All cyclic polyester and preparation method thereof

Abstract

The invention discloses all-cyclic polyester and a preparation method thereof, and belongs to the technical field of high polymer materials. The full-alicyclic polyester comprises a reaction product of a cyclic dibasic acid component and a cyclic dihydric alcohol component, the cyclic dibasic acid component comprises one or more than two of alicyclic dibasic acid containing an alicyclic structure with more than four members and derivatives thereof, and the mass content of trans-form in the cyclic dibasic acid component is more than 90%; the cyclic dihydric alcohol component comprises alicyclic dihydric alcohol containing an alicyclic structure with more than four elements, and the mass content of trans-form bodies in the cyclic dihydric alcohol component is more than 90%. The full-alicyclic polyester has the advantages of high melting point, good weatherability and good stability.

Description

Technical Field

[0001] This invention relates to a peralicyclic polyester and its preparation method, belonging to the field of polymer materials technology. Background Technology

[0002] Polyester, as a practical material, is prepared into fibers, films, and plastics, which are widely used in packaging, containers, medical, and electronic fields. Since Carothers and Hill first reported the preparation of high molecular weight polyester in 1932, significant breakthroughs have been made in polyester technology development for synthesis and new market applications.

[0003] Based on their structural characteristics, polyesters can be basically divided into three types: aromatic polyesters, aliphatic polyesters, and aromatic-aliphatic polyesters.

[0004] Aromatic polyesters are polyarylates prepared from aromatic diols, such as bisphenol A and diphenols, and aromatic diacids, such as terephthalic acid or isophthalic acid. Due to their desirable physical properties, polyarylates are used in high-end plastics applications; however, their high production cost has prevented large-scale application.

[0005] Currently, polyesters and copolyesters with monomers composed of some aromatic compounds, such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), are semi-crystalline and have ideal properties such as high melting point and good hydrolytic stability. However, due to the presence of benzene rings in the molecular chain, they also have problems such as poor weather resistance due to ultraviolet absorption and difficulty in biodegradation.

[0006] Aliphatic polyesters are prepared from aliphatic dicarboxylic acids and aliphatic diols. Numerous studies have shown that aliphatic-based polyesters have lower melting points and poorer hydrolytic stability.

[0007] Therefore, there is an urgent need to develop new polyesters that combine a high melting point with good weather resistance and stability, and can meet the needs of different applications. Summary of the Invention

[0008] To address the aforementioned technical problems, the present invention aims to provide a fully alicyclic polyester and its preparation method. The fully alicyclic polyester of the present invention possesses both a high melting point and good weather resistance and stability.

[0009] To achieve the above objectives, a first aspect of the present invention provides a fully alicyclic polyester comprising a reaction product of a cyclic diacid component and a cyclic diol component; wherein the cyclic diacid component comprises one or more alicyclic diacids and their derivatives containing a tetracyclic or more alicyclic structures, and the trans-form content of the cyclic diacid component is 90% or more by mass; wherein the cyclic diol component comprises an alicyclic diol containing a tetracyclic or more alicyclic structures, and the trans-form content of the cyclic diol component is 90% or more by mass.

[0010] According to a specific embodiment of the present invention, preferably, the derivative of the alicyclic dicarboxylic acid includes an ester formed from an alicyclic dicarboxylic acid.

[0011] According to a specific embodiment of the present invention, preferably, the cyclic dicarboxylic acid component includes one or more of the following: C4-C14 alicyclic dicarboxylic acids containing a monoalicyclic structure and their derivatives, and C8-C14 alicyclic dicarboxylic acids containing a dialicyclic structure and their derivatives; the monoalicyclic structure includes one or more of the following: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; the dialicyclic structure includes decahydronaphthyl and / or bicyclohexyl (i.e., bicyclohexyl). Specifically, the cyclic dicarboxylic acid component includes one or more of the following: 1,1-cyclobutyldicarboxylic acid, dimethyl 1,1-cyclobutyldicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, dimethyl 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dimethyl 1,3-cyclohexanedicarboxylic acid, (trans,trans)-[1,1'-bicyclohexane]-4,4'-dicarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, and decahydro-2,6-naphthalenedicarboxylic acid.

[0012] According to a specific embodiment of the present invention, preferably, the mass content of the trans-form in the cyclic dicarboxylic acid component is 99%~100%.

[0013] According to a specific embodiment of the present invention, preferably, the cyclic diol component includes C4-C14 alicyclic diols containing a monoalicyclic structure and / or C8-C14 alicyclic diols containing a dialicyclic structure; the monoalicyclic structure includes one or more of cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; the dialicyclic structure includes decahydronaphthyl and / or bicyclohexyl (i.e., bicyclohexyl). Specifically, the cyclic diol component includes one or more of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 4,4'-bicyclohexanol, and 1,5-decahydronaphthyldiol.

