Patent Grant
8198371
The present invention generally relates to polymer blends comprising polyesters made from terephthalic acid; 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 1,4-cyclohexanedimethanol; and copolymers made from acrylonitrile, butadiene, and styrene (ABS). The blends are characterized by a unique combination of properties such as heat resistance, toughness, high modulus, and good flowability. The blends can be formed into, for example, molded articles, films, and fibers.
Molding plastics, films, and fibers can be produced from a variety of plastic materials by a variety of processes such as extrusion blow molding, stretch blow molding, etc. These plastic materials may comprise mixtures of structurally different polymers or copolymers, which are referred to as polymer blends.
Polymer blending technology generally rests on the premise of property additivity. Typically, blending with a higher modulus polymer to increase stiffness will reduce the toughness and flowability of a given polymer.
In the present invention, however, it has been surprisingly discovered that adding a higher modulus ABS copolymer to a certain polyester results in a blend with not only a higher modulus than the original polyester, but also with better flowability and excellent toughness. In some cases, the blends even have greater toughness—particularly, low temperature toughness—than either of the component polymers.
The present invention generally relates to polymer blend compositions prepared by blending polyesters made from terephthalic acid; 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 1,4-cyclohexanedimethanol, with copolymers made from acrylonitrile, butadiene, and styrene (ABS) monomers. These polymer blends have a combination of toughness, heat resistance, high modulus, and good flowability making them particularly useful in films, fibers, packaging, and engineering molding plastics.
In one embodiment, the invention provides a polymer blend comprising:
(a) 5 to 95 weight percent of a polyester comprising:
(b) 5 to 95 weight percent of a copolymer comprising acrylonitrile, butadiene, and styrene (ABS) monomers.
In another embodiment, the invention provides a polymer blend comprising:
(a) 60 to 95 weight percent of a polyester comprising:
(b) 5 to 40 weight percent of a copolymer comprising 20 to 40 weight percent of acrylonitrile monomers, 20 to 40 weight percent of butadiene monomers, and 40 to 60 weight percent of styrene monomers.
Surprisingly, it has been discovered that blends of (a) a copolyester comprising terephthalic acid; 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 1,4-cyclohexanedimethanol residues, with (b) a copolymer comprising acrylonitrile, butadiene, and styrene (ABS) monomers can have a combination of toughness, heat resistance, high modulus, and good flowability.
According to the present invention, there is provided a polymer blend comprising:
(a) 5 to 95 weight percent of a polyester comprising:
(b) 5 to 95 weight percent of a copolymer comprising acrylonitrile, butadiene, and styrene (ABS) monomers.
In one embodiment, the blend comprises 60 to 95 weight percent of the polyester and 5 to 40 weight percent of the ABS compolymer. In another embodiment, the blend comprises about 70 to 90 weight percent of the polyester and about 10 to 30 weight percent of the ABS copolymer.
The polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols, which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. The polyesters of the present invention, therefore, can contain substantially equal molar proportions of acid residues (100 mole %) and diol residues (100 mole %) such that the total moles of repeating units is equal to 100 mole %. The mole percentages provided herein, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 30 mole % of isophthalic acid residues, based on the total acid residues, means that there are 30 moles of isophthalic acid residues for every 100 moles of acid residues. In another example, a polyester containing 30 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, based on the total diol residues, means that there are 30 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues for every 100 moles of diol residues.
The term “polyester,” as used herein, is intended to include “copolyesters.”
The term “residue,” as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. Therefore, reference to a dicarboxylic acid is intended to include the dicarboxylic acid itself and any derivative of the dicarboxylic acid, including its associated isomers, acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and mixtures thereof, useful in a reaction with a diol to make a polyester. Examples of esters of the dicarboxylic acids useful in this invention include the dimethyl, diproplyl, diisopropyl, dibutyl, diphenyl, etc.
For example, the term “terephthalic acid” is intended to include terephthalic acid itself as well as any derivative of terephthalic acid, including its associated isomers, acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and mixtures thereof, useful in a reaction with a diol to make a polyester.
In one embodiment, terephthalic acid may be used as the diacid starting material for the polyester component. In another embodiment, isophthalic acid may be used as the diacid starting material. In another embodiment, mixtures of terephthalic acid and isophthalic acid may be used as the diacid starting material.
