DE1914175A1 - Process and accelerator for the vulcanization of rubbers with a low degree of unsaturation - Google Patents
Process and accelerator for the vulcanization of rubbers with a low degree of unsaturationInfo
- Publication number
- DE1914175A1 DE1914175A1 DE19691914175 DE1914175A DE1914175A1 DE 1914175 A1 DE1914175 A1 DE 1914175A1 DE 19691914175 DE19691914175 DE 19691914175 DE 1914175 A DE1914175 A DE 1914175A DE 1914175 A1 DE1914175 A1 DE 1914175A1
- Authority
- DE
- Germany
- Prior art keywords
- dithiocarbamate
- vulcanization
- accelerator
- zinc
- thiazole
- 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.)
- Granted
Links
- 238000004073 vulcanization Methods 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 22
- 229920001971 elastomer Polymers 0.000 title claims description 11
- 239000005060 rubber Substances 0.000 title claims description 10
- 239000012990 dithiocarbamate Substances 0.000 claims description 26
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 18
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 14
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229920002943 EPDM rubber Polymers 0.000 claims description 9
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 7
- -1 ammonium ions Chemical class 0.000 claims description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 5
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- AJZRXKAXBVGYMQ-UHFFFAOYSA-N C(N)(SCCC1CCCCC1)=S.[Na] Chemical compound C(N)(SCCC1CCCCC1)=S.[Na] AJZRXKAXBVGYMQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 claims description 2
- 229940116901 diethyldithiocarbamate Drugs 0.000 claims description 2
- ILXWFJOFKUNZJA-UHFFFAOYSA-N ethyltellanylethane Chemical group CC[Te]CC ILXWFJOFKUNZJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- QGTHALAWFUFVCU-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;lead(2+) Chemical compound [Pb+2].CN(C)C([S-])=S.CN(C)C([S-])=S QGTHALAWFUFVCU-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 239000011701 zinc Substances 0.000 claims 2
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- 150000002895 organic esters Chemical group 0.000 claims 1
- 239000008036 rubber plasticizer Substances 0.000 claims 1
- 241001441571 Hiodontidae Species 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QNTARNCGFNQQRP-UHFFFAOYSA-N 5-carbamothioylsulfanylpentyl carbamodithioate Chemical compound NC(=S)SCCCCCSC(N)=S QNTARNCGFNQQRP-UHFFFAOYSA-N 0.000 description 2
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- UDWCKMMKPOGURO-UHFFFAOYSA-N 1,2-dihydropyrazolo[3,4-b]pyridin-4-one Chemical compound O=C1C=CNC2=C1C=NN2 UDWCKMMKPOGURO-UHFFFAOYSA-N 0.000 description 1
- ZBSGNEYIENETRW-UHFFFAOYSA-N 2,3-bis(hydroxymethyl)phenol Chemical compound OCC1=CC=CC(O)=C1CO ZBSGNEYIENETRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VKYRIWUNGHGDGX-UHFFFAOYSA-N [S].C1(=CC=CC=C1)NC(=N)NC1=CC=CC=C1 Chemical compound [S].C1(=CC=CC=C1)NC(=N)NC1=CC=CC=C1 VKYRIWUNGHGDGX-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens 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
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
Classifications
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- 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
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
- C08K5/31—Guanidine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
Verfahren und Beschleuniger zur Vulkanisation von Kautschuken mit geringem UnSättigungsgrad Process and accelerator for the vulcanization of rubbers with a low degree of unsaturation
Die Erfindung "betrifft ein Verfahren zur Vulkanisation von Kautschuken mit geringem Unsattigungsgrad, insbesondere von Isobutylen-Isopren-Copolymeren (1IR), Äthylen-Propylen-Dien-Terpolymeren (EPDM) oder deren Mischungen, unter Verwendung von Schwefel, einem DithiocarlDamat-Beschleuniger und einem Thiazol-Beschleuniger. The invention "relates to a method of vulcanization of rubbers with a low degree of unsaturation, especially of isobutylene-isoprene copolymers (1IR), Ethylene-propylene-diene terpolymers (EPDM) or their Mixtures, using sulfur, a dithiocarl damate accelerator and a thiazole accelerator.
