Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the subject of the invention is a composition useful as a plasticizer for polymers, comprising at least one ester of 1,4: 3,6 dianhydrohexitol and a second compound which functions as a plasticizer.
• Another aspect of the invention relates to the use of this 1,4,4,6-dianhydrohexitol ester as a polymer gelation accelerator.
• these polymers may have disadvantages, such as in particular their mechanical properties which may be insufficient for certain uses. For example, they may have a very low elongation at break at room temperature or be poorly resistant to impact.
• melt behavior of these polymers it may be necessary to modify the melt behavior of these polymers, in particular to be able to implement them in coating-type transformation processes or in calendering.
• the polymer it is necessary for the polymer to have exceeded its melting temperature, or even its gelling temperature, and thus the polymer has, in this gelled state, a viscosity adapted to the forming process in order to be able to be properly transformed.
• these polymers can be mixed with "plasticizers”.
• plasticizer any product which, when it is mixed in sufficient quantity with a polymer, has the function of reducing the glass transition temperature of said polymer.
• the plasticizers are generally mixed with the polymer, which allows the softening temperature of the polymer to be lowered.
• This mixing can be done by different methods of implementation.
• polyvinyl chloride for example, the polymer can be converted into an object by various techniques for processing thermoplastic materials, and in particular by extrusion, calendering or coating by a plastisol-type process.
• the PVC is mixed with the plasticizer by supplying this system with energy, in the form of temperature and mechanical energy. In the case of extrusion or mixing, this mixing is done in a closed system. In the case of a mixture on rolls, this mixing is done in an open system.
• the polymer can then be shaped, for example by thermoforming or calendering processes. Generally, a dry blending step is carried out before the thermomechanical mixing step.
• a mixture is generally produced to form a PVC paste, this paste is then shaped by a coating or molding step in which the paste is heated in an oven to form the part.
• the polymer is properly melted or gelled to be able to be shaped satisfactorily and thus ensure that the object formed at the end of the process has good properties.
• plasticizers of the family of phthalic esters are generally used. To this day, it is still very generally dioctyl phthalate or diisononyl phthalate. These plasticizers are very effective for the plasticization of polymers, and are readily available on the market, at a relatively low cost.
• plasticizers have also been developed in recent years, such as cyclohexane polycarboxylic acid and its derivatives, which have been the subject of patent applications WO 00/78853 and WO 99 / 32427.
• diisononyl ester of dicarboxylic acid 1 2-cyclohexane commercially available from BASF under the Hexamoll ®.
• plasticizer may also be mentioned the derivatives of glycerol esters, such as Grindsted ® obtained from glycerol and castor oil and commercialized by Danisco. These plasticizers have the advantage of being obtained from biobased products.
• 1,4,4,6-dianhydrohexitol derivatives as polymer plasticizers has already been described in WO 99/45060. These derivatives do not have the toxicity problems of phthalates. These plasticizers also have the advantage of being at least partially biobased. The mechanical properties of the plasticized polymers with these derivatives are excellent, close to those obtained with phthalate type plasticizers.
• the Applicant explains the accelerating effect of gelation, in that the substance penetrates quickly into the polymer and is intercalated between the chains of this polymer.
• the network of polymer molecules is thus rendered very quickly "looser", which allows a rapid gelation and introduction of the plasticizer easier between the polymer chains and which has the effect of obtaining a plasticized polymer faster.
• the consequence for the process is that the polymer can thus be processed faster, and / or with less thermomechanical energy.
• DIBP diisobutyl phthalate
• JAYFLEX TM MB 10 monobenzoate isodecyl
• SANTICIZER ® 9500 monobenzoate 2-ethyl hexyl
• VOC volatile organic compounds
• Example a mixture of phthalates, useful as a plasticizer said mixture comprising phthalic acid esters of saturated alcohols to 7 carbon atoms (molecular weight equal to 362 g. Mol " 1 ) as well as esters of phthalic acid and alcohols saturated with 10 carbon atoms (with a molar mass equal to 446 g, mol -1 ).
