WO2020134850A1 - Degradable bio-based masterbatch and preparation method therefor and application thereof, - Google Patents
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- C08J5/18—Manufacture of films or sheets
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- 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
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Definitions
- the invention relates to a degradable bio-based masterbatch, a preparation method and application thereof, and belongs to the field of polymer material modification.
- the particle diameter D 50 of the bio-filler is 0.8-6 ⁇ m; more preferably, the particle diameter D 50 of the bio-filler is 1-5 ⁇ m.
- the biological filler is derived from at least one of animal bones, eggshells, coral, shells, oysters, and nacre.
- the puncture energy is related to the modulus of elasticity and the aliphatic-aromatic copolyester with excellent industrial processability.
- the source of monomer synthesis limits the application of these polyesters, for example, which significantly reduces the possibility of consuming resources (raw materials) from non-renewable carbon.
- the aliphatic polyester, aliphatic-aromatic copolyester used in the present invention and polymers of natural origin are all known on the market, and the resulting biodegradable polyester composition is obtained according to the specific ratio combination described in the present invention It is biodegradable and has excellent mechanical properties. And, due to its excellent mechanical properties and biodegradability, the composition is particularly suitable for manufacturing films and film bags, such as food packaging films and bags for collecting organic waste.
- the inorganic filler is selected from talc, montmorillonite, kaolin, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicate, At least one of mica, glass fiber, mineral fiber;
- the bio-filler is derived from natural biomass resources, and the particle size D 50 of the bio-filler is 0.5-8 ⁇ m; the biodegradable polyester and the bio-filler The weight ratio is 20-40: 60-80; in the degradable bio-based masterbatch, 60%-100% of the total carbon weight is derived from bio-based carbon.
- the biodegradable polyester compositions of the test groups 1 to 7 and the control groups 1 to 4 all of them are the same except that the melt index of the biodegradable polyester is different.
- This effect example also tested the tear strength of the biodegradable polyester composition of the test group 1-7 and the control group 1-4 according to the test method of the performance of the biodegradable polyester composition of Examples 1-7, and the test result As shown in Table 5.
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Abstract
A degradable bio-based masterbatch and a preparation method therefor and an application thereof, which relate to the field of polymer material modification. The biodegradable bio-based masterbatch comprises biodegradable polyester and bio-filler. The melt flow index of the biodegradable polyester is 8-80g/10min, and the melt flow index of the biodegradable polyester is measured with 2.16kg weight at 190°C according to ASTM D1238. The bio-filler is obtained from natural biomass resources, and the particle diameter D50 of the bio-filler is 0.5-8 μm; the weight ratio of the biodegradable polyester to the bio-filler is (20-40): (60-80); in the biodegradable bio-based masterbatch, 60% -100% of the total carbon weight is derived from bio-based carbon. The biodegradable bio-based masterbatch is prepared by using the bio-filler as a raw material. Meanwhile, a biodegradable polyester composition is prepared by using the biodegradable bio-based masterbatch as a raw material, and the biodegradable polyester composition is good in biodegradability and has excellent mechanical properties.
Description
本发明涉及一种可降解生物基母粒及其制备方法与应用,属于高分子材料改性领域。The invention relates to a degradable bio-based masterbatch, a preparation method and application thereof, and belongs to the field of polymer material modification.
可生物降解聚酯是以生物资源为原料的一类高分子材料。相对于以石化资源为原料的石油基高分子,可生物降解聚酯能够在生物或生物化学作用过程中或生物环境中发生降解,是目前生物降解塑料研究中非常活跃和市场应用最好的降解材料之一。Biodegradable polyester is a type of polymer material with biological resources as raw materials. Compared with petroleum-based polymers that use petrochemical resources as raw materials, biodegradable polyesters can degrade in the course of biological or biochemical interactions or biological environments, and are currently very active in biodegradable plastics research and the best market application of degradation One of the materials.
中国专利CN 102597105A报道了以脂族二酸如己二酸、芳族二酸如对苯二甲酸和脂族二醇为原料获得的生物可降解的脂族-芳族聚酯是文献中和市场上已知的。这些聚合物的构成单体不可再生,这样不管它们的生物降解能力如何,它们对环境都会造成显著影响。Chinese patent CN 102597105A reported that the biodegradable aliphatic-aromatic polyesters obtained from aliphatic diacids such as adipic acid, aromatic diacids such as terephthalic acid and aliphatic diols are neutralized in the literature and market Known. The constituent monomers of these polymers are not renewable, so that regardless of their biodegradability, they will have a significant impact on the environment.
此外,目前市面上出售的这类聚酯具有小于48摩尔%的芳族酸的量,因为在该阈值以上,这些聚酯的生物降解百分比显著降低。这明显限制了聚酯与可堆肥性相关联的高机械性质的用途,例如用于制造收集有机废物的袋子。In addition, such polyesters currently on the market have an amount of aromatic acid of less than 48 mol%, because above this threshold, the percentage of biodegradation of these polyesters is significantly reduced. This clearly limits the use of polyester with high mechanical properties associated with compostability, such as for the manufacture of bags for collecting organic waste.
堆肥是模仿自然界中使有机物回到生命循环的过程从而以受控和加速形式再现这些过程的工业方法。在自然界中,已产生的并不再有生命的有机物(干树叶、树枝、动物残骸等)被土壤中存在的微生物分解,这使其回到自然循环中。留下的较难降解的组分构成腐殖质,因此考虑到其缓慢但不断释放营养元素(氮、磷、钾等)以确保土地的持续肥力的能力,这些腐殖质是植物的重要食物提供者。因此工业堆肥是为了降低获得一类腐殖质,即堆肥所必需的时间和相对于自然获得的产物改进最终产物的品质而提供用于自然界中自发发生的微生物活动的合理管理的结构的方法。Composting is an industrial method that mimics the process of returning organic matter to life cycle in nature to reproduce these processes in a controlled and accelerated form. In nature, organic matter that has been produced and no longer lives (dry leaves, branches, animal debris, etc.) is decomposed by microorganisms present in the soil, which returns it to the natural cycle. The remaining hard-to-degrade components constitute humus, so considering its ability to slowly but continuously release nutrients (nitrogen, phosphorus, potassium, etc.) to ensure the continued fertility of the land, these humus are important food providers for plants. Industrial composting is therefore a method of providing a structure for the rational management of spontaneously occurring microbial activities in nature in order to reduce the time required to obtain a type of humus, ie composting, and to improve the quality of the final product relative to naturally obtained products.
