CN106519711A - Low-hardness tear-resistant and high-temperature-resistant TPE and preparation method thereof - Google Patents
Low-hardness tear-resistant and high-temperature-resistant TPE and preparation method thereof Download PDFInfo
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Abstract
The invention discloses low-hardness tear-resistant and high-temperature-resistant TPE. Raw materials of the low-hardness tear-resistant and high-temperature-resistant TPE include, by weight, 50-200 parts of a hydrogenated styrene-butadiene-styrene segmented copolymer, 100-300 parts of processing oil, 20-80 parts of polyolefin elastomer, 20-80 parts of polypropylene, 20-40 parts of a compound flexibilizer, 50-150 parts of filler and 0.5-4 parts of an antioxidant. The invention further discloses a preparation method of the low-hardness tear-resistant and high-temperature-resistant TPE mentioned above. The preparation method includes the following steps that S1, the hydrogenated styrene-butadiene-styrene segmented copolymer and the processing oil are taken and mixed, and then the antioxidant, the filler, the polypropylene, the polyolefin elastomer and the compound flexibilizer are sequentially added and mixed to obtain a material A; and S2, the material A obtained in the step S1 is subjected to melt extrusion through a twin-screw extruder, cooled and granulated to obtain the low-hardness tear-resistant and high-temperature-resistant TPE. The low-hardness tear-resistant and high-temperature-resistant TPE is soft in touch sense, high in strength, high in rebound elasticity, resistant to the high temperature and high in tearing strength.
Description
Technical field
The present invention relates to thermoplastic elastomer (TPE) technical field, more particularly to a kind of soft anti tear high temperature resistant TPE and its
Preparation method.
Background technology
Thermoplastic elastomer (TPE) (Thermoplastic Elastomer, abbreviation TPE) is that a class has rubber at normal temperatures
High resiliency, high intensity, high resilience, at high temperature plasticization molding again are convenient to process, the height of the particular advantages such as recoverable
Molecular material.The soft-touch of TPE, fatigue resistance have excellent weather resistance, and have good toleration to ozone, ultraviolet, electric arc,
Which both can be separately formed, it is also possible to the material coating and bonding such as polypropylene, polyethylene, Merlon, polystyrene.
At present, from shore 35A to shore 55D, maximum operation (service) temperature scope is at 80 DEG C to 135 for the hardness range of TPE material
DEG C so as to range of application is restricted, when particularly requiring all very high to low compression set deformation and high temperature resistant so as to should
With bringing great inconvenience；In addition, the relative mechanical property of general low-durometer material is weaker, hardness is less than shore on the market
The tensile strength of the material of 45A is not more than 8MPA, and pants type tearing strength is typically also not more than 8kN/m, which has limited TPE material and exist
Application in terms of soft, tear-resistant material.
The content of the invention
Based on background technology exist technical problem, the present invention propose a kind of soft anti tear high temperature resistant TPE and its
Preparation method, soft-touch of the present invention, intensity height, resilience height, high temperature resistant, tearing toughness are high.
A kind of soft anti tear high temperature resistant TPE proposed by the present invention, its raw material include by weight：Hydrogenated styrene-
Butadiene-styrene block copolymer 50-200 parts, processing oil 100-300 parts, polyolefin elastomer 20-80 parts, polypropylene 20-
80 parts, composite toughing agent 20-40 parts, filler 50-150 parts, antioxidant 0.5-4 parts.
Preferably, the weight portion of hydrogenated styrene-butadiene-styrene block copolymers can for 60,65,70,75,
80、85、90、95、100、105、110、115、120、125、130、135、140、145、150、155、160、165、170、175、
180、185、190。
Preferably, hydrogenation of the weight average molecular weight for 27-30 ten thousand in hydrogenated styrene-butadiene-styrene block copolymers
The content of styrene butadiene styrene block copolymer (SBS) is not less than 50wt%, hydrogenation of benzene second of the weight average molecular weight less than 100,000
The content of alkene-butadiene-styrene block copolymer is not less than 10wt%.
Preferably, weight average molecular weight is benzene second in the hydrogenated styrene-butadiene-styrene block copolymers of 27-30 ten thousand
The content of alkene is 27-33wt%, and weight average molecular weight is less than in 100,000 hydrogenated styrene-butadiene-styrene block copolymers
Cinnamic content is 16-20wt%.
