CN111848909A - 一种ndi基闭孔微孔弹性体及其一步法生产方法 - Google Patents

一种ndi基闭孔微孔弹性体及其一步法生产方法 Download PDF

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CN111848909A
CN111848909A CN202010763501.0A CN202010763501A CN111848909A CN 111848909 A CN111848909 A CN 111848909A CN 202010763501 A CN202010763501 A CN 202010763501A CN 111848909 A CN111848909 A CN 111848909A
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ndi
parts
reaction
based closed
antioxidant
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岳兴龙
方超
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Jiangsu Macro Green Material Technology Co ltd
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Jiangsu Macro Green Material Technology Co ltd
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Abstract

本发明公开一种NDI基闭孔微孔弹性体及其一步法生产方法，所述闭孔微孔弹性体定位组分按重量份计包括：NDI液体7.5～15份，多元醇15～30份，扩链剂0.2～3份，添加剂1～43份；其中，所述NDI液体为片状NDI熔融后加入脱水的二元醇制得；所述多元醇为聚醚多元醇；所述扩链剂为小分子二醇；所述添加剂按重量份计包括：抗氧化剂0.2～10份；UV稳定剂0.2～5份；催化剂0.1～3份；阻聚剂0.1～5份；乳化剂0.2～15份；匀泡剂0.2～5份。所述一步法生产方法包括制备NDI液、分装入釜、聚合反应和挤出切粒等步骤。本发明制备方法步骤简单、工艺过程易于控制，经超临界发泡获得的NDI基热塑性聚氨酯弹性体为闭孔结构，性能优异，具有更高的抗冲击性和强度。

Description

一种NDI基闭孔微孔弹性体及其一步法生产方法
技术领域
本发明涉及一种NDI基闭孔微孔弹性体及其一步法生产方法。
背景技术
聚氨酯弹性体因其出众的综合性能，被广泛应用于工业生产的各个领域。然而在动态条件下，聚氨酯弹性体内生热较大，并且耐高温性能也较差，由此限制了聚氨酯弹性体在一些苛刻条件领域中的应用，所以改善聚氨酯弹性体动态及耐热性能具有重要的意义。
目前市场上聚酯弹性体较为常用的是基于甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)体系制备的，但是他们所制备的聚氨酯弹性体的耐疲劳性和强度有待提高。1,5-萘二异氰酸酯(NDI)相对于TDI、MDI具有更高的熔点，其合成的聚酯具有硬度高、耐热性好、动态性能优异、耐磨性好及回弹性好等特点，在在纺织工业和汽车工业中还具备重要的应用价值。但因NDI是一种极其活泼的化合物，所以合成的预聚物贮存稳定性不好，且相对传统TDI、MDI体系，其生产工艺更为复杂。微孔聚氨酯弹性体具有弹性体材料良好的物理机械性能和泡沫材料的柔软舒适性。材料的泡沫孔径较小，介于0.1～10μm范围之间，泡孔尺寸分布较窄且泡孔均匀。在传统化学发泡工艺中，异氰酸酯与化学发泡剂反应产生二氧化碳，二氧化碳首先会溶解在液相中，当达到饱和溶解度后，二氧化碳开始从液相中逸出产生气泡，随着气泡进一步增多，液相中的气泡碰撞融合，气泡尺寸增加，气泡壁变薄，最终形成网络状开放式微孔结构。然而，相对于开孔式弹性体，闭孔发泡材料具有独立泡孔结构，内部泡孔和泡孔之间有壁膜隔开，不互相连通，具有极其优良的抗冲击性、反弹性和强度，因此在高性能弹性体中应用较多。
