技术领域Technical field
本申请涉及高分子材料技术领域，更具体地说，它涉及一种低收缩性阻燃聚丙烯塑料及其制备方法。The present application relates to the technical field of polymer materials, and more specifically, to a low-shrinkage flame-retardant polypropylene plastic and its preparation method.
背景技术Background technique
塑料是具有特殊性能的高分子材料，其具有质量轻、化学稳定性好、耐腐蚀、绝缘性好、成型方便、成本低的特点，广泛应用于电子工业、汽车制造、航空航天、工业等领域。聚丙烯是一种由丙烯单体经催化聚合而成的半结晶热塑性塑料。聚丙烯具有价格低廉、低密度、耐黄变及抗老化性、耐腐蚀性、良好的成型加工等特点，这使聚丙烯在汽车、家电、医疗等领域的应用逐年增加。Plastic is a polymer material with special properties. It has the characteristics of light weight, good chemical stability, corrosion resistance, good insulation, convenient molding, and low cost. It is widely used in the electronics industry, automobile manufacturing, aerospace, industry and other fields. . Polypropylene is a semi-crystalline thermoplastic made from the catalytic polymerization of propylene monomer. Polypropylene has the characteristics of low price, low density, resistance to yellowing and aging, corrosion resistance, and good molding processing. This makes the application of polypropylene in automobiles, home appliances, medical and other fields increasing year by year.
近年来，电子电器、建筑、航空与汽车行业的快速发展对塑料的性能提出的更高的要求。其中，阻燃型的塑料不易燃烧，火焰传播速率小，质量损失速率及释热速率较低，而且具有一定的自熄性。但聚丙烯材料的阻燃性差，不能满足阻燃要求，并且多采用卤素阻燃剂，燃烧过程会放出卤化氢对人体造成严重的危害；而且聚丙烯收缩率大，壁厚制品容易凹陷，对一些尺寸精度较高的零件，难以达到要求。In recent years, the rapid development of electronic appliances, construction, aviation and automobile industries has put forward higher requirements for the performance of plastics. Among them, flame-retardant plastics are not easy to burn, have a small flame propagation rate, low mass loss rate and heat release rate, and have certain self-extinguishing properties. However, polypropylene materials have poor flame retardancy and cannot meet flame retardant requirements, and halogen flame retardants are often used. The combustion process will release hydrogen halide, causing serious harm to the human body. Moreover, polypropylene has a large shrinkage rate, and thick-walled products are prone to dents, which is harmful to the human body. Some parts with high dimensional accuracy are difficult to meet the requirements.
针对上述中的相关技术，发明人发现聚丙烯材料在实际应用中收缩率较大，产品尺寸不稳定；不具备阻燃防火要求，极易燃烧，危害极大。Regarding the above-mentioned related technologies, the inventor found that polypropylene material has a large shrinkage rate in practical applications and the product size is unstable; it does not meet the flame retardant and fire protection requirements, is extremely easy to burn, and is extremely harmful.
发明内容Contents of the invention
为了使聚丙烯不仅具有一定的机械强度，而且收缩率降低，阻燃性提高，本申请提供一种低收缩性阻燃聚丙烯塑料及其制备方法。In order to make polypropylene not only have certain mechanical strength, but also reduce shrinkage and improve flame retardancy, this application provides a low shrinkage flame retardant polypropylene plastic and its preparation method.
第一方面，本申请提供一种低收缩性阻燃聚丙烯塑料，采用如下的技术方案：In the first aspect, this application provides a low-shrinkage flame-retardant polypropylene plastic, adopting the following technical solution:
一种低收缩性阻燃聚丙烯塑料，包括以下重量百分比的原料：20-30％均聚聚丙烯、20-30％共聚聚丙烯、10-20％长纤硅灰石、25-30％无卤阻燃剂、2-8％增韧剂、0.5-1.5％抗氧化剂和0.5-1.5％润滑剂，所述无卤阻燃剂为磷-氮膨胀型无卤阻燃剂。A low-shrinkage flame-retardant polypropylene plastic, including the following raw materials in weight percentages: 20-30% homopolymer polypropylene, 20-30% copolymer polypropylene, 10-20% long-fiber wollastonite, 25-30% free Halogen flame retardant, 2-8% toughening agent, 0.5-1.5% antioxidant and 0.5-1.5% lubricant, the halogen-free flame retardant is a phosphorus-nitrogen expanded halogen-free flame retardant.
通过采用上述技术方案，由于采用均聚聚丙烯和共聚聚丙烯作为主料，并添加一定的长纤硅灰石，其具有一定的纤维状、针状结构，分散于聚丙烯材料中，可以明显改善基体的机械性能，提高制品的热稳定性和尺寸稳定性，磷-氮膨胀型无卤阻燃剂具有阻燃效率高、低烟及低毒的优点，润滑剂通过自身内胎润滑性的相互配合，使材料配方中的阻燃剂和填充物充分分散，使聚丙烯材料挤出表面摩擦系数低，挤出材料表面光滑平整，抗氧剂能使聚丙烯在高温下不产生分解，从而制得不仅具有一定的机械强度，而且收缩率也大幅度降低，并且具有很好的阻燃性的聚丙烯材料。By adopting the above technical solution, homopolymerized polypropylene and copolymerized polypropylene are used as the main materials, and a certain amount of long-fiber wollastonite is added, which has a certain fibrous and needle-like structure and is dispersed in the polypropylene material. Improve the mechanical properties of the matrix and improve the thermal stability and dimensional stability of the product. Phosphorus-nitrogen expanded halogen-free flame retardant has the advantages of high flame retardant efficiency, low smoke and low toxicity. The lubricant interacts with the lubrication of its own inner tube. Together, the flame retardants and fillers in the material formula are fully dispersed, so that the friction coefficient of the extruded surface of the polypropylene material is low and the surface of the extruded material is smooth and flat. The antioxidant can prevent the polypropylene from decomposing at high temperatures, thereby making the product It is a polypropylene material that not only has a certain mechanical strength, but also has a greatly reduced shrinkage rate and has good flame retardancy.
可选的，所述聚丙烯塑料包括以下重量百分比的原料：25.5％均聚聚丙烯、25.5％共聚聚丙烯、15％长纤硅灰石、28％无卤阻燃剂、5％增韧剂、0.5％抗氧剂、0.5％润滑剂。Optionally, the polypropylene plastic includes the following weight percentage raw materials: 25.5% homopolymerized polypropylene, 25.5% copolymerized polypropylene, 15% long-fiber wollastonite, 28% halogen-free flame retardant, 5% toughening agent , 0.5% antioxidant, 0.5% lubricant.
通过采用上述技术方案，各原料用量更加精确，使得制成的聚丙烯材料力学强度高、阻燃性能好，且收缩率小，尺寸稳定性好。By adopting the above technical solution, the dosage of each raw material is more precise, so that the polypropylene material produced has high mechanical strength, good flame retardant properties, small shrinkage and good dimensional stability.
可选的，所述磷-氮膨胀型无卤阻燃剂包括质量比为5:1-1.2:0.05-0.1的高聚合度II型聚磷酸铵、三嗪成炭剂和聚四氟乙烯。Optionally, the phosphorus-nitrogen expanded halogen-free flame retardant includes high polymerization degree II ammonium polyphosphate, triazine carbon-forming agent and polytetrafluoroethylene in a mass ratio of 5:1-1.2:0.05-0.1.
