Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to a composition of a blend of polyamide resin and of polyester resin with improved compatibility, and more particularly a composition of a blend with improved compatibility between the above two resins, which are generally known to be incompatible with one another.
• Polyamide resin possesses better mechanical, chemical, and thermal properties and properties of adherence to paint, etc., and is therefore used in many areas.
• a polyamide resin has low dimensional stability and the mechanical properties of the polyamide resin decrease with absorption of water. Accordingly, there has been an attempt to improve the properties of the polyamide resin by mixing polyamide resin in the molten state with another thermoplastic resin (for example, a polyester resin) to form a mixture in the molten state.
• a thermoplastic polyamide resin displays low compatibility with a thermoplastic polyester resin, a mixture formed only from the two resins has poor processability and properties.
• U.S. Pat. No. 4,150,674 describes the use of a lactam terpolymer as a compatibilizer when mixing a polyamide resin with a polyester resin and the use of the product thus obtained for fabrics.
• U.S. Pat. No. 5,055,509 describes the introduction of arylphosphonyl nitride as compatibilizer.
• the effects of compatibilization of these compounds have not been clearly verified and the resultant products do not give the required properties.
• the aim of the present invention is to propose a composition of a blend of a polyamide resin and of a polyester resin that has improved compatibility.
• Another aim of the present invention is to propose a resin blend composition of a thermoplastic polyamide resin and of a thermoplastic polyester resin whose mechanical properties (properties of strength, bending strength, elasticity, abrasion resistance, impact strength), chemical properties (resistance to solvents), heat resistance, dimensional stability, combability, etc. are improved.
• the present invention proposes a resin blend composition of a polyamide resin and of a polyester resin with improved compatibility, which comprises a) a polyamide resin, b) a polyester resin and c) an epoxy resin.
• composition according to the present invention is a composition of a blend of a polyamide resin and of a polyester resin displaying improved compatibility, which comprises at least:
• thermoplastic polyamide resin from 1 to 98 wt. % of a thermoplastic polyamide resin
• the polyamide resin included in the composition of the present invention can be any thermoplastic polyamide resin.
• a polyamide resin can comprise a polyamide-6 that can be obtained as products of ring-opening polymerization of lactams such as ⁇ -caprolactam and ⁇ -dodecalactam; polyamide polymers that can be obtained from amino acids such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; aliphatic, cycloaliphatic or aromatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonahexamethylenediamine, m-xylenediamine, p-xylenediamine, 1,3-bisaminomethylcyclohexane,
• examples of the polyamide resin can comprise polyamide-6, polyamide-66, polyamide-610, polyamide-11, polyamide-12, polyterephthalamide, polyisophthalamide, and polyaramids.
• the polyamide matrix can notably be a polymer comprising branched or hyperbranched star or H macromolecular chains, and possibly linear macromolecular chains.
• the polymers comprising said star or H macromolecular chains are described for example in documents FR2743077, FR2779730, U.S. Pat. No. 5,959,069, EP0632703, EP0682057 and EP0832149.
• the polyamide matrix of the invention can be a polymer of the random tree type, preferably a copolyamide having a random tree structure. These copolyamides of random tree structure as well as the method of production thereof are notably described in document WO99/03909.
• the matrix of the invention can also be a composition comprising a linear thermoplastic polymer and a star, H and/or tree thermoplastic polymer as described above.
• the matrix of the invention can also comprise a hyperbranched copolyamide of the type of those described in document WO 00/68298.
• the composition of the invention can also comprise any combination of linear, star, H, tree, hyperbranched copolyamide thermoplastic polymer as described above.
• the relative viscosity of the polyamide resin can vary from 2.0 to 3.7 (a solution of 1 g of polymer in 100 ml of 90% formic acid, measured at 25° C.). In another embodiment, the number-average molecular weight of the polyamide resin can vary from about 5000 to 70 000.
• the content of the polyamide resin can be selected according to the required properties.
• the polyamide resin can be included in an amount from 1 to 98 wt. % relative to the total weight of the composition.
• the polyester resin included in the composition of the present invention can be a polymeric compound that has ester bonds in its backbone.
• polyester resin can comprise a homopolymer or a copolymer that can be obtained by condensation of a dicarboxylic acid (or of its derivatives that can form an ester) with a diol (or its derivatives that can form an ester), or a mixture thereof.
• an example of dicarboxylic acid can comprise an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-, 1,5-, 2,6- or 2,7-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether carboxylic acid, 5-sodium sulfoisophthalic acid, etc.; an aliphatic dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, etc.; a cycloaliphatic dicarboxylic acid such as 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, etc.; and derivatives thereof that can form an ester, but without being limited thereto.
• aromatic dicarboxylic acid such as terephthalic
• said dicarboxylic acid can be used in the form of a derivative that can form an ester such as a derivative substituted with an alkylalkoxy, or a halogen, etc., and an ester obtained from a lower alcohol, e.g. dimethyl ester.
• examples of said diols can comprise an aliphatic glycol with 2 to 20 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc.; a long-chain glycol with a molecular weight from 400 to 6000 such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc.; and derivatives thereof that can form an ester, but without being limited thereto.
• said diols can be used in the form of their derivatives that can form an ester such as a derivative substituted with an alkyl group, alkoxy group or a halogen, etc.
• examples of homopolymer or copolymer of the latter can comprise polybutylene terephthalate, polybutylene (terephthalate/isophthalate), polybutylene (terephthalate/adipate), polybutylene (terephthalate/sebacate), polybutylene (terephthalate/decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate/isophthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/5-sodium sulfoisophthalate), polybutylene (terephthalate/5-sodium sulfoisophthalate), polypropylene terephthalate, polyethylene naphthalate, polycyclohexanedimethylene terephthalate, but without being limited thereto.
• polyester resin other than the above compounds can comprise a polyester resin copolymerized with a copolymerizable monomer, e.g. a hydroxycarboxylic acid such as glycolic acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, etc.; and a lactone compound such as propiolactone, butyrolactone, caprolactone, valerolactone, etc.
• a hydroxycarboxylic acid such as glycolic acid, hydroxybenzoic acid, hydroxyphenylacetic acid, naphthylglycolic acid, etc.
• a lactone compound such as propiolactone, butyrolactone, caprolactone, valerolactone, etc.
• examples of polyester resin can comprise a polyester resin derived from compounds forming a multifunctional ester such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimesic acid, pyromellitic acid or a polyester resin having a branched or crosslinked structure in an amount at which the polyester resin maintains thermoplasticity.
• a polyester resin derived from compounds forming a multifunctional ester such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimesic acid, pyromellitic acid or a polyester resin having a branched or crosslinked structure in an amount at which the polyester resin maintains thermoplasticity.
• the content of polyester resin can be selected according to the required properties.
• the polyester resin can be included in an amount from 1 to 98 wt. % relative to the total weight of the composition.
• the polyester resin can notably be a recycled polyester notably obtained from articles at the end of their useful life or production wastes. These polyesters can be obtained from textile goods, bottles, films or industrial plastics, notably composites.
• the polyesters can be used directly or after one or more possible treatments, notably of hydrolysis or with the aim of separating the fillers and additives from the polyester compositions.
• the waste can for example be crushed or ground in the form of fragments, powders or granules.
• a compound having two epoxy groups or more per molecule can be used in an epoxy resin. If an epoxy resin is added, it is possible to obtain, by chemical bonding between a polyamide and/or a polyester, a blend of resins with improved compatibility between the polyamide resin and the polyester resin.
• examples of the epoxy resin can comprise an epoxy resin of the DGEBA (diglycidyl ether of bisphenol A) type, an epoxy resin of the DGEBF (diglycidyl ether of bisphenol F) type, an epoxy resin of the hydrogenated BPA (hydrogenated bisphenol A) type, a brominated epoxy resin, a cycloaliphatic epoxy resin, an epoxy resin of the aliphatic polyglycidyl type, an epoxy resin of the glycidyl amine type, etc., but without being limited thereto.
• the epoxy resin can be used alone or as a combination of two or more types.
• the epoxy resin can be obtained, for example, by reaction of bisphenol A, of bisphenol F, of hydrogenated or brominated bisphenol A or bisphenol F, or of compounds having two or more hydroxyl groups with epichlorohydrin, or can be readily obtained commercially.
• the number of functional groups of the epoxy resin can be one or more, for example, four or more, depending on the degree of polymerization and the form of the chemical substance.
• the epoxy resin can be either in the form of a liquid phase or of a solid phase.
• the epoxy equivalent weight can vary in the range from 2100 to 6000 g/eq, and preferably in values greater than 2200 g/eq, more preferably greater than 2300 g/eq, even more preferably greater than 2500 g/eq; notably in the range from 2200 to 6000 g/eq, in the range from 2300 to 6000 g/eq or in the range from 2500 to 6000 g/eq.
• an epoxy resin having an epoxy equivalent weight below the aforementioned range, the viscosity of the composition of the blend of resins increases, with a consequent deterioration of processability.
• the epoxy equivalent weight (EEW) of a resin can be measured by various known methods. We may notably mention the standards JIS K 7236-1986, ASTM D1652-73, and ISO 3001-1978. In the case of a distribution of the epoxy equivalent weight for an epoxy resin, the average value is taken into account.
• the content of epoxy resin can vary from 0.01 to 10 wt. % relative to the total weight of the composition. In another embodiment, the content of epoxy resin can vary from 0.05 to 7 wt. %, or from 0.1 to 5 wt. %. If the content of epoxy resin exceeds the above ranges, for example, the viscosity of the composition of the blend of resins can increase and/or the fluidity of the composition deteriorates, with a consequent deterioration of processability and causing problems during processing.
• a composition of a blend of resins can moreover comprise other polymeric resins, for example, polyethylene, polystyrene, polypropylene, ABS resin, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polyacetal, polysulfone, polyether sulfone, polyetherimide, polyether ketone, a polylactic acid resin, a polysulfone resin, an elastomer resin or mixtures thereof.
• polymeric resins for example, polyethylene, polystyrene, polypropylene, ABS resin, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polyacetal, polysulfone, polyether sulfone, polyetherimide, polyether ketone, a polylactic acid resin, a polysulfone resin, an elastomer resin or mixtures thereof.
• composition can comprise fibrous and/or nonfibrous fillers.
• fibrous fillers we may mention glass fibers, carbon fibers, natural fibers, aramid fibers, and nanotubes, notably of carbon.
• natural fibers we may mention hemp and flax.
• nonfibrous fillers we may notably mention all particulate and lamellar fillers and/or exfoliating or nonexfoliating nanofillers such as alumina, carbon black, aluminosilicate clays, montmorillonites, zirconium phosphate, kaolin, calcium carbonate, diatoms, graphite, mica, silica, titanium dioxide, zeolites, talc, wollastonite, polymeric fillers such as, for example, particles of dimethacrylates, glass beads or glass powder.
• the composition comprises several types of reinforcing fillers.
• the filler used most can be glass fibers, of the so-called chopped type, notably having a diameter between 7 and 14 ⁇ m.
• These fillers can have surface oiling that ensures mechanical adhesion between the fibers and the polyamide matrix.
• the concentration by weight of reinforcing fillers or simple fillers is advantageously between 1 and 60 wt. % relative to the total weight of the composition, preferably between 15 and 50 wt. %.
• the composition can also comprise agents for modifying impact strength. It is generally elastomeric polymers that can be used for this purpose. Agents for modifying resilience are generally defined as having a tensile modulus ASTM D-638 less than about 500 MPa. Examples of suitable elastomers are ethylene-acrylic ester-maleic anhydride, ethylene-propylene-maleic anhydride, EPDM (ethylene-propylene-diene monomer) optionally with a grafted maleic anhydride. The concentration by weight of elastomer is advantageously between 0.1 and 30% relative to the total weight of the composition.
• Agents for modifying impact strength comprising functional groups that are reactive with the polyamide are notably preferred.
• the proportion by weight of these agents in the total composition is notably between 0.1 and 40%.
• additives such as antioxidants, thermal stabilizers, absorbers of UV radiation such as aromatic amines, hindered phenols, phosphorus and sulfur, etc., dispersants, dyes, pigments, surface-active agents, stripping agents, lubricants, plasticizers, agents for improving lustre, which are generally used as agents for treatment of plastics, can be used for imparting various effects.
• the composition according to the present invention can notably comprise fireproofing agents generally used in the field of polyamides; i.e. compounds for decreasing the spread of flames and/or having fireproofing properties, which are well known by a person skilled in the art.
• fireproofing agents are usually employed in fireproofed compositions and are notably described, for example, in U.S. Pat. No. 6,344,158, U.S. Pat. No. 6,365,071, U.S. Pat. No. 6,211,402 and U.S. Pat. No. 6,255,371, cited here as reference.
• composition comprises at least one fireproofing agent selected from the group comprising:
• a synergistic combination of compounds containing phosphorus is notably preferred, such as oxides of phosphines, phosphonic acids or salts thereof or phosphinic acids or salts thereof, and cyclic phosphonates; with nitrogen-containing derivatives such as melam, melem, melamine phosphate, melamine polyphosphates, melamine pyrophosphates or ammonium polyphosphates.
• the composition can comprise from 1 to 40 wt. % of fireproofing agents, relative to the total weight of the composition.
• the composition of the resin blend of polyamide resin and of polyester resin can be obtained by mixing the components in the molten state by means of a conventional extruder, for example a single-screw extruder or a twin-screw extruder, etc.
• a general range for the temperature of the barrel inside the extruder can be adjusted taking into account the melting point of the resin.
• the temperature can be set at 250° C.
• the temperature can be set at 280° C.
• the resin blend composition of the present application can be processed into desired forms such as a pellet, a flat product, a fiber, a strand, a film, a sheet, a pipe, a hollow body, a box, etc., by processing techniques such as conventional calandering, compression molding, blow-molding, injection molding, fusion molding, etc., but the forms or methods of treatment are not limited to these.
• composition according to the present invention can be used according to the general use of a polyamide resin or of a polyester resin.
• a polyamide resin or of a polyester resin For example, it can be applied in various ways to general accessories of precision machinery, to automobile accessories, to electrical-electronic accessories, to materials of construction, to films, to fibers, to sports equipment, etc.
• the resin blend composition of the present invention and the comparative composition are prepared, respectively, and their tensile strength, their elongation in tension, their processability, etc., are then compared, on the basis of which the superior effects of the resin blend composition of polyamide resin and polyester resin of the present invention are described in detail.
• A-1 Polyamide-66 thermoplastic resin ⁇ trade name: Technyl 23A, manufactured by Rhodia ⁇ .
• A-2 Polyamide-6 thermoplastic resin ⁇ trade name: Toplamide 1011, manufactured by Hyosung ⁇ .
• B-1 Polyethylene terephthalate resin ⁇ trade name: ESLON PET-2211, manufactured by Woongjin Chemical ⁇ .
• B-2 Polybutylene terephthalate resin ⁇ trade name: TRIBIT 1500 NA, manufactured by Samyang Corporation ⁇ .
• C-3 Ethylene resin grafted with a glycidyl methacrylate group. Trade name: Lotarder A8900, manufactured by Arkema.
• the components selected above are mixed uniformly in a super-mixer according to each mixture ratio of the examples and comparative examples.
• the temperatures of the barrel inside the extruder are set to about 250° C. when the polyamide-6 resin is used, and to about 280° C. when the polyamide-66 resin is used, taking into account the melting point of the resin used, and the gas within the screws is exhausted at a rotary speed of the screws from 250 to 300 rev/min and a vacuum pump pressure from to 70 cm Hg.
• the components are perfectly mixed inside the extruder barrel and the strand formed is cooled rapidly in a bath of cold water and pelletized at a specified size using a pelleter.
• An injection molding machine German, ENGEL having a closing force of 80 tonnes and an injection volume of 189.44 cc (6.4 oz) is used for preparing samples for the various tests of properties. After preparing the sample of the composition by molding in conditions of a molding temperature in the general range taking account of the melting point of the resin used, a molding temperature of 80° C., an injection pressure from 50 to 80 bar, an injection speed from 40 to 60 mm/s, an injection time of three seconds and a cooling time of fifteen seconds.
• Example 2 Example 3
• Example 4 Example 5
• Example 6 A-1 57 57 40 59.7 A-2 57 40 B-1 40 57 40 B-2 40 40 57 C-1 3 3 3 3 3 3 0.3
• Tensile 80 79 71 67 56 79 strength (MPa) Elongation in 120 70 90 130 100 30 tension (%) Peeling 5 5 5 5 5 5 5 5 5 5
• compositions comprising recycled polyesters
• the protocol is the same as mentioned above.
• the components selected above are employed according to each mixture ratio of the examples and are presented in the following table, with the properties indicated.
• Example 10 Example 11 A-1 58.8 58.8 58.8 B-1 39.2 19.6 — B-3 — 19.6 29.2 C-1 1.5 1.5 1.5 1.5
• the organophosphorus compound is Exolit OP1230 from the company Clariant.
• MPP is melamine polyphosphate.
• a blend according to the present invention makes it possible to obtain quite remarkable fireproofing properties, while using a smaller amount (30% reduction) of fireproofing agents in the formulation.
• the protocol is the same as mentioned above.
• the components are employed according to each mixture ratio of the examples and are presented in the following table, with the properties indicated.
• the red phosphorus is RPM 460 FerroFlam.
• a blend according to the present invention makes it possible to obtain quite remarkable fireproofing properties while using a smaller amount (40% reduction) of fireproofing agents in the formulation.
• a composition of a blend of resins with remarkably improved compatibility can be obtained by adding a specific epoxy resin to a blend of a polyamide resin and of a polyester resin, which are well known for having no compatibility.
• the blend of resins with improved compatibility can have excellent properties such as mechanical properties (strength properties, bending strength, elasticity, abrasion resistance, impact strength), chemical properties (resistance to solvents), heat resistance, dimensional stability, combability, etc.

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• 2010
  • 2010-06-18 KR KR1020187032908A patent/KR101999081B1/ko active IP Right Grant
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