CN117327455A - 一种耐老化发泡光伏胶膜制备方法 - Google Patents
一种耐老化发泡光伏胶膜制备方法 Download PDFInfo
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- CN117327455A CN117327455A CN202311137067.5A CN202311137067A CN117327455A CN 117327455 A CN117327455 A CN 117327455A CN 202311137067 A CN202311137067 A CN 202311137067A CN 117327455 A CN117327455 A CN 117327455A
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical class CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 3
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 241000605372 Fritillaria Species 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
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- VRFNYSYURHAPFL-UHFFFAOYSA-N [(4-methylphenyl)sulfonylamino]urea Chemical compound CC1=CC=C(S(=O)(=O)NNC(N)=O)C=C1 VRFNYSYURHAPFL-UHFFFAOYSA-N 0.000 claims description 2
- 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 group 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 claims description 2
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
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- WDUJLXIMFAPCKD-UHFFFAOYSA-N ethane-1,2-diol;[2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound OCCO.C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C WDUJLXIMFAPCKD-UHFFFAOYSA-N 0.000 claims description 2
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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 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
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- C09J7/10—Adhesives in the form of films or foils without carriers
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- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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- H—ELECTRICITY
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/322—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of solar panels
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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Abstract
一种耐老化发泡光伏胶膜制备方法,涉及一种光伏胶膜制备方法,本发明光伏胶膜包括以下重量组份:乙烯‑醋酸乙烯共聚物(EVA)30‑100份、热塑性聚烯烃弹性体(POE)30‑100份、乙烯‑甲基丙烯酸甲酯(EMMA)0‑30份、EVA接枝马来酸酐(EVA‑g‑MAH)0‑7份、交联剂0‑5份、助交联剂0‑3份、偶联剂0‑2份、光稳定剂0.1‑2份、抗氧剂0.5‑3份、发泡剂1‑5份、填充剂0‑15份、防老剂0‑1份。本发明能够有效改善EVA光伏胶膜的耐老化性、抗功率衰减率及力学性能,同时为光伏组件在存储、安装和使用过程中起到支撑、缓冲的作用,为改性EVA光伏胶膜提供有意义的基础研究。
Description
技术领域
本发明涉及光伏胶膜制备方法,特别是涉及一种耐老化发泡光伏胶膜制备方法。
背景技术
光伏胶膜是保护太阳电池片的关键,由于光伏组件长期处于室外环境下工作,所以要求光伏胶膜要由良好的耐老化性、抗紫外线性、阻水性、抗抗诱导电势衰减性(PDI)。常见的光伏胶膜有EVA胶膜、白色EVA胶膜、POE胶膜、共挤型EPE胶膜、PVB胶膜等。
热塑性聚烯烃弹性体(Thermoplastic Polyolefin Elastomers)简称POE,是由C-C和C-H结构组成的一种半结晶型聚合物,具有均匀的短支链分布和相对分子质量分布范围较窄的特点,其中叔碳原子的含量相对较低。这种高分子链结构的特点使得聚烯烃弹性体表现出卓越的耐候性和抗诱导电势衰减性能。然而,POE胶膜在界面粘结性和成本方面存在一些问题,通常需要与其他材料共混进行改性加工,改善这些问题。具有良好粘结性的乙烯-醋酸乙烯共聚物(EVA)和良好的耐老化性的乙烯-甲基丙烯酸甲酯(EMMA)可以与POE性能互补。
乙烯-醋酸乙烯共聚物(Ethylene-Vinyl Acetate,)简称为EVA,是一种由易结晶的乙烯单体和乙酸乙酯共聚制得的聚合物,通常醋酸乙烯含量在5%至40%之间,具有比重轻、耐水性、易加工性、粘结性且价格低廉等特点,被广泛应用于光伏胶膜、汽车行业、建筑材料等领域,其中VA含量一般为28%至33%的EVA常应用于光伏胶膜领域。同时EVA也可以作为发泡材料使用,目前EVA发泡材料使用存在弹性不足、永久变形大等问题,限制其应用范围,因此对EVA材料改性发泡具有一定的研究意义。
发泡主要作用表现为在基体加入物理或化学发泡剂、交联剂及其他助剂后进行模压、挤出、或超临界发泡,气体在材料中逸出形成泡孔,即可以得到发泡材料。在光伏胶膜中,使用发泡材料可以起到缓冲的作用,避免光伏组件在受到外力作用时,太阳电池片遭受损坏。
将POE、EVA和EMMA共混,可以改善材料的粘结性和抗老化性能,同时加入EVA-g-MAH相容剂可以提高界面结合能力,改善分子间相容性。同时将中间层EVA材料和POE共混改性发泡,可以得到弹性大、强度适中的发泡材料。
发明内容
本发明的目的在于提供一种耐老化发泡光伏胶膜制备方法,耐老化发泡光伏胶膜由三层结构组成。本发明第一层和第三层采用POE、EVA和EMMA共混,并加入EVA-g-MAH作为POE/EVA/EMMA体系的相容剂,该方法可以提高材料的耐老化性、粘结性、拉伸强度、断裂伸长率,和减少加工成本。第二层采用EVA和POE共混发泡,该方法可以提高EVA材料的弹性、降低材料的永久变形,为光伏组件在存储、安装和使用过程中起到支撑、缓冲的作用。
本发明的目的是通过以下技术方案实现的:
一种耐老化发泡光伏胶膜制备方法,所述方法包括以下制备过程:
(1)将热塑性聚烯烃弹性体、乙烯醋酸乙烯酯、乙烯-甲基丙烯酸甲酯、EVA接枝马来酸酐、交联剂、助交联剂、偶联剂、光稳定剂、抗氧剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料A。将乙烯醋酸乙烯酯和热塑性聚烯烃弹性体交联剂、助交联剂、发泡剂、填充剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料B;
(2)将预混料A作为第一层和第三层,预混料B作为中间层,分别放入三台双螺杆挤出机中,使用三层挤出工艺进行加工,塑化,挤出成型,加工温度设置为110℃,然后依次进行辊压、冷却、牵引、剪切,得到共混物;
(3)对步骤(2)所得共混物在UV波长为300-400nm的汞或卤素光源进行辐照交联、在加工温度为175℃发泡,得到光伏胶膜;
光伏胶膜由以下质量份数原料组成:乙烯-醋酸乙烯共聚物(EVA) 30-100份、热塑性聚烯烃弹性体(POE) 30-100份、EVA接枝马来酸酐(EVA-g-MAH) 0-7份、乙烯-甲基丙烯酸甲酯(EMMA) 0-40份、交联剂 0-5份、助交联剂 0-3份、偶联剂 0-2份、光稳定剂 0.1-2份、抗氧剂 0.5-3份、发泡剂 1-5份、填充剂 0-15份、防老剂 0-1份。
所述的一种耐老化发泡光伏胶膜制备方法,所述光伏胶膜或由以下质量份数原料组成:乙烯-醋酸乙烯共聚物(EVA) 40-100份、热塑性聚烯烃弹性体(POE) 40-100份、EVA接枝马来酸酐(EVA-g-MAH) 0-5份、乙烯-甲基丙烯酸甲酯(EMMA) 0-30份、交联剂 0-4份、助交联剂 0-2份、偶联剂 0-1份、光稳定剂 0.1-1份、抗氧剂 0.5-2份、发泡剂1-3份、填充剂5-15份、防老剂 0-0.7份。
所述的一种耐老化发泡光伏胶膜制备方法,所述乙烯-醋酸乙烯共聚物的乙酸乙烯含量在28%-33%,熔体流动速率在20-150g/min中的一种或几种;乙烯-醋酸乙烯共聚物为VA含量为32%,密度为0.957g/cm3,熔体流动速率为43g/10min,(190℃,2.16kg)。
所述的一种耐老化发泡光伏胶膜制备方法,所述热塑性聚烯烃弹性体(POE)为乙烯-辛烯共聚物、乙烯-丙烯共聚物、乙烯-丁烯共聚物和乙烯-己烯共聚物中的一种或几种;热塑性聚烯烃弹性体(POE)为乙烯-辛烯共聚物和乙烯-丙烯共聚物;乙烯-辛烯共聚物密度分别为0.873g/cm3、0.872g/cm3,熔体流动速率分别为14 g/10min、4.8g/10min,(190℃,2.16kg)。
所述的一种耐老化发泡光伏胶膜制备方法,所述乙烯-丙烯共聚物为乙烯含量在9%-20%中的一种或几种;乙烯-丙烯共聚物乙烯含量为16%,密度为0.874 g/cm3,熔体流动速率为1.4g/10min,(230℃,2.16kg)。
所述的一种耐老化发泡光伏胶膜制备方法,所述EVA接枝马来酸酐(EVA-g-MAH)的乙烯乙酸含量为32%,接枝率为1.8%;乙烯-甲基丙烯酸甲酯MMA含量为18%,熔体流动速率为7g/10min。
所述的一种耐老化发泡光伏胶膜制备方法,所述交联剂为过氧化二异丙苯、过氧化苯甲酰、过氧化马来酸叔丁酯、硫磺、偶氮二异丁腈、二亚乙基三胺、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-双(过氧化叔丁基)己烷和双叔丁基过氧化异丙基苯中的一种或几种;交联剂优选过氧化二异丙苯。
所述的一种耐老化发泡光伏胶膜制备方法,所述助交联剂为三烯丙基异氰尿酸酯、邻苯二甲酸二烯丙酯、三聚异氰酸三丙烯酸酯、三羟基甲基丙烷三丙烯酸脂、甲基丙烯酸异丙酯、三羟基甲基丙烷三甲基丙烯酸酯、二缩三丙二醇二丙烯酸酯、羟乙基甲基丙烯酸酯、季戊四醇三丙烯酸酯乙二醇二乙基二烯丙基醚、二甲基丙烯酸乙二醇酯、乙氧化三羟基丙烷三丙烯酸酯中的一种或几种;助交联剂优选三烯丙基异氰尿酸酯。
所述的一种耐老化发泡光伏胶膜制备方法,所述光稳定剂为光屏蔽剂类、紫外线吸收剂类、猝灭剂类、自由基捕获剂类中的一种或几种;偶联剂优选硅烷偶联剂,进一步优选为3-氨基丙基甲基二乙氧基硅烷;光稳定剂优选紫外线吸收剂类的UV770;抗氧剂为受阻酚类或亚磷酸酯类中的一种或几种;抗氧剂优选受阻酚类的Irganox 1010。
所述的一种耐老化发泡光伏胶膜制备方法,所述发泡剂为偶氮二甲酰胺、N,N'-二亚硝基五亚甲基四胺、4,4-氧化双苯磺酰肼、正己烷、碳酸氢钠、对甲苯磺酰氨基脲和超临界CO2物理发泡剂中的一种或几种;发泡剂优选偶氮二甲酰胺;填充剂为滑石粉、玻璃微珠、碳酸钙、钛白粉、三氧化二铝、二氧化硅、二氧化钛、贝母、高岭土、炭黑、二硫化钼中的一种或几种;填充剂优选滑石粉;防老剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯,三[2,4-二叔丁基苯基]亚磷酸酯中的一种或几种;防老剂优选四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯。
本发明的优点与效果是:
本发明的第一层和第三层采用POE、EVA和EMMA共混,并加入EVA-g-MAH作为POE/EVA/EMMA/EVA-g-MAH体系的相容剂,该方法可以提高材料的耐老化性、粘结性、拉伸强度、断裂伸长率,和减少加工成本。第二层采用EVA和POE共混发泡,该方法可以提高EVA材料的弹性、降低材料的永久变形,为光伏组件在存储、安装和使用过程中起到支撑、缓冲的作用。本发明可以有效地提升所制备材料的综合性能,并降低加工成本,为光伏组件的可靠性和耐用性提供了新的途径,并为进一步研究和应用提供了有力支持。
实施方式
下面结合实施例对本发明进行详细说明。
对比例1
一种耐老化发泡光伏胶膜,各组份质量份数如下:第一、三层:POE(PV 8669) 90份;EVA(150W) 10份;EMMA(WH303) 0份;EVA-g-MAH 0份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂0份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜,包括以下步骤:
(1)将热塑性聚烯烃弹性体、乙烯醋酸乙烯酯、乙烯-甲基丙烯酸甲酯、EVA接枝马来酸酐、交联剂、助交联剂、偶联剂、光稳定剂、抗氧剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料A。将乙烯醋酸乙烯酯和热塑性聚烯烃弹性体交联剂、助交联剂、发泡剂、填充剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料B。
(2)将预混料A作为第一层和第三层,预混料B作为中间层,分别放入三台双螺杆挤出机中,使用三层挤出工艺进行加工,塑化,挤出成型,加工温度设置为110℃,然后依次进行辊压、冷却、牵引、剪切,得到共混物。
(3)对步骤(2)所得共混物在UV波长为300-400nm的汞或卤素光源进行辐照交联、在加工温度为175℃发泡,得到光伏胶膜。
对比例2
一种耐老化发泡光伏胶膜,各组份质量份数如下:第一、三层:POE(PV 8669) 90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W) 70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂2份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同对比例1一样。
实施例1
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 0份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂0份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏封装胶膜具体实施步骤如下:
(1)将热塑性聚烯烃弹性体、乙烯醋酸乙烯酯、乙烯-甲基丙烯酸甲酯、EVA接枝马来酸酐、交联剂、助交联剂、偶联剂、光稳定剂、抗氧剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料A。将乙烯醋酸乙烯酯和热塑性聚烯烃弹性体交联剂、助交联剂、发泡剂、填充剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料B。
(2)将预混料A作为第一层和第三层,预混料B作为中间层,分别放入三台双螺杆挤出机中,使用三层挤出工艺进行加工,塑化,挤出成型,加工温度设置为110℃,然后依次进行辊压、冷却、牵引、剪切,得到共混物。
(3)对步骤(2)所得共混物在UV波长为300-400nm的汞或卤素光源进行辐照交联、在加工温度为175℃发泡,得到光伏胶膜。
实施例2
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 1份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂0份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例3
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂0份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例4
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂1份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例5
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂3份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例6
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8660)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂2份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例7
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(6102FL)90份;EVA(150W) 5份;EMMA(WH303) 5份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂2份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例8
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)80份;EVA(150W) 10份;EMMA(WH303) 10份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂2份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
实施例9
一种耐老化发泡光伏封装胶膜,各组份质量份数如下:第一、三层:POE(PV 8669)70份;EVA(150W) 15份;EMMA(WH303) 15份;EVA-g-MAH 3份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;填充剂10份;防老剂0.5份。第二层:EVA(150W)70份;POE(6102FL) 30份;交联剂3份;助交联剂1份;硅烷偶联剂0.5份;光稳定剂0.3份;抗氧剂0.5份;发泡剂2份;填充剂10份;防老剂0.5份。
上述耐老化发泡光伏胶膜具体实施步骤同实施例1一样。
上述对比例和实施例,按照GB/T 279848-2018测试材料高温热老化性能,GB/T6344-2008 测试材料力学力学性能。
测试结果
将对比例和实施例制备的耐老化发泡光伏胶膜性能进行对比,结果表明,对比例1与实施例1、2、3相比,在POE/EVA共混物中加入EMMA,可以提高材料的剥离强度,提高材料的粘结性及抗老化性,同时在保持POE/EVA/EMMA共混物配比不变时,加入EVA-g-MAH可以提高材料的相容性,提高界面结合力;比例2和实施例6、7相比,不同点在于POE所用牌号不同,可以发现在相同配比下,PV8669对材料的影响较大;对比例2与实施例4、5相比可知,随着发泡剂含量增加,共混物的拉伸强度和断裂伸长率提高,力学性能得到改善。
表1为对比例和实施例性能对比结果。
表1
测试项目 | 高温老化前剥离强度(N/m) | 高温老化后与背板剥离强度(N/cm) | 功率衰减率(%) | 拉伸强度/(MPa) | 断裂伸长率/(%) | 泡孔平均直径(mm) |
对比例1 | 8250 | 6170 | 31.81 | 20.2 | 443.3 | 0.032 |
对比例2 | 8794 | 6643 | 34.38 | 23.0 | 476.3 | 0.052 |
实施例1 | 8570 | 6324 | 33.01 | 21.2 | 442.1 | 0.038 |
实施例2 | 8665 | 6555 | 33.01 | 22.8 | 476.8 | 0.038 |
实施例3 | 8778 | 6621 | 33.02 | 23.1 | 477.2 | 0.037 |
实施例4 | 8795 | 6702 | 33.01 | 22.9 | 475.2 | 0.042 |
实施例5 | 8789 | 6715 | 33.01 | 23.4 | 501.2 | 0.051 |
实施例6 | 8760 | 6571 | 32.99 | 22.5 | 504.5 | 0.049 |
实施例7 | 8853 | 6787 | 12.24 | 22.3 | 487.7 | 0.039 |
实施例8 | 11032 | 6996 | 31.98 | 23.6 | 508.7 | 0.051 |
实施例9 | 11021 | 6958 | 32.00 | 23.8 | 558.3 | 0.052 |
。
Claims (10)
1.一种耐老化发泡光伏胶膜制备方法,其特征在于,所述方法包括以下制备过程:
(1)将热塑性聚烯烃弹性体、乙烯醋酸乙烯酯、乙烯-甲基丙烯酸甲酯、EVA接枝马来酸酐、交联剂、助交联剂、偶联剂、光稳定剂、抗氧剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料A。将乙烯醋酸乙烯酯和热塑性聚烯烃弹性体交联剂、助交联剂、发泡剂、填充剂按照不同的质量比混合均匀,得到简单共混物,然后在双螺杆挤出机中进行两次共混得到预混料B;
(2)将预混料A作为第一层和第三层,预混料B作为中间层,分别放入三台双螺杆挤出机中,使用三层挤出工艺进行加工,塑化,挤出成型,加工温度设置为110℃,然后依次进行辊压、冷却、牵引、剪切,得到共混物;
(3)对步骤(2)所得共混物在UV波长为300-400nm的汞或卤素光源进行辐照交联、在加工温度为175℃发泡,得到光伏胶膜;
光伏胶膜由以下质量份数原料组成:乙烯-醋酸乙烯共聚物(EVA) 30-100份、热塑性聚烯烃弹性体(POE) 30-100份、EVA接枝马来酸酐(EVA-g-MAH) 0-7份、乙烯-甲基丙烯酸甲酯(EMMA) 0-40份、交联剂 0-5份、助交联剂 0-3份、偶联剂 0-2份、光稳定剂 0.1-2份、抗氧剂 0.5-3份、发泡剂 1-5份、填充剂 0-15份、防老剂 0-1份。
2.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述光伏胶膜或由以下质量份数原料组成:乙烯-醋酸乙烯共聚物(EVA) 40-100份、热塑性聚烯烃弹性体(POE) 40-100份、EVA接枝马来酸酐(EVA-g-MAH) 0-5份、乙烯-甲基丙烯酸甲酯(EMMA)0-30份、交联剂 0-4份、助交联剂 0-2份、偶联剂 0-1份、光稳定剂 0.1-1份、抗氧剂 0.5-2份、发泡剂1-3份、填充剂 5-15份、防老剂 0-0.7份。
3.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述乙烯-醋酸乙烯共聚物的乙酸乙烯含量在28%-33%,熔体流动速率在20-150g/min中的一种或几种;乙烯-醋酸乙烯共聚物为VA含量为32%,密度为0.957g/cm3,熔体流动速率为43g/10min,(190℃,2.16kg)。
4.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述热塑性聚烯烃弹性体(POE)为乙烯-辛烯共聚物、乙烯-丙烯共聚物、乙烯-丁烯共聚物和乙烯-己烯共聚物中的一种或几种;热塑性聚烯烃弹性体(POE)为乙烯-辛烯共聚物和乙烯-丙烯共聚物;乙烯-辛烯共聚物密度分别为0.873g/cm3、0.872g/cm3,熔体流动速率分别为14 g/10min、4.8g/10min,(190℃,2.16kg)。
5.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述乙烯-丙烯共聚物为乙烯含量在9%-20%中的一种或几种;乙烯-丙烯共聚物乙烯含量为16%,密度为0.874 g/cm3,熔体流动速率为1.4g/10min,(230℃,2.16kg)。
6.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述EVA接枝马来酸酐(EVA-g-MAH)的乙烯乙酸含量为32%,接枝率为1.8%;乙烯-甲基丙烯酸甲酯MMA含量为18%,熔体流动速率为7g/10min。
7.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述交联剂为过氧化二异丙苯、过氧化苯甲酰、过氧化马来酸叔丁酯、硫磺、偶氮二异丁腈、二亚乙基三胺、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-双(过氧化叔丁基)己烷和双叔丁基过氧化异丙基苯中的一种或几种;交联剂优选过氧化二异丙苯。
8.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述助交联剂为三烯丙基异氰尿酸酯、邻苯二甲酸二烯丙酯、三聚异氰酸三丙烯酸酯、三羟基甲基丙烷三丙烯酸脂、甲基丙烯酸异丙酯、三羟基甲基丙烷三甲基丙烯酸酯、二缩三丙二醇二丙烯酸酯、羟乙基甲基丙烯酸酯、季戊四醇三丙烯酸酯乙二醇二乙基二烯丙基醚、二甲基丙烯酸乙二醇酯、乙氧化三羟基丙烷三丙烯酸酯中的一种或几种;助交联剂优选三烯丙基异氰尿酸酯。
9.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述光稳定剂为光屏蔽剂类、紫外线吸收剂类、猝灭剂类、自由基捕获剂类中的一种或几种;偶联剂优选硅烷偶联剂,进一步优选为3-氨基丙基甲基二乙氧基硅烷;光稳定剂优选紫外线吸收剂类的UV770;抗氧剂为受阻酚类或亚磷酸酯类中的一种或几种;抗氧剂优选受阻酚类的Irganox 1010。
10.根据权利要求1所述的一种耐老化发泡光伏胶膜制备方法,其特征在于,所述发泡剂为偶氮二甲酰胺、N,N'-二亚硝基五亚甲基四胺、4,4-氧化双苯磺酰肼、正己烷、碳酸氢钠、对甲苯磺酰氨基脲和超临界CO2物理发泡剂中的一种或几种;发泡剂优选偶氮二甲酰胺;填充剂为滑石粉、玻璃微珠、碳酸钙、钛白粉、三氧化二铝、二氧化硅、二氧化钛、贝母、高岭土、炭黑、二硫化钼中的一种或几种;填充剂优选滑石粉;防老剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯,三[2,4-二叔丁基苯基]亚磷酸酯中的一种或几种;防老剂优选四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯。
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