CN100594113C - 木粉填充的聚氯乙烯复合材料及其泡沫制品 - Google Patents

木粉填充的聚氯乙烯复合材料及其泡沫制品 Download PDF

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CN100594113C
CN100594113C CN200680023500A CN200680023500A CN100594113C CN 100594113 C CN100594113 C CN 100594113C CN 200680023500 A CN200680023500 A CN 200680023500A CN 200680023500 A CN200680023500 A CN 200680023500A CN 100594113 C CN100594113 C CN 100594113C
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pvc
composite
wood powder
wood
coupling agent
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CN101213063A (zh
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L·M·马图亚纳
P·A·海登
B·沙
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Michigan State University MSU
University of Michigan
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Abstract

公开了挤出的PVC和木粉的复合材料组合物，其含有脱乙酰壳多糖或甲壳质作为偶联剂。该复合材料组合物具有改善的物理和机械性能。

Description

木粉填充的聚氯乙烯复合材料及其泡沫制品
相关申请的相互参照
本申请享有在2005年4月29日提交的美国临时申请60/676,203的优先权。
有关联邦资助研究或开发的声明
不适用
通过光盘提交的材料的引用参考
不适用
发明背景
(1)发明领域
本发明涉及复合材料组合物，其包括木粉和聚氯乙烯(PVC)聚合物，其中甲壳质和/或脱乙酰壳多糖被用作天然的偶联剂。所得到的复合材料组合物具有改善的性能。
(2)相关技术的说明
木材-塑料复合材料(WPCs)已经成为工程材料的重要一族。在各种不同的应用中，它们部分地代替了固体的加压处理过的木材或其它材料(Clemons，C.M.，Forest Prod.J.，52(6)，10-18(2002))。虽然在材料成本和劲度方面，WPCs优于未填充的纯聚合物，但是其强度性能(拉伸性能、弯曲性能和冲击性能)通常低于未填充的聚合物(Matuana，L.M.，Woodhams，R.T.，Balatinecz，J.J.和Park，C.B.，Polym.Compos.，19(4)，446.455(1998)；和Matuana，L.M.，Balatinecz，J.J.，和Park，C.B.，Polym.Eng.Sci.，38(5)：765-773(1998))。降低的强度有可能是由于在将亲水性的木质纤维(高表面张力)与疏水性的聚合物基体(低表面张力)混合期间各相的天然不相容性造成的(Matuana，L.M.，Woodhams，R.T，Balatinecz，J.J.和Park，C.B.，Polym.Compos.，19(4)，446-455(1998)；Matuana，L.M.，Balatinecz，J.J.，和Park，C.B.，Polym.Eng.Sci.，38(5)：765-773(1998)；Li，W.和Matuana，L.M.，J.Appl.Polym.Sci.，88(2)，278-286(2003)；和Matuana，L.M.，Park，C.B.和Balatinecz，J.J.，J.Vinyl Addit.Technol.，3(4)，265-273(1997))。相不相容性产生非常弱的相互作用，并因此在纤维和基体之间产生弱的界面(差的界面粘附)。
设计WPCs的一个方法是利用偶联剂对木质纤维表面进行改性以提高强度(Woodhams，R.T，Thomas，G.和Rodgers，D.K.，Polym.Eng.Sci.，24：1166-1177(1984))。偶联剂将木质纤维的亲水表面转变为较为疏水的表面，由此减小木质纤维的表面张力，使得它们更为紧密地与熔融聚合物的表面张力匹配。结果是，通过例如在被处理纤维和聚合物基体之间的分散和机械联锁机制，润湿和粘合性都得到了改善(Woodhams，R.T.，Thomas，G.和Rodgers，D.K.，Polym.Eng.Sci.，24：1166-1177(1984))。
由于其在木纤维亲水表面向较为疏水表面的转变中的强效应，马来酸酐官能化的聚烯烃通常被用作聚烯烃/木纤维复合材料的合适的偶联剂(Li，W.和Matuana，L.M.，J.Appl.Polym.Sci.，88(2)，278-286(2003)；和Woodhams，R.T.，Thomas，G.和Rodgers，D.K.，Polym.Eng.Sci.，24：1166-1177(1984))。类似地，为了增强木纤维与用于生产WPCs的第二大塑料PVC基体之间的界面粘附力，一些研究者已经分析了各种不同纤维处理的效果，包括利用不同类型的异氰酸酯、马来酸酐、硅烷等作为偶联剂(Kokta，B.V.，Maldas，D.，Daneault，C.和Beland，R.，J.Vinyl Technol.，12(3)，146-153(1990)；Kokta，B.V.，Maldas，D.，Daneault，C.和Beland，P.，Polum.Plast.Technol.Eng.，29(1-2)，87-118(1990)；和Kokta，B.V.，Maldas，D.，Daneault，C.和Beland，R.，Polym.Compos.，11(2)，84-89(1990))。通过这些化学处理，复合材料的大部分机械性能与含有未处理纤维的复合材料相比都得到了改善。但是，复合材料的性能劣于未填充PVC的性能，这表明，与聚烯烃/木纤维复合材料不同，将木纤维的亲水表面转变为疏水表面这一公知的主张，对于增强PVC对木纤维的粘附性方面是无效的。
但是，我们以前的研究显示，当PVC被用作WPCs中的基体时，酸-碱的相互作用在增强界面粘附力中是显著的影响因素，其中一个相充当电子给体(碱)而另一相充当电子受体(酸)(Matuant，L.M.，Woodhams，R.T，Balatinecz，J.J.和Park，C.B.，Polym.Compos.，19(4)，446-455(1998)；和Matuana，L.M.，Balatinecz，J.J.，和Park，C.B.，Polym.Eng.Sci.，38(5)：765-773(1998))。因此，对与PVC一起使用的木纤维的表面改性应当被设计为改变酸-碱在基体/纤维界面的相互作用，以改善这些复合材料的性能。例如，通过利用γ-氨基丙基三乙氧基硅烷进行表面改性来改变木纤维的酸性特征，与未填充PVC相比，具有相等拉伸强度和更大模量的PVC/木纤维复合材料被开发出来(Matuana，L.M.，Woodhams，R.T，Balatinecz，J.J.和Park，C.B.，Polym.Compos.，19(4)，446-455(1998))。根据路易斯酸-碱理论，氨基硅烷的使用成功地对木材表面进行了改性，并且促进了木材与PVC之间的相互作用(Matuana，L.M.，Woodhams，R.T.，Balatinecz，J.J.和Park，C.B.，Polym.Compos.，19(4)，446-455(1998))。
尽管具有这些优点，但是γ-氨基丙基三乙氧基硅烷没有被广泛地用作PVC/木纤维复合材料的偶联剂，这主要是因为它成本高，而且由于其对水解的敏感性及其自凝结性，很难均匀的涂覆木纤维表面。因此，在这种应用中氨基硅烷不是理想的偶联剂。
甲壳质(图1A)是继纤维素之后第二丰富的天然聚合物，它是从甲壳动物的甲壳中提取出来的。脱乙酰壳多糖(图1B)是甲壳质的脱乙酰基形式。这些聚合物可以广泛地得到，是无毒、生物相容的，而且比很多合成偶联剂的成本低。甲壳质的乙酰胺官能度和脱乙酰壳多糖的胺官能度应该允许这些聚合物以类似于氨基硅烷的方式与木材和PVC相互作用，并且借此增强PVC和木质纤维之间的界面粘附力，同时潜在地改善其它性质，而且更加成本有效。
一些研究人员已经报告了甲壳质和脱乙酰壳多糖与不同聚合物在各个应用领域的使用(Yang，A.和Wu，R.，J.Appl.Polym.Sci.，84(3)，486-492(2002)；Zhang，W.，Liu，L.，Ren，L.和Wang，F.，J.Appl.Polym.Sci.，64(11)，2127-2130(1997)；Souza Rosa，R.C.R.和Andrade，C.T，J.Appl.Polym.Sci.，92(4)，2706-2713(2004)；Ratajska，R.和Boryniec，S.，Polym.Adv.Technol.，10(10)，625-633(1999)；Thwe，M.M.和Liao，K.，Plast.Rubber Compos.，31(10)，422431(2002)；Sato，K.，Ota，H.和Omura，Y.，Adv.Chitin Sci.，2，897-901(1997)和Umemura，K.，Inoue，A.和Kawai，S.，J.Wood Sci.，49(3)，221-226(2003))。在一种研究中，甲壳质纤维与聚己内酯(PCL)之间的界面粘附力通过对复合材料进行辐射处理得到提升。与由未处理甲壳质纤维制备的复合材料相比，这种处理显示复合材料机械性能的整体提高。这种界面结合的提高是自由基接枝反应的结果(Yang，A.和Wu，R.，Appl.Polym.Sci.，84(3)，486-492(2002))。还有报道称脱乙酰壳多糖已经被交联为聚合物基体(Zhang，Q.，Liu，K.，Ren，L.和Wang，F.，J.Appl.Polym.Sci.，64(11)，2127-2130(1997))。该方法使用甲醛作为交联剂，甲醛是公知的致癌物并且对环境是有危害的。
还通过注塑方法将甲壳质薄片以0-30wt％混入增塑的淀粉基体中，制备出可生物降解的复合材料。与未填充的淀粉相比，甲壳质薄片提高了复合材料的弹性模量、拉伸应力和抗水性(Souza Rosa，R.C.R.和Andrade，C.T.，J.Appl.Polym.Sci.，92(4)，2706-2713(2004))。合成聚合物的可生物降解性也可以通过混入天然可生物降解聚合物如脱乙酰壳多糖来得到提高(Ratajska，M.和Boryniec，S.，Polym.Adv.Technol.，10(10)，625-633(1999))。
脱乙酰壳多糖还被应用在木材工业中。例如，当脱乙酰壳多糖与醛类化合物反应时形成席夫碱。脱乙酰壳多糖的这种性质在与从胶合板的胶缝中释放出的甲醛反应中十分有用，由此减少甲醛向环境的总体释放。因此，脱乙酰壳多糖可以被用作木材的功能性覆盖剂(Sato，K.，Ota，H.和Omura，Y.，Adv.Chitin Sci.，2，897-901(1997))。脱乙酰壳多糖作为木材环境友好粘合剂的使用也已经在文献中得到报道。由脱乙酰壳多糖制成的胶展示出优异的抗水性，并且被建议作为合成粘合剂的替代品(Umemura，K.，Inoue，A.和Kawai，S.，J.Wood Sci.，49(3)，221-226(2003))。
现有技术并未公开甲壳质或脱乙酰壳多糖在PVC/木纤维复合材料中作为粘附力促进剂的应用。
发明目的
本发明的目的在于提供甲壳质或脱乙酰壳多糖作为PVC/木纤维复合材料组合物及其发泡产物的偶联剂。本发明的另一目的在于提供成本有效的复合材料组合物，该组合物可以利用常规的设备容易地制备出来。
这些和其它的目的将通过参考下述说明和附图逐步清晰。
发明简述
本发明涉及一种复合材料组合物，其包括以下物质的挤出混合物：
(a)偶联剂，其选自甲壳质、脱乙酰壳多糖及其混合物；
(b)聚氯乙烯(PVC)；和
(c)干燥的木粉，其中偶联剂的含量至多为木粉的10重量％。优选地，其中木粉的粒度为约1-1,000微米。进一步地，包含约30-70重量％的木粉。更进一步地，其中该组合物还包括抗冲改性剂、用于键合由PVC产生的任何HCl的温度稳定剂和润滑剂。更进一步地，作为泡沫制品。
另外，本发明涉及一种制备复合材料组合物的方法，包括：
(a)共混以下物质的混合物：
(1)偶联剂，其选自甲壳质、脱乙酰壳多糖及其混合物；
(2)聚氯乙烯(PVC)；和
(3)木粉，其中偶联剂的含量至多为木粉的约10重量％；以及
(b)在介于约150℃与PVC或木粉分解温度之间的高温下，挤出共混后的混合物，以形成复合材料组合物。
优选地，其中挤出机具有反向旋转的双螺杆。最为优选的，其中作为额外的步骤：在高温和高压下压制复合材料组合物以提供成形制品。优选的，其中在步骤(a)的混合物中提供发泡剂，该发泡剂在高温下会膨胀为气体。
附图说明
图1是(a)甲壳质和(b)脱乙酰壳多糖的结构。
优选实施方案的说明
在木质纤维和塑料之间的有效界面粘附性对于木材塑料复合材料的加工性能和最终性能都起到决定性的作用。偶联剂被添加到木材塑料复合材料中，用以促进亲水木材表面和疏水聚合物基体之间的粘附性，但是迄今为止，关于用于PVC/木纤维复合材料并可显著改善其性能且成本有效的偶联剂，还没有相关的报道。下列实施例显示了甲壳质和脱乙酰壳多糖这两种天然高分子作为PVC/木纤维复合材料及其发泡制品的新型偶联剂的应用。根据配方，向PVC/木粉复合材料中添加甲壳质和脱乙酰壳多糖偶联剂，与不添加偶联剂的PVC/木粉复合材料相比，可以将复合材料的弯曲强度提高大约50％，并将弯曲模量提高大约30％。
实施例
实验
材料
甲壳质和脱乙酰壳多糖被用作偶联剂。偶联剂的浓度以木粉的重量为基准为0-10wt％。PVC(K值-66)与作为填料的尺寸为425微米(40目)的木粉一同使用，所述木枫来自硬木枫树类或软木松树类。木粉含量在75-120phr之间变化。锡稳定剂被用作热稳定剂。硬脂酸钙和石蜡被用作润滑剂。不同的丙烯酸类加工助剂Paraloid K-120和Paraloid K-175与抗冲改性剂Paraloid KM-334一起也被用在配方当中。木粉在105℃的烘箱中干燥48小时，以在配混和加工之前使水份含量小于1％。所有其它的化学物质和添加剂均可原样使用。最终的配方在表1中示出。
表1.PVC/木粉复合材料中所使用的配方
1甲壳质和脱乙酰壳多糖的浓度以复合材料中木粉重量为基准为0-10wt％。
通过压塑进行的复合材料制造
将表1所示配方中所有的组分加入到高强度混合器中(Papenmeier，TGAHK20)，并在室温下混合10分钟。混合后的配方随后通过32mm锥形反向旋转双螺杆挤出机进行配混，形成10mm直径的棒状物，其中该挤出机的L/D比为13∶1(C.W.Brabender Instruments Inc.)。在挤出期间的所有区域的温度分布设定在190℃且挤出速度保持在40rpm。被挤出的棒状物在190℃、6200KPa压力的液压机(Erie Mill Co.)中被压塑5分钟，成型为板条。模具随后在冷压机中被冷却至室温。
通过挤塑进行的复合材料制造
如上文所述，称量表1所示配方中不同的添加剂并在高强度间歇式混合机中混合10分钟。被混合的各批料随后以40rpm在反向旋转的双螺杆挤出机中被挤出，形成25.4mm宽×9.5mm高的矩形截面。从料斗到口模的挤出温度分布设定为190-175-170-180℃。
性能测试
复合材料的机械性能通过三点弯曲模式的弯曲试验确定。数据以断裂模量(MOR或弯曲强度)和弹性模量(MOR或弯曲强度)被收集。弯曲测试所用的试样从压塑板和挤塑型材上切下，并在步入式调理室中调理48小时，而后在23℃±2℃、相对湿度(RH)为50％±5％的条件下进行测试。弯曲试验在Instron 4206万能试验机上进行，该万能试验机装有依照ASTM标准D790的系列IX软件。对于压塑试样十字头速度为1.9mm/min，而对于挤塑型材试样十字头速度为4.1mm/min。每个配方测试至少8个试样。
动态力学分析(DMA)在Perkin Elmer(DMA 7e)仪器上以三点弯曲模式进行，以确定试样的存储模量(弹性模量)、损耗模量(粘性模量)以及tanδ。在氦气氛下、以25℃-150℃的温度扫描模式在1Hz的频率和5℃/分钟的加热速率下进行测试。
试样的尺寸稳定性依据吸水率(WA)和厚度膨胀率(ThS)进行测试。试样在水中煮沸2小时。
表2到5概括了试验结果。
表2：以不同偶联剂浓度制备的PVV/枫木粉复合材料与
对照试样相比较的机械性能(压塑试构
Figure C20068002350000091
1甲壳质和脱乙酰壳多糖的wt.％基于木粉的重量。不含有和含有甲壳质/脱乙酰壳多糖的复合材料包含75phr的木粉(枫木)。
表3：偶联剂对纯硬质PVC和PVC/木粉复合材料的动态力学性能的影响
1含有75phr木粉(枫木)的压塑试样
表4：以不同偶联剂浓度制备的PVC/枫木粉复合材料与
对照试样相比较的机械性能(挤塑试样)
Figure C20068002350000102
1甲壳质和脱乙酰壳多糖的wt％基于木粉的重量。
表5：尺寸稳定性，即水中煮沸2小时后试样的吸水率(WA)和厚度膨胀率(ThS)
Figure C20068002350000111
可以得出以下结论：
·甲壳质和脱乙酰壳多糖的使用提高了PVC/木粉复合材料的弯曲强度和弯曲模量。
·与未经偶联的复合材料相比，包含甲壳质和脱乙酰壳多糖聚合物的复合材料具有更大的弯曲强度，可与纯PVC匹敌。
·包含甲壳质和脱乙酰壳多糖聚合物的复合材料的弯曲模量超过纯PVC和未经偶联的PVC/木粉复合材料的。
·储能模量(E′或材料的弹性分量)和损耗模量(E″或材料的粘性分量)都随PVC基体中木粉的加入而得到提高，与所使用的偶联剂类型和测试温度无关。
·木粉的加入提高了聚合物基体的粘性，即，损耗模量E″。
·与未经偶联的复合材料相比，由甲壳质和脱乙酰壳多糖制备的复合材料在储能模量和损耗模量方面显示出更大的提高。
·甲壳质和脱乙酰壳多糖的使用提高了复合材料的吸水性和尺寸稳定性。
·当木粉被加入到PVC基体中时，PVC的玻璃化转变温度(tanδ峰最大值)没有受到明显影响。
泡沫制品实施例
木粉、PVC、化学发泡剂(CFAs)和偶联剂(甲壳质和脱乙酰壳多糖)在转速为20.3hp的高强度混合机(Papenmeier，TGAHK20型)中干混5分钟。可以制备三(3)种不同的配方：i)单独的PVC，ii)无偶联剂的PVC/木粉复合材料，和iii)含有偶联剂的PVC/木粉复合材料。CFAs、木粉和偶联剂的添加量可以变化。混合之后，配混的材料通过单螺杆或双螺杆挤出机(C.W.Brabender)挤出，以形成发泡试样。加工条件(温度分布和螺杆转速)根据发泡剂确定。
发泡之后，挤出物立刻被浸入水浴中以冷却发泡结构，并在气泡生长期间通过晶胞聚结使晶胞的劣化最小化。未发泡试样的密度(ρf)可以根据ASTM标准D792确定。空隙率(VF)或与之相当的试样中达到的密度降低可以根据公知的程序来计算得出。
美国公开的专利申请2005/0176836A1描述了多种可使用的发泡剂，并且该申请的公开内容被全文引入于此作为参考。
预期前述说明只是本发明的示例性说明，且本发明只能通过下附的权利要求得到限制。

Claims (10)

1.一种复合材料组合物，包括以下物质在介于150℃与PVC或木材分解温度之间的高温下挤出的挤出混合物：
(a)偶联剂，其选自甲壳质、脱乙酰壳多糖及其混合物；
(b)聚氯乙烯(PVC)；和
(c)干燥的木粉，其中偶联剂的含量至多为木粉重量的10wt％。
2.权利要求1的组合物，其中木粉的粒度为1-1,000微米。
3.权利要求1或2的组合物，包含30-70wt％的木粉。
4.权利要求1或2的组合物，其中复合材料组合物还包括抗冲改性剂、温度稳定剂和滑润剂，所述温度稳定剂用于键合由PVC中产生的HCl。
5.权利要求1的复合材料组合物，其是泡沫制品。
6.权利要求1或2的组合物，其在水中是稳定的。
7.一种制备复合材料组合物的方法，所述方法包括：
(a)共混以下物质的混合物：
(1)偶联剂，其选自甲壳质、脱乙酰壳多糖及其混合物；
(2)聚氯乙烯(PVC)；和
(3)水份含量小于1wt％的干燥木粉，其中偶联剂的含量至多为木粉重量的10wt％；和
(b)在挤出机中，在介于150℃与PVC或木材分解温度之间的高温下，挤出共混后的混合物，以形成复合材料组合物。
8.权利要求7的方法，其中挤出机具有反向旋转的双螺杆。
9.权利要求7或8的方法，其中作为额外的步骤，被挤出的复合材料组合物在高温高压下被压制以提供成形制品。
10.权利要求7或8的方法，其中在步骤(a)的混合物中提供发泡剂，该发泡剂在高温下膨胀为气体。
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CA2607010C (en) 2010-10-26
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