WO1993006143A1 - Heat-stable petroleum resins, a preparation method therefor, and uses thereof for formulating hot-melt adhesives - Google Patents
Heat-stable petroleum resins, a preparation method therefor, and uses thereof for formulating hot-melt adhesives Download PDFInfo
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- WO1993006143A1 WO1993006143A1 PCT/FR1991/000739 FR9100739W WO9306143A1 WO 1993006143 A1 WO1993006143 A1 WO 1993006143A1 FR 9100739 W FR9100739 W FR 9100739W WO 9306143 A1 WO9306143 A1 WO 9306143A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
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- the present invention relates to new thermally stable petroleum resins, essentially aromatic and useful for the formulation of hot-melt adhesives, as well as their preparation.
- resins comprising a copolymer consisting essentially of 81 to 99% by weight of alkenylaromatic units and from 1 to 19% by weight of terpene units, said said resins being further characterized (by proton and carbon 13 NMR) by the presence of about 0.1 to 0.7%, preferably 0.1 to 0.5%, of hydrogens bound to unsaturated carbons not -aromatics.
- Such resins generally have a Gardner color (measured at 50% by mass in toluene) of between 1 and 4 and a softening point of between 80 ° and 150 ° C approximately, more precisely between 85 ° C and 110 ° C approximately. . They have a thermal stability remarkably superior to those of known resins, as well as all of the favorable physical properties allowing them to be formulated successfully in the ⁇ nofusibles adhesives, in particular for applications such as book binding, paper gluing , metals, glass, synthetic thermoplastic resins, woven or non-woven materials, etc.
- alkenylaromatic units which can enter into the constitution of the resins according to the invention, mention may in particular be made of units derived from styrene, alphamethylstyrene, indene, vinyitoluene, methylindenes, betamethylstyrene and paratertiobutyistyrene.
- terpene units which can enter into the constitution of the resins according to the invention, mention may in particular be made of units derived from unsaturated cyclic terpenes, preferably monounsaturated, in particular monocyclic ones such as 1-p- menthen and tetramethylcyclohexene and monounsaturated bicyclics such as pinenes, keels, limonene, 4 (10) -thujene, 5-isopropyIbicyclo [3.1.0] hex-2-ene, 4-methylenepinane, 2-bornene, 2,2,7-trimethyl-2-norbornene and camphene as well as certain bi-unsaturated monocyclic terpenes such as menthadienes.
- unsaturated cyclic terpenes preferably monounsaturated, in particular monocyclic ones such as 1-p- menthen and tetramethylcyclohexene and monounsaturated bicyclics such as pinenes, keels
- the resin copolymer according to the invention only comprises terpene and alkenylaromatic units. If it happens to contain patterns of aliphatic dienes, this can only be as residual impurity imperfectly removed during its preparation and in any case, in proportion less than 0.2% by weight.
- a second object of the present invention consists in a process for manufacturing the resins described above, comprising a first step in the treatment of a cut of alkenylaromatic monomers with a view to eliminating from this cut most of the chromophoric compounds, for example aliphatic compounds. and / or unsaturated cycloaliphatics, capable of coloring the resin and or altering its properties, then a second step of cationic copolymerization of a mixture comprising (a) from 88% to 99% by weight approximately of the treated cut obtained at l 'resulting from the first step and (b) from 1 to 12% by weight approximately of a cut comprising at least one terpene monomer.
- the desired resin is extracted by removing the copolymerization product from the traces of cationic initiators present.
- the methods of treatment of the first stage, of cationic copolymerization of the second stage and of final post-treatment are well known in the field of petroleum resins.
- the resins according to the invention may comprise, in addition to the alkenylaromatic / terpene copolymer described above, an effective amount of at least one stabilizing agent against degradation by light and / or thermal degradation, such as, for example, pentaerythritol diphosphite, polyal ylpiperidines as described in patent US-A-4,863,981, derivatives of 2,2,6,6-tetramethyl 4-piperidinyl as described in patent JP-A-58 / 104,942 (in particular bis (tetramethyl-2,2,6,6 piperidinyl-4) sebacate cited by patent application EP-A-155 912) and their mixtures in all proportions.
- at least one stabilizing agent against degradation by light and / or thermal degradation such as, for example, pentaerythritol diphosphite, polyal ylpiperidines as described in patent US-A-4,863,981, derivatives of 2,2,6,6-tetramethyl 4-piperidiny
- stabilizing agents are present in the resin according to the invention, they are preferably introduced after the post-treatment step for the elimination of the catalytic residues.
- a final object of the present invention consists in the use, as a component of an adhesive formulation, of a thermally stable petroleum resin comprising a copolymer consisting essentially of 81 to 99% by weight of alkenylaromatic units and from 1 to 19%. by weight of terpene units, said resin being further characterized (by proton and carbon 13 NMR) by the presence of 0.1% to 0.7% of hydrogens linked to aromatic unsaturated carbons.
