CN116948238B - 一种超耐低温耐紫外透明聚偏氟乙烯薄膜及其制备方法 - Google Patents
一种超耐低温耐紫外透明聚偏氟乙烯薄膜及其制备方法 Download PDFInfo
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- CN116948238B CN116948238B CN202310895083.4A CN202310895083A CN116948238B CN 116948238 B CN116948238 B CN 116948238B CN 202310895083 A CN202310895083 A CN 202310895083A CN 116948238 B CN116948238 B CN 116948238B
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- polyvinylidene fluoride
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 31
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
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- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 11
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 10
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 9
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- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 8
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- KWWIRECSSLQAKF-UHFFFAOYSA-N ClCCl.BrC(C(=O)Br)(C)C Chemical compound ClCCl.BrC(C(=O)Br)(C)C KWWIRECSSLQAKF-UHFFFAOYSA-N 0.000 claims description 7
- KZIBQYUFIVUOHY-UHFFFAOYSA-N bis(2-methylpropyl)alumane toluene Chemical compound Cc1ccccc1.[H][Al](CC(C)C)CC(C)C KZIBQYUFIVUOHY-UHFFFAOYSA-N 0.000 claims description 7
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
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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 claims description 3
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims description 3
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- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 abstract description 2
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08J5/18—Manufacture of films or sheets
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- 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
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Abstract
本发明涉及薄膜材料技术领域,公开了一种超耐低温耐紫外透明聚偏氟乙烯薄膜及其制备方法;将聚偏氟乙烯、乙烯‑丙烯酸酯橡胶和增容剂熔融共混均匀后,加入丙烯酸酯增韧剂A和丙烯酸酯增韧剂B熔融共混均匀后,挤出造粒,流延成膜,得到超耐低温聚偏氟乙烯薄膜;将超耐低温聚偏氟乙烯薄膜表面羟基化处理接着与2‑溴代异丁酰溴反应,形成溴引发剂,最后通过铜催化剂将改性紫外线吸收剂与聚偏氟乙烯薄膜进行连接,得到超耐低温耐紫外透明聚偏氟乙烯薄膜。
Description
技术领域
本发明涉及薄膜材料技术领域,具体为一种超耐低温耐紫外透明聚偏氟乙烯薄膜及其制备方法。
背景技术
随着双面发电技术的发展,双玻组件的应用持续扩大,然而双玻组件也有其局限性,在运输、安装、和运维过程中,由于双面采用玻璃的原因,会比普通组件力学性能差,以及玻璃重量的问题出现组件变形,易破碎等问题。然而透明背板的出现,为双面发电组件提供了新的组合形式,相比传统双玻组件而言加工简单,不易开裂,重量轻,然而透明背板中间层选用没有钛白粉的PET,为使更好的延长组件使用寿命,更加需要耐候性能优异的透明氟膜作为空气面保护层。
目前PVDF膜一般是白色且单层结构,缺点在于不透明的,耐低温性能差,不能在透明背板中应用,单层结构,在生产过程中为提高耐老化后力学性能,过多加入PMMA,薄膜容易粘在一起导致麻点、褶皱等外观缺陷、使用过程中薄膜容易吸水,长期遭受紫外线照射后发生PVDF膜黄变、开裂等,影响材料的使用寿命;同时过多无机粉体和分散剂的加入连续生产时会有析出造成薄膜外观缺陷。
因此,发明一种超耐低温耐紫外透明聚偏氟乙烯薄膜具有重要意义。
发明内容
本发明的目的在于提供一种超耐低温耐紫外透明聚偏氟乙烯薄膜及其制备方法,以解决上述背景技术中提出的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法,包括以下步骤:
S1:将六亚甲基二胺氨基甲酸盐、二苯胍和助剂加入乙烯-丙烯酸酯橡胶中混炼,170-175℃硫化20-25min,170-175℃硫化4-5h,得到丙烯酸酯增韧剂A;将N,N-(4,4’-亚甲基二苯基)双马来酰亚胺加入1,6-己二醇二丙烯酸酯中,120-125℃反应1.5-2h,得到丙烯酸酯增韧剂B;
S2:将聚偏氟乙烯、乙烯-丙烯酸酯橡胶和增容剂熔融共混均匀后,加入丙烯酸酯增韧剂A和丙烯酸酯增韧剂B熔融共混均匀后,挤出造粒,流延成膜,得到超耐低温聚偏氟乙烯薄膜;
S3:将超耐低温聚偏氟乙烯薄膜置于氢氧化锂溶液中,80-85℃搅拌24-36h,洗涤,干燥后置于硼氢化钠-异丙醇溶液中,20-25℃搅拌17-24h,洗涤干燥后置于二异丁基氢化铝-甲苯溶液中,20-25℃搅拌65-70h,洗涤,干燥,得到羟基化聚偏氟乙烯薄膜;将羟基化聚偏氟乙烯薄膜置于二氯甲烷、三乙胺和4-二甲氨基吡啶混合溶液中,加入2-溴代异丁酰溴-二氯甲烷溶液中,氮气氛围下冰浴反应2-3h,20-25℃反应12-14h,洗涤,
干燥,得到溴化聚偏氟乙烯薄膜;
S4:将改性紫外线吸收剂、溴化铜、2,2’-联吡啶鼓泡除氧30-45min,加入抗坏血酸搅拌均匀后,加入溴化聚偏氟乙烯薄膜氮气氛围下65-70℃反应6-8h,洗涤,干燥,得到超耐低温耐紫外透明聚偏氟乙烯薄膜。
进一步的,所述增容剂按如下方法制备:
将甲基丙烯酸甲酯、4,4’-偶氮双(4-氰基戊酸)和1,3,5-三聚氰酸三烯丙基酯加入四氢呋喃中,氮气氛围下60-65℃反应4-5h,提纯,干燥,得到端羧基甲基丙烯酸甲酯;将端羧基甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、1,4-苯二酚和N,N-二甲基甲酰胺加入二甲苯中,140-145℃反应10-12h,提纯,干燥,得到大分子甲基丙烯酸甲酯;将大分子甲基丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯和偶氮二异丁腈加入甲苯中,真空下60-65℃反应5-6h,提纯,干燥,得到增容剂。
进一步的,所述端羧基甲基丙烯酸甲酯中,甲基丙烯酸甲酯:4,4’-偶氮双(4-氰基戊酸):1,3,5-三聚氰酸三烯丙基酯的质量比为(20-30):(0.5-0.9):(0.9-1.4);
进一步的,所述大分子甲基丙烯酸甲酯中,端羧基甲基丙烯酸甲酯:甲基丙烯酸缩水甘油酯的质量比为(10-15):(1-1.5);
进一步的,所述增容剂中,大分子甲基丙烯酸甲酯:甲基丙烯酸甲酯:甲基丙烯酸缩水甘油酯的质量比为(1-2):(2-4):(7-14)。
进一步的,所述改性紫外线吸收剂按如下方法制备:
将2,4-二羟基二苯甲酮、甲基丙烯酸缩水甘油酯氮气氛围下搅拌均匀,加入氢氧化钠80-85℃反应7-8h,提纯,干燥,得到紫外线吸收剂;将紫外线吸收剂溶于丙酮中,加入盐酸、乙酰丙酮和去离子水,20-25℃搅拌20-25min,加入钛酸正丁酯,20-25℃搅拌3-4h,得到改性紫外线吸收剂。
进一步的,所述紫外线吸收剂中,2,4-二羟基二苯甲酮:甲基丙烯酸缩水甘油酯的质量比为(8-9):(5.5-6.5);所述改性紫外线吸收剂中,紫外线吸收剂:乙酰丙酮:钛酸正丁酯的质量比为1:(1.25-1.95):(0.4-0.8)。
进一步的,所述助剂为防老剂445、脱模助剂WS180。
进一步的,所述丙烯酸酯增韧剂A中,乙烯-丙烯酸酯橡胶:六亚甲基二胺氨基甲酸盐:二苯胍的质量比为100:1:(3-4);
进一步的,所述丙烯酸酯增韧剂B中,N,N-(4,4’-亚甲基二苯基)双马来酰亚胺:1,6-己二醇二丙烯酸酯的质量比为(1-1.5):(1-1.2)。
进一步的,所述超耐低温聚偏氟乙烯薄膜中,各原料组分占比按质量份数计,聚偏氟乙烯60-80份,乙烯-丙烯酸酯橡胶3-10份,增容剂3-10份,丙烯酸酯增韧剂A3-5份,丙烯酸酯增韧剂B3-5份。
进一步的,所述羟基化聚偏氟乙烯薄膜中,氢氧化锂溶液浓度为1.8-2.0mol/L,硼氢化钠异丙醇溶液浓度为0.078-0.086mol/L,二异丁基氢化铝-甲苯溶液浓度为0.104-0.115mol/L;所述溴化聚偏氟乙烯薄膜中,2-溴代异丁酰溴-二氯甲烷溶液浓度为15-17wt%。
进一步的,所述超耐低温耐紫外透明聚偏氟乙烯薄膜中,每1平方厘米聚偏氟乙烯薄膜所需改性紫外线吸收剂的量为0.22-0.25g。
与现有技术相比,本发明所达到的有益效果是:
本发明为了满足聚偏氟乙烯薄膜超耐低温的性能优点,选择了乙烯-丙烯酸酯橡胶作为超耐低温增韧剂的基体,利用六亚甲基氨基甲酸二胺和二苯胍对乙烯-丙烯酸酯橡胶进行进一步硫化处理,通过二次硫化增大橡胶交联程度,完善交联网络,在保持六亚甲基氨基甲酸二胺与乙烯-丙烯酸酯橡胶交联单体反应形成交联键的基础上,提高二苯胍的加入量进一步降低玻璃化温度,提高材料耐低温性能。虽然自制得到的丙烯酸酯增韧剂A具有优异的耐低温性能以及力学性能,但其存在着耐高温老化性能降低和相容性差的问题。因此,本发明通过自制具有耐高温抗老化性能的丙烯酸酯增韧剂B和增容剂,已解决随之而来产生的问题。
本发明通过将N,N-(4,4’-亚甲基二苯基)双马来酰亚胺引入1,6-己二醇二丙烯酸酯中,利用双马来酰亚胺独特的耐高温抗老化性能,解决了加入丙烯酸酯增韧剂A导致的耐高温老化性能降低的问题。接着,通过甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯和自制的大分子甲基丙烯酸甲酯聚合制备得到增容剂,其结构具有甲基丙烯酸甲酯的主链和沿主线随机分布的环氧基团结构,在增容剂与乙烯-丙烯酸酯橡胶共混过程中,乙烯-丙烯酸酯橡胶交联单体链段中的羧基与增容剂上的环氧基团发生反应,生成接枝共聚物,由于增容剂两侧在界面处的应力平衡,使得制备得到的接枝共聚物准确位于丙烯酸酯增韧剂A与聚偏氟乙烯界面处,从而起到了增容的效果,提高了共混物的延展性和透明性,使得制备得到的聚偏氟乙烯薄膜具有优异的耐低温性能。同时,选取丙烯酸类的增韧剂,该增韧剂折射率在1.5左右,此折射率与主材相近,解决了产品成膜后表面发雾,导致透光率不高的缺陷。
本发明为了进一步满足聚偏氟乙烯薄膜具有耐紫外的性能同时匹配主材以及增韧剂的折射率,选择了以2,4-二羟基二苯甲酮和甲基丙烯酸缩水甘油酯制备得到的紫外线吸收剂为基体,通过控制二氧化钛杂化过程中钛酸正丁酯加入的量来调整紫外线吸收剂的折射率,使其处在1.5左右,能够与主材以及增韧剂相匹配。为了使得经过二氧化钛杂化后的改性紫外线吸收剂能够均匀分布在聚偏氟乙烯薄膜表面,本发明通过电子活化再生原子转移自由基聚合的方法,先对聚偏氟乙烯薄膜表面进行羟基化处理,接着使其表面羟基与2-溴代异丁酰溴反应形成溴引发剂,最后通过铜催化剂将改性紫外线吸收剂与聚偏氟乙烯薄膜进行连接,成功将改性紫外线吸收剂接枝在其表面,防止其迁移以及分布不均对折射率造成的影响。使得制备得到的聚偏氟乙烯薄膜具有优异的紫外线吸收、紫外线屏蔽、耐紫外的性能。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
需要说明的是,本发明所有涉及的原料的购买厂家没有任何特殊的限制示例性地包括:乙烯-丙烯酸酯橡胶购自美国杜邦公司,型号为VamacHT,其余原料均为市售工业品。
增容剂按如下方法制备:将20g甲基丙烯酸甲酯、0.5g4,4’-偶氮双(4-氰基戊酸)和0.9g1,3,5-三聚氰酸三烯丙基酯加入四氢呋喃中,氮气氛围下60℃反应4h,提纯,干燥,得到端羧基甲基丙烯酸甲酯;将10g端羧基甲基丙烯酸甲酯、1g甲基丙烯酸缩水甘油酯、0.01g1,4-苯二酚和0.02gN,N-二甲基甲酰胺加入100mL二甲苯中,140℃反应10h,提纯,干燥,得到大分子甲基丙烯酸甲酯;将1g大分子甲基丙烯酸甲酯、2g甲基丙烯酸甲酯、7g甲基丙烯酸缩水甘油酯和0.4g偶氮二异丁腈加入20mL甲苯中,真空下60℃反应5h,提纯,干燥,得到增容剂。
改性紫外线吸收剂按如下方法制备:将8g2,4-二羟基二苯甲酮、5.5g甲基丙烯酸缩水甘油酯氮气氛围下搅拌均匀,加入0.2g氢氧化钠80℃反应7h,提纯,干燥,得到紫外线吸收剂;将10g紫外线吸收剂溶于丙酮中,加入3g盐酸、12.5g乙酰丙酮和5g去离子水,20℃搅拌20min,加入4g钛酸正丁酯,20℃搅拌3h,得到改性紫外线吸收剂。
实施例1:一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法:S1:1g将六亚甲基二胺氨基甲酸盐、3g二苯胍和助剂加入100g乙烯-丙烯酸酯橡胶中混炼,170℃硫化20min,170℃硫化4h,得到丙烯酸酯增韧剂A;将1gN,N-(4,4’-亚甲基二苯基)双马来酰亚胺加入1g1,6-己二醇二丙烯酸酯中,120℃反应1.5h,得到丙烯酸酯增韧剂B;
S2:将80g聚偏氟乙烯、3g乙烯-丙烯酸酯橡胶和3g增容剂在190℃350rpm条件下熔融共混均匀后,加入3g丙烯酸酯增韧剂A和3g丙烯酸酯增韧剂B熔融在190℃
350rpm条件下共混均匀后,挤出造粒,将粒子干燥后,投入流延机,210℃输送、熔融与挤压,并汇流至流延模头,模头温度为220℃,经模头挤出后拉伸、冷却定型,切边收卷,得到超耐低温聚偏氟乙烯薄膜;
S3:将2×1cm2大小超耐低温聚偏氟乙烯薄膜置于1.8mol/L氢氧化锂溶液中,80℃搅拌24h,洗涤,干燥后置于0.078mol/L硼氢化钠-异丙醇溶液中,20℃搅拌17h,洗涤干燥后置于0.104mol/L二异丁基氢化铝-甲苯溶液中,20℃搅拌65h,洗涤,干燥,得到羟基化聚偏氟乙烯薄膜;将羟基化聚偏氟乙烯薄膜置于20mL二氯甲烷、3mL三乙胺和0.1mL4-二甲氨基吡啶混合溶液中,加入30mL15wt%2-溴代异丁酰溴-二氯甲烷溶液中,氮气氛围下冰浴反应2h,20℃反应12h,洗涤,干燥,得到溴化聚偏氟乙烯薄膜;
S4:将0.44g改性紫外线吸收剂、4.8mg溴化铜、9.9mg2,2’-联吡啶溶解于15mL甲醇中,鼓泡除氧30min,加入300mg抗坏血酸搅拌均匀后,加入溴化聚偏氟乙烯薄膜氮气氛围下65℃反应6h,洗涤,干燥,得到超耐低温耐紫外透明聚偏氟乙烯薄膜。
实施例2:一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法:S1:1g将六亚甲基二胺氨基甲酸盐、4g二苯胍和助剂加入100g乙烯-丙烯酸酯橡胶中混炼,170℃硫化20min,170℃硫化4h,得到丙烯酸酯增韧剂A;将1gN,N-(4,4’-亚甲基二苯基)双马来酰亚胺加入1g1,6-己二醇二丙烯酸酯中,120℃反应1.5h,得到丙烯酸酯增韧剂B;
S2:将70g聚偏氟乙烯、6g乙烯-丙烯酸酯橡胶和6g增容剂在190℃350rpm条件下熔融共混均匀后,加入4g丙烯酸酯增韧剂A和4g丙烯酸酯增韧剂B熔融在190℃
350rpm条件下共混均匀后,挤出造粒,将粒子干燥后,投入流延机,210℃输送、熔融与挤压,并汇流至流延模头,模头温度为220℃,经模头挤出后拉伸、冷却定型,切边收卷,得到超耐低温聚偏氟乙烯薄膜;
S3:将2×1cm2大小超耐低温聚偏氟乙烯薄膜置于1.8mol/L氢氧化锂溶液中,80℃搅拌24h,洗涤,干燥后置于0.078mol/L硼氢化钠-异丙醇溶液中,20℃搅拌17h,洗涤干燥后置于0.104mol/L二异丁基氢化铝-甲苯溶液中,20℃搅拌65h,洗涤,干燥,得到羟基化聚偏氟乙烯薄膜;将羟基化聚偏氟乙烯薄膜置于20mL二氯甲烷、3mL三乙胺和0.1mL4-二甲氨基吡啶混合溶液中,加入30mL15wt%2-溴代异丁酰溴-二氯甲烷溶液中,氮气氛围下冰浴反应2h,20℃反应12h,洗涤,干燥,得到溴化聚偏氟乙烯薄膜;
S4:将0.50g改性紫外线吸收剂、4.8mg溴化铜、9.9mg2,2’-联吡啶溶解于15mL甲醇中,鼓泡除氧30min,加入300mg抗坏血酸搅拌均匀后,加入溴化聚偏氟乙烯薄膜氮气氛围下65℃反应6h,洗涤,干燥,得到超耐低温耐紫外透明聚偏氟乙烯薄膜。
实施例3:一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法:改性紫外线吸收剂按如下方法制备:将8g2,4-二羟基二苯甲酮、5.5g甲基丙烯酸缩水甘油酯氮气氛围下搅拌均匀,加入0.2g氢氧化钠80℃反应7h,提纯,干燥,得到紫外线吸收剂;将10g紫外线吸收剂溶于丙酮中,加入3g盐酸、12.5g乙酰丙酮和5g去离子水,20℃搅拌20min,加入8g钛酸正丁酯,20℃搅拌3h,得到改性紫外线吸收剂;
S1:1g将六亚甲基二胺氨基甲酸盐、4g二苯胍和助剂加入100g乙烯-丙烯酸酯橡胶中混炼,170℃硫化20min,170℃硫化4h,得到丙烯酸酯增韧剂A;将1gN,N-(4,4’-亚甲基二苯基)双马来酰亚胺加入1g1,6-己二醇二丙烯酸酯中,120℃反应1.5h,得到丙烯酸酯增韧剂B;
S2:将70g聚偏氟乙烯、10g乙烯-丙烯酸酯橡胶和10g增容剂在190℃350rpm条件下熔融共混均匀后,加入5g丙烯酸酯增韧剂A和5g丙烯酸酯增韧剂B熔融在190℃
350rpm条件下共混均匀后,挤出造粒,将粒子干燥后,投入流延机,210℃输送、熔融与挤压,并汇流至流延模头,模头温度为220℃,经模头挤出后拉伸、冷却定型,切边收卷,得到超耐低温聚偏氟乙烯薄膜;
S3:将2×1cm2大小超耐低温聚偏氟乙烯薄膜置于1.8mol/L氢氧化锂溶液中,80℃搅拌24h,洗涤,干燥后置于0.078mol/L硼氢化钠-异丙醇溶液中,20℃搅拌17h,洗涤干燥后置于0.104mol/L二异丁基氢化铝-甲苯溶液中,20℃搅拌65h,洗涤,干燥,得到羟基化聚偏氟乙烯薄膜;将羟基化聚偏氟乙烯薄膜置于20mL二氯甲烷、3mL三乙胺和0.1mL4-二甲氨基吡啶混合溶液中,加入30mL15wt%2-溴代异丁酰溴-二氯甲烷溶液中,氮气氛围下冰浴反应2h,20℃反应12h,洗涤,干燥,得到溴化聚偏氟乙烯薄膜;
S4:将0.50g改性紫外线吸收剂、4.8mg溴化铜、9.9mg2,2’-联吡啶溶解于15mL甲醇中,鼓泡除氧30min,加入300mg抗坏血酸搅拌均匀后,加入溴化聚偏氟乙烯薄膜氮气氛围下65℃反应6h,洗涤,干燥,得到超耐低温耐紫外透明聚偏氟乙烯薄膜。
对比例1:一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法:S1:3g将六亚甲基二胺氨基甲酸盐、1g二苯胍和助剂加入100g乙烯-丙烯酸酯橡胶中混炼,170℃硫化20min,170℃硫化4h,得到丙烯酸酯增韧剂A;将1gN,N-(4,4’-亚甲基二苯基)双马来酰亚胺加入1g1,6-己二醇二丙烯酸酯中,120℃反应1.5h,得到丙烯酸酯增韧剂B;
其余步骤与实施例1相同。
对比例2:一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法:S2:将80g聚偏氟乙烯、3g乙烯-丙烯酸酯橡胶和3g增容剂在190℃350rpm条件下熔融共混均匀后,加入5g丙烯酸酯增韧剂A和5g丙烯酸酯增韧剂B熔融在190℃350rpm条件下共混均匀后,挤出造粒,将粒子干燥后,投入流延机,210℃输送、熔融与挤压,并汇流至流延模头,模头温度为220℃,经模头挤出后拉伸、冷却定型,切边收卷,得到超耐低温聚偏氟乙烯薄膜;
其余步骤与实施例1相同。
对比例3:一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法:改性紫外线吸收剂按如下方法制备:将8g2,4-二羟基二苯甲酮、5.5g甲基丙烯酸缩水甘油酯氮气氛围下搅拌均匀,加入0.2g氢氧化钠80℃反应7h,提纯,干燥,得到紫外线吸收剂;将10g紫外线吸收剂溶于丙酮中,加入3g盐酸、12.5g乙酰丙酮和5g去离子水,20℃搅拌20min,加入12g钛酸正丁酯,20℃搅拌3h,得到改性紫外线吸收剂;
其余步骤与实施例1相同。
试验:按下表中的测试方法对实施例1-3和对比例1-3制备的聚偏氟乙烯薄膜进行性能测试。
结论:实施例1-3制备得到的聚偏氟乙烯薄膜具有优异的耐低温性能和耐紫外性能。
对比例1中,制备丙烯酸酯增韧剂A过程中加入六亚甲基二胺氨基甲酸盐的量远大于二苯胍的量,导致交联程度增大,分子链运动能力下降,耐低温性能降低。
对比例2中,制备超耐低温聚偏氟乙烯薄膜过程中,相容剂与乙烯-丙烯酸酯橡胶加入量过少导致界面相容性下降,耐低温性能,力学性能降低。
对比例3中,制备改性紫外线吸收剂过程中,加入过量钛酸正丁酯导致部分粒子反应过快,没有与基体连接导致团聚现象发生,导致粒径增大分布不均,造成折射率不匹配,耐紫外性能下降。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。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 (4)
1.一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法,其特征在于:包括以下步骤:
S1:将六亚甲基二胺氨基甲酸盐、二苯胍和助剂加入乙烯-丙烯酸酯橡胶中混炼,170-175℃硫化20-25min,170-175℃硫化4-5h,得到丙烯酸酯增韧剂A;将N,N-(4,4’-亚甲基二苯基)双马来酰亚胺加入1,6-己二醇二丙烯酸酯中,120-125℃反应1.5-2h,得到丙烯酸酯增韧剂B;
S2:将聚偏氟乙烯、乙烯-丙烯酸酯橡胶和增容剂熔融共混均匀后,加入丙烯酸酯增韧剂A和丙烯酸酯增韧剂B熔融共混均匀后,挤出造粒,流延成膜,得到超耐低温聚偏氟乙烯薄膜;
S3:将超耐低温聚偏氟乙烯薄膜置于氢氧化锂溶液中,80-85℃搅拌24-36h,洗涤,干燥后置于硼氢化钠-异丙醇溶液中,20-25℃搅拌17-24h,洗涤干燥后置于二异丁基氢化铝-甲苯溶液中,20-25℃搅拌65-70h,洗涤,干燥,得到羟基化聚偏氟乙烯薄膜;将羟基化聚偏氟乙烯薄膜置于二氯甲烷、三乙胺和4-二甲氨基吡啶混合溶液中,加入2-溴代异丁酰溴-二氯甲烷溶液中,氮气氛围下冰浴反应2-3h,20-25℃反应12-14h,洗涤,干燥,得到溴化聚偏氟乙烯薄膜;
S4:将改性紫外线吸收剂、溴化铜、2,2’-联吡啶鼓泡除氧30-45min,加入抗坏血酸搅拌均匀后,加入溴化聚偏氟乙烯薄膜氮气氛围下65-70℃反应6-8h,洗涤,干燥,得到超耐低温耐紫外透明聚偏氟乙烯薄膜;
所述增容剂按如下方法制备:将甲基丙烯酸甲酯、4,4’-偶氮双(4-氰基戊酸)和1,3,5-三聚氰酸三烯丙基酯加入四氢呋喃中,氮气氛围下60-65℃反应4-5h,提纯,干燥,得到端羧基甲基丙烯酸甲酯;将端羧基甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯、1,4-苯二酚和N,N-二甲基甲酰胺加入二甲苯中,140-145℃反应10-12h,提纯,干燥,得到大分子甲基丙烯酸甲酯;将大分子甲基丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯和偶氮二异丁腈加入甲苯中,真空下60-65℃反应5-6h,提纯,干燥,得到增容剂;
所述端羧基甲基丙烯酸甲酯中,甲基丙烯酸甲酯:4,4’-偶氮双(4-氰基戊酸):1,3,5-三聚氰酸三烯丙基酯的质量比为(20-30):(0.5-0.9):(0.9-1.4);所述大分子甲基丙烯酸甲酯中,端羧基甲基丙烯酸甲酯:甲基丙烯酸缩水甘油酯的质量比为(10-15):(1-1.5);所述增容剂中,大分子甲基丙烯酸甲酯:甲基丙烯酸甲酯:甲基丙烯酸缩水甘油酯的质量比为(1-2):(2-4):(7-14);
所述改性紫外线吸收剂按如下方法制备:将2,4-二羟基二苯甲酮、甲基丙烯酸缩水甘油酯氮气氛围下搅拌均匀,加入氢氧化钠80-85℃反应7-8h,提纯,干燥,得到紫外线吸收剂;将紫外线吸收剂溶于丙酮中,加入盐酸、乙酰丙酮和去离子水,20-25℃搅拌20-25min,加入钛酸正丁酯,20-25℃搅拌3-4h,得到改性紫外线吸收剂;
所述紫外线吸收剂中,2,4-二羟基二苯甲酮:甲基丙烯酸缩水甘油酯的质量比为(8-9):(5.5-6.5);所述改性紫外线吸收剂中,紫外线吸收剂:乙酰丙酮:钛酸正丁酯的质量比为1:(1.25-1.95):(0.4-0.8);
所述丙烯酸酯增韧剂A中,乙烯-丙烯酸酯橡胶:六亚甲基二胺氨基甲酸盐:二苯胍的质量比为100:1:(3-4);所述丙烯酸酯增韧剂B中,N,N-(4,4’-亚甲基二苯基)双马来酰亚胺:1,6-己二醇二丙烯酸酯的质量比为(1-1.5):(1-1.2);
所述超耐低温聚偏氟乙烯薄膜中,各原料组分占比按质量份数计,聚偏氟乙烯60-80份,乙烯-丙烯酸酯橡胶3-10份,增容剂3-10份,丙烯酸酯增韧剂A3-4份,丙烯酸酯增韧剂B3-4份。
2.根据权利要求1所述的一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法,其特征在于:所述羟基化聚偏氟乙烯薄膜中,氢氧化锂溶液浓度为1.8-2.0mol/L,硼氢化钠异丙醇溶液浓度为0.078-0.086mol/L,二异丁基氢化铝-甲苯溶液浓度为0.104-0.115mol/L;所述溴化聚偏氟乙烯薄膜中,2-溴代异丁酰溴-二氯甲烷溶液浓度为15-17wt%。
3.根据权利要求1所述的一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法,其特征在于:所述超耐低温耐紫外透明聚偏氟乙烯薄膜中,每1平方厘米聚偏氟乙烯薄膜所需改性紫外线吸收剂的量为0.22-0.25g。
4.根据权利要求1-3任一项所述的一种超耐低温耐紫外透明聚偏氟乙烯薄膜的制备方法制备得到的聚偏氟乙烯薄膜。
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