CN113226756A - 由至少三个聚酯层构成的多层系统、其生产及其用途 - Google Patents
由至少三个聚酯层构成的多层系统、其生产及其用途 Download PDFInfo
- Publication number
- CN113226756A CN113226756A CN201980083490.7A CN201980083490A CN113226756A CN 113226756 A CN113226756 A CN 113226756A CN 201980083490 A CN201980083490 A CN 201980083490A CN 113226756 A CN113226756 A CN 113226756A
- Authority
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- China
- Prior art keywords
- multilayer system
- polyester
- polyester layer
- group
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 150000003254 radicals Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 5
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- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- 239000004631 polybutylene succinate Substances 0.000 claims description 4
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 229920001634 Copolyester Polymers 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
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- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- JJGBFZZXKPWGCW-UHFFFAOYSA-N 2,3-bis[8-[3-[(3-pentyloxiran-2-yl)methyl]oxiran-2-yl]octanoyloxy]propyl 8-[3-[(3-pentyloxiran-2-yl)methyl]oxiran-2-yl]octanoate Chemical compound CCCCCC1OC1CC1C(CCCCCCCC(=O)OCC(COC(=O)CCCCCCCC2C(O2)CC2C(O2)CCCCC)OC(=O)CCCCCCCC2C(O2)CC2C(O2)CCCCC)O1 JJGBFZZXKPWGCW-UHFFFAOYSA-N 0.000 description 1
- HREXIBFZDJHFCF-UHFFFAOYSA-N 2,6-dibromo-4-propylphenol Chemical compound CCCC1=CC(Br)=C(O)C(Br)=C1 HREXIBFZDJHFCF-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 239000007857 degradation product Substances 0.000 description 1
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical group C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 125000005481 linolenic acid group Chemical group 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 238000010943 off-gassing Methods 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
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- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000559 poly(Bisphenol A-co-epichlorohydrin) Polymers 0.000 description 1
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Classifications
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- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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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
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- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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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
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- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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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
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Abstract
本发明涉及一种由至少三个聚酯层构成的多层系统,其生产及其用于生产包装、保护膜、粘附膜、太阳能电池或医疗材料的用途,以及还有由其生产的太阳能电池。
Description
本发明涉及一种由至少3个聚酯层构成的多层系统,涉及其生产并且涉及其用于生产包装、保护膜、粘附膜、太阳能电池或医疗材料的用途,并且还涉及由其生产的太阳能电池。
聚酯膜具有多种可能应用,包括在太阳能电池中的应用。一个常见问题是其缺乏水解稳定性(WO 2010113920)。许多种碳二亚胺已经证明了作为针对热塑性塑料的水解稳定剂的优点。然而,这些碳二亚胺具有缺点,即它们在处理期间发出与健康相关的气体。膜拉伸的生产步骤是特别有问题的,因为在此不能采用有效的抽气装置。
在聚合物膜的生产工艺期间在一些情况下排放气态异氰酸酯是有害健康的,并且因此需要安装在一些情况下在工艺上不适用的综合性且昂贵的抽气装置(EP-A-0 838500)。
包含环氧化植物油作为稳定剂的聚酯膜描述于EP-A-1 634 914和EP-A-1 842871中。这些聚酯膜没有对于碳二亚胺典型的毒性降解产物的问题,鉴于实现了油类的合适选择和膜的水解稳定化,并入到聚酯基质中是良好的,尽管这仅在高浓度的环氧化物下发生,并且与碳二亚胺的使用相比长期的稳定化较差。这种在生产中的应用还具有缺点,即经常发生对于凝胶形成具有极端倾向的生产间隔。当凝胶水平过高时,这会导致脱落并且膜的生产暂时变得不可能。然后必须中断生产并且清理挤出物。
因此需要一种由聚酯层构成、特别是用于膜的系统,其在处理期间具有明显降低的异氰酸酯排放,并且表现出非常良好的长期水解稳定化。
现在已经令人意外地发现由至少3个聚酯层构成的多层系统是水解稳定的并且在处理期间表现出明显减少的异氰酸酯排放,其中内聚酯层含有碳二亚胺并且在顶部和底部被另外的聚酯层包围,这些另外的聚酯层中的至少一个含有环氧化物。
本发明提供了一种由至少3个聚酯层构成的多层系统,其具有以下构造:
-至少一个含有至少一种碳二亚胺的聚酯层(I),
-至少一个在该聚酯层(I)的顶部上的聚酯层(II),和
-至少一个在该聚酯层(I)的底部上的聚酯层(III),
其中这些聚酯层(II)或(III)中的至少一个含有至少一种环氧化物。这些碳二亚胺优选地是式(I)的化合物
R1-R2-(-N=C=N-R2-)n-R1 (I),
其中
n表示从1至500、优选3至20、非常特别优选4至20的整数,
R1表示系列-NCO、-NCNR3-NHCONHR3、-NHCONR3R4或-NHCOOR5的基团,其中R3和R4是相同或不同的并且各自独立地表示系列C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基或C6-C18-芳基的基团,并且R5表示系列C1-C22-烷基、C6-C12-环烷基、C6-C18-芳基或C7-C18-芳烷基的基团和具有2-22个碳原子的不饱和烃基或烷氧基聚氧亚烷基,
R2表示经由包含总计7至30个碳原子的C1-C8-亚烷基和亚芳基桥接的C1-C12-烷基取代的C6-C18-亚芳基、C7-C18-烷基芳基取代的C6-C18-亚芳基和任选地C1-C12-烷基取代的亚芳基,优选地
其中R6、R7和R8各自彼此独立地表示甲基或乙基,其中每个苯环仅带有一个甲基。
特别优选的碳二亚胺是式(II)的化合物,
其中R1选自-NCO、-NHCONHR3、-NHCONR3R4或
-NHCOOR5,
其中R3和R4是相同或不同的并且表示C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基或C6-C18-芳基,
R5表示C1-C22-烷基、C6-C12-环烷基、C6-C18-芳基或C7-C18-芳烷基或具有2-22个碳原子、优选12-20个碳原子、特别优选16-18个碳原子的不饱和烃基,或烷氧基聚氧亚烷基,并且
R6、R7和R8各自彼此独立地表示甲基或乙基,其中每个苯环仅带有一个甲基,并且n=1至20。
根据本发明采用的式(I)、优选式(II)的碳二亚胺的碳二亚胺含量(通过用草酸滴定测量的NCN含量)优选地是按重量计2%-16%、优选按重量计4%-13%、特别优选按重量计6%-12%。
根据本发明采用的式(I)、优选式(II)的碳二亚胺优选具有通过GPC粘度测定法测定的1000-20 000g/mol、优选1500-10 000g/mol、特别优选2000-5000g/mol的平均摩尔质量(Mw)。
物理、机械和流变特性通常由多分子性(重均分子量与数均分子量的比率)决定。此比率也称为多分散性,并且是摩尔质量分布(MMD)宽度的量度。根据本发明优选的是具有通过凝胶渗透色谱法(GPC)测定的在从1.2至2.2的范围内、特别优选在从1.4至1.8的范围内的多分散性D=Mw/Mn的式(II)的碳二亚胺。
根据本发明采用的碳二亚胺是可商购的化合物,例如由朗盛德国有限公司(Lanxess Deutschland GmbH)以名称出售的聚合物碳二亚胺。然而,这些碳二亚胺还可以例如通过在EP-A-3018124中描述的方法来生产。
聚酯层(I)、(II)和/或(III)优选是热塑性聚酯的层。本发明的上下文中优选的聚酯优选是聚对苯二甲酸烷基酯,优选是聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚己二酸对苯二甲酸丁二醇酯(PBAT)、聚对苯二甲酸丙二醇酯(PTT)、及其共聚酯、热塑性聚酯弹性体(TPE E)、乙烯乙酸乙烯酯(EVA)、聚乳酸(PLA)和/或PLA衍生物、聚丁二酸丁二醇酯(PBS)、聚羟基链烷酸酯(PHA)和各种共混物和/或基于聚酯的热塑性聚氨酯(TPU)。
特别优选各自独立地用作聚酯层(I)、(II)和(III)的是聚对苯二甲酸烷基酯,诸如尤其优选聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯或聚己二酸对苯二甲酸丁二醇酯和聚乳酸(PLA)及其共聚酯。
多层系统中的聚酯层(I)、(II)和(III)可以由相同的聚酯构成或者由不同的聚酯构成。
环氧化物优选是基于每分子具有两个或更多个环氧基团的分子的化合物。这些化合物优选是至少一种环氧化天然油或至少一种环氧化脂肪酸酯或至少一种合成环氧化的化合物。当根据本发明采用的环氧化物具有至少一个末端环氧基团、每个分子总共至少两个环氧基团时是特别优选的。
优选采用的环氧化物还包括环氧化天然油或环氧化脂肪酸酯。
优选的环氧化天然油是基于来自以下项的组的至少一种油:橄榄油、亚麻籽油、花生油、棕榈油、大豆油和鳕鱼肝油。特别优选亚麻籽油或大豆油,非常特别优选亚麻籽油。
环氧化天然油通常通过本领域技术人员熟悉的方法生产,如例如Angew.Chem.[应用化学]2000,112,2292-2310中所披露的。
优选的环氧化脂肪酸酯是由具有10至40个碳原子、优选具有16至22个碳原子的不饱和的脂肪族羧酸通过与具有2至40个碳原子、优选2至6个碳原子的脂肪族饱和醇的反应,并且随后与过氧化物、优选过氧化氢反应获得的。
环氧化脂肪酸酯优选通过一元或二元不饱和羧酸与脂肪族饱和醇反应生产。特别优选的是采用从以下项的组中选择至少一种羧酸作为一元或二元羧酸:壬酸、棕榈酸、月桂酸、十七烷酸、十二烷二酸、山嵛酸、硬脂酸、癸酸、褐煤酸、亚油酸、亚麻酸和油酸,并且随后与过氧化物、优选过氧化氢反应。
优选采用的脂肪族饱和醇是选自以下项的组的1元至4元醇:正丁醇、正辛醇、硬脂醇、乙二醇、丙二醇、新戊二醇、季戊四醇和甘油。甘油是尤其优选的。
还可以采用不同环氧化脂肪酸酯和/或环氧化天然油的混合物。
然而,同样可能采用合成环氧化化合物,包括例如芳香族环氧化聚合物或缩合产物。这些例如通过芳香族醇与甲醛反应产生,其随后与过氧化物反应。可采用的芳香族醇特别地包括单核或多核酚。
优选的单核苯酚是间苯二酚或对苯二酚。
优选的多核苯酚是双(4-羟苯基)甲烷、2,2-双(4-羟苯基)丙烷、2,2-双(3,5-二溴-4-羟苯基)丙烷或4,4'-二羟基二苯基砜。
苯酚与甲醛的优选缩合产物是苯酚酚醛清漆。
在本发明的进一步优选实施例中,采用具有两个末端环氧官能团的芳香族环氧化合物。这些优选是双酚A与环氧氯丙烷的低聚反应产物,该低聚反应产物具有根据EN ISO10927确定的在从900至1200g/mol范围内的平均分子量以及根据ISO 3001测定的在每当量从450至600克范围内的环氧指数。特别优选采用来自双酚A与环氧氯丙烷的反应的式(III)的反应产物,
其中a表示从0至10、优选1至8、特别优选1至6、非常特别优选2至3的平均数。
环氧化物优选通过根据US 2002/0128428 A1的方法生产,并且然后具有根据ENISO 10927的900至1200g/mol(这在式(III)中对应于在从2至3范围内的a)的平均分子量以及根据ISO 3001测定的每当量450至600克的环氧指数。
优选采用合成环氧化合物,其具有在从0℃至150℃范围内、特别优选50℃至120℃、非常特别优选在从60℃至110℃范围内并且特别是在从75℃至95℃范围内的根据DIN51920的梅特勒软化点(Mettler softening point)。梅特勒软化点是样品从具有直径为6.35mm的流出开口的圆柱形喷嘴流出,因此中断位于19mm之下的光闸的温度。为此,将样品在空气中在恒定条件下加热。
优选采用合成环氧化物,其根据DIN 16945经由滴定具有160至2000g/eq、优选250至1200g/eq、特别优选350至1000g/eq并且尤其优选在从450至800g/eq范围内的平均环氧当量重量(EEW,含有一摩尔的环氧键合氧的树脂的克数)。
尤其优选作为式(III)的化合物采用的是聚(双酚A-共-环氧氯丙烷)[CAS编号25068-38-6],其优选具有通过MALDI-TOF质谱法、通过基质辅助激光解析/电离飞行时间质谱法(根据EN ISO 10927)测定的在从600至1800g/mol范围内的数均分子量(Mn),例如从洛伊纳公司(Leuna Harze GmbH)作为可获得。
在所示的单元中,R9、R10各自彼此独立地表示H或C1-C8-烷基,R11表示C1-C8-烷基,x和y彼此独立地表示从1至20的平均数,并且z表示从2至20的平均数。链末端由彼此独立地表示H或C1-C8-烷基的端基R*形成。
该环氧化物优选地符合式(IV)
其中R9、R10各自彼此独立地表示H或C1-C8-烷基,R11表示C1-C8-烷基,x和y彼此独立地表示从1至20的平均数,并且z表示从2至20的平均数,其中端基R*彼此独立地表示H或C1-C8-烷基。
在优选或替代性实施例中,环氧化脂肪酸甘油酯、特别是环氧化植物油用作环氧化物。这些通过不饱和脂肪酸的甘油三酯的反应性烯烃基团的环氧化作用来获得。环氧化脂肪酸甘油酯可以由不饱和脂肪酸甘油酯(优选植物油)和有机过氧羧酸(Prilezhaev反应)开始来生产。用于生产环氧化天然油的方法例如在Smith,March,March’s AdvancedOrganic Chemistry[March的高级有机化学],第5版,Wiley-Interscience[威利出版社],纽约,2001中描述。优选的环氧化脂肪酸甘油酯是环氧化天然油,特别优选环氧化大豆油[CAS编号8013-07-8]。
根据本发明的多层系统中聚酯层(I)的比例通常是在按重量计10%与按重量计99%之间,优选在按重量计30%与按重量计90%之间,并且根据本发明的多层系统中聚酯层(I)的比例特别优选是基于多层系统的总重量在按重量计50%至按重量计70%之间。
聚酯层(II)和(III)含有环氧化物是优选的。聚酯层(II)和(III)不含碳二亚胺是进一步优选的。
在本发明的优选实施例中,聚酯层(I)中碳二亚胺的量是基于聚酯层(I)按重量计0.2%至3%,优选按重量计0.5%至1.5%。
在本发明的进一步优选实施例中,聚酯膜(II)和/或(III)中的至少一个中环氧化物的量是基于聚酯层(II)或聚酯层(III)按重量计0.1%至6%,优选按重量计0.5%至4%。
在本发明的优选实施例中,含有碳二亚胺的聚酯层(I)的重量分数是基于多层系统的总重量按重量计70%至按重量计95%。
在本发明的进一步优选实施例中,聚酯层的厚度优选是在11与500微米之间,并且特别优选在24与300微米之间。
在含有碳二亚胺的层的多层实施例中,含有碳二亚胺的层的厚度总和典型地大于10微米且小于500微米,并且特别优选大于40微米且小于300微米。
聚酯层(II)和/或聚酯层(III)优选是薄的以尽可能少地损害整体膜的水解稳定性,即这些层在每种情况下优选薄于5微米,特别优选薄于3微米并且理想地薄于0.8微米。然而,已经证明了聚酯层(II)和/或聚酯层(III)不薄于0.1微米是有利的。
本发明还进一步提供了一种用于生产多层系统的方法,其特征在于将该含有碳二亚胺的聚酯层(I)和任选地含有环氧化物的聚酯层(II)和(III)共挤出以提供多层系统。
共挤出方法是本领域已知的。因此还可以在根据本发明的多层系统的生产工艺中采用在共挤出的环境中采用的常用温度和压力。温度优选是200℃至300℃。
此方法优选以一种方式进行,使得通过任选地在添加粘合促进剂的情况下使用至少两个挤出机进行共挤出来由聚酯层(I)和聚酯层(II)和(III)来生产根据本发明的多层系统。
尤其是在聚酯层(I)的挤出期间,碳二亚胺的分解可能导致形成异氰酸酯。在此方法中,针对挤出优选采用槽模来生产聚酯层。在根据本发明的生产方法的优选变体中,将抽气装置附接到槽模。
为了生产聚酯层(I),将聚酯与碳二亚胺混合并挤出。
为了生产聚酯层(II)和(III),在挤出期间将聚酯中的至少一种与环氧化物混合。对此可以使用常用的计量系统。
然后将聚酯层(I)与聚酯层(II)和(III)以一种方式挤出,使得聚酯层(I)在相反侧上被聚酯层(II)和(III)包围。
优选进行用于生产根据本发明的多层系统的层的方法,使得将针对聚酯层(I)用式(I)的碳二亚胺改性并且针对聚酯层(II)和/或(III)用环氧化物改性的对应聚酯熔体通过平膜模头挤出,将由此获得的层引出并且在一个或多个辊(优选冷却辊)上冷却为大体上无定形的预层以进行固结,然后将该层任选地重新加热并且优选双向拉伸(取向),并且将双向拉伸的层经受热定形。因此其优选以膜形式获得。已经证明了在挤出区中不超过295℃的温度是有利的。
模头的区域并且尤其是模唇的区域和其近端区域不高于290℃、优选不高于285℃并且特别优选不高于275℃是特别有利的。温度越高,稳定剂上的热应力越高,并且因此凝胶形成的倾向越高。
双向拉伸通常顺序地进行。这优选地包括初始地在纵向方向上(即,在机器方向=MD上)拉伸,并且随后在横向方向上(即,垂直于机器方向=TD)拉伸。这产生分子链的取向。纵向方向上的拉伸可使用根据所需的拉伸比在不同速度下运行的两个辊进行。
进行拉伸的温度可以在相对宽的范围内并且根据层的所需特性变化。纵向拉伸以及还有横向拉伸通常在Tg+10℃至Tg+60℃(Tg=层的玻璃化转变温度)下进行。纵向拉伸比通常在从2.0:1至6:1、优选3:1至4.5:1的范围内。横向拉伸比通常在从2:1至5:1、优选3:1至4.5:1的范围内,并且任选进行的第二纵向和横向拉伸的比率是1.1:1至5:1。
纵向拉伸可以任选地与横向拉伸同时进行(同时拉伸)。已经证明了纵向方向和横向方向的拉伸比在每种情况下大于3.0是特别有利的。
在随后的热定形中,将该层在150℃至260℃、优选200℃至245℃的温度下优选保持约0.1s至10s。随后,或在热定形期间进行,在横向方向上并且任选地还在纵向方向上将该层松弛0%至15%,优选1.5%至8%,并且然后将该层冷却并且以常用方式卷绕。
本发明还进一步提供了根据本发明的多层系统用于生产诸如优选用于太阳能电池或医疗领域中的包装、保护膜或用于生产粘附膜的用途。
根据本发明的多层系统优选用于生产太阳能电池的保护膜。因此本发明同样涵盖含有多层系统的太阳能电池。
在本发明中,根据本发明的多层系统用作太阳能电池中的底片膜。根据本发明的多层系统可用于本领域已知的所有太阳能电池中。
太阳能电池的生产是根据现有技术中描述的方法进行的,从经由铸造工艺、布里奇曼(Bridgman)法、EFG(限边送膜生长)工艺或切克劳斯基(Czochralski)工艺生产硅的标准方法开始,并且随后生产Si晶片和前述材料层的层压,其中使用根据本发明的多层系统代替用作标准物的底片膜。
本发明的范围涵盖所有在上文和下文中列举的基团、指数、参数以及它们自身之间的解释的一般或优选的定义,即,包括以任何所希望的组合在对应的范围与优选范围之间。
根据本发明的多层系统使得能够首次提供一种水解稳定化的聚酯多层系统。
以下实施例用于解释本发明,而没有任何限制性作用。
实施例
实施例1
在以下项上进行测试:
1)碳二亚胺A:具有按重量计约11.8%的NCN含量、D=约1.8并且Mw=2300g/mol的式(II)的聚合型碳二亚胺,其中n=约3-4,R6、R7、R8各自独立地表示甲基或乙基,其中每个苯环带有仅一个甲基,并且R1=-NHCOOR5并且R5=环己基。
2)碳二亚胺母料B:可从英威达德国有限公司(Invista Deutschland GmbH)获得的具有0.8特性粘度的聚对苯二甲酸乙二醇酯(PET),将其与按重量计10%的碳二亚胺A混合并挤出。
3)稳定剂C:式(III)的环氧化物,其中n=在2-3的范围内,该环氧化物具有500至700g/eq的环氧当量重量(DIN 16945)和在75℃与90℃之间的软化点(梅特勒,DIN 51920)(CAS编号25068-38-6)。
4)可从英威达德国有限公司获得的具有0.8特性粘度的聚对苯二甲酸乙二醇酯(PET)。
使用聚对苯二甲酸乙二醇酯作为聚酯,使用用于内部聚酯层(I)的挤出机和用于外部聚酯层(II)和(III)的共挤出机来生产表1中列举的多层系统。将抽气装置附接到槽模。表1总结了用量以及还有使用针对异氰酸酯的标准化指示器管的拉伸区域中的定性排放测量(测量持续时间约30min.)和PET多层膜的水解稳定性的结果。
水解稳定性的测量
针对水解测试,将这些层在蒸汽中120℃的温度下储存24小时并且在0和24小时之后测量其断裂伸长率。
表1中报告的水解稳定性的值由以下计算导出:断裂伸长率[%]=(24小时之后的断裂伸长率/0小时之后的断裂伸长率)x100。
表1:
发明实施例展示了根据本发明的多层系统的积极作用,因为所述系统没有显示异氰酸酯的排气,无论是否结合了良好的水解稳定性。
Claims (14)
1.一种由至少3个聚酯层构成的多层系统,其具有以下构造:
-至少一个含有至少一种碳二亚胺的聚酯层(I),
-至少一个在该聚酯层(I)的顶部上的聚酯层(II),和
-至少一个在该聚酯层(I)的底部上的聚酯层(III),其特征在于,这些聚酯层(II)或(III)中的至少一个含有至少一种环氧化物,
其中该聚酯层(I)中碳二亚胺的量是基于该聚酯层(I)按重量计0.2%至3%。
2.根据权利要求1所述的多层系统,其特征在于,该碳二亚胺是式(I)的化合物
R1-R2-(-N=C=N-R2-)n-R1 (I),
其中
n表示从1至500、优选3至20、非常特别优选4至20的整数,
R1表示系列-NCO、-NCNR3、-NHCONHR3、-NHCONR3R4或-NHCOOR5中的基团,
其中R3和R4是相同或不同的并且各自独立地表示系列C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基或C6-C18-芳基中的基团,并且R5表示系列C1-C22-烷基、C6-C12-环烷基、C6-C18-芳基或C7-C18-芳烷基中的基团、或具有2至22个碳原子的不饱和烃基、或烷氧基聚氧亚烷基,
R2表示经由包含总计7至30个碳原子的C1-C8-亚烷基或亚芳基桥接的C1-C12-烷基取代的C6-C18-亚芳基、C7-C18-烷基芳基取代的C6-C18-亚芳基或任选地C1-C12-烷基取代的亚芳基,优选地
其中R6、R7和R8各自彼此独立地表示甲基或乙基,其中每个苯环仅带有一个甲基。
4.根据权利要求1至3中至少一项所述的多层系统,其特征在于,该聚酯层(I)、(II)和/或(III)是热塑性聚酯。
5.根据权利要求1至4中至少一项所述的多层系统,其特征在于,该聚酯选自聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚己二酸对苯二甲酸丁二醇酯(PBAT)、聚对苯二甲酸丙二醇酯(PTT)和共聚酯、热塑性聚酯弹性体(TPE E)、乙烯乙酸乙烯酯(EVA)、聚乳酸(PLA)和/或PLA衍生物、聚丁二酸丁二醇酯(PBS)、聚羟基链烷酸酯(PHA)和各种共混物和/或基于聚酯的热塑性聚氨酯。
6.根据权利要求1至5中至少一项所述的多层系统,其特征在于,这些环氧化物是基于每分子具有两个或更多个环氧基团的分子的化合物。
8.根据权利要求1至7中至少一项所述的多层系统,其特征在于,该聚酯层(I)中碳二亚胺的量是基于该聚酯层(I)按重量计0.5%至1.5%。
9.根据权利要求1至7中至少一项所述的多层系统,其特征在于,该聚酯层(II)或(III)中的至少一个中环氧化物的量是基于该聚酯层(II)或(III)按重量计0.1%至6%。
10.根据权利要求1至8中至少一项所述的多层系统,其特征在于,该含有碳二亚胺的聚酯层(I)的重量分数是基于该多层系统的总重量按重量计70%至按重量计90%。
11.一种用于生产根据权利要求1至10中任一项所述的多层系统的方法,其特征在于,将该含有碳二亚胺的聚酯层(I)和任选地含有环氧化物的聚酯层(II)和(III)共挤出以提供多层系统。
12.根据权利要求11所述的方法,其特征在于,将该聚酯层(I)挤出并且通过共挤出将这些聚酯层(II)和(III)在此聚酯层(I)周围挤出。
13.根据权利要求1至10中任一项所述的多层系统用于生产包装、保护膜、粘附膜、太阳能电池或医疗材料的用途。
14.一种太阳能电池,其包括至少一个根据权利要求1至10中任一项所述的多层系统。
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PCT/EP2019/085236 WO2020126966A1 (de) | 2018-12-17 | 2019-12-16 | Multischichtsystem aus mindestens 3 polyesterschichten, dessen herstellung und verwendung |
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