JP7433996B2 - Styrene composition containing long fibers - Google Patents

Description

The present invention relates to compositions comprising long fibers dispersed in a thermoplastic polymer matrix containing one or more styrene polymers, moldable compositions derived from the compositions, and moldable compositions made based on such compositions. Regarding molded products. The present invention also relates to long fibers dispersed in a thermoplastic polymer matrix containing one or more styrene polymers, moldable compositions, and methods of making molded articles.

Thermoplastic polymers are utilized to make molded parts in a variety of industries, such as automobiles, toys, appliances, farm and lawn tractors and implements, medical devices, food service items, electronics parts, and the like. Thermoplastic polymers provide significant advantages to molded articles, such as lower weight, design flexibility, and controlled conductivity than some alternative materials. In some applications, thermoplastic polymers present challenges such as higher liner coefficient of expansion (CLTE), lower modulus of elasticity, lower conductivity, and higher brittleness than alternative materials. Fillers, such as fibers, may be added to improve the CLTE, modulus, and conductivity based on the nature and content of the fibers. The backbone of the thermoplastic polymer can be modified to add elasticity, or the elastomeric polymer can be blended with the base thermoplastic polymer to reduce the brittleness of molded parts derived from thermoplastic materials. Thermoplastic polymer systems containing styrene polymers modified by elastomeric monomers or blended with elastomeric polymers impart very good properties at high temperatures, such as thermal stability, relatively high modulus and good modulus of elasticity. Recognized. Molded parts made from many thermoplastic polymer systems require relatively thick cross-sections (eg, thick walls) to provide the strength and stiffness necessary for the desired application. One advantage of parts molded from thermoplastic systems is that the surface of the molding can be modified to suit functional or aesthetic requirements, and surface-modified parts can be made using several polymer systems and processing techniques. It can be relatively shiny. In some applications, low gloss is desired. This may present further challenges to component manufacturers. Polymer systems based on styrene polymers, especially those modified to impart elastomeric properties, have improved stiffness, modulus and modulus at elevated temperatures, thereby achieving desired properties through the use of thinner cross-sections. make it possible to achieve.

Thermoplastic polymer systems containing styrenic polymers are disclosed, for example, in WO 2011/023541; WO 2005/090451; US 8,030,393 and US 7,135,520, which are hereby incorporated by reference in their entirety. Modified by fibers. Such systems have not achieved commercial success due to problems with pellet fastness, such as poor adhesion of the polymer matrix to the fibers, and poor flowability, which make processing of such materials challenging. Thus, despite the desirable properties of styrenic polymer systems, fiber-modified systems do not impart all of the desired properties and are not processable.

Therefore, what is needed are thermoplastic concentrates containing styrenic polymers and fibers that exhibit improved pellet robustness and flow properties, and thermoplastic concentrates based on styrene polymers and fibers that exhibit improved pellet robustness and flow properties. It is a moldable composition with low water absorption and good elastic retention at high temperatures. It is further desirable that such moldable compositions facilitate the production of molded parts with thinner cross-sections needed to meet service strength requirements and impart low gloss to the grained surfaces. What is needed is a concentrate of fibers in thermoplastic polymer systems containing styrenic polymers that has an improved balance of properties, such as high stiffness, good practical ductility, high thermal performance and good processability; It is a moldable composition derived from this. What is also needed are commercially viable methods of making such concentrates, moldable compositions derived therefrom, and molded parts.

The present invention comprises one or more styrene copolymers containing from about 10 to about 50 weight percent, based on the polymer matrix, of one or more unsaturated nitrile compound-derived monomer units and one or more elastomer monomer units; and 30 to about 90% by weight of one or more polyamides. The present invention relates to a composition in which the styrene copolymer exhibits a melt flow rate of about 6 or greater. In some preferred embodiments, the polymer matrix further comprises one or more components that compatibilize the styrene copolymer and the polyamide, present in an amount greater than or equal to about 0.1% by weight of the polymer matrix. Preferred long fibers include glass or carbon fibers. Preferably, the long fibers have a length of about 3 to about 30 mm. Preferably the fibers are derived from a woven mat or fiber bundle. These compositions are useful for introducing long fibers into a base polymer system, where the base polymer system is a moldable composition that can be utilized to create molded structures for widespread use. It is a thing. The composition of long fibers in a polymer matrix is commonly referred to as a concentrate, ie, a concentrate of long fibers in a polymer matrix. The base polymer system may be referred to as a dilute polymer because the contact of the base polymer with the composition of long fibers in the polymer matrix results in a composition having a lower concentration of long fibers than is contained in the described concentrate. This is because it causes

The present invention also relates to a moldable composition comprising a dilute polymer composition comprising one or more thermoplastic polymers having a melt flow rate of 5 or more, which composition comprises long fibers and polymers as described above. Contains a matrix. The one or more thermoplastic polymers may include one or more polyesters, polycarbonates, polyamides, styrenic polymers, or blends thereof. Preferably, the diluent polymer contains one or more styrenic polymers, or a blend of one or more styrenic polymers and other thermoplastic polymers, such as those disclosed herein. Preferably, the moldable composition contains no more than about 5% elastomer (rubber) component. Preferably, the moldable composition contains about 1% or less of a compound that makes thermoplastic polymers, including styrenic polymers, compatible with polyamides. The invention further relates to molded articles derived from these compositions.

