PBSA resin composition as well as preparation method and application thereof

Abstract

The invention relates to a PBSA resin composition as well as a preparation method and application thereof. The PBSA resin composition comprises PBSA resin, a titanium element and a phosphorus element, the weight content of the titanium element in the PBSA resin composition is 20 to 150ppm; the weight content of the phosphorus element in the PBSA resin composition is 2 to 100 ppm. The titanium element and the phosphorus element with specific contents are introduced into the PBSA resin, so that the prepared PBSA resin composition has excellent low-temperature toughness, heat resistance and aging resistance, and the application range of the PBSA resin is expanded.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a PBSA resin composition and a preparation method and application thereof. Background Art

[0002] At present, with the continuous development of the national economy, the consumption of plastic products is increasing, and synthetic plastics are playing an increasingly important role in production and life. However, since most plastic products cannot be degraded after being discarded, they exist for a long time and accumulate to cause serious white pollution. With the continuous aggravation of pollution and the continuous enhancement of people's environmental awareness, it is more and more urgent to seek a plastic product that can meet people's use needs and environmental protection needs, which has aroused widespread interest among researchers. Among them, degradable resins have become a hot topic of research due to their degradation characteristics and economic characteristics.

[0003] Polybutylene succinate-adipate (PBSA) resin is a completely biodegradable polymer with similar properties to polybutylene succinate (PBS). After the introduction of adipic acid copolymer units, the flexibility of PBSA molecular chain increases and the crystallinity decreases. It is more easily degraded into H under the action of bacteria or enzymes. 2 O and CO 2 and other substances, thereby reducing the generation of plastic waste and being harmless to the environment. PBSA has a moderate melting point and good performance. It can replace general polyethylene or polypropylene and enter the field of general plastics, completely solving the pollution caused by traditional plastics to the environment. PBSA is widely used in packaging films (shopping bags, garbage bags, etc.), paper coating, medical supplies, foam materials, agricultural mulch and other fields. For example, CN115011093A discloses a biodegradable high barrier packaging film and its preparation method and application, which belongs to the field of biodegradable food film processing technology. The biodegradable high barrier packaging film is composed of 60-70 parts of PGA, 40-30 parts of PBSA and 0-0.7 parts of ADR4468, and the sum of PGA and PBSA is 100 parts; the raw materials used for the biodegradable high barrier packaging film prepared by it are all biodegradable, green, environmentally friendly and non-toxic.

[0004] Although the PBSA resin sold on the market is a green and environmentally friendly biodegradable material, its general mechanical strength is poor, especially its toughness is insufficient at low temperatures. CN106700441A discloses a method for preparing a lignin-modified PBSA biodegradable plastic, comprising the following steps: (1) vacuum drying polybutylene succinate / adipate and lignin; (2) adding the dried polybutylene succinate / adipate, lignin, chain extender, antioxidant, plasticizer, lubricant, and heat stabilizer into a high-speed mixer and mixing them thoroughly; (3) extruding the mixture through a twin-screw extruder for granulation; (4) blowing the lignin-PBSA composite plastic pellets at a certain temperature to obtain a lignin-modified PBSA biodegradable plastic; the biomass lignin that exists in large quantities in nature is used to prepare the biodegradable plastic by compounding with PBSA, and after the compound modification, the biodegradable plastic meets the requirements of complete degradation, and at the same time, the mechanical properties of the pure PBSA resin are enhanced. However, the PBSA resin obtained still has the problems of poor heat resistance and aging resistance.

[0005] Therefore, how to provide a PBSA resin composition with good low-temperature toughness, heat resistance and aging resistance has become a problem to be solved urgently in the art. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a PBSA resin composition and a preparation method and application thereof. By introducing specific contents of titanium and phosphorus into the PBSA resin, the prepared PBSA resin composition has excellent low-temperature toughness, heat resistance and aging performance, thereby expanding the application range of the PBSA resin.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a PBSA resin composition, the PBSA resin composition comprising PBSA resin, titanium element and phosphorus element;

[0009] The weight content of titanium in the PBSA resin composition is 20-150ppm, for example, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm or 140ppm, and specific values ​​between the above values. Due to space limitations and for simplicity, the present invention no longer exhaustively lists the specific values ​​included in the range.

