JPH04502646A - Polymer blend of polycarbonate, styrene terpolymer and glass fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polymer blend of polycarbonate, styrene terpolymer and glass fiber Related application This application is filed under co-pending U.S. Patent Application No. 165, filed March 8, 1988, This is a continuation in part of No. 462.

Branch of development The present invention uses polycarbonate; styrene, acrylonitrile and maleic anhydride. styrene terpolymer and glass fibers. Ru. More specifically, the present invention provides superior physical properties including modulus and heat distortion temperature. The present invention relates to the above polymer blend composition exhibiting a combination of:

Background of the invention Polymer blend compositions used in engineering applications have high heat resistance, good strength, It is necessary to exhibit a combination of strength and good modulus. Furthermore, the blend composition must exhibit good melt flow properties to facilitate processing and molding. polycarbonate Carbonate is a popular blending ingredient due to its toughness and relatively high softening temperature. It is. However, the melt flow characteristics are relatively poor, and the melt flow characteristics can be improved. To achieve this, polycarbonate is often combined with one or more other polymers. Rend. The resulting blends usually exhibit improved melt flow properties, but Other properties such as heat resistance and impact strength deteriorate.

Examples of blend compositions of this type are known. For example, Grabowski's US patent No. 3,130,177 discloses that polycarbonate-1 and polybutadiene, Blends with acrylonitrile grafted polymers are disclosed and Grabous In U.S. Pat. -Blends with styrene, methyl methacrylate, and styrene graft copolymers have been developed. It is shown. No. 4,205.1.40 to Liebik et al. of diene rubber graft polymers and styrene polymers such as carbonate and ABS. A thermoplastic molding composition comprising a blend is disclosed. polycarbonate and Styrene-maleic anhydride copolymer, ABS resin and styrene-acrylonitrile Similar blends with Lurandom copolymers are described in Henton U.S. Pat. No. 4,218. No. 544. U.S. Pat. No. 4,472°554 to Grigo et al. In the specification, graft polymers such as polycarbonate and ABS, and polymer acidic A thermoplastic molding composition comprising a blend of curing agents is disclosed. Jones et al. U.S. patent bundles 4,569,969 and 4,663.389, and European patents Application No. 135.493 also describes polycarbonate, ABS polymer and Polymer blends of styrene polymers are disclosed. These blends are It exhibits various physical properties depending on the types and ratios of the components included.

Parsons co-pending U.S. patent application Ser. carbonate, styrene-acrylonitrile-maleic anhydride terpolymer, and The role of blend compatibilizer between polycarbonate and styrene terpolymer A blend composition comprising a small amount of ABS resin is disclosed. This composition exhibits an excellent combination of impact strength, heat resistance and modulus.

Additionally, glass can be added to thermoplastic compositions for applications requiring high tensile, compressive and flexural strength. It is also known to add fibers. Styrene-maleic anhydride copolymer, and glass containing styrene-maleic anhydride copolymer in combination with polycarbonate and polycarbonate The filling composition is manufactured by Arco under the trade name Dirag (registered trademark) and Alloy (registered trademark). and is currently commercially available from Monsando under the registered trademark Rikidon. Also, British Patent No. 1,365,329 describes a glass fiber-containing styrene resin composition. No. 4,487,881 to Loring et al. Polycarbonate, grafted elastomer, polyanhydride and glass fiber blends is disclosed. These compositions also exhibit various combinations of physical properties. Ru.

Outline of the invention That is, the object of the present invention is to provide excellent heat resistance, good strength and good modulus. The objective is to provide polymer blend compositions that exhibit a combination of physical properties.

Another object of the invention is to blend various engineering thermoplastic blends. Demonstrates an excellent combination of heat resistance, strength and modulus that allows it to be used in hard applications. An object of the present invention is to provide a polymer blend composition. Yet another object of the invention is , exhibiting improved properties, especially compared to the individual components of the composition. An object of the present invention is to provide the above-mentioned composition.

