FR2512037A1 - Silica reinforced elastomer compsn. - contains silane and/or succinimide additive to enhance reinforcing effect - Google Patents
Silica reinforced elastomer compsn. - contains silane and/or succinimide additive to enhance reinforcing effect Download PDFInfo
- Publication number
- FR2512037A1 FR2512037A1 FR8116743A FR8116743A FR2512037A1 FR 2512037 A1 FR2512037 A1 FR 2512037A1 FR 8116743 A FR8116743 A FR 8116743A FR 8116743 A FR8116743 A FR 8116743A FR 2512037 A1 FR2512037 A1 FR 2512037A1
- Authority
- FR
- France
- Prior art keywords
- sep
- parts
- silica
- silane
- rubber
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 23
- 229920001971 elastomer Polymers 0.000 title claims abstract description 10
- 239000000654 additive Substances 0.000 title claims abstract description 9
- 230000000996 additive effect Effects 0.000 title claims abstract description 9
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 title claims abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims description 5
- 229910000077 silane Inorganic materials 0.000 title claims 2
- 230000003014 reinforcing effect Effects 0.000 title abstract description 5
- 229960002317 succinimide Drugs 0.000 title description 3
- 239000000806 elastomer Substances 0.000 title 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000005060 rubber Substances 0.000 claims abstract description 9
- 150000004756 silanes Chemical class 0.000 claims abstract description 5
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008117 stearic acid Substances 0.000 claims abstract description 4
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000004014 plasticizer Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkenyl succinic acid Chemical compound 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000007906 compression Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 230000003068 static effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 102100034003 FAU ubiquitin-like and ribosomal protein S30 Human genes 0.000 description 1
- 101000732045 Homo sapiens FAU ubiquitin-like and ribosomal protein S30 Proteins 0.000 description 1
- 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 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSFXLBMRGCVEMO-UHFFFAOYSA-N [SiH4].[S] Chemical class [SiH4].[S] GSFXLBMRGCVEMO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DYVXECCRJMEWLQ-UHFFFAOYSA-N carbamoyliminocarbamic acid Chemical compound NC(=O)N=NC(O)=O DYVXECCRJMEWLQ-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- YYUPXWUUUZXFHG-UHFFFAOYSA-N ethoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OCC YYUPXWUUUZXFHG-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer 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
- 238000001556 precipitation Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
COMPOSITION ELASTOMERIQUE RENFORCEE PAR
DES SILICES A GRANDE SURFACE SPECIFIQUE
La présente invention a pour objet une composition élastomérique renforcée par des silices à grande surface spécifique.ELASTOMERIC COMPOSITION REINFORCED BY
SILICA WITH HIGH SPECIFIC SURFACE
The present invention relates to an elastomeric composition reinforced by silicas with a large specific surface area.
On sait que l'on a proposé depuis longtemps de faire appel à des charges blanches telles que silices pour le renforcement des matières polymères et notamment des caoutchoucs. We have known that it has been proposed for a long time to use white fillers such as silicas for reinforcing polymeric materials and especially rubbers.
En particulier. l'on a essayé de relier leur comportement avec un certain nombre de critères de la silice. C'est ainsi que l'on a voulu établir une currélation entre ce comportement et la surface spécifique de la silice appréciée selon la méthode BET. iris cette méthode qui rend compte de la surface totale de la silice surface externe et microporosité, s'est avérée bien insuffisante à elle seule pour être représentative des silices comme charges renfor çantes. In particular. an attempt has been made to relate their behavior to a number of silica criteria. Thus, it has been sought to establish a correlation between this behavior and the specific surface area of the silica, which is evaluated according to the BET method. This method, which accounts for the total surface area of silica outer surface and microporosity, proved to be quite inadequate in itself to be representative of silicas as reinforcing fillers.
C'est pourquoi, en particulier dans le BF 2 353 486, l'on a fait appel à un critère supplémentaire, la surface CTAB (surface externe par adsorption de bromure de cethyl trtmethyl ammonium à pH 9, selon la méthode exposée par JAY, JANSEN et G. KRAUS dans Rubber
Chemistry and Technology 44 (1971) p. 1257-1296. This is why, in particular in BF 2 353 486, an additional criterion was used, the CTAB surface (external surface by adsorption of cetyl trimethyl ammonium bromide at pH 9, according to the method described by JAY, JANSEN and G. KRAUS in Rubber
Chemistry and Technology 44 (1971) p. 1257-1296.
