CN107841131A - A kind of nylon 11/PLA bio-based high polymer alloy and its preparation method and application - Google Patents
A kind of nylon 11/PLA bio-based high polymer alloy and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 title claims description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 17
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- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
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- 230000003078 antioxidant effect Effects 0.000 claims description 9
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 8
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
本发明公开了一种尼龙11/聚乳酸生物基高分子合金，含有以下重量份的物质：30～70份尼龙11、30～70份聚乳酸、1～8份相容剂、0.1～0.6份稳定剂，所述尼龙11/聚乳酸生物基高分子合金的制备方法为：将PA11基体树脂、PLA树脂、相容剂和热稳定剂经真空干燥后，先通过高速混合机混合均匀，再通过双螺杆挤出机挤出均匀造粒，最后在真空烘箱中干燥除去水分。本发明尼龙11/聚乳酸生物基高分子合金的主要原料为生物基材料，降低了对石油基高分子材料的需求，该尼龙11/聚乳酸生物基高分子合金材料拉伸强度大，模量高，抗冲击性能高且热稳定性好，价格便宜，且其生产加工工艺对设备要求低，适合大规模工业化生产。The invention discloses a nylon 11/polylactic acid bio-based polymer alloy, which contains the following substances in parts by weight: 30-70 parts of nylon 11, 30-70 parts of polylactic acid, 1-8 parts of compatibilizer, 0.1-0.6 parts Stabilizer, the preparation method of the nylon 11/polylactic acid bio-based polymer alloy is: after vacuum drying the PA11 matrix resin, PLA resin, compatibilizer and thermal stabilizer, first mix them uniformly by a high-speed mixer, and then pass Extruded by a twin-screw extruder to uniformly granulate, and finally dried in a vacuum oven to remove moisture. The main raw material of the nylon 11/polylactic acid bio-based polymer alloy of the present invention is a bio-based material, which reduces the demand for petroleum-based polymer materials. The nylon 11/polylactic acid bio-based polymer alloy material has high tensile strength and high modulus. High, high impact resistance and good thermal stability, cheap, and its production and processing technology requires low equipment, suitable for large-scale industrial production.
Description
技术领域technical field
本发明涉及高分子材料技术及生态环境材料领域，尤其涉及一种高性能生物基来源的尼龙11/聚乳酸合金及其制备方法和应用。The invention relates to the fields of polymer material technology and ecological environment materials, in particular to a high-performance bio-based nylon 11/polylactic acid alloy and its preparation method and application.
背景技术Background technique
高分子材料是国民经济的支柱产业之一，其绝大部分来源于石油产品，但我国石油资源十分短缺，随着中国石油对外依存度的攀升，石油战略安全问题已经十分严峻地摆在我们面前，石油资源匮乏成为制约经济和社会可持续发展的“瓶颈”。同时高分子材料很难降解，产生的白色污染严重影响人类生存环境，利用可再生生物资源开发高分子新材料，是能源替代的重要途径。Polymer materials are one of the pillar industries of the national economy, and most of them come from petroleum products. However, my country's petroleum resources are very short. With the rising dependence of China's petroleum on foreign countries, the issue of petroleum strategic security has become very serious in front of us. , the lack of oil resources has become a "bottleneck" restricting the sustainable development of economy and society. At the same time, polymer materials are difficult to degrade, and the white pollution produced seriously affects the living environment of human beings. The development of new polymer materials using renewable biological resources is an important way to replace energy.
聚乳酸（PLA）是一种生物基高分子材料，其具有较高的强度和模量，可以从可再生的生物资源（淀粉和糖类）中制备，摆脱了对石油资源的依赖，而且其具有独特的生物可降解性和生物相容性，吸引了人们的极大关注，现在，聚乳酸材料的应用己经由最初的包装材料等短使用周期商品和用后回收困难的商品发展到农林水产业、土木建筑业、日常生活用品等具有较长使用周期的商品，甚至用作汽车、电子电器领域等高性能的耐久性商品。但是，由于聚乳酸树脂结晶速度慢，成型制品收缩率大，尺寸稳定性差，本身质脆，加工热稳定性差，以及制品耐久性差等缺点，限制了其作为工程塑料的应用。Polylactic acid (PLA) is a bio-based polymer material with high strength and modulus, which can be prepared from renewable biological resources (starch and sugar), getting rid of the dependence on petroleum resources, and its It has unique biodegradability and biocompatibility, which has attracted great attention from people. Now, the application of polylactic acid materials has developed from the initial packaging materials and other short-use cycle commodities and commodities that are difficult to recycle after use to agriculture, forestry and water. Industrial, civil engineering and construction industries, daily necessities and other products with a long life cycle, and even used as high-performance durable products such as automobiles and electronic appliances. However, due to the slow crystallization rate of polylactic acid resin, large shrinkage rate of molded products, poor dimensional stability, brittleness, poor thermal stability during processing, and poor durability of products, its application as engineering plastics is limited.