• the ester made from 7-carbon saturated alcohols is used as a gelling accelerator.
• the advantage advanced for this composition is that it is not very volatile, compared to compositions comprising the most common gelling accelerator, for example dibutyl or isobutyl phthalates. However, this plasticizing mixture is not completely satisfactory in terms of plasticization speed.
• the Applicant has even been able to verify (see examples) that the C 7 phthalic ester is very little effective as a gelling accelerator when it is combined with other types of plasticizers than phthalates, for example a diester of 1,4: 3,6-dianhydrohexitol or an ester of the polycarboxylic acid cyclohexane.
• some of these plasticizers may have freezing temperatures close to 0 ° C.
• this freezing temperature can be problematic, even prohibitive because the plasticizer is then difficult to manipulate.
• compositions capable of plasticizing polymers which remain liquid, even at temperatures up to -10 ° C., or even -15 ° C.
• This plasticizing composition comprises a compound (A) acting as a gelling accelerator and a compound (B) acting as a plasticizer.
• composition comprising:
• 1,4-3,6-dianhydrohexitol esters selected from the monoesters and diesters of isosorbide, isomannide and isoidide and whose ester groups of 1, 4: 3,6-dianhydrohexitol are groups comprising 1 to 24 carbon atoms, preferably groups comprising from 6 to 12 carbon atoms;
• esters of polycarboxylic acid cyclohexane esters of polycarboxylic acid cyclohexane
• esters of phthalic acid esters of phthalic acid
• composition according to the invention has the further advantage of having a better cold resistance than the already known plasticizer compositions. This is particularly true for compositions where the compound (B) is a 1,4,4,6-dianhydrohexitol ester.
• the invention also relates to a method of manufacturing an object based on a plasticized polymer composition comprising a polymer (C) and the composition containing (A) and (B) according to the invention.
• This process comprises the following steps: A step of selecting the ester (A), the compound (B) and the polymer (C);
• the step of introducing the constituents (A), (B) and (C) into the mixer can be done separately or through a mixture of constituents, and simultaneously or sequenced; the mixing and heating steps can be performed simultaneously or sequentially.
• Figure 1 shows the evolution of the viscosity as a function of temperature of a polymer paste comprising a polyvinyl chloride and a gelling accelerator.
• the compound (A) is a 1,4: 3,6-dianhydrohexitol ester (A) whose molecular weight ranges from 255 to 345 g. mol "1 , and selected from monoesters and diesters of isosorbide, isomannide or isoidide.
• the ester groups of the ester (A) are chosen so that the molar mass of (A) ranges from 255 to 345 g. . mol "1
• the ester group may be derived from a carboxylic acid, that is to say capable of being obtained by reacting a carboxylic acid with an alcohol of 1, 4: 3,6-dianhydrohexitol.
• the ester group is a valerate group
• the 1,4: 3,6-dianhydrohexitol ester groups are groups comprising from 2 to 8 carbon atoms. that is, the acid reacting with 1,4: 3,6-dianhydrohexitol comprises from 2 to 8 carbon atoms.
• the ester group of the ester (A) is an alkyl group, that is to say that the ester is obtained by reaction of 1,4: 3,6-dianhydrohexitol with one or more saturated monocarboxylic acids.
• the alkyl group may be a cycloalkyl, linear alkyl or alkyl group branched.
• the alkyl group is linear or branched, most preferably linear.
• This ester (A) may be chosen from 1, 4: 3,6-dianhydrohexitol dipropionate, 1,4: 3,6-dianhydrohexitol dibutyrate, 1,4: 3,6-dianhydrohexitol diisobutyrate, divalerate and the like.
