CN104955895B - 用于固定缠绕物品的组合物 - Google Patents
用于固定缠绕物品的组合物 Download PDFInfo
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- CN104955895B CN104955895B CN201480006198.2A CN201480006198A CN104955895B CN 104955895 B CN104955895 B CN 104955895B CN 201480006198 A CN201480006198 A CN 201480006198A CN 104955895 B CN104955895 B CN 104955895B
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- component
- acid
- imide
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- unsaturated
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- 238000004804 winding Methods 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 150000002148 esters Chemical class 0.000 claims abstract description 28
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 25
- 150000003628 tricarboxylic acids Chemical class 0.000 claims abstract description 25
- 150000003949 imides Chemical class 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 13
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 13
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 28
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- 238000005470 impregnation Methods 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 229920003055 poly(ester-imide) Polymers 0.000 claims description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
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- 125000003118 aryl group Chemical group 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
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- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 26
- -1 (methyl) acryloyl group Chemical group 0.000 abstract description 24
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- 150000005846 sugar alcohols Polymers 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 150000008065 acid anhydrides Chemical class 0.000 abstract 4
- 230000008023 solidification Effects 0.000 abstract 2
- 238000007711 solidification Methods 0.000 abstract 2
- 238000009738 saturating Methods 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 21
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
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- 239000007795 chemical reaction product Substances 0.000 description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Chemical class 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 6
