# US 10,370,487 B2 · Poly(ester-carbonate) copolymers, articles formed therefrom, and methods of manufacture

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- Number: US 10,370,487 B2
- Document ID: US10370487B2
- Status: Granted
- Kind: B2
- Application number: 16/096,502
- Filed: 2017-04-28
- Published: 2019-04-18
- Granted: 2019-08-06
- Earliest claimed: 2016-04-28
- Assignees: Sabic Global Technologies B.V.
- Applicants: Sabic Global Technologies B.V.
- Inventors: Tony Farrell; Paul Dean Sybert; James Alan Mahood
- Web page: https://patentgrep.com/patent/US10370487B2

## CPC

- C08G 63/64: Polyesters containing both carboxylic ester groups and carbonate groups
- C08K 5/13: Phenols; Phenolates
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

A poly(ester-carbonate) copolymer comprises carbonate units of the formula (I); and ester units of the formula (II) wherein: T is a C2-20 alkylene, a C6-20 cycloalkylene, or a C6-20 arylene; and R1 and J are each independently (a) a bisphenol A divalent group and (b) a C16 or higher divalent group (b), wherein the C16 or higher divalent group is present in an amount of 40 to 50 mol %; the ester units are present in an amount of 40 to 60 mol %; the poly(ester-carbonate) copolymer has a weight average molecular weight of 18,000 to 24,000 Daltons; and a sample of the composition has a glass transition temperature of 210° C. to 235° C. as determined by differential scanning calorimetry (DSC) as per ASTM D3418 with a 20° C./min heating rate; and a melt viscosity of less than 1050 Pa-s at 644 sec-1 and 350° C., determined according to ISO 11443.

## Claims

### Claim 1

A poly(ester-carbonate) copolymer, comprising
carbonate units of the formula
and
ester units of the formula
wherein:
T is a C2-20 alkylene, a C6-20 cycloalkylene, or a C6-20 arylene; and
R1 and J are each independently
(a) a bisphenol A divalent group of the formula
and
(b) a C16 or higher divalent group (b) of the formula
wherein
Rc and Rd are each independently a C1-12 alkyl, C2-12 alkenyl, C3-8 cycloalkyl, or C1-12 alkoxy,
each R6 is independently C1-3 alkyl or phenyl,
Xa is a C6-12 polycyclic aryl, C3-18 mono- or polycycloalkylene, C3-18 mono- or polycycloalkylidene, a -(Q1)x-G-(Q2)y- group wherein Q1 and Q2 are each independently a C1-3 alkylene, G is a C3-10 cycloalkylene, x is 0 or 1, and y is 1, and
m and n are each independently 0 to 4;
provided that
the C16 or higher divalent group (b) is present in an amount of 40 mol % to 50 mol % based on the total moles of the bisphenol A divalent groups and the C16 or higher divalent groups;
the ester units are present in an amount of 40 mol % to 60 mol % based on the sum of the moles of the carbonate units and the ester units; and
wherein
the poly(ester-carbonate) copolymer has a weight average molecular weight of 18,000 Daltons to 24,000 Daltons, as measured by gel permeation chromatography, using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopolycarbonate references; and
a sample of the composition has
a glass transition temperature of 210° C. to 235° C. as determined by differential scanning calorimetry (DSC) as per ASTM D3418 with a 20° C./min heating rate; and
a melt viscosity of less than 1050 Pa·s at 644 sec−1 and 350° C., determined according to ISO11443.

### Claim 2 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, having one or more of the following properties:
a shift in melt viscosity of less than 25% at 350° C. over 30 min under a nitrogen atmosphere as measured in a small amplitude oscillatory time sweep rheology at a fixed angular frequency of 10 radians/sec;
a glass transition temperature of 220° C. to 235° C. as determined by differential scanning calorimetry (DSC) as per ASTM D3418 with a 20° C./min heating rate;
a Vicat B120 of 220 to 225° C., measured according to ISO 306;
a melt viscosity of less than 1000 Pa·s at 644 sec−1 and 350° C., determined according to ISO11443; or
a yellowness index of less than 18 determined in accordance with ASTM D1925.

### Claim 3 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein
R1 and J are each independently the bisphenol A divalent group or the C16 or higher divalent group; and
at least a portion of the J groups are the C16 or higher divalent group.

### Claim 4 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein greater than 20 mol % and less than 35 mol % of the J groups are the C16 or higher group based on the total moles of the J groups.

### Claim 5 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein T is a C6-20 divalent aromatic group.

### Claim 6 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein T is a divalent isophthaloyl group, a divalent terephthaloyl group, or a combination thereof.

### Claim 7 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein the C16 or higher divalent group has the formula:
wherein
Rc and Rd are each independently C1-3 alkyl or phenyl,
each R2 is independently hydrogen or C1-4 alkyl,
m and n are each independently 0 to 4,
each R3 is independently C1-4 alkyl or hydrogen, and
g is 0 to 10.

### Claim 8 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein the C16 or higher divalent group is derived from 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, or a combination thereof.

### Claim 9 (depends on 1)

A thermoplastic composition comprising the poly(ester-carbonate) copolymer of claim 1.

### Claim 10 (depends on 9)

The thermoplastic composition of claim 9, further comprising a polycarbonate homopolymer, a second poly(ester-carbonate) different from the poly(ester-carbonate) copolymer, a copolycarbonate, or a combination comprising at least one of the foregoing.

### Claim 11 (depends on 9)

The thermoplastic composition of claim 9, wherein the composition has a haze of less than 15% and a transmission greater than 75%, each measured in accordance with ASTM D1003 using the color space CIE1931 (Illuminant C and a 2° observer) at a 3.2 mm thickness.

### Claim 12 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein a metalized sample of the poly(ester-carbonate) copolymer has a defect onset temperature that is within 10 degrees Celsius of the heat deflection temperature of the poly(ester-carbonate) copolymer measured flat on a 80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO 75/Bf.

### Claim 13 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein a metalized sample of the poly(ester-carbonate) copolymer has a defect onset temperature of 200 to 220° C.

### Claim 14 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein the poly(ester-carbonate) copolymer at a given temperature has a melt viscosity of less than 1050 Pa·s at 644 sec−1 and has a shift in melt viscosity of less than 25% at the given temperature over 30 min under a nitrogen atmosphere as measured in a small amplitude oscillatory time sweep rheology at a fixed angular frequency of 10 radians/sec.

### Claim 15 (depends on 1)

The poly(ester-carbonate) copolymer of claim 1, wherein the copolymer has a melt flow rate of 10 to 30 cm3/10 minutes measured at 330° C. under a load of 2.16 kg in accordance with ASTM D1238-04.

### Claim 16 (depends on 1)

An article comprising the copolymer of claim 1, wherein the article is a molded article, a thermoformed article, an extruded film, an extruded sheet, one or more layers of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article.

### Claim 17 (depends on 16)

The article of claim 16, wherein the article is a metallized article comprising the copolymer, wherein the defect onset temperature of the metallized article is within 10° C. of the heat deflection temperature of the copolymer measured flat on a 80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO 75/Bf.

### Claim 18 (depends on 17)

The article of claim 17, comprising
a substrate comprising the copolymer; and
a metal layer disposed on at least one side of the substrate.

### Claim 19 (depends on 18)

The article of claim 18, further comprising a protective layer disposed on the metal layer.

### Claim 20 (depends on 1)

A method for the manufacture of the poly(ester-carbonate) copolymer of claim 1, the method comprising:
providing a slurry comprising water, a water-immiscible organic solvent, a phase transfer catalyst, and bisphenol A;
co-feeding to the slurry a solution comprising aqueous NaOH or aqueous KOH, an aromatic dicarboxylic halide of the formula
wherein T is a C2-20 alkylene, a C6-20 cycloalkylene, or a C6-20 arylene, and
a dihydroxy compound of the formula
or a combination comprising at least one of the foregoing, wherein
Rc and Rd are each independently a C1-12 alkyl, C2-12 alkenyl, C3-8 cycloalkyl, or C1-12 alkoxy,
each R6 is independently C1-3 alkyl or phenyl, and
m and n are each independently 0 to 4
to provide a polyester oligomer; and
reacting the polyester oligomer with a carbonate source to provide the poly(ester-carbonate).