CN111019217B - 一种纳米复合聚合物材料 - Google Patents
一种纳米复合聚合物材料 Download PDFInfo
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- CN111019217B CN111019217B CN201911337138.XA CN201911337138A CN111019217B CN 111019217 B CN111019217 B CN 111019217B CN 201911337138 A CN201911337138 A CN 201911337138A CN 111019217 B CN111019217 B CN 111019217B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 21
- 239000002861 polymer material Substances 0.000 title claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000155 melt Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000007822 coupling agent Substances 0.000 claims description 37
- 239000002086 nanomaterial Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- -1 isocyanate compounds Chemical class 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052621 halloysite Inorganic materials 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
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- 229920002223 polystyrene Polymers 0.000 claims description 4
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- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
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- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- UELITFHSCLAHKR-UHFFFAOYSA-N acibenzolar-S-methyl Chemical compound CSC(=O)C1=CC=CC2=C1SN=N2 UELITFHSCLAHKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920005692 JONCRYL® Polymers 0.000 description 5
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- 239000002159 nanocrystal Substances 0.000 description 5
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
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- 238000010096 film blowing Methods 0.000 description 2
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- BEQDKWKSUMQVMX-UHFFFAOYSA-N 2,4-dimethyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC(C)=N1 BEQDKWKSUMQVMX-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- AUJGKKUMHNTYTQ-UHFFFAOYSA-N CCC[Si](OCC)(OCC)OC(C)OC1OC1C Chemical compound CCC[Si](OCC)(OCC)OC(C)OC1OC1C AUJGKKUMHNTYTQ-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229940093629 isopropyl isostearate Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- NEOZOXKVMDBOSG-UHFFFAOYSA-N propan-2-yl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC(C)C NEOZOXKVMDBOSG-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