In another embodiment, the present invention provides one or more monomer units containing from about 10 to about 50 weight percent, based on the polymer matrix, of one or more unsaturated nitrile compound-derived monomer units and one or more elastomer monomer units. a styrene copolymer and about 20 to about 90 weight percent of one or more polyamides, the method comprising: The method is such that the styrene copolymer exhibits a melt flow rate of about 6 or higher under ambient conditions. In some embodiments, the method may further include cutting the fiber mat or fiber bundle having a polymer matrix surrounding the fiber mat or fiber bundle into lengths of about 3 to about 30 mm. In some embodiments, the components of the polymer matrix are blended prior to contacting the polymer matrix with the fiber mat or bundle.

The concentrate of fibers dispersed in the polymer matrix of the present invention imparts improved pellet toughness and flowability, and the moldable compositions based on the concentrate of long fibers in the polymer matrix have lower It exhibits water absorption and good elastic retention, facilitates the production of molded parts with thinner cross-sections needed to meet service strength requirements, and can impart low gloss to grained surfaces. Concentrates and moldable compositions derived therefrom provide an improved balance of properties, such as high stiffness, good practical ductility, high thermal performance and good processability. Such concentrates and methods of making moldable compositions and molded parts derived therefrom are commercially viable. Concentrates and moldable compositions can be utilized in a variety of industries, such as automobiles, toys, appliances, farm and lawn tractors and tools, medical devices, food service items, electronic devices, and the like. Examples of parts that may be made from moldable compositions include automotive lift gates, instrument panel carriers, front end carriers, door modulus, seat backs, seat bottoms, radiator fans, interior trim, and cases for electronic devices. Or a housing etc.

The description and figures presented herein are intended to inform those skilled in the art of the invention, its principles and its practical application. Therefore, the specific embodiments of the invention described are not intended to be exhaustive or limiting of the invention. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as can be gleaned from the following claims and are incorporated by reference within the written detailed description.

The present invention relates to concentrates of fibers in thermoplastic polymer systems containing styrene polymers or copolymers. Preferably, the styrenic polymer or copolymer further comprises an elastomeric component. The elastomeric component can include an elastomeric comonomer in the backbone of a styrene copolymer or an elastomeric polymer that is compatible with and blended with the styrene polymer or copolymer. Elastomeric components are often referred to as rubbers based on their properties. The thermoplastic polymer system can include a styrene polymer or copolymer and an elastomeric component. Additionally, the thermoplastic system can include other thermoplastic polymers.

