CN1898070A - 聚烯烃-聚酰胺树脂组合物的制造方法 - Google Patents
聚烯烃-聚酰胺树脂组合物的制造方法 Download PDFInfo
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- CN1898070A CN1898070A CNA2004800384472A CN200480038447A CN1898070A CN 1898070 A CN1898070 A CN 1898070A CN A2004800384472 A CNA2004800384472 A CN A2004800384472A CN 200480038447 A CN200480038447 A CN 200480038447A CN 1898070 A CN1898070 A CN 1898070A
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- polyolefin
- polyamide
- fusing point
- antioxidant
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
本发明提供一种聚烯烃-聚酰胺树脂组合物的制造方法,所述方法排出量多、可以长时间运转、并且生产性优异。该聚烯烃-聚酰胺树脂组合物的制造方法的特征在于,将(a)聚烯烃、(b)聚酰胺、(c)硅烷偶联剂、(d)熔点为70℃~170℃的第1抗氧化剂和(e)熔点为180℃~300℃的第2抗氧化剂熔融-混炼、挤出、以及施加拉伸来进行牵引拉伸或压延,据此将(b)聚酰胺以平均纤维直径小于等于1μm的纤维状分散在(a)聚烯烃中,制成颗粒状的组合物。
Description
技术领域
本发明涉及可以合适地用作橡胶或树脂的增强材料的聚烯烃-聚酰胺树脂组合物的制造方法。
背景技术
为了提高橡胶或树脂等的弹性模量或机械强度,向其中配合玻璃纤维或无机填充剂。若配合有这些物质,则其刚性、弹性模量、强度、抗蠕变性增大,但是成型品的外观变差,成型品变重。
专利文献1和专利文献2中,公开了将热塑性聚酰胺纤维作为微细的纤维分散在作为基质的聚烯烃和橡胶状聚合物中而形成的组合物。若将所得组合物与橡胶配合则可以提高其机械性质。但是,所配合的橡胶受到限制,而且其有可能在混炼中发生凝胶化。特别地,该橡胶在高温下存在易凝胶化的趋势,强度、拉伸率、弹性模量等有可能不能表现出本来的性质。
另一方面,作为聚酰胺超细纤维的制造方法,专利文献3中公开了一种作为皮革用基材构成成分的多成分纤维,该纤维具有褶皱,其内外层的边界线具有特定的范围。专利文献4中公开了一种粗细为0.1丹尼尔的聚酰胺超细纤维,其是通过下述方法得到的:将聚酰胺通过混合高速纺丝获得混合高速纺丝纤维,然后以溶剂除去聚苯乙烯和聚乙二醇,以获得所述聚酰胺超细纤维。专利文献5、专利文献6、专利文献7中公开了一种轻量复合纤维,其在聚丙烯和聚酰胺的界面不产生剥离。该纤维的目的在于利用芯鞘纤维以改善聚丙烯的染色性。但是,对于这些方法或纤维,其目的是从口径小的纺丝喷嘴进行挤出,然后进行高速纺丝、溶剂处理以及熔融,以此来得到0.1丹尼尔~1丹尼尔(d)的超细纤维,所以其生产性差,不是经济上可行的制造方法。此外,这些纤维是超细纤维的连续纤维,在作为光泽或手感良好的织物、合成皮革的原料方面具有优异性,但是当其被填充于橡胶或树脂中进行混炼时,由于其为连续纤维,因而难以通过混炼进行分散。
