CN105524362B - A kind of preparation method of rubber-plastic composition - Google Patents
A kind of preparation method of rubber-plastic composition Download PDFInfo
- Publication number
- CN105524362B CN105524362B CN201410514226.3A CN201410514226A CN105524362B CN 105524362 B CN105524362 B CN 105524362B CN 201410514226 A CN201410514226 A CN 201410514226A CN 105524362 B CN105524362 B CN 105524362B
- Authority
- CN
- China
- Prior art keywords
- weight
- nylon
- rubber
- parts
- dosage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of rubber-plastic composition, this method includes：(1) halogenated butyl rubber, low molecule amount nylon and activator are subjected to banburying and granulation, obtain modified rubber；(2) heating melting and extruding pelletization after modified rubber, copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and vulcanization accelerator that step (1) obtains being blended, the weight average molecular weight of low molecule amount nylon is 5,000 25000 dalton, the melt mass flow rate that low density polyethylene (LDPE) determines according to GB/T3682 2000 is 0.1 10g/10min, and density is 0.915 0.925g/cm3The rubber-plastic composition prepared by this method has good machinability and blowing property, blow-up ratio of the rubber-plastic composition during blown film is improved well, and causes the thermoplastic film made from rubber-plastic composition provided by the invention that there is excellent mechanical property and excellent air-tightness.
Description
Technical field
The present invention relates to a kind of preparation method of rubber-plastic composition.
Background technology
Thermoplastic elastomers have a variety of possible structures, its product both possessed traditional cross-linking vulcanized rubber high resiliency,
The ageing-resistant every excellent properties of grade, while but also with the characteristics of common plasticses are easy to process, processing mode is more, can typically use note
The processing mode production such as modeling, extrusion, blowing.
CN101296997A discloses a kind of composition for thermoplastic elastomer, and said composition includes：At least one halogenation
Containing isobutylene elastomer；At least one fusing point is about 170-260 DEG C of nylon resin, and the plasticising of low-molecular weight polymer type nylon
Agent.The composition for thermoplastic elastomer has excellent air-tightness, durability and pliability.But it is prepared by said composition
Film causes film bubble easily occur because nylon has stronger hygroscopicity, and the inflation of nylon is smaller, also seriously
Limit the blow-up ratio of such composition.
EP0722850A1 discloses a kind of polymer composition for tire, and said composition includes：At least one thermoplastic
Property resin and at least one elastomeric component, the thermoplastic resin is selected from polyamide, polyester resin etc., the elastomer
Component is selected from butadiene and its hydride, olefinic rubber, silicon rubber, halogen-containing rubber etc..EP0969039A1 discloses one kind
Composition for thermoplastic elastomer, said composition include the elastomeric component containing the nylon resin that fusing point is 170-230 DEG C, and
The isobutene of halogenation-p-methylstyrene copolymer.
EP0722850A1 and EP0969039A1 is based on binary composition, namely Iso-butylene-based elastomers and polyamide
Class is blended, while rubber carries out dynamic vulcanization in extrusion, obtains described composition, and such composition is requiring thin
Film thickness is larger, in the case of blow-up ratio is less, with respect to the inner liner of Iso-butylene-based elastomers preparation, has the advantages that really.
The addition of nylon, the air-tightness of inner liner is not only increased, while elastomer can be made to realize blowfilm shaping, traditional rubber before changing
The processing mode of glue.But nylon, while have excellent air-tightness, its relatively limited blowing still has said composition
In place of some shortcomings.
CN102066475A discloses a kind of method of Production development vulcanized alloy, and the alloy contains at least one isobutyl
Alkene elastomer and at least one thermoplastic resin, this method comprise the following steps：(a) by the thermoplastic resin and at least one
Plasticizer is mixed to form resin concentrates in the first melt-processed device；(b) by the elastomer, at least one vulcanizing agent with
And the resin concentrates are fed to the feed throat of the second melt-processed device；(c) will be described interior in the second melt-processed device
Tolerant mixing is to form dynamic vulcanization alloy under dynamic vulcanization conditions, and its elastomer is as the continuous phase in thermoplastic resin
In vulcanization or partial vulcanization particle dispersed phase exist.Although the product obtained using this method has good impermeability
And low-temperature flexibility, but the technological process of this method is grown, and high energy consumption.
The content of the invention
It is an object of the invention to provide overcoming, rubber-plastic composition of the prior art inflation during blown film is smaller, warm
The defects of mechanical property of plastic films is poor and a kind of preparation method of rubber-plastic composition is provided.
To achieve these goals, the present invention provides a kind of preparation method of rubber-plastic composition, and this method includes：
(1) halogenated butyl rubber and low molecule amount nylon and activator are subjected to banburying and granulation, obtain modified rubber；
(2) modified rubber that obtains step (1), copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and
Heating melting and extruding pelletization after vulcanization accelerator is blended,
Wherein, the weight average molecular weight of the low molecule amount nylon is 5000-25000 dalton, the low density polyethylene (LDPE)
It is 0.1-10g/10min according to the GB/T3682-2000 melt mass flow rates determined, the density of the low density polyethylene (LDPE)
For 0.915-0.925g/cm3。
The preparation method of rubber-plastic composition provided by the invention is few by being added in the dynamic vulcanization system of modified rubber
The low density polyethylene (LDPE) of amount so that the modified rubber of dynamic vulcanization is better dispersed in nylon mixture, and is caused by this
Rubber-plastic composition prepared by method has good machinability and blowing property, improves rubber-plastic composition well in blown film
During blow-up ratio, and make it that there is excellent power using thermoplastic film made from rubber-plastic composition provided by the invention
Learn performance and excellent air-tightness；The thermoplastic film is apparent more uniform simultaneously.In addition, the rubber phase of the thermoplastic film
Particle diameter is small and particle size distribution range is narrower so that the thin flexible film is preferable.