类似地,家庭堆肥是将来自厨房和花园食物碎屑的有机物质堆积在堆肥箱中或在地上挖掘出的洞中,并在比工业堆肥温和的条件下需氧降解的方法。特别地,家庭堆肥法中的需氧降解在室温(通常10至45℃)下进行。Similarly, household composting is a method of accumulating organic matter from kitchen and garden food debris in a compost bin or a hole dug in the ground, and aerobic degradation under milder conditions than industrial composting. In particular, the aerobic degradation in the household composting process takes place at room temperature (typically 10 to 45°C).
然而,现有技术中,生物降解性能较佳且能用于堆肥的生物可降解聚酯较少。However, in the prior art, the biodegradability is better and less biodegradable polyester can be used for composting.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足之处而提供一种可降解生物基母粒及其制备方法与应用,含有该母粒的生物可降解聚酯组合物具有优异的生物降解性能和撕裂强度。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a degradable bio-based masterbatch and its preparation method and application, the biodegradable polyester composition containing the masterbatch has excellent biodegradability and tear Crack strength.
为实现上述目的,本发明采取的技术方案为:一种可降解生物基母粒,其包括生物降解聚酯和生物填料,所述生物降解聚酯的熔融指数为8-80g/10min,所述生物降解聚酯的熔融指数是根据ASTM D1238使用2.16kg重量并在190℃的温度测量;所述生物填料来自于天然的生物质资源,所述生物填料的粒径D
50为0.5~8μm;所述生物降解聚酯和生物填料的重量比为20-40:60-80;
In order to achieve the above object, the technical solution adopted by the present invention is: a degradable bio-based masterbatch, which includes a biodegradable polyester and a bio-filler, the melt index of the biodegradable polyester is 8-80g/10min, The melt index of biodegradable polyester is measured according to ASTM D1238 using a weight of 2.16 kg and a temperature of 190°C; the biological filler is derived from natural biomass resources, and the particle diameter D 50 of the biological filler is 0.5-8 μm; The weight ratio of the biodegradable polyester and the bio-filler is 20-40: 60-80;
所述可降解生物基母粒中,占总碳重量60%-100%的碳来源于生物基的碳。In the biodegradable bio-based masterbatch, 60%-100% of the total carbon weight is derived from bio-based carbon.
本发明选用合适粒径的生物填料制备母粒,可以制备高填充(≥65%)的生物基填充母粒,在降低母粒成本的基础上,保持母粒的使用性能,该母粒与其他降解材料形成组合物,具有较好的降解性能。The invention selects biological filler with suitable particle size to prepare masterbatch, which can prepare biofilled masterbatch with high filling (≥65%). On the basis of reducing the cost of masterbatch, the performance of masterbatch is maintained. The degradable material forms a composition and has better degradation performance.
需说明的是,上述生物填料,其粒径越大越不易团聚,有利于在生物降解聚酯中的分散;但当生物填料的粒径D
50超过8μm时,由于生物填料的颗粒过大,它会影响后续薄膜等产品的表面特性(粗糙度),进而影响了产品的性能。
It should be noted that the above-mentioned bio-fillers, the larger the particle size, the less likely to agglomerate, which is beneficial to the dispersion in biodegradable polyester; but when the particle size D 50 of the bio-filler exceeds 8 μm, because the particles of the bio-filler are too large, it Will affect the surface characteristics (roughness) of subsequent films and other products, which in turn affects the performance of the product.
作为本发明所述可降解生物基母粒的优选实施方式,所述生物降解聚酯和生物填料的重量比为25-35:65-75。研究表明,生物降解聚酯与生物填料的重量比会影响含有所述可降解生物基母粒的聚酯组合物的生物降解性能和撕裂强度,在该优选重量比范围内,最终所得聚酯组合物的生物降解性能和撕裂强度均更优异。As a preferred embodiment of the biodegradable bio-based masterbatch of the present invention, the weight ratio of the biodegradable polyester and bio-filler is 25-35:65-75. Studies have shown that the weight ratio of biodegradable polyester to biofiller will affect the biodegradability and tear strength of the polyester composition containing the degradable bio-based masterbatch. Within this preferred weight ratio, the resulting polyester The biodegradability and tear strength of the composition are more excellent.
作为本发明所述可降解生物基母粒的优选实施方式,所述生物降解聚酯的熔融指数为10-60g/10min;更优选地,所述生物降解聚酯的熔融指数为15-45g/10min。含有本发明可降解生物基母粒的聚酯组合物的生物降解性能和撕裂强度亦会受到母粒中生物降解聚酯熔融指数的影响,当所述生物降解聚酯的熔融指数为10-60g/10min时,所得聚酯组合物的生物降解性能和撕裂强度均更好,尤其是当其熔融指数为15-45g/10min时,所得聚酯组合物的生物降解性能和撕裂强度最佳。As a preferred embodiment of the degradable bio-based masterbatch of the present invention, the melt index of the biodegradable polyester is 10-60g/10min; more preferably, the melt index of the biodegradable polyester is 15-45g/ 10min. The biodegradability and tear strength of the polyester composition containing the degradable bio-based masterbatch of the present invention are also affected by the melt index of the biodegradable polyester in the masterbatch, when the melt index of the biodegradable polyester is 10- At 60g/10min, the biodegradability and tear strength of the obtained polyester composition are better, especially when the melt index is 15-45g/10min, the biodegradability and tear strength of the obtained polyester composition are the most good.
作为本发明所述可降解生物基母粒的优选实施方式,所述生物填料的粒径D
50为0.8~6μm;更优选地,所述生物填料的粒径D
50为1~5μm。
As a preferred embodiment of the biodegradable bio-based masterbatch of the present invention, the particle diameter D 50 of the bio-filler is 0.8-6 μm; more preferably, the particle diameter D 50 of the bio-filler is 1-5 μm.
