CN108350206B - 用于生产交联发泡pvc泡沫体的聚合物混合物的配方和生产该泡沫体的方法 - Google Patents

用于生产交联发泡pvc泡沫体的聚合物混合物的配方和生产该泡沫体的方法 Download PDF

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CN108350206B
CN108350206B CN201680066934.2A CN201680066934A CN108350206B CN 108350206 B CN108350206 B CN 108350206B CN 201680066934 A CN201680066934 A CN 201680066934A CN 108350206 B CN108350206 B CN 108350206B
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R·布雷森
F·纳特
M·雷浓
U·托格森
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Abstract

一种用于生产交联发泡PVC泡沫体的聚合物混合物的配方，该配方为包括PVC、异氰酸酯、酸酐和一种或多种成核剂的类型，其中所述成核剂由孔隙度为1‑100nm，优选2‑50nm的成核材料组成。相对于生产交联PVC泡沫体的已知配方，根据本发明的配方即使不使用偶氮化合物也提供了获得所需的稳定性、成核度和发泡度的优点。

Description

用于生产交联发泡PVC泡沫体的聚合物混合物的配方和生产 该泡沫体的方法
技术领域
本发明涉及用于生产交联发泡PVC泡沫体的聚合物混合物的配方。同样的发明也延及用于生产所述交联发泡PVC泡沫体的方法。
本发明的领域涉及用于生产诸如PVC面板等的发泡材料的交联发泡PVC泡沫体，其被用作复合材料领域中的核心。
背景技术
交联发泡PVC泡沫体在传统上由包括以下的混合物起始制备：PVC、具有交联功能的异氰酸酯、预定用于在发泡期间和交联阶段与水和异氰酸酯反应以形成酰胺的酸酐、基于用于形成气体的偶氮化合物(偶氮二异丁腈AZDN)的发泡剂、以及也基于偶氮化合物(偶氮二甲酰胺ADC)的成核剂和稳定剂。
具体而言，在交联PVC泡沫体的生产领域中，传统的ADC发挥成核功能，提供具有小闭孔(直径为0.4-0.6mm)的发泡材料，其用于赋予发泡产品的均匀结构，并具有良好的机械性能。ADC还具有稳定化功能，在压机中在所述混合物的模制过程中抑制PVC的分解反应。
然而，上述传统混合物具有使用偶氮化合物例如ADC和AZDN的缺点，因为它们是危险的，所以这是不希望的。ADC事实上在REACH的黑名单中，因为其被分类为高度关注(VHC)物质。而且，AZDN是一种粉末形式的物质，其被分类为易爆物质并且易于释放有毒物质。
US 2007/200266 A1涉及由含有PVC、异氰酸酯或聚异氰酸酯、有机酸酐和化学发泡剂的起始混合物生产交联PVC泡沫体的方法。
WO2014/106867 A1公开了一种生产硬质发泡物体的方法，其中在制造所述物体时使用有机偶氮化合物。
发明内容
本发明的主要目的是提供一种用于生产发泡PVC泡沫体的聚合物混合物的配方，与传统配方不同，即使在不存在偶氮衍生物的情况下也能获得所需的稳定性、成核度和发泡度。
本发明的另一个目的是提供一种适于使用上述聚合物混合物的配方生产发泡PVC泡沫体的方法。
这些和其它目的是分别通过聚合物混合物的配方、交联发泡PVC泡沫体和权利要求1、8和10的方法来实现的。本发明的优选实施方式在其余权利要求中被提出。
相对于用于生产交联PVC泡沫体的已知配方，根据本发明的配方即使在不存在偶氮衍生物的情况下也提供了获得所需的稳定性、成核度和发泡度的优点。
此外，通过在本发明的配方中使用在室温下的酸酐液体，获得的优点在于，在压机的加热阶段，不必提供用于熔化传统固态酸酐的热量。通过这种方式，液体酸酐和异氰酸酯发生反应，同时形成用于PVC泡沫体的发泡的所需量的CO2，而无需从用于熔化起始PVC的反应环境中移除热量。
酸酐和异氰酸酯之间的上述反应有利地允许获得碱性酰亚胺结构，随后完成反应，导致形成在PVC链周围的交联结构。通过这种方式，最终结构在高酰亚胺结构的存在下得以生成，被称为“互穿网络”(IPN)，适于赋予PVC泡沫体比传统性能更高的热性能。
还令人惊讶地发现，通过单独或相互组合使用根据本发明的量的沸石和碳酸氢钠(小于3重量％)，通过反应环境中的热效应形成的、来自PVC并且负责降解相同聚合物的HCl通过这些物质被多价螯合和中和，由此产生热稳定并且没有降解缺陷的发泡产品。
附图说明
根据以下对本发明的配方和方法的一些优选实施方式的描述，以纯粹示例性和非限制性目的而示出的这些和其它目的、优点和特征变得显而易见。
在这些中：
-图1至图4通过光学显微镜分别示出了根据已知技术和根据本发明的三个实施例的交联发泡PVC泡沫体的蜂窝状结构；
-图5示出了前面附图的泡沫体的热导率值的趋向；
-图6示出了图1至图4的泡沫体的树脂吸附值的趋向；
-图7示出了在图1至图4的泡沫体中在动态机械分析(DMA)中作为温度的函数的储存模量的趋向的曲线图；
-图8和图9分别示出了本发明的沸石和碳酸钠的显微镜放大的多孔结构；
-图10和图11分别示意性地示出了具有无孔表面和多孔表面的成核剂的成核实例。
具体实施方式
本发明的用于生产交联发泡PVC泡沫体的聚合物混合物目的是提供不含偶氮化合物的发泡材料，其特征在于：存在直径小于或等于0.6mm的闭孔，即足够小以赋予发泡产品的均匀结构，具有低热导率、降低的树脂吸附和更高的玻璃化转变温度。
为了使气体能够产生稳定的核心，能够形成具有小直径的闭孔，必须超过一定的能量阈值，由于这个原因，其必须尽可能低。该能量阈值具体取决于所述核心的临界半径，其进而取决于气泡和聚合物块之间的界面张力。在本发明的聚合物混合物体系中，由于存在成核剂而变得不均匀，超过的自由能AGet由下式表示：
Figure BDA0001662260430000033
其中：
△Get＝非均匀自由能，即在成核剂存在下
△Gom＝均匀自由能，即在成核剂不存在下
Figure BDA0001662260430000031
其中
Figure BDA0001662260430000032
是润湿角。
此外，当
Figure BDA0001662260430000041
时，为了获得低的△Get值，
Figure BDA0001662260430000042
必须接近零，即角度
Figure BDA0001662260430000043
必须高。为此，根据本发明，将具有多孔表面的材料用作生产交联发泡PVC泡沫体的成核剂。
在这种情况下，事实上并且如图10和图11中更好地示出的，在气泡1表面处的切线t1与多孔成核位点3的相应壁2之间形成的角度
Figure BDA0001662260430000044
大于在气泡4表面处的切线t2与无孔成核位点6的相应壁5之间形成的角度
Figure BDA0001662260430000045
适于本发明目的的成核剂是：例如，图8的沸石，孔径范围为2-50nm；以及图9的碳酸氢钠，孔径为约100nm。用于本发明目的的成核剂的孔隙率为1-100nm，更优选2-50nm。此外，根据本发明，在交联PVC泡沫体的形成过程的热压制阶段，有利地获得所需的碳酸氢钠孔隙度。
根据本发明，CO2气相通过异氰酸酯和酸酐之间的以下反应给出：
Figure BDA0001662260430000046
其中，
R1＝C6H12；C9H18；C12H24；C10H18；C13H10；C6H4；C7H5；C10H6；C16H11；C7H6
R2＝C6H6；C7H6；C6H8；C6H10；C14H26；C3H4；C3H6；C5H10；C10H18；C4H8；C7H10；C7H8；C4H4O2；C6H12；C7H12。
根据本发明的优选变型，CO2气相通过异氰酸酯和酸酐之间的以下反应给出：
Figure BDA0001662260430000047
其中：
R1＝C6H4，C7H6
R2＝C6H12；C9H18；C12H24；C10H18；C13H10；C6H4；C7H5；C10H6；C16H11；C7H6；
R3＝C6H6；C7H6；C6H8；C6H10；C14H26；C3H4；C3H6；C5H10；C10H18；C4H8；C7H10；C7H8；C4H4O2；C6H12；C7H12。
可以观察到，在这些反应中，不再使用具有用于产生N2的发泡剂功能的传统的偶氮化合物。
适于本发明的沸石是硅铝酸盐类型的：
xMO·ySiO2·zAl2O3
其中：
x＝0-0.5
y＝0-0.5
z＝0.5-1
M＝Na，K，Ca，NH4，Fe。
此外，尽管沸石仅用作稳定剂和成核剂，但本发明的碳酸氢钠还增加了有助于孔发泡的作用，通过与来自PVC的盐酸反应而产生CO2：
NaHCO3+HCl→NaCl+CO2+H2O
为了不从PVC熔化过程中除去热量，碳酸氢盐的使用量有利且优选地低于3重量％。此外，也为了同样的目的，所用的酸酐是在室温下为液态的那些，特别是具有下式的酸酐：
Figure BDA0001662260430000051
其中，
R3＝C6H6；C7H6；C6H8；C6H10；C14H26；C3H4；C3H6；C5H10；C10H18；C4H8；C7H10；C7H8；C4H4O2；C6H12；C7H12。
通过这种方式，不再需要具有用于熔化传统固态酸酐的热量。另外，使用本发明的液态酸酐将酰亚胺结构引入到反应环境中，这对于形成具有更好热性能的IPN-互穿网络是必需的。
以重量计，以下配方含有：
PVC 30-60％
异氰酸酯 20-60％
液态酸酐 3-40％
所述配方还包括：
沸石 少于3％
碳酸氢钠 少于3％
这对于本发明是优选的。
在表中，比较了以下配方：
A：已知技术的配方，其中使用了偶氮衍生物，具有成核和稳定功能(ADC)，并且还具有发泡剂(AZDN)的功能(图1)；
B：本发明的配方，仅具有碳酸氢钠(图2)；
C：本发明的配方，具有碳酸氢钠和沸石(图3)；
D：本发明的配方，仅具有沸石(图4)。
对使用这些配方获得的泡沫体进行测试：关于热导率，其必然尽可能低，树脂吸附量必然具有最小值，玻璃化转变温度优选为高。下表列出了这些试验的结果，其中混合物中化合物的量以重量百分比表示：
Figure BDA0001662260430000061
Figure BDA0001662260430000071
从该表可以观察到，交联发泡PVC泡沫体具有直径小于或等于0.6mm的闭孔，即足够小以赋予发泡产品的均匀结构，其热导率低于0.030W/m°K，树脂吸附低于300g/m2，玻璃化转变温度高于100℃。
前面表的交联发泡PVC泡沫体的表面具有图1至图4所示的外观，其中可以观察到本发明泡沫体中孔直径的减小。使用包括大量沸石的图4的配方D获得了最佳结果。
在本发明的方法中，通过首先向混合器中引入液体组分(异氰酸酯和酸酐)，然后是多孔稳定剂和成核剂的粉末，最后是PVC，来制备聚合物混合物。在真空下进行混合以汽提空气，将如此获得的混合物倒入模具中，将模具在压机中的压力(80-180巴)下加热至160-180℃的温度，持续达用于熔化PVC以及异氰酸酯-酸酐交联反应和气相形成所需的时间。在该热压缩期间，可能存在的碳酸氢钠获得本发明的多孔结构。
然后将由热压制(其中已经部分发生异氰酸酯和酸酐之间的交联反应并且形成了酰亚胺和CO2)得到的材料在水蒸气的存在下在80-99℃和45-70℃的温度下分别进行发泡和交联过程。在此阶段，水与剩余的异氰酸酯和酸酐试剂反应，从而完成交联反应并产生额外量的CO2。因此获得本发明的交联发泡PVC泡沫体(称为“互穿网络”-IPN)，在具有相同孔直径的情况下，其在热导率、树脂吸附和玻璃化转变温度方面的性能相对于已知技术的泡沫体更高。

Claims (11)

1.一种用于生产交联发泡PVC泡沫体的聚合物混合物，所述混合物包括PVC、异氰酸酯、酸酐和一种或多种成核剂，其特征在于，所述酸酐在室温下是液体，所述成核剂包括多孔成核材料并且不含偶氮化合物，
其中，所述成核剂包括以小于3重量％的量存在于所述混合物中的多孔沸石和以小于3重量％的量存在于所述混合物中的多孔碳酸氢钠中的任意一种或两种。
2.根据权利要求1所述的混合物，其特征在于，所述成核剂的孔隙率为1-100nm。
3.根据权利要求2所述的混合物，其特征在于，所述成核剂的孔隙率为2-50nm。
4.根据权利要求2所述的混合物，其特征在于，所述多孔沸石包含以下硅铝酸盐类型：
xMO·ySiO2·zAl2O3
其中：
x＝0-0.5
y＝0-0.5
z＝0.5-1
M＝Na，K，Ca，NH4，Fe。
5.根据权利要求1所述的混合物，其特征在于，所述酸酐具有下式：
Figure FDA0002906095580000011
其中，
R3＝C6H6；C7H6；C6H8；C6H10；C14H26；C3H4；C3H6；C5H10；C10H18；C4H8；C7H10；C7H8；C4H4O2；C6H12；C7H12。
6.根据前述权利要求中的任一项所述的混合物，其特征在于，包括：
PVC 30-60％
异氰酸酯 20-60％
液态酸酐 3-40％
其中存在
沸石 少于3％
碳酸氢钠 少于3％。
7.使用根据前述权利要求中的任一项所述的混合物获得的交联发泡PVC泡沫体，其特征在于，所述交联发泡PVC泡沫体具有：直径小于或等于0.6mm的闭孔，即足够小以赋予发泡产品的均匀结构，热导率低于0.030W/m°K，树脂吸附低于300g/m2，以及玻璃化转变温度高于100℃。
8.根据权利要求7所述的泡沫体，其特征在于，所述泡沫体具有“互穿网络”-IPN结构。
9.一种用于生产根据权利要求7所述的交联发泡PVC泡沫体的方法，其特征在于，所述方法包括通过异氰酸酯和所述液体酸酐之间的以下反应给出CO2气相：
Figure FDA0002906095580000021
其中，
R1＝C6H12；C9H18；C12H24；C10H18；C13H10；C6H4；C7H5；C10H6；C16H11；C7H6
R2＝C6H6；C7H6；C6H8；C6H10；C14H26；C3H4；C3H6；C5H10；C10H18；C4H8；C7H10；C7H8；C4H4O2；C6H12；C7H12，
所述方法还包括通过由多孔成核材料制成的成核剂的存在而给出成核相，并且所述CO2气相和成核相在不存在偶氮化合物的情况下进行。
10.根据权利要求9所述的方法，其特征在于，异氰酸酯和酸酐之间的所述反应如下：
Figure FDA0002906095580000031
其中：
R1＝C6H4，C7H6；
R2＝C6H12；C9H18；C12H24；C10H18；C13H10；C6H4；C7H5；C10H6；C16H11；C7H6；
R3＝C6H6；C7H6；C6H8；C6H10；C14H26；C3H4；C3H6；C5H10；C10H18；C4H8；C7H10；C7H8；C4H4O2；C6H12；C7H12。
11.根据权利要求9和10中任一项所述的方法，其特征在于，所述方法包括：
-通过首先向混合器中引入液态的异氰酸酯和酸酐，接着引入多孔稳定剂和成核剂的粉末，最后引入PVC，来制备聚合物混合物，在真空下进行混合以汽提空气；
-将由此获得的聚合物混合物转移到模具中，将所述模具在压机中的压力下在一温度下加热持续达用于熔化PVC以及异氰酸酯-酸酐交联反应和形成所述气相所需的时间；
-在水蒸气的存在下完成交联反应。
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