CN102002149B - 聚乳酸-硫化锌纳米复合材料的制备方法 - Google Patents
聚乳酸-硫化锌纳米复合材料的制备方法 Download PDFInfo
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- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 33
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 32
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- -1 aryl tin Chemical compound 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
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- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- GAAKLDANOSASAM-UHFFFAOYSA-N undec-10-enoic acid;zinc Chemical compound [Zn].OC(=O)CCCCCCCCC=C GAAKLDANOSASAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229940118257 zinc undecylenate Drugs 0.000 claims description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 claims 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- XIVNZHXRIPJOIZ-UHFFFAOYSA-N octadecanoic acid;zinc Chemical compound [Zn].CCCCCCCCCCCCCCCCCC(O)=O XIVNZHXRIPJOIZ-UHFFFAOYSA-N 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 20
- 239000004626 polylactic acid Substances 0.000 abstract description 20
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
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Abstract
本发明提供一种聚乳酸-硫化锌纳米复合材料的制备方法，在高压反应釜中，按一定比例放入丙交酯、催化剂、锌盐、硫源和溶剂，控制反应温度和时间，使混合溶液在高温密闭体系中进行反应，这样使单体、催化剂、锌盐、硫源和溶剂充分接触，且不会挥发，从而使反应完全；然后将反应溶液沉淀过滤干燥，即得到聚乳酸-硫化锌纳米复合材料。本发明将纳米硫化锌的制备和聚乳酸的聚合一步完成，得到的聚乳酸-硫化锌纳米复合材料透明且具有抗紫外和光致发光特性，聚乳酸的分子量高。本发明反应过程中所用溶剂的量相对较少，反应条件温和，制备方法简单，具备很好的规模化生产前景。
Description
技术领域
本发明涉及一种聚乳酸-硫化锌纳米复合材料的制备方法，尤其涉及一种在高压釜中采用溶剂热合成法在丙交酯开环聚合的同时原位制备纳米硫化锌的新方法。本发明属于复合材料技术领域。
背景技术
