CN101193668A

CN101193668A - Dialysis filter shell comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

Info

Publication number: CN101193668A
Application number: CNA2006800205804A
Authority: CN
Inventors: E·D·克劳福德; D·S·波特; G·W·康奈尔
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2005-06-17
Filing date: 2006-03-30
Publication date: 2008-06-04
Also published as: CN101193942A; CN101203541A; CN101193733A; CN101193932A; CN101193946A; CN101193935B; CN101203543B; CN101193978A; CN101193943A; CN101203540A; CN101193945A; CN101193939A; CN101193979A; CN101193944A; CN101193938A; CN101203543A; CN101193980A; CN101193933B; CN101193937A; CN101193932B

Abstract

Disclosed are polyester compositions comprising polyesters which comprise (a) a dicarboxylic acid component having terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues or ester residues thereof; 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 1,4-cyclohexanedimethanol residues.

Description

Comprise by 2,2,4 4-tetramethyl-1,3-cyclobutanediol and 1, the dialysis filter shell of the polymer blend that the 4-cyclohexanedimethanol forms

Invention field

Generality of the present invention relates to the dialysis filter shell that comprises polymer blend, this polymer blend is by p-phthalic acid or its ester or its mixture, 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol, with 1, the preparation of 4-cyclohexanedimethanol, have two or more certain combination of high impact, high glass-transition temperature (Tg), toughness, some logarithmic viscosity number, low ductile-brittle transition temperature, good color and transparency, low-density, chemical resistance, hydrolytic stability and long crystallization half-life, this allows them to be configured as goods easily.For example, dialysis filter shell of the present invention can have certain combination of two or more following performances: toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

Background of invention

Dialysis filter shell can be by multiple plastic material by several different methods, for example injection moulding production.Merlon is widely used in multiple molding and extrusion molding is used.

Poly-(p-phthalic acid 1,4-hexamethylene dimethyl ester) (PCT), and be a kind of only based on p-phthalic acid or its ester or its mixture and 1, and the polyester of 4-cyclohexanedimethanol is known in this area and have commercially available.This polyester is rapid crystallization when being cooled off by melt, makes to form very difficulty of amorphous goods by methods known in the art such as extrusion molding, injection moulding etc.For the crystalline rate of the PCT that slows down, can prepare the copolyesters that comprises other dicarboxylic acids or glycol such as M-phthalic acid or ethylene glycol.These ethylene glycol-or the PCT of phthalic acid-modification also be known in this area and have commercially available.

A kind of common copolyesters that is used to produce thin film, thin plate and mechanograph is by p-phthalic acid, 1,4-cyclohexanedimethanol and ethylene glycol.Though these copolyesters are useful in many final uses field, when comprising enough modification ethylene glycol so that long crystallization half-life to be provided in prescription, they are demonstrating defective such as glass transition temperature and impact strength aspect of performance.For example, by p-phthalic acid, 1, the copolyesters with sufficiently long crystallization half-life of 4-cyclohexanedimethanol and ethylene glycol can provide amorphous products, and this product demonstration it is believed that than undesirable higher ductile-brittle transition temperature of compositions disclosed here and lower glass transition temperature.

4, the Merlon of 4 '-isopropylidene biphenol (bisphenol-a polycarbonate) has been used as polyester succedaneum known in the art and has been well-known engineering moulded plastic.Bisphenol-a polycarbonate is transparent high performance plastics, and it has good physical property, for example dimensional stability, high-fire resistance and good impact strength.Although bisphenol-a polycarbonate has many good physical properties, its higher melt viscosity causes the melt processable of difference, and this Merlon shows the chemical resistance of difference.It also is difficult to hot forming.

Comprise 2,2,4,4-tetramethyl-1, the polymer of 3-cyclobutanediol have also carried out general description in the art.Yet these polymer show high logarithmic viscosity number, high melt viscosity and/or high Tg (glass transition temperature) usually, make that the equipment that is used for industry is not enough to make or post polymerization is processed these materials.

Therefore, this area need comprise the dialysis filter shell of at least a polymer, this polymer has the combination of two or more performances that are selected from least a following performance: the toughness of polyester, high glass-transition temperature, high impact, hydrolytic stability, chemical resistance, long crystallization half-life, low ductile-brittle transition temperature, good color and transparency, lower density and/or hot formability remain on the machinability on the standard device that is used for industry simultaneously.

Summary of the invention

It is believed that with regard to one or more following performances: high impact, hydrolytic stability, toughness, chemical resistance, good color and transparency, long crystallization half-life, low ductile-brittle transition temperature, lower proportion and/or hot formability, some dialysis filter shell that comprises polymer blend is more superior than polyester known in the art and Merlon, described polymer blend is by p-phthalic acid, its ester or its mixture, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol forms, and has some monomer composition, logarithmic viscosity number and/or glass transition temperature.These compositionss it is believed that aspect thermostability similar with Merlon, and remain machinable on standard industry equipment.

On the one hand, the present invention relates to comprise the dialysis filter shell of at least a polymer blend, described polymer blend comprises at least a polyester, and described polyester comprises:

(a) dicarboxylic acid component comprises:

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

Ii) 0-30mol%'s has an aromatic dicarboxylic acid residue of 20 carbon atoms at the most; With

Iii) 0-10mol%'s has an aliphatic dicarboxylic acid residue of 16 carbon atoms at the most; With

(b) diol component comprises:

I) 2,2,4 of 10-99mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 1-90mol%, 4-cyclohexanedimethanol residue,

Wherein total mol% of dicarboxylic acid component is 100mol%, and total mol% of diol component is 100mol%; With

Wherein said polyester concentration with 0.5g/100ml in 60/40 (wt/wt) phenol/sym-tetrachloroethane is 0.1-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 100-200 ℃ Tg.

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-70mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 30-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester concentration with 0.5g/100ml in 60/40 (wt/wt) phenol/sym-tetrachloroethane is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 100-160 ℃ Tg.

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-70mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 30-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester concentration with 0.5g/100ml in 60/40 (wt/wt) phenol/sym-tetrachloroethane is 0.35-0.75dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 100-150 ℃ Tg.

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-60mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 40-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester has 100-150 ℃ Tg.

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-90mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 10-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester has 100-200 ℃ Tg.

(I) at least a polyester comprises:

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 10-99mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 1-90mol%, 4-cyclohexanedimethanol residue and

(II) residue of at least a branching agent;

Wherein said polyester has 100-200 ℃ Tg.

(I) at least a polyester comprises:

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 10-99mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 1-90mol%, 4-cyclohexanedimethanol residue and

(II) at least a heat stabilizer or its product;

Wherein said polyester has 100-200 ℃ Tg.

On the one hand, polymer blend comprises at least a Merlon.

On the one hand, polymer blend does not comprise Merlon.

On the one hand, be used for polyester of the present invention and comprise the glycol residue that is less than 15mol%, for example 0.01-is less than the glycol residue of 15mol%.

On the one hand, be used for polyester of the present invention and do not comprise glycol residue.

On the one hand, be used for polymer blend of the present invention and comprise at least a heat stabilizer and/or its product.

On the one hand, be used for polyester of the present invention and do not comprise branching agent, perhaps selectively, at least a branching agent before the polyester or during add.

On the one hand, be used for polyester of the present invention and comprise at least a branching agent, and do not consider to add its method or order.

On the one hand, be used for polyester of the present invention can't help alone or in combination 1, ammediol or 1,4-butanediol preparation.In others, alone or in combination 1, ammediol or 1,4-butanediol can be used for preparation and are used for polyester of the present invention.

In one aspect of the invention, the cis-2,2 that is used for used some polyester of the present invention, 4,4-tetramethyl-1, the mol% of 3-cyclobutanediol are greater than 50mol% or greater than 55mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or greater than 70mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; Cis-2,2,4 wherein, 4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1, total mol% of 3-cyclobutanediol amounts to and equals 100mol%.

In one aspect of the invention, be used for 2,2,4 of used some polyester of the present invention, 4-tetramethyl-1, the mol% of the isomer of 3-cyclobutanediol are 30-70mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or 30-70mol% trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or 40-60mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or 40-60mol% trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, cis-2,2 wherein, 4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1, total mol% of 3-cyclobutanediol amounts to and equals 100mol%.

On the one hand, polymer blend is used for dialysis filter shell, includes but not limited to moulding article, includes but not limited to injection-molded item.

Equally, on the one hand, use polymer blend of the present invention can before melt-processed or thermoforming, minimize and/or get rid of drying steps.

On the one hand, it can be amorphous or hemicrystalline being used for some polyester of the present invention.On the one hand, be used for some polyester of the present invention and can have lower degree of crystallinity.Therefore being used for some polyester of the present invention can have essentially amorphous form, means that polyester comprises unordered substantially polymer areas.

The accompanying drawing summary

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

Fig. 2 is presented at the middle comonomer of notched izod impact strength test (ASTM D256,1/8 inch thick, 10 mil breach) to brittle-ductile transition temperature (T _Bd) the figure of influence.

Fig. 3 shows 2,2,4,4-tetramethyl-1, and 3-cyclobutanediol compositions is formed the figure to the influence of the glass transition temperature (Tg) of copolyesters.

Detailed Description Of The Invention

By can more easily understanding the present invention with reference to the detailed description of following certain embodiments of the invention and work embodiment.

According to purpose of the present invention, certain embodiments of the present invention are recorded in the summary of the invention and are further described under this. Equally, other embodiment of the present invention is described in this.

It is believed that the polyester that is included in the dialysis filter shell of the present invention that is recorded in this and/or polymer blend can have the unique combination such as high impact, medium two or more physical properties to high glass-transition temperature, chemical resistance, hydrolytic stability, toughness, low ductile-brittle transition temperature, good color and transparency, low-density, long crystallization half-life and good processability, allow them to be configured as goods thus easily. In some embodiments of the present invention, polyester has special performance combination and/or the performance combination of good impact strength, heat resistance and processability and/or the combination of two or more above-mentioned performances of good impact strength, heat resistance, chemical resistance, density, never thought in the past that these performance combinations were present in the dialysis filter shell that comprises polymer blend, described polymer blend comprises polyester disclosed herein.

Used term " dialysis filter shell " refers to have the protectiveness shell of a plurality of openings be used to holding a plurality of doughnuts or pipe herein, can be used for the patient is introduced or discharge dislysate. In one embodiment, the cross-sectional area of an opening in the protectiveness shell is 0.001 cm²-less than 50cm²。

In one embodiment, dialysis filter shell has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

Used term " polyester " is intended comprising " copolyesters " and is interpreted as representing reacting the synthetic polymer for preparing by one or more bifunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctionality hydroxy compounds and/or multifunctional hydroxy compounds herein. Usually the bifunctional carboxylic acid can be dicarboxylic acids, and the difunctionality hydroxy compounds can be dihydroxy alcohol, for example glycol. In addition, used term " diacid " or " dicarboxylic acids " comprise polyfunctional acid, for example branching agent among the application. Used term " glycol " includes but not limited to dihydroxylic alcohols, glycol and/or multifunctional hydroxy compounds among the application. Selectively, the bifunctional carboxylic acid can be hydroxycarboxylic acid, P-hydroxybenzoic acid for example, and the difunctionality hydroxy compounds can be the virtue nuclear with 2 hydroxyl substituents, for example quinhydrones. Used term " residue " expression herein is incorporated into any organic structure in the polymer by polycondensation and/or esterification by corresponding monomer. Used term " repetitive " expression herein has dicarboxylic acid residue and the diol residue by the combination of carbonyl oxygen base. Therefore, for example, dicarboxylic acid residue can be derived from carboxylic acid halides, ester, salt, acid anhydrides or its mixture of dicarboxylic acid monomer or its combination. Therefore, used term dicarboxylic acids intends comprising any derivative of dicarboxylic acids and dicarboxylic acids herein, comprise for carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture of its combination of the course of reaction of glycol reaction preparation polyester. Any derivative of terephthalic acid (TPA) itself and residue and terephthalic acid (TPA) intended comprising in used term " terephthalic acid (TPA) " herein, comprises for preparing carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture or its residue of its combination of the course of reaction of polyester with the glycol reaction.

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

Be used for polyester of the present invention and usually can and be incorporated into polyester polymers as dicarboxylic acids and the glycol preparation of their corresponding residue by equal proportion reaction basically. Therefore, polyester of the present invention can comprise basically sour residue (100mol%) and glycol (and/or multifunctional hydroxy compounds) residue (100mol%) of equimolar ratio example, so that the total mole number of repetitive equals 100 mol%. 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, polyester comprises the 30mol% M-phthalic acid, is illustrated in altogether that polyester comprises the 30mol% isophthalic acid residues in the 100mol% acid residue. Therefore, in every 100mol acid residue, there is the 30mol isophthalic acid residues. In another example, based on the total diol residue, polyester comprises the 30mol% TMCBD, is illustrated in altogether that polyester comprises 30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue in the 100mol% diol residue. Therefore, in every 100mol diol residue, there is 30mol TMCBD residue.