Styrenic polymers generally relate to polymers or copolymers containing polymerized alkenyl aromatic compounds. The alkenyl group is covalently bonded to the aromatic ring such that the compound is preferably polymerizable by free radical polymerization. The compounds may contain one or more aromatic rings, preferably one or two aromatic rings, more preferably one aromatic ring. The aromatic ring may be unsubstituted or substituted with substituents that do not interfere with the polymerization of the styrene polymer, the preparation of the concentrates of the invention, or the shaping of the moldable composition into the desired structure. Good too. Preferably the substituent is halogen or alkyl, more preferably bromine, chlorine or C _1-4 alkyl group, most preferably methyl group. Alkenyl groups contain straight or branched carbon chains having one or more double bonds, preferably one double bond. Alkenyl groups useful in styrene polymers include those that, when attached to an aromatic ring, are capable of polymerization to form styrene polymers or copolymers. Preferably, the alkenyl group has 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, most preferably 2 carbon atoms. Preferred styrene monomers include styrene, alpha methylstyrene, divinylbenzene, n-phenyl-maleimide and chlorinated styrene, and more preferred styrene monomers include alpha methylstyrene and styrene. The styrene copolymer may contain elastomeric comonomers to introduce elastomeric properties to the resulting thermoplastic composition. Any copolymer that may be copolymerized with styrene monomer and introduce some elastomeric properties to the copolymer may be utilized. Examples of types of elastomer comonomers include alkadienes, particularly their conjugated alkadienes. Preferred elastomer monomers include conjugated alkadienes, such as butadiene and isoprene, among others. Most preferred is butadiene. The styrene copolymer may further include comonomers that polymerize with unsaturated groups in the styrene monomer. Preferred monomers copolymerizable with the styrene monomer include acrylates, methacrylates, acrylonitrile, methacrylonitrile, and mixtures thereof, with acrylonitrile being most preferred. Preferred styrene copolymers include styrene alkadiene copolymers, styrene acrylonitrile (SAN) and acrylonitrile-butadiene-styrene (ABS) terpolymers. Preferred styrene copolymers containing elastomeric monomers include acrylonitrile-butadiene-styrene (ABS) terpolymers, styrene-alkadiene copolymer systems, hydrogenated styrene-alkadiene copolymer systems, and the like, including acrylonitrile-butadiene-styrene (ABS) terpolymers. It is more preferable. The styrenic polymer may include a blend of one or more styrene homopolymers and one or more styrene copolymers containing one or more elastomeric comonomers. Copolymers may be random or block copolymers. Preferred styrenic copolymers contain elastomer comonomer at a concentration of about 5% by weight or greater, more preferably about 10% by weight or greater. Preferred styrenic copolymers contain elastomer comonomer at a concentration of about 20% by weight or less, more preferably about 15% by weight or less. Alternatively, the styrene polymer may be blended with an elastomeric polymer. The styrene copolymer may be blended with any elastomeric polymer that forms a homogeneous blend with the styrene copolymer and introduces elastomeric properties to the blend. Examples of elastomeric polymers with which styrene polymers may be blended include styrene copolymers containing the elastomeric comonomers disclosed above, poly(meth)acrylates, poly(meth)acrylonitrile, ethylene-propylene diene rubber, polyalkadienes, Examples include thermoplastic polyurethane. Preferred elastomeric polymers include poly(meth)acrylate, poly(meth)acrylonitrile, ethylene-propylene diene rubber, and the like. The styrenic polymer or copolymer used in the concentrate may be any styrenic polymer or copolymer in which long fibers can be dispersed, but the composition may contain monomer units derived from one or more unsaturated nitrile compounds and one One or more styrene copolymers containing the above elastomer monomer units are included. Most preferably, the styrene polymer or copolymer comprises an acrylonitrile butadiene styrene terpolymer or an acrylonitrile butadiene styrene terpolymer and a styrene acrylonitrile copolymer. In the moldable compositions useful in this invention, the preferred amount of elastomeric monomer or polymer is about 0% by weight or greater, and most preferably about 4% by weight or greater. In the thermoplastic compositions useful in this invention, the preferred amount of elastomer monomer or polymer is about 10% by weight or less, and most preferably about 5% by weight or less. The amount of one or more styrene copolymers in the concentrate is sufficient to improve fiber dispersion in the composition to be reinforced. Preferably, the amount of one or more styrene copolymers utilized in the concentrate is about 10% by weight or more, more preferably about 20% by weight or more, based on the weight of the polymer utilized in the concentrate. , most preferably about 30% by weight or more. Preferably, the amount of one or more styrene copolymers in the polymer composition utilized in the concentrate is about 50% by weight or less, based on the weight of the polymer utilized in the concentrate, and more preferably about 40% by weight. % or less, most preferably about 30% or less by weight.

In one embodiment, the invention is a concentrate of reinforcing fibers in thermoplastic compositions. Preferably, the concentrate contains long fibers, and generally the length of the fibers is based on the length of the pellets or structures made from the fibers and thermoplastic polymer. The length is generally the longest dimension. The length is preferably selected to provide the fiber with improved coefficient of linear expansion, modulus, impact resistance, heat resistance, etc. when incorporated into the final composition. Preferably, the fibers have a length of about 3 mm or more, more preferably about 9 mm or more. Preferably, the fibers have a length of about 30 mm or less, more preferably about 13 mm or less. The fibers may include any fiber that imparts improved coefficient of linear expansion, modulus, impact resistance, heat resistance, etc. when dispersed in the final composition. Exemplary fiber types include polymer fibers, carbon fibers, glass fibers, and the like. The most preferred fibers are carbon and glass fibers, with glass fibers being most preferred. Preferably, the concentration of fiber in the concentrate is about 30% by weight or greater, more preferably about 50% by weight or greater, and most preferably about 60% by weight or greater. The concentration of fiber in the concentrate is about 80% by weight or less, more preferably about 75% by weight or less, and most preferably about 70% by weight or less.

The concentrate further includes one or more polyamides to improve the robustness of the fiber concentrate and the flowability of the concentrate. Any polyamide that provides these benefits may be utilized in the concentrate. Polyamides are reaction products of diamines and dicarboxylic acids. The polyamides used in the blends of the present invention are well known in the art and include semicrystalline and amorphous resins having a molecular weight of at least 5,000 and commonly referred to as nylons. Suitable polyamides include U.S. Patent Nos. 2,071,250; 2,071,251; 2,130,523; 2,130; 948; 2,241,322; 2,312,966; 2,512,606; 3,393,210; 2,071,250; No. 2,071,251; No. 2,130,523; No. 2,130,948; No. 2,241,322: No. 2,312,966; No. 2,512,606 Examples include those listed in the No. Polyamides may be produced by condensation of equal amounts of saturated dicarboxylic acids containing 4 to 12 carbon atoms with diamines, where the diamines contain 4 to 14 carbon atoms. Excess diamine may be used to provide an excess of amine end groups over carboxyl end groups in the polyamide. Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azeramide (nylon 69), polyhexamethylene sebacamide (nylon 610), and polyhexamethylene dodecanoamide (nylon 612). Polyamides include lactams, ie, polycaprolactam, polylaurate lactam, poly-11-aminoundecanoic acid, produced by ring opening of bis(para-aminocyclohexyl)methandodecanoamide). Polyamides prepared by copolymerization of two of the above-mentioned polymers or by terpolymerization of the above-mentioned polymers or their constituents, such as adipic acid, hexamethylene diamine isophthalate copolymers, can also be used in the present invention. Preferably the polyamide is linear with a melting point above 200°C. The term "nylon" as used herein refers to nylon containing conventional formulation ingredients as known to those skilled in the art. Examples of polyamide resins are nylon 4, nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, and the like. These polyamide resins may be used alone or in combination. The amount of polyamide in the concentrate is sufficient to improve the robustness of the fiber concentrate and the flowability of the concentrate. Preferably, the amount of polyamide in the polymer composition utilized in the concentrate is about 30% by weight or greater, more preferably about 40% by weight or greater, based on the weight of the polymer utilized in the concentrate; Most preferably it is about 50% by weight or more. Preferably, the amount of polyamide in the polymer composition utilized in the concentrate is about 90% by weight or less, more preferably about 80% by weight or less, based on the weight of the polymer utilized in the concentrate; Most preferably it is about 70% by weight or less.

