CN114656681B - 一种微球发泡尼龙材料的制备方法 - Google Patents
一种微球发泡尼龙材料的制备方法 Download PDFInfo
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- CN114656681B CN114656681B CN202210374764.1A CN202210374764A CN114656681B CN 114656681 B CN114656681 B CN 114656681B CN 202210374764 A CN202210374764 A CN 202210374764A CN 114656681 B CN114656681 B CN 114656681B
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- nylon
- microsphere foaming
- microsphere
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- 229920001778 nylon Polymers 0.000 title claims abstract description 134
- 239000004005 microsphere Substances 0.000 title claims abstract description 129
- 238000005187 foaming Methods 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 77
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 36
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001746 injection moulding Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
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- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
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- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 4
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
本发明公开了一种微球发泡尼龙材料的制备方法,其利用己内酰胺阴离子聚合制备得到混合有微球发泡剂的MC尼龙,进一步将其破碎造粒为尼龙微球发泡母粒,然后将其与尼龙、助剂利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,最后加入到注塑机中注塑成型得到微球发泡尼龙材料。本发明的微球发泡尼龙材料的制备方法解决了可膨胀微球发泡剂发泡温度范围与尼龙材料加工温度范围不匹配的问题,并且通过制作母粒预分散的方式解决了微球发泡剂分散不均的问题。
Description
技术领域
本发明属于发泡尼龙材料领域,具体涉及一种微球发泡尼龙材料的制备方法。
背景技术
尼龙为韧性角状半透明或乳白色结晶性树脂,作为工程塑料的尼龙分子量一般为1.5-3万。尼龙具有很高的机械强度,软化点高,耐热,摩擦系数低,耐磨损,具有自润滑性、吸震性和消音性,耐油,耐弱酸,耐碱和一般溶剂;电绝缘性好,有自熄性,无毒,无臭,耐候性好等。尼龙材料目前已成为发展最快的工程塑料,经常被用于制造各种汽车、电子电器、电动工具等关键结构零部件。
