CN101193943B

CN101193943B - 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: CN101193943B
Application number: CN2006800205626A
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: 2012-09-05
Anticipated expiration: 2026-03-30
Also published as: CN101193943A; CN101193937A; CN101193942B; CN101193932A; CN101203543A; CN101203544B; CN101193733A; CN101193977A; CN101193932B; CN101203543B; CN101203544A; CN101193944A; CN101193721A; CN101193935B; CN101193978A; CN101193939A; CN101203542A; CN101193936A; CN101193937B; CN101193940A

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 the second-order transition temperature of appropriateness

The cross reference of related application

The right of priority of application below the application requires 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 Application 60/750,547 (applying date is on December 15th, 2005), all these documents are introduced this paper as a reference with its full content.

Technical field

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; Process 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 have at least two kinds unique combination in the following performance: the second-order transition temperature (Tg), toughness, a certain logarithmic viscosity number of high impact, appropriateness, low tough brittle transition temperature, good color and the transparency, low density and long crystallization half-life, this makes it be easy to be configured as film and/or thin plate.

Background technology

Poly terephthalic acid 1,4-hexamethylene two methylene esters (PCT), a kind of only based on the polyester of terephthalic acid and 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 through 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 dicarboxylicacid or glycol such as m-phthalic acid or terepthaloyl moietie.These terepthaloyl moietie are asked that perhaps the PCT of phthalic acid modification is also known in the art and are commercially available getting.

A kind of copolyesters commonly used that is used to produce film, thin plate and moulded product is processed by terephthalic acid, 1,4 cyclohexane dimethanol and terepthaloyl moietie.Though in the application that these copolyesters can be used for many terminals using, when competent modification terepthaloyl moietie is contained in the preparation so that when long crystallization half-life is provided, they demonstrate deficiency at the aspect of performance like 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 terepthaloyl moietie are processed provides amorphous products, and than compsn disclosed herein, these products demonstrate higher tough brittle transition temperature and lower second-order transition temperature.

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.

Usually also described in the art and contained 2,2,4,4-tetramethyl--1, the polymkeric substance of 3-cyclobutanediol.Yet usually, these polymkeric substance demonstrate high logarithmic viscosity number, high melt viscosity and high glass-transition temperature, make the used not competent manufacturing of equipment or these materials of post polymerization processing in the industry.

Thereby; The film and/or the thin plate that need comprise polymer blend in the art; Said polymer blend comprises at least a polyester; It has and is selected from following two kinds at least a or the combination of more kinds of performances: the second-order transition temperature of toughness, appropriateness, good shock strength, stability to hydrolysis, chemical resistant properties, 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

It is believed that certain combination with logarithmic viscosity number and/or second-order transition temperature, (it comprises terephthalic acid, its ester or its mixture again to comprise polymer blend; 1,4 cyclohexane dimethanol; With 2; 2,4,4-tetramethyl--1; The 3-cyclobutanediol) some film and/or thin plate are at following film and the thin plate processed by polyester known in the art and polycarbonate of being superior to aspect at least one: stability to hydrolysis, toughness, chemical resistant properties, lower proportion and hot-forming property.These films and/or thin plate it is believed that and aspect thermotolerance, are similar to by those of polycarbonate, and on standard industry equipment, still can process.

In one aspect, 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 said 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 logarithmic viscosity number is that 0.10-is less than 1.0dL/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 85-120 ℃.

(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 logarithmic viscosity number is that 0.35-is less than 1.0dL/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 85-120 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 5-is less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) greater than the 1,4 cyclohexane dimethanol residue of 50-95mol%,

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

Wherein the logarithmic viscosity number of polyester is 0.50-1.2dL/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 85-120 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,

The Tg of wherein said polyester is 85-120 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,

Wherein logarithmic viscosity number is 0.50-1.2dL/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 85-120 ℃.

In one aspect, 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:

Ii) greater than the 1,4 cyclohexane dimethanol residue of 50-95mol%,

Wherein the logarithmic viscosity number of polyester is 0.50-1.2dL/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 95-115 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,

Wherein, the logarithmic viscosity number of said polyester is 0.50-1.2dL/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 95-115 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

Ii) greater than the 1,4 cyclohexane dimethanol residue of 50-95mol%,

Wherein, the logarithmic viscosity number of said polyester is that 0.50-is less than 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 85-120 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

Ii) greater than the 1,4 cyclohexane dimethanol residue of 50-95mol%,

Wherein, the logarithmic viscosity number of said polyester is that 0.50-is less than 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 95-115 ℃.

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,

(a) dicarboxylic acid component, it comprises:

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

(b) diol component, it comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,

Wherein, the logarithmic viscosity number of said polyester is 0.60-0.72dL/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 95-115 ℃.

(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 1-98.99mol%,

Iii) 0.01-is less than 15mol% terepthaloyl moietie;

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

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

Wherein logarithmic viscosity number 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

Wherein the Tg of polyester is 85-120 ℃.

(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 Tg of polyester is 85-120 ℃; Randomly, wherein before the said polyester or during add one or more branching agents.

(a) dicarboxylic acid component, it comprises:

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

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

(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%; With

(c) from the 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

Wherein the Tg of polyester is 85-120 ℃.

In one aspect, 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, 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

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

At least a thermo-stabilizer or its reaction product;

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 85-135 ℃.

In one aspect, the film and/or the thin plate that comprise the useful polymer blend of the present invention comprise at least a polycarbonate.

In one aspect, the polymer blend that can be used for film of the present invention and/or thin plate does not comprise polycarbonate.

In one aspect, the polyester that can be used for film of the present invention and/or thin plate comprises the glycol residue less than 15mol%, and for example 0.01-is less than the 15mol% glycol residue.

In one aspect, the polyester that can be used for film of the present invention or thin plate does not comprise glycol residue.

In one aspect, 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.

In one aspect, the polymer blend 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 at least a branching agent.

In one aspect, the polyester that can be used for film of the present invention or thin plate comprises at least a branching agent, and this and the method or the sequence independence that wherein add it.

In one aspect, the polymer blend that can be used for film of the present invention or thin plate prepares by at least a branching agent, and this and the method or the sequence independence that wherein add it.

In one aspect, 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, and the 4-butyleneglycol is processed.In others, 1, ammediol or 1, the 4-butyleneglycol perhaps with array configuration ground, can be used to prepare polyester of the present invention separately.In one aspect of the invention, can be used for suitable-2,2,4 in some useful polyester of the present invention; 4-tetramethyl--1, the molecular fraction of 3-cyclobutanediol are greater than 50mol% or greater than suitable-2,2,4 of 55mol%; 4-tetramethyl--1, the 3-cyclobutanediol is perhaps greater than suitable-2,2 of 70mol%; 4,4-tetramethyl--1,3-cyclobutanediol; Wherein suitable-2,2,4,4-tetramethyl--1,3-cyclobutanediol be with anti--2,2,4,4-tetramethyl--1, and total molecular fraction of 3-cyclobutanediol equals 100mol% altogether.

In one aspect of the invention, can be used for 2,2,4 in some useful polyester of the present invention, 4-tetramethyl--1, the molecular fraction of the isomer of 3-cyclobutanediol is suitable-2,2 of 30-70mol%; 4,4-tetramethyl--1,3-cyclobutanediol or 30-70mol%'s is anti--2,2,4,4-tetramethyl--1,3-cyclobutanediol; Perhaps 40-60mol%'s is suitable-2,2,4,4-tetramethyl--1, anti--2,2 of 3-cyclobutanediol or 40-60mol%; 4,4-tetramethyl--1,3-cyclobutanediol, wherein suitable-2,2,4; 4-tetramethyl--1,3-cyclobutanediol be with anti--2,2,4,4-tetramethyl--1, and total molecular fraction of 3-cyclobutanediol equals 100mol% altogether.

In addition, in one aspect in, in some film of the present invention or thin plate, use these specific polymer blends to minimize and/or eliminated the drying step before melt-processed and/or thermoforming.

In one aspect; The polymer blend that can be used for film of the present invention or thin plate 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.

In one aspect, the polyester that can be used for film of the present invention or thin plate can be unbodied or hemicrystalline.In one aspect, some polyester useful to the present invention possibly have lower percent crystallinity.To useful some polyester of the present invention thereby possibly have unbodied basically form, mean that polyester comprises the unordered basically zone of polymkeric substance.

Description of drawings

Fig. 1 shows the soonest figure of the influence of crystallization half-life of comonomer to modification PCT copolyesters.

Fig. 2 is presented at the middle comonomer of test with notched test piece (ASTM D256,1/8 inch thick, 10 mil otch) to tough brittle transition temperature (T _Bd) the figure of influence.

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

Detailed description and work embodiment through with reference to following certain embodiments of the present invention can more easily understand the present invention.According to the object of the invention, certain embodiments of the present invention are described in the summary of the invention and further and describe hereinafter.Equally, other embodiment of the present invention has been described among this paper.

