CN101193933A

CN101193933A - Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature

Info

Publication number: CN101193933A
Application number: CNA2006800205378A
Authority: CN
Inventors: E·D·克劳福德; D·S·麦克威廉斯; D·S·波特; G·W·康奈尔
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2005-06-17
Filing date: 2006-03-30
Publication date: 2008-06-04
Anticipated expiration: 2026-03-30
Also published as: CN101193668A; CN101203541A; CN101193721A; CN101193945A; CN101193936A; CN101193935B; CN101193936B; CN101203543B; CN101203540A; CN101193944A; CN101193935A; CN101193932A; CN101193978A; CN101193943B; CN101193980A; CN101213239A; CN101193933B; CN101193940A; CN101193733A; CN101193979A

Abstract

Described are films or sheets comprising polyesters which comprise (a) a dicarboxylic acid component having terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues; 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 1,4-cyclohexanedimethanol residues.

Description

Comprise and contain cyclobutanediol and have logarithmic viscosity number and the film and/or the thin plate of certain bonded polymer blend of high glass-transition temperature

The cross reference of related application

[0001] the application requires the right of priority of following application according to 35 U.S.C. § 119 (e): U.S. Provisional Application 60/691,567 (applying date is on June 17th, 2005), U.S. Provisional Application 60/731,454 (applying date is on October 28th, 2005), U.S. Provisional Application 60/731,389 (applying date is on October 28th, 2005), U.S. Provisional Application 60/739,058 (applying date is on November 22nd, 2005), U.S. Provisional Application 60/738,869 (applying date is on November 22nd, 2005), U.S. Provisional Application 60/750,692 (applying date is on December 15th, 2005), U.S. Provisional Application 60/750,693 (applying date is on December 15th, 2005), U.S. Provisional Application 60/750,682 (applying date is on December 15th, 2005) and U.S. Provisional Applications 60/750,547 (applying date is on December 15th, 2005), all these documents are incorporated herein by reference with its full content.

Technical field

[0002] relate generally to of the present invention comprises the film and/or the thin plate of polymer blend, and this polymer blend comprises at least a polyester, and it is by terephthalic acid, its ester or its mixture; 2,2,4,4-tetramethyl--1,3-cyclobutanediol; Make with 1,4 cyclohexane dimethanol, and have certain combination of logarithmic viscosity number and second-order transition temperature (Tg).These films and/or thin plate comprise at least a polyester or at least a polymer blend, it it is believed that two or more certain combination that has in the following performance: high impact, high glass-transition temperature (Tg), toughness, for example low tough brittle transition temperature, a certain logarithmic viscosity number, good color and the transparency, low density, chemical resistant properties, stability to hydrolysis and long crystallization half-life, this makes it be easy to be configured as goods.

Background technology

[0003] poly terephthalic acid 1, and 4-hexamethylene two methylene esters (PCT) are a kind of only based on terephthalic acid, its ester or its mixture; With the polyester of 1,4 cyclohexane dimethanol, known in the art and be commercially available getting.This polyester is when the crystallization promptly from melt of when cooling, this make by methods known in the art as extrude, injection moulding and similar approach be difficult to form amorphous goods.Slack-off for the crystallization rate that makes PCT, can prepare the copolyesters that contains other dicarboxylic acid or glycol such as m-phthalic acid or ethylene glycol.The PCT of these ethylene glycol or isophthalate modified is also known in the art and be commercially available getting.

[0004] a kind of copolyesters commonly used that is used to produce film, thin plate and moulded product is made by terephthalic acid, 1,4 cyclohexane dimethanol and ethylene glycol.Though these copolyesters can be used in the application that many terminals use, when competent modification ethylene glycol is contained in the preparation so that when long crystallization half-life is provided, they demonstrate deficiency at the aspect of performance as second-order transition temperature and shock strength etc.For example, have sufficiently long crystallization half-life by terephthalic acid, 1, the copolyesters that 4-cyclohexanedimethanol and ethylene glycol are made can provide amorphous products, than composition disclosed herein, these products demonstrate to it is believed that it is the performance of the tough brittle transition temperature that do not make us desirably higher and lower second-order transition temperature.

[0005] 4,4 '-polycarbonate (bisphenol-a polycarbonate) of isopropylidene biphenol has been used as the alternative of polyester known in the art and has been well-known engineering moulded plastic.Bisphenol-a polycarbonate is a kind of transparent high performance plastics with good physicals such as form-stability, high heat resistance and good shock strength.Though bisphenol-a polycarbonate has many good physicalies, its higher melt viscosity causes the melt processability of difference and polycarbonate to show the chemical resistant properties of going on business.It also is difficult to thermoforming in addition.

[0006] also described usually in the art and contained 2,2,4,4-tetramethyl--1, the polymkeric substance of 3-cyclobutanediol.Yet usually, these polymkeric substance may demonstrate high logarithmic viscosity number and high melt viscosity and/or high Tg (second-order transition temperature), make that used not competent manufacturing of equipment or post polymerization processed these materials in the industry.

[0007] thereby, need to comprise the film and/or the thin plate of polymer blend or polyester in the art, it has the combination that is selected from two or more following performances: toughness, high glass-transition temperature, high impact, stability to hydrolysis, toughness, chemical resistant properties, good color and the transparency, long crystallization half-life, low tough brittle transition temperature, good color and the transparency, lower density and/or the hot-forming property of polyester keep processing characteristics on the used standard equipment simultaneously in industry.

Summary of the invention

[0008] it is believed that have logarithmic viscosity number and second-order transition temperature certain in conjunction with, comprise terephthalic acid residue, its ester or its mixture; 1,4 cyclohexane dimethanol; With 2,2,4,4-tetramethyl--1, some film and/or the thin plate of 3-cyclobutanediol residue, following one or more aspect in be better than polyester known in the art and polycarbonate: high impact, stability to hydrolysis, long crystallization half-life, low tough brittle transition temperature, toughness or shock strength, chemical resistant properties, good color and the transparency, long crystallization half-life, lower proportion and/or hot-forming property.These films and/or thin plate it is believed that and are similar to aspect thermotolerance by those of polycarbonate, and still can process on standard industry equipment.

[0009] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With

The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is that 0.35-is less than 0.70dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110-200 ℃.

[0010] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) greater than 2,2,4 of 81-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) 1-is less than the 1,4 cyclohexane dimethanol residue of 19mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110-200 ℃.

[0011] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-85mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 15-60mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

[0012] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-85mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 15-60mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is greater than 148-200 ℃.

[0013] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-80mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 20-60mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

[0014] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 40-is less than 2,2,4 of 80mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) greater than the 1,4 cyclohexane dimethanol residue of 20-60mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

[0015] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60mol%,

Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110-200 ℃.

[0016] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-64.9mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-59.9mol%,

Iii) 0.10-is less than 15mol% ethylene glycol;

Wherein the logarithmic viscosity number of polyester is 035-0.75dL/g or littler, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110-200 ℃.

[0017] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-55mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 45-60mol%,

[0018] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 45-55mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 45-55mol%,

[0019] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60mol%,

Wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration;

Wherein the Tg of polyester be 110-200 ℃ and

Randomly, wherein before the described polymer polymerizing or during add one or more branching agents.

[0020] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:

(A) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 1-99mol% and

(B) residue of at least a branching agent;

Wherein total molecular fraction of dicarboxylic acid component be 100m0l% and

Total molecular fraction of diol component is 100mol%; With

[0021] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:

(A) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60mol%,

(B) residue of at least a branching agent;

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

[0022] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:

(A) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60mol% and

(B) residue of at least a branching agent;

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

[0023] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:

(A) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 1-99mol% and

(B) at least a thermo-stabilizer or its reaction product;

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration;

Wherein the Tg of polyester is 110-200 ℃.

[0024] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:

(A) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60mol% and

(B) at least a thermo-stabilizer or its reaction product;

Wherein the Tg of polyester is 110-200 ℃.

[0025] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:

(A) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 35-60mol% and

(B) at least a thermo-stabilizer or its reaction product;

Wherein the Tg of polyester is 110-200 ℃.

[0026] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60mol%,

Wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With

Wherein the Tg of polyester is 110-150 ℃.

[0027] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60mol%,

Wherein the Tg of polyester is 120-135 ℃.

[0028] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is greater than 148 ℃ to 200 ℃ at the most.

[0029] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 127 ℃-200 ℃.

[0030] the present invention relates to a kind of film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-80mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 20-99mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is greater than 124 ℃-200 ℃.In other embodiments, Tg can be for greater than 125 ℃-200 ℃; Perhaps greater than 126 ℃-200 ℃; Perhaps greater than 127 ℃-200 ℃.

[0031] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) greater than 50 to 99mol% at the most 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) 1-is less than the 1,4 cyclohexane dimethanol residue of 50mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110 ℃-200 ℃.

[0032] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) greater than 50 to 80mol% at the most 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) 20-is less than the 1,4 cyclohexane dimethanol residue of 50mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is 0.35-01.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110 ℃-200 ℃.

[0033] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein the logarithmic viscosity number of polyester is greater than 0.76 to 1.2dL/g at the most, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; Wherein the Tg of polyester is 110 ℃-200 ℃.

[0034] in one aspect in, the polymer blend that can be used for film of the present invention or thin plate comprises at least a polycarbonate.

[0035] in one aspect in, the polymer blend that can be used for film of the present invention or thin plate does not comprise polycarbonate.

[0036] in one aspect in, the polyester that can be used for film of the present invention or thin plate comprises less than 15mol% ethylene glycol or 0.10-15mol% glycol residue, for example 0.01-is less than the 15mol% glycol residue.

[0037] in one aspect in, the polyester that can be used for film of the present invention or thin plate does not comprise ethylene glycol.

[0038] in one aspect in, the polymer blend that can be used for film of the present invention or thin plate comprises at least a thermo-stabilizer or its reaction product.

[0039] in one aspect in, the polyester that can be used for film of the present invention or thin plate does not comprise branching agent, perhaps, before the polymerization of polyester or during add branching agent.

[0040] in one aspect in, the polyester that can be used for film of the present invention or thin plate comprises branching agent, and this and the method or the sequence independence that wherein add it.

[0041] in one aspect in, the polyester that can be used for film of the present invention or thin plate is not by separately or with 1 of array configuration, ammediol or 1, the 4-butyleneglycol is made.In others, 1, ammediol or 1, the 4-butyleneglycol separately or with array configuration ground, can be used to prepare the polyester that can be used for film of the present invention or thin plate.

[0042] in one aspect of the invention, can be used for suitable-2,2 in some useful polyester of film of the present invention or thin plate, 4,4-tetramethyl--1, the molecular fraction of 3-cyclobutanediol is greater than 50mol% or greater than suitable-2 of 55mol%, 2,4,4-tetramethyl--1,3-cyclobutanediol or greater than suitable-2 of 70mol%, 2,4,4-tetramethyl--1,3-cyclobutanediol; Wherein suitable-2,2,4,4-tetramethyl--1,3-cyclobutanediol and anti--2,2,4,4-tetramethyl--1, total molecular fraction of 3-cyclobutanediol equals 100mol% altogether.

[0043] in one aspect of the invention, can be used for 2,2,4 in some useful polyester of film of the present invention or thin plate, 4-tetramethyl--1, the molecular fraction of the isomer of 3-cyclobutanediol are suitable-2,2,4 of 30-70mol%, 4-tetramethyl--1, anti--2,2 of 3-cyclobutanediol and 30-70mol%, 4,4-tetramethyl--1,3-cyclobutanediol, perhaps 40-60mol%'s suitable-2,2,4,4-tetramethyl--1, anti--2,2 of 3-cyclobutanediol and 40-60mol%, 4,4-tetramethyl--1,3-cyclobutanediol, wherein suitable-2,2,4,4-tetramethyl--1,3-cyclobutanediol and anti--2,2,4,4-tetramethyl--1, total molecular fraction of 3-cyclobutanediol equals 100mol% altogether.

[0044] in one aspect in, can be used for polymer blend of the present invention can use with the various types of film and/or thin plate, includes but not limited to cast film and/or thin plate, calendered film and/or thin plate, compression molded films and/or thin plate, solution plastic casting film and/or thin plate.The method of making film and/or thin plate includes but not limited to extrusion molding, calendering, compression moulding and solution casting.

[0045] in addition, in one aspect in, use polymer blend of the present invention can minimize and/or eliminate drying step before melt-processed and/or thermoforming.

[0046] in one aspect in, can be unbodied or hemicrystalline to some useful polyester of the present invention.In one aspect, some polyester useful to the present invention may have lower degree of crystallinity.To useful some polyester of the present invention thereby may have unbodied basically form, mean that polyester comprises the unordered basically zone of polymkeric substance.

Description of drawings

[0047] Fig. 1 shows the figure of comonomer to the influence of the fastest crystallization half-life of modification PCT copolyesters.

[0048] Fig. 2 is presented at the figure of the middle comonomer of notched izod shock strength test (ASTM D256,1/8 inch thick, 10 mil otch) to the influence of tough brittle transition temperature (Tbd).

[0049] Fig. 3 shows 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol is formed the figure to the influence of the second-order transition temperature (Tg) of copolyesters.

Detailed description of the invention

[0050] can more easily understand the present invention by detailed description and work embodiment with reference to following certain embodiments of the present invention. According to purpose of the present invention, certain embodiments of the present invention are described in the summary of the invention and further and are described hereinafter. Other embodiment of the present invention has been described equally, herein.

[0051] it is believed that and contain the combination that film with polyester of described composition herein and/or thin plate can have two or more for example following physical properties: high impact, high glass-transition temperature, chemical resistance, hydrolytic stability, toughness, for example low tough brittle transition temperature, good color and the transparency, low-density and long crystallization half-life and good processing characteristics allow them to be configured as goods thus easily. In some embodiments of the present invention, polyester has the combination of performance of the combination of performance of uniqueness of good impact strength, heat resistance, chemical resistance, density and/or good impact strength, heat resistance and processing characteristics and/or the combination of one or more described performances, and being considered before these exists.

[0052] as used in this article, term " polyester " comprises copolyesters and is interpreted as referring to the synthetic polymer that the reaction by one or more difunctionalitys and/or polyfunctional carboxylic acids and one or more difunctionality hydroxy compounds and/or multifunctional hydroxy compounds prepares. Usually, the bifunctional carboxylic acid can be dicarboxylic acids, and the difunctionality hydroxy compounds can be dihydroxylic alcohols, for example glycol (glycol) and glycol (diol). As using among the application, term " glycol " includes but not limited to glycol, glycol and/or multifunctional hydroxy compounds, for example branching agent. Perhaps, the bifunctional carboxylic acid can be hydroxycarboxylic acid, P-hydroxybenzoic acid for example, and the difunctionality hydroxy compounds may be the aryl nucleus with 2 hydroxyl substituents, for example quinhydrones. As used in this article, term " residue " refers to be incorporated into by polycondensation and/or esterification by corresponding monomer any organic structure of polymer. As used in this article, term " repetitive " refers to have by the dicarboxylic acid residue of carbonyl oxygen base group bonding and the organic structure of diol residue. Therefore, for example, dicarboxylic acid residue can be derived from dicarboxylic acid monomer or its relevant carboxylic acid halides, ester, salt, acid anhydrides or its mixture. Therefore, as used in this article, term dicarboxylic acids intention comprises any derivative of dicarboxylic acids and dicarboxylic acids, comprises carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture that it is relevant, and they can be used for course of reaction with glycol with the preparation polyester. In addition, as using among the application, term " diacid " comprises the polyfunctional acid, such as branching agent. As used in this article, term " terephthalic acid (TPA) " intention comprises any derivative of terephthalic acid (TPA) itself and its residue and terephthalic acid (TPA), comprise carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture or its residue that it is relevant, they can be used for course of reaction with glycol with the preparation polyester.

[0053] in one embodiment, terephthalic acid (TPA) can be used as parent material. In another embodiment, dimethyl terephthalate (DMT) can be used as parent material. In another embodiment, the mixture of terephthalic acid (TPA) and dimethyl terephthalate (DMT) can be used as parent material and/or intermediate materials.