中国专利CN 102352094 A公开了一种高韧高耐热聚乳酸合金材料及其制备方法，其提供的高韧高耐热聚乳酸合金材料含有10-80份聚乳酸、10-80份耐热型人工高分子、5-15份增韧剂、0.4-1份水解抑制剂、0.1-1份抗老化剂、0.1-1份抗氧剂。其后，中国专利CN102504504 A，在上述专利的基础上，进一步优化了技术方案，提供了一种高抗冲击耐热聚乳酸合金材料及其制备方法，所述合金材料组分包括：39-70wt％的聚乳酸、20-45wt％的耐热高分子、6-15wt％的抗冲击改性剂、0.4-1wt％的水解抑制剂、0.5-1wt％的熔体增强剂及0.1-2wt％的抗氧剂。但是，由以上专利的实施例的详细记载可知，前述发明专利仅仅是通过共混形成高分子合金的方法解决了聚乳酸抗冲击强度和耐热性难以同时改进的困难情况，使得制备的高分子合金材料在抗冲击性和耐热性能方面有所改善，拓展了聚乳酸的应用领域，但是对于伸拉强度、弯曲强度等指标则未详细报导，因而其综合性能不得而知。Chinese patent CN 102352094 A discloses a high-toughness and high-heat-resistant polylactic acid alloy material and its preparation method. The high-toughness and high-heat-resistant polylactic acid alloy material provided by it contains 10-80 parts of polylactic Artificial polymer, 5-15 parts of toughening agent, 0.4-1 part of hydrolysis inhibitor, 0.1-1 part of anti-aging agent, 0.1-1 part of antioxidant. Thereafter, the Chinese patent CN102504504 A further optimized the technical solution on the basis of the above-mentioned patents, and provided a high-impact heat-resistant polylactic acid alloy material and its preparation method. The alloy material components include: 39-70wt % polylactic acid, 20-45wt% heat-resistant polymer, 6-15wt% impact modifier, 0.4-1wt% hydrolysis inhibitor, 0.5-1wt% melt enhancer and 0.1-2wt% Antioxidant. However, from the detailed description of the examples of the above patents, it can be known that the aforementioned invention patent only solves the difficult situation that the impact strength and heat resistance of polylactic acid are difficult to improve simultaneously by blending to form a polymer alloy, so that the prepared polymer Alloy materials have improved impact resistance and heat resistance, expanding the application field of polylactic acid, but the indicators such as tensile strength and bending strength have not been reported in detail, so their comprehensive properties are unknown.
中国专利CN 106496973 A公开了一种聚乳酸/尼龙6合金生物降解材料及其制备方法，该发明方法主要是针对目前制备聚乳酸共混或共聚可生物降解高分子材料合金存在的技术局限性，以及与聚乳酸单体共聚的高分子材料单体材料成本较高且种类较少的技术问题，以尼龙6与聚乳酸进行共混。通过添加增容剂、增塑剂和络合剂，降低尼龙6的结晶和提高聚乳酸与尼龙6的相容性，来解决非生物降解高分子材料尼龙6变成生物降解高分子材料的难题。但是，尼龙6的熔点较低，而且工艺温度范围很宽，在加工过程中很容易吸收水分，并因受潮（水含有超过0.25%）而造成成型改变，此外成型后的产品存在一定的收缩性，其制成的高分子合金材料的多种机械品质和特性都要受到吸湿性和收缩性的影响，因此加工使用极不方便。Chinese patent CN 106496973 A discloses a polylactic acid/nylon 6 alloy biodegradable material and its preparation method. The inventive method is mainly aimed at the technical limitations of the current preparation of polylactic acid blended or copolymerized biodegradable polymer material alloys. As well as the technical problem of higher cost and fewer types of polymer material monomers copolymerized with polylactic acid monomers, nylon 6 is blended with polylactic acid. By adding compatibilizer, plasticizer and complexing agent, reduce the crystallization of nylon 6 and improve the compatibility of polylactic acid and nylon 6, to solve the problem of non-biodegradable polymer material nylon 6 into biodegradable polymer material . However, the melting point of nylon 6 is low, and the process temperature range is very wide. It is easy to absorb moisture during processing, and the molding will be changed due to moisture (water content exceeds 0.25%). In addition, the molded product has a certain degree of shrinkage. , the various mechanical qualities and characteristics of the polymer alloy materials made of it are affected by hygroscopicity and shrinkage, so it is extremely inconvenient to process and use.
