AU628390B2 - A method of production of bitumen lstynenel conjugated diene products with use of a s coupling agent - Google Patents

Description

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OPI DATE 02/04/90 AOJP DATE 10/05/90 APPLN. ID 42176 89

PCT

PCT NUMBER PCT/FR89/00453 DEMANDE INTERNATIONALE PUBLIEE EN VERTU DU TRAITE DE COOPERATION EN MATIERE DE BREVETS (PCT) (51) Classification internationale des brevets 5 (11) Numiro de publication internationale: WO 90/02776 C08L 95/00, C10C 3/02 Al (C08L 95/00, 53/02) (43) Date de publication internationale: 22 mars 1990 (22.03.90) (21) Numiro de la demande internationale: PCT/FR89/00453 (74) Mandataire: BOILLOT, Marc; Soci6t& Nationale Elf Aquitaine, Dept. Proprit6 Industrielle, Tout Elf, F- (22) Date de dip8t international: 8 septembre 1989 (08.09.89) 92078 Paris-La Dffense C6dex 45 (FR).

Donnies relatives i la priorite: (81) Etats disign6s: AU, BR, DK, JP, NO, US.

88/11825 9 septembre 1988 (09.09.88) FR Publie (71) Diposant (pour tous les Etats disignis sauf US): ELF FRAN- Avec rapport de recherche internationale.

CE [FR/FR]; Tour Elf, 2, place de la Coupole, La De- Avant lexpiration du dlai privu pour la modification des fense 6, F-92400 Courbevoie revendications, sera republie si de telles modifications sont recues.

(72) Inventeurs; et Inventeurs/Diposants (US seulement) PLANCHE, Jean- Pascal (FR/FR]; 13, rue Boileau, F-69006 Lyon (FR).

TRAVERS, Frangois [FR/FR]; 22, rue Salvador-Allende, F-42350 La Talaudiere ZINS, Annie [FR/ FR]; La Rivoire, F-38200 Seyssuel (FR).

(54)Title: METHOD FOR THE PREPARATION OF BITUMEN-POLYMER COMPOSITIONS (54)Titre: PROCEDE DE PREPARATON DE COMPOSITIONS BITUME-POLYMERE (57) Abstract Bitumen-polymer compositions are prepared, between 1000C and 2300C, by mixing bitumen with a copolymer of styren and a conjugated diene and a coupling agent susceptible of providing sulfur, the copolymer and the coupling agent being added to the bitumen either directly or in the form of a mother solution in hydrocarbonaceous oil, and by maintaining the mixture under stirring conditions between 100*C and 2300C during at least ten minutes. The coupling agent is formed either by associating sulfur and/or hydrocarbon polysulfur to at least one sulfur-donor or non sulfur-donor curing accelerator or it consists of at least one sulfur-donor curing accelerator, the quantity of coupling agent used being selected in order to obtain a sulfur quantity representing from 0.5 to 10 by weight of the copolymer. The bitumen-polymer compositions obtained are usable as surface road coats, covers and sealing coatings and present a constant quality of their properties.

(57) Abrige On prepare des compositions bitume-polymre en m6lbiangeant, entre 1000C et 230*C, un bitume avec un copolymere de styr~ne et d'un dibne conjugu6 et un agent de couplage susceptible de fournir du soufre, le copolymere et l'agent de couplage 6tant ajoutes au bitume soit directement soit sous la forme d'une solution mere dans une huile hydrocarbonie, puis en maintenant le tout sous agitation entre 100C et 23000 pendant au moins dix minutes. L'agent de couplage est soit constitu6 en associant du soufre et/ou un polysulfure d'hydrocarbyle A au moins un acc6l6rateur de vulcanisation non donneur de soufre ou donneur de soufre ou bien consiste en au moins un acc616rateur de vulcanisation donneur de soufre, la quantit6 d'agent de couplage utilisee 6tant choisie pour fournir une quantit6 d soufre representant 0,5 A 10 en poids du copolymbre. Les compositions bitume-polymere obtenues sont utilisables pour la rtalisation de revetements superficiels routiers, d'enrob6s et de revtements d'tanch6it6 et presentent une qualit6 constante de propribths.

W090/02776 PCT/FR89/00453 A METHOD OF PRODUCTION OF BITUMEN/STYRENE/CONJUGATED DIENE PRODUCTS WITH USE OF A SULFUR COUPLING AGENT The invention concerns a process for the production of bitumenpolymer blends. It also refers to the use of the blends obtained for preparing coatings and particularly road surface coatings, material coatings and also waterproof coatings and relates equally to a polymer mother liquor which can be used to obtain the said blends.

The use of bituminous blends for various surface coatings, and in particular for road surface coatings, provided that these blends possess a certain number of essential mechanical properties,is well known These mechanical properties are assessed in practice by determining, by means of standardised tests, a series of mechanical properties, of which the the most usual are the following softening point, expressed in °C and determined by the Bille and Anneau test specified in standard NFT 66 008, embrittlement point, or Fraass point, expressed in °C and V determined according to standard IP 80/53, penetration expressed in tenths of mm and determined according to standard NFT 66 004 rheological characteristics during tension determined according to NFT 46 002 and comprising the values Stress at the threshold Ts in bars elongation at the threshold Zs in stress at the breakage point Tr in bars ~elongation at breakage Zr in In general, traditional bitumens do not have all the required properties at the same time, and it has been known for a long time that the additions of various polymers to these traditional bitumens makes it possibly to improve the mechanical properties of the latter and to produce blends of bitumen-polymer which have mechanical properties which are better than those of the bitumens alone.

W090/02776 PCT/FR89/00453 2 Polymers capable of being added to bitumens are mostly elastomers such as poly-isoprene, butyl rubber, polybutylene, polyisobutylene, copolymers of ethylene/vinyl acetate, polymethacrylate, polychloroprene, tertiary polymer of ethylene/propylene/butadiene (EPDM), polynorbornene, or else statistical sequenced copolymers of styrene and a conjugated diene.

Among the polymers which are added to bitumens, the statistical or sequenced copolymers of styrene and a conjugated diene, and especially of styrene and butadiene or of styrene and isoprene, are particularly efficient as they dissolve very easily in the bitumens and confer on them excellent mechanical and dynamic properties and especially very good viscoelastic properties.

It is well known, furthermore, that the stability of the bitumenpolymer mixtures can be improved by chemical coupling of the polymer to the bitumen, this improvement besides making it possible to enlarge the field of utilisation of the bitumen-polymer mixtures.

Bitumen-copolymer mixtures in which a statistical or sequenced copolymer of styrene or of a conjugated diene such as butadiene or isoprene is coupled to the bitumen, can be produced by making use of the processes described in the references FR-A-2376188; FR-A-2429241 and FR-A-2528439. In these processes the said copolymer is incorporated together with a source of sulfur into the bitumen, while stirring at a temperature of between 130 0 C and 230°C. The blend so formed is then stirred further for at least fifteen minutes at a temperature of between 130°C and 230°C. The source of sulfur consists of chemically free sulfur (FP-A-2376188 and FR/-A-2429241) or of a polysulfide (FR-A-2528439) and the incorporation of the copolymer and the source of sulfur into the bitumen is carried out either by direct addition of the said ingredients to the bitumen (FR/-A-2376188 and FR/-A-3538439) or else by first producing a mother liquor of the copolymer and the source of sulfur in a hydrocarbon oil, and subsequently adding the said mother liquor to the bitumen. (FR/-A-2429241 and FR/-A-2528439).

