Butanediic acid composition and polyesters and polyester composites prepared therefrom

Abstract

The present invention provides a butanediic acid composition, a polyester prepared thereby, and a polyester composite material. [Solution] The butanediic acid composition comprises butanediic acid, a compound containing sulfate ions, and a phosphorus compound, wherein the mass content of sulfate ions in the butanediic acid composition is 240 to 500 ppm, and the mass content of phosphorus in the butanediic acid composition is 0.5 to 40 ppm. By blending the compound containing sulfate ions and the phosphorus compound in specific amounts, polyester can be prepared using the butanediic acid composition as a raw material, thereby ensuring the production efficiency of polyester and obtaining a polyester that combines low acid value and high viscosity. Furthermore, corrosion of polyester or its composition to metal equipment can be reduced during the extrusion process of the polyester composite material, thereby ensuring the quality of the polyester composite material.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparing polyesters, and specifically relates to a butanedioic acid composition, a polyester prepared therefrom, and a polyester composite material.

Background Art

[0002] Polybutylene succinate (PBS) is prepared by the esterification and polycondensation reaction of butanedioic acid and 1,4-butanediol, and can also be obtained by general molding devices by methods such as extrusion, injection molding, blow molding, spinning, blister molding, lamination, foaming, etc. The products have a wide range of uses, and the main application fields include the packaging fields such as wrap films, delivery bags, disposable tableware, etc.

[0003] However, due to the performance defects of pure PBS resin itself, it is often difficult to meet the needs of the application side. Therefore, usually, the PBS resin needs to be mixed with other materials for modification and processed into a polyester composite material that meets the needs of end-use through a thermoforming process such as biaxial screw extrusion. Since the PBS resin itself contains a certain number of carboxyl groups and has low thermal stability, it is prone to thermal decomposition during processing and releases acidic substances, but the acidic substances may corrode metal equipment. Therefore, when thermoforming is required for the preparation of polyester composite materials and the thermoforming device contains metal parts, for example, when thermoforming is carried out using a screw extruder, etc., the screw extruder is prone to serious corrosion when used for a certain period in the production of polyester composite materials. The corrosion of the screw extruder not only reduces the processing ability of the screw extruder, such as the reduction of shear force and dispersion force, but may also cause foreign matters in the polyester composite material, leading to a decrease in product quality.

[0004] Therefore, developing a butanediic acid composition that exhibits high reactive activity, improves polyester production efficiency, yields polyesters with both low acid value and high viscosity, and reduces corrosion of polyester composite materials to equipment during the thermoforming process is an urgent issue that needs to be addressed in this field. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a butanediic acid composition and polyesters and polyester composite materials prepared therefrom, in order to address the shortcomings of the prior art. By preparing the polyester using the butanediic acid composition as a raw material, the reaction activity is high, the polyester production efficiency is high, and the resulting polyester has a low acid value and high viscosity. Furthermore, when the polyester composite material is prepared by a thermoforming process, the degree of corrosion to the equipment is low. [Means for solving the problem]

[0006] To achieve this objective, the present invention employs the following technical solutions.

[0007] In a first aspect, the present invention provides a butanediic acid composition comprising butanediic acid, a compound containing sulfate ions, and a phosphorus compound, wherein the mass content of sulfate ions in the butanediic acid composition is 240 to 500 ppm, and the mass content of phosphorus in the butanediic acid composition is 0.5 to 40 ppm.

[0008] In this invention, compounds containing sulfate ions can improve the esterification efficiency of butanediic acid, thereby improving the production efficiency of polyester, and are also advantageous in obtaining low-acid-value, high-viscosity polyesters and polyester composite materials. Furthermore, low-acid-value polyesters are also advantageous in reducing the corrosion of polyester to equipment during processing. Based on the action of electron coordination, phosphorus compounds can form structurally stable metal complexes with metal ions by the donation of electron pairs by phosphorus atoms. The metal complexes can cover the metal surface, protect the metal, and slow down the corrosion of polyester material to metal equipment during processing. By blending compounds containing sulfate ions and phosphorus compounds in specific proportions, polyester can be prepared using the butanediic acid composition as a raw material, thereby ensuring the production efficiency of polyester and obtaining polyester with a lower acid value and a whiter color. In addition, when preparing polyester composite materials using the polyester as a base resin, the corrosion of polyester to metal equipment can be reduced, and the quality of the polyester composite material can be ensured.

[0009] In the present invention, the mass content of sulfate ions in the butanediic acid composition is 240 to 500 ppm, for example, 240 ppm, 245 ppm, 250 ppm, 255 ppm, 260 ppm, 265 ppm, 270 ppm, 275 ppm, 280 ppm, 285 ppm, 290 ppm, 295 ppm, 300 ppm, 305 ppm, 310 ppm, 315 ppm, 320 ppm, 325 ppm, 330 ppm, 335 ppm, 340 ppm. PM, 345 ppm, 350 ppm, 355 ppm, 360 ppm, 365 ppm, 370 ppm, 375 ppm, 380 ppm, 385 ppm, 390 ppm, 395 ppm, 400 ppm, 405 ppm, 410 ppm, 415 ppm, 420 ppm, 430 ppm, 440 ppm, 450 ppm, 460 ppm, 470 ppm, 480 ppm, 490 ppm, 500 ppm, or any of the above ranges.

[0010] In this invention, if the mass content of sulfate ions is too low, the esterification efficiency is low, the residence time is long, and the resulting polyester has a high acid value and low viscosity, which may cause corrosion of the equipment. If the mass content of sulfate ions is too high, the corrosiveness to metals is relatively high, and in an aqueous environment, it dissolves easily in water, forming a sulfuric acid solution. Released H + The ions acidify the solution, further accelerating the corrosion of the metal.

[0011] In the present invention, the mass content of phosphorus in the butanediic acid composition is 0.5 to 40 ppm, and may be, for example, 0.5 ppm, 1 ppm, 2 ppm, 4 ppm, 6 ppm, 8 ppm, 10 ppm, 12 ppm, 14 ppm, 16 ppm, 18 ppm, 20 ppm, 22 ppm, 24 ppm, 26 ppm, 28 ppm, 30 ppm, 32 ppm, 34 ppm, 36 ppm, 38 ppm, 40 ppm, or any of the above values.

[0012] In this invention, if the mass content of the phosphorus element is too low, corrosion of the equipment during heat processing becomes severe. If the content is too high, the catalyst activity is deactivated, the catalytic efficiency decreases, and as a result, the residence time of the polymerization reaction increases, the acid value of the polyester increases, causing it to yellow, and some corrosion also occurs.

[0013] Preferably, the mass content of sulfate ions in the butanediic acid composition is 320 to 480 ppm, more preferably 370 to 420 ppm.

[0014] Preferably, the mass content of phosphorus in the butanediic acid composition is 2 to 25 ppm, more preferably 5 to 20 ppm.

[0015] Preferably, the compound containing sulfate ions includes sulfuric acid and / or sulfates.

[0016] Preferably, the sulfate comprises one or at least two of the following: sodium sulfate, magnesium sulfate, potassium sulfate, or iron sulfate.