[0054] polyester that can be used for film of the present invention or thin plate can and be incorporated in the polyester polymers dicarboxylic acids and glycol preparation as their corresponding residue by equal proportion reaction basically usually. Therefore, the polyester that can be used for film of the present invention or thin plate can comprise basically sour residue (100mol%) and glycol (and/or the multifunctional hydroxyl mixture) residue (100mol%) of equimolar ratio, so that the total mole number of repetitive equals 100mol%. Therefore, the mole percent that provides in the present disclosure can be based on the total mole number of sour residue, the total mole number of diol residue or the total mole number of repetitive. For example, based on the total acid residue, contain the polyester of 30mol% M-phthalic acid, refer to that polyester comprises the 30mol% isophthalic acid residues in the acid of 100mol% altogether residue. Therefore, in every 100mol acid residue, there is the 30mol isophthalic acid residues. In another example, based on the total diol residue, contain 30mol%2,2,4,4-tetramethyl-1, the polyester of 3-cyclobutanediol refers to that polyester comprises 30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue in 100mol% diol residue altogether. Therefore, in every 100mol diol residue, there is the TMCBD residue of 30mol. In other side of the present invention, can be used for film of the present invention and/or thin plate polyester Tg including, but not limited to: 85-200 ℃; 190 ℃ of 85-; 85-180 ℃; 85-170 ℃; 85-160 ℃; 85-155 ℃; 85-150 ℃; 85-145 ℃; 85-140 ℃; 85-138 ℃; 85-135 ℃; 85-130 ℃; 85-125 ℃; 85-120 ℃; 115 ℃ of 85-; 85-110 ℃; 85-105 ℃; 85-100 ℃; 85-95 ℃; 85-90 ℃; 90-200 ℃; 90-190 ℃; 90-180 ℃; 90-170 ℃; 90-160 ℃; 90-155 ℃; 90-150 ℃; 145 ℃ of 90-; 90-140 ℃; 90-138 ℃; 90-135 ℃; 90-130 ℃; 90-125 ℃; 90-120 ℃; 90-115 ℃; 90-110 ℃; 90-105 ℃; 90-100 ℃; 90-95 ℃; 95-200 ℃; 95-190 ℃; 95-180 ℃; 95-170 ℃; 95-160 ℃; 95-155 ℃; 95-150 ℃; 95-145 ℃; 140 ℃ of 95-; 95-138 ℃; 95-135 ℃; 95-130 ℃; 95-125 ℃; 95-120 ℃; 95-115 ℃; 95-110 ℃; 95-105 ℃; 95-is less than 105 ℃; 95-100 ℃; 100-200 ℃; 100-190 ℃; 100-180 ℃; 100-170 ℃; 100-160 ℃; 100-155 ℃; 100-150 ℃; 100-145 ℃; 100-140 ℃; 100-138 ℃; 100-135 ℃; 100-130 ℃; 100-125 ℃; 100-120 ℃; 100-115 ℃; 100-110 ℃; 105-200 ℃; 105-190 ℃; 105-180 ℃; 105-170 ℃; 105-160 ℃; 105-155 ℃; 105-150 ℃; 105-145 ℃; 105-140 ℃; 105-138 ℃; 105-135 ℃; 105-130 ℃; 105-125 ℃; 105-120 ℃; 105-115 ℃; 105-110 ℃; Greater than 105-125 ℃; Greater than 105-120 ℃; Greater than 105-115 ℃; Greater than 105-110 ℃; 110-200 ℃; 110-195 ℃; 110-190 ℃; 110-185 ℃; 110-180 ℃; 110-175 ℃; 110-170 ℃; 110-165 ℃; 110-160 ℃; 110-155 ℃; 110-150 ℃; 110-145 ℃; 110-138 ℃; 110-140 ℃; 110-135 ℃; 110-130 ℃; 110-125 ℃; 110-120 ℃; 110-115 ℃; 115-200 ℃; 115-195 ℃; 115-190 ℃; 115-185 ℃; 115-180 ℃; 115-175 ℃; 115-170 ℃; 115-165 ℃ 115-160 ℃; 115-155 ℃; 115-150 ℃; 115-145 ℃; 115-140 ℃; 115-138 ℃; 115-135 ℃; 115-125 ℃; 115-120 ℃; 120-200 ℃; 120-195 ℃; 120-190 ℃; 120-185 ℃ 120-180 ℃; 175 ℃ 120-170 ℃ of 120-; 120-165 ℃; 120-160 ℃; 120-155 ℃; 120-150 ℃; 120-145 ℃; 120-140 ℃; 120-138 ℃; 120-135 ℃; 125-180 ℃; 125-170 ℃; 125-160 ℃; 125-155 ℃; 125-150 ℃; 125-145 ℃; 125-140 ℃; 125-138 ℃; 125-135 ℃; 135-180 ℃; 127-180 ℃; 127-170 ℃; 127-160 ℃; 127-150 ℃; 127-145 ℃; 127-140 ℃; 127-138 ℃; 127-135 ℃; 130-200 ℃; 130-195 ℃; 130-190 ℃; 130-185 ℃; 130-180 ℃; 130-175 ℃; 130-170 ℃; 165 ℃ 130-160 ℃ of 130-; 130-155 ℃; 130-150 ℃; 130-145 ℃; 130-140 ℃; 130-138 ℃; 130-135 ℃; 135-170 ℃; 135-160 ℃; 135-155 ℃; 135-150 ℃; 135-145 ℃; 135-140 ℃; 135-135 ℃; 140-200 ℃; 140-195 ℃; 140-190 ℃; 140-185 ℃; 140-180 ℃; 140-170 ℃; 140-165 ℃; 140-160 ℃; 140-155 ℃; 140-150 ℃; 140-145 ℃; 148-200 ℃; 148-190 ℃; 148-180 ℃; 148-170 ℃; 148-160 ℃; 148-155 ℃; 148-150 ℃; 150-200 ℃; 150-195 ℃; 150-190 ℃; 150-185 ℃; 150-180 ℃; 150-175 ℃; 150-170 ℃; 150-165 ℃; 150-160 ℃; 150-155 ℃; 155-200 ℃; 150-190 ℃; 150-180 ℃; 150-170 ℃; 150-160; 155-190 ℃; 155-180 ℃; 155-170 ℃; With 155-165 ℃; Greater than 124 ℃-200 ℃ at the most; Greater than 125 ℃-200 ℃ at the most; Greater than 126 ℃-200 ℃ at the most; Greater than 148 ℃-200 ℃ at the most.

[0055] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 1-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-99mol%1,4-cyclohexanedimethanol; 1-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-99mol%1,4-cyclohexanedimethanol; 1-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-99mol%1,4-cyclohexanedimethanol; 1-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-99mol%1,4-cyclohexanedimethanol; 1-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-99mol%1,4-cyclohexanedimethanol, 1-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-99mol%1,4-cyclohexanedimethanol; 1-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-99mol%1,4-cyclohexanedimethanol; 1-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-99mol%1,4-cyclohexanedimethanol; 1-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-99mol%1,4-cyclohexanedimethanol; 1-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-99mol%1,4-cyclohexanedimethanol; 1-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-99mol%1,4-cyclohexanedimethanol; 1-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-99mol%1,4-cyclohexanedimethanol; 1-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-99mol%1,4-cyclohexanedimethanol; 1-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-99mol%1,4-cyclohexanedimethanol; 1-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-99mol%1,4-cyclohexanedimethanol; 1-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-99mol%1,4-cyclohexanedimethanol; 1-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-99mol%1,4-cyclohexanedimethanol; 1-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-99mol%1,4-cyclohexanedimethanol; 1-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-99mol%1,4-cyclohexanedimethanol; And 1-5mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95-99mol%1,4-cyclohexanedimethanol.

[0056] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 5-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-95mol%1, the 4-cyclohexanedimethanol; 5-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-95mol%1,4-cyclohexanedimethanol; 5-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-95mol%1,4-cyclohexanedimethanol; 5-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-95mol%1,4-cyclohexanedimethanol; 5-is less than 35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65-95mol%1,4-cyclohexanedimethanol; 5-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-95mol%1,4-cyclohexanedimethanol; 5-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-95mol%1,4-cyclohexanedimethanol; 5-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-95mol%1,4-cyclohexanedimethanol; 5-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-95mol%1,4-cyclohexanedimethanol; 5-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-95mol%1,4-cyclohexanedimethanol; Greater than 5-less than 10mol%2,2,4,4-tetramethyl-1, the 3-cyclobutanediol and less than 90-greater than 95mol%1, the 4-cyclohexanedimethanol; 5.5mol%-9.5mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 94.5mol%-90.5mol%1,4-cyclohexanedimethanol; And 6-9mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 94-91mol%1,4-cyclohexanedimethanol.

[0057] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 10-100mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 0-90mol%1,4-cyclohexanedimethanol; 10-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-90mol%1,4-cyclohexanedimethanol; 10-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-90mol%1,4-cyclohexanedimethanol; 10-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-90mol%1,4-cyclohexanedimethanol; 10-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-90mol%1,4-cyclohexanedimethanol; 10-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-90mol%1,4-cyclohexanedimethanol, 10-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-90mol%1,4-cyclohexanedimethanol; 10-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-90mol%1,4-cyclohexanedimethanol; 10-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-90mol%1,4-cyclohexanedimethanol; 10-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-90mol%1,4-cyclohexanedimethanol; 10-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-90mol%1,4-cyclohexanedimethanol; 10-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-90mol%1,4-cyclohexanedimethanol; 10-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-90mol% 1,4-CHDM; 10-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-90mol%1,4-cyclohexanedimethanol; 10-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-90mol%1,4-cyclohexanedimethanol; 10-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-90mol%1,4-cyclohexanedimethanol; 10-is less than 35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65-90%1,4-cyclohexanedimethanol; 10-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-90mol%1,4-cyclohexanedimethanol; 10-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-90mol%1,4-cyclohexanedimethanol; 10-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-90mol%1,4-cyclohexanedimethanol; And 10-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-90mol%1,4-cyclohexanedimethanol.

[0058] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 14-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-86mol%1,4-cyclohexanedimethanol; 14-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-86mol%1,4-cyclohexanedimethanol; 14-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-86mol%1,4-cyclohexanedimethanol; 14-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-86mol%1,4-cyclohexanedimethanol; 14-86mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 14-86mol%1,4-cyclohexanedimethanol, 14-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-86mol%1,4-cyclohexanedimethanol; 14-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-86mol%1,4-cyclohexanedimethanol; 14-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-86mol%1,4-cyclohexanedimethanol; 14-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-86mol%1,4-cyclohexanedimethanol; 14-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-86mol%1,4-cyclohexanedimethanol; 14-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-86mol%1,4-cyclohexanedimethanol; 14-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-86mol%1,4-cyclohexanedimethanol; 14-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-86mol%1,4-cyclohexanedimethanol; 14-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-86mol%1,4-cyclohexanedimethanol; 14-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-86mol%1,4-cyclohexanedimethanol; 14-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-86mol%1,4-cyclohexanedimethanol; 14-24mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 76-86mol%1,4-cyclohexanedimethanol; And 14-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-86mol%1,4-cyclohexanedimethanol.

[0059] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 15-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-85mol%1,4-cyclohexanedimethanol; 15-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-85mol%1,4-cyclohexanedimethanol; 15-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-85mol%1,4-cyclohexanedimethanol; 15-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-85mol%1,4-cyclohexanedimethanol; 15-86mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-86mol%1,4-cyclohexanedimethanol, 15-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-85mol%1,4-cyclohexanedimethanol; 15-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-85mol%1,4-cyclohexanedimethanol; 15-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-85mol%1,4-cyclohexanedimethanol; 15-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-85mol%1,4-cyclohexanedimethanol; 15-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-85mol%1,4-cyclohexanedimethanol; 15-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-85mol%1,4-cyclohexanedimethanol; 15-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-85mol%1,4-cyclohexanedimethanol; 15-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-85mol%1,4-cyclohexanedimethanol; 15-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-85mol%1,4-cyclohexanedimethanol; 15-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-85mol%1,4-cyclohexanedimethanol; 15-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-85mol%1,4-cyclohexanedimethanol; 15-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-85mol%1,4-cyclohexanedimethanol; And 15-24mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 76-85mol%1,4-cyclohexanedimethanol.

[0060] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 20-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-80mol%1,4-cyclohexanedimethanol; 20-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-80mol%1,4-cyclohexanedimethanol; 20-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-80mol%1,4-cyclohexanedimethanol; 20-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-80mol%1,4-cyclohexanedimethanol; 20-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-80mol%1,4-cyclohexanedimethanol, 20-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-80mol%1,4-cyclohexanedimethanol; 20-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-80mol%1,4-cyclohexanedimethanol; 20-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-80mol%1,4-cyclohexanedimethanol; 20-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-80mol%1,4-cyclohexanedimethanol; 20-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-80mol%1,4-cyclohexanedimethanol; 20-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-80mol%1,4-cyclohexanedimethanol; 20-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-80mol%1,4-cyclohexanedimethanol; 20-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-80mol%1,4-cyclohexanedimethanol; 20-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-80mol%1,4-cyclohexanedimethanol; 20-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-80mol%1,4-cyclohexanedimethanol; 20-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-80mol%1,4-cyclohexanedimethanol; And 20-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-80mol%1,4-cyclohexanedimethanol.

[0061] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 25-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-75mol%1,4-cyclohexanedimethanol; 25-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-75mol%1,4-cyclohexanedimethanol; 25-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-75mol%1,4-cyclohexanedimethanol; 25-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-75mol%1,4-cyclohexanedimethanol; 25-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-75mol%1,4-cyclohexanedimethanol, 25-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-75mol%1,4-cyclohexanedimethanol; 25-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-75mol%1,4-cyclohexanedimethanol; 25-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-75mol%1,4-cyclohexanedimethanol; 25-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-75mol%1,4-cyclohexanedimethanol; 25-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-75mol%1,4-cyclohexanedimethanol; 25-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-75mol%1,4-cyclohexanedimethanol; 25-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-75mol%1,4-cyclohexanedimethanol; 25-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-75mol%1,4-cyclohexanedimethanol; 25-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-75mol%1,4-cyclohexanedimethanol; 25-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-75mol%1,4-cyclohexanedimethanol; And 25-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-75mol%1,4-cyclohexanedimethanol.

[0062] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 30-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-70mol%1,4-cyclohexanedimethanol; 30-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-70mol%1,4-cyclohexanedimethanol; 30-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-70mol%1,4-cyclohexanedimethanol; 30-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-70mol%1,4-cyclohexanedimethanol; 30-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-70mol%1,4-cyclohexanedimethanol, 30-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-70mol%1,4-cyclohexanedimethanol; 30-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-70mol%1,4-cyclohexanedimethanol; 30-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-70mol%1,4-cyclohexanedimethanol; 30-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-70mol%1,4-cyclohexanedimethanol; 30-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-70mol%1,4-cyclohexanedimethanol; 30-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-70mol%1,4-cyclohexanedimethanol; 30-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-70mol%1,4-cyclohexanedimethanol; 30-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-70mol%1,4-cyclohexanedimethanol; 30-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-70mol%1,4-cyclohexanedimethanol; 30-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-70mol%1,4-cyclohexanedimethanol.

[0063] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 35-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-65mol%1,4-cyclohexanedimethanol; 35-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-65mol%1,4-cyclohexanedimethanol; 35-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-65mol%1,4-cyclohexanedimethanol; 35-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-65mol%1,4-cyclohexanedimethanol; 35-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-65mol%1,4-cyclohexanedimethanol, 35-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-65mol%1,4-cyclohexanedimethanol; 35-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-65mol%1,4-cyclohexanedimethanol; 35-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-65mol%1,4-cyclohexanedimethanol; 35-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-65mol%1,4-cyclohexanedimethanol; 35-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-65mol%1,4-cyclohexanedimethanol; 35-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-65mol%1,4-cyclohexanedimethanol; 35-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-65mol%1,4-cyclohexanedimethanol; 35-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-65mol%1,4-cyclohexanedimethanol; 35-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-65mol%1,4-cyclohexanedimethanol.

[0064] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 40-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-60mol%1,4-cyclohexanedimethanol; 40-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-60mol%1,4-cyclohexanedimethanol; 40-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-60mol%1,4-cyclohexanedimethanol; 40-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-60mol%1,4-cyclohexanedimethanol; 40-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-60mol%1,4-cyclohexanedimethanol, 40-be less than 80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 20-60mol% 1,4-CHDM; 40-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-60mol% 1,4-CHDM; 40-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-60mol% 1,4-CHDM; 40-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-60mol% 1,4-CHDM; 40-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-60mol% 1,4-CHDM; 40-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-60mol% 1,4-CHDM; 40-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-60mol%1,4-cyclohexanedimethanol; 40-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-60mol%1,4-cyclohexanedimethanol; And 40-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-60mol%1,4-cyclohexanedimethanol.

[0065] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 45-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-55mol%1,4-cyclohexanedimethanol; 45-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-55mol%1,4-cyclohexanedimethanol; 45-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-55mol%1,4-cyclohexanedimethanol; 45-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-55mol%1,4-cyclohexanedimethanol; 45-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-55mol%1,4-cyclohexanedimethanol, 45-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-55mol%1,4-cyclohexanedimethanol; 45-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-55mol%1,4-cyclohexanedimethanol; 45-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-55mol%1,4-cyclohexanedimethanol; 45-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-55mol%1,4-cyclohexanedimethanol; Greater than 45-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-be less than 55mol%1, the 4-cyclohexanedimethanol; 45-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-55mol%1,4-cyclohexanedimethanol; 45-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-55mol%1,4-cyclohexanedimethanol; Greater than 45-52mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 48-55mol%1,4-cyclohexanedimethanol; 46-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-54mol%1,4-cyclohexanedimethanol; And 48-52mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 48-52mol%1,4-cyclohexanedimethanol.

[0066] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: greater than 50-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-be less than 50mol%1, the 4-cyclohexanedimethanol, and greater than 50-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-be less than 50mol%1, the 4-cyclohexanedimethanol.

[0067] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 55-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-45mol%1,4-cyclohexanedimethanol; 55-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-45mol%1,4-cyclohexanedimethanol; 55-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-45mol%1,4-cyclohexanedimethanol; 55-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-45mol%1,4-cyclohexanedimethanol; 55-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-45mol%1,4-cyclohexanedimethanol, 55-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-45mol%1,4-cyclohexanedimethanol; 55-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-45mol%1,4-cyclohexanedimethanol; 55-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-45mol%1,4-cyclohexanedimethanol; And 55-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-45mol% 1,4-CHDM.

[0068] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 60-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-40mol%1,4-cyclohexanedimethanol; 60-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-40mol%1,4-cyclohexanedimethanol; 60-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-40mol%1,4-cyclohexanedimethanol; 60-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-40mol%1,4-cyclohexanedimethanol; 60-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-40mol%1,4-cyclohexanedimethanol, 60-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-40mol%1,4-cyclohexanedimethanol; And 60-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-40mol%1,4-cyclohexanedimethanol.

[0069] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 65-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-35mol%1,4-cyclohexanedimethanol; 65-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-35mol%1,4-cyclohexanedimethanol; 65-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-35mol%1,4-cyclohexanedimethanol; 65-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-35mol%1,4-cyclohexanedimethanol; 65-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-35mol%1,4-cyclohexanedimethanol, 65-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-35mol%1,4-cyclohexanedimethanol; And 65-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-35mol%1,4-cyclohexanedimethanol.

[0070] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 70-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-30mol%1,4-cyclohexanedimethanol; 70-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-30mol%1,4-cyclohexanedimethanol; 70-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-30mol%1,4-cyclohexanedimethanol; 70-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-30mol%1,4-cyclohexanedimethanol; 70-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-30mol%1,4-cyclohexanedimethanol.

[0071] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 75-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-25mol%1,4-cyclohexanedimethanol; 75-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-25mol%1,4-cyclohexanedimethanol; 75-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-25mol%1,4-cyclohexanedimethanol; And 75-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-25mol%1,4-cyclohexanedimethanol.

[0072] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 80-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-20mol%1,4-cyclohexanedimethanol; 80-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-20mol%1,4-cyclohexanedimethanol; 80-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-20mol%1,4-cyclohexanedimethanol; Greater than 80-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-be less than 20mol%1, the 4-cyclohexanedimethanol; With greater than 81-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-be less than 19mol%1, the 4-cyclohexanedimethanol.