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- 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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Abstract
本发明公开了一种纳米复合聚合物材料,该材料由树脂熔体、第二反应助剂和第二纳米填料按照熔融共混的方式制备而成;树脂熔体的制备过程如下:将聚合物、第一纳米填料、复配型稳定剂、开口剂、第一反应助剂、界面相容剂在螺杆挤出机中混合挤出。本发明所提供的纳米复合聚合物材料,所含两种填料表面的改性基团可发生原位化学反应,从而实现纳米填料在材料中的良好分散和与聚合物基体的良好相容,提高了纳米复合聚合物材料的力学性能。
Description
技术领域
本发明涉及聚合物纳米复合领域,尤其涉及一种纳米复合聚合物材料。
背景技术
聚烯烃是国民经济的重要基础行业之一,以其优异的机械性能和化学稳定性,被广泛应用于交通、农业、军事、电子、医疗、卫生和日常生活用品等领域。在大部分情况下,聚乙烯树脂通常需要混合填料,填料对于聚烯烃塑料产品的性能有着十分显著的效果。
通常可以通过加入纳米颗粒的方式提高力学性能,但由于纳米粒子粒径小、比表面积较大,容易在基体中发生团聚现象,因此分散性良好是制备性能优良的纳米复合材料的关键性问题。一般可以通过表面化学修饰纳米颗粒,提高其与基体的相容性,但存在表面不易修饰的纳米粒子,因此为了提高此类纳米粒子在基体中的分散性,CN 108299579A公开了一种石墨烯/纳米二氧化硅/聚苯乙烯杂化材料,该方法是在反应釜内原位乳液聚合,并只对纳米二氧化硅进行偶联剂改性,石墨烯与纳米二氧化硅之间相互作用力不强。CN109929141A报道了一种聚乙烯亚胺改性的氧化石墨烯PEI-GO,该方法只应用于将氧化石墨烯用于聚乙烯亚胺中,不具有普适性。CN106117949B报道了一种高密度聚乙烯材料的复合材料,其中填料包含石墨烯和碳纳米管,但仅仅利用两者之间的氢键作用,并经过表面修饰,无法实现填料在基体中的优良分散。CN107602987A公开了一种含石墨烯和碳纳米管的高分子PTC复合材料及制备方法,同样该方法仅利用了填料之间的物理相互作用实现分散。
发明内容
本发明的目的是针对现有技术的不足,提供一种纳米复合聚合物材料,可以达到分散纳米粒子的要求。
本发明的目的是通过以下技术方案实现的:
一种纳米复合聚合物材料,其特征在于,由质量百分比为80-99.8%的树脂熔体、0.1-5%的第二反应助剂和质量百分比为0.1-15%的第二纳米填料按照熔融共混的方式制备而成;所述树脂熔体由质量分数为75-99.7%的聚合物、0.1-5%的抗氧剂、0.1-5%的第一反应助剂、0.1-15%的第一纳米填料在螺杆挤出机中连续混合挤出制得。第一纳米填料与第二纳米填料之间存在原位反应。
进一步地,所述聚合物为聚乙烯、聚烯烃热塑性弹性体、聚氯乙烯、聚丙烯、聚苯乙烯、ABS、乙丙橡胶、丁腈橡胶、聚酰胺、聚甲醛、聚碳酸酯或聚苯醚。
进一步地,所述的第一纳米填料通过以下方法制备得到:将第一纳米材料用溶液稀释后,加入质量为填料质量的5-20%的第一偶联剂,在70-130℃进行搅拌反应,反应2-8小时,反应结束后,进行干燥处理后得到修饰后的第一纳米填料;所述溶液为乙醇水溶液或甲苯溶液;所述第一偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的一种,第一纳米材料为粒径为10-100纳米的二氧化硅、碳酸钙、氧化锌、二氧化钛中的一种或多种按照任意配比混合组成。
进一步地,所述的第二纳米填料通过以下方法制备得到:将第二纳米填料用溶液稀释后,加入质量为填料质量的5-20%的第二偶联剂,在70-130℃进行搅拌反应,反应2-8小时,反应结束后,进行干燥处理后得到修饰后的第二纳米填料;所述溶液为乙醇水溶液或甲苯溶液;所述第二偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的一种。所述的第二纳米填料为长径比为10-1000的纤维素、纤维素纳米晶、纤维素纳米纤维、木质素、碱性木质素、埃洛石中的一种或多种按照任意配比混合组成。
进一步地,所述第一偶联剂优选γ―(2,3-环氧丙氧)丙基三甲氧基硅烷,γ-氨丙基三乙氧基硅烷或3-异氰酸酯基丙基三乙氧基硅烷。
进一步地,所述第二偶联剂优选γ―(2,3-环氧丙氧)丙基三甲氧基硅烷,γ-氨丙基三乙氧基硅烷或3-异氰酸酯基丙基三乙氧基硅烷。
进一步地,所述抗氧剂由BTH、DSTP、DLTP、168、264、300、425、626、627、1010、1076中的一种或多种按照任意配比混合组成。