[0017] Preferably, the phosphorus compound comprises one or at least two of the following: nucleic acids, phospholipids, diisooctyl phosphate, diethyl phosphate, triethyl phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid, phosphorous acid, or sodium phosphate. Preferably, the mass fraction of butanediic acid in the butanediic acid composition is 99.5% or more, and may be in the range of 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or any of the above values, preferably the mass fraction of butanediic acid is 99.7% or more, and more preferably the mass fraction of butanediic acid is 99.8% or more.

[0018] In the present invention, with respect to the sulfate ion-containing compound and phosphorus compound in the butanediic acid composition, the butanediic acid composition can be obtained by adding the sulfate ion-containing compound and phosphorus compound externally. In addition, during the preparation of butanediic acid, some compounds may remain in the butanediic acid, thereby forming the butanediic acid composition.

[0019] In the present invention, when the butanediic acid composition is formed with some compounds remaining in the butanediic acid during its preparation, the raw materials for the preparation include petroleum resources or biomass resources.

[0020] In the present invention, the method for preparing the butanediic acid composition includes microbial fermentation, chemical synthesis, or external preparation. When microbial fermentation or chemical synthesis is employed, the sulfate ion-containing compound and the phosphorus compound may be derived from the residue of any substance containing sulfate ions or phosphorus added during preparation.

[0021] For example, when preparing a butanediic acid composition using petroleum resources as raw materials by chemical synthesis, the compound containing sulfate ions may originate from sulfuric acid in the electrolyte used in the catalytic hydrogenation of maleic anhydride, or from sulfates added externally as needed.

[0022] When adopting the microbial fermentation method, the phosphorus compound may be derived from nucleic acids, phospholipids, etc. of microorganisms, or may be derived from dioctyl phosphate, diethyl phosphate, triethyl phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid, phosphorous acid, or sodium phosphate added during fermentation.

[0023] When preparing a succinic acid composition by microbial fermentation using biomass resources as raw materials, the compound containing sulfate ions may be sulfuric acid added to adjust the pH value of the fermentation system or to acidify succinate, or a sulfate added externally as required. The phosphorus compound may be a phosphorus compound remaining in the process of preparing succinic acid by microbial fermentation, or an externally added phosphorus compound.

[0024] In the present invention, the biomass resources include plant resources and / or animal resources, and plant resources are preferred.

[0025] In the present invention, the plant resources refer to biomass resources that can convert solar energy into forms such as starch and cellulose through photosynthesis and store it, and the animal resources refer to biomass resources that grow and develop by preying on plants. The plant resources or animal resources also include products obtained by processing plant resources or animal resources.

[0026] In the present invention, by way of example, the plant resources include, but are not limited to, wood, rice straw, rice husk, rice bran, old rice, corn, sugarcane, cassava, corn stalk, cassava starch residue, bagasse, vegetable oil residue, buckwheat, soybean, food waste, etc.

[0027] In the present invention, it is necessary to convert the biomass resource into a carbon source, then prepare a crude succinic acid solution using this carbon source as a raw material, and then purify the crude succinic acid solution to obtain the succinic acid composition. Examples of the method for converting into a carbon source include, but are not limited to, chemical treatment, physical treatment, biological treatment, etc. Exemplarily, as the chemical treatment, acid treatment (e.g., treatment with strong acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, etc.), alkali treatment, ammonia freeze cooking explosion method, solvent extraction treatment, supercritical fluid treatment, oxidant treatment, etc. may be employed. As the physical treatment, grinding treatment, cooking explosion treatment, microwave treatment, electron beam irradiation treatment, etc. may be used. As the biological treatment, microorganism treatment, enzyme treatment, etc. may be used.

[0028] In the present invention, examples of the carbon source include hexose sugars such as glucose, mannose, galactose, fructose, sorbose, tagatose, pentose sugars such as arabinose, xylose, ribose, xylulose, ribulose, disaccharides or polysaccharides such as pentosan, sucrose, starch, cellulose, etc., but are not limited thereto. Preferably, they are glucose, fructose, xylose, and particularly preferably glucose.

[0029] In the present invention, the microorganism used in the microorganism fermentation method may be any microorganism capable of producing dicarboxylic acid. Exemplarily, it includes anaerobic bacteria, facultative anaerobic bacteria, aerobic bacteria, etc. Examples of the anaerobic bacteria may include the genus Anaerobiospirillum (US5143833A), examples of the facultative anaerobic bacteria may include the genus Actinobacillus (US5504004A), the genus Escherichia (US5770435A), etc., and examples of the aerobic bacteria may include the genus Corynebacterium (Japanese Patent Laid-Open No. 11-113588, CN103183813A). These documents are incorporated herein by reference, but preferably, aerobic bacteria such as the genus Corynebacterium are used.

[0030] For example, taking microbial fermentation as an example, the method for preparing the butanediic acid composition is: Step (1) involves preparing a butanediic acid fermentation liquid (a conventional method may be used, for example, by referring to the method described in CN118459331A) using biomass resources as raw materials, filtering the butanediic acid fermentation liquid, adding excess calcium hydroxide to it, completely precipitating the butanediic acid, filtering it, and obtaining calcium butanediic acid. (2) Mix the calcium butane obtained in step (1) with concentrated sulfuric acid and adjust the pH value to 1.2 to 3 (for example, 1.2, 1.3, 1.5, 1.6, 1.8, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, or any of the above values) to obtain a stock solution of butane with a mass concentration of 65 to 80 g / L (for example, 65 g / L, 68 g / L, 70 g / L, 72 g / L, 75 g / L, 78 g / L, 80 g / L, or any of the above values), (3) Step (3) is to subject the butanediic acid stock solution obtained in step (2) to a forward cross flow extraction with a phosphate extractant to obtain a butanediic acid-supported organic phase, and then subject the butanediic acid-supported organic phase to a reverse cross flow extraction with water to obtain an aqueous butanediic acid solution, wherein the volume of the butanediic acid stock solution is 1 L, the mass of the phosphate extractant is 2 to 55 g (for example, 2 g, 5 g, 8 g, 10 g, 12 g, 15 g, 18 g, 20 g, 22 g, 24 g, 26 g, 28 g, 30 g, 32 g, 34 g, 36 g, 38 g, 40 g, 42 g, 44 g, 46 g, 48 g, 50 g, 52 g, 54 g, 55 g, or any of the above values), and the volume of the butanediic acid-supported organic phase is 1 L, the mass of the water The amount is 30-95g (for example, 30g, 32g, 35g, 38g, 40g, 42g, 45g, 48g, 50g, 52g, 55g, 58g, 60g, 62g, 65g, 68g, 70g, 72g, 75g, 78g, 80g, 82g, 85g, 88g, 90g, 92g, 95g, or within the range of any of the above values), and the phosphate extractant comprises at least one of diisooctyl phosphate, diethyl phosphate, or triethyl phosphate, and the number of times the forward cross flow extraction and reverse cross flow extraction are performed independently of each other, for example, 1, 2, 3, 4, 5, 6, 7, 8, or within the range of any of the above values, in step (3), Step (4) involves passing the butanediic acid aqueous solution obtained in step (3) through a cation exchange resin column at a flow rate of 0.5 to 2.5 BV / h (for example, 0.5 BV / h, 0.6 BV / h, 0.8 BV / h, 1 BV / h, 1.1 BV / h, 1.2 BV / h, 1.3 BV / h, 1.4 BV / h, 1.5 BV / h, 1.6 BV / h, 1.7 BV / h, 1.8 BV / h, 1.9 BV / h, 2 BV / h, 2.1 BV / h, 2.2 BV / h, 2.3 BV / h, 2.4 BV / h, 2.5 BV / h, or any of the above values), and eluting it with 2 to 7 times the mass of the butanediic acid aqueous solution (for example, 3 times, 4 times, 5 times, 6 times, or any of the above values) to obtain a butanediic acid effluent. Step (5) involves sequentially decolorizing the butanediic acid effluent obtained in step (4) with activated carbon and filtering to obtain a butanediic acid filtrate, wherein the volume of the butanediic acid effluent is 1 L, and the mass of the activated carbon is 0.5 to 10 g (for example, 0.5 g, 1 g, 2 g, 3 g, 4 g, 5 g, 5.2 g, 5.5 g, 5.8 g, 6 g, 6.2 g, 6.5 g, 6.8 g, 7 g, 7.2 g, 7.5 g, 7.8 g, 8 g, 8.5 g, 9 g, 9.5 g, 10 g, or any of the above values). The process includes step (6) of obtaining the butanediic acid composition by vacuum distillation of the butanediic acid filtrate obtained in step (4), cooling and crystallizing it.

