Formula design of plastic profile

2021-11-23 16:23:10 26
本文转载自网络,如有侵权,请联络删除:  塑料科技塑料型材配方设计王文广张军2孙浩3候馨3(1.沈阳奇美塑料材料开发中心,辽宁沈阳110013辽宁省电力有限公司大连培训中心,辽宁大连;沈阳市产品质量监视测验所,辽宁沈阳110021)工助剂。抗老化体系。填充体系的选取。参与量。搭配关系及搭配比例等,并配有详细的配方实例。

1 overview of plastic profile plastic profile refers to discontinuous extruded products with non-circular section shape. It is a new chemical building material originated in Germany in the 1960s. Because it has the advantages of energy saving, heat insulation, sound insulation, good sealing, anti-corrosion, flame retardant, beautiful appearance and abundant resources, it has been first applied on a small scale in Germany and other European regions. In the late 1970s, Germany, Austria and the United States successively developed new formulations of HPVC profiles, so that plastic profiles were rapidly popularized and applied. At present, the spread rate of plastic doors and windows has reached more than 70% in prosperous regions such as Europe and North America.

China introduced the twin-screw extruder of Otis Cincinnati company in the 1980s and began to consume plastic profiles. Due to price, quality and other factors, in the 1990s, although they had the processing ability of plastic profiles, they were not popularized and applied. Later, with the help and promotion of government policies, plastic profiles began to spread gradually. By the end of 2000, the processing capacity of plastic profiles in China had reached 1 million tons / year. It is estimated that by 2001, the processing capacity will reach 1.3 million tons in 7 years. The processing facilities are imported from the whole set to be gradually localized.

Since 1995, the actual use of plastic profiles in China has increased at a rate of 30% per year. By 2000, the actual use of plastic profiles has reached 300000 tons / year. It is estimated that it will reach 400000 tons in 2001 and 500000 tons / year in 2005. According to the plan of establishing the Ministry of education, by 2001, the spread rate of plastic doors and windows in China will reach more than 25%, including more than 50% in Northeast, North and East China and more than 30% in southeast coastal areas.

At present, China's plastic profile processing enterprises are springing up. However, the state has established the Ministry to focus on cultivating enterprises with an annual processing capacity of more than 6000 tons / year, and plans to form 100000 ~ 200000 ton large enterprises. At present, there are more than 40 enterprises with a certain scale in China: Dalian Shide Co., Ltd. (120000 tons / year), Anhui Wuhu conch Co., Ltd. (90000 tons / year), Liaoning Liaoshen plastic material Co., Ltd. (50000 tons / year), Liaoning Zhongwang Company (30000 tons / year), Shenyang Jiuli company (10000 tons / year).

2. Materials and performance requirements for plastic profiles. PVC resin is the main raw material for plastic profiles, especially for doors and windows. The share of PVC resin is more than 99%. PVC plastic profiles include PVC (unplasticized commonly known as unprazieipvc) and h-pvc or R-PVC (hard PVC or rigid PVC due to its strong texture).

In addition to PVC resin, other resins are consumed alone, and the application amount of profiles is very small, as long as ABS and GFRP, but the amount is less than 1%. It can be said that PVC is unique in profiles.

Other plastics Ma, PPC, PVDF, ASA, etc. that can be used for profile composite. The detailed composite products are as follows: SPVC is used as sealing material to composite with HPVC profile, which can improve the sealing performance of large doors and windows; Different colors of HPVC are compounded to make color surface profiles; Suspension tight resin is often used for ordinary HPVC profiles, and its detailed brand and application are shown in the table. Alele gallicpushinghougvc materials are stable Lead salts organic! The combination of metal soap PMMA and HPVC can add the coloring beauty and weather resistance of HPVC; In addition to single resin and composite resin, plastic profiles also have low foaming plastic profiles and wood fiber high filling profiles. Their properties are closer to wood and have the advantages of sawing, planing and nailing. In order to reach the plastic profile standard specified in the national standard (gb-8814-98), the following requirements are put forward for the properties of raw materials for profiles: good processability. The cross-section shape of plastic profiles is mostly complex, which contains reinforcing bars with a wall thickness of 1mm, which requires good processing activity of raw materials and excellent rheological properties.

