KR100523915B1 - Blends Composition of Polycarbonate and Polyolefin - Google Patents

Abstract

The present invention relates to a blend composition of polycarbonate and polyolefin, 1 to 99 parts by weight of polycarbonate resin, 1 to 99 parts by weight of olefinic homopolymer or copolymer and 0.1 to Modified olefin homopolymer or copolymer having amino group introduced therein By including 30 parts by weight, it is possible to improve the compatibility of the polycarbonate and polyolefin blend to have excellent properties such as impact resistance, heat resistance, light weight.

Description

Blend Composition of Polycarbonate and Polyolefin

The present invention relates to blend compositions of polycarbonates and polyolefins. More particularly, the present invention relates to a blend composition of polycarbonate and polyolefin comprising a modified olefin homopolymer or copolymer having an amino group introduced therein, in order to improve their compatibility. .

Polycarbonate resin is a useful engineering plastic widely used in various fields such as electric, electronics, home appliances, precision machinery, and automobiles because of its excellent impact resistance, dimensional stability, transparency, self-extinguishing mechanical strength and heat resistance and low molding shrinkage. . However, the existing polycarbonate resin has a disadvantage in that the impact strength is sharply reduced at a site where stress is concentrated when the molded product is manufactured because of its high use environment, residual stress, and notch sensitivity. In addition, since the fluidity is lower than that of other thermoplastic resins, high processing temperatures are required during molding, resulting in thermal decomposition of the resin due to overheating and a decrease in molecular weight thereof, and easily decomposed into strong acids and strong alkalis.

Many studies have been made to improve the disadvantages of such polycarbonate resins. The most known method among these studies is a method of introducing an impact modifier or an olefin resin into a polycarbonate resin. U.S. Patent No. 4,245,058 discloses a method of adding an olefinic resin such as polypropylene and an acrylic copolymer to a polycarbonate resin to increase impact resistance. However, when a polyolefin resin, such as polypropylene or polyethylene, is introduced in a predetermined amount or more, there are many limitations in practical applications due to the peeling phenomenon due to the weak compatibility between the polycarbonate resin and the olefin resin.

In order to improve such weak compatibility, Korean Patent Application Nos. 1997-0058181, 1999-7004650, and the like disclose modified modified olefin resins in which a reactor is introduced to increase the compatibility of a blend of polycarbonate resin and olefin resin. Although it was formulated and improved the physical properties as an additive, the reaction was not performed smoothly by the reactor introduced into the modified olefin system used to increase the compatibility did not act as an effective compatibilizer.

U.S. Patent No. 4,496,693 attempts to increase the compatibility of the blend and improve the physical properties by adding a metal catalyst to the polycarbonate resin and the olefin resin, but the impact resistance is reduced by the molecular weight of the polycarbonate is reduced by the added metal catalyst It was.

US Patent Nos. 3,130,177, 4,472,554, 4,390,657, 4,847,153, 4,886,855 and the like are prepared by blending acrylonitrile-butadiene-styrene copolymer (ABS) on polycarbonate resin to increase impact strength. This resin is widely used in electrical and electronic products and automotive interior materials while having excellent physical properties. However, since the blend of the polycarbonate resin and the acrylonitrile-butadiene-styrene copolymer is a blend of incompatible resins, specific processing conditions and specific use conditions are required, and physical properties change significantly depending on the molding conditions. In addition, increasing the content of acrylonitrile in order to increase chemical resistance lowers the compatibility and it is difficult to maintain an appropriate impact strength.

In order to solve the above problems, the present invention, in the blend composition of polycarbonate and polyolefin, including modified olefin homopolymer or copolymer with amino group introduced to improve the compatibility of the blend, impact resistance, chemical resistance, fluidity An object of the present invention is to provide a blend composition of polycarbonate and olefin having excellent physical properties.

The above and other objects of the present invention can be achieved by the present invention described below.

