WO2023071014A1 - 一种高挺度高强韧可全降解pbat/pla树脂组合物及其制备方法 - Google Patents

一种高挺度高强韧可全降解pbat/pla树脂组合物及其制备方法 Download PDF

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WO2023071014A1
WO2023071014A1 PCT/CN2022/079629 CN2022079629W WO2023071014A1 WO 2023071014 A1 WO2023071014 A1 WO 2023071014A1 CN 2022079629 W CN2022079629 W CN 2022079629W WO 2023071014 A1 WO2023071014 A1 WO 2023071014A1
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pbat
pla
calcium carbonate
resin composition
parts
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PCT/CN2022/079629
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French (fr)
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史鹏伟
汤俊杰
郭品强
纪永鹏
朱从山
段浩
金光润
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佳易容聚合物(上海)有限公司
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Priority to KR1020247017595A priority Critical patent/KR20240091044A/ko
Publication of WO2023071014A1 publication Critical patent/WO2023071014A1/zh
Priority to US18/646,999 priority patent/US20240270959A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention belongs to the technical field of polymer material modification, and in particular relates to a fully degradable PBAT/PLA resin composition with high stiffness, high strength and toughness and a preparation method thereof.
  • PBAT and PLA are currently the two fully degradable polymers with the most research, the largest output, and the highest degree of commercialization.
  • the two materials are blended and modified to achieve complementary advantages, so that the material has high strength and good toughness, which is also one of the hot spots in the modification of degradable materials.
  • the PBAT material is soft due to its low crystallinity.
  • the film made of the PBAT/PLA alloy based on PBAT has low stiffness and poor texture, giving people a "soft and collapsed" appearance. cheap feeling.
  • Patent CN 111378259 A discloses a small molecular compound containing epoxy groups as a compatibilizer for PBAT/PLA composites, which promotes the improvement of the mechanical properties of PBAT/PLA composites, especially while maintaining high rigidity and Toughness; but the small molecule compatibilizer has defects such as difficulty in feeding, large addition amount (0.5-2 parts), and residual monomers that have a large impact on the smell of the product.
  • Patent CN 109504041 A discloses a TPS/PLA/PBAT blended modified biodegradable resin prepared by a chain extender, using KL ⁇ E as a chain extender to improve the compatibility of the two-phase system; Coal Chemical Institute KL ⁇ E series Like BASF's ADR series chain extenders, they are all epoxy chain extenders, but their molecular weights are lower, below 10,000.
  • Patent CN105199347 A uses sodium-based montmorillonite to enhance masterbatch blending and modification to obtain PLA/PBAT composite materials with excellent performance, but montmorillonite has a layered structure that is difficult to peel off and is difficult to industrialize; in addition, montmorillonite can improve composite materials. Strength, but the size in a single direction is still small, which has a limited effect on improving the stiffness of the material.
  • Patent CN109825048 A uses OMMT and EGMA to synergistically improve the strength and toughness of the material.
  • EGMA improves the problem of poor adhesion at the two-phase interface.
  • OMMT acts as a physical cross-linking point to improve the strength of the material.
  • OMMT also has a small size in a single direction , has a limited effect on improving the stiffness of the material.
  • Patent CN 110079065 A and CN 106750253 A mainly focuses on improving the compatibility of PLA/PBAT composite materials, patent CN In 110079065 A, the compatibilizer is 1 ⁇ 10%, and the addition amount is relatively large; patent CN The compatibilizer in 106750253 A can play the role of light stabilizer and antibacterial agent, but the synthesis steps of the compatibilizer are complicated, and the environmental protection of the raw materials used needs to be verified.
  • One of the objectives of the present invention is to provide a fully degradable PBAT/PLA resin composition with high stiffness, high strength and toughness.
  • the second object of the present invention is to provide a method for preparing a fully degradable PBAT/PLA resin composition with high stiffness and high toughness.
  • the invention provides a fully degradable PBAT/PLA resin composition with high stiffness, high strength and toughness, including PLA, PBAT, calcium carbonate whiskers, high molecular weight chain extension compatibilizer, coupling agent and auxiliary agent.