[0073] except above-mentioned listed glycol, also can be by 1,3-PD, BDO or the preparation of its mixture to the polyester that the polymer blend that can be used for film of the present invention or thin plate is useful. Expection is by 1, ammediol, BDO or the preparation of its mixture can have at least one in the scope of at least one and/or glycol described herein or diacid in the scope of at least one in the scope of Tg described herein, logarithmic viscosity number described herein to film of the present invention or the useful composition of thin plate. In addition or alternatively, also can be prepared with at least a following amount by 1,4-CHDM the useful polyester of being made by 1,3-PD or Isosorbide-5-Nitrae-butanediol or its mixture of film of the present invention or thin plate: 0.1-99mol%; 0.1-95mol%; 0.1-90mol%; 0.1-85mol%; 0.1-80mol%; 0.1-75mol%; 0.1-70mol%; 0.1-60mol%; 0.1-50mol%; 0.1-40mol%; 0.1-35mol%; 0.1-30mol%; 0.1-25mol%; 0.1-20mol%; 0.1-15mol%; 0.1-10mol%; 0.1-5mol%; 1-99mol%; 1-95mol; 1-90mol%; 1-85mol%; 1-80mol%; 1-70mol%; 1-60mol%; 1-50mol%; 1-40mol%; 1-35mol%; 1-30mol%; 1-25mol%; 1-20mol%; 1-15mol%; 1-10mol%; 1-5mol%; 5-99mol%; 5-95mol; 5-90mol%; 5-85mol%; 5-80mol%; 5-75mol%; 5-70mol%; 5-60mol%; 5-50mol%; 5-40mol%; 5-35mol%; 5-30mol%; 5-25mol%; 5-20mol%; And 5-15mol%; 5-10mol%; 10-99mol%; 10-95mol; 10-90mol%; 10-85mol%; 10-80mol%; 10-75mol%; 10-70mol%; 10-60mol%; 10-50mol%; 10-40mol%; 10-35mol%; 10-30mol%; 10-25mol%; 10-20mol%; 10-15mol%; 20-99mol%; 20-95mol; 20-90mol%; 20-85mol%; 20-80mol%; 20-75mol%; 20-70mol%; 20-60mol%; 20-50mol%; 20-40mol%; 20-35mol%; 20-30mol%; And 20-25mol%.

[0074] for certain embodiments of the invention, the polyester that can be used for film of the present invention or thin plate can demonstrate any following logarithmic viscosity number, and as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethanes at 25 ℃ in concentration: 0.35-is less than 0.70dL/g; 0.35-0.68dL/g; 0.35-less than 0.68dL/g; 0.35-0.65dL/g; 0.40-0.70dL/g; 0.40-less than 0.70dL/g; 0.40-0.68dL/g; 0.40-less than 0.68dL/g; 0.40-0.65dL/g; 0.45-less than 0.70dL/g; 0.45-0.68dL/g; 0.45-less than 0.68dL/g; 0.45-0.65dL/g; 0.50-less than 0.70dL/g; 0.50-0.68dL/g; 0.50-less than 0.68dL/g; 0.50-0.67dL/g; 0.50-0.66dL/g; 0.50-0.65dL/g; 0.55-less than 0.70dL/g; 0.55-0.68dL/g; 0.55-less than 0.68dL/g; 0.55-0.65dL/g; 0.58-less than 0.70dL/g; 0.58-0.68dL/g; 0.58-less than 0.68dL/g; Or 0.58-0.65dL/g.

[0075] for embodiment of the present invention, be 0.35-0.75dL/g or higher to the logarithmic viscosity number of the useful polyester of film of the present invention or thin plate wherein, these polyester also can demonstrate any following logarithmic viscosity number, and as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethanes at 25 ℃ in concentration: 0.35-is less than 0.75dL/g; 0.35-0.72dL/g; Or 0.35-0.70dL/g.

[0076] for embodiment of the present invention, the polyester that can be used for film of the present invention or thin plate can show at least one in the following logarithmic viscosity number, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethanes: 0.10-1.2dL/g at 25 ℃ in concentration; 0.10-11dL/g; 0.10-1dL/g; 0.10-less than 1dL/g; 0.10-0.98dL/g; 0.10-0.95dL/g; 0.10-0.90dL/g; 0.10-0.85dL/g; 0.10-0.80dL/g; 0.10-0.75dL/g; 0.10-less than 0.75dL/g; 0.10-0.72dL/g; 0.10-0.70dL/g; 0.10-less than 0.70dL/g; 0.10-0.68dL/g; 0.10-less than 0.68dL/g; 0.10-0.65dL/g; 0.10-0.6dL/g; 0.10-0.55dL/g; 0.10-0.5dL/g; 0.10-0.4dL/g; 0.10-0.35dL/g; 0.20-1.2dL/g; 0.20-1.1dL/g; 0.20-1dL/g; 0.20-less than 1dL/g; 0.20-0.98dL/g; 0.20-0.95dL/g; 0.20-0.90dL/g; 0.20-0.85dL/g; 0.20-0.80dL/g; 0.20-0.75dL/g; 0.20-less than 0.75dL/g; 0.20-0.72dL/g; 0.20-0.70dL/g; 0.20-less than 0.70dL/g; 0.20-0.68dL/g; 0.20-less than 0.68dL/g; 0.20-0.65dL/g; 0.20-0.6dL/g; 0.20-0.55dL/g; 0.20-0.5dL/g; 0.20-0.4dL/g; And 0.20-0.35dL/g.

[0077] for embodiment of the present invention, wherein logarithmic viscosity number is 0.35-1.2dL/g, these also can demonstrate any following logarithmic viscosity number to film of the present invention or the useful polyester of thin plate, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethanes: 0.35-1.2dL/g at 25 ℃ in concentration; 0.35-1.1dL/g; 0.35-1dL/g; 0.35-less than 1dL/g; 0.35-0.98dL/g; 0.35-0.95dL/g; 0.35-0.9dL/g; 0.35-0.85dL/g; 0.35-0.8dL/g; 0.35-0.75dL/g; 0.35-less than 0.75dL/g; 0.35-0.72dL/g; 0.40-1.2dL/g; 0.40-1.1dL/g; 0.40-1dL/g; 0.40-less than 1dL/g; 0.40-0.98dL/g; 0.40-0.95dL/g; 0.40-0.9dL/g; 0.40-0.85dL/g; 0.40-0.8dL/g; 0.40-0.75dL/g; 0.40-less than 0.75dL/g; 0.40-0.72dL/g; Greater than 0.42-1.2dL/g; Greater than 0.42-1.1dL/g; Greater than 0.42-1dL/g; Greater than 0.42-less than 1dL/g; Greater than 0.42-0.98dL/g; Greater than 0.42-0.95dL/g; Greater than 0.42-0.9dL/g; Greater than 0.42-0.85dL/g; Greater than 0.42-0.80dL/g; Greater than 0.42-0.75dL/g; Greater than 0.42-less than 0.75dL/g; 0.42-0.70dL/g; 0.42-less than 0.70dL/g; Greater than 0.42-0.72dL/g; Greater than 0.42-0.70dL/g; Greater than 0.42-0.68dL/g; Greater than 0.42-less than 0.68dL/g; 0.42-0.68dL/g; Greater than 0.42-0.65dL/g; 0.45-1.2dL/g; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; 0.45-0.95dL/g; 0.45-0.9dL/g; 0.45-0.85dL/g; 0.45-0.80dL/g; 0.45-0.75dL/g; 0.45-less than 0.75dL/g; 0.45-0.72dL/g; 0.45-0.70dL/g; 0.50-1.2dL/g; 0.50-1.1dL/g; 0.50-1dL/g; 0.50-less than 1dL/g; 0.50-0.98dL/g; 0.50-0.95dL/g; 0.50-0.9dL/g; 0.50-0.85dL/g; 0.50-0.80dL/g; 0.50-0.75dL/g; 0.50-less than 0.75dL/g; 0.50-0.72dL/g; 0.50-0.70dL/g; 0.55-1.2dL/g; 0.55-1.1dL/g; 0.55-1dL/g; 0.55-less than 1dL/g; 0.55-0.98dL/g; 0.55-0.95dL/g; 0.55-0.9dL/g; 0.55-0.85dL/g; 0.55-0.80dL/g; 0.55-0.75dL/g; 0.55-less than 0.75dL/g; 0.55-0.72dL/g; 0.55-0.70dL/g; 0.58-1.2dL/g; 0.58-1.1dL/g; 0.58-1dL/g; 0.58-less than 1dL/g; 0.58-0.98dL/g; 0.58-0.95dL/g; 0.58-0.9dL/g; 0.58-0.85dL/g; 0.58-0.80dL/g; 0.58-0.75dL/g; 0.58-less than 0.75dL/g; 0.58-0.72dL/g; 0.58-0.70dL/g; 0.60-1.2dL/g; 0.60-1.1dL/g; 0.60-1dL/g; 0.60-less than 1dL/g; 0.60-0.98dL/g; 0.60-0.95dL/g; 0.60-0.90dL/g; 0.60-0.85dL/g; 0.60-0.80dL/g; 0.60-0.75dL/g; 0.60-less than 0.75dL/g; 0.60-0.72dL/g; 0.60-0.70dL/g; 0.60-less than 0.70dL/g; 0.60-0.68dL/g; 0.60-less than 0.68dL/g; 0.60-0.65dL/g; 0.65-1.2dL/g; 0.65-1.1dL/g; 0.65-1dL/g; 0.65-less than 1dL/g; 0.65-0.98dL/g; 0.65-0.95dL/g; 0.65-0.90dL/g; 0.65-0.85dL/g; 0.65-0.80dL/g; 0.65-0.75dL/g; 0.65-less than 0.75dL/g; 0.65-0.72dL/g; 0.65-0.70dL/g; 0.65-less than 0.70dL/g; 0.68-1.2dL/g; 0.68-1.1dL/g; 0.68-1dL/g; 0.68-less than 1dL/g; 0.68-0.98dL/g; 0.68-0.95dL/g; 0.68-0.90dL/g; 0.68-0.85dL/g; 0.68-0.80dL/g; 0.68-0.75dL/g; 0.68-less than 0.75dL/g; 0.68-0.72dL/g; Greater than 0.70dL/g-1.2dL/g; Greater than 0.76dL/g-1.2dL/g; Greater than 0.76dL/g-1.1dL/g; Greater than 0.76dL/g-1dL/g; Greater than 0.76dL/g-less than 1dL/g; Greater than 0.76dL/g-0.98dL/g; Greater than 0.76dL/g-0.95dL/g; Greater than 0.76dL/g-0.90dL/g; Greater than 0.80dL/g-1.2dL/g; Greater than 0.80dL/g-1.1dL/g; Greater than 0.80dL/g-1dL/g; Greater than 0.80dL/g-less than 1dL/g; Greater than 0.80dL/g-1.2dL/g; Greater than 0.80dL/g-0.98dL/g; Greater than 0.80dL/g-0.95dL/g; Greater than 0.80dL/g-0.90dL/g.

[0078] expection can have at least one and at least one of scope of described monomer for composition herein in the scope of logarithmic viscosity number described herein to film of the present invention or the useful composition of thin plate, except as otherwise noted. Also expect to have at least one and at least one of scope of described monomer for composition herein in the scope of Tg described herein to film of the present invention or the useful composition of thin plate, except as otherwise noted. Also expect and to have in the scope of Tg described herein at least one to film of the present invention or the useful composition of thin plate, in the scope of logarithmic viscosity number described herein at least one and at least one of scope of described monomer for composition herein, except as otherwise noted.

[0079] for expectation to film of the present invention or the useful polyester of thin plate, the mol ratio of cis/trans TMCBD since separately pure form or its mixture can change. In certain embodiments, the mole percent of cis and/or trans TMCBD is greater than 50mol% cis and trans less than 50mol%; Perhaps greater than 55mol% cis and trans less than 45mol%; Perhaps 30-70mol% cis and 70-30% are trans; Perhaps the trans and 50-30% cis of the trans or 50-70mol% of 40-60mol% cis and 60-40mol% or 50-70mol% cis and 50-30% are trans; Perhaps 60-70mol% cis and 30-40mol% are trans; Perhaps greater than the 70mol% cis with 30mol% is trans at the most; Wherein the summation of the mole percent of cis and trans-TMCBD equals 100mol%. The mol ratio of cis/trans 1,4-CHDM can be at following range: 50/50-0/100, for example, and 40/60-20/80.

[0080] in certain embodiments, terephthalic acid (TPA) or its ester, dimethyl terephthalate (DMT) for example, the perhaps mixture of terephthalic acid (TPA) and its ester has consisted of most or all of the dicarboxylic acid component that is used to form the polyester that can be used for film of the present invention or thin plate. In certain embodiments, the terephthalic acid residue can consist of the dicarboxylic acid component of the polyester of being used to form of part or all film of the present invention or thin plate, its concentration is 70mol% at least, such as 80mol% at least, at least 90mol%, at least 95mol%, at least 99mol%, or even 100mol%. In certain embodiments, in order to produce film or the useful polyester than high impact of thin plate, can use the terephthalic acid residue of higher amount. In one embodiment, dimethyl terephthalate (DMT) is part or all for the preparation of the dicarboxylic acid component of the polyester that can be used for film of the present invention or thin plate. With regard to the purpose of present disclosure, term " terephthalic acid (TPA) " and " dimethyl terephthalate (DMT) " are used interchangeably in this article. In all embodiments, can use 70-100mol%; Or 80-100mol%; Or 90-100mol%; Or 99-100mol%; Or the terephthalic acid (TPA) of 100mol% and/or dimethyl terephthalate (DMT).

[0081] except the terephthalic acid residue, the dicarboxylic acid component who can be used for the polyester of film of the present invention or thin plate can comprise at the most 30mol%, at the most 20mol%, at the most 10mol%, at the most 5mol% or one or more modified aromatic dicarboxylic acids of 1mol% at the most. Another embodiment comprises 0mol% modified aromatic dicarboxylic acids. Therefore, if present, expect that the amount of one or more modified aromatic dicarboxylic acids can be extended from any these above-mentioned endpoint values, comprise for example 0.01-30mol%, 0.01-20mol%, 0.01-10mol%, 0.01-5mol% and 0.01-1mol%. In one embodiment, can be used for modified aromatic dicarboxylic acids of the present invention and include but not limited to have those of 20 carbon atoms at the most, and they can be linear, para-orientation or symmetrical. Can be used for example to the modified aromatic dicarboxylic acids of the useful polyester of film of the present invention or thin plate include but not limited to M-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, Isosorbide-5-Nitrae-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid and anti--4,4 '-stilbene dioctyl phthalate and ester thereof. In one embodiment, the modified aromatic dicarboxylic acids is M-phthalic acid.

[0082] carboxyl acid component that can be used for the polyester of film of the present invention or thin plate can further be used at the most 10mol%, for example at the most 5mol% or at the most one or more of 1mol% contain the aliphatic dicarboxylic acid of 2-16 carbon atom, for example malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid come modification. Some embodiment also can comprise 0.01mol% or more, such as 0.1mol% or more, and 1mol% or more, 5mol% or more, perhaps 10mol% or more one or more modification aliphatic dicarboxylic acids. Another embodiment comprises 0mol% modification aliphatic dicarboxylic acid. Therefore, if present, expect that the amount of one or more modification aliphatic dicarboxylic acids can be extended from any these above-mentioned endpoint values, comprise for example 0.01-15mol% and 0.1-10mol%. Total mole percent of dicarboxylic acid component is 100mol%.

[0083] can replace dicarboxylic acids with the ester of terephthalic acid (TPA) and other modification dicarboxylic acids or their corresponding esters and/or salt. The suitable example of dicarboxylic ester includes but not limited to the ester of dimethyl, diethyl, dipropyl, diisopropyl, dibutyl and diphenyl. In one embodiment, described ester is selected from lower at least a: methyl, ethyl, propyl group, isopropyl and phenylester.

[0084] 1,4-CHDM can be cis, trans or its mixture, and for example cis/trans ratios is 60: 40-40: 60. In another embodiment, anti-form-1, the amount of 4-cyclohexanedimethanol can be 60-80mol%.

[0085] diol component of polyester portion that can be used for the polymer blend of film of the present invention or thin plate can comprise 25mol% or still less one or more are not the modification glycol of TMCBD or 1,4-CHDM; In one embodiment, the polyester that can be used for film of the present invention or thin plate can comprise one or more modification glycol less than 15mol%. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise 10mol% or one or more modification glycol still less. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise 5mol% or one or more modification glycol still less. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise 3mol% or one or more modification glycol still less. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise the modification glycol of 0mol%. Some embodiment also can comprise 0.01mol% or more, such as 0.1mol% or more, and 1mol% or more, 5mol% or more, perhaps 10mol% or more one or more modification glycol. Therefore, if present, expect that the amount of one or more modification glycol can be extended from any these above-mentioned endpoint values, comprise for example 0.01-15mol% and 0.1-10mol%.

[0086] glycol except TMCBD and 1,4-CHDM may be referred to the useful modification glycol of the polyester that can be used for film of the present invention or thin plate, and 2-16 carbon atom can be comprised. The example of suitable modification glycol is including, but not limited to ethylene glycol, diethylene glycol (DEG), 1,2-PD, 1,3-PD, neopentyl glycol, BDO, 1,5-PD, 1,6-hexylene glycol, paraxylene glycol or its mixture. In one embodiment, the modification glycol is ethylene glycol. In another embodiment, the modification glycol is including, but not limited to 1,3-PD and/or BDO. Other-embodiment in, get rid of ethylene glycol as the modification glycol. In another embodiment, get rid of 1,3-PD and BDO as the modification glycol. In another embodiment, get rid of NPG as the modification glycol.

[0087] polyester and/or the Merlon useful to the polymer blend in film of the present invention or the thin plate, respectively based on total mole percent of glycol or diacid residues, can comprise 0-10mol%, the residue of one or more branched monomers of 0.01-5mol%, 0.01-1mol%, 0.05-5mol%, 0.05-1mol% or 0.1-0.7mol% or 0.1-0.5mol% for example, it is also referred to as branching agent in this article, has 3 or more carboxyl substituent, hydroxyl substituent or its combination. In certain embodiments, can before the polyester and/or during and/or add afterwards branched monomer or branching agent. Therefore, the polyester that can be used for film of the present invention or thin plate can be linearity or branch. Merlon also may be linearity or branch. In certain embodiments, can before the polycarbonate polymerization and/or during and/or add afterwards branched monomer or branching agent.