通过采用上述技术方案，高聚合度II型聚磷酸铵中含磷量高，含氮量大，热稳定性好，同时具有价格便宜，毒性低，使用安全等优点，阻燃效率高，受热燃烧时少烟、低毒、无有害气体和熔滴产生，其通过生成致密的炭层，起到隔热、隔氧作用，达到阻燃目的，采用三嗪成炭剂对高聚合度II型聚磷酸铵进行阻燃能力改善，在燃烧过程中，三嗪成炭剂与聚磷酸铵通过一系列的酯化和交联炭化反应，同时聚磷酸铵分解产生磷酸及多聚磷酸能促进聚丙烯的成炭，在聚丙烯材料表面形成膨胀炭层，阻碍了裂解产生的可燃性气体想火焰表面扩散以及外部的热量和氧气向材料内部扩散，起到隔热和隔氧作用，很好的保护了内部材料的进一步降解和燃烧，使得聚不成的热分解速率降低，提高了聚丙烯材料的热稳定性，提高了材料的阻燃性；在高聚合度II聚磷酸铵与聚丙烯混合时，由于强极性的聚磷酸铵与非极性的聚丙烯基体间的极性差异较大，导致聚磷酸铵与聚丙烯基体的相容性较差，因此采用聚四氟乙烯对高聚合度II聚磷酸铵和三嗪成炭剂进行表面包覆，以改善二者与聚丙烯基体的相容性，使它们能与聚丙烯基体很好的相容在一起，且在基体中的分散性更好，从而改善提高聚丙烯材料的力学性能。By adopting the above technical solution, the high degree of polymerization II ammonium polyphosphate contains high phosphorus, large nitrogen content, good thermal stability, and has the advantages of cheap price, low toxicity, safe use, high flame retardant efficiency, and no burning when heated. It has less smoke, low toxicity, and no harmful gases and droplets. It generates a dense carbon layer to insulate heat and oxygen, and achieves the purpose of flame retardancy. Triazine carbon-forming agent is used to treat type II polyethylene with a high degree of polymerization. Ammonium phosphate improves the flame retardancy. During the combustion process, the triazine carbon-forming agent and ammonium polyphosphate undergo a series of esterification and cross-linking carbonization reactions. At the same time, ammonium polyphosphate decomposes to produce phosphoric acid and polyphosphoric acid, which can promote the decomposition of polypropylene. It forms an expanded carbon layer on the surface of the polypropylene material, which prevents the flammable gases produced by cracking from diffusing to the flame surface and the external heat and oxygen from diffusing into the material. It plays the role of heat insulation and oxygen insulation, and provides good protection. Further degradation and combustion of internal materials reduces the thermal decomposition rate of the polypropylene material, improves the thermal stability of the polypropylene material, and improves the flame retardancy of the material; when high polymerization degree II ammonium polyphosphate is mixed with polypropylene, due to The polarity difference between the highly polar ammonium polyphosphate and the non-polar polypropylene matrix is large, resulting in poor compatibility between the ammonium polyphosphate and the polypropylene matrix. Therefore, polytetrafluoroethylene is used for high polymerization degree II polypropylene. Ammonium phosphate and triazine carbon-forming agent are surface-coated to improve their compatibility with the polypropylene matrix, so that they can be well compatible with the polypropylene matrix and have better dispersion in the matrix. , thereby improving the mechanical properties of polypropylene materials.
可选的，所述润滑剂包括质量比为1:0.8-1.2的硬脂酸类润滑剂和硅酮母粒。Optionally, the lubricant includes stearic acid lubricant and silicone masterbatch with a mass ratio of 1:0.8-1.2.
通过采用上述技术方案，硬脂酸类润滑剂、硅酮母粒与聚丙烯基体的相容性好，可以提高阻燃剂和长纤硅灰石的分散性，使共混材料挤出时，加工效率提高，克服材料粘结，提高成品的平滑度和光泽度，改善成品外观，硅酮母粒作为优异的外润滑及，能够改善材料的分散减少挤出口模积垢，降低设备的磨损，提高出料速度及使制品变形小，同样对长纤硅灰石和阻燃剂的分散性，硬脂酸类润滑剂和硅酮母粒通过自身内外润滑性能，使材料配方中的阻燃剂和长纤硅灰石充分分散，挤出表面摩擦系数降低，聚丙烯材料表面效果光滑平整。By adopting the above technical solution, the stearic acid lubricant, silicone masterbatch and polypropylene matrix have good compatibility, which can improve the dispersion of the flame retardant and long-fiber wollastonite, so that when the blended material is extruded, Improve processing efficiency, overcome material adhesion, improve the smoothness and gloss of finished products, and improve the appearance of finished products. Silicone masterbatch serves as excellent external lubrication and can improve material dispersion, reduce extrusion die fouling, and reduce equipment wear. Improve the discharging speed and reduce the deformation of the product. It also improves the dispersion of long-fiber wollastonite and flame retardants. Stearic acid lubricants and silicone masterbatch use their own internal and external lubrication properties to reduce the flame retardants and flame retardants in the material formula. The long fiber wollastonite is fully dispersed, the friction coefficient of the extrusion surface is reduced, and the surface effect of the polypropylene material is smooth and flat.
可选的，所述硅酮母粒由以下方法制成：将硅酮粉分散于无水乙醇中，制成浓度为8-10wt％的分散液；将凹凸棒土加入到去离子水中，制成浓度为3-5wt％的悬浮液；将硅溶胶加入到去离子水中，制成浓度为3-5wt％的硅溶胶溶液；Optionally, the silicone masterbatch is made by the following method: dispersing silicone powder in anhydrous ethanol to make a dispersion with a concentration of 8-10wt%; adding attapulgite to deionized water to prepare to form a suspension with a concentration of 3-5wt%; add silica sol to deionized water to prepare a silica sol solution with a concentration of 3-5wt%;
将分散液、悬浮液和硅溶胶溶液混合，经喷雾干燥，制得硅酮母粒，硅酮粉、硅溶胶和凹凸棒土的质量比为2-2.5:2.5-3:5。The dispersion, suspension and silica sol solution are mixed and spray-dried to prepare silicone masterbatch. The mass ratio of silicone powder, silica sol and attapulgite is 2-2.5:2.5-3:5.
通过采用上述技术方案，凹凸棒土表面大量的羟基以及纤维状晶体结构，使得其具有强烈的吸附性能，凹凸棒土和二氧化硅在水中可以完全紧密的吸附在一起，通过硅酮粉加入到凹凸棒土和二氧化硅的悬浮水溶液中，硅酮粉能负载于凹凸棒土和二氧化硅中，各个组分相互隔离形成松散的结构，添加到聚丙烯中，在外加螺杆剪切作用下，松散结构易于分散在集体中，凹凸棒土和二氧化硅的加入能提高聚丙烯的刚性，喷雾干燥避免了凹凸棒土、二氧化硅和硅酮粉的团聚，分散性得到提高，凹凸棒土和二氧化硅成为成核剂，聚丙烯材料中原本不能结晶的无定形部分转变为结晶，获得更高的结晶度，能减少聚丙烯的球晶尺寸，提高球晶界面结合强度，晶体更为致密，减少对入射光的散射和折射，增加光泽度，而且球晶从数量较少的大尺寸变成大量的小尺寸的密集晶体后，由于球晶的细化，可以使材料吸收更多的能量，提高冲击强度；而硅酮粉由于分子链之间的摩擦系数少，平均分散嵌入聚丙烯分子链中，均匀分布在聚丙烯结构中，减少了聚丙烯分子链段之间的摩擦和聚丙烯分子链段和加工设备之间的摩擦，提高了聚丙烯的滑动性，润滑作用增强，挤出性能得到提高，改善了聚丙烯材料的润滑性，使聚丙烯材料表面更加光滑，光泽度得到明显提高。By adopting the above technical solution, the large number of hydroxyl groups and fibrous crystal structure on the surface of attapulgite makes it have strong adsorption performance. Attapulgite and silica can be completely and tightly adsorbed together in water. Silicone powder is added to In the suspended aqueous solution of attapulgite and silica, silicone powder can be loaded in the attapulgite and silica. Each component is isolated from each other to form a loose structure. When added to polypropylene, under the action of external screw shear , the loose structure is easy to disperse in the collective. The addition of attapulgite and silica can improve the rigidity of polypropylene. Spray drying avoids the agglomeration of attapulgite, silica and silicone powder, and the dispersion is improved. Attapulgite Soil and silica become nucleating agents, and the amorphous part of the polypropylene material that was originally unable to crystallize becomes crystallized to obtain a higher degree of crystallinity, which can reduce the size of polypropylene spherulites, improve the bonding strength of the spherulite interface, and make the crystals more In order to be dense, the scattering and refraction of incident light are reduced, the gloss is increased, and after the spherulites change from a small number of large-sized to a large number of small-sized dense crystals, the material can absorb more due to the refinement of the spherulites. The energy of the silicone powder increases the impact strength; because the silicone powder has a small friction coefficient between molecular chains, it is evenly dispersed and embedded in the polypropylene molecular chain and evenly distributed in the polypropylene structure, reducing the friction and friction between the polypropylene molecular chain segments. The friction between polypropylene molecular segments and processing equipment improves the sliding properties of polypropylene, enhances lubrication, improves extrusion performance, improves the lubricity of polypropylene materials, and makes the surface of polypropylene materials smoother and glossier. significantly improved.
