(51) Int Cl.: C09K 5/10 ( )

Transcription

1 (19) (12) EUROPEAN PATENT SPECIFICATION (11) EP B1 (4) Date of publication and mention of the grant of the patent: Bulletin 08/4 (21) Application number: (22) Date of filing: (1) Int Cl.: C09K / (06.01) (86) International application number: PCT/US02/0129 (87) International publication number: WO 02/ ( Gazette 02/43) (4) PROCESS FOR THE MANUFACTURE OF TEMPERATURE-SENSITIVE POLYMERS VERFAHREN ZUR HERSTELLUNG TEMPERATUREMPFINDLICHER POLYMERE PROCEDE DE FABRICATION DE POLYMERES SENSIBLES A LA TEMPERATURE (84) Designated Contracting States: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR () Priority: US P (43) Date of publication of application: Bulletin 04/03 (73) Proprietor: Solutia Inc. St. Louis, Missouri (US) (72) Inventors: BROWN, Jerry, L. Heflin, AL (US) NOTTE, Pattick, P., B. 10 Wavre (BE) (74) Representative: Albrecht, Thomas Kraus & Weisert Patent- und Rechtsanwälte Thomas-Wimmer-Ring München (DE) (6) References cited: EP-A WO-A-89/07634 WO-A-98/0483 DE-A US-A DATABASE WPI Section Ch, Week Derwent Publications Ltd., London, GB; Class A23, AN XP & JP A (MITSUBISHI RAYON CO LTD), 26 July 198 ( ) EP B1 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). Printed by Jouve, 7001 PARIS (FR)

2 1 EP B1 2 Description RACKGROUND OF THE INVENTION [0001] The present invention relates to a process for the manufacture of temperature-sensitive polymers utilizing a heat transfer fluid comprising a hydrocarbon fluid selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic- or alicyclio-substituted aromatic hydrocarbons, or mixtures thereof, the hydrocarbon fluid having a boiling point from 2 C to C and a melting point less than C. The present invention further relates to a process for manufacturing temperature-sensitive polymers utilizing a heat transfer fluid comprising a fluid selected from phenylcyclohexane (also known as cyclohexylbenzene), bicyclohexane (also known as bicyclohexyl), hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof. [0002] Heat transfer fluids, which can also be termed "heat carries", are used to transfer heat energy between systems of different temperatures. Heat transfer fluids generally are eminently well-known and have been used commercially for a long time. The large majority of commercial transfer fluids, including Therminol VP-1, (Solutia Inc.), Diphyl DT (Bayer A.G.), Dowtherm A (Dow Chemical) and Therm S0 (Nippon Steel), all consist of a binary system of about 26% biphenyl and 74% diphenyloxide. Such heat transfer fluids are characterized by a boiling point of about 26 C at atmospheric pressure and, in addition, exhibit desirable in-use properties including oxidative and thermal stability, good heat transfer properties, virtually no equipment corrosion and good economy. Irrespective of such benefits, boiling temperatures of commercial heat transfer fluids, generally above C, are too high for the manufacture, including extrusion, of temperature-sensitive polymers, such as Nylon 6 and PIT (polytrimethylene terephthalate), and can lead to difficulties in the processing of the polymer and, consequently, undesirably altered in-use properties of the extruded article. In fact, a boiling point difference exceeding about 2 C can lead to a different crystallization behavior of the polymer in the extruded article and thus yield an article exhibiting modified bulk and surface characteristics. The problem had been known for a long time and no completely satisfactory commercially-viable approaches, e.g. heat transfer fluids meeting essentially all the desired performance properties, for eliminating the difficulties have been made available up to now. [0003] Polymer manufacturing temperatures exceeding about 24 C, can be detrimental to the quality of the extruded article made from temperature-sensitive polymers. The lowering and control of the boiling temperature of heat transfer fluids was normally achieved by applying partial vacuum. However, the use of reduced pressures requires supplementary equipment and, more importantly, selected pressures can, and normally will, vary considerably during industrial polymer manufacturing operations to thus yield deficient polymer articles. The prior art relating to the manufacture of extruded polymer articles, and the use of heat transfer fluids in such an arrangement, is well-known in the relevant technical community. U.S. Patent No. 3,92,013 teaches the use of binary and ternary eutectic solvent mixtures for use in disperse dye carrier formulations to improve handling properties at ambient temperatures. A binary mixture of from -% biphenyl and -4% naphthalene was found to possess a suitably lowered crystallization point so that dye carrier properties become easier. U.S. Patent No.,397,491 describes heat transfer fluids, containing substituted