可膨胀微球发泡剂是日本生产的一种新型的特种发泡剂,可膨胀微球发泡剂是一种乳白色的微小球状塑料颗粒,直径10-45微米。当加热到一定温度时,发泡剂的体积可以迅速膨胀增大到自身的几十倍,从而达到发泡的效果。当加热的一定温度时,热塑性壳体软化,壳体里面的气体膨胀,发泡剂的体积可以增大到自身得几十倍,同时核壳结构并不破坏,从而达到发泡的效果。使用可膨胀微球发泡剂具有诸多优势,例如:(1)获得良好的机械性能,与其他类型发泡剂不同,可膨胀微球发泡剂没有泡孔,从而避免泡孔不均匀、泡孔破裂、泡孔回弹性差等缺点,完整的球形结构保证了良好的机械性能;(2)优良的弹性,热塑性壳体有优异的耐压性,表面可承受300公斤/平方厘米的压力,良好的回弹性可以承受多次循环加压/卸压而不破裂;(3)优异的发泡性能,可具有达到原来20-70倍的独立发泡效果,发泡后仍是一完整的密闭体,具有传统化学发泡剂无法比拟的发泡效果;(4)环保性能,聚合物微球无毒无污染,可作为环保型发泡剂在高端产品及高附加价值产品中使用。
但目前这种好用且性能优异的发泡剂却无法在尼龙材料中进行使用,这是由于这种特殊的发泡剂是一种核壳结构,外壳为热塑性丙烯酸聚合物,内核为烷烃气体组成的球状塑料颗粒,其结构成分限制了其发泡温度范围一般小于200℃;而尼龙材料的加工温度一般高于200℃,微球发泡剂在此温度下还未与基体混合均匀就已开始发泡,从而导致其无法应用于尼龙发泡。此外,由于尼龙属于半结晶型聚合物,当温度超过其熔点,其黏度急剧降低,容易在基体中产生塌陷、串泡、并泡,导致泡孔难以控制,限制了尼龙发泡材料的应用范围。因此如何控制尼龙的发泡行为受到了研究者们的关注,而如何使得微球发泡剂能够在尼龙基体中混合均匀且不会提前发泡从而获得性能优异的微球发泡尼龙材料也成为了待解决的一项难题。
发明内容
本发明的目的在于克服现有技术存在的不足,提供一种微球发泡尼龙材料的制备方法。
为了实现以上目的,本发明的技术方案为:
一种微球发泡尼龙材料的制备方法,包括如下步骤:
(1)将己内酰胺单体在反应容器中加热至110-140℃使其融化,抽真空脱水,依次加入引发剂和微球发泡剂,继续抽真空搅拌脱水;
(2)向反应容器中加入催化剂,搅拌得到反应液,将反应液浇铸或抽注到140-160℃的模具中,保温后进行脱模,得到混合有微球发泡剂的MC尼龙;
(3)将步骤(2)中得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒;
(4)将步骤(3)中得到的尼龙微球发泡母粒与尼龙、助剂利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,得到共混粒料,在挤出时双螺杆挤出机的料筒温度范围为180-240℃;
(5)将步骤(4)中得到的共混粒料加入到注塑机中注塑成型得到微球发泡尼龙材料。
作为优选,引发剂选自甲醇钠、氢氧化钠、氢氧化钾、己内酰胺钠、金属钠、金属钾中的至少一种,引发剂与己内酰胺单体的重量份比例为0.1-5:100。
作为优选,催化剂选自甲苯二异氰酸酯、己二异氰酸酯、六亚甲基二异氰酸酯、三苯甲烷三异氰酸酯、二苯甲烷二异氰酸酯中的至少一种,催化剂与己内酰胺单体的重量份比例为0.1-2:100。
作为优选,微球发泡剂为可膨胀且具有核壳结构的微小球状颗粒,其外壳为热塑性丙烯酸聚合物,其内核为烷烃气体,微球发泡剂的粒径范围在10-50微米,外壳的厚度为2-15微米,微球发泡剂与己内酰胺单体的重量份比例为10-40:100。
作为优选,微球发泡剂的起始发泡温度为160-200℃,最大发泡温度为200-250℃。
作为优选,尼龙选自PA6、PA11、PA12、PA1010、PA610中的至少一种。
作为优选,助剂选自抗氧剂、光稳定剂、热稳定剂、增韧剂、增塑剂、润滑剂、着色剂、荧光增白剂、阻燃剂中的至少一种。
作为优选,尼龙微球发泡母粒与尼龙的重量份比例为10-40:100;助剂与尼龙的重量份比例为0.1-20:100。