中国专利CN 102391628A使用了聚乳酸和尼龙11作为原料，制备了一种聚乳酸/尼龙11合金材料，该发明方法是通过添加第三组份EGMA-g-SAN(聚乙烯-甲基丙烯酸缩水甘油酯接枝聚苯乙烯-丙烯晴)，从而改善合金材料的界面粘结性和材料力学性能，但是该方法未能解决制备的聚乳酸/尼龙11合金材料不稳定易降解的技术问题，制备的高分子合金材料的使用寿命低，制品易变色，发黄。此外，其添加的第三组份价格比较昂贵。Chinese patent CN 102391628A uses polylactic acid and nylon 11 as raw materials to prepare a polylactic acid/nylon 11 alloy material. The inventive method is to add the third component EGMA-g-SAN (polyethylene-glycidyl methacrylate ester-grafted polystyrene-acrylonitrile), thereby improving the interface adhesion and material mechanical properties of the alloy material, but this method fails to solve the technical problem that the prepared polylactic acid/nylon 11 alloy material is unstable and easy to degrade, and the prepared The service life of polymer alloy materials is low, and the products are easy to change color and turn yellow. In addition, the price of the third component added is relatively expensive.
发明内容Contents of the invention
本发明的目的就是为了解决尼龙11/聚乳酸合金在加工过程中相容性和稳定性差的问题，制备出了一种增强增韧的尼龙11/聚乳酸生物基高分子合金材料，所制备的材料拉伸强度大，模量高，抗冲击性能得到提高、加工过程中热稳定性好、价格便宜、对设备要求低，适合工业化生产。The purpose of the present invention is to solve the problem of poor compatibility and stability of nylon 11/polylactic acid alloy during processing, and to prepare a reinforced and toughened nylon 11/polylactic acid bio-based polymer alloy material. The prepared The material has high tensile strength, high modulus, improved impact resistance, good thermal stability during processing, low price, low equipment requirements, and is suitable for industrial production.
本发明是通过以下技术方案实现。The present invention is realized through the following technical solutions.
本发明所述的尼龙11/聚乳酸生物基高分子合金主要由尼龙11、聚乳酸、相容剂、稳定剂组成，主要的含意是尼龙11/聚乳酸生物基合金必不可少的组成成分有尼龙11、聚乳酸、相容剂和两种稳定剂共五种成分，其质量份数分别为，30～70份尼龙11、30～70份聚乳酸、1～8份相容剂、0.1～0.6份稳定剂。The nylon 11/polylactic acid bio-based polymer alloy of the present invention is mainly composed of nylon 11, polylactic acid, a compatibilizer, and a stabilizer, and the main meaning is that the indispensable components of the nylon 11/polylactic acid bio-based alloy are Nylon 11, polylactic acid, compatibilizer and two kinds of stabilizers are five components in total, and the parts by mass are respectively 30-70 parts of nylon 11, 30-70 parts of polylactic acid, 1-8 parts of compatibilizer, 0.1-70 parts 0.6 parts stabilizer.
一种优选的技术方案为，所述尼龙11/聚乳酸生物基高分子合金还含有0～80份添加剂，所述添加剂可以为颜料、增塑剂，填料或是它们的任意组合；一种更为优选的技术方案为，本发明所述的填料为下列之一或它们的任意组合：玻璃纤维、碳酸钙、层状硅酸盐、炭黑、白炭黑、粘土或硅氧烷。A preferred technical solution is that the nylon 11/polylactic acid bio-based polymer alloy also contains 0 to 80 parts of additives, and the additives can be pigments, plasticizers, fillers or any combination thereof; a more The preferred technical solution is that the filler described in the present invention is one of the following or any combination thereof: glass fiber, calcium carbonate, layered silicate, carbon black, white carbon black, clay or siloxane.
进一步地，本发明所述的尼龙11/聚乳酸生物基高分子合金中，所述相容剂为树脂级苯乙烯类反应型相容剂SAG008（苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物）。Further, in the nylon 11/polylactic acid bio-based polymer alloy of the present invention, the compatibilizer is a resin-grade styrenic reactive compatibilizer SAG008 (styrene-acrylonitrile-glycidyl methacrylate copolymer).
进一步地，本发明所述的尼龙11/聚乳酸生物基高分子合金中，所述稳定剂为由Irganox1076和Irgafos168复配组成的抗氧剂，按照质量比，Irganox1076：Irgafos168=（3～20）：10。Further, in the nylon 11/polylactic acid bio-based polymer alloy of the present invention, the stabilizer is an antioxidant composed of Irganox1076 and Irgafos168, according to the mass ratio, Irganox1076:Irgafos168=(3～20) :10.