目前针对NDI基聚酯弹性体的研究和生产越来越多。2005年，中国专利文献CN200510111548.4公布了一种NDI基聚氨酯微孔弹性体的制备方法，该发明首先将过量的多异氰酸酯与多元醇在120～140℃条件下反应，形成端-NCO基的预聚体，然后将预聚体与扩链剂组分按比例混合，反应料液注入温度为80～95℃的模具中，预熟化后脱模，最后经过后熟化得到产品。该发明制备步骤较为繁琐，并且发泡方式有待优化。2019年，中国专利文献CN201910424918.1又公布了一种耐湿热老化NDI基聚氨酯微孔弹性体及其制备方法，该方法需要将计量好的聚碳酸酯改性聚己内酯多元醇、聚酯多元醇、生物基多元醇加入反应釜中，反应完成后制得A组分；再将计量好的交联剂、扩链剂、催化剂、泡沫稳定剂和发泡剂混合均匀，制得B组分；最后将A组分和B组分分别加入浇注机中，浇注成模后熟化，得到NDI基聚氨酯微孔弹性体。该工艺的生产步骤同样较为繁琐，不利于成本较高、性能较为活泼的NDI的生产和推广。
发明内容
针对上述存在的问题，本发明提供一种NDI基闭孔微孔弹性体及一步法生产的方法，通过进一步改进发泡工艺，利用超临界发泡技术得到NDI基闭孔微孔弹性体，以解决现有NDI基聚氨酯微孔弹性体生产工艺繁琐、NDI预聚物反应活性高和稳定性差的技术问题。具体技术方案如下：
一种NDI基闭孔微孔弹性体，其组分按重量份计包括：
NDI液体7.5～15份，
多元醇15～30份，
扩链剂0.2～3份，
添加剂1～43份；
其中，所述NDI液体为片状NDI熔融后加入脱水的二元醇制得；所述多元醇为聚醚多元醇；所述扩链剂为小分子二醇；所述添加剂按重量份计包括：抗氧化剂0.2～10份；UV稳定剂0.2～5份；催化剂0.1～3份；阻聚剂0.1～5份；乳化剂0.2～15份；匀泡剂0.2～5份。
优选的，所述脱水后的二元醇，其水分含量在0.01～0.03％；所述NDI和二元醇之间的摩尔比为3～5.5:1。
优选的，所述聚醚多元醇为聚氧化丙烯二醇、聚四氢呋喃二醇、四氢呋喃-氧化丙烯共聚二醇、接枝型聚醚多元醇、聚四氢呋喃多元醇、杂环改性聚醚多元醇中的一种或几种组成。
优选的，所述扩链剂小分子二醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、2,3-丁二醇、1,5-戊二醇、甘油、二甘醇、三甘醇、新戊二醇、山梨醇中的一种或几种组成。
优选的，所述抗氧化剂为抗氧剂1010、抗氧剂1076、抗氧剂CA、抗氧剂164、抗氧剂DNP中的一种或几种组成。
优选的，所述UV稳定剂为苯并三唑类稳定剂包括UV-326、UV-328、UV-770、UV-622、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯中的一种或几种组成。
优选的，所述催化剂为为辛酸亚锡、二月桂酸二丁基锡、钛酸异丙酯、柠檬酸钛、二丁基羟基氧化锡、N,N-二甲基环己胺、三乙胺、N-乙基吗啉、甲基吗啉、N,N’-二乙基哌嗪、三乙醇胺、二甲基乙醇胺、吡啶、N,N’-二甲基吡啶中的一种或几种组成。
优选的，所述阻聚剂为对苯二酚、对苯醌、甲基氢醌、对羟基苯甲醚、2-叔丁基对苯二酚、2，5-二叔丁基对苯二酚中的一种或几种组成。
优选的，所述乳化剂为脂肪酸皂、烷基硫酸盐、烷基苯磺酸盐、磷酸盐、N-十二烷基二甲胺及其他胺衍生物、季铵盐、聚氧乙烯醚、聚氧丙烯醚、环氧乙烷和环氧丙烷嵌段共聚物、多元醇脂肪酸酯、聚乙烯醇中的一种或几种组成。
优选的，所述匀泡剂为聚硅烷一氧化烯烃嵌段共聚物硅油。
前述的NDI基闭孔微孔弹性体，其生产方法包括如下步骤，该方法为一步法具体为：