  • composition is prepared from raw materials including the following components and parts by weight:
  • Coupling agent 0.01-0.1 part
  • the calcium carbonate whiskers have a length of 10-30 ⁇ m, a diameter of 0.5-1.0 ⁇ m, and an aspect ratio of ⁇ 20.
  • the high molecular weight chain extension compatibilizer is a polymer containing epoxy groups, with a weight average molecular weight Mw of 20000-50000, an epoxy equivalent of 290-310g/mol, and a glass transition temperature Tg ⁇ 80°C.
  • Described coupling agent is at least one of ⁇ -aminopropyltriethoxysilane, ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -(methacryloxy)propyltrimethoxysilane kind.
  • the coupling agent is ⁇ -glycidyl etheroxypropyl trimethoxysilane (KH560).
  • the weight average molecular weight Mw of PBAT is 100000-150000, and the weight average molecular weight Mw of PLA is 80000-120000.
  • the auxiliary agents include antioxidants, lubricants and anti-blocking agents.
  • the present invention also provides a method for preparing a fully degradable PBAT/PLA resin composition with high stiffness, high strength and toughness, comprising the following steps: S1, weighing the following components in parts by weight: PBAT: 60-80 parts; PLA: 10 ⁇ 30 parts; calcium carbonate whiskers: 5 ⁇ 15 parts; high molecular weight chain extension compatibilizer: 0.3 ⁇ 0.6 parts; coupling agent: 0.01 ⁇ 0.1 parts; auxiliary agent: 0.3 -0 .5 servings.
  • the calcium carbonate whiskers are treated with a coupling agent, then mixed with PBAT, melted and blended by a twin-screw extruder, extruded and granulated to obtain calcium carbonate whiskers masterbatch.
  • step S3 Premix the calcium carbonate whisker masterbatch prepared in step S2 with PLA, a high molecular weight chain extension compatibilizer, and additives, melt extrude, and granulate to obtain a fully degradable PBAT/PLA resin combination with high stiffness, high strength, and toughness thing.
  • step S2 the parameters used for the melt blending are: the temperature of the feed section is 80-120°C, the temperature of the plasticizing section is 140-160°C, the temperature of the homogenization section is 160-180°C, and the screw speed is 300-600rpm .
  • step S3 the parameters used for the melt blending are: the temperature of the feed section is 80-120°C, the temperature of the plasticizing section is 160-180°C, the temperature of the homogenization section is 180-210°C, and the screw speed is 300-600rpm .
  • the present invention has following beneficial effect: (1) the use of high molecular weight chain extension compatibilizer: the present invention adopts high molecular weight chain extension compatibilizer as the chain extension compatibilizer of PBAT/PLA composite material , compared with traditional low molecular weight chain extenders (such as the ADR series of Basf and the KLE4370 of domestic Coal Chemical Institute, the molecular weight is all between 5000-10000), the weight average molecular weight of the high molecular weight chain extension compatibilizer used in the present invention 20000 ⁇ 50000.
  • Low-molecular-weight chain extenders have a better effect of increasing viscosity and chain extension in single-component condensation polymers such as PLA, PET, etc.
  • High-molecular-weight chain-extending compatibilizers are more suitable for improving the compatibility of alloy systems, such as PBAT/PLA alloys, PLA/PBAT alloy, PBS (PBSA)/PBAT alloy, etc.
  • Calcium carbonate whisker filling with high aspect ratio with traditional zero-dimensional material fillers (such as calcium carbonate, silicon dioxide, starch, etc.), two-dimensional fillers (such as montmorillonite, talc, graphene, etc.)
  • traditional zero-dimensional material fillers such as calcium carbonate, silicon dioxide, starch, etc.
  • two-dimensional fillers such as montmorillonite, talc, graphene, etc.
  • the size of calcium carbonate whiskers is in the micron level, which will not affect the appearance of the final film product, and its price is low, and it is easier to disperse in the resin matrix after treatment.
  • Fig. 1 is the force-displacement curve and the microstructure schematic diagram of the filler used for the fully degradable PBAT/PLA resin composition film with high stiffness and high toughness in the present invention, respectively corresponding to the mechanics of the resin composition in Example 2 and Comparative Example 2 curve.
  • Figure 2 is a schematic diagram of the stability of the granulation process in Example 1.