Also, the preparation process of rubber-plastic composition provided by the invention is simple, reduces mill technique and reduce rubber
The heat ageing degree of raw material in molding composition.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of rubber-plastic composition, and this method includes：
(1) halogenated butyl rubber, low molecule amount nylon and activator are subjected to banburying and granulation, obtain modified rubber；
(2) modified rubber that obtains step (1), copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and
Heating melting and extruding pelletization after vulcanization accelerator is blended,
Wherein, the weight average molecular weight of the low molecule amount nylon is 5000-25000 dalton, the low density polyethylene (LDPE)
It is 0.1-10g/10min according to the GB/T3682-2000 melt mass flow rates determined, the density of the low density polyethylene (LDPE)
For 0.915-0.925g/cm3。
In the present invention, the rubber that dynamic vulcanization refers to not crosslink and the thermoplastic polymer (example that can not vulcanize
Such as resin) under shear at high temperature effect, it is blended and heats melting, in the presence of crosslinking agent, rubber vulcanizes.Thus sulphur
The rubber formed after change is mutually evenly dispersed in resin phase with micron-sized particle.
In the present invention, property of the melt mass flow rate of the low density polyethylene (LDPE) to the rubber-plastic composition of the present invention
There can be significant impact, specifically, when low density polyethylene (LDPE) is less than according to GB/T3682-2000 melt mass flow rates
0.1g/10min or during higher than 10g/10min, the blowing of the rubber-plastic composition or processability decline.
Under preferable case, the low density polyethylene (LDPE) is according to the GB/T3682-2000 melt mass flow rates determined
0.2-5g/10min, more preferably 0.3-2g/10min.
In the present invention, the density of the low density polyethylene (LDPE) has significant to the performance of the rubber-plastic composition of the present invention
Influence, specifically, when the density of the low density polyethylene (LDPE) is less than 0.915g/cm3Or higher than 0.925g/cm3When, the rubber and plastic
The blowing of composition or processability decline.
Under preferable case, the density of the low density polyethylene (LDPE) is 0.920-0.923g/cm3。
According to the present invention, above-mentioned density that what the low density polyethylene (LDPE) can be well known to those skilled in the art meet and
Melt mass flow rate requirement various low density polyethylene (LDPE)s, usually, the low density polyethylene (LDPE) be tubular reactor or
The low density polyethylene homopolymer produced in tank reactor by high pressure method.Under preferable case, the low density polyethylene (LDPE)
For the low density polyethylene homopolymer produced in tubular reactor by high pressure method.
In the present invention, the measure of density is with reference to GB/T1033-2008 methods measure.The measure of melt mass flow rate
With reference to GB/T3682-2000 methods measure, condition determination includes：Measurement temperature is 190 DEG C, load 2.16kg.
According to the present invention, the low molecule amount nylon, copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent,
There is no particular limitation for the dosage of vulcanization accelerator and activator, can be changed in wider scope, as long as making obtained rubber
Molding composition has excellent machinability and blowing property.Usually, with respect to the halobutyl rubber of 100 parts by weight
Glue, the dosage of the low molecule amount nylon are 1-20 parts by weight, and the dosage of the copolymer nylon is 10-80 parts by weight, the length
The dosage of carbon chain nylon is 1-30 parts by weight, and the dosage of the low density polyethylene (LDPE) is 1-30 parts by weight, the use of the vulcanizing agent
Measure as 0.15-10 parts by weight, the dosage of the vulcanization accelerator is 0.1-5 parts by weight, and the dosage of the activator is 0.1-5 weights
Measure part；Under preferable case, with respect to the butyl rubber of the halogenation of 100 parts by weight, the dosage of the low molecule amount nylon is 5-15 weights
Part is measured, the dosage of the copolymer nylon is 20-60 parts by weight, and the dosage of the long carbon chain nylon is 10-25 parts by weight, described low
The dosage of density polyethylene is 10-20 parts by weight, and the dosage of the vulcanizing agent is 0.8-6 parts by weight, the vulcanization accelerator
Dosage is 0.5-3 parts by weight, and the dosage of the activator is 0.5-3 parts by weight；In the case of most preferably, with respect to 100 parts by weight
Halogenation butyl rubber, the dosage of the low molecule amount nylon is 8-12 parts by weight, and the dosage of the copolymer nylon is 30-50
Parts by weight, the dosage of the long carbon chain nylon is 15-20 parts by weight, and the dosage of the low density polyethylene (LDPE) is 12-16 parts by weight,
The dosage of the vulcanizing agent is 2-4 parts by weight, and the dosage of the vulcanization accelerator is 1-2 parts by weight, the dosage of the activator
For 1-2 parts by weight.
In the present invention, the halogenated butyl rubber is the halogenated butyl rubber containing reactive halogen.The halobutyl
The preferred chlorine of halogen and/or bromine in rubber, on the basis of the weight of the halogenated butyl rubber, in the halogenated butyl rubber
The content of halogen is preferably 1-2.5 weight %, more preferably 1.5-2 weight %.
In the present invention, the halogenated butyl rubber is the rubbery copolymer of isobutene and a small amount of isoprene.Wherein, with
On the basis of the total amount of halogenated butyl rubber, the content of isobutene is 98.0-99.4 weight %, and the content of isoprene is 0.6-
2.0 weight %, under preferable case, the content of isobutene is 98.2-98.7 weight %, and the content of isoprene is 1.3-1.8 weights
Measure %.
According to the present invention, in order that modified rubber has more preferable compatibility, the halobutyl rubber with nylon mixture
The Mooney viscosity of glue can be 28-60, preferably 35-55, most preferably 41-51.The Mooney viscosity can be according to GB/
Method disclosed in T1232.1-2000 determines to obtain, wherein, preheating time 1min, rotation time 8min, test temperature is
125℃。
In the preparation of modified rubber, the nylon of the low molecule amount plays a part of plasticizer, and its addition is advantageous to
Modified rubber is scattered during following process, and in order to obtain excellent processing effect, the weight of the low molecule amount nylon is equal
Molecular weight is preferably 12000-18000 dalton.The low molecule amount nylon can be selected from nylon 6, nylon66 fiber, nylon 11, Buddhist nun
One or more in dragon 12 and NYLON610, the preferably one or more in nylon 6, nylon66 fiber and NYLON610.