可选的，所述均聚聚丙烯的熔融指数为10-15g/10min，所述共聚聚丙烯的熔融指数为25-27g/10min。Optionally, the melt index of the homopolymerized polypropylene is 10-15g/10min, and the melt index of the copolymerized polypropylene is 25-27g/10min.
通过采用上述技术方案，采用成型性强、流动性好的共聚聚丙烯和均聚聚丙烯作为基料，在较低的挤出温度下即可制得共混均匀的聚丙烯产品，且以上熔融指数共混的均聚聚丙烯和共聚聚丙烯的拉伸性强，弯曲模量高。By adopting the above technical solution and using copolymer polypropylene and homopolymer polypropylene with strong moldability and good fluidity as base materials, uniformly blended polypropylene products can be produced at a lower extrusion temperature, and the above melt Index blended homopolypropylene and copolymer polypropylene have strong stretchability and high flexural modulus.
可选的，所述增韧剂为乙烯-辛烯共聚物，在190℃、2.16kg条件下的熔融指数为20g/10min。Optionally, the toughening agent is an ethylene-octene copolymer, with a melt index of 20g/10min at 190°C and 2.16kg.
通过采用上述技术方案，乙烯-辛烯共聚物能较好的改善共聚聚丙烯、均聚聚丙烯、长纤硅灰石等组分的相容性，提高聚丙烯材料的力学强度。By adopting the above technical solution, ethylene-octene copolymer can better improve the compatibility of copolymerized polypropylene, homopolymerized polypropylene, long-fiber wollastonite and other components, and improve the mechanical strength of polypropylene materials.
可选的，所述抗氧剂选自亚磷酸酯类抗氧剂、硫酯类抗氧剂和受阻分类抗氧剂中的一种或几种。Optionally, the antioxidant is selected from one or more of phosphite antioxidants, thioester antioxidants and hindered classification antioxidants.
通过采用上述技术方案，抗氧剂能保护阻燃剂，以防阻燃剂在挤出时，由于挤出速度较慢，阻燃剂在挤出机中停留时间长而产生降解，使得阻燃性下降。By adopting the above technical solution, the antioxidant can protect the flame retardant from degrading during extrusion due to the slow extrusion speed and long residence time of the flame retardant in the extruder, making the flame retardant sexual decline.
第二方面，本申请提供一种低收缩性阻燃聚丙烯塑料的制备方法，采用如下的技术方案：In the second aspect, this application provides a method for preparing low-shrinkage flame-retardant polypropylene plastic, adopting the following technical solution:
一种低收缩性阻燃聚丙烯塑料的制备方法，包括以下步骤：A preparation method of low-shrinkage flame-retardant polypropylene plastic, including the following steps:
制备无卤阻燃剂：将高聚合度II型聚磷酸铵在20-30℃搅拌8-10min，加入三嗪成炭剂，升温至50-60℃，搅拌50-60min，降温至20-30℃，边搅拌边加入聚四氟乙烯，搅拌8-10min，冷却25-30min，制得无卤阻燃剂；Preparation of halogen-free flame retardant: Stir high polymerization degree II ammonium polyphosphate at 20-30°C for 8-10 minutes, add triazine carbonizer, raise the temperature to 50-60°C, stir for 50-60 minutes, and cool to 20-30 ℃, add polytetrafluoroethylene while stirring, stir for 8-10 minutes, and cool for 25-30 minutes to prepare a halogen-free flame retardant;
原料选取：按照质量百分比，分别称取20-30％均聚聚丙烯、20-30％共聚聚丙烯、10-20％长纤硅灰石、25-30％无卤阻燃剂、2-8％增韧剂、0.5-1.5％抗氧化剂和0.5-1.5％润滑剂；Selection of raw materials: According to mass percentage, weigh 20-30% homopolypropylene, 20-30% copolymerized polypropylene, 10-20% long fiber wollastonite, 25-30% halogen-free flame retardant, 2-8 % toughener, 0.5-1.5% antioxidant and 0.5-1.5% lubricant;
混合搅拌：将无卤阻燃剂加入到长纤硅灰石中，在20-30℃下搅拌25-30min，制得1号料包；将均聚聚丙烯、共聚聚丙烯、增韧剂、抗氧剂和润滑剂混合，在20-30℃下搅拌50-60min，制得2号料包；Mixing and stirring: Add the halogen-free flame retardant to the long-fiber wollastonite and stir for 25-30 minutes at 20-30°C to prepare No. 1 material package; add homopolymerized polypropylene, copolymerized polypropylene, toughening agent, Mix antioxidant and lubricant, stir at 20-30°C for 50-60 minutes, and prepare No. 2 material package;
共混改性：将2号料包加入到主喂料口，1号料包通过侧喂料口加入，挤出温度为160-210℃，挤出条状物料，冷却；Blending modification: Add the No. 2 bag to the main feeding port, and add the No. 1 bag through the side feeding port. The extrusion temperature is 160-210°C, and the strip material is extruded and cooled;
风冷压制：将条状物料以2-5cm的间距依次排开，以15-16℃的冷风持续风冷28-30min，以1-2MPa的压力压3-5s，包装，制得低收缩性阻燃聚丙烯材料。Air-cooling pressing: Arrange the strip materials one by one at a distance of 2-5cm, continue air-cooling with cold air at 15-16°C for 28-30 minutes, press with a pressure of 1-2MPa for 3-5s, and package to obtain low shrinkage Flame retardant polypropylene material.