  • Fig. 3 is a schematic diagram of the unstable phenomenon in the granulation process of Comparative Example 1.
  • invention 1-4 can fully degrade the PBAT/PLA resin composition, comprising the following raw material groups in parts by weight: .
  • PBAT was placed in an oven at 80°C for more than 3 hours to remove moisture, and the weight average molecular weight Mw of PBAT was 100000-150000; PLA was placed in an oven at 65°C for more than 5 hours. , remove moisture, PLA weight average molecular weight Mw is 80000 ⁇ 120000; high molecular weight chain extension compatibilizer: brand HPC 3510P; commercially available; low molecular weight chain extender: KL ⁇ E4370 or ADR 4468, commercially available; coupling agent KH560 and Additives; commercially available.
  • Example 1-4 provides a high-stiffness, high-strength, fully degradable PBAT/PLA resin composition, which is prepared according to the components and contents in Table 1.
  • Table 1 embodiment 1-4 each component and component content (by weight).
  • the preparation method of embodiment 1-2 is as follows: S1, take raw material according to table 1; S2, calcium carbonate whisker is processed with coupling agent, mixes with PBAT then through twin-screw extruder melt-blending, extruding Calcium carbonate whisker masterbatches were obtained from the pellets; the parameters used for melt blending were: the temperature of the feed section was 80°C, the temperature of the plasticizing section was 140°C, the temperature of the homogenization section was 160°C, and the screw speed was 300rpm.
  • step S3 Premix the calcium carbonate whisker masterbatch prepared in step S2 with PLA, a high molecular weight chain extension compatibilizer, and additives, melt extrude, and granulate to obtain a fully degradable PBAT/PLA resin combination with high stiffness, high strength, and toughness
  • the parameters used for melt blending are: the temperature of the feed section is 80°C, the temperature of the plasticizing section is 160°C, the temperature of the homogenization section is 180°C, and the screw speed is 300rpm.
  • the preparation method of embodiment 3-4 is as follows: S1, take raw material according to table 1; S2, calcium carbonate whisker is processed with coupling agent, mixes with PBAT then, through twin-screw extruder melting blending, extruding Calcium carbonate whisker masterbatches were obtained from the pellets; the parameters used in the melt blending were: the temperature of the feed section was 120°C, the temperature of the plasticizing section was 160°C, the temperature of the homogenization section was 180°C, and the screw speed was 600rpm. S3.
  • the calcium carbonate whisker masterbatch prepared in step S2 with PLA, a high molecular weight chain extension compatibilizer, and additives, melt extrude, and granulate to obtain a fully degradable PBAT/PLA resin combination with high stiffness, high strength, and toughness
  • the parameters used in the melt blending are: the temperature of the feed section is 120°C, the temperature of the plasticizing section is 160°C, the temperature of the homogenization section is 180°C, and the screw speed is 600rpm.
  • Comparative Example 1 The raw material components and preparation method of this comparative example are basically the same as in Example 1, except that the high molecular weight chain extender compatibilizer is replaced by the low molecular weight chain extender KL ⁇ E4370.
  • Figure 2 shows the granulation process of Example 1 of the present invention;
  • Figure 3 shows the granulation process of Comparative Example 1, and the results show that high molecular weight chain extension compatibilizer can fully degrade the combination of high stiffness, high strength and toughness PBAT/PLA resin Improvement of material processability and compatibility.
  • Comparative Example 2 The raw material components and preparation method of this comparative example are basically the same as in Example 1, except that the high molecular weight chain extender compatibilizer is replaced by the low molecular weight chain extender ADR 4468.
  • Comparative Example 3 In order to verify the influence of general-purpose calcium carbonate and calcium carbonate whiskers on improving the toughness and stiffness of a fully degradable PBAT/PLA resin composition with high stiffness and high toughness, comparative example 2 is set.
  • the raw material components and preparation method of this comparative example are basically the same as in Example 2, except that the calcium carbonate whiskers are replaced by general-purpose calcium carbonate powder.
  • Comparative Example 4 Comparative Example 3 is for comparison with Example 3 to verify the effect of the coupling agent KH560 on improving the strength of the fully degradable PBAT/PLA resin composition with high stiffness and high toughness.
  • the raw material components and preparation method of this comparative example are basically the same as in Example 3, except that no coupling agent is added.
  • Comparative Example 5 This comparative example is to compare and verify the impact of segmented granulation process on the stiffness and toughness of the high-strength, tough and fully degradable PBAT/PLA resin composition.
  • the preparation method of the PBAT/PLA resin composition comprises the following steps: PBAT, PLA, calcium carbonate whiskers treated with coupling agent, high molecular weight chain extension compatibilizer and other auxiliary agents are obtained through premixing, melt extrusion and granulation
  • the PBAT/PLA resin composition Wherein the process parameter that melt blending adopts is identical with the process parameter of step S3 among the embodiment 4.
  • Comparative example 6 The raw material components and preparation method of this comparative example are basically the same as those in Example 4, except that PLA is not added as a reinforcing resin.
  • Performance test test the sample obtained by embodiment 1-4 and comparative example 1-5 is subjected to the following performance test: tensile strength and elongation are tested according to ISO 527 standard, and tensile rate 50mm/min; Stiffness test adopts Thai Burr (Taber) type stiffness tester test, the composition is made into a film with a thickness of 30 ⁇ m before the test.
  • the relevant test data are shown in Table 2 below.
  • the resin compositions prepared by adopting the formula and process of the present invention all have excellent strength, toughness and stiffness. Because the calcium carbonate whiskers and PLA adopted in the present invention are uniformly distributed in the PBAT matrix resin as a dispersion, the dispersed phase PLA plays a reinforcing role on the PBAT resin, and the calcium carbonate whiskers play a role in strengthening and improving the stiffness of the final film product.
  • the two reinforcing materials have excellent synergy in phase or morphology.
  • Fig. 1 is the force-displacement curve of embodiment 2 and comparative example 3 resin composition film among the present invention. It can be seen that calcium carbonate whisker fills compared with traditional calcium carbonate filler, and calcium carbonate whisker itself has extremely high The strength and length-to-diameter ratio are better in improving the strength and stiffness of the material, and can maintain a high elongation. This is the key to the high stiffness and high strength performance of the composition.
  • Fig. 2 is the traction granulation process of the resin composition that adopts high molecular weight chain extension compatibilizer in embodiment 1
  • Fig. 3 adopts low molecular weight chain extender KL-E4370 and ADR4468 respectively in comparative example 1 and comparative example 2 as chain extension
  • the traction granulation process of the resin composition of agent From the results of comparative example 1 and comparative example 2 and embodiment 1, the high molecular weight chain extension compatibilizer is more suitable for improving the compatibility of PBAT/PLA alloy, making traction The granular process is more stable.
  • the calcium carbonate whisker that coupling agent is processed has higher strength and elongation at break.
  • the staged granulation process can realize the synergistic strengthening and toughening effect of PLA and calcium carbonate whiskers in phase or form. Playing a reinforcing role, calcium carbonate whiskers play a role in strengthening and improving the stiffness of the final film product.
  • PLA can achieve the effect of reinforcing PBAT and improving stiffness, and the reinforcing effect of pure calcium carbonate whiskers is poor.

