TWI471344B - 製造含聚丁二烯之模製物的新穎方法 - Google Patents
製造含聚丁二烯之模製物的新穎方法 Download PDFInfo
- Publication number
- TWI471344B TWI471344B TW98136592A TW98136592A TWI471344B TW I471344 B TWI471344 B TW I471344B TW 98136592 A TW98136592 A TW 98136592A TW 98136592 A TW98136592 A TW 98136592A TW I471344 B TWI471344 B TW I471344B
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- Prior art keywords
- polybutadiene
- rubber
- mixture
- filler
- processing aid
- Prior art date
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- 229920002857 polybutadiene Polymers 0.000 title claims description 36
- 239000005062 Polybutadiene Substances 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 14
- 238000000465 moulding Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 10
- 239000000945 filler Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 10
- -1 retarders Chemical class 0.000 claims description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000010455 vermiculite Substances 0.000 claims description 6
- 229910052902 vermiculite Inorganic materials 0.000 claims description 6
- 235000019354 vermiculite Nutrition 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
- 239000005061 synthetic rubber Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 31
- 229920001971 elastomer Polymers 0.000 description 24
- 239000005060 rubber Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 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 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009778 extrusion testing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 1
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 1
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YOWMSIHCBHNOSS-UHFFFAOYSA-N C(C=C)(=O)O.C[Zn]C Chemical compound C(C=C)(=O)O.C[Zn]C YOWMSIHCBHNOSS-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- BTEJNOXJSMLYAY-UHFFFAOYSA-N ClC1=C(C(C2=CC=CC=C2)OOC(C2=C(C=C(C=C2)Cl)Cl)C2=CC=CC=C2)C=CC(=C1)Cl Chemical compound ClC1=C(C(C2=CC=CC=C2)OOC(C2=C(C=C(C=C2)Cl)Cl)C2=CC=CC=C2)C=CC(=C1)Cl