专利文献8中公开了一种聚烯烃-聚酰胺树脂组合物,该组合物中,平均纤维直径为0.2μm~0.6μm的微细聚酰胺纤维均一地分散于聚烯烃基质中,同时聚烯烃和纤维在界面上键合;由于该聚烯烃-聚酰胺树脂组合物是在颗粒状态下得到的,因而当将其在树脂或橡胶中混炼时,其具有易分散性和补强性。该专利文献8中所述的聚烯烃-聚酰胺树脂组合物是如下制得的:将(a)聚烯烃、(b)聚酰胺和(c)硅烷偶联剂熔融-混炼,进行挤出,施加拉伸来进行牵引拉伸或压延,据此使(b)聚酰胺在(a)聚烯烃中分散成平均纤维直径小于等于1μm的纤维状以此形成颗粒状,从而制得所述聚烯烃-聚酰胺树脂组合物。此时,添加季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)]丙酸酯(チバ-スペシヤルテイ-ケミカルズ(株)制,Irganox 1010)作为抗氧化剂。
专利文献1:特开平7-238189号公报
专利文献2:特开平9-59431号公报
专利文献3:特开昭63-75108号公报
专利文献4:特开昭54-73921号公报
专利文献5:特开平3-279419号公报
专利文献6:特开平4-272222号公报
专利文献7:特开平4-281015号公报
专利文献8:特开平11-106570号公报
发明内容
但是,专利文献8中所述的聚烯烃-聚酰胺树脂组合物的制造方法中,使用了熔点约为110℃的抗氧化剂,这种熔点较低的抗氧化剂在双螺杆挤出机中进行混炼和反应时不能充分地发挥作用,因此会产生聚烯烃的凝胶化(当使用聚丙烯时产生分解),在挤出机中产生焦烧。由此导致排出量少、线材断裂多。此外,由于有必要频繁地进行诸如除去该挤出机内的焦料等装置清理工作,因而机器不能长时间运转,从而存在生产性极差的问题。特别地,为进行除去焦料的清理则需要将挤出机等装置进行拆卸,因而对生产性有极大的影响。
因此,本发明的目的在于提供一种聚烯烃-聚酰胺树脂组合物的制造方法,该方法的排出量多、并可以长时间运转、生产性优异。
为了达到上述目的,本发明提供了聚烯烃-聚酰胺树脂组合物的制造方法,其特征在于,将(a)聚烯烃、(b)聚酰胺、(c)硅烷偶联剂、(d)熔点为70℃~170℃的第1抗氧化剂和(e)熔点为180℃~300℃、优选为200℃~300℃、进一步优选为200℃~290℃的第2抗氧化剂进行熔融混炼、挤出、以及施加拉伸来进行牵引拉伸或压延,据此将(b)聚酰胺以平均纤维直径小于等于1μm的纤维状分散在(a)聚烯烃中,制成颗粒状的组合物。
如上所述,在本发明涉及的聚烯烃-聚酰胺树脂组合物的制造方法中,组合使用(d)成分和(e)成分两种抗氧化剂,据此可以使所提供的聚烯烃-聚酰胺树脂组合物的制造方法具有排出量多、可以长时间运转、生产性优异的优点。
具体实施方式
在本发明的聚酰胺-聚烯烃树脂组合物的制造方法中,(a)成分为聚烯烃,优选熔点为80℃~250℃的聚烯烃。其中,可以使用维卡软化点大于等于50℃的聚烯烃,特别地,可以使用维卡软化点为50℃~200℃的聚烯烃。作为上述聚烯烃的优选例子,可以举出优选使用诸如碳原子数为2~8的烯烃的均聚物或共聚物;碳原子数为2~8的烯烃与苯乙烯、氯苯乙烯或α-甲基苯乙烯等芳香族乙烯化合物的共聚物;碳原子数为2~8的烯烃与乙酸乙烯酯的共聚物;碳原子数为2~8的烯烃与丙烯酸或其酯的共聚物;碳原子数为2~8的烯烃与甲基丙烯酸或其酯的共聚物;以及碳原子数为2~8的烯烃与乙烯硅烷化合物的共聚物。
作为具体例子,可举出例如,高密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯、聚丙烯、乙烯-丙烯嵌段共聚物、乙烯-丙烯无规共聚物、聚4-甲基-1-戊烯、聚1-丁烯、聚1-己烯、乙烯-醋酸乙烯酯共聚物、乙烯-乙烯醇共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-丙烯酸-2-乙基己酯共聚物、乙烯-丙烯酸羟乙基酯共聚物、乙烯-乙烯基三甲氧基硅烷共聚物、乙烯-乙烯基三乙氧基硅烷共聚物、乙烯-乙烯硅烷共聚物、乙烯-苯乙烯共聚物和丙烯-苯乙烯共聚物等。或者优选使用氯化聚苯乙烯、溴化聚苯乙烯、氯磺化聚乙烯等卤化聚烯烃。
作为(a)成分中特别优选的聚烯烃,可以举出例如高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线型低密度聚乙烯(LLDPE)、聚丙烯(PP)、乙烯-丙烯嵌段共聚物、乙烯-丙烯无规共聚物、乙烯-醋酸乙烯酯共聚物(EVA)、乙烯-丙烯酸乙酯共聚物(EEA)以及乙烯-乙烯醇共聚物,其中,最优选熔体流动指数(MFI)为0.2g/10min~50g/10min(克/10分钟)的聚烯烃。这些聚烯烃可以仅使用1种,也可以至少2种组合使用。
(b)成分为主链中具有酰氨基的热塑性聚酰胺(下文称为聚酰胺),其熔点为135℃~350℃,而且该熔点比(a)成分的聚烯烃的熔点高,其中优选该聚酰胺的熔点为160℃~265℃。作为所述(b)成分,优选为可通过挤出和拉伸提供强韧纤维的聚酰胺。
作为聚酰胺的具体例子,可以举出例如,尼龙6、尼龙66、尼龙6-尼龙66共聚物、尼龙610、尼龙612、尼龙46、尼龙11、尼龙12、尼龙MXD6、亚二甲苯基二胺和己二酸的缩聚物、亚二甲苯基二胺和庚二酸的缩聚物、亚二甲苯基二胺和辛二酸的缩聚物、亚二甲苯基二胺和壬二酸的缩聚物、亚二甲苯基二胺和癸二酸的缩聚物、四亚甲基二胺和对苯二甲酸的缩聚物、六亚甲基二胺和对苯二甲酸的缩聚物、八亚甲基二胺和对苯二甲酸的缩聚物、三甲基六亚甲基二胺和对苯二甲酸的缩聚物、十亚甲基二胺和对苯二甲酸的缩聚物、十一亚甲基二胺和对苯二甲酸的缩聚物、十二亚甲基二胺和对苯二甲酸的缩聚物、四亚甲基二胺和间苯二甲酸的缩聚物、六亚甲基二胺和间苯二甲酸的缩聚物、八亚甲基二胺和间苯二甲酸的缩聚物、三甲基六亚甲基二胺和间苯二甲酸的缩聚物、十亚甲基二胺和间苯二甲酸的缩聚物、十一亚甲基二胺和间苯二甲酸的缩聚物以及十二亚甲基二胺和间苯二甲酸的缩聚物等。
作为这些聚酰胺中特别优选的具体例子,可以举出例如尼龙6(PA6)、尼龙66(PA66)、尼龙12(PA12)、尼龙6-尼龙66共聚物等。所述聚酰胺可以是其中的1种或至少2种。这些聚酰胺优选具有10000~200000的分子量。
作为(c)成分硅烷偶联剂的具体例子,可以举出乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、乙烯基三乙酰基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基甲基二甲氧基硅烷、γ-环氧丙氧基丙基甲基二乙氧基硅烷、γ-环氧丙氧基丙基乙基二甲氧基硅烷、γ-环氧丙氧基丙基乙基二乙氧基硅烷、N-β-(氨基乙基)氨基丙基三甲氧基硅烷、N-β-(氨基乙基)氨基丙基三乙氧基硅烷、N-β-(氨基乙基)氨基丙基甲基二甲氧基硅烷、N-β-(氨基乙基)氨基丙基乙基二甲氧基硅烷、N-β-(氨基乙基)氨基丙基乙基二乙氧基硅烷、γ-氨基丙基三乙氧基硅烷、N-苯基-γ-氨基丙基三甲氧基硅烷、γ-[(氯化)N-(β-甲基丙烯酰氧基乙基)-N,N-二甲基铵]丙基甲氧基硅烷和苯乙烯基二氨基硅烷等。其中,特别优选具有易脱离的基团和/或极性基团及乙烯基的硅烷偶联剂,所述易脱离的基团是通过从烷氧基等除去氢原子而获得的。
相对于100重量份的(a)成分和(b)成分,(c)成分硅烷偶联剂优选为0.1重量份~5.5重量份,特别优选为0.2重量份~3.0重量份。若硅烷偶联剂的量小于0.1重量份,则得不到强度高的组合物,若硅烷偶联剂的量大于5.5重量份,则得不到弹性模量优异的组合物。若硅烷偶联剂的量小于0.1重量份,则与(a)成分和(b)成分之间不能形成牢固的键,只能得到强度低的组合物。另一方面,若硅烷偶联剂的量大于5.5重量份,则由于成分(b)不能变为良好的微细纤维,仍然只能得到弹性模量差的组合物。