Preferably, the weight portion of composite toughing agent can for 21,22,23,24,25,26,27,28,29,30,31,32,
33、34、35、36、37、38、39。
Preferably, in the preparation process of composite toughing agent, after sodium-based montmorillonite and water ultrasonic disperse uniform, ten are added
Six alkyl trimethyl ammonium bromide aqueous solutions, heat up, and filter cake is filtered to take in stirring, is washed, be dry, pulverize and obtain modified montmorillonoid；Will
During aramid fiber adds vinyltrimethoxy silane ethanol solution, heat up, ultrasound filters to take filter cake, washs, is dried to obtain and changes
Property aramid fiber；Modified montmorillonoid, modification of aramid fiber, MA-g-PP compatilizers, polypropylene are mixed, Jing Double-screws machine is squeezed
Go out to obtain composite toughing agent.
Preferably, in the preparation process of composite toughing agent, after sodium-based montmorillonite and water ultrasonic disperse uniform, ten are added
Six alkyl trimethyl ammonium bromide aqueous solutions, are warming up to 30-40 DEG C, with the speed stirring 1.5-2.5h of 800-1000r/min, filter
Filter cake is taken, is washed, be dry, pulverize to 200-400 mesh and obtain modified montmorillonoid；Aramid fiber is added into vinyl trimethoxy silicon
In alkane ethanol solution, 50-60 DEG C being warming up to, power being adjusted to 200-300W, ultrasonic 3-4h filters to take filter cake, it is washing, dry
To modification of aramid fiber；Modified montmorillonoid, modification of aramid fiber, MA-g-PP compatilizers, polypropylene are mixed, 110- is warming up to
140 DEG C, Jing Double-screws machine extrusion obtains composite toughing agent.
Preferably, in the preparation process of composite toughing agent, cetyl trimethylammonium bromide aqueous solution need to be adjusted with hydrochloric acid
Section pH=6-7.
Preferably, in the preparation process of composite toughing agent, the mass fraction of vinyltrimethoxy silane ethanol solution
For 1-3wt%.
Preferably, in the preparation process of composite toughing agent, sodium-based montmorillonite, water, cetyl trimethylammonium bromide
Weight ratio is 7-9：600-700：2.9-3.8.
Preferably, in the preparation process of composite toughing agent, aramid fiber, the weight ratio of vinyltrimethoxy silane are
10-15：1-3.
Preferably, in the preparation process of composite toughing agent, modified montmorillonoid, modification of aramid fiber, MA-g-PP are compatible
Agent, polyacrylic weight ratio are 0.3-0.4：0.05-0.15：0.5-0.7：15-20.
Preferably, the weight portion of processing oil can for 110,120,130,140,150,160,170,180,190,200,
210、220、230、240、250、260、270、280、290。
Preferably, processing oil be paraffin oil, naphthenic oil, at least one in aromatic naphtha.
Preferably, the kinematic viscosity (100 DEG C) of processing oil is 10-40mm2/s。
Preferably, the weight portion of polyolefin elastomer can be 25,30,35,40,45,50,55,60,65,70,75.
Preferably, polyolefin elastomer be ethylene-octene polyolefin elastomer, in Ethylene/Butylene polyolefin elastomer
It is at least one.
Preferably, polyolefin elastomer melt index (190 DEG C of 2.16Kg) is 0.5-10g/10min, Mooney viscosity (ML
(1+4) 121 DEG C) for 3-30.
Preferably, polyacrylic weight portion can be 25,30,35,40,45,50,55,60,65,70,75.
Preferably, polypropylene be COPP, at least one in HOPP.
Preferably, polyacrylic bending moduluses are not more than 1100MPa, and melt index is 0.5-5g/10min.
Preferably, the weight portion of filler can be 60,70,80,90,100,110,120,130,140.
Preferably, filler is Pulvis Talci, kieselguhr, Calcium Carbonate, at least one in clay.
Preferably, the weight portion of antioxidant can be 1,1.5,2,2.5,3,3.5.
Preferably, antioxidant be antioxidant 1010, at least one in antioxidant 1790, irgasfos 168.
The invention allows for the preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, be warming up to 40-80 DEG C, mix 10-
30min, then sequentially adds antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent, continues mixing 10-20min
Obtain material A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE.
Preferably, in S2, the feeding rotating speed of double screw extruder is 30-80r/min, and screw speed is 200-400r/
Min, screw slenderness ratio are 40-64, and processing temperature is 140-240 DEG C.