[0014] According to a specific embodiment of the present invention, preferably, the mass content of the trans form in the cyclic diol component is 99% to 100%.

[0015] According to a specific embodiment of the present invention, preferably, the reaction product of the cyclic diacid component and the cyclic diol component includes: the cyclic diacid component and the cyclic diol component first undergo an esterification reaction and / or an ester exchange reaction, and then undergo a polycondensation reaction to obtain the product.

[0016] According to a specific embodiment of the present invention, preferably, the molar ratio of the cyclic dicarboxylic acid component and the cyclic diol component is 0.95 to 1.20.

[0017] According to a specific embodiment of the present invention, preferably, the intrinsic viscosity of the full alicyclic polyester is 0.5~1.2 dL / g.

[0018] According to a specific embodiment of the present invention, preferably, the melting point of the full alicyclic polyester is 200~300℃.

[0019] According to a specific embodiment of the present invention, preferably, the growth rate of the b-value in CIEL*a*b* of the full alicyclic polyester before and after the weathering test is less than 10%, and the weathering test includes: at a wavelength of 340 nm and an irradiance of 0.76 W / m 2 Placed at 40°C for 24 hours under ×nm light.

[0020] According to a specific embodiment of the present invention, preferably, the intrinsic viscosity of the full alicyclic polyester changes by 0.1% to 3% before and after the hydrolysis resistance test, wherein the hydrolysis resistance test includes boiling in water at 70°C for 4 days.

[0021] According to a specific embodiment of the present invention, preferably, the intrinsic viscosity of the full alicyclic polyester changes by 0.5-5% before and after the chemical resistance test, wherein the chemical resistance test includes placing it in acetone, toluene or vegetable oil at room temperature for 5 hours.

[0022] A second aspect of the present invention provides a method for preparing the above-mentioned polycyclic aliphatic polyester, comprising the following steps:

[0023] (1) The cyclic dicarboxylic acid component and the diol component are subjected to a first reaction in the presence of a first catalyst, the first reaction including esterification and / or transesterification to obtain an intermediate product;

[0024] (2) The intermediate product is subjected to a second reaction in the presence of a second catalyst and a stabilizer, the second reaction including a polycondensation reaction, to obtain the full alicyclic polyester.

[0025] According to a specific embodiment of the present invention, preferably, in step (1), the molar ratio of the cyclic dicarboxylic acid component and the cyclic diol component is 0.95~1.20.

[0026] According to a specific embodiment of the present invention, preferably, in step (1), the first catalyst includes one or more of the following: antimony catalyst, titanium catalyst, manganese catalyst, germanium catalyst, tin catalyst, alkali metal catalyst and alkaline earth metal catalyst.

[0027] According to a specific embodiment of the present invention, preferably, in step (1), the amount of the first catalyst added is 0.5 to 5% of the molar amount of the cyclic dicarboxylic acid component.

[0028] According to a specific embodiment of the present invention, preferably, in step (1), the temperature of the first reaction is 170~250℃, the pressure is atmospheric pressure, and the time is 2~5h.

[0029] According to a specific embodiment of the present invention, preferably, in step (2), the second catalyst includes one or more of germanium-based catalysts, tin-based catalysts, titanium-based catalysts and antimony-based catalysts.

[0030] According to a specific embodiment of the present invention, preferably, in step (2), the amount of the second catalyst added is 0.1 to 10% of the molar amount of the cyclic dicarboxylic acid component.

[0031] According to a specific embodiment of the present invention, preferably, in step (2), the stabilizer includes a phosphorus stabilizer and / or a silicon stabilizer; the phosphorus stabilizer includes one or more of phosphoric acid compounds and phosphate ester compounds; the silicon stabilizer includes one or more of silicate compounds and silicate ester compounds.

[0032] According to a specific embodiment of the present invention, preferably, in step (2), the amount of stabilizer added is 0.1 to 10% of the molar amount of the cyclic dicarboxylic acid component.

[0033] According to a specific embodiment of the present invention, preferably, in step (2), the temperature of the second reaction is 250~270°C, the pressure is below 100Pa, and the time is 3~4h.

