Patent Application
20240209206
The present invention relates to a polycarbonate (PC) composition. In particular, the present invention relates to a polycarbonate composition with high level of comparative tracking index and good flame retardancy, and a shaped article made from the same.
Polycarbonate is widely used for a variety of applications, such as automotive, electric and electronic fields due to excellent optical, mechanical and heat resistant properties as well as excellent thermal processing ability thereof.
Copolycarbonates, as special types of polycarbonates, are widely used in electrical and electronic sectors, as housing material of lights, and in applications where particular thermal and mechanical properties are required, for example blow dryers, applications in the automotive sector, plastic covers, diffuser screens or waveguide elements and lamp covers or lamp bezels.
It is known that the heat distortion resistance of polycarbonate can be improved by introducing a specific building block based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (Bisphenol TMC) into polycarbonate backbone. The copolycarbonate obtained thereby (so-called high-Tg polycarbonate) is expensive. Furthermore, the flowability of such kind of copolycarbonates is not high due to its relatively higher glass transition temperature (Tg).
Recently, there is a trend to miniaturize electronic and electrical devices in the field of electric and electronic applications. This prompted the adoption of more complicated and compacted design of electrical devices including plastic housings or parts. Therefore, safety-related properties of plastic materials, such as comparative tracking index (CTI) and flame retardancy, were required in the field of electronics and electrical applications.
For instance, a high level of flame retardancy (e.g., V0 rating at 1.5 mm as determined according to UL94-2015) and high CTI rank (e.g., CTI=600 V as determined according to IEC60112:2011) are required for plastic materials. However, it has been well known that the comparative tracking index for standard polycarbonate resin is only around 250 V or even below.
Furthermore, introducing flame retardant agents into standard bisphenol A based polycarbonate was commonly believed to be harmful to the CTI performance of finished blends, the more the flame retardant, the lower the CTI will be, more details can be found in S. Sullalti et al., “Effect of phosphorus based flame retardants on UL94 and Comparative Tracking Index properties of poly(butylene terephthalate)”, Polymer Degradation and Stability, 2012.
U.S. Pat. No. 4,900,784 A discloses a polymer mixture which consists of a polybutylene terephthalate, a brominated polystyrene, an aromatic polycarbonate and an agent to improve the impact strength, which shows a combination of good flame-retardancy and a high level of comparative tracking index.
Thus, it is still a challenge to obtain polycarbonate compositions having high CTI, good flowability, and good flame retardancy.
One objective of the present application is thus to provide a polycarbonate composition which has a good combination of comparative tracking index and flame retardancy.
Another object of the present application is to provide an article which has a good combination of comparative tracking index and flame retardancy.
In a first aspect, the present invention provides a polycarbonate composition comprising the following components, relative to the total weight of the composition:
As used herein, the content by weight of the unit of formula (1) in the polycarbonate composition (C1/C/W) is calculated as follows:
Wherein
The inventors have discovered unexpectedly that the composition according to the present invention has a comparative tracking index up to 600V as determined according to IEC60112:2011, and a flame-retardancy level of V0 as determined according to UL94-2015.
Comparative tracking index (CTI) means a numerical value of the maximum voltage at which five test specimens in test period withstand 50 drops of specified electrolyte liquid without tracking failure and without a persistent flame occurring, as determined according to IEC60112:2011.
In a second aspect, the present invention provides a shaped article made from a polycarbonate composition according to the first aspect of the present invention.
In a third aspect, the present invention provides a process for preparing the shaped article mentioned above, comprising injection moulding, extrusion moulding, blow moulding or thermoforming the polycarbonate composition according to the first aspect of the present invention.
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 . . . ”.
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.
Throughout the instant application, the term “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones. As used herein, the use of the term “comprising” also discloses the embodiment wherein no features other than the specifically mentioned features are present (i.e. “consisting of”).
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”.
According to the first aspect, the polycarbonate composition according to the present invention comprises a copolycarbonate.
In the present application, the copolycarbonate refers to the polycarbonate comprising
The units of formula (1) can be derived from a diphenol of formula (1′):
Preferably, the unit of formula (1) has the following formula (1a),
wherein * indicates the position where formula (1a) is connected to the polymer chain, i.e., the unit of formula (1) is derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) having the formula (1′a):
The units of formula (2) can be derived from a diphenol of formula (2′):
Preferably, the unit of formula (2) has the following formula (2a),
wherein * indicates the position where formula (2a) is connected to the polymer chain, i.e., the unit of formula (2) is derived from bisphenol A, i.e. the diphenol of formula (2′a).
