MXPA98003823A - Polycarbonate and polybut mixtures - Google Patents

Abstract

The present invention involves blends of polycarbonate resin with a small amount of an aliphatic C4 polyalpha-olefin homopolymer or copolymer, or functionalized derivatives thereof.

Description

BONATO AND POLYBUTHENE POLICE MIXTURES BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a novel processing aid for polycarbonate and, more particularly, to mixtures containing polycarbonate and an effective amount of polyalpha olefin of G; aliphatic, functionalized polymer of aliphatic polyalpha-olefin or a hydrogenated polyalpha-olefin.

Description of the Related Art Polycarbonate aromatic resins have excellent mechanical strength, impact resistance and thermal resistance and, therefore, are used as engineering plastics in many fields. The improvement of the processing capacity by enhancing the flow characteristics by adding processing aid is a typical practice in the development of plastic materials. However, the addition of processing aid, for example plasticizer, in the polycarbonate leads to a surprising reduction of its impact resistance. For example, when resorcinol diphosphate (RDP) or tetraxylhydroquinone diphosphate (TXHQDP) is added to the polycarbonate, the polycarbonate flow is improved. However, the notched Izod impact strength of such a polycarbonate blend is reduced to a value as low as 0.0543 kg-m / cm from 0.3258 kg-m / cm even when the loading of RDP or TXHQDP is as low as the 4% of the total composition. The search for a new solution to improve flow without sacrificing other physical properties is a constant challenge in the development of polycarbonate blends. This and other objects which appear hereinafter have been achieved in a general sense in accordance with the present invention through the discovery that by incorporating a small amount of polyalphaolefin from C * to C aliphatic, specifically polybutene or an epoxy polybutene -functionalized, to the polycarbonate, the polycarbonate flow is substantially improved while maintaining the impact ductility determined by the Dynatup and Izod tests with notch.

BRIEF DESCRIPTION OF THE INVENTION According to the invention, a polymer mixture is now provided which contains: (A) from 10 to 99.9% by weight of polycarbonate; and (8) from 0.1 to 10% by weight of a polyalphaolefin of C * to C aliphatic.