Ceci a permis de mieux appréhender le problème des silices comme chargea renforçantes et de faire un certain nombre dSobser- vations. This made it possible to better understand the problem of silicas as reinforcing agents and to make a certain number of observations.
Les travaux de la Demanderesse ont en particulier permis d'établir une augmentation des propriétés mécaniques en général, et de la résistance au déchlrement pantalon en particulier, lorsque la surface CTAB de la silice renforçante augmentez
Malheureusement, cette amélioration s'accompagne d'une diminution sensible des propriétés dynamiques, ce qui fait que l'on est pratiquement limite à des silices de surface spécifique ne dépassant pas 180 m2/g. The work of the Applicant has in particular made it possible to establish an increase in the mechanical properties in general, and the pantile resistance in particular, when the CTAB surface of the reinforcing silica increase.
Unfortunately, this improvement is accompanied by a significant decrease in dynamic properties, so that it is practically limited to silicas with a specific surface area of not more than 180 m 2 / g.
Or maintenant on a trouvé, et c'est ce qui fait l'objet de la présente invention, que l'on obtenait une amélioration spectaculaire des propriétés renforçantes d'une silice de précipitation de surface
CTAB supérieure à 180 m2/g, avantageusement comprise entre 200 et 300 m2/g par incorporation dans la composition élastomérique d'un additif du groupe des silane, des succinimides et des compositions, silanes-succinimides.However, it has now been found, and this is the subject of the present invention, that a dramatic improvement in the reinforcing properties of a surface precipitation silica is obtained.
CTAB greater than 180 m 2 / g, advantageously between 200 and 300 m 2 / g by incorporation in the elastomeric composition of a silane group additive, succinimides and silane-succinimide compositions.
Les sucçinimides selon l'invention sont des alcényl succitimides obtenus par condensation d'une polyamine ou un anhydride alcenyl succinique dont le radical alcemyle contient de 3 à 100, de préférence de 3 à 80 atomes de carbone, tel que décrit dans les demandes françaises 79 31219 du 20.12.1979 et 80 04037 du 25.02.1980. The succinimides according to the invention are alkenyl succitides obtained by condensation of a polyamine or an alcenyl succinic anhydride whose alkemyl radical contains from 3 to 100, preferably from 3 to 80 carbon atoms, as described in the French applications. 31219 of 20.12.1979 and 80.04037 of 25.02.1980.
Une formulation selon l'invention se caractérise en particulier par le fait que pour 100 parties en poids de caoutchouc naturel ou synthétique, de 0,2 à 5 parties d'un agent de vulcanisation, de 0,2 à 6,0 parties d'accélérateur, de 0,0 à 6,0 parties d'antioxydant, de
O à 50 parties de plastifiant, de 0,1 à 10 parties de Zno, de 0,1 à 5 parties d'acide steartique, elle renferme de 10 à 100 parties en poids de silice de surface spécifique CTAB supérieure à 180 m2/g, et de 1 à 10 % par rapport à la silice, d'un additif du groupe des silanes, des succinimides et des compositions silanes-succinimides.A formulation according to the invention is characterized in particular by the fact that for 100 parts by weight of natural or synthetic rubber, from 0.2 to 5 parts of a vulcanizing agent, from 0.2 to 6.0 parts of accelerator, from 0.0 to 6.0 parts of antioxidant,
From 0 to 50 parts of plasticizer, from 0.1 to 10 parts of Zno, from 0.1 to 5 parts of stearic acid, it contains from 10 to 100 parts by weight of CTAB specific surface silica greater than 180 m 2 / g and from 1 to 10% with respect to the silica, a silane group additive, succinimides and silane-succinimide compositions.
Selon l'invention, les silanes répondent à la formule genérale R'# Si (OR)3 dans laquelle R' = groupe organique réactif tel que mercapto, azo etc... généralement relié par une courte channe alkyle à l'atome de silicium
OR = groupe hydrolysable
Les silanes selon l'invention sont notamment des silanes soufrés du type
gamma-mercaptopropyltriméthoxysillane ou bis-(3 triethoxysi lylpropyl)-tétrasulfure. According to the invention, the silanes correspond to the general formula R '# Si (OR) 3 in which R' = reactive organic group such as mercapto, azo, etc., generally connected by a short alkyl ring to the silicon atom
OR = hydrolysable group
The silanes according to the invention are in particular sulfur silanes of the type
gamma-mercaptopropyltrimethoxysilane or bis (3-triethoxysilylpropyl) tetrasulfide.