For these and other purposes, polycarbonate, styrene-acrylonitrile - a blend composition of the invention comprising a maleic anhydride terpolymer and glass fibers; more achieved. More specifically, glass fibers are polycarbonate, terpolymer and about 5 to about 40% by weight based on glass fiber. Preferably , about 15 to about 65% by weight polycarbonate, more preferably about 20 to about 3% by weight. 5% by weight, and the terpolymer is present in an amount of about 10 to about 80% by weight, more preferably Preferably, it is included in an amount of about 35 to about 75% by weight. This composition has good strength, Exhibits an excellent combination of physical properties including modulus and heat resistance. This brain without significantly adversely affecting the other good properties of the blend composition. small amounts as necessary to obtain other improvements in surface appearance and impact strength, etc. ABS resin may be included.

These and other objects and advantages obtained by the blend compositions of the present invention , will become more clear from the detailed description below.

Detailed explanation The polymer blend composition of the present invention comprises polycarbonate:styrene-acryloni. tolyl-maleic anhydride terpolymers; and polycarbonates, terpolymers and and glass fibers in an amount of about 5% to about 40% by weight, based on glass fibers. this The blend composition exhibits an excellent combination of strength, modulus and heat resistance.

The polycarbonate component included in this blend composition is an aromatic polycarbonate component known in the art. It may be either homopolycarbonate or copolycarbonate. polycar The carbonate component can be used, for example, in an interfacial polycondensation process, in a homogeneous phase polycondensation process or in a transesterification reaction. It can be manufactured according to any method commonly known in the art, such as by can. These methods and their associated reactants, catalysts, solvents, and conditions are within the skill of the art. Well known in the art and see, for example, U.S. Pat. No. 2,964,974. , No. 2,970,137, No. 2,999.835, No. 2.999,846 , No. 3,028゜365, No. 3,153,008, No. 3,187,065 , No. 3,215,668 and No. 3,258,414. Ru. Suitable polycarbonates include, for example, one or more of the following bisphenols: based on.

Dihydroxydiphenyl, bis(hydroxyphenyl)alkane, bis=(hydrogen) Droxyphenyl) cycloalkane, bis-(hydroxyphenyl) sulfide , bis(hydroxyphenyl)ether, bis(hydroxyphenyl)keto bis-(hydroxyphenyl) sulfoxide, bis-(hydroxyphenyl) ) sulfone, α, α-bis-(hydroxyphenyl)diisopropylbenzene, and nuclear-alkylated and nuclear-halogenated derivatives thereof, and mixtures thereof. .

Specific examples of these bisphenols include 4.4=-dihydroxydiphenyl, 2. 2-bis=(4-hydroxyphenyl)propane, 2.4-bis-(4-hydro xyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl) ) cyclohexane, α, α-bis-(4-hydroxyphenyl)-p-diisopropylene Lopylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propyl 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis-( 3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5- dimethyl-4-hydroxyphenyl)propane, bis-(3,5-dimethyl-4 -Hydroxyphenyl)sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl) Droxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl- 4-hy5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene , 2,2-bis=(3,5-dichloro-4=hydroxyphenyl)propane and 2.2-bis(3°5-dibromo-4-hydroxyphenyl)propane.

A particularly preferred bisphenol is more commonly known as bisphenol A. 2,2-bis-(4-hydroxyphenyl)propane.

The polycarbonate component provides the blend composition with good tensile and flexural strength, as well as It is included in the blend composition in an amount sufficient to impart good heat resistance. Preferably , the polycarbonate component is made of polycarbonate, terpolymer and glass fiber. It is included in an amount of about 15 to about 65% by weight based on the total weight. More preferably, Polycarbonate is based on polycarbonate, terpolymer and glass fiber. It is contained in an amount of about 20 to about 35% by weight. The present inventors found that 20% by weight or more The polycarbonate is better than a composition containing a terpolymer and glass fibers in the composition. large, and compared to compositions containing polycarbonate and glass fibers, It has been found that it imparts tensile and bending strength. Furthermore, the present inventors have discovered that polycarbonate More than about 35% by weight of bonate reduces the tensile and flexural modulus of the composition. I found that it started to change.

The second component included in the blend composition is a styrene-acrylonitrile-anhydrous polymer. Consisting of leic acid terpolymer.