In other side of the present invention, the Tg that is used for the polyester of dialysis filter shell of the present invention can be at least a of following scope: 100-200 ℃; 100-190 ℃; 100-180 ℃; 100-170 ℃; 100-160 ℃; 100-155 ℃; 100-150 ℃; 100-145 ℃; 140 ℃ of 100-; 100-138 ℃; 100-135 ℃; 100-130 ℃; 100-125 ℃; 100-120 ℃; 100-115 ℃; 100-110 ℃; 105-200 ℃; 105-190 ℃; 105-180 ℃; 170 ℃ of 105-; 105-160 ℃; 105-155 ℃; 105-150 ℃; 105-145 ℃; 105-140 ℃; 105-138 ℃; 105-135 ℃; 105-130 ℃; 105-125 ℃; 105-120 ℃; 115 ℃ of 105-; 105-110 ℃; Be higher than 25 ℃ of 105-1; Be higher than 105-120 ℃; Be higher than 115 ℃ of 105-; Be higher than 105-110 ℃; 110-200 ℃; 110-190 ℃; 110-180 ℃; 170 ℃ of 110-; 110-160 ℃; 110-155 ℃; 110-150 ℃; 110-145 ℃; 110-140 ℃; 110-138 ℃; 110-135 ℃; 110-130 ℃; 110-125 ℃; 110-120 ℃; 115 ℃ of 110-; 115-200 ℃; 115-190 ℃; 115-180 ℃; 115-170 ℃; 115-160 ℃; 115-155 ℃; 115-150 ℃; 115-145 ℃; 115-140 ℃; 115-138 ℃; 135 ℃ of 115-; 110-130 ℃; 115-125 ℃; 115-120 ℃; 120-200 ℃; 120-190 ℃; 120-180 ℃; 120-170 ℃; 120-160 ℃; 120-155 ℃; 120-150 ℃; 145 ℃ of 120-; 120-140 ℃; 120-138 ℃; 120-135 ℃; 120-130 ℃; 125-200 ℃; 125-190 ℃; 125-180 ℃; 125-170 ℃; 125-160 ℃; 125-155 ℃; 150 ℃ of 125-; 125-145 ℃; 125-140 ℃; 125-138 ℃; 125-135 ℃; 127-200 ℃; 127-190 ℃; 127-180 ℃; 127-170 ℃; 127-160 ℃; 127-150 ℃; 145 ℃ of 127-; 127-140 ℃; 127-138 ℃; 127-135 ℃; 130-200 ℃; 130-190 ℃; 130-180 ℃; 130-170 ℃; 130-160 ℃; 130-155 ℃; 130-150 ℃; 145 ℃ of 130-; 130-140 ℃; 130-138 ℃; 130-135 ℃; 135-200 ℃; 135-190 ℃; 135-180 ℃; 135-170 ℃; 135-160 ℃; 135-155 ℃; 135-150 ℃; 145 ℃ of 135-; 135-140 ℃; 140-200 ℃; 140-190 ℃; 140-180 ℃; 140-170 ℃; 140-160 ℃; 140-155 ℃; 140-150 ℃; 140-145 ℃; 148-200 ℃; 190 ℃ of 148-; 148-180 ℃; 148-170 ℃; 148-160 ℃; 148-155 ℃; 148-150 ℃; 150-200 ℃; 150-190 ℃; 150-180 ℃; 150-170 ℃; 150-160 ℃; 190 ℃ of 155-; 155-180 ℃; 155-170 ℃; With 155-165 ℃.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 10-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-90mol%1,4-cyclohexanedimethanol; 10-95mol% TMCBD and 5-90mol%1, the 4-cyclohexanedimethanol; 10-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-90mol%1,4-cyclohexanedimethanol; 10-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-90mol%1,4-cyclohexanedimethanol; 10-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-90mol%1,4-cyclohexanedimethanol; 10-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-90mol% 1,4-CHDM; 10-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-90 mol%1,4-cyclohexanedimethanol; 10-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-90mol%1,4-cyclohexanedimethanol; 10-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-90mol%1,4-cyclohexanedimethanol; 10-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-90mol%1,4-cyclohexanedimethanol; 10-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-90mol%1,4-cyclohexanedimethanol; 10-is less than the 50mol% TMCBD with greater than 50-90mol%1, the 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-CHDM; 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 75-90mol%1,4-cyclohexanedimethanol; 11-25mol% TMCBD and 75-89mol%1, the 4-cyclohexanedimethanol; 12-25 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-88mol%1,4-cyclohexanedimethanol; And 13-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-87mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 14-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-86mol%1,4-cyclohexanedimethanol; 14-95mol% TMCBD and 5-86mol%1, the 4-cyclohexanedimethanol; 14-90 mol%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; 14-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-86mol%1,4-cyclohexanedimethanol; 14-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-86mol% 1,4-CHDM; 14-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-86 mol%1,4-cyclohexanedimethanol; 14-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-86mol%1,4-cyclohexanedimethanol; 14-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-86mol%1,4-cyclohexanedimethanol; 14-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-86mol%1,4-cyclohexanedimethanol; And 14-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-86mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited to that at least a of following combination range: 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-CHDM; 14-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-86 mol%1,4-cyclohexanedimethanol; 14-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-86mol%1,4-cyclohexanedimethanol; And 14-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-86mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 15-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-85mol%1,4-cyclohexanedimethanol; 15-95mol% TMCBD and 5-85mol%1, the 4-cyclohexanedimethanol; 15-90 mol%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; 15-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-85mol%1,4-cyclohexanedimethanol; 15-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-85mol% 1,4-CHDM; 15-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-85 mol%1,4-cyclohexanedimethanol; 15-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-85mol%1,4-cyclohexanedimethanol; 15-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-85mol%1,4-cyclohexanedimethanol; 15-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-85mol%1,4-cyclohexanedimethanol; And 15-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-85mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited to that at least a of following combination range: 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-CHDM; 15-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-85 mol%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; 15-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-80mol%1,4-cyclohexanedimethanol; And 17-23mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77-83mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 20-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-80mol%1,4-cyclohexanedimethanol; 20-95mol% TMCBD and 5-80mol%1, the 4-cyclohexanedimethanol; 20-90 mol%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-CHDM; 20-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-80 mol%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% TMCBD and 55-80mol%1, the 4-cyclohexanedimethanol; 20-40 mol%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 75-80 mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 25-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-75mol%1,4-cyclohexanedimethanol; 25-95mol% TMCBD and 5-75mol%1, the 4-cyclohexanedimethanol; 25-90 mol%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-CHDM; 25-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-75 mol%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% TMCBD and 55-75mol%1, the 4-cyclohexanedimethanol; 25-40 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-75mol%1,4-cyclohexanedimethanol; 25-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-75mol%1,4-cyclohexanedimethanol; And 25-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-75mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 30-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-70mol%1,4-cyclohexanedimethanol; 30-95mol% TMCBD and 5-70mol%1, the 4-cyclohexanedimethanol; 30-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-70mol%1,4-cyclohexanedimethanol; 30-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-70mol%1,4-cyclohexanedimethanol; 30-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-70mol%1,4-cyclohexanedimethanol; 30-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-70mol% 1,4-CHDM; 30-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-70 mol%1,4-cyclohexanedimethanol; 30-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-70mol%1,4-cyclohexanedimethanol; 30-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-70mol%1,4-cyclohexanedimethanol; 30-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-70mol%1,4-cyclohexanedimethanol; 30-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-70mol%1,4-cyclohexanedimethanol; 30-is less than the 50mol% TMCBD with greater than 50-70mol%1, the 4-cyclohexanedimethanol; 30-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-70mol%1,4-cyclohexanedimethanol; 30-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-70mol%1,4-cyclohexanedimethanol; 30-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-70mol% 1,4-CHDM.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 35-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-65mol%1,4-cyclohexanedimethanol; 35-95mol% TMCBD and 5-65mol%1, the 4-cyclohexanedimethanol; 35-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-65mol%1,4-cyclohexanedimethanol; 35-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-65mol%1,4-cyclohexanedimethanol; 35-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-65mol%1,4-cyclohexanedimethanol; 35-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-65mol% 1,4-CHDM; 35-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-65 mol%1,4-cyclohexanedimethanol; 35-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-65mol%1,4-cyclohexanedimethanol; 35-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-65mol%1,4-cyclohexanedimethanol; 35-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-65mol%1,4-cyclohexanedimethanol; 35-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-65mol%1,4-cyclohexanedimethanol; 35-is less than the 50mol% TMCBD with greater than 50-65mol%1, the 4-cyclohexanedimethanol; 35-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-65mol%1,4-cyclohexanedimethanol; 35-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-65mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 37-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-63mol%1,4-cyclohexanedimethanol; 37-95mol% TMCBD and 5-63mol%1, the 4-cyclohexanedimethanol; 37-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-63mol%1,4-cyclohexanedimethanol; 37-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-63mol%1,4-cyclohexanedimethanol; 37-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-63mol%1,4-cyclohexanedimethanol; 37-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-63mol% 1,4-CHDM; 37-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-63 mol%1,4-cyclohexanedimethanol; 37-63mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 37-63mol%1,4-cyclohexanedimethanol; 37-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-63mol%1,4-cyclohexanedimethanol; 37-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-63mol%1,4-cyclohexanedimethanol; 37-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-63mol%1,4-cyclohexanedimethanol; 37-is less than the 50mol% TMCBD with greater than 50-63mol%1, the 4-cyclohexanedimethanol; 37-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-63mol%1,4-cyclohexanedimethanol; 37-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-63mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 40-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-60mol%1,4-cyclohexanedimethanol; 40-95mol% TMCBD and 5-60mol%1, the 4-cyclohexanedimethanol; 40-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-60mol%1,4-cyclohexanedimethanol; 40-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-60mol%1,4-cyclohexanedimethanol; 40-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-60mol%1,4-cyclohexanedimethanol; 40-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-60mol% 1,4-CHDM; 40-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-60 mol%1,4-cyclohexanedimethanol; 40-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-60mol%1,4-cyclohexanedimethanol; 40-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-60mol%1,4-cyclohexanedimethanol; 40-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-60mol%1,4-cyclohexanedimethanol; 40-is less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50-60mol%1,4-cyclohexanedimethanol; 40-50 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-60mol%1,4-cyclohexanedimethanol; And 40-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-60mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 45-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-55mol%1,4-cyclohexanedimethanol; 45-95mol% TMCBD and 5-55mol%1, the 4-cyclohexanedimethanol; 45-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-55mol%1,4-cyclohexanedimethanol; 45-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-55mol%1,4-cyclohexanedimethanol; 45-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-55mol%1,4-cyclohexanedimethanol; 45-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-55mol% 1,4-CHDM; 45-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-55 mol%1,4-cyclohexanedimethanol; 45-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-55mol%1,4-cyclohexanedimethanol; 45-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-55mol%1,4-cyclohexanedimethanol; Greater than 45-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-be less than 55mol%1, the 4-cyclohexanedimethanol; 45-55mol% TMCBD and 45-55mol%1, the 4-cyclohexanedimethanol; And 45-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-55mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: greater than 50-99mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 5-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-80mol% TMCBD and 20-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; Greater than 50-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-be less than 50mol%1, the 4-cyclohexanedimethanol; Greater than 50-60mol% TMCBD and 40-less than 50mol%1, the 4-cyclohexanedimethanol; And greater than 50-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-are less than the 50mol% 1,4-CHDM.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 50-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-50mol%1,4-cyclohexanedimethanol; 50-95mol% TMCBD and 5-50mol%1, the 4-cyclohexanedimethanol; 50-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-50mol%1,4-cyclohexanedimethanol; 50-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-50mol%1,4-cyclohexanedimethanol; 50-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-50mol%1,4-cyclohexanedimethanol; 50-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-50mol% 1,4-CHDM; 50-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-50 mol%1,4-cyclohexanedimethanol; 50-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-50mol%1,4-cyclohexanedimethanol; 50-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-50mol%1,4-cyclohexanedimethanol; And 50-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-50mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 55-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-45mol%1,4-cyclohexanedimethanol; 55-95mol% TMCBD and 5-45mol%1, the 4-cyclohexanedimethanol; 55-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-45mol%1,4-cyclohexanedimethanol; 55-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-45mol%1,4-cyclohexanedimethanol; 55-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-45mol%1,4-cyclohexanedimethanol; 55-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-45mol% 1,4-CHDM; 55-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-45 mol%1,4-cyclohexanedimethanol; 55-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-45mol%1,4-cyclohexanedimethanol; And 55-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-45mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 60-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-40mol%1,4-cyclohexanedimethanol; 60-95mol% TMCBD and 5-40mol%1, the 4-cyclohexanedimethanol; 60-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-40mol%1,4-cyclohexanedimethanol; 60-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-40mol%1,4-cyclohexanedimethanol; 60-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-40mol%1,4-cyclohexanedimethanol; 60-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-40mol% 1,4-CHDM; And 60-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-40mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 65-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-35mol%1,4-cyclohexanedimethanol; 65-95mol% TMCBD and 5-35mol%1, the 4-cyclohexanedimethanol; 65-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-35mol%1,4-cyclohexanedimethanol; 65-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-35mol%1,4-cyclohexanedimethanol; 65-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-35mol%1,4-cyclohexanedimethanol; 65-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-35mol% 1,4-CHDM; And 65-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-35mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 70-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-30mol%1,4-cyclohexanedimethanol; 70-95mol% TMCBD and 5-30mol%1, the 4-cyclohexanedimethanol; 70-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-30mol%1,4-cyclohexanedimethanol; 70-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-30mol%1,4-cyclohexanedimethanol; 70-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-30mol%1,4-cyclohexanedimethanol; And 70-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-30 mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 75-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-25mol%1,4-cyclohexanedimethanol; 75-95mol% TMCBD and 5-25mol%1, the 4-cyclohexanedimethanol; 75-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-25mol%1,4-cyclohexanedimethanol; 75-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-25mol%1,4-cyclohexanedimethanol; And 75-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-25mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: 80-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-20mol%1,4-cyclohexanedimethanol; 80-95mol% TMCBD and 5-20mol%1, the 4-cyclohexanedimethanol; 80-90 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-20mol%1,4-cyclohexanedimethanol; And 80-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-20mol%1,4-cyclohexanedimethanol.

In other side of the present invention, the diol component that is used for the polyester of dialysis filter shell of the present invention includes but not limited at least a of following combination range: greater than 45-55mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-be less than 55mol%1, the 4-cyclohexanedimethanol; Greater than 45-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-be less than 55mol%1, the 4-cyclohexanedimethanol; 46-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-54 mol%1,4-cyclohexanedimethanol; And 46-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-54mol%1,4-cyclohexanedimethanol.

