WO2020088215A1 - Pha-modified ppc/pbat biodegradable resin and preparation method therefor - Google Patents

Pha-modified ppc/pbat biodegradable resin and preparation method therefor Download PDF

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WO2020088215A1
WO2020088215A1 PCT/CN2019/110724 CN2019110724W WO2020088215A1 WO 2020088215 A1 WO2020088215 A1 WO 2020088215A1 CN 2019110724 W CN2019110724 W CN 2019110724W WO 2020088215 A1 WO2020088215 A1 WO 2020088215A1
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pha
ppc
pbat
biodegradable resin
parts
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PCT/CN2019/110724
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Chinese (zh)
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王庭慰
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南京五瑞生物降解新材料研究院有限公司
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Publication of WO2020088215A1 publication Critical patent/WO2020088215A1/en

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    • 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
    • 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 relates to a PHA modified PPC / PBAT biodegradable resin and a preparation method thereof, belonging to the field of biodegradable plastics.
  • Polypropylene carbonate also known as polymethyl ethylene carbonate, is a fully degradable environmentally friendly plastic synthesized from carbon dioxide and propylene oxide.
  • PBAT is a copolymer of butanediol adipate and butylene terephthalate, which has the characteristics of PBA and PBT, and has both good ductility and elongation at break, as well as good heat resistance And impact performance; in addition, it also has excellent biodegradability, is currently very active in the research of biodegradable plastics and one of the best degradable materials in the market.
  • Blending PPC and PBAT can be used to prepare biodegradable membrane products.
  • PHA Polyhydroxyalkanoates
  • the purpose of the present invention is to provide a PHA-modified PPC / PBAT biodegradable resin, which can greatly improve the mechanical properties of the resin.
  • a PHA-modified PPC / PBAT biodegradable resin prepared from the following parts by weight of raw materials:
  • it is prepared from the following parts by weight of raw materials: 30 parts PPC, 50 parts PBAT, and 20 parts PHA.
  • the PPC is a product of Henan Tianguan Technology Co., Ltd., with a density of 1.2 g / cm 3 , M I : 4-6 g / 10 min, and a melt index of 190 ° C / 2.16 kg softening point: 35 ° C.
  • the PBAT uses BASF's Ecoflex, which has a density of 1.25g / cm 3 , M I : 2-5g / 10min, and a melt index of 190 ° C / 2.16kg.
  • the PHA is a product of Beijing Blue Crystal Technology Co., Ltd., with a density of 1.25g / cm 3 M I : 6-8g / 10min, and a melt index of 190 ° C / 2.16kg.
  • the invention also discloses a preparation method of the PHA-modified PPC / PBAT biodegradable resin, and the steps include:
  • the extruder uses the ⁇ 75 co-rotating 48: 1 model produced by Nanjing Coperion. Extrusion conditions °C: 100 ⁇ 130 °C, r: 200r / min, zone 8-11 is equipped with two vacuum ports. When the die is extruded, the bar is drawn and sent to the pelletizer through air cooling for pelletizing.
  • B Mix the mixture made by A with PBAT at a ratio of 1: 1 through a mixer and send it to a twin-screw extruder for granulation.
  • the extruder is the same as A.
  • Extrusion conditions °C 120-150 °C, r : 250r / min, zone 8-11 is equipped with two vacuum ports. When the die is extruded, the draw bar is transferred to the pelletizer through air cooling for pelletizing.
  • PHA, PPC, and PBAT are all aliphatic resins. They are all biodegradable raw materials, and each has obvious characteristics.
  • the PPC used in the present invention is produced by fermentation of raw materials used for the production of carbon dioxide during wine making.
  • PHA and PPC are dry mixed according to a certain ratio and extruded into a mixed resin, thereby broadening the crystallization temperature range and increasing the glass transition temperature (Tg). Due to the high ductility of PPC, the mixed resin solves the fragility of PHA, and the impact resistance and toughness are greatly improved.
  • Tg glass transition temperature Due to the high ductility of PPC, the mixed resin solves the fragility of PHA, and the impact resistance and toughness are greatly improved.
  • the test data shows that when the mass fraction of PPC reaches 60%, the weak strain of PHA can be increased by 200%. After blending and granulating the mixture with PBAT, the resulting resin has more comprehensive mechanical properties, and is especially suitable for film products. It can be used
  • the PHA-modified PPC / PBAT biodegradable resin is prepared from the following parts by weight of raw materials (for modified material ratio or material content in the product film):
  • the resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
  • the PHA-modified PPC / PBAT biodegradable resin is prepared from the following parts by weight of raw materials (for modified material ratio or material content in the product film):
  • the resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
  • the PHA-modified PPC / PBAT biodegradable resin is prepared from the following parts by weight of raw materials (for modified material ratio or material content in the product film):
  • the resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
  • PPC / PBAT biodegradable resin prepared from the following parts by weight of raw materials:
  • the resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.