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It has now been found that the mechanical characteristics and the stability of bitumen-polymer blends can be substantially further improved where a sequenced copolymer of styrene and of a conjugated diene, especially butadiene and isoprene is coupled with the bitumen by the action of a coupling agent which plays the part of a sulfur donor, if the said sulfur donor contains at least one vulcanisation accelerator playing directly the part of the sulfur donor or completing the action of the latter. The static mechanical characteristics in particular, determined especially by the traction test, are improved at low temperature and are conserved to a large degree after simulated ageing. This conservation of characteristics constitutes a gauge for the stability of the quality of the bitumen-polymer blends which are mostly produced in batches and are, therefore stored at high temperature for a shorter or longer period before being used.

Accordingly the present invention provides a process for the production of bitumen-polymer blends in which, at a temperature of between 100 C and 230 C, bitumen is mixed with a sequenced copolymer of styrene and a conjugated diene, the copolymer being used in a quantity from 0.5 to 15% based on the weight of the bitumen, and with a coupling agent containing a sulfur donating compound, and the mixture so obtained is maintained at a temperature within the said temperature limits, with stirring, for a period of at least minutes, wherein the coupling agent is selected from among: the products M comprised of, by weight, from 1% to 100% of a component A, which consists of one or several sulfur donating vulcanisation accelerators, and from 99% to 0% g of a component B, which consists of one or several vulcanisation agents selected from among elemental sulfur and the hydrocarbon polysulfides, (ii) the products N formed of a mixture of a component C, which consists of one or several non-sulfur donating vulcanisation accelerators, with a product M or with a product D in a weight ratio of component C to product M or to product D varying from 0.01 to i, the said product D c, -3-2 UJ 3 r consisting of that component B containing at least one hydrocarbon polysulfide and optionally elemental sulfur, and (iii) the products K comprised of a mixture of elemental sulfur with a component E in a weight ratio of component E to elemental sulfur varying from 0.01 to 1, the said component E consisting of that component C for which at least one of the non-sulfur donating vulcanisation accelerators it is comprised of is selected from the group consisting of the benzothiazole sulphenamides, the metallic dithiocarbamates and the thiuram monosulfides, the said coupling agent being used in a proportion to furnish a quantity of sulfur representing, by weight, 0.5 to 10% of the copolymer used for producting the bitumen-polymer blend.

Particularly the products M from among which the coupling agent can be selected which contains 10% by weight of the component A and 90% to 0% by weight of component B.

The vulcanisation accelerators, which are sulfur donors and can be used to form component A of product M, can be selected especially from the thioram polysulfides of the general formula R S S R I II N. C C -N R R in which the R's, identical or different, each represent a S25 hydrocarbon radical from C 1 to C12 and for preference from *12

C

1 to C 8 especially an alkyl, cycloalkyl or aryl radical, or else two radicals R, bound to the same nitrogen atom, are bound to each other to form a divalent hydrocarbon radical S from C 2 to C 8 and x is a number varying from 2 to 8. As examples of such vulcanisation accelerators can be quoted the compounds dipentamethylene thiuram disulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, tetraethylethyl disulfide and tetramethyl thiuram disulfide.

As other examples of vulcanisation accelerators which, are sulfur donors, and which can be used to form component A of product M, alkyl phenol disulfides and disulfides such as morpholine disulfides and N,N'caprolactam disulfides, can be cited.

4L- 4 The vulcanisation accelerators which are not sulfur donors and which can be used to form component C of product N can be to advantage sulfur compounds selected from among the benzothiazole sulfonamides and the dithio carbamates of the general formula (I) R S q N C S Y MI

R

in which the R's, identical or different, have the meaning given above, Y represents a metal and q designates the valency of Y, and the monosulfides of thiuram of the general formula

(II)

R S S R I, II N- C -S C-N N (II) R R in which the R's, identical or different, have the meaning given above.

Examples of vulcanisation accelerators of the benzothiazole sulfenamide type can be compounds such as 2-benzothiazole-diethyl sulfenamide, 2-benzothiazole methylene sulfenamide, 2-benzothiazole cyclohexyl sulfenamide, N-oxy diethylene 2-benzothiazole sulfenamide, N-oxy diethylene 2-benzothiazole thiosulfenamide, 2-benzothiazole dicyclohexyl 9 sulfenamide, 2-benzothiazole diisopropyl sulfenamide, S 25 2-benzothiazole terbutyl sulfenamide, N-oxy diethylene thiocarbamyl N'-oxy diethylene sulfenamide.

Among the vulcanisation accelerators of the dithiocarbamate type of the general formula the following ~compounds can be cited in particular: bismuth dimethyldi- 30 thiocarbamate, cadmium diamyl dithiocarbamate, copper dimethyl dithiocarbamate, zinc dibutyl dithiocarbamate, lead diamyl dithiocarbamate, lead diethyl S935 5 I W090/02776 PCT/FR89/00453 6 dithiocarbamate, lead pentamethylene dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, zinc diamyl dithiocarbamate, zinc dibenzyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dimethyl dithiocarbamate and zinc pentamethylene dithiocarbamate.

By way of examples of thiuram monosulfides which conform to the general formula (II) the following compounds can be cited: dipentamethylene thiuram monosulfide, tetrabutyl thiuram monosulfide, tetraethyl thiuram monosulfide and tetramethyl thiuram monosulfide.

The vulcanisation accelerators mentioned above which are not sulfur donors can also be those from which the vulcanisation accelerators from the group of benzothiazole sulfonamides, metallic dithiocarbamates and the thiuram monosulfides, have been selected, which are necessarily present in component E of product K.

Other non sulfur donating vulcanisation accelerators which do not belong to the families defined above, can also be used to form component C of product N or can possibly be present in component E of product K. Such vulcanisation accelerators can be compounds such as mercapto benzothiazole, benzothiazole ethiolate of a metal such as zinc, sodium, copper, benzothiazyl disulfide, N,N'-diethyl thiocarbamyl sulfide of benzothiazyle, diphenyl-1,3guanidine, diortho toluyle guanidine and zinc oxide, this latter compound possibly in the presence of fatty acids such as stearic acid, ethylcaproic acid, lauric acid.

Among the various mixtures capable of being used as coupling agents according to the invention, those which lead to rapid vulcanisation and which limit the risk of pre-vulcanisation, are preferred.

As previously indicated, the component B of the coupling agent consists of one or several vulcanisation agents selected from among hyrlt~c.rQr ee> elemental sulfur and the W090/02776 PCT/FR89/00435 7 It is of advantage if the sulfur being used is in the form of flowers of sulfur, and for preference orthorhombic sulfur crystals, known under the name of alpha sulfur. The bfl polysulfides which are capable of being used as vulcanisation agent in component B of product M or in product D correspond to the genral formula

R

1 (S)m (R (S)m R in which R 1 and R 2 each designate a monovalent hydrocarbon radical from C 2 to C 20 saturated or unsaturated, forming a cycle with the other atom groupings which are associated in the formula, R 3 is a divalent alkyl radical, saturated or unsaturated, between

C

1 and C 20 the representing divalent groupings each formed of m atoms of sulfur, the m's being capable of being different from one of the said groupings to the other, and designating whole numbers from 1 to 6 with at least one of the m's equal or greater than 2, and r representing a whole number which can have a value from zero to In the above mentioned formula the monovalent hydrocarbon radicals R 1 and R 2 between C 1 and C 20 as well as the divalent hydrocarbon radical R 3 between C 1 and C 20 are especially selected from among the aliphatic, alicyclic or aromatic radicals. When the radicals R 1 and R 2 are bound to each other to constitute a divalent hydrocarbon radical between C 1 and C 20 forming a cycle with the other atom groupings associated with the formula, the said divalent radical is similar to the radical R and can also be of the aliphatic, alicyclic or aromatic type. The radicals R 1 and R 2 in particaular are identical and are selected from the alkyl radicals between C 1 and C 2 0 for example ethyl, propyl, hexyl, octyl, nonyl, decyl, octadecyl and the cycloalkyl radicals and

I,

W090/o2776 PCT/FR89/00453 8 aryls between C 6 and C 20 especially benzyl, phenyl, toluyl, cyclohexyl, while the radical R 3 or the divalent radical formed by the combining of R1 and R 2 are selected among the alkyl radicals between C 1 and C 20 or the cycloarylene or arylene radicals, especially phenylene, tolylene, cyclohexylene between C 6 and C 20 Polysulfides which can be used according to the invention are especially those defined by the formula

R

1 (S)n

R

2 in which R 1 and R 2 each designate a monovalent hydrocarbon radical, saturated or unsaturated, between C 1 and C 20 or are bound to each other to form a divalent radical R 3 between C 1 and C 20

R

1

R

2 and R 3 having the same meanings as above, represents a divalent grouping formed by a chain of n atoms of sulfur, n being a whole number between 2 qnd 6.

Preferred polysulfides correspond to the general formula

R

4

R

4 in which R 4 designates a divalent grouping formed by a chain of p atoms of sulfur, p being a whole number between 2 and 5. Examples of such polysulfides are especially dihexyl disulfide, dioctyl disulfide, didodecyl disulfide, ditertiary dodecyl disulfide, dihexa decyl disulfide, dihexyl trisulfide, dioctyl trisulfide, dinonyl trisulfide, ditertiary dodecyl disulfide, dihexadecyl trisulfide, dihexyl tetrasulfide, dioctyl tetrasulfide, dinonyl tetrasulfide, ditertiary dodecyl tetrasulfide, dihexadecyl tetrasulfide, dihexyl pentasulfide, dioctyl pentasulfide, dinonyl pentasulfide, ditertiary dodecyl pentasulfide, dihexadecyl pentasulfide.

Other polysulfides which can be used according to the invention, are for example compounds such as diphenyl trisulfide, dibenzyl trisulfide, diphenyl tetrasulfide, orthotoluyl tetrasulfide, dibenzyl tetrasulfide, dibenzyl pentasulfide, diallyl pentasulfide, tetramethyl tetrathiane.

a r ,r W090/02776 PCT/FR89/00453 9 The bitumen which constitutes the greater part of the bitumencopolymer mixtures according to the invention, is selected from the various bitumens which have a penetration, as defined in standard NFT 66004, of between 5 and 500 and for preference between 20 and 400. Such bitumens can be, in particular, bitumens produced by direct distillation or by vacuum distillation, or again blown or semi-blown bitumens, having a penetration within the limits given above.

The copolymer of styrene and a conjugated diene which is used in the production of the bitumen-copolymer mixture, is to advantage selected from among the sequenced copolymers of styrene and butadiene, styrene and isoprene, styrene and chloroprene, styrene and carboxylated butadiene and styrene and carboxylated isoprene. The copolymer of styrene and conjugated diene, and in particular each of the above cited copolymers have a weight content of styrene of preferentially 15 to 40 The viscometric mean molecular mass of the copolymer of styrene and conjugated diene, and especially that of the copolymer mentioned above can, to advantage, be between 30,000 and 300,000 and for preference is situated between 70,000 and 200,000.

The copolymer of styrene and conjugated dienes, for preference selected from the di- or tri-sequenced copolymers of styrene and butadiene, of styrene and isoprene, of styrene and carboxylated butadiene, styrene and carboxylated isoprene having styrene contents and molecular masses within the limits defined above.

The preferred quantity of copolymer added to the bitumen lies between the limits of o.7 and 10 of the weight of the bitumen.

In a preferred form of designing the process according to the invention the copolymer and the coupling agent are incorporated in the bitumen in the form of a mother liquor of these two products W090/02776 PCT/FR89/00453 in a solvent consisting of a hydrocarbon oil with a distillation range at atmospheric pressure, determined according to the standard ASTM D 86-67, of between 100°C and 450°C and situated especially between 150°C and 370°C.

This hydrocarbon oil which can, in particular, be a petroleum cut of the aromatic type, a petroleum cut of the naphtheno-paraffinic type, a petroleum cut of the paraffinic type, a petroleum cut of the naphtheno-aromatic type, an oil from black coal, or else a vegetable oil, is sufficiently "heavy" to limit the evaporation, at the moment of addition of the mother liquor to the bitumen, and at the same time sufficiently "light" to be mostly eliminated after spreading of the bitumen-copolymer blends contained in it in such a manner as to regain the same mechanical properties which it would have have had, after hot spreading the bitumen-copolymer blend without using the technique of using the mother liquor.

The mother liquor is produced by mixing together the ingredients of which it consists, to wit hydrocarbon oil serving as solvent, copolymer, and a coupling agent, while stirring, at temperatures of between 20 and 170°C, and more particularly between 40 and 120 0

C,

for a time period of around 30 minutes to about 90 minutes, ro as to obtain a complete dissolution of the copolymer and of the coupling agent in the hydrocarbon oil.

The respective concentrations of the copolymer and the coupling agent in the mother liquor can vary considerably as a function especially of the nature of the hydrocarbon oil used for dissolving the copolymer and the coupling agent. In this manner the respective quantities of copolymer and coupling agent can be to advantage to 40 and 0.02 to 15 by weight of the hydrocarbon oil.

A preferred mother liquor contains, calculated on the basis of the hydrocarbon oil used as solvent, 10 to 35 of copolymer and 0,1 to 5 of coupling agent.

W090/02776 PCT/FR89/00453 11 Where the mixtures according to the invention are produced starting directly with the ingredients bitumen, copolymer and coupling agent, the preferred method of operation is to first add together the copolymer and the bitumen in the chosen proportions, at a temperature of between 100°C and 230°C with stirring, for an adequate period of time, in general of the order of several tens of minutes to several hours, so as to produce a homogeneous mixture,; then the coupling agent is added to the mixture so obtained and the whole is maintained with stirring at a temperature of between 100°C and 230 0 C, for example the same as the temperature at which copolymer and bitumen were first blended, for a period of at least 10 minutes, and generally from 10 to 90 minutes, to permit the coupling agent to set free sulfur radicals, and for the sulfur radicals so produced to initiate on the one hand the bonding of the copolymer with the bitumen and on the other hand the bridging of the said copolymer chains between themselves.

The quantities of copolymer blended with the bitumen and of the coupling agent added afterwards to the homogeneous mixture of the bitumen and the said copolymer, are selected so as to be within the limits defined above for these quantities.

In order to prepare bitumen-polymer blends according to the invention using the mother liquor technique, the mother liquor of the copolymer and the coupling agent is blended with the bitumen, while operating at a temperature of between 100 0 C and 2300C with stirring, this being carried out for example by adding the mother liquor to the bitumen which is maintained, while being stirred,at a temperature of between 100°C and 230 0 C, then maintaining the resulting mixture while stirring at a temperature of between 100°C and 230°C, for example at the temperature used for mixing the mother liquor and the bitumen, for a period of at least 10 minutes, and generally between 10 and 90 minutes, to permit, through the action of the coupling agent the bonding of the copolymer to the asphaltenes of the bitumen and the bridging of the chains of the said copolymer among themselves.

/1 C 6, s I i i:S r W090/02776 PCT/FR89/00453 12 The quantity of the mother liquor blended with the bitumen is selected so as to furnish the desired quantities, with respect of the bitumen, of copolymer and coupling agent given in the limits defined above.