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 description 2
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 description 2
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 1
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- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
- C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0485—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations
- C08F299/0492—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
- H01B3/425—Non-saturated polyesters derived from polycarboxylic acids and polyhydroxy compounds, in which at least one of the two components contains aliphatic unsaturation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
本发明提供用于固定缠绕物品的组合物,其包括5wt%至97wt%的至少一种α,β‑不饱和聚酯树脂和/或α,β‑不饱和聚酯酰亚胺树脂,该树脂包括以下组分:至少一种α,β‑烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯;至少一种多元醇;至少一种含(甲基)丙烯酰基的组分;可能的至少一种非α,β‑烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸和/或其酸酐和/或酯;及在α,β‑不饱和聚酯酰亚胺树脂的情况下,具有5元环状酰亚胺部分的至少一种酰亚胺;在上述组分的比例中,不饱和单羧酸、二羧酸和/或三羧酸和/或其酸酐和/或酯,和/或多元醇,和/或非α,β‑烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸和/或其酸酐和/或酯中的至少一种,和/或在α,β‑不饱和聚酯酰亚胺树脂的情况下,具有5元环状酰亚胺部分的酰亚胺包括含有多于八(8)个碳原子的直链和/或支链的脂族部分和/或脂环族部分。本发明的组合物在高含量的α,β‑不饱和聚酯树脂和/或α,β‑不饱和聚酯酰亚胺树脂的情况下也能提供低粘度、低VOC,导致固化排放少,且还提供优异的浸渍性能。固化后,这些浸渍材料表现出高韧性水平以及优异的耐破裂性。
Description
技术领域
本发明涉及一种用于固定缠绕物品的组合物,特别是用于固定电器设备中的电气绕组的组合物,所述组合物向缠绕物品提供特别好的浸渍性能,同时含有非常少量的挥发性有机化合物(VOC),以及固化状态下高的韧性水平和优异的耐破裂性。
背景技术
不饱和聚酯可被用作电气工业中的浸渍树脂,特别用于浸渍缠绕物品,例如电机线圈和电气装置中磁线的绕组,还用于铸造电气装置,例如定子、转子和变压器,以获得机械增韧和固定。
基于溶于苯乙烯的不饱和聚酯的浸渍材料由于它们的低粘度以及良好的机械韧性通常表现出优异的浸渍结果。然而,此类体系表现出在浸渍材料固化时排放苯乙烯,导致大量的挥发性有机化合物(VOC)。因此,对具有低排放至零排放的有韧性的浸渍材料存在强烈需求,这些浸渍材料提供优异的浸渍质量。
例如使用填料能改善机械性能(如韧性),然而,含有此类填料的浸渍材料通常不是非常均质的,且它们的粘度通常很高。这可能导致与组合物的存储条件有关的问题,并且还会导致不能渗透至电气绕组的腔内,以及在电气装置运行期间浸渍质量丧失。
本领域公知的是,实现包括不饱和聚酯的低粘度体系的一种途径是将非极性部分诸如脂肪酸衍生物并入至不饱和聚酯中。
DE-A1695514中描述了包括聚合的脂肪酸和/或其他双官能羧酸的不饱和聚酯树脂,以改善对水解的稳定性。对于用作电气绝缘用组合物中的浸渍树脂的应用,所得产物太软。DE-A1694951公开了包括聚合的脂肪醇代替聚合的脂肪酸的不饱和聚酯。
EP-A0980882中示出了低聚或聚合的脂肪酸和其它多官能羧酸(如马来酸或衣康酸)与多官能多元醇的缩聚。交联后,这些材料表现出良好的热性能和粘附性能,然而,它们特别软,并且不能提供足以用作电气装置用组合物中的浸渍树脂的机械性能。