Von den in der (Technik verwendeten Elastomeren haben das Oopolymerisat aus Isobutylen und Isopren (IIR) und dasOf the elastomers used in (technology) the copolymer of isobutylene and isoprene (IIR) and the
009840/2178009840/2178
19H17519H175
Terpolymer aus Äthylen, Propylen und einem Dien mit nichtkonjugierten Doppelbindungen (EPDM) einen geringen Gehalt an reaktionsfähigen Doppelbindungen, die der Vernetzung zugänglich sind. HR hat üblicherweise einen Unsättigungsgrad zwischen 1 und 3 Mol%, EPDM ist zur Zeit mit einem Unsättigungsgrad zwischen 0,6 und 2,5 Mo1% bekannt. Styrol-Butadien-Kautschuk hat vergleichsweise einen Unsättigungsgrad von etwa 80 Mo1%. Wegen des geringen Anteils an ungesättigten . Bindungen ist die Vulkanisationsgeschwindigkeit von IIE und EPDM selbst bei Verwendung hochwirksamer Ultrabeschleuniger unerwünscht niedrig.Terpolymer of ethylene, propylene and a diene with non-conjugated double bonds (EPDM) low content of reactive double bonds that are accessible to crosslinking. HR usually has a degree of unsaturation between 1 and 3 mol%, EPDM is currently known to have a degree of unsaturation between 0.6 and 2.5 Mo1%. Styrene-butadiene rubber comparatively has a degree of unsaturation of about 80 Mo1%. Because of the low proportion of unsaturated . Bonds, the rate of vulcanization of IIE and EPDM is more effective even when used Ultra accelerator undesirably low.
Zur Vulkanisation derartiger Kautschuke mit geringem Unsättigungsgrad sind verschiedenartige Beschleuniger bekannt. So wird eine Schwefelvulkanisation mit einem Beschleunigersystem aus einem Thiazolderivat und einem Metalldithiocarbamat, eventuell in Kombination mit einem Beschleuniger aus der Klasse der Thiuramsulfide, durchgeführt.Various types of accelerator are used to vulcanize such rubbers with a low degree of unsaturation known. So a sulfur vulcanization with an accelerator system of a thiazole derivative and a Metal dithiocarbamate, possibly in combination with an accelerator from the class of thiuram sulfides, carried out.
Die sogenannte Chinonvulkanisation bedient sich eines Vernetzersystems aus Chinondioxim oder ρ,ρ'-Dibenzoylchinondioxim und Bleioxiden, eventuell unter Zusatz eines Beschleunigers der ThiazoIgruppe.The so-called quinone vulcanization makes use of one Crosslinking system made from quinone dioxime or ρ, ρ'-dibenzoylquinone dioxime and lead oxides, possibly with the addition of an accelerator from the thiazole group.
Ferner geschieht die Harzvulkahisation mit einem System aus Dimethylolphenolharzen und einem halogenhaltigen Aktivator.Furthermore, the resin vulcanization takes place with a system made of dimethylolphenol resins and a halogen-containing activator.
009840/217 8'009840/217 8 '
_ 3 - 19U175_ 3 - 19U175
Die Vulkanisation mit den genannten Systemen wird "bei den bekannten Verfahren "bei Temperaturen von über 140° C und meist im Autoklaven durchgeführt,, um innerhalb wirtschaftlich vertretbarer Zeiten abzulaufen. Lediglich die Chinonvulkanisation verläuft schnell genug, um beispielsweise in der Kabelproduktion in einem kontinuierlichen Vulkanisationsverfahren Verwendung finden zu können, Jedoch ebenfalls bei hohen Temperaturen.The vulcanization with the systems mentioned is "in the known processes" at temperatures of over 140 ° C and usually carried out in an autoclave, to within economically justifiable times to expire. Only the quinone vulcanization runs fast enough, for example in cable production in a continuous vulcanization process Can be used, but also at high temperatures.