BTEJNOXJSMLYAY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CGVUUOPFWNGFMC-UHFFFAOYSA-K bis(2,2-diethylhexanoyloxy)bismuthanyl 2,2-diethylhexanoate Chemical compound [Bi+3].CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O CGVUUOPFWNGFMC-UHFFFAOYSA-K 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
本發明有關一種製造含聚丁二烯之模製物的新穎方法。
含聚丁二烯之模製物主要用於輪胎工業作為側壁或輪面之前板條。此處決定性因素為此等表面光滑及已最小化於其等邊緣之凹痕數目。
具高順式含量及具最小多分散性之聚丁二烯已知提供優異性質於輪胎混合物，如低滾動阻力或低輪胎磨耗。多分散性通常藉由凝膠滲透層析術決定，其為重量平均分子量Mw除以數量平均分子量Mn獲得之商數，如此表示分子量分布之幅度。
如尤其敘述於S.L. Agrawal等人，Rubber World－Akron，2005，第232/3卷，第17至19及56頁，寬廣多分散性有利地影響加工性能，反之狹窄多分散性有利地影響橡膠之服務性質。根據Jochen Schnetger，Lexikon der Kautschuktechnologie[Rubber technology encyclopaedia]，Hthig Verlag Heidelberg，第3版，2003，第319頁，分子量之寬廣分布導致橡膠及橡膠混合物之良好加工性能，尤其明顯於相對低混合物黏度、相對低混合時間及相對低擠壓溫度。為此理由，時常使用具寬廣分子量分布之聚丁二烯，給予可加工性改良，但對輪胎性質輪廓具有不利影響。
因此，在混合物中加工前述具狹窄多分散性之聚丁二烯為困難者。若此等混合物於多數高於90℃之傳統高溫加工，必須大大降低擠壓速度以便獲得可接受的擠壓物品質，此減少方法之成本效益。
因此目的為提供一種製造含聚丁二烯之模製物的新穎之有成本效益的方法，其沒有先前技藝之缺點。
已發現低擠壓溫度對混合物之表面特徵具有有利影響，此為所有較驚訝者，因為其通常是僅較高溫度可改良性質，例如於鈷催化的聚丁二烯情況下。
本發明因此提供一種製造含聚丁二烯之模製物的方法，特徵在於特徵在於將至少一種具順式含量大於95%(較好大於96%)及多分散性小於2.5之聚丁二烯與至少一種填料及與至少一種加工助劑混合，然後於溫度40至75℃(較好40至55℃)擠壓。
使用具順式含量(1,4-順式含量)大於95%(較好大於96%)及多分散性小於2.5(特別好範圍1.7至2.2)之聚丁二烯較好為具有1,2-乙烯基含量小於1%(較好小於0.8%)及孟納(Mooney)黏度ML 1+4於100℃為35至80孟納單位(較好範圍40至75孟納單位)者。使用之彼等較好為釹催化之聚丁二烯(被含釹的系統催化)。此等涉及商業可得之產品。舉例說明，此等可根據EP-A 11 184及EP-A 7027使用含釹的觸媒製造。
術語含釹的觸媒包含以釹化合物為主之戚格勒-納他(Ziegler-Natta)觸媒，此等可溶解於烴。特別好使用羧酸釹，特別是新癸酸釹、辛酸釹、環烷酸釹、2,2-二乙基己酸釹及/或2,2-二乙基庚酸釹。當此等觸媒用於聚合例如丁二烯時，其等呈非常高產率及以高選擇性產生之聚丁二烯，其特別以高比例1,4-順式單元為特色。
在根據本發明方法之具體實例中，使用之填料包括碳黑及/或矽石。
可使用之填料為任何用於橡膠工業之已知填料。此等含括活性及惰性填料兩者。
可提及之實例為：
‧ 精細顆粒矽石，舉例說明經由從矽酸鹽溶液沉澱或火焰水解鹵化矽製造，具比表面積5至1000m2
/g(BET表面積)，較好20至400m2
/g，及具初級顆粒直徑10至400nm。若合適，矽石亦可與其他金屬氧化物(例如Al、Mg、Ca、Ba、Zn、Zr、或Ti之氧化物)成混合氧化物形；
‧ 合成矽酸鹽，例如矽酸鋁，或鹼土金屬矽酸鹽，如矽酸鎂或矽酸鈣，具BET表面積20至400m2
/g及具初級顆粒直徑10至400nm；
‧ 天然矽酸鹽，例如高領土及任何其他由矽石天然出現者；
‧ 玻璃纖維及玻璃纖維產品(蓆墊、繩股)，或玻璃微珠；
‧ 金屬氧化物，例如氧化鋅、氧化鈣、氧化鎂、或氧化鋁；
‧ 金屬碳酸鹽，例如碳酸鎂、碳酸鈣、或碳酸鋅；
‧ 金屬氫氧化物，如氫氧化鋁或氫氧化鎂；