[0088] example of branched monomer includes but not limited to polyfunctional acid or polyfunctional alcohol, such as trimellitic acid, trimellitic anhydride, pyromellitic acid dianhydride, trimethylolpropane, glycerine, pentaerythrite, citric acid, tartaric acid, 3-hydroxyl glutaric acid etc. In one embodiment, the branched monomer residue can comprise 0.1-0.7mol% one or more be selected from following at least a residue: trimellitic anhydride, pyromellitic acid dianhydride, glycerine, D-sorbite, 1,2,6-hexanetriol, pentaerythrite, trimethylolethane and/or trimesic acid. Branched monomer can be added in the pet reaction mixture, perhaps with concentrate form and polyester blend, such as for example United States Patent (USP) 5,654,347 and 5,696, described in 176, its disclosure about branched monomer is incorporated herein by reference.

[00 89] glass transition temperature (Tg) can be to use the TA DSC 2920 of Thermal Analyst Instruments with the determination of scan rate of 20 ℃/min.

[0090] polyester that can be used for film of the present invention or thin plate can be unbodied or hemicrystalline. In one aspect, can have lower degree of crystallinity to film of the present invention or some useful polyester of thin plate. To useful some polyester of film of the present invention or thin plate thereby may have basically unbodied form, mean that polyester comprises the basically unordered zone of polymer.

[0091] in one embodiment, " amorphous " polyester that can be used for film of the present invention or thin plate can have 170 ℃ greater than 5 minutes or 170 ℃ greater than 10 minutes or at 170 ℃ greater than 50 minutes or 170 ℃ of crystallization half-lives greater than 100 minutes. In a kind of embodiment of the present invention, can be greater than 1000 minutes crystallization half-life at 170 ℃. In another embodiment of the present invention, can be greater than 10,000 minutes the crystallization half-life that can be used for the polyester of film of the present invention or thin plate at 170 ℃. The crystallization half-life of the polyester of film of the present invention or thin plate, as used in this article, can measure with the well-known method of those skilled in the art. For example, the crystallization half-life of polyester, t1/2 can measure by the light transmittance of measuring sample along with the time through laser instrument and photoelectric detector on the hot platform of temperature control. This measurement can be performed such: by polymer is exposed to temperature T_max, and the temperature that subsequently it is cooled to expect. Can sample be remained on the temperature of expectation by hot platform subsequently, measure simultaneously light transmittance over time. At first, sample may visually be transparent, has high transmission rate, and becomes opaque along with the sample crystallization. Be the time of light transmittance half between initial light transmittance and final light transmittance crystallization half-life. T_maxBe defined as the required temperature of fusing sample domain (if having domain). Can before measuring crystallization half-life, sample be heated to T_maxTo nurse one's health this sample. For each composition, absolute T_maxTemperature is different. For example PCT can be heated to above certain temperature of 290 ℃ with the melting domain.

[0092] such as the table 1 of embodiment and shown in Figure 1, improving aspect crystallization half-life (being that polymer reaches half required time of its maximum degree of crystallinity) 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol is than other comonomer, and is more effective such as ethylene glycol and M-phthalic acid. By reducing the crystalline rate of PCT, namely improve crystallization half-life, can make amorphous goods based on modification PCT such as extrude, injection moulding etc. by methods known in the art. As shown in table 1, these materials can show than the higher glass transition temperature of other modification PCT copolyesters and lower density.

[0093] for some embodiment of the present invention, the polyester of film of the present invention or thin plate can demonstrate the improvement that toughness is combined with processing characteristics. For example, the logarithmic viscosity number that slight reduction can be used for the polyester of film of the present invention or thin plate causes the melt viscosity of easier processing, keeps simultaneously the good physical property of polyester, for example toughness and heat resistance.

[0094] based on terephthalic acid (TPA), ethylene glycol and 1, improve 1 in the copolyesters of 4-cyclohexanedimethanol, the content of 4-cyclohexanedimethanol can improve toughness, and it can be measured by tough brittle transition temperature in such as the notched izod impact strength test of being measured by ASTM D256. It is believed that it is owing to the flexible of 1,4-CHDM in the copolyesters and conformation performance occur that this toughness is improved by reducing tough brittle transition temperature with 1,4-CHDM. It is believed that with 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol is incorporated among the PCT, improved toughness by reducing tough brittle transition temperature, such as the table 2 of embodiment and shown in Figure 2. In the situation of the rigidity of given TMCBD, this is unexpected.

[0095] in one embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 30,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃. In another embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 20,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃.

[0096] in one embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 15,000 pools, as on the rotation melt rheometer, measuring with 1 radian per second at 290 ℃.

[0097] in one embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 10,000 pools, as on the rotation melt rheometer, measuring with 1 radian per second at 290 ℃. In another embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 6,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃. Viscosity take radian per second as unit is relevant with processing characteristics. When its processing temperature is measured, typical polymers has the viscosity less than 10000 pools, as measuring at 1 radian per second. Generally not in processed polyesters more than 290 ℃. Generally at 290 ℃ of processing Merlon. At 290 ℃, the viscosity of typical 12 melt flow rate (MFR) Merlon under 1 radian per second is 7000 pools.

[0098] polyester of the present invention that can be used for film of the present invention or thin plate can have one or more following performances. The described notched izod impact strength of ASTM D256 is to measure a kind of common method of toughness. The polyester of the present invention that can be used for film of the present invention or thin plate can have one or more following performances. In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the impact strength at 23 ℃ of at least 150J/m (3ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 3.2mm (1/8-inch); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least (400J/m) 7.5ft-lb/in that measure according to ASTM D256 with 10-mil otch in the thick strip of 3.2mm (1/8-inch); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least 1000J/m (18ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 3.2mm (1/8-inch). In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least 150J/m (3ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 6.4mm (1/4-in); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least (400J/m) 7.5ft-lb/in that measure according to ASTM D256 with 10-mil otch in the thick strip of 6.4mm (1/4-in); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least 1000J/m (18ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 6.4mm (1/4-in).

[0099] in another embodiment, to film of the present invention or some useful polyester of thin plate, with when-5 ℃ are measured, compare according to the notched izod impact strength that ASTM D256 measures in the thick strip of 1/8-in with 10-mil otch, the notched izod impact strength that can demonstrate when measuring for 0 ℃ has increased at least 3% or at least 5% or at least 10% or at least 15%. In addition, some other polyester that can be used for film of the present invention or thin plate can also demonstrate according to ASTM D256 in the thick strip of 1/8-in with 10-mil otch measure when measuring for 0 ℃-30 ℃ in the maintenance of plus or minus 5% with interior notched izod impact strength.

[00100] in yet another embodiment, the loss that can demonstrate the maintenance of the notched izod impact strength when measuring for 23 ℃ of measuring with 10-mil otch according to ASTM D256 to film of the present invention or some useful polyester of thin plate in the thick strip of 1/8-in is not more than 70%, than the notched izod impact strength of the identical polyester when uniform temp is measured of measuring with 10-mil otch in the thick strip of 1/8-in according to ASTM D256.

[00101] in one embodiment, the polyester that can be used for film of the present invention or thin plate can demonstrate the tough brittle transition temperature less than 0 ℃, and is defined as ASTM D256 in the thick strip of 1/8-in based on 10-mil otch.

[00102] in one embodiment, the polyester that can be used for film of the present invention or thin plate can demonstrate at least a with lower density, as using the gradient column densities to measure at 23 ℃: 23 ℃ of density less than 1.2g/ml; 23 ℃ of density less than 1.18g/ml; Density at 23 ℃ of 0.8-1.3g/ml; Density at 23 ℃ of 0.80-1.2g/ml; In the density of 23 ℃ of 0.80-less than 1.2g/ml; Density at 23 ℃ of 1.0-1.3g/ml; Density at 23 ℃ of 1.0-1.2g/ml; Density at 23 ℃ of 1.0-1.1g/ml; Density at 23 ℃ of 1.13-1.3g/ml; Density at 23 ℃ of 1.13-1.2g/ml.

[00103] in one embodiment, the polyester that can be used for film of the present invention or thin plate can be visually transparent. Term " visually transparent " is defined as does not in this article obviously have muddiness, dim and/or dirty when visual detection. In another embodiment, when the polyester that can be used for film of the present invention or thin plate and Merlon (including but not limited to bisphenol-a polycarbonate) blend, then blend can be visually transparent.

[00104] in other embodiments of the present invention, the polyester that can be used for film of the present invention or thin plate can have less than 50 or less than 20 yellowness index (ASTM D-1925).

[00105] in one embodiment, can be used for polyester and/or the polymer blend of the present invention of film of the present invention or thin plate, contain or do not contain toner, can have colour L^*、a ^*And b^*, it can be to use by Hunter Associates Lab Inc., Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures. The colour measurement value is the mean value of the value measured at polyester granules or by its injection moulding or the plate of extruding or other object. They are the L by CIE (International Commission on Illumination) (translating)^*a ^*b ^*Colour system is measured, wherein L^*Expression brightness coordinate, a^*Represent red/green coordinate, b^*Expression Huang/blue coordinate. In certain embodiments, the b that can be used for the polyester of film of the present invention or thin plate^*Value can be for-10 to less than 10, and L^*Value can be 50 to 90. In other embodiments, the polyester b that can be used for film of the present invention or thin plate^*Value may reside in one of following ranges :-10 to 9;-10 to 8;-10 to 7;-10 to 6;-10 to 5;-10 to 4;-10 to 3;-10 to 2;-5 to 9;-5 to 8;-5 to 7;-5 to 6;-5 to 5;-5 to 4;-5 to 3;-5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; With 1 to 2. In other embodiments, the L that can be used for the polyester of film of the present invention or thin plate^*Value may reside in one of following ranges: 50-60; 50-70; 50-80; 50-90; 60-70; 60-80; 60-90; 70-80; 79-90.

[00106] in some embodiments, use the polymer blend can be used for film of the present invention or thin plate to minimize and/or eliminated drying steps before melt-processed and/or hot forming.

[00107] can be used for the polyester portion of the polymer blend of film of the present invention or thin plate can be by already known processes preparation in the document, for example by the technique in homogeneous solution, by the ester exchange process in the melt with by two-phase interface technique. Suitable method includes but not limited to make the reaction under the pressure of 100 ℃-315 ℃ temperature and 0.1-760mmHg of one or more dicarboxylic acids and one or more glycol to be enough to form the step of the time of polyester. For the method for producing polyester, referring to United States Patent (USP) 3,772,405, the disclosure of this method is incorporated herein by reference.

[00108] in another aspect, the present invention relates to for the production of the method to the useful polyester of film of the present invention or thin plate. Described method comprises: (I) in the presence of catalyst 150-240 ℃ of heating comprise any polyester of can be used among the present invention the mixture of monomer time of being enough to produce initial polyester; (II) initial polyester of heating steps (I) reaches 1-4 hour under 240-320 ℃ of temperature; (III) remove any unreacted glycol.

[00109] is used for the suitable catalyst of the method including, but not limited to organic zinc or tin compound. Using such catalyst is well-known in the art. To the example of the useful catalyst of the polyester that can be used for film of the present invention or thin plate including, but not limited to zinc acetate, three (2 ethyl hexanoic acid) butyl tin, dibutyltin diacetate and/or dibutyl tin oxide. Other catalyst can include but not limited to based on those of titanium, zinc, manganese, lithium, germanium and cobalt. Catalyst amounts can be 10ppm-20,000ppm or 10-10, and 000ppm, perhaps 10-5000ppm or 10-1000ppm or 10-500ppm, perhaps 10-300ppm or 10-250 are based on catalyst metals with based on the weight of final polymer. The method can be carried out in the mode of batch process or continuous process.

[00110] usually, step (I) can be carried out until 50wt% or more TMCBD react. Step (I) can be carried out under pressure, and pressure limit is that atmospheric pressure is to 100psig. As with any the useful catalyst of the present invention being combined that the term " product " that uses refers to use catalyst and for the preparation of the polycondensation between the additive of the spawn of the polycondensation of any monomer of polyester or esterification and catalyst and any other type or the product of esterification.

[00111] usually, step (II) and step (III) can be carried out simultaneously. These steps can be undertaken by methods known in the art, and for example by reactant mixture is placed under the pressure, pressure limit is that 0.002psig is to being lower than atmospheric pressure, perhaps by being blown into hot nitrogen at mixture.

[00112] the invention still further relates to the blend of the polymer that can be used for film of the present invention or thin plate. Described blend comprises: (a) at least a above-mentioned polyester of 5-95wt%; (b) at least a polymers compositions of 5-95wt%.

[00113] to the suitable example of the useful polymers compositions of the polymer blend that can be used for film of the present invention or thin plate including, but not limited to nylon, be different from described those polyester herein, polyamide is such as the ZYTEL_ from DuPont; Polystyrene, polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, acrylic acid series copolymer, poly-(ether-acid imide) is such as ULTEM_ (poly-(ether-acid imide) is available from General Electric); Polyphenylene oxide is such as poly-(2,6-dimethyl phenylate) or polyphenyl ether/styrene blend such as NORYL 1000_ (blend of poly-(2,6-dimethyl phenylate) and polystyrene resin is available from General Electric); Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ester); Merlon such as LEXAN_ (Merlon is available from General Electric); Polysulfones; Polysulfones ether; Poly-(ether-ketone) with aromatic dihydroxy compound; The perhaps mixture of any above-mentioned polymer. Blend can be by conventional treatment process preparation known in the art, such as melt blending or solution blending. In one embodiment, Merlon is not present in the polymer blend that can be used for film of the present invention or thin plate. If Merlon is for the blend of the polymer blend that can be used for film of the present invention or thin plate, then blend can be visually transparent. Yet, the polymer blend that can be used for film of the present invention or thin plate also expected Merlon eliminating and comprise Merlon.

[00114] can prepare according to known method film of the present invention or the useful Merlon of thin plate, for example by making dihydroxy aromatic compounds and carbonate precursor such as phosgene, haloformate or carbonic ester, molecular weight regulator, acid acceptor and catalyst reaction. Method for the preparation of Merlon is known in the art and for example is described in United States Patent (USP) 4,452, and in 933, wherein the disclosure about the Merlon preparation is incorporated herein this paper as a reference.

[00115] example of suitable carbonate precursor including, but not limited to, carbonyl bromide, phosgene or its mixture; Diphenyl carbonate; Carbonic acid two (halogenophenyl) ester, for example, carbonic acid two (trichlorophenyl) ester, carbonic acid two (tribromo phenyl) ester etc.; Carbonic acid two (alkyl phenyl) ester, for example, carbonic acid two (tolyl) ester; Carbonic acid two (naphthyl) ester; Carbonic acid two (chloronaphthyl, methylnaphthyl) ester or its mixture; Bishaloformate with dihydric phenol.

[00116] example of suitable molecular weight regulator includes but not limited to, phenol, cyclohexanol, methyl alcohol, alkylated phenol such as octyl phenol, p-t-butyl phenol etc. In one embodiment, molecular weight regulator is phenol or alkylated phenol.

[00117] acid acceptor may be organic or examples of inorganic acceptors. Suitable organic acid acceptor can be tertiary amine and including, but not limited to, materials such as pyridine, triethylamine, dimethylaniline, tri-n-butylamine. Examples of inorganic acceptors can be hydroxide, carbonate, bicarbonate or the phosphate of alkali metal or alkaline-earth metal.

[00118] operable catalyst including, but not limited to, usually help those of monomer and phosgene polymerization. Suitable catalyst includes but not limited to, tertiary amine such as triethylamine, tripropyl amine (TPA), N, the N-dimethylaniline, quaternary ammonium compound such as tetraethylammonium bromide, cetyltriethylammonium bromide, four n-heptyl ammonium iodides, four n-pro-pyl bromination ammoniums, tetramethyl ammonium chloride, TMAH, tetrabutylammonium iodide, benzyl trimethyl ammonium chloride and quaternary phosphonium compound such as normal-butyl three phenyl phosphonium bromides and first base three phenyl phosphonium bromides.

[00119] may be copolyestercarbonates also to the useful Merlon of the polymer blend that can be used for film of the present invention or thin plate, as be described in the following United States Patent (USP) those: 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484,4,465,820 and 4,981,898, wherein the disclosure of the relevant copolyestercarbonates of each piece United States Patent (USP) is incorporated herein by reference.

[00120] can be commercially available and/or can prepare by method as known in the art film of the present invention or the useful copolyestercarbonates of thin plate. For example, they can be generally obtain by the mixture reaction that makes at least a dihydroxy aromatic compounds and phosgene and at least a diacid chloride (particularly isophthaloyl chloride, terephthalyl chloride or both).

[00121] in addition, comprise the polymer blend of the polyester that can be used for film of the present invention or thin plate and 0.01-25wt% that polymer blend composition also can comprise the polymer blend gross weight or common additives such as colouring agent, dyestuff, releasing agent, fire retardant, plasticizer, nucleator, stabilizing agent (including but not limited to UV stabilizer, heat stabilizer and/or its product), filler and the impact modifier of 0.01-20wt% or 0.01-15wt% or 0.01-10wt% or 0.01-5wt%. Well-known in the art and the example that can be used for typical commercially available impact modifier of the present invention is including, but not limited to, ethylene/propene terpolymer; Functionalised polyolefin, as comprise those of methyl acrylate and/or GMA; The block copolymer impact modifier of styrene-based; Core/shell type impact modifier with various acrylic acid series. For example, by through applying dura mater or adding in the body through the co-extrusion pressure cap rock, the UV additive can be attached in the goods. Also expect the residue of this additive as the part to the useful polymer blend of film of the present invention or thin plate.

[00122] polyester that can be used for film of the present invention or thin plate can comprise at least a cahin extension agent. Suitable cahin extension agent is including, but not limited to, multifunctional (including but not limited to difunctionality) isocyanates, and multi-functional epoxy's compound comprises for example epoxy (line style) novolaks, and phenoxy resin. In certain embodiments, cahin extension agent can add at the end of polymerization process or after polymerization process. If after polymerization process, add, can introduce cahin extension agent by compounding in conversion process such as injection moulding or during extruding or interpolation. The consumption of cahin extension agent can depend on the composition of used concrete monomer and desired physical property and change, but is generally the about 10wt% of about 0.1wt%-, and the about 5wt% of about 0.1-preferably is based on the gross weight of polyester.