使用(c)成分硅烷偶联剂时,可以并用有机过氧化物。若并用有机过氧化物,则在(a)成分的分子链上形成自由基,通过该自由基与硅烷偶联剂的反应可以促进(a)成分和硅烷偶联剂的反应。相对于100重量份的(a)成分,有机过氧化物的用量为0.01重量份~1.0重量份。作为有机过氧化物,优选其1分钟半衰期温度处于与(a)成分的熔点或(c)成分的熔点中较高一方的熔点相同的温度至比该温度高30℃左右的温度范围。具体地,优选使用1分钟半衰期温度为110℃~200℃左右的有机过氧化物。
作为有机过氧化物的具体例子,可以举出过氧化二-α-枯基、过氧化1,1-二叔丁基-3,3,5-三甲基环己烷、过氧化1,1-二叔丁基环己烷、过氧化2,2-二叔丁基丁烷、过氧化正丁基4,4-二叔丁基戊酸酯、2,2-二(过氧化4,4,-二叔丁基环己烷)丙烷、过氧化2,2,4-三甲基戊基新癸酸酯、过氧化α-枯基新癸酸酯、过氧化叔丁基新己酸酯、过氧化叔丁基新戊酸酯、过氧化叔丁基乙酸酯、过氧化叔丁基月桂酸酯、过氧化叔丁基苯甲酸酯、过氧化叔丁基间苯二甲酸酯等。其中,作为所述有机过氧化物,优选其1分钟的半衰期温度处于熔融混炼温度直至比该温度高30℃左右的范围,具体地,优选使用的有机过氧化物的1分钟半衰期温度为80℃~260℃左右。
(d)成分第1抗氧化剂的熔点在70℃~170℃的范围内,该第1抗氧化剂可列举例如,季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)]丙酸酯、2,6-二叔丁基-4-(4,6-二(辛硫基)-1,3,5-三嗪-2-基氨基)苯酚、2,2’-亚甲基二(4-甲基-6-叔丁基苯酚)、4,4’-硫基二(3-甲基-6-叔丁基苯酚)、2-[1-(2-羟基-3,5-二叔戊基苯基)乙基]-4,6-二叔戊基苯基丙烯酸酯(acryl)、2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基丙烯酸酯(acryl)等。相对于100重量份的(a)成分和(b)成分,(d)成分第1抗氧化剂优选为0.01重量份~5重量份,特别优选为0.05重量份~2重量份。
(e)成分第2抗氧化剂的熔点在180℃~300℃范围内,优选在200℃~300℃范围内,更优选在200℃~290℃范围内,第2抗氧化剂可列举例如,4,4’-丁叉基二(3-甲基-6-叔丁基苯酚)、2-巯基苯并咪唑、3,3’,3”,5,5’,5”-六叔丁基-a,a’,a”-(均三甲苯-2,4,6-三基)三对甲酚、1,3,5-三(3,5-二叔丁基-4-羟基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三-(3,5-二叔丁基-4-羟基苄基)-异氰脲酸酯、1,1,3-三-(2-甲基-4-羟基-5-叔丁基苯基)丁烷、4,4’-丁叉基二(3-甲基-6-叔丁基苯酚)、1,3,5-三甲基-2,4,6-叔(3,5-二叔丁基-4-羟基苄基)苯等。相对于100重量份的(a)成分和(b)成分,(e)成分第2抗氧化剂优选为0.01重量份~5重量份,特别优选为0.05重量份~2重量份。
本发明涉及的聚烯烃-聚酰胺树脂组合物的制造方法中,通过如此使用作为(d)成分和(e)成分的两种抗氧化剂,特别地通过使用(e)成分的抗氧化剂,在聚烯烃-聚酰胺的混炼-反应时,聚烯烃凝胶化少、分解少,可以提高排出量。此外,由于线材断裂减少,同时挤出机内几乎不产生焦烧,因而除去焦料的清理等极少,可以长时间运转,从而可以极大地提高生产性。特别地,由于为进行用于除去焦料的清理需要对挤出机进行拆卸,因此也可以通过减少这种拆卸的必要性来极大地提高生产性。