通过采用上述技术方案，将高聚合度II聚磷酸铵用三嗪成炭剂改善其阻燃性后，用聚四氟乙烯对其进行极性改性，改善无卤阻燃剂与聚丙烯基体的相容性，提高力学强度，制成无卤、低烟、无腐蚀和毒性气体产生的阻燃剂；而且将长纤硅灰石和无卤阻燃剂通过侧喂技工方式，降低其受螺杆挤出长度和时间的影响，既在保证阻燃性的基础上，又能极大的保留硅灰石的针状结构，从而减低聚丙烯材料的收缩率，该方法兼具逻辑严谨、绿色环保、材料来源广、易加工、低耗能和成本低廉等优点，加之赋予其低收缩和阻燃两大功能，同时在稳定和安全两方面优势突出。By adopting the above technical solution, high polymerization degree II ammonium polyphosphate is improved with a triazine carbon-forming agent to improve its flame retardancy, and then polytetrafluoroethylene is used for polar modification to improve the halogen-free flame retardant and the polypropylene matrix. The compatibility of the flame retardant is improved, and the mechanical strength is improved to make a halogen-free, low-smoke, non-corrosive and toxic gas-generating flame retardant; and the long-fiber wollastonite and halogen-free flame retardant are side-fed to reduce their impact on the screw. The influence of extrusion length and time can not only ensure the flame retardancy, but also greatly retain the needle-like structure of wollastonite, thereby reducing the shrinkage rate of polypropylene materials. This method is both logically rigorous and green. It has the advantages of wide source of materials, easy processing, low energy consumption and low cost. In addition, it is endowed with two major functions of low shrinkage and flame retardant. It also has outstanding advantages in stability and safety.
可选的，挤出时，螺杆转速为350-360r/min，挤出功率为280-300W。Optional, during extrusion, the screw speed is 350-360r/min, and the extrusion power is 280-300W.
通过采用上述技术方案，挤出时转速太大容易磨损机器，转速太小会影响生产效率。By adopting the above technical solution, if the rotation speed is too high during extrusion, it will easily wear out the machine, and if the rotation speed is too low, the production efficiency will be affected.
综上所述，本申请具有以下有益效果：To sum up, this application has the following beneficial effects:
1、由于本申请采用均聚聚丙烯、共聚聚丙烯为基料，并添加长纤硅灰石、磷-氮膨胀型无卤阻燃剂、润滑剂和抗氧剂等，长纤硅灰石的针状结构能降低聚丙烯材料的收缩率，同时长纤硅灰石还能改善聚丙烯的阻燃效果和力学强度，磷-氮膨胀型无卤阻燃剂的阻燃效果好，可以达到UL94 V0级，而且低烟、无毒、无熔滴。1. Since this application uses homopolymer polypropylene and copolymer polypropylene as the base material, and adds long-fiber wollastonite, phosphorus-nitrogen expanded halogen-free flame retardants, lubricants and antioxidants, etc., long-fiber wollastonite The needle-like structure can reduce the shrinkage of polypropylene materials. At the same time, long-fiber wollastonite can also improve the flame retardant effect and mechanical strength of polypropylene. The phosphorus-nitrogen expanded halogen-free flame retardant has good flame retardant effect and can reach UL94 V0 grade, low smoke, non-toxic, and no dripping.
2、本申请中优选采用高聚合度II聚磷酸铵、三嗪成炭剂和聚四氟乙烯制备无卤阻燃剂，三嗪成炭剂能增强高聚合度II聚磷酸铵在燃烧时所形成的炭层的致密度，改善隔热、隔氧能力，提高阻燃性，而聚四氟乙烯能改善高聚合度II型聚磷酸铵和三嗪成炭剂的极性，使二者与聚丙烯基体的相容性得到改善，从而增强力学性能。2. In this application, it is preferred to use high polymerization degree II ammonium polyphosphate, triazine char-forming agent and polytetrafluoroethylene to prepare halogen-free flame retardants. The triazine char-forming agent can enhance the effect of high polymerization degree II ammonium polyphosphate during combustion. The density of the formed carbon layer improves the heat insulation and oxygen insulation capabilities, and improves the flame retardancy, while polytetrafluoroethylene can improve the polarity of high polymerization degree II ammonium polyphosphate and triazine carbon-forming agent, making them compatible with The compatibility of the polypropylene matrix is improved, resulting in enhanced mechanical properties.
3、本申请中优选采用硬脂酸类润滑剂和硅酮母粒作为润滑剂，而且硅酮母粒由凹凸棒土、二氧化硅和硅酮粉制成，硅酮粉负载于凹凸棒石和二氧化硅上，形成相互隔离的松散结构，在聚丙烯挤出时，通过螺杆剪切作用，使得松散结构易于分散，从而提高结晶度并使球晶细化，减少入射光的散射和折射，提高光泽度，另外硅酮粉的加入还能改善聚丙烯材料的力学强度。3. In this application, stearic acid lubricants and silicone masterbatch are preferably used as lubricants, and the silicone masterbatch is made of attapulgite, silica and silicone powder. The silicone powder is loaded on attapulgite and attapulgite. On the silica, mutually isolated loose structures are formed. During the extrusion of polypropylene, the loose structure is easily dispersed through screw shear, thereby increasing the crystallinity and refining the spherulites, and reducing the scattering and refraction of incident light. Improve the gloss, and the addition of silicone powder can also improve the mechanical strength of polypropylene materials.
具体实施方式Detailed ways
硅酮母粒的制备例1-4Preparation Example 1-4 of Silicone Masterbatch
制备例1：将硅酮粉分散于无水乙醇中，制成浓度为10wt％的分散液；将凹凸棒土加入到去离子水中，制成浓度为5wt％的悬浮液；将硅溶胶加入到去离子水中，制成浓度为5wt％的硅溶胶溶液，硅酮粉选自东湾山一塑化，型号为SY-306A，硅溶胶选自胶凝鸿鑫达生物科技，型号为HXD-02，凹凸棒土选自安徽明美矿物，型号为701A；Preparation Example 1: Disperse silicone powder in absolute ethanol to make a dispersion with a concentration of 10wt%; add attapulgite to deionized water to make a suspension with a concentration of 5wt%; add silica sol to In deionized water, a silica sol solution with a concentration of 5wt% was made. The silicone powder was selected from Dongwan Shanyi Plasticization, model SY-306A, and the silica sol was selected from gelling Hongxinda Biotechnology, model HXD-02. , Attapulgite is selected from Anhui Mingmei Minerals, model 701A;
将分散液、悬浮液和硅溶胶溶液混合，经喷雾干燥，制得硅酮母粒，硅酮粉、硅溶胶和凹凸棒土的质量比为2.5:2.5:5，喷雾干燥进风口温度为150℃，出风口温度为60℃。Mix the dispersion, suspension and silica sol solution and spray-dry to prepare silicone masterbatch. The mass ratio of silicone powder, silica sol and attapulgite is 2.5:2.5:5, and the spray drying air inlet temperature is 150 ℃, the air outlet temperature is 60 ℃.
制备例2：将硅酮粉分散于无水乙醇中，制成浓度为8wt％的分散液；将凹凸棒土加入到去离子水中，制成浓度为3wt％的悬浮液；将硅溶胶加入到去离子水中，制成浓度为3wt％的硅溶胶溶液，硅酮粉选自东湾山一塑化，型号为SY-306A，硅溶胶选自胶凝鸿鑫达生物科技，型号为HXD-02，凹凸棒土选自安徽明美矿物，型号为701A；Preparation Example 2: Disperse silicone powder in absolute ethanol to make a dispersion with a concentration of 8wt%; add attapulgite to deionized water to make a suspension with a concentration of 3wt%; add silica sol to In deionized water, a silica sol solution with a concentration of 3wt% was made. The silicone powder was selected from Dongwan Shanyi Plasticization, model SY-306A, and the silica sol was selected from gelling Hongxinda Biotechnology, model HXD-02. , Attapulgite is selected from Anhui Mingmei Minerals, model 701A;
将分散液、悬浮液和硅溶胶溶液混合，经喷雾干燥，制得硅酮母粒，硅酮粉、硅溶胶和凹凸棒土的质量比为2:3:5，喷雾干燥进风口温度为150℃，出风口温度为60℃。Mix the dispersion, suspension and silica sol solution and spray-dry to prepare silicone masterbatch. The mass ratio of silicone powder, silica sol and attapulgite is 2:3:5, and the spray drying air inlet temperature is 150 ℃, the air outlet temperature is 60 ℃.
