POLYCARBONATE COMPOSITION

Abstract

The present invention provides a polycarbonate composition and a molded article prepared therefrom. The polycarbonate composition provided by the present invention comprises (50-90) wt. % of polycarbonate, (5-45) wt. % of mineral filler and (1.5-4.5) wt. % of hydroxyl-terminated 5 dendritic branched polyester. The polycarbonate composition and the molded article provided according to the present invention have enhanced impact strength, increased tensile elongation at break, improved flowability and good surface gloss.

Claims

1.-13. (canceled)

14. A polycarbonate composition, comprising: A) 50-90 wt. % of polycarbonate; B) 5-45 wt. % of mineral filler; and C) 1.5-4.5 wt. % of hydroxyl-terminated dendritic branched polyester.

15. The polycarbonate composition according to claim 14, wherein the mineral filler is selected from the group consisting of mica, talc, calcium carbonate, wollastonite, barium sulfate, silica, kaolin, inorganic whiskers and combinations thereof.

16. The polycarbonate composition according to claim 15, wherein the hydroxyl-terminated dendritic branched polyester has a dendritic structure or a three-dimensional spherical structure.

17. The polycarbonate composition according to claim 14, wherein the hydroxyl-terminated dendritic branched polyester is selected from the group consisting of hydroxyl-terminated dendritic polyester, hydroxyl-terminated hyperbranched polyester and a combination thereof.

18. The polycarbonate composition according to claim 17, wherein the hydroxyl-terminated dendritic polyester comprises a plurality of branching units and a plurality of terminal units, the branching units comprise a plurality of branches, each of the plurality of branches has a layered iterative structure, and the plurality of terminal units are respectively located at terminals of the plurality of branches.

19. The polycarbonate composition according to claim 18, wherein the terminal units are selected from hydroxyl group or derivatives thereof, or the branching units are selected from ester products obtained by reacting a polyol(s) with a polyhydroxycarboxy compound(s).

20. The polycarbonate composition according to claim 18, wherein the hydroxyl-terminated dendritic polyester has a four-layer iterative structure.

21. The polycarbonate composition according to claim 17, wherein the hydroxyl-terminated hyperbranched polyester comprises a plurality of terminal units, a plurality of linear units and a plurality of branching units, the branching units comprise a plurality of branches, the plurality of terminal units are respectively located at terminals of the plurality of branches, and the plurality of branching units and the plurality of linear units are randomly distributed within a molecular framework enclosed by the plurality of terminal units.

22. The polycarbonate composition according to claim 21, wherein the branching units are selected from organic residues of trifunctional and/or tetrafunctional compounds.

23. The polycarbonate composition according to claim 14, further comprising a flame retardant, a release agent, a stabilizer, an antistatic agent and a pigment.

24. A method for preparing a polycarbonate composition, comprising the step of mixing the following components: A) 50-90 wt. % of a polycarbonate; B) 5-45 wt. % of a mineral filler; and C) 1.5-4.5 wt. % of hydroxyl-terminated dendritic polyester.

25. A method comprising providing the polycarbonate composition according to claim 14 and preparing injection-molded or thermoformed molded article.

26. A molded article prepared from the polycarbonate composition according to claim 14.

Description

EXAMPLES

[0081] The following examples are intended to be exemplary rather than limiting.

[0082] The ingredients used in the examples and their brief description are as follows:

TABLE-US-00001 Component Trade name Description Supplier A-1 Makrolon A linear polycarbonate based on Covestro AG M2405 bisphenol A, having a weight average molecular weight of 24,500 g/mol (determined by GPC in dichloromethane with a standard polycarbonate) A-2 Makrolon A linear polycarbonate based on Covestro AG OD2015 bisphenol A, having a weight average molecular weight of 20,500 g/mol (determined by GPC in dichloromethane with a standard polycarbonate) B-1 PolyfilHG90 Kaolin (hydrous aluminum silicate) KaMin LLC having an average Stokes equivalent particle size (D50) of 0.2 m B-2 HTP Ultra 5C Talc having an average particle size IMI Fabi (D50) of 0.65 m Impact ABS HRG P60 An acrylonitrile-butadiene-styrene INEOS modifier copolymer (ABS HRG) prepared by Styrolution Group polymerization of an emulsion having GmbH a core-shell structure C CYD2106 A hydroxyl-terminated dendritic Weihai CY branched polyester having a Dendrimer molecular weight of 8000 g/mol and Technology Co., an acid value of 55 10 mg KOH/g Ltd. Release agent PETS Pentaerythritol tetrastearate (PETS) Guangzhou Nuochi Chemical Co., Ltd. Heat Irganox B 900 Heat stabilizer (%) Ciba Specialty stabilizer (%) Chemicals Inc. Citric acid Citric Acid C.sub.6H.sub.8O.sub.7 Univar China Ltd. Carbon black BP800 Carbon black pigment Cabot (China) pigment Ltd.

[0083] In comparative examples and inventive examples, unless otherwise specified, the percentage of each component used refers to the weight percentage of the component relative to the polycarbonate composition prepared, based on that the weight of the polycarbonate composition is 100 wt. %.

[0084] Test Methods

1) MVR (melt volume flow rate): measured at 260 C./5 kg according to ISO 1133-1:2011 to characterize flowability.
2) iMVR: an MVR value measured by keeping a sample at 260 C./5 kg for 15 min to characterize thermal stability.
3) MVR: calculated according to (iMVR-MVR)/MVR*1000% to characterize the degree of degradation of a resin, wherein the greater the value, the higher the degree of degradation.
4) IZOD notched impact strength and unnotched impact strength: measured at 23 C. according to ISO180/A: 2000. Test samples were prepared by injection molding. The dimension was 80 mm10 mm3 mm. The cut radius was 0.25 mm. Ten samples were tested under each experimental condition to obtain impact strength values and fracture types (P, C or NB). P denotes partial break, indicating that the materials have better ductility. C denotes complete break, indicating that the materials are brittle. NB denotes no break. The impact strength values of the ten sample tests were averaged as the test results under the test conditions.
5) MAI (multiaxial impact): the resistance of the surface of a sample material to the damage caused by high-speed impact was tested according to ISO 6603-2:2000. In experimental evaluation, a multiaxial impact sample piece (100 mm100 mm1.5 mm) prepared by injection molding was used. The ductility of a test sample is denoted by its fracture mode value, wherein 1 denotes that the material is ductile and 6 denotes that the material is brittle.

[0085] In the MAI test, the following data that can damage the material can be obtained:

5.1): maximum stress
5.2): total energy
5.3): multiaxial impact-ductility.
6) Gloss: the degree to which the surface of an object is close to a mirror, as denoted by a number. A higher value indicates that the smoothness of the surface of the object is closer to the mirror. Gloss can be evaluated by multiple methods (or instruments). Gloss mainly depends on light source illumination and a viewing angle. Instrument measurement is generally carried out by illumination at an angle of 20, 600 or 850 and detection of signals. The unit of gloss is GU, i.e. gloss unit. The thickness h of a test sample is generally 2 mm. In the present invention, a haze-gloss meter (Model: BYK4601) produced by Germany BYK Inc. was used, and sample gloss was detected by illumination at angles of 200 and 60 and detection of signals according to the standards ISO 13803 and ASTM D523.

[0086] Table 1 shows Comparative Examples 1-3 and Inventive Examples 1-3. As shown in Table 1, each of Comparative Examples 1-3 comprises 15 wt. % of the mineral filler kaolin. In Comparative Example 1, the content of an impact modifier ABS HRG is 0 wt. %, and the polycarbonate composition sample prepared has higher MVR, indicating that a polycarbonate component therein has a higher degree of degradation. 2.5 wt. % and 6 wt. % of impact modifiers ABS HRG are respectively added in Comparative Examples 2 and 3, correspondingly, the polycarbonate compositions prepared have reduced MVR, but also have reduced flowability.