Mais on peut aussi faire appel à des silanes dont le groupe réactif est un carbamoylazoformate. But it is also possible to use silanes whose reactive group is a carbamoylazoformate.
On peut encore citer à titre d'exemple les formules suivantes
- tétrasulfure de di(méthylpropyfdiéthoxysilane)
- hcxaméthylcyclotrisilthiane
- polysulfure d'éthyltriéthoxysilane
- monosulfure de di-méthylpropyléthoxysilane. The following formulas can also be cited as examples:
di (methylpropyldiethoxysilane) tetrasulfide
- hcxamethylcyclotrisilthiane
- ethyltriethoxysilane polysulfide
di-methylpropylethoxysilane monosulfide.
Les succinimides selon l'inycntion sont à base d'alcénylsuccinimides obtenus par condensation d'une polyamine sur un anhydre alcényl-succinique dont le radical alcényle contient de 3 à 100, de préférence de 3 à 12 atomes de carbone, tels que décrits dans la demande française 80 04037 au nom de la Demanderesse. The succinimides according to the invention are based on alkenylsuccinimides obtained by condensation of a polyamine on an alkenylsuccinic anhydride, the alkenyl radical of which contains from 3 to 100, preferably from 3 to 12, carbon atoms, as described in US Pat. French application 80 04037 in the name of the Applicant.
Le caoutchouc est en particulier constitué par du caoutchouc synthétique de type SBR. The rubber is in particular constituted by synthetic rubber of the SBR type.
Exemples
Afin de mettre en évidence l'intérêt de la presente invention, on a réalise des essais en mélange caoutchouc, la mise en oeuvre a été réalisée dans un malaxeur interne BANBURY de 1 litre puis repris au malaxeur à cylindres.Examples
In order to demonstrate the interest of the present invention, tests were carried out in rubber mixture, the implementation was carried out in a 1-liter BANBURY internal mixer and then taken up with the roll kneader.
Les tests suivants ont été faits
TESTS MECANIQUES, STATIQUES ET DYNAMIQUES
10) - Rhéomètre MONSANTO (ASTM D 2084)
Mesure les propriétés rhéologiques du mélange durant la vulcanisation.The following tests were done
MECHANICAL, STATIC AND DYNAMIC TESTS
10) - MONSANTO Rheometer (ASTM D 2084)
Measures the rheological properties of the mixture during vulcanization.
- couple minimal (Cm) : consistance du mélange non vulcanisé (mélange "cru") à la température de l'essai. - minimum torque (Cm): consistency of the unvulcanized mixture ("raw" mixture) at the temperature of the test.
- couple maximal (CM) : consistance du mélange après réticulation. - maximum torque (CM): consistency of the mixture after crosslinking.
- Temps optimum : couple X = (CM-Cm) x 90 + Cm
100
Couple X
100
Couple X
Y minutes = Temps optimum
(ordonnée) (abscisse)
Ces propriétés sont en particulier décrites dans l'Encyclopedia of Polymer Science and Technology volume 12 page 265 (Interscience Puhlishers - John Wiley and Sons, Inc.).Y minutes = optimum time
(ordinate) (abscissa)
These properties are in particular described in the Encyclopedia of Polymer Science and Technology Vol. 12 page 265 (Interscience Puhlishers - John Wiley and Sons, Inc.).
20) - Propriétés statiques
Sont celles qui sont mesurées selon les normes
a) - ASTM D 412-51 T
Résistance rupture Pa Allongement
Module Pa
b) - ASTM D 2240-75
Dureté Shore A
c) - DIN 53516
Abrasion (resistance à 1')
d) NF T 47-126
Déchirement Pantalon Kg/cm
30) - Propriétés dynamiques
ASR1 D 623-67
Flexomètre Goodrich
Cet appareil pennet de soumettre un vulcanisat à des déformations alternées et de déterminer sa tenue à ia fatigue.20) - Static properties
Are those that are measured according to the standards
a) - ASTM D 412-51 T
Resistance rupture Pa Elongation
Pa Module
b) - ASTM D 2240-75
Shore A hardness
c) - DIN 53516
Abrasion (1 'resistance)
d) NF T 47-126
Tearing Trousers Kg / cm
30) - Dynamic Properties
ASR1 D 623-67
Goodrich Flexometer
This apparatus makes it possible to subject a vulcanizate to alternating deformations and to determine its resistance to fatigue.
a) - compression statique (CS %) : Déflexion sous charge constante. a) - static compression (CS%): Deflection under constant load.
b) - Déformation permanente (DP %) : Pourcentage de déformation résiduaire après essai. b) - Permanent deformation (DP%): Percentage of residual deformation after test.
c) - Compression dynamique (CD %) : X de deformation durant l'essai. c) - Dynamic compression (CD%): X deformation during the test.