本发明所述的尼龙11/聚乳酸生物基高分子合金，是通过下述方法制备的：将30～70份尼龙11、30～70份聚乳酸、4～8份相容剂在60～80℃真空干燥12～24小时后，将它们和0.1～0.6份稳定剂、0～80份添加剂加入高速混合机高速混合3～5分钟，然后利用双螺杆挤出机在一定的加热温度控制条件下均匀造粒，最后在60～80℃真空烘箱中干燥12～24小时除去水分，得到所述尼龙11/聚乳酸生物基高分子合金样品，然后将该样品加入到注射机中，注射成型，即可得到所述尼龙11/聚乳酸生物基高分子合金标准产品。The nylon 11/polylactic acid bio-based polymer alloy described in the present invention is prepared by the following method: 30-70 parts of nylon 11, 30-70 parts of polylactic acid, 4-8 parts of compatibilizer at 60-80 After vacuum drying at ℃ for 12 to 24 hours, add them, 0.1 to 0.6 parts of stabilizer and 0 to 80 parts of additives into a high-speed mixer and mix them at high speed for 3 to 5 minutes, and then use a twin-screw extruder under certain heating temperature control conditions Uniform granulation, and finally drying in a vacuum oven at 60-80°C for 12-24 hours to remove moisture, to obtain the nylon 11/polylactic acid bio-based polymer alloy sample, and then add the sample to an injection machine for injection molding, namely The nylon 11/polylactic acid bio-based polymer alloy standard product can be obtained.
进一步地，上述制备过程中，所述双螺杆挤出机内加热温度控制条件为，从加料口到出料口依次设置八个区域，其中一区170～180℃，二区170～180℃，三区180～190℃，四区180～190℃，五区190～200℃，六区190～200℃，七区200～210℃，八区200～210℃，机头190～210℃，主机转速是85～100rpm，喂料速度4.1Hz。Further, in the above preparation process, the heating temperature control condition in the twin-screw extruder is that eight zones are sequentially set up from the feed port to the discharge port, of which the first zone is 170-180°C, the second zone is 170-180°C, The third zone is 180-190°C, the fourth zone is 180-190°C, the fifth zone is 190-200°C, the sixth zone is 190-200°C, the seventh zone is 200-210°C, the eighth zone is 200-210°C, the machine head is 190-210°C, the host The rotating speed is 85～100rpm, and the feeding speed is 4.1Hz.
进一步地，上述制备过程中，所述相容剂为树脂级苯乙烯类反应型相容剂SAG008，其环氧基团含量为8%；所述稳定剂为抗氧剂，抗氧剂由Irganox1076和Irgafos168复配。Further, in the above-mentioned preparation process, the compatibilizer is a resin-grade styrene-type reactive compatibilizer SAG008, and its epoxy group content is 8%; the stabilizer is an antioxidant, and the antioxidant is made of Irganox1076 Compounded with Irgafos168.
本发明所述的尼龙11/聚乳酸生物基高分子合金可以通过成型工艺（挤出成型、注射成型、吹塑成型、模压成型和压延成型）制备合金制品管、棒、纤维丝、薄膜、塑料等部件，应用于汽车、电子、包装、建材等行业。The nylon 11/polylactic acid bio-based polymer alloy described in the present invention can be prepared by molding processes (extrusion molding, injection molding, blow molding, compression molding and calendering) to prepare alloy products tubes, rods, fiber filaments, films, plastics And other components, used in automobiles, electronics, packaging, building materials and other industries.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
（1）本发明尼龙11/聚乳酸生物基高分子合金所采用的主要原料尼龙11和聚乳酸均来自生物基高分子材料。其中尼龙11（PA11）的单体是氨基十一酸，主要由蓖麻油裂解得的十一烯酸经缩聚合成得到，是一种生物基聚合物，相对于其他聚酰胺类材料，具有优良的低吸水性、低温韧性、耐化学性等；而聚乳酸（PLA）具有较高的强度和模量，以及独特的生物可降解性和生物相容性，可以通过可再生的生物资源（淀粉和糖类）制备。因此，本发明尼龙11/聚乳酸生物基高分子合金从原料源头上摆脱了对石油资源的依赖，且其制品可以生物降解，减少了白色污染。(1) The main raw materials used in the nylon 11/polylactic acid bio-based polymer alloy of the present invention are both nylon 11 and polylactic acid from bio-based polymer materials. Among them, the monomer of nylon 11 (PA11) is aminoundecylic acid, which is mainly synthesized by polycondensation of undecylenic acid obtained by cracking castor oil. It is a bio-based polymer. Compared with other polyamide materials, it has excellent properties. Low water absorption, low temperature toughness, chemical resistance, etc.; while polylactic acid (PLA) has high strength and modulus, as well as unique biodegradability and biocompatibility, it can be recycled through renewable biological resources (starch and sugars) preparation. Therefore, the nylon 11/polylactic acid bio-based polymer alloy of the present invention gets rid of the dependence on petroleum resources from the source of raw materials, and its products can be biodegraded, reducing white pollution.
