Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/14—Copolymers of styrene with unsaturated esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

• the present invention relates to the field of transparent polymer materials, particularly to the field of transparent materials having both good transparency, impact resistance, high modulus and good thermal resistance.
• the materials of the invention can be used in the fields of application of polymeric materials requiring transparency and / or good mechanical properties.
• the materials of the invention can be used in construction, household appliances, telephony, office automation as well as in the automobile industry.
• amorphous thermoplastic polymer materials are transparent and have a high mechanical modulus, but their impact resistance is low. These are most often homopolymers or copolymers (such as polymethyl methacrylate, polystyrene, poly [styrene-co-acrylonitrile]) whose glass transition temperature (Tg) is close to 100 ° C. and whose mechanical behavior in traction is that of fragile materials. For this reason, and for certain applications, it is sometimes necessary to formulate them with additives which can provide better impact resistance. However, when the amorphous thermoplastic polymer materials are formulated or are mixed with other products, in particular with conventional impact additives, they lose certain properties, in particular in terms of transparency and mechanical modulus, but also in terms of thermal behavior.
• thermoplastic polymer material which is both impact resistant and transparent exists, it is always difficult or even impossible, to obtain, at the same time, transparency, impact resistance, a high modulus and good thermal resistance.
• the Applicant has found that the solution to this problem is a polymer composition comprising a matrix based on an amorphous thermoplastic polymer, reinforced or not impact-resistant, and a judiciously chosen block copolymer.
• the block copolymer must have a block of elastomeric nature and at least one block partially or entirely compatible with the amorphous matrix.
• the difference in refractive index of the matrix ni and of the block copolymer must be less than or equal to 0.01.
• the composition according to the invention comprises three components, matrix, conventional impact additive, block copolymer, the respective refractive indices of which must not differ between them by more than 0.01.
• Transparency is ensured by adjusting the refractive indices.
• the elastomeric block of the block copolymer provides impact resistance by making the fragile matrix ductile.
• the judicious choice of the other blocks of the block copolymer makes it possible to keep the transparency, a high modulus and a conservation or improvement of the thermal resistance.
• the first object of the invention is a transparent polymer composition having good impact resistance, a high modulus and a good thermal resistance constituted
• the copolymer (III) must have an elastomer block (B) and at least one block partially or fully compatible, in the thermodynamic sense, with the amorphous matrix.
• Component (I) can be a homopolymer or a copolymer chosen from polymers obtained by the polymerization of at least one monomer chosen from the group containing styrene, acrylonitrile, acrylic acid, (meth) acrylates short chain alkyl such as methyl methacrylate.
• the mixture of monomers is chosen so as to have an amorphous, rigid and transparent compound (I) as well as the desired refractive index.
• the polymerization is carried out according to the usual techniques of mass polymerization, in solution or in a dispersed medium such as in suspension, emulsion, precipitating polymerization, etc.
• compound I is a random copolymer of styrene and methyl methacrylate containing from 0 to 55% by weight of styrene.
• This compound (I) is designated below by SM.
• additive (II) It is an additive called "core-shell" commonly used for the shock modification of matrices such as PVC, epoxy resins, poiy (styrene-co-acrylonitirle) or SAN , etc.
• core-shell commonly used for the shock modification of matrices such as PVC, epoxy resins, poiy (styrene-co-acrylonitirle) or SAN , etc.
• core-shell (or core-shell) are structured polymers obtained, in general, by emulsion polymerization in two stages, the first being used for the manufacture of the "core”, which is used as seed of a second stage intended to the manufacture of the "shell".
• the "core” is, more often than not, a polymer (or copolymer) at Tg below ambient temperature, and therefore, in the rubbery state.
• the "core” can consist of a random copolymer of butadiene and styrene, crosslinked or not.
• cores based on polybutadiene alone or copolymers of butadiene and acrylonitrile, or purely acrylic based on copolymers of butyl acrylate and styrene.
• the “shell” is supposed to coat the “core” and provide it with ease of dispersion in the matrix.
• Typical "shells” are those based on poly (methyl methacrylate), copolymers of methyl methacrylate and styrene, purely acrylic copolymers, copolymers of styrene and acrylonitrile, etc.
• MBS which constitutes a preferred impact additive of the invention; it is an additive “core-shell” random copolymer of butadiene - styrene as “core” and a “shell” of PM A or a random copolymer of methyl methacrylate - styrene.
• the MBS used in the examples below is a grade for PVC with a refractive index of the "core" close to 1.54 at room temperature.