CDO : Compression dynamique en début d'essai. CDO: Dynamic compression at the beginning of the test.
CDF : Compression dynamique en fin d'essai. CDF: Dynamic compression at the end of the test.
CD = CDF - CDO : évolution de la compression dynamique qui est en relation avec la tenue à la fatigue. CD = CDF - CDO: evolution of the dynamic compression which is related to fatigue resistance.
d) - T.base : T. entre la température à la surface de l'éprouvette (à sa base) et la température de la chambre,
e) - T. coeur : T. entre la température au coeur de l'éprouvette t la température de la chambre.d) - T.base: T. between the temperature at the surface of the test piece (at its base) and the temperature of the chamber,
e) - T. heart: T. between the temperature at the heart of the test tube t the temperature of the chamber.
f) - conditions des essais
charge 24 lbs, déflexion 22,2 X, fréquence 21,4 Hz
température de la chambre = 500C.f) - conditions of the tests
load 24 lbs, deflection 22.2 X, frequency 21.4 Hz
room temperature = 500C.
Dans cet exemple, on réalise une série d'essais en mettant en oeuvre la formule suivante
SBR 1500 100,00
HUILE DUTREX V.10 20,00
ZnO 4,00
ACIDE STEARIQUE 1,50
SOUFRE ?,80
ANTIOXYGENE IPPD 1,50
(N-ISOPROPYL-N-phényl-N '-phénylènf. diamine)
ANTIOXYGENE 6PPD 1,50
(N-diméthyl 1-3 butyl N'-phenyl-p-phénylèndiamine)
POLYETHYLENE GLYCOL (PEG 4000) 3,00
VULCAFOR CBS (N-cyclohexyl-2 Benzothiazyl 3,00
sulfénamide)
SILICE (1) 60,00
MERCAPTO-SILANE Voir tableau
(1) - Silices : S = 183 m2/g - 195 m2/g -226 m2/g
S = 277 m2 /g - 306 m2/g
Les résultats sont rassemblés dans le tableau suivant.In this example, a series of tests is carried out using the following formula
SBR 1500 100.00
OIL DUTREX V.10 20,00
ZnO 4.00
STEARIC ACID 1.50
SULFUR ?, 80
ANTIOXYGEN IPPD 1.50
(N-ISOPROPYL-N-phenyl-N '-phenylenediamine)
ANTIOXYGEN 6PPD 1.50
(N-dimethyl-1-butyl N'-phenyl-p-phenylenediamine)
POLYETHYLENE GLYCOL (PEG 4000) 3.00
VULCAFOR CBS (N-cyclohexyl-2 Benzothiazyl 3.00
sulphenamide)
SILICE (1) 60.00
MERCAPTO-SILANE See table
(1) - Silica: S = 183 m2 / g - 195 m2 / g -226 m2 / g
S = 277 m2 / g - 306 m2 / g
The results are collated in the following table.
On remarque un effet de synergie remarquable de la silice et de l'additif de vulcanisation selon l'invention. Note a remarkable synergistic effect of the silica and the vulcanization additive according to the invention.