聚乳酸是由玉米、马铃薯等可再生的植物资源中提取出的淀粉发酵或化学合成得到的，它具有良好的生物相容性、生物可降解性、易加工性、无毒无刺激性等优点，其可再生性和可降解性是解决目前环境和资源问题的有效手段，因而受到广泛关注，尤其在手术缝合线、骨折内固定、药物控释系统以及组织工程支架材料等生物医学领域有着较为广泛的应用。为了扩大聚乳酸的应用，改善其功能，聚乳酸与无机纳米材料的复合也引起了人们的广泛关注，如聚乳酸与羟基磷灰石的复合(CN200710030224.7；CN200610053891.2；CN200710157568.4；CN200410033138.8等)，聚乳酸/TiO2复合材料(庄韦；张建华等，复合材料学报，25(3)：8-11；王华林；吴立军等，高分子材料科学与工程，26(3)：82-85)，聚乳酸与蒙脱土复合材料(CN200610010279.7；CN200710171659.3；CN200510030494.9等)；聚乳酸/CdSe/ZnS复合材料(Lee，YK；Hong，SM；Kim，JS，et al.，MACROMOLECULAR RESEARCH，15(4)：330-336)。但聚乳酸与无机纳米复合材料的种类较少，而且常以纳米颗粒与聚乳酸直接复合为主，所制备的复合材料往往失去了聚乳酸的透明性，限制了其广泛应用。纳米硫化锌的制备方法很多(CN200910080996.0；200610024420.9；200810031121.7等)，但往往需要加入分散剂或表面活性剂才能得到分散较好的纳米硫化锌颗粒，这也使其与聚合物复合时带入杂质或是给后续的纯化处理造成困难。
发明内容
本发明的目的在于针对现有制备聚乳酸纳米复合材料技术上的不足，提供一种聚乳酸-硫化锌纳米复合材料的制备方法，制备的纳米复合材料具有良好的功能特性，方法简单，反应条件温和，便于大规模生产。
为实现这样的目的，在本发明的技术方案中，采用的制备方法反应机理有别于以往制备聚乳酸纳米复合材料的方法，将纳米硫化锌的制备和聚乳酸的聚合一步完成。在高压反应釜中，按一定比例放入丙交酯、催化剂、锌盐、硫源和溶剂，控制反应温度和时间，使混合溶液在高温密闭体系中进行反应，这样使单体、催化剂、锌盐、硫源和溶剂充分接触，且不会挥发，从而使反应完全，然后将反应溶液沉淀过滤干燥，即得到聚乳酸-硫化锌纳米复合材料。
本发明的具体方法为：以重量份计，在高压釜中加入25-70份的丙交酯、0.05-1份的催化剂、1-20份锌盐、1-20份硫源和25-50份的溶剂，各成分的总和为100份。高压釜中通入氮气5分钟以脱除氧气，将高压釜盖子拧紧后放入120-200℃的恒温箱中，放置5-12小时，然后取出用水冷却，打开高压釜，将反应溶液倒入乙醇中沉淀过滤，并用乙醇洗涤沉淀5次，然后抽滤，将抽滤得到的粉末在80℃真空烘箱中干燥24小时，即得到聚乳酸-硫化锌纳米复合材料。
本发明制备得到的聚乳酸-硫化锌纳米复合材料粉末经热压可得透明的薄膜，溶解于氯仿可得透明溶液，具有抗紫外性和光致发光特性。
本发明所述的催化剂为烷基烷氧基锡(四价)、芳基锡(四价)、二价锡盐、镁络合物、烷基铝、烷氧基铝或锌络合物，或是它们的混合物。
本发明所述的锌盐为硫酸锌、硝酸锌、氯化锌、醋酸锌、丙烯酸锌、碳酸锌、磷酸锌、硬脂酸锌、硼酸锌、环烷酸锌或十一烯酸锌，或是它们的混合物。
本发明所述的硫源为硫化氢、硫化钠、二硫化碳、硫醇、硫脲、硫代硫酸钠、硫代乙酰胺或二硫化四甲基秋兰姆。
本发明所述的溶剂为丙酮、丁酮、1，2-二氯乙烷、1，2-二氯甲烷、氯仿、四氯化碳、甲苯、环己酮、甲苯环己酮、甲基异丁酮、苯、四氢呋喃或二甲苯，或它们的混合物。
本发明所用设备简单，由于反应是处在密闭高压且汽液固共存状态下，反应物可以充分接触，且丙交酯对硫化锌起分散作用，使纳米硫化锌颗粒尺寸小为5-20纳米，而锌盐对丙交酯的开环聚合有一定的催化作用，因此能够得到纳米硫化锌均匀分散于聚乳酸基体中的聚乳酸-硫化锌纳米复合材料，材料具有很好的透明性，聚乳酸的分子量也较大(大于30万)，且兼具抗紫外性和光致发光性能，可应用于具有荧光标识性的医疗器件。反应过程中所用溶剂的量相对较少，无需添加新的分散剂或表面活性剂，反应条件温和，硫化锌的形成及聚乳酸的聚合一步完成，制备方法简单，具备很好的规模化生产前景。
附图说明
图1为本发明方法得到的聚乳酸-硫化锌纳米复合材料的TEM透射电镜照片。
图2为聚乳酸-硫化锌纳米复合材料溶于氯仿所得的透明溶液。
具体实施方式
以下通过附图和具体的实施例对本发明的技术方案作详细描述。以下实施例是对本发明的进一步说明，而不是限制本发明的范围。
实施例1
在高压反应釜中放入20g丙交酯、0.03g氯化亚锡、0.46g醋酸锌、0.35g二硫化碳、9g甲苯，高压釜中通入氮气5分钟以脱除氧气，将高压釜盖子拧紧放入200℃的烘箱中，放置5小时，然后取出用水冷却，打开高压釜，将反应溶液倒入乙醇中沉淀后过滤，并用乙醇洗涤沉淀5次，然后抽滤，将抽滤得到的粉末在80℃真空烘箱中干燥24小时，即得到聚乳酸-硫化锌纳米复合材料。
得到的聚乳酸-硫化锌纳米复合材料分散性很好，如图1所示，其聚乳酸的粘均分子量为50万。
实施例2
在高压反应釜中加入12g丙交酯、0.1g四苯基卟啉铝烷氧基化合物、5g硝酸锌、4.5g硫脲、20g丙酮，高压釜中通入氮气5分钟以脱除氧气，将高压釜盖子拧紧放入120℃的烘箱中，放置12小时，然后取出用水冷却，打开高压釜，将反应溶液倒入乙醇中沉淀后过滤，并用乙醇洗涤沉淀5次，然后抽滤，将抽滤得到的粉末在80℃真空烘箱中干燥24小时，即得到聚乳酸-硫化锌纳米复合材料。
得到的聚乳酸-硫化锌纳米复合材料溶于氯仿可得透明溶液，如图2所示，其聚乳酸的粘均分子量为35万。
实施例3
在高压反应釜中放入25g丙交酯、0.5g烷基铝、8g环烷酸锌、7g硫代硫酸钠、15g氯仿，高压釜中通入氮气5分钟以脱除氧气，将高压釜盖子拧紧放入160℃的烘箱中，放置8小时，然后取出用水冷却，打开高压釜，将反应溶液倒入乙醇中沉淀后过滤，并用乙醇洗涤沉淀5次，然后抽滤，将抽滤得到的粉末在80℃真空烘箱中干燥24小时，即得到聚乳酸-硫化锌纳米复合材料。
得到的聚乳酸-硫化锌纳米复合材料在300纳米波长激发下可发出365纳米的光，其聚乳酸的粘均分子量为42万。
Claims (5)
1.一种聚乳酸-硫化锌纳米复合材料的制备方法，其特征在于：以重量份计，在高压釜中加入25-70份的丙交酯、0.05-1份的催化剂、1-20份锌盐、1-20份硫源和25-50份的溶剂，各成分的总和为100份；高压釜中通入氮气5分钟以脱除氧气，将高压釜盖子拧紧后放入120-200℃的恒温箱中，放置5-12小时，然后取出用水冷却，打开高压釜，将反应溶液倒入乙醇中沉淀过滤，并用乙醇洗涤沉淀5次，然后抽滤，将抽滤得到的粉末在80℃真空烘箱中干燥24小时，即得到聚乳酸-硫化锌纳米复合材料。
2.根据权利要求1的聚乳酸-硫化锌纳米复合材料的制备方法，其特征在于催化剂为四价烷基烷氧基锡、四价芳基锡、二价锡盐、镁络合物、烷基铝、烷氧基铝或锌络合物，或是它们的混合物。
3.根据权利要求1的聚乳酸-硫化锌纳米复合材料的制备方法，其特征在于锌盐为硫酸锌、硝酸锌、氯化锌、醋酸锌、丙烯酸锌、碳酸锌、磷酸锌、硬脂酸锌、硼酸锌、环烷酸锌或十一烯酸锌，或是它们的混合物。
4.根据权利要求1的聚乳酸-硫化锌纳米复合材料的制备方法，其特征在于硫源为硫化氢、硫化钠、二硫化碳、硫醇、硫脲、硫代硫酸钠、硫代乙酰胺或二硫化四甲基秋兰姆。
5.根据权利要求1的聚乳酸-硫化锌纳米复合材料的制备方法，其特征在于溶剂为丙酮、丁酮、1，2-二氯乙烷、氯仿、四氯化碳、甲苯、环己酮、甲苯环己酮、甲基异丁酮、苯、四氢呋喃或二甲苯，或它们的混合物。
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