diphenyl, exhibiting improved thermal stability at temperatures exceeding 0 C. JP-A describes heat transfer fluids based on mixtures of alkyl naphthalenes and alkylbiphenyls, particularly combinations of diethyl biphenyl and diisopropyl naphthalene. WO pertains to heat transfer agents consisting particularly of diphenylethers of terphenyl, biphenyldiphenyl ethers and naphthalene diphenylethers. JP-A discloses heat transfer agents containing mixtures of biphenyl and/or naphthalene and diphenylether and terphenyl. WO concerns heat transfer fluids exhibiting favorable thermal stability comprising a mixture of tetrahydro(phenylethyl)naphthalene and dibenzyl toluene. [0004] PCT Application no. PCT/EP00/177 discloses a process for manufacture of temperature-sensitive polymers using a heat transfer fluid consisting essentially of a binary mixture of biphenyl and naphthalene in a weight ratio of 6:3 to :4. While this fluid is a stable and efficient heat transfer fluid with a boiling point below 24 C, it is desirable to provide a heat transfer fluid that meets more of the desired heat transfer fluid properties. [000] JP teaches the polymerization of polyester in a liquid heat transfer medium containing inorganic materials. [0006] US discloses a method of producing powders of thermoplastic resin by agitating molten resin in the presence of a dispersing amount of polyalkylene oxide and an alkanolamide surface active agent. [0007] It is desirable to provide a heat transfer fluid useful for the manufacture of temperature-sensitive polymers having a lower boiling point and lower melting point than currently available heat transfer fluids, which preferably also has improved environmental, safety and health properties. [0008] It has now been discovered that a heat transfer fluid selected from a hydrocarbon fluid selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aliphaticor alicyclic-substituted aromatic hydrocarbons, or mixtures thereof, the hydrocarbon fluid having a boiling point from 2 C to C and a melting point less than C, achieves these desired properties, and meets the demands for use in the production of temperature-sensitive polymers. [0009] It has now been further discovered that a preferred heat transfer fluid selected from phenylcyclohex- 2

3 3 EP B1 4 ane, bicyclohexane, hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof achieves these desired properties, and meets the demands for use in the production of temperature-sensitive polymers. BRIEF SUMMARY OF THE INVENTION [00] It is therefore a main object of this invention to provide a new stable and efficient heat transfer fluid with a boiling point between 2 C and C. It is another object of the invention to provide a process for the manufacture, with the aid of heat transfer fluid, of high quality extruded articles made from heat-sensitive polymers. It is still another object of this invention to provide a process for the manufacture of heat-sensitive polymers utilizing a heat transfer fluid having, under atmospheric conditions, a boiling point between 2 C and C, in particular in the range of from 2 C to 24 C. Yet another object of this invention relates to providing a manufacturing arrangement for extruding temperature-sensitive polymers utilizing a beat transfer fluid at a stable temperature, i.e. subject to minimal variations, e.g. 1 C, Still another object of this invention relates to providing a processing arrangement for temperatrue-sensitive polymers to thus manufacture, e.g. extrude, polymer articles having uniformly stable and reproducible surface polymerization properties. The above and other objects of this invention can now be achieved by means of a process for the manufacture of temperature-sensitive polymer whereby a heat transfer fluid of the present invention is used. [0011] According to the invention, a process for the manufacture of temperature-sensitive polymers, or mixtures thereof, is provided whereby a heat transfer fluid is used to control temperature during said manufacture, wherein said heat transfer fluid comprises a hydrocarbon fluid selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic- or alicyclic-substituted aromatic hydrocarbons, or mixtures thereof, said hydrocarbon fluid having a boiling point from 2 C to C and a melting point less than C and wherein the temperature of the process is controlled by the vapor of the heat transfer fluid. [0012] Further according to the invention, a process for the manufacture of temperature-sensitive polymers is provided whereby a heat transfer fluid is used comprising a fluid selected from phenylcyclohexane, bicyclohexane, hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof. [0013] Further according to the present invention, a process for manufacturing temperature-sensitive polymers is provided utilizing a heat transfer fluid, wherein the heat transfer fluid comprises a fluid produced by the catalytic hydrogenation of biphenyl at suitable temperatrue and pressure wherein the hydrogenation is stopped when the refractive index of the reaction mixture at 2 C is in the range of to [0014] Polymer articles are made by means of the process of the invention. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF TEE DRAWING NOT APPLICABLE. DETAILED DESCRIPTION OF THE INVENTION [001] Unless indicated to the contrary, percent and ratio indications, as used in the description and in the claims, refer to weight percent and weight ratio, respectively. The term "temperature-sensitive" or "heat-sensitive" polymers as used in the description and in the claims means polymers having a melting temperature, at ambient conditions, below C, preferably in the range of from 2 C to 248 C, more preferably 23 C to 243 C. The term "manufacture" with respect to temperature-sensitive polymers, as used in the specification and claims, means known polymer manufacturing methods including extrusion, molding and equivalent methods. As used herein, the heat transfer fluid of the invention is a liquid and the heat transfer fluid system being used in conjunction with the manufacture of the temperature-sensitive polymers contains the heat transfer fluid as a liquid. In the process of the invention, however, it is the vaporized portion of the heat transfer fluid that is being used in conjunction with the manufacture of the temperature-sensitive polymers. Depending on the exact composition of the heat transfer fluid and the specific use conditions, this vaporized portion of the heat transfer fluid may not contain the same percentage of all components as present in the heat transfer fluid in liquid form. [0016] A first embodiment of the invention relates to a process for the manufacture of temperature-sensitive polymers, or mixtures thereof, using a heat transfer fluid to control temperature during the manufacture, wherein the heat transfer fluid comprises a hydrocarbon fluid selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic- or alicyclic-substituted aromatic hydrocarbons, or mixtures thereof, said hydrocarbon fluid having a boiling point from 2 C to C and a melting point less than C. The preferred aliphatic hydrocarbons, alicyclic hydrocarbons, and aliphatic- or alicyclicsubstituted aromatic hydrocarbons of the invention have 11 to 1 carbon atoms. The more preferred hydrocarbon fluids of the invention have a melting point less than or equal to C, most preferably less than or equal to C. [0017] Examples of suitable hydrocarbon fluids include, but are not limited to, phenylcyclohexane, bicyclohexane, at least one hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, 1-ethyl-2,3,4-trimethylbenzene, 1,2,3,4-tetrahydro-1-methylnaphthalene, [2-methyl- 1-(1-methylethyl)propyl]benzene, 1,2,3,4-tetrahydro-2-methyl-naphthalene, 1,2,4-trimethyl--(1-methylethyl)benzene, 1,2,3,4-tetrahydro-1,1-dimethylnaphthalene, heptylcy- 3

4 EP B1 6 clopentane, hexylcyclohexane, 1,2,3,4-tetrahydro-1,4-dimethylnaphthalene, hexylbenzene, 1,2,3,4-tetrahydro-6-methylnaphthalene, 1,2,3,4-tetrahydro-2,2-dimethylnaphthalene, 1,2,3,4-tetrahydro--methylnaphthalene, 1,2,3,4-tetrahydro-1,3-dimethylnaphthalene, 2-ethyl- 1,2,3,4-tetrahydronaphthalene, 1,2,3,4-tetrahydro-1,2-dimethylnaphthalene, tridecane, 1,2,3,4-tetrahydro-2,-dimethylnaphthalene,1,2,3,4-tetrahydro-2,8-dimethylnaphthalene, 1,2,3,4-tetrahydro- 2,7-dimethylnaphthalene, 1,3,-triisopropylbenzene, 1,2,3,4-tetrahydro-1,-dimethylnaphthalene, heptylbenzene, 1,2,3,4-tetrahydro-2,6-dimethylnaphthalene, 1,2,3,4-tetrahydro-1,1,6-trimethylnaphthalene, 2-methylnaphthalene, octylcyclopentane, 6-ethyl-1,2,3,4-tetrahydronaphthalene, heptylcyclohexane, 1,2,4-triisopropylbenzene, 1-methylnaphthalene, -ethyl-1,2,3,4-tetrahydro-naphthalene, 1,2,2a,3,4,-hexahydroacenapthylene, 1,2,4,-tetraethylbenzene, and mixtures thereof. [0018] The currently preferred hydrocarbon fluids of the invention are phenylcyclohexane, bicyclohexane, at least one hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof. More preferably, the hydrocarbon fluid of the invention is phenylcyclohexane, bicyclohexane or mixtures thereof, with phenylcyclohexane and blends of phenylcyclohexane and bicyclohexane being most preferred. [0019] A second embodiment of the invention relates to a process for the manufacture of temperature-sensitive polymers, or mixtures thereof, using a heat transfer fluid to control temperature during the manufacture, wherein the heat transfer fluid comprises a fluid selected from phenylcyclohexane, bicyclohexane, at least one hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof. [00] A third embodiment of the invention relates to a process for the manufacture of temperature-sensitive