CN116003922A - EPDM (ethylene-propylene-diene monomer) particle with good weather resistance and preparation method thereof - Google Patents
EPDM (ethylene-propylene-diene monomer) particle with good weather resistance and preparation method thereof Download PDFInfo
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- CN116003922A CN116003922A CN202310162343.7A CN202310162343A CN116003922A CN 116003922 A CN116003922 A CN 116003922A CN 202310162343 A CN202310162343 A CN 202310162343A CN 116003922 A CN116003922 A CN 116003922A
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims abstract description 50
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003245 coal Substances 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 13
- 239000010425 asbestos Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910052895 riebeckite Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 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 claims description 17
- 239000004636 vulcanized rubber Substances 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- HHMXFXBISMCAQW-UHFFFAOYSA-N C(C=C)(=O)O.FC(C(F)(F)OC(C=C)=O)CC(F)(F)F Chemical compound C(C=C)(=O)O.FC(C(F)(F)OC(C=C)=O)CC(F)(F)F HHMXFXBISMCAQW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 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 5
- MCPSMQGVSYDFLC-UHFFFAOYSA-N formaldehyde;2-octylphenol Chemical compound O=C.CCCCCCCCC1=CC=CC=C1O MCPSMQGVSYDFLC-UHFFFAOYSA-N 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 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 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 abstract description 11
- 239000011737 fluorine Substances 0.000 abstract description 11
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 26
- 230000032683 aging Effects 0.000 description 22
- 239000003921 oil Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- -1 hexafluorobutyl Chemical group 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses EPDM particles with good weather resistance and a preparation method thereof, wherein the EPDM particles comprise the following raw materials: (a) at least one ethylene propylene diene monomer; (b) At least contains poly (hexafluorobutyl acrylate) block poly (butyl acrylate); (c) at least comprising coal slag, asbestos powder and a vulcanizing agent. According to the EPDM particles, the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) is added into the raw material, the fluorine-containing block part improves the weather resistance, the non-fluorine part provides compatibility, and the fluorine-containing block polymer has mobility and can migrate to the surface of the particles during molding to form a fluorine protective layer, so that the weather resistance of the EPDM particles is improved.
Description
Technical Field
The invention belongs to the technical field of plastic track particle production and processing, and particularly relates to EPDM particles with good weather resistance and a preparation method thereof.
Background
The plastic track is an indispensable important facility in modern track and field fields, and compared with the traditional soil track, the plastic track has the advantages of good elasticity, skid resistance, wear resistance, weather resistance, easy field nursing, bright color and attractive and tidy appearance. In view of the above advantages, plastic runways are rapidly adopted by various track and field sites soon after appearance. The plastic track has the characteristics of excellent performance, convenient use and the like, is popular with people, and has been subjected to international Ottoman as one of the requirements of international competition fields.
Ethylene Propylene Diene Monomer (EPDM) has incomparable advantages to other rubber particles, not only has excellent weather resistance, burst sun resistance, high temperature resistance, ozone resistance, chemical medium resistance, water resistance and low temperature resistance, electrical insulation and elasticity, but also has excellent color stability; not only has more than ten kinds of bright colors such as red, blue, yellow, green, violet and the like; and the novel anti-skid rubber is attractive and comfortable, moderate in elasticity, good in anti-skid performance, wear-resistant, acid-base-resistant, long in service life and convenient to maintain. The ethylene propylene rubber plastic material can be widely used for paving badminton, tennis, basketball court, track and field, baseball field and football field channels, indoor and outdoor tracks, sports fields and other fields, and has very wide application.
Although EPDM itself has better aging resistance, because a large amount of filler and anti-aging agent are often added into the particles to reduce the cost, most of the filler and anti-aging agent have certain limitation on compatibility with rubber, the addition is not well controlled, surface frosting is easily caused, and the appearance of the rubber product is affected, so that the EPDM particles still have poor ozone erosion resistance, weather resistance and other properties in the use process, and the rubber runway is mostly paved outdoors, in some areas with bad weather, such as larger temperature difference and ultraviolet radiation, especially in the plateau area, the day and night temperature difference is large, aging phenomenon can occur to the EPDM particles after long-term sunlight irradiation, wind and rain and ozone erosion and the treading of athletes, the mechanical property is reduced, the surface of the particles is cracked, obvious yellowing and cracking can occur until serious pulverization are caused, the appearance of the rubber runway is affected after the rain washing, and meanwhile, the mechanical property of the product is remarkably attenuated.