（2）本发明尼龙11/聚乳酸生物基高分子合金充分利用了聚乳酸和尼龙11两者之间物理力学性能的互补性，通过加入具有高浓度含有环氧基团当量的相容剂SAG-008，SAG-008的环氧基团可与聚乳酸中的羧基和羟基以及尼龙11中的羧基和氨基端基发生开环反应起到增容作用和扩链效果，同时相容剂SAG-008具有界面偶联作用，从而可以增大尼龙11/聚乳酸生物基高分子合金材料的特性黏度，进而提高其强度和热加工性能。(2) The nylon 11/polylactic acid bio-based polymer alloy of the present invention makes full use of the complementarity of physical and mechanical properties between polylactic acid and nylon 11, by adding a compatibilizer SAG with a high concentration of epoxy group equivalent -008, the epoxy group of SAG-008 can undergo a ring-opening reaction with the carboxyl and hydroxyl groups in polylactic acid and the carboxyl and amino end groups in nylon 11 to achieve compatibilization and chain extension effects. At the same time, the compatibilizer SAG- 008 has interfacial coupling effect, which can increase the intrinsic viscosity of nylon 11/polylactic acid bio-based polymer alloy material, thereby improving its strength and thermal processing performance.
（3）本发明尼龙11/聚乳酸生物基高分子合金使用了热稳定性优良的树脂级苯乙烯类反应型相容剂SAG008，与市场上其他低分子量相容剂相比，具有更好的热稳定性，而且使用过程中不会出现堵塞加料口，产品也不会产生黑点或变色及过度凝胶化等不良问题，在价格方面也极具竞争优势。(3) The nylon 11/polylactic acid bio-based polymer alloy of the present invention uses a resin-grade styrene-based reactive compatibilizer SAG008 with excellent thermal stability, which has better Thermal stability, and will not block the feeding port during use, and the product will not produce black spots, discoloration, excessive gelation and other adverse problems, and it is also very competitive in terms of price.
（4）本发明尼龙11/聚乳酸生物基高分子合金通过添加由Irganox1010和Irgafos168复配的稳定剂，使得尼龙11单体和聚乳酸单体分子链上的基团之间形成了分子间氢键，进一步增强了二者的两相界面间的相互粘接作用，防止由尼龙11单体和聚乳酸单体的活性端基引发的尼龙11/聚乳酸生物基高分子合金产品降解，提高了合金材料在加工和使用过程中热稳定性，从而使得本发明尼龙11/聚乳酸生物基高分子合金的使用寿命更长。(4) By adding a stabilizer compounded by Irganox1010 and Irgafos168 to the nylon 11/polylactic acid bio-based polymer alloy of the present invention, intermolecular hydrogen is formed between the groups on the molecular chain of the nylon 11 monomer and the polylactic acid monomer bond, which further enhances the mutual bonding between the two phase interfaces, prevents the degradation of nylon 11/polylactic acid bio-based polymer alloy products caused by the active end groups of nylon 11 monomer and polylactic acid monomer, and improves the The alloy material is thermally stable during processing and use, so that the service life of the nylon 11/polylactic acid bio-based polymer alloy of the present invention is longer.
（5）本发明操作工艺简单，原料容易获得，价格便宜，对设备要求低，制备的产品具有较高的强度和韧性，使用寿命较长，尤其是当尼龙11/聚乳酸质量份数之比为70/30，相容剂质量份数为4时，材料的拉伸强度和冲击强度比尼龙11单一组分的还高，得到了一种既增强又增韧的生物基高分子合金，适合在汽车、电子、包装、建材等行业领域大规模工业化生产及推广应用。(5) The operation process of the present invention is simple, the raw materials are easy to obtain, the price is cheap, the requirements for equipment are low, the prepared product has high strength and toughness, and the service life is long, especially when the ratio of nylon 11 to polylactic acid When the mass fraction of the compatibilizer is 70/30 and the mass fraction of the compatibilizer is 4, the tensile strength and impact strength of the material are higher than those of the single component of nylon 11, and a bio-based polymer alloy with both reinforcement and toughness is obtained, which is suitable for Large-scale industrial production and promotion and application in the fields of automobile, electronics, packaging, building materials and other industries.