Preferably, styrene constitutes the majority of the terpolymer composition, thereby The polymer imparts stiffness, good modulus and heat resistance to the resulting blend composition do. Maleic anhydride is added to the terpolymer in sufficient amounts to enhance the properties of the styrene component. Contained in the market. Preferably, maleic anhydride accounts for about 4 to about 2 of the terpolymer. It constitutes 5% by weight. Additionally, the blend composition exhibits good melt stability and The terpolymer acrylic The lonitrile component is preferably used in an amount up to about 20% by weight. More preferably , about 5 to about 20 weight percent acrylonitrile is included in the terpolymer.

Terpolymers are preferably formed by continuous polymerization methods such as are well known in the art. . In practice, the production of styrene-acrylonitrile-maleic anhydride terpolymer The structure is made of a mixture of the terpolymer and a styrene-acrylonitrile copolymer. can be adjusted to form a product that

This terpolymer and copolymers that may be obtained during the production of the terpolymer Mixtures of can be done.

Styrene-acrylonitrile-maleic anhydride terpolymer is good for blending high stiffness, good modulus, and high heat resistance, especially as indicated by the heat distortion temperature. Use in sufficient quantity to provide Preferably the terpolymer is polycarbonate , about 10 to about 80% by weight based on the total weight of the terpolymer and glass fibers. Use in quantity. More preferably, the terpolymer is polycarbonate, terpolymer from about 35% to about 75% by weight, based on fiber and glass fibers.

The third component of the polymer blend composition comprises polycarbonate, terpolymer and From glass fibers used in an amount of about 5 to about 40% by weight based on glass fibers Become. Glass fibers impart improved strength and modulus to blend compositions. Ru. A variety of glass fibers are commercially available and suitable for use in the compositions of the present invention. Are suitable. Glass fibers of various sizes can be used in the compositions of the invention. However, the glass fibers can have an average length of about 0.05 to about 0.5 inches. preferable. As shown in the examples below, glass fibers suitable for use in the present invention include It is commercially available from Owens-Hooning Fiberglass Company. Preferably , glass fiber is approximately based on polycarbonate, terpolymer and glass fiber. It is included in the compositions of the present invention in amounts of 10 to about 30% by weight.

Furthermore, the blend composition of the present invention can optionally contain ABS resin. . If included, ABS resin is a polycarbonate component and a styrene terpolymer. improves the compatibility between the components, so that the resulting blend composition Impact strength of the bonate component, stiffness and good modularity of the styrene terpolymer component maintains heat resistance of both polycarbonate and terpolymer components. Use in sufficient quantity. polycarbonate without adversely affecting the properties of the blend ingredients. - In order to increase the compatibility between the carbonate component and the terpolymer component, ABS resin It should be used in an amount of less than 20% by weight based on the total weight of the composition. Also, the revision To provide good results, ABS resin should be used in an amount of at least about 4% by weight. be. In a preferred embodiment, ABS resin is used in an amount of about 4 to about 19% by weight. Ru.

ABS resins consist of a diene rubber substrate grafted with a rigid graft polymer.

In a preferred embodiment, the rigid graft polymer comprises styrene and acrylonitrile. and the diene rubber substrate consists of polybutadiene. However, those skilled in the art As is well known in the art, rigid polymers can be used to replace styrene with monovinylidene aromatic monomers. acrylic acid ester or methacrylic acid ester in place of polymer and acrylonitrile It is also well within the scope of this invention to use ABS resins formed from monomers. . Additionally, ABS resins may contain dienes other than polybutadiene, as is well known in the art. May contain rubber. In the present invention, when referring to the ABS resin component, Such equivalent polymers are also included. However, polybutadiene and styrene ABS resin grafted with a rigid graft polymer consisting of rylonitrile is preferred. Note that ABS resin is suitable. In this preferred embodiment, the group further includes: AB so that the amount of styrene contained in the raft part is greater than the amount of acrylonitrile. The weight ratio of styrene to acrylonitrile in the rigid graft portion of S resin is approximately 1. ．． Preferably, the ratio is within the range of 1 to about 5:1. The ABS resin component is also the same. It can be manufactured by methods well known in the industry. As is known in the art, AB According to the manufacturing method of S, a graft copolymer of ABS and a non-grafted styrene-acrylic It is possible to obtain products consisting of mixtures with lonitrile copolymers. These mixtures Compounds are also suitable for use in the present invention.

