CN105778299A - High-hardness and low-temperature-resistant TPV material and preparation method thereof - Google Patents
High-hardness and low-temperature-resistant TPV material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 30
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000004611 light stabiliser Substances 0.000 claims abstract description 15
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010881 fly ash Substances 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000004743 Polypropylene Substances 0.000 claims description 26
- 229920001155 polypropylene Polymers 0.000 claims description 24
- 239000010883 coal ash Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005452 bending Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 5
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 230000001404 mediated effect Effects 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000004610 Internal Lubricant Substances 0.000 abstract 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 41
- 238000013329 compounding Methods 0.000 description 8
- 150000001336 alkenes Chemical group 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-hardness and low-temperature-resistant TPV material.The high-hardness and low-temperature-resistant TPV material is prepared from, by weight, 40-60 parts of EPDM, 10-20 parts of PP, 20-40 parts of PE, 10-15 parts of polyolefin elastomer, 5-20 parts of maleic anhydride grafted EPDM, 5-15 parts of novel reinforcing agent, 1-3 parts of vulcanizing agent, 1-3 parts of antioxidant, 5-10 parts of plasticizer, 1-3 parts of light stabilizer, 1-3 parts of internal lubricant and 1-3 parts of processing aid.The TPV material is good in mechanical performance and excellent in low temperature resistance performance and meanwhile is excellent in processability and excellent in appearance.
Description
Technical field
The present invention relates to TPV material technical field, particularly a kind of low temperature resistant TPV material of high rigidity and system thereof
Preparation Method.
Background technology
TPV is the abbreviation of Thermoplastic Vulcanizate, and Chinese is that thermoplasticity EPDM moves
State vulcanized elastomer or thermoplasticity EPDM dynamic perduren, be the ethylene propylene diene rubber of solid cure
EPDM particulate is dispersed in the macromolecular elastomer material of composition in continuous polypropylene PP phase.Thing under TPV normal temperature
Rationality and can be functionally similar to thermoset rubber, at high temperature shows as the characteristic of thermoplastic, can be fast
Speed economy and machine-shaping easily.TPV thermoplasticity EPDM dynamic vulcanization elastomer is by vulcanized rubber material
Ethylene propylene diene rubber EPDM is made to be dispersed in polypropylene PP with the particulate less than 2 micron-scales by dynamic vulcanization
In plastic substrate, the characteristic of rubber with plastics is well combined, obtain the height of excellent combination property
Performance elastomers material.In traditional high rigidity TPV material, PP phase to improve relative to EPDM Phase Proportion,
Making TPV material originally have the performance characteristics of more PP in performance characteristics, the brittle temperature of PP is
-35℃.When less than this temperature, the PP phase in TPV material will low temperature brittleness, thus have influence on entirety
TPV cryogenic property.And along with the proportional amount of reduction of PP phase, the hardness of TPV material can be produced again impact,
Therefore, a kind of TPV material having high rigidity and low temperature resistant two kinds of performances concurrently how is obtained, for existing work
Industry process has great importance.
Summary of the invention
The present invention proposes a kind of low temperature resistant TPV material of high rigidity and preparation method thereof, described TPV material power
Learning functional, resistance to low temperature is excellent, and processing characteristics is excellent simultaneously, good appearance.
The low temperature resistant TPV material of a kind of high rigidity that the present invention proposes, its raw material includes by weight:
Wherein, the method preparing described novel reinforcing agent includes: add flyash in mixed acid solution, super
Phonoresponse, filters, and washing is dried, and grinds, obtains modified coal ash；Add in described modified coal ash
Enter toluene to stir, add Silane coupling agent KH550, ultrasonic reaction, suction filtration, washing, be vacuum dried,
Obtain the flyash of surface active；In the flyash of described surface active, add ethanol stir, add
Monomer ZDMA and initiator A IBN, heat up stirring, is dried, obtains novel reinforcing agent.