The present invention to achieve the above object (a) 1 to 99 parts by weight of polycarbonate resin; (b) 1 to 99 parts by weight of an olefinic homopolymer or copolymer; And (c) 0.1 to 30 parts by weight of a modified olefin homopolymer or copolymer having an amino group introduced therein, to provide a blend composition of polycarbonate and polyolefin.

The present invention may further comprise 0.1 to 150 parts by weight of the (d) additive based on 100 parts by weight of the polycarbonate in the blend composition of (a), (b) and (c).

The polycarbonate resin of (a) may have a weight average molecular weight of 8,000 to 120,000 g / mol and a melt index of 1 to 20 g / 10 min.

The polycarbonate resin of (a) may be a linear or branched homopolymer and copolymer.

The olefin homopolymer or copolymer of (b) may be a homopolymer polymerized by selecting one of C ₂ to C ₈ olefin monomers or a copolymer copolymerized by selecting one or more of the monomers. have.

The modified olefin homopolymer or copolymer in which the amino group of (c) is introduced has a monomer having an amino group selected from the group consisting of primary, secondary, tertiary amines and derivatives thereof in the olefin homopolymer or copolymer. It may be grafted to a graft rate of 10% by weight.

The additive of (d) may be at least one selected from the group consisting of impact modifiers, inorganic fillers, ultraviolet absorbers, heat stabilizers, antioxidants, flame retardants, lubricants, pigments and dyes.

The impact modifier may be an olefinic or acrylic impact modifier, and the inorganic filler may be one selected from the group consisting of glass fibers, carbon fibers, talc, silica, mica, and alumina.

Hereinafter, the present invention will be described in detail.

In the blend of polycarbonate and polyolefin, the present invention provides a polyolefin comprising a modified olefin homopolymer or copolymer having an amino group introduced therein to increase the compatibility of the blend while maintaining excellent physical properties such as impact resistance, chemical resistance, and fluidity. It is characterized in providing a blend composition of carbonate and olefin.

That is, the blend composition of the polycarbonate and polyolefin of the present invention consists of a polycarbonate resin, an olefin homopolymer or copolymer, and a modified olefin homopolymer or copolymer having an amino group introduced therein.

The polycarbonate resin is not particularly limited as long as it is a linear or branched homopolymer and copolymer, but the polycarbonate main chain contains an aromatic diol residue such as phenylene, biphenylene, naphthalene, anthrylsen, or bis (hydroxy). Phenyl) divalent phenolic compounds such as alkylidene, bisphenol-A and substituents such as halogen, alkyl, acyl and the like are preferable.

Further, the polycarbonate resin has a weight average molecular weight of 8,000 to 120,000 g / mol, more preferably 30,000 to 70,000 g / mol, a melt index of 1 to 20 g / 10 min (300 ° C., 1.2 kgf), more preferably 5 It is preferable that it is to 15 g / 10min. When the weight average molecular weight is less than 8,000 g / mol, the fluidity is improved but the impact strength is significantly reduced. When the weight average molecular weight is more than 120,000 g / mol, the impact strength increases but the fluidity decreases, resulting in poor moldability.

In the present invention, the content of the polycarbonate resin as described above is preferably adopted within the range of 1 to 99 parts by weight, but if the content of the polycarbonate resin is reduced within the above range, the chemical resistance increases, but the impact resistance, rigidity and heat resistance When the polycarbonate resin is increased, mechanical properties such as stiffness and impact strength and heat resistance are excellent, but the thickness dependency of impact strength is increased, and fluidity and chemical resistance are deteriorated. Therefore, the content can be appropriately adjusted according to the product of the property to be implemented, the content of the polycarbonate resin is 40 to 80 parts by weight can be obtained a resin product of overall good physical properties.

In the present invention, an olefin homopolymer or copolymer is blended with a polycarbonate resin to improve a polycarbonate resin having high notch sensitivity, high impact resistance, high thickness resistance, low impact strength due to residual stress, and low chemical resistance. .