According to the present invention, the copolymer nylon and long-chain-segment nylon can be various copolymer nylons commonly used in the art and
Long-chain-segment nylon, under preferable case, the copolymer nylon is selected from the copolymer and/or nylon 6 and nylon of nylon 6 and nylon66 fiber
610 copolymer；One kind in nylon 1010, Nylon 1012, nylon 11 12 and nylon 1212 of the long carbon chain nylon or
It is a variety of.
In order that the modified rubber obtained in step (1) and nylon mixture have a more preferable compatibility, under preferable case,
Relative viscosity of the copolymer nylon in 1 weight % concentrated sulfuric acid solution is 2-8 centipoises；The long carbon chain nylon is in 1 weight
The relative viscosity measured in % concentrated sulfuric acid solution is 2-8 centipoises, and in the case of further preferred, the copolymer nylon is in 1 weight
The relative viscosity measured in % concentrated sulfuric acid solution is 3.5-5 centipoises；The long carbon chain nylon is in 1 weight % concentrated sulfuric acid solution
Relative viscosity be 3.5-5 centipoises, most preferably in the case of, phase of the copolymer nylon in 1 weight % concentrated sulfuric acid solution
It is 4.2-4.8 centipoises to viscosity；Relative viscosity of the long carbon chain nylon in 1 weight % concentrated sulfuric acid solution is 4.2-4.8
Centipoise.
The condition determination of above-mentioned relative viscosity is：25 DEG C, determining instrument is Ubbelohde viscometer, capillary inner diameter 1.01-
1.05mm.Using the concentrated sulfuric acid as solvent, nylon is configured to the concentrated sulfuric acid solution that concentration is 1 weight % and is measured.
According to the present invention, the vulcanizing agent can be the various conventional vulcanizations for being used to make rubber molecular chain play cross-linking reaction
Agent, for example, can be insoluble sulfur and/or zinc oxide, preferably insoluble sulfur and zinc oxide.
When the vulcanizing agent is preferably insoluble sulfur and zinc oxide, with respect to the halogenated butyl rubber of 100 parts by weight, institute
The dosage for stating insoluble sulfur can be 0.1-2 parts by weight, preferably 0.3-1 parts by weight, more preferably 0.5-0.8 parts by weight；
With respect to the halogenated butyl rubber of 100 parts by weight, the dosage of the zinc oxide can be 0.05-8 parts by weight, and preferably 0.5-5 is heavy
Measure part, more preferably 1.5-3 parts by weight.Wherein, the zinc oxide is particularly preferably the nanometer that average particulate diameter is 1-100nm
Zinc oxide.
The insoluble sulfur is the allotrope of sulphur, and it does not dissolve in sulfur dioxide and other solvents, is also insoluble in
Rubber, exist in rubber with dispersity；After curing temperature is reached, these insoluble sulfurs being dispersed in rubber have
One " activation stage ", i.e. chain type depolymerisation, accelerate curingprocess rate.Insoluble sulfur dosage is reduced, is advantageous to improve rubber
The ageing properties of glue.
According to the present invention, the vulcanization accelerator can be it is existing it is various can shorten cure time, reduce vulcanization temperature
Degree, reduce vulcanizing agent dosage and improve the material of the mechanical property of rubber, for example, can be second, n-butyl dithiocarbamate
Zinc (trade name：Accelerant B Z), thiazole accelerator is (for example, the N- tert-butyl groups -2-[4-morpholinodithio base sulfenamide (trade name
For TBBS or NS), 2,2'- dibenzothiazyl disulfide (trade names：Altax), curing mercaptobenzothiazoler (commodity
It is entitled：Accelerant MBT S) etc.), the double thiamides (trade names of N, N '-tetramethyl two sulphur：Vulcanization accelerator TMTD), 4,4'- bis- thio two
Morpholine (trade name：Diphenylguanidine TDM), the N- tert-butyl groups-bis- (2-[4-morpholinodithio) sulfenamide (trade name：Accelerator
) and diphenylguanidine (trade name TBSI：Diphenylguanidine) in one or more.
According to the present invention, the activator is the activity for referring to increase vulcanization accelerator, and then reduces the vulcanization and promote
Enter the dosage of agent or shorten the material of cure time.The sulphidity of the rubber and resistance to can be significantly improved by adding a small amount of activating agent
It is hot.Activator of the present invention can be existing various activators, for example, can be stearic acid and/or polyethylene glycol.
Wherein, the equal molecule of the number of the polyethylene glycol can be 200-8000.
According to the present invention, in step (1), the condition of the banburying includes：The speed of rotor is 10-100rpm, is preferably
40-80rpm；Mixing temperature is 50-160 DEG C, preferably 80-150 DEG C；Banburying pressure is 0.1-0.5MPa, preferably 0.2-
0.4MPa；Mixing time is 1-10min, preferably 3-5min.In the present invention, the pressure refers to the absolute pressure of system.
The banburying equipment can be mixing facilities commonly used in the art, such as banbury.
Modified rubber, copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and the vulcanization that step (1) is obtained
The technique of heating melting and extruding pelletization can be realized by double screw extruder after accelerator is blended.The twin-screw
The condition of work of extruder includes：Screw speed is 200-600 revs/min, each zone temperatures (including feeding section is to melting extrusion
Section 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 of extruder can be 0.1-0.5MPa, and the draw ratio of double screw extruder is 56-60, and material is double
The residence time of screw extruder is 10-90s, preferably 30-45s.The draw ratio of the double screw extruder has for screw rod
Imitate the ratio of length and outer screw diameter.The modified rubber issues lively state sulphur in the condition of work of above-mentioned double screw extruder
Change.
In the preparation process of the rubber-plastic composition, in order to obtain the rubber-plastic composition being more uniformly distributed, in the melting
Before extruding pelletization, further preferably include modified rubber, copolymer nylon, long carbon chain nylon, the low density polyethylene for obtaining step (1)
Alkene, vulcanizing agent and vulcanization accelerator carry out just mixed step.The just mixed method and condition are known to the skilled person,
For example, modified rubber, copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and vulcanization accelerator can be added to
It is uniformly mixed in existing various mixing apparatus, wherein, the mixing apparatus for example can be mixer and/or kneading
Machine.The temperature and time being stirred is known to those skilled in the art, for example, the temperature being stirred can be 25-30
DEG C, the time being stirred can be 1-3 minutes.
