Patent Application
20240270960
The present invention relates to thermoplastic polycarbonate (PC) compositions with a lower odor rank, higher impact strength and good heat resistance, as well as shaped articles made therefrom.
Polycarbonate/ABS (Acrylonitrile-Butadiene-Styrene) alloy is widely used for a lot of applications, especially for automotive interior, due to its excellent property combination of lower emission, excellent mold-processing ability, good economic efficiency and strong physical properties such as high impact strength, high heat resistance, good aesthetic and so on.
However, there has been recently a growing appeal from end users in automotive market for low-odor materials to be used in manufacture of automotive interiors. In that case, PC/ABS blends, though generally believed to make less impact on odor of automotive interior than other types of materials including adhesives and leathers, was often requested to improve its odor performance from the perspective of odor control of the whole vehicle system. For this purpose, great efforts since then have been made by doing multiple degassing compounding or emission regulation of the raw materials (PC and ABS and so on) or PC/ABS recipe optimization or their combinations. However, a big gap is still there between the market demand and industry offers. For instance, typical PC/ABS materials generally shows an odor rank of 3.5-4.0 as evaluated according to PV3900:2000 after being conditioned at 80° C. for 2 hours, while the rank point of 3.0 is desired by the automotive interior market. The cause of bad odor with PC/ABS materials can be traced to the presence of polybutadiene-based rubbers in polymer matrix, which inherently have poor thermal instability and will produce odorous volatile/gas in thermal processing and thus worse odor of the finished materials.
On the other hand, aromatic polyesters (such as PET, PBT, PTT, PETG and PCTG etc.) have been widely considered as potential blending materials with polycarbonate.
US20070129504A1, US20190048185A1, U.S. Pat. No. 6,673,864B2, EP3099743B1, and US20130331492A1 which describe compositions based on PC/aromatic polyester blends either focus on improved flame retardance or on mechanical properties or on chemical resistance or a combination of these features for the finished materials. However, the odor assessment of such PC blends with all kinds of aromatic or aliphatic polyesters had scarcely been mentioned.
There is a continuous need for new compositions to offer desirable odor performance/rank (e.g. 3.0 according to PV3900:2000 after being conditioned at 80° C. for 2 hours) for automotive interior materials, while properties such as good flowability, high impact strength, and high heat resistance are also present.
Thus, one object of the present invention is to provide a thermoplastic polycarbonate composition which has a combination of low odor rank, good impact performance, good flowability, and good heat resistance.
Therefore, an object of the present invention is a thermoplastic polycarbonate composition comprising the following components, relative to the total weight of the composition:
and 2,2,4,4-tetramethyl-1,3-cyclobutylene terephthalate repeating units having the structure
wherein * indicates the position where the unit is connected to the polymer chain and wherein the total content by weight of components A)-C) is not less than 95 wt. %, relative to the total weight of the composition.
Another object of the present invention is a shaped article made from the polycarbonate composition according to the first aspect of the present invention.
Still Another object of the present invention is a process for preparing the shaped article according to the second aspect of the present invention, comprising injection moulding, extrusion moulding, blowing moulding or thermoforming the polycarbonate composition according to the first aspect of the present invention.
Still another object of the present invention is a use of an amorphous copolyester comprising 1,4-cyclohexanedimethylene terephthalate repeating unit having the structure
and 2,2,4,4-tetramethyl-1,3-cyclobutylene terephthalate repeating unit having the structure
wherein * indicates the position where the unit is connected to the polymer chain, for improving the odor rank of a composition comprising an aromatic polycarbonate and a polysiloxane-polycarbonate copolymer. The odor rank is preferably measured according to PV3900:2000 after a sample being conditioned at 80° C. for 2 hours
The polycarbonate composition and the shaped article according to the present invention demonstrate an odor rank of 3.0 as measured according to PV3900: 2000 after being conditioned at 80° C. for 2 hours, an impact strength of higher than 20 KJ/m2 at −30° C. as measured according to ISO 180/A: 2000 and a Vicat temperature of higher then 125° C. as measured according to ISO 306: 2013. The polycarbonate composition according to the present invention also has good flowability, as demonstrated by the melt volume rate determined according to ISO 1133-1: 2011 at a temperature of 260° C. with a plunger load of 5 kg.