具体实施方式Detailed ways
为了进一步理解本发明，下面结合具体实例对本发明进行进一步描述，但本发明的保护范围并不仅限于此。In order to further understand the present invention, the present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.
本发明所有实施例及对比例中所采用的聚乳酸材料由美国Nature Works 公司提供，牌号为2002D；所用尼龙11由法国阿科玛公司提供，牌号为BESN P40 TL；所用相容剂为SAG008（苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物），由佳易容公司提供；所用抗氧剂为巴斯夫公司生产的Irganox1076和Irgafos168。The polylactic acid material adopted in all embodiments of the present invention and comparative examples is provided by U.S. Nature Works company, and the trade mark is 2002D; Nylon 11 used is provided by French Arkema Company, and the trade mark is BESN P40 TL; Compatibilizer used is SAG008 ( Styrene-acrylonitrile-glycidyl methacrylate copolymer), provided by Jiayirong Company; the antioxidants used are Irganox1076 and Irgafos168 produced by BASF.
本发明所得材料拉伸强度测试实验在温度为20℃，相对湿度为50%的环境中进行，使用哑铃型式样，按国标GB/T1040.3-2006进行测试，拉伸速度为50mm/min；弯曲实验按国标GB/T9341-2000进行测试，弯曲速度为2mm/min。拉伸试验机为深圳市新三思材料检测有限公司生产的CMT6104。The tensile strength test of the material obtained in the present invention is carried out in an environment with a temperature of 20°C and a relative humidity of 50%, using a dumbbell-shaped sample, and testing according to the national standard GB/T1040.3-2006, and the tensile speed is 50mm/min; The bending test is carried out according to the national standard GB/T9341-2000, and the bending speed is 2mm/min. The tensile testing machine is CMT6104 produced by Shenzhen Xinsansi Material Testing Co., Ltd.
本发明所得材料冲击试验在同样的环境条件下进行，在悬臂梁冲击试验机上按GB1843-1996进行测。The impact test of the material obtained in the present invention is carried out under the same environmental conditions, and is measured according to GB1843-1996 on an Izod impact testing machine.
实施例1-8。Examples 1-8.
将30～70份尼龙11、30～70份聚乳酸、1～8份反应型相容剂SAG008在60～80℃真空干燥12～24小时后，将它们和0.1～0.6份稳定剂、0～80份添加剂加入高速混合机高速混合3～5分钟，然后通过双螺杆挤出机出料口挤出均匀造粒，最后在60~80℃真空烘箱中干燥12~24小时除去水分，得到所述尼龙11/聚乳酸生物基高分子合金样品。该制备过程中，所述双螺杆挤出机内加热温度控制条件为，从加料口到出料口依次设置八个区域，其中一区170~180℃，二区170~180℃，三区180~190℃，四区180~190℃，五区190~200℃，六区190~200℃，七区200~210℃，八区200~210℃，机头190~210℃，主机转速是85~100rpm，喂料速度4.1Hz。通过控制双螺杆挤出机内加热温度条件，使其经过八个不同的温度区域，可以保证加热温度控制更精确，从而有利于提高本发明合金材料的性能以及保证均匀造粒和顺利出料。After drying 30-70 parts of nylon 11, 30-70 parts of polylactic acid, and 1-8 parts of reactive compatibilizer SAG008 at 60-80°C for 12-24 hours in vacuum, they are mixed with 0.1-0.6 parts of stabilizer, 0- Add 80 parts of additives into a high-speed mixer and mix at high speed for 3-5 minutes, then extrude through the discharge port of the twin-screw extruder to uniformly granulate, and finally dry in a vacuum oven at 60-80°C for 12-24 hours to remove moisture, and obtain the described Nylon 11/polylactic acid bio-based polymer alloy sample. In the preparation process, the heating temperature control conditions in the twin-screw extruder are as follows: eight zones are set in sequence from the feed port to the discharge port, wherein the first zone is 170-180°C, the second zone is 170-180°C, and the third zone is 180°C. ~190°C, 180~190°C for the fourth zone, 190~200°C for the fifth zone, 190~200°C for the sixth zone, 200~210°C for the seventh zone, 200~210°C for the eighth zone, 190~210°C for the machine head, and the speed of the main engine is 85 ~100rpm, feeding speed 4.1Hz. By controlling the heating temperature conditions in the twin-screw extruder so that it passes through eight different temperature zones, more precise control of the heating temperature can be ensured, which is conducive to improving the performance of the alloy material of the invention and ensuring uniform granulation and smooth discharge.
