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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K7/00—Use of ingredients characterised by shape
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

• the present invention relates to polyester-based compositions having improved thermomechanical properties, comprising small mineral particles. These compositions are in particular useful for the manufacture of bottles.
• the present invention also relates to a process for manufacturing these compositions.
• Polyesters in particular polyethylene terephthalate, are thermoplastic polymers widely used for the production of molded or extruded articles They are generally used in the form of threads or fibers, articles molded using an injection molding machine, films (extruded and drawn articles) or containers, for example obtained by an extrusion-blowing process.
• the properties of the articles produced are largely linked to the thermomechanical properties of the polymer, such as the modulus, the ductility, the glass transition temperature, the deformation temperature under load.
• the deformation temperature under load is an important characteristic for the use of polyesters in the form of bottles, more particularly for bottles intended to contain drinks.
• certain drinks must be filled hot in bottles, and possibly in the absence of oxygen This is particularly the case for fruit juices, pasteurized or sterilized products, in particular dairy products, tea or coffee drinks, beer If the filling temperature is too high high, and / or if the liquid remains too long in the bottle beyond a certain temperature, the latter is deformed
• This drawback can limit the field of use of polyester, in particular polyethylene terephthalate, to contain drinks
• some drinks cannot be packaged in polyethylene terephthalate bottles, or may not It can only be so under limited temperature conditions.
• a first proposed solution consists in using a polyethylene or copolymers comprising naphthalic and terephthalic units This solution is however expensive, and it is industrially used only for very specific applications
• Another solution consists in modifying the bottle shaping process in order to overcrystallize the polymer.
• the process according to this solution is generally called "thermofixation” Briefly, it consists in crystallizing a polyester bottle by modifying the blowing operations.
• the implementation of this process requires a significant modification of the bottle manufacturing facilities requiring significant investment
• this overcrystallization process causes the neck of the bottles to crystallize making it non-translucent This may constitute an appearance defect
• the object of the present invention is to provide a use which makes it possible to improve the thermomechanical properties of polyesters, without the need for significant modifications to the manufacturing processes
• the invention provides a polyester-based composition characterized in that it comprises a polyester-based matrix and mineral particles of nanometric size, with a form factor between 1 and 10, in weight concentration between 0 , 01% and 25%
• the matrix of the composition may be based on any polyester. It may consist of a single polymer, polyester, or of a mixture of polymers of which at least one main component is a polyester. It can also consist of a copolymer, the majority of repeating units of which comprise ester functions.
• the polyesters suitable for carrying out the invention are generally obtained by polycondensation from diols and dicarboxylic acids or esters of dicarboxylic acids.
• diols suitable for carrying out the invention mention may be made of ethylene glycol, propyiene glycol, 1, 3-propaned ⁇ ol, 1, 4-butaned ⁇ ol, 1 3- butanediol, 2,2-d ⁇ méthylpropaned ⁇ ol , neopentyl-glycol, 1, 5-pentaned ⁇ ol, 1, 2-hexanediol, 1, 8-octaned ⁇ ol, 1, 10-decaned ⁇ ol, 1, 4-cyclohexaned ⁇ methanol, 1, 5- cyclohexanedimethanol, 1 , 2-cyclohexaned ⁇ méthanol, or mixtures thereof
• terephthalic acid isophtaic acid, orthophthalic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid , 1,3-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, methyl terephtahque acid, 4,4'-d ⁇ phenyld ⁇ carboxylic acid, 2,2'-d ⁇ phenyld ⁇ carboxylic acid, acid 4,4'- diphenyletherdicarboxyhque, 4,4'-d ⁇ phenylmethaned ⁇ carboxylic acid, 4,4'- diphenylsulphonedicarboxylic acid, 4,4'-d ⁇ phenyl- ⁇ sopropyl ⁇ dene-d ⁇ carboxylic acid, sulfo-5- ⁇ sophthalic acid, oxalic acid, succinic acid
• the dicarboxylic acids can be introduced into the polycondensation medium in esterified form, for example by an ethoxy unit or by a methoxy unit.
• polyesters for carrying out the invention are polyethylene terephthalate, polyt ⁇ methylene terephthalate, polybutylene terephthalate, polynaphatalene terephthalate, copolymers and mixtures based on these polyesters
• Nanometric mineral particles suitable for the invention give the composition improved mechanical properties compared to an identical composition not comprising said particles.
• the deformation temperature under load is, for example, higher
• the particles according to the invention have a small form factor, between 1 and 10.
• the form factor is preferably between 1 and 2.
• form factor of a particle we mean the ratio between the largest dimension of a particle and the smallest dimension
• the form factor is defined by the ratio between the length of the platelets and their thickness
• the form factor is defined by the ratio between the length of the needle and the diameter of the cross section of the needle If particles have a substantially spherical shape, we consider that the large dimension is of size equal to the small dimension, the form factor is equal to 1
• nanometric size particles it is meant that the small dimension is less than 200 nm, and that the large dimension is less than 2000 nm, preferably less than 400 nm. According to an even preferred embodiment, the small dimension is less than 100 nm and the large dimension is less than 200 nm
• the particles are of substantially spherical shape with an average diameter less than or equal to 200 nm
• the average diameter is more preferably between 5 and 100 nm