The dicarboxylic acid portion of the polyester may be substituted with up to 20 mol %, but preferably less than 10 mol %, of other aromatic dicarboxylic acids. Examples of suitable other aromatic dicarboxylic acids include 4,4′-biphenyidicarboxylic acid; 1,5-, 2,6-, and 2,7-naphthalenedicarboxylic acid; 4,4′-oxydibenzoic acid; and trans-4,4′-stilbenedicarboxylic acid. In addition, the dicarboxylic acid portion of the polyester may be substituted with aliphatic or cycloaliphatic dicarboxylic acids containing 6 to 12 carbon atoms such as succinic, glutaric, adipic, sebacic, suberic, azelaic, decanedicarboxylic, and dodecanedicarboxylic acids.
The TMCB may be cis, trans, or a mixture of the two. The CHDM may be cis, trans, or a mixture of the two.
The glycol portion of the polyester may contain up to 10 mol %, but preferably less than 5 mol %, of another glycol containing 2 to 16 carbon atoms. Examples of suitable other glycols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and p-xylene glycol. The polyester may also be modified with polyethylene glycols or polytetramethylene glycols.
In one embodiment, the dicarboxylic acid portion of the polyester comprises 100 mole percent of terephthalic acid residues, and the glycol portion of the polyester comprises 5 to 70 mole percent of TMCB residues and 30 to 95 mole percent of CHDM residues. In another embodiment, the dicarboxylic acid portion of the polyester comprises 100 mole percent of terephthalic acid residues, and the glycol portion of the polyester comprises 5 to 50 mole percent of TMCB residues and 50 to 95 mole percent of CHDM residues.
In one embodiment, the polyester component of the polymer blend has a glass transition temperature (Tg) ranging from 90 to 140° C. The Tg may be determined, for example, by using a TA Instruments differential scanning calorimeter (DSC) instrument at a scan rate of 20° C./min.
In another embodiment, the polyester component of the polymer blend has a glass transition temperature ranging from 100 to 130° C.
In one embodiment, the inherent viscosity of the polyester component ranges from 0.4 to 0.9 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.
In another embodiment, the inherent viscosity of the polyester ranges from 0.5 to 0.8 dL/g.
The polyester component of the polymer blend may be prepared by methods known in the art.
The ABS copolymers used in the present invention can be prepared by methods known in the art. For example, it may be made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. The monomers are incorporated into the ABS copolymer as their corresponding residues.
In one embodiment, the ABS component of the polymer blend comprises:
15 to 40 mole % of acrylonitrile monomers;
6 to 40 mole % of butadiene monomers; and
40 to 80 mole % of styrene monomers.
In another embodiment, the ABS component of the polymer blend comprises:
20 to 40 mole % of acrylonitrile monomers;
20 to 40 mole % of butadiene monomers; and
40 to 60 mole % of styrene monomers.
Unless the context indicates otherwise, as used herein, the term “acrylonitrile” is intended to include acrylonitrile itself and any derivative of acrylonitrile that can be used in the preparation of ABS copolymers, such as methacrylonitrile, as well as the corresponding residues thereof, and mixtures thereof. Unless the context indicates otherwise, as used herein, the term “butadiene” is intended to include butadiene itself and any other diene that can be used in the preparation of ABS copolymers, such as ethylene-propylene diene monomer (EPDM), the corresponding residues thereof, and mixtures thereof. The term also includes saturated acrylate elastomer. The butadiene of the ABS copolymer typically exists as a separate phase with a particle size in the range from 0.1 to 5 microns. The butadiene phase may have a bimodal size distribution.
Unless the context indicates otherwise, as used herein, the term “styrene” is intended to include styrene itself and any derivative of styrene that can be used in the preparation of ABS copolymers, such as alpha methylstyrene, as well as the corresponding residues thereof, and mixtures thereof.
The ABS copolymer may be modified by addition of another copolymer such as styrene-maleic anhydride copolymers, methyl methacrylate alpha-methylstryrene copolymers, styrene-maleic anhydride-methyl methacrylate copolymers, and acrylic acid copolymers.
The polymer blend may comprise 0.01 to 25 weight percent of at least one additive chosen from colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, UV light stabilizers, thermal stabilizers, fillers, impact modifiers, processing aids, and reinforcing materials such as glass fibers.
The polymer blends of the present invention can be made by conventional mixing methods known in the art, such as melt blending or solution blending. Suitable methods include, but are not limited to, the steps of mixing the polyester and the ABS copolymer components in powder or granular form in an extruder, extruding the mixture into strands, chopping the strands into pellets, and molding the pellets into the desired article(s).