In a specific embodiment, the weight portion of EPDM can be 41,43,45,47,52,54,56,
58；The weight portion of PP can be 11,12,13,14,15,16,17,18；The weight portion of PE can be
21、22、24、29、30、33、34、36、38、39；The weight portion of polyolefin elastomer can be 10.5,
11.8、12.2、12.9、13.6、14、14.5、14.9；The weight portion of maleic anhydride grafting EPDM is permissible
It is 6,8,9,12,13,14,15,17,18,19；The weight portion of novel reinforcing agent can be 5.9,
6.3、6.8、7.1、8.7、9.3、9.8、10.2、11.3、12.4、13.5、14.6；Vulcanizing agent
Weight portion can be 1.2,1.5,1.7,1.9,2.1,2.3,2.5,2.8；The weight portion of antioxidant can
Think 1.2,1.5,1.7,1.9,2.1,2.3,2.5,2.8；The weight portion of plasticizer can be 6,
6.5、7、7.5、8、8.5、9、9.5；The weight portion of light stabilizer can be 1.2,1.5,1.7,1.9,
2.1、2.3、2.5、2.8；The weight portion of in-lubricant can be 1.2,1.5,1.7,1.9,2.1,2.3,
2.5、2.8；The weight portion of processing aid can be 1.2,1.5,1.7,1.9,2.1,2.3,2.5,2.8.
Preferably, described EPDM is by the ethene of 20-50wt%, the propylene of 40-78wt% and the second of 2-10wt%
Alkenyl norbornene copolymerization forms.
Preferably, described PP is the homopolymerization type poly-third of the copolymerized type propene polymer by 50-80wt% and 20-50wt%
Alkene forms；Preferably, the comonomer of described copolymerized type propene polymer is selected from ethene, butylene, hexene, octene
In a kind of or mixture of at least two, the bending modulus≤1100MPa of described copolymerized type propene polymer, molten
Melting index is 0.5-5.0g/10min；The described polyacrylic melt index of homopolymerization type is 0.5-5.0g/10min.
Preferably, the method preparing described novel reinforcing agent includes: add flyash in mixed acid solution,
Being 20-40KHz in frequency, the sound intensity is 0.1-0.3W/cm2Under conditions of ultrasonic reaction 1-3h, filter, washing,
Dry, grind, obtain modified coal ash；In described modified coal ash, add toluene stir, then add
Entering Silane coupling agent KH550, be 20-40KHz in frequency, the sound intensity is 0.5-0.8W/cm2, temperature is
Ultrasonic reaction 5-7h under conditions of 100-120 DEG C, suction filtration, washing, vacuum drying, obtain the powder of surface active
Coal ash；In the flyash of described surface active, add ethanol stir, add monomer ZDMA and initiator
AIBN, is warming up to 55-75 DEG C, stirs 2-4h, is vacuum dried 6-8h, obtains novel benefit at 60-80 DEG C
Strong agent；Preferably, the method preparing described novel reinforcing agent includes: to being the HCl of 1:3-5 by mol ratio
And H2SO4Mixed acid solution in add 40-60 mesh flyash, be 25-35KHz in frequency, the sound intensity is
0.1-0.2W/cm2Under conditions of ultrasonic reaction 2-3h, filter, washing, dry, grind and obtain modified fine coal
Ash；In described modified coal ash, add toluene stir, add Silane coupling agent KH550, in frequency
For 30-35KHz, the sound intensity is 0.6-0.7W/cm2, temperature be 105-115 DEG C under conditions of ultrasonic reaction 6-7h,
Suction filtration, washing, vacuum drying, obtain the flyash of surface active；In the flyash of described surface active
Add ethanol to stir, add monomer ZDMA and initiator A IBN, be warming up to 60-70 DEG C, stir 2-3h,
At 65-75 DEG C, it is vacuum dried 7-8h, obtains described novel reinforcing agent.
Preferably, flyash, Silane coupling agent KH550, ZDMA, the weight proportion of initiator A IBN are
100:1-5:20-30:0.1-0.5。
Preferably, described polyolefin elastomer is the copolymer of ethylene-octene, tests at 230 DEG C × 2.16Kg
Under the conditions of, melt flow rate (MFR) is 0.5-10g/10min.
Preferably, described vulcanizing agent is by the cumyl peroxide that weight proportion is 4-6:1 and triallyl
Fulminuric acid ester is compounding to be formed；Described antioxidant is to be 0.2-0.7:0.3-1.0:0.3-1.5 by weight proportion
Antioxidant 1010, antioxidant 1098, irgasfos 168 is compounding forms.
Preferably, described plasticizer one in binary acid esters, phosphoric acid ester, the chlorinated paraffin or
The mixture of at least two；Described light stabilizer selected from hindered amine light stabilizer, triazines as light stabilizer,
The mixture of a kind of or at least two in organic nickel complex compound；Described in-lubricant is selected from silicone oil, ethene
A kind of or the mixture of at least two in base bis-stearamides, hydroxy fatty acid series lubricant agent；Described processing
Mixing of the auxiliary agent a kind of or at least two in stearic acid, stearate, metal oxide, silicone
Compound.