The olefin homopolymer or copolymer is a homopolymer polymerized by selecting one of C ₂ to C ₈ olefin monomers such as ethylene, propylene, isopropylene, butylene, isobutylene, or octene, or It may be a copolymer copolymerized by selecting one or more of these monomers.

In addition, the olefin polymer may be prepared using a general Ziegler-Natta catalyst, and may be prepared using a metallocene catalyst to make a more selective structure.

In addition, the composition of the present invention comprises a modified olefin homopolymer or copolymer introduced with an amino group to improve the compatibility between the polycarbonate resin and the olefin polymer as described above, wherein the modified amino acid introduced Olefin polymers include polyethylene, polypropylene, ethylene-propylene copolymers, Grafting a monomer having an amino group selected from the group consisting of primary, secondary, tertiary amines and derivatives thereof in an olefinic homopolymer or copolymer such as ethylene-octene copolymer at a graft rate of 0.1 to 10% by weight desirable. More preferably, it is 0.5-8 weight%. In addition, a modified olefin homopolymer or copolymer having an amino group introduced therein may be prepared using a modified olefin homopolymer or copolymer including a carboxylic acid anhydride group, an epoxy group, a hydroxyl group, a carboxyl group, or an oxazoline group. At the terminal is an amino group selected from the group consisting of primary, secondary, tertiary amines and derivatives thereof, and at the other terminal a reactor capable of reacting with a carboxylic acid anhydride group, an epoxy group, a hydroxy group, a carboxyl group and an oxazoline group. The modified olefin homopolymer or copolymer into which the amino group is introduced may be prepared by reacting with the reaction reagent having the same.

In the present invention, the content of the modified olefin homopolymer or copolymer in which the amino group is introduced is preferably 0.1 to 30 parts by weight. More preferably, it is 2-15 weight part.

Such modified olefin homopolymers or copolymers can generally be prepared by a method of grafting monomers having a reactor to an olefin resin or by replacing a olefin homopolymer or copolymer including a reactor with another reactor. have. One example of a method for grafting a monomer having a reactor to the former olefin resin among these methods is 100 parts by weight of an olefinic homopolymer or copolymer, 0.01 to 1 part by weight of a graft reaction initiator and 1 to 10 parts by weight of a monomer having a reactor. More preferably, after mixing 3-7 parts by weight, more preferably with an extruder, a Brabender mixer, a Haake mixer, a Banbury mixer, and the like Is produced by a twin extruder. An example of a method for substituting a modified olefin in which the reactor has already been introduced by another latter method with another desired reactor is 100 parts by weight of the modified olefinic homopolymer or copolymer and 1 to 15 parts by weight of the reaction reagent used for substitution, preferably After mixing 2 to 7 parts by weight of the extruder, Brabender kneader, Hake kneader and the like is more preferably produced by a twin screw extruder.

The thermoplastic blend composition of the present invention may further comprise suitable additives for each use. The additives include olefinic and acrylic impact modifiers, glass fibers, carbon fibers, talc, silica, mica, alumina, inorganic fillers, ultraviolet absorbers, heat stabilizers, antioxidants, flame retardants, lubricants, pigments, dyes, and the like. In addition, one or more of the above additives may be selected and added in an amount of 0.1 to 150 parts by weight based on 100 parts by weight of polycarbonate, which may be mixed in a conventional mixer, and the mixture may be prepared in pellet form through an extruder.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

The polycarbonate, the olefin polymer, and the modified olefin polymer particularly used in the following Examples and Comparative Examples are as described in Table 1.

