POLYMERIC MATERIALS

Abstract

A composition comprising: (i) a polymeric material (A) having a repeat unit of formula

(O-Ph)n-O-Ph-O-Ph-CO-Ph-   I and a repeat unit of formula

—O-Ph-Ph-O-Ph-CO-Ph-   II wherein Ph represents a phenylene moiety and n represents 0 or 1; and (ii) a polymeric additive comprising one or more of. (a) a polycarbonate; and/or (b) a polymeric material (B) which includes a repeat unit of general formula

##STR00001## wherein R′ and R′″ independently represent a hydrogen atom or an optionally-substituted (preferably un-substituted) alkyl group, and R.sup.3 and R.sup.4 independently represent a hydrogen atom or an optionally-substituted alkyl group, an anhydride-containing moiety or an alkyloxycarbonyl-containing moiety.

Claims

1. A composition comprising: a polymeric material (A) having a repeat unit of formula
—(O-Ph)n-O-Ph-O-Ph-CO-Ph-   I and a repeat unit of formula
—O-Ph-Ph-O-Ph-CO-Ph-   II wherein Ph represents a phenylene moiety and n represents 0 or 1; and (ii) a polymeric additive, wherein said polymeric additive is selected from the group comprising: (a) a polycarbonate; and (b) a polymeric material (B) which includes a repeat unit of general formula ##STR00011## wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom or an optionally-substituted alkyl group, and R.sup.3 and R.sup.4 independently represent a hydrogen atom or an optionally-substituted alkyl group, an anhydride-containing moiety or an alkyloxycarbonyl-containing moiety.

2. A composition according to claim 1, wherein said repeat units I and II are in the relative molar proportions I:II of from 65:35 to 95:5.

3. A composition according to claim 1, wherein n=0 in said polymeric material (A).

4. A composition according to claim 1, wherein said repeat unit of formula I has the structure ##STR00012## and said repeat unit of formula II suitably has the structure ##STR00013##

5. A composition according to claim 4, wherein said polymeric material (A) includes at least 65 mol % of repeat units of formula IV and includes less than 90 mol % of repeat units of formula IV, and wherein said polymeric material (A) includes at least 10 mol % of repeat units of formula V; and less than 36 mol % of repeat units of formula V.

6. A composition according to claim 1, wherein the Tm of said polymeric material (A) is less than 330° C.

7. A composition according to claim 1, wherein said polymeric material has a crystallinity of at least 23%.

8. A composition according to claim 1, wherein said polymeric material has a melt viscosity of at least 170 Pa.Math.s.

9. A composition according to claim 1, wherein said polymeric additive has a softening point of at least 100° C.

10. A composition according to claim 1, wherein said polymeric additive has a decomposition temperature measured by thermogravimetric analysis of less than 400° C.

11. A composition according to claim 1, wherein said polymeric additive is a polycarbonate which includes a repeat unit of general formula ##STR00014##

12. A composition according to claim 1, wherein in said repeat unit of general formula III, R.sup.1 and R.sup.2 both represent a hydrogen atom.

13. A composition according to claim 1, wherein R.sup.3 represents a hydrogen atom or a C1-4 alkyl group.

14. A composition according claim 1, wherein R.sup.4 represents a C.sub.1-10 alkyl group or an alkyloxycarbonyl-containing moiety; and wherein said alkyloxycarbonyl-containing moiety is of formula ##STR00015## wherein the starred carbon atom represents the atom covalently bonded to the carbon atom in moiety —CR.sup.3R.sup.4−; and R.sup.6 represents a C.sub.1-10 alkyl moiety.

15. A composition according to claim 1, wherein R.sup.4 is of formula ##STR00016## wherein the starred carbon atom represents the atom covalently bonded to the carbon atom in moiety —CR.sup.3R.sup.4− and said polymeric material (B) is an acrylate core-shell type polymer.

16. A composition according to claim 15, wherein the core is a polyalkylacrylate and the shell is of formula ##STR00017## wherein R.sup.6 represents a C.sub.1-4 non-substituted alkyl moiety and R.sup.3 represents a hydrogen atom or a C.sub.1-2, group.

17. A composition according to claim 1, wherein R.sup.4 represents an anhydride-containing moiety.

18. A composition according to claim 1, wherein said first repeat unit comprises: ##STR00018## and said second repeat unit comprises: ##STR00019##

19. A composition according to claim 1, wherein said composition has a melt viscosity of less than 225 Pa.Math.s.

20. A composition according to claim 1, wherein said composition has an L* of at least 75; and the ratio of the L* of said composition divided by the L* of said polymeric material (A) is at least 1.05.