In one embodiment, the polymer blend according to the invention comprises:
(a) 60 to 95 weight percent of a polyester comprising:
(b) 5 to 40 weight percent of a copolymer comprising 20 to 40 weight percent of acrylonitrile monomers, 20 to 40 weight percent of butadiene monomers, and 40 to 60 weight percent of styrene monomers.
In another embodiment, the polymer blend comprises about 70 to 90 weight percent of the polyester and about 10 to 30 weight percent of the ABS copolymer.
Another aspect of the present invention relates to articles of manufacture comprising the polymer blends of the invention. Such articles of manufacture can be chosen from films, sheets, fibers, and molded articles.
In one embodiment, the polymer blends of the invention are useful as housing of consumer electronics. Consumer electronics include electronic equipment intended for everyday use. Consumer electronics are most often used in entertainment, communications, and office productivity. Some products classed as consumer electronics include, but are not limited to, personal computers, telephones, MP3 players, audio equipment, televisions, calculators, GPS automotive navigation systems, and playback and recording of video media such as DVDs, CDs, VHS's or camcorders.
In another embodiment, the blends of the invention are useful for and/or in medical equipment housings.
This invention can be further illustrated by the following working examples, although it should be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.
Measurement Methods
The inherent viscosity of the polyesters was determined in a 60/40 (wt/wt) phenol/tetrachloroethane mixture at a concentration of 0.5 g/100 ml at 25° C.
The glass transition temperature (Tg) was determined using a TA Instruments DSC instrument at a scan rate of 20° C./min.
The glycol content and the cis/trans ratio of the polyesters were determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer using either chloroform-trifluoroacetic acid (70-30 volume/volume) for polymers or, for oligomeric samples, 60/40 (wt/wt) phenol/tetrachloroethane with deuterated chloroform added for lock. Peak assignments for 2,2,4,4-tetramethyl-1,3-cyclobutanediol resonances were made by comparison to model mono- and dibenzoate esters of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. These model compounds closely approximate the resonance positions found in the polymers and oligomers.
The melt viscosity was measured using a Rheometrics Dynamic Analyzer (RDA II). The melt viscosity was measured as a function of shear rate, at frequencies ranging from 1 to 400 rad/sec, at the temperatures reported.
Unless otherwise specified, heat deflection temperature was determined at 264 psi according to ASTM D648. Flexural modulus and flexural strength were determined according to ASTM D790. Tensile properties were determined according to ASTM D638. Flatwise impact strength was determined according to ASTM D3763.
Blending Method
Unless otherwise specified, polymer blends were prepared in a 18-mm Leistritz twin-screw extruder. The polymers were premixed by tumble blending and fed into the extruder. The extruded strand was pelletized. The pellets were then injection molded into parts on a Toyo 90 injection molding machine. The extruder was run at 350 rpms at a feed rate to give a machine torque between 80-100%.
Polymer blends were prepared with varying concentrations of copolyester and ABS copolymer.
The copolyester component of the blends contained 100 mole % of terephthalic acid residues, 46.0 mole % of TMCB residues (46.1 mole % cis isomer), and 54 mole % of CHDM residues. The inherent viscosity of the copolyester was measured to be 0.59 dL/g.
The ABS copolymer component of the blends contained 26.2 mole % of acrylonitrile, 29.7 mole % butadiene, and 44.1 mole % styrene.
The copolyester was dried at 90° C. and the ABS copolyester was dried at 80° C. before making the polymer blends according to the method described above. Processing temperatures used during extrusion and molding were in the range of 260 to 290° C.
The compositions and properties of the blends are shown in Table 1.
The two Tg values for some blends in Table 1 suggest that those blends have two phases. It is likely that blend B also has two phases, but the Tg for the 10% ABS phase is too weak to be detected by DSC. Addition of the ABS causes an increase in modulus over the entire range of blend compositions. At the same time, the melt viscosity continuously decreases. The blends also have good low temperature flatwise impact strengths, which, in some cases, are even higher than that of the pure copolyester.
Polymer blends were prepared with varying concentrations of copolyester and ABS copolymer.
The same copolyester of Example 1 was used.
The ABS copolymer component of the blends contained 29.7 mole % of acrylonitrile, 23.3 mole % of butadiene, and 46.9 mole % of styrene.