作为优选,步骤(5)中注塑时注塑机料筒温度为200-260℃,注射压力为60-120MPa,注射速度为30-90mm/s,冷却时间为10-40s。
作为优选,步骤(4)中还加入0-30份填料进行混合,填料选自碳酸钙、硫酸钡、滑石粉、炭黑、石墨烯、玻璃纤维、碳纤维、氧化铝、氮化硼、金属粉、合成橡胶、合成纤维、合成树脂、玻璃微珠、树脂微珠中的至少一种。
相比于现有技术,本发明的有益效果为:
本发明预先通过己内酰胺阴离子聚合法制备混合有微球发泡剂的MC尼龙,并进一步得到尼龙微球发泡母粒,再将其与尼龙进行挤出注塑发泡,尼龙微球发泡母粒在与尼龙进行挤出共混的过程中,由于尼龙微球发泡母粒中的MC尼龙相比普通尼龙具有更高的熔点,可以作为微球发泡剂的保护壳阻隔热源传递,防止微球发泡剂提前膨胀发泡,解决了可膨胀微球发泡剂发泡温度范围与尼龙材料加工温度范围不匹配的问题,并且通过制作尼龙微球发泡母粒并实现预分散的方式解决了微球发泡剂分散不均的问题,使得微球发泡剂能够在尼龙基体中混合均匀且不会提前发泡,并且MC尼龙本身具有比普通尼龙更为优异的机械性能,且与尼龙基体具有良好的相容性,在发泡材料加工成型后,微球发泡母粒能够完全融合于尼龙基体中而不产生相分离从而体现出优异的综合性能,这是利用其他材料改性很难达到的。采用本发明中的制备方法,使得具有良好机械性能、回弹性、优异发泡性能和环保性能的可膨胀微球发泡剂能够与尼龙材料进行共混发泡,从而得到一种综合性能优异的新型发泡尼龙,避免了尼龙材料使用传统物理和化学发泡剂存在的塌陷、串泡、并泡问题。此外,本发明中的尼龙微球发泡母粒的制备过程简易,且适合大量生产及工业化。
具体实施方式
下面通过具体实施例对本发明作进一步详细的描述。
本申请的实施例中提出了一种微球发泡尼龙材料的制备方法,包括如下步骤:
(1)将己内酰胺单体在反应容器中加热至110-140℃使其融化,抽真空脱水20-60min,依次加入引发剂和微球发泡剂,继续抽真空搅拌脱水20-60min,抽真空脱水时的真空度优选在-0.1MPa;其中,引发剂选自甲醇钠、氢氧化钠、氢氧化钾、己内酰胺钠、金属钠、金属钾中的至少一种,引发剂与己内酰胺单体的重量份比例为0.1-5:100。微球发泡剂与己内酰胺单体的重量份比例为10-40:100,微球发泡剂为可膨胀且具有核壳结构的微小球状颗粒,其外壳为热塑性丙烯酸聚合物,其内核为烷烃气体,微球发泡剂的粒径范围在10-50微米,其外壳的厚度在2-15微米,并且具有良好的弹性并可承受较大压力,在加热膨胀之后发泡剂自身并不破裂,同时保持自身的良好性能。微球发泡剂的起始发泡温度为160-200℃,最大发泡温度为200-250℃。在具体实施过程中,可根据各种不同加工温度和工艺要求,选择最合适的微球型号。作为优选,微球发泡剂为美国博力肯、阿克苏诺贝尔、日本松本油脂、日本积水、日本三菱、陶氏、快思瑞科技生产的微球发泡剂,更优选的微球发泡剂牌号为美国博力肯公司200DU35、美国博力肯公司220DU30、日本积水EM501、日本积水P501M1、日本积水P501E1、阿克苏诺贝尔Expancel 980DU 120、广东纳奥新材料FM-H60。
(2)向反应容器中加入催化剂,搅拌1-8min后,得到反应液,将所述反应液浇铸或抽注到140-160℃的模具中,保温20-60min后进行脱模,得到混合有微球发泡剂的MC尼龙;其中,催化剂选自甲苯二异氰酸酯、己二异氰酸酯、六亚甲基二异氰酸酯、三苯甲烷三异氰酸酯、二苯甲烷二异氰酸酯中的至少一种,催化剂与己内酰胺单体的重量份比例为0.1-2:100。
(3)将步骤(2)中得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒。