Aufgabe der Erfindung ist es, ein Vulkanisationsverfahren und einen Beschleuniger dafür zu schaffen, die es ermöglichen, Kautschuke mit geringem Unsättigungs- ■ grad bei mäßig hohen Temperaturen zu vulkanisieren.The object of the invention is to provide a vulcanization process and an accelerator for the make it possible to use rubbers with low unsaturation ■ degree to vulcanize at moderately high temperatures.
Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß neben dem Schwefel, dem Dithiocarbamat-Beschleuniger und dem Thiazol-Beschleuniger ein Guanidin-Beschleuniger und mindestens ein weiterer Dithiocarbamat-Beschleuniger verwendet werden. Damit ist eine schonende Vulkanisation von HR oder EPDM oder deren Mischungen bei Temperaturen unter 100° C innerhalb von 24- Stunden möglich geworden.The method according to the invention is characterized in that that in addition to sulfur, the dithiocarbamate accelerator and the thiazole accelerator, a guanidine accelerator and at least one further dithiocarbamate accelerator be used. This is a gentle vulcanization of HR or EPDM or their mixtures at temperatures below 100 ° C has become possible within 24 hours.
Dithiocarbamate im Sinne der Erfindung sind z.B. Zinkäthyl-phenyl-dithiocarbamat, Zink-dibutyl-dithiocarbamat, Zink-dimethyl-dithiocarbamat, Zink-diäthyl-dithiocarbamat, Kupfer-dimethyl-dithiocarbamat, Cadmium-diäthyl-dithiocarbamat, Tellur-diäthyl-dithiocarbamat, Natriumcyclohexyläthyl-dithiocarbamat, Zink-N-pentamethylendithiocarbamat, Blei-dimethyl-dithiocarbamat, N-Pentamethylenammonium-pentamethylen-dithiocarbamat, u.a· Guanidine im Sinne der Erfindung sind z.B. Diphenylguanidin, Orthotolylbiguanid, Di-o-toIyIguanidin u.a.Dithiocarbamates within the meaning of the invention are e.g. zinc ethyl phenyl dithiocarbamate, Zinc dibutyl dithiocarbamate, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, Copper dimethyl dithiocarbamate, cadmium diethyl dithiocarbamate, Tellurium diethyl dithiocarbamate, sodium cyclohexylethyl dithiocarbamate, Zinc N-pentamethylene dithiocarbamate, Lead dimethyl dithiocarbamate, N-pentamethylene ammonium pentamethylene dithiocarbamate, etc. Guanidines within the meaning of the invention are e.g. diphenylguanidine, Orthotolylbiguanid, Di-o-toIyIguanidin and others
009840/2178009840/2178
19H17519H175
Thiazole im Sinne der Erfindung sind z.B. 2-Mercaptobenzothiazol, Benzothiazyldisulfid, Dibenzothiazyldisulfid und ihre Umsetzungsprodukte.Thiazoles within the meaning of the invention are e.g. 2-mercaptobenzothiazole, benzothiazyl disulfide, Dibenzothiazyl disulfide and their reaction products.
Es ist besonders vorteilhaft,solche Dithiocarbamat-Beschleuniger zu verwenden, die sich durch die an Stickstoff substituierten organischen- Reste unterscheiden und/oder durch die salzartig' gebundenen Metalloder organischen Ammonium-Ionen.It is particularly advantageous to use such dithiocarbamate accelerators to use which differ by the organic radicals substituted on nitrogen and / or by the salt-like bound metal or organic ammonium ions.