polymers, or mixtures thereof, using a heat transfer fluid to control temperature during the manufacture, wherein the heat transfer fluid comprises a fluid prepared by the catalytic hydrogenation of biphenyl at suitable temperature and hydrogen pressure, wherein hydrogenation is stopped when the refractive index of the hydrogenation reaction mixture at 2 C is in the range of to about 1.44, preferably to [0021] The process(es) of the invention are particularly suitable for the manufacture of temperature-sensitive polymers that, under ambient conditions, have a melting point in the range of from 2 C to 248 C, preferably from about 23 C to about 243 C. Such temperaturesensitive polymers include, but are not limited to, nylon 6, nylon 11, nylon 12, polytrimethylene terephthalate, polybutene-1, polybutylene terephthalate, polyethylene terephthalate, polyolefins such as polypropylene and high-density or low-density polyethylene, and mixtures or copolymers thereof, which polymers can at temperatures starting from C and above be subject to surface and bulk polymer deficiencies as well as extrusion limitations. [0022] Other polymers that may be advantageously processed according to the invention are poly(methylmethacrylate), polyacetal, polyionomer, EVA copolymer, cellulose acetate, hard polyvinylchloride and polystyrene or copolymers thereof. More particularly, copolymers of polyethylene terephthalate may also be advantageously used with the heat transfer fluid of the invention. [0023] Other temperature-sensitive polymers which can be manufactured beneficially by means of the process of the invention herein can be readily selected by one of ordinary skill in the art based on routine observations of the resulting articles made by means of conventional fluids having a boiling point of about 26 C. [0024] The heat transfer fluid is characterized, under atmospheric or slight positive pressure conditions, by a boiling point between 2 C and C, preferably between about 2 C and about 24 C, more preferably between about 23 C and about 243 C. The heat transfer fluids of the invention can optionally contain amounts of other basestock components, e.g. biphenyl, diphenyl oxide or a biphenyl/naphthalene mixture, as long as the required fluid properties are achieved. The heat transfer fluids of the invention can also optionally contain additive levels of known compounds that are used for their known functionality in art-established levels. [002] As an example of such compounds, anti-oxidants in levels usually below 0 ppm can be added to the heat transfer fluid to thus augment the oxidative stability of the fluid. [0026] In the embodiments of the invention wherein the heat transfer fluid comprises a fluid selected from phenylcyclohexane, bicyclohexane, at least one hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof, the heat transfer fluids used in the processes of the present invention are produced by the catalytic hydrogenation of biphenyl. The hydrogenation can be conducted using any suitable hydrogenation catalyst known to those of ordinary skill in the art. The currently preferred hydrogenation catalyst is Raney nickel used at a concentration of about 1 to about 3. percent based on the biphenyl charged to the reaction. Suitable temperature and hydrogen pressure are those readily known to those of ordinary skill in the art. Exemplary temperatures for use in the catalytic hydrogenation are about 1 C to about 2 C. Exemplary hydrogen pressure for use in the catalytic hydrogenation is between about 0 psig and about 00 psig. The hydrogenation endpoint is critical in determining the composition of the heat transfer fluid produced. It is convenient to use refractive index as the measure of when the hydrogenation process is to be stopped. Refractive index is measured at 2 C using ASTM D1218 or equivalent. If phenylcyclohexane 4

5 7 EP B1 8 ("PCH") is the desired product, i.e. only one aryl ring is completely saturated, the hydrogenation must be stopped at a refractive index of 1.23 to It should be noted that once hydrogenation is started, one ring will be completely saturated before hydrogenation of the second ring begins. If bicyclohexane is the desired product, i.e. both aryl rings are completely saturated, hydrogenation is continued as long as hydrogen will react or until a refractive index (at 2 C) of is achieved. If a hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane is desired, hydrogenation is stopped when the refractive index is greater than and less than If the heat transfer fluid contains an amount of biphenyl that has not been hydrogenated but less than the amount which would adversely effect the final fluid properties, e.g. up to about 2% biphenyl, the refractive index of the hydrogenation reaction mixture will be less than about [0027] The