(4)将步骤(3)中得到的尼龙微球发泡母粒与尼龙、助剂利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,得到共混粒料,在挤出时所述双螺杆挤出机的料筒温度范围为180-240℃,双螺杆挤出机螺杆转速为100-500r/min;其中,尼龙选自PA6、PA11、PA12、PA1010、PA610中的至少一种,尼龙微球发泡母粒与尼龙的重量份比例为10-40:100;助剂选自抗氧剂、光稳定剂、热稳定剂、增韧剂、增塑剂、润滑剂、着色剂、荧光增白剂、阻燃剂中的至少一种,助剂与尼龙的重量份比例为0.1-20:100。
在具体的实施例中,抗氧剂至少选自茶多酚(TP)、丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)、叔丁基对苯二酚(TBHQ)、抗氧剂1010、抗氧剂245、抗氧剂168、抗氧剂Chinox 20N中的至少一种。所加入的抗氧剂能够延缓聚合物样品在加工过程中的氧化,保证材料能够顺利地进行制备加工并延长其使用寿命,其优选的加入量为0.01-1份。
在具体的实施例中,光稳定剂至少选自炭黑、二氧化钛、氧化锌、亚硫酸钙、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-5-甲基苯基)苯并三唑、2,4,6-三(2-羟基-4-正丁氧基苯基)-1,3,5-均三嗪、2-氰基-3,3-二苯基丙烯酸2-乙基己酯、水杨酸对-叔丁基苯酯、双水杨酸双酚A酯、双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)、2,2’-硫代双(4-特辛基酚氧基)镍、癸二酸双(2,2,6,6-四甲基哌啶)酯、苯甲酸(2,2,6,6-四甲基哌啶)酯、三(1,2,2,6,6-五甲基哌啶基)亚磷酸酯中的至少一种。所加入的光稳定剂能够防止材料制品发生光老化,延长其使用寿命,其优选的加入量为0.01-0.5份。
在具体的实施例中,热稳定剂至少选自三盐基硫酸铅、二盐基亚磷酸铅、二盐基硬脂酸铅、二盐基苯二甲酸铅、三盐基马来酸铅、盐基性硅酸铅、硬脂酸铅、水杨酸铅、二盐基邻苯二甲酸铅、碱式碳酸铅、硬脂酸镉、硬脂酸钡、硬脂酸钙、硬脂酸铅、硬脂酸锌、二月桂酸二正丁基锡、二月桂酸二正辛基锡中的至少一种。所加入的热稳定剂能够使得材料制品在加工或使用过程中不因受热而发生化学变化,或者延缓这些变化来达到延长使用寿命的目的,其优选的加入量为0.1-0.5份。
在具体的实施例中,增韧剂至少选自甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物树脂、氯化聚乙烯树脂、乙烯-醋酸乙烯酯共聚物树脂及其改性物、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-丁二烯共聚物、乙丙胶、三元乙丙胶、顺丁胶、丁苯胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物中的至少一种。所加入的增韧剂能够降低材料制品脆性,增大韧性,提高材料承载强度,其优选的加入量为5-10份。
在具体的实施例中,增塑剂至少选自邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二异辛酯、邻苯二甲酸二庚酯、邻苯二甲酸二异癸酯、邻苯二甲酸二异壬酯、邻苯二甲酸丁苄酯、邻苯二甲酸丁酯乙醇酸丁酯、邻苯二甲酸二环己酯、磷酸三甲苯酯、磷酸(二苯-2-乙基)己酯、己二酸二(2-乙基)己酯、癸二酸二(2-乙基)己酯、环氧甘油酯类、环氧脂肪酸单酯类、环氧四氢邻苯二甲酸酯类、环氧大豆油、环氧硬脂酸(2-乙基)己酯、C5~9酸乙二醇酯、C5~9酸二缩三乙二醇酯、绿化石蜡类、氯代脂肪酸酯、乙二酸1,2-丙二醇系聚酯、癸二酸1,2-丙二醇聚酯、石油磺酸苯酯、偏苯三酸酯、柠檬酸酯中的至少一种。所加入的增塑剂能够增加聚合物的塑性,使得聚合物的硬度、模量、软化温度和脆化温度下降,伸长率、曲挠性和柔韧性提高,其优选的加入量为5-20份。