Sufficient strength and rigidity. It is required that the Rockwell hardness of the profile shall be greater than R85, the tensile strength shall be greater than 37mpa, and the bending elastic modulus shall be greater than the excellent low-temperature impact resistance. It is required that when the profile is at - 10 ° C, the number of falling ball impact cracks tested according to the national standard shall be less than or equal to 1 / 10: the impact strength of simply supported beam is 401 / m2 for household shape (a) and 3211 for indoor type (b) at room temperature, 15K / m2 for household shape (a) and M / N2 for indoor type (b) at - 10 ° C. (4) high fillet weld strength. The uniform fillet weld strength is required to be greater than 3000n, of which the fillet weld strength of the main frame material shall be greater than 6000N, and the fillet weld strength of the main fan material shall be greater than 5000n. Good heat resistance and flame retardancy. The Vicat softening point shall be greater than 83 ° C and the oxygen index shall be more than 38.

(6) excellent weather resistance. When tested according to the natural climate exposure test method, class a profile is 12 months, type B material is 8 months, and when tested according to the plastic xenon lamp light source exposure test method, the impact strength of class a profile is 1000 hours and type B material is 500 hours. The storage value of class A is greater than 2811 and class B is greater than 22K / m2. The dimensional stability is good. It is required that the dimensional change rate shall be less than 25% when heating from room temperature to 100 ° C. (8) good heat insulation and sound insulation performance. The thermal conductivity is required to be small \ \ "IK air sound meter weight isolation volume is greater than 25dB. 3 formula design of ordinary HPVC profile. Ordinary PVC profile refers to the dense profile made of a single resin. At present, the profiles used in the market are mainly ordinary profiles.

PVC resin used for ordinary profiles generally does not add plasticizer or only adds 1 part of plasticizer. Therefore, in order to ensure its good processing activity, resin with slightly lower molecular weight should be selected, which is too low and difficult to meet the strength requirements. Considering two factors, SG-5 or sg-6 resin with uniform molecular weight of about 1000 and K value of 65 ~ 68 can be selected.

Table 1 grades, characteristics and uses of PVC resin new and old grades K value characteristic viscosity uniform degree of polymerization (P) Application: high grade insulating materials, insulating materials for soft products, film, shoe film, hose, artificial leather, hard pipe, hard profile plate, fiber, transparent sheet, injection blow molding bottle, transparent sheet and injection molding PVC resin can meet the needs regardless of import or domestic quality. It is best to fix 2 ~ 3 long-term suppliers during detailed selection to prevent frequent changes in formula and process conditions The import PVC resin is the lowest price in Russia and South Korea and the resources are relatively suffi cient. There are more than 80 domestic PVC resin consumptive manufacturers, scattered in all regions except Tibet. In the 200 year, the annual consumption ability can reach 2 million 160 thousand tons, of which 1 million 940 thousand tons of suspension method and 220 thousand tons of emulsion method, but the actual consumption is 1 million 550 thousand tons: of which 270 thousand tons are used for pipes, 170 thousand for profiles. Tons.

3.2 thermal stability system pure PVC resin has poor thermal stability in processing, and its decomposition temperature is below the melting temperature: the melting temperature is 160 ° C ~ 220, while the thermal decomposition starts at 90 ° C, and it is very important to 140 ° C. The color will change during PVC decomposition, and the color is white pink light yellow red ※ brown ※ black according to the deepening of decomposition level. In order to protect the environment The decomposition temperature of barrier PVC is above the melting temperature to ensure its normal processing. It is necessary to participate in plasticizer in PVC to reduce its melting temperatur e and heat stabilizer to improve its thermal decomposition temperature.

