CN1113732C - 用异氰酸酯和多元醇配方制造反应混合物的方法 - Google Patents

用异氰酸酯和多元醇配方制造反应混合物的方法 Download PDF

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CN1113732C
CN1113732C CN98802573A CN98802573A CN1113732C CN 1113732 C CN1113732 C CN 1113732C CN 98802573 A CN98802573 A CN 98802573A CN 98802573 A CN98802573 A CN 98802573A CN 1113732 C CN1113732 C CN 1113732C
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K·舒尔特
K·克里普尔
W·弗里德里希斯
U·屈策尔
H·－U·维贝尔
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Abstract

本发明涉及一种无需搅拌器的、用异氰酸酯和高粘度多元醇配方制备反应混合物的混合头和方法，其中该两种组分被送入混合区并在其中相互混合，粘度至少为3000毫泊的高粘度组分是在低压下被送入混合区，并且至少有两股低粘度组分(异氰酸酯和还可以是低粘度的多元醇)在高压下被注入高粘度多元醇配方中。

Description

用异氰酸酯和多元醇配方 制造反应混合物的方法
本发明涉及一种无需搅拌器的、用异氰酸酯和多元醇配方制造形成聚氨酯的反应混合物的方法，其中该两种组分系被送入一个混合区并在其中相互混合，同时，其中至少两种组分之一具有高于3000毫泊、优选高于5000毫泊的粘度。
新的应用领域要求制备高粘度的多元醇配方。使用高粘度的组分可提供出很多优点。一般说来，聚醚多元醇、特别是聚酯多元醇的粘度会随着其官能度的增加而增高。为了获取高度的交联度，从而取得更好的机械特性，需要使用较大数量和组分的高官能度的多元醇。
异氰酸酯组分作为一种高粘度组分，也被以预聚物的形态得到应用。
在不带搅拌器的自行净化式混合室内，要想在组分的粘度增高到某一程度下得到满意的混合，目下还有很多困难。“Kunststoff-Handbuch”(塑料手册)卷7第175页最后一节“聚氨酯”(慕尼黑的Carl Hanser Verlag出版社1993年出版)中提到：“虽然以前的可混合粘度极限为1500毫泊，但目前按注射法已能操控超过2000毫泊的粘度”。但在事实上，按照逆流高压注射法，现仍不能加工粘度高于3000毫泊的反应组分。所得的泡沫材料上带有条痕，而且其物理参数会很快下降。因此迄今仍须使用带有搅拌器的混合头。
大家也知道(“Kunststoff-Handbuch”p.125)，提高制备温度可把粘度降至2000至3000毫泊。但是，组分温度的升高会导致系统的反应性加强，以至于使发泡过程失控。
下面的方案涉及多元醇组分用作高粘度组分的，这是用作例子。该方案也适用于以异氰酸酯用作高粘度组分。
本发明的目的是提供出一种不用搅拌器制造导言中所说的那种类型的反应混合物的方法和混合头，并且这种反应形成高质量的产品。
这一目的用下述方法达到了：粘度至少为3000毫泊的多元醇配方在低压下被送入混合区，以及至少两股低粘度组分(异氰酸酯，还可是低粘度多元醇)物流在高压下被注入到高粘度多元醇配方的液流中去。
令人惊喜的是，这一方法使高粘度组分得到了很好的混合。本发明利用下述事实：将高粘度组分被分成两股或更多股支流，虽然其能量发生转移，但总体的能量却增加了。
多元醇配方物流的横截面面积优选比多股异氰酸酯的物流的横截面面积之总和大10到100倍。
还可优选异氰酸酯的加工压力为50至300巴，多元醇配方的压力小于20巴，这样可得到良好的效果。最好压力在70巴和250巴之间，而压力在100巴和200巴之间是特别优选的。
异氰酸酯组分支流的注入优选采用横向流方式。
在此应注意的是，当与横向流输入偏离不太大时仍可取得较好的结果。
注入射流不直接对准混合区的中心轴也是有利的，因为至少近似正切的输入方向由于可造成额外的湍流会使混合度良好。通常，输入点都是均匀地分布在混合区的周边上，而且还可以是只是低粘度的组分从端面输入。
按照经典逆流注射原理，对组分粘度＜2000毫泊的情况来说，可使用下述能量分布公式：
          (mPoly×pPoly)+(mIso×pIso)＝E
若多元醇(粘度4000毫泊)输出量为4kg/min，异氰酸(粘度50毫泊)输出量为6kg/min，则总的输出量为在注射压力100巴下10kg/min，则有下述能量分布：
              (4×100)+(6×100)
多元醇能量400+异氰酸酯能量600＝ 1000
相反，在新方法下，多元醇系在10巴下输入，异氰酸酯系在180巴下分两股以横向流方式相互对向注入：
(mPoly×pPoly)+[(mIso/2×pIso)+(mIso/2×pIso)]＝E
         4×10+(6/2×180)+(6/2×180)
多元醇能量40+异氰酸酯能量1080＝ 1120
按照新方法的另一实施方案，全部物流都在同一平面上引入混合区。
也可以只把多元醇配方的粘度较高的组分在低压下输送，而另外在高压下把低粘度组分和异氰酸酯注入高粘度组分的物流中。
在此可以考虑下述实施例：要处理4kg/min的多元醇，其中2/3为高粘度，1/3为低粘度。高粘度构分在10巴压力下被垂直输入混合区。低粘度构分和6kg/min的异氰酸酯在150巴下从三股各相距120°的支流横向输入。相关的能量计算如下，其中“poly H”为高粘度多元醇，而“poly N”为低粘度多元醇：[(1/3mPolyH×pPoly)+(2/3mPolyN×pPoly)+[(mIso/2×pIso)+(mIso/2×pIso)]＝E
      (1.33×10)+(2.66×150)+(6/2×150)(6/2×150)
多元醇能量413+异氰酸酯能量900＝ 1313
当多元醇配方分解为高粘度组分和低粘度组分时，高粘度构分也可垂直地被引入混合室，同时把低粘度构分以一股物流输入，而把全部的异氰酸酯以另一股物流从相对方向输入：
[(1/3mPolyH×pPoly)+(2/3mPolyN×pPoly)+[(mIso×pIso)＝E
          (1.33×10)+(2.66×150)+(6×150)
多元醇能量413+异氰酸酯能量900＝ 1313
当然，异氰酸酯和/或低粘度多元醇也都可以以多股支流被注入。
一个不带搅拌器的，包括有混合室和多个组分注入孔的混合头，是最适合作为本新方法的实施。
本发明的新颖之处在于：一个入口孔用于高粘度多元醇配方；至少两个入口孔用于低粘度组分(异氰酸酯和还可以是低粘度多元醇)；其中高粘度多元醇配方的入口孔的横截面面积比低粘度组分入口孔的横截面面积的总和要大10到100倍。
这样的混合头是自行净化式的，并且在原则上(视其控制可能性而定)是可以连续作业的，例如对下游的皮带输送装置来说，或者对充注压模工具或其它要充注的空穴来说，也可以是分批继续作业的。
本发明可允许用粘度超过3000毫泊的多元醇组分来制造反应混合物，特别是可用粘度在10,000和50,000毫泊之间的多元醇组分。
多元醇组分的粘度极限受制于所需的输送装置。当粘度高达100,000毫泊时，齿轮泵、螺杆泵或者螺旋输送机都将是适用的输送工具。
下面将参照附图对本发明进行详细论述，附图有：
图1a和1b示出本发明的一个混合头，它的出口是宽缝式喷嘴式。
图2示出本发明的一个混合头，它的出口是匙形或舌形喷嘴式。
图3a和3b示出本发明的一个混合头，它是分批作业用的。
图4a、4b和4c示出本发明的混合头的另一实施方案，它是分批作业用的。
图1a所示本发明的混合头1包括有高粘度多元醇送料管11和异氰酸酯的入口孔12。入口孔12上具有可顶着加有预应力的弹簧移动的密封锥15，当异氰酸酯在所需压力下供料(箭头14)时，该密封锥即开启。混合区13并未经过几何上精确界定，而是简单的直通管道，异氰酸酯注入喷嘴12注入其中。混合区13中并没有任何种类的产生湍流的构件。异氰酸酯注入喷嘴优选不对准混合区13的轴线方向，但围绕与轴线垂直的平面布置，使得在异氰酸酯注入时，高粘度多元醇液流在混合区13内经受一个旋转运动，以有助于混合。混合头1的出口2是宽缝式喷嘴。图1b示出与图1a图面垂直的混合头出口2的断面图。
图2示出与图1a相同的混合头1，但它的出口2是舌形喷嘴式的。
图3a的混合头1适用于泡沫模制件间隙性的分批生产操作。混合头上有密封活塞20，它可在轴向(箭头21)用液力推动。为充注模型，将密封活塞20向回(如箭头21所示)运动，以使高粘度多元醇的入口11和异氰酸酯的注射喷嘴12打开，以使其进入混合区13。混合物从混合区13进入出口管2，通过出口管后，混合物即被引导进入模型。当模型被注满后，密封活塞20就被回到所示位置，通向混合区13的入口11和12就被关闭。与此同时，入口11和12就通过密封活塞20上的沟槽28和29与再循环管道24和25接通，高粘度多元醇和异氰酸酯就分别通过再循环管道24、25被送回它们各自的贮存罐中。就象通常的聚氨酯生产工艺那样，在两批之间的间隙时间内，都保持着再循环物流。混合头上还有一个液力驱动的净化活塞26，在一批的终了，每当密封活塞20运动到密封位置时，净化活塞26就把残存在出口管2中的混合物排出出口管2。图3b示出图3a的A-A截面。在该示例图中，设有三个异氰酸酯的注射喷嘴。混合头的结构变动是可能的，本领域的技术人员根据Becker/Braun的文章(载“Kunststoff-Handbuch”，卷7，聚氨酯，p.177-182，1993)可很容易地推演出来。对本发明来说，主要的是输送高粘度多元醇的管道截面，比之异氰酸酯入口孔要大很多，并具有相应的大截面的再循环管道，这样，高粘度多元醇的输运就可在基本上不加压的状态下进行。
图4a示出本发明用于间歇式分批作业的混合头的另一个实施方案，其中高粘度多元醇的偏转角度被保持得很小。与图3a中相同的部件用相同的符号表示。图4b示出图4a的B-B截面。图4c重显图4a的图形，但其中密封活塞20已移动到密封位置。在引导进入混合区13时，通过送料管11送来的高粘度多元醇液只偏转了20～35°的弯。异氰酸酯的引入(四个入口孔12a和12b被两两相对分布)是采取与多元醇液流相横向的方式。在此，异氰酸酯送料管14a和14b被成对偏置成能使多元醇物流在引入平面上作相对方向的旋转。在一批终了时，异氰酸酯的再循环系通过密封活塞20上的沟槽29进行。高粘度多元醇的再循环是借助于贯穿密封活塞20的孔28进行的，该孔在密封活塞内构成了通向再循环管道24的连结通道。

Claims (5)

1.一种无需搅拌器的、用异氰酸酯和多元醇配方制造反应混合物的方法，其中所述异氰酸酯和多元醇配方被送入混合区并在其中相互混合，其特征在于，粘度至少为3000毫泊的多元醇配方是在低压下被送入混合区，并且至少有两股低粘度异氰酸酯物流在高压下被注入高粘度的多元醇配方的物流中。
2.权利要求1的方法，其特征在于，高粘度多元醇配方物流的横截面面积要比高压物流横截面面积之总和大10到100倍。
3.权利要求1或2的方法，其特征在于，低粘度异氰酸酯物流是在50～250巴的压力下被注入到压力低于20巴的高粘度多元醇配方物流中。
4.权利要求1、2或3的方法，其特征在于，至少有两股低粘度异氰酸酯是以横向流的方式被注入的。
5.权利要求1、2或3的方法，其特征在于，所有物流都是在混合区的同一平面上被引入。
CN98802573A 1997-02-17 1998-02-04 用异氰酸酯和多元醇配方制造反应混合物的方法 Expired - Fee Related CN1113732C (zh)

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DE19706030A DE19706030C2 (de) 1997-02-17 1997-02-17 Verfahren und Vorrichtung zur Herstellung füllstoffhaltiger Polyurethane
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DE19743187A DE19743187A1 (de) 1997-09-30 1997-09-30 Verfahren und Mischkopf zum Herstellen eines Reaktionsgemisches aus einem Isocyanat und einer höherviskosen Polyolformulierung

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