COMPOSITION COMPRISING POLYESTER AND POLYOLEFIN

Abstract

The invention relates to a composition comprising A) a polyester, B) a polyolefin and C) a compatibilizer, wherein A) comprises a first polyester derived from an aromatic dicarboxylic acid, an acyclic aliphatic diol and at least one of a cycloaliphatic diol and spiroglycol and a second polyester different from the first polyester. The invention further relates to an article comprising the composition, particularly a toy block.

Claims

1. A composition comprising A) a polyester, B) a polyolefin and C) a compatibilizer, wherein A) comprises a first polyester derived from an aromatic dicarboxylic acid, an acyclic aliphatic diol and at least one of a cycloaliphatic diol and spiroglycol and a second polyester different from the first polyester.

2. The composition according to claim 1, wherein the amount of the first polyester is 1 to 95 wt % of the total weight of the polyester in the composition and the amount of the second polyester is 5 to 99 wt % of the total weight of the polyester in the composition.

3. The composition according to claim 1, wherein the aromatic dicarboxylic acid is selected from isophthalic, terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether, 4,4′-bisbenzoic acid,1,4- or 1,5-naphthalene dicarboxylic acids, and mixtures thereof, and/or the acyclic aliphatic diol is selected from ethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propane diol, 2-ethyl, 2-methyl, 1,3-propane diol, 1,4-butanediol, 1,3- and 1,5-pentane diol, dipropylene glycol, 2-methyl-1,5-pentane diol, 1,6-hexane diol, triethylene glycol, 1,10-decane diol, and mixtures thereof, and/or the cycloaliphatic diol is selected from the group consisting of dimethanol decalin, dimethanol bicyclo octane, 1,4-cyclohexane dimethanol, and mixtures thereof.

4. The composition according to claim 1, wherein the first polyester is derived from the aromatic dicarboxylic acid, ethylene glycol and 1,4-cyclohexane dimethanol or is derived from the aromatic dicarboxylic acid, ethylene glycol diol and spiroglycol and/or wherein the first polyester has a crystallinity of at most 10% as determined by differential scanning calorimetry using the second cooling curve, wherein the first heating rate is 20° C./min, the first cooling rate is 20° C./min, the second heating rate is 20° C./min, the second cooling rate is 20° C./min and the sample weight is 5 mg, using 140 J/g as the theoretical heat of fusion.

5. The composition according to claim 1, wherein the second polyester is selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polycyclohexylenedimethylene terephthalate.

6. The composition according to claim 1, wherein the amount of A) is at least 75 wt % of the total composition, the amount of B) is 5 to 22.5 wt % of the total composition and the weight ratio of the amount of B) with respect to the amount of C) is 2 to 20.

7. The composition according to claim 1, wherein the amount of B) is 8 to 15 wt % with respect to the total composition.

8. The composition according to claim 1, wherein B) is selected from the group consisting of a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a high density polyethylene (HDPE), polypropylene (PP) and an elastomeric copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and combinations thereof.

9. The composition according to claim 1, wherein C) comprises a copolymer of ethylene and a comonomer selected from the group consisting of an unsaturated carboxylic acid, an anhydrate of unsaturated carboxylic acid, an ester of unsaturated carboxylic acid, glycidylester of unsaturated monocarboxylic acid, a monoglycidylester or polyglycidylester of unsaturated polycarboxylic acid, and unsaturated glycidylether.

10. The composition according to claim 1, wherein the amount of C) is 0.5 to 5 wt %.

11. The composition according to claim 1, wherein the weight ratio of the amount of B) with respect to the amount of C) is 2 to 10 or 3 to 6.

12. An article comprising a stud for fitting into a complementary receptacle and/or comprising a receptacle for fitting into a complementary stud, the article comprising the composition of claim 1.

13. The article according to claim 12, wherein the article is an injection molded article or wherein the article is a building block, a toy block, a hinge or a gear wheel.

14. The article according to claim 12, wherein the article comprises a stud for fitting into a complementary receptacle and the article comprises a receptacle which is complementary to the stud.

15. A process for the preparation of the composition according to claim 1 comprising melt mixing A), B) and C) and optional components.

16. The composition according to claim 1, wherein the amount of the first polyester is 5 to 70 wt % of the total weight of the polyester in the composition and the amount of the second polyester is 30 to 95 wt % of the total weight of the polyester in the composition.

17. The composition according to claim 1, wherein the amount of the first polyester is 10 to 50 wt % of the total weight of the polyester in the composition and the amount of the second polyester is 50 to 90 wt % of the total weight of the polyester in the composition.

18. The composition according to claim 1, wherein C) comprises a copolymer of ethylene and a comonomer selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, an anhydrate of acrylic acid, an anhydrate of methacrylic acid, an anhydrate of maleic acid, an anhydrate of fumaric acid, an anhydrate of itaconic acid, methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydro phthalic acid, glycidylacrylate, glycidylmethacrylate and glycidyl p-styryl carboxylate, a monoglycidylester or polyglycidylester of maleic acid; itaconic acid; citraconic acid; or butenetricarboxylic acid, allylglycidylether, 2-methylallylglycidylether and glycidylether of o-allylphenol.

19. The composition according to claim 1, wherein (C) comprises a copolymer of ethylene and glycidylmethacrylate.

Description

EXPERIMENTS

[0138] Following materials were used.

