CA2080984A1 - Method for continuously preparing thermo-crosslinkable and/or thermoplastic elastomer blends - Google Patents
Method for continuously preparing thermo-crosslinkable and/or thermoplastic elastomer blendsInfo
- Publication number
- CA2080984A1 CA2080984A1 CA002080984A CA2080984A CA2080984A1 CA 2080984 A1 CA2080984 A1 CA 2080984A1 CA 002080984 A CA002080984 A CA 002080984A CA 2080984 A CA2080984 A CA 2080984A CA 2080984 A1 CA2080984 A1 CA 2080984A1
- Authority
- CA
- Canada
- Prior art keywords
- additives
- mixing
- paste
- stage
- pastes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 229920001971 elastomer Polymers 0.000 claims abstract description 43
- 239000000806 elastomer Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 8
- 238000007872 degassing Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000861718 Chloris <Aves> Species 0.000 description 1
- 206010010219 Compulsions Diseases 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- UAGGVDVXSRGPRP-UHFFFAOYSA-N diethylcarbamothioic s-acid Chemical compound CCN(CC)C(S)=O UAGGVDVXSRGPRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 239000012186 ozocerite Substances 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920003246 polypentenamer Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7485—Systems, i.e. flow charts or diagrams; Plants with consecutive mixers, e.g. with premixing some of the components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
ABSTRACT
A method method for continuously preparing thermo-cross-linkable and/or thermoplastic elastomer blends by mixing the powdered or granulated elastomer with plasticizer oil and other additives, said method comprising the steps of:
(a) continuously premixing said elastomer in a premixer with at least part of said plasticizer oil, and optionally with at least part of said other additives, to form a preblend in which said elastomer is decomposed and said additives are embedded in the polymer matrix;
and thereafter (b) continuously completing the mixing of said premix, and op-tionally of the remainder of said additives in a mixing ex-truder.
A method method for continuously preparing thermo-cross-linkable and/or thermoplastic elastomer blends by mixing the powdered or granulated elastomer with plasticizer oil and other additives, said method comprising the steps of:
(a) continuously premixing said elastomer in a premixer with at least part of said plasticizer oil, and optionally with at least part of said other additives, to form a preblend in which said elastomer is decomposed and said additives are embedded in the polymer matrix;
and thereafter (b) continuously completing the mixing of said premix, and op-tionally of the remainder of said additives in a mixing ex-truder.
Description
20~98~ ^
METHOD FOR CONTINUOUSLY PREPARING THERMO-CROSSLINKABLE AND/OR
THERMOPLASTIC ELASTOMER BLENDS
TECHNICAL FIELD
This invention relates to a method for continuously pre-paring thermo-crosslinkable and/or thermoplastic elastomer blends.
"Thermoplastic elastomers (TPE)" is the generally accept-ed designation for materials in which the elastomeric phases (as soft component) are embedded in plastic material (as hard component). Depending on the nature of this embedding one dis-tingishes between block copolymers and polyblends.
, Furthermore, the thermoplastic elastomers may be classi-fied as follows:
1 Types having ~igh hardness 1.1 Copolyesters 1.2 Polyether block amides ,, ' ' ' ' ; ,~
. , " .
. : -, ,; , :.: : . . ~ : .
-` 2~8~
METHOD FOR CONTINUOUSLY PREPARING THERMO-CROSSLINKABLE AND/OR
THERMOPLASTIC ELASTOMER BLENDS
TECHNICAL FIELD
This invention relates to a method for continuously pre-paring thermo-crosslinkable and/or thermoplastic elastomer blends.
"Thermoplastic elastomers (TPE)" is the generally accept-ed designation for materials in which the elastomeric phases (as soft component) are embedded in plastic material (as hard component). Depending on the nature of this embedding one dis-tingishes between block copolymers and polyblends.
, Furthermore, the thermoplastic elastomers may be classi-fied as follows:
1 Types having ~igh hardness 1.1 Copolyesters 1.2 Polyether block amides ,, ' ' ' ' ; ,~
. , " .
. : -, ,; , :.: : . . ~ : .
-` 2~8~
2 Types having low hardness 2.1 Thermoplastic polyurethanes (TPU) 2.1.1 Polyetherurethanes 2.1.2 Polyesterurethanes 2.2 Thermoplastic polyolefins (TPO) 2.2.1 Ethylene-propylene diene elastomer/polypropylene (EPDM/PP) 2.2.2 Acrylonitrile-butadiene copolymer/polypropylene (NBR/PP) 2~3 Styrene block copolymers 2.3.1 Styrene-butadiene-styrene triblock copolymer (SBS~ : .
2.3.2 Styrene-ethylene/butylene-styrene triblock co polymer (SEBS~.
BACXGROUND OF THE INVENTION
So far, the preparation of thermo-crosslinkable and/or thermoplastic elastomer blends, in particular o~ vulcanizable rubber blends, was generally effected, either:
(a) on a two-roll calender;
or preferably (b) in an internal mixer.
~, , , ,, ,, ,, . , . -, . . .. . . .
- - , , : ., .
: . . . .... . .
' '' ' '' . ~
`` 2 ~
In variant (a), the calender comprised two parallel, hor-izontally mounted heatable and coolable hollow rolls. For car-rying out mixing, the crude rubber was put onto the rolls in the form of coarse pieces, and was worked until a smooth sheet was obtained. Thereafter, the processing and vulcanization ad-juvants were batchwisely added, and the rolled sheet were re-peatedly homogenized by cutting and finally cooled with water in order to prevent them from prematurely vulcaniælng.