制备例3：与制备例1的区别在于，未添加凹凸棒土。Preparation Example 3: The difference from Preparation Example 1 is that attapulgite is not added.
制备例4：与制备例1的区别在于，未添加硅溶胶。Preparation Example 4: The difference from Preparation Example 1 is that no silica sol was added.
实施例Example
实施例1：一种低收缩性阻燃聚丙烯塑料，原料用量如表1所示，其中均聚聚丙烯的熔融指数为15g/10min，型号为台塑宁波1120，共聚聚丙烯的熔融指数为25g/10min，型号为韩国SK B380G，抗氧化剂为亚磷酸酯类抗氧剂168，润滑剂为硬脂酸钙，增韧剂为乙烯-辛烯共聚物，在190℃/2.16kg条件下的熔融指数为20g/10min，型号为美国陶氏8402，无卤阻燃剂为磷-氮膨胀型无卤阻燃剂，包括质量比为5:1:0.1的高聚合度II型聚磷酸铵、三嗪成炭剂和聚四氟乙烯，高聚合度II型聚磷酸铵选自什邡市长丰化工，型号为CF-APP201，三嗪成炭剂选自清远市日光东成化工有限公司。Example 1: A low-shrinkage flame-retardant polypropylene plastic. The amount of raw materials is shown in Table 1. The melt index of homopolypropylene is 15g/10min, the model is Formosa Plastics Ningbo 1120, and the melt index of copolymerized polypropylene is 25g/10min, the model is Korean SK B380G, the antioxidant is phosphite antioxidant 168, the lubricant is calcium stearate, the toughening agent is ethylene-octene copolymer, under the conditions of 190℃/2.16kg The melt index is 20g/10min, the model is American Dow 8402, the halogen-free flame retardant is phosphorus-nitrogen expanded halogen-free flame retardant, including high polymerization degree II ammonium polyphosphate with a mass ratio of 5:1:0.1, The triazine carbon-forming agent and polytetrafluoroethylene, high polymerization degree II type ammonium polyphosphate were selected from Shifang Changfeng Chemical Industry, model CF-APP201, and the triazine carbon-forming agent was selected from Qingyuan Riguang Dongcheng Chemical Co., Ltd.
上述低收缩性阻燃聚丙烯材料的制备方法，包括以下步骤：The preparation method of the above-mentioned low-shrinkage flame-retardant polypropylene material includes the following steps:
S1、制备无卤阻燃剂：将高聚合度II型聚磷酸铵加入到高混机内，在30℃下以200r/min的转速搅拌10min，聚磷酸铵的体积为高混机容量的三分之一，然后加入三嗪成炭剂，升温至60℃，以500r/min的转速搅拌60min，降温至30℃，边搅拌边加入聚四氟乙烯，搅拌10min，冷却30min，制得无卤阻燃剂；S1. Preparation of halogen-free flame retardant: Add high polymerization degree II ammonium polyphosphate into the high mixer, stir at 200r/min at 30°C for 10 minutes, the volume of ammonium polyphosphate is three times the high mixer capacity. 1/2, then add triazine carbonizer, raise the temperature to 60°C, stir at 500r/min for 60min, cool to 30°C, add polytetrafluoroethylene while stirring, stir for 10min, cool for 30min, to obtain halogen-free flame retardants;
S2、原料选取：按照表1中的原料用量称取各原料；S2. Raw material selection: Weigh each raw material according to the raw material dosage in Table 1;
S3、混合搅拌：将无卤阻燃剂加入到长纤硅灰石中，在30℃下以200r/min的转速搅拌30min，制得1号料包；将均聚聚丙烯、共聚聚丙烯、增韧剂、抗氧剂和润滑剂混合，在30℃下以500r/min的转速搅拌60min，制得2号料包；S3. Mixing and stirring: Add the halogen-free flame retardant to the long-fiber wollastonite, stir at a speed of 200r/min at 30°C for 30 minutes, and prepare the No. 1 material package; mix homopolymerized polypropylene, copolymerized polypropylene, Mix the toughening agent, antioxidant and lubricant, and stir for 60 minutes at 30°C and 500r/min to prepare No. 2 material package;
S4、共混改性：将2号料包加入到双螺旋挤出机的主喂料口，1号料包通过侧喂料口加入到双螺旋挤出机，挤出温度为210℃，挤出条状物料，冷却，螺杆转速为360r/min，挤出功率为300W；S4. Blending modification: Add No. 2 bag to the main feeding port of the twin-screw extruder, and add No. 1 bag to the twin-screw extruder through the side feeding port. The extrusion temperature is 210°C. Output the strip material, cool it, the screw speed is 360r/min, and the extrusion power is 300W;
S5、风冷压制：将条状物料依次排开，放置在风冷机中，放置的间距为2cm，开启风冷机，设置温度为16℃，持续风冷30min，关闭风冷机，取出条状物料，放置在轧锻机中，以1MPa的压力压5s，捆扎包装，制得低收缩性阻燃聚丙烯材料。S5. Air-cooling pressing: Arrange the strip materials in sequence and place them in the air-cooling machine with a spacing of 2cm. Turn on the air-cooling machine and set the temperature to 16°C. Continue air cooling for 30 minutes. Turn off the air-cooling machine and take out the strips. The materials are placed in a rolling and forging machine, pressed at a pressure of 1MPa for 5 seconds, and bundled and packaged to produce a low-shrinkage flame-retardant polypropylene material.
表1实施例1-4中低收缩性阻燃聚丙烯材料的原料用量Table 1 Amount of raw materials for low shrinkage flame retardant polypropylene materials in Examples 1-4
实施例2：一种低收缩性阻燃聚丙烯材料，原料用量如表1所示，其中均聚聚丙烯的熔融指数为10g/10min，型号为燕山石化K1008，共聚聚丙烯的熔融指数为27g/10min，型号为扬子石化K9927，抗氧化剂为亚磷酸酯类抗氧剂168，润滑剂为硬脂酸钠，增韧剂为乙烯-辛烯共聚物，在190℃/2.16kg条件下的熔融指数为20g/10min，型号为美国陶氏8402，无卤阻燃剂为磷-氮膨胀型无卤阻燃剂，包括质量比为5:1.2:0.05的高聚合度II型聚磷酸铵、三嗪成炭剂和聚四氟乙烯。Example 2: A low-shrinkage flame-retardant polypropylene material. The amount of raw materials is as shown in Table 1. The melt index of homopolypropylene is 10g/10min, the model is Yanshan Petrochemical K1008, and the melt index of copolymerized polypropylene is 27g. /10min, the model is Yangzi Petrochemical K9927, the antioxidant is phosphite antioxidant 168, the lubricant is sodium stearate, the toughening agent is ethylene-octene copolymer, melted at 190℃/2.16kg The index is 20g/10min, the model is American Dow 8402, and the halogen-free flame retardant is a phosphorus-nitrogen expanded halogen-free flame retardant, including high polymerization degree II ammonium polyphosphate and triphosphate with a mass ratio of 5:1.2:0.05. Carbonizer and polytetrafluoroethylene.
