CN1761719A - 包含聚酰胺、聚乙烯醇缩丁醛和矿物填料的组合物以及自其制造的制品 - Google Patents
包含聚酰胺、聚乙烯醇缩丁醛和矿物填料的组合物以及自其制造的制品 Download PDFInfo
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Abstract
公开了包含10～45wt％矿物填料的、采用聚乙烯醇缩丁醛增韧的聚酰胺组合物和共混物。
Description
本申请要求2003年3月14日提交的美国临时申请No 60/454,889的权益。
技术领域
本发明涉及聚酰胺与聚乙烯醇缩丁醛(PVB)的共混物。更具体地说，本发明涉及上述的共混物、制造这种材料的方法以及自此制造的模塑制品。
背景技术
众所周知，诸如接枝橡胶等增韧剂能够用来改善聚酰胺韧性。一般说，参见转让给杜邦公司的US 4,174,358。还已知，能够将矿物填料加入到上述聚酰胺共混物中以增加其硬挺性。参见，例如，U.S.Pat.No.5,965,655、WO 0049081、U.S.Pat.No.5,571,851，U.S.Pat.No.4,795,768、U.S.Pat.No.4,740,538、U.S.Pat.No.4,399,246和U.S.Pat.No.3,419,517。还众所周知，增塑的聚乙烯醇缩丁醛能够作为增韧剂用在，例如，尼龙-6中。一般说，参见还是转让给杜邦公司的US 5,770,654，该专利涉及适于需要良好韧性的种种应用的上述组合物，如在经受毛面处理的包装中。正如本文中所使用的，聚乙烯醇缩丁醛缩写为“PVB”。
增塑的PVB难以作为混料挤出机喂料进行处理，由于其固有的胶粘性。相似地，PVB板是一种难以加工的材料，因为其自身粘合的趋势。PVB片材能够胶粘在一起，即粘结在一起，其粘结强度达到如此程度以致于很难将各层分离。PVB这种自粘合的不可逆性在PVB制造领域中称作“粘连”。一旦PVB“粘连”，就遇到了加工困难。这种粘连倾向使并合PVB的制造工艺徒然复杂化和困难化。所以，以片材形式或以小碎片形式处理PVB的连续工艺进行起来很昂贵，并且因此是不切实际的。
另外，PVB片材与其它材料的融合体(blend)或者其小碎片与其它材料的共混物(blend)能够以与均质PVB组合物相同的方式粘连。PVB与其它聚合物的这种共混物难以以费用效益良好的方式获得。制备PVB与其它聚合物的共混物的优选方法应当利用传统失重螺杆喂料机，这种喂料机遍及工业领域。
在这个领域中的最近工作表明，PVB与聚乙烯和接枝橡胶的共混物足够地不粘，以致能够将它们喂入混料挤出机中。参见，例如WO02/12356，该专利涉及一种自PVB边角料制备粒料的方法。
本发明的目的在于提供填充矿物的PVB增韧聚酰胺组合物。
发明内容
一方面，本发明涉及一种热塑性聚酰胺组合物，包括：(a)约5～约30wt％易流动增韧剂，后者包含约20wt％～约95wt％聚乙烯醇缩丁醛；(b)互补地，95～25wt％聚酰胺，其在约320℃以下是可熔融加工的，数均分子量至少5,000；(c)占总组合物的约10～约45wt％的矿物填料；和(d)任选地，一种偶联剂。
另一方面，本发明涉及一种包括热塑性聚酰胺组合物的制品，所述组合物包括：(a)约5～约30wt％易流动增韧剂，后者包含约20wt％～约95wt％聚乙烯醇缩丁醛；(b)互补地，95～25wt％聚酰胺，其在约320℃以下是可熔融加工的，数均分子量至少5,000；(c)占总组合物的约10～约45wt％矿物填料；和(d)任选地，一种偶联剂。
具体实施方式
在一个实施方案中，本发明涉及一种包含矿物填料的增韧聚酰胺组合物。本发明的组合物包括易流动PVB组合物作为增韧剂，正如WO0212356所述，在此引入作为参考。本发明组合物包括约5wt％～约30wt％，优选约5wt％～约28wt％的，更优选约6wt％～约25wt％，和最优选约7wt％～约25wt％的易流动PVB组合物。增韧剂包括约20～约95wt％，优选约40wt％～约95wt％，更优选约60wt％～约95wt％，和最优选约75wt％～约95wt％PVB。本发明组合物和共混物的典型制备方法包括：生产易流动增韧剂，随后使所得增韧剂与尼龙、偶联剂和其它组分共混，从而生产具有提高的表面性能的增韧聚酰胺共混物。
增韧剂包括，除PVB之外，至少一种成分。此类其它成分能够是单体或聚合物材料，或其混合物。所述其它成分能选自具有活性官能团的聚合物和/或单体，或非活性聚合物和/或单体，例如聚乙烯、聚丙烯、聚氯乙烯、尼龙、其它热塑性材料，或其混合物。优选第二成分是包括诸如酐官能团的活性官能团的聚合物组合物，例如，可以Fusabond品牌商购自杜邦公司者，或者是包括羧酸官能团者。Fusabond聚合物是含有酐官能团的聚烯烃。在增韧剂中的其它成分存在量，对于增韧剂中PVB的量而言只是互补式的，使PVB与其它成分的百分总数为100wt％。
聚酰胺能够是任何无定形或结晶聚酰胺，例如，如U.S.Pat.No.5,770,654所述。优选，聚酰胺在约320℃温度以下是可熔融加工的，数均分子量至少为5,000。聚酰胺组分存在量为约25wt％～约95wt％。优选，聚酰胺组分存在量为约30wt％～约90wt％，更优选约40wt％～约90wt％，最优选约50wt％～约90wt％。
填料存在量为约10～约45wt％。适宜的矿物填料是，例如，煅烧陶土、金属碳酸盐、二氧化钛、硅灰石或滑石。抗氧剂并不需要，然而，优选包括一种。如果包括，抗氧剂存在量至少为约0.1wt％，最多为抗氧剂效果最佳的量。
任选，偶联剂包括在本发明组合物中。偶联剂能够增加聚酰胺组合物的抗张强度，缺口伊佐德和挠曲模量。偶联剂能够是硅烷化合物。优选偶联剂选自γ-氨基丙基三甲氧基硅烷，γ-氨基丙基三乙氧基硅烷，N-2-氨基丙基三烷氧基硅烷，或N-(2-氨基乙基)-3-氨基丙基甲基二烷氧基硅烷。偶联化合物的存在量为至少约0.01wt％。优选，偶联剂存在量为约0.1～约3wt％。更优选偶联剂存在量为约0.3wt％～约2.0wt％，最优选为约0.5wt％～约1.5wt％。
在另一个实施方案中，本发明涉及一种制备本发明增韧聚酰胺组合物的方法。本发明增韧剂能够采用WO 0212356所述方法得到。PVB是一种市售产品，用来赋予许多用途中的玻璃以抗裂荚性，其中包括汽车挡风屏以及家居和建筑物中的窗玻璃。PVB的制备方法是一种众所周知的在醛和醇之间在酸介质中进行的反应。所用的增塑剂也是市售化学品，例如脂族二醇与脂族羧酸的二酯，例如，三甘醇二-2-乙基己酸酯(3GO)，或四甘醇二正庚酸酯(4GT)。原始增塑PVB片材(在本文中所用术语，原始增塑PVB指的是从制造商的辊上第一手得到的PVB)能够，例如，自杜邦公司以品牌BUTACITE市购得到。PVB也能够以其它来源得到，包括自安全或建筑用玻璃制造操作中边缘修整得到的剩余PVB，从汽车或建筑边角料玻璃回收的PVB，在其它工业应用中不能用的PVB，以及其它相似的来源或这些来源的混合物。任何这些来源都能在不脱离本发明精神和范围的条件下进行满意的应用。
在优选实施方案中，本发明涉及一种下述方法，其中，增塑PVB和三种其它成分(活性聚合物如Fusabond、非活性聚合物如聚乙烯、聚丙烯、或乙烯/正丁基和抗氧剂)(1)在间歇工艺或连续工艺中混合；(2)成形为片材，(3)再熔融，(4)以熔体形式过滤，和(5)制造成粒料。
例如，混合能够在约100℃～约280℃高温下进行，优选在约150℃～约220℃下，从而提供均质熔融共混物。自混合程序得到的共混物能够通过某些设备转移到一组辊磨中以便再混合并把共混物压成片材形式。能够把片材条状料或者以连续方式或者以间歇工艺喂入挤出机，但是优选采用，例如，带式喂料机连续喂入片材。一旦片材于挤出机内，就熔融，并且熔体经过滤除去固体污染物。所得聚合物能够通过任何己知或常规方法进行造粒。例如，能使过滤了的熔体分配到有许多孔的模头中。在这种方法中，熔体在模头面处排出模头；模头面恰恰位于充水的槽中水面上方，或者恰恰浸于水表面下以便在熔体排出模头时将其快速冷却(骤冷)。能够使用水下切粒机将排出模头面的聚合物切断形成粒料。水将粒料骤冷，并将它们带到过滤筛网，使其与重力水分离。湿粒料能例如在流化床干燥器中干燥，然后进行包装。
如此得到的粒料能够通过熔体共混与适宜的聚酰胺组合物混合，如U.S.Pat.No.5,770,654所述，在此引入作为参考。例如，适用于本发明的增韧聚酰胺共混物，能够在任何适宜共混或混合的设备中，如班伯里密炼机、Haake混合器、Farrell混合器或挤出机，通过熔体共混或熔体混合来得到。挤出机能够是具有各种强度的螺杆的或者单螺杆或者双螺杆挤出机。混合或共混能够在约200℃～约320℃温度下进行，优选在约230℃～约300℃下进行。共混物能够通过任何已知常规方法造粒。优选，粒料通过切断共混物的挤出铸带条来形成。
具有提高了的粘合性能的增韧聚酰胺能够通过再使任选偶联剂或交联剂与增韧聚酰胺并合来得到。例如，能够将诸如General Electric的市售Silquest A-1100(γ-氨基丙基三乙氧基硅烷)的偶联剂，通过使其包含在增韧聚酰胺组合物本体中，或者通过将其涂布在增韧聚酰胺组合物表面上，进行并合。偶联化合物能够以水溶液形式，以任选一种方式进行并合。所述水溶液的pH能够使用诸如乙酸或柠檬酸的酸来降低。
在另一个实施方案中，本发明涉及一种从本发明聚酰胺组合物得到的制品。本发明的制品包括层合材料制品，具有某种形状的制品等。包含本发明聚酰胺组合物的层合材料，能够构成各种其它制品，例如，玩具、家俱、小汽车、火车、汽车、设备、船只、吸声砖瓦、吸声地板、墙壁、天花板、屋面、屋面材料，或者需要消声和/或韧性聚合物的其它制品。本发明层合材料对可见光而言勉强透明。
在特别优选的实施方案中，本发明硬质聚酰胺组合物能够与其它聚合物材料如热塑性弹性体(TPEs)层合。TPEs是具有类似橡胶性能的热塑性材料，其触感柔软。但是，TPEs一般对常规硬质聚合物没有良好粘性。本发明聚酰胺组合物能够消除这类粘性问题，并且在许多情况下提供适宜的与TPEs的层合材料。
在另一个优选实施方案中，本发明聚酰胺组合物能够与PVB层合形成具有基本消声性能的PVB层合材料。这类层合材料在消声是重要的许多应用中能够找到用处，例如，汽车发动机壳板，诸如洗衣机的设备，干燥器，冰箱，空气调节器，加热炉以及在使用中能够产生强噪音的类似设备。
在还有的另一个实施方案中，层合材料具有至少两个包含本发明聚酰胺组合物的片材，它们粘合到PVB夹层的相对表面上，该层合材料，相对于一个具有两倍于层合聚酰胺片材厚度的厚度的聚酰胺片材来说，具有改善的结构强度。这类层合材料能够应用在各种汽车部件如门板、车尾行李箱、外壳、地板、船体、装运箱或赋予其结构和强度的其他相似用途。
实施例
实施例1～4，对照例C1和C2
使采用杜邦公司市售的“EC0CITETM”、按照WO 0212356所述的程序制备的易流动PVB，与或者Zytel101(杜邦公司市售)或者UltramidB3(BASF市售)和矿物填料(TranslinkTM HF900，市购自Englehard)熔融共混在一起。在熔融共混操作过程中，各组分首先经各个受控失重喂料器喂料。混合物在40mm Werner&Pfleiderer同向旋转双螺杆挤出机中经熔融共混进行配混，其机筒温度为约280℃，模头温度为约290℃。除了矿物之外的所有组分都喂入第一段机筒中，矿物则使用侧喂料器喂入第六段机筒。伴随排气口处于真空下进行挤出。螺杆速度为250rpm，挤出机总喂料速度120磅/小时。测定螺杆马达扭矩百分率，并记录。
所得铸带条在水中骤冷，切成粒料，用氮喷射直至冷却。根据需要通过干燥或另外加入水将所得粒料中水份调节至0.1％～0.2％。按照ISO方法294在注塑机模塑试条。在试条干燥模塑状态，对模塑试条进行测试。测试：冲击—缺口伊佐德(NI)，无缺口伊佐德(UNI)；抗张强度—断裂伸长(TS EL-B)，断裂(TS-B)，屈服(TS-Y)；挠曲模量(Flex Mod)；和扭矩。所有数据均示于表1。
在实施例1～4中应用不同量ECOCITETM GradeH。实施例4应用了第4添加剂：Fusabond A MG-423D(用1％马来酐接枝改性的乙烯/丙烯酸烷基酯/CO25共聚物，市购自杜邦公司)。
市售矿物填充尼龙66(Minlon10B40，市购自杜邦公司)的一些文献值包括在有1中，作为对照例C1，以进行比较。另外，上述实施例1～4所述相同系统和试验方法均用于对照例C2，该例没有任何ECOCITETM Grade H和FusbondA MG-423D。
| 表1ECOCITETM对矿物填充聚酰胺的影响 | ||||||
| 实施例# | C1 | C2 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
| zytel101 | - | 60 | 51 | 48 | 42 | 42 |
| ECOCITETM H(Wt％) | - | 9 | 12 | 18 | 9 | |
| TranslinkHF900 | - | 40 | 40 | 40 | 40 | 40 |
| FusabondA MG423D | - | - | - | - | - | 9 |
| 熔体粘度@280℃/2487s-1(Pa-s) | - | 1729 | 1297 | - | 875 | 1614 |
| NI@23℃(kJ/m2) | 3.98 | 5.56 | 5.7 | 6.0 | 5.7 | 7.1 |
| NI@23℃(J/m) | 32 | 44.5 | 45.8 | 48.7 | 45.7 | 57.0 |
| NI@-30℃(kJ/m2) | 3.98* | 5.2 | 5.2 | 5.0 | 6.5 | |
| NI@-30℃(J/m) | 32 | 41.8 | 42.7 | 40.4 | 53.1 | |
| UNI@23℃(kJ/m2) | 65.05 | 32.4 | 41.8 | 50.4 | 73.7 | |
| UNI@23℃(J/m) | 330.5 | 426.6 | 5088 | 752.7 | ||
| TS EL-B(％) | 3 | 2.88 | 4.9 | 6.5 | 8.7 | 10.1 |
| TS-B(Mpa) | 98 | 86.76 | 65.1 | 55.7 | 44.2 | 40.7 |
| TS-B(psi) | 14200 | 12591.9 | 9451 | 8078 | 6416 | 5902 |
| TS-Y(Mpa) | 86.77 | 65.1 | 55.6 | 44.1 | 40.5 | |
| TS-Y(psi) | 12592.9 | 9445 | 8067 | 6398 | 5878 | |
| Flex Mod(Gpa) | 7.24 | 4.951 | 4.43 | 3.93 | 2.71 | 3.02 |
| Flex Mod(psi) | 1050000 | 718577 | 642169 | 569706 | 392668 | 438044 |
| 扭矩(％) | 63 | 53 | 50 | 43.4 | 52.3 | |
*@-40℃
当挤出机扭矩百分率和在280℃、2487sec-1下熔体粘度，随着向共混物中加入ECOCITETM Grade H以及ECOCITETM Grade H和FusabondA MG-423D的组合，而减少时，通过NI23℃和NI-30℃测定的韧度(分别为在23℃和-30℃测定的缺口伊佐德)增加。
实施例5～8
将上述实施例1～4中的方法和程序同样地用于实施例5～8，只是将Zytel101先与SilquestA-1100预共混，然后再喂入挤出机中。
| 表2硅烷对ECOCITETM与矿物填充聚酰胺的共混物的影响 | ||||
| 实施例5 | 实施例6 | 实施例7 | 实施例8 | |
| zytel101 | 51 | 48 | 42 | 42 |
| 硅烷SilquestA1100 | 0.2 | 0.2 | 0.2 | 0.2 |
| ECOCITETM H(Wt％) | 9 | 12 | 18 | 9 |
| FusabondA MG423D | - | - | - | 9 |
| TranslinkHF900 | 40 | 40 | 40 | 40 |
| 熔体粘度@280℃/2487s-1(Pa-s) | 2337 | 2124 | 1860 | 2125 |
| NI@23℃(kJ/m2) | 3.86 | 4.66 | 3.76 | 4.26 |
| NI@23℃(J/m) | 30.71 | 37.1 | 30.03 | 34.2 |
| NI@-30℃(kJ/m2) | 60 | 59.23 | 48.39 | 47.98 |
| NI@-30℃(J/m) | 601.22 | 592.93 | 484.39 | 480.73 |
| UNI@23℃(kJ/m2) | 5.6 | 4.455 | 6.204 | 8.33 |
| UNI@23℃(J/m) | 77.868 | 70.48 | 66.237 | 39.539 |
| TS EL-B(％) | 11301.635 | 10229.343 | 9613.563 | 5738.618 |
| TS-B(Mpa) | 77.947 | 70.56 | 66.298 | 39.6 |
| TS-B(psi) | 11313.104 | 10240.886 | 9622.41 | 5747.502 |
| TS-Y(Mpa) | 6.228 | 5.664 | 5.778 | 3.354 |
| TS-Y(psi) | 903983 | 822127 | 838608 | 486765 |
| 挠曲模量(Gpa) | 54 | 57 | 58 | 61 |
实施例7的SEM(扫描电子显微镜)图
在聚合物表面暴露于甲醇蒸气以抽取PVB前后，通过SEM检测实施例7的聚合物。如下文中在断裂拉伸试条的横断面的SEM图中所示，聚合物基材中分散的PVB尺寸小于0.5μm。拉伸试条制自实施例7的材料，并在断裂之前采用液氮冷却。图1为在甲醇抽取之前者，图2为在甲醇抽取之后者。
Claims (9)
1.一种热塑性聚酰胺组合物，包括：(a)约5～约30wt％易流动增韧剂，后者包含约20wt％～约95wt％聚乙烯醇缩丁醛；(b)互补地，95～25wt％聚酰胺，其在约320℃以下是可熔融加工的，数均分子量至少5,000；(c)占总组合物的约10～约45wt％的矿物填料；和(d)任选地，一种偶联剂。
2.权利要求1的组合物，其中增韧剂包含一种或多种含有酐官能团的聚合物和一种或多种含有羧酸官能团的聚合物。
3.权利要求1的组合物，其中增韧剂还包含非活性聚合物。
4.权利要求3的组合物，其中非活性聚合物选自聚乙烯、聚丙烯、聚氯乙烯、尼龙、烯烃共聚物及其混合物。
5.权利要求1的组合物，其中填料是选自煅烧粘土、金属碳酸盐、二氧化钛、硅灰石或滑石的一种矿物。
6.权利要求1的组合物，包含一种：偶联剂，其中该偶联剂是一种氨基硅烷化合物，其含量为约0.1～约1wt％。
7.权利要求1的组合物，其中聚酰胺选自尼龙6、尼龙11、尼龙12、尼龙66、尼龙6/10、尼龙12/12；以及ε-己内酰胺与六亚甲基二胺和己二酸的共聚物。
8.从权利要求1组合物制备的制品。
9.权利要求8的制品，其中该制品选自玩具、家俱、小汽车、火车、汽车、设备、船只、吸声砖瓦、吸声地板、墙壁、天花板、屋面以及屋面材料。
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| DE19938159A1 (de) * | 1999-08-16 | 2001-02-22 | Huels Troisdorf | Verbundsicherheitsglas sowie PVB-Folie zu seiner Herstellung |
| MXPA03001180A (es) * | 2000-08-10 | 2003-09-05 | Du Pont | Proceso para la conversion de desecho de polivinil butiral en granulos procesables. |
| US7138454B2 (en) * | 2002-09-06 | 2006-11-21 | E. I. Du Pont De Nemours And Company | Toughened, glass filled polyamide compositions and blends having improved stiffness, and articles made therefrom |
| US20050004308A1 (en) * | 2003-03-14 | 2005-01-06 | Win-Chung Lee | Polyamide and polyvinylbutyral compositions and blends having enhanced surface properties and articles made therefrom |
-
2004
- 2004-03-12 CN CNA200480006968XA patent/CN1761719A/zh active Pending
- 2004-03-12 JP JP2006507150A patent/JP2006520421A/ja active Pending
- 2004-03-12 EP EP04720463A patent/EP1606350A1/en not_active Withdrawn
- 2004-03-12 CA CA002518526A patent/CA2518526A1/en not_active Abandoned
- 2004-03-12 BR BRPI0408051-3A patent/BRPI0408051A/pt not_active IP Right Cessation
- 2004-03-12 MX MXPA05009613A patent/MXPA05009613A/es unknown
- 2004-03-12 KR KR1020057017089A patent/KR20050111356A/ko not_active Application Discontinuation
- 2004-03-12 US US10/799,056 patent/US20040266931A1/en not_active Abandoned
- 2004-03-12 AU AU2004221893A patent/AU2004221893A1/en not_active Abandoned
- 2004-03-12 WO PCT/US2004/007730 patent/WO2004083307A1/en active Application Filing
- 2004-03-15 TW TW093106839A patent/TW200502295A/zh unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987708A (zh) * | 2015-08-03 | 2015-10-21 | 金宝丽科技（苏州）有限公司 | 一种纤维增强尼龙复合材料及其制备方法 |
| CN106497038A (zh) * | 2016-11-02 | 2017-03-15 | 安徽隆宇塑业有限公司 | 一种尼龙66复合材料 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2004221893A1 (en) | 2004-09-30 |
| CA2518526A1 (en) | 2004-09-30 |
| JP2006520421A (ja) | 2006-09-07 |
| BRPI0408051A (pt) | 2006-02-14 |
| KR20050111356A (ko) | 2005-11-24 |
| EP1606350A1 (en) | 2005-12-21 |
| US20040266931A1 (en) | 2004-12-30 |
| WO2004083307A1 (en) | 2004-09-30 |
| TW200502295A (en) | 2005-01-16 |
| MXPA05009613A (es) | 2005-10-18 |
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