作为本发明所述可降解生物基母粒的优选实施方式,如下(a)~(b)中的至少一项:As a preferred embodiment of the degradable bio-based masterbatch of the present invention, at least one of the following (a) to (b):
(a)所述生物降解聚酯为聚乳酸、聚羟基烷酸酯(PHA)、聚琥珀酸丁二醇酯(PBS)、聚己二酸丁二醇酯共聚丁二酸丁二醇酯(PBSA)、聚己二酸-对苯二甲酸丁二醇酯(PBAT)、聚琥珀酸对苯二甲酸丁二醇酯(PBST)、聚癸二酸对苯二甲酸丁二醇酯(PBSeT)中的至少一种;(a) The biodegradable polyester is polylactic acid, polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene adipate copolybutylene succinate ( PBSA), polybutylene terephthalate (PBAT), polybutylene terephthalate succinate (PBST), polybutylene terephthalate sebacate (PBSeT) At least one of
(b)所述生物填料来自动物骨头、蛋壳类、珊瑚、贝壳、牡蛎、珍珠层中的至少一种。(b) The biological filler is derived from at least one of animal bones, eggshells, coral, shells, oysters, and nacre.
另外,本发明还提供了上述可降解生物基母粒的制备方法,其包括以下步骤:将可降解生物基母粒中的组分按比例混匀后投入双螺杆挤出机中,于140-220℃挤出、造粒,得到所述可降解生物基母粒。In addition, the present invention also provides a method for preparing the above-mentioned degradable bio-based masterbatch, which includes the following steps: the components in the degradable bio-based masterbatch are mixed in proportion and then put into a twin-screw extruder at 140- Extrusion and granulation at 220°C to obtain the degradable bio-based masterbatch.
另外,本发明还提供了一种生物可降解聚酯组合物,其包括下述重量份的组分:脂肪族聚酯或脂肪族-芳香族共聚酯50~90份,天然来源的聚合物0~35份,上述可降解生物基母粒5~40份,无机填料0~5份,助剂0~4份。In addition, the present invention also provides a biodegradable polyester composition, which includes the following parts by weight of components: aliphatic polyester or aliphatic-aromatic copolyester 50 to 90 parts, a polymer of natural origin 0 to 35 parts, 5 to 40 parts of the above degradable bio-based masterbatch, 0 to 5 parts of inorganic filler, and 0 to 4 parts of auxiliary.
上述生物可降解聚酯组合物中,脂肪族-芳香族共聚酯中芳香族单体如对苯二甲酸的存在与获得具有足够高的熔融温度、充足结晶速率、相关机械性质如极限强度、刺穿能和弹性模量、以及优异的工业可加工特性的脂肪族-芳香族共聚酯有关。但是,不管生物降解能力如何,单体的合成来源限制这些聚酯的应 用,例如会显著降低来自不可再生碳的资源(原料)的消耗的可能性。In the above-mentioned biodegradable polyester composition, the presence of aromatic monomers such as terephthalic acid in the aliphatic-aromatic copolyester and obtaining a sufficiently high melting temperature, sufficient crystallization rate, related mechanical properties such as ultimate strength, The puncture energy is related to the modulus of elasticity and the aliphatic-aromatic copolyester with excellent industrial processability. However, regardless of the biodegradability, the source of monomer synthesis limits the application of these polyesters, for example, which significantly reduces the possibility of consuming resources (raw materials) from non-renewable carbon.
另一方面,合成来源的脂肪族单体如己二酸的高含量尽管对实现合适水平的生物可降解性而言是合意的,但这样不仅提高这些聚酯的环境影响,还使其机械性质变差。此外,脂肪族单体的高含量显著降低聚酯的熔融温度和降低其在高温下的结晶速率,由此要求在聚酯的工业加工过程中使用更大千卡数和更长冷却时间。这些限制对这些聚酯的工业可加工性具有不利影响。On the other hand, although the high content of synthetically derived aliphatic monomers such as adipic acid is desirable for achieving a suitable level of biodegradability, this not only improves the environmental impact of these polyesters, but also makes them mechanical Get worse. In addition, the high content of aliphatic monomers significantly reduces the melting temperature of the polyester and reduces its crystallization rate at high temperatures, thereby requiring the use of larger kcal and longer cooling times in the industrial processing of polyesters. These restrictions have an adverse effect on the industrial processability of these polyesters.
填料是塑料常用的添加剂之一,添加填料可以使聚酯组合物保持较好的性能,但其添加量太大就会影响聚酯组合物的性能,且其过高的添加量是很难实现的。Filler is one of the commonly used additives in plastics. Adding filler can keep the polyester composition to maintain better performance, but too much addition will affect the performance of the polyester composition, and its excessive addition is difficult to achieve of.
本发明采用的脂肪族聚酯、脂肪族-芳香族共聚酯与天然来源的聚合物均是市面上已知的,按照本发明所述特定的配比组合,所得生物可降解聚酯组合物生物可降解性好且具有优异的机械性质。并且,由于其优异的机械性质和生物可降解性,所述组合物特别适用于制造薄膜和薄膜袋,例如:食品包装薄膜和收集有机废物的袋子。研究表明,采用本发明生物可降解聚酯组合物制备的12μm±1μm薄膜根据标准ASTM D-882/88测试的纵向撕裂强度≥1100mN,制备的12μm±1μm薄膜根据标准ASTM D-882/88测试的横向撕裂强度≥2800mN。The aliphatic polyester, aliphatic-aromatic copolyester used in the present invention and polymers of natural origin are all known on the market, and the resulting biodegradable polyester composition is obtained according to the specific ratio combination described in the present invention It is biodegradable and has excellent mechanical properties. And, due to its excellent mechanical properties and biodegradability, the composition is particularly suitable for manufacturing films and film bags, such as food packaging films and bags for collecting organic waste. The research shows that the 12μm±1μm film prepared by the biodegradable polyester composition of the present invention has a longitudinal tear strength ≥1100mN according to the standard ASTM D-882/88, and the prepared 12μm±1μm film is according to the standard ASTM D-882/88 Tested transverse tear strength ≥ 2800mN.
更为重要是,本发明生物可降解聚酯组合物根据意大利标准UNI 11355:2010是可家庭堆肥的。More importantly, the biodegradable polyester composition of the present invention is family compostable according to the Italian standard UNI 11355:2010.
作为本发明所述生物可降解聚酯组合物的优选实施方式,如下(Ⅰ)~(Ⅳ)中的至少一种:As a preferred embodiment of the biodegradable polyester composition of the present invention, at least one of the following (I) to (IV):
(Ⅰ)所述脂肪族聚酯为聚琥珀酸丁二醇酯(PBS)、聚己二酸丁二醇酯共聚丁二酸丁二醇酯(PBSA)中的至少一种,所述脂肪族-芳香族共聚酯为聚己二酸-对苯二甲酸丁二醇酯(PBAT)、聚琥珀酸对苯二甲酸丁二醇酯(PBST)、聚癸二酸对苯二甲酸丁二醇酯(PBSeT)中的至少一种;(I) The aliphatic polyester is at least one of polybutylene succinate (PBS) and polybutylene adipate co-polybutylene succinate (PBSA), the aliphatic -The aromatic copolyester is polybutylene adipate-butylene terephthalate (PBAT), polybutylene succinate terephthalate (PBST), polybutylene sebacate terephthalate At least one of esters (PBSeT);
(∏)所述天然来源的聚合物为淀粉、聚乳酸中的至少一种;(∏) The polymer of natural origin is at least one of starch and polylactic acid;
(Ⅲ)所述无机填料选自滑石粉、蒙脱土、高岭土、石墨、石膏、导电炭黑、氯化钙、氧化铁、白云石、二氧化硅、硅灰石、二氧化钛、硅酸盐、云母、 玻璃纤维、矿物纤维中的至少一种;(III) The inorganic filler is selected from talc, montmorillonite, kaolin, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicate, At least one of mica, glass fiber, mineral fiber;
(Ⅳ)所述助剂为增塑剂、脱模剂、表面活性剂、蜡、防静电剂、染料、UV吸收剂、UV稳定剂中的至少一种。(IV) The auxiliary agent is at least one of plasticizer, mold release agent, surfactant, wax, antistatic agent, dye, UV absorber, and UV stabilizer.
再者,本发明还提供了上述生物可降解聚酯组合物的制备方法,其包括以下步骤:将生物可降解聚酯中的组分按比例混匀后投入单螺杆吹膜机中,于120-180℃吹膜,或者混匀后投入挤出机中,于140-220℃挤出、造粒,得到所述生物可降解聚酯。Furthermore, the present invention also provides a method for preparing the above-mentioned biodegradable polyester composition, which includes the following steps: the components in the biodegradable polyester are mixed in proportion and then put into a single-screw film blowing machine at 120 -180°C blown film, or mixed and put into an extruder, extruded and granulated at 140-220°C to obtain the biodegradable polyester.
最后,本发明还提供了一种含有上述生物可降解聚酯组合物的薄膜或薄膜袋。本发明的生物可降解聚酯组合物可用于制备薄膜、薄膜袋或其他复合材料等,例如,其可用于制造(1)单-和双-取向膜,和与其它聚合材料多层层合的薄膜、(2)用于农业领域的薄膜、(3)用于食品、和用于包裹废物的贴附膜、(4)拌种设备、(5)胶合剂、(6)用于有机废物收集的袋子、(7)热成形单层和多层食品包装、(8)使用挤出涂布法获得的涂层、含纸、塑料、铝或金属化薄膜的层的多层层合材料、(9)用于制造通过烧结获得的零件的发泡或可发泡珠粒、(10)发泡和半发泡产品,包括使用预发泡粒子形成的泡沫块、(11)泡沫片和用于食品包装的由它们获得的容器、(12)水果和蔬菜容器、(13)含胶凝化、解体的和/或复合的淀粉、天然淀粉、面粉或植物或无机天然填料的复合材料、(14)纤维,其中芯由刚性聚合物构成;共混复合纤维,具有从圆形到多叶形的不同断面的纤维;-短纤维、经纺和无纺织物,用在卫生保健产品中和用在农业和服装领域中。Finally, the present invention also provides a film or film bag containing the above-mentioned biodegradable polyester composition. The biodegradable polyester composition of the present invention can be used to prepare films, film bags or other composite materials, etc. For example, it can be used to manufacture (1) single- and double-oriented films, and multilayer laminated with other polymeric materials Films, (2) Films used in the agricultural field, (3) Foods, and adhesive films used to wrap waste, (4) Seed dressing equipment, (5) Adhesives, (6) Organic waste collection Bags, (7) thermoformed single-layer and multi-layer food packaging, (8) coatings obtained by extrusion coating, multi-layer laminates containing layers of paper, plastic, aluminum or metalized films, ( 9) Foamed or expandable beads for manufacturing parts obtained by sintering, (10) Foamed and semi-foamed products, including foam blocks formed using pre-expanded particles, (11) Foam sheets and Food packaging containers obtained from them, (12) Fruit and vegetable containers, (13) Compound materials containing gelatinized, disintegrated and/or compound starch, natural starch, flour or plant or inorganic natural fillers, (14 ) Fibers, where the core is composed of rigid polymers; blended composite fibers, fibers with different cross sections from round to multi-lobed; short fibers, warp and non-woven fabrics, used in health care products and in In the field of agriculture and clothing.
与现有技术相比,本发明的有益效果为:本发明以生物填料为原料制得了可降解生物基母粒,同时,本发明以该可降解生物基母粒为原料制得了生物可降解聚酯组合物,该生物可降解聚酯组合物生物可降解性好且具有优异的机械性质。更为重要是,本发明生物可降解聚酯组合物根据意大利标准UNI11355:2010是可家庭堆肥的。Compared with the prior art, the beneficial effects of the present invention are: the present invention uses bio-fillers as raw materials to make biodegradable bio-based masterbatch, and at the same time, the present invention uses the biodegradable bio-based masterbatch as raw materials to make biodegradable polymer An ester composition. The biodegradable polyester composition has good biodegradability and excellent mechanical properties. More importantly, the biodegradable polyester composition of the present invention is family compostable according to the Italian standard UNI11355:2010.
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对 本发明作进一步说明。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described in combination with specific embodiments below.
下述实施例中,未作特别说明的物质均从市购得到。生物降解聚酯的熔融指数是根据ASTM D1238使用2.16kg重量并在190℃的温度测量,生物填料的粒径D
50参照GB/T 19077.1《粒度分析激光衍射法》方法测定。
In the following examples, all materials that are not specified are commercially available. The melt index of the biodegradable polyester is measured according to ASTM D1238 using a weight of 2.16 kg and a temperature of 190°C. The particle size D 50 of the biofiller is determined according to the method of GB/T 19077.1 "Particle size analysis laser diffraction method".