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resins usefully employed according to the present invention are those known and previously described in the prior art. In general, polycarbonate resins can be prepared from one or more multi-hydride compounds by reacting the multi-hydride compounds such as diphenol, with a carbonate precursor such as phosgene, a halogen formate or a carbonate ester such as diphenyl carbonate or dimethyl. The preferred diphenol is 2,2-bis (4-hydroxyphenyl) propane (which is also referred to as bisphenol A). Generally speaking, such polycarbonate polymers can be represented as possessing recurring structural units of the formula: - (- 0-A-0-C (= 0) -) n, in which A is an aromatic or divalent radical of a dihydric or halogen or phenylalkyl-substituted phenol. Preferably, the carbonate polymers used in this invention have an intrinsic viscosity (as measured in methylene chloride at 25 ° C.) Ranging from about 0.30 to about 1.00 dl / g. The dihydric phenols which can be used provide such nuclear aromatic compounds, which contain as functional groups two hydroxy radicals, each of which is directly linked to a carbon atom of the aromatic nucleus. Typically dihydric phenols include, but are not limited thereto: 2,2-bis (4-hydroxyphenyl) propane; hydroquinone; resorcinol; 2,2-bis (4-hydroxyphenyl) pentane; 2,4 '- (dihydroxyphenyl) methane; bis- (2-hydroxy phenyl) methane; bis- (4-hydroxyphenyl) methane; 2,4'-dihydroxynaphthalene; bis- (4-hydroxy phenol) sulfon; bis- (3,5-dimethyl-4-hydroxyphenyl sulfone; bis- (3,5-dimethyl-4-hydroxyphenyl) propane; bis- (3,5-dihalogeno-4-hydroxyphenyl) propane; bis- (3,5 -dihalogen-4-hydroxyphenyl) sulfone, 2,2'-bishydroxy phenyl fluorocarbon, l-bis (4-hydroxyphenyl-9-cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dihalogen ether diphenyl and ether 4,4 '-dihydroxy 2,5 dihydroxydi phenyl Other dihydric phenols which are also suitable for use in the preparation of polycarbonates are described in U.S. Patent Nos. 2,999,835, 3,038,365, 3,334,154 and 4,131,575. Branched polycarbonates they are also useful, such as those described in the US Patent Numbers 3,635,895 and 4,001,184. These aromatic polycarbonates can also be copolyzed with linear or branched aliphatic Cs to C12 diols, or linear or aromatic diacids or polysiloxanes or polyesters, or otherwise known as polyester carbonates. The polycarbonate resins can be prepared with these starting materials by any of several known methods, such as the known interfacial, solution or melting processes. In general, one or more polycarbonates may be incorporated into the mixture of the present invention in amounts of about 10 to 99.9% by weight, preferably 20 to 99.5% by weight and most preferably 40 to 98.5% by weight. In cases where polycarbonate resins are incorporated, the ratio of the first polycarbonate to the second polycarbonate can vary from about 10 to 90 to about 90 to 10% by weight. The aliphatic C α to C α polyalpha olefins contemplated in this invention are prepared by polymerizing one or more C α α-olefins, to C α, using catalyst as described in US Patents. Nos. 2,957,930, 3,985,822, 4,431,570, 4,431,571 and 4,431,572 which are incorporated herein by reference. The alpha-olefin of aliphatic CA is defined as a class of unsaturated aliphatic hydrocarbons having one or more double bonds, with at least one double bond on carbon number 1, using the naming rules of IUPAC (International Union of Pure and Applied Chemistry). For simplicity, the typical monomer described above is referred to herein as alpha-olefin and reference is made herein to the polymer prepared by polymerization of such monomers as polyalpha-olefin polymer. In general, the hydrocarbon supply material for producing these polyalpha olefins is generally a mixture of 1-butene, trans-2-butene, cis-2-butene, isobutylene, 2-methyl-1-propene, 1- Pentene, 4-methylpentene, 1-hexene, 1-octene and 1-nonene. The concentration of alpha-olefins in the mixture may range from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, most preferably from 0.4 to 3% by weight and most preferably still from 0.5 to 2.5% by weight. Ethylene and propylene supply material can also be incorporated as comonomers up to about 20% by weight with the alpha-olefins. For the specific case of preparing polybutene polymer, the supply material used may contain from about 5% to about 100% by weight of isobutylene. For this specific case, it is preferable to use butene stream rich in isobutylene in which 70% or more is isobutylene. The polyalphaolefins contemplated in this invention are prepared by polymerizing one or more alpha-olefins. They are prepared by polymerizing a mixture of CA to C ole olefins by methods which are well known in the art to obtain an olefin polymer of C to C a with a range of molecular weights in the range of about 100 to about 5,000 g / mol, as determined by gel permeation chromatography using narrowly dispersed polystyrene as standards. Generally speaking, the polymerization reaction is a Friedel-Crafts reaction using a catalyst such as aluminum chloride or boron trifluoride and is extensively disclosed in the technical and patent literature. The hydrocarbon supply material can be a refinery fraction, a pure onoolefin or a mixture of monoolefins. The monoolefin supply material in which the olefin contains from 3 to 16 carbon atoms is preferred. If a pure olefin is used which is gaseous under ambient conditions, it is necessary either to control the reaction pressure by dissolving the olefin in a solvent medium, inert under the reaction conditions, in order to keep the olefin in the liquid phase. In the case of isobutylene, which is typical of monoolefins, the supply material used in the polymerization process can be pure isobutylene or a mixed hydrocarbon supply material from A to C, such as that resulting from thermal or catalytic fractionation operation. This is a liquid when it is under pressure and therefore no diluent is needed. A polymerization temperature is selected based on the desired molecular weight in the product. As is well known in the art, lower temperatures are used to obtain higher molecular weight products while higher temperatures are used to obtain lighter products. The polymerization can be carried out in the full range of temperatures generally associated with the conventional polybutene polymerization, ie from about 100 ° C to about 50 ° C. The resulting polymer typically includes various forms of butene, for example, butene, 1-butene, trans-2-butene, cis-2-butene, and may contain a small amount of propene and minor amounts of polymerization by-products. Typically, isobutene constitutes from about 80% to about 95% of the total polyalphaolefin polymer. Also useful in the present invention are hydrogenated polyalpha-olefin polymers, such as those described in U.S. Pat. No. 5,177,277. The epoxidized polyalpha olefins are described in the U.S. Patent. No. 3,382,255 in which the polyalphaolefin is dissolved in heptane or another suitable solvent and reacted with performic, peracetic, perbenzoic, perphthalic and other 40% acid. Other functionalized polyalpha olefins included as part of this invention include maleic anhydride, maleimide, N-alkyl substituted maleimide, N-aryl or N-substituted aryl-maleimides. Polyalphaolefin polymers, for example, polybutene, are commercially available in a variety of classes through the Aco Chemical Company. Included within the present invention are polybutene polymers which are homopolymers, copolymers, unsaturated, hydrogenated and functionalized polymers. In addition, certain additives may be included in the resin composition of the present invention, such as antistatic agents, fillers, pigments, colorants, antioxidants, thermal stabilizers, ultraviolet light absorbers, lubricants and other additives commonly employed in polycarbonate compositions. Suitable stabilizers that may be optionally incorporated into the compositions of the present invention include, but are not limited to, clogged phenolic antioxidants, for example Irganox * 1076, Ultrano? * 257 phosphites, eg, Ultranox 626, Irgafox * 168 , and thioesters, for example dilaurylthiopropyanate, or a combination thereof. Suitable antistatic agents which may optionally be incorporated into the compositions of the present invention include, but are not limited to, the reaction products of polyethylene oxide block polymers with epichlorohydrin, polyurethanes, polyamides, polyesters or polyetheresteramides. Suitable flame retardants are, but are not limited to, phosphorous compounds, most commonly phosphonates or phosphates as described in the US Patent.