A kind of preparation method of the low temperature resistant TPV material of high rigidity, including: by EPDM, PP, PE, polyolefin
Elastomer, maleic anhydride are grafted EPDM, novel reinforcing agent, antioxidant, light stabilizer, in-lubricant and add
Work auxiliary agent adds in kneader to be mediated, and obtains premix；Double screw extruder is sent in described premix
In carry out plasticating for the first time, obtain semi-finished product particle after pelletizing；By described semi-finished product particle and vulcanizing agent, increasing
After moulding agent mixing, it is re-fed in double screw extruder carrying out second time and plasticates, after pelletizing, obtain described high rigidity
Low temperature resistant TPV material.
Preferably, the kneading temperature carrying out mediating in kneader is 100-130 DEG C, and kneading time is
10-15min；Preferably, the processing temperature carrying out plasticating for the first time in double screw extruder is 160-190 DEG C,
Screw speed 200-400r/min；Preferably, double screw extruder carries out the processing temperature that second time is plasticated
Degree is 180-200 DEG C, screw speed 200-400r/min.
In the present invention, on the basis of the conventional constituents of TPV material, more PP use PE material is carried out
Part substitutes, and controls processing technology well so that PE well can merge with EPDM, due to the low temperature of PE material
Brittle temperature is generally below-50, substantially increases the resistance to low temperature of TPV material；Additionally, so that
Described TPV material obtains good mechanical property, is also added into a kind of novel reinforcing agent component in the application,
It first passes through and flyash is carried out surface modification, after flyash pickling, makes smoother densification originally
Particle surface becomes coarse, reacts rear surface with silane coupler and is activated, then by ZDMA in-situ polymerization,
Thus flyash is produced parcel, then improve the interface interaction between the base-material such as flyash and EPDM, improve it
Dispersiveness in described base-material and stability, and remain its distinctive structure of flyash, this is conducive to filling
The supplement effect of flyash, the very big hardness performance that must enhance goods and strength character are waved in distribution；In addition
During preparation TPV material, TPV material also introduces polyolefin elastomer at high proportion, is playing into one
While step improves material resistance to low temperature, the processing characteristics that thermoplastic elastic material is excellent can be given；This
Outer the application is also added into the vulcanizing agent system of specific proportioning, make EPDM with polyolefinic melt blending mistake
Cheng Shixian dynamic vulcanization, not only improves the mechanical mechanics property of TPV material, it is often more important that add material
The consistency of material, heat-resisting, the antioxygenic property of reinforcing material；The plasticizer of certain content, the light that add are steady
Determining agent, antioxidant and processing aid then makes TPV material have good processing characteristics and resistance to heat aging
Can, described in the TPV material not only mechanical property for preparing the most fabulous with resistance to low temperature, but also permissible
Recycling use, meets circular economy concept.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of low temperature resistant TPV material of high rigidity, its raw material includes by weight:
Wherein, described EPDM is by the ethene of 20wt%, the propylene of 78wt% and the vinyl norbornene of 2wt%
Alkene copolymerization forms；Described PP is made up of the copolymerized type propene polymer of 50wt% and the homopolymerization type polypropylene of 50wt%,
The comonomer of described copolymerized type propene polymer is ethene, the bending modulus of described copolymerized type propene polymer≤
1100MPa, melt index is 0.5g/10min；The described polyacrylic melt index of homopolymerization type is 5.0g/10min；
The method preparing described novel reinforcing agent includes: to being HCl and H of 1:3 by mol ratio2SO4Mixing
Adding the flyash of 60 mesh in acid solution, be 20KHz in frequency, the sound intensity is 0.3W/cm2Under conditions of ultrasonic
Reaction 1h, filters, and washing is dried, and grinds and obtains modified coal ash；Add in described modified coal ash
Toluene stirs, and adds Silane coupling agent KH550, is 40KHz in frequency, and the sound intensity is 0.5W/cm2,
Temperature be 120 DEG C under conditions of ultrasonic reaction 5h, suction filtration, washing, vacuum drying, obtain surface active
Flyash；In the flyash of described surface active, add ethanol stir, add monomer ZDMA and initiation
Agent AIBN, is warming up to 75 DEG C, stirs 2h, is vacuum dried 6h, obtains novel reinforcing agent at 80 DEG C；Its
Middle flyash, Silane coupling agent KH550, ZDMA, the weight proportion of initiator A IBN are 100:1:30:0.1；
Described polyolefin elastomer is the copolymer of ethylene-octene, under 230 DEG C × 2.16Kg test condition,
Melt flow rate (MFR) is 0.5g/10min；
Described vulcanizing agent is by the cumyl peroxide that weight proportion is 6:1 and triallyl fulminuric acid
Ester is compounding to be formed；Described antioxidant is to be the antioxidant 1010 of 0.2:1.0:0.3, antioxidant by weight proportion
1098, irgasfos 168 is compounding forms.