DE-A1770566描述了能用于电气装置的浸渍的不饱和聚酯的制备,该不饱和聚酯含有酰亚胺,其基于二-环辛烯三羧酸。该聚酯可包含脂肪酸。交联后的材料表现出良好的热性能、电气性能和机械性能,然而所得的浸渍树脂含挥发性反应性稀释物,导致材料的挥发性有机物含量(VOC)高。
DE-A2460768描述了用于在电气装置用的浸渍组合物中使用的不饱和聚酯酰亚胺树脂,该树脂可含有二聚的脂肪酸。这些树脂优选溶解于苯乙烯中,导致挥发性有机物含量(VOC)高。
WO2008/067967描述了不饱和聚酯多元醇,其含有二聚的脂肪醇和二聚的脂肪酸的非极性结构。这些不饱和聚酯多元醇进一步被转化成用于涂料、弹性体和热塑性应用的聚氨酯。为此目的,不饱和聚酯多元醇必须携带每聚合物分子最少两个羟基官能团(twohydroxyl functionalities)。此类不饱和聚酯多元醇不适于用在电气装置用浸渍组合物中,因为羟基官能度高,这改善了与电场的相互作用,由此降低了交联后的材料的绝缘性能。此外,上述不饱和聚酯多元醇对于电气装置用浸渍组合物中的应用来说太软了。
公知的是,低粘度、低-VOC浸渍树脂通常含有高水平的反应性稀释剂,导致弱机械性能,诸如强脆性。
发明内容
本发明提供一种用于固定缠绕物品的组合物,所述组合物包括:
A)5wt%至97wt%的至少一种α,β-不饱和聚酯树脂和/或α,β-不饱和聚酯酰亚胺树脂,所述至少一种α,β-不饱和聚酯树脂和/或α,β-不饱和聚酯酰亚胺树脂包括以下组分:至少一种α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯;至少一种多元醇;至少一种含(甲基)丙烯酰基的组分;可能的至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯;以及,在α,β-不饱和聚酯酰亚胺树脂的情况下,具有5元环状酰亚胺部分的至少一种酰亚胺,在这些组分的比例中,其中,所述不饱和的单羧酸、二羧酸和/或三羧酸和/或其酸酐和/或酯,和/或所述多元醇,和/或所述非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸和/或其酸酐和/或酯中的至少一种,和/或,在所述α,β-不饱和聚酯酰亚胺树脂的情况下,所述具有5元环状酰亚胺部分的酰亚胺包括含有多于八(8)个碳原子的直链和/或支链的脂族部分和/或脂环族部分;
B)0至60wt%的不同于A)的至少一种不饱和聚酯树脂和/或不饱和聚酯酰亚胺树脂;
C)2wt%至80wt%的至少一种单体不饱和组分和/或低聚不饱和组分,在20℃下测量,该至少一种单体不饱和组分和/或低聚不饱和组分在20℃下具有0至1毫巴的蒸汽压;
D)0至40wt%的不同于C)的至少一种单体不饱和组分和/或低聚不饱和组分,在20℃下测量,该至少一种单体不饱和组分和/或低聚不饱和组分在20℃下具有0至10毫巴的蒸汽压;
E)0.1wt%至15wt%的至少一种添加剂;以及
F)0至30wt%的含环氧和/或缩水甘油醚和/或酯部分的单体和/或聚合物;
其中,wt%基于所述组合物的总重量。
本发明的组合物在高含量的a,β-不饱和聚酯树脂和/或a,β-不饱和聚酯酰亚胺树脂的情况下提供低粘度、导致低固化排放的低VOC,并且还提供优异的浸渍性能。固化后,这些浸渍材料表现出高韧性水平以及优异的耐破裂性。
具体实施方式
通过阅读以下详细说明,本领域普通技术人员将更易理解本发明的特征和优点。应理解的是,本发明的这些特定特征(为了清楚起见在独立的实施方式的上下文中描述)还可以单个实施方式的组合提供。相反,本发明的各个特征(为了简要,在单个实施方式的上下文描述)还可单独提供或者以任何子组合提供。此外,单数的表述也可包括复数(例如“一(a)”和“一种(an)”可指一个,或者一个或多个),除非文中另作特别声明。
数值范围的公开用于作为包括最小值和最大值之间每个值的连续的范围。
文中所述的术语“通常”或“通常地”是指“如本领域技术人员已知的”。
文中所述的数均摩尔质量Mn用凝胶渗透色谱法(GPC;二乙烯基苯交联的聚苯乙烯作为固定相,四氢呋喃作为液相,聚苯乙烯标准)根据ISO13885-1标准测定。
术语“(甲基)丙烯酰基”在本文中是指丙烯酰基(acryl)和/或甲基丙烯酰基(methacryl)。
本文中的术语“羟值”定义为根据标准DIN 53240测定的,氢氧化钾的mg数,其等于使1g树脂乙酰化的乙酸的mg数。
本文中的术语“酸值”定义为DIN EN ISO 2114标准中描述的中和树脂的酸基所需的氢氧化钾的mg数。
根据本发明的组合物包括5wt%至97wt%,优选10wt%至90wt%,更优选15wt%至85wt%范围中的至少一种α,β-不饱和聚酯树脂和/或α,β-不饱和聚酯酰亚胺树脂作为组分A),wt%基于所述组合物的总重量。
组分A)的树脂可具有0至120mg KOH/g,优选0至80mg KOH/g的羟值;0至70mg KOH/g,优选0至50mg KOH/g的酸值;以及,如果将至少一种多异氰酸酯附加地用于制备树脂A),可能的每100g树脂具有0至0.1mol的氨基甲酸酯基浓度。
组分A)通过以下反应获得:
(a)至少一种α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯;
(b)至少一种多元醇;
(c)在α,β-不饱和聚酯酰亚胺树脂的情况下,具有以下通式的具有5元环状酰亚胺部分的至少一种酰亚胺:
其中,
R1为脂族部分、脂环族部分或芳族部分,其中,R1中的羰基位于1,2-位(1,2-position),并且该脂族部分、脂环族部分或芳族部分含有至少一个其它的反应性羧基或羟基或C=C双键,或它们的组合;
R2为含有2至20个碳原子的脂族部分、芳族部分或脂环族部分,该脂族部分、芳族部分或脂环族部分还可含有氧原子或氮原子;
R3为脂族部分、脂环族部分或芳族部分,在该脂族部分、脂环族部分或芳族部分中,R3的4个羰基中的至少2个位于1,2-位,并且X为羟基或羧基官能团;
(d)至少一种含(甲基)丙烯酰基((meth)acylic group)的组分;以及
(e)可能的至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯;
在组分(a)至(e)的比例中,其中,组分(a)至(c)或组分(e)中的至少一种包括含有多于八(8)个碳原子的直链和/或支链的脂族部分和/或脂环族部分。
以本领域技术人员已知的如下方式选择组分(a)至(e)的比例,使得:100g组分A)含有0.03mol至0.5mol的可聚合的α,β-烯属不饱和基团组分(a);并且在所述聚酯酰亚胺树脂的情况下,A)中亚氨基键合的氮(imidically bonded nitrogen)的量为至少0.3wt%,优选至少1.0wt%;所述wt%基于树脂A)的重量。
组分A)的数均分子量Mn的范围例如为400至10000g/mol,优选600至3000g/mol。
上述含有多于8个碳原子的直链和/或支链的脂族部分和/或脂环族部分例如可以是十二碳烯琥珀酸酐、蓖麻油和/或蓖麻油的衍生物、二聚的脂肪酸和/或二聚的脂肪醇。优选二聚的脂肪酸和/或二聚的脂肪醇。
优选地,上述至少一种多元醇(b)包括含有多于八(8)个碳原子的直链和/或支链的脂族部分和/或脂环族部分。在至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯(e)被用于制备组分(A)的情况下,优选该反应组分(e)包括含有多于八(8)个碳原子的直链和/或支链的脂族部分和/或脂环族部分。
上述α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯(a)为常规的α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯,例如含有4个或5个碳原子的二羧酸和/或它们的酸酐或酯。实例为马来酸酐,富马酸、衣康酸和/或它们的酸酐,亚甲基丙二酸、柠康酸酐或中康酸。
优选使用马来酸酐和/或富马酸。
多元醇(b)为常规的每个分子含有多于一个,优选2个、3个或4个羟基官能团的醇。实例为含有2至18个碳原子的双官能或三官能的醇,例如1,4-二羟甲基环己烷、2,2-双-(4-羟基环己基)-丙烷、乙二醇、丙二醇、1,3-丙二醇、新戊二醇(NPG)、三羟甲基丙烷(TMP)、丙三醇、二聚的脂肪醇、蓖麻油、三(羟乙基)异氰脲酸酯(THEIC)和季戊四醇。还可能使用羧基官能的醇,诸如二羟甲基丙酸。使用官能团大于2的醇导致支化结构。此外,上述醇可为聚醚多元醇、聚烯烃多元醇和/或聚合物多元醇,例如聚乙二醇、聚丙二醇、聚四氢呋喃,环氧乙烷和/或环氧丙烷与含有2个至4个羟基的多官能醇(例如丙三醇、三羟甲基乙烷、三羟甲基丙烷、三乙醇胺或季戊四醇),或者与含有2个至4个羟基的多官能酚(例如儿茶酚、氢醌、双酚A或双酚F)加成的反应产物。其它实例为由自由基聚合得到的羟基官能的均聚物或共聚物;数均摩尔质量为400g/mol至8000g/mol的羟基官能的聚碳酸酯或羟基官能的聚酯;或者聚烯烃多元醇,诸如乙烯、丙烯、丁烯、辛烷、异戊二烯、丁二烯、氯丁二烯和/或它们的组合的羟基官能的聚合物。
优选的多元醇(b)为1,3-丙二醇、新戊二醇、THEIC、聚乙二醇、羟基官能的聚丁二烯、三羟甲基丙烷、二聚的脂肪醇和/或蓖麻油。
除至少一种多元醇(b)以外,在制备组分A)时可以以本领域技术人员公知的方式并入少量的单醇,其量提供组分A)的不超过33%的羟基官能团。实例为8(9)-羟基三环[5.2.1.02.6]癸-3-烯、苯酚、己醇和异癸醇。
至少一种含有5元环状酰亚胺部分的酰亚胺(c)可为常规的酰亚胺,它们为三羧酸或它们的酸酐(例如偏苯三酸酐、3,3′,4-二苯甲酮三羧酸酐),丙三羧酸(tricarballylicacid)或不饱和的脂环族、芳族或脂族的二羧酸的酸酐(例如四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、邻苯二甲酸酐、内-亚甲基四氢邻苯二甲酸酐、琥珀酸酐、十二碳烯琥珀酸酐或马来酸酐),与脂族、脂环族、杂环或芳族氨基醇或氨基羧酸的反应产物。适宜的氨基醇例如为乙醇胺、丙醇胺、丁醇胺、它们的高级同系物、4-氨基环己醇、4-氨基苯甲醇或芳族氨基取代的苯基醚醇。合适的氨基羧酸例如为氨基乙酸、氨基丙酸、氨基己酸(aminocapronic acid)和4-氨基苯甲酸。
酰亚胺(c)的其它实例为四羧酸或其酸酐(例如均苯四酸酐、二苯甲酮四羧酸二酐、丁烷四羧酸二酐、环戊烷四羧酸二酐)与脂族、脂环族、杂环或芳族的氨基醇或氨基羧酸的反应产物;和/或为2mol的三羧酸或其酸酐(例如偏苯三酸酐、丙三羧酸或3,3′,4-二苯甲酮三羧酸酐)与1mol的芳族二胺(例如4,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基醚、4,4′-二氨基二苯基硫醚、4,4′-二氨基二苯基砜)或脂族二胺和/或脂环族二胺(例如4,4′-二氨基二环己基甲烷,乙二胺、丙二胺)或脂族醚胺的反应产物。除了上述二胺以外,还可使用相应的二异氰酸酯。
优选的酰亚胺(c)为四氢邻苯二甲酸酐或偏苯三酸酐与乙醇胺的反应产物。
用于至少一个(甲基)丙烯酰基官能的组分(d)的实例为官能的聚酯(甲基)丙烯酸酯、官能的聚醚(甲基)丙烯酸酯、官能的硅酮(甲基)丙烯酸酯、官能的(甲基)丙烯酰化的聚丁二烯或官能的氨基甲酸酯(甲基)丙烯酸酯,其中官能团例如可为羟基、羧基、环氧基和/或异氰酸酯基。其它实例为羧基(甲基)丙烯酸酯及其衍生物,诸如酸性卤化物、羟基(甲基)丙烯酸酯、环氧基(甲基)丙烯酸酯和氨基(甲基)丙烯酸酯,例如羟丁基(甲基)丙烯酸酯、(甲基)丙烯酸缩水甘油酯、三羟甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、(甲基)丙烯酰氯。
优选(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酰氯和羟乙基(甲基)丙烯酸酯。
可能的至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯(e)可为常规的脂族、脂环族和/或芳族的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯,特别是烷基链上含有1至4个碳原子的烷基酯。实例为二环戊二烯二马来酸酯、四氢邻苯二甲酸酐、内-亚甲基四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、偏苯三酸酐、均苯四酸酐、对苯二甲酸、间苯二甲酸、四氯邻苯二甲酸、六氯邻苯二甲酸、己二酸、戊二酸、癸二酸、二聚的脂肪酸、聚合的脂肪酸、十二碳烯琥珀酸酐、蓖麻油的羧基官能的衍生物、羧基官能的聚烯烃。还可能使用羟基官能的羧酸,诸如二羟甲基丙酸。
优选蓖麻油的羧基官能的衍生物、四氢邻苯二甲酸酐、十二碳烯琥珀酸酐、二聚的脂肪酸和己二酸。
此外,组分A)中可并入一种或多种多异氰酸酯,例如含有2个或更多个异氰酸酯基的多异氰酸酯,例如含有6至18个碳原子的脂族、脂环族或芳族的二异氰酸酯,例如1,6-六亚甲基二异氰酸酯、2,4′-二环己基甲烷二异氰酸酯和4,4′-二环己基甲烷二异氰酸酯、3-异氰酸基甲基-3,5,5-三甲基环己基异氰酸酯、2,2,3-三甲基六亚甲基二异氰酸酯和2,4,4-三甲基六亚甲基二异氰酸酯、环己酮-1,3-二异氰酸酯和环己酮-1,4-二异氰酸酯,2,4-甲代亚苯基二异氰酸酯和2,6-甲代亚苯基二异氰酸酯、2,4′-二苯基甲烷二异氰酸酯和4,4′-二苯基甲烷二异氰酸酯,通过多异氰酸酯与亚化学计量的量的多元醇反应得到的多异氰酸酯,或者上述多异氰酸酯的三聚产物,或者具有由上述多异氰酸酯制得的缩二脲结构的产物,或者具有由上述多异氰酸酯制得的脲二酮结构的产物。优选芳族异氰酸酯,例如2,4′-二苯基甲烷二异氰酸酯和4,4′-二苯基甲烷二异氰酸酯及它们的混合物。
本发明的至少一种树脂A)可通过本领域技术人员公知的方法制备,例如通过反应组分(a)至(d)或(a)至(e)的聚酯化,在加热下,例如在120℃至240℃的温度下,在熔融方法中,于惰性气体下,或者在共沸过程中,可能地在聚酯化催化剂的存在下。
对于根据本发明的组合物的组分B),可使用范围为0至60wt%,优选0至50wt%,更优选0至40wt%的与A)不同的至少一种不饱和聚酯树脂和/或不饱和聚酯酰亚胺树脂,wt%基于所述组合物的总重量。至少一种树脂B)可具有例如500g/mol至10000g/mol范围内的数均分子量。如果存在,组分B)的量通常至少为0.1wt%。
B)的实例为通常由多元羧酸、多元醇,以及含有氨基的化合物(如果它们含有酰亚胺)制备的缩合产物,提供与A)不同的不饱和聚酯树脂和/或不饱和聚酯酰亚胺树脂。
将2wt%至80wt%,优选2wt%至60wt%(wt%基于组合物的总重量)的20℃下为0至1毫巴,优选0至0.5毫巴的蒸汽压(在20℃下测得)的至少一种单体不饱和组分和/或低聚不饱和组分用作组分C)。该组分可为常规的含有一个或多个乙烯双键或丙烯双键的烯属不饱和组分,它们可自由基聚合。组分C)的实例可为邻苯二甲酸二烯丙基酯、三烯丙基异氰脲酸酯、二烯丙基双酚A、季戊四醇三烯丙基醚或季戊四醇四烯丙基醚。组分C)也可以包括丙烯酸酯或甲基丙烯酸酯,如羟乙基(甲基)丙烯酸酯、羟丙基(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯、二环戊二烯(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯和三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯和季戊四醇三(甲基)丙烯酸酯、环氧树脂(甲基)丙烯酸酯,环氧乙烷或环氧丙烷与多元醇加聚的反应产物的(甲基)丙烯酸酯,其中多元醇例如为三羟甲基丙烷,或季戊四醇,以及低聚(乙二醇)或低聚(丙二醇)的(甲基)丙烯酸酯。
组分C)的优选实例为己二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯和环氧乙烷与三羟甲基丙烷加聚的反应产物的(甲基)丙烯酸酯,或它们的混合物。
如DE-A-2040094、DE-A-2719903、DE-A-3247058和EP-A-0255802中所述的,至多50wt%,优选0至10wt%的组分C)可由含有可聚合基团的单体构成,例如马来酸二烷基酯或富马酸二烷基酯,其中该烷基含有1个至4个碳原子,或者例如单马来酰亚胺或双马来酰亚胺。如果存在,组分C)的含量通常为至少0.1wt%。
将0wt%至40wt%(wt%基于组合物的总重量)的20℃下为0至10毫巴,优选0至5毫巴的蒸汽压(在20℃下测得)的不同于C)的至少一种单体不饱和组分和/或低聚不饱和组分用作组分D)。该组分可为常规的含有一个或多个乙烯双键或烯丙基双键的烯属不饱和组分,它们可自由基聚合。组分D)的实例为苯乙烯、乙烯基甲苯、对甲基苯乙烯、叔丁基苯乙烯、二乙烯基苯、N-乙烯基吡咯烷酮、羟丁基乙烯基醚、丁二醇乙烯基醚、三乙二醇二乙烯基醚、邻苯二甲酸二烯丙酯、富马酸二烯丙酯、三烯丙基磷酸酯,三烯丙基异氰脲酸酯、二烯丙基苯、二烯丙基双酚A,季戊四醇三烯丙基醚或季戊四醇四烯丙基醚。组分D)也可以是丙烯酸酯或甲基丙烯酸酯,如(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、苯氧基乙基(甲基)丙烯酸酯、二环戊二烯(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯,三羟甲基丙烷二(甲基)丙烯酸酯和三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯和季戊四醇三(甲基)丙烯酸酯、环氧树脂(甲基)丙烯酸酯、环氧乙烷或环氧丙烷与多元醇(诸如三羟甲基丙烷或季戊四醇)的加聚的反应产物的(甲基)丙烯酸酯,以及低聚的(乙二醇)或低聚的(丙二醇)的(甲基)丙烯酸酯。如果存在,组分D)的含量通常为至少0.1wt%。
D)的优选实例为苯乙烯、乙烯基甲苯、己二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯,以及环氧乙烷与三羟甲基丙烷的加聚反应产物的(甲基)丙烯酸酯,或它们的混合物。
如DE-A-2040094、DE-A-2719903、DE-A-3247058和EP-A-0255802中所述的,至多50wt%,优选0至10wt%的组分D)可由含有可聚合基团的单体构成,例如马来酸二烷基酯或富马酸二烷基酯,其中该烷基含有1个至4个碳原子,或者例如单马来酰亚胺或双马来酰亚胺。如果存在这种单体,它们的含量通常为组分D)的至少0.1wt%。
将0.1wt%至15wt%的至少一种添加剂用作本发明的组分E),wt%基于组合物的总重量。这可以是本领域技术人员公知的添加剂,例如,增量剂、增塑组分、促进剂,例如金属的盐,取代的胺;引发剂,例如光引发剂,诸如含氯的光引发剂、芳族酮、羟烷基苯酮;引发剂,如过氧化物,过氧化氢、酮过氧化物;热敏引发剂,诸如C-C-不稳定的1,2-位取代的四苯基乙烷,例如具有通式YPh2C-CPh2Y,其中,Ph:苯基,Y:-OH、-OCH3,-OC6H5,-CH3,-CN,-NH2,-Cl或-OSi(CH3)3;稳定剂(抑制剂),例如,氢醌、醌、醌型抑制剂、酚型抑制剂,金属的有机盐和/或有空间位阻的脂族胺或芳族胺;烷基酚,烷基酚醚,消泡剂和流动控制剂。为了调节特定性能,例如固化速度、表面硬度和表面平整度,可添加不同于A)和B)的其它的可聚合低聚物、聚合物或共聚物,例如液态的聚丁二烯(如(甲基)丙烯酸酯化的聚丁二烯)、环氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、不饱和聚酯和聚酯酰亚胺。其它添加剂可为纤维样增强剂,其基于碳、玻璃、聚酰胺、聚酯、聚丙烯腈,聚芳酰胺、聚酰胺酰亚胺或聚碳酸酯纤维或填料,例如白垩、滑石、氢氧化铝、石英粉、板岩粉、粘土或微白云石(microdolomite);有机颜料和无机颜料、染料、诱发触变性的试剂以及减缩剂。上述组合物中此类添加剂的含量取决于相应的应用,并且是本领域技术人员公知的。
将0至30wt%的含有环氧和/或缩水甘油醚和/或酯部分的单体和/或聚合物用作本发明的组分F),wt%基于组合物的总重量。这可为单体和/或聚合物,诸如双酚A二缩水甘油醚、双酚F二缩水甘油醚,和/或适宜的低聚物和聚合物,缩水甘油,脂族环氧化物和/或芳族环氧化物,诸如氧化苯乙烯、甲基丙烯酸缩水甘油酯、叔碳酸缩水甘油酯、环氧化的聚丁二烯、聚氯丁二烯和聚异戊二烯。如果存在,组分F)的含量通常为至少0.1wt%。
本发明组合物的组分A)、B)、C)、D)、E)和F)可以作为容易制备出的材料按任何顺序混合。组分A)、B)和/或D)和/或E)和/或F)还可溶解在C)中,并且随后混合在一起,并且组分A)、B)和/或C)和/或E)和/或F)还可溶解在D)中,并且随后混合在一起。还能预混合组合C)和D),然后将组分A)和/或B)和/或E)和/或F)溶解在该混合物中。