ABS resin is a blend between a polycarbonate component and a terpolymer component. at least 30% by weight, preferably at least 50% by weight to achieve % of diene rubber substrate. In a preferred embodiment, ABS resin is about 50 to about 75% by weight, more preferably about 60 to about 70% by weight of diengo. including the base material.

The blend compositions of the invention can be used, for example, in single and twin screw extruders, mixing rolls and internal mills. Can be manufactured on conventional mixing and compounding equipment including mixers etc. . In addition, the blend composition may include, for example, compounding agents, adhesives, stabilizers, lubricants, A variety of conventional additives including glidants, flame retardants, mold release agents, antistatic agents, etc. can be included.

Examples of additives of this type are U.S. Pat. No. 4,289,668 and U.S. Pat. No. 42, each specification.

The following examples illustrate specific embodiments of the present invention. Implemented unless otherwise specified The percentages given throughout the examples are weight percentages. Polycarbonate used in the example carbonate (PC), styrene-acrylonitrile-maleic anhydride terpolymer - (SAMA), glass fiber (GF) and ABS resin will be explained below.

PC-1+ A port obtained from Mobay Chemical Company with the designation M-50. Recarbonate, PC-2: Registered from General Electric Company Polycarbonate obtained under the trademark Lexan trade name, SAMA-1: This terpolymer contains about 21 to 22% by weight of anhydrous polymer. 4 and was produced under steady-state conditions in a single reactor. supply used % is 81% by weight of styrene, approximately 9% of acrylonitrile, and approximately 9% of maleic anhydride. It was 10 to 11%. The conversion rate of monomer to polymer is about 50%; The resulting hot water was continuously pumped into a vacuum extruder where unreacted styrene was removed. and acrylonitrile were removed and recycled to the reactor. Terpolymer is a differential Absence of Tg at 104-108°C using scanning calorimetry (DSC) analysis method As shown, most or all of the styrene-acrylonitrile copolymer It didn't include much, SAMA-2: This terpolymer contains approximately 10-11% by weight maleic anhydride. and in a two-reactor system, the production bath described in the SAMA-1 production process was added to the second reactor system. reactor, where unreacted styrene and acrylonitrile are further polymerized. Manufactured. This terpolymer was shown to have two Tg's revealed by DSC analysis. contained up to about 50% by weight of styrene-acrylonitrile copolymer. , GF-1: 0CF408 from Ohinges-Corning Fiberglass Company Glass fibers (cut struts) with an average length of 3/16 inch obtained under the designation ), GF-2 Ni Oinges-Corning Faino (-0 from Glass Company) Glass fiber (cut) having an average length of 1/8 inch obtained under the designation CF497. ABS: This ABS resin contains 50% by weight of polybutadiene groups. 50% by weight of styrene-acrylonitrile copolymer grafted onto the substrate; It consisted of Styrene versus acrylonitrile in graft copolymers The weight ratio was 3:1.

Example 1 In this example, 30% by weight of PC-1, 40% by weight of SAMA-1 and 30% by weight of A composition of the invention was prepared consisting of % GF-1 by weight. This example and the following implementation In the example, the blending operation is performed using a single screw extruder with a low compression screw. The resulting blend was then pelletized and formed into test specimens. Furthermore , in this and the following examples, according to ASTM-D-256 (Method E). Impact strength was measured in accordance with ASTM-D648. Accordingly, thermal deformation was measured at 265 ps i using an unannealed injection molded sample. , and strength and modulus were measured according to ASTM-D638. Main implementation The example composition has a reverse notched impact strength of 3.7 foot bonds/inch at room temperature, 27 7″F heat distortion temperature (1/8″ sample), 26,400 psi bending strength and It exhibited a flexural modulus of 16.0 x 105 psi. In this way, the composition has a good Exhibited a combination of physical properties.