Preferably, processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, 185 DEG C of three area's temperature, 4th area
190 DEG C of temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature, ten area's temperature 215
DEG C, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
In the preparation process of above-mentioned composite toughing agent, the effect of hydrochloric acid is to adjust pH, does not specify its concentration, does not specify 16
The concentration of alkyl trimethyl ammonium bromide aqueous solution, determines its concentration according to concrete operations.
In the preparation process of above-mentioned composite toughing agent, MA-g-PP is bulking agent, is commercially available.
The present invention can carry out post-production by injection, blowing, extrusion.
The hydrogenated styrene-butadiene-styrene block copolymers that the present invention is selected have good tensile strength, resilience
Property, impact resistance and ageing resistance are good with polypropylene compatible；Polyolefin elastomer has that density is little, bending is big, low temperature impact
Hit performance height, high temperature resistant, easy processing, it is reusable the features such as；Polypropylene has that density is little, stress cracking resistance is good, wear-resisting
High, the heat-resist and good chemical stability of property；Three cooperates, and the present invention can be kept to have soft, sense of touch
While soft, the resistance to elevated temperatures and tear resistance of the present invention are greatly improved；Antioxidant can further increase the present invention
Aging resistance, antioxygenic property；Filler, hydrogenated styrene-butadiene-styrene block copolymers, polyolefin elastomer, poly- third
Alkene cooperates can further increase the shock resistance of the present invention；Montmorillonite high temperature resistant, good impact resistance；Aramid fiber weight
Amount is light, good shock resistance, high temperature resistant, good toughness；It is modified to montmorillonite intercalation from cetyl trimethylammonium bromide, expand
The interlamellar spacing of montmorillonite, is grafted aramid fiber from vinyltrimethoxy silane, increased the nonpolar of aramid fiber,
In the presence of bulking agent MA-g-PP so that montmorillonite, aramid fiber are dispersed in polypropylene, polypropylene intercalation is entered and is covered
Between de- soil layer, and montmorillonite is partially stripped, then with hydrogenated styrene-butadiene-styrene block copolymers, polyolefin elastic
Body, polypropylene are dispersed, and hydrogenated styrene-butadiene-styrene block copolymers, polyolefin elastomer, polypropylene can be with
Further intercalation enters montmorillonite, and be connected with the modification of aramid fiber crosslinking outside layer, so as to greatly increase intensity of the invention,
Shock resistance, toughness, resilience, tear resistance, prevention crackle are produced；Composite toughing agent is cooperated with filler, can be with
Further increase the shock resistance of the present invention；From the SEBS block copolymerization of high low-molecular-weight
Thing is coordinated according to proper ratio with ethylene octane copolymer, polypropylene, increases triangular viscosity intensity, so as to increase the present invention
Tensile strength and tear resistance；Each material is prepared using dynamic blending technology according to rational proportioning and production technology
The present invention so that the present invention has good elasticity, compression resistant morphotropism, high temperature resistant, resistance to ag(e)ing and mechanical property.
Specific embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of soft anti tear high temperature resistant TPE, its raw material include by weight：SEBS
100 parts of block copolymer, 200 parts of processing oil, 50 parts of polyolefin elastomer, 50 parts of polypropylene, 30 parts of composite toughing agent, filler
100 parts, 2 parts of antioxidant.
The preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, are warming up to 60 DEG C, mix 20min,
Then antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent are sequentially added, is continued mixing 15min and is obtained material
A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE.
Embodiment 2
A kind of soft anti tear high temperature resistant TPE, its raw material include by weight：SEBS
50 parts of block copolymer, kinematic viscosity (100 DEG C) are 40mm2100 parts of the paraffin oil of/s, melt index (190 DEG C of 2.16Kg) is
10g/10min, Mooney viscosity (121 DEG C of ML (1+4)) is 3 80 parts of ethylene-octene polyolefin elastomer, and bending moduluses are
1100MPa, COPP 80 part of the melt index for 0.5g/10min, 20 parts of composite toughing agent, 150 parts of Pulvis Talci, antioxygen
1,010 0.5 parts of agent；
Wherein, in hydrogenated styrene-butadiene-styrene block copolymers, weight average molecular weight is 270,000 hydrogenation of benzene second
The content of alkene-butadiene-styrene block copolymer be 50wt%, weight average molecular weight be 90,000 hydrogenated styrene-butadiene-
The content of styrene block copolymer is 50wt%.
The preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, are warming up to 40 DEG C, mix 30min,
Then antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent are sequentially added, is continued mixing 10min and is obtained material
A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE, wherein, the feeding rotating speed of double screw extruder is 80r/min, and screw speed is 200r/min, screw slenderness ratio
For 64, processing temperature is 140-240 DEG C, and processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, three area's temperature
185 DEG C, 190 DEG C of four area's temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature,
Ten 215 DEG C of area's temperature, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
Embodiment 3
A kind of soft anti tear high temperature resistant TPE, its raw material include by weight：SEBS
200 parts of block copolymer, kinematic viscosity (100 DEG C) are 10mm2300 parts of the naphthenic oil of/s, melt index (190 DEG C of 2.16Kg)
For 0.5g/10min, Mooney viscosity (121 DEG C of ML (1+4)) is 30 20 parts of Ethylene/Butylene polyolefin elastomer, and bending moduluses are
1050MPa, HOPP 20 part of the melt index for 5g/10min, 40 parts of composite toughing agent, 50 parts of kieselguhr, antioxidant
1790 4 parts；
Wherein, in hydrogenated styrene-butadiene-styrene block copolymers, weight average molecular weight is 300,000 hydrogenation of benzene second
The content of alkene-butadiene-styrene block copolymer is 90wt%, and weight average molecular weight is 8.5 ten thousand hydrogenated styrene-fourth two
The content of alkene-styrene block copolymer is 10wt%；
In the preparation process of composite toughing agent, after sodium-based montmorillonite and water ultrasonic disperse uniform, addition is adjusted with hydrochloric acid
The cetyl trimethylammonium bromide aqueous solution of section pH=7, is warming up to 30 DEG C, with the speed stirring 1.5h of 1000r/min, filters
Filter cake is taken, is washed, be dry, pulverize to 400 mesh and obtain modified montmorillonoid；It is 3wt% ethylene that aramid fiber is added mass fraction
In base trimethoxy silane ethanol solution, 50 DEG C are warming up to, power are adjusted to 300W, ultrasonic 3h filters to take filter cake, wash, do
It is dry to obtain modification of aramid fiber；Modified montmorillonoid, modification of aramid fiber, MA-g-PP compatilizers, polypropylene are mixed, is warming up to
140 DEG C, Jing Double-screws machine extrusion obtains composite toughing agent, wherein, sodium-based montmorillonite, water, cetyl trimethylammonium bromide
Weight ratio be 7：700：2.9, aramid fiber, the weight ratio of vinyltrimethoxy silane are 15：1, it is modified montmorillonoid, modified
Aramid fiber, MA-g-PP compatilizers, polyacrylic weight ratio are 0.4：0.05：0.7：15.
The preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, are warming up to 80 DEG C, mix 10min,
Then antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent are sequentially added, is continued mixing 20min and is obtained material
A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE, wherein, the feeding rotating speed of double screw extruder is 30r/min, and screw speed is 400r/min, screw slenderness ratio
For 40, processing temperature is 140-240 DEG C, and processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, three area's temperature
185 DEG C, 190 DEG C of four area's temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature,
Ten 215 DEG C of area's temperature, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
Embodiment 4
A kind of soft anti tear high temperature resistant TPE, its raw material include by weight：SEBS
90 parts of block copolymer, kinematic viscosity (100 DEG C) are 30mm2150 parts of the aromatic naphtha of/s, melt index (190 DEG C of 2.16Kg) is
8g/10min, Mooney viscosity (121 DEG C of ML (1+4)) is 10 60 parts of ethylene-octene polyolefin elastomer, and bending moduluses are
1000MPa, COPP 70 part of the melt index for 2g/10min, 25 parts of composite toughing agent, 120 parts of Calcium Carbonate, antioxidant
168 2 parts；
Wherein, in hydrogenated styrene-butadiene-styrene block copolymers, weight average molecular weight is 280,000 hydrogenation of benzene second
The content of alkene-butadiene-styrene block copolymer be 80wt%, weight average molecular weight be 80,000 hydrogenated styrene-butadiene-
The content of styrene block copolymer is 20wt%；
Weight average molecular weight be 280,000 hydrogenated styrene-butadiene-styrene block copolymers in cinnamic content be
33wt%, weight average molecular weight be 80,000 hydrogenated styrene-butadiene-styrene block copolymers in cinnamic content be
16wt%；