Th2 internal mixer according to variant (b) comprised a closed mixing chamber and two heatable and coolable mixing pad-dles arranged in said mixing chamber. This feature did provide, it is true, a higher mixing speed and a more intensive mixing effect than variant (a). However, due to the applied speed of rotation, the crude rubber blend in the internal mixer was so strongly heated that no crosslinking reagents could be added.
Therefore, it was often necessary either - to arrange a calender downstream of said internal mixer and to add sulfur and accelerators to the crude blend removed from the internal mixer on said calender only;
or alternatively ~, : ,, ; ,., :
2 ~
- to prepare a preblend without sulfur and accelerator in a first mixing passage through said interior mixer, and there-after to prepare the final blend with addition of sulfur and accelerator in a second mixing passage through said interior mixer.
Besides the effectiveness of the mixing aggregate, the order and the moment of addition of the adjuvants have a deci-sive influence on the elastomer ~uality. Thus, it was necessary to first add difficultly mixable plasticizers which do not ini-tiate crosslinking, and to add vulcanizing agents at the end only.
So far, the attempts for achieving a continuous mixing in mixing extruders failed for the abovementioned compulsion of observing this order. Calculations show that a spindle length of the order of 40-D would be necessary (D being the spindle diameter). This is technically difficult to realize and econom-ically unattractive.
Furthermore, the use of plasticized elastomers or the ad-dition of large q~lantities of plasticizers was critical since the shearing forces produceable in the mixture were no longer sufficient for a regular mixing.
.
.
2~sn~
OBJECTS OF THE INVENTION
It is a primary object of the present invention is to provide a method for continuously preparing thermo-crosslink-able and/or thermoplastic elastomer blends which avoids the abovementioned disadvantages of the prior art.
It is a further object of the invention to provide a method for continuously preparing thermo~crosslinkable and/or thermoplastic elastomer blends, in particular of vulcanizable rubbPr blends, which allows using simple mixers or mixing ex-truders.
SUMMARY OF THE INVENTION
To meet these and other objects, the present invention provides a method for continuously preparing thermo-crosslink-able and/or thPrmoplastic elastomer blends by mixing the pow-dered or granulated elastomer with plasticizer oil and other additives, said method comprising the steps of:
(a) continuously premixing said elastomer in a premixer with at least part of said plasticizer oil, and optionally with at least part of said other additives, to form a preblend in which said elastomer is decomposed and said additives are embedded in the polymer matrix;
and thereafter (b) continuously completing the mixing of said premix, and op-tionally o~ the remainder of said additives in a mixing ex~
truder.
In the method according to the invention, said premixer of said first step ~a) has the function of decomposing the elastomer to such an extent that a mixing with the adjuvants becomes possible. Thus a large part of the total mixing process is e~fected in said premixer, whereas the function of said mix-ing extruder is reduced to a simple aftermixing. This was most surprising to a person skilled in the art~
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In applying the method according to the invention, all known groups of adjuvants can be used, that is to say:
1 Crosslinking systems, in particular vulcanization agents.
2 Fillers, namely:
:
' , 2 0 ~
2.1 Active fillers which result :in a decisive improvement of the mechanical properties, particularly of the tensile strength and the abrasion resistance, such as: types of active black carbon, aluminium and calcium silicate, and zinc oxide; or 2.2 Inactive fillers which do not result in a quantitative improvement of the vulcanized goods, for example calcium and magnesium carbonate, kaolin, barite, kieselguhr, and various clays;
2.3 For elastomers which are not filled with carbon black:
dyes, namely:
2.3.1 Inorganic pigments, for example lithopone, titani-um dioxide, iron oxide, and chrome oxide green; or 2.3.2 Organic dyes, for example azo, alizarin and phthalocyanine dyes.
2.3.2 Styrene-ethylene/butylene-styrene triblock co polymer (SEBS~.
BACXGROUND OF THE INVENTION
So far, the preparation of thermo-crosslinkable and/or thermoplastic elastomer blends, in particular o~ vulcanizable rubber blends, was generally effected, either:
(a) on a two-roll calender;
or preferably (b) in an internal mixer.
~, , , ,, ,, ,, . , . -, . . .. . . .
- - , , : ., .
: . . . .... . .
' '' ' '' . ~
`` 2 ~
In variant (a), the calender comprised two parallel, hor-izontally mounted heatable and coolable hollow rolls. For car-rying out mixing, the crude rubber was put onto the rolls in the form of coarse pieces, and was worked until a smooth sheet was obtained. Thereafter, the processing and vulcanization ad-juvants were batchwisely added, and the rolled sheet were re-peatedly homogenized by cutting and finally cooled with water in order to prevent them from prematurely vulcaniælng.
Th2 internal mixer according to variant (b) comprised a closed mixing chamber and two heatable and coolable mixing pad-dles arranged in said mixing chamber. This feature did provide, it is true, a higher mixing speed and a more intensive mixing effect than variant (a). However, due to the applied speed of rotation, the crude rubber blend in the internal mixer was so strongly heated that no crosslinking reagents could be added.
Therefore, it was often necessary either - to arrange a calender downstream of said internal mixer and to add sulfur and accelerators to the crude blend removed from the internal mixer on said calender only;
or alternatively ~, : ,, ; ,., :
2 ~
- to prepare a preblend without sulfur and accelerator in a first mixing passage through said interior mixer, and there-after to prepare the final blend with addition of sulfur and accelerator in a second mixing passage through said interior mixer.
Besides the effectiveness of the mixing aggregate, the order and the moment of addition of the adjuvants have a deci-sive influence on the elastomer ~uality. Thus, it was necessary to first add difficultly mixable plasticizers which do not ini-tiate crosslinking, and to add vulcanizing agents at the end only.
So far, the attempts for achieving a continuous mixing in mixing extruders failed for the abovementioned compulsion of observing this order. Calculations show that a spindle length of the order of 40-D would be necessary (D being the spindle diameter). This is technically difficult to realize and econom-ically unattractive.
Furthermore, the use of plasticized elastomers or the ad-dition of large q~lantities of plasticizers was critical since the shearing forces produceable in the mixture were no longer sufficient for a regular mixing.
.
.
2~sn~
OBJECTS OF THE INVENTION
It is a primary object of the present invention is to provide a method for continuously preparing thermo-crosslink-able and/or thermoplastic elastomer blends which avoids the abovementioned disadvantages of the prior art.
It is a further object of the invention to provide a method for continuously preparing thermo~crosslinkable and/or thermoplastic elastomer blends, in particular of vulcanizable rubbPr blends, which allows using simple mixers or mixing ex-truders.
SUMMARY OF THE INVENTION
To meet these and other objects, the present invention provides a method for continuously preparing thermo-crosslink-able and/or thPrmoplastic elastomer blends by mixing the pow-dered or granulated elastomer with plasticizer oil and other additives, said method comprising the steps of:
(a) continuously premixing said elastomer in a premixer with at least part of said plasticizer oil, and optionally with at least part of said other additives, to form a preblend in which said elastomer is decomposed and said additives are embedded in the polymer matrix;
and thereafter (b) continuously completing the mixing of said premix, and op-tionally o~ the remainder of said additives in a mixing ex~
truder.
In the method according to the invention, said premixer of said first step ~a) has the function of decomposing the elastomer to such an extent that a mixing with the adjuvants becomes possible. Thus a large part of the total mixing process is e~fected in said premixer, whereas the function of said mix-ing extruder is reduced to a simple aftermixing. This was most surprising to a person skilled in the art~
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In applying the method according to the invention, all known groups of adjuvants can be used, that is to say:
1 Crosslinking systems, in particular vulcanization agents.
2 Fillers, namely:
:
' , 2 0 ~
2.1 Active fillers which result :in a decisive improvement of the mechanical properties, particularly of the tensile strength and the abrasion resistance, such as: types of active black carbon, aluminium and calcium silicate, and zinc oxide; or 2.2 Inactive fillers which do not result in a quantitative improvement of the vulcanized goods, for example calcium and magnesium carbonate, kaolin, barite, kieselguhr, and various clays;
2.3 For elastomers which are not filled with carbon black:
dyes, namely:
2.3.1 Inorganic pigments, for example lithopone, titani-um dioxide, iron oxide, and chrome oxide green; or 2.3.2 Organic dyes, for example azo, alizarin and phthalocyanine dyes.
3 Plasticizers for improving the processing properties, the elasticity, and the cold-behavior, namely:
3.1 For non-polar or weakly polar crude rubber types (for example natural rubber (NR), styrene-butadiene copoly-mers (SBR~, polybutadiene (BR), isobutylene-isoprene co-polymers (IIR)): mineral oil products.
.
, . , :
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:' ' ' " ` '' :,' ' :, : `
2~93'~
3.2 For more polar types (for example acrylonitrile-buta-diene copolymer (NBR) and polychlorobutadiene (CR)):
phthalates (for example dibut:yl and dioctylphthalate), phosphoric esters (for example tricresyl phosphate), and aromatic mineral oils.
3.3 Further processing adjuvants, for exampie factices (i.e vegetable oils treated with sulfur or sulfur chlori~e), lanoline, soft paraffin, soft polyethylene, bitumen, and pitch.
3.1 For non-polar or weakly polar crude rubber types (for example natural rubber (NR), styrene-butadiene copoly-mers (SBR~, polybutadiene (BR), isobutylene-isoprene co-polymers (IIR)): mineral oil products.
.
, . , :
", .: . , : ., ' ! .
:' ' ' " ` '' :,' ' :, : `
2~93'~
3.2 For more polar types (for example acrylonitrile-buta-diene copolymer (NBR) and polychlorobutadiene (CR)):
phthalates (for example dibut:yl and dioctylphthalate), phosphoric esters (for example tricresyl phosphate), and aromatic mineral oils.
3.3 Further processing adjuvants, for exampie factices (i.e vegetable oils treated with sulfur or sulfur chlori~e), lanoline, soft paraffin, soft polyethylene, bitumen, and pitch.
4 Age protectors for improving the resistance of the finished vulcanized good against oxygen, the action of light, and dy-namic strain, namely:
4.1 For protecting elastomers the macromolecules of which contain double bonds against oxygen and ozone: antioxi-dants, for example amines and phenols;
4.2 Screening agents, in particular paraffinic substances, for example ceresin and ozocerite;
4.3 For retarding the hydrolysis of elastomers having the 'endency to hydrolyze (for example polyurethane elasto-mers (PU) and ethylene-vinylacetate copolymers (EVA):
polycarbodiimine.