• the mineral particles suitable for information are preferably chosen from particles based on metal oxides, for example silica, titanium dioxide, alumina, zirconia They may include a surface treatment or coating Such treatments may for example be intended to improve the dispersion of particles in the polymer, to protect the particles from deterioration, or to protect the effect of the particles on the polymer. All the surface treatments and deposits known in the field of fillers for polymers, and in particular known and used for fillers of dimension greater than those concerned by the invention, can be used. It is possible, for example, to use particles of titanium dioxide partially or entirely coated with a silica-based compound.
• Silica-based particles are the preferred fillers for the implementation of the invention. All known types of silicas can be used. By way of example, mention may be made of combustion silicas, precipitation silicas, silica soils.
• the concentration by weight of particles in the composition is between 0.1 and 20%. It is preferably between 5 and 15%.
• the fillers are introduced into the polymer according to known methods for introducing mineral fillers into a polymer.
• a first method consists in introducing the particles into the polyester synthesis medium, generally before the polymerization has started.
• the polymerization is subsequently carried out in the presence of the particles.
• the particles can be introduced in the form of powder or in the form of a dispersion in a liquid medium.
• a second method consists in introducing the particles in the form of powder into molten polyester and mixing by shearing in order to obtain a uniform dispersion.
• This operation can, for example, be carried out using a mixer, with single or double screw.
• a third method consists in introducing the particles in the form of a masterbatch into the molten polymer.
• masterbatch is meant a composition comprising a high concentration of fillers and a polymer matrix compatible with polyester.
• the masterbatch can be produced according to one of the preceding methods.
• the introduction of the masterbatch into the molten polymer can be carried out using a shear mixing device.
• the particles are introduced in the form of a sol into the polyester synthesis medium.
• the soil can for example be an aqueous or glycolic soil. Silica soils are particularly suitable for this embodiment.
• a process for the preparation of compositions according to this embodiment comprises for example the following steps: a) introduction into a mixture of at least one diol with at least one dicarboxylic acid or one dicarboxylic acid ester of a silica sol of which the particles have an average diameter less than or equal to 200 nm b) Esterification or transesterification of the acid or of the acid ester with the diol, c) Polycondensation under vacuum of the esterification product,
• This process for manufacturing the compositions is conventional, with the exception of the introduction of silica sol. Such methods are, for example, described in The techniques of the engineer J 6 020. 2151 -2160.
• Step b) of esterification or transesterification is a step commonly carried out in industrial processes for the manufacture of polyesters. These two routes are, for example, mainly used for the manufacture of poly (ethylene terephthalate).
• ethyl terephthalate is a transesterification reaction.
• the molten DMT is dissolved in excess ethylene glycol (EG), the EG / DMT molar ratio being approximately 1.9 to 2.2, and the reaction is carried out at atmospheric pressure at temperatures of approximately 130 ° C. to 250 ° C. It requires the presence of a catalyst such as, for example, manganese acetate.
• EG ethylene glycol
• the methanol released by the reaction is removed by distillation.
• the excess ethylene glycol is removed by evaporation after the transesterification reaction.
• the catalyst which is also a catalyst for the degradation of the polyester is blocked with phosphorous compounds after the reaction.
• the product resulting from the transesterification is a mixture of bis-hydroxyethyl terephthalate (BHET) and of oligomers.
• BHET bis-hydroxyethyl terephthalate
• the second way is called "direct esterification". It is an esterification reaction of terephthalic acid with ethylene glycol. It is carried out at temperatures from 130 ° C to 280 ° C. Terephthalic acid, melted at these temperatures, is not soluble in ethylene glycol but is soluble in the ester produced from the reaction. The solubilization of the reagent in the medium is therefore progressive. Ethylene glycol is present with an EG / Terephthalic Acid molar ratio of approximately 1 to 1.5. The result of this reaction is a mixture of oligomers having terminal functions in the form of terephthalic acid or hydroxyethyl terephthalate.
• the subsequent polycondensation stages are generally catalyzed using metallic compounds, for example by compounds of antimony, titanium or germanium. They can be catalyzed by any polycondensation catalyst for polyesters. They are generally carried out under reduced pressure, in order to promote the departure of the ethylene glycol formed during the condensation reaction.
• the polymer is then shaped, for example by extruding a rod through an orifice, cooling, and granulation by cutting the rod.
• the shaping is generally preceded by filtering in the molten phase.
• the stages of polycondensation in the melt phase and of shaping can be followed by a step of post-condensation in the solid phase.
• the compositions for example in the form of granules, can be shaped for the production of molded articles. They can more particularly be used for the manufacture of bottles.
• the methods of manufacturing bottles from thermoplastic polymers are suitable for the use of the compositions of the invention.
• the extrusion blow molding process is generally preferred.
• the bottles thus obtained from the compositions of the invention can be filled with liquids at high temperature and / or liquids remaining hot in the bottle for an extended time. Indeed, the improvement of the thermomechanical properties of the compositions of the invention makes it possible to reduce the deformation of the bottles at high temperatures.
• Viscosity index (IV, in ml / g): measurement according to standard ISO 1628/5: measurement in a solution of the composition at 0.5% in a phenol / orthodichlorobenzene mixture 50/50 by weight, at 25 ° C.