• the ester (A) is a divalerate of 1,4: 3,6-dianhydrohexitol or a dihexanoate of 1,4: 3,6-dianhydrohexitol, preferably a divalerate of 1,4: 3,6-dianhydrohexitol.
• the 1,4: 3,6-dianhydrohexitol ester (A) is an isosorbide ester.
• esters are particularly effective, particularly in their preferred variants.
• isomannide, isoidide and isosorbide can be obtained respectively from mannitol, iditol and sorbitol, which are themselves obtained from starch
• the esters of 1, 4: 3, 6-Dianhydrohexitol useful for the invention also have the advantage of being partially biobased or even completely biobased if an acid also bio-based is used.
• the composition according to the invention comprises at least one ester (A), that is to say that it may comprise a mixture of esters (A) described above.
• esters are known and can be obtained by an esterification reaction of 1,4: 3,6-dianhydrohexitol with at least one carboxylic acid.
• This carboxylic acid may be ethanoic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid and octanoic acid.
• the synthesis of these esters is presented for example in the document WO 99/45060 already cited.
• the compound (B) is a compound whose molar mass is greater than 345 g. mol "1 and which is selected from:
• 1,4: 3,6-dianhydrohexitol esters chosen from isosorbide, isomannide and isoidide monoesters and diesters and whose ester groups of 1, 4: 3,6-dianhydrohexitol; are groups comprising from 1 to 24 carbon atoms, preferably groups comprising from 6 to 12 carbon atoms;
• the compounds (B) must be chosen to have a molar mass greater than 345 g. mol "1.
• the molar mass of compound (B) may range for example from 350 to 1000 g. mol" 1, preferably from 390 to 600 g. mol "1 .
• composition according to the invention comprises at least one compound (B), that is to say that it may comprise a mixture of compounds (B) useful for the invention.
• the compound (B) is a diester of 1, 4: 3,6-dianhydrohexitol or an ester of the polycarboxylic acid cyclohexane.
• the ester of 1,4: 3,6-dianhydrohexitol (B) is very preferably an ester of isosorbide.
• the ester group of the ester (B) is an alkyl group, that is to say that the ester is obtained by reaction of 1,4: 3,6-dianhydrohexitol with one or more saturated monocarboxylic acids.
• the alkyl group may be a cycloalkyl, linear alkyl or branched alkyl group.
• the alkyl group is linear or branched, most preferably linear.
• the ester group (s) of the 1,4: 3,6-dianhydrohexitol ester comprise from 1 to 24 carbon atoms, i.e. the 1,4: 3,6 dianhydrohexitol comprises from 1 to 24 carbon atoms.
• the ester group or groups comprise from 4 to 16 carbon atoms, preferably from 5 to 1 1, for example from 6 to 12, most preferably from 7 to 10.
• This ester (B) may be chosen from 1,4: 3,6-dianhydrohexitol diheptanoate, 1,4: 3,6-dianhydrohexitol dioctanoate, 1,4: 3,6-dianhydrohexitol dinonanoate, 1, 4: 3,6- dianhydrohexitol, 1, 4: 3,6-dianhydrohexitol diundecanoate, 1,4: 3,6-dianhydrohexitol didodecanoate, 1,4: 3,6-dianhydrohexitol heptanoate hexanoate, 1,4-heptanoate octanoate: 3,6-Dianhydrohexitol, 1,4-3,6-dianhydrohexitol heptanoate nonanoate, 1,4: 3,6-dianhydrohexitol heptanoate decanoate, 1,4-3,6-dianhydrohexitol hept
• this ester (B) is capable of being produced by esterification reaction of 1,4: 3,6-dianhydrohexitol with a carboxylic acid or a mixture of these acids.
• a carboxylic acid mention may be made of butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid and acid.
• octanoic nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid.
• These compounds (B) can be obtained by carrying out an esterification reaction between 1,4: 3,6-dianhydrohexitol with one or more carboxylic acids.