Embodiment 2
A kind of low temperature resistant TPV material of high rigidity, its raw material includes by weight:
Wherein, described EPDM is by the ethene of 50wt%, the propylene of 40wt% and the vinyl norbornene of 10wt%
Alkene copolymerization forms；Described PP is made up of the copolymerized type propene polymer of 80wt% and the homopolymerization type polypropylene of 20wt%；
The comonomer of described copolymerized type propene polymer is butylene, the bending modulus of described copolymerized type propene polymer≤
1100MPa, melt index is 5.0g/10min；The described polyacrylic melt index of homopolymerization type is 0.5g/10min；
The method preparing described novel reinforcing agent includes: to being HCl and H of 1:5 by mol ratio2SO4Mixing
Adding the flyash of 40 mesh in acid solution, be 40KHz in frequency, the sound intensity is 0.1W/cm2Under conditions of ultrasonic
Reaction 3h, filters, and washing is dried, and grinds and obtains modified coal ash；Add in described modified coal ash
Toluene stirs, and adds Silane coupling agent KH550, is 20KHz in frequency, and the sound intensity is 0.8W/cm2,
Temperature be 100 DEG C under conditions of ultrasonic reaction 7h, suction filtration, washing, vacuum drying, obtain surface active
Flyash；In the flyash of described surface active, add ethanol stir, add monomer ZDMA and initiation
Agent AIBN, is warming up to 55 DEG C, stirs 4h, is vacuum dried 8h, obtains novel reinforcing agent at 60 DEG C；Its
Middle flyash, Silane coupling agent KH550, ZDMA, the weight proportion of initiator A IBN are 100:5:20:0.5；
Described polyolefin elastomer is the copolymer of ethylene-octene, under 230 DEG C × 2.16Kg test condition,
Melt flow rate (MFR) is 10g/10min；
Described vulcanizing agent is by the cumyl peroxide that weight proportion is 4:1 and triallyl fulminuric acid
Ester is compounding to be formed；Described antioxidant is to be the antioxidant 1010 of 0.7:0.3:1.5, antioxidant by weight proportion
1098, irgasfos 168 is compounding forms.
Embodiment 3
A kind of low temperature resistant TPV material of high rigidity, its raw material includes by weight:
Wherein, described EPDM is by the ethene of 35wt%, the propylene of 59wt% and the vinyl norbornene of 6wt%
Alkene copolymerization forms；Described PP is made up of the copolymerized type propene polymer of 65wt% and the homopolymerization type polypropylene of 35wt%,
The comonomer of described copolymerized type propene polymer is hexene, the bending modulus of described copolymerized type propene polymer≤
1100MPa, melt index is 2.5g/10min；The described polyacrylic melt index of homopolymerization type is 3.0g/10min；
The method preparing described novel reinforcing agent includes: to being HCl and H of 1:4 by mol ratio2SO4Mixing
Adding the flyash of 50 mesh in acid solution, be 25KHz in frequency, the sound intensity is 0.2W/cm2Under conditions of ultrasonic
Reaction 2.5h, filters, and washing is dried, and grinds and obtains modified coal ash；Add in described modified coal ash
Entering toluene to stir, add Silane coupling agent KH550, be 35KHz in frequency, the sound intensity is 0.6W/cm2,
Temperature be 115 DEG C under conditions of ultrasonic reaction 6.5h, suction filtration, washing, vacuum drying, obtain surface active
Flyash；In the flyash of described surface active, add ethanol stir, add monomer ZDMA and draw
Send out agent AIBN, be warming up to 70 DEG C, stir 2.5h, at 65 DEG C, be vacuum dried 7.5h, obtain described novel
Reinforcing agent；Wherein flyash, Silane coupling agent KH550, ZDMA, the weight proportion of initiator A IBN are
100:3:25:0.3；
Described polyolefin elastomer is the copolymer of ethylene-octene, under 230 DEG C × 2.16Kg test condition,
Melt flow rate (MFR) is 5g/10min；Described vulcanizing agent is to be the cumyl peroxide of 5:1 by weight proportion
Compound with iso-cyanuric acid triallyl ester and form；Described antioxidant is to be 0.5:0.6:0.9 by weight proportion
Antioxidant 1010, antioxidant 1098, irgasfos 168 is compounding forms；
Described plasticizer is the mixture of binary acid esters, chlorinated paraffin；Described light stabilizer is hindered amines
Light stabilizer, the mixture of organic nickel complex compound；Described in-lubricant is silicone oil, hydroxy aliphatic acids lubrication
The mixture of agent；Described processing aid is the mixture of metal oxide, silicone.