在具体的实施例中,润滑剂至少选自固体石蜡、微晶石蜡、液体石蜡、低分子量聚乙烯、氧化聚乙烯蜡、硬脂酸、羟基硬脂酸、脂肪酸低级醇酯、脂肪酸多元醇酯、天然蜡、酯蜡和皂化蜡、硬脂酰胺或硬脂酸酰胺、油酰胺或油酸酰胺、芥酸酰胺、硅酮、N,N’-乙撑双硬脂酰胺、硬脂醇、硬脂酸铅、硬脂酸钙、硬脂酸钡、硬脂酸镁、硬脂酸锌中的至少一种。所加入的润滑剂能够提高聚合物样品的润滑性、减少摩擦、降低界面粘附性能,其优选的加入量为0.5-1份。
在具体的实施例中,着色剂至少选自钛白、铬黄、镉红、铁红、钼铬红、群青、铬绿、炭黑、立索尔宝红BK、色淀红C、苝红、嘉基R红、酞菁红、永固洋红HF3C、塑料大红R和克洛莫红BR、永固橙HL、耐晒黄G、汽巴塑料黄R、永固黄3G、永固黄H2G、酞青蓝B、酞青绿、塑料紫RL、苯胺黑、硫靛红、还原黄4GF、士林蓝RSN、盐基性玫瑰精、油溶黄中的至少一种。所加入的着色剂可以使材料制品呈现出所需要的颜色,增加表面色彩,其优选的加入量为0.3-0.8份。
在具体的实施例中,荧光增白剂至少选自二苯乙烯联苯二磺酸钠(荧光增白剂CBS)、4,4-双(5甲基-2-苯并噁唑基)二苯乙烯(荧光增白剂KSN)、2,2-(4,4’-二苯乙烯基)双苯并噁唑(荧光增白剂OB-1)中的至少一种。所加入的荧光增白剂能使所染物质获得类似荧石的闪闪发光的效应,其优选的加入量为0.002-0.03份,荧光增白剂一般与其他种类的助剂同时加入。
在具体的实施例中,阻燃剂至少选自红磷、磷酸三甲酚酯、磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯二苯酯、三(2,3-二溴丙基)磷酸酯、磷酸三(2,3-二氯丙)酯、高含氯量氯化石蜡、1,1,2,2-四溴乙烷、十溴联苯醚、全氯环戊癸烷、三氧化二锑、氢氧化铝、氢氧化镁、硼酸锌、氯桥酸酐、双(2,3-二溴丙基)反丁烯二酸酯、四溴双酚A、四溴邻苯二甲酸酐中的至少一种。所加入的阻燃剂能够增加材料制品的耐燃性,其优选的加入量为1-20份。
在具体的实施例中,步骤(4)中还加入0-30份填料进行混合,填料选自碳酸钙、硫酸钡、滑石粉、炭黑、石墨烯、玻璃纤维、碳纤维、氧化铝、氮化硼、金属粉、合成橡胶、合成纤维、合成树脂、玻璃微珠、树脂微珠中的至少一种。
(5)将步骤(4)中得到的共混粒料加入到注塑机中注塑成型得到微球发泡尼龙材料,注塑时注塑机料筒温度为200-260℃,注射压力为60-120MPa,注射速度为30-90mm/s,冷却时间为10-40s。
本申请的实施例中先将己内酰胺单体与微球发泡剂反应得到混合有微球发泡剂的MC尼龙,单体浇铸型尼龙(MC尼龙)是20世纪60年代初采用己内酰胺阴离子聚合技术发展起来的新型热塑性工程塑料,其采用己内酰胺单体在强碱存在下形成阴离子并快速聚合,可生成分子量高达10万以上的线形聚合物。该反应聚合时间短,可采用单体浇铸、反应注射和反应挤出成型。同时,相比于普通尼龙,MC尼龙在制备过程中的温度也较低,脱水温度110-140℃,成型温度140-170℃,在此温度下加入微球发泡剂进行原位聚合可以得到混合有微球发泡剂的MC尼龙,并进一步破碎得到微球发泡母粒,并且其具有比普通尼龙更优异的机械性能,将其与尼龙材料进行共混发泡,可以得到一种以可膨胀微球作为发泡剂的性能优异的新型发泡尼龙。
下面通过具体的实施例与对比例来进一步说明。
对比例1
将100重量份PA6(日本三菱,1010N2)、0.2重量份滑石粉、0.5重量份硅酮、0.2重量份抗氧剂1010、0.2重量份二月桂酸二正丁基锡利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,得到共混粒料,挤出机料筒温度范围为220-250℃,螺杆转速为200r/min。造粒后的样品在鼓风烘箱中干燥后,取100重量份共混粒料与10份碳酸氢钠发泡母粒利用注塑机进行注塑成型,注塑机料筒温度为220-260℃,注射压力为80-100MPa,注射速度为50-80mm/s,冷却时间为25s,脱模后得到发泡尼龙材料。
实施例1
