阅读说明：本技术 可发泡的热塑性聚酯共聚物 (Foamable thermoplastic polyester copolymers ) 是由 B·阿尔-法胡德 R·K·耶哈 M·伯里克斯 N·加迪贡 于 2018-06-05 设计创作，主要内容包括：本发明涉及一种热塑性聚酯共聚物,其包含相对于该热塑性聚酯共聚物的总重量计50-1000ppm的源自具有≥3个羟基结构部分的醇的结构部分。这种热塑性聚酯共聚物允许生产高品质发泡制品,同时减少对引入共聚物中的添加剂的需要。(The present invention relates to a thermoplastic polyester copolymer comprising 50 to 1000ppm of moieties derived from an alcohol having 3 or more hydroxyl moieties, relative to the total weight of the thermoplastic polyester copolymer. Such thermoplastic polyester copolymers allow for the production of high quality foamed articles while reducing the need for additives to be incorporated into the copolymers.)

1. A thermoplastic polyester copolymer comprising 50 to 1000ppm, relative to the total weight of the thermoplastic polyester copolymer, of moieties derived from an alcohol having ≥ 3 hydroxyl moieties, wherein the thermoplastic polyester copolymer comprises ≥ 0.5 wt.% and ≤ 8.0 wt.% of moieties derived from a chain extender, relative to the total weight of the thermoplastic polyester copolymer.

2. The thermoplastic polyester copolymer according to claim 1, wherein the chain extender is selected from diepoxides, dianhydrides, diisocyanates, bisoxazines, bisoxazolines, or bislactams.

3. The thermoplastic polyester copolymer according to any one of claims 1 to 2, wherein the chain extender is a compound selected from the group consisting of: 2,2 ' -methylene-bis (4, 1-phenylene oxide) dioxirane, 2 ' -ethylene-bis (4, 1-phenylene oxide) dioxirane, 2 ' - (1-methylethylene) -bis (4, 1-phenylene oxide) bis (3-methyl-oxirane), 4 ' -bis (1, 2-epoxypropoxy) biphenyl, 2 ' - ((1,1 ' -biphenyl)) 4,4 ' -diylbis (oxy)) dioxirane, 1, 4-bis (1, 2-epoxypropoxy) benzene, 2 ' - (1, 4-phenylenebis (oxy) dioxirane, 2 ' - ((1,1 ' -binaphthalene) -2,2 ' -diylbis (oxy)) dioxirane, ((6 ' -oxiranylmethoxy (2,2 ' -binaphthalene) -6-yl) oxy) oxirane, 2 ' - (1, 6-naphthalenediylbis (oxy)) dioxirane, 2 ' - ((1,1 ' -biphenyl) -4,4 ' -diylbis (oxy)) bis (2-methyl-oxirane), 2 ' - (2, 6-naphthalenediylbis (oxy)) bis (2-methyl-oxirane), 2,2 '- (methylenebis (4, 1-phenoxyene)) bis (2-methyl-oxirane), 2' - (1, 4-phenylenebis (oxy)) bis (2-methyl-oxirane), (2-methyl-4- ((oxiranyloxy) methyl) phenoxy) oxirane, or (2, 6-dimethyl-4- ((oxiranyloxy) methyl) phenoxy) oxirane.

4. The thermoplastic polyester copolymer of any of claims 1-3 wherein the chain extender is 2, 2' - (1-methylethylidene) -bis (4, 1-phenylene oxy) diepoxy ethane.

5. The thermoplastic polyester copolymer according to any one of claims 1 to 4, wherein the thermoplastic polyester copolymer is a polymer selected from the group consisting of: poly (ethylene terephthalate) copolymers, poly (n-trimethylene terephthalate) copolymers, poly (butylene terephthalate) copolymers, poly (ethylene naphthalate) copolymers, or poly (ethylene furan dicarboxylate) copolymers.

6. The thermoplastic polyester copolymer according to any one of claims 1 to 5, wherein the alcohol is a compound according to the following formula:

wherein R1 is a moiety containing 1 to 10 carbon atoms, and wherein n is an integer ≥ 3 and ≤ 6.

7. The thermoplastic polyester copolymer of claim 6, wherein R1 is a moiety selected from the group consisting of: methyl, ethyl, propyl, tert-butyl, neopentyl or hexamethylethyl.

8. The thermoplastic polyester copolymer of any of claims 1-7, wherein the alcohol having greater than or equal to 3 hydroxyl moieties is selected from tetrahydroxymethane, trihydroxymethane, 1,2, 2-tetrahydroxyethane, hexahydroxyethane, glycerol, 1,3, 5-pentanetriol, xylitol, pentaerythritol, 2,2,3, 3-tetrakis (hydroxymethyl) -1, 4-butanediol, 2, 3-bis (hydroxymethyl) -1, 4-butanediol, tris (2-hydroxyethyl) methane, or tetrakis (2-hydroxyethyl) methane.