• the ester is a monoester. It is a diester in the case where the two alcohol functions of the diol have reacted in an esterification reaction.
• the 1,4: 3,6-dianhydrohexitol ester is preferably a diester.
• the 1,4: 3,6-dianhydrohexitol diester may comprise different ester groups, that is to say that the diester is obtained with 2 different acids.
• esters of the cyclohexane polycarboxylic acid are known and are described for example in the application WO 99/32427 or the application WO 00/78853. Provided that their molar mass exceeds 345 g. mol "1 , the esters of the polycarboxylic acid cyclohexane cited on page 14 line 14 to page 9 line 9 of the application WO 00/78853 can be used as compound (B).
• the cyclohexane dicarboxylic acid esters are used.
• the cyclohexane polycarboxylic acid esters are diisonoyl esters, as for example the diisosonyl ester of 1,2-cyclohexane dicarboxylic acid.
• the latter is marketed by BASF under the brand Hexamoll ® .
• Phthalic acid esters (or phthalates) are also well known plasticizers. By way of example, it may be dioctyl phthalate or diisononyl phthalate. These compounds can be obtained by reacting phthalic acid with an alcohol.
• Glycerol esters are known and can be for example glycerol esters sold by the company Danisco under the Grinsted ® brand. These compounds (B) can be obtained by carrying out an esterification reaction between glycerol with a carboxylic acid, for example one of the carboxylic acids already mentioned for the manufacture of 1,4-3,6-dianhydrohexitol esters.
• carboxylic acid (s) reacting with 1, 4: 3,6-dianhydrohexitol or glycerol are chosen so that the compound (B) has a molar mass greater than 345 g. mol "1.
• the one or more alcohols reacted with the polycarboxylic cyclohexane or phthalic acid are selected so that the ester compound (B) has a molecular weight greater than 345 g. mol" 1.
• the composition according to the invention comprises, relative to the total mass of the composition, at least 50% of (A) and (B), preferably at least 80%, more preferably at least 90%, and even more preferentially at least 95%.
• the composition according to the invention is very advantageously composed of (A) and (B).
• the mass quantity of (A) is advantageously from 0.1 to 99% relative to the total weight of (A) and (B), advantageously from 0.5 to 50% .
• the advantages of the process and of the composition according to the invention are particularly marked when the mass quantity of (A) is in the range from 1 to 25% relative to the total weight of (A) and (B), advantageously ranging from 2 to 20%, for example ranging from 4 to 19%.
• composition according to the invention which is a plasticizer composition capable of rapidly polymerizing polymers, has the additional advantage of having a very good resistance to cold.
• Another subject of the invention relates to the use of the composition according to the invention for plasticizing a polymer (C).
• the invention also relates to a process for plasticizing a polymer, characterized in that it comprises a step of mixing said polymer with the composition according to the invention.
• the invention also relates to a method for reducing the glass transition temperature of a polymer, characterized in that it comprises a step of mixing said polymer with the composition according to the invention.
• the mixing is preferably carried out using thermomechanical energy so as to intimately mix the composition and the polymer.
• the polymer to be plasticized (C) may be chosen from vinyl polymers such as polyvinyl chloride, polyurethanes, polyesters, cellulosic polymers, starches, acrylic polymers, polyacetates and polyamides and mixtures of these polymers.
• vinyl polymers such as polyvinyl chloride, polyurethanes, polyesters, cellulosic polymers, starches, acrylic polymers, polyacetates and polyamides and mixtures of these polymers.
• it is a vinyl polymer, preferably polyvinyl chloride.
• polyvinyl chloride is meant according to the present invention homopolymers of vinyl chloride or copolymers comprising vinyl chloride, for example vinyl acetate / vinyl chloride copolymers.
• the polymer thus obtained is a plasticized polymer with the composition containing (A) and (B).
• Constituents (A) and (B), which are naturally in the liquid state, are introduced between the solid polymer chains and a plasticized polymer consisting of a solid phase results.