Embodiment 4
A kind of low temperature resistant TPV material of high rigidity, its raw material includes by weight:
Wherein, described EPDM is by the ethene of 30wt%, the propylene of 65wt% and the vinyl norbornene of 5wt%
Alkene copolymerization forms；Described PP is made up of the copolymerized type propene polymer of 60wt% and the homopolymerization type polypropylene of 40wt%,
The comonomer of described copolymerized type propene polymer is the mixture of butylene, hexene, octene, described copoly type poly-third
Bending modulus≤the 1100MPa of alkene, melt index is 3.5g/10min；The polyacrylic melted finger of described homopolymerization type
Number is 4.0g/10min；
The method preparing described novel reinforcing agent includes: to being HCl and H of 1:4 by mol ratio2SO4Mixing
Adding the flyash of 40 mesh in acid solution, be 35KHz in frequency, the sound intensity is 0.1W/cm2Under conditions of ultrasonic
Reaction 2h, filters, and washing is dried, and grinds and obtains modified coal ash；Add in described modified coal ash
Toluene stirs, and adds Silane coupling agent KH550, is 30KHz in frequency, and the sound intensity is 0.7W/cm2,
Temperature be 105 DEG C under conditions of ultrasonic reaction 6h, suction filtration, washing, vacuum drying, obtain surface active
Flyash；In the flyash of described surface active, add ethanol stir, add monomer ZDMA and initiation
Agent AIBN, is warming up to 60 DEG C, stirs 2h, is vacuum dried 7h, obtains described novel reinforcing agent at 75 DEG C；
Wherein flyash, Silane coupling agent KH550, ZDMA, the weight proportion of initiator A IBN are 100:4:24:0.2；
Described polyolefin elastomer is the copolymer of ethylene-octene, under 230 DEG C × 2.16Kg test condition,
Melt flow rate (MFR) is 4g/10min；Described vulcanizing agent is to be the cumyl peroxide of 5:1 by weight proportion
Compound with iso-cyanuric acid triallyl ester and form；Described antioxidant is to be 0.4:0.7:0.9 by weight proportion
Antioxidant 1010, antioxidant 1098, irgasfos 168 is compounding forms；
Described plasticizer is chlorinated paraffin；Described light stabilizer is organic nickel complex compound；Described in-lubricant is
Hydroxy fatty acid series lubricant agent；Described processing aid is silicone.
The preparation method of the low temperature resistant TPV material of high rigidity described in above-described embodiment 1-4, including: by EPDM,
PP, PE, polyolefin elastomer, maleic anhydride grafting EPDM, novel reinforcing agent, antioxidant, light stabilizer,
In-lubricant and processing aid add in kneader to be mediated, and obtains premix；Described premix is sent into
Double screw extruder is carried out plasticate for the first time, after pelletizing, obtain semi-finished product particle；By described semi-finished product particle
After mixing with vulcanizing agent, plasticizer, it is re-fed in double screw extruder carrying out second time and plasticates, after pelletizing
To the low temperature resistant TPV material of described high rigidity；Wherein, the kneading temperature carrying out mediating in kneader is
100-130 DEG C, kneading time is 10-15min；The processing temperature plasticated for the first time is carried out in double screw extruder
Degree is 160-190 DEG C, screw speed 200-400r/min；In double screw extruder, carry out second time plasticate
Processing temperature be 180-200 DEG C, screw speed 200-400r/min.
TPV material described in above-described embodiment 1-4 is carried out performance test, and result is as shown in the table:
In embodiment 1-4, on the basis of the conventional constituents of TPV material, more PP is used PE material
Carry out part replacement, control processing technology well so that PE well can merge with EPDM, due to PE material
Brittle temperature is generally below-50, substantially increases the resistance to low temperature of TPV material；Additionally, in order to
Make described TPV material obtain good mechanical property, the application is also added into a kind of novel reinforcing agent group
Point, it first passes through and flyash is carried out surface modification, after flyash pickling, makes smoother originally cause
Close particle surface becomes coarse, reacts rear surface with silane coupler and is activated, more poly-by ZDMA
Close, thus flyash is produced parcel, then improve the interface interaction between the base-material such as flyash and EPDM, carry
Its dispersiveness in described base-material high and stability, and remain its distinctive structure of flyash, this is favourable
In giving full play to the supplement effect of flyash, the very big hardness performance that must enhance goods and strength character；
During this external preparation TPV material, TPV material also introduces polyolefin elastomer at high proportion, playing
While improving material resistance to low temperature further, the processing characteristics that thermoplastic elastic material is excellent can be given；
The application is also added into the vulcanizing agent system of specific proportioning in addition, make EPDM with polyolefinic melt blending
Process realizes dynamic vulcanization, not only improves the mechanical mechanics property of TPV material, it is often more important that add
The consistency of material, heat-resisting, the antioxygenic property of reinforcing material；The plasticizer of certain content of addition, light
Stabilizer, antioxidant and processing aid then make TPV material have good processing characteristics and resistant to thermal aging
Performance, described in the TPV material not only mechanical property for preparing the most fabulous with resistance to low temperature, but also can
With recycling use, meet circular economy concept.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office
Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this
The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention
Within the scope of.
Claims (10)
1. the low temperature resistant TPV material of high rigidity, it is characterised in that its raw material includes by weight:
Wherein, the method preparing described novel reinforcing agent includes: add flyash in mixed acid solution, super
Phonoresponse, filters, and washing is dried, and grinds, obtains modified coal ash；Add in described modified coal ash
Entering toluene to stir, add Silane coupling agent KH550, ultrasonic reaction, suction filtration, washing, vacuum is done
Dry, obtain the flyash of surface active；In the flyash of described surface active, add ethanol stir,
Adding monomer ZDMA and initiator A IBN, heat up stirring, is dried, obtains novel reinforcing agent.
The low temperature resistant TPV material of high rigidity the most according to claim 1, it is characterised in that described EPDM
It is to be formed by the ethene of 20-50wt%, the propylene of 40-78wt% and the vinyl norbornene copolymerization of 2-10wt%.
The low temperature resistant TPV material of high rigidity the most according to claim 1 and 2, it is characterised in that described
PP is made up of the copolymerized type propene polymer of 50-80wt% and the homopolymerization type polypropylene of 20-50wt%；Preferably,
The comonomer of described copolymerized type propene polymer one in ethene, butylene, hexene, the octene or at least
The mixture of two kinds, the bending modulus≤1100MPa of described copolymerized type propene polymer, melt index is
0.5-5.0g/10min；The described polyacrylic melt index of homopolymerization type is 0.5-5.0g/10min.
4. according to the low temperature resistant TPV material of high rigidity described in any one of claim 1-3, it is characterised in that
The method preparing described novel reinforcing agent includes: adds flyash in mixed acid solution, in frequency is
20-40KHz, the sound intensity is 0.1-0.3W/cm2Under conditions of ultrasonic reaction 1-3h, filter, washing, dry,
Grind, obtain modified coal ash；In described modified coal ash, add toluene stir, add silane
Coupling agent KH550, is 20-40KHz in frequency, and the sound intensity is 0.5-0.8W/cm2, temperature is 100-120 DEG C
Under conditions of ultrasonic reaction 5-7h, suction filtration, washing, vacuum drying, obtain the flyash of surface active；To
The flyash of described surface active adds ethanol stir, adds monomer ZDMA and initiator A IBN,
It is warming up to 55-75 DEG C, stirs 2-4h, at 60-80 DEG C, be vacuum dried 6-8h, obtain novel reinforcing agent；
Preferably, the method preparing described novel reinforcing agent includes: to being HCl and H of 1:3-5 by mol ratio2SO4
Mixed acid solution in add 40-60 mesh flyash, be 25-35KHz in frequency, the sound intensity is
0.1-0.2W/cm2Under conditions of ultrasonic reaction 2-3h, filter, washing, dry, grind and obtain modified fine coal
Ash；In described modified coal ash, add toluene stir, add Silane coupling agent KH550, at frequency
Rate is 30-35KHz, and the sound intensity is 0.6-0.7W/cm2, temperature be 105-115 DEG C under conditions of ultrasonic reaction
6-7h, suction filtration, washing, vacuum drying, obtain the flyash of surface active；Powder to described surface active
Coal ash adds ethanol stir, add monomer ZDMA and initiator A IBN, be warming up to 60-70 DEG C, stir
Mix 2-3h, at 65-75 DEG C, be vacuum dried 7-8h, obtain described novel reinforcing agent.
