preparation example 2, unlike, in step (2), do not add Low Density Polyethylene-2, obtain reference rubber-plastic composition DA1.
Embodiment 1-4
By the rubber-plastic composition A1-A4 for preparing in preparation example 1-4 respectively in inflation film manufacturing machine (ALPHA company, model is AMT100) on, adopt flat crowded upward type, carry out the blown film test of thermoplastic elastomer, each zone temperatures of inflation film manufacturing machine controls respectively: 150 DEG C, 220 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C, obtains the film that thickness is respectively 25 μm, 30 μm, 35 μm, 40 μm.
Comparative example 1
Adopt and carry out blown film with the mode of embodiment 1-4 by prepare the rubber-plastic composition DA1 prepared in comparative example 1, obtain the reference film that thickness is 30 μm, through observation, the thermoplastic film obtained apparent uneven.
Test case
This test case is for illustration of the mensuration of the performance of film provided by the invention.
Above-described embodiment 1-4 and comparative example 1 are obtained film and carries out performance test, test result is in table 1, and described performance test comprises:
(1) maximum blow-up ratio: under the not destroyed prerequisite of guarantee film bubble, film bubble is blown as far as possible to maximum, the ratio of vesicle diameter and port mould diameter;
(2) measure with reference to GB/T1040-2006: horizontal elongation rate of tensile failure, laterally 50% stress at definite elongation, longitudinal elongation rate of tensile failure and longitudinal 50% stress at definite elongation, determining instrument is tensilon (American I NSTRON company, model 5566);
(3) measure oxygen permeability coefficient with reference to GB/T1038-2000, metering equipment is Jinan blue streak VAC-V2 type pressure differential gas permeameter, and condition determination is 23 DEG C.
(4) rubber phase size distribution: adopt atomic force microscope (Multimode8 type, BRUKER company of Germany) observe, and rubber phase size is added up, obtain rubber phase particle diameter normal distribution, calculate rubber phase size by statistical method.
Table 1
From the results shown in Table 1, a small amount of Low Density Polyethylene is added in the dynamic vulcanization system of modified rubber and nylon mixture, can be good at improving the otherness of the inflation of rubber-plastic composition in the blown film process when transverse and longitudinal performance of film, the film simultaneously obtained is apparent more even.Although the membership that adds of Low Density Polyethylene causes the resistance to air loss of film to decline, comparatively speaking, the degree of decline is little, still has excellent resistance to air loss; Secondly, the rubber phase particle diameter of the film that this preparation method obtains is little and size distribution is narrower.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a preparation method for rubber-plastic composition, the method comprises:
(1) halogenated butyl rubber, lower molecular weight nylon and activator are carried out banburying and granulation, obtain modified rubber;
(2) modified rubber, copolymer nylon, long carbon chain nylon, Low Density Polyethylene, vulcanizing agent and vulcanization accelerator that step (1) obtains are carried out blended post-heating melting and extruding pelletization,
Wherein, the weight-average molecular weight of described lower molecular weight nylon is 5000-25000 dalton, described Low Density Polyethylene is 0.1-10g/10min according to the melt mass flow rate that GB/T3682-2000 measures, and the density of described Low Density Polyethylene is 0.915-0.925g/cm
3.
2. method according to claim 1, wherein, described Low Density Polyethylene is 0.2-5g/10min according to the melt mass flow rate that GB/T3682-2000 measures, and the density of described Low Density Polyethylene is 0.920-0.923g/cm
3.
3. method according to claim 1, wherein, the described halogenated butyl rubber of relative 100 weight parts, the consumption of described lower molecular weight nylon is 1-20 weight part, and the consumption of described copolymer nylon is 10-80 weight part, and the consumption of described long carbon chain nylon is 1-30 weight part, the consumption of described Low Density Polyethylene is 1-30 weight part, the consumption of described vulcanizing agent is 0.15-10 weight part, and the consumption of described vulcanization accelerator is 0.1-5 weight part, and the consumption of described activator is 0.1-5 weight part.
4. the method according to claim 1 or 3, wherein, with the weight of described halogenated butyl rubber for benchmark, the content of halogen in described halogenated butyl rubber is 1-2.5 % by weight, described halogen is chlorine and/or bromine, and the mooney viscosity of described halogenated butyl rubber is 28-60.
5. the method according to claim 1 or 3, wherein, the weight-average molecular weight of described lower molecular weight nylon is 12000-18000 dalton, preferably, described lower molecular weight nylon be selected from nylon 6, nylon66 fiber, nylon 11, nylon 12 and NYLON610 one or more; Described copolymer nylon is selected from the multipolymer of nylon 6 with nylon66 fiber and/or the multipolymer of nylon 6 and NYLON610; Described long carbon chain nylon be selected from nylon 1010, Nylon 1012, nylon 11 12 and nylon 1212 one or more.
6. the method according to claim 1 or 3 or 5, wherein, the solution solvent viscosity ratio of described copolymer nylon in the concentrated sulfuric acid solution of 1 % by weight is 2-8 centipoise; The solution solvent viscosity ratio of described long carbon chain nylon in the concentrated sulfuric acid solution of 1 % by weight is 2-8 centipoise.
7. the method according to claim 1 or 3, wherein, described vulcanizing agent is insoluble sulfur and/or zinc oxide; Described vulcanization accelerator is zinc dibutyl dithiocaarbamate, the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, 2,2'-dibenzothiazyl disulfide, curing mercaptobenzothiazole, N, one or more in N '-tetramethyl-two sulphur two thiamide, 4,4'-dithio morpholines, the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide and vulkacit D; Described activator is stearic acid and/or polyoxyethylene glycol.
8. method according to claim 1, wherein, in step (1), the condition of described banburying comprises: the speed of rotor is 10-100rpm; Banburying temperature is 50-160 DEG C; Banburying pressure is 0.1-0.5MPa; The banburying time is 1-10min.
9. method according to claim 1, wherein, step (1) described banburying is carried out under auxiliary agent exists, and relative to the described halogenated butyl rubber of 100 weight parts, the consumption of described auxiliary agent is 1-40 weight part.
10. method according to claim 9, wherein, described auxiliary agent is one or more in leveler, stablizer and tackifier, and described tackifier are one or more in terpine resin, Gum Rosin, petroleum resin and resol; Described stablizer is one or more in epoxy soybean oil, calcium stearate and Magnesium Stearate; Described leveler is one or more in the mixture of group aliphatic resin and anine, group aliphatic resin and the mixture of cycloparaffin series's resin and the mixture of group aliphatic resin, cycloparaffin series's resin and aromatic resin.
11. methods according to claim 1, wherein, be blended in described in step (2) under auxiliary agent exists and carry out, relative to the described halogenated butyl rubber of 100 weight parts, the consumption of described auxiliary agent is 1-35 weight part.
12. methods according to claim 11, wherein, described auxiliary agent is one or more in thermo-stabilizer, compatilizer and softening agent, and described thermo-stabilizer is two or more in hindered phenol type antioxidant, phosphite type oxidation inhibitor, copper halide type stablizer and hindered amine type light stabilizer; Described compatilizer is one or more in maleic anhydride graft terpolymer EP rubber, maleic anhydride grafted polyethylene-octene copolymer and maleic anhydride grafted polyethylene; Described softening agent is N-butylbenzenesulfonamide and/or N-ethyl adjacency pair toluol sulfonamide.
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| CN110358172A (en) * | 2019-07-02 | 2019-10-22 | 江苏南翔橡胶制品有限公司 | A kind of high rebound, the compound rubber-plastics material of low-gravity butyl renewable rubber and preparation method thereof |
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