技术领域technical field
本发明涉及一种降解速率可控的生物分解复合薄膜材料及其制备方法。The invention relates to a biodegradable composite film material with controllable degradation rate and a preparation method thereof.
背景技术Background technique
近年来，研究人员试图在传统塑料的基础上研究出环境友好的薄膜材料，例如，CN1931905A中公开一种将淀粉与聚乙烯及助剂直接共混后所制得的薄膜材料，但该薄膜的拉伸强度偏低，并且淀粉在提高塑料可降解性能的同时，一方面会造成其物理机械性能如拉伸强度等下降，使其加工困难，另一方面还存在亲水性太强，与大部分通用树脂之间的相容性很差，致使材料的力学性能大幅下降。此外，虽然这种材料中可塑性淀粉含量可较高，但由于PE等基体本身不具有生物降解性。虽然这些技术制备的塑料会因淀粉的降解而更易于塌陷，但未降解的聚合物碎片仍然会造成环境污染。In recent years, researchers have attempted to develop environmentally friendly film materials on the basis of traditional plastics. For example, CN1931905A discloses a film material made by directly blending starch, polyethylene and additives, but the film's The tensile strength is low, and while starch can improve the degradability of plastics, on the one hand, it will cause a decrease in its physical and mechanical properties such as tensile strength, making it difficult to process. On the other hand, it is also too hydrophilic, which is different from large The compatibility between some general-purpose resins is very poor, resulting in a significant drop in the mechanical properties of the material. In addition, although the content of plastic starch in this material can be high, the matrix itself such as PE is not biodegradable. Although plastics produced by these techniques are more prone to collapse due to starch degradation, undegraded polymer fragments can still cause environmental pollution.
发明内容Contents of the invention
为解决上述技术问题，本发明提供一种机械性能好，降解更加迅速、彻底，不会对环境产生危害的降解迅速、彻底的生物复合材料及其制备方法。采用本发明降解迅速、彻底的生物复合材料制成的薄膜，具有较好的机械性能，且降解速率可控的生物分解复合材料薄膜及其制备方法；采用本发明制备的材料具备较好的加工性能、较高的撕裂强度、断裂伸长率和拉伸强度，并通过各组分比例的调整可对材料的降解时间进行控制。In order to solve the above technical problems, the present invention provides a biocomposite material with good mechanical properties, rapid and thorough degradation, and no harm to the environment, and a preparation method thereof. The film made of the rapidly and thoroughly degradable biological composite material of the present invention has good mechanical properties, and the biodegradable composite material film and its preparation method with controllable degradation rate; the material prepared by the present invention has better processing Performance, high tear strength, elongation at break and tensile strength, and the degradation time of the material can be controlled by adjusting the proportion of each component.
本发明的降解速率可控的生物分解复合薄膜材料，其包括The biodegradable composite film material with controllable degradation rate of the present invention comprises
所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种20-80重量份比例进行混合得到；The matrix resin is obtained by mixing polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) in proportions of 20-80 parts by weight each;
所述的其他生物分解聚合物为：聚丁二酸丁二(醇)酯(PBS)、聚丙撑碳酸酯(PPC)、3-羟基丁酸-3羟基戊酸共聚酯(PHBV)、对苯二甲酸-丁二醇-己二酸共聚酯(PBAT)中的至少一种；The other biodegradable polymers mentioned are: polybutylene succinate (PBS), polypropylene carbonate (PPC), 3-hydroxybutyric acid-3 hydroxyvaleric acid copolyester (PHBV), p- At least one of phthalic acid-butylene glycol-adipic acid copolyester (PBAT);
所述的热稳定剂为：四(β-(3，5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯、2，2′-亚甲基双(4-甲基-6-叔丁基苯酚)、4，4′-硫代双-(6-叔丁基-3-甲基苯酚)中的至少一种；The heat stabilizer is: tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol ester, 2,2'-methylenebis(4-methyl-6 - at least one of tert-butylphenol), 4,4'-thiobis-(6-tert-butyl-3-methylphenol);
所述的成核剂为：滑石粉、氮化硼、对苯二甲酸、二亚苄基山梨糖醇中的至少一种；The nucleating agent is: at least one of talcum powder, boron nitride, terephthalic acid, and dibenzylidene sorbitol;
所述的相容剂为：聚氧乙烯聚氧丙烯醚嵌段共聚物、过氧化苯甲酰、乙烯与甲基丙烯酸缩水甘油酯共聚物中的至少一种；The compatibilizer is: at least one of polyoxyethylene polyoxypropylene ether block copolymer, benzoyl peroxide, ethylene and glycidyl methacrylate copolymer;
所述的增塑剂为：甘油、硬脂酸、乳酸乙酯、聚乙二醇、环氧大豆油、柠檬酸三乙酯、乙酰基柠檬酸三正丁酯中的至少一种；The plasticizer is: at least one of glycerin, stearic acid, ethyl lactate, polyethylene glycol, epoxidized soybean oil, triethyl citrate, and acetyl tri-n-butyl citrate;
所述的开口剂为：油酸酰胺、二氧化硅、芥酸酰胺中的至少一种。The anti-blocking agent is at least one of oleic acid amide, silicon dioxide and erucic acid amide.
本发明的降解速率可控的生物分解复合薄膜材料，其中所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种30-60重量份比例进行混合得到；所述其他生物分解聚合物5-30重量份；所述热稳定剂为0.8-1.2重量份；所述成核剂为1-4重量份；所述相容剂为2-4重量份；所述增塑剂为5-10重量份；所述开口剂为1-4重量份。The biodegradable composite film material with controllable degradation rate of the present invention, wherein the matrix resin is polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 30-60 5-30 parts by weight of the other biodegradable polymers; 0.8-1.2 parts by weight of the heat stabilizer; 1-4 parts by weight of the nucleating agent; 2-4 parts by weight; the plasticizer is 5-10 parts by weight; the opening agent is 1-4 parts by weight.
本发明的降解速率可控的生物分解复合薄膜材料，其中所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种40-50重量份比例进行混合得到；所述其他生物分解聚合物10-20重量份；所述热稳定剂为0.9-1.1重量份；所述成核剂为2-3重量份；所述相容剂为2.5-3.5重量份；所述增塑剂为6-8重量份；所述开口剂为2-3重量份。The biodegradable composite film material with controllable degradation rate of the present invention, wherein the matrix resin is polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 40-50 10-20 parts by weight of the other biodegradable polymers; 0.9-1.1 parts by weight of the heat stabilizer; 2-3 parts by weight of the nucleating agent; 2.5-3.5 parts by weight; the plasticizer is 6-8 parts by weight; the opening agent is 2-3 parts by weight.
本发明的降解速率可控的生物分解复合薄膜材料的制备方法，包括如下步骤：The preparation method of the biodegradable composite film material with controllable degradation rate of the present invention comprises the following steps:
A、准备以下原料：A. Prepare the following raw materials:
基体树脂、其他生物分解聚合物、热稳定剂、成核剂、相容剂、增塑剂、开口剂；Matrix resin, other biodegradable polymers, thermal stabilizers, nucleating agents, compatibilizers, plasticizers, blocking agents;
所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种20-80重量份比例进行混合得到；增加3-羟基丁酸-3-羟基己酸共聚酯(PHBH)用量，可提高最终产品的降解速度，减少降解所需的时间；减少3-羟基丁酸-3-羟基己酸共聚酯(PHBH)用量，可降低最终产品的降解速度，增加降解所需的时间；The matrix resin is obtained by mixing polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to the ratio of 20-80 parts by weight each; adding 3-hydroxybutyric acid-3 The amount of -hydroxycaproic acid copolyester (PHBH) can increase the degradation rate of the final product and reduce the time required for degradation; reducing the amount of 3-hydroxybutyric acid-3-hydroxycaproic acid copolyester (PHBH) can reduce the final product The degradation rate of the product, increasing the time required for degradation;