One form of execution particularly preferred for the production of bitumen-copolymer blends according to the invention by way of the mother liquor technique, consists of mixing at a temperature of between 100 0 C and 230 0 C and with stirring, of 80 to 95 by weight of bitumen with 20 to 5 by weight of the mother liquor, the latter containing, by weight based on the hydrocarbon oil serving as solvent, 10 to 35 of copolymer of styrene and conjugated diene and 0.1 to 5 of coupling agent, followed by maintaining the mixture so obtained, under stirring, at a temperature of between 100 0

C

and 230 0 C, and for preference at the temperature used for blending the bitumen with the mother liquor, for a period at least equal to 10 minutes, and for preferehLce of between 10 and 60 minutes.

The bitumen-copolymer blends obtained by the process according to the invention can be used for producing various coatings, and in particular road surface coatings. The bitumen-copolymer blends of the invention produced by the mother liquor technique are particularly well suited for this application as they can be used directly, employing the traditional spreading methods.

The invention is illustrated by the following non-limiting examples.

The rheological and mechanical characteristics of the bitumencopolymer blends to which reference is made in these examples are those which have been defined above, to wit, penetration, softening point, Fraass point and rheological characteristics during traction.

EXAMPLE 1: Preparation of a sample bitumen-polymer blend by direct addition of the copolymer and the coupling agent to the bitumen.

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W090/02776 PCT/FR89/00453 13 While operating at 170 0 C with stirring, 1,000 parts of bitumen,produced by direct atmospheric distillation, which has a penetration of 82, a Bille and Anneau softening point of 48°C, a Fraass point equal to -18.5 0 C and a kinematic viscosity at 160°C of 1.7x10 m /s are mixed with with 31 parts by weight of a di-sequenced copolymer of styrene and of butadiene having a mean molecular mass equal to around 75,000 and containing 25 by weight of styrene.

After 3 hours, 10 minutes of mixing with stirring a homogeneous mass is obtained.

To this mass maintained at 170 0 C, one part by weight of crystallised sulfur is then added and the whole is further stirred for 60 minutes to form the bitumen-polymer blend.

In table I the principal characteristics of the bitumen-polymer blend so obtained, are given before and after having submitted it to the ageing test known as the "Rolling Film Oven Test" which is given in the ASTM D 2872 standard. The bitumen-polymer blends before and after the ageing test are designated respectively "Product Ial" and "Product Ia2".

Table I also gives the corresponding characteristics of the initial bitumen before and after the ageing test (respectively "Product Ibl" and "Product Ib2").

By referring to the values given in table I it can be seen that the use of a coupling agent consisting of crystallised sulfur leads to a bitumen-polymer blend the elastomeric characteristics of which differentiate it clearly from the bitumen (cf the results of the traction test). Furthermore, the stability on ageing of the bitumen-polymer blend is improved with respect to that observed in pure bitumen.

TABLE I Characteristics Penetration Softening FraassTRCINES Poutat 25 C Point Point

-_TACTONES

(/0m)TEMP. SPEED V' s Er Prdut /1 m) B A (C)Qc mm/mn bars bars a 75 95 20 500 2,3 0,5 23 >900 500 20 5.6 15 330 a 95 720 500 4,4 1,8 20 >900 500 2,5 9,1 13 180 I 24 85 20 500 1.2 0 15 >900 1 5 500

FRAGILE

I b2 51 50 15 5 500 1,8 0 15 F >900 500 FRAGILE

I-.

:r W)90/02776 PCT/FR89/00453 EXAMPLE 2 Preparation of a bitumen-polymer blend according to the invention by direct incorporation of the copolymer and the coupling agent into the bitumen.

The process is operated as described in example 1, however, using as coupling agent a mixture of 0.8 parts by weight of crystallised sulfur and 0.2 parts by weight of a sulfur donating vulcanisation accelerator, consisting of tetramethyl thiuram disulfide.

In table II analogous characteristics to those figuring in table I are given for the bitumen-polymer blends obtained in examples 1 and 2. The same notations designate the characteristics which correspond to the bitumen-polymer blends before and after the ageing test.

As shown by the results presented in table II the use of a sulfur donating vulcanisation accelerator, mixed with the crystallised sulfur to constitute the coupling agent leads to the production of a bitumen-polymer blend which has substantially improved elastomeric properties, especially at low temperature, when compared with the properties observed in the sample bitumen-polymer blend in which a coupling agent consisting solely of crystallised sulfur was used.

Furthermore, stability on ageing of the bitumen-polymer blend according to the invention is clearly improved when compared to that of the sample bitumen-polymer blend.

TABLE II Characteristics Penetration softening Fraass TRACTION TEST at 25 C Point Point TM. SED V-O s E Product (1/10 iuu) B A (0C) (60 mm/mn bars bars 500 2,3 0,5 23 >900 a 75 955 500 20 5,6 15 330 500 4,4 1,8 20 >900 a 95 75 500 25 9.1 13 180 500 3.1 1,3 25 >900 a 1 64 56 -23 500 23 9,5 22 >900 500 3,3 1.3 20 >900 1a 2 44 63 -18 T .8 150 11 5 500 ?298 150 T W090/02776 PCT/FR89/02776 17 EXAMPLES 3 TO 7 Production of bitumen-polymer blends according to the invention by direct incorporation of the copolymer and the coupling agent into the bitumen.

Operation is as described in example 2 with, however, certain modifications which are outlined below, the other operating conditions being those of the example 2.

In example 3 the coupling agent consisted of a mixture of 0.2 parts by weight of tetramethyl thiuram disulfide and of 0.7 parts by weight of crystallised sulfur, and the temperature was equal to 160 0

C.

In example 4 the coupling agent was formed from a blend of 0.1 parts by weight of a non sulfur donating vulcanisation accelerator consisting of 2-benzothiazole dicyclohexyl sulfenamide and of 0.8 parts by weight of crystallised sulfur, and the reaction temperature was equal to 180°C.

In example 5 the coupling agent consisted of a mixture of 0.15 parts by weight of a sulfur donating vulcanisation accelerator which consisted of morpholine disulfide and of 0.75 parts by weight of crystallised sulfur, the reaction temperature being 140'C.

In example 6 the coupling agent consisted of a mixture of 0.2 parts by weight of two non sulfur donating vulcanisation accelerators, to wit 2-benzothiazole diisopropyl sulfenamide and zinc dimethyl dithio carbamate, used in quantities by weight equal to 0.8 parts by weight of crystallised sulfur, the reaction temperature being maintained at 140 0

C.

In example 7 the coupling agent consisted of a mixture of 2 parts by weight of a sulfur donating vulcanisation accelerator which consisted of dipentamethylene thiuram tetrasulfide and of 0.6 parts by weight of a non sulfur donating vulcanisation accelerator which consisted of zinc oxide, the coupling reaction taking place at 1400C.

T

I

W090/02776 PCT/FR89/00453 18 The characteristics of the bitumen-polymer blends so obtained are given in table III, before and after their being submitted to the ageing test.

The bitumen-polymer blends before ageing are designated "Product while the corresponding bitumen-polymer blends after ageing are designated by "Product P representing the number of the example in Roman numerals.

Lur dQ q Characteristics Product [11 a 1 III a 2 IV a 2 V.a.l V.a.2 VI.*.1 VI.a.2 VII.a.1 VII.a.2 TABLE III Softening Fraas Penetration at 25 C (1/10 as) TRACTION TEST Point a A 65 57 62 53 Point

TEMP.

(C)

SPEED 1 7 m/an bars

WC

bars

E.

