CN103044829B - 由含增塑剂的聚乙烯醇缩(异)醛制成的膜 - Google Patents
由含增塑剂的聚乙烯醇缩(异)醛制成的膜 Download PDFInfo
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- CN103044829B CN103044829B CN201210252535.9A CN201210252535A CN103044829B CN 103044829 B CN103044829 B CN 103044829B CN 201210252535 A CN201210252535 A CN 201210252535A CN 103044829 B CN103044829 B CN 103044829B
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- Prior art keywords
- polyvinyl alcohol
- weight
- film
- aldehyde
- different
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 132
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 125
- 239000004014 plasticizer Substances 0.000 title claims abstract description 67
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 7
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- -1 aliphatic ketone compound Chemical class 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004806 diisononylester Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 claims description 4
- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 claims description 4
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- ATEWGLBNLCOVDI-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol nonanoic acid Chemical class OCCOCCOCCO.CCCCCCCCC(O)=O ATEWGLBNLCOVDI-UHFFFAOYSA-N 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 112
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 109
- 229940068984 polyvinyl alcohol Drugs 0.000 description 102
- 150000001299 aldehydes Chemical class 0.000 description 49
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 36
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 27
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229920002554 vinyl polymer Polymers 0.000 description 18
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 17
- 150000002148 esters Chemical class 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 13
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 12
- 229920002689 polyvinyl acetate Polymers 0.000 description 12