So führt z.B. die Verwendung eines Vulkanisations-' beschleunigen, bestehend aus Zink-äthylphenyldithiocarbamat, Zinkdibutyldithiocarbamat, Diphenylguanidin und 2-Mercaptobenzothiazol in Gegenwart von Schwefel innerhalb von 24- Stunden bei nur 80° C selbst in einem Butylkautschuk mit nur 1 Mol% Ungesättigtheit zu voller Ausvulkanisation. Die Anvulkanisationszeit (scorch time) kann durch Variation der Mengenverhältnisse der Beschleuniger in einem solchen Bereich geregelt werden, daß ein Einmischen des gesamten Vulkanisatipnssystems im Innenmischer (Stempelkneter, Banbury-Mischer) möglich ist.For example, the use of a vulcanization 'accelerate, consisting of zinc ethylphenyldithiocarbamate, Zinc dibutyldithiocarbamate, diphenylguanidine and 2-mercaptobenzothiazole in the presence of sulfur within 24 hours at only 80 ° C even in a butyl rubber with only 1 mol% unsaturation too full vulcanization. The scorch time (scorch time) can be achieved by varying the proportions of the accelerator in a be regulated in such a range that mixing of the entire Vulkanisatipnssystem in the internal mixer (Stamp kneader, Banbury mixer) is possible.
Ein besonderer Vorzug der erfindungsgemäßen Vulkanisation bei Temperaturen unter 100° C liegt darin, daß kein Heißdampf verwendet werden muß, keine druckfesten Vulkanisationskessel erforderlich sind und auch bei dickeren Schichten gleichmäßig und außerordentlich schonend durchvulkanisierte und weitgehend spannungsfreie Artikel erhalten werden. Andererseits ist es durchaus möglich, mit dem genannten Vulkanisationssystem z.B. Profile im Salzbad (LCM-Verfahren) zu vulkanisieren, da die VulkanisationsgeschwindigkeitA particular advantage of the vulcanization according to the invention at temperatures below 100 ° C. is that no superheated steam has to be used, no pressure-resistant vulcanization kettles are required and also with thick layers evenly and extremely gently vulcanized and largely tension-free Item to be received. On the other hand, it is quite possible to use the vulcanization system mentioned, for example, to create profiles in a salt bath (LCM process) vulcanize as the vulcanization rate
- 5 009840/2178 - 5 009840/2178
bei dem erfindungsgemäßen Verfahren bei hohen Temperaturen sehr, schnell ist. Vorzugsweise wird die Vulkanisation in Heißluft durchgeführt.is very, fast in the method according to the invention at high temperatures. Preferably will the vulcanization is carried out in hot air.
In vorteilhafter Weise werden 0,5 bis 4,0 Gewichtsteile Dithiocarbamate, 0,1 bis 1,0 Gewichtsteile eines Thiazole, 0,1 bis 1,0 Gewichtsteile eines Guanidine und 0,5 bis 2,0 Gewichtsteile Schwefel auf 100 Gewichtsteile Kautschuk verwendet.Advantageously, 0.5 to 4.0 parts by weight of dithiocarbamates and 0.1 to 1.0 parts by weight are used of a thiazole, 0.1 to 1.0 parts by weight of a guanidine and 0.5 to 2.0 parts by weight of sulfur used on 100 parts by weight of rubber.
Vorzugsweise wird die. Vulkanisation bei Temperaturen von 70 bis 12<
durchgeführt.Preferably the. Vulcanization at temperatures from 70 to 12 <
carried out.
von 70 bis 120° G, insbesondere von 75 Ms 90° C,from 70 to 120 ° G, especially from 75 Ms 90 ° C,
In an sich bekannter Weise können dem Kautschuk Verstärkerfüllstoffe, Weichmacher, Extenderöle, Lichtschutzmittel, Alterungsschutzmittel und dergleichen zugesetzt' werden.In a manner known per se, reinforcing fillers, plasticizers, extender oils, Light stabilizers, anti-aging agents and the like are added.