• Component (III) is a block copolymer corresponding to the following general formula YBY 'in which B is a block of elastomeric character, Y and Y' may be of identical or different chemical composition, and at least one of the two is at least partially compatible with the compound (I).
• the monomer used to synthesize the elastomeric block B can be a diene chosen from butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 2-phenyl-1, 3 butadiene.
• B is advantageously chosen from poly (dienes), in particular poly (butadiene), poly (isoprene) and their random copolymers, or alternatively from poly (dienes) partially or completely hydrogenated.
• the polybutadienes those with the lowest glass transition temperature, Tg, are advantageously used, for example polybutadiene-1, 4 of Tg (around -90 ° C.) lower than that of polybutadiene-1, 2. (around 0 ° C).
• B blocks can also be hydrogenated. This hydrogenation is carried out according to the usual techniques.
• the blocks B consist mainly of poiybutadiene-1, 4.
• the Tg of B is less than 0 ° C and preferably less than - 40 ° C.
• Y and Y ′ can be obtained by the polymerization of at least one monomer chosen from the group containing styrene and short chain methacrylates such as methyl methacrylate.
• Y is a block composed mainly of styrene
• Y ′ is different from a block composed mainly of styrene.
• M consists of methyl methacrylate monomers or contains at least 50% by mass of methyl methacrylate, preferably at least 75% by mass of methyl methacrylate.
• the other monomers constituting this block can be acrylic monomers or not, be reactive or not.
• reactive functions By way of nonlimiting examples of reactive functions, mention may be made of: oxirane functions, amine functions, carboxyl functions.
• the reactive monomer can be a hydrolyzable monomer leading to acids.
• the other monomers which can constitute the block Y ' non-limiting examples that may be mentioned are glycidyl methacrylate, tert-butyl methacrylate.
• Advantageously M consists of polymethyl methacrylate (PMMA) syndiotactic at least 60%.
• Y has a chemical composition different from Y ', as in the case of the examples below, Y is designated by S.
• This block can be obtained by the polymerization of vinyl aromatic compounds such as for example styrene, ⁇ -methyl styrene, vinyltoluene.
• the Tg of Y (or S) is advantageously greater than 23 ° C and preferably greater than 50 ° C.
• the block copolymer, Y-B-Y ', according to the invention is designated below by SBM.
• the SBM has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
• the SBM triblock advantageously has the following composition expressed as a mass fraction, the total being 100%:
• M between 10 and 80% and preferably between 15 and 70%.
• B between 2 and 80% and preferably between 5 and 70%.
• the SBM can contain at least one diblock SB in which the blocks S and B have the same properties as the blocks S and B of the triblock SBM. They consist of the same monomers and possibly comonomeres as the S blocks and the B blocks of the SBM triblock.
• the blocks B of the SB diblock consist of monomers chosen from the same family as the family of monomers available for the blocks B of the S-BM triblock.
• the dibloc SB has a number-average molar mass which can be between 5000 g / mol and 500000 g / mol, preferably between
• the S-B diblock advantageously consists of a mass fraction of B of between 5 and 95% and preferably between 15 and
• SBM The mixture of diblock S-B and triblock S-B-M is hereinafter designated SBM.
• SBM The mixture of diblock S-B and triblock S-B-M is hereinafter designated SBM.
• This mixture advantageously comprises between 5 and 80% of S-B diblock for respectively 95 to 20% of S-B-M triblock.
• SBM block compositions
• component (III) according to the present invention may very well be a mixture of S-B diblocks and S-B-M triblocks.
• V PS . v PB d and v m MA are the volume fractions of the polystyrene (PS), polybutadiene (PBd) and polymethyl methacrylate (PMMA) blocks of the SBM triblock, and n P , n P ⁇ d andn mm are the refractive indices of polystyrene, polybutadiene and poly (methyl methacrylate).
• PS polystyrene
• PMMA polymethyl methacrylate
• n P , n P ⁇ d andn mm are the refractive indices of polystyrene, polybutadiene and poly (methyl methacrylate).
• a conventional impact additive is used in the composition, it must be chosen so that its refractive index is equal to those of the matrix and the block copolymer , within the tolerance limit of 0.01 difference.
• compositions of the invention can be obtained in different ways.
• the product thus obtained is then used if necessary after mixing with the third component.
• core-shell shock additive or on its own, when there is no need to modify the matrix with a “core-shell” shock additive.
• Extrusion processing is the preferred method, although other techniques such as calendering may be used. Processing by extrusion can be carried out in one or more stages and the composition is obtained in the form of granules.
• Compounding route consists of mixing the two or three components of the invention (SM + SBM + if necessary the shock additive
• the “compounding route” can include one or more stages of implementation (extrusion); when it is a question of mixing the three components, it may be necessary or desirable to carry out two or more stages of implementation involving at least two of the components for the first and the three components for the last.