[0087] As shown in Table 1, a hydroxyl-terminated dendritic branched polyester component and a mineral filler kaolin component are added in each of Inventive Examples 1-3. The formulation of Inventive Example 1 comprises 1.6 wt. % of a hydroxyl-terminated dendritic branched polyester component and 15 wt. % of kaolin; and the polycarbonate composition sample prepared has a tensile elongation at break of 1.110.sup.2% which is about 90 times that of Comparative Example 1 and about 6 times that of Comparative Example 3, and also has greatly improved notched impact strength and unnotched impact strength.

[0088] Formulations of Inventive Examples 2 and 3 respectively comprise 2.5 wt. % and 4.0 wt. % of a hydroxyl-terminated dendritic branched polyester component and 15 wt. % of kaolin; and the notched impact strength of the polycarbonate composition samples prepared is about 10 times that of Comparative Example 3.

[0089] The comparison between Inventive Examples 1-3 and Comparative Examples 1-3 can show that, compared with the polycarbonate composition sample having a formulation comprising the impact modifier ABS HRG component and 15 wt. % of the kaolin component, the polycarbonate composition sample having a formulation comprising the hydroxyl-terminated dendritic branched polyester component and 15 wt. % of the kaolin component exhibits better effects, and has improved process flowability, tensile elongation at break, impact strength and surface gloss.

[0090] The polycarbonate composition samples prepared in Comparative Examples 1-3 have a multiaxial impact-ductility test value of 5, i.e. the polycarbonate composition samples exhibit brittle fracture in the test.

[0091] In Inventive Examples 1-3, with the increase of the amount of the hydroxyl-terminated dendritic branched polyesters added, the polycarbonate composition samples have obviously reduced multiaxial impact-ductility test values, and the values are reduced to 1 in Inventive Examples 1 and 2, i.e. the polycarbonate composition samples exhibit tough fracture.

[0092] In Inventive Examples 1-3, injection-molded articles of the polycarbonate composition samples comprising the hydroxyl-terminated dendritic branched polyester components and the kaolin components have improved surface gloss.

TABLE-US-00002 TABLE 1 Comparative Examples 1-3 and Inventive Examples 1-3 Formulation of polycarbonate Comparative Comparative Comparative Inventive Inventive Inventive composition Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Component A-1 (PC) 51.0 49.5 47.3 50.0 49.5 48.5 Component A-2 (PC) 33.0 32.0 30.7 32.4 32.0 31.5 Component B-1 (kaolin) 15.0 15.0 15.0 15.0 15.0 15.0 Impact modifier ABS HRG 0 2.5 6 0 0 0 Component C (CYD2106) 0 0 0 1.6 2.5 4 Release agent PETS 0.4 0.4 0.4 0.4 0.4 0.4 Heat stabilizer B900 0.1 0.1 0.1 0.1 0.1 0.1 Carbon black pigment CB 0.5 0.5 0.5 0.5 0.5 0.5 Performance of polycarbonate composition Test Comparative Comparative Comparative Inventive Inventive Inventive prepared condition Unit Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 MVR 260 C., 5 kg cm.sup.3/10 115 57.3 24.9 33.8 36.2 51.4 min iMVR 260 C., 5 kg, cm.sup.3/10 158 70.9 28.5 41.5 42.2 53.9 15 min min MVR 260 C., 5 kg % 37.39 11.83 3.13 6.70 5.22 2.17 Tensile 50 mm/min % 1.2 9.1 17 1.1 10.sup.2 90 84 elongation at break (%) Izod notched 23 C., 4 mm, kJ/m.sup.2 2.5 C 4.1 C 5.7 C 16P 54P 56P impact strength 5.5 J Izod unnotched 23 C., 4 mm, kJ/m.sup.2 4.4 C 83 C 1.9 10.sup.2 C NB NB NB impact strength 11 J Multiaxial 23 C. N 453 888 4468 4730 4563 4406 impact-maximum stress Multiaxial J 0.78 1.3 34.0 45 43 39 impact-total energy Multiaxial 5.0 5.0 5.0 1.0 1.0 2.0 impact-ductility Gloss h = 2 mm, GU 37.0 48.9 41.4 78.4 88.9 88.5 20 h = 2 mm, GU 77.7 83.8 79.3 97.0 100 99.5 60