preferred heat transfer fluids of the present invention have improved environmental, safety and health properties. For example, the preferred fluids of the invention are not on the reportable quantity (RQ) lists of CERCLA or RCRA. In addition, the preferred fluids of the invention are not listed as hazardous air pollutants (HAP) by the Clean Air Act. [0028] The currently preferred heat transfer fluids of the invention are phenylcyclohexane, bicyclohexane, at least one hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof. More preferably, the hydrocarbon fluid of the invention is phenylcyclohexane, bicyclohexane or mixtures thereof, with phenylcyclohexane or blends of phenylcyclohexane and bicyclohexane being most preferred. [0029] A fourth embodiment is a heat transfer fluid comprising a mixture of phenylcyclohexane and bicyclohexane wherein the weight ratio of phenylcyclohexane to bicyclohexane is about 1:99 to about 99:1, preferably about 0:0 to about 99:1, more preferably about 70: to about 99:1, and most preferably about 90: to about 99: The process of claim 1 wherein said hydrocarbon fluid has a melting point less than or equal to C. 3. The process of claim 1 wherein said heat transfer fluid further comprises biphenyl, diphenyl oxide or a bipheoyl/naphthalene mixture, provided the heat transfer fluid has a boiling point from 2 C to C and a melting point less than C. 4. The process of claim 1 wherein said heat transfer fluid comprises a fluid selected from phenylcyclohexane, bicyclohexane, at least one hydrogenated biphenyl having a level of hydrogenation between phenylcyclohexane and bicyclohexane, or mixtures thereof.. The process of claim 4 wherein said heat transfer fluid is selected from phenylcyclohexane, bicyclohexane or mixtures thereof. 6. The process of claim wherein said heat transfer fluid is bicyclohexane. 7. The process of claim wherein said heat transfer fluid is phenylcyclohexane. 8. The process of claim wherein said heat transfer fluid is a mixture of phenylcyclohexane and bicyclohexane. 9. The process of claim 4 wherein said heat transfer fluid further comprises biphenyl, diphenyl oxide or a biphenyl/naphthalene mixture, provided the heat transfer fluid has a boiling point from 2 C to C and a melting point less than C.. The process of claim 1 wherein the temperature-sensitive polymer has, under ambient conditions, a melting point in the range of from 2 C to 248 C and wherein the boiling point of said heat transfer fluid is, under ambient conditions, about 2 C to about 24 C. Claims 1. A process for the manufacture of temperature-sensitive polymers, or mixtures thereof, whereby a heat transfer fluid is used to control temperature during said manufacture, wherein said heat transfer fluid comprises a hydrocarbon fluid selected from alipbatic hydrocarbons, alicyclic hydrocarbons, aliphatic- or alicyclic-substituted aromatic hydrocarbons, or mixtures thereof, said hydrocarbon fluid having a boiling point from 2 C to C and a melting point less than C and wherein the temperature of the process is controlled by the vapor of the heat transfer fluid The process of claim wherein the boiling point of said heat transfer fluid is in the range of from about 23 C to about 243 C. 12. The process of claim 1 wherein said temperaturesensitive polymer is selected from nylon 6, nylon 11, nylon 12, polytrimethylene terephthalate, polybutene-1, polybutylene terephthalate, polyethylene terephthalate, polypropylene, or high-density or lowdensity polyethylene, said polymer having a melting point, under ambient conditions, in the range of from about 2 C to about 248 C. 13. The process of claim 1 wherein said temperaturesensitive polymer is polyethylene terephthalate or a

6 9 EP B1 copolymer thereof. polystyrene. 14. The process of claim 1 wherein said temperaturesensitive polymer is selected from poly(methylmethacrylate), a polyacetal, a polyionomer, an EVA copolymer, cellulose acetate, hard polyvinylchloride or polystyrene. 1. A process of claim 1 wherein said heat transfer fluid comprises a fluid prepared by the catalytic hydrogenation of biphenyl wherein the hydrogenation is stopped when the refractive index of the hydrogenation reaction mixture at 2 C is in the range of to The process of claim 1 wherein the refractive index of said heat transfer fluid is to The process of claim 1 wherein the refractive index of said heat transfer fluid is A heat transfer fluid comprising a mixture of phenylcyclohexane and bicyclohexane wherein the weight ratio of phenylcyclohexane to bicyclohexane provides a boiling point in the range of from about 2 C to about 24 C for the manufacture of heat sensitive polymers according to claim A heat transfer fluid of claim 2 wherein the weight ratio of phenylcyclohexane to bicyclohexane is about 0:0 to about 99: A heat transfer