TABLEAU
SILICE
<tb> Surface <SEP> 183 <SEP> m2/g <SEP> 195 <SEP> m2/g <SEP> 226 <SEP> m2/g <SEP> 277 <SEP> m2/g <SEP> 306 <SEP> m2/g
<tb> MERCAPTO-SILANE
<tb> % <SEP> en <SEP> poids <SEP> par <SEP> rapport <SEP> 0 <SEP> 3 <SEP> % <SEP> 0 <SEP> 3,25% <SEP> 0 <SEP> 3,65% <SEP> 0 <SEP> 4,6 <SEP> % <SEP> 0 <SEP> 5,1 <SEP> %
<tb> à <SEP> la <SEP> silice
<tb> (% <SEP> = <SEP> fonction <SEP> de <SEP> surface <SEP> en <SEP> % <SEP> par <SEP> rapport <SEP> à
<tb> la <SEP> silice)
<tb> MELANGE <SEP> NON <SEP> VULCANISE
<tb> ESSAI <SEP> AU <SEP> RHEOMETRE
<tb> 150 C
<tb> COUPLE <SEP> MINIMAL
<tb> (viscosité) <SEP> 12 <SEP> 10,5 <SEP> 12,5 <SEP> 11 <SEP> 23 <SEP> 16 <SEP> 28 <SEP> 20 <SEP> 31 <SEP> 23
<tb> TEMPS <SEP> OPTIMUM <SEP> VULCANI- <SEP> 12 <SEP> 8,75 <SEP> 12,5 <SEP> 9,25 <SEP> 17,5 <SEP> 12,5 <SEP> 21,0 <SEP> 15,0 <SEP> 28,0 <SEP> 21
<tb> SATION <SEP> (mn)
<tb> PROPRIETES <SEP> STATIQUES
<tb> DES <SEP> VULCANISATS
<tb> RESISTANCE <SEP> RUPTURE <SEP> Pa* <SEP> 177 <SEP> 214 <SEP> 179 <SEP> 209 <SEP> 195 <SEP> 228 <SEP> 197 <SEP> 230 <SEP> 194 <SEP> 237
<tb> DURETE <SEP> SHORE <SEP> A <SEP> 69 <SEP> 70 <SEP> 69 <SEP> 71 <SEP> 72 <SEP> 74 <SEP> 74 <SEP> 77 <SEP> 76 <SEP> 79
<tb> MODULE <SEP> à <SEP> 300 <SEP> % <SEP> ALL. <SEP> 25 <SEP> 70 <SEP> 26 <SEP> 70 <SEP> 36 <SEP> 76 <SEP> 44 <SEP> 82 <SEP> 48 <SEP> 87
<tb> Pa <SEP> *
<tb> DECHIREMENT <SEP> PANTALON <SEP> 22 <SEP> 34 <SEP> 26 <SEP> 38 <SEP> 33 <SEP> 46 <SEP> 45 <SEP> 56 <SEP> 50 <SEP> 58
<tb> kg/cm
<tb> ABRSION <SEP> DIN <SEP> (perte) <SEP> 204 <SEP> 144 <SEP> 206 <SEP> 140 <SEP> 184 <SEP> 122 <SEP> 187 <SEP> 123 <SEP> 185 <SEP> 120
<tb> * Multiplier les chiffres par 105 pour obtenir la valeur en Pa. SILICA
<tb> Surface area <SEP> 183 <SEP> m2 / g <SEP> 195 <SEP> m2 / g <SEP> 226 <SEP> m2 / g <SEP> 277 <SEP> m2 / g <SEP> 306 <SEP > m2 / g
<tb> MERCAPTO-SILANE
<tb>% <SEP> at <SEP> weight <SEP> with <SEP> report <SEP> 0 <SEP> 3 <SEP>% <SEP> 0 <SEP> 3.25% <SEP> 0 <SEP> 3.65% <SEP> 0 <SEP> 4.6 <SEP>% <SEP> 0 <SEP> 5.1 <SEP>%
<tb> to <SEP> the <SEP> silica
<tb> (% <SEP> = <SEP> function <SEP> of <SEP> surface <SEP> in <SEP>% <SEP> by <SEP> report <SEP> to
<tb> the <SEP> silica)
<tb> MIXING <SEP> NO <SEP> VULCANIZED
<tb> TEST <SEP> AU <SEP> RHEOMETER
<tb> 150 C
<tb> COUPLE <SEP> MINIMAL
<tb> (viscosity) <SEP> 12 <SEP> 10.5 <SEP> 12.5 <SEP> 11 <SEP> 23 <SEP> 16 <SEP> 28 <SEP> 20 <SEP> 31 <SEP> 23
<tb> TIME <SEP> OPTIMUM <SEP> VULCANI- <SEP> 12 <SEP> 8.75 <SE> 12.5 <SEP> 9.25 <SE> 17.5 <SE> 12.5 <SEP> 21.0 <SEP> 15.0 <SEP> 28.0 <SEP> 21
<tb> SATION <SEP> (mn)
<tb> PROPERTIES <SEP> STATIC
<tb> DES <SEP> VULCANISATS
<tb> RESISTANCE <SEP> BREAK <SEP> Pa * <SEP> 177 <SEP> 214 <SEP> 179 <SEP> 209 <SEP> 195 <SEP> 228 <SEP> 197 <SEP> 230 <SEP> 194 <SEP> 237
<tb> HARDNESS <SEP> SHORE <SEP> A <SEP> 69 <SEP> 70 <SEP> 69 <SEP> 71 <SEP> 72 <SEP> 74 <SEP> 74 <SEP> 77 <SEP> 76 <SEP > 79
<tb> MODULE <SEP> to <SEP> 300 <SEP>% <SEP> ALL. <SEP> 25 <SEP> 70 <SEP> 26 <SEP> 70 <SEP> 36 <SEP> 76 <SEP> 44 <SEP> 82 <SEP> 48 <SEP> 87
<tb> Pa <SEP> *
<tb> TEACHING <SEP> PANTS <SEP> 22 <SEP> 34 <SEP> 26 <SEP> 38 <SEP> 33 <SEP> 46 <SEP> 45 <SEP> 56 <SEP> 50 <SEP> 58
<tb> kg / cm
<tb> ABRESS <SEP> DIN <SEP> (loss) <SEP> 204 <SEP> 144 <SEP> 206 <SEP> 140 <SEP> 184 <SEP> 122 <SEP> 187 <SEP> 123 <SEP> 185 <SEP> 120
<tb> * Multiply numbers by 105 to get the value in Pa.