1)制备NDI液：在氮气保护下，将片状NDI加入反应器中，加热至融化，在搅拌状态下，在氮气保护下升温，连续加入脱水后的二元醇，搅拌并控制釜温在100℃至128℃，获得NDI液体；
2)分装入釜：将步骤1)中制备的NDI液体装入反应釜A中；将多元醇装于反应釜B中；先将抗氧剂、UV稳定剂、阻聚剂、乳化剂及匀泡剂等添加剂装入反应釜C中，再缓慢将小分子扩链剂装入反应釜C中，同时用扩链剂进行冲洗，避免粉末状添加剂及少量添加剂粘在釜口，以备浇注挤出；
3)聚合反应：将步骤2)中分装在反应釜A、B、C中，各釜中的物料通过浇注机按预定的比例2～6:1～4:1～3注入双螺杆反应挤出机中，并在双螺杆反应挤出机中进行聚合反应，反应时间为0.2～4小时；
4)发泡挤出：在双螺杆挤出机中聚合反应后的物料再经安装有超临界发泡设备的单螺杆发泡挤出机进行超临界发泡，并进入冷却水槽水中切粒，即可得到NDI基闭孔微孔弹性体。
作为优选的技术方案的，步骤2)中，所述反应釜A的釜内温度为85～95℃，所述反应釜B的釜内温度为85～110℃，所述反应釜C的釜内温度为35～70℃。
作为优选的技术方案的，步骤3)中，所述浇注机包括分别安装于反应釜A、B、C下方的高精准计量泵和质量流量计，以用于将反应釜中三种物料注入双螺杆挤出机中的混合头；所述高精准计量泵为MF型三向计量泵，计量泵温度控制在25～85℃。
作为优选的技术方案的，步骤4)中，所述双螺杆反应挤出机和单螺杆发泡挤出机的工艺温度段均设定为80～240℃，所述水中切粒的水温控制为8～20℃。
优选的，所述双螺杆反应挤出机和单螺杆发泡挤出机相连通形成从双级螺杆挤出装置，其中三个反应釜内的物料在双螺杆反应挤出机中反应，再经单螺杆发泡挤出机中发泡挤出。所述单螺杆发泡挤出机在传统单螺杆挤出机的基础上安装超临界发泡装置。超临界发泡装置由压力罐、高压泵、储压釜和稳压阀构成，其中压力罐中储存二氧化碳，经高压泵将二氧化碳打入储压釜中，储压釜恒温在40～45度，经过稳压阀调节至合适压力(7～15MPa)注入单螺杆发泡挤出机中，完成超临界发泡。
本发明的有益效果是：
本发明方法经双级螺杆机反应-发泡一步法合成，制备方法步骤简单、工艺过程易于控制，经超临界发泡获得的NDI基热塑性聚氨酯弹性体为闭孔结构，性能优异，具有更高的抗冲击性和强度。本发明的工艺中，首先得到NDI液体，从而避免了固体片状NDI在熔化过程中的升华和变质。物料直接通过浇注机同时进入双级螺杆机中反应发泡，能得到分子量最大化的物质，同时显示出本发明工艺稳定的性能及可靠性。通过阻聚剂的加入可以减缓聚合速率，能够更好的控制聚合反应程度，另外加入乳化剂后，能够更好的将提高弹性体中各组分的相容性。水中切粒的工艺简捷、减少了工艺环节，提高了产品质量，工业化程度高。超临界发泡技术的应用，能够得到闭孔弹性体，提高了产品的强度性能。
附图说明
图1为本发明一步法生产NDI基闭孔微孔弹性体的工艺流程示意图。
图2为本发明聚合-发泡挤出系统示意图。
图中：1、电机主箱；2、双螺杆反应挤出机反应机箱；3、单螺杆发泡挤出机反应机箱；4、料斗；5、压力罐；6、高压泵；7、储压釜；8、稳压阀。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合实施例，对本发明的技术方案进行清楚、完整地描述。其中实施例1～3为NDI基闭孔微孔弹性体的生产方法，实施例4为效果例。
实施例1
本实施例是一种NDI基闭孔微孔弹性体及其生产方法，所述NDI基闭孔微孔弹性体的组分按重量份计包括：NDI液体7.5份；聚醚多元醇15份；扩链剂0.2份；抗氧化剂0.2份；UV稳定剂0.2份；催化剂0.1份；阻聚剂0.1份；乳化剂0.2；匀泡剂0.2份。其中，NDI液体为片状NDI与乙二醇共混制得，所述聚醚多元醇为聚氧化丙烯二醇，所述扩链剂为乙二醇，所述抗氧化剂为抗氧剂1010，所述UV稳定剂为苯并三唑类稳定剂UV-326，所述催化剂为辛酸亚锡，所述阻聚剂对苯醌，所述乳化剂为聚氧乙烯醚，所述匀泡剂为聚硅烷一氧化烯烃嵌段共聚物硅油。
本实施例中，所述NDI基闭孔微孔弹性体的生产方法为一步法，具体步骤如下：
1)制备NDI液：在氮气保护下，将片状NDI连续加入脱水后的二元醇中，控制釜温在125℃下搅拌，获得NDI液体；所述脱水后的二元醇，其水分含量在0.02％；所述NDI和二元醇之间的摩尔比为3:1。
2)分装入釜：将步骤1)中制备的NDI液体装入反应釜A中；将聚氧化丙烯二醇装于反应釜B中；将抗氧剂1010、UV-326、辛酸亚锡、对苯醌、聚氧乙烯醚和聚硅烷一氧化烯烃嵌段共聚物硅油共同装入反应釜C中，然后缓慢加入乙二醇，以备浇注挤出。所述反应釜A的釜内温度为85℃，所述反应釜B的釜内温度为90℃，所述反应釜C的釜内温度为35℃。
3)聚合反应：将步骤2)中分装在各反应釜中的物料按4:2:2的比例通过浇注机注入安装有超临界发泡设备的双螺杆挤出机中，并在双螺杆挤出机反应机箱中于80℃条件下进行聚合反应，反应1h；所述浇注机包括分别安装于反应釜A、B、C下方的高精准计量泵和质量流量计，以及用于将反应釜中三种物料注入双螺杆挤出机中的混合头，如图1所示。优选的，所述高精准计量泵为MF型三向计量泵，计量泵温度控制在25℃。
4)挤出切粒：将在双螺杆挤出机中聚合反应后的物料通入安装有超临界发泡设备的单螺杆发泡挤出机进行超临界发泡，并进入冷却水槽水中切粒，即可得到NDI基闭孔微孔弹性体。所述单螺杆挤出机的反应机箱温度设定为110℃，所述水中切粒的水温控制为10℃。本实施例中，所述超临界发泡装置由压力罐5、高压泵6、储压釜7和稳压阀8构成，其中压力罐1中储存二氧化碳，经高压泵6将二氧化碳打入储压釜7中，储压釜7恒温在40℃，经过稳压阀8调节至合适压力(7～15MPa)注入单螺杆发泡挤出机中，完成超临界发泡。
实施例2
本实施例也是一种NDI基闭孔微孔弹性体及其生产方法，本实施例中所述NDI基闭孔微孔弹性体的组分按重量份计包括：NDI液体10份；聚醚多元醇20份；扩链剂1.5份；抗氧化剂5份；UV稳定剂3份；催化剂2份；阻聚剂2份；乳化剂8份；匀泡剂2份。所述聚醚多元醇为聚四氢呋喃二醇或聚酯多元醇与聚碳酸酯多醇的混合物，所述扩链剂为1,4-丁二醇和甘油的混合物，所述抗氧化剂为抗氧剂CA，所述UV稳定剂为苯并三唑类稳定剂UV-770和UV-622的混合物，所述催化剂为二月桂酸二丁基锡与钛酸异丙酯混合物，所述阻聚剂为2，5-二叔丁基对苯二酚；所述乳化剂为N-十二烷基二甲胺；所述匀泡剂为聚硅烷一氧化烯烃嵌段共聚物硅油。
本实施例中，所述NDI基闭孔微孔弹性体一步法生产方法与实施例1中的方法一致，其不同之处在于：
步骤1)中制备NDI液时：与片状NDI共混的二元醇水分含量为0.03％；中，釜温控制为126℃，且所述NDI和二元醇之间的摩尔比为4.5:1。
步骤2)分装入釜：装NDI液体的反应釜A的釜内温度为90℃；装聚醚多元醇的混合物反应釜B的釜内温度为110℃，所述聚醚多元醇为聚酯多元醇与聚碳酸酯多醇混合物使，二者先混合再加入应釜B；装扩链剂和添加剂的反应釜C釜内温度控制为60℃，先将添加剂装入反应釜C中，然后缓慢加入乙二醇，以备浇注挤出。
步骤3)中聚合反应：各反应釜中的物料按4.5:2:1.5的比例注入双螺杆反应挤出机中，计量泵温度控制在25℃，双螺杆反应挤出机反应机箱2中聚合反应的温度为160℃，反应时间0.6h。
步骤4)挤出切粒：单螺杆发泡挤出机反应机箱3中发泡反应的温度为150℃，反应时间0.5小时，储压釜7恒温在45℃，水中切粒的水温控制为8℃。
实施例3
本实施例同样是一种NDI基闭孔微孔弹性体及其生产方法，本实施例中所述NDI基闭孔微孔弹性体的组分按重量份计包括：NDI液体15份；聚醚多元醇30份；扩链剂3份；抗氧化剂10份；UV稳定剂5份；催化剂3份；阻聚剂5份；乳化剂15；匀泡剂5份。所述聚醚多元醇为接枝型聚醚多元醇或杂环改性聚醚多元醇，所述扩链剂为新戊二醇与山梨醇的混合物，所述抗氧化剂为抗氧剂DNP，所述UV稳定剂为苯并三唑类稳定剂双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯，所述催化剂为柠檬酸钛，所述阻聚剂为2-叔丁基对苯二酚；所述乳化剂为十二烷基苯磺酸钠；所述匀泡剂为聚硅烷一氧化烯烃嵌段共聚物硅油。
本实施例中，所述NDI基闭孔微孔弹性体一步法生产方法也与实施例1中的方法一致，其不同之处在于：
步骤1)中制备NDI液时：与片状NDI共混的二元醇水分含量为0.01％；中，釜温控制为128℃，且所述NDI和二元醇之间的摩尔比为5.5:1。
步骤2)分装入釜：装NDI液体的反应釜A的釜内温度为95℃；装聚醚多元醇的混合物反应釜B的釜内温度为100℃；装扩链剂和添加剂的反应釜C釜内温度控制为70℃，先将添加剂装入反应釜C中，然后缓慢加入扩链剂新戊二醇与山梨醇先混合物，以备浇注挤出。
步骤3)中聚合反应：各反应釜中的物料按3:2:1的比例注入双螺杆反应挤出机中，计量泵温度控制在85℃，双螺杆反应挤出机反应机箱2中聚合反应的温度为260℃，反应时间为1.2h。
步骤4)挤出切粒：单螺杆发泡挤出机反应机箱3中发泡反应的温度为280℃，反应时间为1h，所述水中切粒的水温控制为12℃。储压釜7恒温在40℃，
实施例4效果例
在干燥器中将1～3生产的NDI基闭孔微孔弹性体颗粒在85℃下干燥1.5小时，消除其粘附的水分。然后分别在Mannesmann D60-182注塑机上生产测试样条S1、S2、S3，同时以市场购得的同类聚酯弹性体制成测试样条D作为对比。生产测试样条均采用以下的温度分布：1区：185℃，2区：201℃，3区：205℃，4区：210℃。熔体温度为216℃，并且将各测试样条在112℃下调理18h，然后冲压出条进行力学试验。其测试结果如表1所示。
表1.各测试样条力学试验测试结果
项目 样条D 样条S1 样条S2 样条S3
拉伸应力100％(MPa) 9.2 15.3 15.8 17.7
拉伸应力300％(MPa) 18.3 24.6 25.2 30.4
屈服力(MPa) 42 48 50 52
断裂伸长率(％) 520 470 450 470
撕裂(graves)(kN/m) 100 105 107 108
冲击回弹性(％) 48 56 55 58
磨耗(DIN)(mm3) 30 18 14 15
密度(g/mm3) 1.16 1.12 1.12 1.13
由上表可见，本发明方法生产的NDI基闭孔微孔弹性体，相比于市场同类聚氨酯弹性体产品，弹性体的密度差别不大，由于1,5-萘二异氰酸酯(NDI)具有更高的熔点，并且通过超临界发泡得到闭孔体系，其拉伸应力得到大幅提高(约提高60～90％)，冲击回弹性提高15～20％，材料强度的提高导致撕裂强度提高10％左右，磨耗也得到大大降低，因此本发明经一步法所得弹性体材料性能优异，具有更高的抗冲击性和强度。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的。此外，应当理解，虽然本说明书按照实施方式加以描述，但并非只包含一个的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (10)

1.一种NDI基闭孔微孔弹性体，其特征在于，其组分按重量份计包括：
NDI液体7.5～15份，
多元醇15～30份，
扩链剂0.2～3份，
添加剂1～43份；
其中，所述NDI液体为片状NDI熔融后加入脱水的二元醇制得；所述多元醇为聚醚多元醇；所述扩链剂为小分子二醇；所述添加剂按重量份计包括：抗氧化剂0.2～10份；UV稳定剂0.2～5份；催化剂0.1～3份；阻聚剂0.1～5份；乳化剂0.2～15份；匀泡剂0.2～5份。
2.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述脱水后的二元醇，其水分含量在0.01～0.03%；所述NDI和二元醇之间的摩尔比为3～5.5:1。
3.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述聚醚多元醇为聚氧化丙烯二醇、聚四氢呋喃二醇、四氢呋喃-氧化丙烯共聚二醇、接枝型聚醚多元醇、聚四氢呋喃多元醇、杂环改性聚醚多元醇中的一种或几种组成。
4.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述扩链剂小分子二醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、2,3-丁二醇、1,5-戊二醇、甘油、二甘醇、三甘醇、新戊二醇、山梨醇中的一种或几种组成。
5.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述抗氧化剂为抗氧剂1010、抗氧剂1076、抗氧剂CA、抗氧剂164、抗氧剂DNP中的一种或几种组成；所述UV稳定剂为苯并三唑类稳定剂UV-326、UV-328、UV-770、UV-622以及双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯中的一种或几种组成。
6.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述催化剂为辛酸亚锡、二月桂酸二丁基锡、钛酸异丙酯、柠檬酸钛、二丁基羟基氧化锡、N,N-二甲基环己胺、三乙胺、N-乙基吗啉、甲基吗啉、N,N’-二乙基哌嗪、三乙醇胺、二甲基乙醇胺、吡啶、N,N’-二甲基吡啶中的一种或几种组成。
7.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述阻聚剂为对苯二酚、对苯醌、甲基氢醌、对羟基苯甲醚、2-叔丁基对苯二酚、2，5-二叔丁基对苯二酚中的一种或几种组成；所述乳化剂为脂肪酸皂、烷基硫酸盐、烷基苯磺酸盐、磷酸盐、N-十二烷基二甲胺及其他胺衍生物、季铵盐、聚氧乙烯醚、聚氧丙烯醚、环氧乙烷和环氧丙烷嵌段共聚物、多元醇脂肪酸酯、聚乙烯醇中的一种或几种组成。
8.根据权利要求1所述的NDI基闭孔微孔弹性体，其特征在于：所述匀泡剂为聚硅烷一氧化烯烃嵌段共聚物硅油。
9.一种NDI基闭孔微孔弹性体生产方法，其特征在于，该方法为一步法生产权利要求1～8任一项所述的NDI基闭孔微孔弹性体，具体包括如下步骤：
1）制备NDI液：在氮气保护下，将片状NDI加入反应器中，加热至融化，在搅拌状态下，在氮气保护下升温，连续加入脱水后的二元醇，搅拌并控制釜温在100℃至128℃，获得NDI液体；
2）分装入釜：将步骤1）中制备的NDI液体装入反应釜A中；将多元醇装于反应釜B中；先将抗氧剂、UV稳定剂、阻聚剂、乳化剂及匀泡剂等添加剂装入反应釜C中，再缓慢将小分子扩链剂装入反应釜C中，同时用扩链剂进行冲洗，避免粉末状添加剂及少量添加剂粘在釜口，以备浇注挤出；
3）聚合反应：将步骤2）中分装在反应釜A、B、C中的物料通过浇注机按预定的比例2～6:1～4:1～3注入双螺杆反应挤出机中，并在双螺杆反应挤出机中进行聚合反应，反应时间为0.2～4h；
4）发泡挤出：在双螺杆挤出机中聚合反应后的物料再经安装有超临界发泡设备的单螺杆发泡挤出机进行超临界发泡，并于水中挤出切粒，即可得到NDI基闭孔微孔弹性体。
10.根据权利要求9所述的NDI基闭孔微孔弹性体生产方法，其特征在于：
步骤2）中，所述反应釜A的釜内温度为85～95℃，所述反应釜B的釜内温度为85～110℃，所述反应釜C的釜内温度为35～70℃；
步骤3）中，所述浇注机包括分别安装于反应釜A、B、C下方的高精准计量泵和质量流量计，以用于将反应釜中三种物料注入双螺杆挤出机中的混合头；
步骤4）中，所述双螺杆挤反应出机和单螺杆发泡挤出机的工艺温度段均设定为80～240℃，所述水中切粒的水温控制为8～20℃。
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1354000A (en) * 1970-09-08 1974-05-22 Basf Ag Production of profiled articles of expanded plastics material
JP2006315261A (ja) * 2005-05-12 2006-11-24 Japan Steel Works Ltd:The 複合スクリュ混練押出機および押出発泡成形方法
CN101538387A (zh) * 2008-03-17 2009-09-23 中国科学院宁波材料技术与工程研究所 聚丙烯发泡材料及其生产方法
CN102432818A (zh) * 2011-11-18 2012-05-02 上海珀理玫化学科技有限公司 1,5-萘二异氰酸酯基聚氨酯微孔弹性体的制备方法
CN105623098A (zh) * 2016-03-15 2016-06-01 广州市香港科大霍英东研究院 一种长纤维增强聚丙烯微孔发泡材料的制备方法
CN205556527U (zh) * 2015-12-27 2016-09-07 南京新月材料科技有限公司 一种连续法制备微泡聚合物珠粒系统
CN106632978A (zh) * 2016-12-22 2017-05-10 山东奥邦化学科技股份有限公司 基于1,5‑萘‑二异氰酸酯的热塑性聚氨酯一步法连续制备方法
CN109762313A (zh) * 2018-12-29 2019-05-17 恒天纤维集团有限公司 一种高倍率聚乳酸发泡片材的制备方法
CN110466169A (zh) * 2019-08-16 2019-11-19 莱州市国梁包装制品股份有限公司 一种一步法二氧化碳发泡聚乳酸装置及工艺

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1354000A (en) * 1970-09-08 1974-05-22 Basf Ag Production of profiled articles of expanded plastics material
JP2006315261A (ja) * 2005-05-12 2006-11-24 Japan Steel Works Ltd:The 複合スクリュ混練押出機および押出発泡成形方法
CN101538387A (zh) * 2008-03-17 2009-09-23 中国科学院宁波材料技术与工程研究所 聚丙烯发泡材料及其生产方法
CN102432818A (zh) * 2011-11-18 2012-05-02 上海珀理玫化学科技有限公司 1,5-萘二异氰酸酯基聚氨酯微孔弹性体的制备方法
CN205556527U (zh) * 2015-12-27 2016-09-07 南京新月材料科技有限公司 一种连续法制备微泡聚合物珠粒系统
CN105623098A (zh) * 2016-03-15 2016-06-01 广州市香港科大霍英东研究院 一种长纤维增强聚丙烯微孔发泡材料的制备方法
CN106632978A (zh) * 2016-12-22 2017-05-10 山东奥邦化学科技股份有限公司 基于1,5‑萘‑二异氰酸酯的热塑性聚氨酯一步法连续制备方法
CN109762313A (zh) * 2018-12-29 2019-05-17 恒天纤维集团有限公司 一种高倍率聚乳酸发泡片材的制备方法
CN110466169A (zh) * 2019-08-16 2019-11-19 莱州市国梁包装制品股份有限公司 一种一步法二氧化碳发泡聚乳酸装置及工艺

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
谷松涛，等: ""微孔注塑发泡聚氨酯成型工艺及微观结构研究"", 《橡塑技术与装备》 *
陈士宏，等: ""可进行超临界CO2辅助挤出的双阶挤出机组的设计"", 《塑料》 *

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