有机基质调控碳酸钙的仿生合成及其改性PVC研究
摘要
碳酸钙(CaCO_3)是一种价格低廉、补强性能好、光泽度高、磨损率低的无机填料,可以有效地降低制品的成本、提高制品的力学性能、改善制品的外观。目前,CaCO_3已经被应用于塑料、橡胶、造纸、涂料、油墨等诸多行业,但由于CaCO_3与有机基材的相容性较差,在一定程度上限制了CaCO_3的使用。本文通过仿生合成的方法制备CaCO_3,以期改变其形貌,提高其相容性,并将其添加于普遍适用、需求量大的通用型树脂聚氯乙烯(PVC)中,研究在本论中所有机基质存在下合成的碳酸钙对PVC力学性能的影响规律,并与无有机基质存在下合成的碳酸钙对PVC力学性能的影响进行对比研究,探索前种方法合成的碳酸钙对PVC的力学性能的有益影响是否优于后者,并揭示其机理。
首先,以十二烷基苯磺酸钠(SDBS)、乙二醇、聚乙烯醇(PVA)和聚乙二醇400(PEG-400)为有机模板,分别采用三种不同的方法:复分解法、尿素水解法、碳化法仿生合成了CaCO_3,并采用电子扫描显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、粉末X射线衍射仪(XRD)进行表征。结果表明,仿生合成的CaCO_3在晶体形貌上有较大改观,在复分解法中,合成的CaCO_3主要呈纺锤形;在尿素水解法中,分别得到了规则的正六边形、细长条形、花形三种CaCO_3形貌;在碳化法中,合成的CaCO_3呈不规则块状。
第二部分将用复分解法仿生合成的CaCO_3应用于PVC中,并测试其拉伸性能和抗冲性能。结果表明:复分解法仿生合成CaCO_3的加入对PVC的拉伸性能、断裂伸长率、抗冲性能都有显著地提高,明显优于普通CaCO_3。(1)一般用量在5~10份时拉伸强度达到最大值:添加量为5份时,以SDBS为有机基质的CaCO_3样品比相同含量下无有机基质的CaCO_3样品提高了约12%;添加量为10份时,以SDBS/乙二醇为有机基质的CaCO_3样品比相同含量下无有机基质的CaCO_3样品提高了约12%;此外以乙二醇为有机基质的CaCO_3样品,在添加量为20份时,比相同含量下无有机基质的CaCO_3样品提高了约11%。(2)添加仿生合成CaCO_3的PVC的断裂伸长率都大于未添加CaCO_3的115%,在碳酸钙的添加量相同时,以PVA为有机基质的CaCO_3比相同含量下无有机基质的CaCO_3样品相比提高了93%左右。(3)在抗冲性能方面:添加量为10份时,以SDBS和SDBS/乙二醇为有机基质的CaCO_3样品不能被抗冲机冲断,性能最优;添加量为5份时,以乙二醇为有机基质的CaCO_3样品比相同含量下其他样品提高了88%;添加量为30份时,以PEG-400为有机基质的CaCO_3样品比相同含量下无有机基质的CaCO_3样品提高了约63%。
Calcium carbonate (CaCO_3) is one kind of widely used inorganic filler with low-cost, excellent reinforcing effect, high gloss and low wearabiligy. CaCO_3 can effectively reduce the cost, improve the mechanical properties and the appearance of the products. Currently, CaCO_3 has been widely used in plastic, rubber, papermaking, coatings, printing ink et.. As widely used inorganic filler, the poor compatibility of CaCO_3 with polymers restricts its extensive application. In this work, CaCO_3 was synthesized by a biomimetic method to achieve crystals with different shape. The synthesized CaCO_3 were applied to polyvinyl chloride (PVC) to improve its mechanical properties. Research the influence of calcium carbonate using organic matrix for the mechanical properties of PVC, and comparative with the ordinary CaCO_3, explore the former method for PVC synthesis if better than that of the latter or not, and reveals its mechanism.
Part I: for the biomimetic synthesis of CaCO_3, sodium dodecyl benzene sulfonate (SDBS), glycol, polyvinyl alcohol (PVA) and polyethylene glycol 400 (PEG-400) were used as the organic templates, respectively. Three methods were used to synthesize CaCO_3: metathesis method, urea hydrolysis method and cabonization method, last we character them with scanning electron microscope, fourier transform infrared spectroscopy, X-ray powder diffraction. The results show that the crystal morphology of CaCO_3 changes a lot, we get spindle-shaped CaCO_3 by metathesis method; regular hexagon, slightness bar, flower shape CaCO_3 by urea hydrolysis method; irregular square block by cabonization.
Part II: The synthesized CaCO_3 by biomimetic method were applied to PVC, and the tensile properties and impact strength were characterized. (1) Compared with the addition of commercial used CaCO_3, the addition of CaCO_3 significantly improved the tensile strength, the elongation at break and impact strength. The tensile strength reached the maximum at loading of 5 ~ 10%. At the same amount (5%) of CaCO_3, the tensile strength was improved by 12% for the SDBS modified CaCO_3 than the common CaCO_3. When the CaCO_3 loading is 10%, the tensile strength was improved by 12% for the SDBS/glycol modified CaCO_3 added system than the original CaCO_3 one. When the CaCO_3 loading is 20%, the tensile strength was improved by 11% for the glycol modified CaCO_3 added system than the original CaCO_3 one. (2) The elongation at break was improved by 115% for the biomimetic synthesized CaCO_3 . (3) For the impact strength, after the addition of SDBS and SDBS/glycol modified CaCO_3, the impact strength is beyond the range of the impact machine, indicating the high toughness.
首先,以十二烷基苯磺酸钠(SDBS)、乙二醇、聚乙烯醇(PVA)和聚乙二醇400(PEG-400)为有机模板,分别采用三种不同的方法:复分解法、尿素水解法、碳化法仿生合成了CaCO_3,并采用电子扫描显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、粉末X射线衍射仪(XRD)进行表征。结果表明,仿生合成的CaCO_3在晶体形貌上有较大改观,在复分解法中,合成的CaCO_3主要呈纺锤形;在尿素水解法中,分别得到了规则的正六边形、细长条形、花形三种CaCO_3形貌;在碳化法中,合成的CaCO_3呈不规则块状。
第二部分将用复分解法仿生合成的CaCO_3应用于PVC中,并测试其拉伸性能和抗冲性能。结果表明:复分解法仿生合成CaCO_3的加入对PVC的拉伸性能、断裂伸长率、抗冲性能都有显著地提高,明显优于普通CaCO_3。(1)一般用量在5~10份时拉伸强度达到最大值:添加量为5份时,以SDBS为有机基质的CaCO_3样品比相同含量下无有机基质的CaCO_3样品提高了约12%;添加量为10份时,以SDBS/乙二醇为有机基质的CaCO_3样品比相同含量下无有机基质的CaCO_3样品提高了约12%;此外以乙二醇为有机基质的CaCO_3样品,在添加量为20份时,比相同含量下无有机基质的CaCO_3样品提高了约11%。(2)添加仿生合成CaCO_3的PVC的断裂伸长率都大于未添加CaCO_3的115%,在碳酸钙的添加量相同时,以PVA为有机基质的CaCO_3比相同含量下无有机基质的CaCO_3样品相比提高了93%左右。(3)在抗冲性能方面:添加量为10份时,以SDBS和SDBS/乙二醇为有机基质的CaCO_3样品不能被抗冲机冲断,性能最优;添加量为5份时,以乙二醇为有机基质的CaCO_3样品比相同含量下其他样品提高了88%;添加量为30份时,以PEG-400为有机基质的CaCO_3样品比相同含量下无有机基质的CaCO_3样品提高了约63%。
Calcium carbonate (CaCO_3) is one kind of widely used inorganic filler with low-cost, excellent reinforcing effect, high gloss and low wearabiligy. CaCO_3 can effectively reduce the cost, improve the mechanical properties and the appearance of the products. Currently, CaCO_3 has been widely used in plastic, rubber, papermaking, coatings, printing ink et.. As widely used inorganic filler, the poor compatibility of CaCO_3 with polymers restricts its extensive application. In this work, CaCO_3 was synthesized by a biomimetic method to achieve crystals with different shape. The synthesized CaCO_3 were applied to polyvinyl chloride (PVC) to improve its mechanical properties. Research the influence of calcium carbonate using organic matrix for the mechanical properties of PVC, and comparative with the ordinary CaCO_3, explore the former method for PVC synthesis if better than that of the latter or not, and reveals its mechanism.
Part I: for the biomimetic synthesis of CaCO_3, sodium dodecyl benzene sulfonate (SDBS), glycol, polyvinyl alcohol (PVA) and polyethylene glycol 400 (PEG-400) were used as the organic templates, respectively. Three methods were used to synthesize CaCO_3: metathesis method, urea hydrolysis method and cabonization method, last we character them with scanning electron microscope, fourier transform infrared spectroscopy, X-ray powder diffraction. The results show that the crystal morphology of CaCO_3 changes a lot, we get spindle-shaped CaCO_3 by metathesis method; regular hexagon, slightness bar, flower shape CaCO_3 by urea hydrolysis method; irregular square block by cabonization.
Part II: The synthesized CaCO_3 by biomimetic method were applied to PVC, and the tensile properties and impact strength were characterized. (1) Compared with the addition of commercial used CaCO_3, the addition of CaCO_3 significantly improved the tensile strength, the elongation at break and impact strength. The tensile strength reached the maximum at loading of 5 ~ 10%. At the same amount (5%) of CaCO_3, the tensile strength was improved by 12% for the SDBS modified CaCO_3 than the common CaCO_3. When the CaCO_3 loading is 10%, the tensile strength was improved by 12% for the SDBS/glycol modified CaCO_3 added system than the original CaCO_3 one. When the CaCO_3 loading is 20%, the tensile strength was improved by 11% for the glycol modified CaCO_3 added system than the original CaCO_3 one. (2) The elongation at break was improved by 115% for the biomimetic synthesized CaCO_3 . (3) For the impact strength, after the addition of SDBS and SDBS/glycol modified CaCO_3, the impact strength is beyond the range of the impact machine, indicating the high toughness.
引文
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[3] Severin K, Johnsson K. 37th EFS/EUCHEM Conferenceon Stereochemistry[J]. CHIMIA, 2002, 56: 7-8.
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[6] Mann S. Biomineraliztion: Principles and concepts in bioinorganic materials chemistry[M]. Oxford University Press, 2001, 6-23.
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