CN114426752B - 聚乙烯醇树脂组合物及膜 - Google Patents
聚乙烯醇树脂组合物及膜 Download PDFInfo
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- CN114426752B CN114426752B CN202011096077.5A CN202011096077A CN114426752B CN 114426752 B CN114426752 B CN 114426752B CN 202011096077 A CN202011096077 A CN 202011096077A CN 114426752 B CN114426752 B CN 114426752B
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- polyvinyl alcohol
- film
- resin composition
- formula
- carbon atoms
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 61
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 59
- 239000011342 resin composition Substances 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 239000004014 plasticizer Substances 0.000 claims description 11
- 229920002472 Starch Polymers 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 239000002904 solvent Substances 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- -1 acetoxyl groups Chemical group 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004049 embossing Methods 0.000 description 4
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- 239000000575 pesticide Substances 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical group NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical group C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 3
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical group CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- 150000005846 sugar alcohols Polymers 0.000 description 2
- YVAQHFNMILVVNE-UHFFFAOYSA-N 3-(prop-2-enoylamino)propanoic acid Chemical compound OC(=O)CCNC(=O)C=C YVAQHFNMILVVNE-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
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- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
- C08J2329/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/08—Ethers
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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Abstract
本发明属于聚乙烯醇技术领域,具体涉及一种聚乙烯醇树脂组合物。所述树脂组合物,包括含式(I)所示单体单元的改性聚乙烯醇和增塑剂:式(I)中,R1为氢原子或碳原子数为1‑8的直链状或支链状的烷基;R2为氢离子、金属离子、氨基或者碳原子数为1‑8的直链状或支链状的烷基;R3为碳原子数为1‑10的直链状或支链状的烷基;式(I)所示单体单元相对于全部单体单元的含有率为0.05mol%‑10mol%;所述改性聚乙烯醇的粘均聚合度为300‑3000,醇解度为70mol%‑99.5mol%。本发明的树脂组合物形成的膜冷水溶解性和耐化学溶剂性能优异。
Description
技术领域
本发明属于聚乙烯醇技术领域,具体涉及一种聚乙烯醇树脂组合物及膜。
背景技术
聚乙烯醇(简称PVA)树脂为白色固体,外型分絮状、颗粒状和粉状三种,无毒无味、无污染,可在80-90℃水中溶解。其水溶液具有良好的粘接性和成膜性,能耐油类、润滑剂和烃类等大多数有机溶剂,具有长链多元醇酯化、醚化、缩醛化等化学性质。目前,聚乙烯醇树脂主要用于纺织行业经纱浆料、织物整理剂、维尼纶纤维原料;建筑装潢行业107胶、内外墙涂料、粘合剂;化工行业聚合乳化剂、分散剂等;造纸行业纸品粘合剂;农业土壤改良剂、农药粘附增效剂和聚乙烯醇膜;日用化妆品、高频淬火剂等领域。
其中,聚乙烯醇膜主要用作定量包装农药、洗涤用洗剂、漂白剂、化妆制品、工业用化学品等的水溶性膜。这种采用水溶膜的定量密封包装也被称为单元包装,在使用时将单元包装直接投入水中,使内容物连同包装膜一起溶解或分散在水中。该单元包装的优点是:使用时可避免直接接触危险化学品;在使用时无需进行计量等。
随醇解度越高,聚乙烯醇的结晶度增大、冷水溶解性降低,因此,单元包装的冷水溶解性膜一般采用部分醇解的未改性聚乙烯醇。采用部分醇解的未改性聚乙烯醇的水溶性膜进行包装时,若内容物中含有碱性或酸性物质时存在以下问题:在保存过程中,部分醇解的未改性聚乙烯醇膜中残留的乙酰氧基会发生醇解,使得结晶度升高,膜易出现不溶于水的情况。此外,在用部分醇解的未改性聚乙烯醇膜进行包装时,若内容物含有农药、杀菌剂等含氯化合物,则在长期放置的情况下,膜会发生着色或固化,且水溶性随着时间的延长而降低,从而出现膜不溶于水或难溶于水的情况。
发明内容
有鉴于此,本发明的目的在于提供一种形成的膜冷水溶解性和耐化学溶剂性能优异的聚乙烯醇树脂组合物。
为实现上述目的,本发明的技术方案为:
树脂组合物,包括含式(I)所示单体单元的改性聚乙烯醇和增塑剂:
式(I)中,R1为氢原子或碳原子数为1-8的直链状或支链状的烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基等);R2为氢离子、金属离子、氨基(如四甲基铵基、四乙基铵基、四丙基铵基、单甲基铵基、二甲基铵基、三甲基铵基等)或者碳原子数为1-8的直链状或支链状的烷基;R3为碳原子数为1-10的直链状或支链状的烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基等);
式(I)所示单体单元相对于全部单体单元的含有率为0.05mol%-10mol%;所述改性聚乙烯醇的粘均聚合度为300-3000,醇解度为70mol%-99.5mol%。
本发明中,所述全部单体单元是指构成改性聚乙烯醇的单体单元的合计。
发明人在研究过程中意外发现,包括含式(I)所示单体单元的改性聚乙烯醇和增塑剂、:
式(I)中,R1为氢原子或碳原子数为1-8的直链状或支链状的烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基等);R2为氢离子、金属离子、氨基(如四甲基铵基、四乙基铵基、四丙基铵基、单甲基铵基、二甲基铵基、三甲基铵基等)或者碳原子数为1-8的直链状或支链状的烷基;R3为碳原子数为1-10的直链状或支链状的烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基等);