0/0 S r c/ I I i i i 26 20 500 2.1 0.7 23 >900 500 18 6.8 22 >900 2.0 >900 19 23 500 21 9.1 27 340 20 500 2.3 00- 18 >900 >900 I I~t 4 20 500 4.2 1.9 28 >900 18

I

2,5 >900 20 500 21 6.2 20 >900 T t 4-4 20 500 4.4 1.9 29 >900 65 18 T I I I 20 500 2.6 1 21, >900 16 -4 1 5 500 22 7 2 0 1>900 39 14 00 Ln wo i 20 28 >900 22 1- I 4 23 >900 >900 t I I I 4 20 >900 5 500 1 23 9.9 1 25 j 410 L I I I I 1 I WO 0/02776 PCT/FR89/00453 EXAMPLE 8 Production of a sample bitumen-polymer blend by the mother liquor technique.

a Preparation of the mother liquor The operation was carried out in a stainless steel reactor fitted with a stirrer and with a double mantle capable of having a heat exchange fluid flowing through it.

The hydrocarbon oil used as solvent to form the mother liquor was a petroleum cut of naphtheno-aromatic character with the following properties: ASTM initial distillation point equal to 176°C ASTM distillation end point equal to 352 0 C (measured according to ASTM standard D 86-67) flash point (standard Luchaire NP T 60103) of 79 0

C

theoretical density (ASTM standard D 1657-64) equal to 0.956 233 parts by weight of the petroleum cut was introduced into the reactor and the petroleum cut was was heated, while being stirred, to a temperature of around 100°C by circulating a hot fluid through the double mantle of the reactor.

While maintaining this temperature and stirring, 2 parts by weight of crystallised sulfur and 54 parts by weight of a powder, incorporating 2 of silica as anti-foamant, of a non-sequenced copolymer of styrene and butadiene containing 25 of styrene and possessing a mean viscosimetric molecular weight of around 75,000, was added.

After one hour of stirring at the temperature of around 100°C a homogeneous and fluid solution is obtained at ambient tempersture which is characterised by the following values of kinematic viscosity: kinematic viscosity measured at 50°C 12.10 x 10-4m2/s kinematic viscosity measured at 100°C 2.92 x 10 -m /s This solution constituted the mother liquor used for the production of the bitumen-polymer blend.

W090/02776 PCT/FR90/00453 21 b Production of the bitumen-polymer blend 1700 parts of a bitumen, distilled at atmospheric pressure, were pumped into a vessel equipped with stirrers and provided with vapour phase reheaters. The bitumen had the following initial physical properties softening point (test B A) 48°C Fraass point 18.5°C penetration 82 1/10 mm 4 2 kinematic viscosity at 160 0 C 1.70 x 10 m /s 300 parts of the mother liquor, prepared as described above was then added to the content of the vessel which was maintained at 170 0 C with stirring.

After stirring for 30 minutes at the temperature of 170°C a fluid bitumen-polymer blend was obtained which had a dynamic viscosity at 160 0 C equal to 0.098 Pa.s, that is to say a viscosity comparable to that of a bitumen having a penetration within the limits 180-220, and capable of being charged directly into a traditional medium asphalt spreader.

The properties of the bitumen-polymer blend so obtained, before and after having been submitted to a thermal treatment consisting of bringing up to 160C in a heater a sealed metallic vessel which contains the bitumen-polymer blend, and maintaining the said vessel at this temperature for 60 days, are given in table IV. This test permits the simulation of the evolution of the product during extended storage. The bitumen-polymer blend is designated by "Product VIII.a.l" before the thermal treatment and by "Product VIII.a.2" after thermal treatment.

By comparison table IV also shows, before and after the above mentioned thermal treatment, the corresponding characteristics of the initial bitumen by 12 in weight, with respect to the bitumen, of the solvent used for preparing the mother liquor ("Product VIII.b.l" and "Product VIII.b.2" respectively), and of the bitumen-polymer blend produced in a similar manner to that described in example 8, but omitting the crystallised sulfur. ("Product VIII.c.l" and Product VIII.c.2").

RA

9 IirrnP W090/02776 PCT/FR89/00453 In the product designations the 1 and 2 define the bitumenpolymer blends respectively before and after the thermal treatment.

A-

TABLE IV Chractritstics Viscosity Pseudo TRACTION TEST (Rheomat) Viscosity at 160 C TEMP. SPEED 7- Q-r Es Er Product (Poise) (9C) mi/mn bars bars VIII a 1 1901 100 10 500 5.6 1,6 15 >900 VIII a 2 1,2 114 10 500 4,1 2.6 20 >900 VIII b 1 0,7 so 10 500 FRAGILE VIII b 2 0,85 80 10 500 FRAGILE VIII.C.1 0,81 84 10 500 6,3 0 15 300 VIII.C.2 0,97 96 -10 500 FRAGILE j

J

W090/02776 PCT/FR89/O0453 24 As follows from a comparison of the results listed in table IV the use of crystallised sulfur as coupling agent in the technique using motLer liquor leads to the production of a fluxed bitumen-polymer blend having elastomeric properties. After storage at elevated temperature the product gives a residual binder the properties of which are close to those of the bitumen-polymer blend before thermal treatment.

EXAMPLE 9 Production of a bitumen-polymer blend according to the invention by the mother liquor technique.

The operation is carried out as described in example 8 by forming, however, a mother liquor starting with 243.6 parts by weight of the petroleum cut, 54 parts by weight of the di-sequenced copolymer of styrene and butadiene and of a coupling agent consisting of 0.4 parts by weight of a sulfur donating vulcanisation accelerator consisting of tetramethyl thiuram disulfide and of 1.5 parts by weight of crystallised sulfur.

Table V gives, for the bitumen-polymer blend obtained, the characteristics of which are analogous to those given in table IV for the sample blend of example 8, the table V also including the characteristics of the sample blend so as to facilitate the comparison.

The scrutiny of the results presented in table V shows that the use of a coupling agent according to the invention in the technique of producing the bitumen-polymer blend using mother liquor leads to the production of a bitumen-polymer blend exhibiting clearly improved elastomeric characteristics, in particular the stress at rupture Tr, with respect to those of the sample bitumen-polymer blend for the production of which (example 8) only crystallised sulfur is used as coupling agent.

g:y (j~ TABLE V Ch'aacttri sti cs V i si t y Pseudo TRACTION TEST (Rheomat) V i Ssi ty at 160 C ()TEHP. SPEED TsVi ES (cr Product (Poio) (00 mm/mn bars bars%% VIII a 1 1,01 100 10 500 4,6 1.6 15 >900 VIII a 2 1,20 114 10 500 4.1 2,6 20 >900 L IX. a. 1 1,21 116 10 500 4,6 2.5 17 >900 IX. a. 2 1,30 125 -10 500 5,2 3,4 22 >900 W090/02776 PCT/FR89/00453 26 Besides, the stability on storage at high temperature, for example 1600 C for two months, of the bitumen-polymer blend according to the invention (example is much improved with rspect to that of the sample blend (example the elastomeric properties of the blend according to the invention stored in this manner (Product IX.a.2) being fully as good as those of a freshly produced blend (Product IX.a.1).

EXAMPLES 19 AND 11 Production of bitumen-polymer blends according to the invention by the mother liquor technique.

The operation is carried out as described in example 9, however, with certain variations which are detailed below, the other operating conditions being the same as in example 9.

In example 11 the vulcanisation accelerator present in the coupling agent consisted of zinc dimethyl dithio carbamate, a nonsulfur donating vulcanisation accelerator.