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Abstract

本发明涉及一种高挺度高强韧可全降树脂组合物，包含以下重量份的原料组分：PBAT：60-80份；PLA：10-30份；碳酸钙晶须：5‑15份；高分子量扩链相容剂：0.3-0.6份；偶联剂：0.01-0.1份；和其他加工助剂。制备方法包括以下步骤：先将碳酸钙晶须用偶联剂处理，后与PBAT混合后经双螺杆挤出机挤出造粒得到碳酸钙晶须母粒；再将碳酸钙晶须母粒、PLA、高分子量扩链相容剂、助剂经预混、熔融挤出、造粒得到高挺度高强韧可全降解PBAT/PLA树脂组合物。本发明的优点在于该组合物为可全降解树脂组合物，碳酸钙晶须和PLA对PBAT基体起到协同增强增韧效果，最终薄膜制品具有很高的挺度，且成本提高不明显，易实现规模化生产。

Description

一种高挺度高强韧可全降解PBAT/PLA树脂组合物及其制备方法 技术领域
本发明属于高分子材料改性技术领域，具体涉及一种高挺度高强韧可全降解PBAT/PLA树脂组合物及其制备方法。
 背景技术
PBAT和PLA是目前研究最多、产量最大、商业化程度最高的两种可全降解聚合物。将两种材料通过共混改性，实现优势互补，使材料具有较高强度的同时具有良好的韧性，也是目前可降解材料改性的热点之一。与传统的PE薄膜相比，PBAT材料由于结晶度低，材质较软，在以PBAT为主的PBAT/PLA合金制备的薄膜挺度低，质感较差，给人一种“软塌塌”的廉价感。
很多专利集中在改善PBAT/PLA复合材料的相容性和强度，并未关注到如何提高最终薄膜制品的挺度。如何提高PBAT/PLA复合材料的相容性和强韧性，且同时保持材料薄膜制品的高挺度是该领域研究技术人员面临的最大难题。
专利CN 111378259 A公开了一种含有环氧基团的小分子化合物作为PBAT/PLA复合材料的相容剂，促进了PBAT/PLA复合材料力学性能的改善，尤其是同时保持了较高的刚性和韧性；但该小分子相容剂存在加料困难、添加量大(0 .5‑2份)、残留单体对制品气味影响大等缺陷。
专利CN 109504041 A公开了一种采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂，采用KL‑E作为扩链剂提升两相体系的相容性；煤化院KL‑E系列和BASF公司ADR系列扩链剂一样，都是环氧类扩链剂，但其分子量较低，都在10000以下。
专利CN105199347 A用钠基蒙脱土增强母料共混改性得到性能优异的PLA/PBAT复合材料，但是蒙脱土是层状结构存在剥离困难，难以工业化；此外蒙脱土虽然可以改善复合材料强度，但在单一方向尺寸仍较小，对提高材料挺度作用有限。
专利CN109825048 A采用OMMT与EGMA协同提升材料的强度和韧性，EGMA改善了两相界面粘合较差的问题，OMMT起到物理交联点的作用进而提升材料强度，OMMT同样存在单一方向尺寸较小，在提高材料挺度方面作用有限。
专利CN 110079065 A和CN 106750253 A主要集中在改善PLA/PBAT复合材料相容性方面，专利CN 110079065 A中相容剂为1‑10％，添加量较大；专利CN 106750253 A中相容剂可以起到的光稳定剂和抗菌剂的效果，但是相容剂合成步骤复杂，使用的原料环保性有待验证。
 技术问题
为了提高PBAT/PLA复合材料的相容性和强韧性，且同时保持材料薄膜制品的高挺度。本发明的目的之一是提供一种高挺度高强韧可全降解PBAT/PLA树脂组合物。本发明的第二个目的是，提供一种高挺度高强韧可全降解PBAT/PLA树脂组合物的制备方法。
 技术解决方案
本发明提供一种高挺度高强韧可全降解PBAT/PLA树脂组合物，包括PLA、PBAT、碳酸钙晶须、高分子量扩链相容剂、偶联剂和助剂。
进一步，所述的组合物由包括以下组分及重量份的原料制备得到：
PBAT                                60-80份；
PLA                                  10-30份；
碳酸钙晶须                      5-15份；
高分子量扩链相容剂      0.3-0.6份；
偶联剂                              0.01-0.1份；
助剂                                  0.3-0.5份。
所述的碳酸钙晶须长度10‑30μm，直径0 .5‑1 .0μm，长径比≥20。
所述的高分子量扩链相容剂为含有环氧基团的聚合物，重均分子量Mw为20000‑50000，环氧当量为290‑310g/mol，玻璃化转变温度Tg≥80℃。
所述的偶联剂为γ‑氨丙基三乙氧基硅烷，γ‑缩水甘油醚氧丙基三甲氧基硅烷，γ‑(甲基丙酰氧)丙基三甲氧基硅烷其中的至少一种。
作为优选方案，所述的偶联剂为γ‑缩水甘油醚氧丙基三甲氧基硅烷(KH560)。
所述的PBAT重均分子量Mw为100000‑150000，PLA重均分子量Mw为80000‑120000。
所述助剂包括抗氧剂、润滑剂和开口剂。
本发明还提供一种高挺度高强韧可全降解PBAT/PLA树脂组合物的制备方法，包括如下步骤：S1、称取以下重量份数的组分：：PBAT：60‑80份；PLA：10‑30份；碳酸钙晶须：5‑15份；高分子量扩链相容剂：0 .3‑0 .6份；偶联剂：0 .01‑0 .1份；助剂0 .3‑0 .5份。
S2、将碳酸钙晶须用偶联剂处理，然后与PBAT混合后经双螺杆挤出机熔融共混、挤出造粒得到碳酸钙晶须母粒。
S3、将步骤S2制备的碳酸钙晶须母粒与PLA、高分子量扩链相容剂、助剂经预混、熔融挤出、造粒得到高挺度高强韧可全降解PBAT/PLA树脂组合物。
步骤S2中，所述熔融共混采用的参数为：进料段温度为80‑120℃、塑化段温度为140‑160℃、均化段温度为160‑180℃，螺杆转速为300‑600rpm。
步骤S3中，所述熔融共混采用的参数为：进料段温度为80‑120℃、塑化段温度为160‑180℃、均化段温度为180‑210℃，螺杆转速为300‑600rpm。
 有益效果
与现有技术相比，本发明具有如下的有益效果：(1)高分子量扩链相容剂的使用：本发明采用高分子量扩链相容剂作为PBAT/PLA复合材料的扩链相容剂，与传统的低分子量扩链剂(如Basf的ADR系列和国内煤化院的KLE4370，分子量都在5000‑10000之间)相比，本发明中用到的高分子量扩链相容剂重均分子量20000‑50000。低分子量扩链剂在单一组分缩聚物如PLA、PET等体系增粘扩链效果较好，高分子量扩链相容剂更适合用来改善合金体系的相容性，如PBAT/PLA合金、PLA/PBAT合金、PBS(PBSA)/PBAT合金等。
(2)高长径比的碳酸钙晶须填充：与传统的零维材料填料(如碳酸钙、二氧化硅、淀粉等)、二维填料(如蒙脱土、滑石粉、石墨烯等)相比，碳酸钙晶须本身具有极高的强度和长径比，只需要少量添加即可明显提高材料的强度和挺度。碳酸钙晶须尺寸在微米级，不会影响最终薄膜制品的外观，且其价格低廉，处理后在树脂基体中较易分散。
(3)高挺度及协同强韧效果：碳酸钙晶须和PLA分散相同时分布在PBAT基体树脂中，分散相PLA对PBAT树脂起到增强作用；碳酸钙晶须起到增强和提高最终薄膜制品挺度的作用。该方法制备的树脂组合物，不提高成本的情况下改善薄膜制品挺度，提供高强韧的可全降解树脂组合物，且成本较低，易实现规模化生产。
 附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显。
图1为本发明中的高挺度高强韧可全降解PBAT/PLA树脂组合物薄膜的力‑位移曲线及所用填料微观结构示意图，分别对应实施例2和对比例2中的树脂组合物的力学曲线。
图2为实施例1造粒过程稳定性示意图。
图3为对比例1造粒过程不稳定现象示意图。
 本发明的实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
 实施例1‑4的高挺度高强韧可全降解PBAT/PLA树脂组合物，包含以下重量份的原料组：
Figure 43144dest_path_image001
。
需要说明的是，下述实施例和对比例中：PBAT放置在80℃的烘箱中干燥3h以上，除去水分，PBAT重均分子量Mw为100000‑150000；PLA放置在65℃的烘箱中干燥5h以上，除去水分，PLA重均分子量Mw为80000‑120000；高分子量扩链相容剂：牌号HPC 3510P；市售；低分子量扩链剂：KL‑E4370或ADR 4468，市售；偶联剂KH560及助剂；市售。
实施例1‑4：实施例1‑4提供一种高挺度高强韧可全降解PBAT/PLA树脂组合物，分别按表1中的组分及含量进行备料。
表1实施例1‑4各组分及组分含量(重量份计)。
Figure 600027dest_path_image002
Figure 601481dest_path_image003
。
实施例1‑2的制备方法如下：S1、根据表1称取原料；S2、将碳酸钙晶须用偶联剂处理，然后与PBAT混合后经双螺杆挤出机熔融共混、挤出造粒得到碳酸钙晶须母粒；熔融共混采用的参数为：进料段温度为80℃、塑化段温度为140℃、均化段温度为160℃，螺杆转速为300rpm。
S3、将步骤S2制备的碳酸钙晶须母粒与PLA、高分子量扩链相容剂、助剂经预混、熔融挤出、造粒得到高挺度高强韧可全降解PBAT/PLA树脂组合物；熔融共混采用的参数为：进料段温度为80℃、塑化段温度为160℃、均化段温度为180℃，螺杆转速为300rpm。
实施例3‑4的制备方法如下：S1、根据表1称取原料；S2、将碳酸钙晶须用偶联剂处理，然后与PBAT混合后经双螺杆挤出机熔融共混、挤出造粒得到碳酸钙晶须母粒；所述熔融共混采用的参数为：进料段温度为120℃、塑化段温度为160℃、均化段温度为180℃，螺杆转速为600rpm。S3、将步骤S2制备的碳酸钙晶须母粒与PLA、高分子量扩链相容剂、助剂经预混、熔融挤出、造粒得到高挺度高强韧可全降解PBAT/PLA树脂组合物；所述熔融共混采用的参数为：进料段温度为120℃、塑化段温度为160℃、均化段温度为180℃，螺杆转速为600rpm。
对比例1：本对比例原料组分和制备方法与实施例1基本一致，不同之处在于高分子量扩链相容剂替换为低分子量扩链剂KL‑E4370。图2所示为本发明的实施例1造粒过程；图3所示为对比例1造粒过程，结果表明高分子量扩链相容剂对高挺度高强韧可全降解PBAT/PLA树脂组合物加工性和相容性的改善效果。
对比例2：本对比例原料组分和制备方法与实施例1基本一致，不同之处在于高分子量扩链相容剂替换为低分子量扩链剂ADR 4468。
对比例3：为了验证通用碳酸钙和碳酸钙晶须对改善高挺度高强韧可全降解PBAT/PLA树脂组合物强韧性和挺度的影响，设置对比例2。
本对比例原料组分和制备方法与实施例2基本一致，不同之处仅在于碳酸钙晶须替换为通用碳酸钙粉。
对比例4：对比例3是为了对比实施例3进行比对，验证偶联剂KH560对改善高挺度高强韧可全降解PBAT/PLA树脂组合物强度的影响。
本对比例原料组分和制备方法与实施例3基本一致，不同之处在于不添加偶联剂。
对比例5：本对比例是为了对比验证分段造粒工艺对高强韧可全降解PBAT/PLA树脂组合物挺度和强韧性的影响，对比例5所述的高挺度高强韧可全降解PBAT/PLA树脂组合物的制备方法包括以下步骤：将PBAT，PLA，偶联剂处理的碳酸钙晶须，高分子量扩链相容剂及其他助剂经预混、熔融挤出、造粒获得的PBAT/PLA树脂组合物；其中熔融共混采用的工艺参数与实施例4中步骤S3的工艺参数完全相同。
对比例6：本对比例原料组分和制备方法与实施例4基本一致，不同之处仅在于不添加PLA作为补强树脂。
性能测试试验：将实施例1‑4和对比例1‑5所得到的试样进行以下性能测试：拉伸强度和伸长率按ISO 527标准测试，拉伸速率50mm/min；挺度测试采用泰伯尔(Taber)式挺度测定仪测试，测试前将组合物制成30μm厚的薄膜。相关测试数据见下表2。
表1实施例1‑4与对比例1‑6物性测试数据。
Figure 534802dest_path_image004
。
根据表2中实施例1‑4结果来看，采用本发明的配方和工艺制备的树脂组合物都具有优异的强韧性和挺度。因为本发明采用的碳酸钙晶须和PLA同时作为分散均匀分布在PBAT基体树脂中，分散相PLA对PBAT树脂起到增强作用，碳酸钙晶须起到增强和提高最终薄膜制品挺度的作用。两种增强材料在相态或形态上起到优异的协同。
图1为本发明中的实施例2和对比例3树脂组合物薄膜的力‑位移曲线；可以看出，碳酸钙晶须填充与传统的碳酸钙填料相比，碳酸钙晶须本身具有极高的强度和长径比，在提高材料的强度和挺度方面效果更好，且能保持较高的延伸率。效果，这是该组合物具有高挺度高强韧性能的关键。
图2为实施例1中采用高分子量扩链相容剂的树脂组合物牵引造粒过程，图3为对比例1和对比例2中分别采用低分子量扩链剂KL‑E4370和ADR4468为扩链剂的树脂组合物牵引造粒过程；从对比例1与对比例2和实施例1结果来看，高分子量扩链相容剂更适合用来改善PBAT/PLA合金的相容性，使得牵引造粒过程更加稳定。
从对比例4和实施例3结果来看，偶联剂处理过的碳酸钙晶须具有更高的强度和断裂伸长率。从对比例5和实施例4结果来看，分段造粒工艺能够实现PLA和碳酸钙晶须两种增强材料在相态或形态上起到的协同增强增韧效果，分散相PLA对PBAT树脂起到增强作用，碳酸钙晶须起到增强和提高最终薄膜制品挺度的作用。从对比例6和实施例4结果来看，PLA能够实现对PBAT的补强和提高挺度的效果，单纯的碳酸钙晶须补强效果较差。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

  1. 一种高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，包括PLA、PBAT、碳酸钙晶须、高分子量扩链相容剂、偶联剂和助剂。
  2. 根据权利要求1所述的高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，所述的组合物由包括以下组分及重量份的原料制备得到：
    PBAT    60-80份；
    PLA      10-30份；
    碳酸钙晶须 5-15份；
    高分子量扩链相容剂      0.3-0.6份；
    偶联剂  0.01-0.1份；
    助剂      0.3-0.5份。
  3. 根据权利要求1所述的高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，所述的碳酸钙晶须长度10‑30μm，直径0 .5‑1 .0μm。
  4. 根据权利要求1所述的高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，所述的高分子量扩链相容剂为含有环氧基团的共聚物，重均分子量Mw为20000‑50000，环氧当量为290‑310g/mol，玻璃化转变温度Tg≥80℃。
  5. 根据权利要求1所述的高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，所述的偶联剂为γ‑氨丙基三乙氧基硅烷，γ‑缩水甘油醚氧丙基三甲氧基硅烷，γ‑(甲基丙烯酰氧)丙基三甲氧基硅烷其中的至少一种。
  6. 根据权利要求1所述的高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，所述的PBAT重均分子量Mw为100000‑150000，PLA重均分子量Mw为80000‑120000。
  7. 根据权利要求1所述的高挺度高强韧可全降解PBAT/PLA树脂组合物，其特征在于，所述助剂包括抗氧剂、润滑剂和开口剂。
  8. 一种如权利要求1‑8任一项所述的高挺度高强韧可全降解PBAT/PLA树脂组合物的制备方法，其特征在于，包括如下步骤：S1、称取以下重量份数的组分：PBAT：60‑80份；PLA：10‑30份；碳酸钙晶须：5‑15份；高分子量扩链相容剂：0.3‑0.6份；偶联剂：0.01‑0.1份；助剂0.3‑0.5份；S2、将碳酸钙晶须用偶联剂处理，然后与PBAT混合后经双螺杆挤出机熔融共混、挤出造粒得到碳酸钙晶须母粒；S3、将步骤S2制备的碳酸钙晶须母粒与PLA、高分子量扩链相容剂、助剂经预混、熔融挤出、造粒得到高挺度高强韧可全降解PBAT/PLA树脂组合物。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤S2中，所述熔融共混采用的参数为：进料段温度为80‑120℃、塑化段温度为140‑160℃、均化段温度为160‑180℃，螺杆转速为300‑600rpm。
  10. 根据权利要求8所述的制备方法，其特征在于，步骤S3中，所述熔融共混采用的参数为：进料段温度为80‑120℃、塑化段温度为160‑180℃、均化段温度为180‑210℃，螺杆转速为300‑600rpm。
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CN113861636A (zh) * 2021-10-27 2021-12-31 佳易容聚合物(上海)有限公司 一种高挺度高强韧可全降解pbat/pla树脂组合物及其制备方法

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CN116875003B (zh) * 2023-08-08 2024-06-07 江西塑高新材料有限公司 一种吹膜级高填充降解塑料母粒及其制备方法

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