- the resin described above can enter into the composition of a hot-melt adhesive formulation further comprising: a) a copolymer of ethylene and vinyl acetate or of alkyl acrylate or methacrylate, or else a terpolymer ethylene, alkyl (meth) acrylate and maleic anhydride, and b) a third compound chosen from microcrystalline polymer waxes, paraffins and esters of rosin acids hydrogenated from heavy alcohol.
- said formulation comprises, per 100 parts by weight, from 20 to 45 parts of petroleum resin, from 20 to 70 parts of polymer (a) and from 5 to 45 parts of compound (b). It can also comprise an effective amount of at least one antioxidant such as for example a phenol derivative or a phosphite.
- the petroleum resin according to the invention plays the role of a so-called "tackifying" resin.
- the resins according to the invention can also be used as reinforcing or optionally tackifying resins in adhesive formulations comprising natural rubber or synthetic rubbers such as polyisoprene, butyl rubbers, chlorobutyl, bromobutyl, chloroprene, elastomers ethylene / propylene / diene and the copolymers, linear or star, with styrene / isoprene or styrene / butadiene blocks.
- natural rubber or synthetic rubbers such as polyisoprene, butyl rubbers, chlorobutyl, bromobutyl, chloroprene, elastomers ethylene / propylene / diene and the copolymers, linear or star, with styrene / isoprene or styrene / butadiene blocks.
- Example 1 is given by way of illustration and without limitation of the present invention. Unless otherwise indicated, the quantities and proportions are expressed by weight.
- the prepotymerisate is distilled under reduced pressure to remove the prepolymer in the heavy distillation fraction and recover 51.4% parts of a treated cut of low color ( ⁇ 1G) and composed mainly styrene (11.2%), vinyl toluenes (14.2%), indene
- the essential composition of the resin is determined by pyrolysis: styrene 16.4%, vinyltoluenes 20.9%, indene 23.8%, methylindene 4.6%, alphamethylstyrene 2.8%, betamethylstyrene 5.4%, alphapinene 13, 6% and unidentified (12.5%). Analysis of this resin by nuclear magnetic resonance of the proton and carbon 13 shows the following distribution of the hydrogen atoms:
- the resin of Example 1 is used to make the following hot-melt adhesive formulation:
Abstract
Resins including a copolymer which essentially comprises 81-99 % wt. of alkenylaromatic units and 1-19 % wt. of terpene units, and further characterized in that they contain 0.1-0.7 % of hydrogens bonded to non-aromatic unsaturated carbons. A method for preparing the resins comprises a first step of treating a cut of alkenylaromatic monomers to remove essentially all the chromophoric compounds which might dye the resin and/or spoil its properties, and a second step of cationically copolymerizing a mixture which comprises (a) 88-99 % wt. of treated cut resulting from the first step, and (b) 1-12 % wt. of a cut which includes at least one terpene monomer. Said resins are useful as components for adhesive formulations.
Description
RESINES DE PETROLE THERMIQUEMENT STABLES, LEUR PROCEDE DE PREPARATION ET LEUR APPLICATION A LA FORMULATION D'ADHESIFS THERMOFUSIBLES. THERMALLY STABLE OIL RESINS, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO THE FORMULATION OF HOT MELT ADHESIVES.
La présente invention concerne de nouvelles résines de pétrole thermiquement stables, essentiellement aromatiques et utiles pour la formulation d'adhésifs thermofusibles, ainsi que leur préparation.The present invention relates to new thermally stable petroleum resins, essentially aromatic and useful for the formulation of hot-melt adhesives, as well as their preparation.
On connaît déjà par la demande de brevet EP-A-011.393 des résines de pétrole possédant des points de ramollissement de 70°C à 160°C et une couleur Gardner de 2 à 3 obtenus en copolymérisant (a) une coupe d'oléfines et dioléfines ayant 5 à 6 atomes de carbone, ladite coupe provenant du craquage du pétrole et (b) du limonène en l'absence de carvestrène. Ce document décrit comme préférées des résines comprenant au moins 50,1 % en poids de pipérylène et/ ou isoprène, le restant étant constitué de limonène et le cas échéant de monomères aromatiques insaturés.There are already known from patent application EP-A-011,393 petroleum resins having softening points from 70 ° C to 160 ° C and a Gardner color of 2 to 3 obtained by copolymerizing (a) a section of olefins and diolefins having 5 to 6 carbon atoms, said cut coming from the cracking of petroleum and (b) of limonene in the absence of carvestrene. This document describes as preferred resins comprising at least 50.1% by weight of piperylene and / or isoprene, the remainder consisting of limonene and, where appropriate, unsaturated aromatic monomers.
On connait également par la demande de brevet EP-A- 132.291 des résines de pétrole utiles pour formuler des adhésifs thermofusibles, comprenant un copolymère contenant :Also known from patent application EP-A-132,291 are petroleum resins useful for formulating hot-melt adhesives, comprising a copolymer containing:
- de 5 à 80 % en poids de composé aromatique à insaturation oléfinique,- from 5 to 80% by weight of olefinically unsaturated aromatic compound,
- de 5 à 80 % en poids d'oléfines et/ ou dioléfines Cg - C& et- from 5 to 80% by weight of Cg olefins and / or diolefins - C & and
- de 7 à 45 % en poids de terpènes, ce copolymère étant obtenu par copolymérisation d'un mélange contenant moins de 2 % en poids de (di) cyclopentadiène. Ce document décrit des résines ayant des couleurs Gardner de- from 7 to 45% by weight of terpenes, this copolymer being obtained by copolymerization of a mixture containing less than 2% by weight of (di) cyclopentadiene. This document describes resins with Gardner colors from
1,5 à 3 et des points de ramollissement de 60 à 120°C.1.5 to 3 and softening points from 60 to 120 ° C.
Enfin, on connait par la demande de brevet EP-A-233.074 des résines majoritairement à entièrement aromatiques, ayant un point de ramollissement de 75° à 160°C et une couleur Gardner de 1,6 à 4, caractérisées (par RMN du proton et du carbone 13) par la présence de :Finally, we know from patent application EP-A-233,074 resins predominantly entirely aromatic, having a softening point of 75 ° to 160 ° C and a Gardner color of 1.6 to 4, characterized (by proton NMR and carbon 13) by the presence of:
- 1 à 15 %, de préférence 2 à 8 %, d'hydrogènes liés à des carbones insaturés non-aromatiques,- 1 to 15%, preferably 2 to 8%, of hydrogens linked to non-aromatic unsaturated carbons,
- 50 à 80 %, de préférence 62 à 72 %, d'hydrogènes liés à des carbones saturés, et - 15 à 35 %, de préférence 22 à 32 %, d'hydrogènes liés à des carbones aromatiques.
Toutes les résines décrites par ces trois documents souffrent d'une stabilité thermique insuffisante et/ou, dans le cas des deux premiers documents cités, des inconvénients liés à la présence de proportions significatives d'oléfines et/ou dioléfines. Le problème technique que la présente invention s'est attachée à résoudre consiste à définir des résines de pétrole possédant une stabilité thermique supérieure à celle des résines connues, notamment par les documents déjà cités, ne présentant pas les inconvénients liés à la présence de proportions significatives d'oléfines et/ou dioléfines et possédant toutes les propriétés habituellement exigées pour leur formulation dans des adhésifs thermofusibles.- 50 to 80%, preferably 62 to 72%, of hydrogens linked to saturated carbons, and - 15 to 35%, preferably 22 to 32%, of hydrogens linked to aromatic carbons. All the resins described by these three documents suffer from insufficient thermal stability and / or, in the case of the first two documents cited, drawbacks linked to the presence of significant proportions of olefins and / or diolefins. The technical problem which the present invention has endeavored to solve consists in defining petroleum resins having a thermal stability greater than that of known resins, in particular by the documents already cited, not having the drawbacks linked to the presence of significant proportions. olefins and / or diolefins and having all the properties usually required for their formulation in hot-melt adhesives.
De manière surprenante, il a été découvert que l'ensemble de ces contraintes techniques peut être résolu par des résines comprenant un copolymère constitué essentiellement de 81 à 99 % en poids de motifs alcénylaromatiques et de 1 à 19 % en poids de motifs terpéniques, lesdites résines étant en outre caractérisées (par RMN du proton et du carbone 13) par la présence de 0,1 à 0,7 % environ, de préférence de 0,1 à 0,5 %, d'hydrogènes liés à des carbones insaturés non-aromatiques.Surprisingly, it has been discovered that all of these technical constraints can be resolved by resins comprising a copolymer consisting essentially of 81 to 99% by weight of alkenylaromatic units and from 1 to 19% by weight of terpene units, said said resins being further characterized (by proton and carbon 13 NMR) by the presence of about 0.1 to 0.7%, preferably 0.1 to 0.5%, of hydrogens bound to unsaturated carbons not -aromatics.
De telles résines possèdent généralement une couleur Gardner (mesurée à 50 % en masse dans le toluène) comprise entre 1 et 4 et un point de ramollissement compris entre 80° et 150°C environ, plus précisément entre 85°C et 110°C environ. Elles possèdent une stabilité thermique remarquablement supérieure à celles des résines connues, ainsi que l'ensemble des propriétés physiques favorables permettant de les formuler avec succès dans les adhésifs theπnofusibles, notamment en vue d'applications telles que la reliure de livres, le collage de papier, de métaux, de verre, de résines synthétiques thermoplastiques, de matériaux tissés ou non-tissés, etc.Such resins generally have a Gardner color (measured at 50% by mass in toluene) of between 1 and 4 and a softening point of between 80 ° and 150 ° C approximately, more precisely between 85 ° C and 110 ° C approximately. . They have a thermal stability remarkably superior to those of known resins, as well as all of the favorable physical properties allowing them to be formulated successfully in theπnofusibles adhesives, in particular for applications such as book binding, paper gluing , metals, glass, synthetic thermoplastic resins, woven or non-woven materials, etc.
Comme exemples de motifs alcénylaromatiques pouvant entrer dans la constitution des résines selon l'invention, on peut citer notamment les motifs dérivés du styrène, de l'alphaméthylstyrène, de l'indène, du vinyitoluène, des méthylindènes, du bétaméthylstyrέne et du paratertiobutyistyrène. Comme exemples de motifs terpéniques pouvant entrer dans la constitution des résines selon l'invention, on peut citer notamment les motifs dérivés de terpènes cycliques insaturés, de préférence monoinsaturés, notamment monocycliques tels que le 1-p-
menthène et le tétraméthylcyclohexène et bicycliques monoinsaturés tels que les pinènes, carènes, le limonène, le 4(10)-thujène, le 5- isopropyIbicyclo[3.1.0]hex-2-ène, le 4-méthylènepinane, le 2-bornène, le 2,2,7-triméthyl-2-norbornène et le camphène ainsi que certains terpènes monocycliques bi-insaturés tels que les menthadiènes. Ces motifs peuvent être introduits dans le copolymère des résines selon l'invention soit sous la forme de monomères purs soit le plus souvent sous la forme de coupes essentiellement terpéniques telles que des essences de térébenthine contenant des mélanges d'un grand nombre de terpènes. Le copolymère des résines selon l'invention ne comprend que des motifs terpéniques et alcénylaromatiques. S'il advient qu'il contienne des motifs de diènes aliphatiques, cela ne peut être qu'à titre d'impureté résiduelle imparfaitement éliminée au cours de sa préparation et en tous les cas, en proportion inférieure à 0,2 % en poids. Un second objet de la présente invention consiste en un procédé de fabrication des résines décrites précédemment comprenant une première étape de traitement d'une coupe de monomères alcénylaromatiques en vue d'éliminer de cette coupe l'essentiel des composés chromophores, par exemple des composés aliphatiques et/ou cycloaliphatiques insaturés, susceptibles de colorer la résine et ou d'altérer ses propriétés, puis une seconde étape de copolymérisation cationique d'un mélange comprenant (a) de 88 % à 99 % en poids environ de la coupe traitée obtenue à l'issue de la première étape et (b) de 1 à 12 % en poids environ d'une coupe comprenant au moins un monomère terpénique. A l'issue de cette seconde étape, on extrait la résine voulue en débarasssant le produit de copolymérisation des traces d'amorceurs cationiques présents. Les méthodes de traitement de la première étape, de copolymérisation cationique de la seconde étape et de post-traitement final sont bien connues dans le domaine des résines de pétrole. Les résines selon l'invention peuvent comprendre, outre le copolymère alcénylaromatique/terpénique décrit précédemment une quantité efficace d'au moins un agent stabilisant contre la dégradation par la lumière et/ou la dégradation thermique, tel que par exemple le pentaerythritol diphosphite, des polyal ylpipéridines comme décrites dans le brevet US-A-4 863 981, des dérivés de 2,2,6,6-tétraméthyl 4- pipéridinyle comme décrits dans le brevet JP-A-58/104 942 (en particulier
le bis (tétraméthyl-2,2,6,6 pipéridinyl-4) sebacate cité par la demande de brevet EP-A-155 912) et leurs mélanges en toutes proportions. Par quantité efficace on entend généralement leur introduction à raison de jusqu'à 2 % environ en poids par rapport au copolymère. Lorsque de tels agents stabilisants sont présents dans la résine selon l'invention, ils sont de préférence introduits après l'étape de post-traitement pour l'élimination des résidus catalytiques.As examples of alkenylaromatic units which can enter into the constitution of the resins according to the invention, mention may in particular be made of units derived from styrene, alphamethylstyrene, indene, vinyitoluene, methylindenes, betamethylstyrene and paratertiobutyistyrene. As examples of terpene units which can enter into the constitution of the resins according to the invention, mention may in particular be made of units derived from unsaturated cyclic terpenes, preferably monounsaturated, in particular monocyclic ones such as 1-p- menthen and tetramethylcyclohexene and monounsaturated bicyclics such as pinenes, keels, limonene, 4 (10) -thujene, 5-isopropyIbicyclo [3.1.0] hex-2-ene, 4-methylenepinane, 2-bornene, 2,2,7-trimethyl-2-norbornene and camphene as well as certain bi-unsaturated monocyclic terpenes such as menthadienes. These units can be introduced into the copolymer of resins according to the invention either in the form of pure monomers or most often in the form of essentially terpene cuts such as turpentine essences containing mixtures of a large number of terpenes. The resin copolymer according to the invention only comprises terpene and alkenylaromatic units. If it happens to contain patterns of aliphatic dienes, this can only be as residual impurity imperfectly removed during its preparation and in any case, in proportion less than 0.2% by weight. A second object of the present invention consists in a process for manufacturing the resins described above, comprising a first step in the treatment of a cut of alkenylaromatic monomers with a view to eliminating from this cut most of the chromophoric compounds, for example aliphatic compounds. and / or unsaturated cycloaliphatics, capable of coloring the resin and or altering its properties, then a second step of cationic copolymerization of a mixture comprising (a) from 88% to 99% by weight approximately of the treated cut obtained at l 'resulting from the first step and (b) from 1 to 12% by weight approximately of a cut comprising at least one terpene monomer. At the end of this second step, the desired resin is extracted by removing the copolymerization product from the traces of cationic initiators present. The methods of treatment of the first stage, of cationic copolymerization of the second stage and of final post-treatment are well known in the field of petroleum resins. The resins according to the invention may comprise, in addition to the alkenylaromatic / terpene copolymer described above, an effective amount of at least one stabilizing agent against degradation by light and / or thermal degradation, such as, for example, pentaerythritol diphosphite, polyal ylpiperidines as described in patent US-A-4,863,981, derivatives of 2,2,6,6-tetramethyl 4-piperidinyl as described in patent JP-A-58 / 104,942 (in particular bis (tetramethyl-2,2,6,6 piperidinyl-4) sebacate cited by patent application EP-A-155 912) and their mixtures in all proportions. By effective amount is generally meant their introduction at a rate of up to about 2% by weight relative to the copolymer. When such stabilizing agents are present in the resin according to the invention, they are preferably introduced after the post-treatment step for the elimination of the catalytic residues.
Enfin, un dernier objet de la présente invention consiste en l'utilisation comme composant d'une formulation adhesive d'une résine de pétrole theπniquement stable comprenant un copolymère constitué essentiellement de 81 à 99 % en poids de motifs alcénylaromatiques et de 1 à 19 % en poids de motifs terpéniques, ladite résine étant en outre caractérisée (par RMN du proton et du carbone 13) par la présence de 0,1 % à 0,7 % d'hydrogènes liés à des carbones insaturés aromatiques. Plus particulièrement la résine décrite ci-dessus peut entrer dans la composition d'une formulation adhesive thermofusible comprenant en outre: a) un copolymère d'éthylène et d'acétate de vinyle ou d' acrylate ou méthacrylate d'alkyle, ou bien un terpolymère d'éthylène, de (méth)acrylate d'alkyle et d'anhydride maléique, et b) un tiers composé choisi parmi les cires polymères micro¬ cristallines, les paraffines et les esters d'acides colophaniques hydrogénés d'alcool lourd.Finally, a final object of the present invention consists in the use, as a component of an adhesive formulation, of a thermally stable petroleum resin comprising a copolymer consisting essentially of 81 to 99% by weight of alkenylaromatic units and from 1 to 19%. by weight of terpene units, said resin being further characterized (by proton and carbon 13 NMR) by the presence of 0.1% to 0.7% of hydrogens linked to aromatic unsaturated carbons. More particularly, the resin described above can enter into the composition of a hot-melt adhesive formulation further comprising: a) a copolymer of ethylene and vinyl acetate or of alkyl acrylate or methacrylate, or else a terpolymer ethylene, alkyl (meth) acrylate and maleic anhydride, and b) a third compound chosen from microcrystalline polymer waxes, paraffins and esters of rosin acids hydrogenated from heavy alcohol.
Généralement ladite formulation comprend, pour 100 parties en poids, de 20 à 45 parties de résine de pétrole, de 20 à 70 parties de polymère (a) et de 5 à 45 parties de composé (b). Elle peut en outre comprendre une quantité efficace d'au moins un antioxydant tel que par exemple un dérivé de phénol ou un phosphite. Dans une telle formulation, la résine de pétrole selon l'invention joue le rôle d'une résine dite "tackifiante".Generally said formulation comprises, per 100 parts by weight, from 20 to 45 parts of petroleum resin, from 20 to 70 parts of polymer (a) and from 5 to 45 parts of compound (b). It can also comprise an effective amount of at least one antioxidant such as for example a phenol derivative or a phosphite. In such a formulation, the petroleum resin according to the invention plays the role of a so-called "tackifying" resin.
Les résines selon l'invention peuvent également être utilisées comme résines renforçantes ou éventuellement tackifiantes dans des formulations adhésives comprenant du caoutchouc naturel ou des caoutchoucs synthétiques tels que le polyisoprène, les caoutchoucs butyle, chlorobutyle, bromobutyle, le chloroprène, les élastomères
éthylène/propylène/diène et les copolymères, linéaires ou en étoile, à blocs styrène/isoprène ou styrène/butadiène.The resins according to the invention can also be used as reinforcing or optionally tackifying resins in adhesive formulations comprising natural rubber or synthetic rubbers such as polyisoprene, butyl rubbers, chlorobutyl, bromobutyl, chloroprene, elastomers ethylene / propylene / diene and the copolymers, linear or star, with styrene / isoprene or styrene / butadiene blocks.
Les exemples suivants sont donnés à titre illustratif et non limitatif de la présente invention. Sauf indication contraire, les quantités et proportions sont exprimées en poids. Exemple 1The following examples are given by way of illustration and without limitation of the present invention. Unless otherwise indicated, the quantities and proportions are expressed by weight. Example 1
100 parties d'une coupe aromatique ayant une coloration de 6-100 parts of an aromatic cut having a coloration of 6-
7G et comprenant 14 % de styrène, 9,4 % de vinyltoluènes, 10,5 % d'indène, 6,5 % de méthyl indènes, 1,3 % d'alphaméthylstyrène, 2,8 % de bétaméthylstyrène et le solde d'aromatiques alkylés sont prépolymérisées par 0,3 partie de H2SO à 96 % à 70°C pendant 30 minutes.7G and comprising 14% of styrene, 9.4% of vinyltoluenes, 10.5% of indene, 6.5% of methyl indenes, 1.3% of alphamethylstyrene, 2.8% of betamethylstyrene and the balance of alkylated aromatics are prepolymerized with 0.3 part of 96% H 2 SO at 70 ° C for 30 minutes.
Après neutralisation par la soude et lavage à l'eau, le prépotymérisat est distillé sous pression réduite pour éliminer le prépolymère dans la fraction lourde de distillation et récupérer 51,4 % parties d'une coupe traitée de faible coloration (<1G) et composée essentiellement de styrène (11,2 %), vinyltoluènes (14,2 %), indèneAfter neutralization with sodium hydroxide and washing with water, the prepotymerisate is distilled under reduced pressure to remove the prepolymer in the heavy distillation fraction and recover 51.4% parts of a treated cut of low color (<1G) and composed mainly styrene (11.2%), vinyl toluenes (14.2%), indene
(15,6 %), méthylindènes (3,1 %), alphaméthylstyrène (1,8 %), bétaméthylstyrène (4,7 %), non identifiés polymérisables (6 %) et le solde d'aromatiques alkylés. A cette fraction (50 parties) sont additionnées 4,7 parties d'alphapinène et 6,9 parties de solvants aromatiques (comme xylènes et toluène) et polymérisées en présence de 0,082 partie de BFQ à(15.6%), methylindenes (3.1%), alphamethylstyrene (1.8%), betamethylstyrene (4.7%), unidentified polymerisables (6%) and the balance of alkylated aromatics. To this fraction (50 parts) are added 4.7 parts of alphapinene and 6.9 parts of aromatic solvents (such as xylenes and toluene) and polymerized in the presence of 0.082 part of BFQ to
40°C pendant 45 minutes. Après neutralisation et lavage on récupère après extraction sous pression réduite, 33 parties de résine ayant une coloration40 ° C for 45 minutes. After neutralization and washing, after extraction under reduced pressure, 33 parts of resin having a coloration are recovered.
(en solution à 50 % en masse dans le toluène) de 2 Gardner et un point de ramollissement de 103°C.(50% by mass solution in toluene) of 2 Gardner and a softening point of 103 ° C.
La composition essentielle de la résine est déterminée par pyrolyse : styrène 16,4 %, vinyltoluènes 20,9 %, indène 23,8 %, méthylindène 4,6 %, alphaméthylstyrène 2,8 %, bétaméthylstyrène 5,4 %, alphapinène 13,6 % et non identifiés (12,5 %). L'analyse de cette résine par résonance magnétique nucléaire du proton et du carbone 13 montre la répartition suivante des atomes d'hydrogène :The essential composition of the resin is determined by pyrolysis: styrene 16.4%, vinyltoluenes 20.9%, indene 23.8%, methylindene 4.6%, alphamethylstyrene 2.8%, betamethylstyrene 5.4%, alphapinene 13, 6% and unidentified (12.5%). Analysis of this resin by nuclear magnetic resonance of the proton and carbon 13 shows the following distribution of the hydrogen atoms:
- 0,3 % d'hydrogènes liés à des carbones insaturés non- aromatiques, - 63,7 % d'hydrogènes liés à des carbones saturés, et- 0.3% of hydrogens linked to non-aromatic unsaturated carbons, - 63.7% of hydrogens linked to saturated carbons, and
- 36 % d'hydrogènes liés à des carbones aromatiques.
Exemple 2- 36% of hydrogens linked to aromatic carbons. Example 2
On utilise la résine de l'exemple 1 pour réaliser la formulation adhesive thermofusible suivante :The resin of Example 1 is used to make the following hot-melt adhesive formulation:
- résine : 1 partie - copolymère éthylène/acétate de vinyle d'indice de fluidité 50 dg/min., à 23 % d'acétate, commercialisé par DUPONT DE NEMOURS sous l'appellation ELVAX 310 : 1 partie- resin: 1 part - ethylene / vinyl acetate copolymer with a flow index 50 dg / min., 23% acetate, marketed by DUPONT DE NEMOURS under the name ELVAX 310: 1 part
- cire microcristalline commercialisée par MOBIL OIL sous l'appellation MW 145 : 1 partie Cette formulation a les caractéristiques ci-après :- microcrystalline wax sold by MOBIL OIL under the name MW 145: 1 part This formulation has the following characteristics:
. point de ramollissement (ASTM E 28) = 78°C. softening point (ASTM E 28) = 78 ° C
. viscosité à 175°C à 4,65 s"1 = 5700 mPas. viscosity at 175 ° C at 4.65 s " 1 = 5700 mPas
. point de trouble = 67°C. cloud point = 67 ° C
. Traction sur joints (ASTM D638) . modules = 49,4 MPa. Joint traction (ASTM D638). modules = 49.4 MPa
. contrainte à la rupture = 4,3 MPa. breaking stress = 4.3 MPa
. allongement à la rupture = 144 %. elongation at break = 144%
.Cisaillement sur assemblages hêtre (NF 76-107) :Shear on beech joints (NF 76-107):
. contrainte maximale = 2,6 MPa
. maximum stress = 2.6 MPa
Claims
1. Résines de pétrole thermiquement stables comprenant un copolymère constitué essentiellement de 81 à 99 % en poids de motifs alcénylaromatiques et de 1 à 19 % en poids de motifs terpéniques, lesdites résines étant en outre caractérisées par la présence de 0,1 à 0,7 % d'hydrogènes liés à des carbones insaturés non-aromatiques.1. Thermally stable petroleum resins comprising a copolymer consisting essentially of 81 to 99% by weight of alkenylaromatic units and from 1 to 19% by weight of terpene units, said resins being further characterized by the presence of 0.1 to 0, 7% of hydrogens linked to non-aromatic unsaturated carbons.
2. Résines de pétrole selon la revendication 1, caractérisées par une couleur Gardner comprise entre 1 et 4. 2. Petroleum resins according to claim 1, characterized by a Gardner color between 1 and 4.
3. Résines de pétrole selon l'une des revendications 1 et 2, caractérisées par un point de ramollissement compris entre 80°C et 150°C.3. Petroleum resins according to one of claims 1 and 2, characterized by a softening point between 80 ° C and 150 ° C.
4. Résines de pétrole selon l'une des revendications 1 à 3, caractérisées en ce que les motifs alcénylaromatiques sont choisis parmi ceux dérivés du styrène, de ralphaméthylstyrène, de l'indène, du vinyltoluène, des méthyiindènes du bétaméthylstyrène et du paratertiobutylstyrène.4. Petroleum resins according to one of claims 1 to 3, characterized in that the alkenylaromatic units are chosen from those derived from styrene, ralphamethylstyrene, indene, vinyltoluene, methylthindenes from betamethylstyrene and paratertiobutylstyrene.
5. Résines de pétrole selon l'une des revendications 1 à 4, caractérisées en ce que les motifs terpéniques proviennent d'essences de térébenthine.5. Petroleum resins according to one of claims 1 to 4, characterized in that the terpene units come from turpentine essences.
6. Procédé de fabrication de résines de pétrole selon l'une des revendications 1 à 5, comprenant une première étape de traitement d'une coupe de monomères alcénylaromatiques en vue d'éliminer de cette coupe l'essentiel des composés chromophores susceptibles de colorer la résine et/ ou d'altérer ses propriétés, puis une seconde étape de copolymérisation cationique d'un mélange comprenant (a) de 88 à 99 % en poids de la coupe traitée obtenue à l'issue de la première étape et (b) de 1 à 12 % en poids d'une coupe comprenant au moins un monomère terpénique.6. A method of manufacturing petroleum resins according to one of claims 1 to 5, comprising a first step of treatment of a cut of alkenylaromatic monomers in order to eliminate from this cut most of the chromophoric compounds capable of coloring the resin and / or alter its properties, then a second step of cationic copolymerization of a mixture comprising (a) from 88 to 99% by weight of the treated cut obtained at the end of the first step and (b) 1 to 12% by weight of a cut comprising at least one terpene monomer.
7. Utilisation d'une résine de pétrole selon l'une des revendications 1 à 5 comme composant d'une formulation adhesive.7. Use of a petroleum resin according to one of claims 1 to 5 as a component of an adhesive formulation.
8. Utilisation selon la revendication 7, caractérisée en ce que la formulation adhesive comprend en outre :8. Use according to claim 7, characterized in that the adhesive formulation further comprises:
(a) un copolymère d'éthylène et d'acétate de vinyle ou d' acrylate ou méthacrylate d'alkyle, ou bien un terpolymère d'éthylène, de (méth) acrylate d'alkyle et d'anhydride maléique, et(a) a copolymer of ethylene and vinyl acetate or of alkyl acrylate or methacrylate, or alternatively a terpolymer of ethylene, of alkyl (meth) acrylate and of maleic anhydride, and
(b) un tiers composé choisi parmi les cires polymères micro-cristallines, les paraffines et les esters d'acides colophaniques hydrogénés et d'alcool lourd. (b) a third compound chosen from microcrystalline polymer waxes, paraffins and esters of hydrogenated rosin acids and heavy alcohol.
9. Utilisation selon la revendication 8, caractérisée en ce que la formulation adhesive comprend, pour 100 parties en poids, de 20 à 45 parties de résine de pétrole, de 20 à 70 parties de polymère (a) et de 5 à 45 parties de composé (b). 9. Use according to claim 8, characterized in that the adhesive formulation comprises, per 100 parts by weight, from 20 to 45 parts of petroleum resin, from 20 to 70 parts of polymer (a) and from 5 to 45 parts of compound (b).
10. Utilisation selon la revendication 7, caractérisée en ce que la formulation adhesive comprend en outre du caoutchouc naturel ou un caoutchouc synthétique choisi parmi le polyisoprene, les caoutchoucs butyle, chlorobutyle, bromobutyle, k chloroprène, les élastomères éthylène/propylène/diène et les copolymères à blocs, linéaires ou en étoile, styrène/isoprène ou styrène/butadiène. 10. Use according to claim 7, characterized in that the adhesive formulation also comprises natural rubber or a synthetic rubber chosen from polyisoprene, butyl, chlorobutyl, bromobutyl, k chloroprene rubbers, ethylene / propylene / diene elastomers and the block, linear or star copolymers, styrene / isoprene or styrene / butadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR1991/000739 WO1993006143A1 (en) | 1991-09-19 | 1991-09-19 | Heat-stable petroleum resins, a preparation method therefor, and uses thereof for formulating hot-melt adhesives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FR1991/000739 WO1993006143A1 (en) | 1991-09-19 | 1991-09-19 | Heat-stable petroleum resins, a preparation method therefor, and uses thereof for formulating hot-melt adhesives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993006143A1 true WO1993006143A1 (en) | 1993-04-01 |
Family
ID=9408976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1991/000739 WO1993006143A1 (en) | 1991-09-19 | 1991-09-19 | Heat-stable petroleum resins, a preparation method therefor, and uses thereof for formulating hot-melt adhesives |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1993006143A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733911A (en) * | 1996-01-26 | 1998-03-31 | Hitachi Chemical Co., Ltd. | Method for inducing death of neoplastic cells using piperazne derivatives |
| EP0842984A1 (en) * | 1996-05-28 | 1998-05-20 | Nippon Petrochemicals Co., Ltd. | Hot-melt composition and modified aromatic petroleum resin for use therein |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0318217A2 (en) * | 1987-11-25 | 1989-05-31 | Exxon Chemical Patents Inc. | Adhesive formulations |
-
1991
- 1991-09-19 WO PCT/FR1991/000739 patent/WO1993006143A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0318217A2 (en) * | 1987-11-25 | 1989-05-31 | Exxon Chemical Patents Inc. | Adhesive formulations |
Non-Patent Citations (4)
| Title |
|---|
| CHEMICAL ABSTRACTS, Vol. 109, No. 14, 3 October 1988, page 4, Abstract No. 110974x, Columbus, Ohio, US., KHAN A. RASHEED et al., "Cationic Copolymerization of Vinyltoluene and Alpha-pinene"; & PAK. J. SCI. IND. RES., 1988, 31(3), 159-62. * |
| CHEMICAL ABSTRACTS, Vol. 111, No. 18, 30 October 1989, page 12, Abstract No. 154556h, Columbus, Ohio, US., TANAKA KOJI et al., "Manufacture of Hydrocarbon Resins With High Softening Temperature"; & JP,A,01 033 112, 3 February 1989. * |
| CHEMICAL ABSTRACTS, Vol. 93, No. 12, 22 September 1980, page 46, Abstract No. 115614r, Columbus, Ohio, US; & JP,A,55 065 248 (NIPPON OIL CO., LTD.), 16 May 1980. * |
| DIALOG INFORMATION SERVICE, File 351, WORLD PATENT INDEX 81-90, Dialog Accession No. 004766238, (TOHR, TOHO CHEM IND LTD. et al), "Light Coloured Petroleum Resin mfr. from Aromatic Unsaturated Hydrocarbon cpds. and Aliphatic Unsaturated Hydrocarbon cpds., Mixed and Copolymerised"; & JP,A,61 197 616, (01-09-86), 8641. * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733911A (en) * | 1996-01-26 | 1998-03-31 | Hitachi Chemical Co., Ltd. | Method for inducing death of neoplastic cells using piperazne derivatives |
| US5859013A (en) * | 1996-01-26 | 1999-01-12 | Hitachi Chemical Co., Ltd. | Method for inducing death of neoplastic cells using piperazine derivatives |
| US6054437A (en) * | 1996-01-26 | 2000-04-25 | Hitachi Chemical Research Center, Inc. | Method for inducing death of neoplastic cells using piperazine derivatives |
| EP0842984A1 (en) * | 1996-05-28 | 1998-05-20 | Nippon Petrochemicals Co., Ltd. | Hot-melt composition and modified aromatic petroleum resin for use therein |
| EP0842984A4 (en) * | 1996-05-28 | 1999-09-15 | Nippon Petrochemicals Co Ltd | Hot-melt composition and modified aromatic petroleum resin for use therein |
| US6172146B1 (en) | 1996-05-28 | 2001-01-09 | Nippon Petrochemicals, Co. Ltd. | Hot-melt composition and a modified aromatic petroleum resin used therefor |
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