• the polymer concentration used for the calculation of the viscosity index is the actual polymer concentration, taking into account the presence of the particles in the composition.
• Thermomechanical properties module at 23 ° C, Module at 160 ° C, Glass transition temperature (Tg). Dynamical measurement (Dynamical mechanical analysis) on an RSA device, on polymer test pieces of 40 * 4 * 2 mm, after drying and crystallization at 130 ° C under vacuum for 16 hours.
• HDT Deformation temperature under load
• the dry polymer is plasticized at 290 ° C. so as to destroy any germ of crystallization.
• the molten product is injected into a mold whose thickness varies gradually to obtain plates of thickness between 2 and 6 mm.
• the temperature of the mold walls is conditioned at 37 ° C. We note at what thickness e a slight haze appears corresponding to the beginning of crystallization.
• EXAMPLE 1 In a 7.5-liter polymerization reactor, making it possible to obtain 3 kg of polymer by polycondensation, provided with stirring with a coupler to monitor the viscosity of the reaction medium, of various introduction locks, of a column distillation to remove the water formed during the esterification, as well as the excess of ethylene glycol, and a direct vacuum circuit for the polycondensation step, there are introduced: - 2656 g of terephthalic acid ( 16.0 mol)
• the esterification time is 66 minutes (time required for the distillation of water).
• the pressure is then brought back to atmospheric pressure in 20 minutes.
• An antimony oxide solution is introduced into the reaction medium (250 ppm in Sb, relative to the polymer).
• the pressure is maintained for 20 minutes at atmospheric pressure, before a progressive vacuum of 1 bar at less than 1 mm of mercury in 90 minutes.
• the reaction mass is brought to 285 ° C when the pressure drops below 1 mm of mercury.
• the polycondensation time is defined as the time necessary to reach the target viscosity level from the moment the pressure is less than 1 mm of mercury.
• the polycondensation time is 32 minutes.
• the stirring is stopped and the reactor is pressurized to 3 bars to pour the polymer in the form of rods and cut rods in the form of granules.
• the polymer granules are dried under vacuum for 15 hours at 50 ° C.
• the polyester has an HDT of 67 ° C, a Tg of 107 ° C and a modulus measured at
• Example 2 (comparative example) Example 1 is repeated, except for the silica sol.
• the esterification time is 54 minutes with a polycondensation time is 67 minutes.
• the polyester obtained has a Tg of 99 ° C, an HDT of 59 ° C and modules measured at 23 ° C of 988 Mpa and at 160 ° C of 61 Mpa.
• Example 3 A composition according to Example 1 is prepared, by introducing the following mixture of acids in place of terephthalic acid:
• Example 4 A composition is prepared according to Example 1, except that the aqueous sol of silica particles is an aqueous sol of silica nanoparticles 25 nm in diameter, sold by the company Hoechst under the name Klébosol® 30R25 Time esterification is 68 minutes and the polycondensation time is 32 minutes.
• the composition obtained has a Tg of 107 ° C, with an HDT of 67 ° C and modules measured at 25 ° C and 160 ° C of 1195 Mpa and 88 Mpa respectively.
• a composition is prepared according to Example 1, except that the following compounds are introduced:
• the composition has a Tg of 103 ° C and measurement modules at 23 ° C and 160 ° C of 1015 Mpa and 65 Mpa respectively
• compositions produced in Examples 1 to 5 are collated in Table I below.
• Example 3 above is reproduced using an amount of isophthalic acid corresponding to 1.9 mole% of the total amount of terephthalic and isophthalic acids
• the composition thus obtained has an IV of 72.1. It is used for the manufacture of bottles with a capacity of 600 ml.
• the bottles are obtained by implementing an injection / blowing process in an integrated ABS NISSEI F100 machine. the resistance to hot deformation of these bottles, a test known as
• hot filling is carried out This test consists of filling the bottles with water at different temperatures and comparing the volume of water used with the volume necessary to fill a cold bottle. The greater the difference in volume, the less the polymer is resistant to hot deformation.
• bottles were produced with a polyester manufactured according to the same process with the same isophthalic acid content but without nanoparticulate silica filler ( example 7)
• a polyester composition was produced according to the method of Example 3, but using 2.5% isophthalic acid and an amount of aqueous sol of silica nanoparticles Klebosol ® 40R50 to obtain a composition comprising 5% by weight of SiO 2 .
• the polyester has a viscosity index of 80.3 after crystallization. Part of this polyester is subjected to solid phase post-condensation to obtain a viscosity index of 87.6.
• a so-called "pasteurization” test was carried out to determine their resistance to hot deformation. This test consists of cold filling a bottle with carbonated water containing 5.5 g of CO2 / I and then capping the bottle. The bottle used has a 28 mm neck and a straight, smooth cylindrical body with a petaloid bottom. The bottle is immersed in a bath at 63 ° C with a temperature rise of 15 min and temperature maintenance for 15 min. The bottle is then cooled for 10 min in a shower to return to room temperature. The volume of the bottle is determined before the test and after the heating test by filling the bottle with water and weighing. The difference in volume between these two measurements expressed in% of variation (VRB) measures the resistance to deformation thereof and therefore of the material used.
• VRB in% of variation
• Example 8 was repeated but using 6% isophthalic acid and as nanofiller silica Klebosol ® 30R25 to obtain a polyester composition comprising 5% of the weight of S ⁇ O 2 and a viscosity index, after post-condensation in the solid phase, equal to 86.4
• a polyester comprising 2.3 mole% of isophthalic acid obtained according to the method of Example 3, and containing no nanometric filler was used for the manufacture of bottles according to the shaping methods used in Examples 8 and 9 Polyester has a viscosity index of 100 The pasteurization test carried out on these bottles leads to a VRB of 6.5%