Preferably, the copolycarbonate comprises units derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) and bisphenol A.
Preferably, the copolycarbonate does not comprise units derived from a diphenol other than a diphenol of formula (1′) and a diphenol of formula (2′).
Preferably, the copolycarbonate does not comprise units derived from a diphenol other than bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) and bisphenol A.
The diphenols of formula (1′) and formula (2′) are known and can be prepared by processes known from literatures (for example H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).
The mole content of the units of the formula (1) in the copolycarbonate is 24-70 mol %, more preferably 40-70 mol %, based on the total mole number of units of formula (1) and formula (2).
The mole content of the units of the formula (2) in the copolycarbonate is 30-76 mol %, more preferably 30-60 mol %, based on the total mole number of units of formula (1) and formula (2).
The copolycarbonate used in the composition according to the present invention is commercially available or can be produced by a process known in the art.
For example, the copolycarbonate used in the composition according to the present invention can be produced by an interfacial process. In particular, the diphenols of the formula (1′) and (2′) and optional branching agents are dissolved in aqueous alkaline solution and reacted with a carbonate source, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture comprising an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound. The reaction procedure can also be conducted in a multistep process.
Such processes for the preparation of copolycarbonate are known in principle as two-phase interfacial processes, for example from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, page 33 et seq., and on Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, page 325, and the underlying conditions are therefore familiar to the person skilled in the art.
The concentration of the diphenols in the aqueous alkaline solution is from 2 wt. % to 25 wt. %, preferably from 2 wt. % to 20 wt. %, more preferably from 2 wt. % to 18 wt. % and even more preferably from 3 wt. % to 15 wt. %. The aqueous alkaline solution consists of water in which hydroxides of alkali metals or alkaline earth metals are dissolved. Sodium and potassium hydroxides are preferred.
The concentration of the amine compound is from 0.1 mol % to 10 mol %, preferably 0.2 mol % to 8 mol %, particularly preferably 0.3 mol % to 6 mol % and more particularly preferably 0.4 mol % to 5 mol %, relative to the mole amount of diphenol used.
The carbonate source is phosgene, diphosgene or triphosgene, preferably phosgene. Where phosgene is used, a solvent may optionally be dispensed with and the phosgene may be passed directly into the reaction mixture.
Tertiary amines, such as triethylamine or N-alkylpiperidines, may be used as a catalyst. Suitable catalysts are trialkylamines and 4-(dimethylamino)pyridine. Triethylamine, tripropylamine, triisopropylamine, tributylamine, trisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.
Halogenated hydrocarbons, such as methylene chloride, chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof, or aromatic hydrocarbons, such as, toluene or xylenes, are suitable as an organic solvent. The reaction temperature may be from −5° C. to 100° C., preferably from 0° C. to 80° C., particularly preferably from 10° C. to 70° C. and very particularly preferably from 10° C. to 60° C. The preparation of the copolycarbonates by the melt transesterification process, in which the diphenols are reacted with diaryl carbonates, generally diphenyl carbonate, in the presence of catalysts, such as alkali metal salts, ammonium or phosphonium compounds, in the melt, is also possible.
The melt transesterification process is described, for example, in 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 DE-C 1031 512.
In the transesterification process the aromatic dihydroxy compounds already described in the case of the phase boundary process are transesterified with carbonic acid diesters with the aid of suitable catalysts and optionally further additives in the melt.
The reaction of the aromatic dihydroxy compound and of the carbonic acid diester to give the copolycarbonate can be carried out batchwise or preferably continuously, for example in stirred vessels, thin-film evaporators, falling-film evaporators, stirred vessel cascades, extruders, kneaders, simple disc reactors and high-viscosity disc reactors.
Preferably, the copolycarbonate is selected from block copolycarbonates and random copolycarbonates. More preferably, the copolycarbonate is selected from random copolycarbonates.
Advantageously, the copolycarbonate has a weight average molecular weight (Mw) ranging from 16000 g/mol to 40000 g/mol, preferably from 17000 g/mol to 32000 g/mol, as determined by Gel Permeation Chromatography (GPC) in methylene chloride at 25° C. using a polycarbonate standard with an UV-IR detector.
As an example for commercial products of the copolycarbonate suitable for the composition according to the present invention, mention can be made of the products sold under the name APEC® by the company Covestro Polymer (China), which are polycarbonate copolymers made from the copolymerization of carbonyl chloride with bisphenol A (BPA) and 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl) cyclohexane (BPTMC).