‧ 金屬鹽，具有3至8個碳原子之α,β-不飽和脂肪酸(如丙烯酸或甲基丙烯酸)之鋅或鎂鹽，實例為丙烯酸鋅、二丙烯酸鋅、甲基丙烯酸鋅、二甲基丙烯酸鋅及其混合物；
‧ 碳黑：此處欲被使用之碳黑為由所製造之碳黑，其等BET表面積為9至200m2
/g，如下列碳黑：SAF-、ISAF-LS、ISAF-HM、ISAF-LM、ISAF-HS、CF、SCF、HAF-LS、HAF、HAF-HS、FF-HS、SPF、XCF、FEF-LS、FEF、FEF-HS、GPF-HS、GPF、APF、SRF-LS、SRF-LM、SRF-HS、SRF-HM及MT，或根據ASTM下列碳黑：N110、N219、N220、N231、N234、N242、N294、N326、N327、N330、N332、N339、N347、N351、N356、N358、N375、N472、N539、N550、N568、N650、N660、N754、N762、N765、N774、N787及N990；
‧ 橡膠凝膠，特別是以聚丁二烯、丁二烯-苯乙烯共聚物、丁二烯-丙烯腈共聚物及聚氯平為主者。
較好使用之填料為精細顆粒矽石、碳黑及/或丙烯酸或甲基丙烯酸之鋅鹽。
提及的填料可單獨或呈混合物使用。在特別好具體實例中，使用之填料包括由淡色填料(例如精細顆粒矽石)與碳黑組成之混合物，淡色填料與碳黑之混合比率為0.05至20，較好為0.1至15。
此處填料之使用量範圍較好為10至500重量份填料，以100重量份橡膠為基。特別好使用20至200重量份。
除了提及之聚丁二烯以外，亦可使用其它橡膠，實例為天然橡膠或其它合成橡膠。此等用量通常範圍為0.5至85重量%，較好為10至70重量%，以橡膠混合物中橡膠之總量為基。額外添加的橡膠用量再度取決於各自未來用途。
文獻已知之合成橡膠以舉例說明列舉於此處。其等尤其含括
BR －聚丁二烯
IR －聚異戊二烯
SBR －苯乙烯-丁二烯共聚物，具有苯乙烯含量為1至60重量%，較好為20至50重量%
IIR －異丁烯-異戊二烯共聚物
ABR －丁二烯-丙烯酸C1
-C4
-烷酯共聚物
CR －聚氯平
NBR －丁二烯-丙烯腈共聚物，具有丙烯腈含量為5至60重量%，較好為10至40重量%
HNBR －部分氫化或完全氫化之NBR橡膠
EPDM －乙烯-丙烯-二烯三元共聚物
及亦此等橡膠之混合物。製造機動車輛輪胎之有興趣材料為玻璃轉移溫度高於-50℃之更特別天然橡膠、乳態SBR與溶液SBR，具高順式含量(＞90%)之聚丁二烯橡膠，及亦具有乙烯基含量高至80%之聚丁二烯橡膠，及亦此等混合物。此處涉及商業可得的起始材料。
供本發明目的用，加工助劑包括，例如用於橡樛混合物交聯用之物質(交聯劑)，或改良用於特定目的之所得硫化物的物理性質之物質。
使用之交聯劑特別包括硫或硫供體化合物。適合交聯化學品實例為有機過氧化物，如過氧化二異丙苯、第三丁基過氧化異丙苯、雙(第三丁基過氧基異丙基)苯、過氧化二第三丁基、過氧化二苯甲醯、過氧化雙(2,4-二氯苯甲醯)、過苯甲酸第三丁酯，及亦有機偶氮化合物，例如偶氮雙異丁腈與偶氮雙環己腈，及亦二-與多巰基化合物，例如二巰基乙烷、1,6-二巰基己烷、1,3,5-三巰基三、及巰基為終端之多硫橡膠(如雙氯乙基縮甲醛與多硫化鈉的經巰基終端之反應產物)。再者如提及有可能使用進一步加工助劑，例如已知的反應加速劑、抗氧化劑、熱穩定劑、光穩定劑、抗臭氧化劑、加工助劑、塑化劑、膠黏劑、發泡劑、染料、顏料、蠟、增效劑，如DAE(蒸餾芳香族萃取物)油、TDAE(經處理的蒸餾芳香族萃取物)油、MES(溫和萃取溶劑合物)油、RAE(剩餘芳香族萃取物)油、TRAE(經處理的剩餘芳香族萃取物)油、環烷與重環烷油、有機酸、阻滯劑、金屬氧化物及亦活化劑。
使用之較好加工助劑為反應加速劑、抗氧化劑、抗臭氧化劑、增效劑(如傳統環烷、芳香族或脂族增效劑油)、有機酸(如硬脂酸)、阻滯劑、金屬氧化物(例如氧化鋅)、及亦活化劑(如矽烷)。
加工助劑較好範圍為0.1至20%，以使用之橡膠為基，且取決於混合物想要的性質輪廓。
混合物可舉例說明經由將橡膠與填料及進一步混合組份在適合混合裝置(如捏合機、輥機或擠壓機)之中或之上摻混而製造。
針對使用混合物舉例說明於輪胎工業中、或於製造工業橡膠產品中或於高爾夫球工業中，混合物係用於製造模製物，多數呈擠出物、輪廓或前板條形式。模製物可舉例說明在適合裝置中(例如擠壓機或壓延機)製造。
該加工期間之溫度取決於使用之橡膠。當使用100phr根據本發明聚丁二烯時，較好溫度為40至55℃。與例如苯乙烯-丁二烯橡膠之混合物中，溫度較好為50至75℃，取決於苯乙烯-丁二烯橡膠之比例。此處1phr之含意為1g物質，以100g聚合物為基。
必要溫度多數藉由使用機械能量完成，其中將混合物舉例說明在螺桿為主的擠壓機內部延著相對長路徑揉捏並如此加熱。成形方法多數使用強迫加熱混合物之鑄模。較好意圖在於模製物為尺寸上穩定，具有光滑表面，且在側面或隅角不具有凹痕。