[00123] heat stabilizer is the compound of stabilized polyester between polyester manufacturing and/or rear polymerization period, includes but not limited to phosphorus-containing compound, its include but not limited to phosphoric acid, phosphorous acid, phosphonic acids, phosphinic acids, phosphonous acid with and various ester and salt. These may reside in the useful polymer blend of the present invention. Ester can be (ester) of alkyl, branched alkyl, substituted alkyl, two sense alkyl, alkyl ether, aryl and substituted aryl. In one embodiment, the number that is present in the ester group in the specific phosphorus-containing compound can change to the maximum that allows based on the number that is present in the hydroxyl the used heat stabilizer at the most from zero. Term " heat stabilizer " intention comprises its product. As referring to heat stabilizer with the term " product " that uses that the useful heat stabilizer of film of the present invention or thin plate is combined and for the preparation of the polycondensation between the additive of the spawn of the polycondensation between any monomer of polyester or esterification and catalyst and any other type or the product of esterification. Heat stabilizer can be used to prepare the polyester that can be used for film of the present invention or thin plate.

[00124] reinforcing material can be used in the useful composition of film of the present invention or thin plate. Reinforcing material can include but not limited to carbon filament, silicate, mica, clay, talcum, titanium dioxide, wollastonite, sheet glass, bead and fiber and polymer fiber and its combination. In one embodiment, reinforcing material is glass such as fibrous glass long filament, the mixture of glass and talcum, glass and mica and glass and polymer fiber.

[00125] in another embodiment, the invention still further relates to goods, it comprises film and/or thin plate, and this film and/or thin plate comprise described polymer blend herein.

[00126] method that polyester is configured as film and thin plate is well-known in the art. Can be used for film of the present invention and/or thin plate and can have the thickness that any meeting it will be apparent to those skilled in the art. In one embodiment, the thickness of film of the present invention is for being not more than 40mil. In one embodiment, the thickness of film of the present invention is for being not more than 35mil. In one embodiment, the thickness of film of the present invention is for being not more than 30mil. In one embodiment, the thickness of film of the present invention is for being not more than 25mil. In one embodiment, the thickness of film of the present invention is for being not more than 20mil.

[00127] in one embodiment, gauge of sheet of the present invention is for being not less than 20mil. In another embodiment, gauge of sheet of the present invention is for being not less than 25mil. In another embodiment, gauge of sheet of the present invention is for being not less than 30mil. In another embodiment, gauge of sheet of the present invention is for being not less than 35mil. In another embodiment, gauge of sheet of the present invention is for being not less than 40mil.

[00128] the invention still further relates to film and/or the thin plate that comprises polymer blend of the present invention. The method that polyester is configured as film and/or thin plate is well-known in the art. The example of film of the present invention and/or thin plate includes but not limited to cast film and/or thin plate, calendered film and/or thin plate, compression molded films and/or thin plate, solution plastic casting film and/or thin plate. The method of making film and/or thin plate includes but not limited to extrusion molding, calendering, compression moulding and solution casting.

[00129] example by the potential goods of film and/or thin plate preparation includes but not limited to monodirectional tension film, biaxially oriented film, shrinkable film (no matter being unidirectional or biaxial tension), liquid crystal display film (including but not limited to diffuser thin plate, compensation film and protective film), hot formed thin plate, plate process film (graphic arts film), outdoor sign, skylight, coating, coated article, painting products, laminates, laminated product and/or plural layers or thin plate.

[00130] example of plate process film is including, but not limited to nameplate, membrane switch facing; Point of purchase display; Plane on the washing machine or in-mold decoration panel; Plane touch panel on the refrigerator; Flat board on the stove; Automotive trim; The automobile instrument group; Phone cover; Heating and Ventilation Control display; The automobile control panel; Automobile gear gear panel; Control display device or the alarm signal of fascia; Facing on the household implements, dial plate or display; Facing on the washing machine, dial plate or display; Facing on the dish-washing machine, dial plate or display; The keypad of electronic equipment; The keypad of mobile phone, PDA (laptop computer) or remote controllers; The display of electronic equipment; The display of hand-held electric subset such as phone and PDA; Panel and the shell of movement or standard telephone; Logo on the electronic equipment; Logo with mobile phone.

[00131] plural layers or thin plate refer to be extruded into the thin plate by a plurality of layers of section that forms that connect by vertical rib each other. The example of plural layers or thin plate includes but not limited to greenhouse and commercial canopy.

[00132] example of extrudate include but not limited to for plate technique, application, outdoor sign, skylight film, be used for film and liquid crystal display (LCD) film of resin glass laminates, described liquid crystal display (LCD) film includes but not limited to diffuser thin plate, compensation film and protective film.

[00133] as used in this article, abbreviation " wt " refers to " weight ".

[00134] following examples further illustrate and how can make and estimate film of the present invention or useful polyester and/or the polymer blend of thin plate, and are intended that and illustrate the present invention purely and be not intended to limit its scope.Unless otherwise indicated, umber is a weight part, temperature for degree centigrade or be in room temperature, pressure is or near atmospheric gas pressure.

Embodiment

Measuring method

[00135] logarithmic viscosity number of polyester is that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration.

[00136] except as otherwise noted, otherwise second-order transition temperature (Tg) is TA DSC 2920 instruments that use Thermal Analyst Instruments according to ASTMD3418 with the determination of scan rate of 20 ℃/min.

[00137] glycol content of composition and cis/trans ratios are measured by proton magnetic resonance (PMR) (NMR) spectrum.All NMR spectrums all are recorded on the JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer, for polymkeric substance, use chloroform-trifluoroacetic acid (70-30 volume/volume), perhaps for the oligopolymer sample, use 60/40 (wt/wt) phenol/tetrachloroethane, and for locking the deuterate chloroform that the peak adds.By with model 2,2,4,4-tetramethyl--1, the list and the dibenzoate of 3-cyclobutanediol compare, and carry out 2,2,4,4-tetramethyl--1, the peak of 3-cyclobutanediol resonance is pointed out.These model compounds are very near the resonant position that exists in polymkeric substance and oligopolymer.

[00138] crystallization half-life, t1/2, be by on the hot platform of temperature control along with the time is measured through the transmittance of laser apparatus and photoelectric detector measure sample.This measurement is performed such: polymkeric substance is exposed to temperature T _Max, and subsequently it is cooled to desired temperatures.By hot platform sample is remained on desired temperatures subsequently, measure transmittance simultaneously over time.At first, sample visually is transparent, has high transmission rate, and becomes opaque along with the sample crystallization.Being recorded as transmittance crystallization half-life is the time of a half between initial transmittance and the final transmittance.T _MaxBe defined as the required temperature of fusing sample domain (if having domain).The T that reports in following examples _MaxRepresentative was heated every kind of sample to nurse one's health the temperature of this sample before measuring crystallization half-life.T _MaxTemperature depends on to be formed and generally is different for every kind of polyester.For example, may need PCT is heated to above certain temperature of 290 ℃ with the fusion domain.

[00139] density is to use the gradient column density 23 ℃ of mensuration.

[00140] melt viscosity of report is measured by using Rheometrics DynamicAnalyzer (RDA II) herein.In the temperature of being reported, with the variation of the frequency measurement melt viscosity of 1-400 radian per second with shearing rate.Zero shears melt viscosity (η ₀) be by the melt viscosity under the zero shearing rate estimated of extrapolation data by model known in the art.This step is realized automatically by RheometricsDynamic Analyzer (RDA II) software.

[00141] polymkeric substance is 80-100 ℃ of dry 24 hours and injection moulding and obtain 1/8 * 1/2 * 5-inch and 1/4 * 1/2 * 5-inch deflection strip on Boy 22S mould machine in vacuum drying oven.According to ASTM D256, to be cut into length be 2.5 inches and carry out otch along this 1/2 inch width and obtain the 10-mil otch with these strips.Measure 23 ℃ average izod impact strength by the observed value of 5 battens.

[00142] in addition, use 5 battens of 5 ℃ of incremental testings to measure the brittle-ductile transition temperature in differing temps.Temperature when tough brittle transition temperature is defined as 50% batten and lost efficacy in the fragility mode of being represented by ASTM D256.

[00143] colour of report is to use the Inc. by Hunter Associates Lab herein, Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures.The color measurenent value is at polyester granules or the mean value of the value of measuring on by its injection moulding or the plate of extruding or other object.They are by the L of CIE (International Commission on Illumination) (translating) ^*a ^*b ^*Colour system is definite, wherein L ^*Expression luminance brightness coordinate, a ^*Represent red/green coordinate, b ^*Expression Huang/blue coordinate.

[00144] in addition, use the Carver press 240 ℃ of compression moulding 10-mil film.

[00145] unless otherwise mentioned, otherwise the cis/trans ratios that is used for the 1,4 cyclohexane dimethanol of following examples is about 30/70, and can be 35/65-25/75.Unless otherwise mentioned, otherwise be used for 2,2,4 of following examples, 4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol is about 50/50.

[00146] following abbreviation is applicable to whole work embodiment and accompanying drawing:

TPA	Terephthalic acid
TPA	Terephthalic acid	DMT	Dimethyl terephthalate (DMT)
TMCD	2,2,4,4-tetramethyl--1,3-cyclobutanediol	DMT	Dimethyl terephthalate (DMT)
TMCD	2,2,4,4-tetramethyl--1,3-cyclobutanediol	CHDM
	1,4 cyclohexane dimethanol	CHDM
	1,4 cyclohexane dimethanol	IV	Logarithmic viscosity number
η ₀	Zero shears melt viscosity	IV	Logarithmic viscosity number
η ₀	Zero shears melt viscosity	Tg	Second-order transition temperature
T _bd	Tough brittle transition temperature	Tg	Second-order transition temperature
T _bd	Tough brittle transition temperature	T _max	The conditioning temperature that measure crystallization half-life

Embodiment 1

[00147] present embodiment illustrates 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol is more effective than ethylene glycol or m-phthalic acid aspect the crystallization rate that reduces PCT.In addition, present embodiment illustrates 2,2,4,4-tetramethyl--1, the benefit of 3-cyclobutanediol aspect second-order transition temperature and density.

[00148] as described below, prepare multiple copolyesters.These copolyesters all adopt the 200ppm dibutyl tin oxide as Preparation of Catalyst, with minimum catalyst type and concentration to Study on Crystallization during the influence of nucleogenesis.The cis/trans ratios of 1,4 cyclohexane dimethanol is 31/69, and 2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol is recorded in the table 1.

[00149] for present embodiment, each sample has enough similar logarithmic viscosity number, thereby in fact gets rid of this as variable in crystallization rate is measured.

[00150] is increment at 140-200 ℃ with 10 ℃, carries out measurement, and measuring result is recorded in the table 1 from the crystallization half-life of melt.Generally appear at about 170-180 ℃ as the minimum value of temperature variant crystallization half-life the fastest crystallization half-life of every kind of sample.The fastest crystallization half-life of sample is plotted among Fig. 1 as the function to the mol% of the comonomer of PCT modification.

[00151] data presentation, 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than ethylene glycol and m-phthalic acid aspect reduction crystallization rate (promptly improving crystallization half-life).In addition, 2,2,4,4-tetramethyl--1,3-cyclobutanediol have improved Tg and have reduced density.

Table 1

Crystallization half-life (minute)

Embodiment	Comonomer (mol%) ¹	IV (dl/g)	Density (g/ml)	T _g (℃)	T _max (℃)	140℃ (min)	150℃ (min)	160℃ (min)	170℃ (min)	180℃ (min)	190℃ (min)	200℃ (min)
Embodiment	Comonomer (mol%) ¹	IV (dl/g)	Density (g/ml)	T _g (℃)	T _max (℃)	140℃ (min)	150℃ (min)	160℃ (min)	170℃ (min)	180℃ (min)	190℃ (min)	200℃ (min)	1A	20.2％A ²	0.630	1.198	87.5	290	2.7	2.1	1.3	1.2	0.9	1.1	1.5
1B	19.8％B	0.713	1.219	87.7	290	2.3	2.5	1.7	1.4	1.3	1.4	1.7	1A	20.2％A ²	0.630	1.198	87.5	290	2.7	2.1	1.3	1.2	0.9	1.1	1.5
1B	19.8％B	0.713	1.219	87.7	290	2.3	2.5	1.7	1.4	1.3	1.4	1.7	1C	20.0％C	0.731	1.188	100.5	290	＞180	＞60	35.0	23.3	21.7	23.3	25.2
1D	40.2％A ²	0.674	1.198	81.2	260	18.7	20.0	21.3	25.0	34.0	59.9	96.1	1C	20.0％C	0.731	1.188	100.5	290	＞180	＞60	35.0	23.3	21.7	23.3	25.2
1D	40.2％A ²	0.674	1.198	81.2	260	18.7	20.0	21.3	25.0	34.0	59.9	96.1	1E	34.5％B	0.644	1.234	82.1	260	8.5	8.2	7.3	7.3	8.3	10.0	11.4
1F	40.1％C	0.653	1.172	122.0	260	＞10 days	＞5 days	＞5 days	19204	＞5 days	＞5 days	＞5 days	1E	34.5％B	0.644	1.234	82.1	260	8.5	8.2	7.3	7.3	8.3	10.0	11.4
1F	40.1％C	0.653	1.172	122.0	260	＞10 days	＞5 days	＞5 days	19204	＞5 days	＞5 days	＞5 days	1G	14.3％D	0.646 ³	1.188	103.0	290	55.0	28.8	11.6	6.8	4.8	5.0	5.5
1H	15.0％E	0.728 ⁴	1.189	99.0	290	25.4	17.1	8.1	5.9	4.3	2.7	5.1	1G	14.3％D	0.646 ³	1.188	103.0	290	55.0	28.8	11.6	6.8	4.8	5.0	5.5

The remainder of the diol component of polyester is a 1,4 cyclohexane dimethanol in 1 table 1; And the dicarboxylic acid component's of polyester remainder is a dimethyl terephthalate (DMT) in the table 1; If do not describe dicarboxylic acid, then it is the 100mol% dimethyl terephthalate (DMT).

2 100mol%1, the 4-cyclohexanedimethanol.

3 240 ℃ of grinding polyester press membrane by embodiment 1G.The gained film has the logarithmic viscosity number value of 0.575dL/g.

4 240 ℃ of grinding polyester press membrane by embodiment 1H.The gained film has the logarithmic viscosity number value of 0.0.652dL/g.

Wherein:

A is a m-phthalic acid

B is an ethylene glycol

C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (about 50/50 cis/trans)

D is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (98/2 cis/trans)

E is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (5/95 cis/trans)

[00152] as table 1 and shown in Figure 1, improving aspect crystallization half-life (being that polymkeric substance reaches half required time of its maximum degree of crystallinity), 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than other comonomer such as ethylene glycol and m-phthalic acid.By the crystallization rate (improving crystallization half-life) that reduces PCT, can be by the methods known in the art manufacturing based on as described herein 2,2,4,4-tetramethyl--1, the amorphous goods of the PCT of 3-cyclobutanediol modification.As shown in table 1, these materials can show than higher second-order transition temperature of other modification PCT copolyesters and lower density.

[00153] preparation of the polyester shown in the table 1 is described below.

Embodiment 1A

What [00154] present embodiment illustrated target consists of 80mol% dimethyl terephthalate (DMT) residue, 20mol% dimethyl isophthalate residue and 100mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (28/72 cis/trans).

[00155] mixture with 56.63g dimethyl terephthalate (DMT), 55.2g 1,4 cyclohexane dimethanol, 14.16g dimethyl isophthalate and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 290 ℃ in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, applied vacuum gradually then in ensuing 5 minutes and reached 100mmHg up to the flask internal pressure.In ensuing 5 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 87.5 ℃, and logarithmic viscosity number is 0.63dl/g.NMR analysis revealed polymkeric substance comprises 100mol%1,4-cyclohexanedimethanol residue and 20.2mol% dimethyl isophthalate residue.

Embodiment 1B

What [00156] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol% glycol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (32/68 cis/trans).

[00157] mixture with 77.68g dimethyl terephthalate (DMT), 50.77g 1,4 cyclohexane dimethanol, 27.81g ethylene glycol and 0.0433g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 210 ℃ in 60 minutes subsequently gradually 200 ℃ of heating in 5 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 280 ℃ at 210 ℃.In case be in 280 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg up to the flask internal pressure.In ensuing 10 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 87.7 ℃, and logarithmic viscosity number is 0.71dl/g.NMR analysis revealed polymkeric substance comprises the 19.8mol% glycol residue.

Embodiment 1C

What [00158] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

[00159] with 77.68g dimethyl terephthalate (DMT), 48.46g 1,4-cyclohexanedimethanol, 17.86g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.This polyester is to prepare to the described similar mode of embodiment 1A.A obtains high melt viscosity, transparent and colourless polymkeric substance visually, and second-order transition temperature is 100.5 ℃, and logarithmic viscosity number is 0.73dl/g.NMR analysis revealed polymkeric substance comprises 80.5mol%1,4-cyclohexanedimethanol residue and 19.5mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1D

What [00160] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 40mol% dimethyl isophthalate residue and 100mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (28/72 cis/trans).

[00161] mixture with 42.83g dimethyl terephthalate (DMT), 55.26g 1,4 cyclohexane dimethanol, 28.45g dimethyl isophthalate and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 290 ℃ in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, applied vacuum gradually then in ensuing 5 minutes and reached 100mmHg up to the flask internal pressure.In ensuing 5 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 81.2 ℃, and logarithmic viscosity number is 0.67dL/g.NMR analysis revealed polymkeric substance comprises 100mol%1,4-cyclohexanedimethanol residue and 40.2mol% dimethyl isophthalate residue.

Embodiment 1E

What [00162] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 40mol% glycol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

[00163] mixture with 81.3g dimethyl terephthalate (DMT), 42.85g 1,4 cyclohexane dimethanol, 34.44g ethylene glycol and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 210 ℃ in 60 minutes subsequently gradually 200 ℃ of heating in 5 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 280 ℃ at 210 ℃.In case be in 280 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg up to the flask internal pressure.In ensuing 10 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 82.1 ℃, and logarithmic viscosity number is 0.64dl/g.NMR analysis revealed polymkeric substance comprises the 34.5mol% glycol residue.