Preferably, the copolycarbonate is present in an amount ranging from 30 wt. % to 80 wt. %, more preferably from 35 wt. % to 75 wt. %, even more preferably from 35 wt. % to 71 wt. %, relative to the total weight of the composition according to the present invention.
According to the first aspect, the polycarbonate composition according to the present invention comprises a homopolycarbonate comprising an unit of formula (2).
In the present application, the homopolycarbonate refers to the polycarbonate comprising an unit of formula (2) as defined above.
The unit of formula (2) is derived from a diphenol of formula (2′):
Preferably, the unit of formula (2) is derived from the diphenol of formula (2′a), i.e. bisphenol A.
The homopolycarbonate used in the composition according to the present invention is commercially available or can be produced by a process known in the art.
For example, the homopolycarbonate can be produced by referring to the preparation process described with respect to component A.
Preferably, the homopolycarbonate has a weight average molecular weight (Mw) ranging from 24,000 g/mol to 28,000 g/mol, as determined by Gel Permeation Chromatography (GPC) in methylene chloride at 25° C. using a polycarbonate standard with an UV-IR detector.
As commercial products of homopolycarbonates suitable for use in the composition according to the present invention, mention can be made of Makrolon® 2400 and Makrolon® 2600 sold by the company Covestro Polymer (China).
Preferably, the homopolycarbonate is present in the polycarbonate composition according to the present invention in an amount ranging from 10 wt. % to 40 wt. %, more preferably 12 wt. % to 35 wt. %, relative to the total weight of the composition.
According to the first aspect, the polycarbonate composition according to the present invention comprises a phosphorous flame retardant.
Preferably, the phosphorus flame retardant suitable for use in the composition according to the present invention are selected from monomeric and oligomeric phosphoric and phosphonic acid esters, phosphazenes, and mixtures thereof.
Preferred monomeric and oligomeric phosphoric and phosphonic acid esters are phosphorus compounds of formula (3).
Preferably, R1, R2, R3 and R4, independently of one another, each denotes C1-C4 alkyl, phenyl, naphthyl, or phenyl C1-C4 alkyl, wherein the aromatic groups R1, R2, R3 and R4 can themselves be substituted with halogen and/or alkyl groups, preferably chlorine, bromine and/or C1-C4 alkyl. Particularly preferred aryl residues are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
Preferably, X in formula (3) denotes a mononuclear or polynuclear aromatic residue with 6 to 30 carbon atoms.
More preferably, X, is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. Particularly preferably, X is derived from bisphenol A.
Preferably, n is equal to 1.
Preferably, q denotes a number from 0 to 20, particularly from 0 to 10, and in the case that a mixture of phosphorus compounds of the general formula (3) are used, a average value from 0.8 to 5.0, preferably 1.0 to 3.0, more preferably 1.05 to 2.00, and particularly preferably from 1.08 to 1.60.
Phosphorus compounds of formula (3) are in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethylcresyl phosphate, tri(isopropylphenyl)phosphate, resorcinol bridged oligophosphate and bisphenol A bridged oligophosphate. The use of oligomeric phosphoric acid esters of formula (3) derived from bisphenol A is particularly preferred.
Most preferred phosphorus compounds of formula (3) is bisphenol A based oligophosphate according to formula (4).
The phosphorus compounds of formula (3) are known (cf. e.g. EP-A 0 363 608, EP-A 0 640 655) or can be produced by known methods in an analogous manner (e.g. Ullmanns Enzyklopadie der technischen Chemie, vol. 18, pp. 301 ff. 1979; Houben-Weyl, Methoden der organischen Chemie, vol. 12/1, p. 43; Beilstein vol. 6, p. 177).
Preferred phosphazenes are cyclic phosphazenes of formula (5):
The phosphazenes and their preparation are described e.g. in EP-A 728 811, DE-A 1 961 668 and WO 97/40092.
The following are preferred: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazenes, as well as phosphazenes of the following structures:
In the compounds shown above, k=1, 2 or 3.
Preferably, the trimer content (k=1) is from 98.5 to 100 mol %, preferably from 99 to 100 mol %, based on the cyclic phosphazenes.
In the case where the phosphazene of formula (5) is halogen-substituted on the phosphorus, e.g. from incompletely reacted starting material, the proportion of this phosphazene halogen-substituted on the phosphorus is preferably less than 1000 ppm, more preferably less than 500 ppm.
The phosphazenes can be used on their own or as a mixture, i.e. the radicals R can be identical or 2 or more radicals in formula (5) can be different. Preferably, the radicals R of a phosphazene are identical.