In example 11 the vulcanistation accelerator present in the coupling agent consisted of tetramethyl thiuram monosulfide, a non-sulfur donating vulcanisation accelerator.

The characteristics of the bitumen-polymer blends obtained, before and after having submitted them to the thermal storage test defined in example 8, are given in table VI.

The bitumen-polymer blends are designated, before and after storage, with notations comparable to those used in the previous examples.

9 TABLE VI Charmactermistics Viscosity Pseudo TRACTION TEST (Rheonat) Viscosity Product a 16 C'()TEMP. SPEED q- 6s E (Poise) (0C) *Im/mn bars bars %6 0/ X.a.1 1,20 1.12 10 500 5,7 2.6 18 >900 X a 2 1,40 131 10 500 5,2 3,0 23 >900 XI. a. 1 1,16 110 10 500 6,0 2.4 16 >900 XI. a. 2 1,41 132 10 500 5,5 3.4 21 >900

Claims (31)

1. 2. A process according to claim 1 wherein the coupling agent is used in the righ proportion to furnish a quantity of sulfur representing, by weight, 1 to 8% of the copolymer used C U o. •e 28 pY- .1 to produce the bitumen-polymer blend.
2. 3. A process according to claim 1 or 2 wherein the products contain, by weight, 10% to 100% of the compound A and 90% to 0% of the compound B.
3. 4. A process according to one of the claims 1 to 3 wherein the non-sulfur donating vulcanisation accelerator(s) used to form the compoun C of product N are selected from among the benzothiazole sulfenamides, and especially among the 2-benzothiazole sulfenamides. A process according to one of the claims 1 to 3 wherein the non-sulfur donating vulcanisation accelerator(s), used to form compound C of product N, or present in the compound E as dithiocarbamates, are selected from among the dithiocarbamates of the general formula I i R- N- C- S q Y in which the R's, identical or different, each represent a hydrocarbon radical from C 1 to C 12 and for preference from C 1 to C 8 especially an alkyl, aryl or cycloalkyl radical, or else the two R radicals which are bound to the nitrogen atom are bonded among themselves to form a divalent 25 hydrocarbon radical from C 2 to C 8 Y representing a metal 2 o S and q designating the valency of Y.
4. 6. A process according to one of the claims 1 to 3 :wherein the non-sulfur donating vulcanisation accelerator(s), used to form the compound C of product N, or present in compound E as thiuram monosulfides, are selected from among the thiuram monosulfides of the general formula (III) R S S R |1 N- C-S-C-N 35 R R in which the R's, identical or different, each representing a hydrocarbon radical from C 1 to C 12 and for preference from C 1 to C 8 especially an alkyl, aryl or cycloalkyl radical, or else two radicals R bound to the same nitrogen atom are 29 I_ 1 bonded amongst each other to form a divalent hydrocarbon radical from C 2 to C 8
5. 7. A process according to one of the claims 1 to 6 wherein the weight ratio of compound C to product D or to product M in the product N, which is the coupling agent, varies from 0.05 to
6. 8. A process according to one of claims 1 to 6 wherein the weight ratio of compound E to elemental sulfur in the product K varies from 0.05 to
7. 9. A process according to one of the claims 1 to 8 wherein the compound A of product M consists of one or several sulfur donating vulcanisation accelerator(s) selected from among a group formed by a) the thiuram polysulfides of the formula R S S R N- C C-N R \R in which the R's, identical or different, each represent a hydrocarbon radical from C 1 to C 12 and for preference from C 1 to C 8 especially an alkyl, cycloalkyl or aryl radical, or else two radicals R, bound to the same nitrogen atom, are bonded among themselves to form a divalent hydrocarbon radical from C 1 to C 8 and, x is a number varying from 2 to 8, b) the alkyl phenyl disulfides and c) disulfides such as morpholine disulfides and N,N'-caprolactam disulfide. 25 •co oeooo e *e eee*
8. 10. A process according to one of the claims 1 to 9 wherein the compound B which enters into the composition of product M or the sulfur associated with compound E, consist of orthorhomic crystallised sulfur. orthorhombic crystallised sulfur. .35
9. 11. A process according to one of the claims 1 to 9 wherein the compound B which enters into the composition of product M -or product D consists of or contains one or several hydrocarbon sulfide(s) of the general formula R 1 (S)m (R3 (S)m)r R 2 30 in which R 1 and R 2 each designate a monovalent hydrocarbon radical, saturated or unsaturated, from C 1 to C 20 or are bonded to each other to form a divalent hydrocarbon radical, saturated or unsaturated, forming a cycle with the other groups of atoms associated in the formula, R 3 is a divalent hydrocarbon radical from C 2 to C 20 saturated or unsaturated, from C 1 to C 20 the -(S)m representing divalent groupings, each formed of m atoms of sulfur, the m's may be different from one of the said groups to another and designating whole numbers varying from 1 to 6, with at least one of the m's equal or greater to 2 and r representing a whole number taking the value of zero to
10. 12. A process according to claim 11 wherein the said polysulfide(s) are of the general formula R 4 (S)p R in which R 4 designates an alkyl radical from C6 to C 1 6 and represents a divalent grouping formed by a chain of p atoms of sulfur, p being a whole number varying from 2 to
11. 13. A process according to one of the claims 1 to 12 wherein the bitumen has a penetration of between 5 to 500 and for preference between 20 and 400, the said bitumen being more 25 especially selected from among the bitumens distilled at atmospheric pressure or under vacuum and from blown or semi-blown bitumens.
12. 14. A process according to one of the claims 1 to 13 wherein the copolymer is selected from among the statistical or sequenced copolymers of styrene with a conjugated diene selected from among butadiene, isoprene, chloroprene, carboxylated butadiene and carboxylated isoprene.
13. 15. A process according to one of the claims 1 to 14 wherein the copolymer has a weight content of styrene varying from 15% to
14. 16. A process according to one of the claims 1 to 31 wherein the copolymer possesses a mean viscosimetric molecular mass of between 70,000 and 200,000.
15. 17. A process according to one of the claims 1 to 16 wherein the quantity of copolymer added to the bitumen is between 0.7% and 10% by weight of the bitumen.
16. 18. A process according to one of the claims 1 to 17 wherein the copolymer and the coupling agent are incorporated into the bitumen in the form of a mother liquor of these two products in a solvent consisting of a hydrocarbon oil with a distillation range at atmospheric pressure of between 100°C and 450°C and more particularly between 160°C and 370 0 C.
17. 19. A process according to claim 18 wherein the hydrocarbon oil is selected from among petroleum cuts of an aromatic type, petroleum cuts of a naphtheno-paraffinic type, petroleum cuts of a naphtheno-aromatic type, petroleum cuts of a paraffinic type, coal oils or vegetable oils. A process according to the claims 18 and 19 wherein the mother liquor is prepared by adding together the materials of which it is composed with stirring, at temperatures of between 20 and 170 0 C and for preference between 40 and 25 120 0 C.
18. 21. A process according to one of the claims 18 to wherein the respective quantities of copolymer and coupling j agent represent from 5% to 40% and from 0.02% to 15% of the weight of hydrocarbon oil.
19. 22. A process according to claim 21 wherein the mother 4 liquor contains 10 to 35% of copolymer and 0.1 to 5% of coupling agent, by weight, based on the hydrocarbon oil.
20. 23. A process according to one of the claims 18 to 22 wherein the following are added together at a temperature of between 100 C and 230°C and with stirring: from 80 to by weight of bitumen and 20 to 5% by weight of the mother I k 32- '7' liquor, the latter containing, by weight, based on the hydrocarbon oil which is serving as solvent, 10 to 35% of copolymer of styrene and conjugated diene and 0.1 to 5% of coupling agent; the mixture so obtained is maintained with stirring at a temperature of between 100°C and 230 C, and for preference at the temperature used when adding together the bitumen and the mother liquor, for a period of at least minutes, and for preference of between 10 and 60 minutes.
21. 24. Use of the bitumen-polymer blends obtained by the process according to one of the claims 1 to 23 for the production of coatings and in particular of road surface coatings.
22. 25. Polymer mother liquor, which can be used especially for the production of bitumen-polymer blends, comprising a hydrocarbon oil with a distillation range at atmospheric pressure of between 100°C and 450°C, and, in solution in this oil, a copolymer of styrene and a conjugated diene and a coupling agent in amounts respectively representing to 40% and 0.02 to 15% of the weight of the hydrocarbon oil, wherein the coupling agent is selected from among: the products M comprised of, by weight, from 1% to 100% of a component A, which consists of one or several 25 sulfur donating vulcanisation accelerators, and from 99% to 0% of a component B, which consists of one or several S vulcanisation agents selected from among elemental sulfur and ee the hydrocarbon polysulfides, the products N formed of a mixture of a component C, which consists of one or several non-sulfur donating vulcanisation accelerators, with a product M or with a product D in a weight ratio of component C to product M or to product D varying from 0.01 to 1, the said product D consisting of that component B containing at least one hydrocarbon polysulfide and optionally elemental sulfur, and (iii) the products K comprised of a mixture of elemental -sulfur with a component E in a weight ratio of component E to elemental sulfur varying from 0.01 to 1, the 33 said component E consisting of that component C for which at least one of the non-sulfur donating vulcanisation accelerators it is comprised of is selected from the group consisting of the benzothiazole sulphenamides, the metallic dithiocarbamates and the thiuram monosulfides.
23. 26. Mother liquor according to claim 25 wherein the products M contain, by weight, 10% to 100% of the compound A and 90% to 0% of the compound B.
24. 27. Mother liquor according to claim 26 wherein the said non-sulfur donating vulcanisation accelerator(s) used to form compound C of product N are selected from among the benzothiazole sulfenamides, and more particularly from among the 2-benzothiazole sulfenamides.
25. 28. Mother liquor according to claim 25 or 26 wherein the non-sulfur donating vulcanisation accelerators used to form compound C of product N or present in compound E such as dithiocarbamates are selected from among the dithiocarbamates of the general formula (I) N C- SY R/ q (I) 0 0 00 .:0.0 in which the R's, identical or different, each represent a hydrocarbon radical from C 1 to C 12 and for preference from C 1 to C 8 especially an alkyl, aryl or cycloalkyl radical, or else the two radicals R bound to the nitrogen atom are bonded among themselves to form a divalent hydrocarbon radical from C 2 to C 8 Y representing a metal and q designating the valency of Y.
26. 29. Mother liquor according to claim 25 or 26 wherein the non-sulfur donating vulcanisation accelerator(s) used for producing compound C of product N in compound E such as thiuram monosulfides are selected from among thiuram monosulfides of the general formula (II) RA4 Ir 34 S S R N- C S C- N R (II) in which the R's, identical or different, each represent a hydrocarbon radical from C 1 to C 12 and for preference from C 1 to C 8 especialy an alkyl, aryl or cycloalkyl radical, or else two radicals R bound to the same nitrogen atom are bonded among themselves to form a divalent hydrocarbon radical from C 2 to C 8 Mother liquor according to on of the claims 25 to 29 wherein the weight ratio of the compound C to product D or to product M in the product N varies from 0.05 to
27. 31. Mother liquor according to claim 25 wherein the weight ratio of compound E to the elemental sulfur in product K varies from 0.05 to
28. 32. Mother liquor according to one of the claims 25 to wherein the compound A consists of or contains one or several sulfur donating vulcanisation accelerator(s) selected from among the group formed by a) the thiuram polysulfides of the formula S S R S S II 1 N C C -N R/ x in which the R's, identical or different, each represent a hydrocarbon radical from C 1 to C12 and for preference from C 1 to C 8 especially an alkyl, cycloalkyl or aryl radical, or else two radicals R, bound to the same nitrogen atom, are bonded among themselves to form a divalent hydrocarbon radical from C 2 to C 8 and x is a number varying from 2 to 8, b) the phenol alkyl disulfides and c) disulfides such as morpholine disulfides and caprolactam N,N'-disulfides.
29. 33. Mother liquor according to one of the claims 25 to 32 wherein the compound B of product M or the elemental sulfur associated with compound E consists of orthorhombic crystallised sulfur. 35
30. 34. Mother liquor according to one of the claims 25 to 32 wherein the compound 13 of product M or the product D consist of or contain one or several hydrocarbon polysulfides of the general formula (S)m mr 3 (S)m R2 in hih 1an R2 eahdesignate a monovalent hydrocarbon radical, saturated or unsaturated, forming a cycle with the other atom groups associated in the formula, R3is a divalent hydrocarbon radical, saturated or unsaturated, from C 2 to C 20 the m- represent divalent groups each formed of m atoms of sulfur,~ the m's possibly varying from one of the said groups to another and designating whole numbers varying from 1 to 6 with atc least one of the m's equal or greater than 2, and r representing a whole number having the values from zero to ten. Mother liquor according to claim 34 wherein the said polysulfide(s) forming the compound B have the general formula P 4 -R p 4 in which R designates an alkyl radical between C and 46 C 1 and represents a divalent group formed by chains of p atoms of sulfur, p being a whole number varying from 2 to V. 25 36. Mother liquor according to one of the claims 25 to 1) wherein the copolyme: is selected from among the sequenced copolymers of styrene with a conjugated diene selected from among butadiene, isoprene, chloroprene, carboxylated butadiene and carboxylated isoprene.