所述的其他生物分解聚合物为：聚丁二酸丁二(醇)酯(PBS)、聚丙撑碳酸酯(PPC)、3-羟基丁酸-3-羟基戊酸共聚酯(PHBV)、对苯二甲酸-丁二醇-己二酸共聚酯(PBAT)中的至少一种；The other biodegradable polymers mentioned are: polybutylene succinate (PBS), polypropylene carbonate (PPC), 3-hydroxybutyric acid-3-hydroxyvaleric acid copolyester (PHBV), At least one of terephthalic acid-butylene glycol-adipic acid copolyester (PBAT);
所述的热稳定剂为：四(β-(3，5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯、2，2′-亚甲基双(4-甲基-6-叔丁基苯酚)和4，4′-硫代双-(6-叔丁基-3-甲基苯酚)中的至少一种；The heat stabilizer is: tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol ester, 2,2'-methylenebis(4-methyl-6 - at least one of tert-butylphenol) and 4,4'-thiobis-(6-tert-butyl-3-methylphenol);
所述的成核剂为：滑石粉、氮化硼、对苯二甲酸、二亚苄基山梨糖醇中的至少一种；The nucleating agent is: at least one of talcum powder, boron nitride, terephthalic acid, and dibenzylidene sorbitol;
所述的相容剂为：聚氧乙烯聚氧丙烯醚嵌段共聚物、过氧化苯甲酰、乙烯与甲基丙烯酸缩水甘油酯共聚物中的至少一种；The compatibilizer is: at least one of polyoxyethylene polyoxypropylene ether block copolymer, benzoyl peroxide, ethylene and glycidyl methacrylate copolymer;
所述的增塑剂为：甘油、硬脂酸、乳酸乙酯、聚乙二醇、环氧大豆油、柠檬酸三乙酯、乙酰基柠檬酸三正丁酯中的至少一种；The plasticizer is: at least one of glycerin, stearic acid, ethyl lactate, polyethylene glycol, epoxidized soybean oil, triethyl citrate, and acetyl tri-n-butyl citrate;
所述的开口剂为：油酸酰胺、二氧化硅、芥酸酰胺中的至少一种；The opening agent is: at least one of oleic acid amide, silicon dioxide, and erucic acid amide;
将上述各种原料放置在干燥烘箱中，进行烘干，干燥温度为40℃-80℃，干燥时间为6-10小时；Place the above-mentioned various raw materials in a drying oven for drying, the drying temperature is 40°C-80°C, and the drying time is 6-10 hours;
B、充分干燥后，按照100重量份的基体树脂、0-40重量份的其他生物分解聚合物、0.5-1.5重量份的热稳定剂、0.3-5重量份的成核剂、1-5重量份的相容剂、2-15重量份的增塑剂、0.3-5重量份开口剂的比例，将原料加入到高速混合机，在高速混合机里对原料进行混合，混合时间为5-10分钟；B. After fully drying, according to 100 parts by weight of matrix resin, 0-40 parts by weight of other biodegradable polymers, 0.5-1.5 parts by weight of heat stabilizer, 0.3-5 parts by weight of nucleating agent, 1-5 parts by weight of The proportion of the compatibilizer of 2-15 parts by weight, the plasticizer of 2-15 parts by weight, and the opening agent of 0.3-5 parts by weight are added to the high-speed mixer, and the raw materials are mixed in the high-speed mixer. The mixing time is 5-10 minute;
C、将混合后的原料挤出造粒，制成本发明的降解速率可控的生物分解复合薄膜材料。C. Extruding and granulating the mixed raw materials to make the biodegradable composite film material with controllable degradation rate of the present invention.
本发明的降解速率可控的生物分解复合薄膜材料的制备方法，其中所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种30-60重量份比例进行混合得到；所述其他生物分解聚合物5-30重量份；所述热稳定剂为0.8-1.2重量份；所述成核剂为1-4重量份；所述相容剂为2-4重量份；所述增塑剂为5-10重量份；所述开口剂为1-4重量份。The preparation method of the biodegradable composite film material with controllable degradation rate of the present invention, wherein said base resin is polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 30-60 parts by weight are obtained by mixing; 5-30 parts by weight of the other biodegradable polymer; 0.8-1.2 parts by weight of the heat stabilizer; 1-4 parts by weight of the nucleating agent; The container is 2-4 parts by weight; the plasticizer is 5-10 parts by weight; the opening agent is 1-4 parts by weight.