下述实施例中,PLA表示聚乳酸、PHA表示聚羟基烷酸酯、PBS表示聚琥珀酸丁二醇酯、PBSA表示聚己二酸丁二醇酯共聚丁二酸丁二醇酯、PBAT表示聚己二酸-对苯二甲酸丁二醇酯、PBST表示聚琥珀酸对苯二甲酸丁二醇酯、PBSeT表示聚癸二酸对苯二甲酸丁二醇酯。In the following examples, PLA represents polylactic acid, PHA represents polyhydroxyalkanoate, PBS represents polybutylene succinate, PBSA represents polybutylene adipate copolybutylene succinate, PBAT represents Poly adipate-butylene terephthalate, PBST means polybutylene terephthalate succinate, and PBSeT means polybutylene terephthalate sebacate.
实施例1~7Examples 1-7
实施例1~7所述可降解生物基母粒的组成组分如表1所示。实施例1~7可降解生物基母粒的制备方法为:将可降解生物基母粒中的组分按比例混匀后投入双螺杆挤出机中,于140-220℃挤出、造粒,得到所述可降解生物基母粒。The components of the degradable bio-based masterbatch described in Examples 1 to 7 are shown in Table 1. Examples 1 to 7 The preparation method of the biodegradable bio-based masterbatch is as follows: the components in the biodegradable bio-based masterbatch are mixed in proportion and then put into a twin-screw extruder, extruded and granulated at 140-220°C To obtain the degradable bio-based masterbatch.
实施例1~7生物可降解聚酯组合物的组成组分如表2所述,实施例1~7生物可降解聚酯组合物的制备方法为:将生物可降解聚酯中的组分按比例混匀后投入单螺杆吹膜机中,于120-180℃吹膜,或者混匀后投入挤出机中,于140-220℃挤出、造粒,得到所述生物可降解聚酯。The components of the biodegradable polyester compositions of Examples 1-7 are described in Table 2, and the preparation method of the biodegradable polyester compositions of Examples 1-7 is as follows: After mixing in proportion, it is put into a single-screw film blowing machine to blow the film at 120-180°C, or after mixing, it is put into an extruder, and is extruded and granulated at 140-220°C to obtain the biodegradable polyester.
同时,将实施例1~7生物可降解聚酯组合物分别制成12μm±1μm薄膜,根据标准ASTM D-882/88测试其纵向撕裂强度和横向撕裂强度,据标准ISO 16929(2013)测试其12周后的生物降解率,测试结果如表2所示。At the same time, the biodegradable polyester compositions of Examples 1-7 were made into 12μm±1μm films respectively, and their longitudinal tear strength and transverse tear strength were tested according to the standard ASTM D-882/88, according to the standard ISO 16929 (2013) The biodegradation rate after 12 weeks was tested, and the test results are shown in Table 2.
表1 实施例1~7可降解生物基母粒Table 1 Examples 1-7 Biodegradable Masterbatch
表2 实施例1~7生物可降解聚酯组合物Table 2 Examples 1-7 Biodegradable polyester composition
由表2可见,采用本发明可降解生物基母粒制得的生物可降解聚酯组合物具有优异的生物降解性能和撕裂强度。It can be seen from Table 2 that the biodegradable polyester composition prepared by using the degradable bio-based masterbatch of the present invention has excellent biodegradability and tear strength.
效果例1Effect example 1
本发明可降解生物基母粒中生物降解聚酯与生物填料的重量比会影响含有该母粒的生物可降解聚酯组合物的生物降解性能和撕裂强度。为了考察生物降解聚酯与生物填料的重量比对生物可降解聚酯组合物的生物降解性能和撕裂强度的影响,本效果例制备了下述试验组1~5和对照组1~4的生物可降解聚酯组合物。试验组1~5和对照组1~4的生物可降解聚酯组合物由下述重量份的组分组成:脂肪族聚酯或脂肪族-芳香族共聚酯50~90份,天然来源的聚合物0~35份,可降解生物基母粒5~40份,无机填料0~5份,助剂0~4份;所述可降解生物基母粒包括生物降解聚酯和生物填料,所述生物降解聚酯的熔融指数为8-80g/10min,所述生物降解聚酯的熔融指数是根据ASTM D1238使用2.16kg重量并在190℃的温度测量;所述生物填料来自于天然的生物质资源,所述生物填料的粒径D
50为0.5~8μm;所述生物降解聚酯和生物填料的重量比如下述表3所 示,所述可降解生物基母粒中,占总碳重量60%-100%的碳来源于生物基的碳。试验组1~5和对照组1~4的生物可降解聚酯组合物中,除生物降解聚酯和生物填料的重量比不同之外,其它全部相同。
The weight ratio of biodegradable polyester to biofill in the degradable bio-based masterbatch of the present invention will affect the biodegradability and tear strength of the biodegradable polyester composition containing the masterbatch. In order to investigate the effect of the weight ratio of biodegradable polyester to biofiller on the biodegradability and tear strength of the biodegradable polyester composition, this effect example prepared the following test groups 1 to 5 and control groups 1 to 4. Biodegradable polyester composition. The biodegradable polyester compositions of the test groups 1 to 5 and the control groups 1 to 4 are composed of the following parts by weight: aliphatic polyester or aliphatic-aromatic copolyester 50 to 90 parts, of natural origin 0 to 35 parts of polymer, 5 to 40 parts of biodegradable bio-based mother particles, 0 to 5 parts of inorganic filler, and 0 to 4 parts of additives; the degradable bio-based mother particles include biodegradable polyester and bio-fillers. The melt index of the biodegradable polyester is 8-80g/10min. The melt index of the biodegradable polyester is measured according to ASTM D1238 using a weight of 2.16kg and a temperature of 190°C; the bio-filler is derived from natural biomass Resources, the particle size D 50 of the bio-filler is 0.5-8 μm; the weight of the biodegradable polyester and bio-filler is shown in Table 3 below, and the biodegradable bio-based masterbatch accounts for 60% of the total carbon weight %-100% of carbon is derived from bio-based carbon. In the biodegradable polyester compositions of the test groups 1 to 5 and the control groups 1 to 4, all except the weight ratio of the biodegradable polyester and the biofiller are the same.
本效果例还按照实施例1~7生物可降解聚酯组合物性能的测试方法,测试了试验组1~5和对照组1~4的生物可降解聚酯组合物的生物降解率和撕裂强度,测试结果如表3所示。In this effect example, the biodegradable polyester composition of the test group 1 to 5 and the control group 1 to 4 were also tested for biodegradation rate and tearing according to the test methods for the performance of the biodegradable polyester composition in Examples 1 to 7. The strength and test results are shown in Table 3.
表3table 3
由表3可见,生物降解聚酯和生物填料的重量比在本发明范围内时,得到的生物可降解聚酯组合物的生物降解性能和撕裂强度均更好,尤其当生物降解聚酯和生物填料的重量比为25-35:65-75时,所得聚酯组合物的生物降解性能和撕裂强度均尤其优异。It can be seen from Table 3 that when the weight ratio of biodegradable polyester and biofiller is within the scope of the present invention, the biodegradable polyester composition obtained has better biodegradability and tear strength, especially when biodegradable polyester and When the weight ratio of the bio-filler is 25-35:65-75, the biodegradability and tear strength of the resulting polyester composition are particularly excellent.
效果例2Effect example 2
本发明可降解生物基母粒中生物降解聚酯的熔融指数会影响含有该母粒的 生物可降解聚酯组合物的生物降解性能和撕裂强度。为了考察生物降解聚酯的熔融指数对生物可降解聚酯组合物的生物降解性能和撕裂强度的影响,本效果例制备了下述试验组1~7和对照组1~4的生物可降解聚酯组合物。试验组1~7和对照组1~4的生物可降解聚酯组合物由下述重量份的组分组成:脂肪族聚酯或脂肪族-芳香族共聚酯50~90份,天然来源的聚合物0~35份,可降解生物基母粒5~40份,无机填料0~5份,助剂0~4份;所述可降解生物基母粒包括生物降解聚酯和生物填料,所述生物降解聚酯的熔融指数如表4所示,所述生物填料来自于天然的生物质资源,所述生物填料的粒径D
50为0.5~8μm;所述生物降解聚酯和生物填料的重量比为20-40:60-80;所述可降解生物基母粒中,占总碳重量60%-100%的碳来源于生物基的碳。试验组1~7和对照组1~4的生物可降解聚酯组合物中,除生物降解聚酯的熔融指数不同之外,其它全部相同。
The melt index of the biodegradable polyester in the degradable bio-based masterbatch of the present invention will affect the biodegradability and tear strength of the biodegradable polyester composition containing the masterbatch. In order to investigate the influence of the melt index of the biodegradable polyester on the biodegradable performance and tear strength of the biodegradable polyester composition, this effect example prepared the following biodegradable test groups 1-7 and control groups 1-4 Polyester composition. The biodegradable polyester composition of the test group 1-7 and the control group 1-4 is composed of the following parts by weight of components: aliphatic polyester or aliphatic-aromatic copolyester 50-90 parts, natural source 0 to 35 parts of polymer, 5 to 40 parts of biodegradable bio-based mother particles, 0 to 5 parts of inorganic filler, and 0 to 4 parts of additives; the degradable bio-based mother particles include biodegradable polyester and bio-fillers. The melt index of the biodegradable polyester is shown in Table 4. The bio-filler is derived from natural biomass resources, and the particle size D 50 of the bio-filler is 0.5-8 μm; the biodegradable polyester and the bio-filler The weight ratio is 20-40: 60-80; in the degradable bio-based masterbatch, 60%-100% of the total carbon weight is derived from bio-based carbon. In the biodegradable polyester compositions of the test groups 1 to 7 and the control groups 1 to 4, all of them are the same except that the melt index of the biodegradable polyester is different.
本效果例还按照实施例1~7生物可降解聚酯组合物性能的测试方法,测试了试验组1~7和对照组1~4的生物可降解聚酯组合物的生物降解率和撕裂强度,测试结果如表4所示。In this effect example, the biodegradable polyester composition in the test groups 1 to 7 and the control group 1 to 4 were also tested for biodegradation rate and tearing according to the test method for the performance of the biodegradable polyester composition in Examples 1 to 7. The strength and test results are shown in Table 4.
表4Table 4
由表4可见,当可降解生物基母粒中生物降解聚酯的熔融指数为10-60g/10min时,所得生物可降解聚酯组合物的生物降解性能和撕裂强度均更好,尤其是当其熔融指数为15-45g/10min时,所得聚酯组合物的生物降解性能和撕裂强度最佳。It can be seen from Table 4 that when the melt index of the biodegradable polyester in the degradable bio-based masterbatch is 10-60 g/10min, the biodegradable polyester composition obtained has better biodegradability and tear strength, especially When the melt index is 15-45 g/10min, the obtained polyester composition has the best biodegradability and tear strength.
效果例3Effect example 3
本发明可降解生物基母粒中生物填料的粒径影响含有该母粒的生物可降解聚酯组合物的撕裂强度。为了考察生物填料的粒径对生物可降解聚酯组合物的撕裂强度的影响,本效果例制备了下述试验组1~7和对照组1~4的生物可降解聚酯组合物。试验组1~7和对照组1~4的生物可降解聚酯组合物由下述重量份的组分组成:脂肪族聚酯或脂肪族-芳香族共聚酯50~90份,天然来源的聚合物0~35份,可降解生物基母粒5~40份,无机填料0~5份,助剂0~4份;所述可降解生物基母粒包括生物降解聚酯和生物填料,所述生物降解聚酯的熔融指数为8-80g/10min,所述生物降解聚酯的熔融指数是根据ASTM D1238使用2.16kg重量并在190℃的温度测量;所述生物填料来自于天然的生物质资源,所述生物填料的粒径D
50如表5所示;所述生物降解聚酯和生物填料的重量比为20-40:60-80;所述可降解生物基母粒中,占总碳重量60%-100%的碳来源于生物基的碳。试验组1~7和对照组1~4的生物可降解聚酯组合物中,除生物填料的粒径不同之外,其它全部相同。
The particle size of the bio-filler in the degradable bio-based masterbatch of the present invention affects the tear strength of the biodegradable polyester composition containing the masterbatch. In order to investigate the influence of the particle size of the bio-filler on the tear strength of the biodegradable polyester composition, this effect example prepared the biodegradable polyester compositions of the following test groups 1-7 and control groups 1-4. The biodegradable polyester composition of the test group 1-7 and the control group 1-4 is composed of the following parts by weight of components: aliphatic polyester or aliphatic-aromatic copolyester 50-90 parts, natural source 0 to 35 parts of polymer, 5 to 40 parts of biodegradable bio-based mother particles, 0 to 5 parts of inorganic filler, and 0 to 4 parts of additives; the degradable bio-based mother particles include biodegradable polyester and bio-fillers. The melt index of the biodegradable polyester is 8-80g/10min. The melt index of the biodegradable polyester is measured according to ASTM D1238 using a weight of 2.16kg and a temperature of 190°C; the bio-filler is derived from natural biomass Resources, the particle size D 50 of the bio-filler is shown in Table 5; the weight ratio of the biodegradable polyester and bio-filler is 20-40: 60-80; the degradable bio-based masterbatch accounts for the total Carbon weight 60%-100% carbon is derived from bio-based carbon. In the biodegradable polyester compositions of the test groups 1 to 7 and the control groups 1 to 4, except for the particle size of the bio-filler, all others are the same.