The low temperature resistant TPV material of high rigidity the most according to claim 4, it is characterised in that flyash,
Silane coupling agent KH550, ZDMA, the weight proportion of initiator A IBN are 100:1-5:20-30:0.1-0.5.
6. according to the low temperature resistant TPV material of high rigidity described in any one of claim 1-5, it is characterised in that
Described polyolefin elastomer is the copolymer of ethylene-octene, under 230 DEG C × 2.16Kg test condition, and melt
Flow rate is 0.5-10g/10min.
7. according to the low temperature resistant TPV material of high rigidity described in any one of claim 1-6, it is characterised in that
Described vulcanizing agent is by the cumyl peroxide that weight proportion is 4-6:1 and iso-cyanuric acid triallyl ester
Compound and form；Described antioxidant is to be the antioxidant of 0.2-0.7:0.3-1.0:0.3-1.5 by weight proportion
1010, antioxidant 1098, irgasfos 168 compound and form.
8. according to the low temperature resistant TPV material of high rigidity described in any one of claim 1-7, it is characterised in that
Mixing of the described plasticizer a kind of or at least two in binary acid esters, phosphoric acid ester, chlorinated paraffin
Compound；Described light stabilizer is selected from hindered amine light stabilizer, triazines as light stabilizer, organic nickel complex compound
In a kind of or mixture of at least two；Described in-lubricant selected from silicone oil, vinyl bis-stearamides,
The mixture of a kind of or at least two in hydroxy fatty acid series lubricant agent；Described processing aid selected from stearic acid,
The mixture of a kind of or at least two in stearate, metal oxide, silicone.
9. according to a preparation method for the low temperature resistant TPV material of high rigidity described in any one of claim 1-8,
It is characterized in that, including: by EPDM, PP, PE, polyolefin elastomer, maleic anhydride grafting EPDM, new
Type reinforcing agent, antioxidant, light stabilizer, in-lubricant and processing aid add in kneader to be mediated,
Obtain premix；Described premix is sent in double screw extruder and carry out plasticating for the first time, obtain after pelletizing
Semi-finished product particle；After being mixed with vulcanizing agent, plasticizer by described semi-finished product particle, it is re-fed into twin-screw extrusion
Machine carries out second time plasticate, after pelletizing, obtain the low temperature resistant TPV material of described high rigidity.
The preparation method of the low temperature resistant TPV material of high rigidity the most according to claim 9, its feature exists
In, the kneading temperature carrying out mediating in kneader is 100-130 DEG C, and kneading time is 10-15min；Excellent
Selection of land, the processing temperature carrying out plasticating for the first time in double screw extruder is 160-190 DEG C, screw speed
200-400r/min；Preferably, the processing temperature carrying out plasticating for the second time in double screw extruder is
180-200 DEG C, screw speed 200-400r/min.
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| CN109666224A (en) * | 2018-12-24 | 2019-04-23 | 宁波汉吉高分子材料有限公司 | Sealing strip made of a kind of TPV of lasting self-lubricating and preparation method thereof the and TPV |
| CN111117081A (en) * | 2019-12-30 | 2020-05-08 | 苏州顶材新材料有限公司 | Dynamic fully-vulcanized thermoplastic polyolefin elastomer and preparation method thereof |
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| CN102181101A (en) * | 2011-03-31 | 2011-09-14 | 上海东明橡塑制品有限公司 | Building sealing strip based on thermoplastic ethylene-propylene-diene monomer (EPDM) rubber material and preparation method of building sealing strip |
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Application publication date: 20160720 |