• the polymer (C) Prior to mixing with (A) and (B), the polymer (C) may be in any form, for example in the form of granules or powder.
• a polymer paste comprising a mixture of a polymer powder and the composition according to the invention.
• This paste is generally called plastisol and can form objects by the methods described below.
• the average particle diameter of the powder is between 1 and 30 ⁇ , for example between 1 and 20 ⁇ .
• this type of powders can be obtained by preparing the PVC by emulsion or micro-suspension.
• This paste is generally obtained by mechanical mixing, preferably without heating, of the polymer powder (C) with (A) and (B). During mixing, the polymer (C) disintegrates and the average diameter of the polymer particles decreases.
• the particles In the plastisol, the particles generally have an average diameter of approximately 0.5 to 30 ⁇ , for example from 0.5 to 20 ⁇ .
• the mixtures thus obtained are called plastisols which are, according to the amounts of (A), (B) and (C), more or less fluid.
• plastisols are prepared in fast mixers of turbine type, mixers planetary or slow mixers that are horizontal planetary mixers with Z blades.
• the constituents (A), (B) and (C) are advantageously in mass proportions such that the sum of (A) and (B) ranges from 1 to 900 parts per 100 parts of polymer (C), advantageously from 5 to 1 50 parts, preferably from 1 0 to 120 parts of (A) and (B). They can be introduced into the mixing system by any suitable means, such as feeding hopper, or manually.
• the amounts of plasticizer be from 30 to 80 parts of (A) and (B) per 100 parts of polymer powder.
• optional additives (A), (B) and (C) may also be used. These additives may be chosen from stabilizers, anti-UV agents, fillers, dyes, pigments, blowing agents, emulsifiers, viscosity-lowering agents other than (A), thickeners, demoulding agents, agents and the like. matting agents, antistatic agents, fungicidal agents and odoriferous agents. The amounts of each additive are chosen to provide the desired properties during the implementation of the process or for the object finally obtained. These additives may be introduced into the composition directly or in a mixture.
• the amount of optional additive generally ranges from 1 to 600 parts per 100 parts of polymer (C), generally from 2 to 80 parts. It is still possible according to the invention to manufacture objects comprising the plasticized polymer composition by using a method of manufacturing an object based on a plasticized polymer composition containing a polymer (C) and the constituents (A) and (B) as used in the composition of the invention. This process comprises:
• the step of introducing the constituents (A), (B) and (C) into the mixer can be done separately or through a mixture of constituents, and simultaneously or sequenced;
• the mixing and heating steps can be performed simultaneously or sequentially.
• the constituents (A) and (B) are introduced into the mixing system via the composition according to the invention.
• the method comprises a thermomechanical mixing step.
• the thermomechanical mixing step is performed in a mixing system which is a mixer for thermoplastics.
• This mixer can be chosen from mixers, BUSS mixers, roll mixers and extruders.
• Constituents (A) and (B) can be introduced as one or more masterbatches.
• the thermomechanical mixing step is carried out at a temperature adapted to the polymer (C) transformation temperature.
• the temperature of the mixture during thermomechanical mixing is preferably between 60 and 200 ⁇ for PVC.
• thermomechanical mixture it is possible to use a polymer in any type of form.
• thermomechanical mixing a preliminary step of dry blending of the constituents (A), (B) and (C) is advantageously carried out before the thermomechanical mixing.
• This dry mixing can be carried out in a simple mechanical mixer.
• the method according to the invention is particularly advantageous when the shaping step is a calendering step.
• the calendering is performed in a calandreuse, which is an open system.
• the process is particularly advantageous in this case, because the amounts of VOCs emitted during the process are particularly low compared to those emitted in processes using other gelling accelerators that compounds (A).
• the object can also advantageously be shaped by other methods, in particular by injection, injection extrusion, molding, extrusion molding, thermoforming, extrusion forming, extrusion sheathing, extrusion blow molding. Coextrusion techniques can also be used to form multilayer objects.