fluid of claim 2 wherein the weight ratio of phenylcyclohexane to bicyclohexane is about 70: to about 99: A heat transfer fluid of claim 2 wherein the weight ratio of phenylcyclohexane to bicyclohexane is about 90: to about 99: The process of claim 1 wherein the refractive index of said heat transfer fluid is 1.23 to Patentansprüche 19. The process of claim 1 wherein said heat transfer fluid further comprises biphenyl, diphenyl oxide or a biphenyl/naphthalene mixture, provided the heat transfer fluid has a boiling point from 2 C to C and a melting point less than C.. The process of claim 1 wherein the temperaturesensitive polymer has, under ambient conditions, a melting point in the range of from 2 C to 248 C and wherein the boiling point of said heat transfer fluid is, under ambient conditions, about 2 C to about 24 C. 21. The process of claim wherein said temperaturesensitive polymer has a melting point in the range of from about 23 C to about 243 C. 22. The process of claim 1 wherein said temperaturesensitive polymer is selected from nylon 6, nylon 11, nylon 12, polytrimethylene terephthalate, polybutene-1, polybutylene terephthalate, polyethylene terephthalate, polypropylene, or high-density or lowdensity polyethylene, said polymer having a melting point, under ambient conditions, in the range of from about 2 C to about 248 C. 23. The process of claim 1 wherein said temperaturesensitive polymer is polyethylene terephthalate or a copolymer thereof. 24. The process of claim 1 wherein said temperaturesensitive polymer is selected from poly(methylmethacrylate), a polyacetal, a polyionomer, an EVA copolymer, cellulose acetate, hard polyvinylchloride or Verfahren zur Herstellung von temperatursensitiven Polymeren oder von Gemischen davon, wobei ein Wärmeübertragungsmedium verwendet wird, um die Temperatur während der Herstellung zu kontrollieren, wobei das Wärmeübertragungsmedium ein Kohlenwasserstoffmedium, ausgewählt aus aliphatischen Kohlenwasserstoffen, alicyclischen Kohlenwasserstoffen, aliphatisch oder alicyclisch substituierten aromatischen Kohlenwasserstoffen und Gemischen davon, umfasst, wobei das Kohlenwasserstoffmedium einen Siedepunkt von 2 C bis C und einen Schmelzpunkt von niedriger als C aufweist, und wobei die Temperatur des Verfahrens mittels des Dampfes des Wärmeübertragungsmediums kontrolliert wird. 2. Verfahren nach Anspruch 1, wobei das Kohlenwasserstoffmedium einen Schmelzpunkt von niedriger als oder gleich C aufweist. 3. Verfahren nach Anspruch 1, wobei das Wärmeübertragungsmedium weiterhin Biphenyl, Diphenyloxid oder ein Biphenyl/Naphthalin-Gemisch umfasst, mit der Maßgabe, dass das Wärmeübertragungsmedium einen Siedepunkt von 2 C bis C und einen Schmelzpunkt von niedriger als C aufweist. 4. Verfahren nach Anspruch 1, wobei das Wärmeübertragungsmedium ein Medium umfasst, ausgewählt aus Phenylcyclohexan, Bicyclohexan, mindestens einem hydrierten Biphenyl mit einem Hydrierungsgrad zwischen Phenylcyclohexan und Bicyclohexan und Gemischen davon. 6

7 11 EP B1 12. Verfahren nach Anspruch 4, wobei das Wärmeübertragungsmedium ausgewählt ist aus Phenylcyclohexan, Bicyclohexan und Gemischen davon. 6. Verfahren nach Anspruch, wobei das Wärmeübertragungsmedium Bicyclohexan ist. 7. Verfahren nach Anspruch, wobei das Wärmeübertragungsmedium Phenylcyclohexan ist. 8. Verfahren nach Anspruch, wobei das Wärmeübertragungsmedium ein Gemisch aus Phenylcyclohexan und Bicyclohexan ist. liegt. 16. Verfahren nach Anspruch 1, wobei der Brechungsindex des Wärmeübertragungsmediums 1,477 bis 1,236 beträgt. 17. Verfahren nach Anspruch 1, wobei der Brechungsindex des Wärmeübertragungsmediums 1,477 beträgt. 18. Verfahren nach Anspruch 1, wobei der Brechungsindex des Wärmeübertragungsmediums 1,23 bis 1,236 beträgt. 9. Verfahren nach Anspruch 4, wobei das Wärmeübertragungsmedium weiterhin Biphenyl, Diphenyloxid oder ein Biphenyl/Naphthalin-Gemisch umfasst, mit der Maßgabe, dass das Wärmeübertragungsmedium einen Siedepunkt von 2 C bis C und einen Schmelzpunkt von niedriger als C aufweist.. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer unter Umgebungsbedingungen einen Schmelzpunkt im Bereich von 2 C bis 248 C aufweist und wobei der Siedepunkt des Wärmeübertragungsmediums unter Umgebungsbedingungen etwa 2 C bis etwa 24 C beträgt. 11. Verfahren nach Anspruch, wobei der Siedepunkt des Wärmeübertragungsmediums in dem Bereich von etwa 23 C bis etwa 243 C liegt. 12. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer ausgewählt ist aus Nylon 6, Nylon 11, Nylon 12, Polytrimethylenterephthalat, Polybuten-1, Polybutylenterephthalat, Polyethylenterephthalat, Polypropylen und Polyethylen mit hoher Dichte oder niedriger Dichte, wobei das Polymer einen Schmelzpunkt unter Umgebungsbedingungen in dem Bereich von etwa 2 C bis etwa 248 C aufweist. 13. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer Polyethylenterephthalat oder ein Copolymer davon ist. 14. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer ausgewählt ist aus Poly(methylmethacrylat), einem Polyacetal, einem Polyionomer, einem EVA-Copolymer, Celluloseacetat, hartem Polyvinylchlorid und Polystyrol. 1. Verfahren nach Anspruch 1, wobei das Wärmeübertragungsmedium ein Medium umfasst, das mittels katalytischer Hydrierung von Biphenyl hergestellt wird, wobei die Hydrierung gestoppt wird, wenn der Brechungsindex des Hydrierungsreaktionsgemisches bei 2 C in dem Bereich von 1,477 bis 1, Verfahren nach Anspruch 1, wobei das Wärmeübertragungsmedium weiterhin Biphenyl, Diphenyloxid oder ein Biphenyl/Naphthalin-Gemisch umfasst, mit der Maßgabe, dass das Wärmeübertragungsmedium einen Siedepunkt von 2 C bis C und einen Schmelzpunkt von niedriger als C aufweist.. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer unter Umgebungsbedingungen einen Schmelzpunkt in dem Bereich von 2 C bis 248 C aufweist und wobei der Siedepunkt des Wärmeübertragungsmediums unter Umgebungsbedingungen etwa 2 C bis etwa 24 C beträgt. 21. Verfahren gemäß Anspruch, wobei das temperatursensitive Polymer einen Schmelzpunkt in dem Bereich von etwa 23 C bis etwa 243 C aufweist. 22. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer ausgewählt ist aus Nylon 6, Nylon 11, Nylon 12, Polytrimethylenterephthalat, Polybuten-1, Polybutylenterephthalat, Polyethylenterephthalat, Polypropylen und Polyethylen mit hoher Dichte oder niedriger Dichte, wobei das Polymer einen Schmelzpunkt unter Umgebungsbedingungen in dem Bereich von etwa 2 C bis etwa 248 C aufweist. 23. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer Polyethylenterephthalat oder ein Copolymer davon ist. 24. Verfahren nach Anspruch 1, wobei das temperatursensitive Polymer ausgewählt ist aus Poly(methylmethacrylat), einem Polyacetal, einem Polyionomer, einem EVA-Copolymer, Celluloseacetat, hartem Polyvinylchlorid und Polystyrol. 2. Wärmeübertragungsmedium, umfassend ein Gemisch aus Phenylcyclohexan und Bicyclohexan, wobei das Gewichtsverhältnis von Phenylcyclohexan zu Bicyclohexan einen Siedepunkt in dem Bereich von etwa 2 C bis etwa 24 C bereitstellt, zur Her- 7

8 13 EP B1 14 stellung von wärmesensitiven Polymeren gemäß Anspruch Wärmeübertragungsmedium nach Anspruch 2, wobei das Gewichtsverhältnis von Phenylcyclohexan zu Bicyclohexan etwa 0:0 bis etwa 99:1 beträgt. 27. Wärmeübertragungsmedium nach Anspruch 2, wobei das Gewichtsverhältnis von Phenylcyclohexan zu Bicyclohexan etwa 70: bis etwa 99:1 beträgt. 28. Wärmeübertragungsmedium nach Anspruch 2, wobei das Gewichtsverhältnis von Phenylcyclohexan zu Bicyclohexan etwa 90: bis etwa 99:1 beträgt. Revendications 1. Procédé de préparation de polymères thermosensibles ou de mélanges de ceux-ci, dans lequel un fluide caloporteur est utilisé afin de contrôler la température pendant ladite préparation, dans lequel ledit fluide caloporteur comprend un fluide de type hydrocarbure choisi parmi des hydrocarbures aliphatiques, des hydrocarbures alicycliques, des hydrocarbures aromatiques substitués par un composé aliphatique ou alicyclique, ou des mélanges de ceux-ci, ledit fluide de type hydrocarbure ayant un point d ébullition compris entre 2 C et C et un point de fusion inférieur à C, et dans lequel la température du procédé est contrôlée par la vapeur du fluide caloporteur. 2. Procédé selon la revendication 1, dans lequel ledit fluide de type hydrocarbure a un point de fusion inférieur ou égal à C. 3. Procédé selon la revendication 1, dans lequel ledit fluide caloporteur comprend en outre du biphényle, de l oxyde de diphényle ou un mélange de biphényle/ naphtalène, à la condition que le fluide caloporteur ait un point d ébullition compris entre 2 C et C et un point de fusion inférieur à C. 4. Procédé selon la revendication 1, dans lequel ledit fluide caloporteur comprend un fluide choisi parmi le phénylcyclohexane, le bicyclohexane, au moins un biphényle hydrogéné ayant un niveau d hydrogénation compris entre celui du phénylcyclohexane et celui du bicyclohexane, ou des mélanges de ceux-ci.. Procédé selon la revendication 4, dans lequel ledit fluide caloporteur est choisi parmi le phénylcyclohexane, le bicyclohexane, ou des mélanges de ceuxci Procédé selon la revendication, dans lequel ledit fluide caloporteur est le bicyclohexane. 7. Procédé selon la revendication, dans lequel ledit fluide caloporteur est le phénylcyclohexane. 8. Procédé selon la revendication, dans lequel ledit fluide caloporteur est un mélange de phénylcyclohexane et de bicyclohexane. 