The copolyester was dried at 90° C. and the ABS copolymer was dried at 80° C. before preparing the polymer blends according to the method described above. Processing temperatures used during extruding and molding were in the range of 260 to 290° C. The compositions and properties of the blends are shown in Table 2.
Two Tg values were reported in Table 2 for blends having two phases.
Similar to Example 1, addition of the ABS causes an increase in the modulus and decrease in melt viscosity over the entire range of blend compositions. In at least one case, the low temperature flatwise impact strength of the blend is higher than that of the pure copolyester.
Polymer blends were prepared with varying concentrations of copolyester and ABS copolymer.
The copolyester component of the blends contained 100 mole % of terephthalic acid residues, 23.5 mole % of TMCB residues (54.4 mole % cis isomer), and 76.5 mole % of CHDM residues. The inherent viscosity of the copolyester was measured to be 0.67 dL/g.
The same ABS copolymer of Example 1 was used.
The copolyester was dried at 90° C. and the ABS copolymer was dried at 80° C. before making the blends according to the method described above. Processing temperatures used during extruding and molding were in the range of 260 to 270° C.
The compositions and properties of the blends are shown in Table 3.
In this example, addition of the ABS again causes a continuous increase in modulus. In this case, all of the blend compositions have a higher low temperature flatwise impact strength than the pure copolyester. With the exception of the composition with 10% ABS, all of the blends also have a lower melt viscosity than the pure copolyester.
Polymer blends were prepared with varying concentrations of copolyester and ABS copolymer.
The copolyester used in the blends contained 100 mole % of terephthalic acid residues, 80 mole % of CHDM residues, and 20 mole % of ethylene glycol (EG) residues. The inherent viscosity of the copolyester was 0.75 dL/g.
The same ABS copolymer of Example 1 was used.
The copolyester was dried at 70° C. and the ABS copolymer was dried at 80° C. before preparing the blends according to the method described above. Processing temperatures used during extruding and molding were in the range of 260 to 270° C.
The compositions and properties of the blends are shown in Table 4.
Two Tg values were reported in Table 4 for blends having two phases. Contrary to the blends of Examples 1-3, the flexural modulus of the blends in Table 4 were all less than or equal to the flexural modulus of the neat copolyester. In addition, the melt viscosities of the blends were higher than those of the neat copolyester.
Polymer blends were prepared with varying concentrations of copolyester and ABS copolymer.
The copolyester used in the blends contained 100 mole % of terephthalic acid residues, 62 mole % of CHDM residues, and 38 mole % of EG residues. The inherent viscosity of the copolyester was 0.73 dL/g.
The same ABS copolymer of Example 1 was used.
The copolyester was dried at 70° C. and the ABS copolymer was dried at 80° C. before preparing the blends according the method described above. Processing temperatures used during extruding and molding were in the range of 260 to 270° C. The compositions and properties of the blends are shown in Table 5.
Two Tg values were reported in Table 5 for blends having two phases.
Contrary to the blends of Examples 1-3, the flatwise impact strength measured by both total energy and energy at max load of the polymer blends of this comparative example were all less than those of the neat copolyester.
Polymer blends were prepared with varying concentrations of copolyester and copolymer.
The copolyester used in the blends contained 100 mole % of terephthalic acid residues, 24.8 mole % of TMCB residues (54.6 mole % cis isomer), and 75.2 mole % of CHDM residues. The inherent viscosity was measured to be 0.72 dL/g.
A copolymer of styrene and acrylonitrile (SAN) was used in place of the ABS copolymer. This copolymer contained 37.5 mole % of acrylonitrile and 62.5 mole % of styrene.
The copolyester was dried at 90° C. and the SAN copolymer was dried at 80° C. before preparing the blends according to the method described above. Processing temperatures used during extruding and molding were in the range of 240 to 270° C. The compositions and properties of the blends are shown in Table 6.
Contrary to the blends of Examples 1-3, the flatwise impact strength measured by both total energy and energy at max load of the blends of this comparative example were all less than those of the neat copolyester.
It can be seen from a comparison of the data in the above examples that polymer blends according to the present invention offer a definite advantage over other polymer blends with regard to impact strength, glass transition temperature, modulus, melt viscosity, and/or toughness.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 61/076,239, filed on Jun. 27, 2008; the entire content of which is hereby incorporated by reference.
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