式(I)所示单体单元相对于全部单体单元的含有率为0.05mol%-10mol%;所述改性聚乙烯醇的粘均聚合度为300-3000,醇解度为70mol%-99.5mol%;的树脂组合物形成的膜冷水溶解性和耐化学溶剂性能优异。
进一步,改性聚乙烯醇和增塑剂的质量比为60-100:1-30。
进一步,所述金属为碱金属(如锂、钠、钾等)或碱土金属(如钙等)。
进一步,式(I)所示单体单元相对于全部单体单元的含有率为0.10mol%-8mol%。
进一步,式(I)所示单体单元相对于改性聚乙烯醇的全部单体单元的含有率为0.15mol%-7mol%。
进一步,所述改性聚乙烯醇的粘均聚合度为400-2500,醇解度为84mol%-99.4mol%。
进一步,所述改性聚乙烯醇的粘均聚合度为500-2000,醇解度为86mol%-99.3mol%。
进一步,所述增塑剂包括水、多元醇(如甘油、二甘油、二乙二醇、三乙二醇、丙二醇、二丙二醇、三羟甲基丙烷、季戊四醇、1,3-丁二醇等)、聚醚(如聚乙二醇、聚丙二醇等)、酯(如三乙醇二异辛酸酯等)、聚乙烯基酰胺(如聚乙烯基吡咯烷酮等)和酰胺化合物(如N-甲基吡咯烷酮、二甲基乙酰胺等)中的一种或多种。
进一步,所述增塑剂包括甘油、聚乙二醇和三乙醇二异辛酸酯。
进一步,甘油、聚乙二醇和三乙醇二异辛酸酯的质量比为3-6:2-3:1。
进一步,所述增塑剂的用量为改性聚乙烯醇的2%-30%,以质量百分比计。
进一步,所述树脂组合物还包括淀粉和无机填料。
进一步,以质量份计,配比关系为:改性聚乙烯醇60-100、增塑剂1-30份、淀粉不超过30份和/或无机填料不超过20份。
进一步,所述淀粉包括玉米淀粉、马铃薯淀粉、糊精、氧化淀粉、醚化淀粉和阳离子化淀粉中的一种或多种。
作为上述无机填料,可列举出例如二氧化硅、碳酸钙、氢氧化铝、氧化铝、氧化钛、硅藻土、硫酸钡、硫酸钙、沸石、氧化锌、硅酸、硅酸盐、云母、碳酸镁、高岭土、二氧化硅等。
所述树脂组合物还可根据需要进一步适当含有着色剂、香料、消泡剂、剥离剂、紫外线吸收剂、表面活性剂等其它添加剂。
此外,所述树脂组合物根据需要在不损害本发明效果的范围内还可以含有常规PVA、聚丙烯酰胺、聚丙烯酸或其盐等水溶性高分子。
所述树脂组合物可通过将所述原料混合来制备。具体而言,例如可以通过使这些原料在搅拌釜中溶解或分散至溶剂中并根据需要在其后去除溶剂的方法、在挤出机中进行熔融混练的方法等方法来制备。搅拌溶解时还可以根据需要对混合物料进行加热。
本发明的目的还在于保护膜,所述膜含有包含式(I)所示单体单元的改性聚乙烯醇:
式(I)中,R1为氢原子或碳原子数为1-8的直链状或支链状的烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基等);R2为氢离子、金属离子、氨基(如四甲基铵基、四乙基铵基、四丙基铵基、单甲基铵基、二甲基铵基、三甲基铵基等)或者碳原子数为1-8的直链状或支链状的烷基;R3为碳原子数为1-10的直链状或支链状的烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基等);
式(I)所示单体单元相对于全部单体单元的含有率为0.05mol%-10mol%;所述改性聚乙烯醇的粘均聚合度为300-3000,醇解度为70mol%-99.5mol%。
进一步,式(I)所示单体单元相对于改性聚乙烯醇的全部单体单元的含有率为0.10mol%-8mol%。
进一步,式(I)所示单体单元相对于改性聚乙烯醇的全部单体单元的含有率为0.15mol%-7mol%。
本发明的膜可以仅含有该改性PVA,也可以由该改性PVA与常规PVA、糖类、增塑剂、无机填料、其它添加剂等组合物构成。
本发明的膜适合用作日用洗剂、漂白剂、农药等各种化学品的包装材料。
作为该膜的平均厚度的下限,优选为10μm,更优选为20μm,进一步优选为30μm。
作为该膜的平均厚度的上限,优选为200μm,更优选为150μm,进一步优选为120μm。
该膜的平均厚度在上述范围内时,膜的强度进一步提高。
另一方面,该膜的平均厚度为上述上限以下时,能够以更低的成本来制造膜。
为了提高该膜的抗粘连性,根据需要可以将该膜表面进行辊毛面化,或者将二氧化硅、淀粉等抗粘连用的粉体涂布至该膜,或者进行压花处理。
该膜表面的辊毛面化可通过在制膜时对干燥前的该膜所接触的辊预先形成微细的凹凸来实施。
压花处理通常在形成膜后通过一边施加热、压力一边用压花辊和橡胶辊夹持来进行。
涂布粉体的抗粘连效果大,但根据该膜的用途有时无法使用,因此,作为抗粘连的方法,优选为辊毛面化和压花处理,从抗粘连效果的大小的观点出发,更优选为辊毛面化。
该膜的拉伸断裂强度的下限,优选为2.0kg/cm2,更优选为2.1kg/cm2,进一步优选为2.2kg/cm2。
另一方面,作为该膜的拉伸断裂强度的上限,没有特别限定,例如为5.0kg/cm2。
膜的制造方法
该膜的制造方法没有特别限定,可通过流延法、熔融挤出法等众所周知的方法来制造。例如,将该改性PVA与根据期望的该改性PVA之外的成分溶解于水性溶剂(例如为水),将所得溶液置于平滑的流延面,在上述水性溶剂蒸发后,从上述流延面上剥离时,能够得到透明且均匀的本发明的膜。
作为上述水性溶剂,优选为水。
上述流延面如钢、铝、玻璃、聚合物(例如为聚烯烃、聚乙烯、聚酰胺、聚氯乙烯、聚碳酸酯、聚卤代烃等)等那样地为平滑且硬质的材料即可。
上述水性溶剂的蒸发速度可通过将上述流延面加热或者暴露于加热空气中,或红外线来提高。上述流延面可以是平坦的,例如标准(转鼓型)的工业用制膜用流延机那样地可以为圆筒形的流延面。该膜可通过接着进行烘箱干燥来获得。
本发明的有益效果在于:
本发明的树脂组合物形成的膜冷水溶解性和耐化学溶剂性能优异。
本发明的树脂组合物形成的膜机械强度性能优异,杨氏模量为2.6-3.8Kg/mm2,拉伸断裂强度为2.4-3.1Kg/cm2。
本发明的树脂组合物形成的膜适合用于日用洗剂、漂白剂、农药等各种化学品的包装材料。
具体实施方式
所举实施例是为了更好地对本发明的内容进行说明,但并不是本发明的内容仅限于所举实施例。所以熟悉本领域的技术人员根据上述发明内容对实施方案进行非本质的改进和调整,仍属于本发明的保护范围。
本发明中,聚乙烯醇的粘均聚合度按照《GB/T 12010.9-1989聚乙烯醇树脂平均聚合度测定方法》进行测定;
本发明中,聚乙烯醇的醇解度按照《GB/T 12010.5-2010聚乙烯醇树脂残留乙酸跟(或醇解度)测定方法》进行测定;
本发明中,改性聚乙烯醇中的式(I)所示单体单元的含量通过该改性聚乙烯醇(A)的1H-NMR测定来求出,具体通过使该改性PVA(A)溶解于D2O,并使用600MHz的1H-NMR测定装置在80℃下进行测定求出;
本发明中,杨氏模量和拉伸断裂强度的测定方法(机械强度)具体为:将宽度为10mm的膜在20℃、65%RH的气氛下调湿1星期后,用拉力试验机进行拉伸试验;夹具间隔设为50mm、拉伸速度设为500mm/min;杨氏模量为2.0kg/mm2以上、拉伸断裂强度为2.0kg/cm2以上时判定为“○”(良好),杨氏模量低于2.0kg/mm2或拉伸断裂强度低于2.0kg/cm2时判定为“×”(不良)。
本发明中,膜的水溶性的测定方法具体为:将实施例和比较例中制得厚度45μm的膜切成40mm×40mm的正方形,将其夹入2个磁力框。在调整至4℃的恒温浴中设置放有1升蒸馏水的1升玻璃烧杯,使用5cm的转子在600rpm下进行搅拌。在烧杯内的蒸馏水达到4℃后,将上述磁力框浸入正在搅拌的冷水中,开始测定水溶性。此时,观察膜的溶解状态,测定至膜完全溶解为止的时间(秒数)。至膜完全溶解为止的时间小于100秒时判定为“○”(良好),为100秒以上时判定为“×”(不良)。
本发明中,耐化学品性的评价方法具体为:使用得到的膜,准备2片10×15cm见方的样品;接着,将该膜重合,利用热封器以200℃将3边进行热封;随后,从开口处加入作为化学品的十二烷基磺酸钠和硅藻土的混合物(十二烷基磺酸钠和硅藻土的质量比为1:3)40g,将剩余的1边用热封器以200℃进行热封密封;将该包装袋用铝塑复合膜包裹,并对四边进行热封,从而进行双重密封包装。为了加快试验过程,将该袋放置于40℃的恒温器中,四个星期后取出,通过前述测定方法测定已包装膜的水溶性,考察其与化学品包装前后水溶性的变化。试验前后膜完全溶解时间差低于10秒时判定为“○”(良好),为10秒以上时判定为“×”(不良)。
实施例1
膜,具体采用以下原料按照以下步骤制备而得:
A.改性聚乙烯醇的制备:
使用具备回流冷凝器、原料加料系统、反应液出料系统、温度计、氮气加入系统和搅拌叶片的聚合槽(连续聚合装置);