31. 337. Mother liquor according to one of the claims 25 to 36 :110: wherein the copolymer has a weight content of styrene varying from 15% to 38. Mother liquor according to one of the claims 25 to 37 wherein the copolymer possesses a mean viscosimetric molecul~ar mass of between 30,000 and 300,000, and for preference between 70,000 and 200,000. 36 39. Mother liquor according to one of the claims 25 to 38 wherein the hydrocarbon oil has a distillation range at atmospheric pressure between 150 0 C and 370 0 C. 40. Mother liquor according to one of the claims 25 to 39 wherein the hydrocarbon oil is selected from among petroleum cuts of aromatic type, petroleum cuts of naphtheno-paraffinic type, petroleum cuts of paraffinic type, coal oils and vegetable oils. 41. Mother liquor according to one of the claims 25 to wherein it contains 10 to 35% of copolymer and 0.1 to 5% of coupling agent, by weight, based on the hydrocarbon oil. 42. Mother liquor according to one of the claims 25 to 41, produced by mixing together the ingredients of which it is composed, with stirring at temperatures of between 20 and 170 0 C and for preference between 40 and 120 0 C. 43. A process according to claim 1 substantially as hereinbefore described with reference to any one of the examples. S. 44. Mother liquor according to claim 25 substantially as 25 hereinbefore described with reference to any one of the 0 examples. DATED: 16 June 1992 PHILLIPS ORMONDE FITZPATRICK Attorneys for: 0| ELF FRANCE 37 9I ;c INTERNATIONAL SEARCH REPORT International Application No PCT FR 8 9 00453 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC Int.C1. 5 C 08 L 95/00, C 10 C 08 L 95/00, C 08 L 53:) II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols Int.Cl. 5 C 08 L; C10 C Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched a III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, with indication, where appropriate, of the relevant passages 12 Ralevant to Claim No. 1 3 X GB, A, 2025986 (ELF UNION) 30 January 1-3,10,13- 1980, see abstract; claims 26,33,36-42 FR, A, 2429241 (cited in the application) A EP, A, 0096638 (ELF FRANCE) 21 December 1,2,10-24, 1983, see claims 33-42' FR, A, 2528439 (cited in the application) A US, A, 3751389 (TETSUYA HOTTA) 7 August 1973, see abstract; column 3, lines 49-51 Special categories of cited documents: to later document published after the international filing date document defining the general state of the rrt which is not or priority date and not in conflict with the application but A" con derfini tho e ralt ofthe ,rt whpach ncited to understand the principle or theory underlying the considered to be of particular relevenc, invention earlier document but published on or after the international document of particular relevance; the claimed invention filing dat cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (a speiined) document of particular relevance' the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this Inirnational Search Report 18 December 1989 (18.12.89) 24 January 1990 (24.01.90) International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE Form PCT/ISA/210 (second sheet) (January 1915) 16,_- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. FR 8900453 SA 31208 This annex lists the patent family members relating to the patent documents cited in the ahove-mentioned international scarch report. The members are as contained in the European Patent Office EDP file on 16/01/91i The European Patent Office is in no way liable for these particulars which are merely given for the purpoe of information. Patent document Publication Patent family Publication cited in search report date member(s) date GB-A- 2025986 30-01-80 FR-A,B 2429241 18-01-80 AT-B- 372970 12-12-83 BE-A- 877112 15-10-79 CA-A- 1137242 07-12-82 CH-A- 639985 15-12-83 DE-A,C 2925106 03-01-80 JP-A- 55003492 11-01-80 NL-A- 7904837 28-12-79 SE-B- 429135 15-08-83 SE-A- 7905446 22-12-79 US-A- 4242246 30-12-80 EP-A- 0096638 21-12-83 FR-A,B 2528439 16-12-83 AU-B- 557742 08-01-87 AU-A- 1560283 .15-12-83 AU-B- 582284 16-03-89 AU-A- 6468186 29-01-87 CA-A- 1209293 05-08-86 CH-A- 661051 30-06-87 JP-A- 59004648 11-01-84 US-A- 4554313 19-11-85 US-A- 4567222 28-01-86 US-A- 3751389 07-08-73 None Z For more details about this annex :see Official Journal of the European Patent Office, No. 12/82 V RAPPORT DE RECHERCHE INTERNATIONALE Demance international. N-P T F 9 0 I. CLASSEMENT DE L-INVENTION (Sit pluateurs symooles de classification sont aopiicables, Illo iflioquef tousl Selon Is classification internationalei dest brevets (CIS) ou a I& lots solon Ia classification nationale at I& CIS C 08 Li 95/00, C 10 C 08 L 95/00, C 08 L 33:02) 11, DOMAINES SUR LESQUELS LA RECHERCHE A PORTE Qocurnentation minimal.i conhulite I Systime de class ification Syniboles an classification C 08 L; C 10 C Documentation consultlls autre due [a documentation ininimale dons [a ineaure ouj do Isls documents font Partin des domaines our [@equals I& recherche a Poto 11l. DOCUMENTS CONSIOCRIS COMME PERTINENTS atgreIdentification des documents cit~s,11 avec: indication, aot necessaire. N, des revendications Catgoiedes passages pertinents 12 visc iS3 X GB, A, 2025986 (ELF UNION) 30 janvier 1980, 1-3,10,13- voir r6sujn6; revendications 26,33,36-4 FR, A, 2429241 (cite dans la demande) A EP, A, 0096638 (ELF FRANCE) 21 d6cembre 1,2,10-24, 1983, voirrevendications 33-42 FR, A, 2528439 (citd dans la demande) A 'US, A, 3751389 (TETSUYA HOTTA) 7 aodt 1973, voir r6sum6; colonne 3, lignes 49-51 Cat~gortes apilctalos do documents citts: tiala document ult~riour oublid Portlrleurementh la date do dolp6t it A a document d~finissant 1'6tat 96niral do Is technique, non intern allional ou A as data do pr iorite et napooartentant Paz consd tocomot prtiuliooromnt ertientA li*tat dolI& technique pertinent, mats cots Pour comorendre conid~A cmm.paricut~rmen pettnntIs prtnctple ou Is tholoart constituent In base do linvention m E* document arntilrteur, mats oublit Is date do ddpdt Interne- a X a document Particulibromeiint pvinent: I'Invention revendi- tional ou apron coneo date quile ne pout 6tre contaidrds comm. nouvelle ou comm., a L a document pouvant tater un doute aur une roendication do Impliquant une activit4 Inventive prioritt ou cits Pour determiner lei Cate, dO publicatton d'une m sdcmn atcihent pertinent; Inrvention reven- autre citation ou Pour une, raison paciales (toile qu'indiqueo) *sdocume no t aticlre cni~l om oiun n o 0 ao document so ritfirant A une divulgatton orals, A un usage, A activit6 inventive, lraue Is document eot easocit ik un OU une enositioon ou taus autros moytona pluateurs autres document& do mia nature, cone combt- a P lo document publil avant Is date do d*06t international, maia naison Atant 6vidente Pour unes personne du metier. postilrieurement AIs date do Prioritt revendliquills itA a document qul talt Pantie dotIs mime famille do brevets IV. CERTIFICATION Date Ak lquall. In recherche Internationaie a 6116 offectivement Date dsoidition du Pr~atint rapport do recherche titeriiatiotials 1 ddocembre 1989 24 JAN4 1990 Administration chargto de I& recherche internationalet Sinture d~qa~=M OFFICE EtJROPEEN DES BREVETS TA N 4 LUS Formulate.t PCTIISA 1210 (deuilom. feuille) lJonview IM) uy wt:!1nt1, I rto 6 or tne copolymer used yo -28 ANNEXE AU RAPPORT DE RECHERCHE INTERNATIONALE RELATIF A LA DEMANDE INTERNATIONALE NO. FR 8900453 SA 31208 La prisente annexe indique les membres de la famille de brevets relatifs aux documents brevets cites dans le rapport de recherche internationale vis6 ci-dessus. Lesdits membres sont contenus au fichier informatique de I'Olflce europen des brevets i la date du 16/01/99 Les renseignements fournis sont donnis a titre indicatif et n'engagent pas la responsabilit6 de l'Office europeen des brevets. Document brevet cite Date de .Membre(s) de Ia Date de au rapport de recherche T publication Famille de brevet(s) publication GB-A- 2025986 30-01-80 FR-A,B 2429241 18-01-80 AT-B- 372970 12-12-83 BE-A- 877112 15-10-79 CA-A- 1137242 07-12-82 CH-A- 639985 15-12-83 DE-A,C 2925106 03-01-80 JP-A- 55003492 11-01-80 NL-A- 7904837 28-12-79 SE-B- 429135 15-08-83 SE-A- 7905446 22-12-79 US-A- 4242246 30-12-80 EP-A- 0096638 21-12-83 FR-A, B 2528439 16-12-83 AU-B- 557742 08-01-87 AU-A- 1560283 15-12-83 AU-B- 582284 16-03-89 AU-A- 6468186 29-01-87 CA-A- 1209293 05-08-86 CH-A- :661051 30-06-87 JP-A- 59004648 11-01-84 US-A- 4554313 19-11-85 US-A- 4567222 28-01-86 US-A- 3751389 07-08-73 Aucun Pour tout renseignement concernant cette annexe :voir Journal Ofliciel de I'Ofice europeen des brevets, No.12/82