此處所得模製物之品質較好使用Garvey鑄模根據DIN 2230-96於擠壓測試中評估。
取決於該聚丁二烯的比例，當加工溫度降低至40至75℃或在無進一步橡膠成分的混合物情況下降低至數值低於55℃，發現非常容易加工根據本發明具多分散性小於2.5之聚丁二烯且在模製物上產生光滑表面。此方法容許利用此等狹窄分布的聚丁二烯之適宜性質，當與其他聚丁二烯比較時如顯著減少滾動阻力、顯著改良回跳彈性或顯著降低磨耗，良好加工性例如於輪胎工藝之各種混合物、於高爾夫球工業或製造工業橡膠產品。
以下實施例用來闡述本發明，但不具結果限制影響。
製造橡膠混合物包括BUNATM
CB 22與BUNATM
CB 25作為Nd催化的聚丁二烯，及亦(比較用)220與221作為共-聚丁二烯。聚丁二烯之分析結果係載述於表1。表2列出混合物之組份。最初在無硫與加速劑下於1.5L捏合機中製造混合物。然後在輥上於40℃摻混混合物組份硫與加速劑。
PDI=多分散性或多分散性指數
將下列物質用於對混合物之研究：
CE=比較實施例
為了評估表面，透過Garvey鑄模從發明實施例1與2之未硫化混合物及CE1與CE2製造擠出物並研究。使用具Garvey鑄模尺寸16mm/10d之Brabender袖珍擠壓機進行擠壓試驗。根據DIN2230-96評分系統B評估表面品質。輪廓品質自A8至A10被評估為良好，品質自C3至E1被評估為劣等。然而，亦可根據外形在無評分系統下進行評估。
圖1描繪對擠壓的模製物所記錄之表面品質，此處使用之縮寫如下：
I：比較實施例CE1於90℃
II：比較實施例CE1於55℃
III：比較實施例CE2於90℃
IV：比較實施例CE2於55℃
V：發明實施例1於90℃
VI：發明實施例1於55℃
VII：發明實施例2於90℃
VIII：發明實施例2於55℃
對於90℃，桶溫度控制為90℃，鑄模溫度控制為105℃。對於55℃，桶與鑄模的溫度控制於55℃。
可見比較實施例CE1及CE2中對於90℃擠壓模製物(I及III)(具評分A9)之表面品質較對於55℃(II及IV)(具評分C3至D2)本質上更光滑。在發明實施例1及2中，聚丁二烯對於55℃(VI及VIII)(具評分A8至A9)較對於90℃(V及VII)(具評分C3至D2)展現更光滑模製物表面。
圖式清楚顯示低溫對於根據發明實施例1及2混合物的表面輪廓之良好影響。使用具多分散性小於2.5之順-聚丁二烯可結合硫化性質，取決於該聚丁二烯的比例，若加工溫度降低至40至75℃或在無進一步橡膠成分的混合物情況下降低至數值低於55℃，其與其他聚丁二烯相較為非常良好於簡單製造具光滑表面的模製物，如顯著減少滾動阻力、改良回跳彈性或減少磨耗。
較低溫度容許，例如使用Nd催化的聚丁二烯在一般對其他混合物之更高溫度所使用的相同高速下擠壓混合物，且此強調根據本發明方法之品質。
圖1描繪對擠壓的模製物所記錄之表面品質。
Claims (5)
- 一種製造含聚丁二烯的模製物之方法，其特徵在於將至少一種具順式含量大於95%及多分散性小於2.5之聚丁二烯與至少一種填料及與至少一種加工助劑混合，然後於溫度40至75℃擠壓。
- 根據申請專利範圍第1項之方法，其特徵在於使用之聚丁二烯包括由含釹的系統催化之聚丁二烯。
- 根據申請專利範圍第1或2項之方法，其特徵在於使用之填料包括細顆粒矽石、碳黑及/或丙烯酸或甲基丙烯酸之鋅鹽。
- 根據申請專利範圍第1或2項之方法，其特徵在於使用之加工助劑包括交聯劑、反應加速劑、抗氧化劑、熱穩定劑、光穩定劑、抗臭氧劑、加工助劑、塑化劑、膠黏劑、發泡劑、染料、顏料、蠟、增效劑、有機酸、阻滯劑、及/或金屬氧化物、及/或活化劑。
- 根據申請專利範圍第1或2項之方法，其特徵在於亦使用進一步合成橡膠，實例為聚丁二烯、苯乙烯-丁二烯橡膠及/或天然橡膠。
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| CN103694507A (zh) * | 2013-12-24 | 2014-04-02 | 苏州华东橡胶工业有限公司 | 一种改性聚丁二烯橡胶的配方 |
| EP3390516A4 (en) * | 2015-12-15 | 2019-11-13 | Columbian Chemicals Company | CARBON BLACK COMPOSITION COMPRISING A SULFUR DONOR |
| JP6859816B2 (ja) * | 2017-04-03 | 2021-04-14 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物の製造方法 |