The composition utilized to disperse the fibers in the concentrate may further include one or more polymers or copolymers that compatibilize the composition containing the styrene polymer or copolymer and polyamide. Any polymer or copolymer that compatibilizes a composition containing a styrene polymer or copolymer and a polyamide may be utilized. Exemplary compatibilizers include styrene-maleimide copolymers, styrene polymers or copolymers with maleic anhydride grafted to the backbone (e.g., maleic anhydride grafted acrylonitrile-butadiene-styrene (ABS)), acrylamide grafts. Examples of the compatibilizer include acrylonitrile-butadiene-styrene (ABS) and ethylene-styrene-glycidyl methacrylate graft copolymer, and preferred compatibilizers include styrene-maleic acid imide copolymer. The compatibilizer is utilized in an amount sufficient to homogenize the blend of the thermoplastic composition containing the styrene polymer or copolymer and one or more polyamides. Preferably, the amount of compatibilizer is about 0.5% by weight or more, and more preferably about 1% by weight or more, based on the polymer matrix in which the fibers are dispersed. Preferably, the amount of compatibilizer is about 10% by weight or less, and more preferably about 5% by weight or less, based on the polymer matrix in which the fibers are dispersed.

The concentrate may further include impact modifiers. Any impact modifier that improves the impact properties of molded articles made from the concentrate and forms a homogeneous mixture with the polyamide may be utilized. Preferred impact modifiers include elastomeric polyolefins and modified polyolefins. As elastomeric polyolefins, propylene-ethylene copolymers available under the trademarks VERSIFY ^(trademark) plastomers and elastomers, polyolefin elastomers available under the trade marks AFFINITY and AFFINITY GA ^(trademark) polyolefin elastomers and ENGAGE ^(trademark) polyolefin elastomers, trademark INFUSE ^(trademark) Olefin block copolymers available include olefin block copolymers. Preferred modified polyolefins include copolymers of olefins and unsaturated acids, anhydrides, or imides, or copolymers of polyolefins and unsaturated acids, anhydrides, or imides grafted onto the polyolefin backbone. Preferred polyolefins include polyethylene and polypropylene, with polyethylene being preferred. Examples of useful modified polyolefins are ethylene acrylic acid copolymers available from Dow Chemical Midland Michigan under the trademark PRIMACOR resin, and polyethylene grafted with maleic anhydride, available under the trademark AMPLIFY functional polymers. The impact modifier is present in an amount sufficient to improve the impact properties of the molding compositions of the present invention. The impact modifier may be present in an amount of about 1% or more, preferably about 5% or more, and most preferably about 10% or more by weight of the concentrate. The impact modifier may be present in an amount up to about 20%, most preferably up to about 15% by weight of the concentrate.

The concentrate includes fibers dispersed in a polymer matrix as described herein. The amount of polymer composition in the concentrate is selected to facilitate blending of the fibers into the final composition used to make the desired product. Generally, concentrates are used to incorporate fibers into moldable compositions to improve the CLTE and modulus of the moldable composition. The smallest possible amount of polymer matrix is utilized in the concentrate to provide the greatest flexibility in the incorporation of the fibers into the final moldable composition utilized to make the final product. desirable. Preferably, the polymeric composition utilized to disperse the fibers is about 20% by weight of the concentrate, most preferably about 30% or more. Preferably, the polymer matrix utilized to disperse the fibers is no more than about 70% by weight of the concentrate, most preferably no more than about 60%. Preferably, the concentration of fiber in the concentrate is about 30% or more, more preferably 40% or more by weight of the concentrate. Preferably, the concentration of fiber in the concentrate is about 80% or less, more preferably 70% or less by weight of the concentrate. The fibers may have a sizing agent coated on the surface of the fibers. The sizing agent is adapted to improve adhesion of the fibers to the thermoplastic composition in the coating. Any sizing agent that improves the adhesion of the thermoplastic composition to the fibers may be utilized.