进一步地,所述第一反应助剂由氮丙啶、环氧类、异氰酸酯类、钛酸酯类、恶唑啉类中的一种或多种按照任意配比混合组成。所述第二反应助剂由多环氧基或胺基化合物、双酚A型环氧树脂、硅烷偶联剂、缩水甘油酯、碳化二亚胺、异氰酸酯类化合物、氯化苄中的一种或多种按照任意配比混合组成。
进一步地,所述纳米复合聚合物材料通过加工制得薄膜、片材或板材用于制备包装材料、农用薄膜材料、高强度薄膜材料、高强度片材、高强度板材。所述薄膜的厚度为5~200μm,所述片材的厚度为200μm~2mm。
进一步地,所述加工方法包括吹膜法、流延法、溶液浇筑法、旋涂法、压延法、多层共挤法、双向拉伸法、层压法。
与现有技术相比,本发明的有益效果是,针对纳米粒子在聚合物基体中分散性及相容性差的问题,基于相容好的纳米粒子在聚合物基体中的良好分散,利用其与不好相容的纳米粒子之间的化学键相互作用,使不好相容的纳米粒子与聚合物的相容性和分散性提高,从而制备了一种力学性能良好的一种纳米复合聚合物材料。通过调控两种粒子的化学修饰程度和质量比,可得到不同力学性能的可生物降解薄膜。本发明所述纳米复合聚合物材料具备良好的力学性能,生产工艺简单,适合于大规模生产。
具体实施方式
下面结合具体实施方式对本发明的技术方案作进一步具体说明。
实施例1
1、修饰纳米填料
第一纳米材料选用粒径为30纳米的二氧化硅:将98.5%的二氧化硅溶于9850%的按质量比为1:9的水与乙醇混合溶液中,得填料有机溶液;加入质量为二氧化硅质量的5%的偶联剂(选用γ―(2,3-环氧丙氧)丙基三甲氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用长径比为50的纳米纤维素:将90%的纳米纤维素溶于9760%的按质量比为1:9的水与乙醇混合溶液中,得填料有机溶液;加入质量为纳米纤维素质量的5%的偶联剂(γ-氨丙基三乙氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为80%的聚合物(选用聚乙烯)、14.9%的第一纳米填料、5%的第一反应助剂(选用氮丙啶)、0.1%的抗氧剂DSTP在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为80.1%的树脂熔体、5%的第二反应助剂(选用碳化二亚胺)14.9%的第二纳米填料在螺杆挤出机中连续混合挤出,经吹膜加工即得PE复合薄膜。
经上述步骤所得的复合薄膜,其厚度为25μm,经万能材料试验机测得其拉伸强度可达40MPa,弹性模量可达100MPa,断裂伸长率800%左右。
实施例2
1、修饰纳米填料
第一纳米材料选用粒径为50纳米的碳酸钙:将95%的碳酸钙溶于1000%的按质量比为1:8的水与乙醇混合溶液中,得填料有机溶液;加入质量为碳酸钙质量的5.5%的偶联剂(选用γ-氨丙基三乙氧基硅烷),在80℃进行搅拌反应,反应7.5小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用长径比为20的纤维素纳米晶:将88%的纤维素纳米晶溶于7760%的按质量比为1:8的水与乙醇混合溶液中,得填料有机溶液;加入质量为纤维素纳米晶质量的10%的偶联剂(γ―(2,3-环氧丙氧)丙基三甲氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为98.4%的聚合物(选用聚丙烯)、0.5%的第一纳米填料、0.1%的第一反应助剂(选用Joncryl ADR4368)、1%的抗氧剂BTH在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为99.4%的树脂熔体、0.1%的第二反应助剂(选用甲基二异氰酸酯)、0.5%的第二纳米填料在螺杆挤出机中连续混合挤出,经双向拉伸加工即得PP复合薄膜。
经上述步骤所得的复合薄膜,其厚度为100μm,经万能材料试验机测得其拉伸强度可达60MPa,弹性模量可达1GPa,断裂伸长率200%左右。
实施例3
1、修饰纳米填料
第一纳米材料选用粒径为60纳米的二氧化钛:将20%的二氧化钛溶于1950%的按质量比为1:9.5的水与乙醇混合溶液中,得填料有机溶液;加入质量为二氧化钛质量的19.5%的偶联剂(选用异硬脂酰基钛酸异丙酯),在85℃进行搅拌反应,反应2.5小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用长径比为80的埃洛石:将38%的埃洛石溶于4760%的按质量比为1:8.5的水与乙醇混合溶液中,得填料有机溶液;加入质量为埃洛石质量的6%的偶联剂(γ-氨丙基三甲氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为93%的聚合物(选用聚氯乙烯)、2%的第一纳米填料、2%的第一反应助剂(选用Joncryl ADR4370)、3%的抗氧剂1010在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为91%的树脂熔体、1%的第二反应助剂(选用环氧类化学物SMC)、8%的第二纳米填料在螺杆挤出机中连续混合挤出,经流延加工即得PVC复合薄膜。
经上述步骤所得的复合薄膜,其厚度为300μm,经万能材料试验机测得其拉伸强度可达100MPa,弹性模量可达3000MPa,断裂伸长率600%左右。
实施例4
1、修饰纳米填料
第一纳米材料选用粒径为50纳米的碳酸钙:将5%的碳酸钙溶于600%的甲苯溶液中,得填料有机溶液;加入质量为碳酸钙质量的15%的偶联剂(γ―(2,3-环氧丙氧)丙基三乙氧基硅烷),在120℃进行搅拌反应,反应4小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用木质素:将18%的木质素溶于1760%的的甲苯溶液中,得填料有机溶液;加入质量为木质素质量的8%的偶联剂(γ-氨丙基三甲氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为89.5%的聚合物(选用聚苯乙烯)、4%的第一纳米填料、1.5%的第一反应助剂(选用Joncryl ADR4380)、5%的抗氧剂168在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为84.5%的树脂熔体、2.5%的第二反应助剂(选用缩水甘油酯)、13%的第二纳米填料在螺杆挤出机中连续混合挤出,经热压加工即得PS复合薄膜。
经上述步骤所得的复合薄膜,其厚度为290μm,经万能材料试验机测得其拉伸强度可达90MPa,弹性模量可达4000MPa,断裂伸长率150%左右。
实施例5
1、修饰纳米填料
第一纳米材料选用粒径为30纳米的氧化锌:将43%的氧化锌溶于4550%的甲苯溶液中,得填料有机溶液;加入质量为氧化锌质量的10%的偶联剂(γ-氨丙基三甲氧基硅烷),在125℃进行搅拌反应,反应5小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用碱性木质素:将24%的碱性木质素溶于5060%的的甲苯溶液中,得填料有机溶液;加入质量为碱性木质素质量的8%的偶联剂(3-异氰酸酯基丙基三乙氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为80%的聚合物(选用乙丙橡胶)、12%的第一纳米填料、3%的第一反应助剂(选用二苯基甲烷二异氰酸酯)、5%的抗氧剂264在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为88.5%的树脂熔体、3.5%的第二反应助剂(选用氯化苄)、8%的第二纳米填料在螺杆挤出机中连续混合挤出,经溶液浇筑即得乙丙橡胶复合薄膜。
经上述步骤所得的复合薄膜,其厚度为1000μm,经万能材料试验机测得其拉伸强度可达40MPa,弹性模量可达10MPa,断裂伸长率900%左右。
实施例6
1、修饰纳米填料
第一纳米材料选用粒径为80纳米的二氧化硅:将20%的二氧化硅溶于3000%的甲苯溶液中,得填料有机溶液;加入质量为二氧化硅质量的8%的偶联剂(γ-氨丙基三乙氧基硅烷),在120℃进行搅拌反应,反应6小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用长径比为20的纤维素纳米晶和长径比为150的纤维素纳米纤维按照质量比为1:2混合组成:将50%的第二纳米材料溶于6200%的的甲苯溶液中,得填料有机溶液;加入质量为第二纳米材料质量的8%的偶联剂(3-异氰酸酯基丙基三甲氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为85%的聚合物(选用聚碳酸酯)、8%的第一纳米填料、4%的第一反应助剂(选用钛酸正四丁酯)、3%的抗氧剂300在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为88.5%的树脂熔体、4.5%的第二反应助剂(选用双酚A型环氧树脂)、7%的第二纳米填料在螺杆挤出机中连续混合挤出,经注塑加工即得PC复合薄膜。
经上述步骤所得的复合薄膜,其厚度为3000μm,经万能材料试验机测得其拉伸强度可达80MPa,弹性模量可达150MPa,断裂伸长率190%左右。
实施例7
1、修饰纳米填料
第一纳米材料选用粒径为95纳米的二氧化硅:将60%的第一纳米材料溶于7800%的按质量比为1:8的水与乙醇混合溶液中,得填料有机溶液;加入质量为第一纳米材料质量的12%的偶联剂(N-2-氨乙基-3-氨丙基甲基二甲氧基硅烷),在90℃进行搅拌反应,反应3.5小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用长径比为40的纤维素纳米晶和长径比为70的埃洛石按照质量比为2:3混合组成:将20%的第二纳米材料溶于3200%的甲苯溶液中,得填料有机溶液;加入质量为第二纳米材料质量的8%的偶联剂(3-异氰酸酯基丙基三乙氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为91.2%的聚合物(选用聚酰胺)、3.5%的第一纳米填料、4.8%的第一反应助剂(选用二甲基恶唑啉)、0.5%的抗氧剂627在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为88.2%的树脂熔体、4.8%的第二反应助剂(选用质量为1:1的二甲基异氰酸酯与碳化二亚胺)、7%的第二纳米填料在螺杆挤出机中连续混合挤出,经热压加工即得PA复合薄膜。