In the prior art, chinese patent application number 201710569858.3 discloses an aging-resistant ethylene propylene diene monomer rubber composition, which comprises the following raw materials in parts by weight: 100 parts of ethylene propylene diene monomer, 5 parts of zinc oxide, 1 part of stearic acid, 3230 35 parts of alkali white carbon black, 140 parts of calcium bicarbonate, 65 parts of paraffin base oil, 2.5 parts of PEG4000, 1.5 parts of accelerator CZ, 1.0 part of accelerator M, 1.5 parts of accelerator BZ, 0.5 part of accelerator DTDM, 0.5 part of accelerator TT and 1.0 part of S. The invention changes the common white carbon black into the present novel white carbon black 3230, improves the heat resistance of the product without adding a large amount of heat-resistant anti-aging agent, and has better ageing resistance. However, the patent also increases the aging resistance of rubber by adding inorganic carbon black, the compatibility of white carbon black and EPDM are limited, so that the weather resistance is limited, and the mechanical properties of rubber materials can be reduced due to the excessive addition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide EPDM particles with good weather resistance and a preparation method thereof, wherein the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) is added into the raw materials, the part containing fluorine is used for improving the weather resistance, the part containing fluorine is used for providing compatibility, the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) has migration, and the poly (butyl acrylate) block poly (butyl acrylate) can migrate to the surface of the particles during molding to form a fluorine protection layer, so that the weather resistance of the EPDM particles is improved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
EPDM particles with good weather resistance comprise the following raw materials:
(a) At least one ethylene propylene diene monomer;
(b) At least contains poly (hexafluorobutyl acrylate) block poly (butyl acrylate);
(c) At least contains coal slag, asbestos powder and vulcanizing agent.
Preferably, the (a) component is 15-65 parts by weight, the (b) component is 1-3 parts by weight, and the (c) component is 25-50 parts by weight.
Preferably, the ethylene content in the ethylene propylene diene monomer in the component (a) is 60-75%, and the Mooney viscosity is 60-70.
Preferably, the number average molecular weight of the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) in the component (b) is 3000-10000, wherein the content of the hexafluorobutyl acrylate is 20-60%.
Preferably, the preparation method of the poly (hexafluorobutyl acrylate) segmented poly (butyl acrylate) comprises the following steps:
(1) Adding butyl acrylate, azodiisobutyronitrile and trithioester into tetrahydrofuran, uniformly stirring, then stirring for reaction under nitrogen atmosphere, adding methanol aqueous solution after the reaction is finished, precipitating, filtering and drying to obtain a polybutyl acrylate RAFT macromolecular initiator;
(2) Adding the polybutyl acrylate RAFT macromolecular initiator, hexafluorobutyl acrylate and azodiisobutyronitrile obtained in the step (1) into tetrahydrofuran, uniformly stirring, performing constant-temperature reaction in a nitrogen atmosphere, precipitating with methanol after the reaction is finished, filtering and drying to obtain the polybutyl acrylate hexafluorobutyl acrylate block polybutyl acrylate.
Preferably, in the step (1), the mass ratio of the butyl acrylate to the azodiisobutyronitrile to the trithioester is 100-130:1-1.5:3-6, the mass concentration of the aqueous methanol solution is 50%, the temperature of the stirring reaction is 60-90 ℃, and the reaction time is 5-10 hours; in the step (2), the mass ratio of the polybutyl acrylate RAFT macroinitiator to the hexafluorobutyl acrylate to the azodiisobutyronitrile is 100-150:40-80:2-4, the temperature of the constant temperature reaction is 70-100 ℃, and the reaction time is 10-20h.
Preferably, the mass ratio of the coal slag, the asbestos powder and the vulcanizing agent in the component (c) is 10-20:10-20:5-10; the vulcanizing agent is one or more of sulfur, dicumyl peroxide and octyl phenol-formaldehyde vulcanizing resin; the mesh number of the coal slag is 300-400 mesh; the mesh number of the asbestos powder is 600-800 meshes.
Preferably, component (c) further comprises an accelerator TMTD, an antioxidant 1098 and naphthenic oil 4010; 2-4 parts of accelerator TMTD, 1-3 parts of antioxidant 1098 and 401010-20 parts of naphthenic oil.