| CN110951123B (zh) * | 2019-12-11 | 2021-11-16 | 浙江威格尔传动股份有限公司 | 一种超耐磨皮带的制作工艺 |
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-
2008
- 2008-10-30 DE DE200810053888 patent/DE102008053888A1/de not_active Withdrawn
-
2009
- 2009-10-23 US US13/124,746 patent/US20110288193A1/en not_active Abandoned
- 2009-10-23 RU RU2011121398/05A patent/RU2542226C2/ru not_active IP Right Cessation
- 2009-10-23 KR KR1020117012330A patent/KR101361937B1/ko not_active IP Right Cessation
- 2009-10-23 JP JP2011533690A patent/JP5444364B2/ja not_active Expired - Fee Related
- 2009-10-23 CN CN200980143046.6A patent/CN102197075B/zh not_active Expired - Fee Related
- 2009-10-23 WO PCT/EP2009/063954 patent/WO2010049356A1/de active Application Filing
- 2009-10-23 BR BRPI0919866A patent/BRPI0919866A2/pt not_active Application Discontinuation
- 2009-10-23 EP EP09752318A patent/EP2342273A1/de not_active Withdrawn
- 2009-10-28 AR ARP090104157 patent/AR078595A1/es not_active Application Discontinuation
- 2009-10-29 TW TW98136592A patent/TWI471344B/zh not_active IP Right Cessation
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| US7244192B2 (en) * | 2002-11-21 | 2007-07-17 | Sri Sports Limited | Rubber composition for golf ball |
| US20060264560A1 (en) * | 2003-05-22 | 2006-11-23 | Jsr Corporation | Method for producing modified conjugated diene polymer and rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2342273A1 (de) | 2011-07-13 |
| BRPI0919866A2 (pt) | 2015-12-15 |
| RU2011121398A (ru) | 2012-12-10 |
| KR20110089323A (ko) | 2011-08-05 |
| WO2010049356A1 (de) | 2010-05-06 |
| RU2542226C2 (ru) | 2015-02-20 |
| US20110288193A1 (en) | 2011-11-24 |
| CN102197075B (zh) | 2015-04-29 |
| TW201035135A (en) | 2010-10-01 |
| AR078595A1 (es) | 2011-11-23 |
| JP2012506931A (ja) | 2012-03-22 |
| DE102008053888A1 (de) | 2010-05-06 |
| KR101361937B1 (ko) | 2014-02-13 |
| JP5444364B2 (ja) | 2014-03-19 |
| CN102197075A (zh) | 2011-09-21 |
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