Example 2 In this example, the PC-1, SAMA-2, and GF-1 or GF-2 are A composition was prepared. The weight percentages of these components were varied as shown in Table 1 below. . These compositions were similarly tested for reverse notch impact strength, heat distortion temperature, tensile strength and modulus. The results are also shown in Table 1. Indicated.

Table 1 PC-1655522,59--- 3AMA-2253567, 58190 impact strength, room temperature, 6.05°3 2, 4 2.4 2.31/8 inch 266 255 241 236 2351 /4 inch 259 255 242 242 236 Tensile strength, psj 12 700　12700　10600　9100　9900 Tensile modulus, 6. 4 6.8 8.3 8.2 8.5psixlo5 Bending strength, pat 19800 19700 16700 14600 138 00 bending modulus, 6.7 7.0 7.9 8.1 8.1.5 patX10 As is clear from Table 1, compositions 2A to 2D are according to the present invention; Composition 2E is a comparative composition that does not contain polycarbonate. The present invention shown in Table 1 Due to the physical properties of the composition, 22.5% polycarbonate by weight, 67.5% by weight Composition 2C containing 10% terpolymer and 10% glass fibers is particularly advantageous. combination of measured physical properties, in particular heat distortion temperature, and tensile and bending strength. Furthermore, according to this embodiment, PC-1, SAMA-2, and GF-1 or GF-2 The following is an example of a composition of the present invention consisting of: The weight percentages of the ingredients were varied as shown in Table 2.

The resulting composition was tested for reverse notch impact strength, heat distortion temperature, and tensile and bending strength. The results were also shown in Table 2.

Table 2 PC-1655545208--- 8AMA-2152535607280 Impact strength, room temperature, 5.7 5.9 5 ．． 1 4.0 2.93,7 feet / inch J to leg [man5 awakening, 1: 1/8 inch 280 270 257 252 244 239 1/4 inch 273 266 254 250 242 240 Tensile strength, psi 134 00 15200 14900 14700 13800 13800 Tensile Moji Yuras, 8,5 10.2 9,7 11.7 11.6 11.5psiX 105 Bending strength, psi 20000 21900 22000 20800 196 00 19300 bending modulus, 8.7 9.5 9,4 12.0 12 ．． 0 12.0psiX10 As is clear from the compositions listed in Table 2, compositions 3A to 3E are according to the present invention. and exhibits excellent properties, while Composition 3F contains polycarbonate. There is no comparative composition. In addition, the composition 3D of the present invention has a heat deformation temperature, tensile strength and It exhibited an exceptional combination of physical properties including flexural strength and modulus.

Example 4 This example illustrates a composition of the invention that also includes ABS. For details, see this Their composition contains PC-1, SAMA-2, GF-1 and ABS in the amounts shown in Table 3. It consisted of The resulting composition was tested for reverse notch impact strength, heat distortion temperature, and tensile strength. And the bending strength and modulus were measured, and the results are also shown in Table 3. Ta.

Table 3 PC-14,513,51841216SAMA-276,572,06368 6456GF-1101010202020 ABS 9.04.5 9 8 4 8 Impact strength, room temperature, 3.4 2.8 4 ．． 3 3.9 3.8 4.1 Heat distortion temperature, 1/8 inch 237 237 239 243 244 244 1/4 inch 234 240 240 241 247 241 Tensile strength, psj 110 00 10500 12900 15000 15200 16200 Tensile Moji Yuras, 7.8 7.7 7.5 11.0 11.3 10.8psiX1 05 Bending strength, I) si 17900 16600 19500 23800 23 200 24400 bending modulus, 7.5 7.7? , 0 10.0 1 2.0 11.0psix105 Generally, compositions 4D to 4F containing 20% by weight glass fibers contain 10% by weight glass fibers. It showed improved properties compared to compositions 4A to 4C containing fibers. Also, the composition Products 4C and 4F contained suitable amounts of polycarbonate components.

Example 5 According to this example, the preferred ranges of polycarbonate, terpolymer and glass 1 illustrates a blend composition of the present invention containing fibers. Some of these compositions are In addition, it also contained an ABS resin component as required. The weight percent of the composition is shown in Table 4. Ta. These compositions were tested for reverse notched and unnotched impact strength, heat distortion temperature, and were subjected to tensile and bending strength and modulus measurements, and the results are also shown in Table 4. It was shown to.