TABLEAU (suite)
PROPRIETES <SEP> DYNAMIQUES
<tb> DES <SEP> VULCANISATS <SEP> Compression <SEP> statique <SEP> 24 <SEP> lbs <SEP> - <SEP> Déflexion <SEP> 22,2 <SEP> % <SEP> F <SEP> = <SEP> 21,4 <SEP> Hz <SEP> T <SEP> = <SEP> 50 C
<tb> FLEXOMETRE <SEP> GOODRICH
<tb> COMPRESSION <SEP> STATIQUE <SEP> 13,1 <SEP> 13,1 <SEP> 12,9 <SEP> 12,5 <SEP> 11,2 <SEP> 9,45 <SEP> 9,8 <SEP> 8,2 <SEP> 8,7 <SEP> 7,6
<tb> COMPRESSION <SEP> DYNAMIQUE <SEP> 8,2 <SEP> 4,7 <SEP> 8,0 <SEP> 4,5 <SEP> 6,5 <SEP> 3,5 <SEP> 5,5 <SEP> 2,3 <SEP> 2,2 <SEP> 0,8
<tb> Origine <SEP> %
<tb> COMPRESSION <SEP> DYNAMIQUE <SEP> 12,4 <SEP> 5,8 <SEP> 12,1 <SEP> 5,7 <SEP> 14,0 <SEP> 5,2 <SEP> 16,8 <SEP> 4,3 <SEP> 17,2 <SEP> 1,5
<tb> Finale <SEP> %
<tb> # <SEP> CDF <SEP> - <SEP> CDO <SEP> % <SEP> 4,2 <SEP> 1,1 <SEP> 4,1 <SEP> 1,2 <SEP> 7,5 <SEP> 1,7 <SEP> 11,3 <SEP> 2,0 <SEP> 15,0 <SEP> 2,3
<tb> # <SEP> T.basse <SEP> C <SEP> 35 <SEP> 25,5 <SEP> 34,5 <SEP> 25,0 <SEP> 42 <SEP> 26 <SEP> 47 <SEP> 27,5 <SEP> 50 <SEP> 28
<tb> # <SEP> T.Coeur <SEP> C <SEP> 118,5 <SEP> 85,5 <SEP> 119 <SEP> 85,0 <SEP> 142 <SEP> 88 <SEP> > 150 <SEP> 92 <SEP> > 150 <SEP> 96
<tb> DEFORMATION <SEP> PERMANENTE% <SEP> 6,3 <SEP> 2,75 <SEP> 6,3 <SEP> 2,70 <SEP> 9,5 <SEP> 2,9 <SEP> 13,5 <SEP> 3,1 <SEP> 15,3 <SEP> 3,2
<tb> <SEP> DYNAMIC PROPERTIES
<tb> DES <SEP> VULCANISATS <SEP> Static <SEP> Compression <SEP> 24 <SEP> lbs <SEP> - <SEP> Deflection <SEP> 22.2 <SEP>% <SEP> F <SEP> = <SEP> 21.4 <SEP> Hz <SEP> T <SEP> = <SEP> 50 C
<tb> FLEXOMETER <SEP> GOODRICH
<tb> COMPRESSION <SEP> STATIC <SEP> 13.1 <SEP> 13.1 <SEP> 12.9 <SEP> 12.5 <SEP> 11.2 <SEP> 9.45 <SEP> 9.8 <SEP> 8.2 <SEP> 8.7 <SEP> 7.6
<tb> COMPRESSION <SEP> DYNAMIC <SEP> 8.2 <SEP> 4.7 <SEP> 8.0 <SEP> 4.5 <SEP> 6.5 <SEP> 3.5 <SEP> 5.5 <SEP> 2.3 <SEP> 2.2 <SEP> 0.8
<tb> Origin <SEP>%
<tb> COMPRESSION <SEP> DYNAMIC <SEP> 12.4 <SEP> 5.8 <SEP> 12.1 <SEP> 5.7 <SEP> 14.0 <SEP> 5.2 <SEQ> 16.8 <SEP> 4.3 <SEP> 17.2 <SEP> 1.5
<tb> Final <SEP>%
<tb>#<SEP> CDF <SEP> - <SEP> CDO <SEP>% <SEP> 4.2 <SEP> 1.1 <SEP> 4.1 <SEP> 1.2 <SEP> 7.5 <SEP> 1.7 <SEP> 11.3 <SEP> 2.0 <SEP> 15.0 <SEP> 2,3
<tb>#<SEP> LowType <SEP> C <SEP> 35 <SEP> 25.5 <SEP> 34.5 <SEP> 25.0 <SEP> 42 <SEP> 26 <SEP> 47 <SEP > 27.5 <SEP> 50 <SEP> 28
<tb>#<SEP> T.Core <SEP> C <SEP> 118.5 <SEP> 85.5 <SEP> 119 <SEP> 85.0 <SEP> 142 <SEP> 88 <SEP>> 150 <SEP> 92 <SEP>> 150 <SEP> 96
<tb> DEFORMATION <SEP> PERMANENT% <SEP> 6.3 <SEP> 2.75 <SEP> 6.3 <SEP> 2.70 <SEP> 9.5 <SEP> 2.9 <SEP> 13, <SEP> 3.1 <SEP> 15.3 <SEP> 3.2
<Tb>
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8116743A FR2512037B1 (en) | 1981-09-03 | 1981-09-03 | ELASTOMERIC COMPOSITION REINFORCED BY SILICA WITH A LARGE SPECIFIC SURFACE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8116743A FR2512037B1 (en) | 1981-09-03 | 1981-09-03 | ELASTOMERIC COMPOSITION REINFORCED BY SILICA WITH A LARGE SPECIFIC SURFACE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2512037A1 true FR2512037A1 (en) | 1983-03-04 |