本效果例还按照实施例1~7生物可降解聚酯组合物性能的测试方法,测试了试验组1~7和对照组1~4的生物可降解聚酯组合物的撕裂强度,测试结果如表5所示。This effect example also tested the tear strength of the biodegradable polyester composition of the test group 1-7 and the control group 1-4 according to the test method of the performance of the biodegradable polyester composition of Examples 1-7, and the test result As shown in Table 5.
表5table 5
由表5可见,当可降解生物基母粒中生物填料的粒径D
50为0.8~6μm时,所得生物可降解聚酯组合物的撕裂强度更好,尤其是当生物填料的粒径D
50为1~5μm时,所得聚酯组合物的撕裂强度最佳。
It can be seen from Table 5 that when the particle size D 50 of the bio-filler in the degradable bio-based masterbatch is 0.8 to 6 μm, the tear strength of the resulting biodegradable polyester composition is better, especially when the particle size D of the bio-filler When 50 is 1 to 5 μm, the obtained polyester composition has the best tear strength.
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention rather than limiting the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, persons of ordinary skill in the art should understand that The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
- 一种可降解生物基母粒,其特征在于,包括生物降解聚酯和生物填料,所述生物降解聚酯的熔融指数为8-80g/10min,所述生物降解聚酯的熔融指数是根据ASTM D1238使用2.16kg重量并在190℃的温度测量;所述生物填料来自于天然的生物质资源,所述生物填料的粒径D 50为0.5~8μm;所述生物降解聚酯和生物填料的重量比为20-40:60-80; A biodegradable bio-based masterbatch, which is characterized by comprising biodegradable polyester and bio-filler, the melt index of the biodegradable polyester is 8-80g/10min, the melt index of the biodegradable polyester is according to ASTM D1238 uses a weight of 2.16kg and is measured at a temperature of 190°C; the bio-filler comes from natural biomass resources, the particle size D 50 of the bio-filler is 0.5-8 μm; the weight of the biodegradable polyester and bio-filler The ratio is 20-40: 60-80;所述可降解生物基母粒中,占总碳重量60%-100%的碳来源于生物基的碳。In the biodegradable bio-based masterbatch, 60%-100% of the total carbon weight is derived from bio-based carbon.
- 如权利要求1所述的可降解生物基母粒,其特征在于,所述生物降解聚酯和生物填料的重量比为25-35:65-75。The degradable bio-based masterbatch according to claim 1, wherein the weight ratio of the biodegradable polyester and bio-filler is 25-35: 65-75.
- 如权利要求1所述的可降解生物基母粒,其特征在于,所述生物降解聚酯的熔融指数为10-60g/10min;优选地,所述生物降解聚酯的熔融指数为15-45g/10min。The degradable bio-based masterbatch according to claim 1, wherein the melt index of the biodegradable polyester is 10-60g/10min; preferably, the melt index of the biodegradable polyester is 15-45g /10min.
- 如权利要求1所述的可降解生物基母粒,其特征在于,所述生物填料的粒径D 50为0.8~6μm;优选地,所述生物填料的粒径D 50为1~5μm。 The degradable bio-based masterbatch according to claim 1, wherein the particle size D 50 of the bio-filler is 0.8-6 μm; preferably, the particle size D 50 of the bio-filler is 1-5 μm.
- 如权利要求1~4任一项所述的可降解生物基母粒,其特征在于,如下(a)~(b)中的至少一项:The degradable bio-based masterbatch according to any one of claims 1 to 4, wherein at least one of the following (a) to (b):(a)所述生物降解聚酯为聚乳酸、聚羟基烷酸酯、聚琥珀酸丁二醇酯、聚己二酸丁二醇酯共聚丁二酸丁二醇酯、聚己二酸-对苯二甲酸丁二醇酯、聚琥珀酸对苯二甲酸丁二醇酯、聚癸二酸对苯二甲酸丁二醇酯中的至少一种;(a) The biodegradable polyester is polylactic acid, polyhydroxyalkanoate, polybutylene succinate, polybutylene adipate copolybutylene succinate, polyadipate-p At least one of butylene glycol phthalate, polybutylene succinate terephthalate, and polybutylene terephthalate sebacate;(b)所述生物填料来自动物骨头、蛋壳类、珊瑚、贝壳、牡蛎、珍珠层中的至少一种。(b) The biological filler is derived from at least one of animal bones, eggshells, coral, shells, oysters, and nacre.
- 如权利要求1~5任一项所述可降解生物基母粒的制备方法,其特征在于,包括以下步骤:将可降解生物基母粒中的组分按比例混匀后投入双螺杆挤出机中,于140-220℃挤出、造粒,得到所述可降解生物基母粒。The preparation method of biodegradable bio-based masterbatch according to any one of claims 1 to 5, characterized in that it comprises the steps of: mixing the components in the biodegradable bio-based masterbatch in proportion and putting it into a twin screw for extrusion In the machine, it is extruded and granulated at 140-220°C to obtain the degradable bio-based masterbatch.