The invention also provides a preparation method of the EPDM particles with good weather resistance, which comprises the following steps:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing to obtain a mixture after the internal mixing is finished;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, placing the rubber plate in the step S3 into a vulcanizing tank for vulcanizing, opening a valve after vulcanizing is completed, and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
Preferably, the banburying in the step S2 is carried out at the temperature of 90-110 ℃ for 15-25min;
preferably, the vulcanizing temperature in the step S4 is 175-210 ℃, the vulcanizing time is 60-90min, and the vulcanizing pressure is 0.8-1MPa.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the EPDM particles with good weather resistance, the hexafluorobutyl polyacrylate block polybutyl acrylate is prepared by a RAFT polymerization method, then the prepared hexafluorobutyl polyacrylate block polybutyl acrylate is introduced into an EPDM particle formula, and the added hexafluorobutyl polyacrylate block polybutyl acrylate has a 'shielding' effect on a main chain by fluorocarbon bonds, so that the EPDM particles have very high chemical inertness, nonflammability, oxidation resistance, corrosion resistance and radiation resistance, and therefore, the fluorine-containing block part can improve weather resistance, and the fluorine-containing part can provide compatibility; meanwhile, the fluorine-containing part in the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) has small surface tension and mobility, so that the fluorine-containing part can migrate to the surface of the EPDM particles during vulcanization molding of the EPDM particles to form a fluorine protective layer, and the weather resistance of the EPDM particles is effectively improved under the condition that the mechanical properties of the EPDM particles are not influenced.
(2) The EPDM particles with good weather resistance provided by the invention have the advantages that the formula of the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) is simple, the process is stable and controllable, stable amplified preparation can be carried out, and the industrialization advantage is obvious; the addition of the coal slag as the filler in the formula is beneficial to waste utilization, reduces the production cost, improves the heat resistance and flame retardance of the product, avoids the occurrence of melting of the EPDM particles at high temperature, improves the heat stability of the EPDM particles, and improves the comprehensive performance of the EPDM particles.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The ethylene propylene diene monomer is purchased from Dongguan city Shandong feather plastic raw material Co., ltd, and the brand is American Cheng Xiao EPDM (Tao Shidu Bunt) IP 4785HM, and the Mooney viscosity is [ ML (1+4) 100 ℃ C. ]60-70.
The preparation method of the trithioester comprises the following steps: 5g of dodecyl mercaptan, 80mL of acetone, 10mL of distilled water and 0.54g of tetrapropylammonium bromide are added into a three-necked flask, 1g of NaOH is added, stirring is carried out at room temperature, after the NaOH is completely dissolved, the mixture is put into an ice bath, 1.5mL of carbon disulfide is dropwise added into the solution under strong stirring at a slow speed, stirring is carried out for 20min, 3.82g of 2-bromopropionic acid is added into the mixed solution and stirred at room temperature for reaction for 12h, the solvent is removed by rotary evaporation until the volume of 1/4 of the original volume of the mixed solution is reached, the residue is placed into a beaker, 100mL of 2mol/L hydrochloric acid is slowly added for acidification, 150mL of distilled water is added for dilution, precipitate is collected, and yellow trithiocarbonate crystals are obtained by recrystallization in diethyl ether/petroleum ether, so as to obtain trithioester.
Example 1
EPDM particles with good weather resistance comprise the following raw materials: 350g of ethylene propylene diene monomer, 25g of poly (hexafluorobutyl acrylate) block poly (butyl acrylate), 170g of coal mine slag, 130g of asbestos powder, 80g of octyl phenol-formaldehyde vulcanized resin, 35g of accelerator TMTD, 1098 g of antioxidant and 4010 g of naphthenic oil 170g.
A preparation method of EPDM particles with good weather resistance comprises the following steps:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing at 105 ℃ for 20min to obtain a mixture after the internal mixing is finished;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, putting the rubber plate in the step S3 into a vulcanizing tank for vulcanization, wherein the vulcanization temperature is 200 ℃, the vulcanization time is 70min, the vulcanization pressure is 0.9MPa, and after the vulcanization is finished, opening a valve and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
The preparation method of the poly (hexafluorobutyl acrylate) segmented poly (butyl acrylate) comprises the following steps:
(1) 120g of butyl acrylate, 1.3g of azodiisobutyronitrile and 5g of trithioester are added into 400mL of tetrahydrofuran, the mixture is stirred uniformly, then stirred and reacted under nitrogen atmosphere, the reaction temperature is 80 ℃, the reaction time is 7 hours, and after the reaction is completed, methanol aqueous solution (the mass ratio is 1:1) is added, and the precipitation, the filtration and the drying are carried out, so as to obtain the polybutyl acrylate RAFT macromolecular initiator;
(2) Adding the polybutyl acrylate RAFT macroinitiator (140 g), 70g of hexafluorobutyl acrylate and 3g of azodiisobutyronitrile obtained in the step (1) into 400mL of tetrahydrofuran, uniformly stirring, carrying out constant-temperature reaction at 90 ℃ for 13h under nitrogen atmosphere, precipitating with methanol after the reaction is finished, filtering and drying to obtain the polybutyl acrylate hexafluorobutyl acrylate segmented polybutyl acrylate with the number average molecular weight of 7000.