No., 178,281 which may optionally be incorporated into the resin mixture of the present invention. For example, these classes of compounds include, but are not limited to, RDP (resorcinol diphosphate), TPP (triphenyl phosphate), PTFE and halogenated materials, etc. Suitable fillers that may optionally be incorporated into the compositions of the present invention include, but are not limited to, talc, fiberglass, carbon fiber, clay silica, mica, conductive metals and minerals, etc. Suitable mold releasing agents which may optionally be incorporated into the compositions of the present invention include, but are not limited to, PETS (pentaerythritol tetraesterate) and glyceryl monostearate.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The invention is more readily understood by reference to specific embodiments that are representative of the invention. It should be understood, however, that specific modalities are provided only for purposes of illustration and understanding, and that the invention can be put into practice in a manner different from that specifically illustrated and described without deviating from its spirit and scope. The ingredients used in this example are: PC100 Polycarbonate having a weight average molecular weight of about 53,000, as determined by gel permeation chromatography using polystyrene as standards. The intrinsic viscosity is about 0.55 as measured in methylene chloride at 25 * C. PC140 Polycarbonate having a weight average molecular weight of about 45,000, as determined by gel permeation chromatography using polystyrene as standards. The intrinsic viscosity is about 0.50, as measured in methylene chloride at 25 ° C. Polybutene L-65 Copolymer of polybutylene, isobutylene and butene, having a number average molecular weight of 440 and a weight-average molecular weight of 550, as determined by gel permeation chromatography using polystyrene as standards.

EXAMPLE I Compositions containing the ingredients listed in Table I (expressed as parts by weight) were prepared by mixing the components in a Henschel mixer for about 1 minute and then adding the mixture to the extruder hopper. In a typical small-scale laboratory experiment, a twin-screw, twin-screw, interregulation, worm, 30-mm WP extruder was used to combine these mixtures at 320-400 RPM with a melting temperature of approximately 293.3 -298.8 ° C. All test specimens were injection molded in a Toshiba ISE170 injection molding machine using a side injection orifice test mold at an adjusted barrel temperature of 276.6 ° C and at a mold temperature of 65.5 ° C. The test specimens were 3.2+ 0.2 mm thick unless otherwise specified. The ASTM test procedures were as follows: D256 Impact of Izod with notch D3835 Viscosity of capillary fusion D638 Resistance to tension, modulus of elongation D790 Module and resistance to bending D3763 * Multiaxial impact (Dynatup) * In which the method of ductile deficiency is defined as a perforation of the test layer without the fractions radii more than 10 mm beyond the center of the point of impact.