Polycarbonate PC Bisphenol-A polycarbonate with a weight average molecular weight of 50,000 g / mol and a melt index of 10.5 g / 10 min (300 ° C, 1.2 kg) Olefin Polymer PP Single Polymerized Polypropylene with Melt Index of 8g / 10min (230 ℃, 2.16kg) Modified Olefin Polymer with Amino Group GA-PP Modified polypropylene with an amino group grafted and melt index of 10g / 10min (230 ℃, 2.16kg) APP-75 Modified polypropylene with 0.75% by weight of amino group and melt index of 50g / 10min (230 ℃, 2.16kg) APP-125 Modified polypropylene with 1.25% by weight of amino group and melt index of 110g / 10min (230 ℃, 2.16kg) Modified Olefin-Based Polymer Incorporated with Other Groups PP-GMA Modified polypropylene with 1.25 wt% glycidyl methacrylate group, melt index 8 g / 10 min (230 ° C., 2.16 kg) PP-MAH Modified polypropylene with 1.25% by weight of carboxylic anhydride graft, melt index 110g / 10min (230 ° C, 2.16kg) additive MBS Acrylic impact modifier

In the modified olefin polymer of Table 1, GA-PP is a biaxial compressor (product name: polypropylene, 2- (butylamino) ethyl methacrylate as a monomer to be grafted and di (butylperoxy) diisopropylbenzene as an initiator. leistritz) and the extrudate obtained by extruding the extruded extrudate in the form of a strand after mixing at 160, 170, 170, 170 and 170 ° C barrel temperature, 100 rpm mixing speed, 50% torque and 10 kg / hr feed rate. Cooled, pulverized to obtain pellets and prepared by drying in a breathable oven at 70 ° C. for 3 hours.

APP-75 and APP-125 also used PP-MAH and 1- (2-aminoethyl) piperazine, a polypropylene grafted with carboxylic acid anhydride, to a twin screw extruder (trade name: leistritz) for 190, 200, 200, After extruding the mixture obtained by blending at the barrel temperature of 200 and 220 ° C., the mixing speed of 100 rpm, the torque of 40% and the feeding speed of 12 kg / hr, and extruding, the extrudate was cooled in the form of strands and pulverized to obtain pellets. It was prepared by drying in a breathable oven at 70 ℃ for 3 hours.

[Examples 1 to 7 and Comparative Examples 1 to 5]

Table 2 shows the mixing composition and physical properties, which were blended under the mixing conditions of the barrel temperature of 240, 250, 250, 260 and 260 ° C., the mixing speed of 200 rpm, the torque of 50% and the feed rate of 10 kg / hr. The extrudate obtained by extruding in a twin screw extruder (product name: leistritz) is cooled in the form of strands, pulverized to obtain pellets, and the obtained pellets are dried in a breathable oven at 120 ° C. for 3 hours, followed by 75 tons of battenfeld Test specimens were prepared in an injection molding machine.

Tensile strength and elongation of the prepared test specimens were based on ASTM D638, impact resistance was evaluated according to ASTM D256 at 23 ° C and -30 ° C, and heat deformation temperature was evaluated according to ASTM D648. Indicated.

division Example Comparative example One 2 3 4 5 6 7 One 2 3 4 5 Composition (part by weight) Polycarbonate PC 75 75 80 80 75 75 70 75 80 75 70 70 Olefin Polymer PP 20 15 10 10 15 10 23 25 20 20 23 23 Modified Olefin Polymer GA-PP - - 10- - - - - - - - - - APP-75 5 - - - - - - - - - - - APP-125 - 10 - 10 5 10 7 - - - - - PP-GMA - - - - - - - - - - 7 - PP-MAH - - - - - - - - - - - 7 MBS - - - - 5 5 - - - 5 - - Properties Tensile Strength (MPa) 45 51 47 52 45 52 50 40 43 42 44 35 Elongation at Break (%) 30 150 40 150 30 130 30 10 10 10 14 10 Impact Strength (1/8 ", 23 ℃, Notch) (kgcm / cm) 25 75 60 95 43 85 35 20 40 35 15 20 Impact Strength (1/8 ", -30 ℃, Notch) (kgcm / cm) - - - - 20 35 - 10 - 18 - - Heat Deflection Temperature (℃) 118 120 120 122 114 116 115 113 118 110 114 112

As shown in Table 2, Comparative Examples, which are simple blends of polycarbonate and polypropylene, have low mechanical properties as incompatible blends, and Examples prepared by adding modified olefin-based polymers having an amino group as a compatibilizer are introduced. It can be seen that the strength and heat resistance are high. As a result, it can be confirmed that the compatibility of polycarbonate and polypropylene is improved.