上述低收缩性阻燃聚丙烯材料的制备方法，包括以下步骤：The preparation method of the above-mentioned low-shrinkage flame-retardant polypropylene material includes the following steps:
S1、制备无卤阻燃剂：将高聚合度II型聚磷酸铵加入到高混机内，在20℃下以200r/min的转速搅拌8min，聚磷酸铵的体积为高混机容量的三分之一，然后加入三嗪成炭剂，升温至50℃，以500r/min的转速搅拌50min，降温至20℃，边搅拌边加入聚四氟乙烯，搅拌8min，冷却20min，制得无卤阻燃剂；S1. Preparation of halogen-free flame retardant: Add high polymerization degree II ammonium polyphosphate into the high mixer, stir for 8 minutes at 20°C at 200r/min, and the volume of ammonium polyphosphate is three times the high mixer capacity. 1/2, then add triazine carbonizer, raise the temperature to 50°C, stir for 50min at 500r/min, cool to 20°C, add polytetrafluoroethylene while stirring, stir for 8min, cool for 20min, to obtain halogen-free flame retardants;
S2、原料选取：按照表1中的原料用量称取各原料；S2. Raw material selection: Weigh each raw material according to the raw material dosage in Table 1;
S3、混合搅拌：将无卤阻燃剂加入到长纤硅灰石中，在20℃下以200r/min的转速搅拌25min，制得1号料包；将均聚聚丙烯、共聚聚丙烯、增韧剂、抗氧剂和润滑剂混合，在20℃下以500r/min的转速搅拌50min，制得2号料包；S3. Mixing and stirring: Add the halogen-free flame retardant to the long-fiber wollastonite, stir for 25 minutes at 20°C at a speed of 200r/min, and prepare No. 1 material bag; mix homopolymerized polypropylene, copolymerized polypropylene, Mix the toughening agent, antioxidant and lubricant, and stir at 500r/min for 50min at 20°C to prepare No. 2 material bag;
S4、共混改性：将2号料包加入到双螺旋挤出机的主喂料口，1号料包通过侧喂料口加入到双螺旋挤出机，挤出温度为160℃，挤出条状物料，冷却，螺杆转速为350r/min，挤出功率为280W；S4. Blending modification: Add No. 2 bag to the main feeding port of the twin-screw extruder, and add No. 1 bag to the twin-screw extruder through the side feeding port. The extrusion temperature is 160°C. Output the strip material, cool it, the screw speed is 350r/min, and the extrusion power is 280W;
S5、风冷压制：将条状物料依次排开，放置在风冷机中，放置的间距为5cm，开启风冷机，设置温度为15℃，持续风冷28min，关闭风冷机，取出条状物料，放置在轧锻机中，以2MPa的压力压3s，捆扎包装，制得低收缩性阻燃聚丙烯材料。S5. Air-cooling pressing: Arrange the strip materials in sequence and place them in the air-cooling machine with a spacing of 5cm. Turn on the air-cooling machine, set the temperature to 15°C, and continue air cooling for 28 minutes. Turn off the air-cooling machine and take out the strips. The materials are placed in a rolling and forging machine, pressed at a pressure of 2MPa for 3 seconds, and bundled and packaged to produce a low-shrinkage flame-retardant polypropylene material.
实施例3-4：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，原料用量如表1所示。Example 3-4: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the amount of raw materials is as shown in Table 1.
实施例5：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，均聚聚丙烯的熔融指数为6g/10min，选自上海石化Y600。Example 5: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the homopolymer polypropylene has a melt index of 6g/10min and is selected from Shanghai Petrochemical Y600.
实施例6：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，均聚聚丙烯的熔融指数为20g/10min，选自印度石化H200MA。Example 6: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the homopolymer polypropylene has a melt index of 20g/10min and is selected from Indian Petrochemical H200MA.
实施例7：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，共聚聚丙烯的熔融指数为30g/10min，选自北京燕山K9035。Example 7: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the copolymerized polypropylene has a melt index of 30g/10min and is selected from Beijing Yanshan K9035.
实施例8：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，共聚聚丙烯的熔融指数为10g/10min，选自韩国晓星J640。Example 8: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the copolymerized polypropylene has a melt index of 10g/10min and is selected from Hyosung J640 in South Korea.
实施例9：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，润滑剂包括质量比为1:1.2的硬脂酸钙和硅酮母粒，硅酮母粒由制备例1制成。Example 9: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the lubricant includes calcium stearate and silicone masterbatch with a mass ratio of 1:1.2. The silicone masterbatch is prepared from Preparation Example 1 made.
实施例10：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，润滑剂包括质量比为1:0.8的硬脂酸钙和硅酮母粒，硅酮母粒由制备例3制成。Example 10: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the lubricant includes calcium stearate and silicone masterbatch with a mass ratio of 1:0.8. The silicone masterbatch is prepared from Preparation Example 3 made.
实施例11：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，润滑剂包括质量比为1:1.2的硬脂酸钙和硅酮母粒，硅酮母粒由制备例3制成。Example 11: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the lubricant includes calcium stearate and silicone masterbatch with a mass ratio of 1:1.2. The silicone masterbatch is prepared from Preparation Example 3 made.
实施例12：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，润滑剂包括质量比为1:1.2的硬脂酸钙和硅酮母粒，硅酮母粒由制备例4制成。Example 12: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the lubricant includes calcium stearate and silicone masterbatch with a mass ratio of 1:1.2. The silicone masterbatch is prepared from Preparation Example 4 made.
实施例13：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，润滑剂包括质量比为1:1.2的硬脂酸钙和硅酮母粒，硅酮母粒型号为KJ-A01。Example 13: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the lubricant includes calcium stearate and silicone masterbatch with a mass ratio of 1:1.2, and the silicone masterbatch model is KJ -A01.
实施例14：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，磷-氮膨胀型无卤阻燃剂中未添加三嗪成炭剂。Example 14: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that no triazine carbon-forming agent is added to the phosphorus-nitrogen expanded halogen-free flame retardant.
实施例15：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，磷-氮膨胀型无卤阻燃剂中未添加聚四氟乙烯。Example 15: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that no polytetrafluoroethylene is added to the phosphorus-nitrogen expanded halogen-free flame retardant.
对比例Comparative ratio
对比例1-4：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，原料用量如表2所示。Comparative Example 1-4: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the amount of raw materials is as shown in Table 2.
表2对比例1-4中低收缩性阻燃聚丙烯材料的原料用量Amount of raw materials used for low shrinkage flame retardant polypropylene materials in Comparative Examples 1-4 in Table 2
对比例5：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，无卤阻燃剂为氢氧化铝。Comparative Example 5: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the halogen-free flame retardant is aluminum hydroxide.
对比例6：一种低收缩性阻燃聚丙烯材料，与实施例1的区别在于，将长纤硅灰石和无卤阻燃剂制成的1号包与2号包混合后通过主喂料口加入到双螺旋挤出机内。Comparative Example 6: A low-shrinkage flame-retardant polypropylene material. The difference from Example 1 is that the No. 1 bag and the No. 2 bag made of long-fiber wollastonite and halogen-free flame retardant are mixed and then passed through the main feed into the twin-screw extruder.