在反应容器中加入100重量份己内酰胺单体,升温至120℃使物料融化,抽真空脱水30min后加入0.2重量份氢氧化钠,搅拌均匀后加入20重量份微球发泡剂(美国Polychem公司,200DU35),继续抽真空搅拌脱水30min,然后加入0.2重量份甲苯-2,4-二异氰酸酯,搅拌5min后将反应液注入到已经预热至160℃模具中,保温40min后进行脱模;将得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒。
将100重量份PA6(日本三菱,1010N2)、40重量份尼龙微球发泡母粒、0.1重量份抗氧剂168、0.2重量份抗氧剂1010、0.2重量份二月桂酸二正丁基锡利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,挤出机料筒温度范围为210-240℃,螺杆转速为100r/min。造粒后的样品在鼓风烘箱中干燥后,利用注塑机进行注塑成型,注塑机料筒温度为220-260℃,注射压力为80-100MPa,注射速度为50-80mm/s,冷却时间为25s,脱模后得到表面平滑,无明显外观缺陷,内部泡孔均匀细腻,具有良好回弹性的微球发泡尼龙材料。
实施例2
在反应容器中加入100重量份己内酰胺单体,升温至110℃使物料融化,抽真空脱水30min后加入2.0重量份己内酰胺钠,搅拌均匀后加入30重量份微球发泡剂(美国Polychem公司,220DU30),继续抽真空搅拌脱水30min,然后加入1.0重量份甲苯-2,4-二异氰酸酯,搅拌5min后将反应液注入到已经预热至160℃模具中,保温50min后进行脱模;将得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒。
将100重量份PA610(杜邦,LC3060 NC010)、30重量份尼龙微球发泡母粒、0.2重量份抗氧剂168、0.1重量份2-羟基-4-甲氧基二苯甲酮、0.2重量份二月桂酸二正丁基锡、5重量份邻苯二甲酸二丁酯利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,挤出机料筒温度范围为210-240℃,螺杆转速为100r/min。造粒后的样品在鼓风烘箱中干燥后,利用注塑机进行注塑成型,注塑机料筒温度为220-260℃,注射压力为90-110MPa,注射速度为50-80mm/s,冷却时间为25s,脱模后得到表面平滑,无明显外观缺陷,内部泡孔均匀细腻,具有良好回弹性的微球发泡尼龙材料。
实施例3
在反应容器中加入100重量份己内酰胺单体,升温至130℃使物料融化,抽真空脱水30min后加入0.4重量份甲醇钠,搅拌均匀后加入30重量份微球发泡剂(广东纳奥,FM-H60),继续抽真空搅拌脱水30min,然后加入0.6重量份六亚甲基二异氰酸酯,搅拌5min后将反应液注入到已经预热至160℃模具中,保温40min后进行脱模;将得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒。
将100重量份PA1010(杜邦,LC1010 NC010)、40重量份尼龙微球发泡母粒、0.1重量份抗氧剂168、0.2重量份抗氧剂1010、0.2重量份二月桂酸二正丁基锡利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,挤出机料筒温度范围为180-230℃,螺杆转速为100r/min。造粒后的样品在鼓风烘箱中干燥后,利用注塑机进行注塑成型,注塑机料筒温度为200-240℃,注射压力为80-110MPa,注射速度为50-80mm/s,冷却时间为25s,脱模后得到表面平滑,无明显外观缺陷,内部泡孔均匀细腻,具有良好回弹性的微球发泡尼龙材料。
实施例4