[0139] PET: copolymer of terephtalic acid, isophtalic acid and diethylene glycol, intrinsic viscosity of 0.800 dl/g as determined by according to ASTM D4603 and MVI of 20 dg/min (2.16 kg, 280° C.) according to ISO 1133 (SABIC® PET BC-112 as commercially available from SABIC)

[0140] PCCD: copolymer of cyclohexylenedicarboxylic acid and cyclohexane-1,4-dimethanol PCTG: copolymer of terephtalic acid, diethylene glycol and cyclohexane-1,4-dimethanol (molar ratio between diethylene glycol and cyclohexane-1,4-dimethanol is 20:80)

[0141] PETG: copolymer of terephtalic acid, diethylene glycol and cyclohexane-1,4-dimethanol (molar ratio between diethylene glycol and cyclohexane-1,4-dimethanol is 70:30)

[0142] SPG: copolymer of terephthalic acid, ethylene glycol and spiroglycol

[0143] POE: copolymer of ethylene and 1-octene, MFI of 5 dg/min according to ASTM D1238 (2.16 kg, 190° C.), density of 0.87 g/cm.sup.3 according to ASTM D792

[0144] Compatibilizer: commercial name LOTADER AX 8840; copolymer of ethylene and glycidylmethacrylate, MFI of 5 dg/min according to ASTM D1238 (2.16 kg, 190° C.), density of 0.964 g/cm.sup.3 according to ASTM 1183

[0145] Components shown in Table 1 were melt-mixed in a twin-screw extruder. The following properties were measured and summarized in Table 1.

[0146] Gloss: ISO 2813 at a measurement angle of 60°

[0147] MVR: ISO1133 (2.16 kg and 265° C.), 300 seconds

[0148] Notched impact strength: ISO180, 23° C.

[0149] Charpy notched impact strength: ISO 179-1, 23° C.

[0150] Tensile modulus: ISO527

[0151] Shrinkage: ISO 294-4

[0152] Heat Deflection Temperature: ISO75

[0153] Vicat temperature: ISO306

TABLE-US-00001 TABLE 1A CE1 CE2 E3 E4 E5 CE6 PET wt % 90.0 70.0 70.0 70.0 70.0 90.0 PCCD wt % 20 PCTG wt % 20 PETG wt % 20 SPG wt % 20 POE wt % 8.9 8.9 8.9 8.9 8.9 8.9 compatibilizer wt % 1.1 1.1 1.1 1.1 1.1 1.1 IRGANOX 1010 wt % 0.3 0.3 0.3 0.3 0.3 0.3 IRGAFOS 168 wt % 0.25 0.25 0.25 0.25 0.25 0.25 talc wt % 0.2 Gloss/60° 104 100 103 103 102 103 MVR 265 C./ cc/10′ 14.5 17.4 15.8 17.2 17.2 14.1 2.16 KG/300 sec Notched Impact kJ/m.sup.2 9.1 11.4 36.8 13.2 7.4 9.3 Strength 23° C. Charpy notched kJ/m.sup.2 11.3 13.3 34.4 16.8 10.4 11.8 Impact Strength 23° C. Tensile Modulus MPa 2117 1755 1807 1896 2125 2227 Shrinkage T-bar % 1.2 1.2 0.9 0.8 0.8 1.2 HDT 1.8 MPa ° C. 69 66 69 68 71 70 VICAT B120 ° C. 93 85 84 75 91 93 The amounts of Irganox 1010 and Irgafos 168 and talc are wt part per 100 wt part of the total of polyester, polyolefin and compatibilizer.

[0154] Comparing E3-E5 vs CE1 and CE2, it can be understood that the use of the polyester made from two types of diols leads to lower shrinkage. In particular, E4 and E5 have very low shrinkages. E5 has a very favorable combination of various mechanical properties, in particular a very high tensile modulus. In addition, the shrinkage of the compositions of the invention is very similar to the shrinkage of a typical ABS and PC resins. For example, CYCOLAC™ RESIN MG47F, which is ABS that is commercially available from SABIC, has a shrinkage T-bar in the range of 0.5 to 0.8%. For example, polymer LEXAN™ Resins_144R and 104R, which are polycarbonate resins that are commercially available from SABIC have a shrinkage T-bar in the range of 0.5 to 0.7%.

[0155] DSC measurements were performed for polyesters shown in Tabel 2. About 5 mg of granulate sample was weighed and placed in a DSC pan. The lid was crimped on the pan to ensure a closed atmosphere. The sample pan was placed in a DSC cell, and then heated, at a rate of approximately 20° C./min, to a temperature of 280° C. The sample was kept at this temperature for one minute. Then the sample was cooled at a rate of 20° C./min to 20° C., and kept isothermally at that temperature for one minute. The sample was again heated and cool as described before. (second heat and cool curve). The percent crystallinity was calculated by dividing the heat of fusion (Hf), determined from the second heat curve, by a theoretical heat of fusion of 140 J/g for PET, and multiplying this quantity by 100 (% cryst.=(Hf/140 J/g)×100.

TABLE-US-00002 TABLE 2 Tc 1st Hf 1st Crystal- Tc 2nd Hf 2nd Crystal- cool Cool linity cool Cool linity curve curve 1st Cool curve curve 2nd Cool (° C.) (J/g) curve (%) (° C.) (J/g) curve (%) PET 173.6 32.2 23.0 169.2 30.2 21.6 PET:PCCD = 160.6 27.5 19.6 155.7 25.0 17.9 70:20 (weight) PET:PCTG = 158.0 17.6 12.6 150.9 7.6 5.4 70:20 (weight) PET:PETG = 148.6 7.1 5.1 144.7 3.5 2.5 70:20 (weight) PET:SPG = 161.9 19.8 14.1 155.9 8.6 6.1 70:20 (weight)

[0156] It can be understood that the crystallinity (from second cool curve) is substantially lower when the polyester comprises PCTG, PETG or SPG. In particular, the use of PETG leads to a polyester with an extremely low crystallinity. It is believed that this causes the decrease in the shrinkage of the composition comprising these polyesters, and other beneficial mechanical properties.