• a method of the plastisol type with the previously described polymer paste is used to form the object according to the invention.
• the shaping step is generally a step of coating, dipping, slugging or rotational molding of the polymer paste, thereby forming a preformed object.
• the heating step of the method is a step of firing said preformed object, which can take place during the shaping step of the preformed object (this is the case, for example, with soaking, sludging or rotational molding) or take place after the shaping step of the preformed object (this is the case for example of the coating).
• This cooking step can be carried out at a temperature of between 60 and 300 °, for example between 100 and 250 ° C. It can be done under air or in a controlled atmosphere, for example under an inert atmosphere.
• the shaping step of the object is preferably a step of coating the polymer paste on a support, this coating being performed before the step of firing said coated support.
• the coating step may be carried out on a textile support, a synthetic polymer or a paper.
• the coating can be carried out using any coating head, for example using a squeegee or a cylinder.
• This coating may be, according to a first sub-variant, a so-called “coated coating” as described above or according to a second sub-variant, a coating called “coating without support”.
• the support of the coated support can be detached after firing and the method further comprises a subsequent step of separating the carrier to form a plasticized film or sheet of polymer.
• a support may be made of silicone paper.
• the baking step is generally carried out in an oven, for example a tunnel oven.
• Another object of the invention relates to an object comprising the plasticized polymer composition, which is obtainable by the method of the invention.
• the object comprising the plasticized polymer composition may be any type of object, such as a film, a sheet, a granule, a floor covering, a wall covering, a plastic coated fabric, especially an artificial leather, for example for footwear, for leather goods or for furniture, a tarpaulin, a liner for example for a pool, a blind, a flexible container, a garment, a medical product, a glove, a boot, a gasket, a protective coating, a window mannequin , a toy for example a balloon or a doll, a tube, profiles including window profiles, automotive parts such as dashboard, seat, tank or headrest. These parts may be foamed or meringue parts, that is to say comprising air cells. They can also be on the contrary of the mass parts.
• the Applicant has also discovered that certain 1,4: 3,6 dianhydrohexitol ester compounds have the ability to accelerate the plasticization or gelation of polymers, this by emitting small amounts of VOCs during the process of implementation. .
• the invention thus also relates to the use of the esters (A) previously described as gelling accelerators in a polymer shaping process.
• a compound is considered to be a gelling accelerator when it has the ability to melt the polymer more rapidly than a diisononyl phthalate plasticizer (DINP).
• a simple way to measure it is to form a first mixture from 60 parts of compound and 100 parts of a polymer powder and to measure the development of the viscosity of this mixture as a function of temperature using a rheometer plan-plan.
• this mixture can be deposited in a rheometer, and a shear rate of 10 sec -1 can be applied with a rotation angle of 2 ° C.
• the mixture is conditioned for 10 minutes in applying the shear rate mentioned above and then the temperature is increased in the rheometer, for example at a rate of 5.7 K / min and the viscosity of this first mixture is measured until the polymer melts and its viscosity reaches 10 Pa.s -1 .
• This test is repeated in which a second mixture identical to the first mixture is used, with the difference that the DIN P replaces the test compound. If the first mixture comprising the test compound reaches a viscosity of 10 Pa.s -1 at a lower temperature than the second mixture, then the test compound is a gelation accelerator.
• the invention also relates to a process for accelerating the gelation of a mixture comprising a polymer and a plasticizer, characterized in that an ester of 1,4: 3,6-dianhydrohexitol (A) is added to said mixture according to the invention.
• A 1,4: 3,6-dianhydrohexitol
• invention whose molar mass ranges from 255 to 345 g. mol "1 , selected from isosorbide, isomannide and isoidide monoesters and diesters, Particular embodiments of the invention will now be described in detail in the following examples. particular do not limit the present invention.