The polycarbonate compositions and the shaped articles according to the present invention are suitable for interior applications which require relatively low odor rank (not more than 3.0, as measured according to PV3900: 2000 after being conditioned at 80° C. for 2 hours), excellent impact strength, and good heat resistance, such as automotive interior applications etc.
Other subjects and characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow.
In that which follows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions “between . . . and . . . ” and “from . . . to . . . ”.
As used herein, the expression “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. When the definition of a term in the present description conflicts with the meaning as commonly understood by those skilled in the art the present invention belongs to, the definition described herein shall apply.
Unless otherwise specified, all numerical values expressing amount of ingredients and the like which are used in the description and claims are to be understood as being modified by the term “about”.
Technical features described for each element in the present application can combined in any way on the provision that there is no conflict. Preferred, particularly preferred embodiments described for the composition according to the invention apply as well for a shaped articled made from the composition according to the invention or the process or the claimed use.
The polycarbonate composition according to the present invention comprises an aromatic polycarbonate as component A.
In the present application, references to “polycarbonate” do not include polysiloxane-polycarbonate copolymers.
According to the invention, “polycarbonate” is to be understood as meaning both homopolycarbonates and copolycarbonates, in particular aromatic ones. These polycarbonates may be linear or branched in known fashion. According to the invention, mixtures of polycarbonates may also be used.
A portion, preferably up to 80 mol %, more preferably of 20 mol % to 50 mol %, of the carbonate groups in the polycarbonates used in accordance with the invention may have been replaced by aromatic dicarboxylic ester groups. Polycarbonates of this type that incorporate not only acid radicals derived from carbonic acid but also acid radicals derived from aromatic dicarboxylic acids in the molecular chain are referred to as aromatic polyester carbonates. For the purposes of the present invention, they are covered by the umbrella term “thermoplastic aromatic polycarbonates”.
Replacement of the carbonate groups by the aromatic dicarboxylic ester groups proceeds essentially stoichiometrically and also quantitatively and the molar ratio of the reaction partners is therefore also reflected in the final polyester carbonate. The aromatic dicarboxylic ester groups can be incorporated either randomly or blockwise.
Aromatic polycarbonates selected in accordance with the invention preferably have weight-average molecular weights Mw of 15 000 to 40 000 g/mol, more preferably of 16 000 to 34 000 g/mol, even more preferably of 17 000 to 33 000 g/mol, most preferably of 19 000 to 32 000 g/mol. The values for Mw here are determined by a gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (made of bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany; calibration according to method 2301-0257502-09D (2009 Edition in German) from Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. Column combination of crosslinked styrene-divinylbenzene resins. Diameter of analytical columns: 7.5 mm; length: 300 mm. Particle sizes of column material: 3 μm to 20 μm. Concentration of solutions: 0.2% by weight. Flow rate: 1.0 ml/min, temperature of solutions: 30° C. Detection using a refractive index (RI) detector.
The polycarbonates are preferably produced by the interfacial process or the melt transesterification process, which have been described many times in the literature.
With regard to the interfacial process reference is made for example to H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 33 et seq., to Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, Chapt. VIII, p. 325, to Dres. U. Grigo, K. Kircher and P. R- Müller “Polycarbonate” in Becker/Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 118-145 and also to EP 0 517 044 A1.
The melt transesterification process is described, for example, in the “Encyclopedia of Polymer Science”, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), and in patent specifications DE 10 31 512 A and U.S. Pat. No. 6,228,973 B1.
Particulars pertaining to the production of polycarbonates are disclosed in many patent documents spanning approximately the last 40 years. Reference may be made here by way of example to Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P. R. Müller, H. Nouvertné, BAYER AG, “Polycarbonates” in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718, and finally to U. Grigo, K. Kirchner and P. R. Müller “Polycarbonate” in Becker/Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.