[0010] The weight content of phosphorus in the PBSA resin composition is 2-100 ppm, for example, it can be 5 ppm, 8 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm or 90 ppm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0011] Titanium has a catalytic effect on the reaction. If the added amount is too small, the polymerization reaction will proceed slowly. If the added amount is too large, the PBSA resin will be more easily degraded. Phosphorus can improve the color of the product, but there will be a certain complexation between phosphorus and titanium-containing compounds. If too much phosphorus is added, the activity of the catalyst will decrease, the polymerization speed will slow down, and the possibility of thermal degradation of the resin during the polymerization process will be increased. If too little phosphorus is added, the product color cannot be effectively improved.

[0012] The weight contents of phosphorus and titanium in the PBSA resin composition were determined by ICP-OES analysis with reference to US EPA method 3052:1996, according to the following procedure: 0.1 g of the PBSA resin composition was weighed, crushed, and 5 mL of nitric acid was added to completely immerse the PBSA resin composition, and then 1.0 mL of hydrogen peroxide was dropped into it for reaction for 2 min, and the mixture was sealed in a microwave digestion tank and digested at 210° C. for 3 h. After cooling to room temperature, the mixture was filtered through a 0.45 μm filter membrane, and then diluted to 50 mL with distilled water, and tested by ICP-OES.

[0013] The ICP-OES test was performed using a Spectro arcos FHS12 inductively coupled plasma optical emission spectrometer (AMETEK, USA).

[0014] Preferably, the weight ratio of titanium element to phosphorus element in the PBSA resin composition is (2-20):1, for example, it can be 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1 or 18:1, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and is further preferably (3-15):1, and further preferably (5.5-10):1.

[0015] Preferably, the source of the titanium element includes a titanium-containing compound.

[0016] Preferably, the titanium-containing compound comprises an organic titanate.

[0017] Preferably, the organic titanate has a structure as shown in Formula I:

[0018]

[0019] Among them, the R 1 -R 4 Each is independently selected from a C1-C10 straight chain or branched alkyl group (for example, C2, C3, C4, C5, C6 or C8, etc.), a C6-C20 aryl group (for example, C8, C10, C12, C14, C16 or C18, etc.).

[0020] Preferably, the R 1 -R 4 same.

[0021] Preferably, the titanium-containing compound is n-butyl titanate and / or isopropyl titanate.

[0022] Preferably, the source of phosphorus comprises a phosphorus-containing compound.

[0023] Preferably, the phosphorus-containing compound includes any one of phosphoric acid, phosphorous acid, hypophosphorous acid, phosphates or phosphate esters, or a combination of at least two thereof.

[0024] Preferably, the phosphate ester includes any one of triethyl phosphate, trimethyl phosphate, tributyl phosphate or triphenyl phosphate, or a combination of at least two thereof.

[0025] Preferably, the content of structural units based on butylene succinate in the PBSA resin is 90-99 mol%, for example, it can be 91 mol%, 92 mol%, 93 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol% or 98 mol%, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0026] Preferably, the content of structural units based on butylene adipate in the PBSA resin is 1-10 mol%, for example, it can be 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol% or 9 mol%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0027] In the present invention, by optimizing the ratio of butylene succinate structural units to butylene adipate structural units in PBSA resin and matching specific titanium and phosphorus content, the heat resistance of PBSA resin is retained while the toughness and aging properties of the material are improved, thereby obtaining a resin composition with better low-temperature toughness, heat resistance and aging properties.

[0028] Preferably, the melt index of the PBSA resin composition is ≤10g / 10min, for example, it can be 9g / 10min, 8g / 10min, 7g / 10min, 6g / 10min, 5g / 10min, 4g / 10min, 3g / 10min, 2g / 10min or 1g / 10min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range. The melt index is obtained by referring to ISO1133-1:2022 standard and tested at 190°C and 2.16kg weight.

[0029] Preferably, the PBSA resin composition has a notched impact strength of ≥16.5 kJ / m at -15°C. 2 , for example, it can be 17 kJ / m 2 、17.5kJ / m 2 、18kJ / m 2 、19kJ / m 2 、20kJ / m 2 、25kJ / m 2 or 30 kJ / m 2 , as well as specific point values ​​between the above point values, due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0030] In the present invention, the notched impact strength is obtained by referring to ISO180-2023 standard test.

[0031] Preferably, the heat resistance temperature of the PBSA resin composition is ≥75.2°C, more preferably ≥93°C, for example, it can be 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, 92°C, 93.5°C, 94°C, 95°C, 96°C, 98°C, 100°C or 105°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0032] In the present invention, the heat resistance temperature is obtained by referring to the GB / T 1634.2-2019 standard test.

[0033] In the present invention, the heat resistance temperature (HDT) is also called the heat deformation temperature, which refers to the temperature at which the material changes shape during heating and is expressed in °C.

[0034] Preferably, the PBSA resin composition is stored at 60° C. and 95% humidity for 72 hours, and the ratio of the melt flow rate change before and after storage is η≤3.0, for example, it can be 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.0, 1.8 or 1.5, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and it is further preferred that η≤2.75.

[0035] In the present invention, the ratio of the melt flow rate change after storage to that before storage is η=MFR1 / MFR0; wherein MFR1 represents the melt flow rate of the PBSA resin composition after storage for 72 hours at 60° C. and 95% humidity, and MFR0 represents the initial melt flow rate of the PBSA resin composition before storage, and the two test conditions are the same.

[0036] The PBSA resin composition provided by the present invention can pass the household composting test.

[0037] In a second aspect, the present invention provides a method for preparing the PBSA resin composition as described in the first aspect, the preparation method comprising the following steps:

[0038] The PBSA resin composition is obtained by mixing 1,6-hexanediol, 1,4-butanediol, 1,4-succinic acid, a titanium-containing compound and a phosphorus-containing compound to react with each other.

[0039] Preferably, the preparation method comprises the following steps:

[0040] (1) mixing 1,4-butanediol, 1,4-butanediol and a titanium-containing compound to react to obtain a first mixture;

[0041] (2) After mixing the first mixture obtained in step (1) with 1,6-adipic acid, a phosphorus-containing compound is added thereto for reaction to obtain the PBSA resin composition.

[0042] Preferably, the molar ratio of 1,4-butanediol to 1,4-butanediol in step (1) is 1:(1.1-1.6), for example, it can be 1:1.15, 1:1.2, 1:1.3, 1:14 or 1:1.5, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0043] Preferably, the mass ratio of 1,4-butanedioic acid to the titanium-containing compound in step (1) is (500-5000):1, for example, it can be 500:1, 1000:1, 1500:1, 2000:1, 2500:1, 3000:1, 3500:1, 4000:1, 4500:1, 5000:1, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0044] Preferably, the temperature of the reaction in step (1) is 170-240°C, for example, 180°C, 190°C, 200°C, 210°C, 220°C or 230°C, as well as specific values ​​between the above-mentioned points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0045] Preferably, the pressure of the reaction in step (1) is 30-100 kPa, for example, it can be 35 kPa, 45 kPa, 55 kPa, 65 kPa, 75 kPa, 85 kPa or 95 kPa, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0046] Preferably, the reaction time in step (1) is 1-5 h, for example, 1.5 h, 2 h, 3 h, 4 h or 4.5 h, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0047] Preferably, the molar ratio of 1,6-hexanedioic acid to 1,4-butanediol is 1:(9-99), for example, it can be 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80 or 1:90 and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0048] Preferably, the mass ratio of the 1,4-succinic acid to the phosphorus-containing compound is (500-30000): 1, for example, it can be 1000: 1, 4000: 1, 7000: 1, 10000: 1, 13000: 1, 16000: 1, 19000: 1, 22000: 1, 25000: 1, or 28000: 1, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0049] Preferably, the mixing temperature in step (2) is 180-240°C, for example, 190°C, 200°C, 210°C, 220°C, 230°C or 235°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0050] Preferably, the mixing time in step (2) is 2-5 h, for example, 2.5 h, 3 h, 3.5 h, 4 h or 4.5 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0051] Preferably, the reaction temperature in step (2) is 180-250°C, for example, 190°C, 200°C, 210°C, 220°C, 230°C or 245°C, as well as specific values ​​between the above-mentioned points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0052] Preferably, the reaction time in step (2) is 3-7 h, for example, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h or 6.5 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0053] Preferably, the step (2) is performed in the presence of a first protective gas.

[0054] Preferably, the first protective gas includes any one of carbon dioxide, nitrogen, helium or argon, or a combination of at least two of them.

[0055] Preferably, the specific operations of step (2) include:

[0056] After mixing the first mixture obtained in step (1) with 1,6-hexanediol, a first protective gas is introduced, and the temperature is maintained at 180-240° C. for 2-5 hours. Then, the phosphorus-containing compound is added and maintained for 10-30 minutes (for example, 12 minutes, 15 minutes, 18 minutes, 20 minutes, 22 minutes, 25 minutes, 28 minutes, etc.), and the pressure is reduced to less than 200 Pa (for example, 180 Pa, 160 Pa, 140 Pa, 120 Pa, 100 Pa, 80 Pa, 50 Pa, etc.), and the mixture is heated to 230-250° C. and maintained for 3-6 hours.

[0057] Preferably, the reaction in step (2) is followed by granulation.

[0058] Preferably, the granulation is carried out in the presence of a second protective gas.

[0059] Preferably, the second protective gas includes any one of nitrogen, helium or argon, or a combination of at least two of them.

[0060] Preferably, the preparation method comprises the following steps:

[0061] (1) mixing 1,4-butanediol, 1,4-butanediol and a titanium-containing compound, and reacting at 170-240° C. and 30-100 kPa for 1-5 hours to obtain a first mixture;

[0062] (2) mixing the first mixture obtained in step (1) with 1,6-hexanediol, introducing a first protective gas, maintaining the temperature at 180-240° C. for 2-5 hours, adding a phosphorus-containing compound, maintaining the temperature for 10-30 minutes, reducing the pressure to less than 200 Pa, heating to 230-250° C., maintaining the temperature for 3-6 hours, and granulating in the presence of a second protective gas to obtain the PBSA resin composition;

[0063] Wherein, the molar ratio of the 1,4-butanediol to the 1,4-butanediol is 1:(1.1-1.6), and the molar ratio of the 1,6-hexanediol to the 1,4-butanediol is 1:(9-99);

[0064] The mass ratio of the 1,4-succinic acid to the titanium-containing compound is (500-5000):1, and the mass ratio of the 1,4-succinic acid to the phosphorus-containing compound is (500-30000):1.

[0065] In a third aspect, the present invention provides a use of the PBSA resin composition as described in the first aspect in the preparation of degradable film bags, straws or tableware.

[0066] Compared with the prior art, the present invention has at least the following beneficial effects:

[0067] The invention provides a PBSA resin composition and a preparation method and application thereof. The PBSA resin composition comprises a PBSA resin and titanium and phosphorus elements with specific contents. The PBSA resin composition has excellent low-temperature toughness, heat resistance and aging performance, a heat resistance temperature of ≥75.2°C, a low-temperature toughness cantilever beam notched impact strength of ≥17.2 J / m, and excellent aging performance. The PBSA resin composition is stored for 72 hours at 60°C and 95% humidity, and a melt flow rate change ratio η before and after the storage is ≤2.90, thereby expanding the application range of the PBSA resin. DETAILED DESCRIPTION

[0068] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0069] In the following specific implementation of the present invention, the materials involved are as follows:

[0070] 1,6-Adipic acid: purity ≥99.8%, Chongqing Huafeng Chemical Co., Ltd.;

[0071] 1,4-Succinic acid: purity ≥99.9%, Shandong Landian Biotechnology Co., Ltd.;

[0072] 1,4-Butanediol: purity ≥99.5%, Wanhua Chemical (Yantai) Sales Co., Ltd.;

[0073] Butyl titanate: purity ≥99.0%, Tianjin Komiou Reagent;

[0074] Isopropyl titanate: purity ≥ 95.0%, Aladdin reagent;

[0075] Triphenyl phosphate: purity ≥98.0%, Aladdin reagent;

[0076] Trimethyl phosphate: purity ≥99.0%, Aladdin reagent.

[0077] Example 1

[0078] A PBSA resin composition, comprising PBSA resin, titanium element and phosphorus element, wherein the weight content of the titanium element is 80.5 ppm, and the weight content of the phosphorus element is 10.2 ppm;

[0079] The PBSA resin composition is prepared by the following method:

[0080] (1) 118 kg (1 mol) of 1,4-butanediol, 135 kg (1.5 mol) of 1,4-butanediol and 0.11 kg of a titanium-containing compound (n-butyl titanate) were mixed and reacted at 180° C. and 40 kPa for 3 h to obtain a first mixture;

[0081] (2) The first mixture obtained in step (1) is mixed with 3.0 kg (0.02 mol) of 1,6-hexanediol, and nitrogen is introduced. After maintaining the temperature at 200° C. for 3 h, 0.02 kg of a phosphorus-containing compound (triphenyl phosphate) is added and maintained for 20 min. The pressure is reduced to less than 200 Pa, and the mixture is heated to 240° C. and maintained for 4 h. Nitrogen is introduced and granulated to obtain the PBSA resin composition.

[0082] Examples 2-10, Comparative Examples 1-4

[0083] A PBSA resin composition is different from Example 1 in that the formula of the resin composition is different, as shown in Table 1 and Table 2, wherein the dosage unit of each component is mass kg; the preparation method and performance testing method of the resin composition are the same as those of Example 1.

[0084] Table 1

[0085]

[0086] Table 2

[0087]

[0088] The above PBSA resin composition was tested as follows:

[0089] 1. Phosphorus and titanium content

[0090] Referring to US EPA method 3052:1996, ICP-OES analysis was performed according to the following procedure: 0.1 g of the PBSA resin composition was weighed, crushed, and 5 mL of nitric acid was added to completely immerse the PBSA resin, and then 1.0 mL of hydrogen peroxide was dropped to react for 2 min, sealed in a microwave digestion tank and digested at 210° C. for 3 h, and then cooled to room temperature, filtered with a 0.45 μm filter membrane, and diluted to 50 mL with distilled water, and tested by ICP-OES, the instrument was a Spectro arcos FHS12 inductively coupled plasma emission spectrometer (AMETEK, USA);

[0091] 2. Melt index and aging performance

[0092] The melt index refers to ISO1133-1:2022 standard, and is measured at 190° C. and with a 2.16 kg weight, by measuring the mass of the resin composition passing through a standard capillary every 10 minutes.

[0093] The aging performance is evaluated by the following method: after the PBSA resin composition of the present invention is prepared, the melt index is tested once, and then the PBSA resin composition is treated in a damp heat aging box at 60°C and 95% humidity for 72 hours, and then placed at 80°C for drying for 6 hours, and the melt index of the PBSA resin composition is tested again, and the ratio of the melt flow rate before and after storage is η=MFR1 / MFR0; wherein MFR1 represents the melt flow rate of the PBSA resin composition after being stored at 60°C and 95% humidity for 72 hours, and MFR0 represents the initial melt flow rate of the PBSA resin composition before storage.

[0094] 3. The content of structural units based on butylene succinate or butylene adipate in PBSA resin was confirmed by hydrogen nuclear magnetic resonance spectroscopy.

[0095] The nuclear magnetic resonance hydrogen spectrometer used was BRUKER AVANCE III HD 400M, and the resin sample was dissolved in deuterated chloroform solvent for testing, and the sample concentration was 0.6 mg / mL.

[0096] 4. Low temperature toughness

[0097] The notched impact strength of the cantilever beam is based on the standard ISO 180-2023. The notched impact specimens prepared are the impact strength of the specimens at -15°C. The greater the notched impact strength, the better the low-temperature toughness, and the smaller the notched impact strength, the worse the low-temperature toughness.

[0098] 5. Heat resistance

[0099] The heat resistance is expressed by heat deformation temperature HDT, according to standard GB / T 1634.2-2019, condition: 0.45MPa, lying flat.

[0100] The test results are shown in Table 3 and Table 4:

[0101] Table 3

[0102]

[0103] Table 4

[0104]

[0105]

[0106] It can be seen from Examples 1-10 that the present invention introduces a specific content of titanium and phosphorus into the PBSA resin to obtain a PBSA resin composition with excellent low-temperature toughness, heat resistance and aging performance, with a heat resistance temperature of ≥75.2°C and a notched impact strength of ≥17.2 kJ / m at -15°C. 2 , the ratio of the melt flow rate change after storage to that before storage is η≤2.90.

[0107] By comparing Example 2 with Example 7, it can be seen that the present invention further adopts a PBSA resin with a specific structural unit to obtain a PBSA resin composition with a higher heat resistance temperature, thereby improving the high temperature resistance of the resin composition.

[0108] By comparing Example 2 with Examples 8 and 9, it can be seen that the present invention further optimizes the ratio of titanium element to phosphorus element in the resin composition, so that the melt flow rate of the resin composition changes less before and after storage, and the notched impact strength is higher.

[0109] By comparing Example 2 with Comparative Examples 1-4, it can be seen that the present invention obtains a PBSA resin composition with excellent low-temperature toughness, heat resistance and aging performance by introducing specific contents of titanium and phosphorus into the PBSA resin, thereby expanding the application range of the PBSA resin.

[0110] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A PBSA resin composition, characterized in that The PBSA resin composition comprises PBSA resin, titanium element and phosphorus element; The weight content of titanium in the PBSA resin composition is 20-150 ppm; The weight content of phosphorus in the PBSA resin composition is 2-100 ppm.

2. PBSA resin composition according to claim 1, characterized in that, The weight ratio of titanium element to phosphorus element in the PBSA resin composition is (2-20):1, preferably (3-15):1, and more preferably (5.5-10):1; Preferably, the source of the titanium element includes a titanium-containing compound; Preferably, the titanium-containing compound comprises an organic titanate; Preferably, the organic titanate has a structure as shown in Formula I: Wherein, the R1-R4 are each independently selected from a C1-C10 straight chain or branched chain alkyl group, a C6-C20 aryl group; Preferably, said R1-R4 are the same; Preferably, the titanium-containing compound is n-butyl titanate and / or isopropyl titanate; Preferably, the source of phosphorus comprises a phosphorus-containing compound; Preferably, the phosphorus-containing compound includes any one or a combination of at least two of phosphoric acid, phosphorous acid, hypophosphorous acid, phosphates or phosphate esters; Preferably, the phosphate ester includes any one of triethyl phosphate, trimethyl phosphate, tributyl phosphate or triphenyl phosphate, or a combination of at least two thereof.

3. PBSA resin composition according to claim 1, characterized in that, The content of structural units based on butylene succinate in the PBSA resin is 90-99 mol%; Preferably, the content of structural units based on butanediol adipate in the PBSA resin is 1-10 mol%.

4. PBSA resin composition according to claim 1, characterized in that, The melt index of the PBSA resin composition is ≤10 g / 10 min, and the melt index is tested at 190° C. and 2.16 kg weight; Preferably, the PBSA resin composition has a notched impact strength of ≥16.5 kJ / m at -15°C. 2 ; Preferably, the heat-resistant temperature of the PBSA resin composition is ≥75.2°C, more preferably ≥93°C; Preferably, the PBSA resin composition is stored at 60° C. and 95% humidity for 72 hours, and the ratio of the melt flow rate change before and after the storage is η≤3.0, and more preferably η≤2.

75.

5. A method for preparing a PBSA resin composition as claimed in any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: The PBSA resin composition is obtained by mixing 1,6-hexanediol, 1,4-butanediol, 1,4-succinic acid, a titanium-containing compound and a phosphorus-containing compound to react with each other.

6. The preparation method according to claim 5, characterized in that: The preparation method comprises the following steps: (1) mixing 1,4-butanediol, 1,4-butanediol and a titanium-containing compound to react to obtain a first mixture; (2) After mixing the first mixture obtained in step (1) with 1,6-adipic acid, a phosphorus-containing compound is added thereto for reaction to obtain the PBSA resin composition.

7. The preparation method according to claim 6, characterized in that: The molar ratio of 1,4-butanediol to 1,4-butanediol in step (1) is 1:(1.1-1.6); Preferably, the mass ratio of 1,4-butanedioic acid to the titanium-containing compound in step (1) is (500-5000):1; Preferably, the reaction temperature in step (1) is 170-240°C; Preferably, the pressure of the reaction in step (1) is 30-100 kPa; Preferably, the reaction time in step (1) is 1-5 h.

8. The preparation method according to claim 6, characterized in that: The molar ratio of 1,6-hexanedioic acid to 1,4-butanedioic acid is 1:(9-99); Preferably, the mass ratio of the 1,4-succinic acid to the phosphorus-containing compound is (500-30000):1; Preferably, the mixing temperature in step (2) is 180-240°C; Preferably, the mixing time in step (2) is 2-5 hours; Preferably, the reaction temperature in step (2) is 180-250°C; Preferably, the reaction time in step (2) is 3-7h; Preferably, the step (2) is carried out in the presence of a first protective gas; Preferably, the first protective gas comprises any one of carbon dioxide, nitrogen, helium or argon, or a combination of at least two thereof; Preferably, the specific operations of step (2) include: After mixing the first mixture obtained in step (1) with 1,6-hexanediol, introducing a first protective gas, maintaining the temperature at 180-240° C. for 2-5 hours, adding a phosphorus-containing compound, maintaining the temperature for 10-30 minutes, reducing the pressure to less than 200 Pa, heating to 230-250° C., and maintaining the temperature for 3-6 hours; Preferably, the reaction in step (2) is followed by granulation; Preferably, the granulation is carried out in the presence of a second protective gas; Preferably, the second protective gas includes any one of nitrogen, helium or argon, or a combination of at least two of them.

9. The preparation method according to claim 5, characterized in that: The preparation method comprises the following steps: (1) mixing 1,4-butanediol, 1,4-butanediol and a titanium-containing compound, and reacting at 170-240° C. and 30-100 kPa for 1-5 hours to obtain a first mixture; (2) mixing the first mixture obtained in step (1) with 1,6-hexanediol, introducing a first protective gas, maintaining the temperature at 180-240° C. for 2-5 hours, adding a phosphorus-containing compound, maintaining the temperature for 10-30 minutes, reducing the pressure to less than 200 Pa, heating to 230-250° C., maintaining the temperature for 3-6 hours, and granulating in the presence of a second protective gas to obtain the PBSA resin composition; Wherein, the molar ratio of the 1,4-butanediol to the 1,4-butanediol is 1:(1.1-1.6), and the molar ratio of the 1,6-hexanediol to the 1,4-butanediol is 1:(9-99); The mass ratio of the 1,4-succinic acid to the titanium-containing compound is (500-5000):1, and the mass ratio of the 1,4-succinic acid to the phosphorus-containing compound is (500-30000):

1.

10. Use of the PBSA resin composition according to any one of claims 1 to 4 in the preparation of degradable film bags, straws or tableware.

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