CN106188969A - 一种用于装饰板的pvc组合物及其制造方法 - Google Patents
一种用于装饰板的pvc组合物及其制造方法 Download PDFInfo
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- CN106188969A CN106188969A CN201610650141.7A CN201610650141A CN106188969A CN 106188969 A CN106188969 A CN 106188969A CN 201610650141 A CN201610650141 A CN 201610650141A CN 106188969 A CN106188969 A CN 106188969A
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 240000002853 Nelumbo nucifera Species 0.000 claims abstract description 50
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims abstract description 50
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000007664 blowing Methods 0.000 claims abstract description 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical group CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical group [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- SUDKDSWHVLJFHP-UHFFFAOYSA-N C(=O)N.C(=O)N.[N] Chemical compound C(=O)N.C(=O)N.[N] SUDKDSWHVLJFHP-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000006084 composite stabilizer Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 11
- 239000004156 Azodicarbonamide Substances 0.000 description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 8
- 235000019399 azodicarbonamide Nutrition 0.000 description 8
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 8
- 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 description 8
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000776450 PVC group Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- BHDAXLOEFWJKTL-UHFFFAOYSA-L dipotassium;carboxylatooxy carbonate Chemical compound [K+].[K+].[O-]C(=O)OOC([O-])=O BHDAXLOEFWJKTL-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- 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
- C08J9/06—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
- 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
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- C08J9/103—Azodicarbonamide
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- C08J2327/00—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
- 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
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- C08J2427/02—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
- C08J2427/12—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 fluorine atoms
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Abstract
本发明提供一种用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，增塑剂10～15份，稳定剂3～4份，润滑剂2～3份，抗静电剂1～2份，阻燃剂10～15份，抗氧剂1～2份，发泡剂1～1.5份，助发泡剂0.5～1份，PTFE 4～5份，改性莲子壳基二氧化硅15～20份。本发明还提供了该用于装饰板的PVC组合物的制造方法。本发明具有较好的耐热性和较强的耐磨性。
Description
技术领域：
本发明涉及一种PVC组合物，特别是涉及一种用于装饰板的PVC组合物及其制造方法。
背景技术：
PVC微发泡材料是以PVC(聚氯乙烯)树脂为主要原料，加以化学助剂，经微发泡挤出生产线制成的具有均匀泡孔结构的一种材料，其密度、性能、外观、质地均与天然木材极为接近，因此亦称“合成木材”，且其防水、放火、防蛀、隔音等性能明显优于天然木材。法国、奥地利、意大利于70年代先后开发成功PVC发泡技术，日本、韩国、我国台湾地区也于80年代开始推广这种技术。我国人口众多，森林资源相对贫乏，所以以塑代木是生产发展的必然趋势。我国装饰行业年产值已突破1000亿大关，并以每年3％的速度增长。以PVC发泡材料代替木材，每年单在建筑领域即可节约木材130万立方米，如果把家具包括进去，每年可节约木材200多万立方米，经济和社会效益极其可观。
目前，PVC微发泡材料广泛应用于客车、火车车厢顶棚、箱体芯层、内部装潢用板、建筑物外墙板、内装饰用板、办公室、住宅、公共场所建筑物隔间，商用装饰架、无尘室用板、吊顶板、网板印刷、电脑刻字、广告标示、展板、标志用板相册板等行业及化工防腐工程、热成型件、冷库用板、特殊保冷工程、环保用板模、运动器材、养殖用材、海滨防潮设施、耐水材料、美工材料及各种轻便隔板代替玻璃天棚等。
例如，公开号为CN103739985A、公开日为2014.04.23、申请人为吴江市董鑫塑料包装厂的中国专利申请公开了“一种PVC装饰板”，其组成成份以质量份数表示法为：PVC100份；MBS5-8份；炭黑1-3份；DOP2-4份；活性重质碳酸钙50-80份；CPE4-6份；环氧大豆油1-5份；三碱式硫酸铅为5-7份；二碱式亚磷酸铅为2-5份；改性剂4-6份；石蜡1-4份；硬脂酸钡2-3份；硬脂酸铅0.5-1份；产品相对密度0.9-0.95，弯曲强度55-65MPa；冲击强度380-400MPa；拉伸强度80-85MPa，氧指数30-35％；产品硬度高、抗静电，可以广泛生产并不断代替现有材料。不过，该装饰板仍存在一定的缺陷：其耐热性不是很好，而且耐磨性较差。
发明内容：
本发明要解决的技术问题是提供一种用于装饰板的PVC组合物，其具有较好的耐热性和较强的耐磨性。
为解决上述技术问题，本发明的技术方案是：
一种用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，增塑剂10～15份，稳定剂3～4份，润滑剂2～3份，抗静电剂1～2份，阻燃剂10～15份，抗氧剂1～2份，发泡剂1～1.5份，助发泡剂0.5～1份，PTFE 4～5份，改性莲子壳基二氧化硅15～20份；其中，改性莲子壳基二氧化硅由以下步骤制得：
(1)将莲子壳用粉碎机粉碎后得到莲子壳粉，用无水乙醇和去离子水分别冲洗15分钟后烘干，加入由体积比为1:1的草酸和硝酸混合而成的混酸溶液中，60℃下恒温回流2小时，取出后用去离子水洗涤至中性，100℃下烘干后得到酸化莲子壳粉；
(2)将步骤(1)所得酸化莲子壳粉置于马弗炉中的石英舟内，通氮气15分钟后以10℃/分的速度升温至550℃，然后保温1小时，在氮气氛围中自然冷却至室温后得到莲子壳炭粉；
(3)将步骤(2)所得莲子壳炭粉加入由质量比为1:2的碳酸钾和氢氧化钾混合而成的混合溶液中，80转/分、90℃下搅拌4小时，出料后过滤，将得到的滤液加热至60℃，加入稀盐酸，开启搅拌，直至体系的ph值为6时停止搅拌，陈化10小时，离心分离后烘干，煅烧后得到莲子壳基二氧化硅；
(4)将步骤(3)所得莲子壳基二氧化硅加入硝酸溶液中，70℃下回流5小时，过滤后用蒸馏水洗涤至中性，烘干后加入DMF、氯化亚砜中，70℃下回流5小时，然后升温至95℃，加入PEG、DMF、三乙胺，通氮气、95℃下回流反应10小时，将得到的产物减压过滤后用蒸馏水反复洗涤，80℃下真空干燥至恒重，得到改性莲子壳基二氧化硅。
优选地，本发明所述增塑剂为马来酸二丁酯。
优选地，本发明所述稳定剂为钡锌复合稳定剂。
优选地，本发明所述润滑剂为氧化聚乙烯蜡。
优选地，本发明所述抗静电剂为导电炭黑。
优选地，本发明所述阻燃剂为硼酸锌。
优选地，本发明所述抗氧剂为抗氧剂BHT。
优选地，本发明所述发泡剂为偶氮二甲酰胺。
优选地，本发明所述助发泡剂为氧化锌。
本发明要解决的另一技术问题是提供上述用于装饰板的PVC组合物的制造方法。
为解决上述技术问题，技术方案是：
将各组份按重量份称重，开启高混机，将PVC、增塑剂、稳定剂、润滑剂、抗静电剂、阻燃剂、抗氧剂、PTFE加入高混机，搅拌至物料温度为95℃后加入助发泡剂、改性莲子壳基二氧化硅，继续搅拌至物料温度为115℃后加入发泡剂，继续搅拌至物料温度为130℃后冷却至40℃，转入挤出机挤出，将得到的挤出料通过发泡模具发泡，得到用于装饰板的PVC组合物。
由上可见，与现有技术相比，本发明具有以下有益效果：
1、莲子壳是人们食用莲子后的废弃物，其成分中灰分和碳的含量较多，且灰分以硅为主，本发明先将其粉碎后冲洗除掉表面吸附的杂物，然后用混酸进行处理，对莲子壳粉中的杂质进行了有效去除，提高了硅含量，再通过高温炭化得到了莲子壳炭粉，然后将其通过碳酸钾和氢氧化钾活化，得到硅酸钠溶液并与稀盐酸反应生成硅酸，再煅烧分解成为耐热性、耐磨性俱佳的莲子壳基二氧化硅，碳酸钾和氢氧化钾起到了很好的活化作用，大大提高了莲子壳粉中的得硅率，与PVC基体共混后，莲子壳基二氧化硅有效提高了PVC组合物的耐热性和耐磨性；
2、莲子壳基二氧化硅呈亲水性，与疏水性的PVC基体之间的相容性不佳，因而本发明先将其通过硝酸溶液处理，在其表面引入了羧基，再与氯化亚砜反应，将羧基转化成酰氯基，然后与PEG进行酯化反应，得到了接枝有PEG的改性莲子壳基二氧化硅，大大改善了莲子壳基二氧化硅与PVC基体之间的相容性和结合力，而且在PVC组合物受到摩擦外力时，PEG分子链可带动莲子壳基二氧化硅粒子迁移至PVC组合物表面，承载消耗摩擦外力，进一步提高了PVC组合物的耐磨性和耐热性。
具体实施方式：
下面将结合具体实施例来详细说明本发明，在此本发明的示意性实施例以及说明用来解释本发明，但并不作为对本发明的限定。
实施例1
用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，马来酸二丁酯10份，钡锌复合稳定剂4份，氧化聚乙烯蜡2.5份，导电炭黑1.2份，硼酸锌11份，抗氧剂BHT 1.2份，偶氮二甲酰胺1份，氧化锌1份，PTFE 4份，改性莲子壳基二氧化硅16份。
其制造方法为：
(1)将莲子壳用粉碎机粉碎后得到莲子壳粉，用无水乙醇和去离子水分别冲洗15分钟后烘干，加入由体积比为1:1的草酸和硝酸混合而成的混酸溶液中，60℃下恒温回流2小时，取出后用去离子水洗涤至中性，100℃下烘干后得到酸化莲子壳粉；
(2)将步骤(1)所得酸化莲子壳粉置于马弗炉中的石英舟内，通氮气15分钟后以10℃/分的速度升温至550℃，然后保温1小时，在氮气氛围中自然冷却至室温后得到莲子壳炭粉；
(3)将步骤(2)所得莲子壳炭粉加入由质量比为1:2的碳酸钾和氢氧化钾混合而成的混合溶液中，80转/分、90℃下搅拌4小时，出料后过滤，将得到的滤液加热至60℃，加入稀盐酸，开启搅拌，直至体系的ph值为6时停止搅拌，陈化10小时，离心分离后烘干，煅烧后得到莲子壳基二氧化硅；
(4)将步骤(3)所得莲子壳基二氧化硅加入硝酸溶液中，70℃下回流5小时，过滤后用蒸馏水洗涤至中性，烘干后加入DMF、氯化亚砜中，70℃下回流5小时，然后升温至95℃，加入PEG、DMF、三乙胺，通氮气、95℃下回流反应10小时，将得到的产物减压过滤后用蒸馏水反复洗涤，80℃下真空干燥至恒重，得到改性莲子壳基二氧化硅；
(5)将各组份按重量份称重，开启高混机，将PVC、马来酸二丁酯、钡锌复合稳定剂、氧化聚乙烯蜡、导电炭黑、硼酸锌、抗氧剂BHT、PTFE加入高混机，搅拌至物料温度为95℃后加入氧化锌、改性莲子壳基二氧化硅，继续搅拌至物料温度为115℃后加入偶氮二甲酰胺，继续搅拌至物料温度为130℃后冷却至40℃，转入挤出机挤出，将得到的挤出料通过发泡模具发泡，得到用于装饰板的PVC组合物。
实施例2
用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，马来酸二丁酯12份，钡锌复合稳定剂3.5份，氧化聚乙烯蜡2份，导电炭黑2份，硼酸锌12份，抗氧剂BHT 1.6份，偶氮二甲酰胺1.1份，氧化锌0.9份，PTFE 4.2份，改性莲子壳基二氧化硅18份。
其制造方法与实施例1一样。
实施例3
用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，马来酸二丁酯14份，钡锌复合稳定剂3.9份，氧化聚乙烯蜡3份，导电炭黑1份，硼酸锌14份，抗氧剂BHT 1.5份，偶氮二甲酰胺1.2份，氧化锌0.8份，PTFE 4.4份，改性莲子壳基二氧化硅20份。
其制造方法与实施例1一样。
实施例4
用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，马来酸二丁酯11份，钡锌复合稳定剂3.2份，氧化聚乙烯蜡2.1份，导电炭黑1.6份，硼酸锌10份，抗氧剂BHT 2份，偶氮二甲酰胺1.3份，氧化锌0.7份，PTFE 4.6份，改性莲子壳基二氧化硅15份。
其制造方法与实施例1一样。
实施例5
用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，马来酸二丁酯13份，钡锌复合稳定剂3.6份，氧化聚乙烯蜡2.8份，导电炭黑1.5份，硼酸锌15份，抗氧剂BHT 1份，偶氮二甲酰胺1.4份，氧化锌0.6份，PTFE 4.8份，改性莲子壳基二氧化硅17份。
其制造方法与实施例1一样。
实施例6
用于装饰板的PVC组合物，包括以下重量份的组份：PVC 100份，马来酸二丁酯15份，钡锌复合稳定剂3份，氧化聚乙烯蜡2.4份，导电炭黑1.8份，硼酸锌13份，抗氧剂BHT 1.8份，偶氮二甲酰胺1.5份，氧化锌0.5份，PTFE 5份，改性莲子壳基二氧化硅19份。
其制造方法与实施例1一样。
将实施例1-6以及对比例的耐热性和耐磨性分别进行测试：
对比例为公开号为CN103739985A的中国专利申请，
耐热性采用热失重分析法测试各待测物的起始分解温度，起始分解温度越高则表明耐热性越好；耐磨性采用失重法测试各待测物的磨损量，磨损量越小则表明耐磨性能越强，测试结果如下表所示。
表1
由表1可看出，本发明实施例1-6的初始分解温度均明显高于对比例，而磨损量均明显低于对比例，证明本发明具有较好的耐热性和较强的耐磨性。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。
Claims (10)
1.一种用于装饰板的PVC组合物，其特征在于，包括以下重量份的组份：PVC 100份，增塑剂10～15份，稳定剂3～4份，润滑剂2～3份，抗静电剂1～2份，阻燃剂10～15份，抗氧剂1～2份，发泡剂1～1.5份，助发泡剂0.5～1份，PTFE 4～5份，改性莲子壳基二氧化硅15～20份；其中，改性莲子壳基二氧化硅由以下步骤制得：
(1)将莲子壳用粉碎机粉碎后得到莲子壳粉，用无水乙醇和去离子水分别冲洗15分钟后烘干，加入由体积比为1:1的草酸和硝酸混合而成的混酸溶液中，60℃下恒温回流2小时，取出后用去离子水洗涤至中性，100℃下烘干后得到酸化莲子壳粉；
(2)将步骤(1)所得酸化莲子壳粉置于马弗炉中的石英舟内，通氮气15分钟后以10℃/分的速度升温至550℃，然后保温1小时，在氮气氛围中自然冷却至室温后得到莲子壳炭粉；
(3)将步骤(2)所得莲子壳炭粉加入由质量比为1:2的碳酸钾和氢氧化钾混合而成的混合溶液中，80转/分、90℃下搅拌4小时，出料后过滤，将得到的滤液加热至60℃，加入稀盐酸，开启搅拌，直至体系的ph值为6时停止搅拌，陈化10小时，离心分离后烘干，煅烧后得到莲子壳基二氧化硅；
(4)将步骤(3)所得莲子壳基二氧化硅加入硝酸溶液中，70℃下回流5小时，过滤后用蒸馏水洗涤至中性，烘干后加入DMF、氯化亚砜中，70℃下回流5小时，然后升温至95℃，加入PEG、DMF、三乙胺，通氮气、95℃下回流反应10小时，将得到的产物减压过滤后用蒸馏水反复洗涤，80℃下真空干燥至恒重，得到改性莲子壳基二氧化硅。
2.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述增塑剂为马来酸二丁酯。
3.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述稳定剂为钡锌复合稳定剂。
4.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述润滑剂为氧化聚乙烯蜡。
5.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述抗静电剂为导电炭黑。
6.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述阻燃剂为硼酸锌。
7.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述抗氧剂为抗氧剂BHT。
8.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述发泡剂为偶氮二甲酰胺。
9.根据权利要求1所述的一种用于装饰板的PVC组合物，其特征在于：所述助发泡剂为氧化锌。
10.根据权利要求1～9任意一项所述的一种用于装饰板的PVC组合物的制造方法，其特征在于：
将各组份按重量份称重，开启高混机，将PVC、增塑剂、稳定剂、润滑剂、抗静电剂、阻燃剂、抗氧剂、PTFE加入高混机，搅拌至物料温度为95℃后加入助发泡剂、改性莲子壳基二氧化硅，继续搅拌至物料温度为115℃后加入发泡剂，继续搅拌至物料温度为130℃后冷却至40℃，转入挤出机挤出，将得到的挤出料通过发泡模具发泡，得到用于装饰板的PVC组合物。
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