- 一种生物可降解聚酯组合物,其特征在于,包括下述重量份的组分:脂肪族聚酯或脂肪族-芳香族共聚酯50~90份,天然来源的聚合物0~35份,权利 要求1~5任一项所述可降解生物基母粒5~40份,无机填料0~5份,助剂0~4份。A biodegradable polyester composition, characterized by comprising the following parts by weight of components: aliphatic polyester or aliphatic-aromatic copolyester 50-90 parts, natural source polymer 0-35 parts The biodegradable bio-based masterbatch according to any one of claims 1 to 5 is 5 to 40 parts, the inorganic filler is 0 to 5 parts, and the auxiliary agent is 0 to 4 parts.
- 如权利要求7所述的生物可降解聚酯组合物,其特征在于,如下(Ⅰ)~(Ⅳ)中的至少一种:The biodegradable polyester composition according to claim 7, wherein at least one of the following (I) to (IV):(Ⅰ)所述脂肪族聚酯为聚琥珀酸丁二醇酯、聚己二酸丁二醇酯共聚丁二酸丁二醇酯中的至少一种,所述脂肪族-芳香族共聚酯为聚己二酸对苯二甲酸丁二醇酯、聚琥珀酸对苯二甲酸丁二醇酯、聚癸二酸对苯二甲酸丁二醇酯中的至少一种;(Ⅰ) The aliphatic polyester is at least one of polybutylene succinate, polybutylene adipate copolymerized butylene succinate, and the aliphatic-aromatic copolyester At least one of polybutylene adipate terephthalate, polybutylene terephthalate succinate, polybutylene terephthalate sebacate;(∏)所述天然来源的聚合物为淀粉、聚乳酸中的至少一种;(∏) The polymer of natural origin is at least one of starch and polylactic acid;(Ⅲ)所述无机填料选自滑石粉、蒙脱土、高岭土、石墨、石膏、导电炭黑、氯化钙、氧化铁、白云石、二氧化硅、硅灰石、二氧化钛、硅酸盐、云母、玻璃纤维、矿物纤维中的至少一种;(III) The inorganic filler is selected from talc, montmorillonite, kaolin, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicate, At least one of mica, glass fiber, mineral fiber;(Ⅳ)所述助剂为增塑剂、脱模剂、表面活性剂、蜡、防静电剂、染料、UV吸收剂、UV稳定剂中的至少一种。(IV) The auxiliary agent is at least one of plasticizer, mold release agent, surfactant, wax, antistatic agent, dye, UV absorber, and UV stabilizer.
- 如权利要求7或8所述生物可降解聚酯组合物的制备方法,其特征在于,包括以下步骤:将生物可降解聚酯中的组分按比例混匀后投入单螺杆吹膜机中,于120-180℃吹膜,或者混匀后投入挤出机中,于140-220℃挤出、造粒,得到所述生物可降解聚酯。The method for preparing a biodegradable polyester composition according to claim 7 or 8, characterized in that it comprises the steps of: mixing the components in the biodegradable polyester in proportion and then putting them into a single screw film blowing machine, The film is blown at 120-180°C, or mixed and put into an extruder, and extruded and pelletized at 140-220°C to obtain the biodegradable polyester.
- 一种含有权利要求7或8所述生物可降解聚酯组合物的薄膜或薄膜袋。A film or film bag containing the biodegradable polyester composition according to claim 7 or 8.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3991864A1 (en) * | 2020-10-29 | 2022-05-04 | Gaia Holding AB | Biodegradable and compostable composition for use as an agricultural film |
EP4438680A1 (en) * | 2023-03-27 | 2024-10-02 | Basf Se | Polyesterblend for home compostable applications |
Families Citing this family (11)
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CN109627709B (en) * | 2018-12-25 | 2021-04-27 | 金发科技股份有限公司 | Degradable bio-based master batch and preparation method and application thereof |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6028160A (en) * | 1998-10-01 | 2000-02-22 | Cortec Corporation | Biodegradable vapor corrosion inhibitor products |
CN101805523A (en) * | 2010-04-06 | 2010-08-18 | 王文广 | Superfine biological powder filling masterbatch and method for preparing same |
CN108219396A (en) * | 2017-12-27 | 2018-06-29 | 杨红梅 | A kind of biodegradable polymer blend and its application |
CN108795001A (en) * | 2018-05-28 | 2018-11-13 | 金发科技股份有限公司 | A kind of biodegradable polymer composition and its application |
CN109627709A (en) * | 2018-12-25 | 2019-04-16 | 金发科技股份有限公司 | A kind of degradable biological base master batch and the preparation method and application thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5667574A (en) * | 1996-11-06 | 1997-09-16 | Chi May Co., Ltd. | Starch-based composition for preparing an environment degradable α-olefinic polymer molding material |
CN102516723A (en) * | 2011-12-12 | 2012-06-27 | 金发科技股份有限公司 | Filling masterbatch used in biodegradable plastic, and preparation method thereof |
CN105504363A (en) * | 2016-01-07 | 2016-04-20 | 东莞市酬勤包装制品有限公司 | Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method |
-
2018
- 2018-12-25 CN CN201811595857.7A patent/CN109627709B/en active Active
-
2019
- 2019-11-29 WO PCT/CN2019/121836 patent/WO2020134850A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6028160A (en) * | 1998-10-01 | 2000-02-22 | Cortec Corporation | Biodegradable vapor corrosion inhibitor products |
CN101805523A (en) * | 2010-04-06 | 2010-08-18 | 王文广 | Superfine biological powder filling masterbatch and method for preparing same |
CN108219396A (en) * | 2017-12-27 | 2018-06-29 | 杨红梅 | A kind of biodegradable polymer blend and its application |
CN108795001A (en) * | 2018-05-28 | 2018-11-13 | 金发科技股份有限公司 | A kind of biodegradable polymer composition and its application |
CN109627709A (en) * | 2018-12-25 | 2019-04-16 | 金发科技股份有限公司 | A kind of degradable biological base master batch and the preparation method and application thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3991864A1 (en) * | 2020-10-29 | 2022-05-04 | Gaia Holding AB | Biodegradable and compostable composition for use as an agricultural film |
WO2022090073A1 (en) * | 2020-10-29 | 2022-05-05 | Gaia Holding Ab | Biodegradable and compostable composition for use as an agricultural film |
EP4438680A1 (en) * | 2023-03-27 | 2024-10-02 | Basf Se | Polyesterblend for home compostable applications |
WO2024200497A1 (en) * | 2023-03-27 | 2024-10-03 | Basf Se | Polyesterblend for home compostable applications |
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