[0093] Table 2 shows Comparative Example 4 and Inventive Examples 4-6. Comparative Example 4 comprises 10 wt. % of the kaolin component and 6 wt. % of an impact modifier ABS HRG. Inventive Examples 4-6 respectively comprise 1.6 wt. %, 2.5 wt. % and 4 wt. % of the hydroxyl-terminated dendritic branched polyester component CYD206 in addition to 10 wt. % of kaolin component.

[0094] Compared with Comparative Example 4, the polycarbonate composition samples prepared in Inventive Examples 4-6 exhibit higher flowability, higher tensile elongation at break and higher impact strength, and injection-molded articles thereof have higher surface gloss.

[0095] The formulation of Inventive Example 6 comprises 10 wt. % of the kaolin component and 4 wt. % of the hydroxyl-terminated dendritic branched polyester component; and the notched impact strength of the polycarbonate composition sample prepared is about 6 times that of Comparative Example 4.

TABLE-US-00003 TABLE 2 Comparative Example 4 and Inventive Examples 4-6 Comparative Inventive Inventive Inventive Composition of formulation Example 4 Example 4 Example 5 Example 6 Component A-1 (PC) 83.0 87.4 86.5 85.0 Component B-1 (kaolin) 10.0 10.0 10.0 10.0 ABS HRG 6 0 0 0 Component C (CYD2106) 0 1.6 2.5 4 Release agent (PETS) 0.4 0.4 0.4 0.4 Heat stabilizer (B900) 0.1 0.1 0.1 0.1 Carbon black pigment (CB) 0.5 0.5 0.5 0.5 Performance of polycarbonate composition Test Comparative Inventive Inventive Inventive prepared condition Unit Example 4 Example 4 Example 5 Example 6 MVR 260 C., 5 kg cm.sup.3/10 14.2 22.7 25.1 35.5 min Tensile 50 mm/min % 78 1.2 10.sup.2 1.3 10.sup.2 1.1 10.sup.2 elongation at break (%) Izod notched 23 C., 4 mm, kJ/m.sup.2 10C 42P 62P 63P impact strength 5.5 J Izod unnotched 23 C., 4 mm, kJ/m.sup.2 NB NB NB NB impact strength 11 J Multiaxial 23 C. N 4525 4922 4836 4636 impact-maximum stress Multiaxial J 40 50 49 43 impact-total energy Multiaxial 1.0 1.0 1.0 1.0 impact-ductility Gloss h = 2 mm, GU 51.6 92.6 94.6 91.8 20 h = 2 mm, GU 86.2 101 102 100 60

[0096] Table 3 shows Comparative Example 5 and Inventive Examples 7-9. As shown in Table 3, Comparative Example 5 comprises 20 wt. % of kaolin component and 6 wt. % of the impact modifier ABS HRG; and Inventive Examples 7-9 respectively comprise 1.6 wt. %, 2.5 wt. % and 4 wt. % of the hydroxyl-terminated dendritic branched polyester component CYD2106 in addition to 20 wt. % of the kaolin component.

[0097] Compared with Comparative Example 5, the polycarbonate composition samples prepared in Inventive Examples 7-9 exhibit higher flowability, higher tensile elongation at break and higher impact strength, and injection-molded articles thereof have higher surface gloss.

[0098] The notched impact strength of the polycarbonate composition sample prepared in Inventive Example 9 is about 15 times that of Comparative Example 5, and an injection-molded article of the polycarbonate composition sample also has improved surface gloss.