本发明的降解速率可控的生物分解复合薄膜材料的制备方法，其中所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种40-50重量份比例进行混合得到；所述其他生物分解聚合物10-20重量份；所述热稳定剂为0.9-1.1重量份；所述成核剂为2-3重量份；所述相容剂为2.5-3.5重量份；所述增塑剂为6-8重量份；所述开口剂为2-3重量份。The preparation method of the biodegradable composite film material with controllable degradation rate of the present invention, wherein said base resin is polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 40-50 parts by weight are mixed; the other biodegradable polymer is 10-20 parts by weight; the thermal stabilizer is 0.9-1.1 parts by weight; the nucleating agent is 2-3 parts by weight; The container is 2.5-3.5 parts by weight; the plasticizer is 6-8 parts by weight; the opening agent is 2-3 parts by weight.
与现有技术相比，本发明的有益效果为：本发明的降解速率可控的生物分解复合薄膜材料及其制备方法，采用本发明特有的配方和工艺步骤，所生产出的降解速率可控的生物分解复合薄膜材料，不仅机械性能好，降解也更加迅速、彻底，采用该材料所制备的薄膜，具备较好的加工性能、较高的撕裂强度、断裂伸长率和拉伸强度，并且降解更加迅速、彻底，其在设定的使用期限后，即可在自然环境中的微生物作用下，经(填埋)3-6个月的很短时间内，就发生完全降解，产物为水、二氧化碳和有机质，不会对环境产生危害。本发明所制备的可控完全降解聚合物薄膜复合材料，在MD和TD两个方向上，均具有高拉伸强度、高抗撕裂强度和可控的降解性，可在包装材料和农用塑料膜领域中广泛应用。采用本发明降解迅速、彻底的生物复合材料制成的薄膜，具有较好的机械性能，且降解速率可控的生物分解复合材料薄膜；所制备的材料具备较好的加工性能、较高的撕裂强度、断裂伸长率和拉伸强度，并通过各组分比例的调整可对材料的降解时间进行控制。Compared with the prior art, the beneficial effects of the present invention are: the biodegradable composite film material with controllable degradation rate and its preparation method of the present invention adopt the unique formula and process steps of the present invention, and the produced degradation rate is controllable The biodegradable composite film material not only has good mechanical properties, but also degrades more rapidly and thoroughly. The film prepared by using this material has good processing performance, high tear strength, elongation at break and tensile strength. And the degradation is more rapid and thorough. After the set period of use, it can be completely degraded in a short period of 3-6 months under the action of microorganisms in the natural environment, and the product is Water, carbon dioxide and organic matter will not harm the environment. The controllable and completely degradable polymer film composite material prepared by the present invention has high tensile strength, high tear resistance and controllable degradability in both directions of MD and TD, and can be used in packaging materials and agricultural plastics. widely used in membrane field. The film made of the rapidly and thoroughly degradable biocomposite material of the present invention has good mechanical properties and is a biodegradable composite film with controllable degradation rate; the prepared material has good processing performance and high tear resistance. Break strength, elongation at break and tensile strength, and the degradation time of the material can be controlled by adjusting the proportion of each component.
具体实施方式detailed description
下面对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。Specific embodiments of the present invention will be further described in detail below. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
依据以下方法对所获得的降解速率可控的生物分解复合材料薄膜进行力学性能测试：The mechanical properties of the obtained biodegradable composite film with controllable degradation rate were tested according to the following methods:
拉伸性能测试依据GB/T1040.3-2006进行，使用哑铃型切刀裁切试样，从MD和TD两个方向冲切，试样尺寸：总长度120mm、窄部分宽度10mm，拉伸速率200mm/min，试验次数n≥5次，结果采用平均值表示。The tensile performance test is carried out according to GB/T1040.3-2006. The sample is cut with a dumbbell-shaped cutter and punched from two directions of MD and TD. The sample size: the total length is 120mm, the narrow part width is 10mm, and the tensile rate is 200mm/min, the number of tests n≥5 times, the results are represented by the average value.
直角撕裂测试依据QB/T1130-1991进行，裁切成标准试样，从MD和TD两个方向冲切，其中夹具间距为60mm，拉伸速度100mm/min，试验次数n≥5次，结果采用平均值表示。The right-angle tear test is carried out according to QB/T1130-1991, cut into standard samples, punched from two directions of MD and TD, where the distance between the clamps is 60mm, the tensile speed is 100mm/min, the number of tests n≥5 times, the result Expressed as an average value.
实施例1：按以下配方及重量份称取各组分Embodiment 1: take each component by following formula and parts by weight
制备方法与条件设定为：The preparation method and conditions are set as:
(1)将基体树脂、改性剂，在烘箱中40-80℃干燥6-10小时，然后按配比称量各组分原料，并手动进行预混，将预混物在双螺杆挤出机上挤出造粒。双螺杆挤出机的温度设定为：一区，110-145℃；二区，120-160℃；三区，145-185℃；四区，145-185℃；五区，145-185℃；机头，145-160℃。(1) Dry the matrix resin and modifier in an oven at 40-80°C for 6-10 hours, then weigh the raw materials of each component according to the proportion, and pre-mix manually, and put the pre-mix on the twin-screw extruder Extrusion granulation. The temperature setting of the twin-screw extruder is: zone one, 110-145°C; zone two, 120-160°C; zone three, 145-185°C; zone four, 145-185°C; zone five, 145-185°C ; Machine head, 145-160°C.
(2)将上述复合聚合物粒料经单螺杆挤出吹塑成膜，单螺杆挤出机的温度设定为：一区，110-130℃；二区，130-150℃；三区，140-170℃；四区，140-185℃；五区，140-185℃；六区，140-160℃；口模温度，145-160℃。其中螺杆转速30-60rpm，牵引速率2-5m/min，卷曲速率3-6m/min。(2) The above-mentioned composite polymer pellets are extruded and blown into a film by single-screw, and the temperature of the single-screw extruder is set as: the first zone, 110-130°C; the second zone, 130-150°C; the third zone, 140-170°C; zone four, 140-185°C; zone five, 140-185°C; zone six, 140-160°C; die temperature, 145-160°C. Among them, the screw speed is 30-60rpm, the pulling speed is 2-5m/min, and the crimping speed is 3-6m/min.
所得制品性能如表1所示。The properties of the product obtained are shown in Table 1.
表1：薄膜厚度18μmTable 1: Film Thickness 18μm
实施例2：按以下配方及重量份称取各组分Embodiment 2: take each component by following formula and parts by weight
加工条件及参数见实施例1；Processing conditions and parameters see embodiment 1;
所得制品性能见表2。The properties of the products obtained are shown in Table 2.
表2：薄膜厚度19μmTable 2: Film Thickness 19μm
实施例3：按以下配方及重量份称取各组分Embodiment 3: take each component by following formula and parts by weight
加工条件及参数见实施例1；Processing conditions and parameters see embodiment 1;
所得制品性能见表3。The properties of the products obtained are shown in Table 3.
表3：薄膜厚度35μmTable 3: Film Thickness 35μm
实施例4：按以下配方及重量份称取各组分Embodiment 4: take each component by following formula and parts by weight
加工条件及参数见实施例1。See embodiment 1 for processing conditions and parameters.
所得制品性能见表4。The properties of the products obtained are shown in Table 4.
表4：薄膜厚度25μmTable 4: Film Thickness 25μm
实施例5：按以下配方及重量份称取各组分Embodiment 5: take each component by following formula and parts by weight
加工条件及参数见实施例1。See embodiment 1 for processing conditions and parameters.
所得制品性能见表5。The properties of the product obtained are shown in Table 5.
表5：薄膜厚度31μmTable 5: Film thickness 31μm
实施例6：按以下配方及重量份称取各组分Embodiment 6: take each component by following formula and parts by weight
加工条件及参数见实施例1。See embodiment 1 for processing conditions and parameters.
所得制品性能见表6。The properties of the products obtained are shown in Table 6.
表6：薄膜厚度29μmTable 6: Film thickness 29μm
实施例7：按以下配方及重量份称取各组分Embodiment 7: take each component by following formula and parts by weight
加工条件及参数见实施例1；Processing conditions and parameters see embodiment 1;
所得制品性能见表2。The properties of the products obtained are shown in Table 2.
表7：薄膜厚度22μmTable 7: Film thickness 22μm
实施例8Example 8
本发明的降解速率可控的生物分解复合薄膜材料，其包括The biodegradable composite film material with controllable degradation rate of the present invention comprises
所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种20或30或40或50或60或70或80重量份比例进行混合得到；The matrix resin is mixed with polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 20 or 30 or 40 or 50 or 60 or 70 or 80 parts by weight get;
所述的其他生物分解聚合物为：聚丁二酸丁二(醇)酯(PBS)、聚丙撑碳酸酯(PPC)、3-羟基丁酸-3羟基戊酸共聚酯(PHBV)、对苯二甲酸-丁二醇-己二酸共聚酯(PBAT)中的一种或二种或三种或四种；The other biodegradable polymers mentioned are: polybutylene succinate (PBS), polypropylene carbonate (PPC), 3-hydroxybutyric acid-3 hydroxyvaleric acid copolyester (PHBV), p- One or two or three or four of phthalic acid-butanediol-adipic acid copolyester (PBAT);
所述的热稳定剂为：四(β-(3，5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯、2，2′-亚甲基双(4-甲基-6-叔丁基苯酚)、4，4′-硫代双-(6-叔丁基-3-甲基苯酚)中的一种或二种或三种；The heat stabilizer is: tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol ester, 2,2'-methylenebis(4-methyl-6 One or two or three of - tert-butylphenol), 4,4'-thiobis-(6-tert-butyl-3-methylphenol);
所述的成核剂为：滑石粉、氮化硼、对苯二甲酸、二亚苄基山梨糖醇中的一种或二种或三种或四种；The nucleating agent is: one or two or three or four of talcum powder, boron nitride, terephthalic acid, and dibenzylidene sorbitol;
所述的相容剂为：聚氧乙烯聚氧丙烯醚嵌段共聚物、过氧化苯甲酰、乙烯与甲基丙烯酸缩水甘油酯共聚物中的一种或二种；The compatibilizer is: one or two of polyoxyethylene polyoxypropylene ether block copolymer, benzoyl peroxide, ethylene and glycidyl methacrylate copolymer;
所述的增塑剂为：甘油、硬脂酸、乳酸乙酯、聚乙二醇、环氧大豆油、柠檬酸三乙酯、乙酰基柠檬酸三正丁酯中的一种或二种或三种或四种或五种或六种或七种；The plasticizer is: one or two of glycerin, stearic acid, ethyl lactate, polyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tri-n-butyl citrate or Three or four or five or six or seven;
所述的开口剂为：油酸酰胺、二氧化硅、芥酸酰胺中的一种或二种或三种。The anti-blocking agent is: one or two or three of oleic acid amide, silicon dioxide and erucic acid amide.
作为本发明的改进，上述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种30-60重量份比例进行混合得到；所述其他生物分解聚合物5-30重量份；所述热稳定剂为0.8-1.2重量份；所述成核剂为1-4重量份；所述相容剂为2-4重量份；所述增塑剂为5-10重量份；所述开口剂为1-4重量份。As an improvement of the present invention, the above-mentioned matrix resin is obtained by mixing polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 30-60 parts by weight; the other 5-30 parts by weight of biodegradable polymer; 0.8-1.2 parts by weight of the thermal stabilizer; 1-4 parts by weight of the nucleating agent; 2-4 parts by weight of the compatibilizer; The agent is 5-10 parts by weight; the opening agent is 1-4 parts by weight.