Preferably, only phosphazenes with identical R are used.
Preferably, all R=phenoxy.
The most preferred phosphazene is phenoxyphosphazene of formula (6) (all R=phenoxy) with an oligomer content where k=1 (C1) of 98.5-100 mol %, preferably 99-100 mol %.
The oligomer of the phosphazenes in the respective blend samples can also be detected and quantified, after compounding, by 31P-NMR (chemical shift; 5 trimer: 6.5 to 10.0 ppm; 5 tetramer: −10 to −13.5 ppm; 5 higher oligomers: −16.5 to −25.0 ppm).
As an example of commercial products of phosphazenes, mention can be made of that sold under the trade name HPCTP from Weihai Jinwei Chem Industry Company.
Preferably, the phosphorus flame-retardant is present in the composition according to the present invention in an amount ranging from 8 wt. % to 25 wt. %, more preferably 8 wt. % to 20 wt. %, relative to the total weight of the composition.
According to the first aspect, the polycarbonate composition of the present invention may optionally comprise an impact modifier.
There is no particular limitation on the impact modifier. Impact modifiers commonly used in polycarbonate composition can be used in the polycarbonate composition according to the present invention.
Preferably, the impact modifier is selected from rubber-modified vinyl (co)polymers comprising,
The wt. % is calculated based on the weight of the rubber-modified vinyl (co)polymer.
The glass transition temperature was determined by means of dynamic differential calorimetry (DSC) in accordance with the standard DIN EN 61006 at a heating rate of 10 K/min with definition of the Tg as the midpoint temperature (tangent method).
The at least one vinyl monomer D1 are preferably mixtures of
The wt. % is calculated based on the weight of the vinyl monomer D1.
Preferred monomer D1.1 is chosen from styrene, α-methylstyrene and methyl methacrylate. Preferred monomer D1.2 is chosen from acrylonitrile, maleic anhydride and methyl methacrylate. More preferably, monomer D1.1 is styrene and monomer D1.2 is selected from acrylonitrile and methyl methacrylate.
As examples of the graft base D2, mention can be made of, diene rubbers, EP(D)M rubbers (i.e., those based on ethylene/propylene and optionally diene), and acrylate, polyurethane, silicone, and ethylene/vinyl acetate rubbers and silicone/acrylate composite rubbers.
Preferred graft base D2 is chosen from diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (e.g. according to D1.1 and D1.2), with the provision that the glass transition temperature of component D2 is below <10° C., preferably <0° C., particularly preferably <−20° C.
Particularly preferred graft base D2 is selected from pure polybutadiene rubber or silicone/acrylate composite rubbers, such as silicone-butylacrylate rubber.
Particularly preferred rubber-modified vinyl (co)polymers are for example, ABS, MBS polymers, methyl methacrylate-grated silicon-butylacrylate rubber, as described e.g. in DE-OS 2 035 390 (=U.S. Pat. No. 3,644,574) or in DE-OS 2 248 242 (=GB 1 409 275) and in Ullmanns, Enzyklopädie der Technischen Chemie, vol. 19 (1980), p. 280 et seq.
The rubber-modified vinyl (co)polymers can be prepared by free radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, in particular by emulsion polymerization.
As examples of commercial products of rubber-modified vinyl (co)polymers can be used in the present invention, mention can be made of:
Advantageously, if presents, the impact modifier is present in the polycarbonate composition according to the present invention in amount ranging from 5 wt. % to 10 wt. %, relative to the total weight of the polycarbonate composition.
According to the first aspect, the polycarbonate composition of the present invention may optionally comprise a rubber-free vinyl copolymer.
Preferably, the rubber-free vinyl copolymer is a copolymer made from
Particular preference is given to a rubber-free copolymer of styrene (E1) and acrylonitrile (E2).
These copolymers are known and can be produced by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
The weight-average molecular weight Mw of the copolymer is preferably from 15 000 to 250 000 g/mol, more preferably from 50 000 to 160 000 g/mol, most preferably from 80 000 to 140 000 g/mol, as determined by gel permeation chromatography (GPC) with polystyrene as standard.
As an example of commercial products of rubber-free vinyl copolymers can be used in the present invention, mention can be made of LUSTRAN® SAN DN50, a styrene-acrylonitrile copolymer of 77 wt. % styrene and 23 wt. % acrylonitrile with a weight average molecular weight Mw of 130000 g/mol.