The production of aromatic polycarbonates is effected for example by reaction of dihydroxyaryl compounds with carbonic halides, preferably phosgene, and/or with aromatic dicarboxyl dihalides, preferably benzenedicarboxyl dihalides, by the interfacial process, optionally using chain terminators and optionally using trifunctional or more than trifunctional branching agents, production of the polyester carbonates being achieved by replacing a portion of the carbonic acid derivatives with aromatic dicarboxylic acids or derivatives of the dicarboxylic acids, specifically with aromatic dicarboxylic ester structural units according to the carbonate structural units to be replaced in the aromatic polycarbonates. Preparation via a melt polymerization process by reaction of dihydroxyaryl compounds with, for example, diphenyl carbonate is likewise possible.
Dihydroxyaryl compounds suitable for the production of polycarbonates are for example hydroquinone, resorcinol, dihydroxydiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, α,α′-bis(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from derivatives of isatin or phenolphthalein and the ring-alkylated, ring-arylated and ring-halogenated compounds thereof.
Preferred dihydroxyaryl compounds are 4,4′-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethylbisphenol A, 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)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and also the bisphenols (I) to (III)
in which R′ in each case stands for C1- to C4-alkyl, aralkyl or aryl, preferably for methyl or phenyl, very particularly preferably for methyl.
Particularly preferred dihydroxyaryl compounds are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxybiphenyl, and dimethylbisphenol A and also the diphenols of formulae (I), (II) and (III).
These and other suitable dihydroxyaryl compounds are described for example in U.S. Pat. Nos. 3,028,635 A, 2,999,825 A, 3,148,172 A, 2,991,273 A, 3,271,367 A, 4,982,014 A und 2,999,846 A, in DE 1 570 703 A, DE 2063 050 A, DE 2 036 052 A, DE 2 211 956 A and U.S. Pat. No. 2,999,846 A, in DE 1 570 703 A, DE 2063 050 A, DE 2 036 052 A, DE 2 211 956 A and DE 3 832 396 A, in FR 1 561 518, in the monograph “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964” and also in JP 62039/1986 A, JP 62040/1986 A and JP 105550/1986 A.
In the case of homopolycarbonates only one dihydroxyaryl compound is used; in the case of copolycarbonates two or more dihydroxyaryl compounds are used. The dihydroxyaryl compounds employed, similarly to all other chemicals and assistants added to the synthesis, may be contaminated with the contaminants from their own synthesis, handling and storage. However, it is desirable to use raw materials of the highest possible purity.
Suitable carbonic acid derivatives are for example phosgene and diphenyl carbonate.
Suitable chain terminators that may be used in the production of polycarbonates are monophenols. Suitable monophenols are for example phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.
Preferred chain terminators are the phenols mono- or polysubstituted by linear or branched C1- to C30-alkyl radicals, preferably unsubstituted or substituted by tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and/or p-tert-butylphenol.
The amount of chain terminator to be employed is preferably 0.1 to 5 mol % based on the moles of diphenols employed in each case. The addition of the chain terminators may be effected before, during or after the reaction with a carbonic acid derivative.
Suitable branching agents are the trifunctional or more than trifunctional compounds familiar in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups. Suitable branching agents are for example 1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5′-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane and 1,4-bis((4′,4″-dihydroxytriphenyl)methyl)benzene and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. The amount of the branching agents for optional employment is preferably 0.05 mol % to 2.00 mol %, based on moles of dihydroxyaryl compounds used in each case. The branching agents may be either initially charged together with the dihydroxyaryl compounds and the chain terminators in the aqueous alkaline phase or added dissolved in an organic solvent before the phosgenation. In the case of the transesterification process the branching agents are employed together with the dihydroxyaryl compounds.
Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxybiphenyl, and the copolycarbonates based on the two monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and also homo- or copolycarbonates derived from the diphenols of formulae (I), (II) and (III)
in which R′ in each case stands for C1- to C4-alkyl, aralkyl or aryl, preferably for methyl or phenyl, very particularly preferably for methyl.
As examples of aromatic polycarbonate suitable for the present invention, mention can be made of those produced from bisphenol A and phosgene, and sold under the trade name Makrolon® 2400, Makrolon® 2600, Makrolon® 2800, Makrolon® 3100 by Covestro Co., Ltd.
The aromatic polycarbonate is present in the polycarbonate composition in an amount ranging from 24 wt. % to 70 wt. %, relative to the total weight of the polycarbonate composition.
The polycarbonate composition according to the present invention comprises a polysiloxane-polycarbonate block copolymer (also named as “SicoPC” in the context of the present application) as component B.
The polysiloxane-polycarbonate copolymer comprises polydiorganosiloxane (also named as “siloxane” in the context of the present application) blocks and polycarbonate blocks.
The polysiloxane-polycarbonate copolymer can be obtained by using a (poly)siloxane of the following formula (1a) as a dihydroxyaryl compound in the process for preparation an aromatic polycarbonate as mentioned previously with respect to component A:
It is also possible to use dihydroxyaryl compounds, in which two or more siloxane blocks of general formula (1a) are linked via terephthalic acid and/or isophthalic acid under formation of ester groups.
Especially preferable are (poly)siloxanes of the formulae (2) and (3)
Also preferably the siloxane block can be derived from one of the following structures:
It is equally preferable, that at least two of the same or different siloxane blocks of the general formulae (IV), (V) or (VI) are linked via terephthalic acid and/isophthalic acid under formation of ester groups.
It is also preferable, if p=0 in formula (1a), V stands for C3-alkylene,
The weight-average molecular weight Mw of the siloxane block, is preferably 3000 to 20 000 g/mol, and more preferably 3500 to 15000 g/mol, determined by gel permeation chromatography using a BPA (bisphenol A) polycarbonate as standard and dichloromethane as eluent. It should be understand that SiCoPC may comprise more than one siloxane block in one polymer chain.
The polysiloxane-polycarbonate block copolymer and the production thereof are described in WO 2015/052106 A2.
Advantageously, the polysiloxane-polycarbonate copolymer is present in the polycarbonate composition according to the present invention in an amount ranging from 15 wt. % to 50 wt. %, preferably from 17.5 wt. % to 45 wt. %, relative to the total weight of the polycarbonate composition.
The polycarbonate composition according to the present invention comprises an amorphous copolyester as component C.
The amorphous copolyester comprises 1,4-cyclohexanedimethylene terephthalate repeating units having the structure
and 2,2,4,4-tetramethyl-1,3-cyclobutylene terephthalate repeating units having the structure
wherein * indicates the position where the unit is connected to the polymer chain.
The amorphous copolyester can be obtained by polymerization of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCBD), terephthalic acid (or dimethyl terephthalate) and 1,4-cyclohexanediol.
According to the different positions of hydroxyl groups, the monomer TMCBD has cis and trans isomers. The C4 ring of the cis-TMCBD is non-planar and the crystals have a dihedral angle of 17.5°, while the trans-TMCBD has a dihedral angle of 0° and has a symmetrical structure; the C4 ring is very stable.
Preferably, the copolyester comprises 10 wt.-% to 90 wt.-% of the cyclohexanedimethylene terephthalate repeating units and 10 wt.-% to 90 wt.-% of the 2,2,4,4-tetramethylcyclobutylene terephthalate repeating units, based on the weight of the copolyester.
Advantageously, the copolyester has a melt volume rate (MVR) of 5 to 30 g/mol, preferably of 8 to 25 g/mol, and more preferably of 10 to 20 g/mol, as measured in accordance with ISO 1133-1: 2011 at 260° C. under a loading of 5 kg.
Advantageously, the copolyester is present in the polycarbonate composition according to the present invention in an amount ranging from 12 wt. % to 37 wt. %, preferably from 15 wt. % to 35 wt. %, relative to the total weight of the polycarbonate composition.
In addition to components A-C mentioned above, the polycarbonate composition according to the present invention can optionally comprise of one or more additional additives conventionally used in polymer compositions, such as lubricants and demoulding agents (e.g. pentaerythritol tetrastearate), antioxidants, stabilizers (such as thermal stabilizers, UV absorbers, IR absorbers), antistatic agents (including inorganic antistatic agents, such as, conductive carbon blacks, carbon fibres, carbon nanotubes and organic antistatic agents), colorants, etc.