Modified rubber, copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and the vulcanization that step (1) is obtained
Heating melting and extruding pelletization, obtain rubber-plastic composition after accelerator is blended.The rubber and plastic polymer so obtained has more
Good blowing property and machinability.The reason for possible is：Under conditions of heating, with copolymer nylon, long-chain-segment nylon with it is low
The mixture of density polyethylene is base resin, and the modified rubber of dynamic vulcanization can preferably disperse, formed modified rubber with
Structure of the structure disperses on " island " in " sea " of base resin.
In the case of, according to the invention it is preferred to, step (1) described banburying is carried out in the presence of auxiliary agent, and the auxiliary agent is uniform
One or more in agent, stabilizer and tackifier.
According to the present invention, the homogenizing agent can be that existing various can play promotes different relative molecular weights, difference
The material of the alternate processing characteristics for quickly and evenly mixing and rubber being improved of the glue of polarity and different viscosities.The homogenizing agent
Can be the group aliphatic resin and mixture of aromatic resin, the mixture of group aliphatic resin and cycloalkanes hydroxy-aromatic resin and fatty family tree
One or more in the mixture of fat, cycloalkanes hydroxy-aromatic resin and aromatic resin.Such as the fatty family tree purchased from German S.S companies
Fat and aromatic resin mixture (trade name 40MS) and group aliphatic resin and cycloalkanes hydroxy-aromatic resin (trade name 60NS), Germany
The mixture (trade name M40) of the group aliphatic resins of KETTLITZ companies, cycloalkanes hydroxy-aromatic resin and aromatic resin.
According to the present invention, the stabilizer is the various materials that can prevent ageing of rubber and degraded, such as can be ring
One or more in oxygen soybean oil, calcium stearate and magnesium stearate.
According to the present invention, the tackifier are the various materials that can improve product cohesive force, such as can be terpenes tree
One or more in fat, rosin resin, Petropols and phenolic resin.The phenolic resin can be octyl phenol formaldehyde tree
Fat (trade name HY-203), t-Butylphenol formaldehyde resin (trade name HY-204) and polynary alkylphenol formaldehyde resin (commodity
Name HY-2006) in one or more；The terpene resin can be α pinene resin, nopinene resin and terpene-styrene
One or more in resin；The rosin resin can be pentalyn, ester gum and hydrogenated rosin glycerine
One or more in ester；The Petropols can be aliphatic C5 Petropols and/or aromatic series C9 Petropols.
According to the present invention, in step (1), relative to the described halogenated butyl rubber of 100 parts by weight, the use of the auxiliary agent
Measure as 1-40 parts by weight.
Under preferable case, the modified rubber is made in the presence of homogenizing agent, stabilizer and tackifier, relative to 100
The halogenated butyl rubber of parts by weight, the dosage of the homogenizing agent is 1-10 parts by weight, more preferably 2-5 parts by weight, is most preferably
3-4 parts by weight；Relative to the halogenated butyl rubber of 100 parts by weight, the dosage of the stabilizer is 1-20 parts by weight, more preferably
5-15 parts by weight, most preferably 6-9 parts by weight；Relative to the halogenated butyl rubber of 100 parts by weight, the dosage of the tackifier is
1-10 parts by weight, more preferably 2-5 parts by weight, most preferably 3-4 parts by weight.
According to the present invention, step (2) is described to be blended in the presence of auxiliary agent and carries out, and the auxiliary agent is heat stabilizer, compatilizer
With the one or more in plasticizer.
According to the present invention, the plasticizer is can be with the various small molecule of the miscible mechanical property for changing nylon of nylon
Material.Such as the plasticizer can be N-butylbenzenesulfonamide and/or N- ethyl adjacency pair toluenesulfonamides.
According to the present invention, the heat stabilizer is being capable of thing compatible with nylon and can preventing nylon generation thermal degradation
Matter, such as the heat stabilizer can be hindered phenol type stabilizer, phosphite type stabilizer, copper halide type stabilizer and be obstructed
Two or more in amine type light stabilizer.
The present invention is not particularly limited to the species of the hindered phenol type stabilizer, for example, can be selected from four [β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester is (referred to as：Antioxidant 1010), 1,3,5- trimethyls -2,4,6- (3,
5- di-t-butyl -4- hydroxyphenylmethyls) benzene is (referred to as：Antioxidant 330), 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls)
Isocyanuric acid is (referred to as：Antioxidant 3114), N, N '-bis- (3- (3,5- di-tert-butyl-hydroxy phenyls) propionos) hexamethylene diamine (letter
Claim：Antioxidant 1098), three (2,4- di-tert-butyl-phenyls) phosphite esters (referred to as：Irgasfos 168) and β-(3,5- di-t-butyls-
4- hydroxy phenyls) the positive octadecanol ester of propionic acid is (referred to as：Antioxidant 1076) in one or more, particularly preferably β-(3,5-
Di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid is (referred to as：Antioxidant 1076) and/or N, N '-bis- (3- (uncles of 3,5- bis-
Butyl -4- hydroxy phenyls) propiono) hexamethylene diamine is (referred to as：Antioxidant 1098).
The present invention is also not particularly limited to the species of the phosphite type stabilizer, for example, can be selected from three (2,
4- di-tert-butyl-phenyls) phosphite ester is (referred to as：Irgasfos 168), double (2,4- DI-tert-butylphenol compounds) pentaerythrite diphosphorous acids
Ester is (referred to as：Antioxidant 626) and double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites are (referred to as：Antioxidant PEP-36)
In one or more, particularly preferably three (2,4- di-tert-butyl-phenyl) phosphite esters (168).
The present invention is also not particularly limited to the species of the copper halide type stabilizer, for example, cuprous iodide.