Die Kombination der Vulkanisationsbeschleuniger zur Durchführung des erfindungsgemäßen Verfahrens enthält ein Dithiocarbamat und ein Thiazol und enthält neben dem Dithiocarbamat und dem Thiazol ein' Guanidin und ein weiteres Dithiocarbamat.The combination of vulcanization accelerators for carrying out the method according to the invention contains a dithiocarbamate and a thiazole and contains in addition to the dithiocarbamate and the thiazole one guanidine and another dithiocarbamate.
Vorzugsweise enthält sie Metall- und/oder Ammoniumsalze von. N-disubstituierten Dithiocarbamaten, wobei die Substituenten Alkyl-, Alkylen-, Cycloalkyl· und/oder Arylreste sind. Insbesondere kommen die genannten Dithiocarbamate, Guanidine und Thiazole in Betracht.It preferably contains metal and / or ammonium salts of. N-disubstituted dithiocarbamates, where the substituents are alkyl, alkylene, cycloalkyl and / or aryl radicals. In particular come the mentioned dithiocarbamates, guanidines and thiazoles into consideration.
009840/2178009840/2178
_ 6 - T9H775_ 6 - T9H775
In den folgenden Beispielen wird die Erfindung anhand von Ausführungsbeispielen erläutert. Die unbenannten Zahlen geben Gewichtsteile an.In the following examples, the invention is illustrated by means of working examples. The unnamed Numbers indicate parts by weight.
HR (1 Mol % Ungesättigtheit) 100,0HR (1 mole % unsaturation) 100.0
FEF-Ruß "50,0FEF carbon black "50.0
HAF-Ruß 35,0HAF carbon black 35.0
SRP-Ruß 30,0SRP carbon black 30.0
ZnO, aktiv 5,0ZnO, active 5.0
Lichtschutzwachs 3>0Light protection wax 3> 0
Stearinsäure 1,0 N-Phenyl-N'-isopropyl-p-phenylendiamin 1,0Stearic acid 1.0 N-phenyl-N'-isopropyl-p-phenylenediamine 1.0
Extenderöl · ■ 10,0Extender oil · ■ 10.0
Polyäthylenwachs 8,0Polyethylene wax 8.0
009840/2178009840/2178
CD OO ■P-O CD OO ■ P-O
Beschleunigersystem Ziiik-äthylphenyldithiocarbamat Accelerator system Ziiik-ethylphenyldithiocarbamat
Zink-dibutyldithiocarbamatZinc dibutyldithiocarbamate
N-Pent amet hy 1 enammoniumpentamethylendithiocarbamat N-Pent amet hy 1 enammonium pentamethylene dithiocarbamate
2-Merkaptobenzothiazol Dibenzothiazyldisulfid Diphenylguanidin Schwefel2-mercaptobenzothiazole dibenzothiazyl disulfide Diphenylguanidine sulfur
Mooney tr Mooney t,,-Mooney tr Mooney t ,, -
Vulkanisationstemperatur (0C) Vulkanisationszeit (h )Vulcanization temperature (0 C) Vulcanization time (h)
Shore AShore A
Reißfestigkeit (kp/cm )Tensile strength (kp / cm)
Bruchdehnung (%)Elongation at break (%)
Spannungswert bei ρ 300 % Dehnung (kp/cm )Stress value at ρ 300 % elongation (kp / cm)
4040
4040
4545
2727
19 U1 719 U1 7
Beispiel 1 zeigt, daß die Vulkanisationsgeschwindigkeit durch entsprechende Variation des Vulkanisationssystems in weiten Grenzen variierbar ist. Fehlt ein Bestandteil, wie das Guanidin in Beispiel 1 C, oder ist nur ein Dithiocarbamat, wie in Beispiel 1 E und 1 F eingesetzt, so verlängern sich bei gleicher Temperatur die Vulkanisationszeiten wesentlich bzw. es werden höhere Vulkanisationstemperaturen erforderlich oder man erhält bei Temperaturen unter 1000G überhaupt keine Vulkanisation, wie in Beispiel 1 F1 wo'nach 96 Stunden bei 80° 0 erst eine Reißfestigkeit von v ' 14,6 kp/cm vorhanden ist, was der green strenght der Mischung entspricht.Example 1 shows that the rate of vulcanization can be varied within wide limits by varying the vulcanization system accordingly. If a component is missing, such as the guanidine in Example 1 C, or if only a dithiocarbamate is used, as in Examples 1 E and 1 F, the vulcanization times are significantly longer at the same temperature or higher vulcanization temperatures are required or temperatures below are obtained 100 0 G no vulcanization at all, as in Example 1 F 1 where after 96 hours at 80 0 a tear strength of v '14.6 kp / cm is present, which corresponds to the green strength of the mixture.