21. A method of making a composition according to claim 1, the method comprising: (a) selecting a polymeric material according to claim 1; (b) selecting a polymeric additive according to claim 1; (c) melt-processing the polymeric material and polymeric additive in a melt-processing apparatus, thereby to produce said composition wherein, suitably, said polymeric material (A) and said polymeric additive are intimately mixed.

22. A method according to claim 21, wherein the polymeric additive is not subjected to a temperature which is greater than 330° C. in the process.

23. A method according to claim 21, which comprises making a composition which has an increased L* compared to the L* of said polymeric material (A), and/or making a composition which has an L* of at least 75.

24. A composition comprising: a polymeric material (A) having a repeat unit of formula
—(O-Ph)n-O-Ph-O-Ph-CO-Ph-   I and a repeat unit of formula
—O-Ph-Ph-O-Ph-CO-Ph-   II wherein Ph represents a phenylene moiety and n represents 0 or 1; and (ii) a polymeric additive comprising one or more of: (a) a polycarbonate; and/or (b) a polymeric material (B) which includes a repeat unit of general formula ##STR00020## wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom or an optionally-substituted alkyl group, and R.sup.3 and R.sup.4 independently represent a hydrogen atom or an optionally-substituted alkyl group, an anhydride-containing moiety or an alkyloxycarbonyl-containing moiety.

25. A composition comprising: (i) a polymeric material (A) having a repeat unit of formula
—(O-Ph)n-O-Ph-O-Ph-CO-Ph-   I and a repeat unit of formula
—O-Ph-Ph-O-Ph-CO-Ph-   II wherein Ph represents a phenylene moiety and n represents 0 or 1; and (ii) a silicon-containing polymeric material.

26. The composition according to claim 25, wherein the silicon-containing polymeric material comprises a silicon-containing graft copolymer, and wherein the silicon-containing graft copolymer is a core-shell type copolymer.

27. The composition according to claim 26, wherein the silicon-containing graft copolymer comprises a polyorganosiloxane component, wherein the core of the silicon-containing graft copolymer comprises the polyorganosiloxane component.

28. The composition according to claim 26, wherein the shell of the silicon-containing graft copolymer comprises one or more of polymerised aromatic vinyl compounds, polymerised vinyl cyanide compounds, polymerised (meth)acrylic ester compounds, and polymerised (meth)acrylic acid compounds.

Description

EXAMPLE 1

Preparation of Polyetheretherketone (PEEK)—polyetherdiphenyletherketone (PEDEK) Copolymer

[0149] A 300 litre vessel fitted with a lid, stirrer/stirrer guide, nitrogen inlet and outlet was charged with diphenylsulphone (125.52 kg) and heated to 150° C. Once fully melted 4,4′-diflurobenzophenone (44.82 kg, 205.4 mol), 1,4-dihydroxybenzene (16.518 kg, 150 mol) and 4,4′-dihydroxydiphenyl (9.311 kg, 50 mol) were charged to the vessel. The contents were then heated to 160° C. While maintaining a nitrogen blanket, dried sodium carbonate (21.368 kg, 201.6 mol) and potassium carbonate (1.106 kg, 8 mol), both sieved through a screen with a mesh of 500 micrometres, were added. The D50 of the sodium carbonate was 98.7 μm. The temperature was raised to 180° C. at 1° C./min and held for 100 minutes. The temperature was raised to 200° C. at 1° C./min and held for 20 minutes. The temperature was raised to 305° C. at 1° C./min and held until desired melt viscosity was reached, as determined by the torque rise of the stirrer. The required torque rise was determined from a calibration graph of torque rise versus MV. The reaction mixture was poured via a band caster into a water bath, allowed to cool, milled and washed with acetone and water. The resulting polymer powder was dried in a tumble dryer until the contents temperature measured 112° C. The MV of the resulting polymer was 225 Pa.Math.s measured according to Example 13 at 340° C. and the crystallinity was 24% measured according to Example 19.

EXAMPLES 2 to 14

Preparation of Compositions

[0150] The raw materials referred to in Tables 1 and 2 were tumble blended and then compounded using a ZSK twin-screw extruder operating with a barrel temperature of 315° C., die temperature of 320° C. and screw speed of 300 rpm. The throughput in each case was 13-14 kg/hour.