The present invention is also not particularly limited to the species of the hindered amine type light stabilizer, for example, succinic acid and (4- hydroxyls
The polymer of base -2,2,6,6- tetramethyl -1- piperidine alcohols) (abbreviation light stabilizer 622), the double -2,2,6,6- tetramethyls of decanedioic acid
Piperidines alcohol ester is (referred to as：Light stabilizer 770) and poly- { [6- [(1,1,3,3- tetramethyl butyls) amino]] -1,3,5- triazines -2,4-
[(2,2,6,6,-tetramethyl-4-piperidyl) imino group] -1,6- oneself two support [(2,2,6,6- tetramethyl -4- piperidyls) imino group]
(referred to as：Light stabilizer 944) in one or more.
According to the present invention, the compatilizer makes modified rubber more preferable to improve the compatibility of modified rubber and modified plastics
Ground is dispersed in the material in modified plastics.Such as the compatilizer can be that maleic anhydride is grafted ethylene propylene diene rubber, maleic acid
One or more in acid anhydride grafted polyethylene-octene copolymer and maleic anhydride grafted polyethylene, the grafting rate are 0.5-1.0
Weight %.
According to the present invention, in step (2), relative to the halogenated butyl rubber of 100 parts by weight, the dosage of the auxiliary agent is 1-
35 parts by weight.
Under preferable case, relative to the halogenated butyl rubber of 100 parts by weight, the dosage of the heat stabilizer is 0.1-5 weights
Measure part, more preferably 0.1-3 parts by weight, most preferably 0.5-1.5 parts by weight；Relative to the halogenated butyl rubber of 100 parts by weight,
The dosage of the compatilizer is 1-20 parts by weight, more preferably 5-15 parts by weight, most preferably 8-10 parts by weight；Relative to 100
The halogenated butyl rubber of parts by weight, the dosage of the plasticizer is 1-10 parts by weight, more preferably 2-8 parts by weight, is most preferably
4-6 parts by weight.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, the assay method for the parameter being related to is as follows：
1st, the isobutene content in brombutyl and isoprene content use the type purchased from Bruker companies of Switzerland
Number for BRUKER 400 nuclear magnetic resonance chemical analyser carry out hydrogen spectrum measure, wherein, solvent is deuterochloroform, and test temperature is normal
Temperature；
2nd, the measure of the density of low density polyethylene (LDPE) is with reference to GB/T 1033-2008 methods.
3rd, the measure of the melt mass flow rate of low density polyethylene (LDPE) is with reference to GB/T 3682-2000 methods, condition determination
Including：Measurement temperature is 190 DEG C, load 2.16kg.
4th, the measure of the relative viscosity of copolymer nylon and long-chain-segment nylon uses one point method, and condition determination is：25 DEG C, measure
Instrument is Ubbelohde viscometer, and capillary inner diameter 1.01-1.05mm, using the concentrated sulfuric acid as solvent, it is 1 weight that nylon is configured into concentration
Amount % concentrated sulfuric acid solution is measured.
In following examples and comparative example,
The brombutyl for the model 2255 that brombutyl produces for ExxonMobil companies, Mooney viscosity
(125 DEG C, 1+8) are 46, wherein, isobutene content is 98.7 weight %, and isoprene content is 1.3 weight %, the content of bromine
For 2 weight %；
The nylon for the trade mark 6106L that low molecule amount nylon produces for Weihui City Hong Yusu industry Co., Ltd, weight average molecular weight
For 15000 dalton；Copolymer nylon is the nylon (PA6/66 copolymer nylons) that the trade mark of Ube company production is 5033B,
Relative viscosity of the copolymer nylon in 1 weight % concentrated sulfuric acid solution is 4.5 centipoises；Long carbon chain nylon is the grand space modeling in Weihui City
The 1012H of industry Co., Ltd production, relative viscosity of the long carbon chain nylon in 1 weight % concentrated sulfuric acid solution is 4.2 centipoises；
Compatilizer is the maleic anhydride modified ethylene propylene diene rubber (EPDM) of ExxonMobil companies production, and the trade mark is
VA1803；
Low density polyethylene (LDPE) -1 is the low density polyethylene that the trade mark of Sinopec Beijing Yanshan Mountain branch company production is LD100AC
Alkene, density 0.923g/cm3, melt mass flow rate 2.0g/10min；
Low density polyethylene (LDPE) -2 is the low density polyethylene that the trade mark of Sinopec Beijing Yanshan Mountain branch company production is LD103
Alkene, density 0.921g/cm3, melt mass flow rate 1.0g/10min；
Low density polyethylene (LDPE) -3 is the low density polyethylene that the trade mark of Sinopec Beijing Yanshan Mountain branch company production is LD165
Alkene, density 0.922g/cm3, melt mass flow rate 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) by the brombutyl of 100 parts by weight, the low molecule amount nylon of 8 parts by weight, the stearic acid of 1 parts by weight, 6
The epoxidized soybean oil of parts by weight, 3 parts by weight tackifier HY-203 (Shanxi chemical research institute), the homogenizing agent 40MS (morals of 3 parts by weight
S.S companies of state) it is put at the beginning of banbury is carried out and mixes, the speed of rotor is 60rpm, and banburying is carried out at 80 DEG C, and banburying pressure is
0.3MPa, mixing time 3.5min, then obtained internal mixing film is granulated in rubber comminutor, obtains being modified rubber
Micelle；
(2) the modified rubber particle that obtains step (1), the zinc oxide of 2 parts by weight, 0.8 parts by weight insoluble sulfur,
The altax (Tianjin La Bo auxiliary agents Co., Ltd) of 2 parts by weight, the copolymer nylon of 30 parts by weight, the Long carbon chain Buddhist nun of 15 parts by weight
Dragon, the plasticizer N-butylbenzenesulfonamide (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 4 parts by weight, the heat of 0.5 parts by weight
Stabilizer Irganox B1171 (BASF AG), the compatilizer VA1803 (ExxonMobil companies) of 8 parts by weight, 16 weight
Stirred in the addition mixer of low density polyethylene (LDPE) -1 of part and at 25 DEG C after carrying out within 1 minute just mixing, the mixture of gained is sent