本发明所涉及的聚烯烃-聚酰胺树脂组合物的制造方法优选具有第一工序、第二工序、第三工序、第四工序和造粒工序,所述第一工序中,将(a)成分聚烯烃、(c)成分硅烷偶联剂、(d)成分第1抗氧化剂和(e)成分第2抗氧化剂熔融混炼,进行化学改性;所述第二工序中,在大于等于(b)成分熔点的温度下,将(b)成分聚酰胺与通过所述第一工序进行了化学改性的(a)成分进行熔融混炼;所述第三工序中,在大于等于(b)成分的熔点的温度下,将(b)成分聚酰胺与通过所述第一工序化学改性了的(a)成分进行熔融混炼-化学改性,并进行挤出;所述第四工序中,在大于等于(a)成分的熔点且小于等于(b)成分的熔点的温度下,对通过所述第三工序进行了熔融混炼-化学改性的挤出物施加拉伸或进行压延;所述造粒工序中,将通过所述第四工序进行了拉伸或压延的组合物冷却至室温来进行造粒。
在上述第一工序中,熔融混炼温度优选大于等于(a)成分的熔点,特别优选比熔点高30℃。若在比熔点高30℃的温度下进行熔融混炼,则其通过与(c)成分硅烷偶联剂发生反应而被化学改性。熔融混炼可以采用对树脂或橡胶进行混炼时通常使用的装置来进行。作为这种装置,可以使用班伯里混炼机、捏炼机、捏炼挤出机、开炼机、单辊混炼机、双轴混炼机等。这些装置中最优选为双轴混炼机,因为其可短时间、连续进行熔融混炼。
在上述第二工序中,熔融混炼温度优选大于等于(b)成分的熔点,优选比熔点高10℃。若熔融混炼温度比(b)成分的熔点低,则不能进行混炼、不能分散成纤维状,因而在比熔点高的温度下、特别优选在比熔点高20℃的温度下进行熔融混炼。
在上述第三工序中,由该挤出工序得到的混炼物优选从纺丝喷嘴、充气模具或T模具挤出。纺丝、挤出均有必要在比(b)的熔点高的温度下实施。具体地,在比(b)成分的熔点高的温度、优选在比该熔点高30℃的温度范围内实施。本工序中,即使在比成分(b)的熔点低的温度下进行熔融-混炼,混炼物也不会具有(b)成分的微细粒子分散于含有(a)成分的基质中的结构。因此,即使对所述的混炼物进行纺丝-拉伸,(b)成分也不能成为微细的纤维。
在上述第四工序中,优选对被挤出的线状或丝状纺丝连续地进行冷却、拉伸或压延处理。进行冷却-拉伸或压延处理的温度低于(b)成分的熔点,二者温度差小于等于10℃。通过拉伸和压延可以形成更强韧的纤维,由此可以进一步发挥作为纤维增强树脂组合物的特性,所以更优选。进行拉伸或压延时,例如,将混炼物从纺丝喷嘴挤出,纺丝成线状或丝状,对此施加拉伸并且将其卷取于线轴等。此外,也可以通过将其切断成颗粒的方法来实施。其中,施加拉伸指的是卷取速度比纺丝喷嘴速度高。卷取速度/纺丝喷嘴速度的比(拉伸比)优选为1.5~100,进一步优选为2~50,特别优选为3~30。
在上述第五工序中,通过采用颗粒化,即使追加树脂或橡胶成分等也可以进行均一地混炼,因此优选使用颗粒状的聚烯烃-聚酰胺树脂组合物。这是由于,若使用颗粒状的树脂组合物,则树脂组合物可以与弹性体均一地混炼,容易得到微细纤维被均一分散的增强弹性体组合物。
上面对第一至第三工序分别说明了每个工序,但是,上述工序也可以使用双轴混炼机以连续的过程来一起进行处理,其中所述双轴混炼机具有能够供给(a)成分、(b)成分、(c)成分、(d)成分和(e)成分的第1进料口~第5进料口,并且具有对应于各个进料口的第1混炼带~第5混炼带。如此使得该方法成为经济、稳定、安全的制造方法。
本发明所涉及的聚烯烃-聚酰胺树脂组合物的制造方法中,也可以适当地添加炭黑、白炭墨、活性碳酸钙、超微粒子硅酸镁、高苯乙烯树脂、酚树脂、木质素、改性三聚氰胺树脂、古马隆-茚树脂、石油树脂等辅助剂;碳酸钙、碱式碳酸镁、粘土、氧化锌(zinc flower)、硅质土(silious earth)、再生橡胶、粉末橡胶、硬质胶粉等各种填充剂;胺-醛类、胺-酮类、胺类、酚类、咪唑类、含硫类抗氧化剂以及含磷类抗氧化剂等稳定剂和各种颜料。
实施例
下文,虽然举出实施例和比较例,对本发明进行更具体的说明,但本发明并不仅限于这些实施例。在实施例和比较例中,对聚烯烃-聚酰胺树脂组合物的制造方法的特性进行如下测定。
排出量:
在第4工序后的造粒工序中,从连续运转开始,每2小时,在造粒机的滑槽口收取1分钟的颗粒,进行称量。进行3次该操作,计算其平均值,将该平均值作为排出量。
