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。

  金属皂类热稳定体系自身兼有光滑作用,配方中只加少许光滑剂即可。

  上下温尺寸变迁率用金属皂类热稳定体系的型材配方如配方3、配方4和配方5所示:配方亚磷酸酯羟基硬脂酸环氧大豆油光滑剂配方亚磷酸酯内外光滑剂环氧酯配方亚磷酸酯内外光滑剂外光滑剂八妒石蜡、聚乙烯蜡化聚脂酸7石蜡聚乙烯蜡等//ww.cnki.net稳定剂,于20世纪90年代开端批量消费,并逐步取得推广应用。稀土类热稳定剂因无毒又称为绿色稳定剂。

  主要产地有:北京、山东淄博、江苏华阳、河北邯郸等。

  稀土类热稳定剂是稀土的氧化物、氢氧化物和有机弱酸盐,其中以稀土的氢氧化物热稳定成效最好。有机弱酸盐的品种有:硬脂酸稀土、脂肪酸稀土、水扬酸稀土、拧檬酸稀土、酒石酸稀土、苹果酸稀土、棕榈酸稀土、肉豆蔻酸稀土、月桂酸稀土、癸酸稀土、辛酸稀土等。

  稀土类热稳定剂的热稳定性极好,可与有机锡类相媲美,比铅盐类大3倍,比金属皂类大4倍。它具有无毒和透明的长处,目前只是价格稍高,介于铅盐和有机锡之间,在配方中的参与份数为3份左右。

  稀土类热稳定体系可与有机锡类热稳定剂并用,以降低有机锡的本钱。

  由于稀土类热稳定体系无光滑作用,应与光滑剂协同参与。下面是详细配方。

  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。

  3.3光滑体系光滑剂可分为内光滑剂和外光滑剂两种,两者的作用不尽雷同,一般要搭配使用。

  内光滑剂在常温下与树脂有一定的相容性,在高温下相容性大,从而产生内塑作用,削弱分子间作用力,减小内摩擦,降低熔体粘度,防止熔体缺陷和熔体破裂,进步活动性,进步制品的产量。HPVC配方常用的内光滑剂有硬脂酸丁酯、聚乙烯蜡、硬脂酸铅等。

  外光滑剂与树脂的相容性小,在加工中析出到熔体外表,降低熔体与接触金属之间的摩擦力,防止熔体粘附模具,改善制品的外观质量。HPVC配方中常用的乙烯蜡等。

  市场上供应光滑剂方式为:单品种供应、夹在复合稳定剂中供应、活性CaC3中含有2%~3%的HSt,在详细使用时要引起留神。

  在HPVC型材加工中,光滑剂起到重要的作用。

  它主要影响下列状况:模具、料筒、螺杆的使用寿命;挤出机的消费才干;消费过程中的能耗;制品外表的光洁度;型材的焊角强度及低温冲击性能。

  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。

  在详细设计HPVC型材配方中光滑体系的品种和参与量时,须要思考的其它因素:视配方中其它助剂而定。配方中填料参与量大时,要多加光滑剂,并以多加内光滑剂为主;不同稳定体系内,光滑剂的参与量不同,稳定剂品种自身光滑作用大时,可少加光滑剂;反之则多加。

  常用稳定剂按其自光滑作用排列如下:金属皂类>复合金属皂铅盐月桂酸马来酸锡>硫醇锡>稀土类。

  见实例配方7和配方8,其中配方7以有机锡为稳定剂,自身光滑作用小,光滑剂参与1~1.5份;配方8中以铅盐为稳定剂,自身具有一定的光滑作用,光滑剂参与0.5~1份。

  配方7配方8有机锡复合铅盐光滑剂卜1.加工助剂不同稳定体系内,光滑剂的参与品种不同。

  在铅盐稳定体系中,选用硬脂酸、硬脂酸丁酯、Pb-St、CaSt、聚乙烯蜡等。

  在金属皂类和稀土类稳定体系中,选用硬脂酸、硬在有机锡类稳定体系中,常用CaS/石蜡光滑体系。

  配方中含有加工助剂时,它自身含有一定的光滑性,光滑剂可少加。

  配方中含有韧剂时,大了粘附金属的倾向,光滑剂应多加。关于CPE韧体系,石蜡易溶于其中,降低韧成效,一般不选石蜡做光滑剂。

  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。

  配方9(双螺杆)配方10(单螺杆)ACR韧剂ACR加工助剂有机锡思考光滑剂的平衡。在详细配方设计中,内外光滑要平衡,前期、中期和后期光滑要平衡。如只满足前期光滑,然后期光滑缺乏,就会招致螺杆均化段、压缩段及口模光滑缺乏,物料剪切激烈,招致分解,温度回升。

  型材采纳挤出成型,粘附金属倾向比压延小,以内光滑为主。

  在铅盐稳定体系中,外光滑剂少加。

  石蜡/硬脂酸配合使用,外光滑成效好。

  (4)视加工条件而定。加工温度高者,光滑剂多加。

  3.4增韧体系HPVC型材属硬制品,其中不含塑剂,因而冲击强度不好。纯HPVC型材的简支梁冲击强度值仅为3~5k/m2,尤其低温冲击强度更低,并且对缺口敏感性大。国标8814―98中规定简支梁冲击强度在常温下户造型要抵达40k/m2,户内型要抵达321kKm2,两者可用于HPVC冲击改性的韧材料有:CPE、ACR、MBS及EVA等,这几种韧材料的性能比较如表5所示。

  改性成效极好好中耐侯性极好好不好好加工依赖性不依赖不依赖本钱上下上下按不同的分类办法,可将HPVC用韧材料分成如下几类:按对加工的依赖性分类。韧成效不依赖加工条件的有:ACR、MBS;韧成效依赖加工条件的有:CPE、EVA.按耐侯性好坏分类。耐侯性好的有:ACR、CPE、EVA耐侯性不好的有:MBS.按在PVC中的分散模式分类。韧剂以网络模式分散的有:CPE、EVA,这类分散模式依赖加工条件;韧剂以粒子模式分散的有:ACR、MBS,这类分散模式不依赖加工条件。

  以上两种不同分散模式的韧剂之间共用有协调目前几种韧材料的应用比例不同,由于EVA的加工温度范围窄,并能显著降低产品的软化温度,如今己很少用;MBS因价格高,主要用于透明制品,应用也不宽泛;在美国,CPE、ACR、EVA三种韧材料的应用状况如表6所示。

  表6ACR、CPE、EVA在美国的应用状况年份无增韧剂有1定的差别,:因而须要停止增韧改性ElecfroWcPublishin!地哪消费水平下降4CR则逐年加fci尤其在兴隆从表6中能够推测出,目前在世界范围内,HPVC型材用韧剂主要用CPE和ACR两种,在不同地域和国家的应用比例不同。以中国市场为例,1999年CPE用量占80%ACR和MBS各占10%;欧洲曾以CPE为主,目前有以ACR为主的趋势;总之,世界各国家更是如此。

  由于ACR和CPE两种材料最常用,现将其比较如下:(1)价格方面。CPE目前的价格比ACR低30%左右,故我国主要使用CPE;随着ACR国产化逐步成熟,其价格也一直降低,现己抵达16000元/吨。

  ⑵改性成效。除ACR的冲击改性成效明显好于CPE外,其它性能也都好于CPE,详细如表7所示。在低参与份数时,ACR的改性成效高于CPE的幅度较大;随参与量的大,两者相差幅度缩小。但尺寸变迁率与之相反,随参与量大,其相差的幅度越来越大。

  表7不同参与量时ACR改性成效高于CPE的百分比参与份冲击强度弯曲模量软化点拉伸强度弯曲强度尺寸变迁加工性能。ACR的加工性能好、塑化工夫短、塑化温度低、熔体强度高,并可进步熔体的流变性能,热稳定性好于CPE兼有加工助剂的部分功能,能够减少加工助剂用量。韧成效对加工条件不敏感详细如表8所示。

  CPE的韧改性成效对加工条件的依赖性大,详细如表8所示:CPE兼有部分光滑作用。

  表8加工温度对CPE和ACR冲击改性成效的影响加工温度(°c)冲击强度(km2)ACR和CPE韧体系的加工条件如表9所示。

  表9ACR和CPE增韧体系的加工条件加工条件料筒温度(°C)连贯体温度(C)螺杆温度(°c)冷却水温(t)塑化工夫平衡扭矩(Nm)最小最大平衡的耐侯性为5级,而CPE的耐侯性仅为3级。

  ACR是PVC韧成效最好的抗冲击改性剂,PVC/ACR改性体系消费的型材各项性能指示均好于PVC/PE改性体系。目前只是ACR的价格较高(国产为16000~17000元/吨,进口为23000元/吨),在国内未获大规模应用。随其价格逐步降低,ACR的使用量会逐步加。在不久的未来,ACR必将部分或全副取代CPE,成为HPVC型材用韧剂的绝对主流。

  ACR韧剂与ACR加工助剂的构造不同,它为一种核-壳构造聚合物,由甲基丙烯酸甲酯、丙烯酸酯、丙烯酸丁酯、丙烯酸乙酯四种单体共聚而成,其核为一类低度交联的丙烯酸酯类橡胶聚合物,壳为甲基丙烯酸甲酯接枝聚合物。

  ACR的韧成效虽与加工条件关系不大,但与稳定体系的品种有关。ACR在不同稳定体系中的韧成效大小次序如下:有机锡稀土金属皂铅盐系其中ACR在有机锡系和铅盐系中参与不同份数的韧成效如表10所示。从表10中能够看出,ACR参与7份时,在有机锡系中的冲击强度比在铅盐中大50%左右。

  表10ACR在铅。锡不同稳定体系中的增韧成效稳定体参与份数缺口冲击强度(km2)弯曲模量(MPa)系铅系锡系1(4)耐侯性4aCR的耐侯性,明显好于tCPEACR―gHo丨我国的主要消费企业有丨:丨安利化工厂威海金目前我国用于抗冲击制品的ACR大都以进口为主,国产ACR的性能与国夕卜还有差距。国外的主要供应商有美国罗门哈斯的KM系列如KM334、323B、355,美国ATOCHEM的D200、D201,英国的ICI,德国的BASF,日本钟渊的FM21,新加坡吴羽的KM334、355、355P,法国阿托公司的D200等我国以进口美国罗门哈斯、日本钟渊、新加坡吴羽的产品为主。

  弘化工原料厂、江苏东台林业化工厂、上海珊瑚化工厂、山西化工钻研院的BKM系列、温州助剂塑料厂、无锡天狗化工集团、海城三和公司、山东益元公司、黑龙江安达新龙化厂、抚顺化工厂、吉化公司、齐鲁石化钻研院等。

  在我国,CPE为最常用的HPVC型材用韧材料,在参与7~10份时韧成效非常显著;同时又具有价格低、耐侯性好、来源宽泛等长处。但CPE韧体系的毛病为在韧同时,会使拉伸强度、弯曲强度、维卡软化点等性能下降洒低温冲击性能一般;韧成效受加工温度影响大,加工温度范围窄。CPE在欧美等兴隆国家的应用量逐年减少,而在我国也有用ACR取代的趋势。

  %~36%要求游离氯的含量要尽可能低,否则会招致耐老化性能差,光晒后制品易发黄,并对缺口敏感性大。

  在详细应用CPE时,一般要留神如下几点:CPE的改性成效强烈地依赖于加工条件,只要在适宜的工艺条件下,CPE的韧作用才可发挥。工艺条件的调整以保障塑化度为60%左右时,型材的冲击强度最高。加工温度对型材冲击强度的详细影响可参见表8所示,加工温度只相差10°Q左右,冲击强度有时可相差一倍以上。这使PVC/CPE体系的加工温度范围比较窄,加工比较难以控制。

  PVC/CPE韧体系的加工温度一般采纳反向设置,即从加料段到均化段逐步降低。

  体系在不同的稳定体系中,韧成效不同。详细韧成效如下:铅盐系>稀土系>有机锡系表11列出了PWCPE在铅盐系和有机锡系中的不同韧成效。

  表11PVC/CPE在铅盐系和有机锡系中的增韧成效稳定体系参与量(份)缺口冲击强度(m2)弯曲强度铅盐系有机锡系从表11中能够看出,同样10份的CPE,在铅盐稳定体系中的韧成效比在有机锡系中大60%左右。

  (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。

  PVC/PE-g-VC/PE体系。CPE-g-VC与PVC的相容性比CPE大,因而CPE-VC即可作为CPE/PVC体系的相容剂,又可独自使用。以CPE-g-VC/CPE复合参与8份为例,比单加CPE的缺口冲击强度大170%,并且刚性损失也减小。

  PVC/PE/刚性有机粒子体系。在PVC/CPE韧体系中参与刚性有机粒子,两者有协同作用,并且刚性、韧性同时进步。常用的刚性有机粒子有:PP、PS、PMMA、AS、SAN.以PS为例,PVC/PE/S(100/0/3)体系的韧成效可比PVC/CPE体系大300%左右。

  PVC/无机刚性粒子体系。刚性无机粒子的粒度要细,一般在0.1ium以下。随刚性无机粒子参与量的大,冲击强度呈抛物线变迁,即存在一个最佳临界值;刚性无机粒子的粒度越细,临界值越大。

  PVC型材常用的刚性无机粒子为碳酸I钙有时使用滑石粉、云母、硅灰石等。

  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。

  HPVC常用的加工助剂为ACR,用于加工的ACR与韧用ACR的构造不同,它为甲基丙烯酸甲酯与丙烯酸酯的共聚物,非核-壳型构造。国产ACR加工助剂的性能己满足须要,详细消费厂家同ACR韧剂消费厂家。

  ACR加工助剂的参与量一般为2~3份左右,在不同的韧体系和热稳定体系中的参与量不同。

  (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抗老化体系HPVC型材制成门窗后,需长期在阳光下曝晒,并经寒冬酷夏、风吹雨淋,这势必会引起不同水平的老化,从而使型材产生变色、龟裂、脱粉等现象,并招致型材的使用性能下降或丢失使用价值。要坚持HPVC型材可使用50年,必需在配方中参与抗老化剂。

  HPVC所用的抗老化剂有紫外光稳定剂和抗氧剂两类,并以紫外光稳定剂为主。

  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。

  钛白粉的参与量与下列因素有关:(1)在不同的稳定体系中,钛白粉的参与量不同。

  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。

  在不同的抗老化体系中,钛白粉的参与量不同。如配方中除钛白粉外,还有其它紫外光稳定剂,钛白粉的参与量可少;反之,则须要多加。

  3.6.2紫外光吸收剂紫外光吸收剂参与的宗旨为吸收因紫外光屏蔽剂未能完全屏蔽而进入型材内的少量紫外光,以抵达抗老化的宗旨。常用的紫外光吸收剂有:UV-531、UV-9等,参与量为0.5份。

  3.6.3抗氧剂抗氧剂参与的宗旨为防止在受热状态下,发作热氧化降解。常用的抗氧剂有抗氧剂1010、双酚A等,参与量为0.5份。

  3.7填充体系填充体系的作用有两个:一是降低型材的本钱;二是进步型材的性能,如刚性、耐热性、尺寸稳定性等。从某种水平上说,为保障型材具有一定的硬度和刚性,填料也是必需参与的助剂品种之一。

  在HPVC型材配方中,最常用的填料为轻质Ca-CO3,为保障型材的性能平衡,对CaC3的要求如下:粒度要细。不同粒度的CaC3,对型材的性能影响不同。例如,在PWCPE韧配方中,参与5份不同粒度的CaC3,对型材的冲击强度影响如下:再如,不同粒度的CaC3对型材的焊角强度影响如表12所示。

  表12不同粒度的CaC3对型材的焊角强度影响类别超细活性CaC3参与份数焊角强度(N)―10冲击破裂数外观较好一般较好的相容性不好,往往会形成型材某些性能的下降。解决办法可用偶联剂或相容剂解决。下面以PVC/aC3(100/0)为例,介绍用钛铝酸酯偶联剂和PVC-g-MAH相容剂解决的成效。

  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。

  3.8.1添加焊角强度改性剂焊角强度改性剂为一种专用于改善焊角强度的助剂,其改性原理为:粘作用――大型材焊接面之间粘合性,起到类似粘合剂的作用。

  扩散作用――促进型材焊接面之间分子互相扩散和环绕纠缠,以大焊接强度。

  焊角强度改性剂的参与量不宜太大,否则会影响型材的冲击强度。下面介绍焊角强度改性剂A和B的详细改性成效,如表13所示。

  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。

  表14CPE的参与量与焊角强度的关系CPE参与量(份)焊角强度(N)3.8.3填充适量外表解决的填料在HPVC型材中填加适量经外表解决的填料,不但不会引起焊角强度的下降,还会适当进步焊角强度,如表11所示。

  3.9着色体系用于户外的HPVC型材要求着色剂的耐侯性好,在使用中不褪色。

  不同颜色型材参与不同的着色剂,详细如下:乳白色参与金红石型钛白粉;瓷白色――在参与金红石型钛白粉的根底上,再参与适量群青或白剂;木纹料参与木纹专用着色母料,韩国LG化学公司和北京天潮色母料公司可提供。

  彩色料――参与相应的着色剂。

  4低发泡HPVC型材配方设计HPVC低发泡型材是指相对密度在0.8左右的一类微孔塑料制品。它属于构造泡沫塑料类别,其制品的芯部发泡,而表层厚度为0.3~1mm左右,不发泡,以保障构造强度。

  由于低发泡型材在外观、性能及二次加工上与天然木材有许多类似之处,故素有合成木材'之称。

  与普通型材相比,低发泡型材具有如下长处:⑴其密度比普通型材低40%左右,出材率高;制品的内应力小到简直为零,型材的尺寸稳定性好、收缩小、弯曲小;优良的隔音、隔热成效;接近木材的二次加工性能,可锯、刨、钉。

  在国外,HPVC低发泡型材的应用比例很大,而在我国则刚刚兴起,尚未形成规模化消费。

  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。

  HPVC最常用的发泡剂为AC(偶氮二甲酰胺),在详细使用时应留神如下几点:°Q高于HPVC的加工温度,必需用适当的助剂停止调整,使其分解温度下降到PVC加工温度范围内。一般常用的调解剂为稳定剂,不同稳定剂对AC分解温度的调解幅度如下:三盐>二盐>PbSOBaSOCaSt稳定剂的浓度不同,AC的温度下降幅度也不同,详细如表14所示。

  表14稳定剂的浓度与AC的分解温度发泡体系三盐(1,分解温度(Q)(2)AC发泡剂分解产生的残留物具有酸性,可形成模具细微的腐蚀。为此,控制发泡剂的参与量,可减少腐蚀性。一般AC的参与量控制在0.2~0.65份之间,如须要再大发泡倍率,可参与适量的NaHC3无机发泡剂辅助之。

  4.3发泡助剂HPVC发泡用发泡助剂包括发泡活化剂、泡孔调理剂和成核剂等。

  1发泡活化剂发泡活化剂主要为铅盐、金属皂类和氧化锌等。它一方面可降低AC的分解温度,另一方面可大AC的发气量。因为铅盐和金属皂类属PVC加工的稳定剂和光滑剂,HPVC原配方中己有时,一般不另外参与。

  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。

  4.6冲击改性剂常用ACR和MBS,其长处为在改善冲击性的同时,兼有发泡调理剂作用。ACR―般参与5~8份,而MBS―般参与8份。

  普通型材中常用的CPE冲击改性剂,其自身熔融粘度大,与发泡后粘度较低的PVC融体分散不均匀,会形成制品外表粗糙无光,重大者甚至会有气泡产生。

  另外,CPE还会使发泡体变脆性并发作破裂。所以,CPE在发泡型材中一般不采纳。

  4.7填料填料的作用为降低本钱、改善融体活动性、大制品的刚性等,同时兼有泡抹成核剂的作用。

  常用的填料为超细活性碳酸钙,参与量为10份以下。

  4.8增塑剂塑剂参与的宗旨为进步泡孔壁的柔软性和熔体的粘弹性。常用1~3份环氧酯,并兼有辅助稳定的作用。

  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。

  4结论经过抵消费设施和加工技术工艺等方面钻研设计改进后,抵达了预期的成效。它不但开发消费出pp膨松撕裂纤维新品种,新特征更合乎广阔客户的使用适用性。而且在原料方面大大加了pp回收料的掺配量,有利于变废为室,节约资源,减少污染公害,开拓废次料回收新门路,降低消费本钱。有效进步产品在市场上的竞争才干,加企业和社会的经济效益。

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