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Containers Having Bodies Formed In One Piece (AREA)
• Wrappers (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=8848610

Family Applications (2)

Family Applications After (1)

Country Status (14)

Cited By (1)

Families Citing this family (12)

Citations (3)

Family Cites Families (7)

• 2000
  • 2000-03-29 FR FR0003965A patent/FR2807049B1/fr not_active Expired - Fee Related
• 2001
  • 2001-03-21 AT AT01917201T patent/ATE362957T1/de not_active IP Right Cessation
  • 2001-03-21 EP EP01917201A patent/EP1268629B1/fr not_active Expired - Lifetime
  • 2001-03-21 KR KR1020027013073A patent/KR100738853B1/ko not_active Expired - Fee Related
  • 2001-03-21 WO PCT/FR2001/000845 patent/WO2001072882A1/fr not_active Ceased
  • 2001-03-21 DE DE60128553T patent/DE60128553D1/de not_active Expired - Lifetime
  • 2001-03-21 JP JP2001571806A patent/JP2003528955A/ja not_active Abandoned
  • 2001-03-21 AU AU2001244288A patent/AU2001244288A1/en not_active Abandoned
  • 2001-03-21 CN CNB01809709XA patent/CN1209401C/zh not_active Expired - Fee Related
  • 2001-03-28 MX MXPA02009572A patent/MXPA02009572A/es active IP Right Grant
  • 2001-03-28 AR ARP010101460A patent/AR027731A1/es active IP Right Grant
  • 2001-03-28 CA CA002401399A patent/CA2401399A1/en not_active Abandoned
  • 2001-03-28 BR BR0109907-8A patent/BR0109907A/pt not_active IP Right Cessation
  • 2001-03-28 US US10/182,029 patent/US20040266917A1/en not_active Abandoned
  • 2001-03-28 WO PCT/BR2001/000030 patent/WO2001072881A1/en not_active Ceased

Patent Citations (3)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events