Example 2
EPDM particles with good weather resistance comprise the following raw materials: 450g of ethylene propylene diene monomer, 25g of poly (hexafluorobutyl acrylate) block poly (butyl acrylate), 130g of coal mine slag, 170g of asbestos powder, 70g of sulfur, 25g of accelerator TMTD, 1098 g of antioxidant and 4010 g of naphthenic oil.
A preparation method of EPDM particles with good weather resistance comprises the following steps:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing at a temperature of 100 ℃ for 20min to obtain a mixture after the internal mixing is completed;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, putting the rubber plate in the step S3 into a vulcanizing tank for vulcanization, wherein the vulcanization temperature is 190 ℃, the vulcanization time is 80min, the vulcanization pressure is 0.9MPa, and opening a valve after the vulcanization is completed, and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
The preparation method of the poly (hexafluorobutyl acrylate) segmented poly (butyl acrylate) comprises the following steps:
(1) 110g of butyl acrylate, 1.2g of azodiisobutyronitrile and 4g of trithioester are added into 400mL of tetrahydrofuran, the mixture is stirred uniformly, then stirred and reacted under nitrogen atmosphere, the reaction temperature is 70 ℃, the reaction time is 8 hours, and after the reaction is completed, methanol aqueous solution (the mass ratio is 1:1) is added, and the precipitation, the filtration and the drying are carried out, so as to obtain the polybutyl acrylate RAFT macromolecular initiator;
(2) Adding the polybutyl acrylate RAFT macroinitiator (120 g), 60g of hexafluorobutyl acrylate and 3g of azodiisobutyronitrile obtained in the step (1) into 400mL of tetrahydrofuran, uniformly stirring, carrying out constant-temperature reaction at 80 ℃ for 17 hours in a nitrogen atmosphere, precipitating with methanol after the reaction is finished, filtering and drying to obtain the polybutyl acrylate hexafluorobutyl acrylate segmented polybutyl acrylate with the number average molecular weight of 8000.
Example 3
EPDM particles with good weather resistance comprise the following raw materials: 650g of ethylene propylene diene monomer, 30g of poly (hexafluorobutyl acrylate) block poly (butyl acrylate), 200g of coal mine slag, 200g of asbestos powder, 100g of octyl phenol-formaldehyde vulcanized resin, 40g of accelerator TMTD, 1098 g of antioxidant and 4010 g of naphthenic oil.
A preparation method of EPDM particles with good weather resistance comprises the following steps:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing at 110 ℃ for 15min to obtain a mixture after the internal mixing is finished;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, putting the rubber plate in the step S3 into a vulcanizing tank for vulcanization, wherein the vulcanization temperature is 210 ℃, the vulcanization time is 60min, the vulcanization pressure is 1MPa, and after the vulcanization is finished, opening a valve and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
The preparation method of the poly (hexafluorobutyl acrylate) segmented poly (butyl acrylate) comprises the following steps:
(1) Adding 130g of butyl acrylate, 1.5g of azodiisobutyronitrile and 6g of trithioester into 400mL of tetrahydrofuran, uniformly stirring, then stirring for reaction under a nitrogen atmosphere, wherein the reaction temperature is 90 ℃, the reaction time is 5 hours, adding a methanol aqueous solution (the mass ratio is 1:1) after the reaction is finished, precipitating, filtering and drying to obtain a polybutyl acrylate RAFT macromolecular initiator;
(2) Adding the polybutyl acrylate RAFT macroinitiator (150 g), 80g of hexafluorobutyl acrylate and 4g of azodiisobutyronitrile obtained in the step (1) into 400mL of tetrahydrofuran, uniformly stirring, carrying out constant-temperature reaction at 70-100 ℃ for 10 hours under nitrogen atmosphere, precipitating with methanol after the reaction is finished, filtering and drying to obtain the polybutyl acrylate hexafluorobutyl acrylate block with the number average molecular weight of 9000.