It is believed that two kind or the combination of more kinds of physicalies of the polyester that can be used for film of the present invention or thin plate described in this paper below for example can having: the second-order transition temperature of high impact, appropriateness, chemical resistant properties, stability to hydrolysis, toughness, low tough brittle transition temperature, good color and the transparency, low density, long crystallization half-life and good processing properties make it be easy to be configured as film or thin plate thus.In some embodiments useful to the present invention; Polyester has two or more the combination of combination and/or said performance of performance of combination and/or good shock strength, thermotolerance and processing characteristics of the particular performances of good shock strength, thermotolerance, chemical resistant properties, density, and these were not considered and are present in the film or thin plate that comprises at least a polyester in the past.

Like what use among this paper, term " polyester " intention comprises " copolyesters " and is interpreted as being meant the synthetic polymer that the reaction through one or more bifunctional carboxylic acids and/or polyfunctional carboxylic acids and one or more difunctionality oxy-compound and/or multifunctional hydroxy compounds prepares.Usually, the bifunctional carboxylic acid can be a dicarboxylicacid, and the difunctionality oxy-compound can be a divalent alcohol, for example glycol (glycol) and glycol (diol).Like what use 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 a hydroxycarboxylic acid, PHB for example, and the difunctionality oxy-compound possibly be the aryl nucleus that has 2 hydroxyl substituents, for example quinhydrones.Like what use among this paper, term " residue " is meant any organic structure that is incorporated into polymkeric substance by corresponding monomer through polycondensation and/or esterification.Like what use among this paper, term " repeating unit " is meant to have through 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; Like what use among this paper; Term dicarboxylicacid intention comprises any verivate of dicarboxylicacid and dicarboxylicacid, 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 reaction process with glycol to prepare polyester.In addition, like what use among the application, term " diacid " comprises the polyfunctional acid, like branching agent.Like what use among this paper; Term " terephthalic acid " intention comprises any verivate of terephthalic acid itself and its residue and terephthalic acid; 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 reaction process with glycol with the preparation polyester.

In one embodiment, terephthalic acid can be used as parent material.In another embodiment, DMT. Dimethyl p-benzenedicarboxylate can be used as parent material.In yet another embodiment, the mixture of terephthalic acid and DMT. Dimethyl p-benzenedicarboxylate can be used as parent material and/or intermediate materials.

The polyester that is used for film of the present invention or thin plate can be prepared with glycol by equal proportion reaction basically and the dicarboxylicacid of corresponding residue that is incorporated in the polyester polymers as them usually.Therefore, can be used for sour residue (100mol%) and glycol (and/or multifunctional hydroxyl mixture) residue (100mol%) that polyester of the present invention can comprise first-class basically mol ratio, make the total mole number of repeating unit equal 100mol%.Therefore, the molar percentage 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 repeating unit.For example,, contain the polyester of 30mol% m-phthalic acid, be meant that polyester comprises the 30mol% isophthalic acid residues in the acid of 100mol% altogether residue based on the total acid residue.Therefore, in every 100mol acid residue, there is the 30mol isophthalic acid residues.In another example,, contain 30mol%2 based on the total diol residue, 2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol is meant that polyester comprises 30mol%2 in 100mol% diol residue altogether, 2,4,4-tetramethyl--1,3-cyclobutanediol residue.Therefore, in every 100mol diol residue, there is 2,2,4 of 30mol, 4-tetramethyl--1,3-cyclobutanediol residue.

In others of the present invention, the Tg that can be used for the polyester of film of the present invention or thin plate can be at least one in the following scope: 85-200 ℃; 85-190 ℃; 85-180 ℃; 85-170 ℃; 85-160 ℃; 85-155 ℃; 85-150 ℃; 85-145 ℃; 85-140 ℃; 85-138 ℃; 85-135 ℃; 85-130 ℃; 85-125 ℃; 85-120 ℃; 85-115 ℃; 85-110 ℃; 85-105 ℃; 85-100 ℃; 85-95 ℃; 85-90 ℃; 90-200 ℃; 90-190 ℃; 90-180 ℃; 90-170 ℃; 90-160 ℃; 90-155 ℃; 90-150 ℃; 90-145 ℃; 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 ℃; 95-140 ℃; 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 ℃; 110-190 ℃; 110-180 ℃; 110-170 ℃; 110-160 ℃; 110-155 ℃; 110-150 ℃; 110-145 ℃; 110-140 ℃; 110-138 ℃; 110-135 ℃; 110-130 ℃; 110-125 ℃; 110-120 ℃; 110-115 ℃; 115-200 ℃; 115-190 ℃; 115-180 ℃; 115-170 ℃; 115-160 ℃; 115-155 ℃; 115-150 ℃; 115-145 ℃; 115-140 ℃; 115-138 ℃; 115-135 ℃; 110-130 ℃; 115-125 ℃; 115-120 ℃; 120-200 ℃; 120-190 ℃; 120-180 ℃; 120-170 ℃; 120-160 ℃; 120-155 ℃; 120-150 ℃; 120-145 ℃; 120-140 ℃; 120-138 ℃; 120-135 ℃; 120-130 ℃; 125-200 ℃; 125-190 ℃; 125-180 ℃; 125-170 ℃; 125-160 ℃; 125-155 ℃; 125-150 ℃; 125-145 ℃; 125-140 ℃; 125-138 ℃; 125-135 ℃; 127-200 ℃; 127-190 ℃; 127-180 ℃; 127-170 ℃; 127-160 ℃; 127-150 ℃; 127-145 ℃; 127-140 ℃; 127-138 ℃; 127-135 ℃; 130-200 ℃; 130-190 ℃; 130-180 ℃; 130-170 ℃; 130-160 ℃; 130-155 ℃; 130-150 ℃; 130-145 ℃; 130-140 ℃; 130-138 ℃; 130-135 ℃; 135-200 ℃; 135-190 ℃; 135-180 ℃; 135-170 ℃; 135-160 ℃; 135-155 ℃; 135-150 ℃; 135-145 ℃; 135-140 ℃; 140-200 ℃; 140-190 ℃; 140-180 ℃; 140-170 ℃; 140-160 ℃; 140-155 ℃; 140-150 ℃; 140-145 ℃; 148-200 ℃; 148-190 ℃; 148-180 ℃; 148-170 ℃; 148-160 ℃; 148-155 ℃; 148-150 ℃; 150-200 ℃; 150-190 ℃; 150-180 ℃; 150-170 ℃; 150-160; 155-190 ℃; 155-180 ℃; 155-170 ℃; With 155-165 ℃.

In others 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: 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; 1-is less than 10mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and, 4-cyclohexanedimethanol greater than 90-99mol%1; 1-9mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 91-99mol%1,4-cyclohexanedimethanol; 1-8mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 92-99mol%1,4-cyclohexanedimethanol; 1-7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 93-99mol%1,4-cyclohexanedimethanol; 1-6mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 94-99mol%1,4-cyclohexanedimethanol; And 1-5mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 95-99mol%1,4-cyclohexanedimethanol; 1-is less than 5mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and, 4-cyclohexanedimethanol greater than 90-99mol%1; Greater than 0.01-10mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 90-be less than 99.99mol%1, the 4-cyclohexanedimethanol; With greater than 0.01-5mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 95-be less than 99.99mol%1, the 4-cyclohexanedimethanol.

In others of the present invention, include but not limited at least a in the following scope combination: 5-less than 50mol%2 for the diol component of the polyester that can be used for film of the present invention or thin plate, 2; 4; 4-tetramethyl--1,3-cyclobutanediol and greater than 50-95mol%1,4-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, and 2,4,4-tetramethyl--1,3-cyclobutanediol and, 4-cyclohexanedimethanol greater than 65-95mol%1; 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 75-90mol%1,4-cyclohexanedimethanol; 10-is less than 50mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and, 4-cyclohexanedimethanol greater than 50-90mol%1; 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, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 65-90mol%1 at the most, 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, 4-cyclohexanedimethanol greater than 75-90mol%1; 14-is less than 50mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50-86mol%1 at the most, 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; 14-25mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-86mol%1,4-cyclohexanedimethanol; 1 5-is less than 50mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and greater than 50-85mol%1 at the most, 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 17-23mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 77-83mol%1,4-cyclohexanedimethanol.

In others 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: 11-99mol%2,2; 4; 4-tetramethyl--1,3-cyclobutanediol and 1-89mol%1,4-cyclohexanedimethanol; 11-95mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-89mol%1,4-cyclohexanedimethanol; 11-90mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-89mol%1,4-cyclohexanedimethanol; 11-85mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-89mol%1,4-cyclohexanedimethanol; 11-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-89mol%1,4-cyclohexanedimethanol, 11-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-89mol%1,4-cyclohexanedimethanol; 11-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-89mol%1,4-cyclohexanedimethanol; 11-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-89mol%1,4-cyclohexanedimethanol; 11-60mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-89mol%1,4-cyclohexanedimethanol; 11-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-89mol%1,4-cyclohexanedimethanol; And 11-50mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-89mol%1,4-cyclohexanedimethanol.

In others 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: 11-is less than 50mol%2; 2,4,4-tetramethyl--1; 3-cyclobutanediol and greater than 50-89mol%1 at the most, 4-cyclohexanedimethanol; 11-45mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-89mol%1,4-cyclohexanedimethanol; 11-40mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-89mol%1,4-cyclohexanedimethanol; 11-35mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-89mol%1,4-cyclohexanedimethanol; 11-30mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-89mol%1,4-cyclohexanedimethanol; 11-25mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-89mol%1,4-cyclohexanedimethanol; 11-20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-89mol%1,4-cyclohexanedimethanol, and 11-15mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-85mol%1,4-cyclohexanedimethanol.

In others 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: 12-99mol%2,2; 4; 4-tetramethyl--1,3-cyclobutanediol and 1-86mol%1,4-cyclohexanedimethanol; 12-95mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-88mol%1,4-cyclohexanedimethanol; 12-90mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-88mol%1,4-cyclohexanedimethanol; 12-85mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-88mol%1,4-cyclohexanedimethanol; 12-86mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 14-88mol%1,4-cyclohexanedimethanol, 12-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-88mol%1,4-cyclohexanedimethanol; 12-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-88mol%1,4-cyclohexanedimethanol; 12-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-88mol%1,4-cyclohexanedimethanol; 12-60mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-88mol%1,4-cyclohexanedimethanol; 12-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-88mol%1,4-cyclohexanedimethanol; And 12-50mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-88mol%1,4-cyclohexanedimethanol;

In others 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: 12-is less than 50mol%2; 2,4,4-tetramethyl--1; 3-cyclobutanediol and greater than 50-88mol%1 at the most, 4-cyclohexanedimethanol; 12-45mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-88mol%1,4-cyclohexanedimethanol; 12-40mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-88mol%1,4-cyclohexanedimethanol; 12-35mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-88mol%1,4-cyclohexanedimethanol; 12-30mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-88mol%1,4-cyclohexanedimethanol; 12-25mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-88mol%1,4-cyclohexanedimethanol; 12-20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-88mol%1,4-cyclohexanedimethanol, and 12-15mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol; And 85-88mol%1, the 4-cyclohexanedimethanol.

In others 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: 13-99mol%2,2; 4; 4-tetramethyl--1,3-cyclobutanediol and 1-87mol%1,4-cyclohexanedimethanol; 13-95mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 5-87mol%1,4-cyclohexanedimethanol; 13-90mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 10-87mol%1,4-cyclohexanedimethanol; 13-85mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-87mol%1,4-cyclohexanedimethanol; 13-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-87mol%1,4-cyclohexanedimethanol, 13-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-87mol%1,4-cyclohexanedimethanol; 13-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-87mol%1,4-cyclohexanedimethanol; 13-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-87mol%1,4-cyclohexanedimethanol; 13-60mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-87mol%1,4-cyclohexanedimethanol; 13-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-87mol%1,4-cyclohexanedimethanol; And 13-50mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-87mol%1,4-cyclohexanedimethanol.

In others 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: 13-is less than 50mol%2; 2,4,4-tetramethyl--1; 3-cyclobutanediol and greater than 50-87mol%1 at the most, 4-cyclohexanedimethanol; 13-45mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 55-87mol%1,4-cyclohexanedimethanol; 13-40mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 60-87mol%1,4-cyclohexanedimethanol; 13-35mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 65-87mol%1,4-cyclohexanedimethanol; 13-30mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-87mol%1,4-cyclohexanedimethanol; 13-25mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-87mol%1,4-cyclohexanedimethanol; 13-20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-87mol%1,4-cyclohexanedimethanol, and 13-15mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol; And 85-87mol%1, the 4-cyclohexanedimethanol.

In others 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: 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; And 14-50mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-86mol%1,4-cyclohexanedimethanol;

In others 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: 14-is less than 50mol%2; 2,4,4-tetramethyl--1; 3-cyclobutanediol and greater than 50-86mol%1 at the most, 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; 14-25mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 75-86mol%1,4-cyclohexanedimethanol; And 14-20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-86mol%1,4-cyclohexanedimethanol.

In others 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: 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; 15-85mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 15-85mol%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; And 15-50mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 50-85mol%1,4-cyclohexanedimethanol.

In others 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: 15-is less than 50mol%2; 2,4,4-tetramethyl--1; 3-cyclobutanediol and greater than 50-85mol%1 at the most, 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 15-20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 80-85mol%1,4-cyclohexanedimethanol.

In others 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: 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; 20-45mol%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.

In others 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: 25-99mol%2,2; 4; 4-tetramethyl--1,3-cyclobutanediol and 1-75mol%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; 25-45mol%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; 25-30mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 70-75mol%1,4-cyclohexanedimethanol.

In others 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: 35-80mol%2,2; 4; 4-tetramethyl--1,3-cyclobutanediol and 20-65mol%1,4-cyclohexanedimethanol; 37-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-63mol%1,4-cyclohexanedimethanol; 40-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-60mol%1,4-cyclohexanedimethanol; 45-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-55mol%1,4-cyclohexanedimethanol; 50-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-50mol%1,4-cyclohexanedimethanol; Greater than 50-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-be less than 50mol%1, the 4-cyclohexanedimethanol; 55-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-45mol%1,4-cyclohexanedimethanol; 60-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-40mol%1,4-cyclohexanedimethanol; 65-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-35mol%1,4-cyclohexanedimethanol; 70-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-30mol%1,4-cyclohexanedimethanol; 40-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-60mol%1,4-cyclohexanedimethanol; 45-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-55mol%1,4-cyclohexanedimethanol; 50-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-50mol%1,4-cyclohexanedimethanol; 55-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-45mol%1,4-cyclohexanedimethanol; 60-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-40mol%1,4-cyclohexanedimethanol; 65-75mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 25-35mol%1,4-cyclohexanedimethanol; 40-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-60mol%1,4-cyclohexanedimethanol; 45-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-55mol%1,4-cyclohexanedimethanol; 50-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-50mol%1,4-cyclohexanedimethanol; Greater than 50-99mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 1-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-80mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 20-be less than 50mol%1, the 4-cyclohexanedimethanol; 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; 55-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-45mol%1,4-cyclohexanedimethanol; 60-70mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 30-40mol%1,4-cyclohexanedimethanol; 40-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-60mol%1,4-cyclohexanedimethanol; 40-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-60mol%1,4-cyclohexanedimethanol; 40-is less than 45mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol and, 4-cyclohexanedimethanol greater than 55-60mol%1; 45-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-55mol%1,4-cyclohexanedimethanol; Greater than 50-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-be less than 50mol%1, the 4-cyclohexanedimethanol; 50-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-50mol%1,4-cyclohexanedimethanol; 55-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-45mol%1,4-cyclohexanedimethanol; 40-60mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-60mol%1,4-cyclohexanedimethanol; 45-60mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 40-55mol%1,4-cyclohexanedimethanol; 45-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-55mol%1,4-cyclohexanedimethanol; Greater than 45-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol, 45-be less than 55mol%1, the 4-cyclohexanedimethanol; And 46-55mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 45-54mol%1,4-cyclohexanedimethanol; And 46-65mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol and 35-54mol%1,4-cyclohexanedimethanol.

Except above-mentioned listed glycol, the polyester that can be used for the polymer blend of film of the present invention or thin plate also can be by 1, ammediol, 1,4-butyleneglycol or the preparation of its mixture.

Except above-mentioned listed glycol; The polyester that can be used for the polymer blend of film of the present invention or thin plate also can be by 1; Ammediol, 1; The preparation of 4-butyleneglycol or 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.In addition or alternatively, the polyester that can be used for film of the present invention or thin plate can be by 1, ammediol or 1, and 4-butyleneglycol or the preparation of its mixture also can be prepared with at least a following amount by 1,4 cyclohexane dimethanol: 0.1-99mol%; 0.1-95mol%; 0.1-90mol%; 0.1-85mol%; 0.1-80mol%; 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%; 5-70mol%; 5-60mol%; 5-50mol%; 5-40mol%; 5-35mol%; 5-30mol%; 5-25mol%; 5-20mol%; And5-15mol%; 5-10mol%; 10-99mol%; 10-95mol%; 10-90mol%; 10-85mol%; 10-80mol%; 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%; 20-70mol%; 20-60mol%; 20-50mol%; 20-40mol%; 20-35mol%; 20-30mol%; And 20-25mol%.

For certain embodiments of the 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/tetrachloroethane: 0.10-1.2dL/g at 25 ℃ in concentration; 0.10-1.1dL/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; 0.20-1.2dL/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; 0.35-1.2dL/g; 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; 0.35-0.90dL/g; 0.35-0.85dL/g; 0.35-0.80dL/g; 0.35-0.75dL/g; 0.35-less than 0.75dL/g; 0.35-0.72dL/g; 0.35-0.70dL/g; 0.35-less than 0.70dL/g; 0.35-0.68dL/g; 0.35-less than 0.68dL/g; 0.35-0.65dL/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; 0.40-0.90dL/g; 0.40-0.85dL/g; 0.40-0.80dL/g; 0.40-0.75dL/g; 0.40-less than 0.75dL/g; 0.40-0.72dL/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; 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 0.42-0.90dL/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; Greater than 0.42-0.72dL/g; Greater than 0.42-less than 0.70dL/g; Greater than 0.42-0.68dL/g; Greater than 0.42-less than 0.68dL/g; With greater than 0.42-0.65dL/g.