Enter to carry out blending heating melting, and the work of extruding pelletization, wherein double screw extruder in the double screw extruder that draw ratio is 56
Include as condition：The rotating speed of adjusting bolt is 300rpm, and each zone temperatures control respectively：150℃、225℃、235℃、240
DEG C, 240 DEG C and 235 DEG C；The vacuum of extruder remains 0.2MPa to 0.5MPa, and material is in the stop of double screw extruder
Between be 45s, obtain 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) by the brombutyl of 100 parts by weight, the low molecule amount nylon of 10 parts by weight, 2 parts by weight stearic acid,
The epoxidized soybean oil of 7.5 parts by weight, 3.5 parts by weight tackifier HY-203 (Shanxi chemical research institute), the homogenizing agent of 3.5 parts by weight
40MS (German S.S companies) is put into banbury and just mix, and the speed of rotor is 40rpm, and banburying is carried out at 100 DEG C, close
Refining pressure is 0.2MPa, mixing time 4min, then obtained internal mixing film is granulated in rubber comminutor, is obtained
Modified rubber particle；
(2) the modified rubber particle that obtains step (1), the zinc oxide of 3 parts by weight, 0.5 parts by weight insoluble sulfur,
Altax (Tianjin La Bo auxiliary agents Co., Ltd), the copolymer nylon of 50 parts by weight, the Long carbon chain of 20 parts by weight of 1.0 parts by weight
Nylon, the plasticizer N-butylbenzenesulfonamides (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 6 parts by weight, 1.5 parts by weight
Heat stabilizer Irganox B1171 (BASF AG), 10 parts by weight compatilizer VA1803 (ExxonMobil companies), 12 weights
Stirred in the addition mixer of low density polyethylene (LDPE) -2 of amount part and at 25 DEG C after carrying out within 2 minutes just mixing, by the mixture of gained
It is 56 to carry out in double screw extruder blending heating melting and extruding pelletization, wherein double screw extruder to be sent into draw ratio
Condition of work includes：The rotating speed of adjusting bolt is 600rpm, and each zone temperatures control respectively：150℃、225℃、230℃、
235 DEG C, 240 DEG C and 235 DEG C；The vacuum of extruder remains 0.2MPa to 0.5MPa, and material stops double screw extruder
It is 35s to stay the time, 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 brombutyl of 100 parts by weight, the low molecule amount nylon of 12 parts by weight, 1.5 parts by weight tristearin
Acid, the epoxidized soybean oil of 8 parts by weight, 4 parts by weight tackifier HY-203 (Shanxi chemical research institute), the homogenizing agent of 4 parts by weight
40MS (German S.S companies), it is put at the beginning of banbury is carried out and mixes, the speed of rotor is 80rpm, and banburying is carried out at 150 DEG C, close
Refining pressure is 0.4MPa, mixing time 5min, then obtained internal mixing film is granulated in rubber comminutor, is obtained
Modified rubber particle；
(2) modified rubber particle, the zinc oxide of 3 parts by weight, the insoluble sulfur of 0.65 parts by weight obtained step (1)
Sulphur, 1.5 parts by weight altax (Tianjin La Bo auxiliary agents Co., Ltd) 40 parts by weight copolymer nylon, the long carbon of 17 parts by weight
Chain nylon, the plasticizer N-butylbenzenesulfonamides (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 5 parts by weight, 1 parts by weight
Heat stabilizer Irganox B1171 (BASF AG), 9 parts by weight compatilizer VA1803 (ExxonMobil companies), 14 weights
Stirred in the addition mixer of low density polyethylene (LDPE) -3 of amount part and at 25 DEG C after carrying out within 2 minutes just mixing, by the mixture of gained
It is sent into the double screw extruder that draw ratio is 56 and carries out the work of blending heating melting and extruding pelletization, wherein double screw extruder
Include as condition：The rotating speed of adjusting bolt is 400rpm, and each zone temperatures control respectively：160℃、225℃、235℃、240
DEG C, 240 DEG C and 235 DEG C；The vacuum of extruder remains 0.2MPa to 0.5MPa, and material is in the stop of double screw extruder
Between be 42s, obtain 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) by the brombutyl of 100 parts by weight, the low molecule amount nylon of 10 parts by weight, 2 parts by weight stearic acid,
The epoxidized soybean oil of 7.5 parts by weight, 3.5 parts by weight tackifier HY-203 (Shanxi chemical research institute), the homogenizing agent of 3.5 parts by weight
40MS (German S.S companies) is put into banbury and just mix, and the speed of rotor is 60rpm, and banburying, banburying are carried out at 80 DEG C
Pressure is 0.3MPa, mixing time 3.5min, and then obtained internal mixing film is sent into rubber comminutor and is granulated, is obtained
To modified rubber particle；
(2) the modified rubber particle that obtains step (1), the zinc oxide of 4 parts by weight, 0.5 parts by weight insoluble sulfur,
The copolymer nylon of altax (Tianjin La Bo auxiliary agents Co., Ltd) 50 parts by weight of 1.0 parts by weight, the Long carbon chain Buddhist nun of 1 parts by weight
Dragon, the plasticizer N-butylbenzenesulfonamide (Beijing Tongdao Hecheng Science and Technology Development Co., Ltd.) of 6 parts by weight, the heat of 1.5 parts by weight
Stabilizer Irganox B1171 (BASF AG), the compatilizer VA1803 (ExxonMobil companies) of 10 parts by weight, 12 weight
The low density polyethylene (LDPE) of part is carried out after just mixing, and blending is carried out in double screw extruder and heats melting and extruding pelletization, wherein double
The condition of work of screw extruder includes：The rotating speed of adjusting bolt is 500rpm, and each zone temperatures control respectively：180℃、
225 DEG C, 230 DEG C, 225 DEG C, 225 DEG C and 235 DEG C；The vacuum of each section remains 0.2MPa to 0.5MPa, and material is in double spiral shells
The residence time of bar extruder is 38s, obtains rubber-plastic composition A4.
Prepare comparative example 1
This comparative example is used to illustrate reference rubber-plastic composition and preparation method thereof.
Method according to preparation example 2 prepares rubber-plastic composition, unlike, it is added without low density polyethylene in step (2)
Alkene -2, obtain reference rubber-plastic composition DA1.