在反应容器中加入100重量份己内酰胺单体,升温至110℃使物料融化,抽真空脱水30min后加入0.5重量份氢氧化钠,搅拌均匀后加入30重量份微球发泡剂(阿克苏诺贝尔,980DU 120),继续抽真空搅拌脱水30min,然后加入0.8重量份二苯甲烷二异氰酸酯,搅拌5min后将反应液注入到已经预热至150℃模具中,保温40min后进行脱模;将得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒。
将100重量份PA6(日本东丽,CM1017)、20重量份尼龙微球发泡母粒、10重量份十溴联苯醚、2重量份三氧化二锑、0.2重量份氧化聚乙烯蜡、0.1重量份抗氧剂168、0.2重量份抗氧剂1010、0.2重量份二月桂酸二正丁基锡利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,挤出机料筒温度范围为210-240℃,螺杆转速为100r/min。造粒后的样品在鼓风烘箱中干燥后,利用注塑机进行注塑成型,注塑机料筒温度为220-260℃,注射压力为80-100MPa,注射速度为50-80mm/s,冷却时间为25s,脱模后得到表面平滑,无明显外观缺陷,内部泡孔均匀细腻,具有良好回弹性的微球发泡尼龙材料。
实施例5
在反应容器中加入100重量份己内酰胺单体,升温至120℃使物料融化,抽真空脱水30min后加入2.0重量份己内酰胺钠,搅拌均匀后加入30重量份可膨胀微球发泡剂(日本积水,P501E1),继续抽真空搅拌脱水30min,然后加入1.0重量份三苯甲烷三异氰酸酯,搅拌5min后将反应液注入到已经预热至150℃模具中,保温40min后进行脱模;将得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒。
将100重量份PA6(日本三菱,1010N2)、30重量份尼龙微球发泡母粒、10重量份滑石粉、0.5重量份氧化聚乙烯蜡、0.1重量份抗氧剂168、0.2重量份抗氧剂1010、0.2重量份二月桂酸二正丁基锡利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,挤出机料筒温度范围为210-240℃,螺杆转速为100r/min。造粒后的样品在鼓风烘箱中干燥后,利用注塑机进行注塑成型,注塑机料筒温度为220-260℃,注射压力为80-100MPa,注射速度为50-80mm/s,冷却时间为25s,脱模后得到表面平滑,无明显外观缺陷,内部泡孔均匀细腻,具有良好回弹性的微球发泡尼龙材料。
将上述对比例1及实施例1-5分别进行密度、拉伸强度、弯曲强度、弯曲模量、缺口冲击强度测试,并将测试标准及结果列于下表。
表1.本发明对比例与实施例性能表
标准 | 对比例1 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
密度(g/cm3) | ISO 1183 | 0.96 | 0.75 | 0.68 | 0.51 | 0.81 | 0.74 |
拉伸强度(MPa) | ISO 527 | 38 | 55 | 38 | 27 | 44 | 59 |
弯曲强度(MPa) | ISO 178 | 42 | 58 | 40 | 33 | 47 | 65 |
弯曲模量(MPa) | ISO 178 | 1600 | 1560 | 1370 | 820 | 1240 | 1720 |
缺口冲击强度(kJ/m2) | ISO 180 | 6 | 23 | 31 | 27 | 15 | 18 |
从表中数据可以看出,相比于传统的发泡尼龙材料,本申请的实施例中的微球发泡尼龙材料在密度更低的前提下,在拉伸强度和弯曲强度方面仍具有不同程度的提升,在弯曲模量方面也有所保持,并且在缺口冲击强度上有了显著提高,实施例3由于采用PA1010作为基体,且发泡密度较低,因此在强度和模量方面偏低,但也体现出了良好的冲击韧性。由于采用的微球发泡剂具有完整的球形结构保证了材料良好的机械性能,并且作为微球发泡母粒基体的MC尼龙也具有比普通尼龙更为优异的机械性能且与尼龙基体具有良好的相容性,因此能够得到综合性能优异的微球发泡尼龙材料。此外,实施例中的微球发泡尼龙材料表面平滑,无明显外观缺陷,内部泡孔均匀细腻,具有良好回弹性,也表明了本发明制备方法对于制备微球发泡尼龙的可行性和适用性。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (9)