9. The thermoplastic polyester copolymer according to any one of claims 1 to 8, wherein the thermoplastic polyester copolymer comprises ≥ 95.0 wt.% of moieties derived from ethylene glycol and terephthalic acid or a diester thereof, relative to the total weight of the thermoplastic polyester copolymer.

10. The thermoplastic polyester copolymer according to any one of claims 1 to 9, wherein the thermoplastic polyester copolymer has an intrinsic viscosity of 0.60dl/g or more and 2.00dl/g or less as determined according to ASTM D2857-95 (2007).

11. Process for producing a thermoplastic polyester copolymer according to any one of claims 1 to 10, wherein the process comprises the steps of: first is an esterification step, wherein a composition comprising an alkylene glycol, a dicarboxylic acid or a diester thereof and an alcohol having 3 or more hydroxyl moieties is reacted to form a polyester oligomer, which is subsequently subjected to polycondensation at a pressure of 0.005 bar or less and a temperature of 275 ℃ and 300 ℃ to obtain a polycondensation product, which, upon curing and drying, is subjected to solid state polycondensation at a temperature of 200 ℃ and 220 ℃ and a vacuum of 20 or less for a period of 5 to 50 hours.

12. A foam comprising the thermoplastic polyester copolymer according to any one of claims 1 to 10.

13. The foam of claim 12 having a foam as determined according to ASTM D6226(2010)<100kg/m³The density of (c).

14. The foam of any of claims 12-13 having an open cell content of 15.0% or less as determined according to ASTM D6226 (2010).

15. A process for producing the foam of any one of claims 12-14 via an extrusion process comprising a first twin screw melt extruder and a second single screw melt extruder arranged in series, wherein a feed composition comprising the thermoplastic polyester copolymer of any one of claims 1-10 is introduced into a feed inlet of the first twin screw melt extruder, wherein an amount of a blowing agent is introduced into the first twin screw melt extruder, and wherein a molten composition comprising the thermoplastic polyester copolymer and the blowing agent is supplied to the feed inlet of the single screw melt extruder upon exiting the twin screw melt extruder and extruded from the single screw melt extruder through a die to form the foam.

Examples	CoPET-1	BC112	HS088	Masspet	CP
						1	98.8	-	-	1.2	4.43
2	98.5	-	-	1.5	4.43
						3	98.2	-	-	1.8	4.43
4	98.5	-	-	1.5	3.13
						5	98.4	-	-	1.6	3.13
6	98.2	-	-	1.8	3.13
						7	-	100.0	-	-	4.43
8	-	97.5	-	2.5	3.0
						9	-	97.5	-	2.5	4.0
10	-	97.5	-	2.5	4.43
						11	-	97.5	-	2.5	5.0
12	100.0	-	-	-	4.43
						13	-	100.0	-	-	3.13
14	-	97.5	-	2.5	3.13
						15	-	97.3	-	2.7	3.38
16	-	-	100.0	-	3.13
						17	-	-	97.5	-	3.13
18	-	-	97.3	-	3.38
						19	100.0	-	-	-	3.13

The amounts in table III represent parts by weight. BC 112 is a PET homopolymer with an intrinsic viscosity of 0.8 dl/g. HC 088 is a PET homopolymer with an intrinsic viscosity of 0.92 dl/g. Both available from SABIC. CP is cyclopentane, examples 1-6 reflect the invention, and examples 7-19 are presented for comparative purposes.

In the foamed material prepared according to the formulation of table III, various properties were determined as described in table IV below.

Table IV: properties of the foamed Material

Foamability refers to the ability to produce a foamed material according to the formulation of a specific example. Table IV shows that the formulations of examples 7, 13 and 16 (commercial PET homopolymer) and of examples 12 and 19 (PET copolymer according to the invention without addition of branching agent) do not produce any foamed material.

Foam density and open cell content were determined according to ASTM D6226(2010) using a densitometer. Compressive strength (Fmax) was determined according to ASTM D1621(2010) using a Zwick tensile tester, where the sample is a stack of 5 foamed sheets or boards, each 4cm in diameter.

In examples 1 to 3 and 8 to 11, foamed sheets were produced according to the above-described method for producing foamed sheets. In examples 4 to 6, 14 to 15 and 17 to 18, the foamed sheet was produced according to the above-described process for producing a foamed sheet. The average foam thickness of those examples reflects the thickness of the board or sheet, when applicable.

The above examples show that with the PET copolymer according to the invention, the amount of chain extender required for producing foamed materials with the desired properties is much smaller with a given amount of blowing agent than with a commercial homopolymer PET material which does not contain units derived from compounds according to formula I, such as pentaerythritol, like the PET copolymer of the invention.