.. . : ::
- :
- . .
2 ~
g Other adjuvants, namely:
4.1 For protecting elastomers the macromolecules of which contain double bonds against oxygen and ozone: antioxi-dants, for example amines and phenols;
4.2 Screening agents, in particular paraffinic substances, for example ceresin and ozocerite;
4.3 For retarding the hydrolysis of elastomers having the 'endency to hydrolyze (for example polyurethane elasto-mers (PU) and ethylene-vinylacetate copolymers (EVA):
polycarbodiimine.
.. . : ::
- :
- . .
2 ~
g Other adjuvants, namely:
5.1 Agant for influencing the st-ickiness, namely:
5.1.1 Agents for reducing the undesired adherence of the crude rubber during its processing, for example paraffin, lanoline, stearic acid and its salts;
5.1.2 Agents for improving the stickiness of the crude rubber during its assembly, ~or example colophoni-um, coumarone resins, alkylphenol acetylene con-densates, as well as low-molecular polyethylenes.
5.2 Adhesives which are necessary for manufacturing firm joints between elastomers and metals, as well as com-pound materials with ~abrics, for example in the tire production and for conveyor belts, namely:
5.2.1 For manufacturing metallic compound materials: for example cobalt naphthenate, recorcin resin, as well as increased quantities of sulfur;
5.2.2 For manufacturing textile compound materials: for example styrene-butadiene-vinylpyridine terpoly-mers in combination with resorcinol formaldehyde resins and special isocyanates.
~: ~
- 10 - 2~ g~
5.3 Foaming agents for the manufacturing of porous vulcaniz-ed goods, for example sulfohydrazides (such as benzene-sul*ohydrazide), nitroso compounds (such as dinitroso-pentamethylenetetramine and am- monium carbonateO
As a general rule, the adjuvants can be used with the commercial grain sizes in the my-range. Their use in paste form provides the possibility of refining them, in particular to pulverize, to disperse or to degas them. This makes it possible to use coarse-grinded and therefore less expensive adjuvants, for example blacX carbons.
In carrying out the method of the invention, at least part of said plasticizer oil and at least part of said other additives may be converted into one or several pastes which are introduced into said premixer of said first step (a).
If pastes are to be prepared from said adjuvants, it is obviously necessary that the quantity of liquid adjuvants, and in particular of plasticizer oil r be high enough.
A single paste may be produced ~rom all additives, said single paste being then introduced into said premixer of said first step (a).
:. ,.: :. : . : -~
,, "., .
Alternatively, said additives may be shar~d for preparingseveral pastes, preferably two pastes, which are then intro-duced into said premixer of said first step (a), either sepa-rately or after being mixed together.
If said adjuvants are to be converted into a paste or pastes, respectively, the quantity of liquid ingredients, in particular that of the plasticizer oil, should obviously be high enough for allowing the effective forming of a paste or of pastes, respectively.
Preferably, groups of adjuvants which remain unchanged for different applications are combined into one paste. For ex~
ample, when working with two pastes, one of them may colour-neutral and the other paste may be coloured. In this way it is possible to use the colour-neutral paste for the manufacturing of differently coloured elastomer mixtures, so that only the coloured paske is to be adapked to the desired colouring.
Said single paste or said pastes, respectively, may be refined before being introduced into said premixer of said first step (a), in particular by pulverization, by dispersing, or by degasification.
... .
- 12 - 2~
Since homogenous mixing of the various ingredients is the easier the quantities of the various adjuvants are equal, it is advisable to prepare first a prepaste of those adjuvants which are needed in relatively small quantities only, and t~ mix said prepaste with the other pasta or pastes, respectively, before mixing it with the elastomer.
Alternatively, part of the additives, which are in pow dered form, may be directly introduced into said premixer of said first step (a) and/or part of the additives, which are in powdered or paste form, may be directly introduced into said mixing extruder of said second step (b). The latter is particu-larly useful if mixtures, for example tire mixtures, are to be prepared in which the quantity of plasticizer is relatively small as compared with that of the the fillers.
Preferably, a continuously working high speed turbomixer is used as premixer, said turbomixer working for example at 2000 r.p.m (revolutions per minute), and in particular a annu-lar zone mixer. As it is generally known, this mixing device has a shaft provided with teeth which rotates with high speed inside a smooth tllbe. Thereby, a turbulent annular zone is pro-duced near the wall of the tube. The decomposition of the elas-tomer and its mixing with the other ingredients is essentially effected exclusively in this zone, due to the high ~rictional forces produced by said turbulence.
:: :
:: . . ... ..
:
, ; .
..
2~g~
The method according to the invention may be used for preparing crosslinkable and/or thermoplastic elastomer blends form all crosslinkable or thermoplastic elastomers, and in par-ticular from:
- natural rubber tNR), - synthetic cis-1,4-polyisoprene (IR), - cis-1,4-polybutadiene (BR), - styrene-butadiene copolymer (SBR), - acrylonitrile-butadiene copolymers (NBR), - poly-2-chlorobutadiene (CR), - isobutylene-isoprene copolymers (IIR), - ethylene-propylene-dien terpolymers (EPDM), - ethylene propylene copolymers (EPM), - ethylene-vinylacetate copolymers (EVA), - polyurethane elastomers (PU), - polysulfide elastomer (PSR), - polyacrylate elastomers (AR), - polyepichlorohydrin elastomers (CHR), - sulfochlorinated polyethylene (CSM), - fluorocarbon elastomers (FE), - silicone elastomers (SIR), - 1,5-trans-polypentenamers (TPR), - ethylene-proyplene-dien elastomer/polyproylene polyblend (EPDM/PP), :~ . . : .