In a preferred embodiment, the concentrate is utilized in the form of pellets, the pellets having fibers oriented in the same direction. Preferably the fibers extend the entire length of the pellet. The concentrate is adapted to be blended with the thermoplastic composition to disperse the fibers in the thermoplastic composition. The concentrates described herein may be made of any polymer in which the fibers can be dispersed, such as styrene polymers or copolymers, terephthalates (polyethylene or polybutylene terephthalate), polyesters, polycarbonates, polyamides, or the like. May be used with blends. The thermoplastic composition preferably comprises a styrenic polymer or copolymer as described above. Preferably, the thermoplastic composition contains a styrene copolymer containing an elastomeric monomer, or a styrene polymer or copolymer blended with an elastomeric polymer or copolymer. Thermoplastic compositions containing styrene polymers or copolymers may be further blended with other polymers such as terephthalates (polyethylene or polybutylene terephthalate), polyesters, polycarbonates, polyamides, and the like. In some embodiments, the concentrate may be blended with a mineral-filled polymer composition. Preferably, the thermoplastic composition comprises one or more of styrene acrylonitrile and acrylonitrile-butadiene-styrene.

In a preferred embodiment, the concentrate is blended with a high melt flow rate thermoplastic polymer, more preferably the high melt flow rate thermoplastic polymer comprises a copolymer of one or more styrene monomers and one or more elastomeric monomers. include. Preferably, the high melt flow rate copolymer exhibits a melt flow rate of about 5 or greater, more preferably 10 or greater, even more preferably about 20 or greater, and most preferably about 50 or greater. Preferably, the melt flow rate is less than or greater than about 200. The melt flow rate is preferably determined according to test method ISO 1133, measured at 220° C. and 10 Kg, and the results are quoted in g/10 min.

The concentrate is blended with a thermoplastic polymer composition to provide the desired fiber concentration. The desired fiber concentration is selected to impart selected target properties and is application dependent. The specific weight ratio of concentrate and thermoplastic polymer is based on the desired fiber level in the final product and concentration in the concentrate. Generally, the fiber concentration may be up to about 60% fiber, more preferably up to about 50%, most preferably up to about 40% by weight fiber in the resulting composition. Generally, the fiber concentration may be about 10% or more fiber by weight in the resulting composition, more preferably about 20% or more, and most preferably about 30% or more. The final composition is commonly utilized in thermoplastic compositions, such as colorants, mold release agents, antioxidants, UV stabilizers, heat stabilizers, fillers, storage stabilizers, slip agents, flame retardants, etc. It may contain other ingredients. The concentrate may be made by any known process for forming concentrates containing fibers, particularly long glass fibers. A preferred process for making the concentrates of the invention comprises a polymer composition used to disperse the fibers under conditions such that the fibers are dispersed in a polymer mixture, preferably in the form of fiber bundles or mats. involves passing the substance through a tank containing the substance. Essentially, the fibers are impregnated with a polymer mixture. The polymer can be dispersed in the carrier or melted so that it can be passed through a bath and impregnated with the polymer. The temperature of the bath is selected such that the polymer is in molten form when the fibers pass through the melting bath. After the polymer solidifies and impregnates the fibers, the impregnated fibers are cut to the desired length. In a preferred embodiment, the fibers are in bundles (rovings) and the impregnated bundles are cut transversely to the fiber direction to create pellets. In some embodiments, the impregnated fibers pass through a die to form the impregnated fibers in a direction transverse to the direction of fiber movement. Preferably, the fibers are shaped before the polymer matrix solidifies. Preferably the pellets have a relatively uniform size.

The concentrate of the present invention is blended with one or more thermoplastic polymers, diluent polymers to create a mixture with the desired fiber content. Preferably, the concentrate and thermoplastic polymer are contacted in the molten state with sufficient mixing to uniformly disperse the fibers in the molten polymer. The temperature at which the concentrate and thermoplastic polymer can come into contact is selected such that the polymers present are in a molten state and can be mixed. For styrene polymers or copolymers, the temperature is preferably about 220°C or higher, more preferably about 240°C or higher, and most preferably about 260°C or higher. For styrene polymers or copolymers, the temperature is preferably about 300°C or less, more preferably about 290°C or less, and most preferably about 280°C or less. Any form of mixing that forms a substantially homogeneous mixture of polymer and fibers may be utilized, such as mixers, appropriately equipped extruders, injection molding machines, and the like. A preferred mixing device is a twin screw extruder having a heating zone capable of heating the concentrate and the thermoplastic polymer to melt them and bring them into a molten state. After mixing, the resulting mixture is preferably cooled and formed into a form that allows the mixture to be used to form a desired shape, eg, pellets. Preferably, the pellets include fibers uniformly dispersed throughout the thermoplastic polymer mixture.

Preferably, the moldable composition includes a sufficient amount of polyamide to impart the desired pellet toughness and pellet flow properties. The concentration of polyamide in the mixture can be any concentration that facilitates production of the desired final product. Preferably, the polyamide concentration in the final thermoplastic polymer composition (moldable composition) is about 4% by weight or more, more preferably about 10% by weight or more, and most preferably about It is 15% by weight or more. Preferably, the polyamide concentration in the final thermoplastic polymer composition is about 50% by weight or less, more preferably about 30% by weight or less, and most preferably about 20% by weight or less, based on the fiber-containing polymer mixture. The concentration of fibers in the mixture can be any concentration that facilitates production of the desired final product. The concentration of fibers in the moldable composition is selected to provide the desired thermal deformation, modulus and impact properties. Preferably, the fiber concentration in the final thermoplastic polymer composition (moldable composition) is about 20% by weight or more, more preferably about 30% by weight or more, and most preferably about It is 40% by weight or more. Preferably, the polyamide concentration in the final thermoplastic polymer composition is about 70% by weight or less, even more preferably about 60% by weight or less, and most preferably about 50% by weight or less based on the fiber-containing polymer mixture. . It is desirable to control the amount of elastomeric material (rubber) in the mixture in order to improve the impact resistance, modulus and flow properties of the resulting mixture. The amount of elastomeric material (rubber) is selected to introduce the desired elasticity, modulus and impact resistance as well as flowability into the polymer mixture produced. Flowability refers to the ability to transport the formed polymer mixture used to form the desired product. Preferably, the concentration of elastomeric material (rubber) in the final thermoplastic polymer composition (moldable composition) is about 0.1% by weight or more, more preferably about 1% by weight or more, based on the weight of the mixture. , most preferably about 2% by weight or more. Preferably, the concentration of elastomeric material (rubber) in the final thermoplastic polymer composition (moldable composition) is about 10% by weight or less, more preferably about 5% by weight or less, most preferably about 5% by weight or less, based on the weight of the mixture. Preferably it is about 4% by weight or less. It is desirable to control the amount of compatibilizer in the mixture in order to improve the impact resistance, modulus and flow properties of the resulting mixture. The amount of compatibilizer is selected to improve the impact resistance and strength properties of the polymer mixture produced. Preferably, the concentration of compatibilizer in the final thermoplastic polymer composition (moldable composition) is about 0% by weight or more, more preferably about 0.1% by weight or more, most preferably about 0.1% by weight or more, based on the weight of the mixture. Preferably it is about 0.3% by weight or more. Preferably, the concentration of compatibilizer in the final thermoplastic polymer composition (moldable composition) is about 5% by weight or less, more preferably about 2% by weight or less, and most preferably about 2% by weight or less, based on the weight of the mixture. It is about 1% by weight or less.

The resulting mixture of concentrate and thermoplastic polymer can be formed into the desired product using known molding processes such as, for example, injection molding, compression molding, thermoforming, and the like. In one preferred embodiment, the concentrate and thermoplastic polymer may be mixed and then immediately formed into the final part. Preferably, the concentrate and thermoplastic polymer are mixed in a single screw extruder, then extruded into the desired shape and introduced into a mold, such as an injection mold, to form the desired shape. The mixture is preferably in a molten state when it is extruded or introduced into a mold. The mixtures of the invention can be used to make the various parts described above.

The resulting formed product has improved properties, such as better elastic retention at elevated temperatures, such as 90°C. The targeted properties discussed below are based on the moldable composition exemplified herein having a 35% long glass fiber composition by weight. Preferably, the product exhibits a tensile modulus of about 9,000 N/M ² or greater, more preferably about 10,000 N/M ² or greater, and most preferably about 11,000 N/M ^{2 or} greater by test method ISO 527. Preferably, the product exhibits a tensile yield of about 105 or greater according to test method ISO 527. The molding compositions of the present invention demonstrate a Charpy impact of about 22 kj/M ² or more, more preferably about 30 kj/M ^{2 or} more by test method ISO 179-1Ea. Preferably, the moldable composition exhibits improved processing properties as demonstrated by having a spiral flow rate of about 60 or greater, more preferably about 70 or greater, as determined by test method ISO 22088-3. The products obtained exhibit low sensitivity to water absorption. The molding composition of the present invention has a weight increase of 1% or less after boiling in water for 1 hour, and a decrease in elastic modulus of 10% or less after such exposure. The parts exhibit improved chemical resistance, low coefficient of linear expansion, and low gloss.

"One or more" as used herein means that at least one or more than one of the listed components may be used as disclosed.

Illustrative embodiments of the invention

The following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

A fiber bundle containing continuous fibers with a diameter of about 5-20 μm is passed through a melting bath of the components listed in Table 1 and pelletized to form a 50-60% by weight glass concentrate. The concentrate is in the form of pellets containing fibers of 11 mm length.

ABS is an acrylonitrile-butadiene-styrene terpolymer. SAN is a styrene acrylonitrile copolymer. AO is an antioxidant, specifically IRGANOX ^™ 12076 antioxidant. IM is a functionalized polyethylene impact modifier, maleic anhydride grafted polyethylene. SMI is a styrene maleic imide copolymer. PA6 is polyamide 6, commonly referred to as nylon 6. The formed pellets are blended in a coffee mill for 10 seconds and after the test the blended pellets show a volume in mm before and after the test. The volumes obtained after the mill test are summarized in Table 2. Examples containing >25% PA in the melt bath show improved pellet robustness. The addition of functionalized polyethylene, known as an impact modifier for PA, also shows a positive effect on pellet fastness.