In addition, the physical property evaluation results of Comparative Example 3 in which only the acrylic impact modifier was added to the blend without addition of the compatibilizer, and Examples 5 and 6 in which the modified olefin polymer having the amino group grafted with the amino group and the acrylic impact modifier were added together In comparison, Comparative Example 3, in which only the acrylic impact modifier was added to the blend without adding the compatibilizer, compared to the simple blend without the compatibilizer, the impact strength at room temperature (23 ° C.) and the impact strength at low temperature (-30 ° C.). Is increased by 75 to 80%, but other physical properties are similar. However, Examples 5 and 6, in which the modified olefin-based polymer grafted with an amino group, which is a compatibilizer, and an acrylic impact modifier are added together, not only increase the impact strength at room temperature and the impact strength at low temperature, but also increase the content of the compatibilizer. As it increased, the other mechanical properties showed a marked improvement.

In addition, Example 7 to which the modified polypropylene with the amino group was introduced is a comparative example in which a modified polypropylene having the same content added to another reactor other than the amino group, that is, glycidyl methacrylate or carboxylic anhydride group, is added as a compatibilizer. Compared to 4 and 5, the heat resistance and other physical properties were improved, and in particular, the tensile strength, the elongation at break, and the impact strength were increased drastically.

As described above, the blend composition of the polycarbonate and the polyolefin according to the present invention includes a modified olefin-based polymer having an amino group introduced therein, thereby increasing the compatibility of the polycarbonate and the polyolefin blend, such as impact resistance, heat resistance, and lightness. It is a useful invention with excellent physical properties.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (8)

(a) 1 to 99 parts by weight of polycarbonate resin; (b) 1 to 99 parts by weight of an olefinic homopolymer or copolymer; And (c) 0.1 to 30 parts by weight of a modified olefin homopolymer or copolymer having an amino group introduced therein; a blend composition of polycarbonate and polyolefin. The method of claim 1, The blend composition of (a), (b) and (c) of the polycarbonate and polyolefin, characterized in that the (d) additive further comprises 0.1 to 150 parts by weight based on 100 parts by weight of the polycarbonate of (a) Blend composition. The method of claim 1, The blend composition of polycarbonate and polyolefin (a) wherein the polycarbonate resin has a weight average molecular weight of 8,000 to 120,000 g / mol and a melt index of 1 to 20 g / 10 min. The method of claim 1, (A) The blend composition of polycarbonate and polyolefin, wherein the polycarbonate resin is a linear or branched homopolymer and copolymer. The method of claim 1, (B) the olefin homopolymer or copolymer is a homopolymer polymerized by selecting one of C ₂ to C ₈ olefin monomers or a copolymer copolymerized by selecting one or more of the monomers. Blend composition of polycarbonate and polyolefin to be. The method of claim 1, The monomer (c) has a monomer having an amino group selected from the group consisting of primary, secondary, tertiary amines and derivatives thereof in the modified olefin homopolymer or copolymer in which the amino group is introduced into the olefin homopolymer or copolymer. A blend composition of polycarbonate and polyolefin, which is grafted at a graft rate of 10% by weight. The method of claim 2, The blend composition of polycarbonate and polyolefin, wherein the additive (d) is selected from the group consisting of impact modifiers, inorganic fillers, ultraviolet absorbers, heat stabilizers, antioxidants, flame retardants, lubricants, pigments and dyes. The method of claim 7, wherein The impact modifier is an olefinic or acrylic impact modifier, and the inorganic filler is a blend composition of polycarbonate and polyolefin, characterized in that one selected from the group consisting of glass fiber, carbon fiber, talc, silica, mica and alumina.