. . .
~ ~J ~
- acrylonitrile-butadien copolymer/polypropylene polyblend (NBR/PP), - styrene-butadiene-styrene triblock copolymer (SBS), - styrene-ethylene/butaylene-styrene triblock copolymer (SEBS).
For preparing commercial semifinished products, the re-sulting mixture is preferably continuously pelleted after the mixing procedure. Preferably, the obtained pellets, depending of the intended use, are either immediately :
- continuously heated in order to vulcanize or crosslink them, respectively;
or - continuously cooled in order to prevent them from vulcaniza-tion or crosslinking, respectively.
Alternatively, the elastomer mixture coming out from the mixing extruder may be directly subject to its final shaping procedure, for example in an extruder or on a calender.
The method according to the invention shows a number of outstanding advantages, as compared with the status of the art, namely:
~;, ~ , . :, .
~o~n~
The admixing of the adjuvants is extremely simple and ener-gy-saving.
The mixing extruder necessary for completing the mixing pro-cedure, i.e. an Pxtruder comprising a mixing zone, can be of simple and light construction, due to the fact that only a low speed of rotation, for example 100 r.p.m. (revolutions per minute), is necessary. A spindle length of 12 D to 18D is quite sufficient. Such mixing extruders have a very high throughput, as compared with the vulcanization devices according to the status of the art.
At the same time, the mixing is extremely energy-saving, since the elastomer is already present in the form of a pow-der or a granulate and does not need to be rendered flowable or kneadable by the application of heat. Accordingly, the mechanical overdimensioning of the mixing device, which was so far necessary, is dropped.
The present problem of a subsequent treatment owing to bub-ble formation does no longer exist, a short degasification segment being just sufficient. A typical mixing extruder may, for example, comprise the following se~ments:
..
, , .
~; , , - Addition of materials (premix ~ eventual powders): 2-D
- Mixing: ~ D
- Degasification: 4-D
- Mixing: 4-D
- Total length: 14-D
The elastomers used can - per se - be unplasticized. This not only facilitates their pulverization or granulation, re-spectively, but also avoids the situation where, due to in-sufficient shearing forces, an effective mixing is no longer possible.
From the point of view of industrial hygiene, it is impor-tant that a dust-free working is possible both at the pre-mixer and at the mixing extruder.
~ . . . . .
': ' '~
-, , : ' ;~` ~ ` ` ' 2 ~
PREPARATION OF THE BLENDS FOR EX~MPLES 1 TO 3 Three vulcanizable rubber blends were prepared form the following ingredients in the manner described hereafter. The "parts" referred to are parts by weight.
No. Component Parts Parts 1 BUNA AP 447 1) 100.0 2 Zinc oxide RS 5.0 3.1 Stearic acid 1.0 3.2 Stearic acid 1.0 :
3 Total stearic acid 2.0 4 Chalk . 250.0 5.1 Paraffinic/naphthenic mineral oil70.0 5.2 Paraffinic/naphthenic mineral oil10.0 5 Total paraffinic/naphthenic mineral oil 80.0 6 Iron oxide red 6.0 7 Sulfur 7.0 8 W LCACIT CZ 2) 1.0 9 W LCACIT LDA 3) 1.0 10 W LCACIT Thiuram 4) 0.4 Total 452.4 :'~
2~'3~
1) EPDM = ethylene-propylene-dien terpolymer -grain size smaller than 10 mm 2) CPS = benzodiacetyl-2-cyclohexyl sulfenamide 3) ZDEC = zinc N diethyl thiocarbamate 4) TMTB = tetramethyl thiuramdisulfide All adjuvants (Nos. 2, 3, 4, 5, 6, 7, 8, 9 and 10) were mixed to from one single paste. This paste/ if desired after homogenization, was premixed with the elastomer (No. 1) in an annular zone mixer, the elastomer thereby being decomposed. The resulting premix was then introduced into the material feed sector of a mixing extruder.
The adjuvants Nos. 2, 3.1, 4, 5.1, 7, 8, 9 and 10 were mixed to form a colour-neutral paste, and the adjuvants Nos.
3.2, 5.2 and 6 were mixed to form a coloured paste. These pastes, if desired after homogenization, were premixed with the elastomer (No. 1) in an annular zone mixer, the elastomer thereby being decomposed. The resulting premix was then intro~
duced into the material feed sector of a mixing extruder.
, , :
2 ~
The adjuvants Nos. 2, 3, 7, 8, 9 and 10 were premixed to form a prepaste, and the adjuvants Nos. 4, 5 and 6 were mixed to form a main paste. Then, the two pastes were combined. The comhined sinqle paste, if desired after homogenization, was premixed with the elastomer (No. 1) in an annular zone mixer, the elastomer thereby being decomposed. The resulting premix was then introduced into the material feed sector of a mixing extruder.
A typical tire mixture was prepared from the following ingredients, the "parts" referred to being again parts by weight:
100 parts rubber parts plasticizer oil 60 to 80 parts carbon.black 8 to 10 parts other adjuvants (including sulfur).