The concentrates of Reference Example 0, Reference Example 1, and Examples 2 to 4 are blended with styrene polymer to prepare test samples. The concentrate is diluted to 35% glass with acrylonitrile-butadiene-styrene (ABS) or styrene acrylonitrile (SAN). The test specimens were tested using test method ISO 179-1eA for Charpy impact, tested using test method ISO 527 for tensile modulus and tensile yield, and tested using test method ISO 75/A for HDT 1.8 MPa without annealing. do. A spiral flow test is carried out in which the material is injected at 260° C. and melted in a 2 mm thick cavity at an injection pressure of 1800 MPa in a tool at 60° C. Chemical resistance is determined using test method ISO 22088-3. A rating of "Poor" means that there is a visual impact on the surface quality, and "OK" means that there is no visual impact on the surface quality. The results are summarized in Table 3.
The results in Table 3 show that the targeted high flow and stiffness are obtained in the styrene phase with the lowest rubber content. For improved yield strength performance, the optimum rubber level is found to be about 2 to about 5% in the final blend. These results also show improvements in yield strength and HDT (heat distortion temperature) for compositions containing 10% PA. Further increases are shown for compositions of 17.5% PA and up to 0.5% compatibilizer. Further increasing the PA content to 26% gives a further jump in the heat resistance of the final blend. The influence of the presence of the compatibilizer itself is demonstrated by the three concentrates listed in Table 4.

Parts by weight, as used herein, refers to 100 parts by weight of the specifically mentioned composition. Any numerical value listed in this application above includes all values from the lower limit to the upper limit in increments of 1 unit, provided that there is also a separation of at least 2 units between any lower limit and any upper limit. Assume that there exists. By way of example, when the amount of a component or the value of a variable process, such as temperature, pressure, time, etc., is stated to be, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70. , 15-85, 22-68, 43-51, 30-32, etc. are intended to be explicitly recited herein. For values less than 1, 1 unit is taken to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These are merely examples of what is specifically intended, and all possible combinations of numerical values between the lowest and highest values recited are likewise expressly recited in this application. should be considered. Unless otherwise stated, all ranges include both endpoints and all numbers between such endpoints. The use of "about" or "approximately" in conjunction with a range applies to both ends of the range. As such, "about 20 to about 30" is intended to cover "about 20 to about 30" including at least the specified endpoint. The term "consisting essentially of" to describe a combination refers to the elements, ingredients, components or steps identified and such other elements, ingredients, components that do not significantly affect the fundamental and novel characteristics of the combination. or contain steps. The use of the term "comprising" or "including" herein to describe a combination of elements, ingredients, components or steps also contemplates embodiments consisting essentially of the element, component, component or step. ing. A plurality of elements, components, components or steps may be provided by a single integrated element, component, component or step. Alternatively, a single integrated element, component, component or step may be divided into separate elements, components, components or steps. Disclosure of "a" or "one" to describe an element, component, component or step is not intended to exclude additional elements, components, components or steps.
Some embodiments of the invention related to the present invention are shown below.
[Aspect 1]
one or more styrene copolymers containing from about 10 to about 50 weight percent, based on the polymer matrix, of monomer units and units derived from one or more unsaturated nitrile compounds and one or more elastomer monomer units; about 30 to about 80 weight percent long fibers dispersed in a composition of about 20 to about 70 weight percent polymer matrix comprising about 90 weight percent of one or more polyamides, the styrene copolymer comprising: The composition has a melt flow rate of about 6 or more.
[Aspect 2]
The composition of embodiment 1, wherein the one or more styrene copolymers contain from about 5 to about 20 weight percent elastomeric monomer units.
[Aspect 3]
The composition according to aspect 1 or 2 above, wherein the long fibers include glass or carbon fibers.
[Aspect 4]
The composition according to any one of aspects 1 to 3 above, wherein the long fibers have a length of about 3 to about 30 mm.
[Aspect 5]
A composition according to any one of the preceding embodiments, wherein the fibers are derived from a woven mat or fiber bundle.
[Aspect 6]
The composition of any one of the preceding embodiments, wherein the polymer matrix comprises from about 20 to about 50% by weight styrene copolymer and from about 50 to about 80% by weight polyamide, based on the polymer matrix.
[Aspect 7]
A moldable composition comprising a dilute polymer composition comprising a thermoplastic polymer containing one or more styrenic polymers having a melt flow rate of 5 or more and a composition according to any one of the preceding embodiments. The moldable composition comprises an elastomer component in an amount of less than 5% by weight or an amount of one or more compounds that compatibilizes the styrene copolymer and the polyamide in an amount of less than or equal to 1% by weight.
[Aspect 8]
8. A moldable composition according to aspect 7, wherein the dilute polymer composition comprises one or more styrenic polymers or copolymers.
[Aspect 9]
Aspect 8 above, wherein the one or more thermoplastic polymers other than styrenic polymers or copolymers comprises one or more polyesters, polycarbonates, polyamides, blends thereof, or blends with one or more styrenic polymers or copolymers. moldable composition.
[Aspect 10]
Any one of embodiments 7 to 9 above, comprising less than about 5% by weight of the elastomeric component and less than or equal to 1% by weight of the polymer matrix of one or more compounds that compatibilize the styrene copolymer and the polyamide. The moldable composition described in .
[Aspect 11]
Any one of embodiments 7-10 above, comprising from about 25 to about 40% by weight of one or more polyamides and from about 10 to 60% by weight long fibers, said percentages being based on the weight of said composition. The moldable composition described in .
[Aspect 12]
The moldable composition of any one of embodiments 7-11 above, containing up to about 5% elastomer component.
[Aspect 13]
A moldable composition according to any one of embodiments 7 to 12 above, comprising less than or equal to 1% by weight of a polymer matrix of one or more compounds that compatibilizes the styrene copolymer and the polyamide.
[Aspect 14]
The moldable composition according to any one of embodiments 7 to 13 above, further comprising an impact modifier.
[Aspect 15]
15. The moldable composition according to aspect 14, wherein the impact modifier comprises a modified polyolefin.
[Aspect 16]
An article comprising the molding composition according to any one of aspects 7 to 15 above.
[Aspect 17]
A method comprising contacting a fiber mat or fiber bundle with a mixture according to any one of aspects 1 to 6 above under conditions such that the fiber mat or fiber bundle is surrounded by a polymer matrix.
[Aspect 18]
18. The method of claim 17, further comprising cutting the fiber mat or fiber bundle having the polymer matrix surrounding the fiber mat or fiber bundle into lengths of about 3 to about 30 mm.
[Aspect 19]
18. The method of embodiment 16 or 17 above, wherein the components of the polymer matrix are blended prior to contacting the polymer matrix with the fiber mat or bundle.
[Aspect 20]
A method comprising molding the composition according to any one of aspects 7 to 15 above to form a molded article.