作为本发明的进一步改进，上述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种40-50重量份比例进行混合得到；所述其他生物分解聚合物10-20重量份；所述热稳定剂为0.9-1.1重量份；所述成核剂为2-3重量份；所述相容剂为2.5-3.5重量份；所述增塑剂为6-8重量份；所述开口剂为2-3重量份。As a further improvement of the present invention, the above-mentioned matrix resin is obtained by mixing polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 40-50 parts by weight; 10-20 parts by weight of other biodegradable polymers; 0.9-1.1 parts by weight of the heat stabilizer; 2-3 parts by weight of the nucleating agent; 2.5-3.5 parts by weight of the compatibilizer; The plasticizer is 6-8 parts by weight; the opening agent is 2-3 parts by weight.
本发明的降解速率可控的生物分解复合薄膜材料的制备方法，包括如下步骤：The preparation method of the biodegradable composite film material with controllable degradation rate of the present invention comprises the following steps:
A、准备以下原料：A. Prepare the following raw materials:
基体树脂、其他生物分解聚合物、热稳定剂、成核剂、相容剂、增塑剂、开口剂；Matrix resin, other biodegradable polymers, thermal stabilizers, nucleating agents, compatibilizers, plasticizers, blocking agents;
所述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种20或30或40或50或60或70或80重量份比例进行混合得到；增加3-羟基丁酸-3-羟基己酸共聚酯(PHBH)用量，可提高最终产品的降解速度，减少降解所需的时间；减少3-羟基丁酸-3-羟基己酸共聚酯(PHBH)用量，可降低最终产品的降解速度，增加降解所需的时间；The matrix resin is mixed with polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 20 or 30 or 40 or 50 or 60 or 70 or 80 parts by weight Obtain; Increase 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) consumption, can improve the degradation rate of final product, reduce the time required for degradation; Reduce 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) The amount of polyester (PHBH) can reduce the degradation rate of the final product and increase the time required for degradation;
所述的其他生物分解聚合物为：聚丁二酸丁二(醇)酯(PBS)、聚丙撑碳酸酯(PPC)、3-羟基丁酸-3羟基戊酸共聚酯(PHBV)、对苯二甲酸-丁二醇-己二酸共聚酯(PBAT)中的一种或二种或三种或四种；The other biodegradable polymers mentioned are: polybutylene succinate (PBS), polypropylene carbonate (PPC), 3-hydroxybutyric acid-3 hydroxyvaleric acid copolyester (PHBV), p- One or two or three or four of phthalic acid-butanediol-adipic acid copolyester (PBAT);
所述的热稳定剂为：四(β-(3，5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯、2，2′-亚甲基双(4-甲基-6-叔丁基苯酚)、4，4′-硫代双-(6-叔丁基-3-甲基苯酚)中的一种或二种或三种；The heat stabilizer is: tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol ester, 2,2'-methylenebis(4-methyl-6 One or two or three of - tert-butylphenol), 4,4'-thiobis-(6-tert-butyl-3-methylphenol);
所述的成核剂为：滑石粉、氮化硼、对苯二甲酸、二亚苄基山梨糖醇中的一种或二种或三种或四种；The nucleating agent is: one or two or three or four of talcum powder, boron nitride, terephthalic acid, and dibenzylidene sorbitol;
所述的相容剂为：聚氧乙烯聚氧丙烯醚嵌段共聚物、过氧化苯甲酰、乙烯与甲基丙烯酸缩水甘油酯共聚物中的一种或二种；The compatibilizer is: one or two of polyoxyethylene polyoxypropylene ether block copolymer, benzoyl peroxide, ethylene and glycidyl methacrylate copolymer;
所述的增塑剂为：甘油、硬脂酸、乳酸乙酯、聚乙二醇、环氧大豆油、柠檬酸三乙酯、乙酰基柠檬酸三正丁酯中的一种或二种或三种或四种或五种或六种或七种；The plasticizer is: one or two of glycerin, stearic acid, ethyl lactate, polyethylene glycol, epoxy soybean oil, triethyl citrate, acetyl tri-n-butyl citrate or Three or four or five or six or seven;
所述的开口剂为：油酸酰胺、二氧化硅、芥酸酰胺中的一种或二种或三种；The opening agent is: one or two or three of oleic acid amide, silicon dioxide, and erucic acid amide;