. ~ '~ ..
9~
The rubber, the plasticizer o:il and the other adjuvants were continuously premixed in an annular zone mixer rotating at 2000 r.p.m. (revolutions per minute~. The resulting blend and the carbon black were then introduced into a vulcanization ex-truder. There, the elastomer blend was completed.
,,, ~ ".
5.1.1 Agents for reducing the undesired adherence of the crude rubber during its processing, for example paraffin, lanoline, stearic acid and its salts;
5.1.2 Agents for improving the stickiness of the crude rubber during its assembly, ~or example colophoni-um, coumarone resins, alkylphenol acetylene con-densates, as well as low-molecular polyethylenes.
5.2 Adhesives which are necessary for manufacturing firm joints between elastomers and metals, as well as com-pound materials with ~abrics, for example in the tire production and for conveyor belts, namely:
5.2.1 For manufacturing metallic compound materials: for example cobalt naphthenate, recorcin resin, as well as increased quantities of sulfur;
5.2.2 For manufacturing textile compound materials: for example styrene-butadiene-vinylpyridine terpoly-mers in combination with resorcinol formaldehyde resins and special isocyanates.
~: ~
- 10 - 2~ g~
5.3 Foaming agents for the manufacturing of porous vulcaniz-ed goods, for example sulfohydrazides (such as benzene-sul*ohydrazide), nitroso compounds (such as dinitroso-pentamethylenetetramine and am- monium carbonateO
As a general rule, the adjuvants can be used with the commercial grain sizes in the my-range. Their use in paste form provides the possibility of refining them, in particular to pulverize, to disperse or to degas them. This makes it possible to use coarse-grinded and therefore less expensive adjuvants, for example blacX carbons.
In carrying out the method of the invention, at least part of said plasticizer oil and at least part of said other additives may be converted into one or several pastes which are introduced into said premixer of said first step (a).
If pastes are to be prepared from said adjuvants, it is obviously necessary that the quantity of liquid adjuvants, and in particular of plasticizer oil r be high enough.
A single paste may be produced ~rom all additives, said single paste being then introduced into said premixer of said first step (a).
:. ,.: :. : . : -~
,, "., .
Alternatively, said additives may be shar~d for preparingseveral pastes, preferably two pastes, which are then intro-duced into said premixer of said first step (a), either sepa-rately or after being mixed together.
If said adjuvants are to be converted into a paste or pastes, respectively, the quantity of liquid ingredients, in particular that of the plasticizer oil, should obviously be high enough for allowing the effective forming of a paste or of pastes, respectively.
Preferably, groups of adjuvants which remain unchanged for different applications are combined into one paste. For ex~
ample, when working with two pastes, one of them may colour-neutral and the other paste may be coloured. In this way it is possible to use the colour-neutral paste for the manufacturing of differently coloured elastomer mixtures, so that only the coloured paske is to be adapked to the desired colouring.
Said single paste or said pastes, respectively, may be refined before being introduced into said premixer of said first step (a), in particular by pulverization, by dispersing, or by degasification.
... .
- 12 - 2~
Since homogenous mixing of the various ingredients is the easier the quantities of the various adjuvants are equal, it is advisable to prepare first a prepaste of those adjuvants which are needed in relatively small quantities only, and t~ mix said prepaste with the other pasta or pastes, respectively, before mixing it with the elastomer.
Alternatively, part of the additives, which are in pow dered form, may be directly introduced into said premixer of said first step (a) and/or part of the additives, which are in powdered or paste form, may be directly introduced into said mixing extruder of said second step (b). The latter is particu-larly useful if mixtures, for example tire mixtures, are to be prepared in which the quantity of plasticizer is relatively small as compared with that of the the fillers.
Preferably, a continuously working high speed turbomixer is used as premixer, said turbomixer working for example at 2000 r.p.m (revolutions per minute), and in particular a annu-lar zone mixer. As it is generally known, this mixing device has a shaft provided with teeth which rotates with high speed inside a smooth tllbe. Thereby, a turbulent annular zone is pro-duced near the wall of the tube. The decomposition of the elas-tomer and its mixing with the other ingredients is essentially effected exclusively in this zone, due to the high ~rictional forces produced by said turbulence.
:: :
:: . . ... ..
:
, ; .
..
2~g~
The method according to the invention may be used for preparing crosslinkable and/or thermoplastic elastomer blends form all crosslinkable or thermoplastic elastomers, and in par-ticular from:
- natural rubber tNR), - synthetic cis-1,4-polyisoprene (IR), - cis-1,4-polybutadiene (BR), - styrene-butadiene copolymer (SBR), - acrylonitrile-butadiene copolymers (NBR), - poly-2-chlorobutadiene (CR), - isobutylene-isoprene copolymers (IIR), - ethylene-propylene-dien terpolymers (EPDM), - ethylene propylene copolymers (EPM), - ethylene-vinylacetate copolymers (EVA), - polyurethane elastomers (PU), - polysulfide elastomer (PSR), - polyacrylate elastomers (AR), - polyepichlorohydrin elastomers (CHR), - sulfochlorinated polyethylene (CSM), - fluorocarbon elastomers (FE), - silicone elastomers (SIR), - 1,5-trans-polypentenamers (TPR), - ethylene-proyplene-dien elastomer/polyproylene polyblend (EPDM/PP), :~ . . : .
. . .
~ ~J ~
- acrylonitrile-butadien copolymer/polypropylene polyblend (NBR/PP), - styrene-butadiene-styrene triblock copolymer (SBS), - styrene-ethylene/butaylene-styrene triblock copolymer (SEBS).
For preparing commercial semifinished products, the re-sulting mixture is preferably continuously pelleted after the mixing procedure. Preferably, the obtained pellets, depending of the intended use, are either immediately :
- continuously heated in order to vulcanize or crosslink them, respectively;
or - continuously cooled in order to prevent them from vulcaniza-tion or crosslinking, respectively.
Alternatively, the elastomer mixture coming out from the mixing extruder may be directly subject to its final shaping procedure, for example in an extruder or on a calender.
The method according to the invention shows a number of outstanding advantages, as compared with the status of the art, namely:
~;, ~ , . :, .
~o~n~
The admixing of the adjuvants is extremely simple and ener-gy-saving.
The mixing extruder necessary for completing the mixing pro-cedure, i.e. an Pxtruder comprising a mixing zone, can be of simple and light construction, due to the fact that only a low speed of rotation, for example 100 r.p.m. (revolutions per minute), is necessary. A spindle length of 12 D to 18D is quite sufficient. Such mixing extruders have a very high throughput, as compared with the vulcanization devices according to the status of the art.
At the same time, the mixing is extremely energy-saving, since the elastomer is already present in the form of a pow-der or a granulate and does not need to be rendered flowable or kneadable by the application of heat. Accordingly, the mechanical overdimensioning of the mixing device, which was so far necessary, is dropped.
The present problem of a subsequent treatment owing to bub-ble formation does no longer exist, a short degasification segment being just sufficient. A typical mixing extruder may, for example, comprise the following se~ments:
..
, , .
~; , , - Addition of materials (premix ~ eventual powders): 2-D
- Mixing: ~ D
- Degasification: 4-D
- Mixing: 4-D
- Total length: 14-D
The elastomers used can - per se - be unplasticized. This not only facilitates their pulverization or granulation, re-spectively, but also avoids the situation where, due to in-sufficient shearing forces, an effective mixing is no longer possible.
From the point of view of industrial hygiene, it is impor-tant that a dust-free working is possible both at the pre-mixer and at the mixing extruder.
~ . . . . .
': ' '~
-, , : ' ;~` ~ ` ` ' 2 ~
PREPARATION OF THE BLENDS FOR EX~MPLES 1 TO 3 Three vulcanizable rubber blends were prepared form the following ingredients in the manner described hereafter. The "parts" referred to are parts by weight.
No. Component Parts Parts 1 BUNA AP 447 1) 100.0 2 Zinc oxide RS 5.0 3.1 Stearic acid 1.0 3.2 Stearic acid 1.0 :
3 Total stearic acid 2.0 4 Chalk . 250.0 5.1 Paraffinic/naphthenic mineral oil70.0 5.2 Paraffinic/naphthenic mineral oil10.0 5 Total paraffinic/naphthenic mineral oil 80.0 6 Iron oxide red 6.0 7 Sulfur 7.0 8 W LCACIT CZ 2) 1.0 9 W LCACIT LDA 3) 1.0 10 W LCACIT Thiuram 4) 0.4 Total 452.4 :'~
2~'3~
1) EPDM = ethylene-propylene-dien terpolymer -grain size smaller than 10 mm 2) CPS = benzodiacetyl-2-cyclohexyl sulfenamide 3) ZDEC = zinc N diethyl thiocarbamate 4) TMTB = tetramethyl thiuramdisulfide All adjuvants (Nos. 2, 3, 4, 5, 6, 7, 8, 9 and 10) were mixed to from one single paste. This paste/ if desired after homogenization, was premixed with the elastomer (No. 1) in an annular zone mixer, the elastomer thereby being decomposed. The resulting premix was then introduced into the material feed sector of a mixing extruder.
The adjuvants Nos. 2, 3.1, 4, 5.1, 7, 8, 9 and 10 were mixed to form a colour-neutral paste, and the adjuvants Nos.
3.2, 5.2 and 6 were mixed to form a coloured paste. These pastes, if desired after homogenization, were premixed with the elastomer (No. 1) in an annular zone mixer, the elastomer thereby being decomposed. The resulting premix was then intro~
duced into the material feed sector of a mixing extruder.
, , :
2 ~
The adjuvants Nos. 2, 3, 7, 8, 9 and 10 were premixed to form a prepaste, and the adjuvants Nos. 4, 5 and 6 were mixed to form a main paste. Then, the two pastes were combined. The comhined sinqle paste, if desired after homogenization, was premixed with the elastomer (No. 1) in an annular zone mixer, the elastomer thereby being decomposed. The resulting premix was then introduced into the material feed sector of a mixing extruder.
A typical tire mixture was prepared from the following ingredients, the "parts" referred to being again parts by weight:
100 parts rubber parts plasticizer oil 60 to 80 parts carbon.black 8 to 10 parts other adjuvants (including sulfur).
. ~ '~ ..
9~
The rubber, the plasticizer o:il and the other adjuvants were continuously premixed in an annular zone mixer rotating at 2000 r.p.m. (revolutions per minute~. The resulting blend and the carbon black were then introduced into a vulcanization ex-truder. There, the elastomer blend was completed.
,,, ~ ".