TABLE-US-00001 TABLE 1 Examples No. 2 3 4 5 6 7 PEEK-PEDEK copolymer 100 wt % 90 wt %  90 wt %  90 wt % 90 wt % 70 wt % of Example 1 Compound B — 5 wt % — — — Compound C — — 5 wt % 10 wt % — Compound D — 5 wt % 5 wt % — 10 wt % — Compound E — — — — 30 wt %

TABLE-US-00002 TABLE 2 Examples No. 8 9 10 11 12 13 14 PEEK-PEDEK copolymer  89 wt %  89 wt % 79 wt % 79 wt % 90 wt % 90 wt %  89 wt % of Example 1 Compound B —  10 wt % 10 wt % — Compound C  10 wt % — — 10 wt % Compound D — — 10 wt % 10 wt % Compound E — — — — Compound F 10 wt % Compound G 10 wt %  10 wt % Additive A 0.5 wt % 0.5 wt % 0.5 wt %  0.5 wt %  0.5 wt % Additive B 0.5 wt % 0.5 wt % 0.5 wt %  0.5 wt %  0.5 wt %

EXAMPLE 15

Preparation of Test Bars

[0151] Standard type 1A ISO test bars (ISO 3167) were injection moulded using each of the compositions of Examples 2 to 14 on an Arburg injection moulding machine with a barrel temperature of 320° C.-335° C., nozzle temperature of 335° C. and a tool temperature of 160° C.

[0152] The compositions and/or test bars were assessed as described in Examples 18 to 19.

EXAMPLE 16

Determination of Melt Viscosity (MV) of Polymers

[0153] Unless otherwise stated herein, this was measured using a Bohlin instruments RH2000 capillary rheometer according to ISO 11443 operating at 340° C. and a shear rate of 1000 s.sup.−1 using a 0.5 mm (capillary diameter)×8.0 mm (capillary length) die with entry angle 180° C.

[0154] Granules are loaded into the barrel and left to pre-heat for 10 minutes. The viscosity is measured once steady state conditions are reached and maintained, nominally 5 minutes after the start of the test.

EXAMPLE 17

Colour Measurements

[0155] Unless otherwise stated herein, colour measurements were carried out on injection moulded ISO test bars made as described in Example 15. The measurements were made using a Konica Sinolta Chromameter with a DP400 data processor operating over a spectral range of 360 nm to 750 nm. A white plate calibration was carried out with a D65 (natural daylight) light source. Colour measurements are expressed at L*, a* and b* coordinates as defined by the CIE 1976 (Nassau, K. Kirk-Othmer Encyclopaedia of Chemical Technology, chapter 7, page 303-341, 2004). Values were determined from a single point on the ISO test bar.

EXAMPLE 18

Mechanical Properties

[0156] The mechanical properties of the compositions of Examples 2 to 14 were tested according to ISO standards using the type 1A (ISO 3187) test bars at 23° C.

EXAMPLE 19

Differential Scanning Calorimetry Assessment of Compositions of Examples 2 to 14

[0157] Crystallinity described herein may be assessed by several methods for example by density, by IR spectroscopy, by x ray diffraction or by differential scanning calorimetry (DSC). The DSC method has been used to evaluate the crystallinity that developed in the polymers from Examples 1 and 2 using a Mettler Toledo DSC1 Star system with FRS5 sensor.

[0158] The Glass Transition Temperature (Tg), the Melting Temperature (Tm) and Heat of Fusions of Melting (ΔHm) for the polymers were determined using the following DSC method.

[0159] An 8 mg sample of each polymer composition was removed from each of the moulded test bars by means of a sharp knife. The sample from each test bar was scanned by DSC as follows: [0160] Step 1 Perform and record a preliminary thermal cycle by heating the sample from 30° C. to 400° C. at 20° C./min. [0161] Step 2 Hold for 5 minutes. [0162] Step 3 Cool at 20° C./min to 30° C. and hold for 5 mins, [0163] Step 4 Re-heat from 3° C. to 40° C. at 2° C./min. recording the Tg, Tn, Tm, ΔHn and ΔHm.

[0164] Tc is measured on the cooling cycle (Step 3) and is the temperature at which the crystallisation exotherm reaches a minimum.

[0165] From the DSC trace resulting from the scan in step 4, the onset of the Tg was obtained as the intersection of the lines drawn along the pre-transition baseline and a line drawn along the greatest slope obtained during the transition. The Tn was the temperature at which the main peak of the cold crystallisation exotherm reaches a maximum. The Tm was the temperature at which the main peak of the melting endotherm reached a maximum.

[0166] The Heat of Fusion for melting (ΔHm) was obtained by connecting the two points at which the melting endotherm deviates from the relatively straight baseline. The integrated area under the endotherm as a function of time yields the enthalpy (mJ) of the melting transition; the mass normalised heat of fusion is calculated by dividing the enthalpy by the mass of the specimen (J/g). The level of crystallisation (X(%)) is determined by dividing the Heat of Fusion of the specimen by the Heat of Fusion of a totally crystalline polymer, which for the PEEK-PEDEK copolymer is 130 J/g and for examples 3-6 is 117 J/g and for example 7 is 91 J/g. The additives are amorphous and do not contribute to the crystallisation peak in the DSC trace. The value of 117 J/g is based on a blend containing 10 wt % of additive and 90 wt % of PEEK-PEDEK. Thus, the Heat of Fusion is 90%×130 J/g=117 J/g.The value of 91J/g is based on a blend containing 30 wt % of PPSU and 70 wt % of PEEK-PEDEK. Thus, the Heat of Fusion is 70%×130 J/g=91 J/g.

[0167] The compositions of Examples 2 to 14 and/or test bars made therefrom were assessed in the tests of Examples 16 to 19. In addition, the time for the test bar to solidify so that it could be injected from the injection moulding machine was assessed and is referred to as the “cooling time” in seconds. Results are provided in Table 3 and 4.

TABLE-US-00003 TABLE 3 Example assessed Assessment 2 3 4 5 6 7 Processing temp, ° C. 340 340 335 335 335 340 Cooling time, moulding(s) 120 35 35 35 120 90 Colour (L*) 72.6 83.8 85.8 86.4 71.8 76.2 Melt Viscosity (Pa .Math. s) 225 180 175 170 170 330 Crystallinity (%) 24 23 26 25 26 23 Tensile Modulus (GPa) 3.5 3.1 3.0 2.8 2.9 3.4 Tensile Strength at yield 92 82 80 71 86 93 (MPa) Tensile Strength at break 64 60 52 52 65 60 (MPa) Tensile Elongation, % 5 16 16 16 20 5 Flexural Modulus (GPa) 3.4 3.0 3.0 2.7 2.9 3.4 Flexural Strength (MPa) 150 133 129 121 133 148 Notched Izod Impact Strength 4.2 7.7 6.0 6.5 6.5 4.1 (KJm.sup.−2)

TABLE-US-00004 TABLE 4 Example assessed Assessment 8 9 10 11 12 13 14 Processing temp, ° C. 335 335 335 335 335 335 335 Cooling time, 35 35 35 35 50 50 50 moulding(s) Colour (L*) 87.1 86.7 86.8 87.9 86.7 87.2 87.7 Melt Viscosity (Pa .Math. s) 150 100 115 120 168 243 281 Tensile Modulus 2.7 3.0 2.7 3.0 2.7 2.8 2.6 (GPa) Tensile Strength at 71 73 70 68 68 68 68 yield (MPa) Tensile Strength at 53 56 58 54 60 59 58 break (MPa) Tensile Elongation, % 15 19 21 18 59 66 68 Flexural Modulus 2.7 2.8 2.8 2.6 2.6 2.6 2.6 (GPa) Flexural Strength 121 129 125 118 111 112 112 (MPa) Notched Izod Impact 8.6 13.5 12.0 12.0 63.6 65.6 60.2 Strength (KJm.sup.−2)
The following should be noted from the results in Table 3 and 4:

[0168] (a) The melt viscosities of the compositions of Examples 3 to 8 and 8 to 12 are significantly less than for Example 2 which is a comparative example which comprises virgin PEEK-PEDEK copolymer (i.e. without any additive). The melt viscosities of Examples 3 to 6 and 8 to 12 are also significantly less than for Example 7 which is a comparative example which includes PPSU as an additive.

[0169] The low melt viscosity of compositions of Examples 3 to 8 and 8 to 12 means they can advantageously be used in producing thin walled parts. They also may be used in producing highly filled parts (e.g. with filler loadings of greater than 40 wt %).

[0170] (b) The crystallinity of the compositions of Examples 3 to 8 is advantageously little affected by inclusion of the additives. Consequently, the chemical resistance of the compositions will be comparable to that of the virgin polymer of Example 2. One skilled in the art would expect the crystallinity of the compositions of examples 8-14 to be similar to those of examples 3-6.

[0171] (c) The mechanical properties of parts made from the compositions of Examples 3 to 6 and 8 to 14 are still high, despite inclusion of the additives. Indeed, in the cases of the properties of Tensile Elongation and Notched Izod Impact Strength, Examples 3 to 6 and 8 to 14 performed far better than the comparative examples. Examples 12-14 in particular exhibited extremely high Tensile Elongation and Notched Izod impact Strength values.

[0172] (d) The colour of the compositions of Examples 3 to 5 and 8 to 14 is significantly improved compared to the colour of the virgin polymer (Example 2). Advantageously, the compositions may be more aesthetically acceptable compared to use of virgin polymer, since in general white polymers and whiter parts made therefrom are desirable—whiteness implies higher purity and quality. Additionally, it is easier to adjust the colour and/or match (e.g. by addition of colourants) a lighter polymer compared to the light brown/beige colour of the Example 2 polymer or virgin PEEK.

[0173] The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.