上述制备过程中，所述相容剂为，其环氧基团含量为8%；所述稳定剂为抗氧剂，抗氧剂由Irganox1076和Irgafos168复配；所述添加剂为颜料、增塑剂，填料中的一种或者两种以上的混合物，其中所述填料又可以为下列之一或它们的任意组合：玻璃纤维、碳酸钙、层状硅酸盐、炭黑、白炭黑、粘土或硅氧烷。In the above-mentioned preparation process, the compatibilizer is, and its epoxy group content is 8%; The stabilizer is an antioxidant, and the antioxidant is compounded by Irganox1076 and Irgafos168; The additive is a pigment, a plasticizer , one or a mixture of two or more fillers, wherein the filler can be one of the following or any combination of them: glass fiber, calcium carbonate, layered silicate, carbon black, white carbon black, clay or silicone.
然后将制备的上述尼龙11/聚乳酸生物基高分子合金样品加入到注射机中，注射成型，即可得到所述尼龙11/聚乳酸生物基高分子合金标准产品，该过程中注射机第一段温度设置170~220℃，第二段温度设置180~230℃，第三段温度设置180~230℃，第四段温度设置190~240℃，喷嘴温度设置185~235℃，注射速度30mm/s，注射时间4s，注射压力30MPa，保压压力30Mpa，保压时间1s，冷却时间30s，成型周期60s。Then add the above-mentioned nylon 11/polylactic acid bio-based polymer alloy sample prepared into the injection machine, and inject molding to obtain the standard product of the nylon 11/polylactic acid bio-based polymer alloy. In this process, the injection machine first The first stage temperature setting is 170~220°C, the second stage temperature setting is 180~230°C, the third stage temperature setting is 180~230°C, the fourth stage temperature setting is 190~240°C, the nozzle temperature setting is 185~235°C, and the injection speed is 30mm/ s, injection time 4s, injection pressure 30MPa, holding pressure 30Mpa, holding time 1s, cooling time 30s, molding cycle 60s.
对本发明方法制备的不同配方比例的尼龙11/聚乳酸生物基高分子合金标准产品进行性能测试，结果见下表1。Performance tests were carried out on the nylon 11/polylactic acid bio-based polymer alloy standard products with different formulation ratios prepared by the method of the present invention, and the results are shown in Table 1 below.
对比例1-4。Comparative Examples 1-4.
采用与实施例1-8同样的合金制备方法制备的不添加尼龙11、以及不添加相容剂SAG008的系列合金样品的性能试验，结果见下表1。The performance test of a series of alloy samples without adding nylon 11 and without adding compatibilizer SAG008 prepared by the same alloy preparation method as in Examples 1-8, the results are shown in Table 1 below.
表1 PLA/PA11共混物原料质量份配比及性能Table 1 Raw material ratio and properties of PLA/PA11 blends
由上表数据可以看出本发明制得尼龙11/聚乳酸生物基高分子合金的拉伸强度、弯曲强度和悬臂梁缺口冲击强度较佳，综合性能优异，特别是当尼龙11/聚乳酸质量份数之比为70/30（即实施例7），相容剂质量份数为4时，材料的拉伸强度和冲击强度比尼龙11单一组分（即对比例4）的还高，得到了一种既增强又增韧的生物基高分子合金，而且由于聚乳酸价格较尼龙11的低，它的加入降低了材料价格，扩展了PA11/PLA的应用范围，能够满足汽车、电子、包装、建材等行业对工程件的要求。It can be seen from the data in the above table that the nylon 11/polylactic acid bio-based polymer alloy prepared by the present invention has better tensile strength, bending strength and notched Izod impact strength, and excellent comprehensive performance, especially when the nylon 11/polylactic acid quality The ratio of the parts is 70/30 (i.e. Example 7), and when the mass fraction of the compatibilizer is 4, the tensile strength and impact strength of the material are higher than that of the single component of nylon 11 (i.e. Comparative Example 4). A bio-based polymer alloy that is both reinforced and toughened, and because the price of polylactic acid is lower than that of nylon 11, its addition reduces the material price and expands the application range of PA11/PLA, which can meet the needs of automobiles, electronics, packaging, etc. , building materials and other industries for engineering parts requirements.