| FR2512037B1 FR2512037B1 (en) | 1986-02-14 |
Family
ID=9261870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8116743A Expired FR2512037B1 (en) | 1981-09-03 | 1981-09-03 | ELASTOMERIC COMPOSITION REINFORCED BY SILICA WITH A LARGE SPECIFIC SURFACE |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2512037B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002088A1 (en) * | 1984-09-28 | 1986-04-10 | Battelle Development Corporation | Optically transparent elastomers |
| WO2000053671A1 (en) * | 1999-03-10 | 2000-09-14 | Bridgestone/Firestone Research, Inc. | Solid silica coupling agent composites in silica rubber |
| FR2803595A1 (en) * | 2000-01-12 | 2001-07-13 | Michelin Soc Tech | RUBBER COMPOSITION FOR USE IN A VULCANIZED CONDITION AS A SAFETY SUPPORT FOR TIRES AND SUCH A SUPPORT |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2206330A1 (en) * | 1972-11-13 | 1974-06-07 | Degussa | |
| FR2353486A1 (en) * | 1976-06-04 | 1977-12-30 | Rhone Poulenc Ind | NEW AMORPHIC SYNTHETIC SILICA, PROCESS FOR OBTAINING AND APPLYING THE SAID SILICA IN VULCANISATES |
| FR2472000A1 (en) * | 1979-12-20 | 1981-06-26 | Rhone Poulenc Ind | PROCESS FOR IMPROVING COMPATIBILITY OF PLASTIFIERS AND LOADS IN POLYMERS |
| FR2476666A1 (en) * | 1980-02-25 | 1981-08-28 | Rhone Poulenc Ind | NOVEL COUPLING METHOD BETWEEN AN ELASTOMER AND A LOAD ESPECIALLY BASED ON A SILICA COMPOUND |
-
1981
- 1981-09-03 FR FR8116743A patent/FR2512037B1/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2206330A1 (en) * | 1972-11-13 | 1974-06-07 | Degussa | |
| FR2353486A1 (en) * | 1976-06-04 | 1977-12-30 | Rhone Poulenc Ind | NEW AMORPHIC SYNTHETIC SILICA, PROCESS FOR OBTAINING AND APPLYING THE SAID SILICA IN VULCANISATES |
| FR2472000A1 (en) * | 1979-12-20 | 1981-06-26 | Rhone Poulenc Ind | PROCESS FOR IMPROVING COMPATIBILITY OF PLASTIFIERS AND LOADS IN POLYMERS |
| EP0032076A2 (en) * | 1979-12-20 | 1981-07-15 | Rhone-Poulenc Chimie De Base | Process for improving the compatibility of oils and fillers in rubber compositions |
| FR2476666A1 (en) * | 1980-02-25 | 1981-08-28 | Rhone Poulenc Ind | NOVEL COUPLING METHOD BETWEEN AN ELASTOMER AND A LOAD ESPECIALLY BASED ON A SILICA COMPOUND |
| EP0034970A1 (en) * | 1980-02-25 | 1981-09-02 | Rhone-Poulenc Chimie De Base | Process for coupling an elastomer and a filler, especially on the basis of a silicium composite |
Non-Patent Citations (1)
| Title |
|---|
| EXBK/77 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002088A1 (en) * | 1984-09-28 | 1986-04-10 | Battelle Development Corporation | Optically transparent elastomers |
| WO2000053671A1 (en) * | 1999-03-10 | 2000-09-14 | Bridgestone/Firestone Research, Inc. | Solid silica coupling agent composites in silica rubber |