将上述各种原料放置在干燥烘箱中，进行烘干，干燥温度为40℃-80℃，干燥时间为6-10小时；Place the above-mentioned various raw materials in a drying oven for drying, the drying temperature is 40°C-80°C, and the drying time is 6-10 hours;
B、充分干燥后，按照100重量份的基体树脂、0-40重量份的其他生物分解聚合物、0.5-1.5重量份的热稳定剂、0.3-5重量份的成核剂、1-5重量份的相容剂、2-15重量份的增塑剂、0.3-5重量份开口剂的比例，将原料加入到高速混合机，在高速混合机里对原料进行混合，混合时间为5-10分钟；B. After fully drying, according to 100 parts by weight of matrix resin, 0-40 parts by weight of other biodegradable polymers, 0.5-1.5 parts by weight of heat stabilizer, 0.3-5 parts by weight of nucleating agent, 1-5 parts by weight of The proportion of the compatibilizer of 2-15 parts by weight, the plasticizer of 2-15 parts by weight, and the opening agent of 0.3-5 parts by weight are added to the high-speed mixer, and the raw materials are mixed in the high-speed mixer. The mixing time is 5-10 minute;
C、将混合后的原料挤出造粒，制成本发明的降解速率可控的生物分解复合薄膜材料。C. Extruding and granulating the mixed raw materials to make the biodegradable composite film material with controllable degradation rate of the present invention.
作为本发明的改进，上述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种30-60重量份比例进行混合得到；所述其他生物分解聚合物5-30重量份；所述热稳定剂为0.8-1.2重量份；所述成核剂为1-4重量份；所述相容剂为2-4重量份；所述增塑剂为5-10重量份；所述开口剂为1-4重量份。As an improvement of the present invention, the above-mentioned matrix resin is obtained by mixing polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 30-60 parts by weight; the other 5-30 parts by weight of biodegradable polymer; 0.8-1.2 parts by weight of the thermal stabilizer; 1-4 parts by weight of the nucleating agent; 2-4 parts by weight of the compatibilizer; The agent is 5-10 parts by weight; the opening agent is 1-4 parts by weight.
作为本发明的进一步改进，上述基体树脂是将聚乳酸(PLA)和3-羟基丁酸-3-羟基己酸共聚酯(PHBH)按照每种40-50重量份比例进行混合得到；所述其他生物分解聚合物10-20重量份；所述热稳定剂为0.9-1.1重量份；所述成核剂为2-3重量份；所述相容剂为2.5-3.5重量份；所述增塑剂为6-8重量份；所述开口剂为2-3重量份。As a further improvement of the present invention, the above-mentioned matrix resin is obtained by mixing polylactic acid (PLA) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolyester (PHBH) according to each 40-50 parts by weight; 10-20 parts by weight of other biodegradable polymers; 0.9-1.1 parts by weight of the heat stabilizer; 2-3 parts by weight of the nucleating agent; 2.5-3.5 parts by weight of the compatibilizer; The plasticizer is 6-8 parts by weight; the opening agent is 2-3 parts by weight.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the technical principle of the present invention, some improvements and modifications can also be made, these improvements and modifications It should also be regarded as the protection scope of the present invention.
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| CN201310009025.3ACN103087484B (en) | 2013-01-11 | 2013-01-11 | Biodegradable composite film material that degradation rate is controlled and preparation method thereof |
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| CN201310009025.3ACN103087484B (en) | 2013-01-11 | 2013-01-11 | Biodegradable composite film material that degradation rate is controlled and preparation method thereof |
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