9. Procédé selon la revendication 4, dans lequel ledit fluide caloporteur comprend en outre du biphényle, de l oxyde de diphényle ou un mélange de biphényle/ naphtalène, à la condition que le fluide caloporteur ait un point d ébullition compris entre 2 C et C et un point de fusion inférieur à C.. Procédé selon la revendication 1, dans lequel le polymère thermosensible a, dans les conditions ambiantes, un point de fusion compris dans la plage allant de 2 C à 248 C et dans lequel le point d ébullition dudit fluide caloporteur est, dans les conditions ambiantes, compris entre environ 2 C et environ 24 C. 11. Procédé selon la revendication, dans lequel le point d ébullition dudit fluide caloporteur est compris dans la plage allant d environ 23 C à environ 243 C. 12. Procédé selon la revendication 1, dans lequel ledit polymère thermosensible est choisi parmi le nylon 6, le nylon 11, le nylon 12, le téréphtalate de polytriméthylène, le polybutylène, le téréphtalate de polybutylène, le téréphtalate de polyéthylène, le polypropylène, ou un polyéthylène haute densité ou basse densité, ledit polymère ayant un point de fusion, dans les conditions ambiantes, compris dans la plage allant d environ 2 C à environ 248 C. 13. Procédé selon la revendication 1, dans lequel ledit polymère thermosensible est le téréphtalate de polyéthylène ou un copolymère de celui-ci. 14. Procédé selon la revendication 1, dans lequel ledit polymère thermosensible est choisi parmi le poly (méthacrylate de méthyle), un polyacétal, un polyionomère, un copolymère d EVA, de l acétate de cellulose, un polychlorure de vinyle dur ou un polystyrène. 1. Procédé selon la revendication 1, dans lequel ledit fluide caloporteur comprend un fluide préparé par hydrogénation catalytique de biphényle, où l hydrogénation est arrêtée lorsque l indice de réfraction du mélange réactionnel d hydrogénation à 2 C est compris dans la plage allant de 1,477 à 1,44. 8

9 1 EP B Procédé selon la revendication 1, dans lequel l indice de réfraction dudit fluide caloporteur est compris entre 1, 477 et Procédé selon la revendication 1, dans lequel l indice de réfraction dudit fluide caloporteur est égal à C, pour la préparation de polymères thermosensibles selon la revendication Fluide caloporteur selon la revendication 2, dans lequel le rapport pondéral entre le phénylcyclohexane et le bicyclohexane est compris entre environ 0: 0 et environ 99: Procédé selon la revendication 1, dans lequel l indice de réfraction dudit fluide caloporteur est compris entre 1.23 et 1, Procédé selon la revendication 1, dans lequel ledit fluide caloporteur comprend en outre du biphényle, de l oxyde de diphényle ou un mélange de biphényle/ naphtalène, à la condition que le fluide caloporteur ait un point d ébullition compris entre 2 C et C et un point de fusion inférieur à C Fluide caloporteur selon la revendication 2, dans lequel le rapport pondéral entre le phénylcyclohexane et le bicyclohexane est compris entre environ 70: et environ 99: Fluide caloporteur selon la revendication 2, dans lequel le rapport pondéral entre le phénylcyclohexane et le bicyclohexane est compris entre environ 90: et environ 99:1.. Procédé selon la revendication 1, dans lequel le polymère thermosensible a, dans les conditions ambiantes, un point de fusion compris dans la plage allant de 2 C à 248 C et dans lequel le point d ébullition dudit fluide caloporteur est, dans les conditions ambiantes, compris entre environ 2 C et environ 24 C Procédé selon la revendication, dans lequel ledit polymère thermosensible a un point de fusion compris dans la plage allant d environ 23 C à environ 243 C. 22. Procédé selon la revendication 1, dans lequel ledit polymère thermosensible est choisi parmi le nylon 6, le nylon 11, le nylon 12, le téréphtalate de polytriméthylène, le polybutylène, le téréphtalate de polybutylène, le téréphtalate de polyéthylène, le polypropylène, ou un polyéthylène haute densité ou basse densité, ledit polymère ayant un point de fusion, dans les conditions ambiantes, compris dans la plage allant d environ 2 C à environ 248 C Procédé selon la revendication 1, dans lequel ledit polymère thermosensible est le téréphtalate de polyéthylène ou un copolymère de celui-ci Procédé selon la revendication 1, dans lequel ledit polymère thermosensible est choisi parmi le poly (méthacrylate de méthyle), un polyacétal, un polyionomère, un copolymère d EVA, de l acétate de cellulose, un polychlorure de vinyle dur ou un polystyrène Fluide caloporteur comprenant un mélange de phénylcyclohexane et de bicyclohexane, dans lequel le rapport pondéral entre le phénylcyclohexane et le bicyclohexane fournit un point d ébullition compris dans la plage allant d environ 2 C à environ 9

10 EP B1 REFERENCES CITED IN THE DESCRIPTION This list of references cited by the applicant is for the reader s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard. Patent documents cited in the description US 3913 A [0003] US A [0003] JP A [0003] WO A [0003] JP A [0003] WO A [0003] EP W [0004] JP B [000] US A [0006]