Das Beispiel 2 zeigt den Vergleich einer Mischung mit konventioneller Beschleunigung (2 A) mit einer Mischung mit erfindungsgemäßer Beschleunigung (Beispiel 2 C). Das Beispiel 2 B zeigt eine Kompromißlösung zwischen beiden Vulkanisationssystemen, das trotz relativ günstiger Mooney-Werte zu einem Produkt mit ungenügenden mechanischen Werten führt.Example 2 shows the comparison of a mixture with conventional acceleration (2 A) with a mixture with acceleration according to the invention (Example 2 C). Example 2B shows a compromise solution between both vulcanization systems, despite relatively favorable Mooney values to a product with insufficient mechanical values.
HR (1 Mol % Ungesättigtheit) 100,0HR (1 mole% unsaturation) 100.0
SRF-Ruß · 30,0SRF carbon black x 30.0
FEF-Ruß ' 30,0FEF carbon black '30.0
HAF-Ruß 20,0HAF carbon black 20.0
Kaolin 50,0Kaolin 50.0
ZnO, aktiv 5,0ZnO, active 5.0
Lichtschutzwachs . 3,0 N-Phenyl-N'-isopropyl-p-phenylendiamin 1,0Light protection wax. 3.0 N-phenyl-N'-isopropyl-p-phenylenediamine 1.0
Extenderöl 10,0Extender Oil 10.0
009840/.2 178009840 / .2 178
-9- 19U175-9- 19U175
Tetramethylenthiuramdisulfid 2-Merkaptobenzothiazol Zink-diäthyldithiocarbamat Zink-äthylphenyldithio carbamat Zink-dibutyldithiocarbamat DiphenylguanidinTetramethylene thiuram disulfide 2-mercaptobenzothiazole zinc diethyldithiocarbamate Zinc ethylphenyldithio carbamate zinc dibutyldithiocarbamate Diphenylguanidine
Schwefelsulfur
Mooney tr (min.)
Mooney t^c (min.)Mooney tr (min.)
Mooney t ^ c (min.)