TABLE I Composition Mix 1 Mix 2 PC 100 100 100 Polybutene L-65 2 Melt viscosity ß 290 * C (poise) 100 / sec. 27803 19986 250 / sec 26024 19347 630 / sec 18971 15107 1000 / sec 14541 11830 1500 / sec 10932 9162 1750 / sec 9524 8091 N. Izod (kg-m / cm), p.amb. 0.9068 0.9774 Dynatup, temp.amb, disk 0.318 (3.353 m.50 #) Alarg. Total (kg-) 8.270 9.227 Dev. Normal 6.16 2.36 Alarg. 8.0247 8.713 Desv. Normal 4.96 0.88 D / SD / B 5/0/0 5/0/0 Dynatup, -30 * C, disk 0.125"(3.353 m / sec, 50tt Total Alarge (kg-m) 8.0951 9.370 Normal deviation 1.5 3.68 Alarg. Max. (kg-m) 7.8895 9,095 Desv. Normal 0.92 5.39 D / SD / B 5/0/0 5/0 / Flexural strength (0.635 cm, 22.7 C, 2.54 cm / min) Flexural strength (kg / cm2) 904.76 995.45 Flexural module (xlO * kg / cm2) 2.12 2.29 Resistance to tension (0.318 cm, 22 .7ßC, 5.08 cm / min) Yield by resistance (kg / cm2) 620.26 652.98 Rupture by resistance (kg / cm2) 726.90 803.53 Rendim. for alarg. (%) 11.06 10.44 Rupture by extension. (%) 191.6 243.5 Energy at break 2929 3984 Light transmission (%) 85.7 87.4 As shown in Table I above, the addition to 2% by weight of polybutene (Amoco Indopol L-65) in PC 100 results in the reduction of the melt viscosity by approximately 15% over a wide range of speed cut from 1000 / sec. at 1750 / sec). Unexpectedly, it was found that either the physical properties of this mixture, Izod impact resistance with notch, Dynatup impact strength at minus 30 * C, tensile stress limit, tensile strength at break, were maintained or improved. strain elongation, flexural strength and flexural modulus. Specifically, while improving the flow by adding polybutene, the impact strength of Izod with notch at a ductile level greater than 0.8688 kg-m / cm2 was maintained. It is also noted that the Dynatup impact resistance which is the result of the incremental improvement of the modulus and the resistance was improved. It is believed that the same effectiveness is applicable in other polycarbonate resins and polycarbonate copolymers and blends containing one or more polycarbonates. This finding provides a unique path to improve flow without adversely affecting the impact resistance of polycarbonate.

EXAMPLE II Compositions containing the ingredients listed in Table II (expressed in parts by weight) were prepared by the same method provided in Table I.

TABLE II Hezcla-3 Blend-i Blend-5 Hezda-6 Hezda-7 Blend-8 Nezcla-9 PC UO 100 100 100 100 100 100 100 PET 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Irganox 1076 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Polybutene L-65 2 4 RBP Linear oil Melt viscosity 50 ser1 10638 9125 7707 7706 7313 8542 6872 100 sec-1 10946 9322 7801 7801 7321 8558 6769 500 sec'1 7158 6364 5368 5368 5248 5931 4990 1000 sec-> 5341 4853 4112 4112 4135 4625 3952 1500 sec-1 4296 3939 3367 3367 3405 3772 3273 2500 sec-1 2385 2251 2051 2051 1959 2298 1930 N. Izod (kg-i / ci), teip. aib Protest 0.9340 0.9177 0.9394 0.9937 0.0815 0.4778 * 0.0760 Desv. norial 0.0272 0.0760 0.0380 0.0597 0.0054 0.04507 0.0054 Dynatup, teip. aib 0.318 disk (3.35 i / sec, 501) Alarg. total (kg-) 8,193 8,0015 8,6333 8,400 7,902 7,546 7,564 Desv. norial 3.8 5.98 2.21 1.51 4.74 2.25 1.13 Alarg. ux. (kg-i) 7,769 7,531 8,152 7,844 7,213 7,111 7,248 Desv. norial 4.1 5.96 1.59 1.57 3.93 2.79 1.13 D / SD / B 5/0/0 5/0/0 5/0/0 5/0/0 5/0/0 5/0/0 5/0/0 Dynatup, -30 * C, 0.318 disk (3.35 i / sec, 501) Alarg. total (kg-i) 7,463 8,576 8,225 8,187 8,174 7,644 7,732 Desv. norial 3.43 6.39 3.32 1.09 5.61 3.1 3.81 Alarg. ux. (kg-i) 6,888 7,931 7,754 7,453 7,670 6,957 7,143 Desv. norial 5.97 8.81 3.62 1.49 5.88 4.21 4.23 D / SD / B 5/0/0 5/0/0 5/0/0 5/0/0 5/0/0 5/0/0 5/0/0 Resist. to flex Resist. at bending (kg / ci2) 936.40 982.09 10004.59 1007.40 1077.70 1039.03 1078.40 Bending module (XlO * kg / ci2) 2.19 2.29 2.40 2.35 2.50 2.45 2.54 TABLE II (Continued) Hezda-3 Nezcla-4 Hezc-5 Nezda-6 Hezda-7 Hezda-8 Hezcla-9 Resist. to the tension Rendii. by tension (kg / ctf) 627.15 645.42 651.75 660.33 688.24 666.73 694.00 Break by tension (-! / «») 664.12 670.52 674.60 674.60 679.59 649.50 605.11 I surrendered, by extension. (t) 11.12 10.81 10.59 10.99 10.59 10.46 10.24 Rupture by extension to 163.5 168.4 173.6 164.3 158.4 146.8 176.1 Energy at break (kg-c?) 2271 2383 2441 2337 2258 2068 2612 * Data point of the individual tests: 17.7, 2.15, 3.21, 2.83, 18.0 are scattered indicating that the test was performed at the ductile-f rile transition temperature.

