CN115894878A - Polyester and molded article - Google Patents

Abstract

The present disclosure provides a polyester and a molded article. The polyester comprises residues of formula (i), formula (ii) and formula (iii):

wherein R is ₁ Is an aromatic group; r is ₂ Is C ₂ ‑C ₆ A straight chain hydrocarbon group; * Representing a connecting bond. The polyester has a number average molecular weight (number average molecular weight) of not less than 15000 and has a degree of dispersion of 2.95 to 5.70. The polyester of the present disclosure has very excellent tensile strength, so that it can meet the industrial demand for manufacturing various products.

Description

Polyester and molded article

Technical Field

The present disclosure relates to a polyester and a molded article.

Background

Conventionally, tricyclodecanedimethanol (TCDDM) monomer can be used in combination in polyester to improve the mechanical strength and heat resistance of polyester. However, since the molecular weight and boiling point of the TCDDM monomer are high and the TCDDM has poor reactivity compared with other reaction monomers, the mechanical properties of the prepared polyester are poor, such as low tensile strength.

Therefore, in response to the above needs, there is a need for polyesters containing TCDDM that have tensile strength that meets the needs of the industry.

Disclosure of Invention

The present disclosure provides a polyester comprising residues of formula (i), formula (ii), and formula (iii):

wherein R is ₁ Is an aromatic group;R ₂ is C ₂ -C ₆ A straight chain hydrocarbon group; * Represents a linkage, wherein the polyester has a number average molecular weight (Mn) of not less than 15000 and has a degree of dispersion of 2.95 to 5.70. Dispersity is defined herein as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), i.e., mw/Mn.

In one or more embodiments of the present disclosure, R ₁ Is composed of

Or a combination of the foregoing.

In one or more embodiments of the disclosure, R ₂ Is C ₂ -C ₄ A straight chain hydrocarbon group.

In one embodiment of the disclosure, R ₂ Is C ₂ A straight chain hydrocarbon group.

In one or more embodiments of the present disclosure, the number average molecular weight of the polyester is 15000 to 25000.

In one or more embodiments of the present disclosure, the number average molecular weight of the polyester is from 16000 to 23000.

In one or more embodiments of the present disclosure, the polyester has a dispersity of 3.00 to 4.50.

In one or more embodiments of the disclosure, the residue of formula (iii) comprises 10% to 90% of the sum of the residue of formula (ii) and the residue of formula (iii).

In one or more embodiments of the disclosure, the residue of formula (iii) comprises 20% to 80% of the sum of the residue of formula (ii) and the residue of formula (iii).

The present disclosure also provides a molded article. The molded article comprises the polyester.

Detailed Description

In order to make the description of the present disclosure more complete and complete, the following description is given for illustrative purposes with respect to the embodiments and specific examples of the present disclosure; it is not intended to be the only form in which a particular embodiment of the disclosure may be practiced or utilized. The following disclosed embodiments may be combined with or substituted for one another where appropriate, and additional embodiments may be added to one embodiment without further recitation or description. In the following description, numerous specific details are set forth to provide a thorough understanding of the following embodiments. However, embodiments of the present disclosure may be practiced without these specific details.

Although the methods disclosed herein are illustrated below as a series of acts or steps, the order in which the acts or steps are presented should not be construed as a limitation of the present disclosure. For example, certain operations or steps may be performed in a different order and/or concurrently with other steps. Moreover, not all illustrated operations, steps and/or features may be required to implement an embodiment of the present disclosure. Further, each operation or step described herein may comprise multiple sub-steps or actions.

The present disclosure provides a polyester. The polyester comprises residues of formula (i), formula (ii), and formula (iii):

wherein R is ₁ Is an aromatic radical, R ₂ Is C ₂ -C ₆ Straight-chain hydrocarbon group represents a connecting bond.

The residue of formula (i) is derived from a diacid monomer. In some embodiments, the diacid monomer comprises an aromatic dicarboxylic acid. In some embodiments, R of formula (i) ₁ Is C ₆ -C ₁₆ An aromatic group. In some embodiments, R of formula (i) ₁ Is composed of

Or a combination of the foregoing, wherein x represents a bond. In some embodiments, the diacid monomer can be, for example, terephthalic acid (PTA) or 1,4-naphthalenedicarboxylic acid (2,6-naphthalene dicarboxylic acid, NDA). In some embodiments, the number of moles of formula (i) comprises 50mol% of the sum of the number of moles of formulae (i) to (iii).

The residue of formula (ii) is derived from an aliphatic linear diol monoAnd (3) a body. In some embodiments of the disclosure, R in formula (ii) ₂ Is C ₂ -C ₄ A straight chain hydrocarbon group. In some embodiments of the disclosure, R ₂ Is C ₂ A straight chain hydrocarbon group.

In some embodiments, the residue of formula (iii) is derived from tricyclodecane dimethanol (TCDDM). In one or more embodiments of the present disclosure, the residue of formula (iii) represents 10% to 90%, preferably 20% to 80%, for example 30%, 40%, 50%, 60% or 70% of the sum of the residue of formula (ii) and the residue of formula (iii). It is noted that if the residue of formula (iii) accounts for 10% to 90% of the total of the residue of formula (ii) and the residue of formula (iii), the polyester of the present disclosure may have higher mechanical strength and heat resistance.

In some embodiments, the polyester further comprises a residue of the following formula (iv):

wherein R is ₃ Is C ₃ -C ₂₀ Hydrocarbyl radical, R ₄ 、R ₅ And R ₆ Is C ₁ -C ₆ Hydrocarbyl radical, n ₁ 、n ₂ 、n ₃ 、n ₄ 、n ₅ And n ₆ Is 0 or 1. In some embodiments, R ₃ Is C ₃ -C ₂₀ Aliphatic hydrocarbon radical or C ₄ -C ₂₀ An aromatic hydrocarbon group.

In some embodiments, the residue of formula (iv) is selected from the group consisting of:

/>

and combinations of the foregoing, wherein denotes a bond.

In some embodiments, the residue of formula (iv) is derived from the group consisting of:

and combinations of the above, wherein x represents a bond. In some embodiments, the residue of formula (iv) comprises 0.1 to 0.55 mole%, for example 0.2, 0.3, or 0.4 mole% of the polyester.

In one or more embodiments of the present disclosure, the polyester has a number average molecular weight of not less than 15,000, preferably 15,000 to 25,000, more preferably 16,000 to 23,000, such as 17,000, 18,000, 19,000, 20,000, 21,000, 22,000. In one or more embodiments of the present disclosure, the polyester has a dispersion of 2.95 to 5.70, preferably 3.10 to 4.50, more preferably 3.13 to 4.50, such as 3.25, 3.50, 3.75, 4.0, or 4.25. It is noted that by controlling the number average molecular weight and the dispersity of the polyester within the above ranges, the mechanical properties of the polyester of the present disclosure can be significantly increased, for example, the polyester can have good tensile strength. In various embodiments, the polyesters of the present disclosure have a tensile strength greater than 130% and an Intrinsic Viscosity (IV) of greater than 0.5Dl/g to 0.8 Dl/g. In the intrinsic viscosity measurement, 250mg of polyester is dissolved in 50ml of a solvent and measured at 25 ℃, wherein the solvent is prepared by mixing the following components in a weight ratio of 60:40 phenol and dichlorobenzene.

The present disclosure also provides a molded article. The molded article comprises the polyester. According to various embodiments, the polyester of the present disclosure may be used for forming materials such as food contact (food contact), automobile molds (automotive molds), consumer household goods (commercial household goods), composite consumer goods (composites), electronics (electronics), equipment housings (device housings), indoor fixtures (in-store fixtures), electronic packaging (electronic packaging), outdoor signs (outdoor signs), personal care goods (personal care), cosmetic packaging (cosmetics packaging), sports equipment tools (sports equipment tools), toys (appliances), and water/sport bottles (water/sport bottles), but is not limited thereto.

The polyesters of the present disclosure may be prepared by one or more methods. For example, the diacid, tricyclodecanedimethanol, and other diols may be mixed with the reactive monomers and the ratio of the diacid to the diol: the molar ratio of the double acid is 1.8-4.0 to carry out esterification reaction. In another embodiment of the present disclosure, the ratio of glycol: in case that the molar ratio of the diacids is 1.5-4.0, 0.2 to 0.8mol% of glycerin, or TMP, is additionally added; or 1.5mol% of HDI. The various methods of preparation provided above are not intended to indicate that the polyesters of the present disclosure can only be prepared by these methods.

In some embodiments of the present disclosure, the polyester may be prepared by the steps comprising: mixing reaction monomers to form a mixture; step (b) subjecting the reaction monomers to an esterification reaction to form oligomers; and a step (c) of further polymerizing the oligomer to form a polymer.

The reaction monomer of the step (a) comprises dibasic acid, aliphatic straight chain diol monomer and tricyclodecane dimethanol. The diacid can be an aromatic dicarboxylic acid such as terephthalic acid or 1,4-naphthalenedicarboxylic acid. The aliphatic linear diol monomer may be, for example, ethylene glycol, 1,3-propanediol, or 1,4-butanediol. In some embodiments, the reactive monomer of step (a) optionally comprises a compound having the structure of formula (iv) above, such as glycerol, trimethylolpropane (TMP), or trimellitic acid (TMA).

In step (a), the reaction monomer is added to the autoclave. The high pressure reactor may be, for example, a vertical reactor, a horizontal reactor, a batch reactor, or a continuous reactor in series, but is not limited thereto. In some embodiments, the reaction monomers are uniformly stirred, wherein the stirring rate is from 100rpm to 500rpm.

In some embodiments, a catalyst may be added in step (a) to promote the reaction. In other embodiments, a catalyst may be added in step (b). CatalysisThe oxidizing agent may be, for example, titanium (IV) butoxide, antimony trioxide (Sb) ₂ O ₃ ) Antimony triacetate (Sb (OAc) ₃ ) Germanium dioxide (GeO) ₂ ) Titanium (IV) isopropoxide, butyl tin tris (2-ethylhexanoate), or a combination thereof, but is not limited thereto. In one embodiment of the present disclosure, titanium (IV) butoxide is used as the catalyst.

In some embodiments, a co-catalyst and/or a thermal stabilizer may be added in step (a). In other embodiments, a co-catalyst and/or a thermal stabilizer may be added in step (b). The promoter may be, for example, copper acetate, zinc acetate, magnesium based catalyst, sodium acetate, potassium acetate, but is not limited thereto, and in one embodiment, no promoter is added. The heat stabilizer may be, for example, triphenyl phosphite (triphenyl phosphate), phosphoric acid, phosphorous acid, hypophosphorous acid and salts thereof, trimethyl phosphate (TMP), triethyl phosphate (TEP), tripropyl phosphate (TPP), 3,9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (3,9-Bis (octadecyloxy) -2,4,8,10-tetroxa-

3,9-diphosphanilo [5.5] undecene), bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite), tris (2,4-di-tert-butylphenyl) phosphite (Tris (2,4-di-tert-butylphenyl) phoshpite), tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenyl Bis (2,4-di-tert-butylphenyl) 4,4' -biphenyldi, but are not limited thereto. In one embodiment of the present disclosure, TMP is used as the thermal stabilizer.

Then, step (b) is performed to subject the reaction monomers to an esterification reaction to form oligomers. Step (b) comprises heating the mixture from step (a) to subject the reactive monomers to an esterification reaction to form oligomers. In some embodiments, the mixture is heated from room temperature to 220 ℃ to 270 ℃. In some embodiments, suitable pressures for step (b) are 1atm and 6atm, preferably 1.7atm and 4atm. In some embodiments, the reaction time of step (b) is 2 to 6 hours. Whether the esterification reaction is completed or not is judged by observing the amount of water or alcohol produced in step (b). Specifically, the theoretical amount of water or alcohol produced after the reaction of all monomers in the mixture can be obtained by theoretical calculation. When the amount of water or alcohol produced in step (b) reaches 80% or more, for example 85%, 90% or 95%, of the theoretical amount of water or alcohol, it means that the esterification reaction is substantially complete.

Then step (c) is performed to further polymerize the oligomer to form a polymer. In some embodiments, step (c) comprises heating the oligomer to 250 ℃ to 300 ℃ and performing a vacuum pump down for 30 to 60 minutes to achieve an ambient pressure of less than 3Torr, preferably less than 1Torr. In some embodiments, the oligomer is polymerized to liberate the diol, which results in a gradual increase in the viscosity of the polymer. In some embodiments, a chain extender, such as Hexamethylene Diisocyanate (HDI), is optionally added. The content of chain extender may be, for example, 0 to 2.5mol%, based on the total moles of the residue of formula (ii) and the residue of formula (iii). The reaction time of step (c) may be, for example, 1.5 hours to 8 hours. When the viscosity of the polymer reaches a specific value, the polymerization is completed, and the product can be collected. The polymer product is subjected to granulation and related inspection, and is dried until the water content is less than 200ppm, preferably less than 100ppm, more preferably less than 50ppm, and then is subjected to injection molding.

The following examples are presented to illustrate specific embodiments of the present invention and to enable those skilled in the art to practice the invention. However, the following examples are not intended to limit the present invention.

Examples 1to 12 provide polyesters containing TCDDM. The TCDDM-containing polyesters of examples 1to 12 have a number average molecular weight of not less than 15000 (for example, a number average molecular weight in the range of 15000 to 25000) and a dispersity in the range of 2.95 to 5.70. The amounts of reactants and reaction steps of examples 1to 12 are described in detail below.

Example 1 the procedure for preparing a polyester comprises steps (a) to (c). In step (a), the following reaction monomers: 100mol% terephthalic acid (PTA), tricyclodecane dimethanol (TCDDM), and Ethylene Glycol (EG) were added in an amount of 150mol% to an autoclave to mix to form a mixture, with an alcohol/acid addition ratio of 1.5, and 0.2mol% glycerol (glycerol) was added. The alcohol/acid addition ratio is the ratio of the sum of the addition of EG and TCDDM to the addition of PTA. The reaction monomers were then stirred uniformly, with a stirring speed of 100 to 500rpm, and 10ppm of titanium (IV) butoxide as catalyst, cocatalyst and/or 40ppm of trimethyl phosphate (TMP) as heat stabilizer were added.

And (b) heating the mixture of the step (a) from room temperature to 210-260 ℃ to perform esterification reaction on the reaction monomers to form oligomer, wherein the pressure is 1-6 atm, and the reaction time is 2-6 hours. When the amount of water or alcohol produced reaches 95% of the theoretical amount of water or alcohol, step (c) is performed in which the oligomer is heated to 260 to 300 ℃, evacuated for 30 minutes under vacuum so that the ambient pressure is less than 1Torr, and the reaction time is 2 to 8 hours. When the viscosity of the polymer reaches a value of IV >0.5dl/g, the polymerization is completed and the polymer product can be collected.

In the polyester of example 1, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 1 had a polydispersity (Mw/Mn) of 3.502, where Mw was 70393 and Mn was 20098.

The reaction monomer type and reaction procedure of example 2 was substantially similar to example 1, however in step (a), the amount of reaction monomers added was 100mol% PTA, the amount of TCDDM and EG added was 180mol%, the alcohol/acid addition ratio was 1.8, and no glycerol was added.

In the polyester of example 2, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 2 had a polydispersity (Mw/Mn) of 3.453, where Mw was 73692 and Mn was 21335.

The reaction monomer type and reaction procedure of example 3 was substantially similar to example 1, however in step (a) the reaction monomers were added at 100mol% PTA, TCDDM and EG at 250mol%, the alcohol/acid addition ratio was 2.5, and no glycerol was added.

In the polyester of example 3, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 1 had a polydispersity (Mw/Mn) of 3.304, where Mw was 74680 and Mn was 22605.

The reaction monomer type and reaction procedure for example 4 is substantially similar to example 1, however in step (a) the reaction monomers are added in an amount of 100mol% PTA, TCDDM and EG are added in an amount of 400mol%, the alcohol/acid addition ratio is 4.0, and no glycerol is added.

In the polyester of example 4, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 1 had a polydispersity (Mw/Mn) of 3.259, where Mw was 70152 and Mn was 21525.

The kind of reaction monomer, the amount of addition of reaction monomer, and the reaction procedure of example 5 were substantially similar to example 1, however, no glycerin was added in step (a), and Hexamethylene Diisocyanate (HDI) was further added as a chain extender in step (c), wherein the amount of addition of HDI was 1.5mol% based on the total moles of PTA.

In the polyester of example 5, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 5 had a polydispersity (Mw/Mn) of 3.205, where Mw was 64494 and Mn was 20123.

The kind of the reaction monomer, the amount of the added reaction monomer and the reaction procedure in example 6 were substantially similar to those in example 1, however, the amount of the added glycerin in step (a) was adjusted to 0.8mol%.

In the polyester of example 6, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 6 had a polydispersity (Mw/Mn) of 4.499 where Mw was 73237 and Mn was 16275.

The reaction monomer species and reaction steps of example 7 are substantially similar to example 1, however in step (a), the reaction monomers are added in an amount of 100mol% of PTA, TCDDM and EG are added in an amount of 190mol%, the alcohol/acid addition ratio is 1.9, and glycerin is replaced with Trimethylolpropane (TMP), wherein TMP is added in an amount of 0.6mol% based on the total moles of PTA.

In the polyester of example 7, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 7 had a dispersity (Mw/Mn) of 4.056 with Mw of 81650 and Mn of 20130.

The reaction monomer species and reaction steps of example 8 are substantially similar to example 1, however, in step (a), 1,4-butanediol (1,4-butandiol, BDO) was substituted for Ethylene Glycol (EG) of example 1, the amount of reaction monomer added was 100mol% PTA, the amount of TCDDM and BDO added was 230mol%, the alcohol/acid addition ratio was 2.3, and no glycerol was added.

In the polyester of example 8, the TCDDM content was 75mol%, the BDO content was 25mol% and the PTA content was 100mol%. The polyester of example 8 had a polydispersity (Mw/Mn) of 3.139, where Mw was 58808 and Mn was 18734.

The reaction monomer type and reaction procedure of example 9 was substantially similar to example 1, however in step (a), the amount of reaction monomers added was 100mol% PTA, the amount of TCDDM and EG added was 200mol%, the alcohol/acid addition ratio was 2.0, and no glycerol was added.

In the polyester of example 9, the TCDDM content was 18.1mol%, the EG content was 71.9mol% and the PTA content was 100mol%. The polyester of example 9 had a polydispersity (Mw/Mn) of 3.162, where Mw was 63592 and Mn was 20112.

The kind of the reactive monomer, the amount of the reactive monomer added and the reaction procedure in example 10 were substantially similar to those in example 9. In the polyester of example 10, the TCDDM content was 24mol%, the EG content was 76mol% and the PTA content was 100mol%. The polyester of example 10 had a polydispersity (Mw/Mn) of 3.709, where Mw was 79323 and Mn was 21385.

The kind of the reaction monomer, the amount of the reaction monomer added and the reaction procedure in example 11 were substantially similar to those in example 9. In the polyester of example 11, the TCDDM content was 47.4mol%, the EG content was 52.6mol% and the PTA content was 100mol%. The polyester of example 11 had a polydispersity (Mw/Mn) of 3.212, where Mw was 62789 and Mn was 19550.

The kind of the reaction monomer, the amount of the reaction monomer added and the reaction procedure in example 12 were substantially similar to those in example 11. In the polyester of example 12, the TCDDM content was 89.9mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of example 12 had a polydispersity (Mw/Mn) of 3.167, where Mw was 62607 and Mn was 19771.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by Gel Permeation Chromatography (GPC). Specifically, the gel permeation chromatography method used the following instrument: SHIMADZU LC-20AT PUMP, SPD-10A, SCL-10Avp Autosampler and COLBOX COLUMN OVEN. The adopted tubular column is HP 10 ³ A、10 ⁴ A、10 ⁵ A has three branches. The standards were polystyrene (polystyrene) from TOSOH corporation, japan, and were formulated in two groups, the first group having a weight average molecular weight (Mw) of 2000000, 434000, 96400, 18100, 5970, 1050, and the second group having a Mw of 950000, 190000, 37900, 9100, 2630, 531. In the preparation, 0.03g of standard substance is weighed according to the group, and 10ml of chloroform (CHCl) is added ₃ ) Dissolution, test calibration curve R ² Reaches 0.99, and the standard product is subjected to parallel test, and the tested molecular weight is equivalent to the standard value. The solvent adopts hexafluoro-2-propanol/chloroform with the volume ratio of 1/9. The oven temperature was 35 ℃ and the flow rate was 0.8 ml/min. The detector used was SHIMADZU SPD-10A, the injection volume was 10. Mu.l, and the analysis time was 45 minutes. The pretreatment method of the sample is that 0.01g of the sample is weighed into an LC sample bottle, 0.1ml of hexafluoro-2-propanol is added, 0.1ml of chloroform is added, the mixture is kept stand at room temperature, 1.5ml of chloroform is added after dissolution, and the mixture is shaken up to be ready for analysis.

It is to be noted that the number average molecular weight of the polymerization products of examples 1to 12 is not less than 15000 (for example, in the range of 15000 to 25000) while the dispersity thereof is in the range of 2.95 to 5.70.

The polymerization products of comparative examples 1to 5 do not satisfy both the conditions of the number average molecular weight of not less than 15000 (for example, in the range of 15000 to 25000) and the dispersity in the range of 2.95 to 5.70. The amounts of reactants and the reaction steps of comparative examples 1to 5 are described in detail below.

The reaction monomer type and reaction procedure of comparative example 1 was substantially similar to example 1, however, in step (a), the reaction monomers were added in an amount of 100mol% of PTA, TCDDM and EG were added in an amount of 120mol%, the alcohol/acid addition ratio was 1.2, and no glycerol was added. In the polyester of comparative example 1, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of comparative example 1 had a polydispersity (Mw/Mn) of 2.883, where Mw was 32271 and Mn was 11193.

The reaction monomer type, the amount of the added reaction monomer and the reaction step of comparative example 2 were substantially similar to those of example 1, that is, the alcohol/acid addition ratio was 1.5, however, no glycerin was added in step (a). In the polyester of comparative example 2, the TCDDM content was 75mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of comparative example 2 had a polydispersity (Mw/Mn) of 5.783, where Mw was 114275 and Mn was 19762.

The kind of reaction monomers and the reaction procedure of comparative example 3 were the same as those of example 1, however, in step (a), methyl propylene glycol (MPDO) was used instead of EG, the amount of the reaction monomers added was 100mol% of PTA, the amount of the reaction monomers added was 190mol% of TCDDM and MPDO, the alcohol/acid addition ratio was 1.9, and glycerol was not added. In the polyester of comparative example 3, the TCDDM content was 75mol%, the MPDO content was 25mol% and the PTA content was 100mol%. The polyester of comparative example 3 had a polydispersity (Mw/Mn) of 3.287, where Mw was 48096 and Mn was 14631.

The kind of the reactive monomer, the amount of the reactive monomer added and the reaction procedure in comparative example 4 were substantially similar to those in example 9, that is, the alcohol/acid addition ratio was 2.0. In the polyester of comparative example 4, the TCDDM content was 9.5mol%, the EG content was 25mol% and the PTA content was 100mol%. The polyester of comparative example 4 had a polydispersity (Mw/Mn) of 2.920, where Mw was 65921 and Mn was 22576.

The reactive monomer of comparative example 5 contained no EG. In step (a), the reaction monomers were added in an amount of 100mol% PTA to 200mol% TCDDM, i.e., an alcohol/acid addition ratio of 2.0. In the polyester of comparative example 5, the TCDDM content was 100mol%, the PTA content was 100mol%, and the EG content was 0. The polyester of comparative example 5 had a polydispersity (Mw/Mn) of 3.140, where Mw was 46054 and Mn was 14667.

The polymerization products of experimental examples 1to 12 and comparative examples 1to 5 were subjected to the measurement of Intrinsic Viscosity (IV) and tensile strength (elasticity in%). Intrinsic viscosity was tested according to ASTM D4603. Tensile strength was tested according to ISO 527. Tables 1 and 2 show the test results of experimental examples 1to 12 and comparative examples 1to 5, respectively.

TABLE 1

TABLE 2

As shown in table 1, the polymerization products of experimental examples 1to 12 have extremely excellent tensile strength in the case of simultaneously satisfying two conditions of a number average molecular weight of not less than 15000 (for example, in the range of 15000 to 25000) and a dispersity in the range of 2.95 to 5.70. Specifically, the tensile strength of experimental examples 1to 12 was more than 130%, and could even be as high as 315%. The polymer products of comparative examples 1to 5 had tensile strengths of only up to 119% (see Table 2). In addition, comparative example 4 has a melting temperature (Tm) value of 227 ℃, which makes comparative example 4 have higher haze, poor appearance and less suitable for subsequent applications.

In summary, the present disclosure provides a TCDDM-containing polyester having a number average molecular weight of not less than 15000 (e.g., in the range of 15000 to 25000) and a dispersity in the range of 2.95 to 5.70. The TCDDM-containing polyesters provided by the present disclosure have very excellent tensile strength, which can meet the industry's needs for the manufacture of a variety of products.

The foregoing summarizes features of several embodiments or examples so that those skilled in the art may better understand the manner in which the present disclosure is made. Those skilled in the art should appreciate that they may readily use the present disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they may make various changes, substitutions, and alterations herein without departing from the spirit and scope of the present disclosure.

Claims (10)

1. A polyester comprising residues of formula (i), formula (ii), and formula (iii):

wherein R is ₁ Is an aromatic group;

R ₂ is C ₂ -C ₆ A straight chain hydrocarbon group;

* It is shown that the connecting key is,

wherein the polyester has a number average molecular weight of not less than 15000 and a degree of dispersion of 2.95 to 5.70.

2. The polyester of claim 1, wherein R ₁ Is composed of

Or a combination of the foregoing.

3. The polyester of claim 1, wherein R ₂ Is C ₂ -C ₄ A straight chain hydrocarbon group.

4. The polyester of claim 3, wherein R ₂ Is C ₂ A straight chain hydrocarbon group.

5. The polyester of claim 1, wherein the number average molecular weight is 15000 to 25000.

6. The polyester as claimed in claim 5, wherein the number average molecular weight is 16000 to 23000.

7. The polyester of claim 1, wherein the dispersity is from 3.00 to 4.50.

8. The polyester of claim 1, wherein the residues of formula (iii) comprise 10% to 90% of a sum of the residues of formula (ii) and the residues of formula (iii).

9. The polyester of claim 8, wherein the residues of formula (iii) comprise 20% to 80% of the sum of the residues of formula (ii) and the residues of formula (iii).

10. A molded article comprising the polyester according to any one of claims 1to 9.