1.一种微球发泡尼龙材料的制备方法,其特征在于,包括如下步骤:
(1)将己内酰胺单体在反应容器中加热至110-140℃使其融化,抽真空脱水,依次加入引发剂和微球发泡剂,继续抽真空搅拌脱水,所述微球发泡剂的起始发泡温度为160-200℃,最大发泡温度为200-250℃,所述微球发泡剂为可膨胀且具有核壳结构的微小球状颗粒,其外壳为热塑性丙烯酸聚合物,其内核为烷烃气体,所述微球发泡剂与己内酰胺单体的重量份比例为10-40:100;
(2)向反应容器中加入催化剂,搅拌得到反应液,将所述反应液浇铸或抽注到140-150℃的模具中,保温后进行脱模,得到混合有微球发泡剂的MC尼龙;
(3)将步骤(2)中得到的混合有微球发泡剂的MC尼龙进行破碎造粒,得到尼龙微球发泡母粒;
(4)将步骤(3)中得到的尼龙微球发泡母粒与尼龙、助剂利用高速混合机中混合均匀,加入到双螺杆挤出机中挤出共混造粒,得到共混粒料,在挤出时所述双螺杆挤出机的料筒温度范围为180-240℃,由于尼龙微球发泡母粒中的MC尼龙相比普通尼龙具有更高的熔点,MC尼龙作为微球发泡剂的保护壳阻隔热源传递,防止微球发泡剂提前膨胀发泡;
(5)将步骤(4)中得到的共混粒料加入到注塑机中注塑成型得到微球发泡尼龙材料。
2.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述引发剂选自甲醇钠、氢氧化钠、氢氧化钾、己内酰胺钠、金属钠、金属钾中的至少一种,所述引发剂与己内酰胺单体的重量份比例为0.1-5:100。
3.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述催化剂选自甲苯二异氰酸酯、己二异氰酸酯、六亚甲基二异氰酸酯、三苯甲烷三异氰酸酯、二苯甲烷二异氰酸酯中的至少一种,所述催化剂与己内酰胺单体的重量份比例为0.1-2:100。
4.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述微球发泡剂的粒径范围在10-50微米,外壳的厚度为2-15微米。
5.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述尼龙选自PA6、PA11、PA12、PA1010、PA610中的至少一种。
6.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述助剂选自抗氧剂、光稳定剂、热稳定剂、增韧剂、增塑剂、润滑剂、着色剂、荧光增白剂、阻燃剂中的至少一种。
7.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述尼龙微球发泡母粒与尼龙的重量份比例为10-40:100;所述助剂与尼龙的重量份比例为0.1-20:100。
8.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述步骤(5)中注塑时注塑机料筒温度为200-260℃,注射压力为60-120MPa,注射速度为30-90mm/s,冷却时间为10-40s。
9.根据权利要求1所述的微球发泡尼龙材料的制备方法,其特征在于,所述步骤(4)中还加入0-30份填料进行混合,所述填料选自碳酸钙、硫酸钡、滑石粉、炭黑、石墨烯、玻璃纤维、碳纤维、氧化铝、氮化硼、金属粉、合成橡胶、合成纤维、合成树脂、玻璃微珠、树脂微珠中的至少一种。
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