For certain embodiments of the 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/tetrachloroethane: 0.45-1.2dL/g at 25 ℃ in concentration; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; 0.45-0.95dL/g; 0.45-0.90dL/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; 0.45-less than 0.70dL/g; 0.45-0.68dL/g; 0.45-less than 0.68dL/g; 0.45-0.65dL/g; 0.50-1.2dL/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; 0.50-0.90dL/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; 0.50-less than 0.70dL/g; 0.50-0.68dL/g; 0.50-less than 0.68dL/g; 0.50-0.65dL/g; 0.55-1.2dL/g; 0.55-11dL/g; 0.55-1dL/g; 0.55-less than 1dL/g; 0.55-0.98dL/g; 0.55-0.95dL/g; 0.55-0.90dL/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; 0.55-less than 0.70dL/g; 0.55-0.68dL/g; 0.55-less than 0.68dL/g; 0.55-0.65dL/g; 0.58-1.2dL/g; 0.5 8-1.1dL/g; 0.58-1dL/g; 0.58-less than 1dL/g; 0.58-0.98dL/g; 0.58-0.95dL/g; 0.58-0.90dL/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; 0.58-less than 0.70dL/g; 0.58-0.68dL/g; 0.58-less than 0.68dL/g; 0.58-0.65dL/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 0.76dL/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.

The polymer blend that expection can be used for film of the present invention or thin plate can have at least one and at least one of the monomeric scope that is used for compsn described in this paper in the scope of logarithmic viscosity number described herein, except as otherwise noted.Also the expection polymer blend that can be used for film of the present invention or thin plate can have at least one and at least one of the monomeric scope that is used for compsn described in this paper in the scope of Tg described herein, except as otherwise noted.Also the expection polymer blend that can be used for film of the present invention or thin plate can have at least one of the monomeric scope that is used for compsn described at least one and this paper in the scope of at least one in the scope of Tg described herein, logarithmic viscosity number described herein, except as otherwise noted.

For the polyester that can be used for film of the present invention or thin plate of expectation, cis/trans 2,2,4,4-tetramethyl--1, the mol ratio of 3-cyclobutanediol is owing to pure form or its mixture separately can change.In certain embodiments, cis and/or trans 2,2,4,4-tetramethyl--1, the molecular fraction of 3-cyclobutanediol 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 40-60mol% cis and 60-40mol% are trans; Perhaps 50-70mol% trans with the 50-30mol% cis; Perhaps trans or 60-70mol% cis of 50-70mol% cis and 50-30% and 30-40mol% are trans; Perhaps greater than 70mol% cis and trans less than 30mol%; Cis and trans-2,2,4 wherein, 4-tetramethyl--1, the summation of the molecular fraction of 3-cyclobutanediol equals 100mol%.The mol ratio of cis/trans 1,4 cyclohexane dimethanol can be at following range: 50/50-0/100, for example, and 40/60-20/80.

In certain embodiments, terephthalic acid or its ester, DMT. Dimethyl p-benzenedicarboxylate for example, the perhaps mixture of terephthalic acid and its ester has constituted 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 constitute part or all the dicarboxylic acid component who is used to form polyester of the present invention, and its concentration is 70mol% at least; As 80mol% at least; At least 90mol%, 95mol%, 99mol% or 100mol% at least at least.In certain embodiments, can use the polyester of terephthalic acid so that obtain the high impulse strength performance with higher amount.With regard to the purpose of present disclosure, the interchangeable in this article use of term " terephthalic acid " and " DMT. Dimethyl p-benzenedicarboxylate ".In one embodiment, DMT. Dimethyl p-benzenedicarboxylate is to be used to prepare to the dicarboxylic acid component's of the useful polyester of the present invention a part or all.In all embodiments, can use 70-100mol%; Or 80-100mol%; Or 90-100mol%; Or 99-100mol%; Or the terephthalic acid of 100mol% and/or DMT. Dimethyl p-benzenedicarboxylate and/or its mixture.

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%, 20mol%, 10mol%, 5mol% or one or more modified aromatic dicarboxylicacid of 1mol% at the most at the most at the most at the most.Another embodiment comprises 0mol% modified aromatic dicarboxylicacid.Therefore; If exist; Expect that the amount of one or more modified aromatic dicarboxylicacid can comprise for example one or more modified aromatic dicarboxylicacid of 0.01-30mol%, 0.01-20mol%, 0.01-10mol%, 0.01-5mol% or 0.01-1mol% from the above-mentioned endpoint value extension of any of these.In one embodiment, can be used for modified aromatic dicarboxylicacid 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 symmetric.The instance that can be used for modified aromatic dicarboxylicacid of the present invention include but not limited to m-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 1,4-, 1,5-, 2,6-, 2, the 7-naphthalic acid with anti--4,4 '-stilbene dioctyl phthalate and ester thereof.In one embodiment, m-phthalic acid is this modified aromatic dicarboxylicacid.

The carboxyl acid component that can be used for the polyester of film of the present invention or thin plate can further be used 10mol% at the most; 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 propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and dodecanedioic acid come modification.Some embodiment also can comprise 0.01mol% or more, like 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,, expect that the amount of one or more modification aliphatic dicarboxylic acids can be extended from the above-mentioned endpoint value of any of these, comprise for example 0.01-10mol% and 0.1-10mol% if exist.Total molecular fraction of dicarboxylic acid component is 100mol%.

The ester that can use terephthalic acid and other modification dicarboxylicacid or their corresponding esters and/or salt replace dicarboxylicacid.The suitable instance of dicarboxylic ester includes but not limited to the ester of dimethyl-, diethylammonium, dipropyl, di-isopropyl, dibutyl and phenylbenzene.In one embodiment, said ester is selected from least a in following: methyl, ethyl, propyl group, sec.-propyl and phenylester.

1,4 cyclohexane dimethanol 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%.

The 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 2,2,4,4-tetramethyl--1, the modification glycol of 3-cyclobutanediol or 1,4 cyclohexane dimethanol; 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, like 0.1mol% or more, and 1mol% or more, 5mol% or more, perhaps 10mol% or more one or more modification glycol.Therefore,, expect that the amount of one or more modification glycol can be extended from the above-mentioned endpoint value of any of these, comprise for example 0.01-15mol% and 0.1-10mol% if exist.

The useful modification glycol of the polyester that can be used for film of the present invention or thin plate is meant except that 2,2,4,4-tetramethyl--1, the glycol outside 3-cyclobutanediol and the 1,4 cyclohexane dimethanol, and can comprise 2-16 carbon atom.The instance of suitable modification glycol is including, but not limited to terepthaloyl moietie, glycol ether, 1,2-Ucar 35,1, ammediol, NSC 6366,1,4-butyleneglycol, 1,5-pentanediol, 1,6-pinakon, p-Xylol glycol or its mixture.In one embodiment, the modification glycol is a terepthaloyl moietie.In another embodiment, the modification glycol includes but not limited to 1, ammediol and/or 1,4-butyleneglycol.In another embodiment, get rid of terepthaloyl moietie as the modification glycol.In another embodiment, get rid of 1, ammediol and 1, the 4-butyleneglycol is as the modification glycol.In another embodiment, get rid of 2 as the modification glycol.Polyester and/or the polycarbonate useful to the polymer blend of film of the present invention or thin plate; Respectively based on total molecular fraction 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 a plurality of carboxyl substituent, hydroxyl substituent or its combination.In certain embodiments, can be before the polyester and/or during and/or add branched monomer or branching agent afterwards.Therefore, the polyester that can be used for film of the present invention or thin plate can be linear or branched.Polycarbonate also possibly be linear or branched.In certain embodiments, can be before the polycarbonate polymerization and/or during and/or add branched monomer or branching agent afterwards.

The instance of branched monomer includes but not limited to polyfunctional acid or polyfunctional alcohol, for example trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, Hydrocerol A, tartrate, 3-hydroxyl pentanedioic 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 acid 1,2-anhydride, pyromellitic acid dianhydride, glycerine, Sorbitol Powder, 1; 2,6-hexanetriol, tetramethylolmethane, trimethylolethane and/or trimesic acid.Can branched monomer be added in the pet reaction mixture, perhaps with enriched material form and polyester blend, like for example USP 5,654,347 and 5,696, described in 176, its disclosure about branched monomer is introduced this paper as a reference.

The TA DSC 2920 that the second-order transition temperature (Tg) that can be used for the polyester of film of the present invention or thin plate is to use Thermal Analyst Instruments is with the determination of scan rate of 20 ℃/min.

To the useful polyester of the present invention can be unbodied or hemicrystalline.In one embodiment, " amorphous " polyester 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, crystallization half-life at 170 ℃ greater than 1000 minutes.In another embodiment of the present invention, to crystallization half-life of the useful polyester of the present invention at 170 ℃ greater than 10,000 minutes.Like what use among this paper, can use the crystallization half-life of polyester the well-known method of those skilled in the art to measure.For example, the crystallization half-life of polyester, t1/2, can through 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 can be performed such: through polymkeric substance is exposed to temperature T _Max, and subsequently it is cooled to desired temperatures.Can sample be remained on desired temperatures through hot platform subsequently, measure transmittance simultaneously over time.At first, sample can be visually transparent, has high transmission rate, and becomes opaque along with the sample crystallization.Be the time of transmittance half between initial transmittance and final 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 compsn, absolute T _MaxTemperature is different.For example can PCT be heated to above certain temperature of 290 ℃ with the fusion domain.

, improving crystallization half-life aspect (being that polymkeric substance reaches half the required time of its maximum percent crystallinity) with shown in Figure 1 like the table 1 of embodiment, 2,2,4,4-tetramethyl--1,3-cyclobutanediol are than other comonomer, and be more effective like terepthaloyl moietie and m-phthalic acid.Through reducing the crystallization rate of PCT, promptly improve crystallization half-life, can make amorphous goods like extrude, injection moulding etc. through methods known in the art based on modification PCT.As shown in table 1, these materials can show than higher second-order transition temperature of other modification PCT copolyesters and lower density.

For some embodiment of the present invention, the polyester of film of the present invention or thin plate can demonstrate toughness and the processing characteristics bonded improves.For example, beat all is that the logarithmic viscosity number that reduces the polyester that can be used for film of the present invention or thin plate a little causes easier melt viscosity of processing, and keeps the good physicals of polyester simultaneously, for example toughness and thermotolerance.

Based on terephthalic acid, terepthaloyl moietie and 1; Improve 1 in the copolyesters of 4-cyclohexanedimethanol; The content of 4-cyclohexanedimethanol can improve toughness, and said toughness can be measured through tough brittle transition temperature in like the notched izod shock strength test of being measured by ASTM D256.It is believed that it is owing to the flexible of 1,4 cyclohexane dimethanol in the copolyesters and conformation performance take place that this toughness is improved through reducing tough brittle transition temperature with 1,4 cyclohexane dimethanol.It is believed that 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is incorporated among the PCT, has improved toughness through reducing tough brittle transition temperature, like the table 2 of embodiment with shown in Figure 2.

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, like what on the rotation melt rheometer, measure at 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 20,000 pools, like what on the rotation melt rheometer, measure at 1 radian per second at 290 ℃.

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 ℃.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, like what on the rotation melt rheometer, measure at 1 radian per second at 290 ℃.The viscosity that with the radian per second is unit is relevant with processing characteristics.When its processing temperature is measured, typical polymers has the viscosity less than 10000 pools, like what measure at 1 radian per second.Generally not in processed polyesters more than 290 ℃.Generally at 290 ℃ of processing polycarbonate.At 290 ℃, the viscosity of typical 12 melt flow rate(MFR) polycarbonate under 1 radian per second is 7000 pools.

In one embodiment, the polyester of film of the present invention or thin plate demonstrates the good notch toughness on thick section.The described notched izod shock strength of ASTM D256 is to measure a kind of domestic method of flexible.In one embodiment; The polyester that can be used for film of the present invention or thin plate demonstrates 23 ℃ of shock strengths with at least 150J/m (3ft-lb/in) of 10-mil otch in the thick strip of 3.2mm (1/8-inch), and film of the present invention or thin plate demonstrate the notched izod shock strength at 23 ℃ of (400J/m) at least 7.5ft-lb/in that in the thick strip of 3.2mm (1/8-inch), measure according to ASTM D256 with 10-mil otch; In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod shock strength at 23 ℃ of 1000J/m at least (18ft-lb/in) that in the thick strip of 3.2mm (1/8-inch), measure according to ASTM D256 with 10-mil otch.In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod shock strength at 23 ℃ of 150J/m at least (3ft-lb/in) that in the thick strip of 6.4mm (1/4-in), measure according to ASTM D256 with 10-mil otch; In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod shock strength at 23 ℃ of (400J/m) at least 7.5ft-lb/in that in the thick strip of 6.4mm (1/4-in), measure according to ASTM D256 with 10-mil otch; In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod shock strength at 23 ℃ of 1000J/m at least (18ft-lb/in) that in the thick strip of 6.4mm (1/4-in), measure according to ASTM D256 with 10-mil otch.

In another embodiment; To film of the present invention or some useful polyester of thin plate; With when-5 ℃ are measured, in the thick strip of 1/8-in, compare according to the notched izod shock strength that ASTM D256 measures with 10-mil otch, the notched izod shock 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 of the present invention 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 shock strength.

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

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.

In one embodiment, use the gradient column density at 23 ℃, the polyester that can be used for film of the present invention or thin plate can demonstrate at least a with lower density: 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.

In one embodiment, the polyester of 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 polyester that can be used for film of the present invention or thin plate and polycarbonate (including but not limited to bisphenol-a polycarbonate) blend, then blend can be visually transparent.

The polyester that can be used for film of the present invention or thin plate has one or more following performances.In other embodiments, 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).

In one embodiment, can be used for the polyester of film of the present invention or thin plate and/or the polymer blend of film of the present invention or thin plate, contain or do not contain toning agent, can have colour L ^*, a ^*And b ^*, it can be to use the Inc. by Hunter Associates Lab, Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures.The color measurenent value is at polyester granules or the MV of the value of measuring on 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 luminance 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 b that can be used for the polyester of 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.

In some embodiments, use the polymer blend that can be used for film of the present invention or thin plate to minimize and/or eliminated the drying step before melt-processed and/or thermoforming.

Can have any moisture content though can be used for the polyester of film of the present invention or thin plate, in one embodiment, their moisture content can be the gross weight of the polyester before the melt-processed of 0.02-1.0wt%.

In certain embodiments, the polyester that before melt-processed, can be used for film of the present invention or thin plate through ordinary method 60 ℃ of-100 ℃ of dryings was less than 2 hours.

The polyester that can be used for film of the present invention or thin plate can be through already known processes preparation in the document, for example through the technology in homogeneous solution, through the ester exchange process in the melt with through two-phase interface technology.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 dicarboxylicacid 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 USP 3,772,405, the disclosure of this method is introduced this paper as a reference.

In another aspect, the present invention relates to be used to produce method to the useful polyester of film of the present invention or thin plate.Said method comprises: (I) in the presence of catalyzer, comprise 150-240 ℃ of heating and can be used for any time that the monomeric mixture of the useful polyester of the present invention is 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.

The appropriate catalyst that is used for this method is including, but not limited to organic zinc or tin compound.Using such catalyzer is well-known in the art.The instance that can be used for catalyzer of the present invention includes but not limited to zinc acetate, three (2 ethyl hexanoic acid) butyl tin, dibutyltin diacetate and/or dibutyl tin oxide.Other catalyzer 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 metal with based on the weight of final polymkeric substance.This method can be carried out with the mode of intermittent process or successive processes.

Usually, step (I) can be carried out up to 50wt% or more 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol reacts.Step (I) can be carried out under pressure, and pressure range is that barometric point is to 100psig.As the combine term " reaction product " that uses of the polyester useful catalysts that can be used for film of the present invention or thin plate being meant and using catalyzer and be used to prepare polycondensation or the product of esterification between the additive of spawn and catalyzer and any other type of any monomeric polycondensation or esterification of polyester with any.

Usually, step (II) and step (III) can be carried out simultaneously.These steps can be carried out through methods known in the art, and for example through reaction mixture is placed under the pressure, pressure range is that 0.002psig is to being lower than barometric point, perhaps through on mixture, being blown into hot nitrogen.

The invention still further relates to blend to the useful polymkeric substance of film of the present invention or thin plate.Said blend comprises: (a) at least a above-mentioned polyester of 5-95wt%; (b) at least a polymeric constituent of 5-95wt%.

The suitable instance of polymeric constituent includes but not limited to; Nylon; Be different from those other polyester described in this paper; Nylon, polymeric amide is like the ZYTEL

from DuPont; Be different from those the polyester described in this paper; PS; Polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer; Polymethylmethacrylate; Acrylic copolymer gathers (ether-imide) like ULTEM

(gathering (ether-imide), available from GeneralElectric); Ppe is as gathering (2; 6-dimethyl-phenylate) or polyphenyl ether/styrene blend such as NORYL 1000

(gather (2; 6-dimethyl-phenylate) and the blend of polystyrene resin, available from General Electric); Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Gather (ester-carbonic ether); Polycarbonate such as LEXAN (polycarbonate is available from General Electric); Polysulfones; Polysulfones ether; With aromatic dihydroxy compound gather (ether-ketone) or any other mixture at prepolymer.Blend can be through conventional treatment process preparation known in the art, like melt blending or solution blending.In one embodiment, polycarbonate is not present in the polymer blend that can be used for film of the present invention or thin plate.If polycarbonate is used for can be used for the blend of the polymer blend of 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 polycarbonate eliminating and comprise polycarbonate.

Can prepare according to currently known methods film of the present invention or the useful polycarbonate of thin plate, for example through making dihydroxy aromatic compounds and carbonate precursor such as phosgene, haloformate or carbonic ether, molecular weight regulator, acid acceptor and catalyst reaction.The method that is used to prepare polycarbonate is known in the art and for example is described in USP 4,452, and in 933, wherein the disclosure about polycarbonate is incorporated herein this paper as a reference.

The instance of suitable carbonate precursor including, but not limited to, carbonyl bromide, carbonyl chloride 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.

The instance of suitable molecular weight regulator includes but not limited to, phenol, hexalin, methyl alcohol, alkylated phenol such as octyl phenol, p-tert-butylphenol etc.In one embodiment, molecular weight regulator is phenol or alkylated phenol.

Acid acceptor possibly be organic or examples of inorganic acceptors.The appropriate organic acceptor can be tertiary amine and including, but not limited to, such as materials such as pyridine, triethylamine, xylidene(s), Tributylamines.Examples of inorganic acceptors can be oxyhydroxide, carbonate, supercarbonate or the phosphoric acid salt of basic metal or earth alkali metal.

Operable catalyzer comprises but is not limited to, help usually monomer and phosgene polymeric those.Appropriate catalyst includes but not limited to; Tertiary amine such as triethylamine, tripropyl amine, N; The N-xylidene(s), quaternary ammonium compound such as tetraethylammonium bromide, cetyltriethylammonium bromide, four n-heptyl ammonium iodides, four n-propyl bromination ammoniums, tetramethyl ammonium chloride, TMAH, tetrabutylammonium iodide, benzyl trimethyl ammonia chloride and quaternary phosphonium compound such as normal-butyl three phenyl phosphonium bromides and first base three phenyl phosphonium bromides.

The polycarbonate useful to the polymer blend of film of the present invention or thin plate possibly be copolyestercarbonates also, as is described in the following 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 USP is introduced this paper as a reference.

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

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 typical additives such as tinting material, dyestuff, releasing agent, fire retardant, softening agent, nucleator, stablizer (including but not limited to UV stabilizer, thermo-stabilizer and/or its reaction 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 instance that can be used for the typical commercially available impact modifier that gets of the present invention is including, but not limited to, ethylene/propene terpolymer; Functionalised polyolefin, as comprise those of methyl acrylate and/or SY-Monomer G; The segmented copolymer impact modifier of styrene-based; Core/shell type impact modifier with various acrylic acid seriess.For example, through through applying dura mater or adding in the body, can the UV additive be attached in the goods through coextrusion cap rock.Also expect the resistates of this additive as a part to the useful polymer blend of film of the present invention or thin plate.

The polyester that can be used for film of the present invention or thin plate can comprise at least a chain extension agent.Suitable chain extension agent is including, but not limited to, multifunctional (including but not limited to difunctionality) isocyanic ester, and the multi-functional epoxyization thing comprises for example epoxy (line style) phenolic varnish, and phenoxy resin.In certain embodiments, chain extension agent can add at the end of polymerization process or after polymerization process.If after polymerization process, add, can introduce chain extension agent through compounding in conversion process such as injection moulding or during extruding or interpolation.The consumption of chain extension agent can depend on used concrete monomeric composition and desired physicals and change, but is generally the about 10wt% of about 0.1wt%-, and the about 5wt% of preferably about 0.1-is based on the gross weight to the useful polyester of film of the present invention or thin plate.

Thermo-stabilizer is a stable compound to the useful polyester of film of the present invention or thin plate during polyester manufacturing and/or post polymerization; Include but not limited to P contained compound, its include but not limited to phosphoric acid, phosphorous acid, phosphonic acids, phospho acid, phosphonous acid with and various ester and salt.These may reside in the polymer blend that can be used for film of the present invention or thin plate.Ester can be (ester) of alkyl, branched-chain alkyl, substituted alkyl, two sense alkyl, alkyl oxide, aryl and substituted aryl.In one embodiment, the number that is present in the ester group in the specific P contained compound can change at the most based on the peak that number allowed that is present in the hydroxyl the used thermo-stabilizer from zero.Term " thermo-stabilizer " intention comprises its reaction product.As being meant thermo-stabilizer with the term " reaction product " that uses that the useful thermo-stabilizer of the polymer blend that can be used for film of the present invention or thin plate is combined and being used to prepare polycondensation or the product of esterification between the additive of spawn and catalyzer and any other type of polycondensation or esterification between any monomer of polyester.

Strongthener can be used in the useful compsn of the present invention.Strongthener can include but not limited to carbon filament, silicate, mica, clay, talcum, titanium oxide, wollastonite, sheet glass, granulated glass sphere and fiber and polymer fiber and its combination.In one embodiment, strongthener is glass such as fiberglass long filament, the mixture of glass and talcum, glass and mica and glass and polymer fiber.

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 the polymer blend described in this paper.

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.

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.

The method that polyester is configured as film and/or thin plate is well-known in the art.The instance 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.

Potential examples of articles by film and/or thin plate preparation includes but not limited to monodirectional tension film, biaxially oriented film, shrinkable film (no matter being unidirectional or two-way stretch), 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 products, painting products, layer compound, laminated product and/or multilayer film or thin plate.

The instance of plate process film is including, but not limited to nameplate, membrane switch facing; Point of purchase indicating meter; 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 indicating meter; The automobile switchboard; Automobile gear speed change mechanism panel; The control indicating meter or the guard signal of fascia; Facing on the household implements, dial plate or indicating meter; Facing on the washing machine, dial plate or indicating meter; Facing on the dishwasher, dial plate or indicating meter; The keypad of electronics; The keypad of mobile telephone, PDA (laptop computer) or remote controllers; The indicating meter of electronics; The indicating meter of portable electronics such as phone and PDA; Move or the panel and the shell of standard telephone; Logo on the electronics; Logo with Cell phone.

Multilayer film or thin plate are meant the thin plate that is extruded into by a plurality of layers of section of forming that connect by vertical rib each other.The instance of multilayer film or thin plate includes but not limited to greenhouse and commercial canopy.

Comprise instance to the extrudate of the useful polyester of the present invention including, but not limited to the film that is used for the plate process application, outdoor sign, skylight, multilayer film, the plastics film that is used for resin glass layer compound and liquid-crystal display (LCD) film, liquid-crystal display (LCD) film includes but not limited to be used for diffuser thin plate, compensation film and the protective film of LCD.

Like what use among this paper, abbreviation " wt " is meant " weight ".

Following examples further illustrate method that polymer blend how can be used for film and/or thin plate and manufacturing polymer blend with and assessment, and intention is to 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

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

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.

The glycol content of compsn and cis/trans ratios are measured through proton nuclear magnetic resonance (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); Perhaps, use 60/40 (wt/wt) phenol/tetrachloroethane for the oligopolymer sample, and for locking the deuterate chloroform that the peak adds.Through 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 in polymkeric substance and oligopolymer, exists.

Crystallization half-life, t1/2, be through 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.Through 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, maybe PCT be heated to above certain temperature of 290 ℃ with the fusion domain.

Density is to use the gradient column density 23 ℃ of mensuration.

The melt viscosity of reporting among this paper is measured through using Rheometrics DynamicAnalyzer (RDA II).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 through model known in the art.This step is realized by RheometricsDynamic Analyzer (RDA II) software automatically.

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.

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 in the fragility mode of being represented by ASTM D256, lost efficacy.

The colour of reporting among this paper is to use the Inc. by Hunter Associates Lab, Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures.The color measurenent value is at polyester granules or the MV 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.

In addition, use the Carver press 240 ℃ of compression moulding 10-mil film.

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.

Below abbreviation is applicable to whole work embodiment and accompanying drawing:

Embodiment 1

Present embodiment illustrates 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol is more effective than terepthaloyl moietie 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.

Be described below, prepare multiple copolyesters.These copolyesters all adopt the 200ppm dibutyl tin oxide as Preparation of Catalyst, with minimize 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.

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

Is increment at 140-200 ℃ with 10 ℃, carries out the measurement from the crystallization half-life of melt, and measuring result is recorded in the table 1.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.

Data presentation, 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than terepthaloyl moietie 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)

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 DMT. Dimethyl p-benzenedicarboxylate in the table 1; If do not describe dicarboxylicacid, then it is the 100mol% DMT. Dimethyl p-benzenedicarboxylate.

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 a terepthaloyl moietie

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)

, improving crystallization half-life aspect (being that polymkeric substance reaches half the required time of its maximum percent crystallinity) with shown in Figure 1 like table 1,2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than other comonomer such as terepthaloyl moietie and m-phthalic acid.Through the crystallization rate (improving crystallization half-life) that reduces PCT, can be through 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 demonstrate than higher second-order transition temperature of other modification PCT copolyesters and lower density.

The preparation of the polyester shown in the table 1 is described below.

Embodiment 1A

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

The mixture of 56.63g DMT. Dimethyl p-benzenedicarboxylate, 55.2g 1,4 cyclohexane dimethanol, 14.16g dimethyl isophthalate and 0.0419g dibutyl tin oxide is placed 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short still 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 290 ℃ with temperature in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, in ensuing 5 minutes, applied vacuum gradually then 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate residue, 20mol% glycol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (32/68 cis/trans).

The mixture of 77.68g DMT. Dimethyl p-benzenedicarboxylate, 50.77g 1,4 cyclohexane dimethanol, 27.81g terepthaloyl moietie and 0.0433g dibutyl tin oxide is placed 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short still 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 210 ℃ with temperature 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate 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).

With 77.68g DMT. Dimethyl p-benzenedicarboxylate, 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 still column.This polyester is to prepare with the said similar mode of embodiment 1A.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate residue, 40mol% dimethyl isophthalate residue and 100mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (28/72 cis/trans).

The mixture of 42.83g DMT. Dimethyl p-benzenedicarboxylate, 55.26g 1,4 cyclohexane dimethanol, 28.45g dimethyl isophthalate and 0.0419g dibutyl tin oxide is placed 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short still 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 290 ℃ with temperature in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, in ensuing 5 minutes, applied vacuum gradually then 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate residue, 40mol% glycol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

The mixture of 81.3g DMT. Dimethyl p-benzenedicarboxylate, 42.85g 1,4 cyclohexane dimethanol, 34.44g terepthaloyl moietie and 0.0419g dibutyl tin oxide is placed 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short still 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 210 ℃ with temperature 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate 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).

With 77.4g DMT. Dimethyl p-benzenedicarboxylate, 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 still 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.The content of flask also was elevated to 260 ℃ with temperature 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate 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).

With 77,68g DMT. Dimethyl p-benzenedicarboxylate, 48.46g 1,4 cyclohexane dimethanol, 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 still 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.The content of flask also was elevated to 260 ℃ with temperature 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 present embodiment illustrated target consists of 100mol% DMT. Dimethyl p-benzenedicarboxylate 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).

With 77.68g DMT. Dimethyl p-benzenedicarboxylate, 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 still column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.When the experiment beginning, stirring velocity is set at 200RPM.The content of flask also was elevated to 260 ℃ with temperature 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, a setting point is 100mmHg, and also stirring velocity is dropped to 100RPM.In ensuing 5 minutes, again the flask internal pressure is reduced to a 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 a 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

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.

Be 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 31/69.Copolyesters based on terepthaloyl moietie 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 said 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.

With material be injection molded into strip and subsequently otch carry out izod test.Obtain the notched izod shock strength with temperature variation, equally it is reported in the table 2.

For given sample, izod impact strength experiences big change (major transition) in little TR.For example, based on the izod impact strength of the copolyesters of 38mol% terepthaloyl moietie 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%.

Data show, with the T that improves PCT _BdTerepthaloyl moietie 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)

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% DMT. Dimethyl p-benzenedicarboxylate.NA=is unavailable.Wherein: B is 2,2,4 for terepthaloyl moietie C, 4-tetramethyl--1,3-cyclobutanediol (50/50 cis/trans)

Embodiment 3

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.The polyester of preparation comprises 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue in the present embodiment.

Be described below, prepare based on DMT. Dimethyl p-benzenedicarboxylate, 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, 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).

With material be injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out the 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 moulding strip.Melt viscosity at 290 ℃ of measurement pellets.

Table 3

Various performance compilations to some useful polyester of the present invention

NA=is unavailable.

Embodiment 3A

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.241b (49.71gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 14.34lb (45.21gram-mol) 1; 4-cyclohexanedimethanol and 4.58lb (14.44gram-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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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.270 ℃ with 90mmHg under 1 hour hold-time after, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to＜1mmHg.Reaction mixture is remained under 290 ℃ of pressure with＜1mmHg power up to whisking appliance no longer raise (70 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 through the 6-mm sieve.The logarithmic viscosity number of polymkeric substance is 0.736dL/g, and Tg is 104 ℃.NMR analysis revealed polymkeric substance comprises 85.4mol%1,4-cyclohexanedimethanol residue and 14.6mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=78.20, a ^*=-1.62, and b ^*=6.23.

Embodiment 3B-embodiment 3D

Polyester described in the embodiment 3B-embodiment 3D is according to preparing with the similar program of the said program of embodiment 3A.The composition and the performance of this polyester are shown in Table 3.

Embodiment 3E

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.24lb (49.71gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 12.61lb (39.77gram-mol) 1; 4-cyclohexanedimethanol, 6.30lb (19.88gram-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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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.270 ℃ with 90mmHg under 1 hour hold-time after, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to＜1mmHg.Reaction mixture 290 ℃ with the maintenance 60 minutes down of the pressure of＜1mmHg.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 through the 6-mm sieve.The logarithmic viscosity number of polymkeric substance is 0.715dL/g, and Tg is 110 ℃.X-ray analysis shows that polyester has 223ppm tin.NMR analysis revealed polymkeric substance comprises 78.6mol%1,4-cyclohexanedimethanol residue and 21.4mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=76.45; a ^*=-1.65; And b ^*=6.47.

Embodiment 3F

Polyester described in the embodiment 3F is according to preparing with the similar program of the said program of embodiment 3A.The composition and the performance of this polyester are shown in Table 3.

Embodiment 3H

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.24lb (49.71gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 12.61lb (39.77gram-mol) 1; 4-cyclohexanedimethanol, 6.30lb (19.88gram-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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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.270 ℃ with 90mmHg under 1 hour hold-time after, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to＜1mmHg.Reaction mixture 290 ℃ with the maintenance 12 minutes down of the pressure of＜1mmHg.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 through the 6-mm sieve.The logarithmic viscosity number of polymkeric substance is 0.590dL/g, and Tg is 106 ℃.NMR analysis revealed polymkeric substance comprises 77.1mol%1,4-cyclohexanedimethanol residue and 22.9mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=83.27; a ^*=-1.34; And b ^*=5.08.

Embodiment 3I

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.24lb (49.71gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 12.61lb (39.77gram-mol) 1; 4-cyclohexanedimethanol, 6.30lb (19.88gram-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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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.270 ℃ with 90mmHg under 1 hour hold-time after, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to 4mmHg.Reaction mixture 290 ℃ with the maintenance 30 minutes down of the pressure of 4mmHg.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 through the 6-mm sieve.The logarithmic viscosity number of polymkeric substance is 0.531dL/g, and Tg is 105 ℃.NMR analysis revealed polymkeric substance comprises 76.9mol%1,4-cyclohexanedimethanol residue and 23.1mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=80.42, a ^*=-1.28, and b ^*=5.13.

Embodiment 3J

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.24lb (49.71gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 12.61lb (39.77gram-mol) 1; 4-cyclohexanedimethanol, 6.30lb (19.88gram-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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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.270 ℃ with 90mmHg under 1 hour hold-time after, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to 4mmHg.When reaction mixture temperature is 290 ℃ and pressure when being 4mmHg, use nitrogen immediately the pressure of pressurized vessel to be increased to 1 normal atmosphere.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that through the 6-mm sieve.The logarithmic viscosity number of polymkeric substance is 0.364dL/g, and Tg is 98 ℃.NMR analysis revealed polymkeric substance comprises 77.5mol%1,4-cyclohexanedimethanol residue and 22.5mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L ^*=77.20, a ^*=-1.47, and b ^*=4.62.

Embodiment 4

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.The polyester of preparation comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

Be described below, prepare based on DMT. Dimethyl p-benzenedicarboxylate, 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol (3 1/69 cis/trans), it has composition shown in the 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).

With material be injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out the 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 moulding strip.Melt viscosity at 290 ℃ of measurement pellets.

Table 4

NA=is unavailable.

Embodiment 4A

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.24lb (49.71 gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 11.82lb (37.28gram-mol) 1; 4-cyclohexanedimethanol and 6.90lb (21.77gram-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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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.270 ℃ with 90mmHg under 1 hour hold-time after, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to＜1mmHg.Reaction mixture is remained under 290 ℃ of pressure with＜1mmHg power up to whisking appliance 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 through the 6-mm sieve.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 4B

The polyester of embodiment 4B is according to preparing with the similar program of the said program of embodiment 4A.The composition and the performance of this polyester are shown in Table 4.

Embodiment 5

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.

Be described below, prepare based on DMT. Dimethyl p-benzenedicarboxylate, 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, it has composition shown in the table 5 and performance.In the table 5 at the most the remainder of the diol component of the polyester of 100mol% be 1,4 cyclohexane dimethanol (31/69 cis/trans).

With polyester be injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out the izod impact test.Obtain the notched izod shock strengths and be reported in the table 5 at 23 ℃.Measure density, Tg and the crystallization half-life of moulding strip.Melt viscosity at 290 ℃ of measurement pellets.

Table 5

NA=is unavailable.

Embodiment 5A

In the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin; Make 21.24lb (49.71gram-mol) DMT. Dimethyl p-benzenedicarboxylate, 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 whisking appliance, carry out.Along with whisking appliance turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture 250 ℃ with the down maintenance 2 hours of 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 290 ℃ of pressure with 2mmHg power up to whisking appliance 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 through the 6-mm sieve.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 6-Comparative Examples

Present embodiment has shown the data that are used for contrast material, and it is shown in Table 6.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% terepthaloyl moietie.PETG is the Eastar 6763 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 31mol% cyclohexanedimethanol (CHDM) and 69mol% terepthaloyl moietie.PCTG is the Eastar DN001 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 62mol% cyclohexanedimethanol (CHDM) and 38mol% terepthaloyl moietie.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 6

The various performance compilations of some commercial polymer

NA=is unavailable

Embodiment 7

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.The polyester of preparation comprises 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue in the present embodiment.

Embodiment 7A-embodiment 7G

With DMT. Dimethyl p-benzenedicarboxylate, 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 drop capabilities.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stirs 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 accomplished, 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 breaks away from glass flask up to it.In flask, stirring polymer material with medium level cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that through the 3mm sieve.This program is changed the copolyesters that is described below that consists of 20mol% with productive target.

Like the said measurement logarithmic viscosity number of above " measuring method " part.As the measuring method part is said in front, measures forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.

Embodiment 7H-embodiment 7Q

These polyester are through carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is carried out in (CTR) reactor drum that heats up continuously.CTR is equipped with single shaft impeller blade whisking appliance, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.Reactor drum be filled with 777g (4mol) DMT. Dimethyl p-benzenedicarboxylate 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).It is 100% output that heating jacket manually is set.Adopt the Camile program control system to make a 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 drum 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.

In polycondensation, the 500ml round-bottomed flask load the 150g that has an appointment more than prepared oligopolymer.This flask equipped has stainless steel whisking appliance 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 whisking appliance apart from complete upset of drag (positioned one full turn from the flask bottom) as.The temperature/pressure by the Camile software control/stirring speed sequence for each embodiment is reported in the following table.

The Camile sequence of embodiment 7H and embodiment 7I

The Camile sequence of embodiment 7N-embodiment 7Q

The Camile sequence of embodiment 7K and embodiment 7L

The Camile sequence of embodiment 7J and embodiment 7M

From flask, reclaim 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 is tested as follows: in 60/40 (wt/wt) phenol/tetrachloroethane, measure logarithmic viscosity number, measure levels of catalysts (Sn) and obtain color (L through transmitted spectrum through XRF 25 ℃ of concentration with 0.5g/100ml ^*, a ^*, b ^*).Obtaining polymkeric substance through 1H NMR forms.Use Rheometrics MechanicalSpectrometer (RMS-800) sample to be carried out the test of thermostability and melt viscosity.

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 with almost linear mode.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.

Table 7

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

NA=is unavailable

Embodiment 8

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.The polyester of preparation comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

With DMT. Dimethyl p-benzenedicarboxylate, 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 drop capabilities.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stirs 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, 1RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is accomplished, 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 breaks away from glass flask up to it.In flask, stirring polymer material with medium level cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that through the 3mm sieve.This program is changed the copolyesters that is described below that consists of 32mol% with productive target.

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 with almost linear mode.

Table 8

NA=is unavailable

Embodiment 9

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.The polyester of preparation comprises 2,2,4 in the present embodiment, 4-tetramethyl--1, and 3-cyclobutanediol residue, its quantity is: 40mol% or more.

Embodiment A-C

These polyester are through carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is carried out in (CTR) reactor drum that heats up continuously.CTR is equipped with single shaft impeller blade whisking appliance, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.Reactor drum be filled with 777g DMT. Dimethyl p-benzenedicarboxylate, 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).It is 100% output that heating jacket manually is set.Adopt the Camile program control system to make a 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 drum 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.

In polycondensation, the 500ml round-bottomed flask be filled with 150g more than prepared oligopolymer.This flask equipped has stainless steel whisking appliance 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 whisking appliance apart from complete upset of drag (positioned one full turn from the flask bottom) as.The temperature/pressure by the Camile software control/stirring speed sequence for these embodiment is reported in the following table, only if followingly explain in addition.

The Camile sequence of polycondensation

The Camile sequence of embodiment A and B

For Embodiment C, the identical sequence in the use in the table, but the time in the stage 7 is 50 minutes.

Embodiment D-K and M

The polyester of these embodiment such as above for the said preparation of embodiment A-C, still, for embodiment A D-K and M, the amount of target tin is 150ppm in final polymkeric substance.Following table has been described the temperature/pressure by the Camile software control/stir speed (S.S.) sequence for these embodiment.

The Camile sequence of embodiment D, F and H

For embodiment D, whisking appliance is transferred to 25rpm in the stage 7, carries out 95 minutes.

The Camile sequence of embodiment E

For embodiment K, the identical sequence in the use in the table, but the time in the stage 7 is 75 minutes.

The Camile sequence of embodiment G

The Camile sequence of example I

The Camile sequence of embodiment J

Embodiment L and K

With DMT. Dimethyl p-benzenedicarboxylate, 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 drop capabilities.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stirs 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 accomplished, 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 breaks away from glass flask up to it.In flask, stirring polymer material with medium level cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that through the 3mm sieve.This program is changed the copolyesters that is described below that consists of 45mol% with productive target.

Table 9

NA=is unavailable

Embodiment 10

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.

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 10

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

NA=is unavailable

Embodiment 11-Comparative Examples

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

With 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 11.Adopt this polyester of 300ppm dibutyl tin oxide preparation.2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol are 65/35.

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 11.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), and is as shown in Figure 1.

Table 11

Crystallization half-life (minute)

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

Embodiment 12

Use 3.5 inches single screw extrusion machine productions to comprise the thin plate of polyester, said 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 prepares.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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following, 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 13

Use 3.5 inches single screw extrusion machine productions to comprise the sheet material of polyester, said 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 prepares.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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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 14-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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 15-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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.

NR=is Unrecorded

Embodiment 16-Comparative Examples

The 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following, 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 17-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following, 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 18-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following, 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.

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

Embodiment 19-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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 20-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 the condition shown in following; 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 21-Comparative Examples

Use 1.25 inches mixed blends that single screw extrusion machine production is made up of 60wt%Teijin L-1250 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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 22-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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 23-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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 24-Comparative Examples

Use 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 stayed reach different time in the baking oven, so that measure of the influence of thin plate temperature, shown in following table part quality.Part quality stretches through 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 in this group experiment, obtains.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 the condition shown in following; 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.

The 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, compares with the commercially available polyester that gets, and polyester of the present invention provides tangible advantage.

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 said 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 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,

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

Total molecular fraction of diol component is 100mol%;

Wherein logarithmic viscosity number is 0.60-0.75dL/g, is that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With

The Tg of wherein said polyester is 85-120 ℃;

Wherein said polyester is according to ASTM D256, under 23 ℃, adopts notched izod shock strength that the thick strip of 1/8-inch of band 10-mil otch measures to be 7.5ft-lb/in at least;

The melt viscosity of wherein said polyester is measured with 1 radian per second at 290 ℃ on the rotation melt rheometer less than 10,000 pools;

Wherein said polymer blend does not contain polycarbonate.

2. the film of claim 1 or thin plate, wherein logarithmic viscosity number is 0.65-0.75dL/g, or 0.60-0.72dL/g.

3. the film of claim 1 or thin plate, wherein this diol component comprises 15-25mol%2, and 2,4; 4-tetramethyl--1,3-cyclobutanediol residue and 75-85mol%1,4-cyclohexanedimethanol residue; Or wherein this diol component comprises 17-23mol%2,2,4; 4-tetramethyl--1,3-cyclobutanediol residue and 77-83mol%1,4-cyclohexanedimethanol residue.

4. the film of claim 1 or thin plate, the Tg of wherein said polyester is 90-115 ℃, or 85-115 ℃, or 95-115 ℃.

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

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

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

8. the film of claim 6 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 99-100mol%.

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

10. the film of claim 8 or thin plate, wherein said polyester comprises 1 of 0.01-10mol%, ammediol residue, 1,4-butyleneglycol residue or its mixture.

11. the film of claim 1 or thin plate, wherein said polyester comprises glycol residue, or wherein said polyester comprises the glycol residue of 0.01-15mol%, or the glycol residue of 0.01-10mol%.

12. 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.

13. 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 70-30mol%; 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol residue.

14. the film of claim 13 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 60-40mol%; 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol residue.

15. 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: gather (ether imide), ppe, polyphenyl ether/styrene blend, polystyrene resin, polyphenylene sulfide, polyphenylene sulfide/sulfone, polysulfones; Polysulfones ether and gather (ether-ketone).

16. the film of claim 1 or thin plate, wherein said polyester comprises the residue of at least a branching agent.

17. the film of claim 16 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 diacid or diol residue.

18. the film of claim 1 or thin plate, the melt viscosity of wherein said polyester are measured with 1 radian per second on the rotation melt rheometer at 290 ℃ less than 6,000 pools.

19. the film of claim 1 or thin plate, wherein said polyester had 170 ℃ of crystallization half-lives greater than 5 minutes, or wherein said polyester had 170 ℃ of crystallization half-lives greater than 50 minutes.

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

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

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

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

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

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

26. the goods of claim 25 wherein according to ASTM D256, under 23 ℃, adopt the thick strip test of 1/4-in of band 10-mil otch, the notched izod shock strength of polyester is 10ft-lbs/in at least.

27. a liquid-crystal display film, it comprises the film or the thin plate of claim 1.

28. the liquid-crystal display film of claim 27, wherein the liquid-crystal display film is the diffuser thin plate, or wherein the liquid-crystal display film is a compensation film.