PVC for profile is a hard material, and no or less plasticizer is added in its formula, so the melting temperature does not decrease or decreases very little. Therefore, it is necessary to participate in a sufficient amount of heat stabilizer to raise its thermal decomposition temperature above the melting temperature, generally more than 220c. Therefore, HPVC profile formula has higher requirements for stabilizer than soft products. On the one hand, the effect of thermal stability is better, on the other hand On the one hand, the number of participation is greater than that of soft products.

The advantages and disadvantages of these four types of heat stabilizers are shown in Table 2.

Table 2 Comparison of four types of heat stabilizers stability effectiveness toxicity transparency participation price lead salts are good, opaque and large, general organotin are good, transparent and small high metal soaps are generally / non opaque / transparent and medium rare earth are good, non transparent and medium high. Among the four stabilizers, lead salts, organotin and metal soaps are traditional varieties and are widely used today Soil stabilizer is a unique variety in China and is gradually spreading all over the world. In HPVC profiles, the varieties of stabilizers applied in countries and regions all over the world are different, as shown in Table 3 and table 4.

Table 3 application proportion of different stabilizers in HPVC profiles in Europe and North America stabilizers Europe and North America lead salt organotin metal soaps Table 4 application status of stabilizers in HPVC profiles in countries and regions around the world stabilizers Germany, France, Italy, North America, South America, Africa, Australia, Taiwan, China lead salt Organotin metal soaps rare earths are rarely unique in the actual selection of stabilizer varieties If one variety is selected, two varieties are often used together. Common coordination systems include lead salts / metal soaps, organotin / metal soaps, organotin / rare earth, etc.

The selection and amount of stabilizer should be determined according to the following criteria: it should be selected according to different processing facilities. The single screw extruder requires good stabilizer effect and large amount of participation. See formula 9 and 10 for details. Formula 9 is a twin-screw extruder with 1.5 parts of organotin; while formula 10 is a single screw extruder with 2 parts of organotin.

It is selected according to the type of toughening agent. When CPE is used as the toughening agent, lead salts and metal soaps are often selected; when ACR is used as the toughening agent, organotin is often selected.

The detailed varieties of lead salt thermal stability systems are: tribasic lead sulfate (tribasic salt), dibasic phosphite (dibasic salt), dibasic lead stearate (dibasic lead) Among them, the thermal stability effect of three salts is better than that of two salts, but the weather resistance of two salts is better than that of three salts. The two salts generally participate in synergy, and the commonly used synergy ratio is 3:1 ~ 3:2. The lead salt thermal stability system is commonly used in CPE toughening system, with the participation of 3 ~ 5 phr.

Lead salt heat stabilizers have little smoothness, so they are often used together with metal soap stabilizers with smoothness. For example, the commonly used combination system is: pay attention when using lead salt in detail. It cannot be used together with sulfide, such as sulfur-containing organic tin, otherwise PBS will be generated and PVC plastic will turn black.

Due to the small size of lead salt stabilizer, it is easy to cause dust in the mixing process and poor working environment. In recent years, a composite lead salt stabilization system has been developed. It is composed of three parts of lead salt heat stabilizer / internal and external smoothing agent / anti-aging agent, and its appearance is granular or flake. Compared with the single lead salt, the advantages of composite lead salt are as follows: larger than the surface, larger thermal stability and better thermal stability. The quantity is relatively small, generally about 4 parts; good processability, suitable for the use of complex molds; good weather resistance, suitable for outdoor doors and windows; good hygiene, can appropriately improve the working environment; and can appropriately improve the fillet weld strength.

At present, the application scope of the composite lead stabilization system is gradually expanding. Its domestic price is 13000 yuan / ton, and the import price is slightly higher. It mainly includes German Henkel company, German bear brand company, Japan shuize company, Jiangsu Jiangdu Xinghuo company, Zhejiang Wenzhou auxiliary factory, Jiangsu Zhenjiang Taili company, etc.

3.2.2 organotin thermal stabilization system the thermal stabilization effect of organotin thermal stabilization system is the best, but due to the high price (about 4 times higher than lead salt) In addition to Taiwan, organotin is less used in China, while it is more used in prosperous countries such as Europe and the United States. There are many varieties of organotin thermal stability systems. Mercaptan butyl tin is mainly used for HPVC profiles, often supplemented by metal soap stabilizers such as cdst to form a synergistic system.

Note that mercaptan organotin cannot be used together with pbcd salt, otherwise PBS and CDs pollution will occur. Organotin stable system is often used in ACR toughening system为0.5~2份。由于有机锡稳定体系本石蜡,氧化聚乙烯蜡等,一般不必硬脂酸,以防影响制品的白度。下面比较铅盐和有机锡不同稳定体系的加工条件与制品性能。11 0.6石蜡卜1.2CdSt0.40.6氧化聚乙烯蜡0.卜合格配方2合格型材性能:拉伸强度(MPa):维卡软化点(°C):落球冲击(一10°c):上下温尺寸变迁率原料本钱(p)加工条件:料筒温度(°c)螺杆温度(°c)机头温度(°c)螺杆转速(Zmin):扭矩:牵引速度(nmin):型材性能:拉伸强度(MPa):维卡软化点(°C):落球冲击(一3.2.3金属皂类热稳定体系金属皂类热稳定体系的热稳定成效一般,因而很少独自使用,常与铅盐类、有机锡类和稀土类复合使用,或不同金属皂类之间协同使用。常用的金属皂类复合准则为不同热稳定机理的金属皂类之间协同成效好,如Cd、Zn金属皂类和Ba、Ca金属皂类之间复合有协同作用:详细如C/Zn.B/Cd.Ba/ZnBa/CZn、Ba/d/Pb等。金属皂类的参与量为3份左右。








  配方6卜1. ESO(环氧大豆油)卜2最近,又开发出稀土类复合稳定体系,其组成同铅盐复合体系类似,价格为17000 ~18000元/吨,有北京华通发公司和广东广阳公司等。







  在详细配方设计中,要想精确地确定光滑剂的品种和用量,是一项非常复杂的工作,须要思考的因素很多。其中一个很主要的准则为:尽可能少参与,控制在最低参与量上,使之抵达临界光滑状态即可。参与太多,会影响制品的塑化度。一般状况下,光滑剂参与1 ~2份左右。光滑剂的参与量对加工性能影响较大,往往0.2份参与量的变迁,就能起到很大作用。









  视不同加工设施而定。加工设施螺杆直径较大者,多参与光滑剂。加工设施使用工夫较短或新设施者,多参与光滑剂。双螺杆挤出机多加,单螺杆挤出机少加,详细参见配方9和配方10所示,双螺杆挤出机加1. 2份,单螺杆挤出机加1.0份。



























  (5)CPE与其它韧材料复合使用,具有不同水平的协同成效。常用的复合体系有:PVC/PE/ACR或MBS体系。CPE属网络分散韧剂,与ACR、MBS等粒子分散类韧剂复合参与,两者有协同作用。一般CPE/ACR(MBS)复合体系中CPE的含量为60 %~80%时协同成效最明显,此时比单用等量CPE的韧成效高12%左右。





  在我国,HPVC型材用韧剂除少数几家进口设施的型材厂如大连实德和芜湖海螺等采纳ACR外,其它大都采纳CPECPE以国产为主,价格低,其性能与进口雷同,目前国产CPE价格11500我国CPE产量根本可满足国内须要,1999年消费才干达6万吨,实际需求量为4万吨。主要消费厂有:山东潍坊亚星化工公司(2 5万吨)、湖北双环化工集团(0.6万吨)、辽阳化纤公司(0. 6万吨)、安徽芜湖化工厂(0.6万吨)、江苏东台林业化工厂(0. 3万吨)、威海化工原料总厂(0.3万吨)、温州华塑集团(0. 25万吨)、江苏新沂电化厂(0.15万吨)、江西星火化工厂(0.1万吨)、上海南汇特种橡胶厂(0.1万吨)、张家口树脂厂(0.1万吨)等。

  1在不定体系中的参与也:同lishin遇体I系中丨1由于h有机锡自身无光稳定作用1钛白粉须要复合铅盐稳定剂4~ 5此配方的详细性能如下::42.1断裂伸长率:144―10°C落球冲击/个简支梁冲击强度23C:―1.5上下温尺寸变迁率:―0.13.5加工助剂HPVC的熔体特性不好,详细熔体缺陷如熔体易破碎、制品外表粗糙、无光泽及鲨鱼皮等。因而,HPVC型材在加工时必需参与加工改性剂,以扭转熔体的上述缺陷,进步塑化速度、大熔体强度,改善制品的外观质量。



  (1)在ACR韧体系中,ACR可不加或少加;而在CPE韧体系中,ACR必需参与2 ~3份,详细如配方12、13所示。配方12为ACR韧体系,ACR加工助剂只需参与0.5~1份;配方13为CPE韧体系,ACR加工助剂需参与2份。

  配方12配方13 ACR韧剂有机锡光滑剂ACR加工助剂详细可参见配方7和配方8.配方7为有机锡稳定体系,有机锡稳定剂的加工性能不好,需参与多量的ACR加工助剂,一般参与量为0. 5~1;配方8为铅盐稳定体系,铅盐稳定剂的加工性能好,因而,参与少量的ACR加工助剂即可,其量为0~0. 5份。

  加工设施不同,ACR的参与量也不雷同,详细可参见配方9和配方10所示。配方10为单螺杆挤出机用配方,ACR的参与量大,一般为3 ~3.5份;配方9为双螺杆挤出机用配方,ACR的参与量小,一般为1.5~2份。



  3.6.1紫外光屏蔽剂这是配方必需参与的重要抗老化剂,参与紫外光屏蔽剂的宗旨为防止紫外线进入制品中。紫外光屏蔽剂有炭黑、钛白粉等,由于塑材颜色的须要,只能选用钛白粉,它还兼有着色作用。钛白粉有锐钛型和金红石型两种,金红石型钛白粉的紫外光屏蔽成效好,是HPVC型材的首选紫外光屏蔽剂。目前国产金红石型钛白粉的耐侯性能远远不迭进口金红石型钛白粉,因而型材消费商大都选进口牌号。市场上通用的进口牌号有美国DuPant公司的902和105、德国Kronos公司的2220,价格一般为22000 ~23000元/吨;国产牌号以甘肃405厂的性能最好,价格为16000在详细使用钛白粉时,首先必需正确选择适宜品种,应选择耐侯性好的,倡议尽可能选用进口品牌。其次,金红石型钛白粉在配方中的参与量太少,只要抵达4份以上才可满足抗紫外线老化的宗旨;卩入量太少,在使用过程中,随工夫推移型材的颜色会逐步变粉红甚至变红。


  在铅盐稳定体系中,由于二盐自身是有一定的光稳定性,钛白粉可少加,一般参与4 ~6份即可;在有机锡稳多加,一般需参与10份以上。







  用钛铝酸酯偶联剂解决,与不解决相比冲击强度进步38%.用PVC-MAH相容剂解决,与不解决相比冲击强度进步42%.用钛铝酸酯偶联剂和PVC-MAH相容剂协同解决,与不解决相比冲击强度进步45%. 3.8焊角强度改善体系国标规定的型材焊角强度均匀值大于3000N,在实际执行中,一般要求60框大于5000N,80框大于在详细配方设计时,进步焊角强度的办法有添加焊角强度改性剂、适量韧剂、经外表解决的填料。




  表13焊角强度改性剂A和B的改性成效焊角强参与量度改性焊角强度(N)剂A -10.落球冲击破裂数焊角强参与量度改性焊角强度(N)剂B -10.落球冲击破裂数3.8.2添加适量增韧剂在配方中参与适量的韧材料,可进步型材的焊角强度,其中ACR的进步幅度大于CPE.以CPE为例,其参与量与焊角强度的关系见表14所示。









  用于发泡的PVC树脂K值的大小要适当,这样树脂塑化时熔领会产生一定的强度和粘弹性,可使发泡气体溶于熔体中而不至于逸出。详细来说,K值太大,树脂粘度大,塑化艰难,要求料筒温度高,螺杆转速大,从而使发泡过程难以控制;K值太小,虽发泡容易,但制品强度低。合理的K值一般为56 ~62.均匀聚合PVC树脂的形态对发泡的影响也很大。悬浮法疏松型树脂发泡制品的外观质量一般,发泡均匀性差;乳液法树脂的泡孔均匀性虽好,外表光洁,但尺寸难以控制。合理的选择为悬浮法和乳液法混合使用,一般比例为悬浮法/浮液法为8C/20~20/0之间。

  4.2发泡剂HPVC的加工温度范围比较窄,一般在170 180°Q之间;要求发泡剂的分解温度要与之相配合,以保障发泡剂在树脂熔融时分解。





  2泡孔调理剂主要作用为促进PVC塑化、熔融,控制PVC熔体强度在适中水平。HPVC发泡配方中使用的泡孔调理剂为ACR加工助剂,参与量为4 3成核剂主要作用为使泡孔细小并均匀,常用的有Ti2,起到成核剂的作用。

  4.4稳定体系常用铅盐类和金属皂类,有三盐、二盐、PbSt、BaSt、CaSt等,它的长处为兼有发泡活化剂和稳定剂的双重作用。而有机锡类或稀土类只要稳定作用,还需协同参与金属皂类,以加发泡活化剂的作用。在HPVC发泡型材配方中,由于AC耗费部分稳定剂,所以稳定剂的参与量应比普通型材偏大一些,以补偿用于AC发泡活化剂耗费部分。一般铅盐的参与量为4~6份,金属皂类的参与量为1. 5~2.5份,两者合计为6~8份湎在普通型材配方中,稳定剂一般只参与3 4.5光滑剂HPVC发泡型材的内光滑选用金属皂类光滑剂,参与量为3~5份,比普通型材配方偏大。外光滑选用硬脂酸、石蜡或PE蜡等,用量为1份以下。







  下面介绍几例发泡配方:配方14三盐二盐配方双螺杆单螺杆有机锡石腊PE蜡此配方的性能:相对密度为0. 85,拉伸强度为18MPa断裂伸长率为20%.配方PVC(悬浮/乳液)三盐PE蜡卜2配方双螺杆单螺杆三盐二盐液体石蜡上接第20页的FMR值大小,选定合理拉伸倍数,保障产品的理化性能指标合乎标准要求,再依据薄膜在电热板的拉伸缩径比例精确选定膜切条宽度。拉伸温度和拉伸倍数是纤维宽的主要影响因素留神配合调理。

  3.6原材料与拉伸倍数由于经过工艺合理改进后消费PP膨松撕裂纤维产品在原材料方面,对MFR值适用范围更广,但为了保障产品质量合乎要求。在投料选择时,主要原料PP应为拉丝级,MFR值为2.;PP回收料以原消费PP编织袋或PP吹膜的边角料回收造粒为隹其MFR值为3;掺用LDPE原料会改善产品的柔软度,减少起毛便于工艺操作,用量10份~15份为宜;LDPE应为吹膜级,MFR值为2~4g/10min;LDPE回收料的MFR值应为3~5g/0min.一般状况下,选用原辅材料的MFR值为3 ~45g/0min范围,其加工工艺容易控制,质量稳定,若MFR值偏小,其加工温度应适当调高,其拉伸强度好,产量低。若MFR值偏大,会呈现薄膜泡管下坠,重大时无法正常消费,所以加工温度应控制较低,加冷却风量,且适当加拉伸倍数,确保拉伸强度。总之,该工艺的拉伸倍数应依据不同原料的MFR值合理控制在45~7倍范围。其拉伸倍数过低会呈现无拉伸化,纤维偏宽偏厚,强度差,膨松柔软性差等不良现象,拉伸倍数过高会呈现纤维化起边毛重大,纤维偏窄等缺陷。


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