Except above-mentioned listed glycol, the polyester that is used for the polymer blend of dialysis filter shell of the present invention also can be by 1,3-PD, BDO or the preparation of its mixture. Expection is by 1, the composition of the present invention of ammediol, BDO or the preparation of its mixture can have at least one of at least one of Tg scope described herein, logarithmic viscosity number scope described herein and/or at least one of glycol described herein or two acid ranges. In addition or selectively, also can be by 1,4-CHDM with at least a following amount preparation: 0.1-99mol% by the polyester of 1,3-PD or BDO or the preparation of its mixture; 0.1-90mol%; 0.1-80mol%; 0.1-70mol%; 0.1-60 mol%; 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%; 1-90mol%, 1-80mol%; 1-70mol%; 1-60mol%; 1-50 mol%; 1-40mol%; 1-35mol%; 1-30mol%; 1-25mol%; 1-20mol%; 1-15mol%; 1-10mol%; 1-5mol%; 5-99mol%, 5-90mol%, 5-80 mol%; 5-70mol%; 5-60mol%; 5-50mol%; 5-40mol%; 5-35mol%; 5-30mol%; 5-25mol%; 5-20mol%; And 5-15mol%; 5-10mol%; 10-99mol%; 10-90mol%; 10-80mol%; 10-70mol%; 10-60mol%; 10-50mol%; 10-40mol%; 10-35mol%; 10-30mol%; 10-25mol%; 10-20mol%; 10-15mol%; 20-99mol%; 20-90mol%; 20-80mol%; 20-70mol%; 20-60mol%; 20-50mol%; 20-40mol%; 20-35mol%; 20-30mol%; And 20-25mol%.

For certain embodiments of the present invention, be used for polyester of the present invention and can be presented at 60/40 (wt/wt) phenol/tetrachloroethanes with at least one in the following logarithmic viscosity number of 25 ℃ of mensuration of the concentration of 0.5g/100ml: 0.10-1.2dL/g; 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; 0.20-1 dL/g; 0.20-less than 1dL/g; 0.20-0.98dL/g; 0.20-0.95dL/g; 0.20-0.90 dL/g; 0.20-0.85dL/g; 0.20-0.80dL/g; 0.20-0.75dL/g; 0.20-less than 0.75 dL/g; 0.20-0.72dL/g; 0.20-0.70dL/g; 0.20-less than 0.70dL/g; 0.20-0.68 dL/g; 0.20-less than 0.68dL/g; 0.20-0.65dL/g; 0.35-1.2dL/g; 0.35-1.1 dL/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; 0.40-0.75 dL/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 0.42-0.90 dL/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 0.70 dL/g; Greater than 0.42-0.68dL/g; Greater than 0.42-less than 0.68dL/g; With greater than 0.42-0.65dL/g.

For certain embodiments of the present invention, be used for polyester of the present invention and can be presented at 60/40 (wt/wt) phenol/tetrachloroethanes with at least one in the following logarithmic viscosity number of 25 ℃ of mensuration of the concentration of 0.5g/100ml: 0.45-1.2dL/g; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; 0.45-0.95dL/g; 0.45-0.90dL/g; 0.45-0.85dL/g; 0.45-0.80 dL/g; 0.45-0.75dL/g; 0.45-less than 0.75dL/g; 0.45-0.72dL/g; 0.45-0.70 dL/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 1 dL/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 0.68 dL/g; 0.50-0.65dL/g; 0.55-1.2dL/g; 0.55-1.1dL/g; 0.55-1dL/g; 0.55-less than 1dL/g; 0.55-0.98dL/g; 0.55-0.95dL/g; 0.55-0.90dL/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; 0.58-1.1dL/g; 0.58-1 dL/g; 0.58-less than 1dL/g; 0.58-0.98dL/g; 0.58-0.95dL/g; 0.58-0.90 dL/g; 0.58-0.85dL/g; 0.58-0.80dL/g; 0.58-0.75dL/g; 0.58-less than 0.75 dL/g; 0.58-0.72dL/g; 0.58-0.70dL/g; 0.58-less than 0.70dL/g; 0.58-0.68 dL/g; 0.58-less than 0.68dL/g; 0.58-0.65dL/g; 0.60-1.2dL/g; 0.60-1.1 dL/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; 0.65-0.75 dL/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 1 dL/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-1 dL/g; Greater than 0.76dL/g-less than 1dL/g; Greater than 0.76dL/g-0.98dL/g; Greater than 0.76 dL/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 0.80 dL/g-0.95dL/g; Greater than 0.80dL/g-0.90dL/g.

Unless otherwise indicated, the expection composition that is used for dialysis filter shell of the present invention can have at least one of logarithmic viscosity number scope as herein described and at least one of the monomer scope for composition as herein described. Unless otherwise indicated, also the expection composition that is used for dialysis filter shell of the present invention can have at least one of Tg scope as herein described and at least one of the monomer scope for composition as herein described. Unless otherwise indicated, also the expection composition that is used for dialysis filter shell of the present invention can have at least one of at least one of Tg scope as herein described, logarithmic viscosity number scope as herein described and at least one of the monomer scope for composition as herein described.

For required polyester, the mol ratio of cis/trans TMCBD is owing to pure form or its mixture separately can change. In certain embodiments, the molar percentage of cis and/or trans TMCBD is greater than 50mol% cis and trans less than 50mol%; Or greater than 55mol% cis and trans less than 45mol%; Or 30-70 mol% cis and 70-30mol% are trans; Or 40-60mol% cis and 60-40mol% is trans or the trans and 50-30mol% cis of 50-70mol% or 50-70mol% cis and 50-30mol% are trans; Or 60-70mol% cis and 30-40mol% are trans; Or greater than 70 mol% cis and trans less than 30mol%; Wherein cis-and the summation of the molar percentage of trans-TMCBD equal 100mol%. The mol ratio of cis/trans 1,4-CHDM can at 50/50-0/100, for example change in the scope of 40/60-20/80.

In certain embodiments, terephthalic acid (TPA) or its ester, the mixture of dimethyl terephthalate (DMT) or terephthalic acid (TPA) and ester thereof for example is configured for forming dicarboxylic acid component most of of the used polyester of the present invention or all. In certain embodiments, the terephthalic acid residue can be with 70mol% at least, as 80mol% at least, at least 90mol%, at least 95mol%, the concentration of 99mol% or 100mol% is configured for forming part or all of dicarboxylic acid component of the used polyester of the present invention at least. In certain embodiments, in order to produce the polyester than high impact, can use the terephthalic acid (TPA) of higher amount. In one embodiment, dimethyl terephthalate (DMT) is part or all for the preparation of the dicarboxylic acid component of the used polyester of the present invention. For the purpose of present disclosure, term " terephthalic acid (TPA) " and " dimethyl terephthalate (DMT) " are used interchangeably in this article. In all embodiments, can use 70-100mol%; Or 80-100mol%; Or 90-100mol%; Or 99-100mol%; Or the terephthalic acid (TPA) of 100mol% and/or dimethyl terephthalate (DMT) and/or its mixture.

Except terephthalic acid (TPA), the dicarboxylic acid component who is used for polyester of the present invention can comprise at the most 30 mol%, 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 exist, expect that the amount of one or more modified aromatic dicarboxylic acids can in any above-mentioned endpoint value scope, comprise for example 0.01-30mol%, 0.01-20mol%, 0.01-10mol%, 0.01-5mol% and 0.01-1mol%. In one embodiment, can be used for modified aromatic dicarboxylic acids of the present invention and include but not limited to have those of 20 carbon atoms at the most, and they can be linear, para-orientation or symmetrical. The example that can be used for modified aromatic dicarboxylic acids of the present invention includes but not limited to M-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, Isosorbide-5-Nitrae-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid and trans-4,4 '-Stilbene dioctyl phthalate and ester thereof. In one embodiment, the modified aromatic dicarboxylic acids is M-phthalic acid.

The dicarboxylic acid component who is used for polyester of the present invention can further use 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 modification. Some embodiment also can comprise 0.01mol% or more, for example 0.1mol% or more, 1mol% or more, 5mol% or more or 10mol% or more one or more modification aliphatic dicarboxylic acids. Another embodiment comprises 0mol% modification aliphatic dicarboxylic acid. Therefore, if exist, expect that the amount of one or more modification aliphatic dicarboxylic acids can in any above-mentioned endpoint value scope, comprise for example 0.01-15mol% and 0.1-10mol%. Total mol% of dicarboxylic acid component is 100mol%.

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

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%.

The diol component that is used for the polyester portion of polymer blend of the present invention can contain 25mol% or still less one or more are not the modification glycol of TMCBD or 1,4-CHDM; In one embodiment, be used for polyester of the present invention and can contain one or more modification glycol less than 15 mol%. In another embodiment, be used for polyester of the present invention and can contain 10mol% or one or more modification glycol still less. In another embodiment, be used for polyester of the present invention and can contain 5mol% or one or more modification glycol still less. In another embodiment, be used for polyester of the present invention and can contain 3mol% or one or more modification glycol still less. In another embodiment, be used for the modification glycol that polyester of the present invention can contain 0mol%. Some embodiment also can comprise 0.01mol% or more, for example 0.1 mol% or more, 1mol% or more, 5mol% or more or 10mol% or more one or more modification glycol. Therefore, if exist, expect that the amount of one or more modification glycol can in any above-mentioned endpoint value scope, comprise for example 0.01-15mol% and 0.1-10mol%.

The modification glycol that is used for the used polyester of the present invention represents the glycol outside TMCBD and the 1,4-CHDM, and can contain 2-16 carbon atom. The example of suitable modification glycol includes but not limited to ethylene glycol, 1,2-PD, 1,3-PD, neopentyl glycol, BDO, 1,5-PD, 1,6-hexylene glycol, paraxylene glycol or its mixture. In one embodiment, the modification glycol is ethylene glycol. In another embodiment, the modification glycol is 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.

The polyester and/or the Merlon that are used for polymer blend of the present invention can comprise 0-10 mol%, 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% for example, be also referred to as branching agent herein, have 3 or a plurality of carboxyl substituent, hydroxyl substituent or its combination, described content is respectively based on total mole percent of glycol or diacid residues. In certain embodiments, can before the polyester and/or during and/or add afterwards branched monomer or reagent. Therefore being used for polyester of the present invention can be linearity or branching. Merlon also can be linearity or branching. In certain embodiments, can before the polycarbonate polymerization and/or during and/or add afterwards branched monomer or reagent.

The example of branched monomer includes but not limited to polyfunctional acid or multifunctional pure, 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, for example such as US5,654,347 and 5,696, described in 176, its disclosure about branched monomer is hereby incorporated by.

Use is used for the glass transition temperature (Tg) of polyester of the present invention with the determination of scan rate of 20 ℃/min from the TA DSC 2920 of Thermal Analyst Instrument.

Since by some be used for that polyester of the present invention shows crystallization half-life long (for example greater than 5 minutes) of 170 ℃, dialysis filter shell that can the production injection moulding. Polyester of the present invention can be unbodied or hypocrystalline. In one aspect, be used for some polyester of the present invention and can have lower degree of crystallinity. Be used for some polyester of the present invention and therefore can have essentially amorphous form, represent that this polyester comprises substantially unordered polymer areas.

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 one embodiment of the invention, this crystallization half-life at 170 ℃ greater than 1000 minutes. In another embodiment of the invention, the crystallization half-life that is used for polyester of the present invention at 170 ℃ greater than 10000 minutes. Can measure the crystallization half-life of polyester used herein with the well-known method of those skilled in the art. For example, t crystallization half-life of polyester_1/2Can determine over time by the light transmittance of measuring sample on the temperature controlled hot platform by laser instrument and photoelectric detector. This measurement can be by being exposed to temperature T with polymer_maxAnd the temperature that subsequently it is cooled to expect is carried out. Can sample be remained on the temperature of expectation by hot platform subsequently, measure simultaneously transmissivity over time. At first, sample can be visually transparent, has high transmission rate, and becomes opaque along with the sample crystallization. Be that light transmittance is the time of a half between initial light transmittance and the final light transmittance crystallization half-life. T_maxBe defined as the required temperature of fusing sample crystal region (if having crystal region). Can before measuring crystallization half-life, sample be heated to T_maxTo nurse one's health this sample. For each composition, absolute T_maxTemperature is different. For example, PCT can be heated to above certain temperature of 290 ℃ with fusion-crystallization zone.

Such as the table 1 of embodiment and shown in Figure 1, improving crystallization half-life, namely polymer reaches half needed time aspect of its maximum degree of crystallinity, and TMCBD is more effective than other comonomer such as ethylene glycol and M-phthalic acid. By reducing the crystalline rate of PCT, namely improve crystallization half-life, can be by manufacturings such as methods known in the art such as extrusion molding, injection mouldings based on the amorphous goods of modification PCT. As shown in table 1, these materials can show than the higher glass transition temperature of other modification PCT copolyesters and lower density.

For certain embodiments of the present invention, polyester can show that the combination of toughness and processability improves. For example, unexpectedly, the logarithmic viscosity number that slight reduction is used for polyester of the present invention obtains the melt viscosity of easier processing, keeps simultaneously the good physical property of polyester, for example toughness and heat resistance.

Raising is based on terephthalic acid (TPA), ethylene glycol and 1, in the copolyesters of 4-cyclohexanedimethanol 1, the content of 4-cyclohexanedimethanol can improve toughness, and described toughness can be determined by the brittle-ductile transition temperature in the notched izod impact strength test of measuring according to ASTM D256. It is believed that by this toughness that reduces the brittle-ductile transition temperature with 1,4-CHDM improve be since in the copolyesters pliability of 1,4-CHDM and conformation behavior occur. It is believed that TMCBD is incorporated among the PCT, improved toughness by reducing the brittle-ductile transition temperature, such as the table 2 of embodiment and shown in Figure 2. This is unexpected in the situation of given TMCBD rigidity.

In one embodiment, be used for the melt viscosity of polyester of the present invention less than 30000 pools, on the rotation melt rheometer, measure with 1 radian per second in 290 ℃. In another embodiment, be used for the melt viscosity of polyester of the present invention less than 20000 pools, on the rotation melt rheometer, measure with 1 radian per second in 290 ℃.

In one embodiment, be used for the melt viscosity of polyester of the present invention less than 15000 pools, on the rotation melt rheometer, measure with 1 radian per second (rad/sec) in 290 ℃. In one embodiment, be used for the melt viscosity of polyester of the present invention less than 10000 pools, on the rotation melt rheometer, measure with 1 radian per second (rad/sec) in 290 ℃. In another embodiment, be used for the melt viscosity of polyester of the present invention less than 6000 pools, on the rotation melt rheometer, measure with 1 radian per second in 290 ℃. Viscosity take radian per second as unit is relevant with processability. When its processing temperature is measured, typical polymers has the viscosity with 1 radian per second mensuration less than 10000 pools. Polyester is generally can not be processed more than 290 ℃. Merlon generally can be processed at 290 ℃. Merlon is 7000 pools 290 ℃ viscosity under typical 12 melt flow of 1rad/sec.

In one embodiment, it is visually transparent being used for some polyester of the present invention. Term " visually transparent " is defined as in this article that do not exist can perceptible darkness, dim and/or muddy when visual detection. In one aspect of the invention, when polyester and Merlon (including but not limited to bisphenol-a polycarbonate) blend, blend can be visually transparent.

Polyester of the present invention has one or more following performances. In other embodiments, being used for polyester of the present invention can have less than 50 or less than 20 yellowness index (ASTM D-1925).

In one embodiment, polyester of the present invention shows excellent notch toughness at thickness portion. The described notched izod impact strength of ASTM D256 is to measure a kind of commonsense method of toughness. When by the test of izod method, polymer can show complete rupture failure pattern (wherein test specimen fragments into two independently parts) or part or non-cracking failure mode (wherein test specimen remains a part). The rupture failure pattern is destroyed relevant with low energy fully. Part or non-cracking failure mode destroy relevant with high energy. The typical thickness that is used for measurement izod toughness is 1/8 ". Under this thickness, it is believed that considerably less polymer shows part or non-cracking failure mode, Merlon namely is a famous example. Yet, when the thickness of one piece of test increases to 1/4 " time, there is not commercially available amorphous materials to show part or non-cracking failure mode. In one embodiment, when in izod test, using 1/4 " during thick sample test, the compositions table of the embodiment of the invention reveals the non-cracking failure mode.

Be used for polyester of the present invention and can have one or more following performances. In one embodiment, being used for polyester of the present invention shows according to ASTM D256 in 23 ℃ of notched izod impact strength with at least 150J/m (3ft-lb/in) of the thick strip 10 mil breach measurement of 3.2mm (1/8-in); In one embodiment, being used for polyester of the present invention shows according to ASTM D256 in 23 ℃ of notched izod impact strength with at least 400J/m (7.5ft-lb/in) of the thick strip 10 mil breach measurement of 3.2mm (1/8-in); In one embodiment, being used for polyester of the present invention shows according to ASTM D256 in 23 ℃ of notched izod impact strength with at least 1000J/m (18ft-lb/in) of the thick strip 10 mil breach measurement of 3.2mm (1/8-in). In one embodiment, being used for polyester of the present invention shows according to ASTM D256 in 23 ℃ of notched izod impact strength with at least 150J/m (3ft-lb/in) of the thick strip 10 mil breach measurement of 6.4mm (1/4-in); In one embodiment, being used for polyester of the present invention shows according to ASTM D256 in 23 ℃ of notched izod impact strength with at least 400J/m (7.5ft-lb/in) of the thick strip 10 mil breach measurement of 6.4mm (1/4-in); In one embodiment, being used for polyester of the present invention shows according to ASTM D256 in 23 ℃ of notched izod impact strength with at least 1000J/m (18ft-lb/in) of the thick strip 10 mil breach measurement of 6.4mm (1/4-in).

In another embodiment, with compare in-5 ℃ of notched izod impact strength that 10 mil breach are measured in the thick strip with 1/8-in according to ASTM D256, when when 0 ℃ is measured, be used for the increase that some polyester of the present invention can show at least 3% or at least 5% or at least 10% or at least 15% notched izod impact strength. In addition, when 10 mil breach are 0 ℃-30 ℃ measurements in the thick strip with 1/8-in according to ASTM D256, are used for some other polyester of the present invention and can show that also plus or minus 5% is with interior notched izod impact strength confining force.

In another embodiment, with compare in the notched izod impact strength of the uniform temp identical polyester that 10 mil breach are measured in the thick strip with 1/8-in according to ASTM D256, when according to ASTM D256 in 23 ℃ with 1/4-in when 10 mil breach are measured in the thick strip, being used for some polyester of the present invention can be not more than 70% notched izod impact strength confining force by display loss.

In one embodiment, be used for polyester of the present invention and/or polymer blend of the present invention and contain or do not contain toner, can have colour L^*、a ^*And b^*, it can use the Inc. by Hunter Associates Lab, 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 plate or other article of its injection moulding or extrusion molding. They are by the L of CIE (International Commission on Illumination) (translating)^*a ^*b ^*Colour system is definite, wherein L^*Expression luminosity coordinate, a^*Represent red/green coordinate, and b^*Expression Huang/blue coordinate. In certain embodiments, the b that is used for polyester of the present invention^*Value can be for-10 to less than 10, and L^*Value can be 50 to 90. In other embodiments, the b that is used for polyester of the present invention^*Value can exist with one of following scope :-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; 1 to 2. In other embodiments, the L that is used for polyester of the present invention^*Value can exist with one of following scope: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.

In one embodiment, being used for polyester of the present invention can show based on being lower than 0 ℃ ductile-brittle transition temperature by ASTM D256 definition with what 1/8 inch strip, 10 mil breach were measured.

In one embodiment, be used at least one that polyester of the present invention can show following density: 23 ℃ of density less than 1.3g/ml; 23 ℃ of density less than 1.2g/ml; 23 ℃ of density less than 1.18 g/ml; The density of 23 ℃ of 0.80-1.3g/ml; The density of 23 ℃ of 0.80-1.2g/ml; 23 ℃ of 0.80-are less than the density of 1.2g/ml; The density of 23 ℃ of 1.0-1.3g/ml; The density of 23 ℃ of 1.0-1.2g/ml; The density of 23 ℃ of 1.0-1.1g/ml; The density of 23 ℃ of 1.13-1.3g/ml; Density with 23 ℃ of 1.13-1.2g/ml.

In some embodiments, use polymer blend of the present invention before melt-processed and/or thermoforming, to minimize and/or get rid of drying steps.

The polyester portion that is used for polymer blend of the present invention can be passed through the known in the literature method, for example passes through the homogeneous solution method, passes through the ester-interchange method in the melt and pass through two-phase interface legal system standby. Suitable method includes but not limited to that one or more dicarboxylic acids and one or more glycol react the step of the time that is enough to form polyester under the pressure of 100 ℃-315 ℃ temperature and 0.1-760mmHg. Referring to USP3,772,405 about preparing the method for polyester, is incorporated herein about the disclosure of this method as a reference.

On the other hand, the present invention relates to comprise the dialysis filter shell of polyester, this polyester is prepared by the method that comprises the following steps:

(I) in the presence of catalyst, comprise the time that the mixture for the monomer of any polyester of the present invention is enough to produce initial polyester 150-240 ℃ of heating;

(II) initial polyester 1-4 hour of 240-320 ℃ of heating steps (I); With

(III) remove any unreacted glycol.

The suitable catalyst that is used for the method includes but not limited to organic zinc or tin compound. Use such catalyst being known in the art. The example that is 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 titanium, zinc, manganese, lithium, germanium and cobalt. The amount of catalyst can be 10-20000ppm or 10-10000ppm, or 10-5000ppm or 10-1000ppm or 10-500ppm, or 10-300ppm or 10-250ppm, based on catalyst metals with based on the weight of final polymer. The method can be carried out with method in batches or continuously.

Typically, step (I) can be carried out until 50wt% or more 2,2,4,4-tetramethyl-1, and the 3-cyclobutanediol reacts. Step (I) can be carried out to the pressure of 100psig at atmospheric pressure. And be used for the interrelate term " product " that uses of any catalyst of the present invention and refer to catalyst and the polycondensation of any monomer for the preparation of polyester or spawn and the polycondensation between catalyst and other additive types or the product of esterification of esterification.

Typically, step (II) and (III) can carry out simultaneously. These steps can be undertaken by methods known in the art, for example by reactant mixture being placed 0.002psig to subatmospheric pressure, perhaps pass through at mixture blowing up hot nitrogen.

The invention further relates to the polyester product by the said method preparation.

The invention further relates to blend polymer. This blend comprises:

(a) at least a above-mentioned polyester of 5-95wt%; With

(b) at least a polymers compositions of 5-95wt%.

The suitable example of polymers compositions includes but not limited to nylon, is different from polyester as herein described, polyamide is such as the ZYTEL  from DuPont; Polystyrene, polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile butadient styrene, polymethyl methacrylate, acrylic acid series copolymer, PEI such as ULTEM  (from the PEI of General Electric); Polyphenylene oxide is such as poly-(2,6-dimethyl phenylate) or polyphenyl ether/styrene blend such as NORYL 1000  (from poly-(2,6-dimethyl phenylate) and the blend of polystyrene resin of General Electric); Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ester); Merlon such as LEXAN  (from the Merlon of General Electric); Polysulfones; Polysulfones ether; Poly-(ether-ketone) with aromatic dihydroxy compound; Or the mixture of any other above-mentioned polymer. Blend can be by conventional machining technology preparation known in the art, for example melt blending or solution blending. In one embodiment, in polymer blend, there is not copolyesters. If use Merlon at the blend that is used for polymer blend of the present invention, then blend can be visually transparent. Yet, be used for polymer blend of the present invention and also expect and get rid of Merlon and comprise Merlon.

Being used for Merlon of the present invention can prepare according to known method, for example by making dihydroxy aromatic compounds and carbonate precursor such as phosgene, haloformate or carbonic ester ester, molecular weight regulator, acid acceptor and catalyst reaction. Method for the preparation of Merlon is known in the art and is recorded in for example USP4, and in 452,933, wherein the disclosure about the Merlon preparation is hereby incorporated by.

The example of suitable carbonate precursor includes but not limited to carbonyl bromide, phosgene or its mixture; Diphenyl carbonate; Carbonic acid two (halogenophenyl) ester, such as 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 dihydroxy phenol.

The 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.

Acid acceptor can be the organic or inorganic acid acceptor. Suitable organic acid acceptor can be tertiary amine, and includes but not limited to the material such as pyridine, triethylamine, dimethylaniline, four butylamine etc. Examples of inorganic acceptors can be hydroxide, carbonate, bicarbonate or the phosphate of alkali metal or alkaline-earth metal.

Operable catalyst includes but not limited to usually to help those of monomer and phosgene polymerization. Suitable catalyst includes but not limited to tertiary amine, for example triethylamine, tripropyl amine (TPA), DMA; 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, benzyltrimethylammonium chloride; With season  compound, for example normal-butyl triphenyl bromination  and methyltriphenylphospbromide bromide .

The Merlon that is used for polymer blend of the present invention can be copolyestercarbonates, such as USP 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484,4,465,820 and 4,981,898 put down in writing those, each of these United States Patent (USP)s piece disclosure about copolyestercarbonates is hereby incorporated by.

Being used for copolyestercarbonates of the present invention can be purchased and/or can be prepared by methods known in the art. For example, they can be typically by at least a dihydroxy aromatic compounds and phosgene and at least a diacid chloride, particularly m-phthaloyl chloride, paraphthaloyl chloride or both mixtures reaction acquisition.

In addition, be used for the polymer blend of dialysis filter shell of the present invention and the common additives that blend polymer also can comprise the 0.01-25wt% of total composition, such as colorant, dyestuff, releasing agent, fire retardant, plasticizer, nucleator, stabilizing agent, include but not limited to UV stabilizing agent, heat stabilizer and/or its product, filler and impact modifying agent. For example, can be by the UV additive being joined in the body or by applying hard conating or being introduced in the dialysis filter shell by coextrusion cover layer (cap layer). Example well known in the art and that can be used for the commercially available impact modifying agent of typical case of the present invention includes but not limited to the ethylene/propene terpolymer; Functionalised polyolefin, as comprise those of methyl acrylate and/or glyceral methacrylate; The block copolymer impact modifying agent of styrene-based; With various acrylic acid series core/shell type impact modifying agents. Also expect the residue of this additive part as polymer blend.

Polyester of the present invention can comprise at least a chain extender. Suitable chain extender includes but not limited to multifunctional (including but not limited to difunctionality) isocyanates, and multi-functional epoxy's compound comprises for example epoxidization phenolic resin, and phenoxy resin. In certain embodiments, chain extender can add at the end of polymerization process or after polymerization process. If after polymerization process, add, then can or add by compounding during conversion process such as injection moulding or extrusion molding and introduce chain extender. The consumption of chain extender can change according to composition and the needed physical property of used concrete monomer, but is generally the about 10wt% of about 0.1wt%-, and the preferred about 5wt% of about 0.1wt%-is based on the gross weight of polyester.

Heat stabilizer is the compound of stabilized polyester between polyester manufacturing and/or rear polymerization period, includes but not limited to phosphorus compound, includes but not limited to phosphoric acid, phosphorous acid, phosphonic acids, phosphinic acids, phosphonous acid and various ester and salt. Described ester can be the 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 compound can change to the maximum that allows based on the oh group number that is present in the used heat stabilizer at the most from zero. Its product intended comprising in term " heat stabilizer ". And the interrelate term " product " that uses of heat stabilizer of the present invention refers to heat stabilizer and the polycondensation of any monomer for the preparation of polyester or spawn and the polycondensation between heat stabilizer and other additive types or the product of esterification of esterification. They may reside in for polymer blend of the present invention.

Reinforcing material can be used for the present composition. 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 combination thereof. In one embodiment, reinforcing material is glass, such as the fibrous glass silk, and the mixture of glass and talcum, glass and mica and glass and polymer fiber.

The invention still further relates to dialysis filter shell as herein described. These dialysis filter shells include but not limited to injection moulding dialysis shell. The method for preparing dialysis filter shell includes but not limited to injection moulding.

For the purpose of present disclosure, term " wt " expression " weight ".

How the following example can prepare and estimate dialysis filter shell of the present invention if further illustrating, and wish it is that of the present invention illustrating do not wished to limit its scope purely.Except as otherwise noted, part be weight portion, temperature is degree centigrade or is in room temperature, and pressure is or near atmospheric pressure.

Embodiment

Method of testing

The logarithmic viscosity number of polyester be in 60/40 (wt/wt) phenol/sym-tetrachloroethane with the concentration of 0.5g/100ml 25 ℃ of mensuration.

Except as otherwise noted, glass transition temperature (Tg) is TA DSC 2920 instruments that use Thermal Analyst Instruments according to ASTM D3418 with the scan rate measurement of 20 ℃/min.

The glycol content of compositions and cis/trans ratios are by proton magnetic resonance (PMR) (NMR) spectral measurement.All NMR spectrums are recorded on the JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer, use chloroform-trifluoroacetic acid (70-30 volume/volume) for polymer, perhaps use 60/40 (wt/wt) phenol/sym-tetrachloroethane that has added deuterochloroform to be used for the lock field for the oligomer sample.By contrasting 2,2,4,4-tetramethyl-1, the model list of 3-cyclobutanediol-and dibenzoate carry out 2,2,4,4-tetramethyl-1, the peak of 3-cyclobutanediol resonance is pointed out.These model compounds are near the resonant position of finding in polymer and oligomer.

Crystallization half-life t _1/2Be to determine over time by the light transmittance of measuring sample on the temperature controlled hot platform by laser instrument and photoelectric detector.This measurement is by being exposed to temperature T with polymer _MaxAnd subsequently it is cooled to desired temperatures and carries out.By hot platform sample is remained on desired temperatures subsequently, measure absorbance simultaneously over time.At first, sample is visually transparent, has high transmission rate, and becomes opaque along with the sample crystallization.Being recorded as light transmittance crystallization half-life is the time of a half between initial light transmittance and the final light transmittance.T _MaxBe defined as the required temperature of fusing sample crystal region (if having crystal region).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, PCT can be heated to above certain temperature of 290 ℃ with the fusion-crystallization zone.

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

Bao Dao melt viscosity is measured by using Rheometrics Dynamic Analyzer (RDA II) herein.In the temperature of being reported with the variation of the frequency measurement melt viscosity of 1-400rad/sec with shear rate.Zero shears melt viscosity (η _o) be by the estimated melt viscosity of data of under zero shear rate, extrapolating with methods known in the art.This step is automatically performed by RheometricsDynamic Analyzer (RDA II) software.

Polymer 80-100 ℃ in vacuum drying oven dry 24 hours, and injection moulding on the Boy22S mould machine obtains 1/8 * 1/2 * 5 inches deflection strips.To be cut into length be 2.5 inches and obtain 10 mil breach along 1/2 inch width otch with these strips according to ASTM D256.Determine 23 ℃ average izod impact strength by measuring 5 samples.

In addition, use 5 samples of 5 ℃ of incremental testings to determine the brittle-ductile transition temperature in different temperatures.Temperature when the brittle-ductile transition temperature is defined as the fragility mode that 50% samples met represented by ASTM D256.

Bao Dao colour is to use the Inc. by Hunter Associates Lab herein, Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures.The colour measurement value is at polyester granules or the meansigma methods of the value of measuring on by the plate of its injection moulding or extrusion molding or other article.They are by the L of CIE (International Commission on Illumination) (translating) ^*a ^*b ^*Colour system is definite, wherein L ^*Expression luminosity coordinate, a ^*Represent red/green coordinate, and b ^*Expression Huang/blue coordinate.

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

Unless otherwise indicated, be used for 1 of following examples, the cis/trans ratios of 4-cyclohexanedimethanol is about 30/70, and can be 35/65-25/75.Unless otherwise indicated, be used for 2,2,4 of following examples, 4-tetramethyl-1, the cis/trans ratios of 3-cyclobutanediol is about 50/50.

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

TPA	P-phthalic acid
TPA	P-phthalic acid	DMT	Dimethyl terephthalate (DMT)
TMCD	2,2,4,4-tetramethyl-1,3-cyclobutanediol	DMT	Dimethyl terephthalate (DMT)
TMCD	2,2,4,4-tetramethyl-1,3-cyclobutanediol	CHDM
	1, the 4-cyclohexanedimethanol	CHDM
	1, the 4-cyclohexanedimethanol	IV	Logarithmic viscosity number
η _o	Zero shears melt viscosity	IV	Logarithmic viscosity number
η _o	Zero shears melt viscosity	T _g	Glass transition temperature
T _bd	The brittle-ductile transition temperature	T _g	Glass transition temperature
T _bd	The brittle-ductile transition temperature	T _max	The conditioning temperature that measure crystallization half-life

Embodiment 1

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 crystalline rate that reduces PCT.In addition, present embodiment illustrates 2,2,4,4-tetramethyl-1, the benefit of 3-cyclobutanediol aspect glass transition temperature and density.

Prepare multiple following 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 nucleation.1, the cis/trans ratios of 4-cyclohexanedimethanol is 31/69, and 2,2,4,4-tetramethyl-1, the cis/trans ratios of 3-cyclobutanediol is recorded in the table 1.

For present embodiment, each sample has enough similar logarithmic viscosity number, gets rid of it effectively as variable thus in crystalline rate is measured.

Be the crystallization half-life of increment measurement melt with 10 ℃ and be recorded in the table 1 at 140-200 ℃.Get the fastest crystallization half-life of every kind of sample as the minima of temperature variant crystallization half-life, generally occur in 170-180 ℃.The fastest crystallization half-life of sample is plotted among Fig. 1 as the function to the mol% of the comonomer of PCT modification.

Data show, 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol is more effective than ethylene glycol and M-phthalic acid aspect reduction crystalline 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 (min)

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

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

2100mol%1, the 4-cyclohexanedimethanol.

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

4 240 ℃ of grinding polyester press membrane by embodiment 1H.The gained thin film has the logarithmic viscosity number value of 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)

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

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

Embodiment 1A

Present embodiment illustrates target group becomes 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).

With 56.63g dimethyl terephthalate (DMT), 55.2g 1, the mixture of 4-cyclohexanedimethanol, 14.16g dimethyl isophthalate and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Mixing speed 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.Reactant mixture kept 60 minutes at 290 ℃, applied vacuum then gradually up to the intrinsic pressure 100mmHg of reaching of flask in ensuing 5 minutes.In ensuing 5 minutes again with the intrinsic pressure 0.3mmHg that is reduced to of flask.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 87.5 ℃, and logarithmic viscosity number is 0.63dl/g.NMR the analysis showed that polymer comprises 100mol%1,4-cyclohexanedimethanol residue and 20.2mol% dimethyl isophthalate residue.

Embodiment 1B

Present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 20mol% glycol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (32/68 cis/trans).

With 77.68g dimethyl terephthalate (DMT), 50.77g 1, the mixture of 4-cyclohexanedimethanol, 27.81g ethylene glycol and 0.0433g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Mixing speed 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.Reactant mixture kept 120 minutes and arrived up to 280 ℃ at 30 minutes internal heating subsequently at 210 ℃.In case reach 280 ℃, in ensuing 5 minutes, apply vacuum gradually up to the intrinsic pressure 100mmHg of reaching of flask.In ensuing 10 minutes again with the intrinsic pressure 0.3mmHg that is reduced to of flask.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 87.7 ℃, and logarithmic viscosity number is 0.71dl/g.NMR the analysis showed that polymer comprises the 19.8mol% glycol residue.

Embodiment 1C

Present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 20mol%2, and 2,4,4-tetramethyl-1,3-cyclobutanediol residue and 80mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

With 77.68g 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 air inlet, 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 polymer visually, glass transition temperature is 100.5 ℃, and logarithmic viscosity number is 0.73dl/g.NMR the analysis showed that polymer comprises 80.5mol%1,4-cyclohexanedimethanol residue and 19.5mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.

Embodiment 1D

Present embodiment illustrates target group becomes 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).

With 42.83g dimethyl terephthalate (DMT), 55.26g 1, the mixture of 4-cyclohexanedimethanol, 28.45g dimethyl isophthalate and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Mixing speed 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.Reactant mixture kept 60 minutes at 290 ℃, applied vacuum then gradually up to the intrinsic pressure 100mmHg of reaching of flask in ensuing 5 minutes.In ensuing 5 minutes again with the intrinsic pressure 0.3mmHg that is reduced to of flask.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 81.2 ℃, and logarithmic viscosity number is 0.67dl/g.NMR the analysis showed that polymer comprises 100mol%1,4-cyclohexanedimethanol residue and 40.2mol% dimethyl isophthalate residue.

Embodiment 1E

Present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 40mol% glycol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

With 81.3g dimethyl terephthalate (DMT), 42.85g 1, the mixture of 4-cyclohexanedimethanol, 34.44g ethylene glycol and 0.0419g dibutyl tin oxide places 500 ml flasks that are equipped with nitrogen air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Mixing speed 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.Reactant mixture kept 120 minutes and arrived up to 280 ℃ at 30 minutes internal heating subsequently at 210 ℃.In case reach 280 ℃, in ensuing 5 minutes, apply vacuum gradually up to the intrinsic pressure 100mmHg of reaching of flask.In ensuing 10 minutes again with the intrinsic pressure 0.3mmHg that is reduced to of flask.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 82.1 ℃, and logarithmic viscosity number is 0.64dl/g.NMR the analysis showed that polymer comprises the 34.5mol% glycol residue.

Embodiment 1F

Present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 40mol%2, and 2,4,4-tetramethyl-1,3-cyclobutanediol residue and 60mol%1, the preparation of the copolyesters of 4-cyclohexanedimethanol residue (31/69 cis/trans).

With 77.4g 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 air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Mixing speed is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reactant mixture kept 120 minutes and arrived up to 290 ℃ at 30 minutes internal heating subsequently at 260 ℃.In case reach 290 ℃, in ensuing 5 minutes, apply vacuum gradually up to the intrinsic pressure 100mmHg of reaching of flask.In ensuing 5 minutes again with the intrinsic pressure 0.3mmHg that is reduced to of flask.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 122 ℃, and logarithmic viscosity number is 0.65dl/g.NMR the analysis showed that polymer comprises 59.9mol%1,4-cyclohexanedimethanol residue and 40.1mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.

Embodiment 1G

Present embodiment illustrates target group becomes 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).

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 air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Mixing speed is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reactant mixture kept 120 minutes and arrived up to 290 ℃ at 30 minutes internal heating subsequently at 260 ℃.In case reach 290 ℃, in ensuing 5 minutes, apply vacuum gradually up to the intrinsic pressure 100mmHg of reaching of flask, and also mixing speed is dropped to 100RPM.In ensuing 5 minutes, drop to 50RPM with the intrinsic pressure 0.3mmHg of being reduced to of flask with mixing speed again.The pressure that keeps 0.3mmHg altogether 60 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 103 ℃, and logarithmic viscosity number is 0.65dl/g.NMR the analysis showed that polymer comprises 85.7mol%1,4-cyclohexanedimethanol residue and 14.3mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.

Embodiment 1H

Present embodiment illustrates target group becomes 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).

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 air inlet, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Mixing speed is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reactant mixture kept 120 minutes and arrived up to 290 ℃ at 30 minutes internal heating subsequently at 260 ℃.In case reach 290 ℃, in ensuing 5 minutes, apply vacuum gradually up to the intrinsic pressure 100mmHg of reaching of flask, and also mixing speed is dropped to 100RPM.In ensuing 5 minutes, drop to 50RPM with the intrinsic pressure 0.3mmHg of being reduced to of flask with mixing speed again.The pressure that keeps 0.3mmHg altogether 60 minutes to remove excessive unreacted glycol.Notice that vacuum system does not reach above-mentioned set point, but the vacuum that produces is enough to obtain high melt viscosity, transparent and colourless polymer visually, glass transition temperature is 99 ℃, and logarithmic viscosity number is 0.73dl/g.NMR the analysis showed that polymer comprises 85mol%1,4-cyclohexanedimethanol residue and 15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.

Embodiment 2

Present embodiment illustrates 2,2,4,4-tetramethyl-1, and the 3-cyclobutanediol is to the flexible improvement based on the copolyesters (comprising p-phthalic acid and 1, the polyester of 4-cyclohexanedimethanol) of PCT.

Preparation as described below is based on 2,2,4,4-tetramethyl-1, the copolyesters of 3-cyclobutanediol.For all samples, 1, the cis/trans ratios of 4-cyclohexanedimethanol is about 31/69.Based on ethylene glycol and 1, the copolyesters of 4-cyclohexanedimethanol is commercially available polyester.The copolyesters of embodiment 2A (Eastar PCTG5445) obtains from Eastman Chemical Co..The copolyesters of embodiment 2B obtains with trade name Spectar from EastmanChemical Co..Embodiment 2C and embodiment 2D prepare with the reprogramming of pilot-scale (each 51-lb batch) according to the described program of embodiment 1A, and have logarithmic viscosity number shown in the following table 2 and glass transition temperature.Embodiment 2C adopts target stannum consumption (dibutyl tin oxide) preparation of 300ppm.End product comprises 295ppm stannum.The colour of the polyester of embodiment 2C is L ^*=77.11; a ^*=-1.50; And b ^*=5.79.Embodiment 2D adopts target stannum consumption (dibutyl tin oxide) preparation of 300ppm.End product comprises 307ppm stannum.The colour of the polyester of embodiment 2D is L ^*=66.72; a ^*=-1.22; And b ^*=16.28.

With material be injection molded into strip and subsequently otch carry out izod test.Obtaining temperature variant notched izod impact strength also also is recorded in the table 2.

For given sample, izod impact strength is little main transformation of temperature range experience.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/mental retardation lost efficacy at lower temperature, and toughness/high energy lost efficacy at higher temperature.This transition temperature is expressed as the brittle-ductile transition temperature T _Bd, it is flexible measuring.T _BdWrite down in table 2 and in Fig. 2, mapped with respect to comonomer mol%.

Data show, with the T that has improved 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 ℃
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	2A	38.0％B	0.68	86	18	NA	NA	NA	1.5	NA	NA	1.5	1.5	32	32	NA
2B	69.0％B	0.69	82	26	NA	NA	NA	NA	NA	NA	2.1	NA	2.4	13.7	28.7	2C	22.0％C	0.66	106	-5	1.5	NA	12	23	23	NA	23	NA	NA	NA	NA
2D	42.8％C	0.60	133	-12	2.5	2.5	11	NA	14	NA	NA	NA	NA	NA	NA	2C	22.0％C	0.66	106	-5	1.5	NA	12	23	23	NA	23	NA	NA	NA	NA

The remainder of the diol component of polyester is 1 in 1 this table, the 4-cyclohexanedimethanol.All polymer prepare by the 100mol% dimethyl terephthalate (DMT).

NA=does not obtain.

Wherein:

B is an ethylene glycol

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

Embodiment 3

Present embodiment illustrates 2,2,4, and 4-tetramethyl-1,3-cyclobutanediol can improve the toughness of the copolyesters (comprising p-phthalic acid and 1, the polyester of 4-cyclohexanedimethanol) based on PCT.Zhi Bei polyester comprises 2,2,4 of 15-25mol% in the present embodiment, 4-tetramethyl-1,3-cyclobutanediol residue.

Preparation as described below is based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl-1, and 3-cyclobutanediol and 1, the copolyesters of 4-cyclohexanedimethanol, it has composition as shown in table 3 and performance.Surplus is 1 to the diol component of maximum 100mol% polyester in the table 3,4-cyclohexanedimethanol (31/69 cis/trans).

With material be injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out the izod test.Obtain notched izod impact strength and be recorded in the table 3 at 23 ℃.Density, Tg and the crystallization half-life of test molding strip.Melt viscosity at 290 ℃ of test pellets.

Table 3

The various performance compilations that are used for some polyester of the present invention

Embodiment	TMCD mol％	% cis TMCD	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TMCD mol％	% cis TMCD	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	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	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	C	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	C	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	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	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

NA=does not obtain.

Embodiment 3A

In the presence of 200ppm catalyst three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (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 rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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 reactant mixture is risen to 270 ℃ and pressure reduced to 90mmHg.270 ℃ and keep 1 hour to 90mmHg after, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reactant 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 pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.736dL/g and 104 ℃ Tg.NMR the analysis showed that polymer comprises 85.4mol%1,4-cyclohexanedimethanol residue and 14.6mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=78.20; a ^*=-1.62; And b ^*=6.23.

Embodiment 3B-embodiment 3D

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

Embodiment 3E

In the presence of 200ppm catalyst three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 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 rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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 reactant mixture is risen to 270 ℃ and pressure reduced to 90mmHg.270 ℃ and keep 1 hour to 90mmHg after, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reactant mixture remain on 290 ℃ and＜following 60 minutes of the pressure of 1mmHg.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.715dL/g and 110 ℃ Tg.X-ray analysis shows that polymer contains 223ppm stannum.NMR the analysis showed that polymer comprises 78.6mol%1,4-cyclohexanedimethanol residue and 21.4mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=76.45; a ^*=-1.65; And b ^*=6.47.

Embodiment 3F

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

Embodiment 3G

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

Embodiment 3H

In the presence of 200ppm catalyst three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 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 rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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 reactant mixture is risen to 270 ℃ and pressure reduced to 90mmHg.270 ℃ and keep 1 hour to 90mmHg after, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reactant mixture remain on 290 ℃ and＜following 12 minutes of the pressure of 1mmHg.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.590dL/g and 106 ℃ Tg.NMR the analysis showed that polymer comprises 77.1mol%1,4-cyclohexanedimethanol residue and 22.9mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=83.27; a ^*=-1.34; And b ^*=5.08.

Embodiment 3I

In the presence of 200ppm catalyst three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 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 rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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 reactant mixture is risen to 270 ℃ and pressure reduced to 90mmHg.270 ℃ and keep 1 hour to 90mmHg after, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to 4mmHg.Reactant mixture is remained on following 30 minutes of the pressure of 290 ℃ and 4mmHg.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.531dL/g and 105 ℃ Tg.NMR the analysis showed that polymer comprises 76.9mol%1,4-cyclohexanedimethanol residue and 23.1mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=80.42; a ^*=-1.28; And b ^*=5.13.

Embodiment 4

Present embodiment illustrates 2,2,4, and 4-tetramethyl-1,3-cyclobutanediol can improve the toughness of the copolyesters (comprising p-phthalic acid and 1, the polyester of 4-cyclohexanedimethanol) based on PCT.In the present embodiment Zhi Bei polyester comprise greater than 25-less than 40mol% big 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.

Preparation as described below is based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl-1, and 3-cyclobutanediol and 1, the copolyesters of 4-cyclohexanedimethanol (31/69 cis/trans), it has composition as shown in table 4 and performance.Surplus is 1 to the diol component of maximum 100mol% polyester in the table 4,4-cyclohexanedimethanol (31/69 cis/trans).

With material be injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out the izod test.Obtain notched izod impact strength and be recorded in the table 4 at 23 ℃.Density, Tg and the crystallization half-life of test molding strip.Melt viscosity at 290 ℃ of test pellets.

Table 4

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

NA=does not obtain.

Embodiment 4A

In the presence of 200ppm catalyst three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 11.82lb (37.28gram-mol) 1,4-cyclohexanedimethanol and 6.90lb (21.77gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Reaction mixture temperature is risen to 270 ℃ then, and pressure is reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reactant 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 pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.714dL/g and 113 ℃ Tg.NMR the analysis showed that polymer comprises 73.3mol%1,4-cyclohexanedimethanol residue and 26.7mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.

Embodiment 4B

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

Embodiment 5

Present embodiment illustrates 2,2,4, and 4-tetramethyl-1,3-cyclobutanediol can improve the toughness of the copolyesters (comprising p-phthalic acid and 1, the polyester of 4-cyclohexanedimethanol) based on PCT.To comprise consumption be 40mol% or bigger by 2,2,4 to Zhi Bei polyester in the present embodiment, 4-tetramethyl-1,3-cyclobutanediol residue.

Preparation as described below is based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl-1, and 3-cyclobutanediol and 1, the copolyesters of 4-cyclohexanedimethanol, it has composition as shown in table 5 and performance.Surplus is 1 to the diol component of maximum 100mol% polyester in the table 5,4-cyclohexanedimethanol (31/69 cis/trans).

With material be injection molded into the thick strip of 3.2mm and 6.4mm and subsequently otch carry out the izod test.Obtain notched izod impact strength and be recorded in the table 5 at 23 ℃.Density, Tg and the crystallization half-life of test molding strip.Melt viscosity at 290 ℃ of test pellets.

Table 5

Embodiment	TMCD mol％	Cis TMCD %	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TMCD mol％	Cis TMCD %	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the crystallization half-life of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	44	46.2	0.657	0.626	727	734	1.172	119	NA	9751
B	45	NA	0.626	0.580	748	237	1.167	123	NA	8051	A	44	46.2	0.657	0.626	727	734	1.172	119	NA	9751
B	45	NA	0.626	0.580	748	237	1.167	123	NA	8051	C	45	NA	0.582	0.550	671	262	1.167	125	19782	5835
D	45	NA	0.541	0.493	424	175	1.167	123	NA	3275	C	45	NA	0.582	0.550	671	262	1.167	125	19782	5835
D	45	NA	0.541	0.493	424	175	1.167	123	NA	3275	E	59	46.6	0.604	0.576	456	311	1.156	139	NA	16537
F	45	47.2	0.475	0.450	128	30	1.169	121	NA	1614	E	59	46.6	0.604	0.576	456	311	1.156	139	NA	16537

NA=does not obtain.

Embodiment 5A

In the presence of 200ppm catalyst 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 rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to 2mmHg.Reactant 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 pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.657dL/g and 119 ℃ Tg.NMR the analysis showed that polymer comprises 56.3mol%1,4-cyclohexanedimethanol residue and 43.7mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=75.04; a ^*=-1.82; And b ^*=6.72.

Embodiment 5B-embodiment 5D

Polyester described in the embodiment 5B-embodiment 5D is according to preparing to the described similar program of embodiment 5A.The composition and the performance of these polyester are shown in Table 5.

Embodiment 5E

In the presence of 200ppm catalyst three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 6.43lb (20.28gram-mol) 1,4-cyclohexanedimethanol and 12.49lb (39.37gram-mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to 2mmHg.With reactant 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 pressurizing vessel is elevated to 1 atmospheric pressure then.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.604dL/g and 139 ℃ Tg.NMR the analysis showed that polymer comprises 40.8mol%1,4-cyclohexanedimethanol residue and 59.2mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=80.48; a ^*=-1.30; And b ^*=6.82.

Embodiment 5F

In the presence of 200ppm catalyst 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 rustless steel pressurizing vessels being furnished with condensation column, 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.Reactant 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 reactant mixture is risen to 270 ℃ and pressure reduced to 90mmHg.270 ℃ and keep 1 hour to 90mmHg after, agitator speed is reduced to 15RPM and pressure is reduced to 4mmHg.When the temperature of reactant mixture is 270 ℃ and pressure when being 4mmHg, use nitrogen that the pressure of pressurizing vessel is elevated to 1 atmospheric pressure immediately.From pressurizing vessel, extrude molten polymer subsequently.Grinding refrigerative extruded polymer sieves by 6-mm.Polymer has the logarithmic viscosity number of 0.475dL/g and 121 ℃ Tg.NMR the analysis showed that polymer comprises 55.5mol%1,4-cyclohexanedimethanol residue and 44.5mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue.The colour of polymer is: L ^*=85.63; a ^*=-0.88; And b ^*=4.34.

Embodiment 6-Comparative Examples

Present embodiment has illustrated the data that are used for contrast material in table 6.PC is the Makrolon 2608 from Bayer, and its nominal consists of 100mol% bisphenol-A residue and 100mol% dipheryl carbonate base ester residue.Makrolon 2608 has the nominal melt flow of use 1.2kg weight at the 20g/10min of 300 ℃ of mensuration.PET is the Eastar 9921 from Eastman Chemical Company, and its nominal consists of 100mol% p-phthalic acid, 3.5mol% cyclohexanedimethanol (CHDM) and 96.5mol% ethylene glycol.PETG is the Eastar 6763 from Eastman ChemicalCompany, and its nominal consists of 100mol% p-phthalic acid, 31mol% cyclohexanedimethanol (CHDM) and 69mol% ethylene glycol.PCTG is the Eastar DN001 from EastmanChemical Company, and its nominal consists of 100mol% p-phthalic acid, 62mol% cyclohexanedimethanol (CHDM) and 38mol% ethylene glycol.PCTA is the Eastar AN001 from Eastman Chemical Company, and its nominal consists of 65mol% p-phthalic acid, 35mol% M-phthalic acid and 100mol% cyclohexanedimethanol (CHDM).Polysulfones is the Udel 1700 from Solvay, and its nominal consists of 100mol% bisphenol-A and 100mol%4,4-two chlorosulfonyl sulfone residues.Udel 1700 has the nominal melt flow of use 2.16kg weight at the 6.5g/10min of 343 ℃ of mensuration.SAN is the Lustran 31 from Lanxess, and its nominal consists of 76mol% styrene and 24mol% acrylonitrile.Lustran 31 has the nominal melt flow of use 3.8kg weight at the 7.5g/10min of 230 ℃ of mensuration.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 polymer title	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	The crystallization half-life of melt (min)
Embodiment	The polymer title	Pellet IV (dl/g)	Molding strip IV (dl/g)	3.2mm thick strip is 23 ℃ notched izod (J/m)	6.4mm thick strip is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	The crystallization half-life of melt (min)	A	PC	12MFR	NA	929	108	1.20	146	NA
B	PCTG	0.73	0.696	NA	70	1.23	87	170℃ 30	A	PC	12MFR	NA	929	108	1.20	146	NA
B	PCTG	0.73	0.696	NA	70	1.23	87	170℃ 30	C	PCTA	0.72	0.702	98	59	1.20	87	150℃ 15
D	PETG	0.75	0.692	83	59	1.27	80	130℃ 2500	C	PCTA	0.72	0.702	98	59	1.20	87	150℃ 15
D	PETG	0.75	0.692	83	59	1.27	80	130℃ 2500	E	PET	0.76	0.726	45	48	1.33	78	170℃ 1.5
F	SAN	7.5MFR	NA	21	NA	1.07	～110	NA	E	PET	0.76	0.726	45	48	1.33	78	170℃ 1.5
F	SAN	7.5MFR	NA	21	NA	1.07	～110	NA	G	PSU	6.5MFR	NA	69	NA	1.24	～190	NA

NA=does not obtain.

Embodiment 7

Present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl-1, and the consumption of 3-cyclobutanediol is to the influence of the glass 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 7F

With dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-ml.To 2,2,4,4-tetramethyl-1, the raw-material NMR of 3-cyclobutanediol the analysis showed that cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/acid ratio example preparation, and is all excessive all from 2,2,4,4-tetramethyl-1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymer, to obtain 300ppm stannum.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.Reduce along with viscosity increases to stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymer to be cooled to be lower than its glass transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing body and break away from glass flask up to it.Stirring polymer body with medium level in flask cools off up to polymer.Taking out polymer and grind from flask makes it sieve by 3mm.This program is changed the copolyesters that becomes 20mol% with the target group of production the following stated.

As measurement logarithmic viscosity number as described in above " method of testing " part.The composition of polyester as described in the Test Methods section in front by ¹H NMR measures.Glass transition temperature is used to add heat determination the second time after the speed quenching of 20 ℃/min by DSC.

Embodiment 7G-embodiment 7P

These polyester are by carrying out ester exchange in the stage of separating and polycondensation reaction prepares.The ester exchange experiment is being carried out in the temperature reaction device (CTR) continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric jacket and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.In this reactor, add 777g (4mol) dimethyl terephthalate (DMT), 230g (1.6mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 460.8g (3.2mol) cyclohexanedimethanol and 1.12g three (2 ethyl hexanoic acid) butyl tin (make and in final polymer, have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Camile method control system makes set point and data acquisition easier.In case the reactant fusion then begins to stir and slowly be increased to 250rpm.The temperature of reactor raises gradually along with the duration of runs.The methanol weight of equaling a record and collecting by the sky.When the progress of methanol stops or in 260 ℃ lower temperature cessation reaction of preliminary election.Adopt nitrogen purging to discharge oligomer and cool to room temperature.Adopt the liquid nitrogen freezing oligomer and be broken into enough little fritter, so that can be weighed in the 500ml round-bottomed flask.

In polycondensation reaction, in the 500ml round-bottomed flask, add the oligomer for preparing above about 150g.This flask is equipped with rustless steel agitator and cap.Glass drying oven is arranged on the last and startup Camile sequence of half moles of polymer complete set of equipments (a half mole polymer rig).In case the oligomer fusion orientates agitator apart from complete upset of drag as.For each embodiment, be reported in the following table by the temperature/pressure/stirring speed sequence of Camile software control.

The Camile sequence of embodiment 7G and embodiment 7H

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

The Camile sequence of embodiment 7M-embodiment 7P

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

The Camile sequence of embodiment 7J and embodiment 7K

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

The Camile sequence of embodiment 7I and embodiment 7L

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

From flask, reclaim resulting polymers, use the chopping of hydraulic pressure chipper, and grind to form 6mm sieve size.Sample to the polymer of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/sym-tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml ^*, a ^*, b ^*).By ¹HNMR obtains polymer and forms.Use Rheometrics Mechanical Spectrometer (RMS-800) that sample is carried out heat stability and melt viscosity test.

Following table has shown the experimental data of the polyester of present embodiment.These data show, for constant logarithmic viscosity number, and 2,2,4,4-tetramethyl-1, the increase of 3-cyclobutanediol content has improved glass transition temperature in almost linear mode.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.

Table 7

Glass transition temperature is with logarithmic viscosity number and form variation

Embodiment	mol％TMCD	% cis TMCD	IV(dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)
Embodiment	mol％TMCD	% cis TMCD	IV(dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	A	20	51.4	0.72	109	11356	19503	5527
B	19.1	51.4	0.60	106	6891	3937	2051	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	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	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	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	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	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	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	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=does not obtain.

Embodiment 8

Present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl-1, and the consumption of 3-cyclobutanediol is to the influence of the glass 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.

With dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-ml.To 2,2,4,4-tetramethyl-1, the raw-material NMR of 3-cyclobutanediol the analysis showed that cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/acid ratio example preparation, and is all excessive all from 2,2,4,4-tetramethyl-1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymer, to obtain 300ppm stannum.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.Reduce along with viscosity increases to stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymer to be cooled to be lower than its glass transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing body and break away from glass flask up to it.Stirring polymer body with medium level in flask cools off up to polymer.Taking out polymer and grind from flask makes it sieve by 3mm.This program is changed the copolyesters that becomes 32mol% with the target group of production the following stated.

Following table has shown the experimental data of the polyester of present embodiment.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.These data show, for constant logarithmic viscosity number, and 2,2,4,4-tetramethyl-1, the increase of 3-cyclobutanediol content has improved glass transition temperature in almost linear mode.

Table 8

Embodiment	TMCD mol％	Cis TMCD%	IV (dl/g)	Tg (℃)	260℃η _o(pool)	275℃η _o(pool)	290℃η _o(pool)
Embodiment	TMCD mol％	Cis TMCD%	IV (dl/g)	Tg (℃)	260℃η _o(pool)	275℃η _o(pool)	290℃η _o(pool)	A	32.2	51.9	0.71	118	29685	16074	8522
B	31.6	51.5	0.55	112	5195	2899	2086	A	32.2	51.9	0.71	118	29685	16074	8522
B	31.6	51.5	0.55	112	5195	2899	2086	C	31.5	50.8	0.62	112	8192	4133	2258
D	30.7	50.7	0.54	111	4345	2434	1154	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	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	G	29.0	51.5	0.67	112	16322	8787	4355

NA=does not obtain.

Embodiment 9

Present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl-1, and the consumption of 3-cyclobutanediol is to the influence of the glass transition temperature of polyester.To comprise consumption be 40mol% or bigger by 2,2,4 to Zhi Bei polyester in the present embodiment, 4-tetramethyl-1,3-cyclobutanediol residue.

Embodiment A-AC

These polyester are by carrying out ester exchange in the stage of separating and polycondensation reaction prepares.The ester exchange experiment is being carried out in the temperature reaction device (CTR) continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric jacket and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.In this reactor, add 777g dimethyl terephthalate (DMT), 375g 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 317g cyclohexanedimethanol and 1.12g three (2 ethyl hexanoic acid) butyl tin (make and in final polymer, have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Camile method control system makes set point and data acquisition easier.In case the reactant fusion then begins to stir and slowly be increased to 250rpm.The temperature of reactor raises gradually along with the duration of runs.The methanol weight of equaling a record and collecting by the sky.When the progress of methanol stops or in 260 ℃ lower temperature cessation reaction of preliminary election.Adopt nitrogen purging to discharge oligomer and cool to room temperature.Adopt the liquid nitrogen freezing oligomer and be broken into enough little fritter, so that can be weighed in the 500ml round-bottomed flask.

In polycondensation reaction, in the 500ml round-bottomed flask, add the oligomer for preparing above the 150g.This flask is equipped with rustless steel agitator and cap.Be arranged on glass drying oven on the half moles of polymer complete set of equipments and start the Camile sequence.In case the oligomer fusion orientates agitator apart from complete upset of drag as.For these embodiment, be reported in the following table by the temperature/pressure/stirring speed sequence of Camile software control, unless in following other explanation.

The Camile sequence of polycondensation reaction

The Camile sequence of embodiment A, C, R, Y, AB, AC

For Embodiment B, C, F, in the use table in identical sequence, but in the stage 7 time be 80 minutes.For embodiment G and J, in the use table in identical sequence, but in the stage 7 time be 50 minutes.For embodiment L, in the use table in identical sequence, but in the stage 7 time be 140 minutes.

The Camile sequence of embodiment E

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

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

The Camile sequence of embodiment H

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

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

The Camile sequence of embodiment K

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

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

The Camile sequence of embodiment S and T

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

Embodiment A D-AK and AT

For preparation as described in embodiment A-AC, but for embodiment A D-AK and AT, the consumption of target stannum is 15ppm to the polyester of these embodiment in final polymer as above.Following table has been put down in writing the temperature/pressure/stir speed (S.S.) sequence by the Camile software control for these embodiment.

The Camile sequence of embodiment A D, AF and AH

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

For embodiment A D, agitator goes to 25rpm 95min in the stage 7.

The Camile sequence of embodiment A E

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

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

The Camile sequence of embodiment A G

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

The Camile sequence of embodiment A I

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

The Camile sequence of embodiment A J

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

Embodiment A L-AS

With dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-ml.The polyester of present embodiment adopts 1.2/1 glycol/acid ratio example preparation, and is all excessive all from 2,2,4,4-tetramethyl-1,3-cyclobutanediol.Add enough tributyltin oxide catalysts in final polymer, to obtain 300ppm stannum.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.Reduce along with viscosity increases to stir, 15RPM is that used minimum stirs.Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymer to be cooled to be lower than its glass transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing body and break away from glass flask up to it.Stirring polymer body with medium level in flask cools off up to polymer.Taking out polymer and grind from flask makes it sieve by 3mm.This program is changed the copolyesters that becomes 45mol% with the target group of production the following stated.

Table 9

Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)
Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	A	43.9	72.1	0.46	131	NA	NA	NA
B	44.2	36.4	0.49	118	NA	NA	NA	A	43.9	72.1	0.46	131	NA	NA	NA
B	44.2	36.4	0.49	118	NA	NA	NA	C	44	71.7	0.49	128	NA	NA	NA
D	44.3	36.3	0.51	119	NA	NA	NA	C	44	71.7	0.49	128	NA	NA	NA
D	44.3	36.3	0.51	119	NA	NA	NA	E	46.1	46.8	0.51	125	NA	NA	NA
F	43.6	72.1	0.52	128	NA	NA	NA	E	46.1	46.8	0.51	125	NA	NA	NA
F	43.6	72.1	0.52	128	NA	NA	NA	G	43.6	72.3	0.54	127	NA	NA	NA
H	46.4	46.4	0.54	127	NA	NA	NA	G	43.6	72.3	0.54	127	NA	NA	NA
H	46.4	46.4	0.54	127	NA	NA	NA	I	45.7	47.1	0.55	125	NA	NA	NA
J	44.4	35.6	0.55	118	NA	NA	NA	I	45.7	47.1	0.55	125	NA	NA	NA
J	44.4	35.6	0.55	118	NA	NA	NA	K	45.2	46.8	0.56	124	NA	NA	NA
L	43.8	72.2	0.56	129	NA	NA	NA	K	45.2	46.8	0.56	124	NA	NA	NA
L	43.8	72.2	0.56	129	NA	NA	NA	M	45.8	46.4	0.56	124	NA	NA	NA
N	45.1	47.0	0.57	125	NA	NA	NA	M	45.8	46.4	0.56	124	NA	NA	NA
N	45.1	47.0	0.57	125	NA	NA	NA	O	45.2	46.8	0.57	124	NA	NA	NA
P	45	46.7	0.57	125	NA	NA	NA	O	45.2	46.8	0.57	124	NA	NA	NA
P	45	46.7	0.57	125	NA	NA	NA	Q	45.1	47.1	0.58	127	NA	NA	NA
R	44.7	35.4	0.59	123	NA	NA	NA	Q	45.1	47.1	0.58	127	NA	NA	NA
R	44.7	35.4	0.59	123	NA	NA	NA	S	46.1	46.4	0.60	127	NA	NA	NA
T	45.7	46.8	0.60	129	NA	NA	NA	S	46.1	46.4	0.60	127	NA	NA	NA
T	45.7	46.8	0.60	129	NA	NA	NA	U	46	46.3	0.62	128	NA	NA	NA
V	45.9	46.3	0.62	128	NA	NA	NA	U	46	46.3	0.62	128	NA	NA	NA
V	45.9	46.3	0.62	128	NA	NA	NA	X	45.8	46.1	0.63	128	NA	NA	NA
Y	45.6	50.7	0.63	128	NA	NA	NA	X	45.8	46.1	0.63	128	NA	NA	NA
Y	45.6	50.7	0.63	128	NA	NA	NA	Z	46.2	46.8	0.65	129	NA	NA	NA
AA	45.9	46.2	0.66	128	NA	NA	NA	Z	46.2	46.8	0.65	129	NA	NA	NA
AA	45.9	46.2	0.66	128	NA	NA	NA	AB	45.2	46.4	0.66	128	NA	NA	NA
AC	45.1	46.5	0.68	129	NA	NA	NA	AB	45.2	46.4	0.66	128	NA	NA	NA
AC	45.1	46.5	0.68	129	NA	NA	NA	AD	46.3	52.4	0.52	NA	NA	NA	NA
AE	45.7	50.9	0.54	NA	NA	NA	NA	AD	46.3	52.4	0.52	NA	NA	NA	NA
AE	45.7	50.9	0.54	NA	NA	NA	NA	AF	46.3	52.6	0.56	NA	NA	NA	NA
AG	46	50.6	0.56	NA	NA	NA	NA	AF	46.3	52.6	0.56	NA	NA	NA	NA
AG	46	50.6	0.56	NA	NA	NA	NA	AH	46 5	51.8	0.57	NA	NA	NA	NA
AI	45 6	51.2	0.58	NA	NA	NA	NA	AH	46 5	51.8	0.57	NA	NA	NA	NA
AI	45 6	51.2	0.58	NA	NA	NA	NA	AJ	46	51.9	0.58	NA	NA	NA	NA
AK	45 5	51.2	0.59	NA	NA	NA	NA	AJ	46	51.9	0.58	NA	NA	NA	NA
AK	45 5	51.2	0.59	NA	NA	NA	NA	AL	45.8	50.1	0.624	125	NA	NA	7696
AM	45.7	49.4	0.619	128	NA	NA	7209	AL	45.8	50.1	0.624	125	NA	NA	7696
AM	45.7	49.4	0.619	128	NA	NA	7209	AN	46.2	49.3	0.548	124	NA	NA	2348
AP	45.9	49.5	0.72	128	76600	40260	19110	AN	46.2	49.3	0.548	124	NA	NA	2348
AP	45.9	49.5	0.72	128	76600	40260	19110	AQ	46.0	50	0.71	131	68310	32480	17817
AR	46.1	49.6	0.383	117	NA	NA	387	AQ	46.0	50	0.71	131	68310	32480	17817
AR	46.1	49.6	0.383	117	NA	NA	387	AS	45.6	50.5	0.325	108	NA	NA	NA
AT	47.2	NA	0.48	NA	NA	NA	NA	AS	45.6	50.5	0.325	108	NA	NA	NA

NA=does not obtain.

Embodiment 10

Present embodiment illustrates 2,2,4,4-tetramethyl-1, and the type advantage of 3-cyclobutanediol isomer (cis or trans) is to the influence of the glass transition temperature of polyester.

Following table has shown the experimental data of the polyester of present embodiment.These data show, for constant logarithmic viscosity number, improving aspect the glass transition temperature, and cis 2,2,4, it is trans 2,2,4 that 4-tetramethyl-1, the effectiveness of 3-cyclobutanediol are 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 (℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	% cis TMCD
Embodiment	mol％ TMCD	IV (dL/g)	T _g (℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	% cis TMCD	A	45.8	0.71	119	N.A.	N.A.	N.A.	4.1
B	43.2	0.72	122	N.A.	N.A	N.A.	22.0	A	45.8	0.71	119	N.A.	N.A.	N.A.	4.1
B	43.2	0.72	122	N.A.	N.A	N.A.	22.0	C	46.8	0.57	119	26306	16941	6601	22.8
D	43.0	0.67	125	55060	36747	14410	23.8	C	46.8	0.57	119	26306	16941	6601	22.8
D	43.0	0.67	125	55060	36747	14410	23.8	E	43.8	0.72	127	101000	62750	25330	24.5
F	45.9	0.533	119	11474	6864	2806	26.4	E	43.8	0.72	127	101000	62750	25330	24.5
F	45.9	0.533	119	11474	6864	2806	26.4	G	45.0	0.35	107	N.A.	N.A.	N.A.	27.2
H	41.2	0.38	106	1214	757	N.A	29.0	G	45.0	0.35	107	N.A.	N.A.	N.A.	27.2
H	41.2	0.38	106	1214	757	N.A	29.0	I	44.7	0.59	123	N.A.	N.A.	N.A.	35.4
J	44.4	0.55	118	N.A.	N.A.	N.A.	35.6	I	44.7	0.59	123	N.A.	N.A.	N.A.	35.4
J	44.4	0.55	118	N.A.	N.A.	N.A.	35.6	K	44.3	0.51	119	N.A.	N.A.	N.A.	36.3
L	44.0	0.49	128	N.A.	N.A.	N.A.	71.7	K	44.3	0.51	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	M	43.6	0.52	128	N.A.	N.A.	N.A.	72.1
N	43.6	0.54	127	N.A.	N.A.	N.A.	72.3	O	41.5	0.58	133	15419	10253	4252	88.7
P	43.8	0.57	135	16219	10226	4235	89.6	O	41.5	0.58	133	15419	10253	4252	88.7
P	43.8	0.57	135	16219	10226	4235	89.6	Q	41.0	0.33	120	521	351	2261	90.4
R	43.0	0.56	134	N.A.	N.A.	N.A.	90.6	Q	41.0	0.33	120	521	351	2261	90.4
R	43.0	0.56	134	N.A.	N.A.	N.A.	90.6	S	43.0	0.49	132	7055	4620	2120	90.6
T	43.1	0.55	134	12970	8443	3531	91.2	S	43.0	0.49	132	7055	4620	2120	90.6
T	43.1	0.55	134	12970	8443	3531	91.2	U	45.9	0.52	137	N.A.	N.A.	N.A.	98.1

NA=does not obtain.

Embodiment 11

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

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

Embodiment 12-Comparative Examples

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

With with the preparation of the similar method of method described in the embodiment 1A only based on p-phthalic 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.

320 ℃ of polymer press membrane by grinding.Be the crystallization half-life of increment measurement melt with 10 ℃ and be recorded in the table 11 at 220-250 ℃.Get the minima of the fastest crystallization half-life of every kind of sample as temperature variant crystallization half-life.Be about 1300 minutes the fastest crystallization half-life of this polyester.This value with as shown in Figure 1 only based on p-phthalic acid and 1, the polyester (PCT) of 4-cyclohexanedimethanol (no comonomer modification) has extremely short crystallization half-life (＜1min) true opposite.

Table 11

Crystallization half-life (min)

Comonomer (mol%)	IV (dl/g)	Tg (℃)	T _max (℃)	220℃ (min)	230℃ (min)	240℃ (min)	250℃ (min)
Comonomer (mol%)	IV (dl/g)	Tg (℃)	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 cis/trans)

Data contrast from above related work embodiment is clearly visible, aspect glass transition temperature, density, slow crystalline rate, melt viscosity and toughness, compares with commercially available polyester, and polyester of the present invention provides remarkable advantages.

The present invention describes in detail with reference to embodiment disclosed herein, but should be appreciated that, can carry out changes and improvements within the spirit and scope of the present invention.

Claims

1. a dialysis filter shell comprises at least a polymer blend, and this polymer blend comprises at least a polyester, and this polyester comprises:

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 10-99mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 1-90mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester has 100-200 ℃ Tg.

2. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.35-1.2dL/g.

3. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.35-1.0dL/g.

4. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g.

5. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.40-0.90dL/g.

6. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.42-0.80dL/g.

7. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.45-0.75dL/g.

8. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.50-0.68dL/g.

9. the dialysis filter shell of claim 1, wherein the logarithmic viscosity number of polyester is 0.60-0.72dL/g.

10. the dialysis filter shell of claim 1, wherein polyester has 100-160 ℃ Tg.

11. the dialysis filter shell of claim 1, wherein polyester has 100-150 ℃ Tg.

12. the dialysis filter shell of claim 1, wherein polyester has 130-145 ℃ Tg.

13. the dialysis filter shell of claim 9, wherein polyester has 130-145 ℃ Tg.

14. the dialysis filter shell of claim 1, wherein the diol component of polyester comprises 2,2,4 of 15-70mol%, 4-tetramethyl-1,1 of 3-cyclobutanediol residue and 30-85mol%, 4-cyclohexanedimethanol residue.

15. the dialysis filter shell of claim 1, wherein the diol component of polyester comprises 2,2,4 of 15-60mol%, 4-tetramethyl-1,1 of 3-cyclobutanediol residue and 40-85mol%, 4-cyclohexanedimethanol residue.

16. the dialysis filter shell of claim 1, wherein the diol component of polyester comprises 2,2,4 of 15-50mol%, 4-tetramethyl-1,1 of 3-cyclobutanediol residue and 50-85mol%, 4-cyclohexanedimethanol residue.

17. the dialysis filter shell of claim 1, wherein the diol component of polyester comprises 2,2,4 of 15-40mol%, 4-tetramethyl-1,1 of 3-cyclobutanediol residue and 60-85mol%, 4-cyclohexanedimethanol residue.

18. the dialysis filter shell of claim 1, wherein the diol component of polyester comprises 2,2,4 of 40-55mol%, 4-tetramethyl-1,1 of 3-cyclobutanediol residue and 45-60mol%, 4-cyclohexanedimethanol residue.

19. the dialysis filter shell of claim 1, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 80-100mol%.

20. the dialysis filter shell of claim 1, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 90-100mol%.

21. the dialysis filter shell of claim 1, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 95-100mol%.

22. the dialysis filter shell of claim 1, wherein polyester comprises 1 of 0.1-25mol%, ammediol residue, 1,4-butanediol residue or its mixture.

23. the dialysis filter shell of claim 1, wherein polyester comprises 1 of 0.1-10mol%, ammediol residue, 1,4-butanediol residue or its mixture.

24. the dialysis filter shell of claim 1, wherein polyester comprises the glycol residue of 0.01-15mol%.

25. the dialysis filter shell of claim 1, wherein 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue is for comprising greater than 50mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residue and less than 50mol% trans-2,2,4,4-tetramethyl-1, the mixture of 3-cyclobutanediol residue.

26. the dialysis filter shell of claim 1, wherein 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue is for comprising greater than 55mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residue and less than 45mol% trans-2,2,4,4-tetramethyl-1, the mixture of 3-cyclobutanediol residue.

27. the dialysis filter shell of claim 1, wherein 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue is for comprising greater than 50mol% cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residue and less than 50mol% trans-2,2,4,4-tetramethyl-1, the mixture of 3-cyclobutanediol residue, and the dicarboxylic acid component comprises the terephthalic acid residue of 80-100mol%.

28. the dialysis filter shell of claim 1, wherein polymer blend comprises at least a following polymer that is selected from: Polyetherimide, polyphenylene oxide, polyphenyl ether/styrene blend, polystyrene resin, polyphenylene sulfide, polyphenylene sulfide/sulfone, poly-(ester-carbonic ester), Merlon, polysulfones, polysulfones ether, poly-(ether-ketone), polyamide, polystyrene, polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile butadient styrene, polymethyl methacrylate and acrylic acid series copolymer.

29. the dialysis filter shell of claim 1, wherein polymer blend comprises at least a Merlon.

30. the dialysis filter shell of claim 1, wherein to comprise at least a gross weight count number with polyester be the residue of the branching agent of 0.01-10wt% to polyester.

31. the dialysis filter shell of claim 1, wherein the melt viscosity of polyester is measured with 1 radian per second in 290 ℃ on the rotation melt rheometer less than 30000 pools.

32. the dialysis filter shell of claim 1, wherein polyester is 170 ℃ of crystallization half-lives that have greater than 100 minutes.

33. the dialysis filter shell of claim 1, wherein polyester is 170 ℃ of crystallization half-lives that have greater than 1000 minutes.

34. the dialysis filter shell of claim 1, wherein polymer blend is 23 ℃ of density that have less than 1.2g/ml.

35. the dialysis filter shell of claim 1, wherein polymer blend comprises at least a heat stabilizer or its product.

36. the dialysis filter shell of claim 1, wherein polyester according to the yellowness index of ASTM D-1925 less than 50.

37. the dialysis filter shell of claim 1, wherein polyester have 23 ℃ according to ASTM D256 with 1/8 inch thick strip in the notched izod impact strength of the 3ft-lb/in at least that measures of 10 mil breach.

38. the dialysis filter shell of claim 1, wherein polyester have 23 ℃ according to ASTM D256 with 1/4 inch thick strip in the notched izod impact strength of the 10ft-lb/in at least that measures of 10 mil breach.

39. the dialysis filter shell of claim 1, wherein polyester comprises at least a catalyst of tin compound or the residue of its product of containing.

40. the dialysis filter shell of claim 1, wherein dialysis filter shell is to have a plurality of protectiveness shells that are used to introduce and/or discharge the opening of dialysis solution.

41. the dialysis filter shell of claim 1, wherein dialysis filter shell is formed by injection moulding.

42. a dialysis filter shell comprises at least a polymer blend, this polymer blend comprises at least a polyester, and this polyester comprises:

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-70mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 30-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester has 100-160 ℃ Tg.

43. the dialysis filter shell of claim 42, wherein the logarithmic viscosity number of polyester is 0.35-0.75dL/g.

44. the dialysis filter shell of claim 42, wherein the logarithmic viscosity number of polyester is 0.45-0.75dL/g.

45. the dialysis filter shell of claim 42, wherein the logarithmic viscosity number of polyester is 0.50-0.68dL/g.

46. the dialysis filter shell of claim 42, wherein the logarithmic viscosity number of polyester is 0.60-0.72dL/g.

47. the dialysis filter shell of claim 42, wherein polyester has 130-145 ℃ Tg.

48. the dialysis filter shell of claim 46, wherein polyester has 130-145 ℃ Tg.

49. the dialysis filter shell of claim 42, wherein dialysis filter shell is to have a plurality of protectiveness shells that are used to introduce and/or discharge the opening of dialysis solution.

50. a dialysis filter shell comprises at least a polymer blend, this polymer blend comprises at least a polyester, and this polyester comprises:

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-70mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 30-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester has 100-150 ℃ Tg.

51. the dialysis filter shell of claim 50, wherein the logarithmic viscosity number of polyester is 0.45-0.75dL/g.

52. the dialysis filter shell of claim 50, wherein the logarithmic viscosity number of polyester is 0.50-0.68dL/g.

53. the dialysis filter shell of claim 50, wherein the logarithmic viscosity number of polyester is 0.60-0.72dL/g.

54. the dialysis filter shell of claim 50, wherein polyester has 130-145 ℃ Tg.

55. the dialysis filter shell of claim 53, wherein polyester has 130-145 ℃ Tg.

56. the dialysis filter shell of claim 50, wherein dialysis filter shell is to have a plurality of protectiveness shells that are used to introduce and/or discharge the opening of dialysis solution.

57. a dialysis filter shell comprises at least a polymer blend, this polymer blend comprises at least a polyester, and this polyester comprises:

(a) dicarboxylic acid component comprises:

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

(b) diol component comprises:

I) 2,2,4 of 15-60mol%, 4-tetramethyl-1,3-cyclobutanediol residue; With

Ii) 1 of 40-85mol%, 4-cyclohexanedimethanol residue,

Wherein said polyester has 100-150 ℃ Tg.

58. the dialysis filter shell of claim 57, wherein the logarithmic viscosity number of polyester is 0.45-0.75dL/g.

59. the dialysis filter shell of claim 57, wherein the logarithmic viscosity number of polyester is 0.50-0.68dL/g.

60. the dialysis filter shell of claim 57, wherein the logarithmic viscosity number of polyester is 0.60-0.72dL/g.

61. the dialysis filter shell of claim 57, wherein polyester has 130-145 ℃ Tg.

62. the dialysis filter shell of claim 57, wherein dialysis filter shell is to have a plurality of protectiveness shells that are used to introduce and/or discharge the opening of dialysis solution.