对比例7：一种阻燃遮光低收缩聚丙烯复合材料，包括29.1kg均聚聚丙烯、10kg共聚聚丙烯、5kg硅灰石、5kg硫酸钙晶须、10kg玻璃纤维、5kg相容剂、15kg钛白粉、20kg阻燃剂、0.2kg抗氧剂、0.5kg润滑剂，均聚聚丙烯的结晶度在60％以上，熔体流动速率不小于20g/10min；所述共聚聚丙烯熔体流动速率不小于30g/10min。硅灰石和硫酸钙晶须平均直径6-8um，平均长度150-200um，预先经过硅烷偶联剂处理。玻璃纤维为泰山玻璃纤维公司的无碱短切玻纤，平均直径11um，预先经过硅烷偶联剂处理。相容剂为马来酸酐接枝聚丙烯，接枝率为0.8％，钛白粉为金红石型，预先经过硅烷偶联剂处理，阻燃剂为十溴二苯乙烷，抗氧剂为亚磷酸酯类抗氧剂，润滑剂为乙烯基双硬脂酰胺。Comparative Example 7: A flame-retardant and light-shielding low-shrinkage polypropylene composite material, including 29.1kg homopolypropylene, 10kg copolymerized polypropylene, 5kg wollastonite, 5kg calcium sulfate whiskers, 10kg glass fiber, 5kg compatibilizer, 15kg Titanium dioxide, 20kg flame retardant, 0.2kg antioxidant, 0.5kg lubricant, the crystallinity of homopolypropylene is above 60%, the melt flow rate is not less than 20g/10min; the melt flow rate of the copolymerized polypropylene Not less than 30g/10min. Wollastonite and calcium sulfate whiskers have an average diameter of 6-8um and an average length of 150-200um, and have been treated with a silane coupling agent in advance. The glass fiber is alkali-free chopped glass fiber from Taishan Glass Fiber Company, with an average diameter of 11um, and has been treated with a silane coupling agent in advance. The compatibilizer is maleic anhydride-grafted polypropylene with a grafting rate of 0.8%. The titanium dioxide is rutile type and has been treated with a silane coupling agent in advance. The flame retardant is decabromodiphenylethane and the antioxidant is phosphorous acid. Ester antioxidant, lubricant is vinyl bis stearamide.
阻燃遮光低收缩聚丙烯复合材料的制备方法包括：按照相应的组分及重量配比称取除硫酸钙晶须、硅灰石和玻璃纤维之外的物料，在高混机中混合15min，将上述原材料混合均匀，将混合后的共混物通过双螺杆挤出机挤出造粒；其中硫酸钙晶须、硅灰石按照相应的重量配比从第6区侧喂料投入，玻璃纤维按照相应的重量配比从第8区侧喂料投入。挤出机的各区温度从喂料段到机头温度依次为160℃、170℃、180℃、190℃、200℃、205℃、200℃、205℃、195℃、185℃，挤出螺杆长径比为44，挤出螺杆转速为400转/分钟。The preparation method of the flame-retardant and light-shielding low-shrinkage polypropylene composite material includes: weighing the materials except calcium sulfate whiskers, wollastonite and glass fiber according to the corresponding components and weight ratios, mixing them in a high mixer for 15 minutes, and The above raw materials are mixed evenly, and the mixed blend is extruded and granulated through a twin-screw extruder; calcium sulfate whiskers and wollastonite are fed from the side of zone 6 according to the corresponding weight ratio, and the glass fiber is fed according to the corresponding weight ratio. The corresponding weight ratio is fed from the side of area 8. The temperature of each zone of the extruder from the feeding section to the die temperature is 160°C, 170°C, 180°C, 190°C, 200°C, 205°C, 200°C, 205°C, 195°C, 185°C. The extrusion screw length is The diameter ratio is 44, and the extrusion screw speed is 400 rpm.
性能检测试验Performance testing test
按照实施例和对比例中的方法制备聚丙烯材料，并参照以下标准进行性能检测，将检测结果记录于表3中。Polypropylene materials were prepared according to the methods in the examples and comparative examples, and performance testing was performed with reference to the following standards, and the testing results were recorded in Table 3.
1、拉伸强度：按照ISO527-1-2012《塑料拉伸性能的测定》进行检测；1. Tensile strength: Tested in accordance with ISO527-1-2012 "Determination of Tensile Properties of Plastics";
2、弯曲模量：按照ISO178-2010《塑料弯曲性能测定》进行检测；2. Bending modulus: tested in accordance with ISO178-2010 "Determination of Bending Properties of Plastics";
3、阻燃等级：按照可燃性UL94等级进行检测；3. Flame retardant level: tested according to the flammability UL94 level;
4、48H后收缩率：按照ISO294-4-2003《塑料热塑材料试样的注塑第4部分模塑收缩收缩率的测定》进行检测；4. Shrinkage after 48H: Tested in accordance with ISO294-4-2003 "Injection Molding of Plastic Thermoplastic Material Samples Part 4 Determination of Molding Shrinkage";
5、光泽度：按照ASTMD523-2018《镜面光泽度的标准测试方法》进行检测。5. Glossiness: Tested in accordance with ASTM D523-2018 "Standard Test Method for Specular Glossiness".
表3低收缩性阻燃聚丙烯材料的性能检测Table 3 Performance testing of low shrinkage flame retardant polypropylene materials
由表3内数据可以看出，实施例1-4制成的聚丙烯材料具有力学强度高，阻燃性好的优点，而且收缩率能控制在0.87％，能较好的抑制后收缩对材料尺寸稳定性的影响，满足各项使用需求，随着长纤硅灰石含量的增加，聚丙烯材料的力学刚性(强度和模量)不断增加，收缩率不断降低。It can be seen from the data in Table 3 that the polypropylene materials made in Examples 1-4 have the advantages of high mechanical strength and good flame retardancy, and the shrinkage rate can be controlled at 0.87%, which can better inhibit the impact of post-shrinkage on the material. The influence of dimensional stability can meet various usage requirements. As the content of long-fiber wollastonite increases, the mechanical rigidity (strength and modulus) of polypropylene materials continues to increase, and the shrinkage rate continues to decrease.
实施例5和实施例6分别减小和增大均聚聚丙烯的熔融指数，实施例7和实施例8中分别增大和减小共聚聚丙烯的熔融指数，表3内显示实施例5-8制成的聚丙烯材料的拉伸强度和弯曲模量降低，力学强度减弱。Examples 5 and 6 respectively reduce and increase the melt index of homopolypropylene. Examples 7 and 8 respectively increase and decrease the melt index of copolypropylene. Table 3 shows Examples 5-8. The tensile strength and flexural modulus of the made polypropylene material are reduced, and the mechanical strength is weakened.
实施例9和实施例10中使用含有硬脂酸钙和硅酮母粒的润滑剂，硅酮母粒分别由制备例1和制备例2制成，表3内数据显示，实施例9和实施例10制成的聚丙烯材料拉伸强度和弯曲模量增加，光泽度得到显著改善，收缩率稍有下降。Lubricants containing calcium stearate and silicone masterbatch were used in Examples 9 and 10. The silicone masterbatch was made from Preparation Example 1 and Preparation Example 2 respectively. The data in Table 3 shows that Embodiment 9 and Implementation The tensile strength and flexural modulus of the polypropylene material made in Example 10 were increased, the gloss was significantly improved, and the shrinkage rate was slightly reduced.
实施例11和实施例12分别采用制备例3和制备例4制成的硅酮母粒，与实施例9和实施例10相比，实施例11和实施例12制成的聚丙烯材料拉伸强度和弯曲模量降低，光泽度减小。Examples 11 and 12 respectively adopt the silicone masterbatches made from Preparation Example 3 and Preparation Example 4. Compared with Examples 9 and 10, the polypropylene materials made from Examples 11 and 12 are stretched. Strength and flexural modulus are reduced, and gloss is reduced.
实施例13中使用市售硅酮母粒，与实施例1相比，聚丙烯材料的力学强度得到改善，光泽度提升，但与实施例9和实施例10相比，聚丙烯材料的力学强度和光泽度下降。Commercially available silicone masterbatch is used in Example 13. Compared with Example 1, the mechanical strength of the polypropylene material is improved and the glossiness is increased. However, compared with Examples 9 and 10, the mechanical strength of the polypropylene material is and loss of gloss.