The person skilled in the art can select the type and the amount of the additional additives so as to not significantly adversely affect the desired properties of the polycarbonate composition according to the present invention.
Preferably, the composition according to the present invention does not comprise butadiene-based rubber.
Advantageously, the total content by weight of components A)-C) is no less than 90 wt. %, preferably no less than 95 wt. %, more preferably no less than 98 wt. %, relative to the total weight of the polycarbonate composition according to the present invention.
In some preferred embodiments, the thermoplastic polycarbonate composition according to the present invention comprises the following components, relative to the total weight of the composition:
In some preferred embodiments, the thermoplastic polycarbonate composition according to the present invention consists of the following components, relative to the total weight of the composition:
The polycarbonate composition according to the present invention can be in the form of, for example, pellets, and can be prepared by a variety of methods involving intimate admixing of the materials desired in the composition.
For example, the materials desired in the composition are first blended in a high speed mixer. Other low shear processes, including but not limited to hand mixing, can also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding directly into the extruder at the throat and/or downstream through a side stuffer. Additives can also be compounded into a masterbatch with a desired polymeric resin and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water bath and pelletized. The pellets can be one-fourth inch long or less as described. Such pellets can be used for subsequent molding, shaping or forming.
Melt blending methods are preferred due to the availability of melt blending equipment in commercial polymer processing facilities.
Illustrative examples of equipment used in such melt processing methods include: co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, and various other types of extrusion equipment.
The temperature of the melt in the processing is preferably minimized in order to avoid excessive degradation of the polymers. It is often desirable to maintain the melt temperature between 230° C. and 350° C. in the molten resin composition, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept short.
In some cases, the molten composition exits from a processing equipment such as an extruder through small exit holes in a die. The resulting strands of the molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.
The polycarbonate composition according to the present invention can be used, for example, for the production of various types of shaped articles.
Another object of the present invention is a shaped article made from the polycarbonate composition according to the first aspect of the present invention.
As used herein, “made from” means that the shaped article comprises the polycarbonate composition according to the first aspect of the present invention, preferably the shaped article consists of the polycarbonate composition according to the first aspect of the present invention.
As examples of shaped articles, mention can be made of, for example, door handle, instrument panel, and body parts or interior trim for commercial vehicles, especially for the motor vehicle sector.
The polycarbonate composition according to the present invention can be processed into shaped articles by a variety of means such as injection moulding, extrusion moulding, blowing moulding or thermoforming to form shaped articles.
Thus, according to the third aspect, the present invention provides a process for preparing the shaped article according to the second aspect of the present invention, comprising injection moulding, extrusion moulding, blowing moulding or thermoforming the polycarbonate composition according to the first aspect of the present invention.
According to the fourth aspect, the present invention provides a use of an amorphous copolyester comprising 1,4-cyclohexanedimethylene terephthalate repeating unit having the structure
and 2,2,4,4-tetramethyl-1,3-cyclobutylene terephthalate repeating unit having the structure
wherein * indicates the position where the unit is connected to the polymer chain, for improving the odor rank of a composition comprising an aromatic polycarbonate and a polysiloxane-polycarbonate copolymer. The odor rank is preferably determined according to PV3900:2000.
The amorphous copolyester, the aromatic polycarbonate and the polysiloxane-polycarbonate copolymer are the same as defined previously.
Preferably, the amorphous copolyester is present in amount ranging from 15 wt. % to 35 wt. % in the composition, relative to the total weight of the composition.
Preferably, the polysiloxane-polycarbonate copolymer is present in an amount ranging from 15 wt. % to 50 wt. %, preferably from 17.5 wt. % to 45 wt. %, relative to the total weight of the polycarbonate composition.
Preferably, the copolyester is present in an amount ranging from 12 wt. % to 37 wt. %, from 15 wt. % to 35 wt. %, relative to the total weight of the polycarbonate composition.
The Examples which follow serve to illustrate the invention in greater detail.
The physical properties of compositions obtained in the examples were tested as follows:
The melt flowability was evaluated by means of the melt volume flow rate (MVR) measured in accordance with ISO 1133-1: 2011 at a temperature of 260° C. with a plunger load of 5 kg or at a temperature of 300° C. with a plunger load of 1.2 kg.
The IZOD notched impact strength was measured in accordance with ISO 180/1A:2000 under the energy of 5.5 J on a notched single gated specimen with dimensions of 80 mm×10 mm×4 mm conditioned under testing temperature for 2 hours.
The Vicat softening temperature was determined in accordance with ISO 306: 2013 on bars of dimensions 80 mm×10 mm×4 mm at a heating rate of 120° C./h.
The tensile stress, the tensile strain at break and tensile modulus were determined at room temperature (23)° ° C. in accordance with ISO 527-2: 2012 on shoulder bars of dimensions 170 mm×10 mm×4 mm.
The odor rank was evaluated in accordance with PV3900-2000 as follows:
A 20 g sample was placed in a 1 L bowl. A test container was closed tightly and aged at a temperature of 80° C. for 2 hours in a preheated desiccator. The evaluation was performed by a minimum of five examiners. The odor was evaluated using the evaluation scale (see Table 1) with grades 1 to 6, with half-steps allowed, for all possible variants.
The materials listed in Table 2 were compounded in a twin-screw extruder (ZSK-25) (from Werner and Pfleiderer) at a speed of rotation of 225 rpm, a throughput of 20 kg/h, and a machine temperature of 260° ° C., and granulated.
The granules obtained were processed on an injection moulding machine (from Arburg) at a melt temperature of 260° C. and a mold temperature of 80° C. to produce test specimens.
The physical properties of compositions obtained were tested and the results were summarized in Table 2.
As shown in Table 2, the composition of comparative example 1 (CE1) not comprising Tritan demonstrates an odor rank of 3.5.
As demonstrated by compositions of comparative examples 2-5 (CE2-CE5) comprising a common impact modifier such as MBS and not comprising SicoPC have the odor rank of 3.5.
It can be seen from Table 2, polycarbonate compositions of invention examples 1-4 (IE1-IE4) demonstrates a combination of good odor rank, good impact strength, good flowability, and good heat resistance. However, such a combination of low odor rank, excellent impact strength, good flowability, and good heat resistance can be achieved only when the Tritan content is in a suitable range (i.e. 15-35 wt. %). When the Tritan content is ≤10 wt. % (CE6) or ≥40 wt. % (CE7 and CE8), the odor rank is not acceptable.
As demonstrated by compositions of comparative examples 9-11 (CE 9-11), pure resins of polycarbonate resin, Tritan, and polysiloxane-polycarbonate copolymer alone all exhibit an odor rank of 3.5, which is above the desired odor rank of 3.0, for auto interior applications.
As demonstrated by comparative examples 12-14 (CE 12-14), other types of amorphous copolyesters (such as PCCD) or semi-crystalline copolyesters (such as PETG and PBT), when blended with polycarbonate, cannot result in the desirable odor rank of 3.0. The odor performance is bad, if ABS is included in the composition (CE 15).
Similarly, the materials listed in Table 3 were compounded, the physical properties of compositions obtained were tested and the results were summarized in Table 3.
It can be seen from Table 3 that when the content of polysiloxane-polycarbonate copolymer is too low (10 wt. % in CE16) or too high (55 wt. % in CE17-CE19), compositions with good odor rank and excellent impact strength at −30° C. cannot be obtained.
It also can be seen from Table 3 that when the contents of the amorphous copolyester and the polysiloxane-polycarbonate copolymer are in a suitable range (i.e. 15-35 wt. %), the polycarbonate compositions obtained (IE5-IE8) can have a desirable combination of odor rank of 3.0, excellent impact strength at −30° C., good flowability and good heat resistance.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/097098 | May 2021 | WO | international |
| 21179185.0 | Jun 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/063993 | 5/24/2022 | WO |