Claims (17)
1. A method for continuously preparing thermo-crosslink-able and/or thermoplastic elastomer blends by mixing the pow-dered or granulated elastomer with plasticizer oil and other additives, said method comprising the steps of:
(a) continuously premixing said elastomer in a premixer with at least part of said plasticizer oil, and optionally with at least part of said other additives, to form a preblend in which said elastomer is decomposed and said additives are embedded in the polymer matrix;
and thereafter (b) continuously completing the mixing of said premix, and op-tionally of the remainder of said additives in a mixing ex-truder.
(a) continuously premixing said elastomer in a premixer with at least part of said plasticizer oil, and optionally with at least part of said other additives, to form a preblend in which said elastomer is decomposed and said additives are embedded in the polymer matrix;
and thereafter (b) continuously completing the mixing of said premix, and op-tionally of the remainder of said additives in a mixing ex-truder.
2. The method of claim 1 wherein at least part of said plasticizer oil and at least part of the other additives are converted into one or several pastes, said paste or pastes, re-spectively, being introduced into said premixer of said first stage (a).
3. The method of claim 2 wherein one single paste is prepared from all additives, said single paste being introduced into said premixer of said first stage (a).
4. The method of claim 2 wherein said additives are shared for preparing several pastes which then are introduced into said premixer of said first step (a).
5. The method of claim 4 wherein two pastes are prepared.
6. The method of claim 5 wherein one paste is colour-neutral and the other paste is coloured.
7. The method of claim 3 wherein said paste is refined before being introduced into said premixer of said first stage (a).
8. The method of claim 7 wherein said paste is refined by pulverization, by dispersing, or by degasification.
9. The method of claim 4 wherein said pastes are refined before being introduced into said premixer of said first stage (a).
10. The method of claim 9 wherein said pastes are refined by pulverization, by dispersing, or by degasification.
11. The method of claim 4 wherein said pastes are sepa-rately introduced into said premixer of said first stage (a).
12. The method of claim 4 wherein part of said additives are combined to form a prepaste which is mixed with at least one of the other pastes before being introduced into said pre-mixer of said first stage (a).
13. The method of claim 1 wherein part of said additives, which are in powder form, is directly introduced into said pre-mixer of said first stage (a).
14. The method of claim 2 wherein part of said additives, which are in powder form, is directly introduced into said pre-mixer of said first stage (a).
15. The method of claim 1 wherein part of said additives, which are in powder or paste form, is directly introduced into said mixing extruder of said second stage (b).
16. The method of claim 2 wherein part of said additives, which are in powder or paste form, is directly introduced into said mixing extruder of said second stage (b).
17. The method of claim 13 wherein additionally part of said additives, which are in powder or paste form, is directly introduced into said mixing extruder of said second stage (b).
15. The method of claim 14 wherein additionally part of said additives, which are in powder or paste form, is directly introduced into said mixing extruder of said second stage (b).
15. The method of claim 14 wherein additionally part of said additives, which are in powder or paste form, is directly introduced into said mixing extruder of said second stage (b).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4134682.3 | 1991-10-21 | ||
DE4134683A DE4134683A1 (en) | 1991-10-21 | 1991-10-21 | METHOD FOR PRODUCING HEAT CROSSLINKABLE AND / OR THERMOPLASTIC ELASTOMER MIXTURES AND APPLICATION OF THE METHOD |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2080984A1 true CA2080984A1 (en) | 1993-04-22 |
Family
ID=6443070
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002080984A Abandoned CA2080984A1 (en) | 1991-10-21 | 1992-10-20 | Method for continuously preparing thermo-crosslinkable and/or thermoplastic elastomer blends |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0539323A1 (en) |
JP (1) | JPH05214113A (en) |
CA (1) | CA2080984A1 (en) |
DE (1) | DE4134683A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19831122B4 (en) * | 1998-07-11 | 2006-01-19 | Nkt Cables Gmbh | Arrangement and method for processing silicone rubber |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1157277A (en) * | 1955-11-24 | 1958-05-28 | Werner & Pfleiderer | Process and apparatus for the continuous preparation of mixtures formed in particular of rubber and plastics |
DE1404968B1 (en) * | 1960-12-08 | 1972-02-03 | Draiswerke Gmbh | MIXING MACHINE |
CH394584A (en) * | 1961-02-14 | 1965-06-30 | Draiswerke Gmbh | Process for the continuous processing of thermoplastics or thermosets |
DE2619605A1 (en) * | 1976-05-04 | 1977-11-24 | Bayer Ag | Flowable mixts. prodn. - from particulate rubber, solid and liq. additives, by short term intensive mixing at elevated temp. in two stages |
DE2625077A1 (en) * | 1976-06-04 | 1977-12-22 | Loedige | Removable liquid feed tubes in ring mixer - tapered within their holding bushes to permit ease of withdrawal |
-
1991
- 1991-10-21 DE DE4134683A patent/DE4134683A1/en active Granted
-
1992
- 1992-10-02 EP EP92810744A patent/EP0539323A1/en not_active Withdrawn
- 1992-10-19 JP JP4280213A patent/JPH05214113A/en active Pending
- 1992-10-20 CA CA002080984A patent/CA2080984A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP0539323A1 (en) | 1993-04-28 |
DE4134683A1 (en) | 1993-04-22 |
DE4134683C2 (en) | 1993-08-19 |
JPH05214113A (en) | 1993-08-24 |
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