A composition, degradable material and use thereof

Abstract

The present invention relates to a composition, a degradable material and application thereof, the composition comprising polybutylene adipate terephthalate, polylactic acid and butanediol trimellitic anhydride modified epoxy resin. The composition of one embodiment of the present invention comprises butanediol trimellitic anhydride modified epoxy resin and polybutylene adipate terephthalate, wherein the butanediol trimellitic anhydride modified epoxy resin can react with the polybutylene adipate terephthalate, so that the use of the composition for film preparation can reduce the precipitation of polybutylene adipate terephthalate after film preparation, and improve the edge sealing performance of the film.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition that can be used for film preparation, in particular to a composition capable of improving the sealability of a film. BACKGROUND

[0002] In the clothing bag, express logistics industry often uses a film bag with a seal pattern as a packaging material, and most of the existing packaging materials are mainly PE materials. However, since such materials do not have biodegradability, they will cause serious pollution problems after being discarded. Biobased degradable polymer materials can be derived from plants and animals and do not rely on increasingly scarce petroleum resources, and can be decomposed by soil, enzymes and other factors to reduce environmental pollution. Such materials comply with the current global trend of environmentally friendly products and have received extensive attention and research. Among them, degradable seal film bag special materials have also been developed and gradually applied in the market.

[0003] Since the seal film bag packaging products (such as express bags, milk tea bags, clothing bags, etc.) are first blown into films and then printed and bagged, the film blowing capacity and bagging capacity of different production plants do not completely match. The film produced may be placed for 1-2 weeks before bagging, which will cause the seal to be loose after being placed, affecting the quality of the film bag. In addition, some production plants will add recycled materials or even increase the filling of material mineral powder to reduce material costs, which further compresses the sealability of the film and seriously affects the promotion of such materials in related industries. SUMMARY

[0004] To overcome at least one of the above-mentioned deficiencies of the prior art, in a first aspect, an embodiment of the present application provides a composition comprising poly(butylene adipate-co-terephthalate), polylactic acid, and butanediol / trimellitic anhydride modified epoxy resin.

[0005] In a second aspect, an embodiment of the present application provides a degradable material prepared by mixing and reacting the components of the above-mentioned composition and then forming.

[0006] In a third aspect, an embodiment of the present application provides the use of the above-mentioned composition or the above-mentioned degradable material in the preparation of a degradable film.

[0007] In a fourth aspect, an embodiment of the present application provides a degradable film prepared using the above-mentioned composition or the above-mentioned degradable material.

[0008] In a fifth aspect, an embodiment of the present application provides a film bag prepared from the above-mentioned degradable film.

[0009] The composition of one embodiment of the present application includes a butanediol / trimellitic anhydride-modified epoxy resin and a polybutylene adipate / terephthalate, wherein the butanediol / trimellitic anhydride-modified epoxy resin is capable of reacting with the polybutylene adipate / terephthalate, so that the use of the composition for film production can reduce the precipitation of the polybutylene adipate / terephthalate after film production, and improve the edge seal performance of the film. DETAILED DESCRIPTION

[0010] The typical embodiments embodying the features and advantages of the present application will be described in detail in the following description. It should be understood that the present application can be varied in a wide range of embodiments, none of which depart from the scope of the present application, and the description is essentially intended to be illustrative only, not to limit the present application.

[0011] One embodiment of the present application provides a composition including a polybutylene adipate / terephthalate (PBAT), a polylactic acid (PLA), and a butanediol / trimellitic anhydride-modified epoxy resin (hereinafter referred to as "BDODET").

[0012] In one embodiment, the mass content of the polybutylene adipate / terephthalate in the composition can be 65 to 80 wt%, further can be 70 to 80 wt%, for example, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, the above content being based on the total weight of the composition.

[0013] In one embodiment, the mass content of the polylactic acid in the composition can be 3 to 8 wt%, further can be 5 to 7 wt%, for example, 4 wt%, 6 wt%, the above content being based on the total weight of the composition.

[0014] In one embodiment, the mass content of the butanediol / trimellitic anhydride-modified epoxy resin in the composition can be 0.2 to 2 wt%, further can be 0.2 to 1 wt%, for example, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, the above content being based on the total weight of the composition.

[0015] In one embodiment, the butanediol / trimeric anhydride modified epoxy resin is prepared by reacting butanediol, epoxy resin, and trimellitic anhydride. Further, the reaction of butanediol, epoxy resin, and trimellitic anhydride can be carried out under the catalysis of a boron trifluoride complex, such as a boron trifluoride diethyl ether complex, and the amount of boron trifluoride complex can be 4-6 mol% of the amount of trimellitic anhydride, for example, 4.5 mol%, 5 mol%, or 5.5 mol%.

[0016] In one embodiment, in the preparation of butanediol / trimeric anhydride modified epoxy resin, butanediol and trimellitic anhydride are first reacted, and then the reaction product is reacted with epoxy resin.

[0017] In one embodiment, butanediol may be 1,4-butanediol (BDO).

[0018] In one embodiment, in the butanediol / trimeric anhydride modified epoxy resin, the molar ratio of the trimellitic anhydride structure to the butanediol structure can be 2:1, or the molar ratio of the trimellitic anhydride structure to the epoxy resin structure can be 1:1. That is, in the preparation of the butanediol / trimeric anhydride modified epoxy resin, esterification is first performed using 1 molecule of butanediol and 2 molecules of trimellitic anhydride to obtain a product with a "trimeric anhydride structure-butanediol structure-trimeric anhydride structure". This product is then reacted with epoxy resin to obtain a butanediol / trimeric anhydride modified epoxy resin with a "epoxy resin-trimeric anhydride structure-butanediol structure-trimeric anhydride structure-epoxy resin" structure.

[0019] In one embodiment, in the preparation of butanediol / trimeric anhydride modified epoxy resin, the molar ratio of trimellitic anhydride to butanediol can be (1.9-2.1):1, for example 2:1; the molar ratio of trimellitic anhydride to epoxy resin can be (0.9-1.1):1, for example 1:1.

[0020] In one embodiment, the epoxy resin is a two-part type A epoxy resin, such as epoxy resin 128.

[0021] In one embodiment, the epoxy equivalent of the epoxy resin is 180 to 200, for example, 190.

[0022] In one embodiment, in the preparation of butanediol / trimeric anhydride modified epoxy resin, butanediol and trimellitic anhydride are first reacted. When the esterification rate reaches 96%, a clear solution is obtained, and then epoxy resin is added to carry out the reaction.

[0023] In one embodiment, the number average molecular weight of the butanediol / trimeric anhydride modified epoxy resin is 1500 to 2500, for example, 1600, 1700, 1800, 2000, 2200, 2300, 2400.

[0024] In one embodiment, the butanediol / trimeric anhydride modified epoxy resin comprises hydroxyl groups, carboxyl groups, and epoxy functional groups, and has one epoxy functional group at each end.

[0025] In one embodiment, the preparation method of butanediol / trimeric anhydride modified epoxy resin includes the following steps:

[0026] Butylene glycol and trimellitic anhydride were reacted at 65–70 °C for 2.5–3 h under the action of boron trifluoride diethyl ether complex; then, epoxy resin (e.g., epoxy resin 128) was added to the system and reacted at 85–95 °C (e.g., 90 °C) for 6–7 h (e.g., 6.5 h) to obtain butylene glycol / trimeric anhydride modified epoxy resin.

[0027] In one embodiment, poly(butylene adipate / terephthalate) is an existing flexible biodegradable polyester elastomer.

[0028] In one embodiment, the melt flow rate (or melt index) of poly(butylene adipate) at 200°C and a load of 2.16 kg is 2 to 5 g / 10 min, for example, 3 g / 10 min or 4 g / 10 min.

[0029] In one embodiment, the melt flow ratio of polybutylene adipate / terephthalate (PBAT) can be less than 30, and more preferably 20 to 30, such as 22, 25, or 28. This melt flow ratio refers to the ratio of the melt flow rate of PBAT at 200°C with a load of 21.6 kg to that with a load of 2.16 kg.

[0030] In one embodiment, the weight-average molecular weight of poly(butylene adipate) / poly(terephthalate) can be 100,000 to 200,000, for example, 120,000, 140,000, 150,000, 160,000, or 180,000.

[0031] In one embodiment, polylactic acid includes L-type polylactic acid and / or D-type polylactic acid.

[0032] In one embodiment, polylactic acid includes L-type polylactic acid and D-type polylactic acid. The mass content of L-type polylactic acid can be 90-95 wt%, for example, 91 wt%, 92 wt%, 93 wt%, or 94 wt%. The mass content of D-type polylactic acid can be 5-10 wt%, for example, 6 wt%, 7 wt%, 8 wt%, or 9 wt%. The sum of the mass contents of L-type and D-type polylactic acid is 100 wt%.

[0033] In one embodiment, the melt flow rate (melt index) of polylactic acid at 190°C and a load of 2.16 kg can be 0.2 to 30 g / 10 min, and more specifically 2 to 20 g / 10 min, for example 0.5 g / 10 min, 1 g / 10 min, 4 g / 10 min, 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, 9 g / 10 min, 10 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 19 g / 10 min, 21 g / 10 min, 22 g / 10 min, and 25 g / 10 min.

[0034] In one embodiment, the composition includes polybutylene adipate / terephthalate, polylactic acid and butanediol / trimeric anhydride modified epoxy resin, and one or more of mineral powder, opening agent and lubricant.

[0035] In one embodiment, the mineral powder may be calcium carbonate and / or talc; the particle size of the mineral powder may be 3000-5000 mesh.

[0036] In one embodiment, the lubricant may be one or more of monoglycerides, calcium stearate, and stearic acid.

[0037] In one embodiment, the opening agent may be polyethylene wax and / or silica.

[0038] In one embodiment, the mineral powder content in the composition can be 12-30 wt%, more preferably 15-25 wt%, for example 18 wt%, 20 wt%, or 22 wt%.

[0039] In one embodiment, the content of the opening agent in the composition may be 0.1 to 0.3 wt%, and more preferably 0.2 to 0.3 wt%.

[0040] In one embodiment, the lubricant content in the composition may be 0.1 to 0.3 wt%, more preferably 0.2 to 0.3 wt%.

[0041] One embodiment of the present invention provides the application of the above-described butanediol / trimeric anhydride modified epoxy resin in the preparation of membranes, particularly biodegradable membranes.

[0042] One embodiment of the present invention provides a biodegradable material prepared by mixing and reacting the components of the above composition.

[0043] In one embodiment, the components of the above composition can be mixed and reacted at 170-200°C and then processed and shaped to obtain a biodegradable material.

[0044] In one embodiment, the melt flow rate of the biodegradable material at 190°C and a load of 2.16 kg is 1.4–2.5 g / 10 min, for example 1.5 g / 10 min, 1.6 g / 10 min, 1.7 g / 10 min, 1.8 g / 10 min, 1.9 g / 10 min, 2.0 g / 10 min, 2.1 g / 10 min, and 2.3 g / 10 min.

[0045] One embodiment of the present invention provides a biodegradable membrane, which is prepared using the above-described composition or biodegradable material.

[0046] One embodiment of the present invention provides a method for preparing the above-mentioned biodegradable membrane, comprising preparing the biodegradable membrane using the above-mentioned composition or biodegradable material.

[0047] In one embodiment, the method for preparing the biodegradable membrane includes the following steps:

[0048] The above composition is extruded at 170–200°C (e.g., extrusion granulation) to obtain a biodegradable composite material;

[0049] Biodegradable composite materials are made into biodegradable films through a film-forming process.

[0050] In one implementation, the extrusion molding process can be carried out in existing equipment, such as a twin-screw extruder.

[0051] In one embodiment, the film-forming process can be an existing technology, such as a blown film process. Furthermore, the blown film temperature in the blown film process can be 150–165°C, for example, 152°C, 155°C, 158°C, 160°C, or 162°C.

[0052] In one embodiment, the extrusion molding temperature can be 175°C, 180°C, 185°C, 190°C, or 195°C.

[0053] In one embodiment, PLA, PBAT, BDODET, mineral powder, opening agent, and lubricant are added to a high-speed mixer according to the formula and mixed for 10-15 minutes to obtain a uniformly mixed premix; then the premix is ​​added to the hopper of a twin-screw extruder and extruded and granulated at 170-200°C to obtain PLA composite material particles with high melt strength.

[0054] One embodiment of the present invention provides a film bag, particularly a side-sealed film bag, made from the aforementioned biodegradable film or the aforementioned biodegradable material. Furthermore, this film bag can be used as a packaging bag.

[0055] One embodiment of the present invention comprises a composition including BDODET and PBAT, wherein BDODET can react with PBAT, further increasing the molecular weight of PBAT (especially the small molecules contained in PBAT), reducing the precipitation of small molecules in the material or membrane, and improving the edge sealing performance of the membrane.

[0056] One embodiment of the present invention provides a biodegradable material or biodegradable membrane. Since BDODET contains functional groups such as carboxyl and hydroxyl groups, it can bind to the surface of mineral powder, improve the dispersibility of mineral powder, increase the filling content of mineral powder, and reduce the cost of the material.

[0057] The biodegradable material of one embodiment of the present invention can be film-made under high production capacity. The prepared film has high edge seal strength and long edge seal duration, and is suitable for the logistics packaging industry.

[0058] The method for preparing a biodegradable material or biodegradable film according to one embodiment of the present invention can promote the reaction of BDODET and PBAT through the high temperature and shearing action of a twin-screw extruder.

[0059] The preparation method of one embodiment of the present invention is simple. The material can be obtained by reactive extrusion and then directly processed into a film, avoiding the complicated processing of some additives in traditional methods, and thus achieving higher production efficiency.

[0060] One embodiment of the present invention provides a biodegradable film or film bag with good edge-sealing timeliness, suitable for use as express packaging. Good edge-sealing timeliness means that from the time the film is made until it is used for bag edge sealing, the edge can be torn by hand to meet the sawtooth requirements, and the edge-sealing strength remains essentially unchanged. In other words, even after the film has been stored for a relatively long time, its performance still meets the bag-making requirements.

[0061] The following describes in further detail the preparation of a biodegradable material and its membrane according to one embodiment of the present invention, with reference to specific examples. The raw materials and testing methods involved in each embodiment and comparative example are as follows.

[0062] Raw materials

[0063] 1. 2003D: PLA, melt flow rate of 5 g / 10 min at 190℃ and 2.16 kg load, manufactured by NatureWorks, USA;

[0064] 2. 3001D: PLA, melt flow rate of 20 g / 10 min at 190℃ and 2.16 kg load, manufactured by NatureWorks, USA;

[0065] 3. T16: PBAT, melt flow rate of 4 g / 10 min at 200℃ and 2.16 kg load, melt flow ratio of 28, weight average molecular weight of 140,000 to 150,000, produced by Wanhua Chemical.

[0066] 4. CC3000: 3000 mesh heavy calcium carbonate, Guangyuan Chemical;

[0067] 5. AH51205: 3000-5000 mesh talc powder, Liaoning Aihai;

[0068] 6. Opening agent: Polyethylene wax, commercially available;

[0069] 7. Lubricant: Magnesium stearate, commercially available;

[0070] 8. Epoxy resin: Nan Ya Epoxy 128, epoxy equivalent 180-190.

[0071] 9. Trimericic anhydride: analytical grade, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0072] 10. Boron trifluoride diethyl ether complex: analytical grade, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0073] 11. 1,4-Butanediol: Analytical grade, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0074] Test methods

[0075] 1. Melt flow rate test

[0076] The melt flow rate was measured using INSTRON CEAST MF30 according to ISO 1133.

[0077] 2. Film edge seal strength test

[0078] The edge seal strength of the film was measured using a single-column testing machine (model ZWICK Z0.5TH) according to QB / T 2358.

[0079] 3. Membrane puncture strength test

[0080] The puncture strength of the film was measured using a single-column testing machine (model ZWICK Z0.5TH) according to GB / T 37841.

[0081] 4. Particle aging test of materials

[0082] The material was aged for 3 days at 85% RH and 85℃ using an ESPEC GPL-2 aging chamber.

[0083] 5. Number-average molecular weight

[0084] The number-average molecular weight of the butanediol / trimeric anhydride modified epoxy resin was determined by GPC.

[0085] Preparation Example

[0086] Under a nitrogen atmosphere, 10 mol of 1,4-butanediol (BDO) and 20 mol of trimellitic anhydride were added to a flask equipped with a condenser. The mixture was heated and stirred until the raw materials were completely and uniformly mixed. 1 mol of boron trifluoride ether was slowly added dropwise to the above reaction solution. The temperature was raised to 70°C and the reaction was carried out for 2.5 h. Then, 20 mol of epoxy resin (Nanya Epoxy 128) was added, and the temperature was raised to 95°C and the reaction was continued for 6 h to obtain butanediol / trimeric anhydride modified epoxy resin (BDODET). The number average molecular weight of the butanediol / trimeric anhydride modified epoxy resin was measured to be approximately 2000.

[0087] Example

[0088] A certain mass of PLA, PBAT, BDODET, mineral powder, opening agent, and lubricant are added to a high-speed mixer and mixed for 10-15 minutes. Then, the mixture is extruded and granulated using a twin-screw extruder at a temperature of 190-210℃ to obtain a biodegradable material in particle form.

[0089] Biodegradable materials of Examples 1-6 and Comparative Examples 1-2 were prepared by using different types and / or amounts of raw materials according to the above process. The types and amounts (mass percentage) of raw materials for each example and comparative example are shown in Table 1.

[0090] Table 1. Types and amounts of raw materials used in each embodiment and comparative example.

[0091]

[0092]

[0093] Application examples

[0094] The biodegradable materials obtained in Examples 1-6 and Comparative Examples 1-2 were used to prepare films according to the following process: film blowing was carried out using a blown film machine at a capacity of 120 kg / h, the die diameter of the blown film machine was 100 mm, the blowing temperature was 160-165 °C, the blow-up ratio was 3.5, and the film thickness was 50-55 μm.

[0095] The films prepared in Examples 1-6 and Comparative Examples 1-2 were left at room temperature for 1 day (1d). A portion of the films were then used in a bag-making machine at 280°C for bag sealing, followed by puncture and side-seal strength tests. The remaining films were left at room temperature. At 7 days (7d), 14 days (14d), and 21 days (21d) after film preparation, the films were taken for bag sealing, and their side-seal strength was tested. The tear patterns of the side seals were also compared by hand. Furthermore, the biodegradable materials prepared in Examples 1-6 and Comparative Examples 1-2 were subjected to initial melt index and melt index tests after 3 days (3d) of double 85 aging. Specific results are shown in Table 2.

[0096] Table 2 shows the test results of material properties and corresponding thin film properties for each embodiment and comparative example.

[0097]

[0098]

[0099] As shown in Table 1, the main difference between Examples 1-6 and Comparative Examples 1-2 is that the raw materials in Comparative Examples 1-2 did not include BDODET. According to the results in Table 2, the initial melt index and the melt index after double 85 aging of the biodegradable materials in Examples 1-6 are significantly lower than the corresponding melt indices of the biodegradable materials in Comparative Examples 1-2, indicating that the introduction of BDODET can reduce the degradation rate of the material and prevent edge seal failure due to aging.

[0100] Furthermore, in Comparative Examples 1 and 2, the film edges of the bag sealing showed straight lines after 1 day of storage, and became completely straight after 7 days. The edge seal strength also decreased significantly with prolonged storage time. In contrast, the films in Examples 1 to 6 still showed jagged edges after 21 days of storage, with only a slight decrease in edge seal strength.

[0101] Therefore, by adding BDODET to the raw materials for preparing biodegradable materials, the embodiments of the present invention can improve the edge seal strength of the prepared film and extend the edge seal duration.

[0102] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0103] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. A biodegradable membrane prepared by means of a composition comprising 65-80 wt% poly(butylene adipate / terephthalate), 3-8 wt% polylactic acid, and 0.2-2 wt% butanediol / trimeric anhydride modified epoxy resin.

2. The biodegradable membrane according to claim 1, wherein, The butanediol / trimethicone modified epoxy resin comprises hydroxyl, carboxyl, and epoxy functional groups; and / or, The number-average molecular weight of the butanediol / trimeric anhydride modified epoxy resin is 1500–2500; and / or, The composition also includes one or more of mineral powder, opening agent, and lubricant.

3. The biodegradable membrane according to claim 2, wherein, The composition comprises 70–80 wt% of the poly(butylene adipate / terephthalate), 5–7 wt% of polylactic acid, and 0.2–1 wt% of the butanediol / triphenyl phthalic anhydride modified epoxy resin; and / or, The mineral powder is present in the composition at a content of 12–30 wt%; and / or, The opening agent is present in the composition at a content of 0.1–0.3 wt%; and / or, The lubricant is present in the composition at a content of 0.1 to 0.3 wt%.

4. The biodegradable membrane according to claim 1, wherein, The polylactic acid has a melt flow rate of 0.2–30 g / 10 min at 190 °C and a load of 2.16 kg; and / or, The poly(butylene adipate) / terephthalate melt flow rate at 200°C and 2.16 kg load is 2–5 g / 10 min; and / or, The weight-average molecular weight of the poly(butylene adipate / terephthalate) is 100,000 to 200,000.

5. The biodegradable membrane according to claim 1, wherein, The polylactic acid has a melt flow rate of 2–20 g / 10 min at 190 °C and a load of 2.16 kg; and / or, The butanediol / trimeric anhydride modified epoxy resin is prepared by reacting butanediol, epoxy resin and trimellitic anhydride.

6. The biodegradable membrane according to claim 5, wherein, In the preparation of the butanediol / trimeric anhydride modified epoxy resin, the molar ratio of trimellitic anhydride to butanediol is (1.9–2.1):1; and / or, the molar ratio of trimellitic anhydride to epoxy resin is (0.9–1.1):1; and / or, In the preparation of the butanediol / trimeric anhydride modified epoxy resin, the butanediol and the trimellitic anhydride are first esterified, and then the epoxy resin is added to carry out the reaction; and / or, The butanediol is 1,4-butanediol; and / or, The epoxy equivalent of the epoxy resin is 180-200; and / or, The epoxy resin is a bisphenol A type epoxy resin.

7. A membrane bag, made from the biodegradable membrane according to any one of claims 1 to 6.

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