• Example 1 Volatility Properties of Gel Accelerators
• the gel accelerators used in the following example are:
• DVI Hydro Accelerator according to the invention: Di-valerate of isosorbide having a molar mass of 314 g. mol "1 ;
• SANTICIZER ® 9500 2-ethyl hexyl monobenzoate (Ferro); Preparation and tests:
• the determination of the volatility of the gelling accelerators is carried out by weighing difference after a residence time defined in a ventilated oven. Fifteen grams of the product to be tested are weighed precisely in a crystallizer. The crystallizer is then placed inside the oven at 180 ° C for 30 minutes. Once this time has elapsed, the crystallizer is placed in a desiccator until cooling. The crystallizer is then weighed and the volatility is then calculated according to the following formula: (plasticizing mass starting - plasticizer mass after stay in oven) x 100 / mass plasticizer starting.
• Table 1 shows the results obtained on the products tested.
• the gelling accelerators used are:
• JAYFLEX TM MB 1 0 Isodecyl monobenzoate (Exxon Mobil) • DHP: phthalic diester of saturated alcohol comprising 7 carbon atoms (accelerator used in US 2007/0027242);
• the plastisol formulations are made using the following products:
• the gelation accelerator is introduced into a plastic container containing the PVC together with the thermal stabilizer.
• the preparation is then agitated using a motor equipped with a RAYNERI type stirring blade, at a slow speed. Then, the mixing speed is increased to 2000 rpm for 150 seconds.
• the preparation is then placed in a vacuum desiccator in order to remove the air bubbles.
• the PVC paste thus obtained is also called "plastisol".
• the paste is then used to measure the development of its viscosity as a function of temperature using a Physica MCR Rheometer type rheometer. To measure this change in viscosity, a drop of the dough is placed on a plate 50 mm in diameter and an angle of 2 °.
• the shear rate chosen is 10 s -1 and the temperature gradient is 5.7 K / min
• the dough is conditioned for 10 minutes by applying the shear rate mentioned above and then the temperature is applied The measurement is stopped when the temperature reaches 150 ° C or if the torque resulting from the measurement reaches a value too high for the measuring system.
• the higher the value of the angle Alpha the higher the rate of increase in the viscosity of the PVC paste, and therefore the more the accelerator is effective.
• the observed Alpha angle for the DVI is significantly higher than those obtained with the CITROFOL ® B2 and JAYFLEX TM MB 10 products. According to these tests, the DHP is still a less good gelation accelerator than the CITROFOL ® B2 products and JAYFLEX TM MB 10. DVI is therefore an excellent gel accelerator for PVC, more efficient than many gelation accelerators on the market.
• the temperature required for the PVC paste to reach a viscosity of 10 Pa.s is the lowest with DVI. This confirms and confirms a greater rapidity of the accelerator according to the invention, since the temperature necessary to initiate gelation is 9 to 16 ° lower compared to the gelling accelerators market tested. Thus, a significant energy gain can be achieved during the gelling of plastisols using the gelation accelerator according to the invention.
• the Applicant has also realized using this same protocol, tests using plasticizing compositions according to the invention and comparative, mixing a plasticizer (P) with a gelling accelerator (AG).
• DVI (accelerator used in the invention): Di-valerate of isosorbide
• DBP dibutyl phthalate
• DHP phthalic diester of saturated alcohol comprising 7 carbon atoms (accelerator used in US 2007/0027242);
• SANTICIZER ® 9500 2-ethyl hexyl monobenzoate (Ferro) Plastisol formulations are made using the following products:
• Plasticizing composition 60 parts with varying ratio of plasticizer and gel accelerators (P / AG)
• BAEROSTAB ® NT 319P Ba / Zn thermal stabilizer, 1, 5 parts
• the temperature for which the PVC paste has reached As a relevant criterion for evaluating the effectiveness of the plasticizing compositions, the temperature for which the PVC paste has reached:
• a viscosity equal to 10 Pa.s (denoted "T at 10 Pa.s")
• a viscosity equal to 100 Pa.s (denoted "T at 100 Pa.s", cf. FIG. 1).