As shown in Table II, polycarbonate containing 2% by weight and 4% by weight of polybutene (Amoco Indopol L-65) bits the 15% and 28% reduction and the melt viscosity (at a cutting speed of 100 sec-1) compared to that of polycarbonate, respectively. While the flow improves for polycarbonate with the addition of polybutene, Izod impact strength is maintained with notch at a ductile level greater than 0.8688 kg-m / cm2. In addition, a 10% increase in Dynatup impact resistance is observed which is a result of incremental module and resistance improvement. When mineral oil or resorcinol diphosphate (RDP) is added to the polycarbonate, a similar flow improvement is observed without adversely affecting Izod notched impact strength at a concentration of 2% by weight. However, when mineral oil or RDP is added at a concentration of 4% by weight, the Izod impact strength with notch of the polycarbonate composition decreases to a brittle level of 0.0815 kg-m / cm2. This finding clearly demonstrates the unique and superior flow balance and Izod impact strength with polybutene notch compared to other additives, such as plasticizers, antiplastifiers or processing aids. The elastic limit to stress is used to measure the capacity of materials that undergo shear deformation and can be used as a ductility index. The material with lower elastic limit tends to produce massive plastic deformation during a fracture process and thus results in a high impact resistance. You can also see the loss of impact resistance of polycarbonate with RDP and mineral oil by the plastic limit at the increased stress. It is evident, as indicated in Table II, that the increase in the yield strength of polycarbonate with added polybutene is lower than that of polycarbonate with RDP or mineral oil added. Therefore, polybutene provides superior balance of flow and impact resistance.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A thermoplastic composition containing: (A) from 10 to 99.9% by weight of a polybibonate; and (B) from 0.1 to 10% by weight of a polyalphaolefin of C to C aliphatic.

2. The thermoplastic composition of claim 1 containing 0.2 to 2.5% by weight of an aliphatic C a to Ci 6 polyalpha olefin.

3. The thermoplastic composition of claim 1, further characterized in that said aliphatic C4 to Ci6 polyalphaolefin is selected from the group consisting essentially of alpha-olefin, 1-butene, trans-2-butene, cis-2- butene, isobutylene, 2-methyl-1-propene, 1-pentene, 4-methylpentene, 1-hexene, 1-octene and 1-nonene, and mixtures thereof.

4. The thermoplastic composition of claim 1, further characterized in that the polyalphaolefin of C * a Cip aliphatic has a number average molecular weight of about 100 to about 5000.

5. The thermoplastic composition of claim 1, characterized also because the polycarbonate resins have a weight average molecular weight higher than 15,000.

6.- The thermoplastic composition of the claim 1, which also contains at least one additional component selected from mineral fillers, fibers, stabilizers, colorants, antistatic additives and lubricants.

7. - A thermoplastic composition containing: (A) from 10 to 99.9% by weight of polycarbonate; and (B) from 0.1 to 10% by weight of a functionalized aliphatic C α to α aliphatic polyalphaolefin.

8. The thermoplastic composition of the claim 7 containing from 0.2 to 2.5% by weight of a polyalphaolefin of aliphatic C α to C α.

9. The thermoplastic composition of claim 7, further characterized in that said aliphatic C * to Ci6 polyalphaolefin is functionalized aliphatic CA to C alylated olefin selected from the group consisting essentially of 1-butene, trans-2- butene, cis-2-butene, isobutylene, 2-methy1-l-propene, l-pentene, 4-methylpentene, 1-hexene, 1-octene and 1-nonene, and mixtures thereof.

10. The thermoplastic composition of claim 7, further characterized in that said functionalized aliphatic C-aliphatic polyalphaolefin has a number average molecular weight of from about 100 to about 5000.

11. The thermoplastic composition of claim 9, further characterized because said polycarbonate resins have a weight average molecular weight higher than 15,000.

12. The thermoplastic composition of claim 9, further characterized in that said polyalphaolefin of aliphatic C "a Cie is epoxy-functionalized.