| FR2803595A1 (en) * | 2000-01-12 | 2001-07-13 | Michelin Soc Tech | RUBBER COMPOSITION FOR USE IN A VULCANIZED CONDITION AS A SAFETY SUPPORT FOR TIRES AND SUCH A SUPPORT |
| EP1116606A1 (en) * | 2000-01-12 | 2001-07-18 | Société de Technologie Michelin | Rubber composition suitable in vulcanised state as safety support for tyre and such a support |
| US6667361B2 (en) | 2000-01-12 | 2003-12-23 | Michelin Recherche Et Technique S.A. | Rubber composition usable in the vulcanized state as a tire safety support and such a support |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2512037B1 (en) | 1986-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2353503C (en) | Improved processability of silica-filled rubber stocks | |
| JP4937503B2 (en) | Carbon black having organic group, method for producing the same, rubber compound containing the carbon black, method for producing the same, use thereof, and molded article comprising the same | |
| US9752008B2 (en) | Esters of cyclohexane polycarboxylic acids as plasticizers in rubber compounds | |
| JP2000265018A (en) | Production of peroxide-vulcanized rubber composition and article essentially consisting of the composition | |
| CA2386098C (en) | Silica-filled elastomeric compounds | |
| JP3175016B2 (en) | High hardness rubber composition | |
| US9163135B2 (en) | Rubber compositions with filler and ketoxime or ketixmo silane | |
| WO2018043088A1 (en) | Vulcanized rubber composition and production process therefor | |
| WO2018165387A1 (en) | Coupled polymer products, methods of making and compositions containing | |
| FR2680795A1 (en) | PROCESS FOR PRODUCING MOLDED MASSES LIABLE TO BE VULCANIZED AND MASSES MOLDED THUS PRODUCED | |
| FR2512037A1 (en) | Silica reinforced elastomer compsn. - contains silane and/or succinimide additive to enhance reinforcing effect | |
| US20180282522A1 (en) | Tire with tread with oxidized carbon black | |
| US10570273B2 (en) | Starch pre-blend, starch-filled rubber composition, and related processes | |
| JP2010196030A (en) | Rubber composition | |
| FR2512036A1 (en) | Silica and carbon black reinforced elastomeric compsn. - contg. silane and/or succinimide additive providing synergistic reinforcing effect of the fillers | |
| JP3375390B2 (en) | Rubber composition for tire tread | |
| JP5593669B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP3325371B2 (en) | Rubber composition | |
| KR102289643B1 (en) | Rubber composition for tire tread | |
| KR102526787B1 (en) | Rubber composition for tire-tread and tire using it | |
| JP2007099896A (en) | Rubber composition | |
| EP4277950A1 (en) | Additives in rubber formulations | |
| JP7372524B2 (en) | Rubber composition for tires and pneumatic tires using the same | |
| JP2004339276A (en) | Rubber composition | |
| WO2023225398A1 (en) | Rubber formulations yielding improved dynamic properties and wear |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ST | Notification of lapse |