Table 4 PC-21530152010 SA105A 57.5 65 55 5577.5GF-117, 51515 1512,5ABS 10-15 10- impact strength, room temperature, Footpon F/I/C With reverse notch 4.3 4.6 5.0 4.8 2.0 without notch 6. 7 5. 1 6. 7 7. 4 1. 9 Heat distortion temperature, T 1/8 inch 236 239 232 238 236 Tensile strength, psi 1 3600　11600　12900　13600　7900 Tensile modulus, 9.1 8.2 7.5 7.9 8.0, 5 5lxlO Bending strength, psi 19360 15800 17950 19400 109 00 bending modulus, 8.8 8.7 7.7 B, 2 8.3 psi x 10 Compositions 5B and 5E showed increased polycarbonate content in the blend. It was shown that the tensile and flexural strength increased. With compositions 5C and 5D, ABS The influence of resin amount variation was shown. Finally, compositions 5A and 5E increase the amount of glass. This example shows the effect of addition on the modulus and strength of the composition. The blend composition of the present invention comprising: Specifically, these compositions are PC- 2, SAMA-2, GF-1 and optionally ABS. these Table 5 shows the weight percent of the components contained in the composition. These compositions are Unnotched impact strength, heat distortion temperature, and tensile and bending strength and modulus The results are also shown in Table 5.

The results shown in Table 5 demonstrate that these compositions have very good strength and modulus properties. It can be seen that the material exhibited good properties, as well as good heat distortion temperature and impact strength.

The foregoing examples are presented to illustrate specific embodiments of the invention and are It is not intended to limit the scope of the composition. Those skilled in the art will understand the scope of the invention Other aspects and advantages within are apparent.

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Claims (16)

[Claims] 1. (a) polycarbonate, (b) styrene-acrylonitrile-maleic anhydride terpolymer and (c) from about 5 to about 50% based on polycarbonate, terpolymers, and glass fibers; Polymer blend composition containing glass fibers in an amount of 40% by weight. 2. Based on polycarbonate, terpolymers and glass fibers from about 15 to about The polymer blend composition of claim 1 comprising 65% by weight polycarbonate. 3. Based on polycarbonate, terpolymers and glass fibers, from about 20 to about 3. The polymer blend composition of claim 2 comprising 35% by weight polycarbonate. 4. Based on polycarbonate, terpolymers and glass fibers, from about 10 to about The polymer blend composition of claim 1 comprising 80% by weight terpolymer. 5. Based on polycarbonate, terpolymers and glass fibers from about 35 to about 5. The polymer blend composition of claim 4 comprising 75% by weight terpolymer. 6. Polycarbonate is aromatic homopolycarbonate or aromatic copolycarbonate 2. The polymer blend composition of claim 1, comprising: 7. 7. The polymer according to claim 6, wherein the polycarbonate is a derivative of bisphenol A. -Blend composition. 8. Claim 1, wherein the terpolymer contains from about 4 to about 25 weight percent maleic anhydride. polymer blend composition. 9. 9. The terpolymer comprises from about 5 to about 20% by weight acrylonitrile. The polymer blend compositions described above. 10. Claim 1, wherein the terpolymer comprises a styrene-acrylonitrile copolymer. polymer blend composition. 11. Claim 1: The glass fibers have an average length of about 0.05 to about 0.5 inches. Polymer blend compositions as described. 12. In addition, sufficient The polymer blend composition of claim 1, comprising an amount of ABS resin. 13. 13. The polymer according to claim 12, wherein the ABS resin is present in an amount less than 20% by weight of the composition. Rimmer blend composition. 14. 14. The polyester of claim 13, wherein the ABS resin is present in an amount of about 4 to about 19% by weight. Merblend composition. 15. 12. The ABS resin comprises at least about 30% by weight diene rubber substrate. Polymer blend compositions as described. 16. Claim 15 wherein the ABS resin comprises about 50 to about 75 weight percent diene rubber substrate. Polymer blend compositions as described.