使用定量泵向该聚合槽中连续供给乙酸乙烯酯(VAC)(630L/h)、甲醇(MeOH)(60L/h)、作为改性剂的N-丙烯酰-β-丙氨酸的20wt%甲醇溶液(122L/h)、以及偶氮二异丁腈的2%wt甲醇溶液(AIBN)(25L/h);
然后,从聚合槽中连续地取出聚合液,使得聚合槽内的液面保持恒定;此时,以从聚合槽中取出的聚合液中的乙酸乙烯酯的聚合率达到40%的方式进行调整;聚合槽的滞留时间为4h;从聚合槽中取出的聚合液的温度为64℃,通过从聚合槽中取出聚合液,并向该聚合液中导入甲醇蒸气,从而去除未反应的乙酸乙烯酯,达到改性聚乙酸乙烯酯(改性PVAc)的甲醇溶液(浓度为35wt%)。
将上述改性PVAc/甲醇溶液(浓度为32wt%)(醇解原料溶液)以4300L/h进行加料,将氢氧化钠/甲醇溶液(浓度为7wt%)(醇解催化剂溶液)以70L/h进行加料(改性PVAc中的氢氧化钠相对于乙酸乙烯酯单元的摩尔比为0.01:1)。使用静态混合器将喂料的醇解原料溶液与醇解催化剂溶液进行混合,将所得混合物载置于带上,在40℃的温度条件下保持18min,进行醇解反应;将通过醇解反应得到的凝胶进行粉碎并脱液,将所得改性PVA颗粒或粉末(树脂成分)以600kg/r的速度连续地供给至干燥机(树脂温度为105℃),干燥机内的粉体的平均滞留时间为4h,其后进行粉碎,得到改性聚乙烯醇。
经检测,该改性聚乙烯醇的粘均聚合度为1550、醇解度为94mol%、式(I)所示单体单元的含有率为3.0mol%。
B.树脂组合物的制作,具体为:
向合成的100质量份改性聚乙烯醇中,添加作为增塑剂的甘油16质量份、作为糖类的醚化淀粉9质量份、作为无机填料的平均粒径为3μm的滑石粉5质量份、以钠元素换算计的乙酸钠0.8质量份以及水,制备成均匀的8wt%水溶液(含水率为92wt%)。
C.膜的制作:将步骤B所得水溶液流延在聚酯膜上并在室温下进行干燥后,从聚酯膜上剥离,从而制作平均厚度为45μm的膜。
实施例2-3及比较例1-4
聚乙烯醇的合成
除表1所示参数外,其他与实施例1相同,进行改性聚乙烯醇的合成。
表1实施例2-3及比较例1-4进行PVA合成的参数
备注:-表示未加入该原料;所述摩尔比为相对于乙酸乙烯酯单元的摩尔比。
除使用表2中示出的实施例1-3及比较例1-4合成的改性聚乙烯醇外,其他按照与实施例1同样操作来制作膜。
检测实施例1-3及对比例1-4制得的改性聚乙烯醇的粘均聚合度、醇解度及式(I)所示单体单元的含量;同时检测实施例1-3及对比例1-4制得的膜的水溶性、耐化学品性和机械强度,结果如表2所示。
表2性能测试结果
备注:-表示未检出。
由表2可知,实施例1-3制得的改性PVA中式(I)所示单体单元的含量为2.5mol%-3.0mol%;实施例1-3的膜化学包装前后,水溶性无显著差异。由此证明,本发明的树脂组合物形成的膜冷水溶解性及耐化学品性优异。
由表2可知,实施例1-3的树脂组合物形成的膜杨氏模量为2.6-3.8Kg/mm2,拉伸断裂强度为2.4-3.1Kg/cm2。由此证明,本发明的树脂组合物形成的膜机械强度优异。
综上,本发明的树脂组合物形成的膜水溶性及耐化学品性优异,机械强度优异。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (4)
1.树脂组合物在化学品包装用膜中的应用,其特征在于,所述树脂组合物包括式(I)所示单体单元的改性聚乙烯醇和增塑剂:
式(I)中,R1为氢原子或碳原子数为1-8的直链状或支链状的烷基;R2为氢离子、金属离子或者碳原子数为1-8的直链状或支链状的烷基;R3为碳原子数为1-10的直链状或支链状的亚烷基;
式(I)所示单体单元相对于全部单体单元的含有率为0.05mol%-10mol%;所述改性聚乙烯醇的粘均聚合度为1400-2400,醇解度为70mol%-99.5mol%。
2.根据权利要求1所述的应用,其特征在于,式(I)所示单体单元相对于全部单体单元的含有率为0.10mol%-8mol%。
3.根据权利要求1所述的应用,其特征在于,所述增塑剂的用量为改性聚乙烯醇的2%-30%,以质量百分比计。
4.权利要求1-3任一项所述的应用,其特征在于,所述树脂组合物还包括淀粉和/或无机填料。
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