[0031] Preferably, the activated carbon decolorization is performed at a temperature of 60-85°C for 30-80 minutes.

[0032] In the present invention, the filtration is performed using an ultrafiltration membrane, and the pore size of the ultrafiltration membrane is 20 to 80 nm, for example, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, or 80 nm, or any of the above values.

[0033] Preferably, the filtration temperature is 40 to 60°C, and may be, for example, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C, 58°C, or 60°C, or any of the above values ​​within that range.

[0034] In this invention, the vacuum distillation is performed at a temperature of 65 to 75°C and a pressure of -0.07 to -0.1 MPa. When the butanediic acid content exceeds 15 wt%, the distillation is stopped, and the concentrated butanediic acid solution is cooled at a low temperature (8°C or below) to crystallize it, thereby obtaining the butanediic acid composition.

[0035] In a second aspect, the present invention provides a polyester, the raw materials for preparing the polyester include the butanediic acid composition described in the first aspect.

[0036] Preferably, the polyester includes an aliphatic polyester.

[0037] Preferably, the polyester is composed of the following: Set the total molar amount to 100 mol%, a1: 65-100 mol% of a derivative of butanediic acid and / or its ester, a2: Component A is a dicarboxylic acid compound containing 0 to 35 mol% of a derivative of a C6-C14 dicarboxylic acid and / or its ester, The butanediol is the butanediol composition described in the first embodiment, comprising at least component A and component B which is 1,4-butanediol in equimolar amounts.

[0038] In the present invention, the molar ratio of component B to component A is (1 to 3):1, and may be, for example, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, or any of the above values, and more preferably (1 to 2):1.

[0039] In the present invention, "the polyester contains the following components" means that the molecular structure of the polyester contains structural units derived from component A and structural units derived from component B. "The dicarboxylic acid compound containing the following components" means that in the molecular structure of the polyester, the dicarboxylic acid structural unit portion contains structural units derived from component a1 and structural units derived from component a2.

[0040] In the present invention, the amount is 65 to 100 mol%, and may be, for example, 65 mol%, 66 mol%, 68 mol%, 70 mol%, 72 mol%, 74 mol%, 76 mol%, 78 mol%, 80 mol%, 82 mol%, 84 mol%, 86 mol%, 88 mol%, 90 mol%, 92 mol%, 94 mol%, 96 mol%, 98 mol%, 100 mol%, or any of the above values.

[0041] In this invention, the mol% range is 0 to 35 mol%, and may be, for example, 0 mol%, 2 mol%, 4 mol%, 6 mol%, 8 mol%, 10 mol%, 12 mol%, 14 mol%, 16 mol%, 18 mol%, 20 mol%, 22 mol%, 24 mol%, 26 mol%, 28 mol%, 30 mol%, 32 mol%, 34 mol%, 35 mol%, or any of the above values.

[0042] In the present invention, when component a1 is selected from succinate derivatives, the butanediic acid composition is used as a raw material to obtain its ester derivative.

[0043] Preferably, the total molar amount of component A is 100 mol%, a1: 72-82 mol% of butanediic acid and / or its ester derivatives, a2: Contains a dicarboxylic acid compound comprising 18-28 mol% of a C6-C14 dicarboxylic acid and / or ester derivative thereof.

[0044] In the present invention, the derivative of succinate includes alkyl succinates, and exemplary the alkyl succinate may be at least one of dimethyl succinate, diethyl succinate, di-n-propyl succinate, diisopropyl succinate, di-n-butyl succinate, diisobutyl succinate, di-t-butyl succinate, di-n-pentyl succinate, diisopentyl succinate, and di-n-hexyl succinate. The alkyl succinate may also be an alkyl ester formed with butanediic acid or an alkyl ester formed with butanediic anhydride, and preferably dimethyl succinate formed with butanediic anhydride is used.

[0045] In the present invention, component a2 is selected from C6-C14 linear dicarboxylic acids, for example, C6, C7, C8, C9, C10, C11, C12, C13, and C14 linear dicarboxylic acids, and exemplary comprises at least one of adipic acid, azelaic acid, sebacic acid, or brassic acid, preferably adipic acid and / or sebacic acid.

[0046] In the present invention, the derivative of the C6-C14 dicarboxylic acid ester includes C6-C14 dicarboxylic acid alkyl esters, and exemplary the alkyl ester may be at least one of dimethyl ester, diethyl ester, di-n-propyl ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-t-butyl ester, di-n-pentyl ester, isopentyl ester, or di-n-hexyl ester, and the alkyl ester may be an alkyl ester formed from a diacid or an alkyl ester formed from a diacid anhydride.

[0047] In the present invention, dicarboxylic acid derivatives or their ester derivatives may be used individually or as a mixture of two or more.

[0048] Preferably, the mass content of sulfate ions in the polyester is 90 to 210 ppm, and may be, for example, 90 ppm, 95 ppm, 100 ppm, 105 ppm, 110 ppm, 115 ppm, 120 ppm, 125 ppm, 130 ppm, 135 ppm, 140 ppm, 145 ppm, 150 ppm, 155 ppm, 160 ppm, 165 ppm, 170 ppm, 175 ppm, 180 ppm, 185 ppm, 190 ppm, 195 ppm, 200 ppm, 205 ppm, 210 ppm, or any of the above values, and more preferably 100 to 160 ppm.

[0049] Preferably, the mass content of phosphides in the polyester is 0.1 to 15 ppm, and may be, for example, 0.1 ppm, 0.2 ppm, 0.5 ppm, 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 11 ppm, 12 ppm, 13 ppm, 14 ppm, 15 ppm, or any of the above values, and more preferably 1 to 10 ppm.

[0050] In the present invention, a polyester possessing both a low acid value and high viscosity can be obtained by using the butanediic acid composition as a raw material. In the present invention, according to standard DIN EN 12634-1998, the acid value of the polyester is 1.2 mg KOH / g or less, and may be in the range of, for example, 0.4 mg KOH / g, 0.5 mg KOH / g, 0.6 mg KOH / g, 0.7 mg KOH / g, 0.8 mg KOH / g, 0.9 mg KOH / g, 1 mg KOH / g, 1.1 mg KOH / g, 1.2 mg KOH / g, or any of the above values. More preferably, the acid value is 1 mg KOH / g or less, and more preferably, the acid value is 0.85 mg KOH / g or less.

[0051] Preferably, according to standard GB / T 17931-1999, the intrinsic viscosity of the polyester is 1.4 dL / g or greater, and may be, for example, 1.4 dL / g, 1.45 dL / g, 1.5 dL / g, 1.55 dL / g, 1.6 dL / g, 1.65 dL / g, 1.7 dL / g, 1.75 dL / g, 1.8 dL / g, 1.9 dL / g, or any of the above values ​​within that range. More preferably, the intrinsic viscosity is 1.52 dL / g or greater, and more preferably, the intrinsic viscosity is 1.63 dL / g or greater.

[0052] In the present invention, the polyester can be prepared using technical methods common in the art, and exemplary the method is: The method includes the steps of: reacting component A and component B in an esterification reaction at a temperature of 140-220°C and a pressure of 0.5-2 bar for 1-6 hours to obtain an esterification product; reacting the esterification product in a pre-condensation polymerization reaction at a temperature of 220-260°C and a pressure of 0.1-1 bar for 40-120 minutes to obtain a pre-condensation polymerization product; and subsequently reacting the pre-condensation polymerization product in a polycondensation reaction at a temperature of 230-280°C and a pressure of 1-3 mbar for 120-180 minutes, slicing and drying to obtain the polyester.

[0053] In the present invention, the raw materials for the esterification reaction further include a crosslinking agent, the crosslinking agent comprising at least one of tartaric acid, citric acid, malic acid, trimethylolpropane, trimethylolethane, pentaerythritol, polyethertriol, glycerin, 1,3,5-trimellitic acid, 1,2,4-trimellitic acid, 1,2,4-trimellitic anhydride, 1,2,4,5-benzenetetracarboxylic acid, or pyromellitic dianhydride, and with the mass of the finished polyester product being 100 wt%, the mass fraction of the crosslinking agent is 0.05 to 1 wt%.

[0054] In the present invention, the esterification reaction and / or pre-condensation polymerization reaction further includes a catalyst, which may be a tin compound, an antimony compound, a cobalt compound, a lead compound, a zinc compound, an aluminum compound, or a titanium compound, more preferably a zinc compound, an aluminum compound, or a titanium compound, and most preferably a titanium compound, which may be tetrabutyl titanate or tetraisopropyl titanate, and the total mass of the catalyst is 0.001 to 1 wt% of the mass of the polycondensation product.

[0055] In a third aspect, the present invention provides a polyester composite material, the polyester composite material being obtained by extrusion processing, and the polyester composite material comprising the polyester described in the second aspect.

[0056] Preferably, the polyester composite material further comprises at least one of polyhydroxyalkanoate, inorganic filler, or auxiliary agent.

[0057] Preferably, the polyester composite material comprises, by weight, 40 to 65 parts by aliphatic polyester, 20 to 30 parts by polyhydroxyalkanoate, 5 to 25 parts by inorganic filler, and 0 to 1 part by auxiliary agent, wherein the raw material for preparing the aliphatic polyester includes the butanediic acid composition described in the first embodiment, or the aliphatic polyester includes the polyester described in the second embodiment.

[0058] In the present invention, the 40 to 65 parts of aliphatic polyester may be, for example, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 65 parts, or any of the above values.

[0059] In the present invention, 20 to 30 parts of polyhydroxyalkanoate may be, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, or any of the above values.

[0060] In the present invention, the 5 to 25 parts of inorganic filler may be, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 25 parts, or any of the above values.

[0061] In the present invention, the amount of the auxiliary agent (0 to 1 part) may be, for example, 0 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, or any of the above values.

[0062] Preferably, the polyhydroxyalkanoate comprises polylactic acid and / or poly-β-hydroxybutyric acid.

[0063] Preferably, the inorganic filler comprises at least one of talc, calcium carbonate, barium sulfate, montmorillonite, or kaolin.

[0064] In the present invention, the auxiliary agent includes, but is not limited to, an antioxidant. The antioxidant includes, but is not limited to, antioxidant 1010.

[0065] In the present invention, the polyester composite material has a screw wear rate (η) of 0.5% or less, preferably 0.4% or less, more preferably 0.29% or less, and particularly preferably 0.13% or less when produced continuously for 168 hours in a twin-screw extruder.

[0066] The polyester and polyester composite materials described in the present invention are also biodegradable.

[0067] In this invention, a substance or mixture of substances is characterized as "biodegradable" if it exhibits a biodegradability of at least 90% as defined in DIN EN 13432.

[0068] Biodegradation typically means that polyester or polyester mixtures decompose within a reasonable time. Decomposition proceeds through enzymatic degradation, hydrolysis, oxidation pathways, and / or exposure to electromagnetic radiation such as ultraviolet light, but most commonly through exposure to microorganisms such as bacteria, yeasts, fungi, and algae. Biodegradability can be quantified by mixing polyester with compost and storing it for a certain period of time. For example, according to DIN EN 13432, during the composting process, CO2-free air is introduced into the mature compost, and the compost is exposed to a specific temperature profile. Here, biodegradability is defined as the percentage of biodegradation expressed as the ratio of the net amount of CO2 released from the sample (after subtracting the amount of CO2 released from compost without the sample) to the maximum amount of CO2 that the sample can release (calculated based on the carbon content in the sample).

[0069] Other methods for determining biodegradability are described in ASTM D5338 and ASTM D6400.

[0070] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and the need for simplicity, this invention does not fully list the specific point values ​​included in the above ranges. [Effects of the Invention]

[0071] Compared to the prior art, the present invention has the following beneficial effects.

[0072] In the butanediic acid composition according to the present invention, by blending a compound containing sulfate ions and a phosphorus compound in specific amounts, polyester can be prepared using the butanediic acid composition as a raw material, thereby ensuring the production efficiency of polyester and obtaining a polyester that possesses both a low acid value and high viscosity. Furthermore, the degree of corrosion of polyester to metal equipment can be reduced, and the quality of the polyester material can be ensured. [Modes for carrying out the invention]

[0073] The technical solutions of the present invention will be further described below using specific embodiments. It will be apparent to those skilled in the art that the above embodiments are intended to aid in understanding the present invention and should not be considered to specifically limit it.

[0074] Unless otherwise specified, the raw materials used in this invention are as follows:

[0075] 1,4-Butanediol: Purchased from Xinjiang Meike Chemical Co., Ltd. Commercially available butanediic acid, high quality specifications: Purchased from Shandong Feiyang Chemical Co., Ltd., butanediic acid content 99.78%, SO4 2- The content is 47 ppm, and the phosphorus element content is 0 ppm. Glycerin: Purchased from Aladdin. Tetrabutyl titanate: Purchased from Jianyi Chemical Import & Export Co., Ltd. Polylactic acid: PLA 3001D, purchased from Natureworks. Talc: HTPultra5 L, purchased from IMIFABI. Calcium carbonate: OM-2T, purchased from Omya Corporation.

[0076] In this invention, SO4 2- The content is measured by ion chromatography, referring to the SN / T 2994-2011 standard.

[0077] The phosphorus content is measured using ICP-OES analysis in accordance with US EPA Method 3052:1996. Approximately 0.1 g of the butanediic acid composition is weighed, 5 mL of nitric acid is added to completely immerse the composition, 1.0 mL of hydrogen peroxide is added dropwise and the mixture is reacted for 2 minutes, then sealed in a microwave decomposition vessel and decomposed at 210°C for 3 hours. After cooling to room temperature, the mixture is filtered through a 0.45 μm filter membrane, diluted to 50 mL with distilled water, and tested by ICP-OES.

[0078] In the present invention, the method for testing the mass content of butanediol in the butanediol composition is carried out with reference to the method for measuring the content of butanediol in Section 4.3 of GB / T 34686-2017.

[0079] Examples 1-6, Comparative Examples 1-4

[0080] Examples 1-6 and Comparative Examples 1-4 each provide a butanediic acid composition containing butanediic acid, a sulfate, and a phosphorus compound, and the mass content of butanediic acid, sulfate, and phosphorus compound in the butanediic acid composition is shown in Table 1.

[0081] Here, the mass content of sulfates is expressed as the mass content of sulfate ions, and the mass content of phosphorus compounds is expressed as the mass content of phosphorus elements.

[0082] The butanediic acid compositions provided in Examples 1-3, 5, 6, and Comparative Example 2 are compositions formed from butanediic acid and sulfates and phosphorus compounds remaining in the butanediic acid during its preparation. The butanediic acid compositions provided in Example 4, Comparative Example 1, Comparative Example 3, and Comparative Example 4 are compositions formed from commercially available butanediic acid (high-quality specification from Shandong Feiyang Chemical Co., Ltd.) with sodium sulfate and / or sodium dihydrogen phosphate added externally. The remainder of the composition consists of water and other impurity acids remaining during the preparation of the butanediic acid composition.

[0083] Comparative Example 5 This comparative example provides high-quality butanediic acid purchased from Shandong Feiyang Chemical Co., Ltd.

[0084] [Table 1]

[0085] The method for preparing the butanediic acid compositions provided in Examples 1-3, Example 5, Example 6, and Comparative Example 2 is as follows.

[0086] Example 1 This example provides a butanediic acid composition, the method for which it is prepared is as follows.

[0087] (1) A butanediic acid ferment broth was prepared using biomass resources as raw materials by fermentation. Conventional methods in the field were used for the preparation of the ferment broth. For example, it can be prepared by referring to the method described in CN118459331A. After filtering the ferment broth to remove cells, excess calcium hydroxide was added to the fermentation liquid, and when no more calcium butanediic acid precipitate was formed in the butanediic acid ferment broth, it was filtered to separate the calcium butanediic acid precipitate.

[0088] (2) Concentrated sulfuric acid was added to the calcium butanediate obtained in step (1) to acidify it, and the pH of the system was adjusted to 2.3 to obtain a stock solution of butanediate with a butanediate content of 72 g / L.

[0089] (3) The stock solution of butanedioctyl acid obtained in step (2) was diluted to 1 L, and 26 g of diisooctyl phosphate was added and extracted three times to obtain a butanedioctyl-supported organic phase. Then, the volume of the butanedioctyl-supported organic phase was diluted to 1 L, and a three-step back-extraction was performed on the butanedioctyl-supported organic phase using 55 g of deionized water to obtain an aqueous butanedioctyl acid solution.

[0090] (4) The butanediic acid aqueous solution obtained in step (3) was passed through a 732 type cation exchange resin column at a flow rate of 1.6 BV / h, and eluted with three times the mass of water relative to the butanediic acid aqueous solution to obtain a butanediic acid effluent.

[0091] (5) The butanediic acid effluent obtained in step (4) was decolorized with activated carbon at 75°C for 60 min to reduce the volume of the butanediic acid effluent to 1 L, and the mass of the activated carbon was set to 8 g (i.e., activated carbon mass 8 g / L). Then, the mixture was filtered at 50°C using an ultrafiltration membrane with a pore size of 40 nm to obtain the butanediic acid filtrate.

[0092] (6) The butanediic acid filtrate obtained in step (5) was subjected to vacuum distillation, with the distillation temperature controlled to 70°C and the pressure to -0.07 to -0.1 MPa. When the butanediic acid content exceeded 15 wt%, the distillation was stopped, and the concentrated butanediic acid solution was cooled at a low temperature (4°C) to crystallize, thereby obtaining white butanediic acid crystals, i.e., the butanediic acid composition.

[0093] Example 2 This example provides a butanediic acid composition. In its preparation method, steps (1) and (2) were the same as in Example 1, but the difference lies in the following step: (3) To the butanediic acid stock solution obtained in step (2), 26 g of diisooctyl phosphate was added to a volume of 1 L and extracted four times to obtain a butanediic acid-supported organic phase. Then, the volume of the butanediic acid-supported organic phase was reduced to 1 L, and a four-step back-extraction was performed on the butanediic acid-supported organic phase using 70 g of deionized water to obtain an aqueous butanediic acid solution.

[0094] (4) The butanediic acid aqueous solution obtained in step (3) was passed through a 732 type cation exchange resin column at a flow rate of 1.5 BV / h, and eluted with four times the mass of water relative to the butanediic acid aqueous solution to obtain a butanediic acid effluent.

[0095] (5) The butanediic acid effluent obtained in step (4) was decolorized with activated carbon at 75°C for 60 min to reduce the volume of the butanediic acid effluent to 1 L, and the mass of the activated carbon was set to 8 g (i.e., activated carbon mass 8 g / L). Then, the mixture was filtered at 50°C using an ultrafiltration membrane with a pore size of 40 nm to obtain the butanediic acid filtrate.

[0096] (6) The butanediic acid filtrate obtained in step (5) was subjected to vacuum distillation, with the distillation temperature controlled to 70°C and the pressure to -0.07 to -0.1 MPa. When the butanediic acid content exceeded 15 wt%, the distillation was stopped, and the concentrated butanediic acid solution was cooled at a low temperature (4°C) to crystallize, thereby obtaining white butanediic acid crystals, i.e., the butanediic acid composition.

[0097] Example 3 This example provides a butanediic acid composition, and in its preparation method, steps (1) and (2) were the same as in Example 1, but the difference lies in the following steps.

[0098] (3) The butanediic acid stock solution obtained in step (2) was diluted to 1 L, 17 g of diethyl phosphate was added, and the solution was extracted three times to obtain a butanediic acid-supported organic phase. Then, the volume of the butanediic acid-supported organic phase was diluted to 1 L, and a three-step back-extraction was performed on the butanediic acid-supported organic phase using 65 g of deionized water to obtain an aqueous butanediic acid solution.

[0099] (4) The aqueous butanediic acid solution obtained in step (3) was passed through a 732 type cation exchange resin column at a flow rate of 1.4 BV / h, and eluted with 5 times the mass of water relative to the aqueous butanediic acid solution to obtain a butanediic acid effluent.

[0100] (5) The butanediic acid effluent obtained in step (4) was decolorized with activated carbon at 70°C for 60 min to reduce the volume of the butanediic acid effluent to 1 L, and the mass of the activated carbon was reduced to 7 g (i.e., activated carbon mass 7 g / L). Then, the mixture was filtered at 50°C using an ultrafiltration membrane with a pore size of 40 nm to obtain the butanediic acid filtrate.

[0101] (6) The butanediic acid filtrate obtained in step (5) was subjected to vacuum distillation, with the distillation temperature controlled to 70°C and the pressure to -0.07 to -0.1 MPa. When the butanediic acid content exceeded 15 wt%, the distillation was stopped, and the concentrated butanediic acid solution was cooled at a low temperature (4°C) to crystallize, thereby obtaining white butanediic acid crystals, i.e., the butanediic acid composition.

[0102] Example 5 This example provides a butanediic acid composition, and in its preparation method, step (1) was the same as in Example 1, but the difference lies in the following steps.

[0103] (2) Concentrated sulfuric acid was added to the calcium butane obtained in step (1) to acidify it and adjust the pH of the system to 1.6 to obtain a stock solution of butane with a butane content of 68 g / L.

[0104] (3) The butanediic acid stock solution obtained in step (2) was increased in volume to 1 L, 5 g of triethyl phosphate was added, and the solution was extracted twice to obtain a butanediic acid-supported organic phase. Then, the volume of the butanediic acid-supported organic phase was increased to 1 L, and a two-stage back-extraction was performed on the butanediic acid-supported organic phase using 50 g of deionized water to obtain an aqueous butanediic acid solution.

[0105] (4) The butanediic acid aqueous solution obtained in step (3) was passed through a 732 type cation exchange resin column at a flow rate of 1.7 BV / h, and eluted with four times the mass of water relative to the butanediic acid aqueous solution to obtain a butanediic acid effluent.

[0106] (5) The butanediic acid effluent obtained in step (4) was decolorized with activated carbon at 70°C for 60 min to reduce the volume of the butanediic acid effluent to 1 L, and the mass of the activated carbon was set to 8 g (i.e., activated carbon mass 8 g / L). Then, the mixture was filtered at 50°C using an ultrafiltration membrane with a pore size of 40 nm to obtain the butanediic acid filtrate.

[0107] (6) The butanediic acid filtrate obtained in step (5) was subjected to vacuum distillation, with the distillation temperature controlled to 70°C and the pressure to -0.07 to -0.1 MPa. When the butanediic acid content exceeded 15 wt%, the distillation was stopped, and the concentrated butanediic acid solution was cooled to a low temperature (4°C) to crystallize, thereby obtaining white butanediic acid crystals, i.e., the bio-based butanediic acid composition.

[0108] Example 6 This example provides a butanediic acid composition, and in its preparation method, step (1) was the same as in Example 1, but the difference lies in the following steps.

[0109] (2) Concentrated sulfuric acid was added to the calcium butane obtained in step (1) to acidify it, and the pH of the system was adjusted to 2.7 to obtain a stock solution of butane with a butane content of 77 g / L.

[0110] (3) The butanediic acid stock solution obtained in step (2) was diluted to 1 L, 21 g of diethyl phosphate was added, and the solution was extracted three times to obtain a butanediic acid-supported organic phase. Then, the volume of the butanediic acid-supported organic phase was diluted to 1 L, and a two-stage back-extraction was performed on the butanediic acid-supported organic phase using 60 g of deionized water to obtain an aqueous butanediic acid solution.

[0111] (4) The butanediic acid aqueous solution obtained in step (3) was passed through a 732 type cation exchange resin column at a flow rate of 1.4 BV / h, and eluted with 6 times the mass of water relative to the butanediic acid aqueous solution to obtain a butanediic acid effluent.

[0112] (5) The butanediic acid effluent obtained in step (4) was decolorized with activated carbon at 75°C for 70 min to reduce the volume of the butanediic acid effluent to 1 L, and the mass of the activated carbon was reduced to 8 g (i.e., activated carbon mass 8 g / L). Then, the mixture was filtered at 50°C using an ultrafiltration membrane with a pore size of 40 nm to obtain the butanediic acid filtrate.

[0113] (6) The butanediic acid filtrate obtained in step (5) was subjected to vacuum distillation, with the distillation temperature controlled to 70°C and the pressure to -0.07 to -0.1 MPa. When the butanediic acid content exceeded 15 wt%, the distillation was stopped, and the concentrated butanediic acid solution was cooled to a low temperature (4°C) to crystallize, thereby obtaining white butanediic acid crystals, i.e., the bio-based butanediic acid composition.

[0114] Comparative Example 2 This comparative example provides a butanediic acid composition, and in its preparation method, step (1) was the same as in Example 1, but the difference lies in the following steps.

[0115] (2) Concentrated sulfuric acid was added to the calcium butane obtained in step (1) to acidify it and adjust the pH of the system to 1.1 to obtain a stock solution of butane with a butane content of 68 g / L.

[0116] (3) The butanediic acid stock solution obtained in step (2) was diluted to 1 L, 30 g of diethyl phosphate was added, and the solution was extracted three times to obtain a butanediic acid-supported organic phase. Then, the butanediic acid-supported organic phase was diluted to 1 L, and a two-stage back-extraction was performed on the butanediic acid-supported organic phase using 60 g of deionized water to obtain an aqueous butanediic acid solution.

[0117] (4) The butanediic acid aqueous solution obtained in step (3) was passed through a 732 type cation exchange resin column at a flow rate of 1.6 BV / h, and eluted with three times the mass of water relative to the butanediic acid aqueous solution to obtain a butanediic acid effluent.

[0118] (5) The butanediic acid effluent obtained in step (4) was decolorized with activated carbon at 70°C for 55 min to reduce the volume of the butanediic acid effluent to 1 L, and the mass of the activated carbon was set to 8 g (i.e., activated carbon mass 8 g / L). Then, the mixture was filtered at 50°C using an ultrafiltration membrane with a pore size of 40 nm to obtain the butanediic acid filtrate.

[0119] (6) The butanediic acid filtrate obtained in step (5) was subjected to vacuum distillation, with the distillation temperature controlled to 70°C and the pressure to -0.07 to -0.1 MPa. When the butanediic acid content exceeded 15 wt%, the distillation was stopped, and the concentrated butanediic acid solution was cooled at a low temperature (4°C) to crystallize, thereby obtaining white butanediic acid crystals, i.e., the butanediic acid composition.

[0120] Application Example 1 This application example provides a polyester, the raw materials for preparing the polyester comprising 350 kg of butanediol, 340 kg of butanediic acid, 1.2 kg of glycerin, and 0.47 kg of tetrabutyl titanate, wherein the butanediic acid is the butanediic acid composition provided in Example 1, and the method for preparing the polyester comprises the following steps.

[0121] (1) Butanediol, 1,4-butanediol, and glycerin were physically mixed. After mixing was complete, the resulting mixture was transferred to an esterification reactor, and the reaction mixture was esterified at a temperature of 180°C and a pressure of 1.0 bar for 3 hours to obtain the esterification product.

[0122] (2) The esterification product obtained in step (1) was transferred to a vertical reactor equipped with a stirring device, tetrabutyl titanate was added, and a pre-condensation polymerization reaction was carried out at a temperature of 245°C and a pressure of 0.36 bar for 85 minutes to obtain a pre-condensation polymerization product.

[0123] (3) The pre-condensation polymerization product obtained in step (2) was transferred to a horizontal reactor with a stirring device and subjected to polycondensation reaction for 150 minutes under conditions of a temperature of 248°C and a pressure of 2.0 mbar. The product was then sliced ​​and dried to obtain the polyester.

[0124] Application Examples 2-6 Examples 2-6 each provide a polyester, and the only difference from Example 1 is that the butanediic acid is the butanediic acid composition provided in Examples 2-6, while the remaining raw materials, amounts used, and preparation methods are all the same as in Example 1.

[0125] Application Example 7 Application Example 7 provides a polyester, the difference from Application Example 1 being that the total molar amount of the dibasic acid is kept constant, and it contains 75 mol% butanediol and 25 mol% sebaciate, the butanediol being the butanediol composition provided in Example 1, further comprising 350 kg of butanediol, 2.2 kg of glycerin, and 0.5 kg of tetrabutyl titanate as raw materials for preparing the polyester, and the method for preparing the polyester includes the following steps.

[0126] (1) Butanediol, sebacic acid, 1,4-butanediol, and glycerin were physically mixed. After mixing was complete, the resulting mixture was transferred to an esterification reactor and the reaction mixture was esterified at a temperature of 210°C and a pressure of 1.2 bar for 5 hours to obtain the esterification product.

[0127] (2) The esterification product obtained in step (1) was transferred to a vertical reactor equipped with a stirring device, tetrabutyl titanate was added, and a pre-condensation polymerization reaction was carried out at a temperature of 255°C and a pressure of 0.56 bar for 100 minutes to obtain a pre-condensation polymerization product.

[0128] (3) The pre-condensation polymerization product obtained in step (2) was transferred to a horizontal reactor with a stirring device and subjected to polycondensation reaction for 125 minutes under conditions of a temperature of 250°C and a pressure of 1.0 mbar. The product was then sliced ​​and dried to obtain the polyester.

[0129] Application Example 8 Application Example 8 provides a polyester, the difference from Application Example 1 being that the total molar amount of the dibasic acid is kept constant, and it contains 68 mol% butanediol and 32 mol% sebaciate, the butanediol being the butanediol composition provided in Example 1, further comprising 350 kg of butanediol, 2.5 kg of glycerin, and 0.55 kg of tetrabutyl titanate as raw materials for preparing the polyester, and the method for preparing the polyester includes the following steps.

[0130] (1) Butanediol, sebacic acid, 1,4-butanediol, and glycerin were physically mixed. After mixing was complete, the resulting mixture was transferred to an esterification reactor, and the reaction mixture was esterified at a temperature of 200°C and a pressure of 1.8 bar for 2 hours to obtain the esterification product.

[0131] (2) The esterification product obtained in step (1) was transferred to a vertical reactor equipped with a stirring device, tetrabutyl titanate was added, and a pre-condensation polymerization reaction was carried out at a temperature of 255°C and a pressure of 0.3 bar for 110 minutes to obtain the pre-condensation polymerization product.

[0132] (3) The pre-condensation polymerization product obtained in step (2) was transferred to a horizontal reactor with a stirring device and subjected to polycondensation reaction for 130 minutes under conditions of a temperature of 255°C and a pressure of 1.5 mbar. The product was then sliced ​​and dried to obtain the polyester.

[0133] Application Example 9 Application Example 9 provides a polyester, the only difference from Application Example 1 being that the total molar amount of dibasic acids is kept constant, and it contains 75 mol% butanediol and 25 mol% adipic acid; the remaining raw materials, amounts used, and preparation method were all the same as in Application Example 1.

[0134] Comparative Application Examples 1-5 Comparative Application Examples 1-5 each provide a polyester, the only difference from Application Example 1 being that the butanediic acid is the butanediic acid composition provided in Comparative Examples 1-4 and the butanediic acid provided in Comparative Example 5, respectively; the remaining raw materials, amounts used, and preparation methods were all the same as in Application Example 1.

[0135] The acid value, viscosity, and SO4 of the polyesters provided in Application Examples 1-9 and Comparative Application Examples 1-5 are as follows: 2- The content of [substance name] and the content of phosphorus were tested.

[0136] Among these, the test method for acid value includes determining the acid value AN (mg KOH / g) of the sample according to the DIN EN 12634 standard of October 1998.

[0137] The solvent mixture used contained 1 part by volume of dimethyl sulfoxide, 8 parts by volume of isopropanol, and 7 parts by volume of toluene, with a total volume of 150 ml.

[0138] In accordance with the DIN EN 12634 standard, the sample was pre-titrated to determine the appropriate sample mass and confirm that the volume of titrant consumed was 2-3 mL. The sample was added to the solvent mixture and heated to 70-85°C to dissolve all of the sample and obtain a clear solution. During titration, the solution temperature was maintained at 65-75°C to prevent sample precipitation. Where appropriate, tetrabutylammonium hydroxide was used as the titrant, and highly toxic tetramethylammonium hydroxide was not used. At the same time, to prevent the solvent mixture from absorbing CO2 from the air and affecting the titrant consumption volume by the blank solvent, the blank solvent must be pre-treated according to the same process as the sample test when testing the titrant consumption volume by the blank solvent. For example, the blank solvent was heated for the same time and temperature before titrating.

[0139] The viscosity test method includes measuring the viscosity at a sample concentration of 5 mg / mL using a phenol / o-dichlorobenzene solution in a 1:1 weight ratio in a constant temperature water bath at 25 ± 0.05 °C, in accordance with GB / T 17931-1999.

[0140] SO4 2- The test methods for determining the content of [substance] and the content of phosphorus are as described above.

[0141] The specific test results are shown in Table 2. ND means that no detection occurred.

[0142] [Table 2]

[0143] As can be seen from Table 2, the polyester prepared using the butanediic acid composition according to the present invention as a raw material has a low acid value and high viscosity, and the polyester has an acid value of 1.18 mg KOH / g or less and a viscosity of 1.45 dL / g or more.

[0144] Comparative application examples revealed that unless the sulfate ion content and phosphorus element content in the butanediic acid composition are within a specific range, it is not possible to obtain a polyester that possesses both a low acid value and high viscosity.

[0145] Application examples 2-1 to 2-12, comparative application examples 2-1 to 2-5

[0146] Application Examples 2-1 to 2-12, and Comparative Application Examples 2-1 to 2-5, each provide polyester composite materials. The formulations of the polyester composite materials, in parts by weight, are shown in Tables 3 and 4. Here, " / " indicates a component not included in the formulation.

[0147] [Table 3]

[0148] [Table 4]

[0149] Performance testing Before processing, the surface of the extruder screw was wiped clean with a cotton cloth, and the diameter at the center of the screw was measured with a caliper. This was tested three times in parallel, and the average value was recorded as D0 (unit: mm). The polyester composite materials provided in Application Examples 2-1 to 2-12 and Comparative Application Examples 2-1 to 2-5 were processed using a twin-screw extruder. After 168 hours of continuous production using the twin-screw extruder, the surface of the screw was wiped with a cotton cloth, and the screw diameter at the same position as before processing was measured with a caliper. This was tested three times in parallel, and the average value was recorded as D1 (unit: mm). The degree of screw corrosion in the twin-screw extruder was evaluated using the change in screw diameter before and after processing. The screw wear rate η was calculated as (ΔD / D0) × 100%, where ΔD = D0 - D1 (unit: mm). A larger screw wear rate η indicates more severe screw corrosion.

[0150] Here, the process parameters for the twin-screw extruder are as follows:

[0151] The temperatures in each region are, in order, 170°C, 180°C, 180°C, 180°C, 190°C, 190°C, 200°C, 200°C, 200°C, and 180°C. The supply rate is 800 kg / h, and the vacuum pressure is -0.07 to -0.1 MPa.

[0152] The specific test results are shown in Table 5.

[0153] [Table 5]

[0154] As can be seen from Table 5, when a polyester composite material formed from polyester prepared using the butanediic acid composition according to the present invention is produced continuously for 168 hours in a twin-screw extruder, the screw wear rate of the twin-screw extruder is 0.5% or less, and corrosion of the polyester material to metal equipment can be significantly reduced.

[0155] However, in the case of the polyester composition provided in the comparative application example, the screw diameter changed significantly after 168 hours of continuous production, and corrosion of the polyester composite material to the equipment was severe.

[0156] The specific embodiments described above have further illustrated the objectives, technical solutions, and beneficial effects of the present invention. However, these are merely specific embodiments of the present invention and do not limit it. It should be understood that any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should also be included within the scope of protection of the present invention.

[0157] The disclosures in this specification may include the following aspects: (Aspect 1) A butanediocre acid composition comprising butanediocre acid, a compound containing sulfate ions, and a phosphorus compound, The mass content of sulfate ions in the butanediic acid composition is 240 to 500 ppm. The butanediic acid composition is characterized in that the mass content of phosphorus element in the butanediic acid composition is 0.5 to 40 ppm. (Aspect 2) The butanediic acid composition according to embodiment 1, characterized in that the mass content of sulfate ions in the butanediic acid composition is 320 to 480 ppm, preferably 370 to 420 ppm. (Aspect 3) The butanediic acid composition according to embodiment 1 or 2, characterized in that the mass content of phosphorus element in the butanediic acid composition is 2 to 25 ppm, more preferably 5 to 20 ppm. (Aspect 4) The aforementioned sulfate ion-containing compound comprises sulfuric acid and / or sulfates, Preferably, the sulfate comprises one or at least two of the following: sodium sulfate, magnesium sulfate, potassium sulfate, or iron sulfate. Preferably, the phosphorus compound comprises one or at least two of the following: nucleic acids, phospholipids, diisooctyl phosphate, diethyl phosphate, triethyl phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid, phosphorous acid, or sodium phosphate. The butanediocre acid composition according to any one of embodiments 1 to 3, characterized in that, preferably, the mass fraction of butanediocre acid in the butanediocre acid composition is 99.5% or more, and more preferably, 99.7% or more. (Appendix 5) A polyester characterized in that the raw materials for preparing the polyester include the butanediic acid composition described in any one of embodiments 1 to 4. (Aspect 6) The aforementioned polyester is Set the total molar amount to 100 mol%, a1: 65-100 mol% of a derivative of butanediic acid and / or its ester, a2: Component A is a dicarboxylic acid compound containing 0 to 35 mol% of a derivative of a C6-C14 dicarboxylic acid and / or its ester, It comprises at least component A and component B, which is 1,4-butanediol in equimolar amounts, The polyester according to embodiment 5, characterized in that the butanediic acid is a butanediic acid composition according to any one of embodiments 1 to 4. (Aspect 7) The mass content of sulfate ions in the polyester is 90 to 210 ppm. Preferably, the polyester according to embodiment 5 or 6 is characterized in that the mass content of phosphorus in the polyester is 0.1 to 15 ppm. (Pattern 8) A polyester composite material, wherein the polyester composite material is a composite material obtained by extrusion processing. The polyester composite material is characterized in that it contains the polyester described in any one of embodiments 5 to 7. (Aspect 9) The polyester composite material according to embodiment 8, characterized in that the polyester composite material further comprises at least one of polyhydroxyalkanoate, inorganic filler, or auxiliary agent. (Aspect 10) The polyester composite material according to embodiment 8 or 9, characterized in that when the polyester composite material is produced continuously for 168 hours using a twin-screw extruder, the screw wear rate is 0.5% or less.

Claims

1. A butanediocre acid composition comprising butanediocre acid, a compound containing sulfate ions, and a phosphorus compound, The mass content of sulfate ions in the butanediic acid composition is 240 to 500 ppm. The butanediic acid composition is characterized in that the mass content of phosphorus in the butanediic acid composition is 0.5 to 40 ppm.

2. The butanediic acid composition according to claim 1, characterized in that the mass content of sulfate ions in the butanediic acid composition is 320 to 480 ppm, preferably 370 to 420 ppm.

3. The butanediic acid composition according to claim 1 or 2, characterized in that the mass content of phosphorus in the butanediic acid composition is 2 to 25 ppm, more preferably 5 to 20 ppm.

4. The aforementioned sulfate ion-containing compound comprises sulfuric acid and / or sulfates, Preferably, the sulfate comprises one or at least two of sodium sulfate, magnesium sulfate, potassium sulfate, or iron sulfate. Preferably, the phosphorus compound comprises one or at least two of the following: nucleic acids, phospholipids, diisooctyl phosphate, diethyl phosphate, triethyl phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid, phosphorous acid, or sodium phosphate. Preferably, the mass fraction of butanediic acid in the butanediic acid composition is 99.5% or more, more preferably 99.7% or more, characterized in that the butanediic acid composition according to claim 1 or 2.

5. A polyester characterized in that the raw materials for preparing the polyester include the butanediic acid composition described in claim 1 or 2.

6. The aforementioned polyester is Set the total molar amount to 100 mol%, a1: 65 to 100 mol% of a derivative of butanediic acid and / or its ester, a2: Component A is a dicarboxylic acid compound containing 0 to 35 mol% of a derivative of a C6-C14 dicarboxylic acid and / or its ester, It contains at least component A and component B, which is 1,4-butanediol in equimolar amounts, The polyester according to claim 5, characterized in that the butanediic acid is the butanediic acid composition according to claim 1 or 2.

7. The mass content of sulfate ions in the polyester is 90 to 210 ppm. Preferably, the polyester according to claim 5, wherein the mass content of phosphorus in the polyester is 0.1 to 15 ppm.

8. A polyester composite material, wherein the polyester composite material is a composite material obtained by extrusion processing. The polyester composite material is characterized in that the polyester composite material includes the polyester described in any one of claims 5.

9. The polyester composite material according to claim 8, further comprising at least one of polyhydroxyalkanoate, inorganic filler, or auxiliary agent.

10. The polyester composite material according to claim 8, characterized in that when the polyester composite material is produced continuously for 168 hours using a twin-screw extruder, the screw wear rate is 0.5% or less.

Images