The inventors have found that with the addition of the rubber-free vinyl copolymer, the flowability of the obtained composition was further improved.
Advantageously, if presents, the rubber-free vinyl copolymer is present in the ploycarbonate composition in amount ranging from 0 wt. % to 8 wt. %, preferably from 3 wt. % to 6 wt. %, relative to the total weight of the polycarbonate composition.
The total amount of the impact modifier (component D) and the rubber-free vinyl copolymer (component E) is no more than 15 wt. %, relative to the total weight of the polycarbonate composition according to the present invention.
In addition to components A-E mentioned above, the polycarbonate compositions according to the present invention can optionally comprise one or more additives conventionally used in polycarbonate compositions. Such additives are, for example, fillers, carbon black, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents, pigments, colorants, lubricants, demoulding agents (such as pentaerythrityl tetrastearate), antioxidants, flow improvers agents, antidripping agents (such as poly(tetrafluoroethylene)), etc.
Such additives are described, for example, in WO 99/55772, pages 15-25, and in “Plastics Additives”, R. Gachter and H. MUller, Hanser Publishers 1983).
The person skilled in the art can select the type of the additives so as not to adversely affect the desired properties of the polycarbonate composition according to the present invention.
The total amount of the additives preferably is up to 4 wt. %, preferably from 0 to 3 wt. %, more preferably 0 to 2 wt. %, relative to the total weight of the polycarbonate composition according to the present invention.
Preferably, the polycarbonate composition according to the present invention comprises the following components, relative to the total weight of the composition:
and phenoxyphosphazene of formula (6) (all R=phenoxy) with an oligomer content where k=1 (C1) of 98.5-100 mol %, preferably 99-100 mol %,
The polycarbonate composition according to the present invention can be in the form of, for example, pellets.
The polycarbonate composition according to the present invention demonstrates a good processing behaviour 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. 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 it 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 melting 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 compositions according to the present invention can be used, for example for the production of various types of shaped articles.
In the second aspect, the present invention also provides a shaped article made from a polycarbonate composition according to the first aspect of the present invention.
As examples of such shaped articles mention can be made of, for example, films; profiles; housing parts, e.g. for domestic appliances or for office machines such as monitors, flat screens, notebooks, printers and copiers; sheets; tubes; electrical conduits; windows, doors and other profiles for the building sector (interior and exterior applications); electrical and electronic parts such as keypads, screen display covers, switches, plugs and sockets; lenses, and body parts or interior trim for commercial vehicles.
The polycarbonate compositions according to the present invention can be processed into shaped articles by a variety of means such as injection moulding, extrusion moulding, blow moulding or thermoforming to form shaped articles.
In the third aspect, the present invention provides a process for preparing the shaped article made from a composition according to the first aspect of the present invention, comprising injection moulding, extrusion moulding, blow moulding or thermoforming the polycarbonate composition according to the present invention.
The present invention will be illustrated in detail below with reference to the examples below. The examples are only for the purpose of illustration, rather than limiting the scope of the present invention.
having an oligomer content where k=1 of 99.9 mol %, and an oligomer content where k≥2 of 0.1 mol %.
The physical properties of specimens in the examples were tested as follows.
The comparative tracking index (CTI) was determined according to IEC60112:2011.
The melt volume flow rate (MVR) was determined according to ISO 1133: 2011 at 300° C. or 330° C. and a loading of 1.2 kg with a Zwick 4106 instrument from Roell.
The flexural modulus was determined according to ISO178:2010 at 2 mm/min.
The flexural strength was determined according to ISO178:2010 at 5 mm/min.
Izod unnotched impact strength was measured on specimens with dimensions of 80 mm×10 mm×4 mm according to ISO180/A:2000 (20° C., 4 mm, 5.5 J).
The burning behavior was evaluated on 127 mm×12.7 mm×1.5 mm bars according to UL94-2015 after the bars were conditioned at 23° C. for 48 hours.
The Vicat softening temperature (TVicat) was determined on test specimens of dimension of 80 mm×10 mm×4 mm according to ISO 306: 2013 with a ram load of 50 N and a heating rate of 120° C./h with a Coesfeld Eco 2920 instrument from Coesfeld Materialtest.
The materials listed in Table 1 were compounded on a twin-screw extruder (ZSK-26) (from Coperion, Werner and Pfleiderer) at a speed of rotation of 225 rpm, a throughput of 20 kg/h, and a machine temperature of 300° C.-330° C. and granulated.
The granules were processed into corresponding testing specimens on an injection moulding machine (from Arburg) with a melting temperature of 300-330° C. and a mold temperature of 60-80° C.