TABLE-US-00004 TABLE 3 Comparative Example 5 and Inventive Examples 7-9 Comparative Inventive Inventive Inventive Composition of formulation Example 5 Example 7 Example 8 Example 9 Component A-1 (PC) 73 77.4 76.5 75 Component B-1 (kaolin) 20.00 20.00 20.00 20.00 ABS HRG 6 0 0 0 Component C (CYD2106) 0 1.6 2.5 4 Release agent (PETS) 0.4 0.4 0.4 0.4 Heat stabilizer (B900) 0.1 0.1 0.1 0.1 Carbon black pigment (CB) 0.5 0.5 0.5 0.5 Performance of polycarbonate composition Test Comparative Inventive Inventive Inventive sample condition Unit Example 5 Example 7 Example 8 Example 9 MVR 260 C., 5 kg cm.sup.3/10 24.2 28.7 25.1 29.3 min Tensile 50 mm/min % 5.8 23 72 67 elongation at break (%) Izod notched 23 C., 4 kJ/m.sup.2 3.9C 7.5C 32P 59P impact strength mm, 5.5 J Izod unnotched 23 C., 4 kJ/m.sup.2 56C 1.7 10.sup.2P NB NB impact strength mm, 11 J Multiaxial 23 C. N 4037 4768 4582 4282 impact-maximum stress Multiaxial J 24 42 43 38 impact-total energy Multiaxial 6.0 1.0 1.0 1.0 impact-ductility Gloss h = 2 mm, GU 32.6 54.8 78.7 85.9 20 h = 2 mm, GU 72.8 87.6 97.3 99.1 60

[0099] Table 4 shows Comparative Example 6 and Inventive Example 10.

[0100] The polycarbonate composition provided by the present invention also exhibits superior performance for other types of fillers. In Comparative Example 6, a formulation of a polycarbonate composition comprises 15 wt. % of talc and 6 wt. % of the impact modifier ABS HRG. In Inventive Example 10, a formulation of a polycarbonate composition comprises 15 wt. % of talc and 2.5 wt. % of the hydroxyl-terminated dendritic branched polyester component CYD2106.

[0101] As shown in Table 4, compared with Comparative Example 6, the polycarbonate composition prepared in Inventive Example 10 has significantly improved flowability, tensile elongation at break, impact strength and surface gloss, and its ductility level also changes from relative brittleness to higher toughness (the value is reduced) in the multiaxial impact test.

TABLE-US-00005 TABLE 4 Comparative Example 6 and Inventive Example 10 Comparative Inventive Composition of formulation Example 6 Example 10 Component A-1 (PC) 47.3 49.4 Component A-2 (PC) 30.6 32.0 Component B-2 (talc) 15.0 15.0 ABS HRG 6 0 Component C (CYD2106) 0 2.5 Release agent (PETS) 0.4 0.4 Heat stabilizer (B900) 0.1 0.1 Citric acid 0.1 0.1 Carbon black (CB) 0.5 0.5 Performance of polycarbonate Comparative Inventive composition sample Test condition Unit Example 6 Example 10 MVR 260 .C, 5 kg cm.sup.3/10 15.9 35.8 min Tensile elongation at 50 mm/min % 13 36 break (%) Izod notched impact 23 C., 4 mm, kJ/m.sup.2 9.6 C 17P strength 5.5 J Izod unnotched impact 23 C., 4 mm, kJ/m.sup.2 1.7 10.sup.2P NB strength 11 J Multiaxial 23 C. N 4444 4650 impact-maximum stress Multiaxial impact-total J 39 40 energy Multiaxial 2.7 1.3 impact-ductility Gloss h = 2 mm, GU 30.8 49.5 20

[0102] It is found from the present invention that the hydroxyl-terminated dendritic branched polyester and the mineral filler (especially kaolin and talc) have a particular synergistic action.

[0103] Although the present invention has been described above in detail for the objects of the present invention, it should be understood that such detailed description is only exemplary. Except the contents defined by the claims, those skilled in the art can make various changes without departing from the spirit and scope of the present invention.