CN108485102A - 一种木质素增强型聚氯乙烯木塑发泡复合材料及其制备方法 - Google Patents
一种木质素增强型聚氯乙烯木塑发泡复合材料及其制备方法 Download PDFInfo
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- CN108485102A CN108485102A CN201810148586.4A CN201810148586A CN108485102A CN 108485102 A CN108485102 A CN 108485102A CN 201810148586 A CN201810148586 A CN 201810148586A CN 108485102 A CN108485102 A CN 108485102A
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- lignin
- parts
- polyvinyl chloride
- composite material
- plastic foam
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Classifications
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- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
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Abstract
本发明公开了一种木质素增强型聚氯乙烯木塑发泡复合材料及其制备方法,它由以下重量份的组分组成:聚氯乙烯100份,木质纤维粉10‑200份,无机粉体2‑200份,稳定剂1‑20份、润滑剂1‑10份、木质素5‑80份,相容剂1‑8份,发泡剂1‑10份,发泡调节剂8‑25份,增强剂0.5‑10份。与现有技术相比,本发明将木质素增强技术与微孔发泡技术相结合,在保证材料轻量化的同时,显著提高了材料的塑化、阻燃、抗紫外、抗老化、生物抗性、抗辐射、流变性能、螺杆挤出性能和耐热性能,以及产品的表面光泽度,同时降低产品的吸水性,获得了一种具有轻量化特征的高性能木质素增强聚氯乙烯木塑发泡复合材料。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种木质素增强型聚氯乙烯木塑发泡复合材料及其制备方法。
背景技术
木塑复合材料是用木纤维或植物纤维填充、增强的改性热塑性材料,经挤出或压制成型的型材、板材或其他制品。其有与木材相似的质感和性能(可锯、可刨、可钉、能弯曲和粘接),同时克服了木材尺寸稳定性差、易燃、易潮、易腐、易蛀、易滋生霉菌等缺点,又避免了单纯树脂资料高温蠕变、低温易脆等不足。但是由于木质纤维素与聚氯乙烯的相容性差,导致聚氯乙烯木塑复合材料的力学性能下降,且硬质聚氯乙烯木塑复合材料的密度比较大,从而限制了硬质聚氯乙烯木塑复合材料的应用。木质素作为一种溶解度参数与聚氯乙烯接近的生物大分子可以极大的改善木粉与聚氯乙烯之间的相容性,提高木粉的填充量,降低生产难度,提升最终的产品性能。
发泡技术是一种能够制备具有独有的致密表层和发泡芯层结构材料的技术,在保证材料基本性能的前提下,显著减轻制件重量,有利于实现材料的轻量化。其中,具有轻量化特征的聚氯乙烯木塑发泡复合材料替代实心材料,在性能满足的情况下,零部件减重10%以上。已在装饰板材和地板部件等领域得到广泛地应用,市场前景广阔。
目前,聚氯乙烯木塑发泡复合材料已得到广泛的研究。申请号:201510846861.6为解决发泡木塑泡孔不均匀、局部突发和鼓泡等现象,将磷石膏烧结处理后语木质素溶液进行混合,且加入微生物发酵以获得聚氯乙烯发泡材料的填料。但其所用木质素为愈创木基木质素或是紫丁香基木质素,而自然界中的木质素多为对羟苯基、愈创木酚和紫丁香基均有的木质素,因此限制了木质素的应用,此外,该专利仅对所生产的填料应用于木塑复合材料中的平衡吸水率进行了检测,但却未对木塑复合材料的力学性能进行比较性评估。因此,本发明将木质素增强技术与微发泡技术相结合,保证轻量化,并且提高各种力学性能以及表明光泽度。
发明内容
本发明要解决的技术问题是提供一种木质素增强型聚氯乙烯木塑发泡复合材料及其制备方法,以解决现有技术存在的性能不佳,使用寿命短等问题。
为解决上述技术问题,本发明采用的技术方案如下:
一种木质素增强型聚氯乙烯木塑发泡复合材料,它包括如下质量份数的组分:
其中,优选配方如下,聚氯乙烯100份、木质纤维粉50份、无机粉体50份、稳定剂8份、润滑剂2份、木质素30-40份、发泡剂4份、发泡调节剂10-15份、增强剂6份。
其中,其组分中还包括相容剂。
进一步的,优选如下质量份数的组分:
聚氯乙烯100份、木质纤维粉50份、无机粉体50份、稳定剂8份、润滑剂2份、木质素30-40份、发泡剂4份、发泡调节剂10-15份、增强剂6份、相容剂6份。
其中,所述的聚氯乙烯的平均聚合度为600~1400,K值为73~82。
其中,所述的木质纤维粉为木粉、竹粉、秸秆粉、糠醛渣、棉杆、木材加工下脚料、木糖渣和稻壳粉中的任意一种或几种的组合。
其中,所述的无机粉体为碳酸钙、硫酸钙、硅酸钙、炭黑、金属氧化物、滑石粉和玻璃纤维粉中的任意一种或几种的组合。
其中,所述的稳定剂为三碱式硫酸铅、二碱式亚硫酸铅、硬脂酸锌、硬脂酸镉、硬脂酸铅、硬脂酸钙、有机锡类稳定剂、环保钙锌和复合铅盐类稳定剂中的任意一种或几种的组合,其中优选环保钙锌稳定剂和复合铅盐稳定剂。
其中,所述的润滑剂为聚乙烯蜡、硬脂酸、硬脂酸钙、硬脂酸锌、多元醇酯、油酸酰胺、微晶石蜡、液体石蜡和乙撑双硬脂酰胺中的任意一种或几种的组合;
其中,所述的木质素为酶解木质素、造纸木质素、碱木质素、有机溶剂木质素、木质素磺酸盐,以及对上述木质素进行酰化、酯化、醚化、酚化、烷基化或脱甲基化改性后的木质素中的任意一种或几种的组合,其中优选酶解木质素、碱木质素和有机溶剂木质素。
其中,所述的发泡剂为碳酸氢铵、碳酸氢钠、偶氮二甲酰胺、甲苯磺酞氨基脲、偶氮二碳酸胺和尿素中的任意一种或几种的组合,其中优选偶氮二酰胺。
其中,所述的发泡调节剂为丙烯酸酯聚合物(ACR)。
其中,所述的增强剂为预定弹性体型冲击改性剂、非预定弹性体冲击改性剂、过度型冲击改性剂和橡胶类抗冲击改性剂中的任意一种或几种的组合;
其中,
所述的预定弹性体型冲击改性剂为甲基丙烯酸-丁二烯-苯乙烯共聚物MBS、丙烯酸酯类改性剂ACR、高弹性丙烯腈-苯乙烯-丁二烯共聚物ABS或高弹性丙烯酸酯类改性剂ACR;
所述的非预定弹性体冲击改性剂为氯化聚乙烯CPE或乙烯-醋酸乙烯酯共聚物EVA;
所述的过度型冲击改性剂为苯乙烯-丁二烯-苯乙烯嵌段共聚物SBS或丙烯腈-苯乙烯-丁二烯共聚物ABS;
所述的橡胶类抗冲击改性剂为乙丙橡胶、三元乙丙橡胶或丁腈乙丙橡胶;
其中,优选氯化聚乙烯和丙烯酸酯类改性剂。
其中,所述的相容剂为小分子偶联剂和/或大分子偶联剂;其中,所述的小分子偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、镁类偶联剂和锡类偶联剂,所述的大分子偶联剂为马来酸酐、丙烯酸、马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸酐接枝聚氯乙烯、马来酸酐接枝聚苯乙烯、丙烯酸接枝聚丙烯、丙烯酸接枝聚乙烯、丙烯酸接枝聚丙烯和丙烯酸接枝聚苯乙烯,其中优选钛酸酯偶联剂。
上述木质素增强型聚氯乙烯木塑发泡复合材料的制备方法,其特征在于,它包括如下步骤:
(1)将配方量的聚氯乙烯、木质纤维粉、无机粉体、稳定剂、木质素、发泡剂、发泡调节剂和增强剂加入混合机中充分混合;
(2)将步骤(1)中得到的混合物加入到双螺杆挤出机中,挤出成型得到木质素增强聚氯乙烯木塑发泡复合材料。
步骤(1)中,将相容剂和其它组分一起于混合机中充分混合。
步骤(1)中,所述的充分混合是指先以800~1000rpm的转速混合至温度为115~130℃,再以100~500rpm的转速通冷水混合至60℃以下。
步骤(2)中,所述的双螺杆挤出机挤出指的是挤出温度为120-220℃,螺杆转速为20-80rpm。
有益效果:
与现有技术相比,本发明具有如下优势:
本发明将木质素作为一种溶解度参数与聚氯乙烯接近的生物大分子,可以极大的改善木粉与聚氯乙烯之间的相容性,提高产品整体性能。将木质素增强技术与微孔发泡技术相结合,在保证材料轻量化的同时,显著提高了材料的力学性能、抗阻燃、抗紫外、抗老化、微生物抗性、抗辐射、流变性能、螺杆挤出性能和耐热性能,以及产品的表面光泽度,降低产品的吸水性。满足建材行业对聚氯乙烯型材轻量化和高性能化的双重要求。该产品可应用到建筑行业的装饰板、地板等板材上,代替现有硬质实心聚氯乙烯木塑复合材料,并可代替部分工程塑料制件,实现建筑材料轻量化;也可用于其它领域,比如汽车、电子、造船工业等。
附图说明
图1a为对比例1中所得产品的扫描电镜图;
图1b为实施例3中所得产品的扫描电镜图。
具体实施方式
对比例1:
原料:聚氯乙烯100份、竹粉60份、碳酸钙20份、复合铅盐稳定剂5份、聚乙烯蜡2份、硬脂酸1份、钛酸酯偶联剂4份、偶氮二甲酰胺3份、丙烯酸酯发泡调节剂10-15份、氯化聚乙烯5份。
制备工艺如下:
(1)将配方量的原料加入混合机中充分混合,先以800~1000rpm的转速混合至温度为115~130℃,再以100~500rpm的转速通冷水混合至60℃以下。
(2)将步骤(1)中得到的混合物加入到双螺杆挤出机中,挤出温度为120-220℃,螺杆转速为20-80rpm,挤出成型。
实施例1:
原料:聚氯乙烯100份、竹粉60份、碳酸钙20份、复合铅盐稳定剂5份、聚乙烯蜡2份、硬脂酸锌1份、碱木质素20份、偶氮二甲酰胺3份、丙烯酸酯发泡调节剂15份、甲基丙烯酸-丁二烯-苯乙烯共聚物MBS 5份。制备工艺同对比例1。
实施例2:
原料:聚氯乙烯100份、桦木粉30份、硫酸钙20份、钙锌复合稳定剂5份、聚乙烯蜡1份、微晶石蜡1份、酶解木质素15份、偶氮二甲酰胺3份、碳酸氢钠1份、丙烯酸酯发泡调节剂12份、高弹性丙烯腈-苯乙烯-丁二烯共聚物ABS 7份。制备工艺同对比例1。
实施例3:
原料:聚氯乙烯100份、杨木粉50份、滑石粉50份、复合铅盐稳定剂6份、多元醇酯2份、硬脂酸1份、有机溶剂木质素30份、钛酸酯偶联剂4份、偶氮二甲酰胺2份、尿素1份、丙烯酸酯发泡调节剂18份、乙烯-醋酸乙烯酯共聚物EVA 8份。制备工艺同对比例1。
木质纤维素与聚合物基体的界面粘结状况是影响复合材料性能的关键因素。图1是对比例中产品与本实施例产品的SEM图,显示了两者的界面粘结状况。a图中,木塑复合材料界面之间存在较大的缝隙;b图显示,在添加木质素后,木质素具有一定的接枝作用,解决了木粉与PVC的相容性问题,使得复合材料所产生的应变从聚合物基体传递到纤维的能力提高,从而提高木塑的力学性能。
实施例4:
原料:聚氯乙烯100份、木糖渣40份、玻璃纤维20份、复合铅盐稳定剂5份、聚乙烯蜡2份、微晶石蜡1份、木质素磺酸盐80份、偶氮二甲酰胺3份、丙烯酸酯发泡调节剂15份、苯乙烯-丁二烯-苯乙烯嵌段共聚物SBS 5份。制备工艺同对比例1。
实施例5:
原料:聚氯乙烯100份、棉杆60份、硅酸钙20份、有机锡类稳定剂5份、聚乙烯蜡2份、乙撑双硬脂酰胺1份、有机溶剂木质素50份、马来酸酐接枝聚氯乙烯5份、偶氮二甲酰胺3份、碳酸氢铵1份、丙烯酸酯发泡调节剂15份、氯化聚乙烯CPE 5份。制备工艺同对比例1。
实施例6:
原料:聚氯乙烯100份、竹粉40份、碳酸钙20份、钙锌复合稳定剂5份、聚乙烯蜡2份、硬脂酸1份、碱木质素50份、马来酸酐接枝聚氯乙烯5份、偶氮二甲酰胺3份、碳酸氢铵1份、丙烯酸酯发泡调节剂15份、三元乙丙橡胶5份。制备工艺同对比例1。
实施例7:
原料:聚氯乙烯100份、稻壳粉170份、玻璃纤维粉20份、复合钙锌稳定剂4份、聚乙烯蜡2份、硬脂酸锌2份、硬脂酸锌1份、造纸木质素50份、偶氮二甲酰胺3份、碳酸氢钠1份、丙烯酸酯发泡调节剂15份、氯化聚乙烯CPE 8份。制备工艺同对比例1。
实施例8:
原料:聚氯乙烯100份、糠醛渣100份、滑石粉20份、钙锌复合稳定剂5份、聚乙烯蜡1.5份、硬脂酸1.5份、碱木质素50份、马来酸酐接枝聚氯乙烯5份、偶氮二甲酰胺3份、碳酸氢铵1份、丙烯酸酯发泡调节剂16份、氯化聚乙烯7份。制备工艺同对比例1。
实施例9:
原料:聚氯乙烯100份、杨木粉50份、硫酸钙50份、铅盐稳定剂5份、聚乙烯蜡2份、硬脂酸锌2份、有机溶剂木质素60份、偶氮二甲酰胺4份、碳酸氢铵2份、丙烯酸酯发泡调节剂12份、氯化聚乙烯7份。制备工艺同对比例1。
对上述复合材料型材产品的表面进行打磨处理。依据GB/T24508—2009《木塑地板》和GB/T16422.3-2014对上述实施例的木糖渣木塑复合材料与对比例产品进行性能检测,检测结果如表1所示。
表1
Claims (17)
1.一种木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,它包括如下质量份数的组分:
2.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,其组分中包括相容剂。
3.根据权利要求2所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,它包括如下质量份数的组分:
4.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的聚氯乙烯的平均聚合度为600~1400,K值为73~82。
5.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的木质纤维粉为木粉、竹粉、秸秆粉、糠醛渣、棉杆、木材加工下脚料、木糖渣和稻壳粉中的任意一种或几种的组合。
6.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的无机粉体为碳酸钙、硫酸钙、硅酸钙、炭黑、金属氧化物、滑石粉和玻璃纤维粉中的任意一种或几种的组合。
7.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的稳定剂为三碱式硫酸铅、二碱式亚硫酸铅、硬脂酸锌、硬脂酸镉、硬脂酸铅、硬脂酸钙、有机锡类稳定剂、环保钙锌和复合铅盐类稳定剂中的任意一种或几种的组合。
8.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的润滑剂为聚乙烯蜡、硬脂酸、硬脂酸钙、硬脂酸锌、多元醇酯、油酸酰胺、微晶石蜡、液体石蜡和乙撑双硬脂酰胺中的任意一种或几种的组合。
9.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的木质素为酶解木质素、造纸木质素、碱木质素、有机溶剂木质素、木质素磺酸盐,以及对上述木质素进行酰化、酯化、醚化、酚化、烷基化或脱甲基化改性后的木质素中的任意一种或几种的组合。
10.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的发泡剂为碳酸氢铵、碳酸氢钠、偶氮二甲酰胺、甲苯磺酞氨基脲、偶氮二碳酸胺和尿素中的任意一种或几种的组合。
11.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的发泡调节剂为丙烯酸酯聚合物。
12.根据权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的增强剂为预定弹性体型冲击改性剂、非预定弹性体冲击改性剂、过度型冲击改性剂和橡胶类抗冲击改性剂中的任意一种或几种的组合。
13.根据权利要求2所述的木质素增强型聚氯乙烯木塑发泡复合材料,其特征在于,所述的相容剂为小分子偶联剂和/或大分子偶联剂;其中,所述的小分子偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、镁类偶联剂和锡类偶联剂,所述的大分子偶联剂为马来酸酐、丙烯酸、马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸酐接枝聚氯乙烯、马来酸酐接枝聚苯乙烯、丙烯酸接枝聚丙烯、丙烯酸接枝聚乙烯、丙烯酸接枝聚丙烯和丙烯酸接枝聚苯乙烯。
14.权利要求1所述的木质素增强型聚氯乙烯木塑发泡复合材料的制备方法,其特征在于,它包括如下步骤:
(1)将配方量的聚氯乙烯、木质纤维粉、无机粉体、木质素、稳定剂、增强剂和发泡剂加入混合机中充分混合;
(2)将步骤(1)中得到的混合物加入到双螺杆挤出机中,挤出成型得到木质素增强聚氯乙烯木塑发泡复合材料。
15.根据权利要求13所述的制备方法,其特征在于,步骤(1)中,将相容剂和其它组分一起于混合机中充分混合。
16.根据权利要求13所述的制备方法,其特征在于,步骤(1)中,所述的充分混合是指先以800~1000rpm的转速混合至温度为115~130℃,再以100~500rpm的转速通冷水混合至60℃以下。
17.根据权利要求13所述制备方法,其特征在于,步骤(2)中,所述的双螺杆挤出机挤出指的是挤出温度为120~220℃,螺杆转速为20~80rpm。
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