连续运转时间:
以将硅烷改性聚烯烃和聚酰胺投入双螺杆挤出机(运转开始)作为起始时间,直到线材被断裂成多种状态,从而不能收集制品为止,将此时间作为连续运转时间。
线材直径的均一性:
从运转开始,每2小时,收集线材的一部分,用卡尺测定。
线材的截断:
挤出的线材被施加拉伸时的张力截断,该截断的根数以相对于时间的比率进行评价。
残胶的产生:
从运转开始,每0.5小时,肉眼观察在纺丝喷嘴上所形成的残胶的大小。
挤出机内的焦烧:
连续运转结束后,拆卸双螺杆挤出机,通过肉眼确认筒内和螺杆的焦烧的状态。
收率:
计算从连续运转开始直到结束(聚烯烃-聚酰胺树脂组合物的制品量)相对于(硅烷改性聚烯烃+聚酰胺的总加入量)的百分率,将该百分率作为收率。
1天的生产量:
测定1天内从连续运转开始直到结束的制品量,以该制品量作为生产量。
实施例1
向100重量份作为(a)成分的低密度聚乙烯[宇部兴产株式会社制,F522,熔点为110℃,MFR=5.0(g/10min)]中加入1.0重量份作为(c)成分的γ-甲基丙烯酰氧基丙基三甲氧基硅烷[信越シリコ一ン,KBM503]、0.5重量份作为(d)成分的季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯](チバ-スペシヤルテイ-ケミカルズ(株)制,Irganox 1010,熔点为110℃)、0.5重量份作为(e)成分的4,4’-丁叉基二(3-甲基-6-叔丁基苯酚)[住友化学工业(株)制,Sumilizer BBMS,熔点为209℃]、以及0.025重量份作为过氧化物的过氧化二-α-枯基[Percumyl D40],在170℃下以班伯里型混炼机进行混炼-反应,接着利用单螺杆挤出机在170℃下进行颗粒化,得到硅烷改性聚苯乙烯。对于得到的硅烷改性聚苯乙烯,将50重量份作为(b)成分的尼龙6(宇部兴产株式会社制,1030B,熔点为215℃~225℃)加入双螺杆挤出机,在240℃下进行混炼-反应,并进行挤出,在空气中冷却,用牵引辊以拉伸比为7进行牵引,在室温下,在5英寸的辊之间拉伸1.5倍来进行造粒。对于颗粒化后的形状,直径为1mm,长度为3mm。用热甲苯处理得到的颗粒,将其中的聚苯乙烯溶出。不溶成分不会紧贴于搅拌翼,悬浊液均一。用扫描电子显微镜观察不溶成分,发现其是直径为0.3μm的微细纤维状。此时的排出量、连续运转时间、线材直径的均一性、线材的断裂、残胶的产生、挤出机内的焦烧、收率和1天的生产量如表1所示。
[表1]
1 | 实施例1 | 实施例2 | 比较例1 |
排出量(kg/小时) | 50 | 50 | 20 |
连续运转时间(小时) | 大于等于24 | 大于等于24 | 8 |
线材直径的均一性 | 均一 | 均一 | 不均一 |
线材的断裂 | 极少 | 少 | 多 |
残胶的产生 | 极少 | 少 | 多 |
挤出机内的焦烧 | 无 | 无 | 有 |
收率(%) | 98 | 96 | 80 |
1天的生产量 | 1176 | 1152 | 108 |
实施例2
在实施例1中使用0.5重量份的2-巯基苯并咪唑[住友化学工业(株)制、Sumilizer MB,熔点为285℃]作为(e)成分来替代4,4’-丁叉基二(3-甲基-6-叔丁基苯酚),使用50重量份尼龙66(宇部兴产株式会社制,2020B,熔点为255℃~265℃)作为(b)成分来替代尼龙6,将双螺杆挤出机的混炼-反应温度设为300℃,除此之外,与实施例1同样的方法来制造聚烯烃-聚酰胺组合物。此时的排出量、连续运转时间、线材直径的均一性、线材的断裂、残胶的产生、挤出机内的焦烧、收率和1天的生产量如表1所示。
比较例1
除了不添加作为抗氧化剂的(e)成分,仅添加1.0重量份的(d)成分抗氧化剂之外,通过与实施例1同样的方法来制造聚烯烃-聚酰胺组合物。此时的排出量、连续运转时间、线材直径的均一性、线材的断裂、残胶的产生、挤出机内的焦烧、收率和1天的生产量如表1所示。