The physical properties (including comparative tracking index (CTI), melt volume flow rate (MVR), flexural modulus, flexural strength, Izod unnotched impact strength, burning behavior) of the compositions obtained were tested and the results were summarized in Table 1.
1)BPTMC content: means BPTMC units content in the polycarbonate composition;¶
2)NB means not break;¶
3)Non-V means the burning behavior class is worse than V2, according to UL94-2015.¶
As used herein, the content by weight of BPTMC unit (CBPTMC/C/W) in a polycarbonate composition is calculated as follows:
Taking invention example 1 as an example, the molar content of BPTMC unit is 70 mol % and the molar content of BPA unit is 30 mol % in CoPC-1, the molecular weight of BPTMC unit is 308 g/mol, the total molecular weight of BPTMC unit and —C═O— is 336 g/mol, the molecular weight of BPA unit (including —C═O—) is 254 g/mol, CoPC-1 is present in an amount of 57.6 wt. % in the polycarbonate composition, thus the content by weight of BPTMC unit in invention example 1 is:
Each Composition of comparative examples 1, 2, 6 and 7 comprising CoPC-1 blended with a flame-retardant (BDP) and an impact modifier (MBS or Si-MBS) does not have a good flame-retardancy even when the flame-retardant content is up to 12 wt. % in the polycarbonate composition.
Each composition of comparative examples 3 and 4 comprising CoPC-1 blended with a flame-retardant (BDP) and an impact modifier (ABS or MBS) and SAN does not possess a good flame-retardancy.
Composition of comparative example 5 comprising PC-3 blended with a flame-retardant (BDP) and an impact modifier (MBS) and SAN does not possess a high comparative tracking index.
Each composition of comparative examples 8-11 not comprising a flame-retardant does not possess a good flame-retardancy and a high comparative tracking index.
As demonstrated by invention examples 1-2, compositions comprising a copolycarbonate (CoPC-1), a homopolycarbonate (PC-3), and a flame retardant (BDP), and having a BPTMC content no less than 24 wt. % relative to the total weight of the composition, possess not only a high comparative tracking index but also a good flame-retardancy.
Similarly, the materials listed in Table 2 were compounded, the physical properties of the compositions obtained were tested and the results were summarized in Table 2.
1)BPTMC content means BPTMC units content in the polycarbonate composition;
2)NA means not tested;
3)NB means not break.
Composition of comparative example 12 comprising PC-3 blended with a flame-retardant (BDP) and an impact modifier (ABS) and SAN does not possess a high comparative tracking index.
Each Composition of comparative examples 13-15, comprising CoPC-1 blended with a homopolycarbonate (PC-1 or PC-3), a flame-retardant (BDP), and an impact modifier (ABS), and having a BPTMC content lower than 24 wt. % relative to the total weight of the composition, does not have a high comparative tracking index.
As demonstrated by invention examples 3-6, compositions comprising a copolycarbonate (CoPC-1), a homopolycarbonate (PC-3) and a flame retardant (BDP), and having a BPTMC content no less than 24 wt. % relative to the total weight of the composition, possess not only a high comparative tracking index but also a good flame-retardancy.
Similarly, the materials listed in Table 3 were compounded, the physical properties of the compositions obtained were tested and the results were summarized in Table 3.
1)BPTMC content means BPTMC units content in the polycarbonate composition;
2)NB means not break.
Each Composition of comparative examples 16-19, comprising no homopolycarbonate and having a BPTMC content no less than 24 wt. % relative to the total weight of the composition, does not have a good flame-retardancy even though the composition comprises up to 18 wt. % of HPCTP relative to the total weight of the composition.
As demonstrated by invention examples 7-11, compositions comprising a copolycarbonate (CoPC-1 or CoPC-2), a homopolycarbonate (PC-2), and a flame retardant (BDP or HPCTP), and having a BPTMC content no less than 24 wt. % relative to the total weight of the composition, possess not only a high comparative tracking index but also a good flame-retardancy.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/089937 | Apr 2021 | WO | international |
| 21174269.7 | May 2021 | EP | regional |
This application is the United States national phase of International Application No. PCT/EP2022/060331 filed Apr. 20, 2022, and claims priority to International Application No. PCT/CN2021/089937 filed Apr. 26, 2021 and European Patent Application No. 21174269.7 filed May 18, 2021, the disclosures of which are hereby incorporated by reference in their entireties.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/060331 | 4/20/2022 | WO |