虽然本发明是结合以上实例进行描述的，但本发明并不限定于上述实施例，而只受所附权利要求的限定，本领域普通技术人员能够容易地对其进行修改和变化，但并不离开本发明的实质构思和范围。需要指出的是，由于增加添加剂属于本发明的进一步的优选实施例，因此，在本实施例1-8中，未给出添加添加剂后尼龙11/聚乳酸生物基高分子合金样品的性能数据，但是根据本领域的公知常识，如中国专利CN 102391628A的记载，本领域技术人员可以合理地推知，添加添加剂后，本发明尼龙11/聚乳酸生物基高分子合金材料的使用性能将得到进一步的改进和优化。凡是在本发明的发明构思的基础上结合本领域的公知常识所做的任何改进或变换都属于本发明的保护范围。Although the present invention has been described in conjunction with the above examples, the present invention is not limited to the above-mentioned embodiments, but is only limited by the appended claims, and those skilled in the art can easily modify and change it, but not depart from the true spirit and scope of the present invention. It should be pointed out that since the addition of additives is a further preferred embodiment of the present invention, therefore, in this embodiment 1-8, the performance data of the nylon 11/polylactic acid bio-based polymer alloy sample after the addition of additives is not given, However, according to the common knowledge in this field, such as the records of Chinese patent CN 102391628A, those skilled in the art can reasonably infer that after adding additives, the performance of the nylon 11/polylactic acid bio-based polymer alloy material of the present invention will be further improved and optimization. Any improvement or transformation made on the basis of the inventive concept of the present invention combined with common knowledge in the field belongs to the protection scope of the present invention.
Claims (10)
- A kind of 1. nylon 11/PLA bio-based high polymer alloy, it is characterised in that the material containing following parts by weight：30~ 70 parts of nylon 11s, 30~70 parts of PLAs, 1~8 part of compatilizer, 0.1~0.6 part of stabilizer.
- 2. nylon 11 as claimed in claim 1/PLA bio-based high polymer alloy, it is characterised in that the nylon 11/poly- Lactic biological based high molecular alloy also contains 0~80 part of additive.
- 3. nylon 11 as claimed in claim 1 or 2/PLA bio-based high polymer alloy, it is characterised in that the compatilizer For SAG008, its epoxy group content is 8%.
- 4. nylon 11 as claimed in claim 1 or 2/PLA bio-based high polymer alloy, it is characterised in that the stabilizer Compounded by Irganox1076 and Irgafos168, according to mass ratio, Irganox1076：Irgafos168=（3~20）：10.
- 5. nylon 11 as claimed in claim 2/PLA bio-based high polymer alloy, it is characterised in that the additive is Pigment, plasticizer, one or more kinds of mixtures in filler.
- 6. nylon 11 as claimed in claim 5/PLA bio-based high polymer alloy, it is characterised in that under the filler is One of row or their any combination：Glass fibre, calcium carbonate, phyllosilicate, carbon black, white carbon, clay or siloxanes.
- 7. a kind of preparation method of nylon 11/PLA bio-based high polymer alloy described in claim 1 or 2, its feature exist In comprising the following steps：30~70 parts of nylon 11s, 30~70 parts of PLAs, 4~8 parts of compatilizers are done in 60~80 DEG C of vacuum After dry 12~24 hours, by them and 0.1~0.6 part of stabilizer, 0~80 part of additive addition high-speed mixer mixed at high speed 3 ~5 minutes, then uniformly it is granulated under the conditions of certain heating and temperature control using double screw extruder, finally at 60~80 DEG C Dried in vacuum drying oven 12~24 hours and remove moisture, obtain nylon 11/PLA bio-based high polymer alloy sample, then will The sample is added in injector, injection moulding, obtains nylon 11/PLA bio-based high polymer alloy standardized product.
- 8. the preparation method of nylon 11 according to claim 7/PLA bio-based high polymer alloy, it is characterised in that In above-mentioned preparation process, heating and temperature control condition is to be set gradually from charge door to discharging opening in the double screw extruder Eight regions, 170 ~ 180 DEG C of its Zhong-1 block, two 170 ~ 180 DEG C of areas, three 180 ~ 190 DEG C of areas, four 180 ~ 190 DEG C of areas, five areas 190 ~ 200 DEG C, six 190 ~ 200 DEG C of areas, seven 200 ~ 210 DEG C of areas, eight 200 ~ 210 DEG C of areas, 190 ~ 210 DEG C of mouth mold, engine speed is 85 ~ 100rpm, rate of feeding 4.1Hz.
- 9. the preparation method of nylon 11 as claimed in claim 7/PLA bio-based high polymer alloy, it is characterised in that on State in preparation process, the compatilizer is resin-grade phenylethylene response type compatilizer SAG008, and its epoxy group content is 8%； The stabilizer is antioxidant, and antioxidant is compounded by Irganox1076 and Irgafos168.
- 10. nylon 11/PLA bio-based high polymer alloy described in a kind of claim 1 or 2 is prepared by moulding process Alloy product pipe, rod, filament, film, plastic components.
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