Embodiment 1F

What [00164] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 40mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

[00165] with 77.4g dimethyl terephthalate (DMT), 36.9g 1,4-cyclohexanedimethanol, 32.5g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.The content of flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 290 ℃ at 260 ℃.In case be in 290 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg up to the flask internal pressure.In ensuing 5 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 122 ℃, and logarithmic viscosity number is 0.65dl/g.NMR analysis revealed polymkeric substance comprises 59.9mol%1,4-cyclohexanedimethanol residue and 40.1mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1G

What [00166] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue (98/2 cis/trans) and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

[00167] with 77.68g dimethyl terephthalate (DMT), 48.46g 1,4-cyclohexanedimethanol, 20.7792,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.The content of flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 290 ℃ at 260 ℃.In case be in 290 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg, and also stirring velocity is dropped to 100RPM up to the flask internal pressure.In ensuing 5 minutes, again the flask internal drop is hanged down to 0.3mmHg, and stirring velocity is dropped to 50RPM.The pressure that keeps 0.3mmHg altogether 60 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 103 ℃, and logarithmic viscosity number is 0.65dl/g.NMR analysis revealed polymkeric substance comprises 85.7mol%1,4-cyclohexanedimethanol residue and 14.3mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1H

What [00168] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue (5/95 cis/trans) and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

[00169] with 77.68g dimethyl terephthalate (DMT), 48.46g 1,4-cyclohexanedimethanol, 20.77g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.When the experiment beginning, stirring velocity is set at 200RPM.The content of flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 290 ℃ at 260 ℃.In case be in 290 ℃, in ensuing 5 minutes, apply vacuum gradually, setting point is 100mmHg,, and also stirring velocity is dropped to 100RPM.In ensuing 5 minutes, again the flask internal pressure is reduced to setting point 0.3mmHg, and stirring velocity is dropped to 50RPM.Keep this pressure altogether 60 minutes to remove excessive unreacted glycol.Notice that vacuum system does not reach above-mentioned setting point, but produced enough vacuum with preparation high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 99 ℃, and logarithmic viscosity number is 0.73dl/g.NMR analysis revealed polymkeric substance comprises 85mol%1,4-cyclohexanedimethanol residue and 15mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 2

[00170] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol have improved the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.

[00171] as described below, prepare based on 2,2,4 4-tetramethyl--1, the copolyesters of 3-cyclobutanediol.For all samples, the cis/trans ratios of 1,4 cyclohexane dimethanol is about 3 1/69.Copolyesters based on ethylene glycol and 1,4 cyclohexane dimethanol is the commercialization polyester.The copolyesters of embodiment 2A (Eastar PCTG5445) obtains from Eastman Chemical Co..The copolyesters of embodiment 2B obtains with trade(brand)name Spectar from Eastman Chemical Co..Embodiment 2C and embodiment 2D adapt to the described process preparation of embodiment 1A with pilot scale (respectively being 15-lb batch), and have logarithmic viscosity number described in the following table 2 and second-order transition temperature.With target tin quantity is that 300ppm (dibutyl tin oxide) prepares embodiment 2C.Final product comprises 295ppm tin.The colour of the polyester of embodiment 2C is L ^*=77.11; a ^*=-1.50; And b ^*=5.79.With target tin quantity is that 300ppm (dibutyl tin oxide) prepares embodiment 2D.Final product comprises 307ppm tin.The colour of the polyester of embodiment 2D is L ^*=66.72; a ^*=-1.22; And b ^*=16.28.

[00172] material is injection molded into strip and subsequently otch carry out izod test.Vary with temperature and obtain the notched izod shock strength, equally it is reported in the table 2.

[00173] for given sample, izod impact strength experiences big change (major transition) in little temperature range.For example, based on the izod impact strength of the copolyesters of 38mol% ethylene glycol in this transformation of 15-20 ℃ of experience.This transition temperature is relevant with the variation of failure mode; Fragility/low-yield in the lesser temps inefficacy, and toughness/high-energy lost efficacy at comparatively high temps.This transition temperature is expressed as tough brittle transition temperature T _Bd, it is that flexible is measured.T _BdBe reported in the table 2 and in Fig. 2, map with respect to comonomer mol%.

[00174] data show, with the T that improves PCT _BdEthylene glycol compare, in PCT, add 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol has reduced T _BdAnd improved toughness.

Table 2

Notched izod impact energy (ft-lb/in)

Embodiment	Comonomer (mol%) ¹	IV (dl/g)	T ₀ (℃)	T _bd (℃)	-20 ℃	-15 ℃	-10 ℃	-5 ℃	0 ℃	5 ℃	10 ℃	15 ℃	20 ℃	25 ℃	30 ℃
Embodiment	Comonomer (mol%) ¹	IV (dl/g)	T ₀ (℃)	T _bd (℃)	-20 ℃	-15 ℃	-10 ℃	-5 ℃	0 ℃	5 ℃	10 ℃	15 ℃	20 ℃	25 ℃	30 ℃	2A	38.0％B	0.68	86	18	NA	NA	NA	1.5	NA	NA	1.5	1.5	32	32	NA
2B	69.0％B	0.69	82	26	NA	NA	NA	NA	NA	NA	2.1	NA	2.4	13.7	28.7	2A	38.0％B	0.68	86	18	NA	NA	NA	1.5	NA	NA	1.5	1.5	32	32	NA
2B	69.0％B	0.69	82	26	NA	NA	NA	NA	NA	NA	2.1	NA	2.4	13.7	28.7	2C	22.0％C	0.66	106	-5	1.5	NA	12	23	23	NA	23	NA	NA	NA	NA
2D	42.8％C	0.60	133	-12	2.5	2.5	11	NA	14	NA	NA	NA	NA	NA	NA	2C	22.0％C	0.66	106	-5	1.5	NA	12	23	23	NA	23	NA	NA	NA	NA

1. the remainder of the diol component of polyester is a 1,4 cyclohexane dimethanol in the table.All polymkeric substance prepare by the 100mol% dimethyl terephthalate (DMT).

NA=is unavailable.

Wherein:

B is an ethylene glycol

C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (50/50 cis/trans)

Embodiment 3

[00175] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.Zhi Bei polyester comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

[00176] as described below, prepare based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol (31/69 cis/trans), it has composition shown in the table 3 and performance.In the table 3 at the most the remainder of the diol component of the polyester of 100mol% be 1,4 cyclohexane dimethanol (31/69 cis/trans).

[00177] material is injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain the notched izod shock strengths and be reported in the table 3 at 23 ℃.Measure density, Tg and the crystallization half-life of molding strip.Melt viscosity at 290 ℃ of measurement pellets.

Table 3

Various performance compilations to some useful polyester of the present invention

Embodiment	TMCD mol％	% cis TMCD	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TMCD mol％	% cis TMCD	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	27	47.8	0.714	0.678	877	878	1.178	113	280	8312
B	31	NA	0.667	0.641	807	789	1.174	116	600	6592	A	27	47.8	0.714	0.678	877	878	1.178	113	280	8312

NA=is unavailable.

Embodiment 3A

[00178] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 11.82lb (37.28gram-mol) 1,4-cyclohexanedimethanol and 6.90lb (2 1.77gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressure containers being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to＜1mmHg.With reaction mixture remain on 290 ℃ and＜pressure of 1mmHg under up to the power of agitator no longer raise (50 minutes).Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that sieve by 6-mm.The logarithmic viscosity number of polymkeric substance is 0.714dL/g, and Tg is 113 ℃.NMR analysis revealed polymkeric substance comprises 73.3mol%1,4-cyclohexanedimethanol residue and 26.7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 3B

[00179] polyester of embodiment 3B is according to preparing to the similar program of the described program of embodiment 3A.The composition and the performance of this polyester are shown in Table 3.

Embodiment 4

[00180] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.Zhi Bei polyester comprises 2,2,4 in the present embodiment, 4-tetramethyl--1, and 3-cyclobutanediol residue, its quantity is: 40mol% or more.

[00181] as described below, prepare based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, it has composition shown in the table table 4 and performance.In the table 4 at the most the remainder of the diol component of the polyester of 100mol% be 1,4 cyclohexane dimethanol (31/69 cis/trans).

[00182] material is injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain the notched izod shock strengths and be reported in the table 4 at 23 ℃.Measure density, Tg and the crystallization half-life of molding strip.Melt viscosity at 290 ℃ of measurement pellets.

Table 4

Embodiment	TMCD mol％	% cis TMCD	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TMCD mol％	% cis TMCD	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	44	46.2	0.657	0.626	727	734	1.172	119	NA	9751
B	45	NA	0.626	0.580	748	237	1.167	123	NA	8051	A	44	46.2	0.657	0.626	727	734	1.172	119	NA	9751
B	45	NA	0.626	0.580	748	237	1.167	123	NA	8051	C	45	NA	0.582	0.550	671	262	1.167	125	19782	5835
D	45	NA	0.541	0.493	424	175	1.167	123	NA	3275	C	45	NA	0.582	0.550	671	262	1.167	125	19782	5835
D	45	NA	0.541	0.493	424	175	1.167	123	NA	3275	E	59	46.6	0 604	0.576	456	311	1.156	139	NA	16537
F	45	47.2	0.475	0.450	128	30	1.169	121	NA	1614	E	59	46.6	0 604	0.576	456	311	1.156	139	NA	16537

NA=is unavailable.

Embodiment 4A

[00183] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 8.84lb (27.88gram-mol) 1,4-cyclohexanedimethanol and 10.08lb (31.77gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressure containers being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then agitator speed is reduced to 15RPM, then the temperature of reaction mixture is risen to 290 ℃ and pressure reduced to 2mmHg.Reaction mixture is remained under the pressure of 290 ℃ and 2mmHg power up to agitator no longer raise (80 minutes).Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that sieve by 6-mm.The logarithmic viscosity number of polymkeric substance is 0.657dL/g, and Tg is 119 ℃.NMR analysis revealed polymkeric substance comprises 56.3mol%1,4-cyclohexanedimethanol residue and 43.7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=75.04; a ^*=-1.82; And b ^*=6.72.

Embodiment 4B-embodiment 4D

[00184] polyester described in the embodiment 4B-embodiment 4D is according to preparing to the similar program of the described program of embodiment 4A.The composition and the performance of this polyester are shown in Table 4.

Embodiment 4E

[00185] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 6.43lb (20.28gram-mol) 1,4-cyclohexanedimethanol and 12.49lb (39.37gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressure containers being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then agitator speed is reduced to 15RPM, then the temperature of reaction mixture is risen to 290 ℃ and pressure reduced to 2mmHg.With reaction mixture remain on 290 ℃ and＜pressure of 1mmHg under up to the power of agitator no longer raise (50 minutes).Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that sieve by 6-mm.The logarithmic viscosity number of polymkeric substance is 0.604dL/g, and Tg is 139 ℃.NMR analysis revealed polymkeric substance comprises 40.8mol%1,4-cyclohexanedimethanol residue and 59.2mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=80.48, a ^*=-1.30, and b ^*=6.82.

Embodiment 4F

[00186] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 8.84lb (27.88gram-mol) 1,4-cyclohexanedimethanol and 10.08lb (3 1.77gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressure containers being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM and pressure is reduced to 4mmHg.When reaction mixture temperature is 270 ℃ and pressure when being 4mmHg, use nitrogen that the pressure of pressurized vessel is increased to 1 normal atmosphere immediately.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that sieve by 6-mm.The logarithmic viscosity number of polymkeric substance is 0.475dL/g, and Tg is 121 ℃.NMR analysis revealed polymkeric substance comprises 55.5mol%1,4-cyclohexanedimethanol residue and 44.5mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=85.63, a ^*=-0.88, and bu=4.34.

Embodiment 5-Comparative Examples

[00187] present embodiment has shown the data that are used for contrast material, and it is shown in Table 5.PC is the Makrolon 2608 from Bayer, and its nominal consists of 100mol% dihydroxyphenyl propane residue and 100mol% diphenyl carbonate residue.Makrolon 2608 has the nominal melt flow rate (MFR) of use 1.2kg weight at the 20g/10min of 300C measurement.PET is the Eastar 9921 from Eastman ChemicalCompany, and its nominal consists of 100mol% terephthalic acid, 3.5mol% cyclohexanedimethanol (CHDM) and 96.5mol% ethylene glycol.PETG is the Eastar 6763 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 31mol% cyclohexanedimethanol (CHDM) and 69mol% ethylene glycol.PCTG is the Eastar DN001 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 62mol% cyclohexanedimethanol (CHDM) and 38mol% ethylene glycol.PCTA is the Eastar AN001 from Eastman Chemical Company, and its nominal consists of 65mol% terephthalic acid, 35mol% m-phthalic acid and 100mol% cyclohexanedimethanol (CHDM).Polysulfones is the Udel 1700 from Solvay, and its nominal consists of 100mol% dihydroxyphenyl propane residue and 100mol%4,4-two chlorosulfonyl sulfone residues.Udel 1700 has the nominal melt flow rate (MFR) of use 2.16kg weight at the 6.5g/10min of 343C measurement.SAN is the Lustran31 from Lanxess, and its nominal consists of 76wt% vinylbenzene and 24wt% vinyl cyanide.Lustran 31 has the nominal melt flow rate (MFR) of use 3.8kg weight at the 7.5g/10min of 230C measurement.Compare with all other resins, embodiments of the invention demonstrate improved toughness in the thick strip of 6.4mm.

Table 5

The various performance compilations of some commercial polymer

Embodiment	The polymkeric substance title	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	The crystallization half-life of melt (min)
Embodiment	The polymkeric substance title	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	The crystallization half-life of melt (min)	A	PC	12MFR	NA	929	108	1.20	146	NA
B	PCTG	0.73	0.696	NB	70	1.23	87	30 at 170 ℃	A	PC	12MFR	NA	929	108	1.20	146	NA
B	PCTG	0.73	0.696	NB	70	1.23	87	30 at 170 ℃	C	PCTA	0.72	0.702	98	59	1.20	87	15 at 150 ℃
D	PETG	0.75	0.692	83	59	1.27	80	2500 at 130 ℃	C	PCTA	0.72	0.702	98	59	1.20	87	15 at 150 ℃
D	PETG	0.75	0.692	83	59	1.27	80	2500 at 130 ℃	E	PET	0.76	0.726	45	48	1.33	78	1.5 at 170 ℃
F	SAN	7.5MFR	NA	21	NA	1.07	～110	NA	E	PET	0.76	0.726	45	48	1.33	78	1.5 at 170 ℃
F	SAN	7.5MFR	NA	21	NA	1.07	～110	NA	G	PSU	6.5MFR	NA	69	NA	1.24	～190	NA

NA=is unavailable

Embodiment 6

[00188] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the amount of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.

Embodiment 6A

[00189] polyester of present embodiment is by carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is carried out in (CTR) reactor that heats up continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.Reactor be filled with 777g (4mol) dimethyl terephthalate (DMT), 230g (1.6mol) 2,2,4,4-tetramethyl--1, three (2 ethyl hexanoic acid) butyl tin of the cyclohexanedimethanol of 3-cyclobutanediol, 460.8g (3.2mol) and 1.12g (make and in final polymkeric substance, will have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Adopt the Camile program control system to make setting point and data gathering become convenient.In case the reactant fusion just begins to stir and slowly be increased to 250rpm.Along with runtime, the temperature of reactor raises gradually.By the equal a record weight of collected methyl alcohol of sky.When 260 ℃ following time of lesser temps of methyl alcohol effusion stopping or being in preliminary election, stopped reaction.Adopt nitrogen purging to discharge oligopolymer and cool to room temperature.Adopt the liquid nitrogen freezing oligopolymer and be broken into enough little fritter, in the 500ml round-bottomed flask of packing into after the process weighing.

[00190] in polycondensation, the 500ml round-bottomed flask is loaded the above prepared oligopolymer of the 150g that has an appointment.This flask equipped has stainless steel agitator and cap.Glassware is arranged on the last and startup Camile sequence of half moles of polymer suite of equipment (a half mole polymer rig).In case the oligopolymer fusion orientates agitator apart from complete upset of drag (positioned one full turn from the flask bottom) as.Following table has been reported the temperature/pressure by the Camile software control/stir speed (S.S.) sequence for present embodiment.

[00191] the Camile sequence of embodiment 6A

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	3	25	5	110	290	90	50
6	5	290	3	25	7	110	290	3	25

[00192] from flask, reclaims resulting polymers, use the chopping of hydraulic pressure knife mill, and be ground to the 6mm size of mesh.Sample to the polymkeric substance of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml ^*, a ^*, b ^*).Obtaining polymkeric substance by 1H NMR forms.Use Rheometrics MechanicalSpectrometer (RMS-800) sample to be carried out the test of thermostability and melt viscosity.

[00193] following table has shown the experimental data of the polyester of present embodiment.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.Data show, usually, for the constant logarithmic viscosity number, 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol level improves second-order transition temperature in almost linear mode.

Table 6

Second-order transition temperature, logarithmic viscosity number and composition

Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	Tg (℃)	260 ℃ of η o (pool)	275 ℃ of η o (pool)	290 ℃ of η o (pool)
Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	Tg (℃)	260 ℃ of η o (pool)	275 ℃ of η o (pool)	290 ℃ of η o (pool)	A	22.7	53	0.69	112	NA	NA	NA

NA=is unavailable

Embodiment 7

[00194] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the amount of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

[00195] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.2,2,4,4-tetramethyl--1, the NMR of 3-cyclobutanediol parent material are analyzed and are shown that cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with vacuum reduction (reduction) ability.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 32mol% with productive target.

[00196] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.

[00197] following table has shown the experimental data of the polyester of present embodiment.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.Data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol level improves second-order transition temperature in almost linear mode.

Table 7

Second-order transition temperature as the function of logarithmic viscosity number and composition

Embodiment	mol％TMCD	% cis TMCD	IV(dL/g)	Tg(℃)	η _o260 ℃ (pool)	η _o275 ℃ (pool)	η _o290 ℃ (pool)
Embodiment	mol％TMCD	% cis TMCD	IV(dL/g)	Tg(℃)	η _o260 ℃ (pool)	η _o275 ℃ (pool)	η _o290 ℃ (pool)	A	31.6	51.5	0.55	112	5195	2899	2088
B	31.5	50.8	0.62	112	8192	4133	2258	A	31.6	51.5	0.55	112	5195	2899	2088
B	31.5	50.8	0.62	112	8192	4133	2258	C	30.7	50.7	0.54	111	4345	2434	1154
D	30.3	51.2	0.61	111	7929	4383	2261	C	30.7	50.7	0.54	111	4345	2434	1154
D	30.3	51.2	0.61	111	7929	4383	2261	E	29.0	51.5	0.67	112	16322	8787	4355

NA=is unavailable

Embodiment 8

[00198] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the amount of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises 2,2,4 in the present embodiment, 4-tetramethyl--1, and 3-cyclobutanediol residue, its quantity is: 40mol% or more.

Embodiment A-AC

[00199] these polyester are by carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is carried out in (CTR) reactor that heats up continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.Reactor be filled with 777g dimethyl terephthalate (DMT), 375g 2,2,4,4-tetramethyl--1, three (2 ethyl hexanoic acid) butyl tin of the cyclohexanedimethanol of 3-cyclobutanediol, 317g and 1.12g (make and in final polymkeric substance, will have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Adopt the Camile program control system to make setting point and data gathering become convenient.In case the reactant fusion just begins to stir and slowly be increased to 250rpm.Along with runtime, the temperature of reactor raises gradually.By the equal a record weight of collected methyl alcohol of sky.When 260 ℃ following time of lesser temps of methyl alcohol effusion stopping or being in preliminary election, stopped reaction.Adopt nitrogen purging to discharge oligopolymer and cool to room temperature.Adopt the liquid nitrogen freezing oligopolymer and be broken into enough little fritter, in the 500ml round-bottomed flask of packing into after the process weighing.

[00200] in polycondensation, the 500ml round-bottomed flask is filled with the above prepared oligopolymer of 150g.This flask equipped has stainless steel agitator and cap.Be arranged on glassware on the half moles of polymer suite of equipment and start the Camile sequence.In case the oligopolymer fusion orientates agitator apart from complete upset of drag as.The temperature/pressure by the Camile software control/stirring speed sequence for these embodiment is reported in the following table, unless followingly explain in addition.

The Camile sequence of polycondensation

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	6	25	5	110	290	90	50
6	5	290	6	25	7	110	290	6	25

[00201] the Camile sequence of embodiment A, C, R, Y, AB, AC

[00202] for Embodiment B, D, F, the identical sequence in the use in the table, but the time in the stage 7 is 80 minutes.For embodiment G and J, the identical sequence in the use in the table, but the time in the stage 7 is 50 minutes.For embodiment L, the identical sequence in the use in the table, but the time in the stage 7 is 140 minutes.

[00203] the Camile sequence of embodiment E

Stage	Time (mm)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (mm)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	300	90	50
6	5	300	7	25	5	110	300	90	50
6	5	300	7	25	7	110	300	7	25

[00204] for example I, the identical sequence in the use in the table, but the vacuum in stage 6 and 7 is 8 holders.For embodiment O, the identical sequence in the use in the table, but the vacuum in stage 6 and 7 is 6 holders.For embodiment P, the identical sequence in the use in the table, but the vacuum in stage 6 and 7 is 4 holders.For embodiment Q, the identical sequence in the use in the table, but the vacuum in stage 6 and 7 is 5 holders.

[00205] the Camile sequence of embodiment H

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	280	90	50
6	5	280	5	25	5	110	280	90	50
6	5	280	5	25	7	110	280	5	25

[00206] for embodiment U and AA, the identical sequence in the use in the table, but the vacuum in stage 6 and 7 is 6 holders.For EXAMPLE V and X, the identical sequence in the use in the table, but in stage 6 and 7, vacuum is 6 holders, stir speed (S.S.) is 15rpm.For embodiment Z, the identical sequence in the use in the table, but in stage 6 and 7, stir speed (S.S.) is 15rpm.

[00207] the Camile sequence of embodiment K

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	300	90	50
6	5	300	6	15	5	110	300	90	50
6	5	300	6	15	7	110	300	6	15

[00208] for embodiment M, the identical sequence in the use in the table, but the vacuum in stage 6 and 7 is 8 holders.For embodiment N, the identical sequence in the use in the table, but in stage 6 and 7, vacuum is 7 holders.

[00209] the Camile sequence of embodiment S and T

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	5	290	6	25	3	30	265	760	50
4	5	290	6	25	5	110	290	6	25

[00210] from flask, reclaims resulting polymers, use the chopping of hydraulic pressure knife mill, and be ground to the 6mm size of mesh.Sample to the polymkeric substance of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml ^*, a ^*, b ^*).Obtaining polymkeric substance by 1H NMR forms.Use Rheometrics MechanicalSpectrometer (RMS-800) sample to be carried out the test of thermostability and melt viscosity.

Embodiment A D-AK and AS

[00211] polyester of these embodiment, for preparation as described in embodiment A-AC, still, for embodiment A D-AK and AS, target tin quantity is 150ppm in final polymkeric substance as above.Following table has been described the temperature/pressure by the Camile software control/stir speed (S.S.) sequence for these embodiment.

[00212] the Camile sequence of embodiment A D, AF and AH

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	400	50	3	30	265	760	50
4	3	265	400	50	5	110	290	400	50
6	5	290	8	50	5	110	290	400	50
6	5	290	8	50	7	110	295	8	50

[00213] for embodiment A D, in the stage 7, agitator is transferred to 25rpm, carries out 95 minutes.

[00214] the Camile sequence of embodiment A E

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	10	245	760	0
2	5	245	760	50	1	10	245	760	0
2	5	245	760	50	3	30	283	760	50
4	3	283	175	50	3	30	283	760	50
4	3	283	175	50	5	5	283	5	50
6	5	283	1.2	50	5	5	283	5	50
6	5	283	1.2	50	7	71	285	1.2	50

[00215] for embodiment A K, the identical sequence in the use in the table, but the time in the stage 7 is 75 minutes.

[00216] the Camile sequence of embodiment A G

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	10	245	760	0
2	5	245	760	50	1	10	245	760	0
2	5	245	760	50	3	30	285	760	50
4	3	285	175	50	3	30	285	760	50
4	3	285	175	50	5	5	285	5	50
6	5	285	4	50	5	5	285	5	50
6	5	285	4	50	7	220	290	4	50

[00217] the Camile sequence of embodiment A I

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	285	90	50
6	5	285	6	50	5	110	285	90	50
6	5	285	6	50	7	70	290	6	50

[00218] the Camile sequence of embodiment A J

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	6	25	5	110	290	90	50
6	5	290	6	25	7	110	295	6	25

Embodiment A L-AR

[00219] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with vacuum reduction (reduction) ability.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 45mol% with productive target.

[00220] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.

[00221] following table has shown the experimental data of the polyester of present embodiment.Data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol level improves second-order transition temperature in almost linear mode.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.

Table 8

Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	η _o260 ℃ (pool)	η _o275 ℃ (pool)	η _o290 ℃ (pool)
Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	η _o260 ℃ (pool)	η _o275 ℃ (pool)	η _o290 ℃ (pool)	A	43.9	72.1	0.46	131	NA	NA	NA
B	44.2	36.4	0.49	118	NA	NA	NA	A	43.9	72.1	0.46	131	NA	NA	NA
B	44.2	36.4	0.49	118	NA	NA	NA	C	44	71.7	0.49	128	NA	NA	NA
D	44.3	36.3	0.51	119	NA	NA	NA	C	44	71.7	0.49	128	NA	NA	NA
D	44.3	36.3	0.51	119	NA	NA	NA	E	46.1	46.8	0.51	125	NA	NA	NA
F	43.6	72.1	0.52	128	NA	NA	NA	E	46.1	46.8	0.51	125	NA	NA	NA
F	43.6	72.1	0.52	128	NA	NA	NA	G	43.6	72.3	0.54	127	NA	NA	NA
H	46.4	46.4	0.54	127	NA	NA	NA	G	43.6	72.3	0.54	127	NA	NA	NA
H	46.4	46.4	0.54	127	NA	NA	NA	I	45.7	47.1	0.55	125	NA	NA	NA
J	44.4	35.6	0.55	118	NA	NA	NA	I	45.7	47.1	0.55	125	NA	NA	NA
J	44.4	35.6	0.55	118	NA	NA	NA	K	45.2	46.8	0.56	124	NA	NA	NA
L	43.8	72.2	0.56	129	NA	NA	NA	K	45.2	46.8	0.56	124	NA	NA	NA
L	43.8	72.2	0.56	129	NA	NA	NA	M	45.8	46.4	0.56	124	NA	NA	NA
N	45.1	47.0	0.57	125	NA	NA	NA	M	45.8	46.4	0.56	124	NA	NA	NA
N	45.1	47.0	0.57	125	NA	NA	NA	O	45.2	46.8	0.57	124	NA	NA	NA
P	45	46.7	0.57	125	NA	NA	NA	O	45.2	46.8	0.57	124	NA	NA	NA
P	45	46.7	0.57	125	NA	NA	NA	Q	45.1	47.1	0.58	127	NA	NA	NA
R	44.7	35.4	0.59	123	NA	NA	NA	Q	45.1	47.1	0.58	127	NA	NA	NA
R	44.7	35.4	0.59	123	NA	NA	NA	S	46.1	46.4	0.60	127	NA	NA	NA
T	45.7	46.8	0.60	129	NA	NA	NA	S	46.1	46.4	0.60	127	NA	NA	NA
T	45.7	46.8	0.60	129	NA	NA	NA	U	46	46.3	0.62	128	NA	NA	NA
V	45.9	46.3	0.62	128	NA	NA	NA	U	46	46.3	0.62	128	NA	NA	NA
V	45.9	46.3	0.62	128	NA	NA	NA	X	45.8	46.1	0.63	128	NA	NA	NA
Y	45.6	50.7	0.63	128	NA	NA	NA	X	45.8	46.1	0.63	128	NA	NA	NA
Y	45.6	50.7	0.63	128	NA	NA	NA	Z	46.2	46.8	0.65	129	NA	NA	NA
AA	45.9	46.2	0.66	128	NA	NA	NA	Z	46.2	46.8	0.65	129	NA	NA	NA
AA	45.9	46.2	0.66	128	NA	NA	NA	AB	45.2	46.4	0.66	128	NA	NA	NA
AC	45.1	46.5	0.68	129	NA	NA	NA	AB	45.2	46.4	0.66	128	NA	NA	NA
AC	45.1	46.5	0.68	129	NA	NA	NA	AD	46.3	52.4	0.52	NA	NA	NA	NA
AE	45.7	50.9	0.54	NA	NA	NA	NA	AD	46.3	52.4	0.52	NA	NA	NA	NA
AE	45.7	50.9	0.54	NA	NA	NA	NA	AF	46.3	52.6	0.56	NA	NA	NA	NA
AG	46	50.6	0.56	NA	NA	NA	NA	AF	46.3	52.6	0.56	NA	NA	NA	NA
AG	46	50.6	0.56	NA	NA	NA	NA	AH	46.5	51.8	0.57	NA	NA	NA	NA
AI	45.6	51.2	0.58	NA	NA	NA	NA	AH	46.5	51.8	0.57	NA	NA	NA	NA
AI	45.6	51.2	0.58	NA	NA	NA	NA	AJ	46	51.9	0.58	NA	NA	NA	NA
AK	45.5	51.2	0.59	NA	NA	NA	NA	AJ	46	51.9	0.58	NA	NA	NA	NA
AK	45.5	51.2	0.59	NA	NA	NA	NA	AL	45.8	50.1	0.624	125	NA	NA	7696
AM	45.7	49.4	0.619	128	NA	NA	7209	AL	45.8	50.1	0.624	125	NA	NA	7696
AM	45.7	49.4	0.619	128	NA	NA	7209	AN	46.2	49.3	0.548	124	NA	NA	2348
AP	45.9	49.5	0.72	128	76600	40260	19110	AN	46.2	49.3	0.548	124	NA	NA	2348
AP	45.9	49.5	0.72	128	76600	40260	19110	AQ	46.0	50	0.71	131	68310	32480	17817
AR	46.1	49.6	0.383	117	NA	NA	387	AQ	46.0	50	0.71	131	68310	32480	17817
AR	46.1	49.6	0.383	117	NA	NA	387	AS	47.2	NA	0.48	NA	NA	NA	NA

NA=is unavailable

Embodiment 9

[00222] present embodiment illustrates 2,2,4,4-tetramethyl--1, and the dominant position of the type of 3-cyclobutanediol isomer (cis or trans) is to the influence of the second-order transition temperature of polyester.

[00223] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with vacuum reduction (reduction) ability.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 45mol% with productive target.

[00224] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.

[00225] following table has shown the experimental data of the polyester of present embodiment.Data show, for the constant logarithmic viscosity number, improving aspect the second-order transition temperature, and cis 2,2,4,4-tetramethyl--1, it is trans 2,2,4 that the effect of 3-cyclobutanediol is about, 4-tetramethyl--1, the twice of 3-cyclobutanediol.

Table 9

2,2,4,4-tetramethyl--1,3-cyclobutanediol cis/trans is formed the influence to Tg

Embodiment	mol％ TMCD	IV (dL/g)	T _g (℃)	η _o260 ℃ (pool)	η _o275 ℃ (pool)	η _o290 ℃ (pool)	% cis TMCD
Embodiment	mol％ TMCD	IV (dL/g)	T _g (℃)	η _o260 ℃ (pool)	η _o275 ℃ (pool)	η _o290 ℃ (pool)	% cis TMCD	A	45.8	0.71	119	N.A.	N.A.	N.A.	4.1
B	43.2	0.72	122	N.A.	N.A.	N.A.	22.0	A	45.8	0.71	119	N.A.	N.A.	N.A.	4.1
B	43.2	0.72	122	N.A.	N.A.	N.A.	22.0	C	46.8	0.57	119	26306	16941	6601	22.8
D	43.0	0.67	125	55060	36747	14410	23.8	C	46.8	0.57	119	26306	16941	6601	22.8
D	43.0	0.67	125	55060	36747	14410	23.8	E	43.8	0.72	127	101000	62750	25330	24.5
F	45.9	0.533	119	11474	6864	2806	26.4	E	43.8	0.72	127	101000	62750	25330	24.5
F	45.9	0.533	119	11474	6864	2806	26.4	G	45.0	0.35	107	N.A.	N.A.	N.A.	27.2
H	41.2	0.38	106	1214	757	N.A.	29.0	G	45.0	0.35	107	N.A.	N.A.	N.A.	27.2
H	41.2	0.38	106	1214	757	N.A.	29.0	I	44.7	0.59	123	N.A.	N.A.	N.A.	35.4
J	44.4	0.55	118	N.A.	N.A.	N.A.	35.6	I	44.7	0.59	123	N.A.	N.A.	N.A.	35.4
J	44.4	0.55	118	N.A.	N.A.	N.A.	35.6	K	44.3	0.51	1 19	N.A.	N.A.	N.A.	36.3
L	44.0	0.49	128	N.A.	N.A.	N.A.	71.7	K	44.3	0.51	1 19	N.A.	N.A.	N.A.	36.3
L	44.0	0.49	128	N.A.	N.A.	N.A.	71.7	M	43.6	0.52	128	N.A.	N.A.	N.A.	72.1
N	43.6	0.54	127	N.A.	N.A.	N.A.	72.3	M	43.6	0.52	128	N.A.	N.A.	N.A.	72.1
N	43.6	0.54	127	N.A.	N.A.	N.A.	72.3	O	41.5	0.58	133	15419	10253	4252	88.7
P	43.8	0.57	135	16219	10226	4235	89.6	O	41.5	0.58	133	15419	10253	4252	88.7
P	43.8	0.57	135	16219	10226	4235	89.6	Q	41.0	0.33	120	521	351	2261	90.4
R	43.0	0.56	134	N.A.	N.A.	N.A.	90.6	Q	41.0	0.33	120	521	351	2261	90.4
R	43.0	0.56	134	N.A.	N.A.	N.A.	90.6	S	43.0	0.49	132	7055	4620	2120	90.6
T	43.1	0.55	134	12970	8443	3531	91.2	S	43.0	0.49	132	7055	4620	2120	90.6
T	43.1	0.55	134	12970	8443	3531	91.2	U	45.9	0.52	137	N.A.	N.A.	N.A.	98.1

NA=is unavailable

Embodiment 10

[00226] present embodiment illustrates and comprises 100mol% dimethyl terephthalate (DMT) residue, 55mol%1,4-cyclohexanedimethanol residue and 45mol%2,2,4,4-tetramethyl--1, the preparation of the copolyesters of 3-cyclobutanediol residue.

[00227] with 97.10g (0.5 mole) dimethyl terephthalate (DMT), 52.46g (0.36 mole) 1,4-cyclohexanedimethanol, 34.07g (0.24 mole) 2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.0863g (300ppm) dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Content in the flask also was elevated to temperature 210 ℃ in 1 hour subsequently 200 ℃ of heating.Reaction mixture kept 2 hours and subsequently at 30 minutes internal heating to 290 ℃ at 210 ℃.In case be in 290 ℃, applied the vacuum of 0.01psig at ensuing 3-5 minute gradually.Keep about altogether 45 minutes of perfect vacuum (0.01psig) to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 125 ℃, and logarithmic viscosity number is 0.64dl/g.

Embodiment 11-Comparative Examples

[00228] present embodiment illustrates based on 100%2,2,4,4-tetramethyl--1, and the polyester of 3-cyclobutanediol has slow crystallization half-life.

[00229] with the preparation of the similar method of method described in the embodiment 1A only based on terephthalic acid and 2,2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol, performance is shown in Table 10.Adopt the 300ppm dibutyl tin oxide to prepare this polyester.2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol are 65/35.

[00230] 320 ℃ of polymkeric substance press membrane by grinding.Is increment at 220-250 ℃ with 10 ℃, carries out the measurement from the crystallization half-life of melt, and measuring result is recorded in the table 10.The fastest crystallization half-life of sample thief is as the minimum value of temperature variant crystallization half-life.Be about 1300 minutes the fastest crystallization half-life of this polyester.This value and the following true contrast that forms: only the polyester (PCT) based on terephthalic acid and 1,4 cyclohexane dimethanol (no comonomer modification) has extremely short crystallization half-life (less than 1 minute), as shown in Figure 1.

Table 10

Crystallization half-life (minute)

Comonomer (mol%)	IV(dl/g)	T _g(℃)	T _max(℃)	220℃ (min)	230℃ (min)	240℃ (min)	250℃ (min)
Comonomer (mol%)	IV(dl/g)	T _g(℃)	T _max(℃)	220℃ (min)	230℃ (min)	240℃ (min)	250℃ (min)	100mol％F	0.63	170.0	330	3291	3066	1303	1888

Wherein: F is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (65/35 trans/cis)

Embodiment 12-Comparative Examples

[00231] use 3.5 inches single screw extrusion machine productions to comprise the thin plate of polyester, described polyester is with 100mol% terephthalic acid residue, 80mol%1,4-cyclohexanedimethanol residue and 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue are that the target composition is prepared.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured logarithmic viscosity number and second-order transition temperature.The measuring result of the logarithmic viscosity number of thin plate is 0.69dl/g.The measuring result of the second-order transition temperature of thin plate is 106 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment G) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 106 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, these thin plates have at least 95% stretching and bubble to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	86	145	501	64	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	N
B	A	86	145	501	64						N
B		100	150	500	63	N
C		100	150	500	63	N	118	156	672	85	N
C	D	135	163	736	94	N	118	156	672	85	N
E	D	135	163	736	94	N	143	166	760	97	N
E	F	150	168	740	94	L	143	166	760	97	N
G	F	150	168	740	94	L	159	172	787	100	L

Embodiment 13-Comparative Examples

[00232] use 3.5 inches single screw extrusion machine productions to comprise the sheet material of polyester, described polyester is with 100mol% terephthalic acid residue, 80mol%1,4-cyclohexanedimethanol residue and 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue are that the target composition is prepared.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured logarithmic viscosity number and second-order transition temperature.The measuring result of the logarithmic viscosity number of thin plate is 0.69dl/g.The measuring result of the second-order transition temperature of thin plate is 106 ℃.Then with thin plate in 100% relative humidity and 25 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 60/40/40% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment G) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 106 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has at least 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	141	154	394	53	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	N
B	A	141	154	394	53	163	157	606	82	N	N
B	C	185	160	702	95	163	157	606	82	N	N
D	C	185	160	702	95	195	161	698	95	N	N
D	E	215	163	699	95	195	161	698	95	N	L
F	E	215	163	699	95	230	168	705	96	L	L
F	G	274	174	737	100	230	168	705	96	L	H
H	G	274	174	737	100	275	181	726	99	H	H

Embodiment 14-Comparative Examples

[00233] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Kelvx 201.Kelvx is by 69.85%PCTG (available from the Eastar of Eastman Chemical Co., it has 100mol% terephthalic acid residue, 62mol%1,4-cyclohexanedimethanol residue and 38mol% glycol residue); 30%PC (bisphenol-a polycarbonate); The blend of forming with 0.15%Weston 619 (stablizer of selling by CromptonCorporation).Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 100 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment E) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 100 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has at least 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	90	146	582	75	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	N
B	A	90	146	582	75	101	150	644	83	N	N
B	C	111	154	763	98	101	150	644	83	N	N
D	C	111	154	763	98	126	159	733	95	N	N
D	E	126	159	775	100	126	159	733	95	N	N
F	E	126	159	775	100	141	165	757	98	N	N
F	G	148	168	760	98	141	165	757	98	N	L

Embodiment 15-Comparative Examples

[00234] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Kelvx 201.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 100 ℃.Then with thin plate in 100% relative humidity and 25 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 60/40/40% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment H) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 100 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	110	143	185	25	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	N
B	A	110	143	185	25	145	149	529	70	N	N
B	C	170	154	721	95	145	149	529	70	N	N
D	C	170	154	721	95	175	156	725	96	N	N
D	E	185	157	728	96	175	156	725	96	N	N
F	E	185	157	728	96	206	160	743	98	L	N
F	G	253	NR	742	98	206	160	743	98	L	H
H	G	253	NR	742	98	261	166	756	100	H	H

NR=is Unrecorded

Embodiment 16-Comparative Examples

[00235] thin plate that uses 3.5 inches single screw extrusion machine productions to form by PCTG 25976 (100mol% terephthalic acid residue, 62mol%1,4-cyclohexanedimethanol residue and 38mol% glycol residue).Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 87 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.17wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 87 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	102	183	816	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	N
B	A	102	183	816	100	92	171	811	99	N	N
B	C	77	160	805	99	92	171	811	99	N	N
D	C	77	160	805	99	68	149	804	99	N	N
D	E	55	143	790	97	68	149	804	99	N	N
F	E	55	143	790	97	57	138	697	85	N	N

Embodiment 17-Comparative Examples

[00236] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 20wt%Teijin L-1250 polycarbonate (bisphenol-a polycarbonate), 79.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 94 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.25wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 94 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	92	184	844	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	92	184	844	100	86	171	838	99	N	H
B	C	73	160	834	99	86	171	838	99	N	N
D	C	73	160	834	99	58	143	787	93	N	N
D	E	55	143	665	79	58	143	787	93	N	N

Embodiment 18-Comparative Examples

[00237] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 30wt%Teijin L-1250 polycarbonate, 69.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 99 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.25wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 99 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	128	194	854	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	128	194	854	100	98	182	831	97	L	H
B	C	79	160	821	96	98	182	831	97	L	N
D	C	79	160	821	96	71	149	819	96	N	N
D	E	55	145	785	92	71	149	819	96	N	N
F	E	55	145	785	92	46	143	0	0	NA	N
F	G	36	132	0	0	46	143	0	0	NA	NA

NA=is inapplicable.0 value shows and do not form thin plate, because it does not draw in mould (may because its temperature is too low).

Embodiment 19-Comparative Examples

[00238] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 40wt%Teijin L-1250 polycarbonate, 59.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 105 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.265wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment 8A-8E) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 105 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	111	191	828	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	111	191	828	100	104	182	828	100	H	H
B	C	99	179	827	100	104	182	828	100	H	N
D	C	99	179	827	100	97	177	827	100	N	N
D	E	78	160	826	100	97	177	827	100	N	N
F	E	78	160	826	100	68	149	759	92	N	N
F	G	65	143	606	73	68	149	759	92	N	N

Embodiment 20-Comparative Examples

[00239] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 50wt%Teijin L-1250 polycarbonate, 49.85wt%PCTG 25976 and 0.15wt%Weston 619.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 111 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.225wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume of acquisition in this group experiment (embodiment A-D).Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 111 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	118	192	815	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	118	192	815	100	99	182	815	100	H	H
B	C	97	177	814	100	99	182	815	100	H	L
D	C	97	177	814	100	87	171	813	100	N	L
D	E					87	171	813	100	N
	E	80	160	802	98	N
	F	80	160	802	98	N	64	154	739	91	N
G	F						64	154	739	91	N
G		60	149	0	0	NA

Embodiment 21-Comparative Examples

[00240] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 60wt%Teijin L-1 250 polycarbonate, 39.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 117 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.215wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 117 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	114	196	813	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	114	196	813	100						H
B		100	182	804	99	H
C		100	182	804	99	H	99	177	801	98	L
C	D	92	171	784	96	L	99	177	801	98	L
E	D	92	171	784	96	L	82	168	727	89	L
E	F	87	166	597	73	N	82	168	727	89	L

Embodiment 22-Comparative Examples

[00241] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 65wt%Teijin L-1250 polycarbonate, 34.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 120 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.23wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 120 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	120	197	825	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	120	197	825	100	101	177	820	99	H	H
B	C	95	174	781	95	101	177	820	99	H	L
D	C	95	174	781	95	85	171	727	88	L	L
D	E	83	166	558	68	85	171	727	88	L	L

Embodiment 23-Comparative Examples

[00242] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 70wt%Teijin L-1250 polycarbonate, 29.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 123 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.205wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A and B) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 123 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	126	198	826	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	126	198	826	100	111	188	822	100	H	H
B	C	97	177	787	95	111	188	822	100	H	L
D	C	97	177	787	95	74	166	161	19	L	L
D	E	58	154	0	0	74	166	161	19	L	NA
F	E	58	154	0	0	48	149	0	0	NA	NA

Embodiment 24-Comparative Examples

[00243] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Teijin L-1250 polycarbonate.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 149 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.16wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 149 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.

Embodiment	The thermoforming condition		Part quality
	The thermoforming condition		Part quality			Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)
	A	152	216	820	100	Heat-up time (s)	The thin plate temperature (℃)	Piece volumes (mL)	Stretch (%)	Bubble (N, L, H)	H
B	A	152	216	820	100	123	193	805	98	H	H
B	C	113	191	179	22	123	193	805	98	H	H
D	C	113	191	179	22	106	188	0	0	H	H
D	E	95	182	0	0	106	188	0	0	H	NA
F	E	95	182	0	0	90	171	0	0	NA	NA

[00244] comparison of the data from above related work embodiment can be clear that, aspect second-order transition temperature, density, slow crystallization rate, melt viscosity and toughness, compare with the commercially available polyester that gets, polyester of the present invention provides tangible advantage.

[00245] the present invention describes in detail with reference to embodiment disclosed herein, but should be appreciated that, can change and change within the spirit and scope of the present invention.

Claims

1. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein total molecular fraction of dicarboxylic acid component be 100mol% and

Total molecular fraction of diol component is 100mol%; With

Wherein, the logarithmic viscosity number of described polyester is that 0.35-is less than 0.70dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With the Tg of wherein said polyester be 110-200 ℃.

2. the film of claim 1 or thin plate, wherein, the logarithmic viscosity number of described polyester is that 0.35-is less than 0.70dL/g.

3. the film of claim 1 or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.40-0.70dL/g.

4. the film of claim 1 or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-0.70dL/g.

5. the film of claim 1 or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-0.75dL/g.

6. the film of claim 1 or thin plate, wherein, the logarithmic viscosity number of described polyester is that 0.58-is less than 0.70dL/g.

7. the film of claim 1 or thin plate, wherein, the logarithmic viscosity number of described polyester is that 0.60-is less than 0.70dL/g.

8. the film of claim 1 or thin plate, the Tg of wherein said polyester is 110-200 ℃.

9. the film of claim 1 or thin plate, the Tg of wherein said polyester is 110-170 ℃.

10. the film of claim 1 or thin plate, the Tg of wherein said polyester is 110-160 ℃.

11. the film of claim 1 or thin plate, the Tg of wherein said polyester are 110-150 ℃.

12. the film of claim 1 or thin plate, the Tg of wherein said polyester are 120-160 ℃.

13. the film of claim 1 or thin plate, the Tg of wherein said polyester are 120-150 ℃.

14. the film of claim 1 or thin plate, the Tg of wherein said polyester are 130-160 ℃.

15. the film of claim 1 or thin plate, the Tg of wherein said polyester are 130-150 ℃.

16. the film of claim 1 or thin plate, the Tg of wherein said polyester are 130-145 ℃.

17. the film of claim 1 or thin plate, the Tg of wherein said polyester are 140-150 ℃.

18. the film of claim 1 or thin plate, the Tg of wherein said polyester are 135-145 ℃.

19. the film of claim 1 or thin plate, the Tg of wherein said polyester are 148-200 ℃.

20. the film of claim 1 or thin plate, the Tg of wherein said polyester are 127-200 ℃.

21. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 1-80mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 20-99mol%1,4-cyclohexanedimethanol residue.

22. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 50-99mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 1-be less than 50mol%1,4-cyclohexanedimethanol residue.

23. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 40-85mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 15-60mol%1,4-cyclohexanedimethanol residue.

24. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 40-80mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 20-60mol%1,4-cyclohexanedimethanol residue.

25. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 40-65mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 35-55mol%1,4-cyclohexanedimethanol residue.

26. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 40-55mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 45-60mol%1,4-cyclohexanedimethanol residue.

27. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 45-55mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 45-55mol%1,4-cyclohexanedimethanol residue.

28. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 46-55mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 45-be less than 55mol%1,4-cyclohexanedimethanol residue.

29. the film of claim 1 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 80-100mol%.

30. the film of claim 1 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 90-100mol%.

31. the film of claim 1 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 95-100mol%.

32. the film of claim 1 or thin plate, wherein said polyester comprises 1, ammediol residue, 1,4-butyleneglycol residue or its mixture.

33. the film of claim 1 or thin-plate composition, wherein polyester comprises the ethylene glycol of 0.01-15mol%.

34. the film of claim 1 or thin-plate composition, wherein polyester comprises the ethylene glycol of 0.01-10mol%.

35. the film of claim 1 or thin plate are wherein said 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue is to comprise suitable-2,2,4 greater than 50mol%, 4-tetramethyl--1,3-cyclobutanediol residue and less than anti--2 of 50mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol residue.

36. the film of claim 1 or thin plate are wherein said 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue is to comprise suitable-2,2,4 greater than 55mol%, 4-tetramethyl--1,3-cyclobutanediol residue and less than anti--2 of 45mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol residue.

37. the film of claim 1 or thin plate are wherein said 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue is comprise 30-70mol% suitable-2,2,4,4-tetramethyl--1, anti--2 of 3-cyclobutanediol residue and 30-70mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol residue.

38. the film of claim 1 or thin plate are wherein said 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue is comprise 40-60mol% suitable-2,2,4,4-tetramethyl--1, anti--2 of 3-cyclobutanediol residue and 40-60mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol residue.

39. the film of claim 1 or thin plate, wherein said polymer blend comprise at least a at least a polymkeric substance that is selected from following: nylon; Be different from described those other polyester herein; Polymeric amide; Polystyrene; Polystyrene copolymer; Styrene acrylonitrile copolymer; Acrylonitrile-butadiene-styrene copolymer; Polymethylmethacrylate; Acrylic copolymer; Poly-(ether-imide); Polyphenylene oxide is as poly-(2,6-dimethyl phenylate); Or polyphenyl ether/styrene blend; Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ether); Polycarbonate; Polysulfones; Polysulfones ether; Poly-(ether-ketone) with aromatic dihydroxy compound; Or its mixture.

40. the film of claim 1 or thin plate, wherein said polymer blend comprises at least a polycarbonate.

41. the film of claim 1 or thin plate, wherein said polyester comprise at least a residue that is used for the branching agent of polyester.

42. the film of claim 1 or thin plate, wherein said polyester comprises the residue of at least a branching agent, and its quantity is: 0.01-10wt%, and based on total molecular fraction of acid or diol residue.

43. the film of claim 1 or thin plate, the melt viscosity of wherein said polyester are less than 30,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃.

44. the film of claim 1 or thin plate, wherein said polyester had 170 ℃ of crystallization half-lives greater than 5 minutes.

45. the film of claim 1 or thin plate, the crystallization half-life of wherein said polyester at 170 ℃ greater than 1000 minutes.

46. the film of claim 1 or thin plate, the crystallization half-life of wherein said polyester at 170 ℃ greater than 10,000 minutes.

47. the film of claim 1 or thin plate, wherein the density at 23 ℃ of described polymer blends is less than 1.2g/ml.

48. the film of claim 1 or thin plate, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product.

49. the film of claim 1 or thin plate, wherein said polyester according to the yellowness index of ASTM D-1925 less than 50.

50. the film of claim 1 or thin plate, wherein in the thick strip of 1/8-in with 10-mil otch according to ASTM D256 under 23 ℃, the notched izod shock strength of described polyester is 3ft-lbs/in at least.

51. the film of claim 1 or thin plate, in the thick strip of 1/8-in with 10-mil otch according to ASTM D256 under 23 ℃, the notched izod shock strength of described polyester is 10ft-lbs/in at least.

52. the film of claim 1 or thin plate, wherein polyester comprises the resistates of at least a catalyzer, described catalyst pack sn-containing compound or its reaction product.

53. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 40-65mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 35-60mol%,

Wherein, the logarithmic viscosity number of described polyester is 0.35-0.75dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With the Tg of wherein said polyester be 110-200 ℃.

54. film or thin plate, it comprises polymer blend, and this polymer blend comprises:

(I) at least a polyester, it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid of 70-100mol%, its ester or its mixture;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 1-99mol% and

(II) residue of at least a branching agent;

Wherein, the logarithmic viscosity number of described polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With

The Tg of wherein said polyester is 110-200 ℃.

55. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.40-1.2dL/g.

56. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.40-1.1dL/g.

57. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.40-1dL/g.

58. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.40-0.9dL/g.

59. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.40-0.8dL/g.

60. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-1.2dL/g.

61. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-1.1dL/g.

62. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-1dL/g.

63. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-0.9dL/g.

64. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.50-0.8dL/g.

65. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.60-0.72dL/g.

66. claim 1,53 and 54 film or thin plate, wherein, the logarithmic viscosity number of described polyester is greater than 0.76-1.2dL/g.

67. film or thin plate, it comprises polymer blend, and this polymer blend comprises: (I) at least a polyester, and it comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the 1,4 cyclohexane dimethanol residue of 1-99mol% and

(II) at least a thermo-stabilizer or its reaction product;

Wherein, the logarithmic viscosity number of described polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration;

The Tg of wherein said polyester is 110-200 ℃.

68. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein, the logarithmic viscosity number of described polyester is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With the Tg of wherein said polyester be greater than 148 ℃ to 200 ℃ at the most.

69. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

Ii) 1-is less than the 1,4 cyclohexane dimethanol residue of 50mol%,

Wherein, the logarithmic viscosity number of described polyester is 0.35-01.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With the Tg of wherein said polyester be 110 ℃-200 ℃.

70. the film of claim 67 or thin plate, the Tg of wherein said polyester are 120-150 ℃.

71. the film of claim 67 or thin plate, the Tg of wherein said polyester are 130-145 ℃.

72. the film of claim 67 or thin plate, wherein logarithmic viscosity number is 0.60-0.75dL/g.

73. the film of claim 67 or thin plate, wherein logarithmic viscosity number is 0.60-0.72dL/g.

74. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:

(a) dicarboxylic acid component, it comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component, it comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,

Wherein, the logarithmic viscosity number of described polyester is greater than 0.76-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With the Tg of wherein said polyester be 110 ℃-200 ℃.

75. the film of claim 1 or thin plate, wherein polyester is unbodied.

76. goods, it comprises the film or the thin plate of claim 1.

77. a liquid-crystal display film, it comprises the polymer blend of claim 1.

78. the liquid-crystal display film of claim 77, it comprises the diffuser thin plate.

79. the liquid-crystal display film of claim 77, it comprises compensation film.

80. the liquid-crystal display film of claim 77, it comprises protective film.

Wherein these goods are formed by the injection drawing blow molding.

81. the film of claim 76 or thin plate, wherein said film or thin plate are by extruding or rolling production.

82. the film of claim 1 or thin plate, its described polyester and quantity that comprises that quantity is 5-95wt% is the blend of at least a polymeric constituent of 5-95wt%, based on the gross weight of described polymer blend.

83. the blend of claim 82, wherein at least a polymeric constituent are selected from following at least a: nylon; Polyester except that the polyester of right requirement 1; Polymeric amide; Polystyrene; Polystyrene copolymer; Styrene acrylonitrile copolymer; Acrylonitrile-butadiene-styrene copolymer; Polymethylmethacrylate; Acrylic copolymer; Poly-(ether-imide); Polyphenylene oxide is as poly-(2,6-dimethyl phenylate); Or polyphenyl ether/styrene blend; Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ether); Polycarbonate; Polysulfones; Polysulfones ether; Poly-(ether-ketone) with aromatic dihydroxy compound.