实施例14和实施例15与实施例1相比，制备磷-氮膨胀型无卤阻燃剂时分别未添加三嗪成炭剂和聚四氟乙烯，实施例14制成的聚丙烯材料阻燃性减弱，实施例15制成的聚丙烯材料的力学强度下降。Compared with Example 1, Examples 14 and 15 did not add triazine carbon-forming agent and polytetrafluoroethylene respectively when preparing the phosphorus-nitrogen intumescent halogen-free flame retardant. The polypropylene material made in Example 14 was resistant to The flammability is weakened, and the mechanical strength of the polypropylene material made in Example 15 is reduced.
对比例1中长纤硅灰石含量增加值25％时，与实施例1相比，材料的阻燃性下降至V1，说明过多的长纤硅灰石影响无卤阻燃剂的成碳阻燃效果。When the content of long-fiber wollastonite in Comparative Example 1 increases by 25%, compared with Example 1, the flame retardancy of the material drops to V1, indicating that too much long-fiber wollastonite affects the carbonization of the halogen-free flame retardant. Flame retardant effect.
对比例2中降低长纤硅灰石的含量，与实施例1相比，聚丙烯材料的阻燃效果减弱，力学强度下降。In Comparative Example 2, the content of long-fiber wollastonite is reduced. Compared with Example 1, the flame retardant effect of the polypropylene material is weakened and the mechanical strength is reduced.
对比例3和对比例4中分别未添加均聚聚丙烯和共聚聚丙烯，与实施例1相比，聚丙烯材料的拉伸强度和弯曲强度下降。In Comparative Example 3 and Comparative Example 4, no homopolypropylene and copolymerized polypropylene were added respectively. Compared with Example 1, the tensile strength and bending strength of the polypropylene material decreased.
对比例5与实施例1相比，使用氢氧化铝作为阻燃剂，其制成的聚丙烯材料阻燃性下降，对比例6中将长纤硅灰石和无卤阻燃剂与其他原料共混，通过主喂料口加入，聚丙烯材料的收缩率增大。Compared with Example 1, Comparative Example 5 uses aluminum hydroxide as the flame retardant, and the flame retardancy of the polypropylene material made from it decreases. In Comparative Example 6, long-fiber wollastonite and halogen-free flame retardant are combined with other raw materials. Mix and add through the main feeding port, the shrinkage rate of the polypropylene material increases.
对比例7采用现有技术制备的聚丙烯材料，与实施例1相比，虽然其具有较强的拉伸强度和弯曲模量，但其收缩率大，阻燃性能不及实施例1。Comparative Example 7 uses a polypropylene material prepared by existing technology. Compared with Example 1, although it has stronger tensile strength and flexural modulus, its shrinkage rate is large and its flame retardant performance is not as good as Example 1.
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contribution as needed, but as long as the rights of this application are All requirements are protected by patent law.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311252172.3ACN117285775A (en) | 2023-09-26 | 2023-09-26 | Low-shrinkage flame-retardant polypropylene plastic and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311252172.3ACN117285775A (en) | 2023-09-26 | 2023-09-26 | Low-shrinkage flame-retardant polypropylene plastic and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN117285775Atrue CN117285775A (en) | 2023-12-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311252172.3APendingCN117285775A (en) | 2023-09-26 | 2023-09-26 | Low-shrinkage flame-retardant polypropylene plastic and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN117285775A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118931057A (en)* | 2024-08-27 | 2024-11-12 | 安徽元臻环保科技有限公司 | MPP cable protection tube with strong Vicat performance and preparation method thereof |
| CN119331343A (en)* | 2024-09-27 | 2025-01-21 | 青岛国恩科技股份有限公司 | A high-rigidity flame-retardant polypropylene plastic and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532727A (en)* | 2011-12-19 | 2012-07-04 | 江苏金发科技新材料有限公司 | Blow molding grade halogen-free flame-retardant polypropylene material and preparation method thereof |
| CN103044762A (en)* | 2012-12-06 | 2013-04-17 | 上海日之升新技术发展有限公司 | Mineral reinforced halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN104119610A (en)* | 2014-07-04 | 2014-10-29 | 广东聚石化学股份有限公司 | V0-level halogen-free flame-retardant reinforced polypropylene composite material and preparation method thereof |
| CN115558204A (en)* | 2022-09-27 | 2023-01-03 | 金旸（厦门）新材料科技有限公司 | Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532727A (en)* | 2011-12-19 | 2012-07-04 | 江苏金发科技新材料有限公司 | Blow molding grade halogen-free flame-retardant polypropylene material and preparation method thereof |
| CN103044762A (en)* | 2012-12-06 | 2013-04-17 | 上海日之升新技术发展有限公司 | Mineral reinforced halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| CN104119610A (en)* | 2014-07-04 | 2014-10-29 | 广东聚石化学股份有限公司 | V0-level halogen-free flame-retardant reinforced polypropylene composite material and preparation method thereof |
| CN115558204A (en)* | 2022-09-27 | 2023-01-03 | 金旸（厦门）新材料科技有限公司 | Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118931057A (en)* | 2024-08-27 | 2024-11-12 | 安徽元臻环保科技有限公司 | MPP cable protection tube with strong Vicat performance and preparation method thereof |
| CN119331343A (en)* | 2024-09-27 | 2025-01-21 | 青岛国恩科技股份有限公司 | A high-rigidity flame-retardant polypropylene plastic and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
| CN112250935B (en) | High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof | |
| CN117285775A (en) | Low-shrinkage flame-retardant polypropylene plastic and preparation method thereof | |
| CN102391608B (en) | Ultrahigh heat-resistant and flame-retardant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof | |
| CN103483676B (en) | Halogen-free flame-retardant linear low-density polyethylene material and preparation method thereof | |
| CN103289290B (en) | A kind of phosphorus system synergistic flame-retardant ABS compound material and preparation method thereof | |
| CN101880451B (en) | A kind of halogen-free flame-retardant polyphenylene ether compound and its preparation method | |
| CN101463155B (en) | Flame-retardant polymer composite material | |
| CN107304268A (en) | A kind of anti-flaming polyolefin composition and preparation method thereof | |
| CN109627568A (en) | Polyolefine cable sheath material and preparation method thereof | |
| CN105348646A (en) | Modified polypropylene base low smoke zero halogen cable material and preparing method | |
| CN112029189A (en) | Halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN101659778A (en) | Expanded halogen-free flame-retardant ABS compound material | |
| CN105593340B (en) | Flexible fire-resistant thermoplastic compositions with high thermomechanical strength, especially for cables | |
| CN114773836A (en) | Anti-fatigue high-gloss nylon heat insulation strip flame-retardant material and preparation method thereof | |
| CN110643165A (en) | High-performance ultraviolet-resistant environment-friendly flame-retardant PC/ABS composite material and preparation method thereof | |
| CN115725136B (en) | High-oxygen-index flame-retardant PP material and preparation method thereof | |
| CN104017360A (en) | Organic clay synergic flame-retardant PA6 (polyamide 6) composite material and preparation method thereof | |
| CN107446368A (en) | Using silane-modified boehmite as wood plastic composite of fire retardant and preparation method thereof | |
| CN103613913B (en) | A kind of Halogen-free flame-retardant thermoplastic polyester elastomer material and preparation method thereof | |
| CN109897371B (en) | Precipitation-proof environment-friendly flame-retardant plastic master batch and preparation method thereof | |
| CN117264322A (en) | Polypropylene composite plastic for new energy battery shell and preparation method thereof | |
| CN111748156A (en) | A halogen-free flame retardant mineral powder reinforced polypropylene composition | |
| CN102649863A (en) | ABS (Acrylonitrile Butadiene Styrene) environment-friendly inflaming retarding compound material and preparation method thereof | |
| CN113185777B (en) | High-flame-retardant polypropylene foamed bead as well as preparation method and application thereof | |
| CN115975296A (en) | A kind of halogen-free flame-retardant polyolefin composition and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |