CN114752197B - 一种高阻隔聚乳酸片材及其制备方法 - Google Patents
一种高阻隔聚乳酸片材及其制备方法 Download PDFInfo
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- CN114752197B CN114752197B CN202210407760.9A CN202210407760A CN114752197B CN 114752197 B CN114752197 B CN 114752197B CN 202210407760 A CN202210407760 A CN 202210407760A CN 114752197 B CN114752197 B CN 114752197B
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 52
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000009998 heat setting Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000138 intercalating agent Substances 0.000 claims description 2
- 159000000014 iron salts Chemical class 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [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
- 239000000243 solution Substances 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 235000013399 edible fruits Nutrition 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 235000014102 seafood Nutrition 0.000 abstract description 4
- 235000013311 vegetables Nutrition 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 6
- 239000005033 polyvinylidene chloride Substances 0.000 description 6
- 239000004110 Zinc silicate Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 235000019352 zinc silicate Nutrition 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229920006381 polylactic acid film Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 229920002635 polyurethane Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 2
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000007740 vapor deposition Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- ZXRRHFSTAFVGOC-UHFFFAOYSA-N [AlH3].[K] Chemical compound [AlH3].[K] ZXRRHFSTAFVGOC-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polypropylene carbonate Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
本发明公开了一种高阻隔聚乳酸片材,制备原料包括以下重量比组分:聚乳酸75‑94%,阻隔填料5‑20%,工艺助剂0.5‑1%;所述聚乳酸重均分子量为10‑20万,多分散指数为1.5‑2.0;所述阻隔填料为有机无机杂化材料;所述工艺助剂为高折光率甲基苯基硅油,其折光率为1.48‑1.50。本发明提供的聚乳酸片材阻隔性能好,在一定范围内可调,加工工艺简单,对设备要求不高,非常适用于蔬菜、水果、海鲜产品的运输和储存包装。
Description
技术领域
本发明属于包装材料技术领域,具体涉及一种高阻隔聚乳酸片材及其制备方法。
背景技术
聚乳酸作为一种生物基可降解材料,具有高强度、高模量、高透明度等性能特点,适用于蔬菜、水果、海鲜产品的运输和储存包装。由于聚乳酸属于半结晶性高分子材料,其结晶时间较长,在挤塑、吹膜等加工工序后结晶度不高,添加成核剂后结晶度通常也小于45%。同时,分子链中的存在极性酯键,具有较大的亲水性。水蒸气比较容易通过与极性基团的作用溶解到聚乳酸材料中,并通过无定型区扩散,使聚乳酸表现出较差的阻水性能。由于包装材料的阻隔性直接影响到产品保鲜和货架期,对于如何改善聚乳酸的阻隔性成为热点课题。
专利CN214873301U公开了一种可生物降解的高阻隔蒸镀聚乳酸薄膜,由上至下依次设置有表面保护涂层、阻隔蒸镀层、底涂层和聚乳酸基材层;聚乳酸基材层为五层共挤双向拉伸层,由上至下依次由第一聚乳酸层、第二聚乳酸层、阻隔层、第三聚乳酸层和第四聚乳酸层组成;第一聚乳酸层、第二聚乳酸层、第三聚乳酸层和第四聚乳酸为PLA/PBAT混合物;阻隔层为聚碳酸亚丙酯或纳米阻隔聚乳酸母粒。
专利CN110774713A公开了一种涂布型高阻隔双向拉伸聚乳酸薄膜及其制备方法,其结构由内至外依次是高阻隔涂层、底涂层、基材层;基材层是由三层共挤双向拉伸PLA薄膜组成。高阻隔涂层采用的耐水改性的PVA涂布液的组分包括:PVA、丙烯酸乳液、聚氨酯乳液、层状硅酸盐、NaOH、水和乙醇;PVA:丙烯酸乳液:聚氨酯乳液的质量比为5:4:1;层状硅酸盐的含量为0.1%-1%;NaOH的中和度为10mol%;PVA涂布液固含量为8-10wt%;PVA选用醇解度为99%的PVA 1799;丙烯酸分子量为20-25万;聚氨酯分子量为3000-5000。
专利CN214927804U公开了一种复合硬片,包括PLA硬片、降解层和PVDC乳胶层,PLA硬片的两侧均设有降解层和PVDC乳胶层,降解层和PVDC乳胶层间为涂布底胶层,可降解聚乳酸和聚偏二氯乙烯复合硬片结构由上至下依次为第一PVDC乳胶层、第一涂布底胶层、第一降解层、PLA硬片、第二降解层、第二涂布底胶层和第二PVDC乳胶层。
上述专利在改善聚乳酸阻隔性方面取得一些效果,但是对于产业化应用还存在一些问题和差距。具体表现为:选择的基材为多层共挤双向拉伸聚乳酸薄膜,对产业化装备和材料的力学和加工性能要求较高;真空蒸镀和表面保护涂层增加了产品加工周期和生产成本;通过涂布复合的工艺复杂;复合的阻隔性树脂材料的成本高;受涂布工艺影响,阻隔填料添加量不宜太多,阻隔性能提升效果有限;聚乳酸微球和氧化石墨烯制备过程存在产业化环保压力;溶剂和水蒸发量较大,生产成本较高。
发明内容
为了解决目前的技术难题,提高聚乳酸的阻隔性,本发明提供一种高阻隔聚乳酸片材及其制备方法,所得片材的阻隔性能好,在一定范围内可调,加工工艺简单,对设备要求不高,非常适用于蔬菜、水果、海鲜产品的运输和储存包装。
本发明一种高阻隔聚乳酸片材,制备原料包括以下重量比组分:聚乳酸75-94%,阻隔填料5-20%,工艺助剂0.5-1%;所述聚乳酸重均分子量为10-20万,多分散指数为1.5-2.0;所述阻隔填料为有机无机杂化材料;所述工艺助剂为高折光率甲基苯基硅油,其折光率为1.48-1.50,用以改善高固体填充配方的加工工艺,同时保持片材的透明度。
更优地,所述有机无机杂化材料为聚合硅酸铝盐,包括聚合硅酸铝锌、聚合硅酸铝铁、聚合硅酸铝钾。
更优地,所述聚合硅酸铝盐是以硅酸钠为原料经过聚硅酸活化和盐基化合成,再通过插层剂硬脂酸和偶联剂KH550表面处理后得到的厚度为0.5-45纳米的层状纳米材料;所述聚硅酸活化的pH值为2.5-3.5,活化80-90min,所述硅酸钠变为聚合硅酸水溶液;所述盐基化合成为在所述聚合硅酸水溶液中依次加入铝盐和锌盐或钾盐或铁盐,即得所述聚合硅酸铝盐凝胶;调节聚硅酸凝胶时间的阻聚剂为草酸、顺丁烯二酸和丙二酸的混合物,凝胶时间为20-100小时。片状纳米填料在双螺杆挤出时受模唇物理尺寸(0.2mm~2mm)限制,在熔体压力的作用下呈层状排列,进而在聚乳酸树脂内部形成一定填充密度的多层纳米填料及其架桥结构,这种结构不利于水蒸气的扩散,提高了聚乳酸片材的阻隔性。
更优地,所述铝盐为氯化铝或者硫酸铝,所述锌盐为氯化锌或者硫酸锌,所述钾盐为氯化钾或硫酸钾,所述铁盐为氯化铁或者硫酸铁;所述铝盐的铝和锌盐的锌或钾盐的钾或铁盐的铁:所述聚合硅酸水溶液中的硅的摩尔比为3:1;所述铝盐的铝:所述锌盐的锌或钾盐的钾或铁盐的铁的摩尔比为2:1。
本发明还提供一种高阻隔聚乳酸片材的制备方法,包括以下加工过程:机械上料、双螺杆挤出、换网器过滤、模具挤出成型、热定型、牵引、热处理烘道、冷定型、牵引、裁断、堆放;所述换网器使用的是通用80目过滤网过滤;所述模具是指原料加温熔融后通过模具来挤出成型,优良合金模唇和可调阻流块,可提供均匀的压力;所述双螺杆挤出条件为螺杆转速100-300转/min,熔体温度180-200℃;所述热定型加热设备为红外加热烘箱,定型温度为105-115℃;所述冷定型是指模具挤出成型的材料再通过真空定型台进行抽真空冷却定型。
与现有技术相比,本发明的有益效果是:
由以上方案制得的高阻隔聚乳酸片材,加工工艺简单,对设备要求不高;由于加入了片状纳米填料,在双螺杆挤出时受模唇物理尺寸(0.2mm~2mm)限制,在熔体压力的作用下呈层状排列,进而在聚乳酸树脂内部形成一定填充密度的多层纳米填料及其架桥结构,不利于水蒸气的扩散,提高了聚乳酸片材的阻隔性,并能在水蒸气透过率为10-120g·(m2·24h)-1范围内可调,适用于蔬菜、水果、海鲜产品的运输和储存包装。
具体实施方式
为了更好理解本发明技术内容,下面提供具体实施例,对本发明做进一步的说明。
实施例1
聚乳酸(重均分子量14万,多分散指数1.8)94%,聚合硅酸铝锌5%,甲基苯基硅油1%,其折光率为1.48。
其中,聚合硅酸铝锌的制备方法:以硅酸钠为原料经过聚硅酸活化和盐基化合成,再通过插层剂硬脂酸和偶联剂KH550表面处理后得到的厚度为0.5-45纳米的层状纳米材料;聚硅酸活化的pH值为3,活化85min,然后硅酸钠变为聚合硅酸水溶液;盐基化合成为在聚合硅酸水溶液中依次加入氯化铝和氯化锌,即得聚合硅酸铝锌凝胶;调节聚硅酸凝胶时间的阻聚剂为草酸、顺丁烯二酸和丙二酸的混合物,凝胶时间为60小时。氯化铝的铝和氯化锌的锌:聚合硅酸水溶液中的硅的摩尔比为3:1;氯化铝的铝:氯化锌的锌的摩尔比为2:1。
按照以上配方比例配料200公斤,加入高速混合机混合5分钟,通过螺旋输送机机械上料到双螺杆挤出机喂料斗,设定双螺杆挤出机各温区温度180℃,熔体温度180℃,模头温度195℃,螺杆转速100转/min,双螺杆挤模唇物理尺寸0.2mm。片材从模头挤出并通过水平牵引至热处理烘道,105℃定型。
实施例2
聚乳酸(重均分子量14万,多分散指数1.8)89%,聚合硅酸铝钾10%,甲基苯基硅油1%,其折光率为1.49。
其中,聚合硅酸铝钾的制备方法:同实施例1中的制备方法,把氯化锌换为氯化钾。
按照以上配方比例配料200公斤,加入高速混合机混合5分钟,通过螺旋输送机机械上料到双螺杆挤出机喂料斗,设定双螺杆挤出机各温区温度180℃,熔体温度190℃,模头温度195℃,螺杆转速150转/min,双螺杆挤模唇物理尺寸为1mm。片材从模头挤出并通过水平牵引至热处理烘道,110℃定型。
实施例3
聚乳酸(重均分子量14万,多分散指数1.8)84%,聚合硅酸铝铁15%,甲基苯基硅油1%,其折光率为1.50。
其中,聚合硅酸铝铁的制备方法:同实施例1中的制备方法,把氯化锌换为氯化铁。
按照以上配方比例配料200公斤,加入高速混合机混合5分钟,通过螺旋输送机机械上料到双螺杆挤出机喂料斗,设定双螺杆挤出机各温区温度180℃,熔体温度195℃,模头温度200℃,螺杆转速250转/min,双螺杆挤模唇物理尺寸为1.5mm。片材从模头挤出并通过水平牵引至热处理烘道,112℃定型。
实施例4
聚乳酸(重均分子量14万,多分散指数1.8)79%,聚合硅酸铝锌20%,甲基苯基硅油1%,其折光率为1.50。
其中,聚合硅酸锌的制备方法同实施例1。
按照以上配方比例配料200公斤,加入高速混合机混合5分钟,通过螺旋输送机机械上料到双螺杆挤出机喂料斗,设定双螺杆挤出机各温区温度180℃,熔体温度200℃,模头温度195℃,螺杆转速300转/min,双螺杆挤模唇物理尺寸为2mm。片材从模头挤出并通过水平牵引至热处理烘道,115℃定型。
对比例1
聚乳酸(重均分子量14万,多分散指数1.8)99%,甲基苯基硅油1%,折光率为1.48。
按照以上配方比例配料200公斤,加入高速混合机混合5分钟,通过螺旋输送机机械上料到双螺杆挤出机喂料斗,设定双螺杆挤出机各温区温度180℃,熔体温度185℃,模头温度195℃,螺杆转速150转/min。片材从模头挤出并通过水平牵引至热处理烘道,108℃定型。
本发明聚乳酸片材经检测后,水蒸气阻隔性能如下表:
水蒸气阻隔性能
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种高阻隔聚乳酸片材,其特征在于,制备原料包括以下重量比组分:聚乳酸75-94%,阻隔填料5-20%,工艺助剂0.5-1%;所述聚乳酸重均分子量为10-20万,多分散指数为1.5-2.0;所述阻隔填料为有机无机杂化材料;所述有机无机杂化材料为聚合硅酸铝盐,是以硅酸钠为原料经过聚硅酸活化和盐基化合成,再通过插层剂硬脂酸和偶联剂KH550表面处理后得到的厚度为0.5-45纳米的层状纳米材料;所述工艺助剂为高折光率甲基苯基硅油,其折光率为1.48-1.50。
2.根据权利要求1所述的高阻隔聚乳酸片材,其特征在于,所述聚合硅酸铝盐包括聚合硅酸铝锌、聚合硅酸铝铁、聚合硅酸铝钾。
3.根据权利要求2所述的高阻隔聚乳酸片材,其特征在于,所述聚硅酸活化的pH值为2.5-3.5,活化80-90min,所述硅酸钠变为聚合硅酸水溶液;所述盐基化合成为在所述聚合硅酸水溶液中依次加入铝盐和锌盐或钾盐或铁盐,即得所述聚合硅酸铝盐凝胶;调节聚硅酸凝胶时间的阻聚剂为草酸、顺丁烯二酸和丙二酸的混合物,凝胶时间为20-100小时。
4.根据权利要求3所述的高阻隔聚乳酸片材,其特征在于,所述铝盐为氯化铝或者硫酸铝,所述锌盐为氯化锌或者硫酸锌,所述钾盐为氯化钾或硫酸钾,所述铁盐为氯化铁或者硫酸铁;所述铝盐的铝和锌盐的锌或钾盐的钾或铁盐的铁:所述聚合硅酸水溶液中的硅的摩尔比为3:1;所述铝盐的铝:所述锌盐的锌或钾盐的钾或铁盐的铁的摩尔比为2:1。
5.根据权利要求1-4任一所述的高阻隔聚乳酸片材的制备方法,其特征在于,包括以下加工过程:机械上料、双螺杆挤出、换网器过滤、模具挤出成型、热定型、牵引、热处理烘道、冷定型、牵引、裁断、堆放;所述换网器使用的是通用80目过滤网过滤;所述模具是指原料加温熔融后通过模具来挤出成型;所述双螺杆挤出条件为螺杆转速100-300转/min,熔体温度180-200℃,双螺杆挤出的模唇物理尺寸为0.2mm~2mm;所述热定型加热设备为红外加热烘箱,定型温度为105-115℃;所述冷定型是指模具挤出成型的材料再通过真空定型台进行抽真空冷却定型。
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