[0034] The present invention has at least the following beneficial effects:

[0035] The per-alicyclic polyester of this invention comprises the reaction product of a cyclic diacid component with a high trans-content cyclic diol component, and a cyclic diol component with a high trans-content cyclic diol component. It combines the advantages of both aromatic and aliphatic polyesters: it possesses not only the good biodegradability and weather resistance of aliphatic polyesters, but also the high melting point and good thermal stability of aromatic polyesters. The per-alicyclic polyester of this invention has a high melting point, similar to that of semi-aromatic polyesters such as PBT, thus exhibiting good thermal stability; as well as good weather resistance, hydrolysis resistance (i.e., hydrolytic stability), and chemical resistance; simultaneously, due to its per-alicyclic structure, it does not contain benzene rings, thus possessing good biodegradability. Therefore, the per-alicyclic polyester of this invention has excellent overall performance and can replace traditional polyesters in packaging containers, electronics, biomedicine, aerospace, and other fields. Detailed Implementation

[0036] To provide a clearer understanding of the technical features, objectives, and beneficial effects of the present invention, the present invention will now be described in detail below, but this should not be construed as limiting the scope of the invention.

[0037] It should be noted that, unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0038] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0039] It should be understood that the terms “comprising,” “including,” and / or “containing” as used herein specify the presence of the stated features, integers, steps, components, or combinations thereof, but do not exclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

[0040] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0041] In the description of this invention, it should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0042] According to a specific embodiment of a first aspect of the present invention, the present invention provides a fully alicyclic polyester comprising a reaction product of a cyclic diacid component and a cyclic diol component; wherein the cyclic diacid component comprises one or more alicyclic diacids and their derivatives containing a tetracyclic or more alicyclic structures, and the mass content of the trans form in the cyclic diacid component is 90% or more (relative to the total mass of the trans and cis forms); wherein the cyclic diol component comprises an alicyclic diol containing a tetracyclic or more alicyclic structures, and the mass content of the trans form in the cyclic diol component is 90% or more (relative to the total mass of the trans and cis forms).

[0043] The peralicyclic polyester of this invention comprises the reaction product of a cyclic dicarboxylic acid component with a high trans-form content and a cyclic diol component with a high trans-form content. Because it uses cyclic monomers with a trans-form content of over 90%, the peralicyclic polyester of this invention is more prone to crystallization, has a higher melting point, and thus exhibits better thermal stability, as well as better hydrolysis and chemical resistance. Furthermore, due to its peralicyclic structure, it also possesses the better biodegradability and weather resistance of aliphatic polyesters. Conversely, if cyclic monomers with a trans-form content lower than that within the scope of this invention are used, the resulting polyester is prone to forming an amorphous state, resulting in poor thermal stability, hydrolysis resistance, chemical resistance, and weather resistance.

[0044] In this invention, the mass content of the trans-form in the cyclic diacid component and the cyclic diol component can be provided by the manufacturer or determined using conventional methods in the art, such as proton nuclear magnetic resonance spectroscopy. Furthermore, the cyclic diacid component and the cyclic diol component with a trans-form mass content of 90% or more can be commercially available or prepared using methods in the prior art; this invention does not impose any special restrictions on their preparation methods.

[0045] In some embodiments, the derivative of the alicyclic diacid includes esters formed from alicyclic diacids. Specifically, the cyclic diacid component includes one or more of alicyclic diacids containing four or more alicyclic structures and esters formed from alicyclic diacids containing four or more alicyclic structures. Preferably, the ester formed from the alicyclic diacid containing four or more alicyclic structures is a dimethyl ester formed from the alicyclic diacid containing four or more alicyclic structures.

[0046] In some embodiments, the cyclic dicarboxylic acid component includes one or more of the following: C4-C14 alicyclic dicarboxylic acids containing a monoalicyclic structure and their derivatives; and C8-C14 alicyclic dicarboxylic acids containing a dialicyclic structure and their derivatives; the monoalicyclic structure includes one or more of the following: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and the dialicyclic structure includes decahydronaphthyl and / or bicyclohexyl (i.e., bicyclohexyl). Specifically, the cyclic dicarboxylic acid component includes one or more of the following: 1,1-cyclobutyldicarboxylic acid, dimethyl 1,1-cyclobutyldicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, dimethyl 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dimethyl 1,3-cyclohexanedicarboxylic acid, (trans,trans)-[1,1'-bicyclohexane]-4,4'-dicarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, and decahydro-2,6-naphthalenedicarboxylic acid.

[0047] In some embodiments, the trans-form content in the cyclic diacid component is 99% to 100% by mass. By controlling the trans-form content in the cyclic diacid component to be 99% to 100% by mass, the fully alicyclic polyester of the present invention further exhibits better thermal stability, hydrolysis resistance, and chemical resistance.

[0048] In some embodiments, the cyclic diol component includes C4-C14 alicyclic diols containing a monoalicyclic structure and / or C8-C14 alicyclic diols containing a dialicyclic structure; the monoalicyclic structure includes one or more of cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; the dialicyclic structure includes decahydronaphthyl and / or bicyclohexyl (i.e., bicyclohexyl). Specifically, the cyclic diol component includes one or more of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 4,4'-bicyclohexanol, and 1,5-decahydronaphthyldiol.

[0049] In some embodiments, the trans-form content in the cyclic diol component is 99% to 100% by mass. By controlling the trans-form content in the cyclic diol component to be 99% to 100% by mass, the fully alicyclic polyester of the present invention further exhibits better thermal stability, hydrolysis resistance, and chemical resistance.

[0050] In some embodiments, the reaction product of the cyclic dicarboxylic acid component and the cyclic diol component includes: the cyclic dicarboxylic acid component and the cyclic diol component first undergo an esterification reaction and / or an transesterification reaction, and then undergo a polycondensation reaction to obtain the product.

[0051] In some embodiments, the molar ratio of the cyclic diacid component to the cyclic diol component is 0.95 to 1.20, preferably 0.99 to 1.05. Controlling the proportion of cyclic monomers within this range is beneficial for the fully aliphatic cyclic polyester of the present invention to have higher viscosity and melting point. However, if the molar ratio of the cyclic diacid component to the cyclic diol component is greater than 1.20, or less than 0.95, it can easily lead to excessively low viscosity and melting point of the polyester, and may also result in poor hydrolysis resistance, chemical resistance, and weather resistance.

[0052] In some embodiments, the intrinsic viscosity of the full alicyclic polyester is 0.5~1.2 dL / g, preferably 0.7~1.0 dL / g.

[0053] In some embodiments, the melting point of the polycycloaliphatic polyester is 200~300°C, preferably 220~260°C.

[0054] In some embodiments, the growth rate of the b-value in CIE L*a*b* before and after the weathering test of the allocycloaliphatic polyester is less than 10%, and the weathering test includes: at a wavelength of 340 nm and an irradiance of 0.76 W / m 2 Placed at 40°C for 24 hours under ×nm light.

[0055] In some embodiments, the intrinsic viscosity of the full alicyclic polyester changes by 0.1-3% before and after the hydrolysis resistance test, preferably by 0.1-1%, and the hydrolysis resistance test includes boiling in water at 70°C for 4 days.

[0056] In some embodiments, the intrinsic viscosity of the full alicyclic polyester changes by 0.5-5% before and after the chemical resistance test, preferably by 0.5-3%, and the chemical resistance test includes placing it in acetone, toluene or vegetable oil at room temperature for 5 hours.

[0057] According to a specific embodiment of the second aspect of the present invention, the present invention provides a method for preparing the above-mentioned polycyclic aliphatic polyester, which includes the following steps:

[0058] (1) The cyclic dicarboxylic acid component and the diol component are subjected to a first reaction in the presence of a first catalyst, the first reaction including esterification and / or transesterification to obtain an intermediate product;

[0059] (2) The intermediate product is subjected to a second reaction in the presence of a second catalyst and a stabilizer, the second reaction including a polycondensation reaction, to obtain the full alicyclic polyester.

[0060] In some embodiments, in step (1), the molar ratio of the cyclic dicarboxylic acid component to the cyclic diol component is 0.95 to 1.20, preferably 0.99 to 1.05.

[0061] In some embodiments, in step (1), the first catalyst includes one or more of the following: antimony-based catalyst, titanium-based catalyst, manganese-based catalyst, germanium-based catalyst, tin-based catalyst, alkali metal-based catalyst, and alkaline earth metal-based catalyst. Specifically, the antimony-based catalyst may include one or more of the following: antimony trioxide, antimony acetate, and antimony glycolate; the titanium-based catalyst may include one or more of the following: tetrabutyl titanate, isopropyl titanate, and titanium dioxide; the manganese-based catalyst may include manganese acetate; the germanium-based catalyst may include germanium dioxide; the tin-based catalyst may include one or more of the following: dibutyltin oxide, stannous isooctanoate, monobutyltriisooctanoate, and dioctyltin oxide; the alkali metal-based catalyst may include one or more of the following: sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium carbonate, and potassium acetate; and the alkaline earth metal-based catalyst may include one or more of the following: calcium oxide, magnesium oxide, barium oxide, calcium hydroxide, barium hydroxide, and calcium acetate.

[0062] In some embodiments, in step (1), the amount of the first catalyst added is 0.5 to 5% of the molar amount of the cyclic dicarboxylic acid component, preferably 1 to 3%.

[0063] In some embodiments, in step (1), the temperature of the first reaction is 170~250°C, the pressure is atmospheric pressure, and the time is 2~5 hours. Preferably, the temperature of the first reaction is 200~250°C.

[0064] In some embodiments, in step (2), the second catalyst includes one or more of germanium-based catalysts, tin-based catalysts, titanium-based catalysts, and antimony-based catalysts. Specifically, the germanium-based catalyst may include germanium dioxide; the tin-based catalyst may include one or more of dibutyltin oxide, stannous isooctanoate, monobutyltriisooctanoate, and dioctyltin oxide; the titanium-based catalyst may include one or more of tetrabutyl titanate, isopropyl titanate, and titanium dioxide; and the antimony-based catalyst may include one or more of antimony trioxide, antimony acetate, and antimony glycolate.

[0065] In some embodiments, in step (2), the amount of the second catalyst added is 0.1 to 10% of the molar amount of the cyclic dicarboxylic acid component, preferably 1 to 10%, and more preferably 2 to 8%.

[0066] In some embodiments, in step (2), the stabilizer includes a phosphorus-based stabilizer and / or a silicon-based stabilizer; the phosphorus-based stabilizer includes one or more of phosphoric acid compounds and phosphate ester compounds; the silicon-based stabilizer includes one or more of silicate compounds and silicate ester compounds. Specifically, the stabilizer may include one or more of phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, silicic acid, methyl orthosilicate, and ethyl orthosilicate. Preferably, the stabilizer includes a phosphorus-based stabilizer and a silicon-based stabilizer, and the molar ratio of the phosphorus-based stabilizer to the silicon-based stabilizer is (2.5~3.5):1.

[0067] In some embodiments, in step (2), the amount of stabilizer added is 0.1 to 10% of the molar amount of the cyclic dicarboxylic acid component, preferably 1 to 8%, more preferably 2 to 6%.

[0068] In some embodiments, in step (2), the temperature of the second reaction is 250~270°C, the pressure is below 100Pa, and the time is 3~4h. By controlling the temperature of the second reaction within the above range, it is beneficial to obtain a fully alicyclic polyester with high viscosity and melting point. However, if the temperature of the second reaction is higher than the above range, it may result in excessively low viscosity and melting point of the polyester, and may also result in excessively high b-value and poor color value of the polyester, while also easily leading to poor hydrolysis resistance, chemical resistance, and weather resistance.

[0069] In some embodiments, during the first reaction in step (1), byproducts (e.g., water) generated can be removed to facilitate a forward reaction. After step (2) is completed, conventional operations such as discharge, cooling, and pelletizing can be performed to obtain polyester pellets.

[0070] The technical solutions of the present invention are specifically illustrated below through embodiments, but the present invention is not limited to these embodiments. Of course, various modifications can be made within the scope of the key points of the present invention.

[0071] Test method:

[0072] Intrinsic viscosity: Referring to GB / T 10247-2008, the sample particles were dissolved in a mixed solution of 1,1,2,2-tetrachloroethane and phenol at a mass ratio of 50:50, and the test was performed in an automatic Ubbelohde viscometer according to the polyester test standard.

[0073] Melting point: Referring to GB / T 19466.1-2004, after rapidly eliminating the thermal history using differential scanning calorimetry (DSC), the temperature is increased from 10℃ to 250℃ at a rate of 10℃ / min, held at the temperature for 5 min, and then decreased to 10℃ at a rate of 10℃ / min, held at the temperature for 5 min, and the cycle is repeated twice.

[0074] Weather resistance: Referring to GB / T 14522-1993, the sample particles were placed in a UVA340 ultraviolet aging test chamber to simulate outdoor sunlight conditions, at a wavelength of 340nm and an irradiance of 0.76W / m. 2 The samples were placed at 40℃ for 24 hours under ×nm illumination, and the color values ​​before and after the test were detected and compared. The b-values ​​in CIE L*a*b* of the samples before and after the test were obtained by colorimeter. The growth rate (%) of b-value = (b-value of sample after test - b-value of sample before test) ÷ b-value of sample before test × 100%.

[0075] Hydrolysis resistance: The sample particles were boiled in water at 70℃ for 4 days, and the intrinsic viscosity of the samples before and after the test was detected and compared.

[0076] Chemical resistance: The sample particles were placed in acetone, toluene or vegetable oil at room temperature for 5 hours, and the intrinsic viscosity of the samples before and after the test was detected and compared.

[0077] Example 1

[0078] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (90% trans-propion content), 1 mol of 1,4-cyclohexanediethanol (90% trans-propion content), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 265 °C, while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0079] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.79 dL / g; melting point is 228℃; b value before light exposure is 8.1, b value after light exposure is 8.9, and the growth rate of b value is 9.88%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.2%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 2.1%.

[0080] Example 2

[0081] After purging the reactor with nitrogen, 0.98 mol of 1,4-cyclohexanedicarboxylic acid (93% trans-isocyanate content), 1 mol of 1,4-cyclohexanediethanol (90% trans-isocyanate content), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 265 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0082] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.83 dL / g; melting point is 220℃; b value before light exposure is 8.5, b value after light exposure is 8.7, and the growth rate of b value is 2.35%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.2%; the change rate of intrinsic viscosity before and after the chemical resistance test in toluene is 1.6%.

[0083] Example 3

[0084] After purging the reactor with nitrogen, 1.10 mol of 1,4-cyclohexanedicarboxylic acid (96% trans-isocyanate content), 1 mol of 1,4-cyclohexanediethanol (90% trans-isocyanate content), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of triethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of germanium dioxide were added to the reactor. The temperature was slowly increased to 265 °C, while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0085] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.81 dL / g; melting point is 233℃; b value before light exposure is 7.9, b value after light exposure is 8.2, and the growth rate of b value is 3.66%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.1%; the change rate of intrinsic viscosity in vegetable oil before and after the chemical resistance test is 0.5%.

[0086] Example 4

[0087] After purging the reactor with nitrogen, 1.20 mol of 1,4-cyclohexanedicarboxylic acid (96% trans-isocyanate content), 1.0 mol of 1,4-cyclohexanediethanol (93% trans-isocyanate content), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 200 °C and atmospheric pressure. During the reaction, byproduct water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of germanium dioxide were added to the reactor. The temperature was slowly increased to 265 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0088] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.76 dL / g; melting point is 235℃; b value before light exposure is 8.4, b value after light exposure is 9.0, and the growth rate of b value is 7.14%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.2%; the change rate of intrinsic viscosity before and after the chemical resistance test in toluene is 1.6%.

[0089] Example 5

[0090] After purging the reactor with nitrogen, 1.20 mol of 1,4-cyclohexanedicarboxylic acid (96% trans-propion content), 1.0 mol of 1,4-cyclohexanediethanol (96% trans-propion content), and 20 mmol of antimony acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 200 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of germanium dioxide were added to the reactor. The temperature was slowly increased to 255 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0091] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.71 dL / g; melting point is 239℃; b value before light exposure is 7.7, b value after light exposure is 8.1, and the growth rate of b value is 5.19%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.3%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 1.5%.

[0092] Example 6

[0093] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (96% trans-propion content), 1 mol of 1,4-cyclohexanediethanol (96% trans-propion content), and 20 mmol of antimony acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 200 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of phosphoric acid, 10 mmol of methyl orthosilicate, and 60 mmol of germanium dioxide were added to the reactor. The temperature was slowly increased to 250 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0094] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.70 dL / g; melting point is 239℃; b value before light exposure is 6.3, b value after light exposure is 6.7, and the growth rate of b value is 6.35%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.6%; the change rate of intrinsic viscosity in vegetable oil before and after the chemical resistance test is 0.6%.

[0095] Example 7

[0096] After purging the reactor with nitrogen, 1 mol of dimethyl 1,4-cyclohexanedicarboxylate (99% trans-propion content), 1 mol of 1,4-cyclohexanediethanol (99% trans-propion content), and 20 mmol of antimony acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of phosphoric acid, 10 mmol of methyl orthosilicate, and 60 mmol of germanium dioxide were added to the reactor. The temperature was slowly increased to 270 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0097] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.86 dL / g; melting point is 244℃; b value before light exposure is 8.0, b value after light exposure is 8.7, and the growth rate of b value is 8.75%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.3%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 2.1%.

[0098] Example 8

[0099] After purging the reactor with nitrogen, 1 mol of dimethyl 1,4-cyclohexanedicarboxylate (99% trans content), 1 mol of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (99% trans content) and 20 mmol of antimony acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 180 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of phosphoric acid, 10 mmol of methyl orthosilicate and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 250 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped and the sample was collected for later use.

[0100] The test results of the full alicyclic polyester in this embodiment are as follows: intrinsic viscosity is 0.65 dL / g; melting point is 223℃; b value before light exposure is 10.0, b value after light exposure is 10.5, and the growth rate of b value is 5%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 0.3%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 2.5%.

[0101] Comparative Example 1

[0102] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (trans-isocyanate content 17%), 1 mol of 1,4-cyclohexanediethanol (trans-isocyanate content 66%), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 265 °C, while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0103] The test results of the fully alicyclic polyester in this comparative example are as follows: intrinsic viscosity is 0.80 dL / g; DSC results show that the polyester is in an amorphous state, with a glass transition temperature of 44℃ and no melting point; the b-value before light exposure is 8.3, and the b-value after light exposure is 15.1, with a b-value growth rate of 81.93%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 4.7%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 14%.

[0104] It can be seen that the comparative example uses a cyclic dicarboxylic acid component with low trans content to react with a cyclic diol component with low trans content, resulting in an amorphous polyester with poor thermal stability, hydrolysis resistance, chemical resistance and weather resistance.

[0105] Comparative Example 2

[0106] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (90% trans-isocyanate content), 1 mol of 1,4-cyclohexanediethanol (66% trans-isocyanate content), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 265 °C, while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0107] The test results of the full alicyclic polyester in this comparative example are as follows: intrinsic viscosity is 0.72 dL / g; melting point is 225℃; b value before light exposure is 8.5, b value after light exposure is 9.2, and the growth rate of b value is 8.23%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 6.1%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 4.6%.

[0108] It can be seen that this comparative example uses a cyclic dicarboxylic acid component with a high trans content and a cyclic diol component with a low trans content to react. Although the polyester obtained has improved performance compared with comparative example 1, its thermal stability, hydrolysis resistance, chemical resistance and weather resistance are still inferior to those of example 1.

[0109] Comparative Example 3

[0110] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (trans-isocyanate content 17%), 1 mol of 1,4-cyclohexanediethanol (trans-isocyanate content 90%), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 265 °C, while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0111] The test results of the full alicyclic polyester in this comparative example are as follows: intrinsic viscosity is 0.65 dL / g; melting point is 217℃; b value before light exposure is 8.9, b value after light exposure is 9.9, and the growth rate of b value is 11.2%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 6.2%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 3.9%.

[0112] It can be seen that this comparative example uses a cyclic dicarboxylic acid component with a low trans content and a cyclic diol component with a high trans content to react. Although the polyester obtained has improved performance compared with comparative example 1, its thermal stability, hydrolysis resistance, chemical resistance and weather resistance are still inferior to those of example 1.

[0113] Comparative Example 4

[0114] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (90% trans-propion content), 1.50 mol of 1,4-cyclohexanediethanol (90% trans-propion content), and 20 mmol of manganese acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 220 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of trimethyl phosphate, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 265 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0115] The test results of the full alicyclic polyester in this comparative example are as follows: intrinsic viscosity is 0.52 dL / g; melting point is 180℃; b value is 5.0 before light exposure and 10.1 after light exposure, with a b value growth rate of 102%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 3.3%; and the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 4.6%.

[0116] It can be seen that the molar ratio of the cyclic dicarboxylic acid component and the cyclic diol component in this comparative example is too small, resulting in the polyester having too low viscosity and melting point, and poor hydrolysis resistance, chemical resistance and weather resistance.

[0117] Comparative Example 5

[0118] After purging the reactor with nitrogen, 1 mol of 1,4-cyclohexanedicarboxylic acid (90% trans-propion content), 1.10 mol of 1,4-cyclohexanediethanol (90% trans-propion content), and 20 mmol of antimony acetate were added to the reactor. The mixture was stirred at 100 rpm and reacted at 240 °C and atmospheric pressure. During the reaction, by-product water was removed and collected. After 3 hours of reaction, 30 mmol of phosphoric acid, 10 mmol of methyl orthosilicate, and 60 mmol of tetrabutyl titanate were added to the reactor. The temperature was slowly increased to 280 °C while the pressure was slowly decreased to below 100 Pa. After 4 hours of reaction, the reaction was stopped, and the sample was collected for later use.

[0119] The test results of the full alicyclic polyester in this comparative example are as follows: intrinsic viscosity is 0.62 dL / g; melting point is 205℃; b value before light exposure is 12.3, b value after light exposure is 18.8, and the b value growth rate is 52.85%; the change rate of intrinsic viscosity before and after the hydrolysis resistance test is 3.6%; the change rate of intrinsic viscosity before and after the chemical resistance test in acetone is 2.9%.

[0120] It can be seen that the polycondensation reaction temperature in this comparative example was too high, resulting in low viscosity and melting point of the polyester, as well as an excessively high b-value, poor polyester color value, and poor hydrolysis resistance, chemical resistance, and weather resistance.

[0121] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A full alicyclic polyester comprising a reaction product of a cyclic diacid component and a cyclic diol component; the cyclic diacid component comprises one or two or more of an alicyclic diacid and a derivative thereof containing a tetra- or more alicyclic structure, a mass content of a trans form in the cyclic diacid component is 90% or more; the cyclic diol component comprises an alicyclic diol containing a tetra- or more alicyclic structure, a mass content of a trans form in the cyclic diol component is 90% or more.

2. The fully aliphatic polyester according to claim 1, wherein, The derivative of the alicyclic diacid comprises an ester formed from the alicyclic diacid.

3. The fully aliphatic polyester of claim 1, wherein, The cyclic diacid component comprises one or two or more of a C4 to C14 alicyclic diacid containing a mono-alicyclic structure and a derivative thereof and a C8 to C14 alicyclic diacid containing a di-alicyclic structure and a derivative thereof; the mono-alicyclic structure comprises one or two or more of a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; the di-alicyclic structure comprises a decahydronaphthyl group and / or a bicyclohexyl group; And / or, the cyclic diacid component comprises one or two or more of 1,1-cyclobutyl dicarboxylic acid, dimethyl 1,1-cyclobutyl dicarboxylate, 1,2-cyclopentane dicarboxylic acid, dimethyl 1,2-cyclopentane dicarboxylate, 1,4-cyclohexane dicarboxylic acid, dimethyl 1,4-cyclohexane dicarboxylate, 1,3-cyclohexane dicarboxylic acid, dimethyl 1,3-cyclohexane dicarboxylate, (trans, trans)-[1,1’-bicyclohexane]-4,4’-dicarboxylic acid, decahydro-1,4-naphthalene dicarboxylic acid, and dimethyl decahydro-2,6-naphthalene dicarboxylate; And / or, a mass content of a trans form in the cyclic diacid component is 99% to 100%.

4. The fully aliphatic polyester of claim 1, wherein, The cyclic diol component comprises a C4 to C14 alicyclic diol containing a mono-alicyclic structure and / or a C8 to C14 alicyclic diol containing a di-alicyclic structure; the mono-alicyclic structure comprises one or two or more of a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; the di-alicyclic structure comprises a decahydronaphthyl group and / or a bicyclohexyl group; And / or, the cyclic diol component comprises one or two or more of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 4,4’-bicyclohexanol, and 1,5-decahydronaphthalenediol; And / or, a mass content of a trans form in the cyclic diol component is 99% to 100%.

5. The fully aliphatic polyester of claim 1, wherein, The reaction product of the cyclic diacid component and the cyclic diol component comprises a product obtained by subjecting the cyclic diacid component and the cyclic diol component to an esterification reaction and / or a transesterification reaction, and then to a polycondensation reaction.

6. The fully aliphatic polyester of claim 1, wherein, A molar ratio of the cyclic diacid component to the cyclic diol component is 0.95 to 1.

20.

7. The fully aliphatic polyester of claim 1, wherein, The full alicyclic polyester has an intrinsic viscosity of 0.5 to 1.2 dL / g; And / or, the full alicyclic polyester has a melting point of 200 to 300°C; and / or the increase in the b value in CIE L*a*b* of the full-rings-atomatic polyester before and after the weather resistance test is 10% or less, the weather resistance test comprising: placing at 40°C under light with wavelength of 340 nm, irradiance of 0.76 W / m 2 ×nm for 24 h; and / or, the change rate of the inherent viscosity of the full aliphatic cyclic polyester before and after a hydrolysis resistance test is 0.1-3%, the hydrolysis resistance test including boiling in water at 70°C for 4 days; and / or, the change rate of the inherent viscosity of the full aliphatic cyclic polyester before and after a chemical resistance test is 0.5-5%, the chemical resistance test including placing in acetone, toluene or vegetable oil at room temperature for 5 hours.

8. A method for preparing the full aliphatic cyclic polyester according to any one of claims 1-7, comprising the following steps: (1) subjecting a cyclic diacid component and a cyclic diol component to a first reaction in the presence of a first catalyst, the first reaction including esterification and / or transesterification, to obtain an intermediate product; (2) subjecting the intermediate product to a second reaction in the presence of a second catalyst and a stabilizer, the second reaction including polycondensation, to obtain the full aliphatic cyclic polyester.

9. The process for the preparation of a full aliphatic cyclic polyester according to claim 8, wherein, In step (1), the molar ratio of the cyclic diacid component to the cyclic diol component is 0.95-1.20; and / or, in step (1), the first catalyst includes one or two or more of an antimony-based catalyst, a titanium-based catalyst, a manganese-based catalyst, a germanium-based catalyst, a tin-based catalyst, an alkali metal-based catalyst and an alkaline earth metal-based catalyst; and / or, in step (1), the first catalyst is added in an amount of 0.5-5% of the molar amount of the cyclic diacid component; and / or, in step (1), the first reaction is carried out at a temperature of 170-250°C, under normal pressure, for 2-5 hours.

10. The method of making a fully aliphatic polyester according to claim 8, wherein, In step (2), the second catalyst includes one or two or more of a germanium-based catalyst, a tin-based catalyst, a titanium-based catalyst and an antimony-based catalyst; and / or, in step (2), the second catalyst is added in an amount of 0.1-10% of the molar amount of the cyclic diacid component; and / or, in step (2), the stabilizer includes a phosphorus-based stabilizer and / or a silicon-based stabilizer; the phosphorus-based stabilizer includes one or two or more of a phosphoric acid compound and a phosphate compound; the silicon-based stabilizer includes one or two or more of a silicic acid compound and a silicate compound; and / or, in step (2), the stabilizer is added in an amount of 0.1-10% of the molar amount of the cyclic diacid component; and / or, in step (2), the second reaction is carried out at a temperature of 250-270°C, under a pressure of 100 Pa or less, for 3-4 hours.