Example 4
EPDM particles with good weather resistance comprise the following raw materials: 200g of ethylene propylene diene monomer, 10g of poly (hexafluorobutyl acrylate) block poly (butyl acrylate), 100g of coal mine slag, 100g of asbestos powder, 50g of dicumyl peroxide, 20g of accelerator TMTD, 1098-10 g of antioxidant and 4010-100 g of naphthenic oil.
A preparation method of EPDM particles with good weather resistance comprises the following steps:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing at the temperature of 95 ℃ for 25min to obtain a mixture after the internal mixing is finished;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, putting the rubber plate in the step S3 into a vulcanizing tank for vulcanization, wherein the vulcanization temperature is 180 ℃, the vulcanization time is 90min, the vulcanization pressure is 0.8MPa, and after the vulcanization is finished, opening a valve and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
The preparation method of the poly (hexafluorobutyl acrylate) segmented poly (butyl acrylate) comprises the following steps:
(1) Adding 100g of butyl acrylate, 1g of azodiisobutyronitrile and 3g of trithioester into 400mL of tetrahydrofuran, uniformly stirring, then stirring for reaction under a nitrogen atmosphere, wherein the reaction temperature is 60 ℃, the reaction time is 10 hours, adding a methanol aqueous solution (the mass ratio is 1:1) after the reaction is finished, precipitating, filtering and drying to obtain a polybutyl acrylate RAFT macromolecular initiator;
(2) Adding 100g of the polybutyl acrylate RAFT macroinitiator obtained in the step (1), 40g of hexafluorobutyl acrylate and 2g of azodiisobutyronitrile into 400mL of tetrahydrofuran, uniformly stirring, carrying out constant-temperature reaction at 70 ℃ for 20 hours in a nitrogen atmosphere, precipitating with methanol after the reaction is finished, filtering and drying to obtain the polybutyl acrylate hexafluorobutyl acrylate segmented polybutyl acrylate with the number average molecular weight of 4000.
Comparative example
EPDM particles with good weather resistance comprise the following raw materials: 350g of ethylene propylene diene monomer, 170g of coal mine slag, 130g of asbestos powder, 80g of octyl phenol-formaldehyde vulcanized resin, 35g of accelerator TMTD, 15g of antioxidant 1098 and 170g of naphthenic oil 4010.
A preparation method of EPDM particles with good weather resistance comprises the following steps:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing at 105 ℃ for 20min to obtain a mixture after the internal mixing is finished;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, putting the rubber plate in the step S3 into a vulcanizing tank for vulcanization, wherein the vulcanization temperature is 200 ℃, the vulcanization time is 70min, the vulcanization pressure is 0.9MPa, and after the vulcanization is finished, opening a valve and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
The vulcanized rubber sheets prepared in examples 1-3 and comparative example S4 were subjected to mechanical property test, wherein the hardness was measured according to the method of standard GB/T531.2-2009; tensile strength and elongation at break were measured according to the method of standard GB/T528-2009; the heat aging treatment is carried out according to the standard GB/T3512-2014, the aging temperature is 90 ℃, and the aging time is 240 hours; ultraviolet aging treatment is carried out by irradiating a tritium lamp with a wavelength of 325nm and a power of 40W for 72 hours according to the standard GB/T16585-1996. The hardness change is the difference between the hardness after aging and the hardness before aging; the method for calculating the tensile strength change rate is as follows: testing the tensile strength after aging according to GB/T528-2009, wherein the ratio of the difference between the tensile strength after aging and the tensile strength before aging is the tensile strength change rate; the calculation method of the elongation at break change rate is as follows: the elongation at break after aging and the difference between the elongation at break after aging and the elongation at break before aging are tested according to GB/T528-2009, and the ratio of the difference to the elongation at break before aging is the elongation at break change rate. The test results are shown in Table 1 below:
TABLE 1
From the changes of physical properties before and after aging in table 1, it can be seen that the EPDM particulate product with good weather resistance prepared by the present invention has less changes in hardness, tensile strength and elongation at break than the comparative examples after heat aging or uv aging treatment, indicating that the product of the present invention has better ageing resistance.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. EPDM particles with good weather resistance are characterized by comprising the following raw materials:
(a) At least one ethylene propylene diene monomer;
(b) At least contains poly (hexafluorobutyl acrylate) block poly (butyl acrylate);
(c) At least contains coal slag, asbestos powder and vulcanizing agent.
