CN101193943A - 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 - Google Patents
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 Download PDFInfo
- Publication number
- CN101193943A CN101193943A CNA2006800205626A CN200680020562A CN101193943A CN 101193943 A CN101193943 A CN 101193943A CN A2006800205626 A CNA2006800205626 A CN A2006800205626A CN 200680020562 A CN200680020562 A CN 200680020562A CN 101193943 A CN101193943 A CN 101193943A
- Authority
- CN
- China
- Prior art keywords
- film
- thin plate
- polyester
- tetramethyl
- cyclobutanediol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
- External Artificial Organs (AREA)
- Materials For Medical Uses (AREA)
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
The cross reference of related application
[0001] the application requires the right of priority of following application according to 35 U.S.C. § 119 (e): U.S. Provisional Application 60/691,567 (applying date is on June 17th, 2005), U.S. Provisional Application 60/731,454 (applying date is on October 28th, 2005), U.S. Provisional Application 60/731,389 (applying date is on October 28th, 2005), U.S. Provisional Application 60/739,058 (applying date is on November 22nd, 2005), U.S. Provisional Application 60/738,869 (applying date is on November 22nd, 2005), U.S. Provisional Application 60/750,692 (applying date is on December 15th, 2005), U.S. Provisional Application 60/750,693 (applying date is on December 15th, 2005), U.S. Provisional Application 60/750,682 (applying date is on December 15th, 2005) and U.S. Provisional Applications 60/750,547 (applying date is on December 15th, 2005), all these documents are incorporated herein by reference with its full content.
Technical field
[0002] relate generally to of the present invention comprises the film and/or the thin plate of polymer blend, and this polymer blend comprises at least a polyester, and it is by terephthalic acid, its ester or its mixture; 2,2,4,4-tetramethyl--1,3-cyclobutanediol; Make with 1,4 cyclohexane dimethanol, and have certain combination of logarithmic viscosity number and second-order transition temperature (Tg).These films and/or thin plate 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
[0003] poly terephthalic acid 1, and 4-hexamethylene two methylene esters (PCT) are a kind of only based on the polyester of terephthalic acid and 1,4 cyclohexane dimethanol, and is known in the art and be commercially available getting.This polyester is when the crystallization promptly from melt of when cooling, this make by methods known in the art as extrude, injection moulding and similar approach be difficult to form amorphous goods.Slack-off for the crystallization rate that makes PCT, can prepare the copolyesters that contains other dicarboxylic acid or glycol such as m-phthalic acid or ethylene glycol.These ethylene glycol or ask that the PCT of phthalic acid modification is also known in the art and be commercially available getting.
[0004] a kind of copolyesters commonly used that is used to produce film, thin plate and moulded product is made by terephthalic acid, 1,4 cyclohexane dimethanol and ethylene glycol.Though these copolyesters can be used in the application that many terminals use, when competent modification ethylene glycol is contained in the preparation so that when long crystallization half-life is provided, they demonstrate deficiency at the aspect of performance as second-order transition temperature and shock strength etc.For example, have sufficiently long crystallization half-life by terephthalic acid, 1, the copolyesters that 4-cyclohexanedimethanol and ethylene glycol are made provides amorphous products, and than composition disclosed herein, these products demonstrate higher tough brittle transition temperature and lower second-order transition temperature.
[0005] 4,4 '-polycarbonate (bisphenol-a polycarbonate) of isopropylidene biphenol has been used as the alternative of polyester known in the art and has been well-known engineering moulded plastic.Bisphenol-a polycarbonate is a kind of transparent high performance plastics with good physicals such as form-stability, high heat resistance and good shock strength.Though bisphenol-a polycarbonate has many good physicalies, its higher melt viscosity causes the melt processability of difference and polycarbonate to show the chemical resistant properties of going on business.It also is difficult to thermoforming in addition.
[0006] also described usually in the art and contained 2,2,4,4-tetramethyl--1, the polymkeric substance of 3-cyclobutanediol.Yet usually, these polymkeric substance demonstrate high logarithmic viscosity number, high melt viscosity and high glass-transition temperature, make that used not competent manufacturing of equipment or post polymerization processed these materials in the industry.
[0007] thereby, need to comprise the film and/or the thin plate of polymer blend in the art, described polymer blend comprises at least a polyester, it has the combination that is selected from following at least a two or more 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
[0008] it is believed that have logarithmic viscosity number and/or second-order transition temperature certain in conjunction with, (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 made by polyester known in the art and polycarbonate of being better than 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 are similar to aspect thermotolerance by those of polycarbonate, and still can process on standard industry equipment.
[0009] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,
Wherein total molecular fraction of dicarboxylic acid component be 100mol% and
Total molecular fraction of diol component is 100mol%; With
Wherein 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 ℃.
[0010] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,
Wherein total molecular fraction of dicarboxylic acid component be 100mol% and
Total molecular fraction of diol component is 100mol%; With
Wherein 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 ℃.
[0011] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 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 described 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 ℃.
[0012] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein the logarithmic viscosity number of polyester is 0.50-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With
The Tg of wherein said polyester is 85-120 ℃.
[0013] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
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 ℃.
[0014] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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) 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 described 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; Wherein the Tg of polyester is 95-115 ℃.
[0015] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein the logarithmic viscosity number of polyester is 0.50-1.2dL/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 ℃.
[0016] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0017] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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) 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 described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0018] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0019] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0020] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 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 described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0021] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this 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 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 70-90mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0022] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, this 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 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0023] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 75-85mol%,
Total molecular fraction of wherein said dicarboxylic acid component is 100mol%, and total molecular fraction of described diol component is 100mol%; With
Wherein, the logarithmic viscosity number of described 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 ℃.
[0024] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 1-98.99mol%,
Iii) 0.01-is less than 15mol% ethylene glycol;
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 ℃.
[0025] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 1-99mol%,
Wherein total molecular fraction of dicarboxylic acid component be 100mol% and
Total molecular fraction of diol component is 100mol%; With
Wherein 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 ℃; Randomly, wherein before the described polyester or during add one or more branching agents.
[0026] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises at least a polyester, described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most;
(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 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 ℃.
[0027] in one aspect in, the present invention relates to a kind of film or thin plate, it comprises polymer blend, this polymer blend comprises:
At least a polyester, it 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%; 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 ℃.
[0028] in one aspect in, the film and/or the thin plate that comprise the useful polymer blend of the present invention comprise at least a polycarbonate.
[0029] in one aspect in, the polymer blend that can be used for film of the present invention and/or thin plate does not comprise polycarbonate.
[0030] in one aspect in, the polyester that can be used for film of the present invention and/or thin plate comprises the glycol residue less than 15mol%, for example 0.01-is less than the 15mol% glycol residue.
[0031] in one aspect in, the polyester that can be used for film of the present invention or thin plate does not comprise glycol residue.
[0032] in one aspect in, the polymer blend that can be used for film of the present invention or thin plate comprises at least a thermo-stabilizer or its reaction product.
[0033] in one aspect in, 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.
[0034] in one aspect in, 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.
[0035] in one aspect in, 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.
[0036] in one aspect in, the polyester that can be used for film of the present invention or thin plate is not by separately or with 1 of array configuration, ammediol or 1, the 4-butyleneglycol is made.In others, 1, ammediol or 1, the 4-butyleneglycol separately or with array configuration ground, can be used to prepare polyester of the present invention.In one aspect of the invention, can be used for suitable-2,2 in some useful polyester of the present invention, 4,4-tetramethyl--1, the molecular fraction of 3-cyclobutanediol is greater than 50mol% or greater than suitable-2 of 55mol%, 2,4,4-tetramethyl--1,3-cyclobutanediol or greater than suitable-2 of 70mol%, 2,4,4-tetramethyl--1,3-cyclobutanediol; Wherein suitable-2,2,4,4-tetramethyl--1,3-cyclobutanediol and anti--2,2,4,4-tetramethyl--1, total molecular fraction of 3-cyclobutanediol equals 100mol% altogether.
[0037] 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 are suitable-2,2,4 of 30-70mol%, 4-tetramethyl--1, anti--2,2 of 3-cyclobutanediol or 30-70mol%, 4,4-tetramethyl--1,3-cyclobutanediol, perhaps 40-60mol%'s suitable-2,2,4,4-tetramethyl--1, anti--2,2 of 3-cyclobutanediol or 40-60mol%, 4,4-tetramethyl--1,3-cyclobutanediol, wherein suitable-2,2,4,4-tetramethyl--1,3-cyclobutanediol and anti--2,2,4,4-tetramethyl--1, total molecular fraction of 3-cyclobutanediol equals 100mol% altogether.
[0038] 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 drying step before melt-processed and/or thermoforming.
[0039] in one aspect in, 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.
[0040] in one aspect in, 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 may have lower degree of crystallinity.To useful some polyester of the present invention thereby may have unbodied basically form, mean that polyester comprises the unordered basically zone of polymkeric substance.
Description of drawings
[0041] Fig. 1 shows the figure of comonomer to the influence of the fastest crystallization half-life of modification PCT copolyesters.
[0042] 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.
[0043] 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
[0044] can more easily understand the present invention by detailed description and work embodiment with reference to following certain embodiments of the present invention. According to purpose of the present invention, certain embodiments of the present invention are described in the summary of the invention and further and are described hereinafter. Other embodiment of the present invention has been described equally, herein.
[0045] it is believed that the described polyester that can be used for film of the present invention or thin plate herein can have the combination of two or more for example following physical properties: the glass transition temperature of high impact, appropriateness, chemical resistance, hydrolytic stability, toughness, low tough brittle transition temperature, good color and the transparency, low-density, long crystallization half-life and good processing characteristics 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 combination of the combination of performance of the combination of performance of uniqueness of good impact strength, heat resistance, chemical resistance, density and/or good impact strength, heat resistance and processing characteristics and/or described performance, and being considered before these is present in the film or thin plate that comprises at least a polyester.
[0046] as used in this article, term " polyester " intention comprises " copolyesters " and is interpreted as referring to the synthetic polymer that the reaction by one or more bifunctional carboxylic acids and/or polyfunctional carboxylic acids and one or more difunctionality hydroxy compounds and/or multifunctional hydroxy compounds prepares. Usually, the bifunctional carboxylic acid can be dicarboxylic acids, and the difunctionality hydroxy compounds can be dihydroxylic alcohols, for example glycol (glycol) and glycol (diol). As using among the application, term " glycol " includes but not limited to glycol, glycol and/or multifunctional hydroxy compounds, for example branching agent. Perhaps, the bifunctional carboxylic acid can be hydroxycarboxylic acid, P-hydroxybenzoic acid for example, and the difunctionality hydroxy compounds may be the aryl nucleus with 2 hydroxyl substituents, for example quinhydrones. As used in this article, term " residue " refers to be incorporated into by polycondensation and/or esterification by corresponding monomer any organic structure of polymer. As used in this article, term " repetitive " refers to have by the dicarboxylic acid residue of carbonyl oxygen base group bonding and the organic structure of diol residue. Therefore, for example, dicarboxylic acid residue can be derived from dicarboxylic acid monomer or its relevant carboxylic acid halides, ester, salt, acid anhydrides or its mixture. Therefore, as used in this article, term dicarboxylic acids intention comprises any derivative of dicarboxylic acids and dicarboxylic acids, comprises carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture that it is relevant, and they can be used for course of reaction with glycol with the preparation polyester. In addition, as using among the application, term " diacid " comprises the polyfunctional acid, such as branching agent. As used in this article, term " terephthalic acid (TPA) " intention comprises any derivative of terephthalic acid (TPA) itself and its residue and terephthalic acid (TPA), comprise carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture or its residue that it is relevant, they can be used for course of reaction with glycol with the preparation polyester.
[0047] in one embodiment, terephthalic acid (TPA) can be used as parent material. In another embodiment, dimethyl terephthalate (DMT) can be used as parent material. In yet another embodiment, the mixture of terephthalic acid (TPA) and dimethyl terephthalate (DMT) can be used as parent material and/or intermediate materials.
[0048] polyester that is used for film of the present invention or thin plate can and be incorporated in the polyester polymers dicarboxylic acids and glycol preparation as their corresponding residue by equal proportion reaction basically usually. Therefore, can be used for polyester of the present invention and can comprise basically sour residue (100mol%) and glycol (and/or the multifunctional hydroxyl mixture) residue (100mol%) of equimolar ratio, so that the total mole number of repetitive equals 100mol%. Therefore, the 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 repetitive. For example, based on the total acid residue, contain the polyester of 30mol% M-phthalic acid, refer to that polyester comprises the 30mol% isophthalic acid residues in the acid of 100mol% altogether residue. Therefore, in every 100mol acid residue, there is the 30mol isophthalic acid residues. In another example, based on the total diol residue, contain 30mol% 2,2,4,4-tetramethyl-1, the polyester of 3-cyclobutanediol refers to that polyester comprises 30mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue in 100mol% diol residue altogether. Therefore, in every 100mol diol residue, there is 2,2,4 of 30mol, 4-tetramethyl-1,3-cyclobutanediol residue.
[0049] in other side 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 ℃; 138 ℃ of 85-; 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 ℃; 138 ℃ of 90-; 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 ℃; 135 ℃ of 95-; 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 ℃; 170 ℃ of 100-; 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 ℃; 200 ℃ of 110-; 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 ℃.
[0050] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 1-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-99mol%1,4-cyclohexanedimethanol; 1-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-99mol%1,4-cyclohexanedimethanol; 1-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-99mol%1,4-cyclohexanedimethanol; 1-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-99mol%1,4-cyclohexanedimethanol; 1-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-99mol%1,4-cyclohexanedimethanol, 1-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-99mol%1,4-cyclohexanedimethanol; 1-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-99mol%1,4-cyclohexanedimethanol; 1-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-99mol%1,4-cyclohexanedimethanol; 1-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-99mol%1,4-cyclohexanedimethanol; 1-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-99mol%1,4-cyclohexanedimethanol; 1-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-99mol%1,4-cyclohexanedimethanol; 1-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-99mol%1,4-cyclohexanedimethanol; 1-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-99mol%1,4-cyclohexanedimethanol; 1-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-99mol%1,4-cyclohexanedimethanol; 1-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-99mol%1,4-cyclohexanedimethanol; 1-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-99mol%1,4-cyclohexanedimethanol; 1-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-99mol%1,4-cyclohexanedimethanol; 1-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-99mol%1,4-cyclohexanedimethanol; 1-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-99mol%1,4-cyclohexanedimethanol; 1-is less than 10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 90-99mol%1,4-cyclohexanedimethanol; 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%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 90-99mol%1,4-cyclohexanedimethanol; 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.
[0051] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 5-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-95mol%1, the 4-cyclohexanedimethanol; 5-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-95mol%1,4-cyclohexanedimethanol; 5-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-95mol%1,4-cyclohexanedimethanol; 5-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-95mol%1,4-cyclohexanedimethanol; 5-is less than 35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65-95mol%1,4-cyclohexanedimethanol; 5-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-95mol%1,4-cyclohexanedimethanol; 5-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-95mol%1,4-cyclohexanedimethanol; 5-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-95mol%1,4-cyclohexanedimethanol; 5-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-95mol%1,4-cyclohexanedimethanol; 5-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-90mol%1,4-cyclohexanedimethanol; 10-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-90mol%1,4-cyclohexanedimethanol; 10-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-90mol%1,4-cyclohexanedimethanol; 10-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-90mol%1,4-cyclohexanedimethanol; 10-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-90mol%1,4-cyclohexanedimethanol; 10-is less than 35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65-90mol%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 greater than 75-90mol%1,4-cyclohexanedimethanol; 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; 1 5-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 17-23mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77-83mol%1,4-cyclohexanedimethanol.
[0052] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0053] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0054] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM;
[0055] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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; With the 85-88mol% 1,4-CHDM.
[0056] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0057] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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; With the 85-87mol% 1,4-CHDM.
[0058] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 14-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-86mol%1,4-cyclohexanedimethanol; 14-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-86mol%1,4-cyclohexanedimethanol; 14-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-86mol%1,4-cyclohexanedimethanol; 14-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-86mol%1,4-cyclohexanedimethanol; 14-86mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 14-86mol%1,4-cyclohexanedimethanol, 14-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-86mol%1,4-cyclohexanedimethanol; 14-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-86mol%1,4-cyclohexanedimethanol; 14-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-86mol%1,4-cyclohexanedimethanol; 14-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-86mol%1,4-cyclohexanedimethanol; 14-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-86mol%1,4-cyclohexanedimethanol; And 14-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-86mol%1,4-cyclohexanedimethanol;
[0059] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0060] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0061] in other side of the present invention, include but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0062] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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-CHDM.
[0063] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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.
[0064] in other side of the present invention, includes but not limited at least a in the following scope combination for the diol component of the polyester that can be used for film of the present invention or thin plate: 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%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 55-60mol%1,4-cyclohexanedimethanol; 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; With 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.
[0065] 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 1,3-PD, BDO or the preparation of its mixture.
[0066] 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-butanediol 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 by 1,3-PD or BDO or the preparation of its mixture, also can be prepared with at least a following amount by 1,4-CHDM: 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%.
[0067] 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/tetrachloroethanes: 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.
[0068] 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/tetrachloroethanes: 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.
[0069] 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 scope of described monomer for composition herein 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 scope of described monomer for composition herein 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 and at least one of scope of described monomer for composition herein in the scope of at least one in the scope of Tg described herein, logarithmic viscosity number described herein, except as otherwise noted.
[0070] for the polyester that can be used for film of the present invention or thin plate of expectation, the mol ratio of cis/trans TMCBD is owing to pure form or its mixture separately can change. In certain embodiments, the mole percent of cis and/or trans TMCBD is greater than 50mol% cis and trans less than 50mol%; Perhaps greater than 55mol% cis and trans less than 45mol%; Perhaps 30-70mol% cis and 70-30% are trans; Perhaps 40-60mol% cis and 60-40mol% are trans; The perhaps trans and 50-30mol% cis of 50-70mol%; Perhaps the 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%; Wherein the summation of the mole percent of cis and trans-TMCBD equals 100mol%. The mol ratio of cis/trans 1,4-CHDM can be at following range: 50/50-0/100, for example, and 40/60-20/80.
[0071] in certain embodiments, terephthalic acid (TPA) or its ester, dimethyl terephthalate (DMT) for example, the perhaps mixture of terephthalic acid (TPA) and its ester has consisted of most or all of the dicarboxylic acid component that is used to form the polyester that can be used for film of the present invention or thin plate. In certain embodiments, the terephthalic acid residue can consist of part or all the dicarboxylic acid component who is used to form polyester of the present invention, and its concentration is 70mol% at least, such as 80mol% at least, at least 90mol%, at least 95mol%, at least 99mol% or 100mol%. In certain embodiments, can use the polyester of the terephthalic acid (TPA) with higher amount in order to obtain higher impact strength performance. With regard to the purpose of present disclosure, term " terephthalic acid (TPA) " and " dimethyl terephthalate (DMT) " are used interchangeably in this article. In one embodiment, dimethyl terephthalate (DMT) is for the preparation of to part or all of the dicarboxylic acid component of the useful polyester of the present invention. In all embodiments, can use 70-100mol%; Or 80-100mol%; Or 90-100mol%; Or 99-100mol%; Or the terephthalic acid (TPA) of 100mol% and/or dimethyl terephthalate (DMT) and/or its mixture.
[0072] except the terephthalic acid residue, the dicarboxylic acid component who can be used for the polyester of film of the present invention or thin plate can comprise at the most 30mol%, at the most 20mol%, at the most 10mol%, at the most 5mol% or one or more modified aromatic dicarboxylic acids of 1mol% at the most. Another embodiment comprises 0mol% modified aromatic dicarboxylic acids. Therefore, if present, expect that the amount of one or more modified aromatic dicarboxylic acids can from any these above-mentioned endpoint values extensions, comprise for example one or more modified aromatic dicarboxylic acids of 0.01-30mol%, 0.01-20mol%, 0.01-10mol%, 0.01-5mol% or 0.01-1mol%. In one embodiment, can be used for modified aromatic dicarboxylic acids of the present invention and include but not limited to have those of 20 carbon atoms at the most, and they can be linear, para-orientation or symmetrical. The example that can be used for modified aromatic dicarboxylic acids of the present invention include but not limited to M-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, Isosorbide-5-Nitrae-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid and anti--4,4 '-stilbene dioctyl phthalate and ester thereof. In one embodiment, M-phthalic acid is this modified aromatic dicarboxylic acids.
[0073] carboxyl acid component that can be used for the polyester of film of the present invention or thin plate can further be used at the most 10mol%, for example at the most 5mol% or at the most one or more of 1mol% contain the aliphatic dicarboxylic acid of 2-16 carbon atom, for example malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid come modification. Some embodiment also can comprise 0.01mol% or more, such as 0.1mol% or more, and 1mol% or more, 5mol% or more, perhaps 10mol% or more one or more modification aliphatic dicarboxylic acids. Another embodiment comprises 0mol% modification aliphatic dicarboxylic acid. Therefore, if present, expect that the amount of one or more modification aliphatic dicarboxylic acids can be extended from any these above-mentioned endpoint values, comprise for example 0.01-10mol% and 0.1-10mol%. Total mole percent of dicarboxylic acid component is 100mol%.
[0074] can replace dicarboxylic acids with the ester of terephthalic acid (TPA) and other modification dicarboxylic acids or their corresponding esters and/or salt. The suitable example of dicarboxylic ester includes but not limited to the ester of dimethyl, diethyl, dipropyl, diisopropyl, dibutyl and diphenyl. In one embodiment, described ester is selected from lower at least a: methyl, ethyl, propyl group, isopropyl and phenylester.
[0075] 1,4-CHDM can be cis, trans or its mixture, and for example cis/trans ratios is 60: 40-40: 60. In another embodiment, anti-form-1, the amount of 4-cyclohexanedimethanol can be 60-80mol%.
[0076] diol component of polyester portion that can be used for the polymer blend of film of the present invention or thin plate can comprise 25mol% or still less one or more are not the modification glycol of TMCBD or 1,4-CHDM; In one embodiment, the polyester that can be used for film of the present invention or thin plate can comprise one or more modification glycol less than 15mol%. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise 10mol% or one or more modification glycol still less. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise 5mol% or one or more modification glycol still less. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise 3mol% or one or more modification glycol still less. In another embodiment, the polyester that can be used for film of the present invention or thin plate can comprise the modification glycol of 0mol%. Some embodiment also can comprise 0.01mol% or more, such as 0.1mol% or more, and 1mol% or more, 5mol% or more, perhaps 10mol% or more one or more modification glycol. Therefore, if present, expect that the amount of one or more modification glycol can be extended from any these above-mentioned endpoint values, comprise for example 0.01-15mol% and 0.1-10mol%.
[0077] the useful modification glycol of the polyester that can be used for film of the present invention or thin plate is referred to glycol except TMCBD and 1,4-CHDM, and can comprise 2-16 carbon atom. The example of suitable modification glycol is including, but not limited to ethylene glycol, diethylene glycol (DEG), 1,2-PD, 1,3-PD, neopentyl glycol, BDO, 1,5-PD, 1,6-hexylene glycol, paraxylene glycol or its mixture. In one embodiment, the modification glycol is ethylene glycol. In another embodiment, the modification glycol includes but not limited to 1,3-PD and/or BDO. In another embodiment, get rid of ethylene glycol as the modification glycol. In another embodiment, get rid of 1,3-PD and BDO as the modification glycol. In another embodiment, get rid of NPG as the modification glycol. Polyester and/or the Merlon useful to the polymer blend of film of the present invention or thin plate, respectively based on total mole percent of glycol or diacid residues, can comprise 0-10mol%, the residue of one or more branched monomers of 0.01-5mol%, 0.01-1mol%, 0.05-5mol%, 0.05-1mol% or 0.1-0.7mol% or 0.1-0.5mol% for example, it is also referred to as branching agent in this article, has 3 or more carboxyl substituent, hydroxyl substituent or its combination. In certain embodiments, can before the polyester and/or during and/or add afterwards branched monomer or branching agent. Therefore, the polyester that can be used for film of the present invention or thin plate can be linearity or branch. Merlon also may be linearity or branch. In certain embodiments, can before the polycarbonate polymerization and/or during and/or add afterwards branched monomer or branching agent.
[0078] example of branched monomer includes but not limited to polyfunctional acid or polyfunctional alcohol, such as trimellitic acid, trimellitic anhydride, pyromellitic acid dianhydride, trimethylolpropane, glycerine, pentaerythrite, citric acid, tartaric acid, 3-hydroxyl glutaric acid etc. In one embodiment, the branched monomer residue can comprise 0.1-0.7mol% one or more be selected from following at least a residue: trimellitic anhydride, pyromellitic acid dianhydride, glycerine, D-sorbite, 1,2,6-hexanetriol, pentaerythrite, trimethylolethane and/or trimesic acid. Branched monomer can be added in the pet reaction mixture, perhaps with concentrate form and polyester blend, such as for example United States Patent (USP) 5,654,347 and 5,696, described in 176, its disclosure about branched monomer is incorporated herein by reference.
[0079] glass transition temperature (Tg) that can be used for the polyester of film of the present invention or thin plate is the TA DSC 2920 that uses Thermal Analyst Instruments with the determination of scan rate of 20 ℃/min.
[0080] can be unbodied or hemicrystalline to the useful polyester of the present invention. 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. As used in this article, can measure with the well-known method of those skilled in the art the crystallization half-life of polyester. For example, the crystallization half-life of polyester, t1/2 can measure by the light transmittance of measuring sample along with the time through laser instrument and photoelectric detector on the hot platform of temperature control. This measurement can be performed such: by polymer is exposed to temperature Tmax, and the temperature that subsequently it is cooled to expect. Can sample be remained on the temperature of expectation by hot platform subsequently, measure simultaneously light transmittance over time. At first, sample can be visually transparent, has high transmission rate, and becomes opaque along with the sample crystallization. Be the time of light transmittance half between initial light transmittance and final light transmittance crystallization half-life. TmaxBe defined as the required temperature of fusing sample domain (if having domain). Can before measuring crystallization half-life, sample be heated to TmaxTo nurse one's health this sample. For each composition, absolute TmaxTemperature is different. For example PCT can be heated to above certain temperature of 290 ℃ with the melting domain.
[0081] such as the table 1 of embodiment and shown in Figure 1, improving aspect crystallization half-life (being that polymer reaches half required time of its maximum degree of crystallinity) 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol is than other comonomer, and is more effective such as ethylene glycol and M-phthalic acid. By reducing the crystalline rate of PCT, namely improve crystallization half-life, can make amorphous goods based on modification PCT such as extrude, injection moulding etc. by methods known in the art. As shown in table 1, these materials can show than the higher glass transition temperature of other modification PCT copolyesters and lower density.
[0082] for some embodiment of the present invention, the polyester of film of the present invention or thin plate can demonstrate the improvement that toughness is combined with processing characteristics. For example, the beat all logarithmic viscosity number that is slight reduction can be used for the polyester of film of the present invention or thin plate causes the melt viscosity of easier processing, keeps simultaneously the good physical property of polyester, for example toughness and heat resistance.
[0083] based on terephthalic acid (TPA), ethylene glycol and 1, improve 1 in the copolyesters of 4-cyclohexanedimethanol, the content of 4-cyclohexanedimethanol can improve toughness, and described toughness can be measured by tough brittle transition temperature in such as the notched izod impact strength test of being measured by ASTM D256. It is believed that it is owing to the flexible of 1,4-CHDM in the copolyesters and conformation performance occur that this toughness is improved by reducing tough brittle transition temperature with 1,4-CHDM. It is believed that TMCBD is incorporated among the PCT, improved toughness by reducing tough brittle transition temperature, such as the table 2 of embodiment and shown in Figure 2.
[0084] in one embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 30,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃. In another embodiment, to the melt viscosity of the useful polyester of film of the present invention or thin plate less than 20,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃.
[0085] 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, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃. Viscosity take radian per second as unit is relevant with processing characteristics. When its processing temperature is measured, typical polymers has the viscosity less than 10000 pools, as measuring at 1 radian per second. Generally not in processed polyesters more than 290 ℃. Generally at 290 ℃ of processing Merlon. At 290 ℃, the viscosity of typical 12 melt flow rate (MFR) Merlon under 1 radian per second is 7000 pools.
[0086] 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 impact strength of ASTM D256 is to measure a kind of common method of toughness. In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates 23 ℃ of impact 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 impact strength at 23 ℃ of at least (400J/m) 7.5ft-lb/in that measure according to ASTM D256 with 10-mil otch in the thick strip of 3.2mm (1/8-inch); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least 1000J/m (18ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 3.2mm (1/8-inch). In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least 150J/m (3ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 6.4mm (1/4-in); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least (400J/m) 7.5ft-lb/in that measure according to ASTM D256 with 10-mil otch in the thick strip of 6.4mm (1/4-in); In one embodiment, the polyester that can be used for film of the present invention or thin plate demonstrates the notched izod impact strength at 23 ℃ of at least 1000J/m (18ft-lb/in) that measure according to ASTM D256 with 10-mil otch in the thick strip of 6.4mm (1/4-in).
[0087] in another embodiment, to film of the present invention or some useful polyester of thin plate, with when-5 ℃ are measured, compare according to the notched izod impact strength that ASTM D256 measures in the thick strip of 1/8-in with 10-mil otch, the notched izod impact strength that can demonstrate when measuring for 0 ℃ has increased at least 3% or at least 5% or at least 10% or at least 15%. In addition, some other polyester 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 impact strength.
[0088] in yet another embodiment, the loss that can demonstrate the maintenance of the notched izod impact strength when measuring for 23 ℃ of measuring with 10-mil otch according to ASTM D256 to film of the present invention or some useful polyester of thin plate in the thick strip of 1/8-in is not more than 70%, than the notched izod impact strength of the identical polyester when uniform temp is measured of measuring with 10-mil otch in the thick strip of 1/8-in according to ASTM D256.
[0089] 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.
[0090] 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 1.2 g/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.
[0091] 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 the polyester that can be used for film of the present invention or thin plate and Merlon (including but not limited to bisphenol-a polycarbonate) blend, then blend can be visually transparent.
[0092] 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).
[0093] 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 toner, can have colour L*、a
*And b*, it can be to use by Hunter Associates Lab Inc., Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures. The colour measurement value is the mean value of the value measured at polyester granules or by its injection moulding or the plate of extruding or other object. They are the L by CIE (International Commission on Illumination) (translating)*a
*b
*Colour system is measured, wherein L*Expression brightness coordinate, a*Represent red/green coordinate, b*Expression Huang/blue coordinate. In certain embodiments, the b that can be used for the polyester of film of the present invention or thin plate*Value can be for-10 to less than 10, and L*Value can be 50 to 90. In other embodiments, the 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.
[0094] in some embodiments, use the polymer blend can be used for film of the present invention or thin plate to minimize and/or eliminated drying steps before melt-processed and/or hot forming.
[0095] can have any moisture although can be used for the polyester of film of the present invention or thin plate, in one embodiment, their moisture can be the gross weight of the polyester before the melt-processed of 0.02-1.0wt%.
[0096] in certain embodiments, before melt-processed, can be used for the polyester of film of the present invention or thin plate less than 2 hours by conventional method 60 ℃ of-100 ℃ of dryings.
[0097] can be used for the polyester of film of the present invention or thin plate can be by already known processes preparation in the document, for example by the technique in homogeneous solution, by the ester exchange process in the melt with by two-phase interface technique. Suitable method includes but not limited to make the reaction under the pressure of 100 ℃-315 ℃ temperature and 0.1-760mmHg of one or more dicarboxylic acids and one or more glycol to be enough to form the step of the time of polyester. For the method for producing polyester, referring to United States Patent (USP) 3,772,405, the disclosure of this method is incorporated herein by reference.
[0098] in another aspect, the present invention relates to for the production of the method to the useful polyester of film of the present invention or thin plate. Described method comprises: (I) comprise the time that the mixture that can be used for any monomer to the useful polyester of the present invention is enough to produce initial polyester 150-240 ℃ of heating in the presence of catalyst; (II) initial polyester of heating steps (I) reaches 1-4 hour under 240-320 ℃ of temperature; (III) remove any unreacted glycol.
[0099] is used for the suitable catalyst of the method including, but not limited to organic zinc or tin compound. Using such catalyst is well-known in the art. The example that can be used for catalyst 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 catalyst can include but not limited to based on those of titanium, zinc, manganese, lithium, germanium and cobalt. Catalyst amounts can be 10ppm-20,000ppm or 10-10, and 000 ppm, perhaps 10-5000ppm or 10-1000ppm or 10-500ppm, perhaps 10-300 ppm or 10-250 are based on catalyst metals with based on the weight of final polymer. The method can be carried out in the mode of batch process or continuous process.
[00100] usually, step (I) can be carried out until 50wt% or more TMCBD react. Step (I) can be carried out under pressure, and pressure limit is that atmospheric pressure is to 100psig. As with any the useful catalyst of the polyester that can be used for film of the present invention or thin plate being combined that the term " product " that uses refers to use catalyst and for the preparation of the polycondensation between the additive of the spawn of the polycondensation of any monomer of polyester or esterification and catalyst and any other type or the product of esterification.
[00101] usually, step (II) and step (III) can be carried out simultaneously. These steps can be undertaken by methods known in the art, and for example by reactant mixture is placed under the pressure, pressure limit is that 0.002psig is to being lower than atmospheric pressure, perhaps by being blown into hot nitrogen at mixture.
[00102] the invention still further relates to blend to the useful polymer of film of the present invention or thin plate. Described blend comprises: (a) at least a above-mentioned polyester of 5-95wt%; (b) at least a polymers compositions of 5-95wt%.
[00103] the suitable example of polymers compositions includes but not limited to, nylon is different from described those other polyester herein, nylon, and polyamide is such as the ZYTEL from DuPont; Be different from described those polyester herein; Polystyrene, polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, acrylic acid series copolymer, poly-(ether-acid imide) is such as ULTEM (poly-(ether-acid imide) is available from General Electric); Polyphenylene oxide is such as poly-(2,6-dimethyl phenylate) or polyphenyl ether/styrene blend such as NORYL 1000 (blend of poly-(2,6-dimethyl phenylate) and polystyrene resin is available from General Electric); Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ester); Merlon such as LEXAN (Merlon is available from General Electric); Polysulfones; Polysulfones ether; Poly-(ether-ketone) or any other mixture at prepolymer with aromatic dihydroxy compound. Blend can be by conventional treatment process preparation known in the art, such as melt blending or solution blending. In one embodiment, Merlon is not present in the polymer blend that can be used for film of the present invention or thin plate. If Merlon is for the blend of the polymer blend that can be used for film of the present invention or thin plate, then blend can be visually transparent. Yet, the polymer blend that can be used for film of the present invention or thin plate also expected Merlon eliminating and comprise Merlon.
[00104] can prepare according to known method film of the present invention or the useful Merlon of thin plate, for example by making dihydroxy aromatic compounds and carbonate precursor such as phosgene, haloformate or carbonic ester, molecular weight regulator, acid acceptor and catalyst reaction. Method for the preparation of Merlon is known in the art and for example is described in United States Patent (USP) 4,452, and in 933, wherein the disclosure about the Merlon preparation is incorporated herein this paper as a reference.
[00105] example of suitable carbonate precursor including, but not limited to, carbonyl bromide, phosgene or its mixture; Diphenyl carbonate; Carbonic acid two (halogenophenyl) ester, for example, carbonic acid two (trichlorophenyl) ester, carbonic acid two (tribromo phenyl) ester etc.; Carbonic acid two (alkyl phenyl) ester, for example, carbonic acid two (tolyl) ester; Carbonic acid two (naphthyl) ester; Carbonic acid two (chloronaphthyl, methylnaphthyl) ester or its mixture; Bishaloformate with dihydric phenol.
[00106] example of suitable molecular weight regulator includes but not limited to, phenol, cyclohexanol, methyl alcohol, alkylated phenol such as octyl phenol, p-t-butyl phenol etc. In one embodiment, molecular weight regulator is phenol or alkylated phenol.
[00107] acid acceptor may be organic or examples of inorganic acceptors. Suitable organic acid acceptor can be tertiary amine and including, but not limited to, materials such as pyridine, triethylamine, dimethylaniline, tri-n-butylamine. Examples of inorganic acceptors can be hydroxide, carbonate, bicarbonate or the phosphate of alkali metal or alkaline-earth metal.
[00108] operable catalyst including, but not limited to, usually help those of monomer and phosgene polymerization. Suitable catalyst includes but not limited to, tertiary amine such as triethylamine, tripropyl amine (TPA), N, the N-dimethylaniline, quaternary ammonium compound such as tetraethylammonium bromide, cetyltriethylammonium bromide, four n-heptyl ammonium iodides, four n-pro-pyl bromination ammoniums, tetramethyl ammonium chloride, TMAH, tetrabutylammonium iodide, benzyl trimethyl ammonium chloride and quaternary phosphonium compound such as normal-butyl three phenyl phosphonium bromides and first base three phenyl phosphonium bromides.
[00109] may be copolyestercarbonates also to the useful Merlon of the polymer blend of film of the present invention or thin plate, as be described in the following United States Patent (USP) those: 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484,4,465,820 and 4,981,898; Wherein the disclosure of the relevant copolyestercarbonates of each piece United States Patent (USP) is incorporated herein by reference.
[00110] can be commercially available and/or can prepare by method as known in the art film of the present invention or the useful copolyestercarbonates of thin plate. For example, they can be generally obtain by the mixture reaction that makes at least a dihydroxy aromatic compounds and phosgene and at least a diacid chloride (particularly isophthaloyl chloride, terephthalyl chloride or both).
[00111] in addition, comprise the polymer blend of the polyester that can be used for film of the present invention or thin plate and 0.01-25wt% that polymer blend composition also can comprise the polymer blend gross weight or common additives such as colouring agent, dyestuff, releasing agent, fire retardant, plasticizer, nucleator, stabilizing agent (including but not limited to UV stabilizer, heat stabilizer and/or its product), filler and the impact modifier of 0.01-20wt% or 0.01-15wt% or 0.01-10wt% or 0.01-5wt%. Well-known in the art and the example that can be used for typical commercially available impact modifier of the present invention is including, but not limited to, ethylene/propene terpolymer; Functionalised polyolefin, as comprise those of methyl acrylate and/or GMA; The block copolymer impact modifier of styrene-based; Core/shell type impact modifier with various acrylic acid series. For example, by through applying dura mater or adding in the body through the co-extrusion pressure cap rock, the UV additive can be attached in the goods. Also expect the residue of this additive as the part to the useful polymer blend of film of the present invention or thin plate.
[00112] polyester that can be used for film of the present invention or thin plate can comprise at least a cahin extension agent. Suitable cahin extension agent is including, but not limited to, multifunctional (including but not limited to difunctionality) isocyanates, and multi-functional epoxy's compound comprises for example epoxy (line style) novolaks, and phenoxy resin. In certain embodiments, cahin extension agent can add at the end of polymerization process or after polymerization process. If after polymerization process, add, can introduce cahin extension agent by compounding in conversion process such as injection moulding or during extruding or interpolation. The consumption of cahin extension agent can depend on the composition of used concrete monomer and desired physical property and change, but is generally the about 10wt% of about 0.1wt%-, and the about 5wt% of about 0.1-preferably is based on the gross weight to the useful polyester of film of the present invention or thin plate.
[00113] heat stabilizer is stable compound to the useful polyester of film of the present invention or thin plate between polyester manufacturing and/or rear polymerization period, include but not limited to phosphorus-containing compound, its include but not limited to phosphoric acid, phosphorous acid, phosphonic acids, phosphinic acids, phosphonous acid with and various ester and salt. These may reside in the polymer blend that can be used for film of the present invention or thin plate. Ester can be (ester) of alkyl, branched alkyl, substituted alkyl, two sense alkyl, alkyl ether, aryl and substituted aryl. In one embodiment, the number that is present in the ester group in the specific phosphorus-containing compound can change to the maximum that allows based on the number that is present in the hydroxyl the used heat stabilizer at the most from zero. Term " heat stabilizer " intention comprises its product. As referring to heat stabilizer with the term " product " that uses that the useful heat stabilizer of the polymer blend that can be used for film of the present invention or thin plate is combined and for the preparation of the polycondensation between the additive of the spawn of the polycondensation between any monomer of polyester or esterification and catalyst and any other type or the product of esterification.
[00114] reinforcing material can be used in the useful composition of the present invention. Reinforcing material can include but not limited to carbon filament, silicate, mica, clay, talcum, titanium dioxide, wollastonite, sheet glass, bead and fiber and polymer fiber and its combination. In one embodiment, reinforcing material is glass such as fibrous glass long filament, the mixture of glass and talcum, glass and mica and glass and polymer fiber.
[00115] in another embodiment, the invention still further relates to goods, it comprises film and/or thin plate, and this film and/or thin plate comprise described polymer blend herein.
[00116] 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.
[00117] 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.
[00118] method that polyester is configured as film and/or thin plate is well-known in the art. The example of film of the present invention and/or thin plate includes but not limited to cast film and/or thin plate, calendered film and/or thin plate, compression molded films and/or thin plate, solution plastic casting film and/or thin plate. The method of making film and/or thin plate includes but not limited to extrusion molding, calendering, compression moulding and solution casting.
[00119] example by the potential goods of film and/or thin plate preparation includes but not limited to monodirectional tension film, biaxially oriented film, shrinkable film (no matter being unidirectional or biaxial tension), liquid crystal display film (including but not limited to diffuser thin plate, compensation film and protective film), hot formed thin plate, plate process film (graphic arts film), outdoor sign, skylight, coating, coated article, painting products, laminates, laminated product and/or plural layers or thin plate.
[00120] example of plate process film is including, but not limited to nameplate, membrane switch facing; Point of purchase display; Plane on the washing machine or in-mold decoration panel; Plane touch panel on the refrigerator; Flat board on the stove; Automotive trim; The automobile instrument group; Phone cover; Heating and Ventilation Control display; The automobile control panel; Automobile gear gear panel; Control display device or the alarm signal of fascia; Facing on the household implements, dial plate or display; Facing on the washing machine, dial plate or display; Facing on the dish-washing machine, dial plate or display; The keypad of electronic equipment; The keypad of mobile phone, PDA (laptop computer) or remote controllers; The display of electronic equipment; The display of hand-held electric subset such as phone and PDA; Panel and the shell of movement or standard telephone; Logo on the electronic equipment; Logo with mobile phone.
[00121] plural layers or thin plate refer to be extruded into the thin plate by a plurality of layers of section that forms that connect by vertical rib each other. The example of plural layers or thin plate includes but not limited to greenhouse and commercial canopy.
[00122] comprise to the example of 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, plural layers, be used for plastic sheeting and liquid crystal display (LCD) film of resin glass laminates, liquid crystal display (LCD) film includes but not limited to diffuser thin plate, compensation film and the protective film for LCD.
[00123] as used in this article, abbreviation " wt " refers to " weight ".
[00124] 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 be intended that and illustrate the present invention purely and be not intended to limit its scope.Unless otherwise indicated, umber is a weight part, temperature for degree centigrade or be in room temperature, pressure is or near atmospheric gas pressure.
Embodiment
Measuring method
[00125] logarithmic viscosity number of polyester is that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration.
[00126] 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.
[00127] glycol content of composition and cis/trans ratios are measured by proton magnetic resonance (PMR) (NMR) spectrum.All NMR spectrums all are recorded on the JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer, for polymkeric substance, use chloroform-trifluoroacetic acid (70-30 volume/volume), perhaps for the oligopolymer sample, use 60/40 (wt/wt) phenol/tetrachloroethane, and for locking the deuterate chloroform that the peak adds.By with model 2,2,4,4-tetramethyl--1, the list and the dibenzoate of 3-cyclobutanediol compare, and carry out 2,2,4,4-tetramethyl--1, the peak of 3-cyclobutanediol resonance is pointed out.These model compounds are very near the resonant position that exists in polymkeric substance and oligopolymer.
[00128] crystallization half-life, t1/2, be by on the hot platform of temperature control along with the time is measured through the transmittance of laser apparatus and photoelectric detector measure sample.This measurement is performed such: polymkeric substance is exposed to temperature T
Max, and subsequently it is cooled to desired temperatures.By hot platform sample is remained on desired temperatures subsequently, measure transmittance simultaneously over time.At first, sample visually is transparent, has high transmission rate, and becomes opaque along with the sample crystallization.Being recorded as transmittance crystallization half-life is the time of a half between initial transmittance and the final transmittance.T
MaxBe defined as the required temperature of fusing sample domain (if having domain).The T that reports in following examples
MaxRepresentative was heated every kind of sample to nurse one's health the temperature of this sample before measuring crystallization half-life.T
MaxTemperature depends on to be formed and generally is different for every kind of polyester.For example, may need PCT is heated to above certain temperature of 290 ℃ with the fusion domain.
[00129] density is to use the gradient column density 23 ℃ of mensuration.
[00130] melt viscosity of report is measured by using Rheometrics DynamicAnalyzer (RDA II) herein.In the temperature of being reported, with the variation of the frequency measurement melt viscosity of 1-400 radian per second with shearing rate.Zero shears melt viscosity (η
0) be by the melt viscosity under the zero shearing rate estimated of extrapolation data by model known in the art.This step is realized automatically by RheometricsDynamic Analyzer (RDA II) software.
[00131] 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.
[00132] in addition, use 5 battens of 5 ℃ of incremental testings to measure the brittle-ductile transition temperature in differing temps.Temperature when tough brittle transition temperature is defined as 50% batten and lost efficacy in the fragility mode of being represented by ASTM D256.
[00133] colour of report is to use the Inc. by Hunter Associates Lab herein, Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures.The color measurenent value is at polyester granules or the mean value of the value of measuring on by its injection moulding or the plate of extruding or other object.They are by the L of CIE (International Commission on Illumination) (translating)
*a
*b
*Colour system is definite, wherein L
*Expression luminance brightness coordinate, a
*Represent red/green coordinate, b
*Expression Huang/blue coordinate.
[00134] in addition, use the Carver press 240 ℃ of compression moulding 10-mil film.
[00135] 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.
[00136] following abbreviation is applicable to whole work embodiment and accompanying drawing:
TPA | Terephthalic acid |
DMT | Dimethyl terephthalate (DMT) |
|
2,2,4,4-tetramethyl--1,3-cyclobutanediol |
CHDM | 1,4 cyclohexane dimethanol |
IV | Logarithmic viscosity number |
η 0 | Zero shears melt viscosity |
Tg | Second-order transition temperature |
T bd | Tough brittle transition temperature |
T max | The conditioning temperature that measure crystallization half-life |
Embodiment 1
[00137] present embodiment illustrates 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol is more effective than ethylene glycol or m-phthalic acid aspect the crystallization rate that reduces PCT.In addition, present embodiment illustrates 2,2,4,4-tetramethyl--1, the benefit of 3-cyclobutanediol aspect second-order transition temperature and density.
[00138] as described below, prepare multiple copolyesters.These copolyesters all adopt the 200ppm dibutyl tin oxide as Preparation of Catalyst, with minimum catalyst type and concentration to Study on Crystallization during the influence of nucleogenesis.The cis/trans ratios of 1,4 cyclohexane dimethanol is 31/69, and 2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol is recorded in the table 1.
[00139] for present embodiment, each sample has enough similar logarithmic viscosity number, thereby in fact gets rid of this as variable in crystallization rate is measured.
[00140] is increment at 140-200 ℃ with 10 ℃, carries out measurement, and measuring result is recorded in the table 1 from the crystallization half-life of melt.Generally appear at about 170-180 ℃ as the minimum value of temperature variant crystallization half-life the fastest crystallization half-life of every kind of sample.The fastest crystallization half-life of sample is plotted among Fig. 1 as the function to the mol% of the comonomer of PCT modification.
[00141] data presentation, 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than ethylene glycol and m-phthalic acid aspect reduction crystallization rate (promptly improving crystallization half-life).In addition, 2,2,4,4-tetramethyl--1,3-cyclobutanediol have improved Tg and have reduced density.
Table 1
Crystallization half-life (minute)
Embodiment | Comonomer (mol%) 1 | IV (dl/g) | Density (g/ml) | T g (℃) | T max (℃) | 140℃ (min) | 150℃ (min) | 160℃ (min) | 170℃ (min) | 180℃ (min) | 190℃ (min) | 200℃ (min) |
1A | 20.2%A 2 | 0.630 | 1.198 | 87.5 | 290 | 2.7 | 2.1 | 1.3 | 1.2 | 0.9 | 1.1 | 1.5 |
1B | 19.8%B | 0.713 | 1.219 | 87.7 | 290 | 2.3 | 2.5 | 1.7 | 1.4 | 1.3 | 1.4 | 1.7 |
1C | 20.0%C | 0.731 | 1.188 | 100.5 | 290 | >180 | >60 | 35.0 | 23.3 | 21.7 | 23.3 | 25.2 |
1D | 40.2%A 2 | 0.674 | 1.198 | 81.2 | 260 | 18.7 | 20.0 | 21.3 | 25.0 | 34.0 | 59.9 | 96.1 |
1E | 34.5%B | 0.644 | 1.234 | 82.1 | 260 | 8.5 | 8.2 | 7.3 | 7.3 | 8.3 | 10.0 | 11.4 |
1F | 40.1%C | 0.653 | 1.172 | 122.0 | 260 | >10 days | >5 days | >5 days | 19204 | >5 days | >5 days | >5 days |
1G | 14.3%D | 0.646 3 | 1.188 | 103.0 | 290 | 55.0 | 28.8 | 11.6 | 6.8 | 4.8 | 5.0 | 5.5 |
1H | 15.0%E | 0.728 4 | 1.189 | 99.0 | 290 | 25.4 | 17.1 | 8.1 | 5.9 | 4.3 | 2.7 | 5.1 |
The remainder of the diol component of polyester is a 1,4 cyclohexane dimethanol in 1 table 1; And the dicarboxylic acid component's of polyester remainder is a dimethyl terephthalate (DMT) in the table 1; If do not describe dicarboxylic acid, then it is the 100mol% dimethyl terephthalate (DMT).
2 100mol%1, the 4-cyclohexanedimethanol.
3 240 ℃ of grinding polyester press membrane by embodiment 1G.The gained film has the logarithmic viscosity number value of 0.575dL/g.
4 240 ℃ of grinding polyester press membrane by embodiment 1H.The gained film has the logarithmic viscosity number value of 0.0.652dL/g.
Wherein:
A is a m-phthalic acid
B is an ethylene glycol
C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (about 50/50 cis/trans)
D is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (98/2 cis/trans)
E is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (5/95 cis/trans)
[00142] as table 1 and shown in Figure 1, improving aspect crystallization half-life (being that polymkeric substance reaches half required time of its maximum degree of crystallinity), 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than other comonomer such as ethylene glycol and m-phthalic acid.By the crystallization rate (improving crystallization half-life) that reduces PCT, can be by the methods known in the art manufacturing based on as described herein 2,2,4,4-tetramethyl--1, the amorphous goods of the PCT of 3-cyclobutanediol modification.As shown in table 1, these materials can demonstrate than higher second-order transition temperature of other modification PCT copolyesters and lower density.
[00143] preparation of the polyester shown in the table 1 is described below.
Embodiment 1A
What [00144] present embodiment illustrated target consists of 80mol% dimethyl terephthalate (DMT) residue, 20mol% dimethyl isophthalate residue and 100mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (28/72 cis/trans).
[00145] mixture with 56.63g dimethyl terephthalate (DMT), 55.2g 1,4 cyclohexane dimethanol, 14.16g dimethyl isophthalate and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 290 ℃ in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, applied vacuum gradually then in ensuing 5 minutes and reached 100mmHg up to the flask internal pressure.In ensuing 5 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 87.5 ℃, and logarithmic viscosity number is 0.63dl/g.NMR analysis revealed polymkeric substance comprises 100mol%1,4-cyclohexanedimethanol residue and 20.2mol% dimethyl isophthalate residue.
Embodiment 1B
What [00146] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol% glycol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (32/68 cis/trans).
[00147] mixture with 77.68g dimethyl terephthalate (DMT), 50.77g 1,4 cyclohexane dimethanol, 27.81g ethylene glycol and 0.0433g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 210 ℃ in 60 minutes subsequently gradually 200 ℃ of heating in 5 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 280 ℃ at 210 ℃.In case be in 280 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg up to the flask internal pressure.In ensuing 10 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 87.7 ℃, and logarithmic viscosity number is 0.71dl/g.NMR analysis revealed polymkeric substance comprises the 19.8mol% glycol residue.
Embodiment 1C
What [00148] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).
[00149] with 77.68g dimethyl terephthalate (DMT), 48.46g 1,4-cyclohexanedimethanol, 17.86g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.This polyester is to prepare to the described similar mode of embodiment 1A.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 19.5 mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.
Embodiment 1D
What [00150] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 40mol% dimethyl isophthalate residue and 100mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (28/72 cis/trans).
[00151] mixture with 42.83g dimethyl terephthalate (DMT), 55.26g 1,4 cyclohexane dimethanol, 28.45g dimethyl isophthalate and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 290 ℃ in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, applied vacuum gradually then in ensuing 5 minutes and reached 100mmHg up to the flask internal pressure.In ensuing 5 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 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 [00152] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 40mol% glycol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).
[00153] mixture with 81.3g dimethyl terephthalate (DMT), 42.85g 1,4 cyclohexane dimethanol, 34.44g ethylene glycol and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 210 ℃ in 60 minutes subsequently gradually 200 ℃ of heating in 5 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 280 ℃ at 210 ℃.In case be in 280 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg up to the flask internal pressure.In ensuing 10 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 82.1 ℃, and logarithmic viscosity number is 0.64dl/g.NMR analysis revealed polymkeric substance comprises the 34.5mol% glycol residue.
Embodiment 1F
What [00154] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 40mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).
[00155] with 77.4g dimethyl terephthalate (DMT), 36.9g 1,4-cyclohexanedimethanol, 32.5g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.Stirring velocity is set at 200RPM in whole experiment.The content of flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 290 ℃ at 260 ℃.In case be in 290 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg up to the flask internal pressure.In ensuing 5 minutes, again the flask internal pressure is reduced to 0.3mmHg.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 122 ℃, and logarithmic viscosity number is 0.65dl/g.NMR analysis revealed polymkeric substance comprises 59.9mol%1,4-cyclohexanedimethanol residue and 40.1mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.
Embodiment 1G
What [00156] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue (98/2 cis/trans) and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).
[00157] with 77,68g dimethyl terephthalate (DMT), 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 distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.Stirring velocity is set at 200RPM in whole experiment.The content of flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 290 ℃ at 260 ℃.In case be in 290 ℃, in ensuing 5 minutes, apply vacuum gradually and reach 100mmHg, and also stirring velocity is dropped to 100RPM up to the flask internal pressure.In ensuing 5 minutes, again the flask internal drop is hanged down to 0.3mmHg, and stirring velocity is dropped to 50RPM.The pressure that keeps 0.3mmHg altogether 60 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 103 ℃, and logarithmic viscosity number is 0.65dl/g.NMR analysis revealed polymkeric substance comprises 85.7mol%1,4-cyclohexanedimethanol residue and 14.3mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.
Embodiment 1H
What [00158] present embodiment illustrated target consists of 100mol% dimethyl terephthalate (DMT) residue, 20mol% 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue (5/95 cis/trans) and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).
[00159] with 77.68g dimethyl terephthalate (DMT), 48.46g 1,4-cyclohexanedimethanol, 20.77g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyl tin oxide place 500 ml flasks that are equipped with nitrogen inlet mouth, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe (Wood ' s metal bath) in flask.When the experiment beginning, stirring velocity is set at 200RPM.The content of flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and subsequently at 30 minutes internal heating to 290 ℃ at 260 ℃.In case be in 290 ℃, in ensuing 5 minutes, apply vacuum gradually, setting point is 100mmHg, and also stirring velocity is dropped to 100RPM.In ensuing 5 minutes, again the flask internal pressure is reduced to setting point 0.3mmHg, and stirring velocity is dropped to 50RPM.Keep this pressure altogether 60 minutes to remove excessive unreacted glycol.Notice that vacuum system does not reach above-mentioned setting point, but produced enough vacuum with preparation high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 99 ℃, and logarithmic viscosity number is 0.73dl/g.NMR analysis revealed polymkeric substance comprises 85mol%1,4-cyclohexanedimethanol residue and 15mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.
[00160] 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.
[00161] as described below, prepare based on 2,2,4 4-tetramethyl--1, the copolyesters of 3-cyclobutanediol.For all samples, the cis/trans ratios of 1,4 cyclohexane dimethanol is about 31/69.Copolyesters based on ethylene glycol and 1,4 cyclohexane dimethanol is the commercialization polyester.The copolyesters of embodiment 2A (Eastar PCTG5445) obtains from Eastman Chemical Co..The copolyesters of embodiment 2B obtains with trade(brand)name Spectar from Eastman Chemical Co..Embodiment 2C and embodiment 2D adapt to the described process preparation of embodiment 1A with pilot scale (respectively being 15-lb batch), and have logarithmic viscosity number described in the following table 2 and second-order transition temperature.With target tin quantity is that 300ppm (dibutyl tin oxide) prepares embodiment 2C.Final product comprises 295ppm tin.The colour of the polyester of embodiment 2C is L
*=77.11; a
*=-1.50; And b
*=5.79.With target tin quantity is that 300ppm (dibutyl tin oxide) prepares embodiment 2D.Final product comprises 307ppm tin.The colour of the polyester of embodiment 2D is L
*=66.72; a
*=-1.22; And b
*=16.28.
[00162] material is injection molded into strip and subsequently otch carry out izod test.Vary with temperature and obtain the notched izod shock strength, equally it is reported in the table 2.
[00163] for given sample, izod impact strength experiences big change (major transition) in little temperature range.For example, based on the izod impact strength of the copolyesters of 38mol% ethylene glycol in this transformation of 15-20 ℃ of experience.This transition temperature is relevant with the variation of failure mode; Fragility/low-yield in the lesser temps inefficacy, and toughness/high-energy lost efficacy at comparatively high temps.This transition temperature is expressed as tough brittle transition temperature T
Bd, it is that flexible is measured.T
BdBe reported in the table 2 and in Fig. 2, map with respect to comonomer mol%.
[00164] data show, with the T that improves PCT
BdEthylene glycol compare, in PCT, add 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol has reduced T
BdAnd improved toughness.
Table 2
Notched izod impact energy (ft-lb/in)
Embodiment | Comonomer (mol%) 1 | IV (dl/g) | T g (℃) | T bd (℃) | -20 ℃ | -15 ℃ | -10 ℃ | -5 ℃ | 0 ℃ | 5 ℃ | 10 ℃ | 15 |
20 ℃ | 25 ℃ | 30 ℃ |
2A | 38.0%B | 0.68 | 86 | 18 | NA | NA | NA | 1.5 | NA | NA | 1.5 | 1.5 | 32 | 32 | NA |
2B | 69.0%B | 0.69 | 82 | 26 | NA | NA | NA | NA | NA | NA | 2.1 | NA | 2.4 | 13.7 | 28.7 |
2C | 22.0%C | 0.66 | 106 | -5 | 1.5 | NA | 12 | 23 | 23 | NA | 23 | NA | NA | NA | NA |
2D | 42.8%C | 0.60 | 133 | -12 | 2.5 | 2.5 | 11 | NA | 14 | NA | NA | NA | NA | NA | NA |
1. the remainder of the diol component of polyester is a 1,4 cyclohexane dimethanol in the table.All polymkeric substance prepare by the 100mol% dimethyl terephthalate (DMT).NA=is unavailable.Wherein: B is 2,2,4 for ethylene glycol C, 4-tetramethyl--1,3-cyclobutanediol (50/50 cis/trans)
[00165] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.Zhi Bei polyester comprises 2,2,4 of 15-25mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.
[00166] as described below, prepare based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, it has composition shown in the table 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).
[00167] material is injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain the notched izod shock strengths and be reported in the table 3 at 23 ℃.Measure density, Tg and the crystallization half-life of molding strip.Melt viscosity at 290 ℃ of measurement pellets.
Table 3
Various performance compilations to some useful polyester of the present invention
Embodiment | TMCD mol% | % cis TMCD | Pellet IV (dl/g) | Molding strip IV (dl/g) | 3.2mm thick strip is 23 ℃ notched izod (J/m) | 6.4mm thick strip is 23 ℃ notched izod (J/m) | Proportion (g/mL) | Tg (℃) | In the crystallization half-life of 170 ℃ of melts (min) | Melt viscosity (pool) under 290 ℃ of 1rad/sec |
A | 15 | 48.8 | 0.736 | 0.707 | 1069 | 878 | 1.184 | 104 | 15 | 5649 |
B | 18 | NA | 0.728 | 0.715 | 980 | 1039 | 1.183 | 108 | 22 | 6621 |
|
20 | NA | 0.706 | 0.696 | 1006 | 1130 | 1.182 | 106 | 52 | 6321 |
D | 22 | NA | 0.732 | 0.703 | 959 | 988 | 1.178 | 108 | 63 | 7161 |
E | 21 | NA | 0.715 | 0.692 | 932 | 482 | 1.179 | 110 | 56 | 6162 |
F | 24 | NA | 0.708 | 0.677 | 976 | 812 | 1.180 | 109 | 58 | 6282 |
G | 23 | NA | 0.650 | 0.610 | 647 | 270 | 1.182 | 107 | 46 | 3172 |
H | 23 | 47.9 | 0.590 | 0.549 | 769 | 274 | 1.181 | 106 | 47 | 1736 |
I | 23 | 48.1 | 0.531 | 0.516 | 696 | 352 | 1.182 | 105 | 19 | 1292 |
J | 23 | 47.8 | 0.364 | NA | NA | NA | NA | 98 | NA | 167 |
NA=is unavailable.
Embodiment 3A
[00168] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.241b (49.71gram-mol) dimethyl terephthalate (DMT), 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 agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to<1mmHg.With reaction mixture remain on 290 ℃ and<pressure of 1mmHg under up to the power of agitator no longer raise (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 sieve by 6-mm.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
[00169] polyester described in the embodiment 3B-embodiment 3D is according to preparing to the similar program of the described program of embodiment 3A.The composition and the performance of this polyester are shown in Table 3.
Embodiment 3E
[00170] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 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 agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to<1mmHg.Reaction mixture 290 ℃ and<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 sieve by 6-mm.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
[00171] polyester described in the embodiment 3F is according to preparing to the similar program of the described program of embodiment 3A.The composition and the performance of this polyester are shown in Table 3.
Embodiment 3H
[00172] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 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 agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to<1mmHg.Reaction mixture 290 ℃ and<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 sieve by 6-mm.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
[00173] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 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 agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to 4mmHg.Reaction mixture kept 30 minutes under the pressure of 290 ℃ and 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 sieve by 6-mm.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
[00174] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 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 agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to 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 sieve by 6-mm.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
[00175] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.Zhi Bei polyester comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.
[00176] as described below, prepare based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol (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).
[00177] material is injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain the notched izod shock strengths and be reported in the table 4 at 23 ℃.Measure density, Tg and the crystallization half-life of molding strip.Melt viscosity at 290 ℃ of measurement pellets.
Table 4
Various performance compilations to some useful polyester of the present invention
Embodiment | TMCD mol% | % cis TMCD | Pellet IV (dl/g) | Molding strip IV (dl/g) | 3.2mm thick strip is 23 ℃ notched izod (J/m) | 6.4mm thick strip is 23 ℃ notched izod (J/m) | Proportion (g/mL) | Tg (℃) | In the crystallization half-life of 170 ℃ of melts (min) | Melt viscosity (pool) under 290 ℃ of 1 rad/sec |
A | 27 | 47.8 | 0.714 | 0.678 | 877 | 878 | 1.178 | 113 | 280 | 8312 |
B | 31 | NA | 0.667 | 0.641 | 807 | 789 | 1.174 | 116 | 600 | 6592 |
NA=is unavailable.
Embodiment 4A
[00178] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71 gram-mol) dimethyl terephthalate (DMT), 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 agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 1 hour hold-time under 270 ℃ and the 90mmHg, agitator speed is reduced to 15RPM, reaction mixture temperature is elevated to 290 ℃ and pressure reduced to<1mmHg.With reaction mixture remain on 290 ℃ and<pressure of 1mmHg under up to the power of agitator no longer raise (50 minutes).Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that sieve by 6-mm.The logarithmic viscosity number of polymkeric substance is 0.714dL/g, and Tg is 113 ℃.NMR analysis revealed polymkeric substance comprises 73.3mol%1,4-cyclohexanedimethanol residue and 26.7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.
Embodiment 4B
[00179] polyester of embodiment 4B is according to preparing to the similar program of the described program of embodiment 4A.The composition and the performance of this polyester are shown in Table 4.
Embodiment 5
[00180] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.
[00181] as described below, prepare based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, it has composition shown in the table 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).
[00182] polyester is injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain the notched izod shock strengths and be reported in the table 5 at 23 ℃.Measure density, Tg and the crystallization half-life of molding strip.Melt viscosity at 290 ℃ of measurement pellets.
Table 5
Various performance compilations to some useful polyester of the present invention
Embodiment | TMCD mol% | % cis TMCD | Pellet IV (dl/g) | Molding strip IV (dl/g) | 3.2mm thick strip is 23 ℃ notched izod (J/m) | 6.4mm thick strip is 23 ℃ notched izod (J/m) | Proportion (g/mL) | Tg (℃) | In the crystallization half-life of 170 ℃ of melts (min) | Melt viscosity under 290 1 rad/sec (pool) |
A | 44 | 46.2 | 0.657 | 0.626 | 727 | 734 | 1.172 | 119 | NA | 9751 |
NA=is unavailable.
Embodiment 5A
[00183] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 8.84lb (27.88gram-mol) 1,4-cyclohexanedimethanol and 10.08lb (31.77gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressure containers being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then agitator speed is reduced to 15RPM, then the temperature of reaction mixture is risen to 290 ℃ and pressure reduced to 2mmHg.Reaction mixture is remained under the pressure of 290 ℃ and 2mmHg power up to agitator no longer raise (80 minutes).Use nitrogen that the pressure of pressurized vessel is elevated to 1 normal atmosphere then.From pressurized vessel, extrude molten polymer subsequently.The polymkeric substance of grind refrigerative, extruding is so that sieve by 6-mm.The logarithmic viscosity number of polymkeric substance is 0.657dL/g, and Tg is 119 ℃.NMR analysis revealed polymkeric substance comprises 56.3mol%1,4-cyclohexanedimethanol residue and 43.7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polymkeric substance is L
*=75.04; a
*=-1.82; And b
*=6.72.
Embodiment 6-Comparative Examples
[00184] 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% ethylene glycol.PETG is the Eastar 6763 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 31mol% cyclohexanedimethanol (CHDM) and 69mol% ethylene glycol.PCTG is the Eastar DN001 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 62mol% cyclohexanedimethanol (CHDM) and 38mol% ethylene glycol.PCTA is the Eastar AN001 from Eastman Chemical Company, and its nominal consists of 65mol% terephthalic acid, 35mol% m-phthalic acid and 100mol% cyclohexanedimethanol (CHDM).Polysulfones is the Udel 1700 from Solvay, and its nominal consists of 100mol% dihydroxyphenyl propane residue and 100mol%4,4-two chlorosulfonyl sulfone residues.Udel 1700 has the nominal melt flow rate (MFR) of use 2.16kg weight at the 6.5g/10min of 343C measurement.SAN is the Lustran31 from Lanxess, and its nominal consists of 76wt% vinylbenzene and 24wt% vinyl cyanide.Lustran 31 has the nominal melt flow rate (MFR) of use 3.8kg weight at the 7.5g/10min of 230C measurement.Compare with all other resins, embodiments of the invention demonstrate improved toughness in the thick strip of 6.4mm.
Table 6
The various performance compilations of some commercial polymer
Embodiment | The polymkeric substance title | Pellet IV (dl/g) | Molding strip IV (dl/g) | 3.2mm thick strip is 23 ℃ notched izod (J/m) | 6.4mm thick strip is 23 ℃ notched izod (J/m) | Proportion (g/mL) | Tg (℃) | The crystallization half-life of melt (min) |
A | PC | 12 MFR | NA | 929 | 108 | 1.20 | 146 | NA |
B | PCTG | 0.73 | 0.696 | NB | 70 | 1.23 | 87 | 30 at 170 ℃ |
C | PCTA | 0.72 | 0.702 | 98 | 59 | 1.20 | 87 | 15 at 150 ℃ |
D | PETG | 0.75 | 0.692 | 83 | 59 | 1.27 | 80 | 2500 at 130 ℃ |
E | PET | 0.76 | 0.726 | 45 | 48 | 1.33 | 78 | 1.5 at 170 ℃ |
F | SAN | 7.5 MFR | NA | 21 | NA | 1.07 | ~110 | NA |
G | PSU | 6.5 MFR | NA | 69 | NA | 1.24 | ~190 | NA |
NA=is unavailable
Embodiment 7
[00185] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the amount of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises 2,2,4 of 15-25mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.
Embodiment 7A-embodiment 7G
[00186] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.2,2,4,4-tetramethyl--1, the NMR of 3-cyclobutanediol parent material are analyzed and are shown that cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 20mol% with productive target.
[00187] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.
Embodiment 7H-embodiment 7Q
[00188] these polyester are by carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is carried out in (CTR) reactor that heats up continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.Reactor be filled with 777g (4mol) dimethyl terephthalate (DMT) 230g (1.6mol) 2,2,4,4-tetramethyl--1, three (2 ethyl hexanoic acid) butyl tin of the cyclohexanedimethanol of 3-cyclobutanediol, 460.8g (3.2mol) and 1.12g (make and in final polymkeric substance, will have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Adopt the Camile program control system to make setting point and data gathering become convenient.In case the reactant fusion just begins to stir and slowly be increased to 250rpm.Along with runtime, the temperature of reactor raises gradually.By the equal a record weight of collected methyl alcohol of sky.When 260 ℃ following time of lesser temps of methyl alcohol effusion stopping or being in preliminary election, stopped reaction.Adopt nitrogen purging to discharge oligopolymer and cool to room temperature.Adopt the liquid nitrogen freezing oligopolymer and be broken into enough little fritter, in the 500ml round-bottomed flask of packing into after the process weighing.
[00189] in polycondensation, the 500ml round-bottomed flask is loaded the above prepared oligopolymer of the 150g that has an appointment.This flask equipped has stainless steel agitator and cap.Glassware is arranged on the last and startup Camile sequence of half moles of polymer suite of equipment (a half mole polymer rig).In case the oligopolymer fusion orientates agitator apart from complete upset of drag (positioned one full turn from the flask bottom) as.The temperature/pressure by the Camile software control/stirring speed sequence for each embodiment is reported in the following table.
[00190] the Camile sequence of embodiment 7H and embodiment 7I
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 6 | 25 |
7 | 110 | 290 | 6 | 25 |
[00191] the Camile sequence of embodiment 7N-embodiment 7Q
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 3 | 25 |
7 | 110 | 290 | 3 | 25 |
[00192] the Camile sequence of embodiment 7K and embodiment 7L
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 2 | 25 |
7 | 110 | 290 | 2 | 25 |
[00193] the Camile sequence of embodiment 7J and embodiment 7M
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 1 | 25 |
7 | 110 | 290 | 1 | 25 |
[00194] from flask, reclaims resulting polymers, use the chopping of hydraulic pressure knife mill, and be ground to the 6mm size of mesh.Sample to the polymkeric substance of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml
*, a
*, b
*).Obtaining polymkeric substance by 1H NMR forms.Use Rheometrics MechanicalSpectrometer (RMS-800) sample to be carried out the test of thermostability and melt viscosity.
[00195] following table has shown the experimental data of the polyester of present embodiment.Data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol level improves second-order transition temperature in almost linear mode.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.
Table 7
Second-order transition temperature as the function of logarithmic viscosity number and composition
Embodiment | mol%TMCD | % cis TMCD | IV(dL/g) | T g(℃) | η o260 ℃ (pool) | η o275 ℃ (pool) | η o290 ℃ (pool) |
A | 20 | 51.4 | 0.72 | 109 | 11356 | 19503 | 5527 |
B | 19.1 | 51.4 | 0.60 | 106 | 6891 | 3937 | 2051 |
C | 19 | 53.2 | 0.64 | 107 | 8072 | 4745 | 2686 |
D | 18.8 | 54.4 | 0.70 | 108 | 14937 | 8774 | 4610 |
E | 17.8 | 52.4 | 0.50 | 103 | 3563 | 1225 | 883 |
F | 17.5 | 51.9 | 0.75 | 107 | 21160 | 10877 | 5256 |
G | 17.5 | 52 | 0.42 | 98 | NA | NA | NA |
H | 22.8 | 53.5 | 0.69 | 109 | NA | NA | NA |
I | 22.7 | 52.2 | 0.68 | 108 | NA | NA | NA |
J | 23.4 | 52.4 | 0.73 | 111 | NA | NA | NA |
K | 23.3 | 52.9 | 0.71 | 111 | NA | NA | NA |
L | 23.3 | 52.4 | 0.74 | 112 | NA | NA | NA |
M | 23.2 | 52.5 | 0.74 | 112 | NA | NA | NA |
N | 23.1 | 52.5 | 0.71 | 111 | NA | NA | NA |
O | 22.8 | 52.4 | 0.73 | 112 | NA | NA | NA |
P | 22.7 | 53 | 0.69 | 112 | NA | NA | NA |
Q | 22.7 | 52 | 0.70 | 111 | NA | NA | NA |
NA=is unavailable
Embodiment 8
[00196] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the amount of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.
[00197] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.2,2,4,4-tetramethyl--1, the NMR of 3-cyclobutanediol parent material are analyzed and are shown that cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 1RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 32mol% with productive target.
[00198] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.
[00199] following table has shown the experimental data of the polyester of present embodiment.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.Data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol level improves second-order transition temperature in almost linear mode.
Table 8
Second-order transition temperature as the function of logarithmic viscosity number and composition
Embodiment | mol%TMCD | % cis TMCD | IV(dL/g) | T g(℃) | η o260 ℃ (pool) | η o275 ℃ (pool) | η o290 ℃ (pool) |
A | 32.2 | 51.9 | 0.71 | 118 | 29685 | 16074 | 8522 |
B | 31.6 | 51.5 | 0.55 | 112 | 5195 | 2899 | 2088 |
C | 31.5 | 50.8 | 0.62 | 112 | 8192 | 4133 | 2258 |
D | 30.7 | 50.7 | 0.54 | 111 | 4345 | 2434 | 1154 |
E | 30.3 | 51.2 | 0.61 | 111 | 7929 | 4383 | 2261 |
F | 30.0 | 51.4 | 0.74 | 117 | 31476 | 17864 | 8630 |
G | 29.0 | 51.5 | 0.67 | 112 | 16322 | 8787 | 4355 |
H | 31.1 | 51.4 | 0.35 | 102 | NA | NA | NA |
NA=is unavailable
Embodiment 9
[00200] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the amount of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises 2,2,4 in the present embodiment, 4-tetramethyl--1, and 3-cyclobutanediol residue, its quantity is: 40mol% or more.
Embodiment A-C
[00201] these polyester are by carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is carried out in (CTR) reactor that heats up continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.Reactor be filled with 777g dimethyl terephthalate (DMT), 375g 2,2,4,4-tetramethyl--1, three (2 ethyl hexanoic acid) butyl tin of the cyclohexanedimethanol of 3-cyclobutanediol, 317g and 1.12g (make and in final polymkeric substance, will have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Adopt the Camile program control system to make setting point and data gathering become convenient.In case the reactant fusion just begins to stir and slowly be increased to 250rpm.Along with runtime, the temperature of reactor raises gradually.By the equal a record weight of collected methyl alcohol of sky.When 260 ℃ following time of lesser temps of methyl alcohol effusion stopping or being in preliminary election, stopped reaction.Adopt nitrogen purging to discharge oligopolymer and cool to room temperature.Adopt the liquid nitrogen freezing oligopolymer and be broken into enough little fritter, in the 500ml round-bottomed flask of packing into after the process weighing.
[00202] in polycondensation, the 500ml round-bottomed flask is filled with the above prepared oligopolymer of 150g.This flask equipped has stainless steel agitator and cap.Glassware is arranged on the last and startup Camile sequence of half moles of polymer suite of equipment (a half mole polymer rig).In case the oligopolymer fusion orientates agitator apart from complete upset of drag (positioned one full turn from the flask bottom) as.The temperature/pressure by the Camile software control/stirring speed sequence for these embodiment is reported in the following table, unless followingly explain in addition.
The Camile sequence of polycondensation
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 6 | 25 |
7 | 110 | 290 | 6 | 25 |
[00203] the Camile sequence of embodiment A and B
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 6 | 25 |
7 | 80 | 290 | 6 | 25 |
[00204] for Embodiment C, the identical sequence in the use in the table, but the time in the stage 7 is 50 minutes.
[00205] from flask, reclaims resulting polymers, use the chopping of hydraulic pressure knife mill, and be ground to the 6mm size of mesh.Sample to the polymkeric substance of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml
*, a
*, b
*).Obtaining polymkeric substance by 1H NMR forms.Use Rheometrics MechanicalSpectrometer (RMS-800) sample to be carried out the test of thermostability and melt viscosity.
Embodiment D-K and M
[00206] for preparation as described in embodiment A-C, still, for embodiment A D-K and M, the amount of target tin is 150ppm to the polyester of these embodiment in final polymkeric substance as above.Following table has been described the temperature/pressure by the Camile software control/stir speed (S.S.) sequence for these embodiment.
[00207] the Camile sequence of embodiment D, F and H
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpM) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 400 | 50 |
5 | 110 | 290 | 400 | 50 |
6 | 5 | 290 | 8 | 50 |
7 | 110 | 295 | 8 | 50 |
[00208] for embodiment D, agitator is transferred to 25rpm in the stage 7, carries out 95 minutes.
[00209] the Camile sequence of embodiment E
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 10 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 283 | 760 | 50 |
4 | 3 | 283 | 175 | 50 |
5 | 5 | 283 | 5 | 50 |
6 | 5 | 283 | 1.2 | 50 |
7 | 71 | 285 | 1.2 | 50 |
[00210] for embodiment K, the identical sequence in the use in the table, but the time in the stage 7 is 75 minutes.
[00211] the Camile sequence of embodiment G
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 10 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 285 | 760 | 50 |
4 | 3 | 285 | 175 | 50 |
5 | 5 | 285 | 5 | 50 |
6 | 5 | 285 | 4 | 50 |
7 | 220 | 290 | 4 | 50 |
[00212] the Camile sequence of example I
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 285 | 90 | 50 |
6 | 5 | 285 | 6 | 50 |
7 | 70 | 290 | 6 | 50 |
[00213] the Camile sequence of embodiment J
Stage | Time (min) | Temperature (℃) | Vacuum (holder) | Stir (rpm) |
1 | 5 | 245 | 760 | 0 |
2 | 5 | 245 | 760 | 50 |
3 | 30 | 265 | 760 | 50 |
4 | 3 | 265 | 90 | 50 |
5 | 110 | 290 | 90 | 50 |
6 | 5 | 290 | 6 | 25 |
7 | 110 | 295 | 6 | 25 |
Embodiment L and K
[00214] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 45mol% with productive target.
[00215] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.
[00216] following table has shown the experimental data of the polyester of present embodiment.Data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol level improves second-order transition temperature in almost linear mode.Fig. 3 has also shown the dependency of Tg to composition and logarithmic viscosity number.
Table 9
Second-order transition temperature as the function of logarithmic viscosity number and composition
Embodiment | mol%TMCD | % cis TMCD | IV(dL/g) | T g(℃) | η o260 ℃ (pool) | η o275 ℃ (pool) | η o290 ℃ (pool) |
A | 44.2 | 36.4 | 0.49 | 118 | NA | NA | NA |
B | 44.3 | 36.3 | 0.51 | 119 | NA | NA | NA |
C | 44.4 | 35.6 | 0.55 | 118 | NA | NA | NA |
D | 46.3 | 52.4 | 0.52 | NA | NA | NA | NA |
E | 45.7 | 50.9 | 0.54 | NA | NA | NA | NA |
F | 46.3 | 52.6 | 0.56 | NA | NA | NA | NA |
G | 46 | 50.6 | 0.56 | NA | NA | NA | NA |
H | 46.5 | 51.8 | 0.57 | NA | NA | NA | NA |
I | 45.6 | 51.2 | 0.58 | NA | NA | NA | NA |
J | 46 | 51.9 | 0.58 | NA | NA | NA | NA |
K | 45.5 | 51.2 | 0.59 | NA | NA | NA | NA |
L | 46.1 | 49.6 | 0.383 | 117 | NA | NA | 387 |
K | 45.6 | 50.5 | 0.325 | 108 | NA | NA | NA |
M | 47.2 | NA | 0.48 | NA | NA | NA | NA |
NA=is unavailable
Embodiment 10
[00217] 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.
[00218] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed and are added in the 500-milliliter list neck round-bottomed flask.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases, reduce and stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, make the decline of Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this wait of 30 minutes) and heated polymerizable thing material and break away from glass flask up to it.Stirring polymer material with medium level in flask cools off up to polymkeric substance.From flask, take out polymkeric substance and grinding so that sieve by 3mm.This program is changed the copolyesters as described below that consists of 45mol% with productive target.
[00219] as measurement logarithmic viscosity number as described in above " measuring method " part.As described in measuring method part in front, measure forming of polyester by 1H NMR.After speed quenching, use second-heating, measure second-order transition temperature by DSC with 20 ℃/min.
[00220] 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
Embodiment | mol% TMCD | IV (dL/g) | T g (℃) | η o260 ℃ (pool) | η o275 ℃ (pool) | η o290 ℃ (pool) | % cis TMCD |
A | 45.8 | 0.71 | 119 | N.A. | N.A. | N.A. | 4.1 |
B | 43.2 | 0.72 | 122 | N.A. | N.A. | N.A. | 22.0 |
C | 46.8 | 0.57 | 119 | 26306 | 16941 | 6601 | 22.8 |
D | 43.0 | 0.67 | 125 | 55060 | 36747 | 14410 | 23.8 |
E | 43.8 | 0.72 | 127 | 101000 | 62750 | 25330 | 24.5 |
F | 45.9 | 0.533 | 119 | 11474 | 6864 | 2806 | 26.4 |
G | 45.0 | 0.35 | 107 | N.A. | N.A. | N.A. | 27.2 |
H | 41.2 | 0.38 | 106 | 1214 | 757 | N.A. | 29.0 |
I | 44.7 | 0.59 | 123 | N.A. | N.A. | N.A. | 35.4 |
J | 444 | 0.55 | 118 | N.A. | N.A. | N.A. | 35.6 |
K | 44.3 | 0.51 | 119 | N.A. | N.A. | N.A. | 36.3 |
L | 44.0 | 0.49 | 128 | N.A. | N.A. | N.A. | 71.7 |
M | 43.6 | 0.52 | 128 | N.A. | N.A. | N.A. | 72.1 |
N | 43.6 | 0.54 | 127 | N.A. | N.A. | N.A. | 72.3 |
O | 41.5 | 0.58 | 133 | 15419 | 10253 | 4252 | 88.7 |
P | 43.8 | 0.57 | 135 | 16219 | 10226 | 4235 | 89.6 |
Q | 41.0 | 0.33 | 120 | 521 | 351 | 2261 | 90.4 |
R | 43.0 | 0.56 | 134 | N.A. | N.A. | N.A. | 90.6 |
S | 43.0 | 0.49 | 132 | 7055 | 4620 | 2120 | 90.6 |
T | 43.1 | 0.55 | 134 | 12970 | 8443 | 3531 | 91.2 |
U | 45.9 | 0.52 | 137 | N.A. | N.A. | N.A. | 98.1 |
NA=is unavailable
Embodiment 11-Comparative Examples
[00221] present embodiment illustrates based on 100%2,2,4,4-tetramethyl--1, and the polyester of 3-cyclobutanediol has slow crystallization half-life.
[00222] 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 the 300ppm dibutyl tin oxide to prepare this polyester.2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol are 65/35.
[00223] 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), as shown in Figure 1.
Table 11
Crystallization half-life (minute)
Comonomer (mol%) | IV(dl/g) | T g(℃) | T max(℃) | 220℃ (min) | 230℃ (min) | 240℃ (min) | 250℃ (min) |
100mol%F | 0.63 | 170.0 | 330 | 3291 | 3066 | 1303 | 1888 |
Wherein: F is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (65/35 trans/cis)
Embodiment 12
[00224] use 3.5 inches single screw extrusion machine productions to comprise the thin plate of polyester, described polyester is with 100mol% terephthalic acid residue, 80mol%1,4-cyclohexanedimethanol residue and 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue are that the target composition is prepared.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured logarithmic viscosity number and second-order transition temperature.The measuring result of the logarithmic viscosity number of thin plate is 0.69dl/g.The measuring result of the second-order transition temperature of thin plate is 106 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment G) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 106 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, these thin plates have at least 95% stretching and bubble to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 86 | 145 | 501 | 64 | |
B | |||||
100 | 150 | 500 | 63 | N | |
C | 118 | 156 | 672 | 85 | N |
D | 135 | 163 | 736 | 94 | N |
E | 143 | 166 | 760 | 97 | N |
F | 150 | 168 | 740 | 94 | L |
G | 159 | 172 | 787 | 100 | L |
Embodiment 13
[00225] use 3.5 inches single screw extrusion machine productions to comprise the sheet material of polyester, described polyester is with 100mol% terephthalic acid residue, 80mol%1,4-cyclohexanedimethanol residue and 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue are that the target composition is prepared.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured logarithmic viscosity number and second-order transition temperature.The measuring result of the logarithmic viscosity number of thin plate is 0.69dl/g.The measuring result of the second-order transition temperature of thin plate is 106 ℃.Then with thin plate in 100% relative humidity and 25 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 60/40/40% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment G) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 106 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has at least 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 141 | 154 | 394 | 53 | N |
B | 163 | 157 | 606 | 82 | N |
C | 185 | 160 | 702 | 95 | N |
D | 195 | 161 | 698 | 95 | N |
E | 215 | 163 | 699 | 95 | L |
F | 230 | 168 | 705 | 96 | L |
G | 274 | 174 | 737 | 100 | H |
H | 275 | 181 | 726 | 99 | H |
Embodiment 14-Comparative Examples
[00226] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Kelvx 201.Kelvx is by 69.85%PCTG (available from the Eastar of Eastman Chemical Co., it has 100mol% terephthalic acid residue, 62mol%1,4-cyclohexanedimethanol residue and 38mol% glycol residue); 30%PC (bisphenol-a polycarbonate); The blend of forming with 0.15%Weston 619 (stablizer of selling by CromptonCorporation).Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 100 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment E) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 100 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has at least 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 90 | 146 | 582 | 75 | N |
B | 101 | 150 | 644 | 83 | N |
C | 111 | 154 | 763 | 98 | N |
D | 126 | 159 | 733 | 95 | N |
E | 126 | 159 | 775 | 100 | N |
F | 141 | 165 | 757 | 98 | N |
G | 148 | 168 | 760 | 98 | L |
Embodiment 15-Comparative Examples
[00227] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Kelvx 201.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 100 ℃.Then with thin plate in 100% relative humidity and 25 ℃ 2 weeks of conditioning down.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 60/40/40% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment H) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 100 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 110 | 143 | 185 | 25 | N |
B | 145 | 149 | 529 | 70 | N |
C | 170 | 154 | 721 | 95 | N |
D | 175 | 156 | 725 | 96 | N |
E | 185 | 157 | 728 | 96 | N |
F | 206 | 160 | 743 | 98 | L |
G | 253 | NR | 742 | 98 | H |
H | 261 | 166 | 756 | 100 | H |
NR=is Unrecorded
Embodiment 16-Comparative Examples
[00228] thin plate that uses 3.5 inches single screw extrusion machine productions to form by PCTG 25976 (100mol% terephthalic acid residue, 62mol%1,4-cyclohexanedimethanol residue and 38mol% glycol residue).Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 87 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.17wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 87 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 102 | 183 | 816 | 100 | N |
B | 92 | 171 | 811 | 99 | N |
C | 77 | 160 | 805 | 99 | N |
D | 68 | 149 | 804 | 99 | N |
E | 55 | 143 | 790 | 97 | N |
F | 57 | 138 | 697 | 85 | N |
Embodiment 17-Comparative Examples
[00229] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 20wt%Teijin L-1250 polycarbonate (bisphenol-a polycarbonate), 79.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 94 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.25wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 94 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 92 | 184 | 844 | 100 | H |
B | 86 | 171 | 838 | 99 | N |
C | 73 | 160 | 834 | 99 | N |
D | 58 | 143 | 787 | 93 | N |
E | 55 | 143 | 665 | 79 | N |
Embodiment 18-Comparative Examples
[00230] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 30wt%Teijin L-1250 polycarbonate, 69.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 99 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.25wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 99 ℃ thermoplastic sheet can thermoforming under condition shown below, and as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 128 | 194 | 854 | 100 | H |
B | 98 | 182 | 831 | 97 | L |
C | 79 | 160 | 821 | 96 | N |
D | 71 | 149 | 819 | 96 | N |
E | 55 | 145 | 785 | 92 | N |
F | 46 | 143 | 0 | 0 | NA |
G | 36 | 132 | 0 | 0 | NA |
NA=is inapplicable.0 value shows and do not form thin plate, because it does not draw in mould (may because its temperature is too low).
Embodiment 19-Comparative Examples
[00231] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 40wt%Teijin L-1250 polycarbonate, 59.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 105 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.265wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment 8A-8E) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 105 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 111 | 191 | 828 | 100 | H |
B | 104 | 182 | 828 | 100 | H |
C | 99 | 179 | 827 | 100 | N |
D | 97 | 177 | 827 | 100 | N |
E | 78 | 160 | 826 | 100 | N |
F | 68 | 149 | 759 | 92 | N |
G | 65 | 143 | 606 | 73 | N |
Embodiment 20-Comparative Examples
[00232] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 50wt%Teijin L-1250 polycarbonate, 49.85wt%PCTG 25976 and 0.15wt%Weston 619.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 111 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.225wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume of acquisition in this group experiment (embodiment A-D).Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 111 ℃ thermoplastic sheet can thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, the thin plate of production has greater than 95% stretching and bubbles to be proved.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 118 | 192 | 815 | 100 | H |
B | 99 | 182 | 815 | 100 | H |
C | 97 | 177 | 814 | 100 | L |
D | 87 | 171 | 813 | 100 | |
E | |||||
80 | 160 | 802 | 98 | N | |
F | 64 | 154 | 739 | 91 | |
G | |||||
60 | 149 | 0 | 0 | NA |
NA=is inapplicable.0 value shows and do not form thin plate, because it does not draw in mould (may because its temperature is too low).
Embodiment 21-Comparative Examples
[00233] uses 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 is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 117 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 114 | 196 | 813 | 100 | |
B | |||||
100 | 182 | 804 | 99 | H | |
C | 99 | 177 | 801 | 98 | L |
D | 92 | 171 | 784 | 96 | L |
E | 82 | 168 | 727 | 89 | L |
F | 87 | 166 | 597 | 73 | N |
Embodiment 22-Comparative Examples
[00234] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 65wt%Teijin L-1250 polycarbonate, 34.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 120 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.23wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 120 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 120 | 197 | 825 | 100 | H |
B | 101 | 177 | 820 | 99 | H |
C | 95 | 174 | 781 | 95 | L |
D | 85 | 171 | 727 | 88 | L |
E | 83 | 166 | 558 | 68 | L |
Embodiment 23-Comparative Examples
[00235] uses 1.25 inches mixed blends that single screw extrusion machine production is made up of 70wt%Teijin L-1250 polycarbonate, 29.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 123 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.205wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A and B) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 123 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 126 | 198 | 826 | 100 | H |
B | 111 | 188 | 822 | 100 | H |
C | 97 | 177 | 787 | 95 | L |
D | 74 | 166 | 161 | 19 | L |
E | 58 | 154 | 0 | 0 | NA |
F | 48 | 149 | 0 | 0 | NA |
NA=is inapplicable.0 value shows and do not form thin plate, because it does not draw in mould (may because its temperature is too low).
Embodiment 24-Comparative Examples
[00236] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Teijin L-1250 polycarbonate.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to suitable dimension.A thin plate is measured second-order transition temperature, and it is 149 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning down.The measuring result of moisture content is 0.16wt%.Using the Brown hot former subsequently is in 2.5: 1 the former to stretch ratio with the thin plate thermoforming.Only use the top heating, thermoforming baking oven for heating device is set at 70/60/60% output.Thin plate is stayed the different time that reaches in the baking oven, so that measure of the influence of thin plate temperature, as shown in following table to part quality.Part quality stretches by volume, the calculating of measuring thermoformed components and the visual inspection thermoformed components is measured.Stretching is to calculate like this: piece volumes is divided by the maximum part volume (embodiment A) that obtains in this group experiment.Any foaming of visual inspection thermoformed components, and with the foaming grading for not having (N), low (L) or high (H).Following result proves, these second-order transition temperatures are that 149 ℃ thermoplastic sheet can not thermoforming under condition shown below, as by before thermoforming not under the situation of predrying thin plate, can not produce and have greater than 95% stretching and blistered thin plate did not prove.
Embodiment | The thermoforming condition | Part quality | |||
Heat-up time (s) | The thin plate temperature (℃) | Piece volumes (mL) | Stretch (%) | Bubble (N, L, H) | |
A | 152 | 216 | 820 | 100 | H |
B | 123 | 193 | 805 | 98 | H |
C | 113 | 191 | 179 | 22 | H |
D | 106 | 188 | 0 | 0 | H |
E | 95 | 182 | 0 | 0 | NA |
F | 90 | 171 | 0 | 0 | NA |
NA=is inapplicable.0 value shows and do not form thin plate, because it does not draw in mould (may because its temperature is too low).
[00237] comparison of the data from above related work embodiment can be clear that, aspect second-order transition temperature, density, slow crystallization rate, melt viscosity and toughness, compare with the commercially available polyester that gets, polyester of the present invention provides tangible advantage.
[00238] 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 (58)
1. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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%;
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
The Tg of wherein said polyester is 85-120 ℃.
2. the film of claim 1 or thin plate, wherein logarithmic viscosity number is that 0.35-is less than 1.0dL/g.
3. the film of claim 1 or thin plate, wherein logarithmic viscosity number is 0.35-0.80dL/g.
4. the film of claim 1 or thin plate, wherein logarithmic viscosity number is 0.35-0.75dL/g.
5. the film of claim 1 or thin plate, wherein logarithmic viscosity number is 0.50-0.75dL/g.
6. the film of claim 1 or thin plate, wherein logarithmic viscosity number is 0.60-0.72dL/g.
7. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 10-90mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue and 10-90mol%1,4-cyclohexanedimethanol residue.
8. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 25-80mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue and 20-75mol%1,4-cyclohexanedimethanol residue.
9. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 40-65mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue and 35-60mol%1,4-cyclohexanedimethanol residue.
10. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 5-less than 50mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue and, 4-cyclohexanedimethanol residue greater than 50-95mol%1.
11. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 10-35mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 65-90mol%1,4-cyclohexanedimethanol residue.
12. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 15-35mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 70-90mol%1,4-cyclohexanedimethanol residue.
13. the film of claim 1 or thin plate, the diol component of wherein said polyester comprises 10-30mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 70-90mol%1,4-cyclohexanedimethanol residue.
14. the film of claim 1 or thin plate, wherein this diol component comprises 15-25mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 75-85mol%1,4-cyclohexanedimethanol residue.
15. the film of claim 1 or thin plate, wherein this diol component comprises 17-23mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol residue and 77-83mol%1,4-cyclohexanedimethanol residue.
16. the film of claim 1 or thin plate, the Tg of wherein said polyester are 90-115 ℃.
17. the film of claim 1 or thin plate, the Tg of wherein said polyester are 85-115 ℃.
18. the film of claim 1 or thin plate, the Tg of wherein said polyester are 95-115 ℃.
19. the film of claim 1 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 80-100mol%.
20. the film of claim 1 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 90-100mol%.
21. the film of claim 1 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 95-100mol%.
22. the film of claim 20 or thin plate, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 99-100mol%.
23. the film of claim 1 or thin plate, wherein said polyester comprises 1, ammediol residue, 1,4-butyleneglycol residue or its mixture.
24. the film of claim 22 or thin plate, wherein said polyester comprises 1 of 0.01-25mol%, ammediol residue, 1,4-butyleneglycol residue or its mixture.
25. the film of claim 1 or thin plate, wherein said polyester comprises glycol residue.
26. the film of claim 1 or thin plate, wherein said polyester comprises the glycol residue of 0.01-15mol%.
27. the film of claim 1 or thin plate, wherein said polyester comprises the glycol residue of 0.01-10mol%.
28. the film of claim 1 or thin plate are wherein said 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is to comprise suitable-2,2,4 greater than 50mol%, 4-tetramethyl--1,3-cyclobutanediol and less than anti--2 of 50mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol.
29. the film of claim 1 or thin plate are wherein said 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is comprise 30-70mol% suitable-2,2,4,4-tetramethyl--1, anti--2 of 3-cyclobutanediol and 70-30mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol.
30. the film of claim 29 or thin plate are wherein said 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is comprise 40-60mol% suitable-2,2,4,4-tetramethyl--1, anti--2 of 3-cyclobutanediol and 60-40mol%, 2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol.
31. 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: poly-(ether imide), polyphenylene oxide, polyphenyl ether/styrene blend, polystyrene resin, polyphenylene sulfide, polyphenylene sulfide/sulfone, poly-(ester-carbonic ether), polycarbonate, polysulfones; Polysulfones ether and poly-(ether-ketone).
32. the film of claim 1 or thin plate, wherein said polymer blend comprises at least a polycarbonate.
33. the film of claim 1 or thin plate, wherein said polyester comprises the residue of at least a branching agent.
34. the film of claim 33 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.
35. the film of claim 1 or thin plate, the melt viscosity of wherein said polyester are less than 30,000 pools, as measuring at 1 radian per second on the rotation melt rheometer at 290 ℃.
36. the film of claim 1 or thin plate, wherein said polyester had 170 ℃ of crystallization half-lives greater than 5 minutes.
37. the film of claim 1 or thin plate, wherein said polyester had 170 ℃ of crystallization half-lives greater than 50 minutes.
38. the film of claim 1 or thin plate, wherein the density at 23 ℃ of described polymer blends is less than 1.2g/ml.
39. the film of claim 1 or thin plate, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product.
40. the film of claim 1 or thin plate, wherein said polyester according to the yellowness index of ASTM D-1925 less than 50.
41. the film of claim 1 or thin plate, in the thick strip of 1/8-in with 10-mil otch according to ASTM D256 under 23 ℃, the notched izod shock strength of described polyester is 10ft-lbs/in at least.
42. the film of claim 1 or thin plate, wherein polyester comprises the resistates of at least a catalyzer, described catalyst pack sn-containing compound or its reaction product.
43. goods, it comprises the film or the thin plate of claim 1.
44. one kind comprises the film of claim 1 or the goods of thin plate, wherein in the thick strip of 1/8-in with 10-mil otch according to ASTM D256 under 23 ℃, the notched izod shock strength of polyester is 3ft-lbs/in at least.
45. one kind comprises the film of claim 1 or the goods of thin plate, wherein in the thick strip of 1/4-in with 10-mil otch according to ASTM D256 at 23 ℃, the notched izod shock strength of polyester is 10ff-lbs/in at least.
46. a liquid-crystal display film, it comprises the film or the thin plate of claim 1.
47. the liquid-crystal display film of claim 46, wherein the liquid-crystal display film is the diffuser thin plate.
48. the liquid-crystal display film of claim 46, wherein the liquid-crystal display film is a compensation film.
49. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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) 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 described diol component is 100mol%;
Wherein, the logarithmic viscosity number of described 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
The Tg of wherein said polyester is 85-120 ℃.
50. the film of claim 49 or thin plate, wherein, the logarithmic viscosity number of described polyester is that 0.50-is less than 0.75dL/g.
51. the film of claim 49 or thin plate, wherein, the logarithmic viscosity number of described polyester is 0.60-0.72dL/g.
52. the film of claim 49 or thin plate, the diol component of wherein said polyester comprises 10-30mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol and 70-90mol%1,4-cyclohexanedimethanol.
53. the film of claim 49 or thin plate, the diol component of wherein said polyester comprises 15-25mol%2,2,4, and 4-tetramethyl--1,3-cyclobutanediol and 75-85mol%1,4-cyclohexanedimethanol.
54. the film of claim 49 or thin plate, the Tg of wherein said polyester are 95-115 ℃.
55. the film of claim 49 or thin plate, the Tg of wherein said polyester are 95-115 ℃.
56. film or thin plate, it comprises at least a polyester, and described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
The ii) aromatic dicarboxylic acid residue of 0-30mol%, it has 20 carbon atoms at the most; With
The iii) aliphatic dicarboxylic acid residue of 0-10mol%, it has 16 carbon atoms at the most; With
(b) diol component, it comprises:
I) 2,2,4 of 1-98.99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
The ii) 1,4 cyclohexane dimethanol residue of 1-98.99mol%,
Iii) 0.01-is less than the 15mol% glycol residue;
Wherein total molecular fraction of dicarboxylic acid component be 100mol% and
Total molecular fraction of diol component is 100mol%;
Wherein logarithmic viscosity number is 0.35-1.2dL/g, as being that 0.5g/100ml measures in 60/40 (wt/wt) phenol/tetrachloroethane at 25 ℃ in concentration; With
The Tg of wherein said polyester is 85-120 ℃.
57. film or thin plate, it comprises polymer blend, and this polymer blend comprises at least a polyester, and described polyester comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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;
(b) diol component, it comprises:
I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With
Ii) the 1,4 cyclohexane dimethanol residue of 1-99mol% and
(c) 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 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
The Tg of wherein said polyester is 85-120 ℃.
58. film or thin plate, it comprises polymer blend, and this polymer blend comprises: (I) at least a polyester, and it comprises:
(a) dicarboxylic acid component, it comprises:
I) terephthalic acid residue of 70-100mol%;
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%; With
(II) 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%;
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
The Tg of wherein said polyester is 85-120 ℃.
Applications Claiming Priority (19)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69156705P | 2005-06-17 | 2005-06-17 | |
US60/691,567 | 2005-06-17 | ||
US73145405P | 2005-10-28 | 2005-10-28 | |
US73138905P | 2005-10-28 | 2005-10-28 | |
US60/731,454 | 2005-10-28 | ||
US60/731,389 | 2005-10-28 | ||
US73905805P | 2005-11-22 | 2005-11-22 | |
US73886905P | 2005-11-22 | 2005-11-22 | |
US60/738,869 | 2005-11-22 | ||
US60/739,058 | 2005-11-22 | ||
US75069205P | 2005-12-15 | 2005-12-15 | |
US75068205P | 2005-12-15 | 2005-12-15 | |
US75054705P | 2005-12-15 | 2005-12-15 | |
US75069305P | 2005-12-15 | 2005-12-15 | |
US60/750,547 | 2005-12-15 | ||
US60/750,682 | 2005-12-15 | ||
US60/750,692 | 2005-12-15 | ||
US60/750,693 | 2005-12-15 | ||
PCT/US2006/012065 WO2007001572A1 (en) | 2005-06-17 | 2006-03-30 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101193943A true CN101193943A (en) | 2008-06-04 |
CN101193943B CN101193943B (en) | 2012-09-05 |
Family
ID=39488210
Family Applications (28)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2006800205804A Pending CN101193668A (en) | 2005-06-17 | 2006-03-30 | Dialysis filter shell comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN2006800205626A Active CN101193943B (en) | 2005-06-17 | 2006-03-30 | 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 |
CNA2006800205819A Pending CN101193944A (en) | 2005-06-17 | 2006-03-30 | Anti-protein articles comprising cyclobutanediol |
CNA2006800205255A Pending CN101203540A (en) | 2005-06-17 | 2006-03-30 | Eye device comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 1,4-cyclohexanedimethanol |
CNA200680020572XA Pending CN101193721A (en) | 2005-06-17 | 2006-03-30 | Preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
CNA2006800205838A Pending CN101193945A (en) | 2005-06-17 | 2006-03-30 | LCD films or sheets comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CNA2006800205895A Pending CN101193980A (en) | 2005-06-17 | 2006-03-30 | Methods for preparing transparent formed articles comprising polymer containing a cyclobutanediol |
CN2006800205607A Active CN101193942B (en) | 2005-06-17 | 2006-03-30 | Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and articles made therefrom |
CN2006800205611A Active CN101193932B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
CNA2006800207458A Pending CN101193946A (en) | 2005-06-17 | 2006-03-30 | Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol |
CNA2006800206489A Pending CN101213239A (en) | 2005-06-17 | 2006-03-30 | Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol |
CN2006800207443A Active CN101203544B (en) | 2005-06-17 | 2006-03-30 | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
CNA2006800205700A Pending CN101193979A (en) | 2005-06-17 | 2006-03-30 | Transparent deoxidizing compositions comprising polymer containing a cyclobutanediol and articles prepared therefrom |
CNA2006800205236A Pending CN101193977A (en) | 2005-06-17 | 2006-03-30 | Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CNA2006800205448A Pending CN101203542A (en) | 2005-06-17 | 2006-03-30 | Optical mediam comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN200680020542.9A Active CN101193936B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions comprising a cyclobutanediol and articles prepared therefrom |
CNA2006800205594A Pending CN101193978A (en) | 2005-06-17 | 2006-03-30 | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
CNA2006800205397A Pending CN101193934A (en) | 2005-06-17 | 2006-03-30 | Container comprising polyester compositions which comprise cyclobutanediol |
CN2006800205433A Active CN101193937B (en) | 2005-06-17 | 2006-03-30 | Bottle comprising polyester compositions which comprise cyclobutanediol |
CN2006800205058A Active CN101203541B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature and product made therefrom |
CNA2006800205452A Pending CN101193938A (en) | 2005-06-17 | 2006-03-30 | Polyester compositions containing high amounts of cyclobutanediol and articles made therefrom |
CNA2006800205490A Pending CN101193940A (en) | 2005-06-17 | 2006-03-30 | Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN2006800205378A Active CN101193933B (en) | 2005-06-17 | 2006-03-30 | 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 |
CNA2006800205467A Pending CN101193939A (en) | 2005-06-17 | 2006-03-30 | Polyester compositions containing cyclobutanediol and articles made therefrom |
CNA2006800205823A Pending CN101193733A (en) | 2005-06-17 | 2006-03-30 | Transparent, multilayered article containing polyesters comprising a cyclobutanediol and its preparing method |
CNA2006800205518A Pending CN101193941A (en) | 2005-06-17 | 2006-03-30 | Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN200680020540XA Active CN101193935B (en) | 2005-06-17 | 2006-03-30 | Feeder comprising polyester compositions which comprise cyclobutanediol |
CN2006800206544A Active CN101203543B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2006800205804A Pending CN101193668A (en) | 2005-06-17 | 2006-03-30 | Dialysis filter shell comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
Family Applications After (26)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2006800205819A Pending CN101193944A (en) | 2005-06-17 | 2006-03-30 | Anti-protein articles comprising cyclobutanediol |
CNA2006800205255A Pending CN101203540A (en) | 2005-06-17 | 2006-03-30 | Eye device comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3- cyclobutanediol and 1,4-cyclohexanedimethanol |
CNA200680020572XA Pending CN101193721A (en) | 2005-06-17 | 2006-03-30 | Preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
CNA2006800205838A Pending CN101193945A (en) | 2005-06-17 | 2006-03-30 | LCD films or sheets comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CNA2006800205895A Pending CN101193980A (en) | 2005-06-17 | 2006-03-30 | Methods for preparing transparent formed articles comprising polymer containing a cyclobutanediol |
CN2006800205607A Active CN101193942B (en) | 2005-06-17 | 2006-03-30 | Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and articles made therefrom |
CN2006800205611A Active CN101193932B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
CNA2006800207458A Pending CN101193946A (en) | 2005-06-17 | 2006-03-30 | Film(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol |
CNA2006800206489A Pending CN101213239A (en) | 2005-06-17 | 2006-03-30 | Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol |
CN2006800207443A Active CN101203544B (en) | 2005-06-17 | 2006-03-30 | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
CNA2006800205700A Pending CN101193979A (en) | 2005-06-17 | 2006-03-30 | Transparent deoxidizing compositions comprising polymer containing a cyclobutanediol and articles prepared therefrom |
CNA2006800205236A Pending CN101193977A (en) | 2005-06-17 | 2006-03-30 | Intravenous components comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CNA2006800205448A Pending CN101203542A (en) | 2005-06-17 | 2006-03-30 | Optical mediam comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN200680020542.9A Active CN101193936B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions comprising a cyclobutanediol and articles prepared therefrom |
CNA2006800205594A Pending CN101193978A (en) | 2005-06-17 | 2006-03-30 | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
CNA2006800205397A Pending CN101193934A (en) | 2005-06-17 | 2006-03-30 | Container comprising polyester compositions which comprise cyclobutanediol |
CN2006800205433A Active CN101193937B (en) | 2005-06-17 | 2006-03-30 | Bottle comprising polyester compositions which comprise cyclobutanediol |
CN2006800205058A Active CN101203541B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature and product made therefrom |
CNA2006800205452A Pending CN101193938A (en) | 2005-06-17 | 2006-03-30 | Polyester compositions containing high amounts of cyclobutanediol and articles made therefrom |
CNA2006800205490A Pending CN101193940A (en) | 2005-06-17 | 2006-03-30 | Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN2006800205378A Active CN101193933B (en) | 2005-06-17 | 2006-03-30 | 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 |
CNA2006800205467A Pending CN101193939A (en) | 2005-06-17 | 2006-03-30 | Polyester compositions containing cyclobutanediol and articles made therefrom |
CNA2006800205823A Pending CN101193733A (en) | 2005-06-17 | 2006-03-30 | Transparent, multilayered article containing polyesters comprising a cyclobutanediol and its preparing method |
CNA2006800205518A Pending CN101193941A (en) | 2005-06-17 | 2006-03-30 | Glass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
CN200680020540XA Active CN101193935B (en) | 2005-06-17 | 2006-03-30 | Feeder comprising polyester compositions which comprise cyclobutanediol |
CN2006800206544A Active CN101203543B (en) | 2005-06-17 | 2006-03-30 | Polyester compositions which comprise cyclobutanediol having certain cis/trans ratios |
Country Status (1)
Country | Link |
---|---|
CN (28) | CN101193668A (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7838620B2 (en) | 2005-06-17 | 2010-11-23 | Eastman Chemical Company | Thermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol |
US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
US8501287B2 (en) * | 2007-11-21 | 2013-08-06 | Eastman Chemical Company | Plastic baby bottles, other blow molded articles, and processes for their manufacture |
US8198371B2 (en) * | 2008-06-27 | 2012-06-12 | Eastman Chemical Company | Blends of polyesters and ABS copolymers |
US8580872B2 (en) * | 2011-07-21 | 2013-11-12 | Eastman Chemical Company | Sulfopolyester polymer compositions with improved water dispersibility |
US20130217830A1 (en) * | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
US9273206B2 (en) * | 2012-07-09 | 2016-03-01 | Eastman Chemical Company | Ternary blends of terephthalate or isophthalate polyesters containing EG, CHDM and TMCD |
CN104769037B (en) * | 2012-10-15 | 2018-10-23 | 旭化成株式会社 | Thermoplastic resin composition and its formed body |
US9447257B2 (en) * | 2014-02-10 | 2016-09-20 | Eastman Chemical Company | Polymers combined with certain additives and devices made thererom |
CN104530582A (en) * | 2014-12-10 | 2015-04-22 | 常州诺瑞格纳米科技有限公司 | Nontoxic green environment-friendly disposable tableware |
KR101849830B1 (en) * | 2015-06-30 | 2018-04-18 | 롯데첨단소재(주) | Polyester resin composition with excellent impact resistance and light reliability and molded article using the same |
CN106189118A (en) * | 2016-08-11 | 2016-12-07 | 苏州柯创电子材料有限公司 | There is insulation film and the manufacture method thereof of vapor water barriers function |
CN106220834A (en) * | 2016-08-11 | 2016-12-14 | 苏州柯创电子材料有限公司 | It is applicable to insulation film and the manufacture method thereof of high steam environment |
US20180171631A1 (en) * | 2016-12-21 | 2018-06-21 | Eastman Chemical Company | Polyester-based tape composites for construction panel reinforcement |
US11274202B2 (en) * | 2017-08-30 | 2022-03-15 | Eastman Chemical Company | Copolyester resin composition with improved melt flow properties |
US10543656B2 (en) * | 2018-01-11 | 2020-01-28 | Eastman Chemical Company | Tough shrinkable films |
CN109781723B (en) * | 2019-03-01 | 2022-01-07 | 广州钰芯传感科技有限公司 | Preparation method and application of hydrogen ion response interdigital electrode |
WO2020263591A1 (en) * | 2019-06-26 | 2020-12-30 | Eastman Chemical Company | Multilayer polymeric cushion films for foldable displays |
KR20220041177A (en) * | 2019-07-29 | 2022-03-31 | 이스트만 케미칼 컴파니 | Process for making polyester with recycled monomers from pyrolysis and methanolysis |
KR20220092907A (en) * | 2019-10-25 | 2022-07-04 | 이스트만 케미칼 컴파니 | Copolyester produced from recycled copolyester |
WO2023206073A1 (en) * | 2022-04-26 | 2023-11-02 | Eastman Chemical (China) Co., Ltd. | Flame retardant copolyester compositions |
WO2023225844A1 (en) * | 2022-05-24 | 2023-11-30 | Eastman Chemical (China) Co., Ltd. | Plastic molded articles for use as vapor/suspension delivery devices |
CN115322348B (en) * | 2022-08-17 | 2024-02-06 | 擎天材料科技有限公司 | Low-temperature-cured semi-crystalline polyester resin and preparation method and application thereof |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3313777A (en) * | 1959-12-18 | 1967-04-11 | Eastman Kodak Co | Linear polyesters and polyester-amides from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols |
FR83790E (en) * | 1959-12-18 | 1964-10-09 | Kodak Pathe | New polymers derived from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols and their industrial applications |
FR1456345A (en) * | 1964-12-07 | 1966-10-21 | Eastman Kodak Co | New process for the preparation of polyesters and new products obtained |
US3502620A (en) * | 1967-05-11 | 1970-03-24 | Eastman Kodak Co | Branched polyesters containing terminal carboxyl groups |
US3629202A (en) * | 1969-09-12 | 1971-12-21 | Eastman Kodak Co | Treating polyesters with organic acids for improved stability |
US4263364A (en) * | 1979-12-14 | 1981-04-21 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheets |
EP0745628B1 (en) * | 1995-05-31 | 2002-04-03 | Shell Internationale Researchmaatschappij B.V. | Copolyester composition |
US5955565A (en) * | 1996-12-28 | 1999-09-21 | Eastman Chemical Company | Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol |
US6011124A (en) * | 1996-12-28 | 2000-01-04 | Eastman Chemical Company | Blends of bisphenol a polycarbonate and polyesters |
US6043322A (en) * | 1996-12-28 | 2000-03-28 | Eastman Chemical Company | Clear polycarbonate and polyester blends |
US5942585A (en) * | 1996-12-28 | 1999-08-24 | Eastman Chemical Company | Polycarbonate and polyester blends |
US5989663A (en) * | 1996-12-30 | 1999-11-23 | Eastman Chemical Company | Blow-molding polyesters from terephthalic acid, 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol, and ethylene glycol |
US6120889A (en) * | 1999-06-03 | 2000-09-19 | Eastman Chemical Company | Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures |
-
2006
- 2006-03-30 CN CNA2006800205804A patent/CN101193668A/en active Pending
- 2006-03-30 CN CN2006800205626A patent/CN101193943B/en active Active
- 2006-03-30 CN CNA2006800205819A patent/CN101193944A/en active Pending
- 2006-03-30 CN CNA2006800205255A patent/CN101203540A/en active Pending
- 2006-03-30 CN CNA200680020572XA patent/CN101193721A/en active Pending
- 2006-03-30 CN CNA2006800205838A patent/CN101193945A/en active Pending
- 2006-03-30 CN CNA2006800205895A patent/CN101193980A/en active Pending
- 2006-03-30 CN CN2006800205607A patent/CN101193942B/en active Active
- 2006-03-30 CN CN2006800205611A patent/CN101193932B/en active Active
- 2006-03-30 CN CNA2006800207458A patent/CN101193946A/en active Pending
- 2006-03-30 CN CNA2006800206489A patent/CN101213239A/en active Pending
- 2006-03-30 CN CN2006800207443A patent/CN101203544B/en active Active
- 2006-03-30 CN CNA2006800205700A patent/CN101193979A/en active Pending
- 2006-03-30 CN CNA2006800205236A patent/CN101193977A/en active Pending
- 2006-03-30 CN CNA2006800205448A patent/CN101203542A/en active Pending
- 2006-03-30 CN CN200680020542.9A patent/CN101193936B/en active Active
- 2006-03-30 CN CNA2006800205594A patent/CN101193978A/en active Pending
- 2006-03-30 CN CNA2006800205397A patent/CN101193934A/en active Pending
- 2006-03-30 CN CN2006800205433A patent/CN101193937B/en active Active
- 2006-03-30 CN CN2006800205058A patent/CN101203541B/en active Active
- 2006-03-30 CN CNA2006800205452A patent/CN101193938A/en active Pending
- 2006-03-30 CN CNA2006800205490A patent/CN101193940A/en active Pending
- 2006-03-30 CN CN2006800205378A patent/CN101193933B/en active Active
- 2006-03-30 CN CNA2006800205467A patent/CN101193939A/en active Pending
- 2006-03-30 CN CNA2006800205823A patent/CN101193733A/en active Pending
- 2006-03-30 CN CNA2006800205518A patent/CN101193941A/en active Pending
- 2006-03-30 CN CN200680020540XA patent/CN101193935B/en active Active
- 2006-03-30 CN CN2006800206544A patent/CN101203543B/en active Active
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101193943B (en) | 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 | |
JP5795615B2 (en) | Polyester compositions containing a small amount of cyclobutanediol and articles made therefrom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |