CN1765976A - Polypropylene foaming premix and its preparation method - Google Patents

Polypropylene foaming premix and its preparation method Download PDF

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CN1765976A
CN1765976A CN 200410086290 CN200410086290A CN1765976A CN 1765976 A CN1765976 A CN 1765976A CN 200410086290 CN200410086290 CN 200410086290 CN 200410086290 A CN200410086290 A CN 200410086290A CN 1765976 A CN1765976 A CN 1765976A
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polypropylene
foam
premix
melt
ii
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CN 200410086290
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CN100389150C (en )
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张薇
张师军
刘涛
尹华
吕明福
段淑清
邵静波
李魁
吕芸
张丽英
王小兰
张�浩
陈力
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Abstract

The invention provides a pre-mix material for polypropylene foam, which comprises: using the polypropylene random copolymer of 100 weight shares with 3.5~6.5% content and 3.0~9.0 MWD and polypropylene of 5~10 weight shares with 1~4g/10min fusion index and 0.3~0.6N fused mass strength as base resin, and fusing with organic foamer. This product has well foam pore structure, even pore diameter, and high foaming ratio with 7~12 foaming multiplying power and 75~129Kg/m3 foam bulk weight, and has wide application.

Description

一种聚丙烯发泡预混料及其制备方法 A foamed polypropylene and its preparation method premix

技术领域 FIELD

本发明涉及一种发泡塑料,进一步地说,是涉及发泡聚丙烯材料的预混料及其制备方法。 The present invention relates to a foamed plastic, and further, it relates to preparation of the premix and foam polypropylene material.

背景技术 Background technique

由于聚丙烯熔融时粘度急剧下降,熔体强度很低,发泡成型非常困难。 Due to a sharp decline in the polypropylene melt viscosity, low melt strength, it is very difficult to foam molding. 因此,常常采用交联工艺来提高体系的熔融粘度,制备发泡聚丙烯。 Thus, the cross-linking process is often used to increase the melt viscosity of the system, the preparation of polypropylene foam. 如美国专利US4766159,是采用辐射交联发泡的方法制备聚丙烯发泡材料。 U.S. Patent No. US4766159, a method for preparing radiation crosslinked foam polypropylene foam. 它采用均聚或共聚聚丙烯,或二者与无规共聚聚丙烯共混树脂为基体,配合化学发泡剂AC及过氧化物交联剂等加工成型后,经辐照再发泡。 It uses homopolymerization or copolymerization polypropylene, random copolymer polypropylene, or a blend of both resin matrix, with the chemical blowing agent and a peroxide crosslinking AC molding process, and then irradiated foamed. 但由于聚丙烯易降解,在交联过程中聚丙烯分子的降解和交联会同时发生,这对发泡材料的最终使用性和力学性能等都会产生影响,泡孔均匀性不容易控制。 However, because polypropylene susceptible to degradation, degradation and crosslinking occur simultaneously during the crosslinking of the polypropylene molecule, which affect the mechanical properties of end-use and the like are foamed materials, the uniformity of the cell is not easy to control.

此外,现有技术中也有采用在聚丙烯中配合其他熔体强度高的树脂,共同发泡得到泡沫材料的方法。 Further, the prior art has employed with other high melt strength polypropylene resins, a common method of foaming the foam obtained. 如美国专利US5,527,573,采用嵌段共聚聚丙烯、无规共聚聚丙烯、传统聚丙烯、高熔体强度聚丙烯的二种或二种以上聚合物为发泡基体,采用物理发泡剂如MeCl、FC-B34、CFC-114、HCFC-1426等通过单螺杆挤出机制备泡沫容重小于80kg/m3的聚丙烯泡沫材料。 U.S. Patent No. US5,527,573, using polypropylene block copolymer, polypropylene random copolymer, conventional polypropylene, high melt strength polypropylene of two or more kinds of polymer foam matrix, such as using physical blowing agents Preparation mechanism foamed polypropylene foam density less than 80kg / m3 of MeCl, FC-B34, CFC-114, HCFC-1426 and the like through a single screw extruder. 但由于混入其他树脂存在相容性的问题,会使泡沫材料的力学性能及耐热温度下降较多。 However, due to compatibility problems mixed in the presence of another resin, mechanical properties and heat resistance of the foam temperature will decrease more. 而且该专利未公开这种发泡基体是否用于化学发泡剂。 Further the patent does not disclose whether this foamed matrix for chemical blowing agents.

发明内容 SUMMARY

针对现有技术中存在的问题,本发明利用一种无规共聚聚丙烯和一种高熔体强度的聚丙烯的混合物进行发泡,可得到高发泡倍率、泡孔均匀、刚性和热稳定性好的聚丙烯泡沫材料。 For the problems in the prior art, the present invention uses one kind of mixture of polypropylene random copolymer and polypropylene is a high-melt strength foam, to obtain a high expansion ratio and uniform cells, rigidity and thermal stability good polypropylene foam.

本发明目的是要提供一种可得到泡孔结构均匀、发泡倍率高、刚性及热稳定性好的聚丙烯发泡材料的发泡预混料。 Object of the present invention is to provide a uniform cell structure can be obtained, a high expansion ratio, rigidity and good thermal stability of polypropylene foam premix foamed material.

本发明的另一个目的是提供所述的发泡预混料的制备方法。 Another object of the present invention to provide the method for preparing the foamed premix.

为达到上述目的,本发明采用一种无规共聚聚丙烯树脂(PPR)和一种经辐照接枝得到的高熔体强度的聚丙烯的混合物作为基础树脂,通过化学发泡,可得到高发泡倍率的发泡聚丙烯材料。 To achieve the above object, the present invention employs a mixture of a polypropylene resin random copolymer (PPR) and a high melt strength polypropylene by radiation grafting as a base resin obtained by chemical foaming, a high-fat expansion ratio foamed polypropylene material.

本发明所述的聚丙烯发泡预混料,包含有共混的以下组分:聚丙烯I、聚丙烯II和有机化学发泡剂。 Polypropylene foam premix according to the present invention, comprises a blend of the following components: Polypropylene I, II polypropylene and organic foaming agents. 其中以聚丙烯I为100重量份数计,聚丙烯II的含量为5~10重量份数,优选为6~8重量份数。 Wherein the polypropylene of 100 I in parts by weight, the content of the polypropylene II is from 5 to 10 parts by weight, preferably 6 to 8 parts by weight.

以上所述的本发明聚丙烯发泡预混料中,聚丙烯I为丙烯和乙烯的无规共聚物,即一种无规共聚聚丙烯(PPR)。 The above-described premix of the present invention, foamed polypropylene, the polypropylene random copolymer I is a propylene and ethylene, that is, a random copolymer polypropylene (PPR). 这种无规共聚聚丙烯的乙烯含量[通过红外(Magna-IR760,Nicolet)及核磁(400M,瑞士AVANCE)测得]为3.5~6.5wt%,优选为4.0~5.0wt%;分子量分布(Mw/Mn)为3.0~9.0,优选为4.2~7.0[凝胶色谱仪GPC(150-CALC/GPC,Waters)测定]。 This random copolymer of ethylene content in polypropylene [by infrared (Magna-IR760, Nicolet) and NMR (400M, Switzerland AVANCE) measured] of 3.5 ~ 6.5wt%, preferably 4.0 ~ 5.0wt%; the molecular weight distribution (Mw / Mn) of 3.0 to 9.0, preferably from 4.2 to 7.0 [gel chromatography GPC (150-CALC / GPC, Waters) measurement]. 其熔融指数为0.10~1.2g/10min(测试仪器:熔融指数仪code 6942,意大利CDAST制造;测试标准ASTMD1238;测试条件:230℃,2.16kg),优选为0.13~0.40g/10min;其熔体拉伸强度(210℃(Rheotens71.97,德国GOTTFERT,210℃))为0.75~4.5N,优选1.35~3.50N。 A melt index of 0.10 ~ 1.2g / 10min (Measuring equipment: melt indexer code 6942, manufactured in Italy CDAST; Standard Test ASTM D1238; test conditions: 230 ℃, 2.16kg), preferably 0.13 ~ 0.40g / 10min; a melt tensile strength (210 ℃ (Rheotens71.97, Germany GOTTFERT, 210 ℃)) is 0.75 ~ 4.5N, preferably 1.35 ~ 3.50N.

以上所述的本发明聚丙烯发泡预混料中,聚丙烯II采用熔融指数为1~4g/10min、熔体强度为0.25~0.60N(200℃测)的聚丙烯(HMSPP)。 The above-described premix of the present invention, the polypropylene foam, the melt index of the polypropylene II 1 ~ 4g / 10min, a melt strength of 0.25 ~ 0.60N (200 ℃ measured) polypropylene (HMSPP). 其熔融指数优选为2~3g/10min。 The melt index is preferably 2 ~ 3g / 10min. 该中聚丙烯具有较高的熔体强度。 The polypropylene having a high melt strength.

本发明所采用的这种乙烯含量、分子量分布在上述范围内无规共聚聚丙烯,具有优异的熔体强度,特别适合于热分解型化学发泡剂制备聚丙烯泡沫材料。 This ethylene content employed in the present invention, a molecular weight distribution in polypropylene random copolymer within the above range, excellent melt strength, is particularly suitable for the preparation of thermally decomposable chemical foaming polypropylene foam. 当化学发泡剂分解时产生大量的气体及热量,泡孔的形成、增长和定型过程中,一般聚丙烯的粘弹性随温度发生很大变化,温度增高时聚丙烯熔体的粘弹性会迅速降低,泡孔破壁塌陷,大小不均,如附图2所示。 Large amount of gas and the heat generated when the chemical foaming agent decomposition, forming cells, the growth and shaping process, generally the viscoelastic polypropylene greatly changes with temperature, the polypropylene melt temperature increases rapidly viscoelasticity reduce, broken cells collapse, non-uniform size, as shown in Figure 2. 而本发明的无规共聚聚丙烯配合高熔体强度的聚丙烯能够满足泡孔形成过程的粘弹性要求,形成泡孔结构均匀发泡体(见附图1)。 And random copolymer polypropylene with the present invention a high melt strength polypropylene can satisfy the requirements of the cell forming the viscoelastic process, to form a uniform foamed cell structure (see Figure 1).

本发明聚丙烯发泡预混料中的聚丙烯II可采用现有技术中熔融指数和熔体强度符合上述条件的聚丙烯,也可优选采用包括以下步骤的方法制备:a.将聚丙烯与多官能团单体混合均匀,得到混合物;b.将上述混合物用氮气充分置换,并在氮气气氛下辐照;c.将上述步骤处理得到的聚丙烯与抗氧剂混合,经挤出造粒得到高熔体强度聚丙烯。 Polypropylene foam premix II of the present invention may employ the prior art polypropylene melt strength and melt index satisfies the above conditions, may be preferably prepared using the method comprising the steps of: a polypropylene with. polyfunctional monomer uniformly mixed to obtain a mixture;. b the above mixture was sufficiently replaced with nitrogen, and irradiated under a nitrogen atmosphere;. c polypropylene processing in the above step was mixed with an antioxidant, obtained by extrusion granulation high melt strength polypropylene.

以上方法中多功能团单体为双官能团或二以上官能团单体,如:1,6-己二醇二丙烯酸酯(HDDA)、新戊二醇二丙烯酸酯(NPGDA)、二乙烯基苯等。 The method of the above polyfunctional monomer is a difunctional monomer, or two or more functional groups, such as: 1,6-hexanediol diacrylate (of HDDA), neopentyl glycol diacrylate (NPGDA), divinylbenzene . 其以聚丙烯为100重量份数计,用量为0.1~3.0份。 Polypropylene which is 100 parts by weight basis, in an amount of 0.1 to 3.0 parts.

与所用原料相比,这种方法得到的聚丙烯熔体拉伸力值变化ΔF大于等于40cN,储能模量G′是空白样的1~2倍。 Compared with the materials used, the polypropylene melt tensile force value variation obtained in this way is not less than 40 cN ΔF, the storage modulus G 'of the blank is 1 to 2 times.

上述聚丙烯II的制备方法步骤a中聚丙烯和多功能团单体的混合为普通的混合,即使用浸渍、搅拌等通常的混合方法使多功能团单体与所用的聚丙烯充分接触、混合均匀。 The polypropylene prepared in step II, a mixture of polypropylene and an ordinary polyfunctional monomer is mixed, i.e. dipping, such as stirring mixing methods generally polyfunctional monomer makes sufficient contact with the polypropylene used, mixed uniform. 在该方法中为了使多功能团单体和聚丙烯最大面积接触、均匀混合以达到有效的提高聚丙烯熔体强度的目的,最好选用粉状(包括球状)的聚丙烯。 In order to make the polyfunctional monomer and the polypropylene maximum contact area in which method, to achieve effective mixing uniformly the purpose of improving the melt strength of polypropylene, the best selection of powder (including spherical shape) polypropylene. 原料聚丙烯的熔融指数为1~5g/10min、熔体强度为0.1N以上,优选0.1~0.5N(200℃测)。 The melt index of the polypropylene starting material 1 ~ 5g / 10min, the melt strength of 0.1N or more, preferably 0.1 ~ 0.5N (200 ℃ measured).

上述聚丙烯II的制备方法所述辐照利用的辐照射线选自电子射线、伽马射线、x-射线或紫外光,优选为电子射线或伽马射线。 II Preparation of the polypropylene irradiation using the selected rays irradiated electron rays, gamma rays, X-rays or ultraviolet light, preferably gamma radiation or electron beam. 辐照剂量为0.2~10kGy,优选为0.5-5kGy。 Exposure dose 0.2 ~ 10kGy, preferably 0.5-5kGy.

辐照后的聚丙烯物料还残存有自由基。 Polypropylene material after irradiation also remnants of free radicals. 按照常规的辐照技术,辐照后的物料需要消除自由基,以免残存自由基与氧作用使聚丙烯降解。 According to conventional irradiation techniques, the material after irradiation is necessary to eliminate the free radicals, so as to avoid residual free radicals with oxygen polypropylene degradation. 所以一般将辐照后的物料于氮气气氛下常温放置若干天,或于高温下放置若干小时。 Therefore, the material after irradiation is generally placed at room temperature under nitrogen atmosphere for several days, or placed under a high temperature for several hours. 本发明一般将辐照后的聚丙烯于100C处理2小时即可消除残余自由基。 The present invention generally irradiated polypropylene after at 100C for 2 hours to remove residual free radicals.

以上所述的本发明聚丙烯发泡预混料中,有机化学发泡剂可采用现有技术中各种适合于聚丙烯发泡的有机化学发泡剂。 The above-described premix of the present invention, the polypropylene foam, organic blowing agents may be employed in a variety of prior art polypropylene foam suitable for organic chemical blowing agents. 其一般分解温度在180-240℃,优选在190-230℃。 Its decomposition temperature is generally 180-240 ℃, preferably at 190-230 ℃. 它们包括但不限于偶氮二甲酰胺(AC)、偶氮二异丁腈、N,N-二亚硝基五次甲基四胺(BN)、对甲苯磺酰氨基尿等。 These include, but are not limited to azodicarbonamide (AC), azobisisobutyronitrile, N, N- dinitroso five tetramine (BN), p-toluenesulfonyl amino group such as urine. 其用量均为常规用量,或根据实际情况的要求进行调整。 Conventional amounts are used in an amount which, according to the requirements or to adjust the actual situation. 本发明预混料中有机化学发泡剂的含量以聚丙烯I为100重量份数计优选为2~6重量份数,更优选为3~5重量份数。 The blowing agent content in organic chemistry to premix the present invention 100 parts by weight of polypropylene I is preferably 2 to 6 parts by weight, more preferably 3 to 5 parts by weight.

以上所述的本发明聚丙烯发泡预混料中,还可包括无机填料。 The above-described polypropylene foam premix of the present invention, may further comprise an inorganic filler. 无机填料包括无机盐类和金属氧化物的固体颗粒,可选自二氧化硅、滑石粉、碳酸钙、氧化锌或氧化镁等。 The inorganic fillers include solid particulate inorganic salts and metal oxides selected from silica, talc, calcium carbonate, zinc oxide, magnesium oxide, or the like. 无机填料在此处作为成核剂使用,其所起的作用就象沸石在沸腾液体中的作用一样对发泡过程非常重要。 The inorganic filler is used here as a nucleating agent, as their role is very important for the foaming process as the role of the zeolite in the boiling liquid. 准确的说,无机填料在发泡时形成热点即气泡生长点,在发泡剂分解时便能在气泡生长点形成气泡,无机填料对于泡孔的均匀分布及稳定生长起到很重要的作用。 Precisely, i.e. the inorganic filler hot air bubbles formed during the foaming growing point, can form bubbles in the bubble growth point at decompose the blowing agent, the inorganic filler is uniformly distributed and stable for the growth of cells play an important role. 无机填料的用量可采用常规用量,或根据实际情况的要求进行调整。 The amount of the inorganic filler may be employed in conventional amounts, or be adjusted according to the requirements of the actual situation. 通过调节无机填料的用量可以控制泡孔的大小。 The size of the cells may be controlled by adjusting the amount of the inorganic filler. 其用量太高则成为填充剂,反而起不到热点的作用了。 The amount is too high to be filler, but no effect of the hot spot. 因此本发明预混料中无机填料用量以聚丙烯I为100重量份数计,优选为0.5~5重量份数,更优选0.5~1.0重量份数。 Accordingly the present invention premix of the inorganic filler in an amount of polypropylene I 100 in parts by weight, preferably 0.5 to 5 parts by weight, more preferred 0.5 to 1.0 wt parts. 无机填料的平均粒径一般为1250目或以上。 The average particle diameter of the inorganic filler is generally 1250 mesh or more.

以上所述的本发明聚丙烯发泡预混料中,还可包括现有发泡技术中常用的加工助剂,以利于稳定发泡,如液体助剂。 The above-described premix of the present invention, the polypropylene foam, the foam may further include a prior art conventional processing aids to facilitate stable foam, such as liquid additives. 液体助剂起到在挤出过程中润滑及发泡时泡孔调整的作用,其加入有利于发泡材料的挤出,也有助于形成均匀稳定、尺寸可控的泡孔。 Liquid adjuvant functions in the cell when the adjustment effect lubrication during extrusion and foaming, facilitate extrusion foaming added material also helps to form a uniform and stable, controllable cell size. 在此液体助剂为液体低分子直链烃或液体低分子有机硅化合物,优选为白油、液体石蜡或硅油。 Adjuvant in the liquid is a liquid hydrocarbon or liquid low molecular weight linear low-molecular organosilicon compounds, preferably white oil, liquid paraffin or silicone oil. 其用量可采用常规用量,或根据实际情况的要求进行调整。 Amounts may be employed in conventional amounts, or be adjusted according to the requirements of the actual situation. 液体助剂加入太少起不到作用,太多则不利于加工。 Liquid additives added to no effect too, too much is not conducive to processing. 因此本发明的预混料中液体助剂用量以聚丙烯I重量份数为100计优选为0.1~1,更优选为0.2~0.5。 Thus the amount of premix liquid adjuvant of the present invention in 100 parts by weight of polypropylene I is preferably from 0.1 to 1, more preferably 0.2 to 0.5.

此外,在本发明的聚丙烯发泡预混料中,还可包括其它的塑料加工常用的助剂,如抗氧剂、阻燃剂等。 Further, the polypropylene foam premix of the present invention may also include other conventional plastics processing aids, such as antioxidants, flame retardants and the like. 其用量均为常规用量,或根据实际情况的要求进行调整。 Conventional amounts are used in an amount which, according to the requirements or to adjust the actual situation.

本发明所述的聚丙烯发泡预混料的制备方法包括以下步骤:将包括所述的聚丙烯I、聚丙烯II和有机化学发泡剂在内的组分进行熔融共混。 Premix polypropylene foam prepared according to the present invention comprises the steps of: comprising the polypropylene I, II and organic foaming polypropylene including melt blending the components. 其中以聚丙烯I为100重量份数计,聚丙烯II的含量为5~10重量份数,优选为6~8重量份数。 Wherein the polypropylene of 100 I in parts by weight, the content of the polypropylene II is from 5 to 10 parts by weight, preferably 6 to 8 parts by weight.

本发明的方法通常是将各个组分一起混合均匀,然后进行熔融共混。 The method of the present invention is generally uniformly mixing the individual components together, and then melt blending. 但为了使发泡预混料中的两种聚丙烯树脂充分共混,使基体树脂质地均匀,优选现将包括上述两种聚丙烯树脂在内的组分混合均匀进行熔融共混;再将所得到的共混料同包括有机化学发泡剂在内的组分混合均匀进行熔融共混。 But in order to sufficiently blending two polypropylene resin foamed premix, the matrix resin is homogeneous, preferably comprising both a polypropylene resin now including melt blending the components mixed; then the the resulting blend with the blowing agent component comprising organic chemistry including melt blended uniformly mixed.

以上所述本发明聚丙烯发泡预混料的制备方法中,聚丙烯I为前述的无规共聚聚丙烯。 The above method of preparation of the present invention, the polypropylene foam premix, the polypropylene random copolymer I of the polypropylene. 这种无规共聚聚丙烯的乙烯含量[通过红外(Magna-IR760,Nicolet)及核磁(400M,瑞士AVANCE)测得]为3.5~6.5wt%,优选为4.0~5.0wt%;分子量分布(Mw/Mn)为3.0~9.0,优选为4.2~7.0[凝胶色谱仪GPC(150-CALC/GPC,Waters)测定]。 This random copolymer of ethylene content in polypropylene [by infrared (Magna-IR760, Nicolet) and NMR (400M, Switzerland AVANCE) measured] of 3.5 ~ 6.5wt%, preferably 4.0 ~ 5.0wt%; the molecular weight distribution (Mw / Mn) of 3.0 to 9.0, preferably from 4.2 to 7.0 [gel chromatography GPC (150-CALC / GPC, Waters) measurement].

以上所述本发明聚丙烯发泡预混料的制备方法中,聚丙烯II采用熔融指数为1~4g/10min、熔体强度为0.25~0.60N的聚丙烯(HMSPP)。 The above method of preparation of the present invention, the polypropylene foam premix, the melt index of the polypropylene II 1 ~ 4g / 10min, the melt strength of the polypropylene is 0.25 ~ 0.60N (HMSPP). 其熔融指数优选为2~3g/10min。 The melt index is preferably 2 ~ 3g / 10min. 该中聚丙烯具有较高的熔体强度。 The polypropylene having a high melt strength. 该种聚丙烯可采用现有技术中熔融指数和熔体强度符合上述条件的聚丙烯,也可按上述的方法制备。 The polypropylene-polypropylene employed in the prior art melt strength and melt index satisfies the above conditions, the method described above can also be prepared.

以上所述本发明聚丙烯发泡预混料的制备方法中,有机化学发泡剂可采用现有技术中各种适合于聚丙烯发泡的有机化学发泡剂。 The above method of preparation of the present invention, the polypropylene foam premix, the organic chemical foaming agent may be employed in a variety of prior art polypropylene foam suitable for organic chemical blowing agents. 其一般分解温度在180-240℃,优选在190-230℃。 Its decomposition temperature is generally 180-240 ℃, preferably at 190-230 ℃. 它们包括但不限于偶氮二甲酰胺(AC)、偶氮二异丁腈、N,N-二亚硝基五次甲基四胺(BN)、对甲苯磺酰氨基尿等。 These include, but are not limited to azodicarbonamide (AC), azobisisobutyronitrile, N, N- dinitroso five tetramine (BN), p-toluenesulfonyl amino group such as urine. 其用量均为常规用量,或根据实际情况的要求进行调整。 Conventional amounts are used in an amount which, according to the requirements or to adjust the actual situation. 在本发明中有机化学发泡剂的含量以聚丙烯I为100重量份数计优选为2~6重量份数,更优选为3~5重量份数。 Content of organic chemistry in the present invention, the blowing agent to 100 parts by weight of polypropylene I is preferably 2 to 6 parts by weight, more preferably 3 to 5 parts by weight.

以上所述本发明聚丙烯发泡预混料的制备方法中,还可包括现有发泡技术中常用的加工助剂,以利于稳定发泡。 The above method of preparation of the present invention, the polypropylene foam premix can further comprise conventional prior art foam processing aid, in order to facilitate a stable foam.

如前述的起到成核剂作用的无机填料,可包括无机盐类和金属氧化物的固体颗粒。 As the nucleating agent plays the role of an inorganic filler, an inorganic salt and solid particles comprise a metal oxide. 可选自二氧化硅、滑石粉、碳酸钙、氧化锌或氧化镁等。 Selected from silica, talc, calcium carbonate, zinc oxide, magnesium oxide, or the like. 其用量均为常规用量,或根据实际情况的要求进行调整。 Conventional amounts are used in an amount which, according to the requirements or to adjust the actual situation. 在本发明中无机填料用量以聚丙烯I为100重量份数计优选为0.5~5重量份数,更优选0.5~1.0重量份数。 In the present invention, the amount of inorganic filler to 100 parts by weight of polypropylene I is preferably from 0.5 to 5 parts by weight, more preferably 0.5 to 1.0 parts by weight. 一般为1250目或以上。 More typically 1250 or mesh.

如前述的起到在挤出过程中润滑及发泡时泡孔调整作用的液体助剂,可为液体低分子直链烃或液体低分子有机硅化合物,优选为白油、液体石蜡或硅油。 As aforementioned functions cells lubrication during extrusion and foaming action to adjust the liquid adjuvant, the liquid may be a low molecular weight straight-chain hydrocarbon or silicone liquid low-molecular organic compound, preferably white oil, liquid paraffin or silicone oil. 其用量均为常规用量,或根据实际情况的要求进行调整。 Conventional amounts are used in an amount which, according to the requirements or to adjust the actual situation. 在本发明中液体助剂用量以聚丙烯I为100重量份数计优选为0.1~1,更优选为0.2~0.5。 In the present invention, the amount of additives in the liquid I is 100 parts by weight of polypropylene is preferably 0.1 to 1, more preferably 0.2 to 0.5.

此外,在本发明的方法涉及的配方组分中还可包括其它的塑料加工常用的助剂,如抗氧剂、阻燃剂等。 Further, in the method of the present invention the formulation components involved may also include other conventional plastics processing aids, such as antioxidants, flame retardants and the like.

在上述本发明的制备方法中物料熔融共混前混合的设备可采用现有技术中所用的各种混料设备,如搅拌机、捏和机等。 Prior to blending in the preparation method of the present invention, the mixing of molten material mixing apparatus may employ various prior art devices used, such as a stirrer, kneader and the like.

上述本发明的方法中所使用的熔融共混设备为橡塑加工业中的通用共混设备,可以是双螺杆挤出机、单螺杆挤出机、开炼机或密炼机等。 The method of melt blending apparatus of the present invention is used for general blending equipment plus rubber industry, it may be a twin-screw extruder, single screw extruder, an open mill mixer, or the like.

本发明的方法中所用到的熔融共混可采用现有技术中的工艺及设备,如共混温度一般控制在155~175℃;熔融共混设备可使用橡塑加工业中的通用共混设备,可以包括开炼机、密炼机、单螺杆挤出机或双螺杆挤出机等。 Melt blending process of the present invention can be used in the prior art process and apparatus, such as a blend of temperature control in 155 ~ 175 ℃; melt blending equipment common blending equipment may be used in the rubber industry It may comprise an open mill, internal mixers, single-screw extruder or a twin-screw extruder.

将上述本发明的聚丙烯发泡预混料成型后得到的型材,恒温加热发泡可得到所需的聚丙烯发泡制品。 The polypropylene foam of the present invention obtained after premix form profiles, thermostatic heating the foamed polypropylene foamed article obtained desired. 其所用到的成型工艺为现有技术中通用的塑料成型工艺,包括压片成型或直接挤出成型、注射成型或用其它方法成型,所得的型材包括片材、异型材等,通常用片材。 Molding process used in the prior art it is common in plastic molding process, including direct compression molding or extrusion molding, injection molding or other molding methods, the resulting profile includes a sheet, profile, usually with a sheet . 其所用到的恒温发泡工艺,可采用现有技术中有机化学发泡剂发泡时所采用的设备和工艺条件。 They are used in the foaming process temperature, process conditions and equipment may be employed when the prior art foaming agent used in organic chemistry. 一般加热可选择在在烘箱或发泡炉中恒温加热发泡或在压机上加热加压发泡。 Alternatively typically heated in an oven or a thermostatic oven heated foamed or foamable foaming heat and pressure on the press. 烘箱或发泡炉恒温加热发泡的发泡温度控制在195~235℃,优选210~235℃;发泡时间3~10分钟,优选4~8分钟。 Foaming oven or furnace heating temperature controlled foaming foaming temperature 195 ~ 235 ℃, preferably 210 ~ 235 ℃; foaming time of 3 to 10 minutes, preferably 4 to 8 minutes. 压机加热加压发泡的温度控制在200~255℃,优选210~235℃;压力0.5~5Mpa;发泡时间3~10分钟,优选4~8分钟。 Heating and pressing the press foaming temperature control 200 ~ 255 ℃, preferably 210 ~ 235 ℃; pressure 0.5 ~ 5Mpa; foaming time 3 to 10 minutes, preferably 4 to 8 minutes.

由此得到的聚丙烯发泡材料的发泡倍率为7~12倍,优选为9~12倍。 The expansion ratio of polypropylene foamed material thus obtained is 7 to 12 times, preferably 9 to 12 times. 其泡沫容重为75~129Kg/m3。 Foam density which is 75 ~ 129Kg / m3.

本发明所述的聚丙烯发泡预混料经过常规发泡后得到的发泡材料,泡孔结构良好,孔径均匀,发泡倍率为7~12倍,优选为9~12倍。 Polypropylene foam premix according to the present invention is obtained after conventional foaming foam material, good cell structure and uniform pore size, an expansion ratio of 7-12 times, preferably 9-12 times. 其泡沫容重为75~129Kg/m3。 Foam density which is 75 ~ 129Kg / m3. 同时具有模量高和热稳定性好等优点。 While having high modulus and good thermal stability. 适合用于节能、隔音、减震缓冲等场合,在汽车、冷藏、建材、包装、运输和农业等多个领域,具有广泛的应用前景。 Suitable for energy saving, sound insulation, shock absorption cushioning and other occasions, in multiple automotive, refrigeration, building materials, packaging, transport and agriculture, with a wide range of applications.

本发明所述发泡聚丙烯材料的制备方法,可以不需要进行交联,因此工艺简单、产品成本低。 The method of the present invention is the preparation of foamed polypropylene material, crosslinking may not be required, thus the process is simple, low cost products.

附图说明 BRIEF DESCRIPTION

图1为实施例2的聚丙烯发泡材料的扫描电镜照片,放大倍数12倍。 Figure 1 is a scanning electron micrograph of a polypropylene foamed material of Example 2, 12-fold magnification.

图2为比较例5的聚丙烯发泡材料的扫描电镜照片,放大倍数13倍。 Comparative Example 2 is a scanning electron micrograph of a polypropylene foamed material 5, 13 times magnification.

具体实施方式 Detailed ways

下面用实施例进一步描述本发明,但本发明的范围不受这些实施例的限制。 The present invention is further described by the following examples, but the present invention is not limited the scope of these embodiments. 本发明的范围在权利要求书中提出。 Scope of the invention in the claims presented.

实施例1~2将聚丙烯I——无规共聚聚丙烯(PPR产地:燕山石化股份公司,乙烯含量:4.1wt%,分子量分布5.2,熔融指数0.223g/10min,熔体拉伸强度190℃测1.98N,210℃测1.40N,230℃测1.1N)、聚丙烯II——高熔体强度聚丙烯(熔融指数2.35g/10min,熔体拉伸强度200℃测0.29N,自制)、有机化学发泡剂与各加工助剂通过高速混合机均匀混合,然后通过双螺杆挤出机熔融共混、挤出造粒。 Example 2 1 ~ I-- polypropylene random copolymer polypropylene (PPR Origin: Yanshan Petrochemical Corporation, ethylene content: 4.1wt%, molecular weight distribution 5.2, melt index 0.223g / 10min, a tensile strength of 190 ℃ melt measuring 1.98N, 210 ℃ measured 1.40N, 230 ℃ measured 1.1N), polypropylene II-- high melt strength polypropylene (melt index 2.35g / 10min, a tensile strength of 200 ℃ melt measured 0.29 N, homemade), organic chemical blowing agents processing aids uniformly mixed with a high-speed mixer, then extruded through a twin screw melt-blending machine, extrusion granulation. 再通过挤出机口模成型形成2~6mm厚片材,共混温度为155~175℃。 And then forming molding 2 ~ 6mm thick sheet by an extruder die, the blending temperature is 155 ~ 175 ℃. 将片材于热烘道上加热发泡,发泡温度为200~255℃,发泡时间为3~10分钟。 The sheet was heated heat drying track foaming expansion temperature was 200 ~ 255 ℃, foaming time of 3 to 10 minutes. 之后冷却得到3~15mm厚度的发泡片材。 After cooling to give 3 ~ 15mm foamed sheet thickness. 其中有机化学发泡剂为偶氮二甲酰胺(AC,天津第一有机化工厂)、加工助剂中的无机填料为二氧化硅(SiO2,德国卡波特公司生产,平均粒径2500目)、液体助剂为白油(北京有机化工厂)、抗氧剂(1010、168,瑞士汽巴加基生产)。 Wherein the organic chemical blowing agent is azodicarbonamide (AC, a first organic Tianjin Chemical Plant), processing aids, inorganic filler is silica (of SiO2, German company Cabot, average particle size of 2500 mesh) , liquid additive is white oil (Beijing organic chemical Plant), antioxidants (1010,168, Switzerland Ba Jiaji steam production). 配方以聚丙烯I重量份数为100份计见表1。 Formulation I parts by weight of polypropylene 100 parts of Table 1. 样品性能测试结果及测试标准见表1。 Test samples and standard performance test results are shown in Table 1.

以上聚丙烯II——高熔体强度聚丙烯(熔融指数2.35g/10min,熔体拉伸强度190℃测0.34N,210℃测0.34N,230℃测0.31N)的制备方法:在聚丙烯粉料(天津第二石化厂,熔融指数4g/10min,熔体强度200℃测0.17N)中加入以聚丙烯为100重量份计,0.35份的1,6-己二醇二丙烯酸酯(市售),在高速搅拌器(1500rpm)中混合10分钟,装入容器中。 Polypropylene II-- above high melt strength polypropylene (melt index 2.35g / 10min, a tensile strength of 190 deg.] C as measured melt 0.34N, 210 ℃ measured 0.34N, 230 ℃ measured 0.31 N) preparation: polypropylene powder (Tianjin second petrochemical plant, a melt index of 4g / 10min, the melt strength measured 200 ℃ 0.17 N) was added to 100 parts by weight of polypropylene, 0.35 parts of 1,6-hexanediol diacrylate (City sale), mixed for 10 minutes () at 1500rpm in a high-speed stirrer, charged in a vessel. 然后用氮气充分置换并密封。 It was then thoroughly purged with nitrogen and sealed. 再用钴源辐照,辐照剂量1.0kGy。 Then the cobalt source radiation, the radiation dose 1.0kGy. 辐照后的物料在100℃下处理2小时,降温后取出,经挤出造粒即为所述高熔体强度聚丙烯。 Treated material after irradiation at 100 ℃ 2 hours, and taken out after cooling, the extruded granulation is the high melt strength polypropylene.

其参数测定:在ARES旋转流变仪上测定储能模量G′,测定温度200℃,剪切速率:0.01秒/弧度,原料聚丙烯的G′为18Pas,高熔体强度聚丙烯G′为47Pas。 Determination of the parameters: measuring the storage modulus G on ARES rotary rheometer ', measured temperature 200 ℃, shear rate: 0.01 sec / rad, the polypropylene material G' is 18Pas, high melt strength polypropylene G ' as 47Pas. 在德国Geottfert Werkstoff Pruefmaschinen公司熔体强度仪上测定熔体强度,熔体测定温度为200℃,测得拉伸力值变化ΔF为13.3cN(该聚丙烯未改性前纯料的拉伸力值为0.17N,经本实施例的实验条件改性后的拉伸力值为0.29N)。 The melt strength in the German company Geottfert Werkstoff Pruefmaschinen melt strength meter, measured melt temperature was 200 ℃, the tensile force measured value change ΔF of 13.3cN (tensile force value before the pure unmodified polypropylene frit of 0.17N, a tensile force by the experimental conditions of the present embodiment is a modified embodiment 0.29N).

实施例3除了无规共聚聚丙烯为齐鲁石化生产(乙烯含量:4.3wt%,分子量分布4.2,熔融指数0.135g/10min,熔体拉伸强度190℃测1.9N,210℃测1.3N,230℃测1.0N)外,其余组分、用量及工艺条件均与实施例1相同。 Example 3 A random copolymer polypropylene as Qilu Petrochemical production (ethylene content: 4.3wt%, molecular weight distribution 4.2, melt index 0.135g / 10min, a tensile strength of 190 deg.] C as measured melt 1.9N, 210 ℃ measured 1.3N, 230 ℃ measured 1.0N), the other components, amounts and process conditions were the same as in Example 1. 配方及样品性能测试结果见表1。 Formula and sample performance test results are shown in Table 1.

比较例1~2除了不加聚丙烯II——高熔体强度聚丙烯以外,其余组分、用量及工艺条件均与实施例1相同。 Example except for adding no high melt strength polypropylene polypropylene II-- outside, 1-2 are the same remaining components, amounts and process conditions as in Comparative Example 1. 配方及样品性能测试结果见表1。 Formula and sample performance test results are shown in Table 1.

比较例3除了不加聚丙烯II——高熔体强度聚丙烯以外,其余组分、用量及工艺条件均与实施例3相同。 Comparative Example 3 except that the polypropylene II-- without high melt strength polypropylene, the rest of the components, process conditions, and amounts were the same as in Example 3. 配方及样品性能测试结果见表1。 Formula and sample performance test results are shown in Table 1.

比较例4除了无规共聚聚丙烯被燕山石化股份公司生产的嵌段共聚聚丙烯1330(乙烯含量:8.9wt%)替换外,其余组分、用量及工艺条件均与实施例1相同。 In addition to the polypropylene random copolymer is produced Yanshan AG 1330 polypropylene block copolymer 4 Comparative Example: outer (ethylene content 8.9wt%) Alternatively, the same as in Example 1 are the remaining components, amounts and process conditions. 配方及样品性能测试结果见表1。 Formula and sample performance test results are shown in Table 1.

比较例5除了不加聚丙烯II——高熔体强度聚丙烯以外,其余组分、用量及工艺条件均与比较例4相同。 In addition to the polypropylene without high melt strength polypropylene II-- outside, they are the same as in Comparative Example 4 Comparative Example 5 remaining components, amounts and process conditions. 配方及样品性能测试结果见表1。 Formula and sample performance test results are shown in Table 1.

上述实施例、比较例中样品性能测试的表标准如下:泡沫容重 GB/T6343-86发泡倍率材料 发泡后的密度与发泡前密度的比弯曲强度 GB/T8812-88尺寸热稳定性 ISO2796 The above Examples and Comparative Examples in Table performance test sample the following criteria: Foam density GB / T6343-86 expansion ratio of bending strength than the material density of the density before foaming and after foaming GB / T8812-88 dimensional thermostability ISO2796

表1 Table 1

*注:由于泡孔结构均匀性很差,难以满足弯曲强度测试用的制样要求,故无法得到该栏数据。 * Note: Due to poor uniformity of cell structure, it is difficult to satisfy the bending strength test sample preparation requirements, it can not obtain the data field.

从表1的测试结果可以看出,使用本发明所述的无规共聚聚丙烯并配合高熔体强度聚丙烯作为发泡的基础树脂所得到的发泡材料,容重低,发泡倍率高,刚性、耐热性良好。 As can be seen from the test results shown in Table 1, using a polypropylene random copolymer with the present invention is a high melt strength polypropylene as a base resin foamed material obtained by foaming, low density, high expansion ratio, rigidity, heat resistance was good. 从附图1照片可见,本发明实施例2得到的发泡聚丙烯材料,其孔径分布均匀、泡孔壁厚薄且均匀。 Figure 1 seen from the photo, the foamed polypropylene obtained in Example 2 of the present invention, the pore size distribution, and uniform cell wall thickness. 从附图2照片可见,比较例5得到的发泡聚丙烯材料,其孔径分布大小不均、泡孔壁厚较厚,而且壁厚不均匀。 Figure 2 seen from the photo, obtained in Comparative Example 5, a foamed polypropylene material, pore size distribution uneven size, cell wall thickness is thick, and uneven wall thickness. 经过比较可见本发明得到的发泡聚丙烯材料的泡孔结构良好,优于比较例。 It is seen by comparison good cell structural foam polypropylene material obtained by the present invention, compared to Comparative Examples.

Claims (9)

  1. 1.一种聚丙烯发泡预混料,包含有共混的以下组分:聚丙烯I、聚丙烯II和有机化学发泡剂;所述聚丙烯I为乙烯含量为3.5~6.5wt%,分子量分布为3.0~9.0的无规共聚聚丙烯;所述聚丙烯II为熔融指数为1~4g/10min、熔体强度为0.25~0.60N的聚丙烯;其中以聚丙烯I为100重量份数计,聚丙烯II含量为5~10重量份数。 A polypropylene foam premixes, comprising a blend of the following components: Polypropylene I, II and organic foaming polypropylene; polypropylene I is the ethylene content of 3.5 ~ 6.5wt%, the molecular weight distribution of 3.0 to 9.0 random polypropylene; polypropylene II is the melt index of 1 ~ 4g / 10min, a melt strength of 0.25 ~ 0.60N polypropylene; polypropylene I wherein 100 parts by weight meter polypropylene II is 5 to 10 parts by weight.
  2. 2.根据权利要求1所述的聚丙烯发泡预混料,其中以聚丙烯I为100重量份数计,聚丙烯II含量为6~8重量份数。 2. The premix according to claim polypropylene foam of claim 1, wherein the polypropylene as 100 I in parts by weight, the content of the polypropylene II 6-8 parts by weight.
  3. 3.根据权利要求1所述的聚丙烯发泡预混料,其特征在于所述聚丙烯I的无规共聚聚丙烯中乙烯含量为4.0~5.0wt%。 According to claim polypropylene foam premix of claim 1, wherein the polypropylene random copolymer polypropylene I, the ethylene content of 4.0 ~ 5.0wt%.
  4. 4.根据权利要求1所述的聚丙烯发泡预混料,其特征在于所述聚丙烯I的无规共聚聚丙烯的分子量分布为4.2~7.0。 The polypropylene foam premix according to claim 1, wherein the molecular weight of the polypropylene random copolymer polypropylene I distribution of 4.2 to 7.0.
  5. 5.根据权利要求1所述的聚丙烯发泡预混料,其特征在于所述聚丙烯I的无规共聚聚丙烯的熔融指数为0.10~1.2g/10min,熔体拉伸强度为0.75~4.50N。 According to claim polypropylene foam premix of claim 1, wherein the polypropylene random copolymer polypropylene has a melt index I 0.10 ~ 1.2g / 10min, a tensile strength of 0.75 to the melt 4.50N.
  6. 6.根据权利要求1所述的聚丙烯发泡预混料,其特征在于所述聚丙烯II的熔融指数为2~3g/10min。 According to claim polypropylene foam premix of claim 1, wherein the melt index of the polypropylene II 2 ~ 3g / 10min.
  7. 7.根据权利要求1所述的聚丙烯发泡预混料,其特征在于所述的有机化学发泡剂为偶氮二甲酰胺或偶氮二异丁腈。 According to claim polypropylene foam premix of claim 1, wherein said organic chemical blowing agent is azodicarbonamide or azobisisobutyronitrile.
  8. 8.根据权利要求1~7之任一项所述的聚丙烯发泡预混料的制备方法,包括将包含有所述聚丙烯I、聚丙烯II、有机化学发泡剂在内的组分按所述组分含量进行熔融共混。 8. The method of claims 1 to 7 Preparation of a premix according to claim polypropylene foam, comprising the polypropylene comprising I, II polypropylene, a blowing agent, including organic chemical components by melt blending the components content.
  9. 9.根据权利要求8所述的聚丙烯发泡预混料的制备方法,包括以下步骤:①将包含有所述聚丙烯I、聚丙烯II在内的组分进行熔融共混,其中组分中不含有有机化学发泡剂;②将上述步骤得到的聚丙烯混合物与包含有所述有机化学发泡剂在内的组分混合均匀进行熔融共混。 9. A method of preparing a premix of the polypropylene foam according to claim 8, comprising the following: ① From the polypropylene comprising the inner I, the polypropylene melt blending component II, wherein component does not contain organic chemical foaming agent; ② the polypropylene mixture obtained in the above step comprising mixing the ingredients with a blowing agent, including organic chemistry melt blended uniformly.
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Cited By (10)

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CN100575404C (en) 2006-07-13 2009-12-30 中国石油化工股份有限公司;中国石油化工股份有限公司北京化工研究院 Expandable polypropylene beading, preparation method thereof, and its foaming beading and foaming molding products
CN101506261B (en) 2006-08-25 2011-04-27 博里利斯技术有限公司 Polypropylene foam
CN101353460B (en) 2008-09-11 2011-11-16 丹阳市华东工程塑料有限公司 Environment-friendly type micro-foaming polypropylene sheet and preparation thereof
CN102888056A (en) * 2011-07-21 2013-01-23 中国石油化工股份有限公司 Antibacterial polypropylene foam material and preparation method thereof
CN102888055A (en) * 2011-07-21 2013-01-23 中国石油化工股份有限公司 High-melt strength polypropylene foam material and preparation method thereof
CN102888054A (en) * 2011-07-21 2013-01-23 中国石油化工股份有限公司 Antistatic polypropylene foam material and preparation method thereof
CN102115561B (en) 2009-12-30 2013-02-20 李晓丽 Physical foaming polypropylene sheet material
CN103044773A (en) * 2012-12-24 2013-04-17 上海普利特复合材料股份有限公司 Melt strength enhancing PP (polypropylene) material and preparation method thereof
CN103131087A (en) * 2013-03-21 2013-06-05 合肥汇邦高分子材料有限责任公司 Injection molding technique of microporous foamed PP (polypropylene) plastic product
CN104292611A (en) * 2013-07-18 2015-01-21 中国石油化工股份有限公司 Foamed polypropylene material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100575404C (en) 2006-07-13 2009-12-30 中国石油化工股份有限公司;中国石油化工股份有限公司北京化工研究院 Expandable polypropylene beading, preparation method thereof, and its foaming beading and foaming molding products
CN101506261B (en) 2006-08-25 2011-04-27 博里利斯技术有限公司 Polypropylene foam
CN101353460B (en) 2008-09-11 2011-11-16 丹阳市华东工程塑料有限公司 Environment-friendly type micro-foaming polypropylene sheet and preparation thereof
CN102115561B (en) 2009-12-30 2013-02-20 李晓丽 Physical foaming polypropylene sheet material
CN102888056A (en) * 2011-07-21 2013-01-23 中国石油化工股份有限公司 Antibacterial polypropylene foam material and preparation method thereof
CN102888055A (en) * 2011-07-21 2013-01-23 中国石油化工股份有限公司 High-melt strength polypropylene foam material and preparation method thereof
CN102888054A (en) * 2011-07-21 2013-01-23 中国石油化工股份有限公司 Antistatic polypropylene foam material and preparation method thereof
CN102888055B (en) 2011-07-21 2014-08-27 中国石油化工股份有限公司 High-melt strength polypropylene foam material and preparation method thereof
CN102888056B (en) 2011-07-21 2014-08-27 中国石油化工股份有限公司 Antibacterial polypropylene foam material and preparation method thereof
CN102888054B (en) 2011-07-21 2014-08-06 中国石油化工股份有限公司 Antistatic polypropylene foam material and preparation method thereof
CN103044773A (en) * 2012-12-24 2013-04-17 上海普利特复合材料股份有限公司 Melt strength enhancing PP (polypropylene) material and preparation method thereof
CN103044773B (en) * 2012-12-24 2015-08-12 上海普利特复合材料股份有限公司 Melt strength polypropylene material and its preparation method of enhancing
CN103131087A (en) * 2013-03-21 2013-06-05 合肥汇邦高分子材料有限责任公司 Injection molding technique of microporous foamed PP (polypropylene) plastic product
CN103131087B (en) * 2013-03-21 2015-09-23 合肥汇邦高分子材料有限责任公司 A microporous pp foamed plastics injection molding process
CN104292611A (en) * 2013-07-18 2015-01-21 中国石油化工股份有限公司 Foamed polypropylene material and preparation method thereof

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