• Table 4 presents the results obtained for the different pastes based on PVC and plasticizing compositions.
• the DVI appears here as a viscosity accelerator as powerful or better than the already known accelerators. It is notably more effective than the DH P, and this whatever the plasticizer used (DEI, D INCH or DINP).
• the DH P does not behave as a gelling accelerator when it is used in a plasticizer mixture with DEI or DINCH, as shown by the gelling temperatures of the polymer, which are very close to the gelation temperature of the plasticized polymer with the IED alone and the DINCH alone.
• plasticized PVC formulations according to the invention and comparative are made using the following products:
• Stabilizer BAEROSTAB ® NT 319P (Ca / Zn powder): 1, 5 parts
• Plasticizer and Gel Accelerator 34 parts The preparation of pressed specimens for the characterization of mechanical properties is done in several stages.
• plasticized PVC sheets are produced using a CARVER type press and a 30 x 30 cm mold in mirror-polished stainless steel provided with a frame 2 mm thick and coated. a mirror polished stainless steel lid.
• the frame is placed inside the mold and 180 g of plasticized PVC powder are poured into it. The powder is evenly distributed and covered with the lid.
• the assembly is placed on the press plate and a closing force of 18,000 kg is programmed for 2 minutes and then cooled to 40 ° C to 50 ° C.
• the PVC plate thus obtained is then demolded.
• PVC specimens were cut (40 ⁇ 40 mm, thickness 2 mm). They are conditioned for 72 hours at 20 ⁇ - 65% RH. The same is done with absorbent supports (CANSON blotter 10x10cm (100 cm 2 )). Then the specimens and the absorbent supports are weighed on a precision balance. Next, the plasticized PVC test pieces are placed between the two absorbent supports, in the center of these. This set is placed between 2 glass plates, and we put on the top a weight of 5 kg. The whole is placed in a ventilated oven at 70 ° C for 4 weeks. After 4 weeks, the test pieces are conditioned again at 20 ° C - 65% RH for 2 days. Finally, they are re-weighed in order to determine the migration rate of the test specimen, as follows: (specimen mass before oven - sample mass after oven) x 100 / specimen mass before oven.
• absorbent supports CANSON blotter 10x10cm (100 cm 2 )
• plasticized polymer One of the essential criteria for any plasticized polymer is its migration rate of the plasticizing composition used. Indeed, it must be minimal if one wishes to preserve the properties of the material in time.
• composition according to the invention has the capacity, after mixing in the polymer, to migrate less compared to comparative compositions using known gelation accelerators, in particular those described in document US 2007/0027242.
• Example 5 Improvement of the freezing point at low temperature of the plasticizer
• the evolution of the viscosity of the plasticizer as a function of the temperature is measured using a Physica MCR Rheometer type rheometer. To measure this change in viscosity, a drop of the plasticizer is placed on a 50 mm diameter plate and an angle of 1 ° (geometry CP 50-1) for a measurement of the viscous and elastic modulus as a function of temperature.
• the temperature gradient is 2 O / min, the temperature sweep of 20 ° C to -50 ° C, the oscillation frequency of 1 Hertz and the deformation of 1 to 0.1%.
• the measured freezing temperature corresponds to the temperature of change of state of the product under test and corresponds to the crossing of the viscous and elastic modules.
• Table 8 shows the measurements of the freezing temperature.
• Plasticizers for PVC are liquid products intended to be stored in storage cans. These can be installed outside the production buildings where they are implemented. It is therefore necessary that the plasticizers have freezing points (temperature at which the product begins to change state to move from the liquid state to that of gel) relatively low. In the opposite case, they must be isolated or even thermoregulated.

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