如表1所示可知,与不添加(e)成分作为抗氧化剂的比较例1相比,添加有(e)成分作为抗氧化剂的实施例1和实施例2中,线材断裂少,排出量多,并且挤出机内无焦烧,因而极少对挤出机进行用于除去焦料等的清理,可以长时间运转,收率多,1天的生产量极多。
比较例2
除了不添加(d)成分作为抗氧化剂,并且仅添加1.0重量份的(e)成分抗氧化剂之外,与实施例1同样地,通过班伯里型混炼机在170℃下进行混炼-反应,接着通过单螺杆挤出机在170℃下进行颗粒化,但是不能稳定连续地进行颗粒化,不能制造聚烯烃-聚酰胺组合物。
Claims (2)
1.一种聚烯烃-聚酰胺树脂组合物的制造方法,其特征在于,将(a)聚烯烃、(b)聚酰胺、(c)硅烷偶联剂、(d)熔点为70℃~170℃的第1抗氧化剂和(e)熔点为180℃~300℃的第2抗氧化剂进行熔融-混炼、挤出、以及施加拉伸来进行牵引拉伸或压延,据此将(b)聚酰胺以平均纤维直径小于等于1μm的纤维状分散在(a)聚烯烃中,制成颗粒状的组合物。
2.如权利要求1所述的聚烯烃-聚酰胺树脂组合物的制造方法,其特征在于,其具有第一工序、第二工序、第三工序、第四工序和造粒工序;
所述第一工序中,将(a)成分聚烯烃、(c)成分硅烷偶联剂、(d)成分第1抗氧化剂和(e)成分第2抗氧化剂熔融混炼,进行化学改性;
所述第二工序中,在大于等于(b)成分的熔点的温度,将(b)成分聚酰胺与通过所述第一工序进行了化学改性的(a)成分进行熔融混炼;
所述第三工序中,在大于等于(b)成分的熔点的温度,将(b)成分聚酰胺与通过所述第一工序化学改性了的(a)成分进行熔融混炼-化学改性,并进行挤出;
所述第四工序中,在大于等于(a)成分的熔点且小于等于(b)成分的熔点的温度,对通过所述第三工序进行了熔融混炼-化学改性的挤出物施加拉伸或进行压延;
所述造粒工序中,将通过所述第四工序进行了拉伸或压延的组合物冷却至室温来进行造粒。
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EP (1) | EP1704977A4 (zh) |
JP (1) | JP4285482B2 (zh) |
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CN105121035B (zh) * | 2013-04-19 | 2017-11-14 | 三菱电机株式会社 | 硅烷交联聚乙烯树脂的成型品的制造方法、棒状成型品的制造方法及其制造装置 |
US20150361615A1 (en) * | 2014-06-12 | 2015-12-17 | Edward J. Negola | Dyed Olefin Yarns And Textile Fabrics Using Such Yarns |
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JPS5853953A (ja) * | 1981-09-28 | 1983-03-30 | Motoo Takayanagi | 炭化水素系重合体組成物 |
US5006603A (en) * | 1986-09-26 | 1991-04-09 | Ube Industries, Ltd. | Fiber-reinforced rubber composition and production process and use thereof |
JP2682921B2 (ja) * | 1990-11-30 | 1997-11-26 | 三井石油化学工業株式会社 | 熱可塑性樹脂組成物 |