根据本发明的组合物的应用可通过本领域已知的方法进行,例如通过浸入浸渍、真空浸渍或滴流浸渍。在浸入浸渍方法中,基材被浸入上述组合物中保持一定时间,或者被拉着通过该组合物。在浸入之前,可将基材加热至低于组合物固化温度的温度。在真空浸渍方法中,将基材置于封闭的容器内,施加真空,然后使本发明的组合物涌入容器中。在滴流浸渍方法中,根据本发明的组合物例如用喷嘴滴流至旋转的基材上。
为了良好的渗透性,将基材加热至低于组合物固化温度的温度是有用的。该加热可通过本领域已知的方法提供,例如在浸渍涂布期间或之前,通过电流或者在烘箱中提供。
在浸渍涂布之后,可固化所涂布的根据本发明的组合物。这可例如通过自由基聚合来进行,并且,对于该自由基聚合,将自由基引发剂作为组分E)的一部分加入至本发明的组合物中是有用的。该固化可通过加热浸渍过的基材和/或用高能辐射辐照浸渍过的基材来进行。
用于固化的热量例如可通过使电流通过绕组来产生;还能使用烘箱或红外(IR)或近红外(NIR)辐射源。加热温度(目标温度)范围可为80至180℃。常规的固化时间例如为1分钟至180分钟,在NIR辐射的情况下,固化时间可较短,例如小于1分钟。根据本发明的组合物还可在使用添加剂的情况下在低于80℃的温度下固化,例如在环境温度下,该添加剂例如为芳族胺,或钴、铜、铈、钒等的盐。
根据本发明的组合物还可通过应用高能辐射,例如紫外(UV)光或电子束来固化。对于UV固化,例如可使用充足的引发剂,例如吸收的波长范围为190nm至450nm的光引发剂。
同时,还能使用光引发剂与热不稳定的引发剂的组合,例如热固化与UV固化的组合。
高能辐射可用于促进固化过程,而且取决于浸渍层的厚度,还能用于所涂布组合物的完全固化。UV和电子束辐射还能用于只使涂布在基材上的本发明的浸渍组合物的表面固化,以减少后续热固化步骤中该组合物的挥发性单体的排放。
根据本发明的组合物可用于多个应用领域。它们特别适用于固定缠绕物品,例如盘绕的基材,特别是盘绕的电线,例如电器装置(例如转子、定子或变压器)中的磁线,或者电力部分中的盘绕的金属箔,或者盘绕的基于玻璃纤维、塑料纤维或塑料箔的基材,并且还可用于纤维的浸渍。
现将通过以下非限制性实施例说明本发明。
实施例1
现有技术的组合物a)
现有技术的组合物a)是商购的杜邦浸渍树脂4302:一种基于不饱和聚酯的柔性浸渍树脂,该不饱和聚酯不满足根据本发明的(A)的组成,溶解于低聚的丙烯酸酯中。
25℃下的粘度:7300毫帕斯卡秒(mPas)。
实施例2
现有技术的组合物b)
现有技术的组合物b)是商购的杜邦浸渍树脂4303:一种基于不饱和聚酯的硬质浸渍树脂,该不饱和聚酯不满足根据本发明的(A)的组成,溶解于低聚的丙烯酸酯中。
25℃下的粘度:900mPas。
实施例3
根据本发明的组合物
组分(A)是基于马来酸酐、新戊二醇、四氢邻苯二甲酸酐、乙醇胺和二聚的脂肪酸的一种不饱和聚酯,其进一步与反应性甲基丙烯酸衍生物反应。组分(A)具有以下性能:酸值7mg KOH/g,平均交联度=2。
将57重量份的组分(A)加热至100℃,并且溶解于41重量份的1,4-丁二醇二甲基丙烯酸酯(组分(C))中。在冷却至<40℃之后,加入1.4重量份的C-C自由基引发剂(苯频哪醇醚(benzpinakol ether),组分(E)),并充分混合。
25℃下的粘度:310mPas。
测试
固化损失
用10g如实施例1至3中描述的液态浸渍材料根据EN60455-3-5:2006测定固化损失:
实施例1(现有技术a)):固化损失=0.5wt%。
实施例2(现有技术b)):固化损失=0.5wt%。
实施例3(根据本发明):固化损失=1.5wt%。
因此,所有的材料被分类为低排放的浸渍树脂。
硬度
将20g如实施例1至3中描述的液态浸渍材料倒入铝盘(上直径64mm,高度10mm)中。使浸渍材料在对流烘箱中于150℃加热1小时。固化后,测定肖氏-D硬度(根据IEC 60455-2的肖氏-D硬度,根据ISO 868的测试方法):
材料 | 硬度(肖氏-D) |
实施例1(现有技术a)) | 47 |
实施例2(现有技术b)) | 81 |
实施例3(本发明) | 66 |
破裂趋势
根据艾仕得涂料系统内部标准010测定破裂趋势:
在铝盘(上直径64mm,高度10mm)中分别装入30段铜线(长度2cm至2.5cm,直径1mm)。一个盘填充20g浸渍材料,一个盘填充10g浸渍材料,并且一个盘填充5g浸渍材料。使浸渍材料在对流烘箱中于150℃固化1小时。冷却后,从盘中取出固化的浸渍材料,并光学检测破裂。
材料 | 破裂趋势 |
实施例1(现有技术a)) | 一些破裂 |
实施例2(现有技术b)) | 很多破裂 |
实施例3(本发明) | 几乎没有破裂 |
如以上数据所示,根据本发明的浸渍材料提供了以下性能的独特组合:由于低粘度而具有的优异的浸渍性能、低固化排放,以及固化后的高韧性水平以及优异的耐破裂性。
Claims (13)
1.一种用于固定缠绕物品的组合物,所述组合物包括:
A)5wt%至97wt%的至少一种α,β-不饱和聚酯酰亚胺树脂,所述至少一种α,β-不饱和聚酯酰亚胺树脂包括以下组分:至少一种α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯;至少一种多元醇;至少一种含(甲基)丙烯酰基的组分;至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯;以及具有5元环状酰亚胺部分的至少一种酰亚胺,在这些组分的比例中,其中,所述α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸和/或其酸酐和/或酯,和/或所述多元醇,和/或所述非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸和/或其酸酐和/或酯,和/或所述具有5元环状酰亚胺部分的酰亚胺中的至少一种包括含有多于八个碳原子的直链和/或支链的脂族部分和/或脂环族部分;
B)0至60wt%的不同于A)的至少一种不饱和聚酯树脂和/或不饱和聚酯酰亚胺树脂;
C)2wt%至80wt%的至少一种单体不饱和组分和/或低聚不饱和组分,在20℃下测量,该至少一种单体不饱和组分和/或低聚不饱和组分具有0至1毫巴的蒸汽压;
D)0至40wt%的不同于C)的至少一种单体不饱和组分和/或低聚不饱和组分,在20℃下测量,该至少一种单体不饱和组分和/或低聚不饱和组分具有0至10毫巴的蒸汽压;
E)0.1wt%至15wt%的至少一种添加剂;以及
F)0至30wt%的含环氧和/或缩水甘油醚和/或酯部分的单体和/或聚合物;
其中,所述wt%基于所述组合物的总重量;并且
其中所述含有多于八个碳原子的直链和/或支链的脂族部分和/或脂环族部分为十二碳烯琥珀酸酐、蓖麻油和/或蓖麻油的衍生物、二聚的脂肪酸和/或二聚的脂肪醇。
2.根据权利要求1所述的组合物,包括10wt%至90wt%的组分A)的所述至少一种α,β-不饱和聚酯酰亚胺树脂。
3.根据权利要求1或2所述的组合物,其中,组分A)通过以下反应获得:
(a)至少一种α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯;
(b)至少一种多元醇;
(c)具有5元环状酰亚胺部分的至少一种酰亚胺,其具有以下通式:
或
或
其中
R1为脂族部分、脂环族部分或芳族部分,在该脂族部分、脂环族部分或芳族部分中,羰基和R1相连于R1的1,2-位,并且该脂族部分、脂环族部分或芳族部分含有至少一个其它的反应性羧基或羟基或C=C双键,或它们的组合;
R2为含有2至20个碳原子的脂族部分、芳族部分或脂环族部分,该脂族部分、芳族部分或脂环族部分还可含有氧原子或氮原子;
R3为脂族部分、脂环族部分或芳族部分,在该脂族部分、脂环族部分或芳族部分中,4个羰基中的至少2个和R3相连于R3的1,2-位,并且
X为羟基或羧基官能团;
(d)至少一种含(甲基)丙烯酰基的组分;以及
(e)至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯;
在组分(a)至(e)的比例中,其中,组分(a)至(c)或组分(e)中的至少一种包括含有多于八个碳原子的直链和/或支链的脂族部分和/或脂环族部分。
4.根据权利要求3的组合物,其中,以如下方式选择组分(a)至(e)的比例,使得:
100g组分A)含有0.03mol至0.5mol的可聚合的α,β-烯属不饱和基团组分(a);并且
A)中亚氨基键合的氮的量为至少0.3wt%;
所述wt%基于树脂A)的重量。
5.根据权利要求3的组合物,其中,以如下方式选择组分(a)至(e)的比例,使得:
100g组分A)含有0.03mol至0.5mol的可聚合的α,β-烯属不饱和基团组分(a);并且
A)中亚氨基键合的氮的量为至少1.0wt%;
所述wt%基于树脂A)的重量。
6.根据权利要求1所述的组合物,其中所述至少一种多元醇包括含有多于八个碳原子的直链和/或支链的脂族部分和/或脂环族部分。
7.根据权利要求1所述的组合物,其中,所述至少一种非α,β-烯属不饱和的单羧酸、二羧酸、三羧酸和/或四羧酸,和/或其酸酐和/或酯,包括含有多于八个碳原子的直链和/或支链的脂族部分和/或脂环族部分。
8.根据权利要求1所述的组合物,其中,所述α,β-烯属不饱和的单羧酸、二羧酸和/或三羧酸,和/或其酸酐和/或酯,为含有4个或5个碳原子的二羧酸和/或它们的酸酐或酯。
9.根据权利要求1所述的组合物,其中,所述多元醇为1,3-丙二醇、新戊二醇、THEIC、聚乙二醇、羟基官能的聚丁二烯、三羟甲基丙烷、二聚的脂肪醇和/或蓖麻油。
10.根据权利要求1所述的组合物,其中,在20℃下测量,所述至少一种单体不饱和组分和/或低聚不饱和组分C)具有0至0.5毫巴的蒸汽压。
11.一种通过以任何顺序混合组分A)至F)来制备根据权利要求1至10中任一项所述组合物的方法。
12.一种固定缠绕物品的方法,所述方法利用根据权利要求1至10中任一项所述的组合物,通过浸入浸渍、真空浸渍或滴流浸渍,然后固化所施用的组合物来固定缠绕物品。
13.一种缠绕物品,所述缠绕物品通过根据权利要求1至10中任一项所述的组合物固定。
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