2. The EPDM particles of claim 1, wherein the (a) component is 15 to 65 parts by weight, the (b) component is 1 to 3 parts by weight, and the (c) component is 25 to 50 parts by weight.
3. The EPDM particles of claim 1 having good weatherability, wherein the ethylene content of the ethylene propylene diene monomer in component (a) is from 60 to 75% and the mooney viscosity is from 60 to 70; (b) The number average molecular weight of the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) in the components is 3000-10000, wherein the content of the poly (hexafluorobutyl acrylate) is 20-60%.
4. The EPDM particles of claim 1, wherein the process for preparing the poly (hexafluorobutyl acrylate) block poly (butyl acrylate) comprises the steps of:
(1) Adding butyl acrylate, azodiisobutyronitrile and trithioester into tetrahydrofuran, uniformly stirring, then stirring for reaction under nitrogen atmosphere, adding methanol aqueous solution after the reaction is finished, precipitating, filtering and drying to obtain a polybutyl acrylate RAFT macromolecular initiator;
(2) Adding the polybutyl acrylate RAFT macromolecular initiator, hexafluorobutyl acrylate and azodiisobutyronitrile obtained in the step (1) into tetrahydrofuran, uniformly stirring, performing constant-temperature reaction in a nitrogen atmosphere, precipitating with methanol after the reaction is finished, filtering and drying to obtain the polybutyl acrylate hexafluorobutyl acrylate block polybutyl acrylate.
5. The EPDM particles of claim 4, wherein the mass ratio of butyl acrylate, azobisisobutyronitrile, trithio in step (1) is 100-130:1-1.5:3-6, the mass concentration of aqueous methanol solution is 50%, the temperature of stirring reaction is 60-90 ℃, and the reaction time is 5-10h; in the step (2), the mass ratio of the polybutyl acrylate RAFT macroinitiator to the hexafluorobutyl acrylate to the azodiisobutyronitrile is 100-150:40-80:2-4, the temperature of the constant temperature reaction is 70-100 ℃, and the reaction time is 10-20h.
6. The EPDM particles of claim 1, wherein the mass ratio of the coal slag, asbestos powder and vulcanizing agent in the (c) component is 10 to 20:10-20:5-10; the vulcanizing agent is one or more of sulfur, dicumyl peroxide and octyl phenol-formaldehyde vulcanizing resin; the mesh number of the coal slag is 300-400 mesh; the mesh number of the asbestos powder is 600-800 meshes.
7. The EPDM particles of claim 1, wherein component (c) further comprises accelerator TMTD, antioxidant 1098 and naphthenic oil 4010; 2-4 parts of accelerator TMTD, 1-3 parts of antioxidant 1098 and 401010-20 parts of naphthenic oil.
8. A process for the preparation of EPDM particles having good weatherability as claimed in any one of claims 1 to 7, characterized by comprising the steps of:
s1, weighing raw materials according to a formula, and adding the component (c) into a high-speed mixer for uniform mixing to obtain a mixture;
s2, adding the mixture, the component (a) and the component (b) in the step S1 into a mixing chamber of an internal mixer, and carrying out internal mixing to obtain a mixture after the internal mixing is finished;
s3, placing the mixture in the step S2 on a conveyor, conveying the mixture into a feed hopper of an extruder by using the conveyor, and extruding the mixture to prepare a rubber plate for later use;
s4, placing the rubber plate in the step S3 into a vulcanizing tank for vulcanizing, opening a valve after vulcanizing is completed, and discharging steam to obtain a vulcanized rubber plate;
s5, putting the vulcanized rubber plate obtained in the step S4 into a pulverizer for pulverizing, and sieving by a vibrating screen, wherein the sieving particle size is 1mm-3mm, so that the EPDM particles with good weather resistance are obtained.
9. The process of claim 8, wherein the banburying in step S2 is carried out at a temperature of 90 to 110 ℃ for 15 to 25 minutes.
10. The method according to claim 8, wherein the vulcanizing temperature in step S4 is 175-210 ℃, the vulcanizing time is 60-90min, and the vulcanizing pressure is 0.8-1MPa.
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