In the preparation process of composite toughing agent, after sodium-based montmorillonite and water ultrasonic disperse uniform, addition is adjusted with hydrochloric acid
The cetyl trimethylammonium bromide aqueous solution of section pH=6, is warming up to 40 DEG C, with the speed stirring 2.5h of 800r/min, filters
Filter cake is taken, is washed, be dry, pulverize to 200 mesh and obtain modified montmorillonoid；It is 1wt% ethylene that aramid fiber is added mass fraction
In base trimethoxy silane ethanol solution, 60 DEG C are warming up to, power are adjusted to 200W, ultrasonic 4h filters to take filter cake, wash, do
It is dry to obtain modification of aramid fiber；Modified montmorillonoid, modification of aramid fiber, MA-g-PP compatilizers, polypropylene are mixed, is warming up to
110 DEG C, Jing Double-screws machine extrusion obtains composite toughing agent, wherein, sodium-based montmorillonite, water, cetyl trimethylammonium bromide
Weight ratio be 9：600：3.8, aramid fiber, the weight ratio of vinyltrimethoxy silane are 10：3, it is modified montmorillonoid, modified
Aramid fiber, MA-g-PP compatilizers, polyacrylic weight ratio are 0.3：0.15：0.5：20.
The preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, are warming up to 50 DEG C, mix 25min,
Then antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent are sequentially added, is continued mixing 12min and is obtained material
A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE, wherein, the feeding rotating speed of double screw extruder is 70r/min, and screw speed is 250r/min, screw slenderness ratio
For 55, processing temperature is 140-240 DEG C, and processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, three area's temperature
185 DEG C, 190 DEG C of four area's temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature,
Ten 215 DEG C of area's temperature, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
Embodiment 5
A kind of soft anti tear high temperature resistant TPE, its raw material include by weight：SEBS
160 parts of block copolymer, kinematic viscosity (100 DEG C) are 20mm2250 parts of the processing oil of/s, melt index (190 DEG C of 2.16Kg)
For 2g/10min, Mooney viscosity (121 DEG C of ML (1+4)) is 20 40 parts of polyolefin elastomer, and bending moduluses are 950MPa, melting
Polypropylene 30 part of the index for 3g/10min, 35 parts of composite toughing agent, 80 parts of filler, 2.5 parts of antioxidant；
Wherein, in hydrogenated styrene-butadiene-styrene block copolymers, weight average molecular weight is 290,000 hydrogenation of benzene second
The content of alkene-butadiene-styrene block copolymer is 60wt%, and weight average molecular weight is 7.5 ten thousand hydrogenated styrene-fourth two
The content of alkene-styrene block copolymer is 40wt%；
Weight average molecular weight be 290,000 hydrogenated styrene-butadiene-styrene block copolymers in cinnamic content be
27wt%, weight average molecular weight be 7.5 ten thousand hydrogenated styrene-butadiene-styrene block copolymers in cinnamic content be
20wt%；
Processing oil is paraffin oil, the mixture of naphthenic oil composition；
Polyolefin elastomer is ethylene-octene polyolefin elastomer, the mixing of Ethylene/Butylene polyolefin elastomer composition
Thing；
Polypropylene is COPP, the mixture of HOPP composition；
Filler is Calcium Carbonate, kieselguhr, the mixture of clay composition；
Antioxidant is antioxidant 1010, the mixture of the composition of antioxidant 1790；
In the preparation process of composite toughing agent, after sodium-based montmorillonite and water ultrasonic disperse uniform, addition is adjusted with hydrochloric acid
The cetyl trimethylammonium bromide aqueous solution of section pH=6.5, is warming up to 35 DEG C, with the speed stirring 2h of 900r/min, filters
Filter cake is taken, is washed, be dry, pulverize to 300 mesh and obtain modified montmorillonoid；It is 2wt% ethylene that aramid fiber is added mass fraction
In base trimethoxy silane ethanol solution, 55 DEG C being warming up to, power being adjusted to 250W, ultrasonic 3.5h filters to take filter cake, wash,
It is dried to obtain modification of aramid fiber；Modified montmorillonoid, modification of aramid fiber, MA-g-PP compatilizers, polypropylene are mixed, is heated up
To 120 DEG C, Jing Double-screws machine extrusion obtains composite toughing agent, wherein, sodium-based montmorillonite, water, cetyl trimethyl bromination
The weight ratio of ammonium is 8：650：3.35, aramid fiber, the weight ratio of vinyltrimethoxy silane are 13：2, modified montmorillonoid,
Modification of aramid fiber, MA-g-PP compatilizers, polyacrylic weight ratio are 0.35：0.1：0.6：17.
The preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, are warming up to 70 DEG C, mix 15min,
Then antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent are sequentially added, is continued mixing 18min and is obtained material
A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE, wherein, the feeding rotating speed of double screw extruder is 40r/min, and screw speed is 350r/min, screw slenderness ratio
For 45, processing temperature is 140-240 DEG C, and processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, three area's temperature
185 DEG C, 190 DEG C of four area's temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature,
Ten 215 DEG C of area's temperature, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
Embodiment 6-9
A kind of soft anti tear high temperature resistant TPE, its proportioning raw materials such as following table,
Wherein, the preparation of composite toughing agent is with embodiment 5.
The preparation method of above-mentioned soft anti tear high temperature resistant TPE, comprises the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and paraffin oil are taken, are warming up to 60 DEG C, mix 20min,
Then sequentially add anti-oxidant Irganox 1010, antioxidant CYANOX1790, anti-oxidant Irganox 168, precipitated calcium carbonate,
Polypropylene, polyolefin elastomer, composite toughing agent, continue mixing 15min and obtain material A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into soft anti tear
High temperature resistant TPE, wherein, the feeding rotating speed of double screw extruder is 55r/min, and screw speed is 300r/min, screw slenderness ratio
For 52, processing temperature is 140-240 DEG C, and processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, three area's temperature
185 DEG C, 190 DEG C of four area's temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature,
Ten 215 DEG C of area's temperature, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
Test example 1
Performance test is carried out to embodiment 6-9, as a result such as following table：
As can be seen from the above table, it is of the invention while keeping compared with soft, with high intensity, high resilience, anti tear
The performances such as intensity height；Still there is Jing after air aging higher tensile strength and elongation at break, resistance to elevated temperatures is good.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, should all be included within the scope of the present invention.
Claims (10)
1. a kind of soft anti tear high temperature resistant TPE, it is characterised in that its raw material includes by weight：Hydrogenated styrene-fourth two
Alkene-styrene block copolymer 50-200 parts, processing oil 100-300 parts, polyolefin elastomer 20-80 parts, polypropylene 20-80
Part, composite toughing agent 20-40 parts, filler 50-150 parts, antioxidant 0.5-4 parts.
2. soft anti tear high temperature resistant TPE according to claim 1, it is characterised in that hydrogenated styrene-butadiene-benzene
Content of the weight average molecular weight for the hydrogenated styrene-butadiene-styrene block copolymers of 27-30 ten thousand in ethylene block copolymer
Not less than 50wt%, weight average molecular weight is not little less than the content of 100,000 hydrogenated styrene-butadiene-styrene block copolymers
In 10wt%；Preferably, weight average molecular weight is benzene second in the hydrogenated styrene-butadiene-styrene block copolymers of 27-30 ten thousand
The content of alkene is 27-33wt%, and weight average molecular weight is less than in 100,000 hydrogenated styrene-butadiene-styrene block copolymers
Cinnamic content is 16-20wt%.
3. soft anti tear high temperature resistant TPE according to claim 1 or claim 2, it is characterised in that in the preparation of composite toughing agent
During, after sodium-based montmorillonite and water ultrasonic disperse uniform, cetyl trimethylammonium bromide aqueous solution is added, heat up, stir
Mix, filter to take filter cake, wash, dry, pulverize and obtain modified montmorillonoid；Aramid fiber is added into vinyltrimethoxy silane second
In alcoholic solution, heat up, ultrasound filters to take filter cake, washs, is dried to obtain modification of aramid fiber；By modified montmorillonoid, modifying aramid fiber
Fiber, MA-g-PP compatilizers, polypropylene are mixed, and Jing Double-screws machine extrusion obtains composite toughing agent.
4. soft anti tear high temperature resistant TPE according to any one of claim 1-3, it is characterised in that in composite toughing agent
Preparation process in, after sodium-based montmorillonite and water ultrasonic disperse uniform, add cetyl trimethylammonium bromide aqueous solution, rise
Temperature with the speed stirring 1.5-2.5h of 800-1000r/min, filters to take filter cake, washs, dry, pulverize to 200- to 30-40 DEG C
400 mesh obtain modified montmorillonoid；Aramid fiber is added in vinyltrimethoxy silane ethanol solution, 50-60 DEG C is warming up to,
Power is adjusted to 200-300W, ultrasonic 3-4h filters to take filter cake, washs, is dried to obtain modification of aramid fiber；Cover de- by modified
Soil, modification of aramid fiber, MA-g-PP compatilizers, polypropylene are mixed, and are warming up to 110-140 DEG C, and Jing Double-screws machine extrusion is obtained
Composite toughing agent.
5. soft anti tear high temperature resistant TPE according to claim 3 or 4, it is characterised in that in the preparation of composite toughing agent
During, cetyl trimethylammonium bromide aqueous solution need to adjust pH=6-7 with hydrochloric acid；Preferably, in the system of composite toughing agent
During standby, the mass fraction of vinyltrimethoxy silane ethanol solution is 1-3wt%；Preferably, in composite toughing agent
In preparation process, sodium-based montmorillonite, water, the weight ratio of cetyl trimethylammonium bromide are 7-9：600-700：2.9-3.8；It is excellent
Selection of land, in the preparation process of composite toughing agent, aramid fiber, the weight ratio of vinyltrimethoxy silane are 10-15：1-3；
Preferably, in the preparation process of composite toughing agent, modified montmorillonoid, modification of aramid fiber, MA-g-PP compatilizers, polypropylene
Weight ratio be 0.3-0.4：0.05-0.15：0.5-0.7：15-20.
6. soft anti tear high temperature resistant TPE according to any one of claim 1-5, it is characterised in that processing oil is paraffin
At least one in oil, naphthenic oil, aromatic naphtha；Preferably, the kinematic viscosity (100 DEG C) of processing oil is 10-40mm2/s。
7. soft anti tear high temperature resistant TPE according to any one of claim 1-6, it is characterised in that polyolefin elastomer
For at least one in ethylene-octene polyolefin elastomer, Ethylene/Butylene polyolefin elastomer；Preferably, polyolefin elastomer
Melt index (190 DEG C of 2.16Kg) is 0.5-10g/10min, and Mooney viscosity (121 DEG C of ML (1+4)) is 3-30.
8. soft anti tear high temperature resistant TPE according to any one of claim 1-7, it is characterised in that polypropylene is copolymerization
At least one in polypropylene, HOPP；Preferably, polyacrylic bending moduluses are not more than 1100MPa, and melt index is
0.5-5g/10min；Preferably, filler is Pulvis Talci, kieselguhr, Calcium Carbonate, at least one in clay；Preferably, antioxidant
For at least one in antioxidant 1010, antioxidant 1790, irgasfos 168.
9. a kind of preparation method of soft anti tear high temperature resistant TPE as described in any one of claim 1-8, it is characterised in that
Comprise the steps：
S1, hydrogenated styrene-butadiene-styrene block copolymers and processing oil are taken, be warming up to 40-80 DEG C, mix 10-
30min, then sequentially adds antioxidant, filler, polypropylene, polyolefin elastomer, composite toughing agent, continues mixing 10-20min
Obtain material A；
S2, the material A Jing double screw extruder melting extrusion obtained in S1, cooling, pelletize are obtained into the resistance to height of soft anti tear
Warm TPE.
10. the preparation method of soft anti tear high temperature resistant TPE according to claim 9, it is characterised in that in S2, double
The feeding rotating speed of screw extruder is 30-80r/min, and screw speed is 200-400r/min, and screw slenderness ratio is 40-64, plus
Work temperature is 140-240 DEG C；Preferably, processing temperature is specially：One 140 DEG C of area's temperature, 180 DEG C of two area's temperature, three area's temperature
185 DEG C, 190 DEG C of four area's temperature, 195 DEG C of five area's temperature, 200 DEG C of six area's temperature, 205 DEG C of seven area's temperature, 210 DEG C of eight area's temperature,
Ten 215 DEG C of area's temperature, 220 DEG C of 11 area's temperature, 230 DEG C of No.12 District temperature, 240 DEG C of 13 area's temperature.
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