Abstract

A PHA-modified PPC/PBAT biodegradable resin, prepared by the following raw materials in parts by weight: PPC: 20-40 parts; PBAT: 30-50 parts; and PHA 10-30 parts. Also disclosed is a preparation method for the PHA-modified PPC/PBAT biodegradable resin. The PHA, PPC, and PBAT are all aliphatic resins, are biodegradable raw materials, and are respectively well-characterized. The PPC is prepared by polymerizing carbon dioxide generated by the fermentation of raw materials during brewing. The PHA and PPC are blended according to a given ratio, and are extruded to form a blend resin, such that the range of crystallization temperature is widened and the glass transition temperature (Tg) is increased. Due to the high ductility of the PPC, the blend resin resolves the problem of the frangibility of the PHA and therefore has significantly improved impact resistance and toughness. Detection data indicates that: when the mass fraction of the PPC reaches 60%, the weak adaptability of the PHA can be improved by 200%; and after the mixture is blended with PBAT for granulation, the obtained resin has comprehensive mechanical properties and is particularly suitable for the preparation of thin-film products.

Description

PHA改性的PPC/PBAT可生物降解树脂及其制备方法PHA modified PPC / PBAT biodegradable resin and preparation method thereof 技术领域Technical field
本发明涉及一种PHA改性的PPC/PBAT可生物降解树脂及其制备方法，属于可生物降解塑料领域。The invention relates to a PHA modified PPC / PBAT biodegradable resin and a preparation method thereof, belonging to the field of biodegradable plastics.
背景技术Background technique
聚碳酸亚丙酯(PPC)，又称为聚甲基乙撑碳酸酯，是以二氧化碳和环氧丙烷为原料合成的一种完全可降解的环保型塑料。Polypropylene carbonate (PPC), also known as polymethyl ethylene carbonate, is a fully degradable environmentally friendly plastic synthesized from carbon dioxide and propylene oxide.
PBAT是己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物，兼具PBA和PBT的特性，既有较好的延展性和断裂伸长率，也有较好的耐热性和冲击性能；此外，还具有优良的生物降解性，是目前生物降解塑料研究中非常活跃和市场应用最好降解材料之一。PBAT is a copolymer of butanediol adipate and butylene terephthalate, which has the characteristics of PBA and PBT, and has both good ductility and elongation at break, as well as good heat resistance And impact performance; in addition, it also has excellent biodegradability, is currently very active in the research of biodegradable plastics and one of the best degradable materials in the market.
将PPC和PBAT共混，可用于制备生物可降解的膜类制品。Blending PPC and PBAT can be used to prepare biodegradable membrane products.
聚羟基脂肪酸酯(polyhydroxyalkanoates,PHA)，是很多微生物合成的一种细胞内聚酯，是一种天然的高分子生物降解材料。它具有很好的生物多样性，尤其是生物相容性，对PPC和PBAT的共混起到增容改性作用。Polyhydroxyalkanoates (PHA) is an intracellular polyester synthesized by many microorganisms and a natural polymer biodegradable material. It has good biodiversity, especially biocompatibility, and it has compatibilizing and modifying effects on the blending of PPC and PBAT.
发明内容Summary of the invention
本发明的目的在于提供一种PHA改性的PPC/PBAT可生物降解树脂，可大幅提高树脂的力学性能。The purpose of the present invention is to provide a PHA-modified PPC / PBAT biodegradable resin, which can greatly improve the mechanical properties of the resin.