Embodiment 1-4
By the rubber-plastic composition A1-A4 prepared in preparation example 1-4 respectively in inflation film manufacturing machine (ALPHA companies, model
AMT100 on), using flat crowded upward type, the blown film experiment of thermoplastic elastomer (TPE) is carried out, each zone temperatures of inflation film manufacturing machine are controlled respectively
System exists：150 DEG C, 220 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C, it is respectively 25 μm, 30 μm, 35 μm, 40 μm to obtain thickness
Film.
Comparative example 1
Using carrying out blown film with the rubber-plastic composition DA1 prepared in comparative example 1 will be prepared by the way of embodiment 1-4, obtain
Thickness is 30 μm of reference film, it is observed that obtained thermoplastic film is apparent uneven.
Test case
This test case is used for the measure for illustrating the performance of film provided by the invention.
Above-described embodiment 1-4 and comparative example 1 are obtained into film and carry out performance test, test result is shown in Table 1, and the performance is surveyed
Examination includes：
(1) maximum blow-up ratio：Under the premise of ensureing that film bubble is not destroyed, film bubble is blown to maximum as far as possible, vesicle diameter with
The ratio of port mould diameter；
(2) determined with reference to GB/T1040-2006：Elongation is broken in horizontal elongation rate of tensile failure, laterally 50% stress at definite elongation, longitudinal direction
50% stress at definite elongation of rate and longitudinal direction, determining instrument is tensilon (INSTRON companies of the U.S., model 5566)；
(3) with reference to GB/T1038-2000 measure oxygen permeability coefficients, sensing equipment is Jinan blue streak VAC-V2 type pressure differential methods
Gas permeability tester, condition determination are 23 DEG C.
(4) rubber phase particle diameter distribution：Carried out using AFM (types of Multimode 8, German BRUKER companies)
Observation, and rubber phase size is counted, rubber phase particle diameter normal distribution is obtained, rubber phase is calculated by statistical method
Particle size.
Table 1
From the results shown in Table 1, added on a small quantity in the dynamic vulcanization system of modified rubber and nylon mixture
Low density polyethylene (LDPE), it can be good at improving inflation of the rubber-plastic composition during the blown film when transverse and longitudinal performance of film
Otherness, while obtained film is apparent more uniform.Although the addition of low density polyethylene (LDPE) can cause the air-tightness meeting of film
Decline, but comparatively, the degree of decline is little, still with excellent air-tightness；Secondly, film made from the preparation method
Rubber phase particle diameter it is small and particle diameter distribution is narrower.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of preparation method of rubber-plastic composition, this method include：
(1) halogenated butyl rubber, low molecule amount nylon and activator are subjected to banburying and granulation, obtain modified rubber；
(2) modified rubber, copolymer nylon, long carbon chain nylon, low density polyethylene (LDPE), vulcanizing agent and the vulcanization for obtaining step (1)
Heating melting and extruding pelletization after accelerator is blended,
Wherein, the weight average molecular weight of the low molecule amount nylon is 5000-25000 dalton, the low density polyethylene (LDPE) according to
The melt mass flow rate of GB/T3682-2000 measure is 0.1-10g/10min, and the density of the low density polyethylene (LDPE) is
0.915-0.925g/cm3,
With respect to the halogenated butyl rubber of 100 parts by weight, the dosage of the low molecule amount nylon is 1-20 parts by weight, described common
The dosage of poly- nylon is 10-80 parts by weight, and the dosage of the long carbon chain nylon is 1-30 parts by weight, the low density polyethylene (LDPE)
Dosage is 1-30 parts by weight, and the dosage of the vulcanizing agent is 0.15-10 parts by weight, and the dosage of the vulcanization accelerator is 0.1-5
Parts by weight, the dosage of the activator is 0.1-5 parts by weight.
2. according to the method for claim 1, wherein, the low density polyethylene (LDPE) determines molten according to GB/T3682-2000
Weight flow rate is 0.2-5g/10min, and the density of the low density polyethylene (LDPE) is 0.920-0.923g/cm3。
3. the method according to claim 11, wherein, on the basis of the weight of the halogenated butyl rubber, the halogenation fourth
Content of halogen in base rubber is 1-2.5 weight %, and the halogen is chlorine and/or bromine, and the Mooney of the halogenated butyl rubber glues
Spend for 28-60.
4. according to the method for claim 1, wherein, the weight average molecular weight of the low molecule amount nylon is 12000-18000
Dalton.
5. according to the method for claim 1, wherein, the low molecule amount nylon is selected from nylon 6, nylon66 fiber, nylon 11, Buddhist nun
One or more in dragon 12 and NYLON610；The copolymer nylon be selected from nylon 6 and nylon66 fiber copolymer and/or nylon 6 with
The copolymer of NYLON610；The long carbon chain nylon in nylon 1010, Nylon 1012, nylon 11 12 and nylon 1212 one
Kind is a variety of.
6. method according to claim 1 or 5, wherein, phase of the copolymer nylon in 1 weight % concentrated sulfuric acid solution
It is 2-8 centipoises to viscosity；Relative viscosity of the long carbon chain nylon in 1 weight % concentrated sulfuric acid solution is 2-8 centipoises.
7. according to the method for claim 1, wherein, the vulcanizing agent is insoluble sulfur and/or zinc oxide；The vulcanization
Accelerator is zinc dibutyl dithiocaarbamate, the N- tert-butyl groups -2-[4-morpholinodithio base sulfenamide, 2,2'- curing two
Benzothiazole, curing mercaptobenzothiazoler, N, N '-sulphur of tetramethyl two double thiamides, 4,4'- dithio morpholines, the tertiary fourths of N-
One or more in base-bis- (2-[4-morpholinodithio) sulfenamide and diphenylguanidine；The activator is stearic acid and/or poly- second
Glycol.
8. according to the method for claim 1, wherein, in step (1), the condition of the banburying includes：The speed of rotor is
10-100rpm；Mixing temperature is 50-160 DEG C；Banburying pressure is 0.1-0.5MPa；Mixing time is 1-10min.