Claims (10)

A moldable composition comprising:
(A) a dilute polymer composition comprising a thermoplastic polymer containing one or more styrenic polymers having a melt flow rate of 5 or more as determined according to test method ISO 1133 measured at 220° C. and 10 kg;
(B) a composition in the form of pellets ;
and said composition (B) has a length of 3 mm to 30 mm in an amount of 50 to 80% by weight of said composition (B) dispersed in a polymer matrix of 20 to 50% by weight of said composition (B). The polymer matrix contains one or more monomer units derived from one or more unsaturated nitrile compounds and one or more elastomer monomer units in an amount of 10 to 40% by weight based on the polymer matrix. of a styrene copolymer and 50 to 90% by weight of one or more polyamides, said styrene copolymer exhibiting a melt flow rate of 6 or more as determined according to test method ISO 1133 measured at 220° C. and 10 kg, and said diluted The polymer and composition (B) are characterized in that the moldable composition comprises less than 5% by weight of the one or more elastomeric monomer units contained in the one or more styrenic copolymers; The moldable composition, wherein the amount of polyamide in the moldable composition is from 4% to less than 50% by weight of the moldable composition. The moldable composition of claim 1, wherein the amount of the one or more elastomer monomer units included in the one or more styrenic copolymers is 0.1% or more by weight based on the moldable composition. Composition. A moldable composition according to claim 1 or 2, wherein the amount of polyamide is from 4% to 30% by weight of the moldable composition. A moldable composition according to any one of claims 1 to 3, wherein the styrenic copolymer in composition (B) has an amount of the one or more elastomeric monomer units from 5% to 15% by weight. thing. A method of forming an article, the method comprising:
(i) providing a fiber-containing composition (B) in the form of pellets , said composition (B) being dispersed in a polymer matrix of 20 to 50% by weight of said composition (B); The composition (B) contains 50 to 80% by weight of long fibers with a length of 3 mm to 30 mm , and the polymer matrix contains 10 to 40% by weight of one or more unsaturated nitriles based on the polymer matrix. one or more styrene copolymers containing compound-derived monomer units and one or more elastomeric monomer units and 50 to 90% by weight of one or more polyamides, said styrene copolymers being measured at 220° C. and 10 kg. a process that exhibits a melt flow rate of 6 or more as determined according to test method ISO 1133;
(ii) separately providing a dilute polymer composition comprising a thermoplastic polymer containing one or more styrenic polymers having a melt flow rate of 5 or more as determined according to test method ISO 1133 measured at 220° C. and 10 kg; ,
(iii) blending the fiber-containing composition and the diluted polymer composition to form a mixture;
(iv) heating the mixture to a temperature sufficient to cause the mixture to melt and form a moldable composition; and (v) molding the moldable composition to form an article.
A method of forming an article, including: 6. The method of claim 5, wherein the polyamide is present in an amount of 4% to 30% by weight of the moldable composition. the moldable composition has the one or more elastomeric monomer units contained in the one or more styrenic copolymers in an amount from 0.1% to 5% by weight of the moldable composition; The method according to claim 5 or 6. A method according to any one of claims 5 to 7, wherein the diluted polymer composition has a melt flow rate of 10 or more. A method according to any one of claims 5 to 8, wherein the dilute polymer composition comprises a styrene polymer or styrene copolymer. A method according to any one of claims 5 to 9, wherein the dilute polymer composition comprises styrene acrylonitrile or an acrylonitrile-butadiene-styrene copolymer.