本发明的目的通过以下技术方案实现：The object of the present invention is achieved by the following technical solutions:
一种PHA改性的PPC/PBAT可生物降解树脂，由以下重量份的原料制备而成：A PHA-modified PPC / PBAT biodegradable resin, prepared from the following parts by weight of raw materials:
PPC   30份PPC 30 copies
PBAT  50份PBAT 50 copies
PHA   20份。20 copies of PHA.
优选的，由以下重量份的原料制备而成：PPC 30份、PBAT 50份、PHA 20份。Preferably, it is prepared from the following parts by weight of raw materials: 30 parts PPC, 50 parts PBAT, and 20 parts PHA.
优选的，所述PPC采用河南天冠科技有限公司产品，其密度1.2g/cm 3， M I:4-6g/10min，融熔指数190℃/2.16kg软化点：35℃。 Preferably, the PPC is a product of Henan Tianguan Technology Co., Ltd., with a density of 1.2 g / cm 3 , M I : 4-6 g / 10 min, and a melt index of 190 ° C / 2.16 kg softening point: 35 ° C.
优选的，所述PBAT采用BASF的Ecoflex,其密度1.25g/cm 3，M I:2-5g/10min，融熔指数190℃/2.16kg。 Preferably, the PBAT uses BASF's Ecoflex, which has a density of 1.25g / cm 3 , M I : 2-5g / 10min, and a melt index of 190 ° C / 2.16kg.
优选的，所述PHA采用北京蓝晶科技有限公司产品，密度1.25g/cm 3M I:6-8g/10min，融熔指数190℃/2.16kg。 Preferably, the PHA is a product of Beijing Blue Crystal Technology Co., Ltd., with a density of 1.25g / cm 3 M I : 6-8g / 10min, and a melt index of 190 ° C / 2.16kg.
本发明还公开了上述PHA改性的PPC/PBAT可生物降解树脂的制备方法，其步骤包括：The invention also discloses a preparation method of the PHA-modified PPC / PBAT biodegradable resin, and the steps include:
A、先将PHA与PPC按6:4经混料机混合后进入双螺杆挤压机造粒，挤压机选用南京科倍隆生产的Φ75同向48:1机型，挤压条件℃：100～130℃，r:200r/min,8-11区装有两真空口，挤压模口时拉条后经风冷送至切粒机切粒。A. Mix PHA and PPC at 6: 4 with a mixer and enter into a twin-screw extruder for granulation. The extruder uses the Φ75 co-rotating 48: 1 model produced by Nanjing Coperion. Extrusion conditions ℃: 100 ～ 130 ℃, r: 200r / min, zone 8-11 is equipped with two vacuum ports. When the die is extruded, the bar is drawn and sent to the pelletizer through air cooling for pelletizing.
B、再将A所造的混合料与PBAT按1:1比例经混料机混合后送入双螺杆挤压机造粒，挤压机同A，挤压条件：℃120-150℃，r:250r/min，8-11区装有两真空口，挤压模口时拉条经风冷传送到切粒机切粒。B. Mix the mixture made by A with PBAT at a ratio of 1: 1 through a mixer and send it to a twin-screw extruder for granulation. The extruder is the same as A. Extrusion conditions: ℃ 120-150 ℃, r : 250r / min, zone 8-11 is equipped with two vacuum ports. When the die is extruded, the draw bar is transferred to the pelletizer through air cooling for pelletizing.
PHA、PPC、PBAT均属于脂肪族树脂，都是可生物降解原料，又各自特点明显。本发明用的PPC是用造酒时原料发酵产生二氧化碳聚合而成，本发明先将PHA与PPC按一定比例干混，挤压加工成混合树脂，从而拓宽了结晶温度范围，提高了其玻璃转化温度(Tg)。由于PPC的高延展性，使得混合树脂解决了PHA的易碎性，抗冲击性能和韧性大幅提高，检测数据表明：当PPC的质量分数达到60％时，PHA的弱应变性可提高200％，将混合物与PBAT共混造粒后，所得树脂其力学性能较全面，尤其适合做薄膜类制品，可制厚度0.01mm的极薄薄膜。PHA, PPC, and PBAT are all aliphatic resins. They are all biodegradable raw materials, and each has obvious characteristics. The PPC used in the present invention is produced by fermentation of raw materials used for the production of carbon dioxide during wine making. In the present invention, PHA and PPC are dry mixed according to a certain ratio and extruded into a mixed resin, thereby broadening the crystallization temperature range and increasing the glass transition temperature (Tg). Due to the high ductility of PPC, the mixed resin solves the fragility of PHA, and the impact resistance and toughness are greatly improved. The test data shows that when the mass fraction of PPC reaches 60%, the weak strain of PHA can be increased by 200%. After blending and granulating the mixture with PBAT, the resulting resin has more comprehensive mechanical properties, and is especially suitable for film products. It can be used to make very thin films with a thickness of 0.01mm.
具体实施方式detailed description
实施例1Example 1
本PHA改性的PPC/PBAT可生物降解树脂，由以下重量份的原料制备而成(为改性后材料配比或制品膜中材料含量)：The PHA-modified PPC / PBAT biodegradable resin is prepared from the following parts by weight of raw materials (for modified material ratio or material content in the product film):
PPC   30份PPC 30 copies
PBAT  50份PBAT 50 copies
PHA   20份。20 copies of PHA.
树脂经吹膜机成膜，膜厚度为0.03mm，按GB/T1040.3检测其性能，性能参数见表1。The resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
实施例2Example 2
本PHA改性的PPC/PBAT可生物降解树脂，由以下重量份的原料制备而成(为改性后材料配比或制品膜中材料含量)：The PHA-modified PPC / PBAT biodegradable resin is prepared from the following parts by weight of raw materials (for modified material ratio or material content in the product film):
PPC   20份PPC 20 copies
PBAT  50份PBAT 50 copies
PHA   30份。30 copies of PHA.
树脂经吹膜机成膜，膜厚度为0.03mm，按GB/T1040.3检测其性能，性能参数见表1。The resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
实施例3Example 3
本PHA改性的PPC/PBAT可生物降解树脂，由以下重量份的原料制备而成(为改性后材料配比或制品膜中材料含量)：The PHA-modified PPC / PBAT biodegradable resin is prepared from the following parts by weight of raw materials (for modified material ratio or material content in the product film):
PPC   40份PPC 40 copies
PBAT  50份PBAT 50 copies
PHA   10份。10 copies of PHA.
树脂经吹膜机成膜，膜厚度为0.03mm，按GB/T1040.3检测其性能，性能参数见表1。The resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
对比例1Comparative Example 1
PPC/PBAT可生物降解树脂，由以下重量份的原料制备而成：PPC / PBAT biodegradable resin, prepared from the following parts by weight of raw materials:
PPC   30份PPC 30 copies
PBAT  70份70 copies of PBAT
树脂经吹膜机成膜，膜厚度为0.03mm，按GB/T1040.3检测其性能，性能参数见表1。The resin is formed into a film by a blown film machine with a film thickness of 0.03mm. Its performance is tested according to GB / T1040.3, and the performance parameters are shown in Table 1.
表1实施例1-3及对比例1的树脂性能检测数据Table 1 Example 1-3 and Comparative Example 1 resin performance test data
Figure PCTCN2019110724-appb-000001
Figure PCTCN2019110724-appb-000001
Figure PCTCN2019110724-appb-000002
Figure PCTCN2019110724-appb-000002
从表1可以看出，PHA对PPC和PBAT共混时改善其相容性，提高共混材料力学性能，尤其是适合做薄膜类的产品各方面性能有很大提升。It can be seen from Table 1 that PHA improves the compatibility of PPC and PBAT when blended, and improves the mechanical properties of the blended materials, especially the performance of all aspects of products suitable for making films has been greatly improved.

Claims (6)

  1. 一种PHA改性的PPC/PBAT可生物降解树脂，由以下重量份的原料制备而成：A PHA-modified PPC / PBAT biodegradable resin, prepared from the following parts by weight of raw materials:
    PPC   20-40份PPC 20-40 copies
    PBAT  30-50份PBAT 30-50 copies
    PHA   10-30份。10-30 copies of PHA.
  2. 根据权利要求1所述的PHA改性的PPC/PBAT可生物降解树脂，其特征在于：由以下重量份的原料制备而成：PPC 30份、PBAT 50份、PHA 20份。The PHA-modified PPC / PBAT biodegradable resin according to claim 1, characterized in that it is prepared from the following parts by weight of raw materials: PPC 30 parts, PBAT 50 parts, PHA 20 parts.
  3. 根据权利要求2所述的PHA改性的PPC/PBAT可生物降解树脂，其特征在于：所述PPC密度1.2g/cm 3M I:4-6g/10min，融熔指数190℃/2.16kg，软化点：35℃。 The PHA-modified PPC / PBAT biodegradable resin according to claim 2, wherein the density of the PPC is 1.2g / cm 3 M I : 4-6g / 10min, and the melt index is 190 ° C / 2.16kg, Softening point: 35 ° C.
  4. 根据权利要求3所述的PHA改性的PPC/PBAT可生物降解树脂，其特征在于：所述PBAT密度1.25g/cm 3M I:2-5g/10min，融熔指数190℃/2.16kg。 The PHA-modified PPC / PBAT biodegradable resin according to claim 3, wherein the density of the PBAT is 1.25g / cm 3 M I : 2-5g / 10min, and the melt index is 190 ° C / 2.16kg.
  5. 根据权利要求4所述的PHA改性的PPC/PBAT可生物降解树脂，其特征在于：所述PHA密度1.25g/cm 3M I:6-8g/10min，融熔指数190℃/2.16kg。 The PHA-modified PPC / PBAT biodegradable resin according to claim 4, wherein the density of the PHA is 1.25g / cm 3 M I : 6-8g / 10min, and the melt index is 190 ° C / 2.16kg.
  6. 一种PHA改性的PPC/PBAT可生物降解树脂的制备方法，其步骤包括：A preparation method of PHA modified PPC / PBAT biodegradable resin, the steps include:
    A、先将PHA与PPC按6:4经混料机混合后进入双螺杆挤压机造粒，挤压机选用南京科倍隆生产的Φ75同向48:1机型，挤压条件℃：100～130℃，r:200r/min,8-11区装有两真空口，挤压模口时拉条后经风冷送至切粒机切粒。A. Mix PHA and PPC at 6: 4 with a mixer and enter into a twin-screw extruder for granulation. The extruder uses the Φ75 co-rotating 48: 1 model produced by Nanjing Coperion. The extrusion conditions are: 100 ～ 130 ℃, r: 200r / min, zone 8-11 is equipped with two vacuum ports. When the die is extruded, the bar is drawn and sent to the pelletizer through air cooling for pelletizing.
    B、再将A所造的混合料与PBAT按1:1比例经混料机混合后送入双螺杆挤压机造粒，挤压机同A，挤压条件：℃120-150℃，r:250r/min，8-11区装有两真空口，挤压模口时拉条经风冷传送到切粒机切粒。B. Mix the mixture made by A with PBAT at a ratio of 1: 1 through a mixer and send it to a twin-screw extruder for granulation. The extruder is the same as A. Extrusion conditions: 120-150 ℃ : 250r / min, zone 8-11 is equipped with two vacuum ports. When the die is extruded, the draw bar is transferred to the pelletizer through air cooling for pelletizing.
PCT/CN2019/110724 2018-11-01 2019-10-12 Pha-modified ppc/pbat biodegradable resin and preparation method therefor WO2020088215A1 (en)

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CN111574815A (en) * 2020-05-25 2020-08-25 南京瑞鑫环保科技有限公司 PHA (polyhydroxyalkanoate) -modified PPC (polypropylene)/TPS (thermoplastic polystyrene) biodegradable resin and preparation method thereof

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