经上述步骤所得的复合薄膜,其厚度为350μm,经万能材料试验机测得其拉伸强度可达110MPa,弹性模量可达1.8GPa,断裂伸长率200%左右。
实施例8
1、修饰纳米填料
第一纳米材料选用粒径为75纳米的氧化锌:80%的氧化锌溶于9950%的甲苯溶液中,得填料有机溶液;加入质量为氧化锌质量的18%的偶联剂(3-巯丙基三甲氧基硅烷),在120℃进行搅拌反应,反应6小时,反应结束后,进行干燥处理后得到修饰后填料。
第二纳米材料选用木质素和长径比为180的纤维素纳米纤维按照质量比为1:3混合组成:将10%的第二纳米材料溶于900%的甲苯溶液中,得填料有机溶液;加入质量为第二纳米材料质量的8%的偶联剂(γ-二乙烯三胺丙基甲基二甲氧基硅烷),在70℃进行搅拌反应,反应8小时,反应结束后,进行干燥处理后得到修饰后填料。
2、树脂加工
将质量百分比为95.8%的聚合物(选用聚苯醚)、3%的第一纳米填料、0.2%的第一反应助剂(选用质量比为1:2的Joncryl ADR4380与Joncryl ADR4368)、1%的抗氧剂1076在螺杆挤出机中连续混合挤出,得树脂熔体;将质量百分比为93.2%的树脂熔体、0.8%的第二反应助剂(选用γ-(2,3-环氧丙氧)丙基三甲氧基硅烷)、6%的第二纳米填料在螺杆挤出机中连续混合挤出,经注塑加工即得PPO复合薄膜。
经上述步骤所得的复合薄膜,其厚度为2000μm,经万能材料试验机测得其拉伸强度可达250MPa,弹性模量可达4000MPa,断裂伸长率10%左右。
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都落入本发明的保护范围。
Claims (7)
1.一种纳米复合聚合物材料,其特征在于,由质量百分比为80-99.8%的树脂熔体、0.1-5%的第二反应助剂和质量百分比为0.1-15%的第二纳米填料按照熔融共混的方式制备而成;所述树脂熔体由质量分数为75-99.7%的聚合物、0.1-5%的抗氧剂、0.1-5%的第一反应助剂、0.1-15%的第一纳米填料在螺杆挤出机中连续混合挤出制得;第一纳米填料与第二纳米填料之间存在原位反应;
所述的第一纳米填料通过以下方法制备得到:将第一纳米材料用溶液稀释后,加入质量为填料质量的5-20%的第一偶联剂,在70-130 ºC进行搅拌反应,反应2-8小时,反应结束后,进行干燥处理后得到修饰后的第一纳米填料;所述溶液为乙醇水溶液或甲苯溶液;所述第一偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的一种,第一纳米材料为粒径为10-100纳米的二氧化硅、碳酸钙、氧化锌、二氧化钛中的一种或多种按照任意配比混合组成;
所述的第二纳米填料通过以下方法制备得到:将第二纳米填料用溶液稀释后,加入质量为填料质量的5-20%的第二偶联剂,在70-130 ºC进行搅拌反应,反应2-8小时,反应结束后,进行干燥处理后得到修饰后的第二纳米填料;所述溶液为乙醇水溶液或甲苯溶液;所述第二偶联剂为硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂中的一种;所述的第二纳米填料为长径比为10-1000的纤维素、木质素、埃洛石中的一种或多种按照任意配比混合组成;
所述第一反应助剂由氮丙啶、环氧类、异氰酸酯类、钛酸酯类、恶唑啉类中的一种或多种按照任意配比混合组成;所述第二反应助剂由多环氧基或胺基化合物、双酚A型环氧树脂、硅烷偶联剂、缩水甘油酯、碳化二亚胺、异氰酸酯类化合物、氯化苄中的一种或多种按照任意配比混合组成。
2.根据权利要求1所述的纳米复合聚合物材料,其特征在于,所述聚合物为聚乙烯、聚烯烃热塑性弹性体、聚氯乙烯、聚丙烯、聚苯乙烯、ABS、丁腈橡胶、聚酰胺、聚甲醛、聚碳酸酯或聚苯醚。
3.根据权利要求1所述的纳米复合聚合物材料,其特征在于,所述第一偶联剂为γ―(2,3-环氧丙氧) 丙基三甲氧基硅烷,γ-氨丙基三乙氧基硅烷或3-异氰酸酯基丙基三乙氧基硅烷。
4.根据权利要求1所述的纳米复合聚合物材料,其特征在于,所述第二偶联剂为γ―(2,3-环氧丙氧) 丙基三甲氧基硅烷,γ-氨丙基三乙氧基硅烷或3-异氰酸酯基丙基三乙氧基硅烷。
5.根据权利要求1-4任一项所述的纳米复合聚合物材料,其特征在于,所述抗氧剂由BTH、DSTP、DLTP、168、300、425、626、627、1010、1076中的一种或多种按照任意配比混合组成。
6.一种权利要求1所述的纳米复合聚合物材料的应用,其特征在于,所述纳米复合聚合物材料通过加工制得薄膜、片材或板材用于制备包装材料、农用薄膜材料、高强度薄膜材料、高强度片材、高强度板材;所述薄膜的厚度为5~200μm,所述片材的厚度为200μm~2mm。
7.根据权利要求6所述的应用,其特征在于,加工方法包括吹膜法、流延法、溶液浇筑法、旋涂法、压延法、多层共挤法、双向拉伸法、层压法。
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