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JP3454481B2 (ja) * | 1993-02-08 | 2003-10-06 | 出光石油化学株式会社 | ポリオレフィン樹脂組成物 |
JP3543011B2 (ja) * | 1993-04-27 | 2004-07-14 | 出光石油化学株式会社 | ポリオレフィン樹脂組成物 |
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US6207737B1 (en) * | 1994-03-14 | 2001-03-27 | Ppg Industries Ohio, Inc. | Glass fiber sizing, sized glass fibers and polyolefin reinforced articles |
JPH0827305A (ja) * | 1994-07-13 | 1996-01-30 | Fuji Photo Film Co Ltd | 写真感光材料の包装材料用着色マスターバッチ樹脂組成物及びその製造方法並びに写真感光材料用包装材料及びその製造方法 |
JP3120711B2 (ja) * | 1995-08-21 | 2000-12-25 | 宇部興産株式会社 | 繊維強化熱可塑性樹脂組成物の製造法 |
JP3661736B2 (ja) * | 1997-09-30 | 2005-06-22 | 宇部興産株式会社 | ポリオレフィン−ポリアミド樹脂組成物の製造方法 |
JPH11181162A (ja) * | 1997-12-24 | 1999-07-06 | Ube Ind Ltd | 高溶融張力ポリオレフィン組成物とその製造法 |
JPH11209535A (ja) * | 1998-01-27 | 1999-08-03 | Ube Ind Ltd | ポリアミド繊維強化熱可塑性エラストマー組成物とその製造法 |
US6376057B1 (en) * | 1998-11-19 | 2002-04-23 | Fuji Photo Film, Co., Ltd. | Packaging material for photographic photosensitive material |
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US6596198B1 (en) * | 2000-04-28 | 2003-07-22 | Albemarle Corporation | Additive system for polymers in pellet form which provides proportioned stabilization and internal mold release characteristics |
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CA2551289A1 (en) | 2005-07-21 |
KR20070003804A (ko) | 2007-01-05 |
JP4285482B2 (ja) | 2009-06-24 |
MY136861A (en) | 2008-11-28 |
EP1704977A4 (en) | 2010-10-27 |
JPWO2005065908A1 (ja) | 2007-07-26 |
US20100140833A1 (en) | 2010-06-10 |
WO2005065908A1 (ja) | 2005-07-21 |
US20060231972A1 (en) | 2006-10-19 |
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