Vulkanisationstemperatur (0O) Vulkanisationszeit (h )Vulcanization temperature ( 0 O) Vulcanization time (h)
Shore AShore A
Reißfestigkeit (kp/cm2) Bruchdehnung (ß) Tensile strength (kp / cm 2 ) Elongation at break (ß)
Spannungswert "bei o
300' % Dehnung (kp/cnr) 49 25 28Voltage value "at o
300% elongation (kg / cm) 49 25 28
Im Beispiel 3 wird eine übliche Beschleunigung von EPDM (Beispiel 3 A und 3 B) mit Tetramethylthiuramdisulfid, Zink-diäthyldithiocarbamat, 2-Merkaptobenzothiazol und Schwefel mit dem erfindungsgemäßen Vulkanisationsverfahren verglichen. Die übliche Beschleuni-In example 3, a customary acceleration of EPDM (example 3 A and 3 B) with tetramethylthiuram disulfide, Zinc diethyl dithiocarbamate, 2-mercaptobenzothiazole and sulfur with the vulcanization method of the present invention compared. The usual acceleration
- 10 -- 10 -
0098A0/21780098A0 / 2178
gung ergibt bei 160° nach 20 Minuten eine optimale Vulkanisation. Versucht man die Vulkanisation bei 80° C drucklos in Heißluft durchzuführen, so sind selbst nach 96 Stunden noch keine optimalen Vulkanisateigenschaften erreicht. Nachteilig bei dem bekannten Verfahren ist auch, daß das in Beispiel 3 A und 3 B verwendete System nach 24- Stunden eine starke Schwefelausblühung zeigt.at 160 ° after 20 minutes, optimum vulcanization is achieved. If you try vulcanization at 80 ° C to be carried out without pressure in hot air, even after 96 hours they are still not optimal Reached vulcanizate properties. Another disadvantage of the known method is that the in Example 3 A and 3 B used system after 24 hours shows strong sulfur efflorescence.
Die Beispiele 3 C - 3 F zeigen, daß durch Variation ρ der Mengenanteile des erfindungsgemäßen Systems die An- und Ausvulkanisationszeit entsprechend variiert werden kann. Fehlt eine Komponente, wie das Diphenylguanidin in Beispiel 3 G» so steigt die An- und Ausvulkanisationszeit auf die Werte des konventionellen Systems an.Examples 3 C-3 F show that by varying ρ the proportions of the system according to the invention, the vulcanization time and vulcanization time can be varied accordingly. If a component is missing, such as the diphenylguanidine in Example 3 G », the vulcanization time increases to the values of the conventional system.
- 11 -- 11 -
009840/21 78009840/21 78
GrundrezepturBasic recipe
VulkanisationssystemI.
Vulcanization system
Bruchdehnung (%) Tensile strength (kp / cm)
Elongation at break (%)
300 % Dehnung (kp/cm )Stress value at ρ
300% elongation (kg / cm)
Claims (16)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691914175 DE1914175C3 (en) | 1969-03-20 | Vulcanizable compounds | |
| FR7009837A FR2039696A5 (en) | 1969-03-20 | 1970-03-19 | |
| BE747772D BE747772A (en) | 1969-03-20 | 1970-03-20 | PROCESS AND ACCELERATOR FOR THE VULCANIZATION OF RUBBER WITH LOW UNSATURATION DEGREE |
| NL7003977A NL7003977A (en) | 1969-03-20 | 1970-03-20 | |
| GB1265626D GB1265626A (en) | 1969-03-20 | 1970-03-20 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691914175 DE1914175C3 (en) | 1969-03-20 | Vulcanizable compounds |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1914175A1 true DE1914175A1 (en) | 1970-10-01 |
| DE1914175B2 DE1914175B2 (en) | 1976-04-29 |
| DE1914175C3 DE1914175C3 (en) | 1976-12-23 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8622772B2 (en) | 2011-03-03 | 2014-01-07 | Sumitomo Wiring Systems, Ltd. | Terminal block and method of molding it |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8622772B2 (en) | 2011-03-03 | 2014-01-07 | Sumitomo Wiring Systems, Ltd. | Terminal block and method of molding it |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1265626A (en) | 1972-03-01 |
| DE1914175B2 (en) | 1976-04-29 |
| NL7003977A (en) | 1970-09-22 |
| BE747772A (en) | 1970-08-31 |
| FR2039696A5 (en) | 1971-01-15 |
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| E77 | Valid patent as to the heymanns-index 1977 | ||
| EHJ | Ceased/non-payment of the annual fee | ||
| EHJ | Ceased/non-payment of the annual fee | ||
| XX | Miscellaneous: |
Free format text: IN HEFT 25 V.22.06.78 S.4437 SP.1 AKTENZEICHEN IN 1244735 BERICHTIGEN |
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| EI | Miscellaneous see part 3 |