9. according to the method for claim 1, wherein, step (1) described banburying is carried out in the presence of auxiliary agent, relative to 100
The halogenated butyl rubber of parts by weight, the dosage of the auxiliary agent is 1-40 parts by weight.
10. according to the method for claim 9, wherein, the auxiliary agent be homogenizing agent, stabilizer and tackifier in one kind or
A variety of, the tackifier are the one or more in terpene resin, rosin resin, Petropols and phenolic resin；The stabilization
Agent is the one or more in epoxidized soybean oil, calcium stearate and magnesium stearate；The homogenizing agent is group aliphatic resin and fragrance
The mixture of resin, the mixture of group aliphatic resin and cycloalkanes hydroxy-aromatic resin and group aliphatic resin, cycloalkanes hydroxy-aromatic resin and fragrant family tree
One or more in the mixture of fat.
11. according to the method for claim 1, wherein, step (2) is described to be blended in the presence of auxiliary agent and carries out, relative to 100
The halogenated butyl rubber of parts by weight, the dosage of the auxiliary agent is 1-35 parts by weight.
12. according to the method for claim 11, wherein, the auxiliary agent is one in heat stabilizer, compatilizer and plasticizer
Kind is a variety of, and the heat stabilizer is hindered phenol type antioxidant, phosphite type antioxidant, copper halide type stabilizer and hindered amine
Two or more in type light stabilizer；The compatilizer is that maleic anhydride is grafted ethylene propylene diene rubber, maleic anhydride grafting gathers
One or more in ethylene-octene copolymer and maleic anhydride grafted polyethylene；The plasticizer is N-butylbenzenesulfonamide
And/or N- ethyl adjacency pair toluenesulfonamides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514226.3A CN105524362B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of rubber-plastic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410514226.3A CN105524362B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of rubber-plastic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105524362A CN105524362A (en) | 2016-04-27 |
| CN105524362B true CN105524362B (en) | 2017-12-22 |
Family
ID=55766906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410514226.3A Active CN105524362B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of rubber-plastic composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105524362B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164842A (en) * | 2016-12-08 | 2018-06-15 | 北京橡胶工业研究设计院有限公司 | Modified brominated butyl rubber composition and preparation method thereof |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0969039A1 (en) * | 1998-01-13 | 2000-01-05 | The Yokohama Rubber Co., Ltd. | Thermoplastic elastomer composition, process for producing the same, and pneumatic tire and hose made with the same |
| JP2001239805A (en) * | 2001-03-07 | 2001-09-04 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| CN101296997A (en) * | 2005-10-27 | 2008-10-29 | 埃克森美孚化学专利公司 | Low-osmosis thermoplastic elastomer composition |
| CN101305046A (en) * | 2005-11-09 | 2008-11-12 | 埃克森美孚化学专利公司 | Thermoplastic elastomer compositions and methods for making the same |
| CN102066475A (en) * | 2008-06-13 | 2011-05-18 | 埃克森美孚化学专利公司 | Process for preparing dynamically vulcanized alloys |
-
2014
- 2014-09-29 CN CN201410514226.3A patent/CN105524362B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0969039A1 (en) * | 1998-01-13 | 2000-01-05 | The Yokohama Rubber Co., Ltd. | Thermoplastic elastomer composition, process for producing the same, and pneumatic tire and hose made with the same |
| JP2001239805A (en) * | 2001-03-07 | 2001-09-04 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| CN101296997A (en) * | 2005-10-27 | 2008-10-29 | 埃克森美孚化学专利公司 | Low-osmosis thermoplastic elastomer composition |
| CN101305046A (en) * | 2005-11-09 | 2008-11-12 | 埃克森美孚化学专利公司 | Thermoplastic elastomer compositions and methods for making the same |
| CN102066475A (en) * | 2008-06-13 | 2011-05-18 | 埃克森美孚化学专利公司 | Process for preparing dynamically vulcanized alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105524362A (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105524357B (en) | A kind of TPV and preparation method thereof | |
| JP5657660B2 (en) | Pneumatic tire with self-sealing ply fitted | |
| CN102725151B (en) | Elastomeric composition for a tire object having a self-sealing property | |
| CN104822764B (en) | Heat-proof aging ethylene vinyl acetate copolymer composition and preparation method thereof | |
| CN102548743A (en) | Tire including a built-in self-sealing and protective layers | |
| JP6018248B2 (en) | tire | |
| Hou et al. | Fabricating 3D printable BIIR/PP TPV via masterbatch and interfacial compatibilization | |
| WO2013179691A1 (en) | Pneumatic tire | |
| CN108137866A (en) | Tyre assembly elastic composition and the tire for including them | |
| CA2190678A1 (en) | Process for preparing elastomeric compounds from granular elastomers and polymers and articles manufactured therefrom | |
| US20100308495A1 (en) | Process for the manufacture of reactive rubber process aids | |
| JP2001113908A (en) | Tire having air permeation preventing layer | |
| JP7053242B2 (en) | Thermoplastic resin composition for pneumatic tire inner liner | |
| CN105524362B (en) | A kind of preparation method of rubber-plastic composition | |
| CN103102578B (en) | Low temperature-resistant thermoplastic elastomer and preparation method thereof | |
| CN105524361B (en) | A kind of thermoplastic vulcanizate composition and preparation method thereof and film | |
| CN115433441A (en) | Full-biodegradable material and preparation method thereof | |
| CN111479872B (en) | Thermoplastic elastomer composition for tire and tire | |
| US9267025B2 (en) | Method for producing thermoplastic elastomer composition | |
| CN105440465B (en) | A kind of rubber-plastic composition and preparation method thereof and film | |
| AU714474B2 (en) | Package for compounding rubber, compounded rubber and tire having tread thereof | |
| JP2017114974A (en) | Air permeation-resistant film and production method of pneumatic tire | |
| CN106957508A (en) | A kind of heat-resistant antifriction thermoplastic elastomer (TPE) and preparation method thereof | |
| CN112759816B (en) | Composition for preparing halogen-free flame-retardant ethylene octene copolymer/polylactic acid thermoplastic elastomer, and preparation method and application thereof | |
| CN108299750A (en) | Thermoplastic vulcanizate composition and elastomer and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |