CN1298342A - 发泡聚合物一纤维复合材料 - Google Patents

发泡聚合物一纤维复合材料 Download PDF

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CN1298342A
CN1298342A CN99805413A CN99805413A CN1298342A CN 1298342 A CN1298342 A CN 1298342A CN 99805413 A CN99805413 A CN 99805413A CN 99805413 A CN99805413 A CN 99805413A CN 1298342 A CN1298342 A CN 1298342A
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D·J·斯坦基
R·艾林斯基
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Abstract

本发明提供了发泡聚合物—纤维复合材料(100)、建筑材料以及制造此类建筑材料的方法。复合材料包括约35—75wt%的聚合物树脂、约25—65wt%的纤维并且其比重小于约1.25g/cm3。低密度源自在热成型如挤出加工过程中向熔融的复合材料前体中引入发泡剂或气体。

Description

发泡聚合物－纤维复合材料
本发明涉及用于地板、扶手、壁板和建筑材料成型的聚合物-纤维复合材料，并更特别涉及轻质且能满足建筑需要而提供足够强度和机械性能的发泡复合材料。
合成木材已在木材受环境条件影响而迅速性能变差的领域用作了木材的代用品。虽然在过去鉴于成本之故其商业推广受到限制，但是现代的回收手段以及低成本挤出的制造能力已拓宽了聚合物-纤维复合材料的应用领域，进入到商业和家居市场。一种由Trex Co.LLC,Winchester,VA制造的此类产品，商品名为TREX，由聚乙烯-木材混合物构成，经挤出成型为地板用板材。5/4in.厚的聚乙烯-木材复合板其强度足以用作地板的板片，但却典型地不太适合作为建筑用木材的替代品，比如一般用来支撑地板的格架构件。
聚乙烯复合材料之所以倍受关注，是因为它能使紧固螺丝“沉头”，即螺帽埋入或至少与板材的表面齐平而无需预先钻孔。这类合成木材制品耐气候性能很好并且相对而言无需保养。安装后，它能抵抗木板经常发生的开裂和翘曲现象。其另外一特点是“颜色耐天候能力”；比如，TREX产品在开始时是淡咖啡色并且在暴露到雨水和阳光后就转变成老化的灰色外观。
聚乙烯-木材复合材料板无需油漆，而且绝无一般会造成普通木材表面损伤的疤节，并且一般会令紧固螺丝更难钉入或拧入。这类复合材料也绝无渗液，并且其光滑的表面构造甚至适于光脚行走。
除了聚乙烯以外，也提到过用于制造合成木材制品的其它塑料。聚氯乙烯(PVC)热塑性塑料与木材纤维混合用以制造门窗等用的挤出材料。参见Andersen Co.的U.S.No.5,486,553。此类材料的设计目的是为了取代建筑木质构件并且典型地其抗张或扬氏模量约为500,000psi或更高。因为一般需要承载，某些增强的木材纤维-PVC制品很致密、相对较重且可能需要预先钻孔以使螺帽能够沉头。
因此，一直都期待一种质轻且无需预先钻孔就能让螺帽沉头的建筑材料。也一直都期待一种能挤出的聚合物－纤维复合材料，它能被各种永久或半永久色着色或者能够赋予老化的外观。
本发明提供发泡聚合物-纤维复合建筑材料，其包括约35-75wt％的聚合物树脂、约25-65wt％的纤维并且比重小于约1.25g/cm3。所得到的复合材料内部包括有大量的孔隙或孔洞，是因复合材料熔融前体中发泡剂或分散的气体的添加所致。
本发明的组合物比类似组成的非发泡合成板轻近10％。优选的乙烯基树脂板比同等厚度的聚乙烯木材复合材料更硬。通过向树脂和木粉混合物中添加发泡剂就能使PVC发泡。这能产生至少占固体约1vol.％优选量的孔隙，其主要集中在由这些混合物制造的挤出复合材料型材的横截面中心区域处。本发明优选的板状构件其抗张和抗弯模量小于500,000psi，一般约为100,000～450,000psi。所制造的板表面无需预先钻孔就能使螺帽沉头。
本发明的聚合物－纤维复合材料也可包括用以在挤出加工过程中提高复合材料熔融前体的熔体强度的添加剂。对此优选的添加剂包括量为0.1～约15wt％的丙烯酸类改性剂。通过添加染料比如金属氧化混合物和二氧化钛、颜料或飘尘等可对由此类复合材料制造的建筑材料进行着色以赋予其老化的外观。为了降低成本，可采用粒径大于30目的大颗粒木粉。
图1：是本发明所优选的发泡聚合物-纤维复合建筑材料一部分的横截面前透视图；
图2：是采用了本发明优选的复合建筑材料的地板构件和房舍一部分的前透视图；
图3：是图1复合建筑材料一侧的横截面视图，显示出一个按沉头方式插入建筑材料表面上顶的螺丝；
图4：是本发明所优选的扶手一部分的横截面前透视图；
图5：是本发明复合材料之比重与木粉浓度关系的示意图；
图6：是本发明复合材料之比重与丙烯酸类改性剂浓度关系的示意图；
图7：是本发明复合材料之比重与化学发泡剂浓度关系的示意图；
图8：是本发明复合材料之抗弯模量与木粉浓度关系的示意图；
图9：是本发明复合材料之抗弯模量与丙烯酸类改性剂浓度关系的示意图；
图10：是本发明复合材料之抗弯模量与化学发泡剂浓度关系的示意图；
图11：是本发明复合材料之抗弯强度与木粉浓度关系的示意图；
图12：是本发明复合材料之抗弯强度与丙烯酸类改性剂浓度关系的示意图；
图13：是本发明复合材料之抗弯强度与化学发泡剂浓度关系的示意图；
本发明的发泡聚合物-纤维复合材料可直接应用或与“capstock”共用或与其它材料如纯或共聚树脂、填充以木材或玻璃纤维的树脂或者添加剂如沙等共挤出，以得到更好的拉伸强度、耐紫外线性能或更能赋予其木材外观的构造。本发明也涉及一种工艺，用以制造发泡聚合物-纤维复合材料，比如建筑材料包括屋顶木瓦、壁板、地板砖、镶板、模制品、建筑构件、台阶、门、窗台和窗框；居室和花园用具比如花盆、花池、装饰瓦、地面板、室外摆设、篱笆和庭院设施；农场和牧场用具包括草场围栏、标杆和畜棚用品；以及船用具，比如甲板、舱壁和桩基。
如图所示并特别是图1，表示的是优选的发泡聚合物-纤维复合材料100，包括约35-75wt％的聚合物树脂、约25-65wt％的纤维，其比重小于约1.25g/cm3并优选大约0.5-1.2g/cm3。复合材料100的内部包括称为孔隙20的大量孔隙或孔洞，是向所述复合材料100熔融前体中添加发泡剂或气体所致。希望在复合材料100中测得的孔隙至少占固体的约1％并优选占约5-40vol.％。本发明的复合材料也可能包括一种或多种添加剂如加工助剂、颜料或增塑剂。
如图2-4所示，本发明的发泡聚合物-纤维复合材料100最适合地板、壁板、扶手、窗框包括装饰物和栏杆以及栏杆柱。虽然复合材料100质地很轻，但一般其抗弯模量、抗张模量和/或扬氏模量约为100,000～450,000psi。如图3所示，复合材料100优选无需预先钻孔就能使紧固螺丝和钉子比如35号螺丝以沉头的形式紧固在复合材料100的表面上或表面内。达到此目的一般是通过采用增塑剂以降低复合材料100的压缩强度和/或通过在复合材料100的熔融前体中精确控制发泡剂或气体以得到含有为聚合物表层10所包围的孔隙20的多孔性体内结构。这种多孔性能，即使不用增塑剂也能将压缩强度降低至足以使紧固螺丝无需预先钻孔就能沉头。这使得图2所示的性能优异的边对边型复合材料板的地板40成为可能。理想地，基于强度和成本考虑，支撑构件和地板柱要由木材制成。
也如图2所示，优选的复合材料100可比如通过挤出而成型为屋舍50等的壁板55或窗框构件58，比如装饰物或栏杆。如图4所示，复合材料100也可成型为扶手45或栏杆柱60。
以下就本发明优选的材料进行详细的说明。复合材料一般含有约35-75wt％的树脂材料比如热塑性和热固性树脂如PVC、聚乙烯、聚丙烯、尼龙、聚酯、聚砜、聚苯氧和聚苯硫、环氧树脂、纤维素等。本发明板材所优选的热塑性材料是PVC。PVC热塑性材料包含了极其广泛的一类商业用热塑性聚合物。氯乙烯单体可制自各种不同的工艺，包括乙炔与氯化氢的反应以及乙烯的直接氯化。聚氯乙烯典型地是通过氯乙烯的自由基聚合反应而制造的。聚合反应结束之后，聚氯乙烯一般与抗冲改性剂、热稳定剂、润滑剂、增塑剂、有机和无机颜料、填料、防霉剂、加工助剂、阻燃剂或如果需要的话，其它常见的添加剂混合。在聚氯乙烯共聚物的制造过程中，聚氯乙烯也可与其它的乙烯基单体混合。此类共聚物可能是线型共聚物、接枝共聚物、无规共聚物、交替共聚物、嵌段共聚物等。能与氯乙烯混合而生成氯乙烯共聚物的单体包括丙烯腈；α-烯烃如乙烯、丙烯等；氯化单体如偏二氯乙烯；丙烯酸酯单体如丙烯酸、甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯酰胺、丙烯酸羟乙酯等；苯乙烯单体如苯乙烯、α-甲基苯乙烯、乙烯基甲苯等；醋酸乙烯酯；或其它常见的烯型不饱和单体组合物。此类单体的用量最高约为50mol％，余下的都是氯乙烯。PVC能通过混合而形成柔软或坚硬、强韧或高强、高或低密度或者物理性能或加工性能任意可调的材料。PVC树脂也可与其它聚合物如ABS、丙烯酸类、聚氨酯和丁腈橡胶混合以改进其耐冲击性能、撕裂强度、弹性或加工性能。可制造出坚硬或柔软的透明性组合物，或者可以着色成几乎任何一种颜色。
在本发明优选的实施方案中，采用的是硬质PVC，可选含有少量的增塑剂。材料硬韧并且可混合出很宽的性能范围，包括耐冲击性能和耐老化性能比如褪色成木灰色的外观。还有其抗张强度约为6,000-7,500psi、百分延伸率约40-80％而抗张模量约为3.5-6.0×106psi。未经氯化可适用至约140°F，若氯化则约为220°F。还有热膨胀系数约为3-6×10-5in./in.°F。
本发明的复合建筑材料可利用热塑性和热固性材料常用的制造方法进行注射或真空模塑、挤出及牵引。在优选的实施方案中，将PVC精研细粉或原始料的混合物混合，而且随后进行加热并经模具挤出以制造长约4-20英尺且厚0.05-6.0in.的板材和其它型材。挤出后的热塑性板材再处以模塑、压延和整理，以得到木材纹理或所需要的构造。
本发明的建筑材料100也可以含有约25-60wt％的纤维，比如玻璃、木材、棉花、硼、碳或石墨纤维。另外也可采用碳酸钙、滑石、二氧化硅等无机填料。纤维在质地上优选“纤维素”型。纤维素纤维可来自回收的纸制品比如农产品纤维、纸浆、新闻纸、软木如松木或落叶树的硬木。对纤维制造而言一般优选硬木，因为其吸水较少。当硬木是本发明纤维的主要来源时，可补以来自多种次要来源的其它纤维，包括软木纤维、天然纤维包括竹、稻草、甘蔗以及从新闻纸、纸箱、计算机打印纸等回收和收集的纤维。本发明可采用约10-100目、优选20-30目的木粉。
本发明优选将树脂和木粉组份与化学发泡剂进行混合或者向树脂和木材纤维的熔融混合物中引入气态介质，以便在混合物通过模塑、挤出或共挤出等方法热成型之前产生大量的滞留气泡。这类用于制造硬质发泡制品的工艺一般是已知的。
在本发明优选的工艺中，一定量的PVC精研细粉与20-30目约草籽大小经过事先干燥除去任何水蒸汽形式残留水份的木粉进行混合。混合物也包括一种熔融增强剂比如高分子量丙烯酸类改性剂，它能提高熔体弹性和强度并能增强孔洞结构、孔隙的增长及分布。
也可向混合物中添加化学发泡剂或气体以便通过发泡来降低复合材料100的密度和重量。如果采用的是化学发泡剂，将其在混合过程中或者在挤出机进料口处混入混合物中。发泡剂在挤出机中分解，向熔体中释入气体比如氮气或CO2。当熔体离开挤出模具时，气体区的压力发生降低，膨胀成为周围聚合物所截留的小孔洞或气泡。
化学发泡剂可以是在热分解过程中释放气体的多种化学品中的任意一种。化学发泡剂也可称为发泡剂。发泡剂或多种发泡剂，若用到一种以上，可选自含有可分解基团如偶氮、N-亚硝基、羧基、碳酸根、含氮杂环和磺酰肼基团的化学品。一般都是固体物质，在加热时经化学反应或在分解过程中释出气体。代表性化合物包括偶氮二碳酰胺、碳酸氢盐、二亚硝基五亚甲基四亚甲基四胺、p,p’-氧代-双(苯磺酰)-肼、苯-1,3-二磺酰肼、偶氮-双(异丁腈)、缩二脲和脲。
发泡剂可以本领域熟练人员已知的多种不同方式添加到聚合物中，比如在挤出机内当树脂处于熔融状态时直接向树脂中添加固体粉末、液体或气体试剂，使试剂在熔融的聚合物中均匀分散。优选在挤出加工之前添加发泡剂并且以固体的形式。改变本发明可发泡组合物的加工温度和压力就能得到千变万化的发泡组合物，取决于发泡剂、树脂及所用纤维素纤维的量和类型。优选的发泡剂选自吸热和放热型，比如二亚硝基五亚甲基四胺、对-甲苯磺酰氨基脲、5-苯四唑、草酸钙、三肼基-对称三连氮、5-苯基-3,6-二氢-1,3,4-噁二嗪-2-酮、3,6-二氢-5,6-二苯基-1,3,4-噁二嗪-2-酮、偶氮二碳酰胺、碳酸氢钠及其混合物。
除了上述之外，可向混合物中添加着色剂，比如染料、色料、飘尘或这些成份的混合物，取决于最终的颜色以及成本考虑。此类添加剂可给出“耐天候能力”或淡灰色或者是蓝、绿或褐等永久色。
通过如下的实施例可进一步理解本发明。
实施例
调制实施例1-16并挤出成型为试板。测定每个配方的机械性能并进行对比。表Ⅰ-所选配方的性能与占100份树脂(PHR)的份数及质量百分比(wt％)的关系
    PHR    wt％  性能
配方 硬质PVC混合物 木粉 丙烯酸类改性剂 发泡剂 比重(g/cm3) 抗弯模量(psi) 抗弯强度(psi)
1   100   68   4   0.5   57.97   39.42   2.32   0.29   1.16   421037   4823
  2   100   100   10   0.5   47.51   47.5l   4.75   0.24   1.07   398042   4286
  3   100   100   4   1.5   48.66   48.66   1.95   0.73   1.09   297233   3397
  4   100   68   10   1.5   55.71   37.88   5.57   0.84   0.83   205162   3158
  5   100   100   4   0.5   48.90   48.90   1.96   0.24   1.17   357212   3790
  6   100   68   10   0.5   56.02   38.10   5.60   0.28   1.09   457829   5353
  7   100   68   4   1.5   57.64   39.19   2.31   0.86   1.06   287530   3964
  8   100   84   7   0.5   52.22   43.86   3.66   0.26   1.11   431283   4769
  9   100   84   4   1   52.91   44.44   2.12   0.53   1.02   260310   3386
  10   100   68   7   1   52.08   43.75   3.65   0.52   0.98   270421   3597
 11   100   100   10   1.5   47.28   47.28   4.73   0.7l   0.94   224739   3058
  12   100   100   10   1   47.39   47.39   4.74   0.47   0.99   256923   3207
  13   100   84   10   1.5   51.15   42.97   5.12   0.77   0.89   227991   3124
  14   100   100   7   1.5   47.96   47.96   3.36   0.72   0.97   271955   2996
  15   100   68   10   1   55.87   37.99   5.59   0.56   0.93   305704   4014
  16   100   84   10   0.5   51.41   43.19   5.14   0.26   1.08   430736   4747
在进行性能对比时，注意到采用如下的优选配方就能得到约200,000psi的目标抗弯模量。
表Ⅱ：优选配方
    PPH PVC混合物
硬质PVC混合物     100
20-30目的硬木粉     68
丙烯酸类改性剂     10.0
化学发泡剂     1.5
碳黑     0.18
此配方给出了成本和机械性能的最佳均衡。
综上所述可知，本发明提供了改进的发泡聚合物-木材复合材料，其比重较低且抗弯模量高同时能让紧固螺丝沉头。其耐久性和强度也相当大。虽然已给出多个实施方案，但这只是出于说明的目的并不对本发明构成限制。对本领域熟练的人员而言各种变化形式都是很容易作出的，并且都是属于本发明在后续权利要求所描述的范围之内的。

Claims (20)

1．一种发泡的聚合物-纤维复合建筑材料，包含：约35-75wt％的聚合物树脂；约25-65wt％的纤维并且比重小于约1.25g/cm3，所述的复合建筑材料包括至少占固体1vol.％的孔隙，其源自向所述复合建筑材料的熔融前体中添加的气态介质或发泡剂。
2．权利要求1的木材复合建筑材料，进一步包含一种提高所述熔融前体熔体强度的添加剂。
3．权利要求2的复合建筑材料，其中所述的添加剂包含丙烯酸类改性剂。
4．权利要求1的复合建筑材料，其中所述的纤维包含纤维素纤维。
5．权利要求1的复合建筑材料，其中所述的熔融前体包含约0.1-2wt％的化学发泡剂和约0.1-15wt％的丙烯酸类改性剂。
6．权利要求1的复合建筑材料，进一步包含占固体约5-40vol.％的孔隙。
7．权利要求6的复合建筑材料，其中所述建筑材料的比重约为0.5-1.2g/cm3。
8．权利要求1的复合建筑材料，进一步包含一种赋予所述建筑材料以老化外观的添加剂，所述添加剂选自：染料、颜料、飘尘或其混合物。
9．权利要求1的复合建筑材料，包含抗弯模量约为100,000-450,000psi。
10．一种发泡的聚合物－木材复合材料，制造自包含下列物质的熔融混合物：约35-75wt％的高分子PVC树脂、约25-65wt％的木材纤维以及发泡剂或气态介质，所述的熔融混合物形成一种比重小于约1.25g/cm3而抗弯模量约为100,000-450,000psi的聚合物-木材复合材料。
11．权利要求10的复合材料，进一步包含一种在挤出过程中提高所述熔融混合物熔体强度的添加剂。
12．权利要求10的复合材料，其中所述的发泡剂包含约0.1-2.0wt％的化学发泡剂。
13．权利要求12的复合材料，其中所述的化学发泡剂在混合过程中或在接近挤出机的底部狭口处混入所述的聚合物和木材纤维中。
14．权利要求10的复合材料，借助所述的发泡剂在所述的复合材料内部形成大量的孔隙或孔洞，能让紧固螺丝不经预先钻孔就可埋入所述复合材料的表面中。
15．一种制造发泡聚合物-纤维素复合建筑材料的方法，包含：
(a)混合约35-75wt％的聚合物树脂、约25-65wt％的纤维素纤维和约0.1-2wt％的发泡剂以形成混合的混合物；
(b)将所述混合过的混合物进料到挤出机中，进而所述的发泡剂开始分解并在所述的混合物熔融时向其中释出气体；而且
(c)经由模具挤出含有所述气体的所述熔融混合物，从而所述的气体形成了滞留在所述聚合物-纤维素纤维复合材料中的微小气泡。
16．权利要求15的方法，其中所述的混合物进一步包含一种能提高熔体弹性和强度的高分子量丙烯酸类改性剂。
17．权利要求15的方法，其中所述的模具包含大致上板状的横截面。
18．一种横截面大致板状的发泡聚合物-木材复合建筑材料，成型自一种包含以下物质的熔融前体：约45-60wt％的聚氯乙烯树脂、约35-55wt％的木粉、约0.1-15wt％的丙烯酸类改性剂；及约0.1-2.0wt％的化学发泡剂；所述建筑材料的比重小于约1.25g/cm3，并且能让紧固螺丝不经预先钻孔就可埋入所述建筑材料的表面中；所述的建筑材料也包含抗弯模量约为100,000-450,000psi。
19．权利要求18的复合建筑材料，其中所述的聚氯乙烯树脂包含一种混合的树脂混合物。
20．权利要求18的复合建筑材料，其中所述的建筑材料包含一种能赋予其老化的木灰色外观的颜料。
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