• the third eg, powder, powder, granules
• This first mixture of two components (granules) can then, more easily, be extruded with the third component (granules), the final result being, as for the "synthetic route", granules of the composition of the invention.
• the granules obtained by one of the two possible routes can then be further processed by the known methods of shaping polymers (extrusion, injection, calendering, etc.), so as to obtain the final form of an article manufactured from the material which is the subject of the invention.
• this final form is dictated by applications in the building industry, household appliances, telephony, office automation, the automobile industry or others.
• compositions to be tested composition and application
• the composition of the 5 products selected (four ternary mixtures SM + SBM + additive "core-shell", and a control) for the evaluation is given in Table I.
• the control chosen was extruded under the same conditions as ternary mixtures.
• the control is a mixture of 60% by weight of an SM copolymer of composition 45/55 (respective percentages by weight of styrene and methyl methacrylate units in the copolymer) with 40% by weight of a “core-shell” additive. »(MBS), but without block copolymer.
• This mixture was manufactured by the applicant under the reference OROGLAS TP327.
• Matrix SM Random copolymer obtained by suspension polymerization composed of 45% by weight of Styrene and 55% by weight of Methyl methacrylate.
• MBS shock additive Classic shock additive called “core-shell” for PVC manufactured and marketed by Rohm & Haas under the reference Paraloid BTA 740.
• Tribloc SBM Two tribiocs were used, namely: the SBM 654, and the SBM 9.88. Both have molecular weights of the polystyrene block, between 20,000 and 30,000 g / mole and respective overall compositions (determined by H NMR) of 35/31/34 and 31/38/31 in percentages by weight of polystyrene / polybutadiene / polymethyl methacrylate, syndiotactic at 60%.
• Antioxidant 0.1% by weight (relative to the mixture) of Irganox 1076 (CIBA) has been added to all products.
• the pressure and torque values are fairly stable and sensitive to the fluidity of the product.
• the pressure and torque reductions for the ternary mixes 2 and 3 were noticed as soon as the product change was made in the extruder.
• the mixtures containing triblock are, at worst, as fluid as the control OROGLAS TP327.
• Table IV presents the results of the mechanical tests for each of the products in Table I.
• Table V shows the measurements of the optical properties. The optical measurements are carried out with a spectro-colorimeter (illuminant D65, observation angle 2 °, values recorded at 560nm) on plates of 100 x 100 x 3 mm.
• Table VI shows the Vicat point measurements (measurement of the thermal resistance of the samples) for each of the products in Table I.
• Tables IV, V and VI make it possible to compare the mechanical and impact resistance properties, as well as the thermal resistance properties of the ternary mixtures SM / SB M / "core-shell" additive which constitute a modality of the invention, by compared to an amorphous thermoplastic SM matrix modified with a conventional core-shell impact additive, but not comprising a block copolymer.
• amorphous thermoplastic SM matrix modified with a conventional core-shell impact additive but not comprising a block copolymer.
• Table V shows that the relative transparency of the ternary mixtures, compared to the control is comparable (very slightly lower) for all the mixtures with the exception of mixture 5 which, once again, is not directly comparable to the control.
• Table VI shows that, for all the ternary mixtures, with the exception of mixture 5, the thermal behavior (Vicat point) of the materials is improved compared to that of the control. Even the mixture 5 which has a lower amount of matrix SM, which should greatly reduce its thermal resistance, has a value close to that of the control which contains more matrix.
• compositions found by the applicant can combine the characteristics of a mechanical modulus (rigidity) equal or greater and of an impact resistance equal to or greater than those of an amorphous thermoplastic polymer matrix modified simply by a conventional impact additive.
• This surprising combination is obtained without significant degradation of the transparency of the materials and with, in addition, a significant improvement in their thermal resistance.
• Table Vil compares the properties of mechanical modulus and breaking energy (related to impact resistance) measured in slow traction
• compositions comprising, according to another form of the invention (that of binary systems, amorphous thermoplastic polymer matrix / block copolymer) an SM matrix and an SBM copolymer, for compared to the matrix SM alone and unmodified shock.
• binary systems amorphous thermoplastic polymer matrix / block copolymer
• SBM copolymer an SBM copolymer
• Table VII shows that in the absence of conventional impact additive of the “core-shell” type, the block copolymer can provide the amorphous thermoplastic matrix with the interesting combination of high mechanical modulus and improved impact resistance.

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• Compositions Of Macromolecular Compounds (AREA)

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• 2003
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