- 239000011118 polyvinyl acetate Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WTTWSMJHJFNCQB-UHFFFAOYSA-N 2-(dibenzylamino)ethanol Chemical compound C=1C=CC=CC=1CN(CCO)CC1=CC=CC=C1 WTTWSMJHJFNCQB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- DLZBUNUDESZERL-UHFFFAOYSA-N 1-o-heptyl 6-o-nonyl hexanedioate Chemical compound CCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCC DLZBUNUDESZERL-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Natural products CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- BJIUNQZHYLBUNL-UHFFFAOYSA-N 6-heptoxy-6-oxohexanoic acid Chemical compound CCCCCCCOC(=O)CCCCC(O)=O BJIUNQZHYLBUNL-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10605—Type of plasticiser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and 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
- C08F16/38—Homopolymers and 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 by an acetal or ketal radical
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- 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
- H01L31/042—PV modules or arrays of single PV cells
-
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- B32—LAYERED PRODUCTS
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Abstract
本发明涉及由含增塑剂的聚乙烯醇缩(异)醛制成的膜。具体地,本发明涉及一种膜,包含具有小于/等于9.4的由公式100×O/(C+H)表示的极性的至少一种非芳族增塑剂和具有60至85重量%的聚乙烯醇缩(异)醛基比例和14至40重量%的聚乙烯醇基比例的聚乙烯醇缩(异)醛的混合物,其中O、C和H表示各个分子中氧、碳和氢原子的数目。该膜在汽车领域、挡风玻璃、建筑领域、立面部件中,或用于制造光伏模块的用途。
Description
技术领域
本发明涉及基于聚乙烯醇缩(异)醛(Polyvinyl(iso)acetal)的含增塑剂的膜,所述膜适用于例如复合安全玻璃(Verbundsicherheitsgläser)中的中间层或光伏模块(Photovoltaikmodule)中的粘合膜。
背景技术
复合安全玻璃通常由两个玻璃板和连接玻璃板的中间膜组成。作为膜材料主要使用含增塑剂的聚乙烯醇缩丁醛(PVB),其可通过使聚乙烯醇与正丁醛反应获得。
这种膜的机械强度和吸湿性特别由增塑剂的类型和用量决定。聚乙烯醇缩丁醛对于各种增塑剂具有不同的吸收能力,超过吸收能力,增塑剂再次渗出。
为了获得在常规应用温度(0至40℃)范围内具有软化温度的PVB膜,就PVB和增塑剂的化学性质而论和就与增塑剂的混合比率而论,必须遵从特定的框架条件。同时,3G8(三甘醇-双-2-乙基己酸酯)已经用作PVB膜的增塑剂。对于这种增塑剂,EP 0877665描述具有不同的残留乙烯醇含量的PVB的吸收能力。
除了受限的增塑剂吸收之外,基于正丁醛的已知PVB膜具有较高的吸湿性,这可能导致复合窗玻璃中不合乎需要的浊度。在用于光伏模块的情况下,高吸湿性可能导致体积电阻低,这是不合乎需要的。此外,吸湿可能导致增塑剂渗出,特别是在升高温度下。
因此理想的将是使用包含较高比例非极性增塑剂的PVB的混合物用于膜制造,以抵销不合乎需要的吸湿性。
现已意外地发现与聚乙烯醇缩(正)醛相比,聚乙烯醇缩(异)醛具有更大的增塑剂相容性。
作为增塑剂的聚乙烯醇缩(异)醛与邻苯二甲酸二丁酯的混合物由J. Fitzhugh和R Croizer,J. Polym. Sci (1951),VIII卷,225-241页描述。该公开文献并未涉及膜的制造及其用途。此外,在该情况下仅使用了极性的芳族增塑剂。
含增塑剂的聚乙烯醇缩(异)醛也由US 2008/0286542已知,其用于制造装饰性玻璃构件的中间层膜。在此描述的用于复合安全玻璃的聚乙烯醇缩(异)醛具有8至30重量%的过低的缩醛化程度,因此显示不充分的增塑剂吸收。因此,US 2008/0286542仅公开多层膜,其中具有低缩醛化程度的含增塑剂的聚乙烯醇缩(异)醛层压在含增塑剂的聚乙烯醇缩(正)醛的两个层之间。
不使用聚乙烯醇缩(异)醛的膜层压体例如由WO 2006/102049 A1、WO 2011/078314 A1、WO 2011/081190 A1、WO 2011/024788 A1、US 2007014976和JP 2011042552已知。其中并未描述聚乙烯醇缩(异)醛的有利性能。
已经意外地发现与相应的聚乙烯醇缩(正)醛相比,在相同的聚乙烯醇含量(PVA含量)下,聚乙烯醇缩(异)醛具有更好的增塑剂相容性。
发明内容
本发明涉及包含至少一种具有小于/等于9.4的由公式100×O/(C+H)表示的极性的非芳族增塑剂和具有60至85重量%的聚乙烯醇缩(异)醛基比例和14至40重量%的聚乙烯醇基比例的聚乙烯醇缩(异)醛的混合物的膜,其中O、C和H表示各个分子中的氧、碳和氢原子的数目。
增塑剂相容性改善导致在室温下存储期间增塑剂从具有聚乙烯醇缩(异)醛的混合物中更少渗出。作为膜表面上的增塑剂膜的结果,增塑剂的渗出变得容易看见。
增塑剂渗出意味着聚合物和增塑剂之间缺乏相容性。这一影响可以由所谓的浊点确定。聚乙烯醇缩醛和增塑剂,例如3G8之间的相容性通过使聚乙烯醇缩醛在所述增塑剂中的热溶液缓慢冷却来测试。溶液变得不透明的温度越低,聚合物和增塑剂越相容。
已经可以确定基于异丁醛的聚乙烯醇缩醛的浊点显著低于基于正丁醛的相同聚乙烯醇缩醛的浊点。这意味着对于给定的使用的聚乙烯醇缩(异)醛的PVA含量,本发明的膜比具有相同PVA含量的基于聚乙烯醇缩正丁醛的膜包含更多的增塑剂。较高的增塑剂含量使得膜的制造更加成本有利,因为增塑剂通常比聚乙烯醇缩醛便宜。
本发明的膜不包含任何芳族增塑剂,即没有具有芳族子结构的增塑剂,例如邻苯二甲酸酯(特别是没有邻苯二甲酸二丁酯)或苯甲酸酯。
本发明的膜包含通过用支化酮化合物使完全或部分皂化的聚乙烯醇缩醛化获得的含增塑剂的聚乙烯醇缩(异)醛。
聚乙烯醇缩(异)醛的聚乙烯醇缩(异)醛基优选通过使至少一种聚乙烯醇与一种或多种包含4至10个碳原子并在酮基的α位或β位处具有至少一个支化的脂族酮化合物反应获得。此外,也可使用包含2至10个碳原子的未支化的脂族酮化合物用于缩醛化。但是,支化的酮化合物的比例应超过支化和未支化的酮化合物的总和的50重量%。
聚乙烯醇缩(异)醛的聚乙烯醇含量可以通过缩醛化期间使用的醛的量来调节。也可使用多种醛进行缩醛化步骤。
本发明使用的聚乙烯醇缩(异)醛的聚乙酸乙烯酯含量可以通过使用水解至相应比例的聚乙烯醇来调节。聚乙烯醇缩(异)醛的极性受聚乙酸乙烯酯含量的影响,由此膜的增塑剂相容性也变化。
聚乙烯醇缩(异)醛具有优选0.1至15重量%,优选0.1至8重量%,和特别是0.1至3重量%,最特别优选0.5至2重量%的聚乙酸乙烯酯基比例。
还可能的是,各层包含具有4至8 mol%,例如4.1至7.9 mol%或5至7 mol%的聚乙酸乙烯酯基比例的聚乙烯醇缩(异)醛和/或聚乙烯醇缩(正)醛,基于各层计。
也可使用交联的聚乙烯醇缩(异)醛,特别是交联的聚乙烯醇缩(异)丁醛。用于交联的适合方法例如在EP 1527107 B1和WO 2004/063231 A1 (含羧基的聚乙烯醇缩醛的热自交联),EP 1606325 A1 (用聚醛交联的聚乙烯醇缩醛)和WO 03/020776 A1 (用乙醛酸交联的聚乙烯醇缩醛)中描述。
为了不损害膜的加工,特别优选使用交联的聚乙烯醇缩(异)醛,其与各种未交联的材料相比,溶液粘度增加25至200%。例如,未交联的材料因此可以具有80 mPas的溶液粘度,交联的材料可以具有100至250 mPas的溶液粘度。根据WO 03/020776 A1,用上述酮化合物和二醛或三醛,例如戊二醛的混合物对聚乙烯醇共缩醛化适用于制造交联的聚乙烯醇缩(异)醛。
为制造聚乙烯醇缩(异)醛,将聚乙烯醇溶于水,用例如异丁醛的酮化合物,在添加酸催化剂情况下进行缩醛化。分离沉淀的聚乙烯醇缩醛,洗涤至中性,任选悬浮在设定为碱性的水性介质中,然后再次洗涤至中性并干燥。
在本发明范围内,聚乙烯醇可以以纯物质的形式,或者以具有不同聚合度或水解度的聚乙烯醇混合物的形式使用。
用于本发明膜的聚乙烯醇缩(异)醛可以具有小于3000,优选为200至2800,最优选为900至2500的平均聚合度。
通常,增塑剂和聚乙烯醇缩醛之间的相容性随着增塑剂极性的下降而降低。因此与具有较低极性的那些增塑剂相比,具有较高极性的增塑剂与聚乙烯醇缩醛更好地相容。另外,低极性的增塑剂的相容性随着缩醛化度上升而提高,即随着羟基数目下降和由此聚乙烯醇缩醛极性下降而提高。
由于缩醛基的支化,本发明的膜具有与基于直链醛的常规体系相比不同的软化点。
本发明的膜优选具有-11至24℃的软化点Tg。
除了含水量之外,软化点对于基于聚乙烯醇缩醛的膜的体积电阻同样起重要作用。与具有相同增塑剂含量的基于聚乙烯醇缩(正)醛的膜相比,在给定湿度和温度下,本发明的膜因此具有更高的软化点和更高的体积电阻。
这一点对用于光伏模块是有利的,因为体积电阻对于模块的长寿命是重要的。
本发明的膜可以包含来自至少一种以下非芳族增塑剂的增塑剂或增塑剂混合物:
- 多元脂肪酸的酯,例如己二酸二烷基酯,例如己二酸二己酯,己二酸二辛酯,己二酸己基环己酯,己二酸庚酯和壬酯的混合物,己二酸二异壬酯,己二酸庚基壬基酯,和己二酸与脂环族酯醇或含醚键的酯醇的酯,癸二酸二烷基酯,例如癸二酸二丁酯,和癸二酸与脂环族酯醇或含醚键的酯醇的酯,环己烷二羧酸的酯,例如1,2-环己烷二羧酸二异壬酯
- 具有一个或多个未支化或支化脂族取代基的多元脂族醇或低聚醚二醇的酯或醚,例如二甘醇、三甘醇或四甘醇与直链或支链脂族或脂环族羧酸的酯;后一组的实例包括二乙二醇-双-(2-乙基己酸酯),三甘醇-双-(2-乙基己酸酯),三甘醇-双-(2-乙基丁酸酯),四甘醇-双-正庚酸酯,三甘醇-双-正庚酸酯,三甘醇-双-正己酸酯,和/或四甘醇二甲醚
- 具有脂族酯醇的磷酸酯,例如三(2-乙基己基)磷酸酯(TOF),磷酸三乙酯
- 柠檬酸、琥珀酸和/或富马酸的酯
- 己二酸二异壬酯(DINA)和二-2-丁氧基乙基己二酸酯(DBEA)
由公式100×O/(C+H)表示的极性小于/等于9.4的非芳族增塑剂最特别适合作为本发明膜的增塑剂,其中O、C和H表示各个分子中氧、碳和氢原子的数目。下表示出可以用于本发明的增塑剂,及其根据公式100×O/(C+H)的极性值。
名称100×O/(C+H)
癸二酸二-2-乙基己酯 (DOS) 5.3
己二酸二-2-乙基己酯 (DOA) 6.3
三甘醇-双-2-丙基己酸酯 8.6
三甘醇-双-异壬酸酯 8.6
癸二酸二-2-丁氧基乙酯 (DBES) 9.4
三甘醇-双-2-乙基己酸酯 (3G8) 9.4
1,2-环己烷二羧酸二异壬基酯 (DINCH) 5.4。
根据该公式,三甘醇-双-2-乙基丁酸酯具有11.11的极性,因而,其与聚乙烯醇缩(异)醛的混合物不适合用于膜的制造。
此外,本发明的膜可以包含本领域技术人员已知的其它添加剂,例如残留量的水,UV吸收剂,抗氧剂,粘附性调节剂,荧光增白剂,稳定剂,着色剂,加工助剂,有机或无机纳米颗粒,热解二氧化硅和/或表面活性物质。
在本发明范围内,粘附性调节剂应理解为表示用其可以调节含增塑剂的聚乙烯醇缩醛膜对玻璃表面的粘附性的化合物。此类化合物是本领域技术人员已知的;为此在实践中经常使用有机酸的碱金属或碱土金属盐,例如乙酸钾/镁。
为改善刚性,膜也可包含0.001至20重量%,优选1至15重量%,特别是5至10重量%的SiO2,任选掺杂有Al2O3或ZrO2。
本发明的膜优选具有工业上常规的总厚度,例如0.38、0.76和1.14 mm (即0.38mm的多倍)。
本发明的膜通常通过挤出来制造,并且在一定条件(熔融压力,熔融温度和模具温度)下形成熔体断裂表面,即随机的表面粗糙度。
备选地,已经制造的本发明的中间层膜可以在至少一对辊之间由压印工艺压印带有规则的非随机的粗糙度。压印的膜在复合玻璃制造期间通常显示改善的脱气性能,并且优选用于汽车领域。
基于聚乙烯醇缩醛的膜的原理性制造和组成在例如EP 185 863 B1、EP 1 118258 B1、WO 02/102591 A1、EP 1 118 258 B1或EP 387 148 B1中描述。
独立于制造方法,本发明的膜具有施加到一侧或更优选双侧上的表面结构,所述表面结构具有15至150 μm,优选15至100 μm,更优选20至80 μm,和特别是40至75 μm的粗糙度Rz。
本发明的膜同样很适用于制造玻璃/膜/塑料层压体,例如用于长期粘合玻璃板与PET层。也可以将本发明的膜与例如由聚碳酸酯或PMMA制成的两个塑料板相粘合。
特别地,本发明的膜可以通过本领域技术人员已知的方式与一个或多个玻璃板层压,用于制造复合安全玻璃。复合安全玻璃可以用于汽车领域,例如用作挡风玻璃,和用于建筑领域,例如用于窗户或透明立面部件,或用于制造家具。
对于具有HUD功能性的挡风玻璃,有利地提供具有楔形剖面的本发明的膜。
本发明膜的另一个用途在于制造光伏模块。
具体实施方式
测量方法
根据DIN EN ISO 3681测定聚乙烯醇的酯值EZ。按照下面公式由酯值计算水解度 HG:HG [重量%] = 100×(100 – 0.1535×EZ)/(100 – 0.0749×EZ)。
根据ASTM D 1396-92测定PVB的聚乙烯醇含量和聚乙酸乙烯酯含量。缩醛化度(=丁缩醛含量)可以作为根据ASTM D 1396-92测定的聚乙烯醇含量和聚乙酸乙烯酯含量的总和距离100的差额部分计算。通过本领域技术人员已知的公式将重量%转换成为mol%。
通过将膜溶解在乙醇中,以及后续的定量气相色谱法来确定膜的增塑剂含量。为了确定各子膜的增塑剂含量,必须在大约一周的调理时间之后,即在增塑剂迁移已经基本结束之后,多层膜再次经分离,并分别测量。
根据DIN 53765,借助于动态差示扫描量热法(DSC),以-50℃至150℃的温度间隔使用10K/min的加热速率测定部分缩醛化的聚乙烯醇的玻璃化转变温度。使用第一个加热匀变,随后为冷却匀变,接着进行第二个加热匀变。根据DIN 51007,基于与第二个加热匀变有关的测量曲线确定玻璃化转变温度的位置。DIN中点(Tg DIN)定义为一半梯段高度处的水平线与测量曲线的交点。梯段高度定义为玻璃化转变前后,中部切线与测量曲线的基线的两个交叉点的垂直距离。
浊点由待检验的增塑剂中聚乙烯醇缩醛的溶解性确定。为此,将聚乙烯醇缩醛(8g)悬浮于相应的增塑剂(100 g)中,并在持续搅拌情况下加热,直到获得透明溶液。一旦已经获得透明性,在第二个搅拌器上将溶液缓慢冷却至室温。浊点可以由伸入溶液中的温度计视觉确定。
膜的拉伸性能的测量
根据ISO 527,以200 mm/min的速率,借助于拉伸测试仪(TIRA公司)测定膜的撕裂强度的值。
根据DIN IEC 60093,在定义的温度和环境湿度(23℃和85%相对空气湿度和23%相对空气湿度)下测定膜的体积电阻率(体积电阻),之后在这些条件下将膜调理至少24小时。使用来自Fetronic GmbH的302 132型板状电极和来自Amprobe的ISO-Digi 5kV电阻测量仪进行测量。测试电压为2.5 kV,施加测试电压后至测定测量值的等待时间为60秒。通过如下方式确保测量电极的平板和膜之间充分的接触,根据DIN EN ISO 4287测量的膜的表面粗糙度Rz应不大于10 μm,即PVB膜的原始表面可能必须在进行电阻测量之前通过热重铸加以平整。
由Karl-Fischer法测定膜的水含量或含水量。为了模拟潮湿条件下的润湿行为,预先将膜在23℃和85%空气相对湿度或23%空气相对湿度下存储24小时。
在23℃和50 %相对湿度下存储膜一周之后视觉确定增塑剂的渗出。
实施例
1) 具有20.3重量%的聚乙烯醇含量的聚乙烯醇缩(正)醛
将100重量份的聚乙烯醇Mowiol 28-99 (来自Kuraray Europe GmbH的商品,平均聚合度为1700)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加57.5重量份的正丁醛,在12℃的温度在搅拌下添加75重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至73℃,并在该温度下搅拌两小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有20.3重量%的聚乙烯醇含量和0.9重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(正)丁醛(n-PVB)。
2) 具有11.9重量%的聚乙烯醇含量的聚乙烯醇缩(正)醛
将100重量份的聚乙烯醇Mowiol 30-92 (来自Kuraray Europe GmbH的商品,平均聚合度为2100)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加66.6重量份的正丁醛和0.06重量份的戊二醛,和在12℃的温度在搅拌下添加100重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至69℃,并在该温度下搅拌两小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有11.9重量%的聚乙烯醇含量和8.8重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(正)丁醛(n-PVB)。
3-4) 分别具有14.1重量%和15.1重量%的聚乙烯醇含量的聚乙烯醇缩(正)醛
根据实施例2进行合成,其中改变正丁醛的量。分别使用56.8和55.8重量份的正丁醛。因此获得分别具有14.1重量%和15.1重量%的聚乙烯醇含量的聚乙烯醇缩(正)丁醛(n-PVB)。
5) 具有14.5重量%的聚乙烯醇含量的聚乙烯醇缩(正)醛
将100重量份的聚乙烯醇Mowiol 28-99 (来自Kuraray Europe GmbH的商品)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加67.4重量份的正丁醛和0.055重量份的戊二醛,和在12℃的温度在搅拌下添加100重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至69℃,并在该温度下搅拌两小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有14.5重量%的聚乙烯醇含量和1.1重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(正)丁醛(n-PVB)。
6) 具有16.0重量%的聚乙烯醇含量的聚乙烯醇缩(正)醛
根据实施例5进行合成,其中改变正丁醛的量。使用62重量份的正丁醛。因此获得具有16.0重量%的聚乙烯醇含量的聚乙烯醇缩(正)丁醛(n-PVB)。
7) 具有20.3重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
将100重量份的聚乙烯醇Mowiol 28-99 (来自Kuraray Europe GmbH的商品)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加57.6重量份的异丁醛,在12℃的温度在搅拌下添加75重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至73℃,并在该温度下搅拌两小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有20.3重量%的聚乙烯醇含量和1.2重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(异)丁醛(i-PVB)。
8) 具有14.4重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
将100重量份的聚乙烯醇Mowiol 30-92(来自Kuraray Europe GmbH的商品)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加68.6重量份的异丁醛和0.06重量份的戊二醛,和在12℃的温度在搅拌下添加100重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至69℃,并在该温度下搅拌两小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有14.4重量%的聚乙烯醇含量和8.7重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(异)丁醛(i-PVB)。
9-11) 分别具有15.6重量%、16.4重量%和17.9重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
根据实施例8进行合成,其中改变异丁醛的量。分别使用67.6、66.6和60.8重量份的异丁醛。因此获得分别具有15.6重量%、16.4重量%和17.9重量%的聚乙烯醇含量的聚乙烯醇缩(异)丁醛(i-PVB)。
12) 具有15.8重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
将100重量份的聚乙烯醇Mowiol 28-99 (来自Kuraray Europe GmbH的商品)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加65重量份的异丁醛和0.055重量份的戊二醛,和在12℃的温度在搅拌下添加170重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至69℃,并在该温度下搅拌一小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有15.8重量%的聚乙烯醇含量和0.9重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(异)丁醛(i-PVB)。
13) 具有16.3重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
根据实施例12进行合成,其中改变异丁醛的量。使用64重量份的异丁醛。因此获得具有16.3重量%的聚乙烯醇含量的聚乙烯醇缩(异)丁醛(i-PVB)。
14) 具有18.2重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
将100重量份的聚乙烯醇Mowiol 28-99 (来自Kuraray Europe GmbH的商品)溶于975重量份的水中,同时加热至90℃。在40℃的温度添加60.8重量份的异丁醛,在12℃的温度在搅拌下添加75重量份的20%盐酸。在聚乙烯醇缩丁醛(PVB)沉淀之后将混合物加热至73℃,并在该温度下搅拌两小时。在冷却到室温之后,分离PVB,用水洗涤至中性,并干燥。获得具有18.2重量%的聚乙烯醇含量和0.9重量%的聚乙酸乙烯酯含量的聚乙烯醇缩(异)丁醛(i-PVB)。
15-17) 分别具有18.2重量%、19.4重量%,20.5重量%和22.3重量%的聚乙烯醇含量的聚乙烯醇缩(异)醛
根据实施例14进行合成,其中改变异丁醛的量。分别使用60.8、59.4、57.5和55.4重量份的异丁醛。因此获得分别具有18.2重量%、19.4重量%、20.5重量%和22.3重量%的聚乙烯醇含量的聚乙烯醇缩(异)丁醛(i-PVB)。
膜的制造
通过挤出制造根据表1的组成的膜。
在表1中可以看出,与基于正丁醛的对比膜相比,在相同的PVA和增塑剂含量,本发明的膜具有更高的软化点。在堪相比较的PVA含量情况下,本发明的膜中的增塑剂相容性更好,如实施例6和7以及2和3所示。
表2显示膜的物理数据。其显示,在相同的PVA含量和增塑剂含量情况下,本发明的膜具有更低的吸湿性。此外,可以清楚地看出与基于正丁醛的堪相比较的膜相比,本发明的膜具有高得多的体积电阻,这对用于太阳能模块是有利的。
本发明的膜的机械性能可以通过使用聚缩(异)醛,借助于增塑剂和PVA含量容易地调节。实施例1和7中可以看出在相同的PVA和增塑剂含量下获得大约相同的撕裂强度。
表格中使用的缩写具有以下含义:
3G8 三甘醇-双-2-乙基己酸酯
DINCH 1,2-环己烷二羧酸二异壬基酯
DINA 己二酸二异壬酯
DBEA: 二-2-丁氧基乙基-己二酸酯。
在混合物中使用以下重量比3G8:DBEA = 10:1;DINCH:DINA = 1:1。
浊度:3G8中的浊点 [℃]
PVA:以[重量%]计的聚乙烯醇基的比例
WM含量:增塑剂含量 [重量%]
渗出:增塑剂渗出(目视)
。
Claims (6)
1.膜,包含具有小于/等于9.4的由公式100×O/(C+H)表示的极性的至少一种非芳族增塑剂和具有60至85重量%的聚乙烯醇缩(异)醛基比例和14至40重量%的聚乙烯醇基比例的聚乙烯醇缩(异)醛的混合物,其中O、C和H表示各个分子中氧、碳和氢原子的数目,其特征在于所述的非芳族增塑剂选自癸二酸二-2-乙基己酯(DOS),己二酸二-2-乙基己酯(DOA),邻苯二甲酸二-2-乙基己基酯(DOP),双-2-丙基己酸三甘醇酯,双-异壬酸三甘醇酯,癸二酸二-2-丁氧基乙酯(DBES),三甘醇-双-2-乙基己酸酯(3G8)和1,2-环己烷二羧酸二异壬基酯(DINCH),
其中所述聚乙烯醇缩(异)醛的聚乙烯醇缩(异)醛基通过使至少一种聚乙烯醇与一种或多种包含4至10个碳原子并且在酮基的α位或β位处具有至少一个支化的脂族酮化合物反应获得。
2.根据权利要求1的膜,其特征在于所述聚乙烯醇缩(异)醛具有200至2800的平均聚合度。
3.根据权利要求1或2的膜,其特征在于所述聚乙烯醇缩(异)醛包含0.1至15重量%的聚乙酸乙烯酯基比例。
4.根据权利要求1至3之一的膜在汽车领域、建筑领域中,或用于制造光伏模块的用途。
5.根据权利要求4的用途,其特征在于所述汽车领域是指挡风玻璃。
6.根据权利要求4的用途,其特征在于所述建筑领域是指立面部件。
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-
2011
- 2011-07-22 EP EP20110175088 patent/EP2548729A1/de not_active Withdrawn
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2012
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- 2012-07-19 US US13/552,683 patent/US20130022825A1/en not_active Abandoned
- 2012-07-20 CN CN201210252535.9A patent/CN103044829B/zh active Active
- 2012-07-23 BR BR102012018240A patent/BR102012018240A2/pt not_active IP Right Cessation
- 2012-07-23 JP JP2012163101A patent/JP5619086B2/ja active Active
- 2012-07-23 KR KR1020120080162A patent/KR101866941B1/ko active IP Right Grant
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EP2548729A1 (de) | 2013-01-23 |
EP2548732A1 (de) | 2013-01-23 |
KR101866941B1 (ko) | 2018-06-14 |
JP5619086B2 (ja) | 2014-11-05 |
EP2548732B1 (de) | 2014-03-19 |
JP2013023692A (ja) | 2013-02-04 |
RU2600358C2 (ru) | 2016-10-20 |
BR102012018240A2 (pt) | 2013-08-06 |
CN103044829A (zh) | 2013-04-17 |
RU2012128572A (ru) | 2014-01-20 |
US20130022825A1 (en) | 2013-01-24 |
KR20130012001A (ko) | 2013-01-30 |
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