DE1178592B - Manufacture of molded parts from polyester molding compounds - Google Patents
Manufacture of molded parts from polyester molding compoundsInfo
- Publication number
- DE1178592B DE1178592B DEB66052A DEB0066052A DE1178592B DE 1178592 B DE1178592 B DE 1178592B DE B66052 A DEB66052 A DE B66052A DE B0066052 A DEB0066052 A DE B0066052A DE 1178592 B DE1178592 B DE 1178592B
- Authority
- DE
- Germany
- Prior art keywords
- polyester
- parts
- molded parts
- molding compounds
- monomers
- 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.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims description 36
- 238000000465 moulding Methods 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000178 monomer Substances 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 12
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920006305 unsaturated polyester Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- 239000000945 filler Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 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
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- QPYKYDBKQYZEKG-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diol Chemical compound CC(C)(C)C(O)O QPYKYDBKQYZEKG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AHRIFIYGSJEEKU-UHFFFAOYSA-N 2-Methylallyl butyrate Chemical compound CCCC(=O)OCC(C)=C AHRIFIYGSJEEKU-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical group CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GBHHYHNRBWGLBL-UHFFFAOYSA-N 3-ethenoxy-2-methylprop-1-ene Chemical compound CC(=C)COC=C GBHHYHNRBWGLBL-UHFFFAOYSA-N 0.000 description 1
- VQMIUUBKKPIDBN-UHFFFAOYSA-N 4-(hydroxymethyl)cyclohexane-1-carboxylic acid Chemical compound OCC1CCC(C(O)=O)CC1 VQMIUUBKKPIDBN-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 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 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- -1 diallyl phthalate Chemical compound 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
Herstellen von Formteilen aus Polyesterformmassen Polyesterformmassen sind bekanntlich Stoffgemische, die als grundlegende Stoffe enthalten 1. äthylenisch ungesättigte, polymerisierbare Polyester und 2. äthylenisch ungesättigte, an die Polyester anpolymerisierbare monomere Verbindungen.Manufacture of molded parts from polyester molding compounds are known to be mixtures of substances that contain the basic substances 1. Ethylenic unsaturated, polymerizable polyester and 2. ethylenically unsaturated, to the Polyester polymerizable monomeric compounds.
Solche Polyesterformmassen sind vielfach und in vielen Varianten in einschlägigen Druckschriften beschrieben ; beispielsweise sei auf das Buch von J. B j o r k s t e n et al » Polyesters and their Applications « (Reinhold Publishing Corporation, New York, 1956) hingewiesen. Such polyester molding compounds are numerous and in many variants described in relevant publications; for example, consider the book of J. B j o r k s t e n et al "Polyesters and their Applications" (Reinhold Publishing Corporation, New York, 1956).
Polyesterformmassen werden für viele Zwecke zusammen mit Verstärkungs-bzw. Füllmitteln aus Glas, wie Glasfasern, Glasfaservliesen, Glasfasergarnen, Glasfasergeweben oder Glaspulvern, verarbeitet. Polyester molding compounds are used for many purposes together with reinforcing or. Fillers made of glass, such as glass fibers, glass fiber nonwovens, glass fiber yarns, glass fiber fabrics or glass powders.
Durch Härten (Polymerisieren) lassen sich aus den Polyesterformmassen zusammen mit den Verstärkungs-bzw. Füllmitteln Formteile nahezu beliebiger Gestalt herstellen. Es ist dabei oft erwünscht, daß die Formteile-etwa gewellte Platten oder Teile für Lichtkuppeln-in hohem Maße lichtdurchlässig, also möglichst klar sind. Dieser Forderung steht jedoch entgegen, daß die Brechungsindizes von gehärteten Polyesterformmassen und Gläsern im allgemeinen verschieden sind. The polyester molding compounds can be hardened (polymerized) together with the reinforcement or. Fillers molded parts of almost any shape produce. It is often desirable that the molded parts - such as corrugated plates or parts for skylights - highly translucent, i.e. as clear as possible are. However, this requirement is opposed to the fact that the refractive indices of hardened Polyester molding compositions and glasses are generally different.
Um diesen Nachteil zu beheben, hat man sich bemüht, durch Modifizieren der Aufbaukomponenten solche Polyesterformmassen herzustellen, die im gehärteten Zustand relativ niedrige, mit Gläsern gleiche oder annähernd gleiche Brechungsindizes haben. In order to remedy this disadvantage, efforts have been made by modifying of the structural components to produce such polyester molding compounds that are cured in the State of relatively low refractive indices that are the same or approximately the same with glasses to have.
So hat man in die Polyester (1) spezielle Diole, etwa 2,2-Dimethylpropandiol- (1,3), oder spezielle Dicarbonsäuren, etwa m-Benzoldicarbonsäure, einkondensiert. So you have in the polyester (1) special diols, such as 2,2-dimethylpropanediol (1,3), or special dicarboxylic acids, such as m-benzenedicarboxylic acid, condensed in.
Auf diese Weise kann man zwar der erwünschten optischen Eigenschaft näher kommen, muß aber hinsichtlich der anderen physikalisch-chemischen Eigenschaften der Formteile die Nachteile in Kauf nehmen, die sich durch das Festlegen auf bestimmte Aufbaukomponenten der Polyester ergeben.In this way you can get the desired optical property come closer, but must with regard to the other physico-chemical properties of the molded parts accept the disadvantages that result from setting certain Structure components of the polyester result.
Um die gewünschten optischen Eigenschaften zu erreichen, hat man auch Massen verwendet, die spezielle Monomere (2) enthalten, insbesondere Methacrylsäuremethylester, gegebenenfalls neben anderen Monomeren, wie Styrol. Der Gehalt an den speziellen Monomeren muß dabei relativ hoch sein, weshalb diese nicht nur die optischen, sondern auch die anderen Eigenschaften der Formmassen und Formteile weit- gehend bestimmen. Der Methacrylsäuremethylester wirkt insbesondere auch stark verzögernd auf die Gelier-und Härtezeiten der Massen. In order to achieve the desired optical properties, one has also uses compounds that contain special monomers (2), in particular methyl methacrylate, optionally in addition to other monomers such as styrene. The content of the special Monomers must be relatively high, which is why these not only the optical, but the other properties of the molding compounds and molded parts determine going. In particular, the methyl methacrylate also has a strongly retarding effect on the gelling agent Hard times of the masses.
Erfindungsgegenstand ist die Verwendung des Acrylsäure-tert.-butylesters als anpolymerisierbares Monomeres-gegebenenfalls neben üblichen weiteren anpolymerisierbaren Monomeren-in Polyesterformmassen, die ungesättigte Polyester und anpolymerisierbare Monomere enthalten, zum Herstellen von Formteilen, deren Brechungsindizes gleich oder annähernd gleich denen von Gläsern sind.-Auf diese Weise ist es möglich, schon bei Verwendung relativ kleiner Mengen eines speziellen Monomeren (Acrylsäure-tert.-butylester) Formteile herzustellen, deren Brechungsindizes gleich oder annähernd gleich denen von Gläsern sind. Ferner brauchen auf diese Weise nachteilige andere physikalisch-chemische Eigenschaften, insbesondere unerwünscht lange Gelier-und Härtezeiten nicht in Kauf genommen zu werden. The subject of the invention is the use of the acrylic acid tert-butyl ester as a polymerizable monomer - optionally in addition to customary further polymerizable monomers Monomers in polyester molding compounds, the unsaturated polyester and polymerizable Monomers contain, for the production of molded parts, whose refractive indices are the same or approximately equal to those of glasses.-In this way it is possible, already when using relatively small amounts of a special monomer (acrylic acid tert-butyl ester) Manufacture molded parts whose refractive indices are equal to or approximately equal to those of glasses are. Furthermore, disadvantageous other physicochemical needs in this way Properties, in particular undesirably long gelation and hardening times, are not accepted to be taken.
Als Polyester (1) eignen sich die üblichen. Sie können durch Schmelzkondensation oder Kondensation unter azeotropen Bedingungen aus ihren Komponenten hergestellt sein. Beispielsweise kann man zweiwertige Alkohole, wie Äthandiol, Propandiol- (1, 2), Propandiol- (1, 3), Diäthylenglykol oder 1-AllyloxypropandioJ-(2, 3), mit-äthylenisch ungesättigten Dicarbonsäuren, wie Malein-oder Fumarsäure, in etwa stöchiometrischen Mengen zu Polyestern umsetzen. In die Polyester können weiterhin andere ungesättigte oder gesättigte Dicarbonsäuren, wie Tetrahydrophthalsäure, Hexachlorendomethylentetrahydrophthalsäure, o-, m-und p-Phthalsäure, Bernsteinsäure oder Adipinsäure, einkondensiert sein, ferner ein-, drei-oder höherwertige Carbonsäuren, wie Propionsäure, 1,2,4-Benzoltricarbonsäure oder 1,2,4,5-Benzoltetracarbonsäure. The usual polyesters (1) are suitable. You can through melt condensation or condensation produced from their components under azeotropic conditions be. For example, dihydric alcohols such as ethanediol, propanediol (1, 2), propanediol- (1, 3), diethylene glycol or 1-allyloxypropanedioJ- (2, 3), with-ethylenic unsaturated dicarboxylic acids, such as maleic or fumaric acid, approximately stoichiometric Convert quantities to polyesters. Other unsaturated substances can still be found in the polyester or saturated dicarboxylic acids, such as tetrahydrophthalic acid, hexachloroendomethylenetetrahydrophthalic acid, o-, m- and p-phthalic acid, succinic acid or adipic acid, condensed be, also mono-, tri- or higher-valent carboxylic acids, such as propionic acid, 1,2,4-benzenetricarboxylic acid or 1,2,4,5-benzene tetracarboxylic acid.
In die Polyester können schließlich auch ein-, drei-oder höherwertige Alkohole, wie Benzylalkohol, 1, 2-Di- (allyloxy)-propanol- (3), Glycerin oder Pentaerythrit, oder Hydroxycarbonsäuren, wie 4-Hydroxymethylcyclohexancarbonsäure, einkondensiert sein.Finally, mono-, trivalent or higher-valency can also be used in the polyester Alcohols, such as benzyl alcohol, 1,2-di- (allyloxy) -propanol- (3), glycerol or pentaerythritol, or hydroxycarboxylic acids, such as 4-hydroxymethylcyclohexanecarboxylic acid, condensed in be.
Als Monomere (2) enthalten die Polyesterformmassen erfindungsgemäß den Acrylsäure-tert.-butylester. According to the invention, the polyester molding compositions contain monomers (2) the acrylic acid tert-butyl ester.
Die Polyesterformmassen können gegebenenfalls und vorteilhafterweise zusätzlich übliche weitere Monomere (2) enthalten. Dies sind meist Verbindungen, die an einen aromatischen Rest gebundene Vinyloder-Alkylvinylgruppen enthalten, wie Styrol, o-, m-, p-oder x-Methylstyrol, Ester und Äther des Vinylalkohols, wie Vinylacrylat, Vinylacetat oder Vinylbutyläther, Acrylsäureester anderer Alkohole als des tert.-Butanols und Methacrylsäureester, wie Äthylacrylat oder Methylmethacrylat, ferner Ester und Äther des Allyl-oder Methallylalkohols, wie Diallylphthalat, 1, 2,3-Tri- (allyloxy)-propan, Methallylbutyrat oder Methallylvinyläther. The polyester molding compositions can optionally and advantageously additionally contain customary further monomers (2). These are mostly connections, which contain vinyl or alkyl vinyl groups bound to an aromatic radical, such as styrene, o-, m-, p- or x-methylstyrene, esters and ethers of vinyl alcohol, such as Vinyl acrylate, vinyl acetate or vinyl butyl ether, acrylic acid esters of other alcohols than tert-butanol and methacrylic acid esters, such as ethyl acrylate or methyl methacrylate, also esters and ethers of allyl or methallyl alcohol, such as diallyl phthalate, 1, 2,3-tri- (allyloxy) propane, methallyl butyrate or methallyl vinyl ether.
Das Gewichtsverhältnis der Polyester (1) zu den Monomeren (2) soll in den Polyesterformmassen etwa I : 0,2 bis 1 : 1,5, vorzugsweise etwa 1 : 0,3 bis 1 : 1, betragen. Die Monomeren sollen zu I bis 100 Gewichtsprozent, vorzugsweise zu 5 bis 60 Gewichtsprozent, aus dem Acrylsäure-tert.-butylester bestehen. Zur Verarbeitung mit Verstärkungs-bzw. Füllstoffen aus Glas kann in einfachen Vorversuchen der genauere Gehalt an Acrylsäure-tert.-butylester ermittelt werden, der, bezogen auf die jeweils verwendete Art des Polyesters und des Glases, die besten optischen Eigenschaften bedingt. The weight ratio of the polyester (1) to the monomers (2) should in the polyester molding compositions about 1: 0.2 to 1: 1.5, preferably about 1: 0.3 to 1: 1. The monomers should be 1 to 100 percent by weight, preferably up to 5 to 60 percent by weight, of which the acrylic acid tert-butyl ester consists. For processing with reinforcement or. Fillers made of glass can be more precise in simple preliminary tests Content of acrylic acid tert-butyl ester can be determined, based on the Type of polyester and glass used, the best optical properties conditional.
Die härtbaren Polyesterformmassen sind zweckmäßigerweise wie üblich gegen ungewollte Polymerisation stabilisiert, etwa durch einen Gehalt an geringen Mengen von Hydrochinon. Die Härtung der Massen kann ebenfalls in der üblichen Weise ausgelöst werden, z. B. durch organische Peroxyde, gegebenenfalls unter Mitverwendung von Polymerisationsbeschleunigern, wie Metallsalzen oder Aminen. The curable polyester molding compositions are expediently as usual Stabilized against unwanted polymerization, for example by a low content Amounts of hydroquinone. The masses can also be cured in the usual manner triggered, e.g. B. by organic peroxides, optionally with use of polymerization accelerators, such as metal salts or amines.
Die vorliegenden Polyesterformmassen sind insbesondere zusammen mit Verstärkungs-bzw. Füllstoffen aus Glas, wie Glasfasern, Glasfaservliesen, Glasfasergarnen, Glasfasergeweben oder Glaspulvern, zum Herstellen hochtransparenter bis klarer Formteile geeignet. The present polyester molding compositions are in particular together with Reinforcement or Fillers made of glass, such as glass fibers, glass fiber fleeces, glass fiber yarns, Glass fiber fabrics or glass powders, for the production of highly transparent to clear molded parts suitable.
Die USA.-Patentschrift 2 642 410 hat ein Verfahren zum Polymerisieren ungesättigter Verbindungen in Gegenwart von organischen Hydroperoxyden und Metallsalzen zum Gegenstand, wobei das Spezifikum des Verfahrens darin besteht, daß durch die gleichzeitige Anwesenheit von organischen Hydroperoxyden und Metallsalzen die Polymerisationsreaktion schnell und kontrollierbar abläuft. Wie in der Patentschrift ausgeführt ist, eignet sich das Verfahren zum Polymerisieren aller polymerisierbaren Verbindungen. U.S. Patent 2,642,410 has a method of polymerizing unsaturated compounds in the presence of organic hydroperoxides and metal salts to the subject, the specificity of the method is that by the simultaneous presence of organic hydroperoxides and metal salts cause the polymerization reaction runs quickly and controllably. As stated in the patent specification, is suitable the process of polymerizing all polymerizable compounds.
Unter der großen Zahl der in der USA.-Patentschrift genannten ungesättigten Verbindungen werden auch a) Ester der Acrylsäure generell, unter anderem der Butyl-und iso-Butylester, b) ungesättigte Polyester generell sowie c) Polyestermassen aus ungesättigten Monomeren und ungesättigten Polyestern generell aufgeführt.Among the great number of unsaturated ones mentioned in the USA patent Compounds are also a) esters of acrylic acid in general, including butyl and isobutyl esters, b) unsaturated polyesters in general and c) polyester compositions unsaturated monomers and unsaturated polyesters are generally listed.
Der gemäß der vorliegenden Erfindung als ungesättigtes Monomeres in Polyestermassen zu verwendende Acrylsäure-tert.-butylester wird indes weder als solcher noch als Komponente für Polyestermassen genannt. That according to the present invention as an unsaturated monomer Acrylic acid tert-butyl ester to be used in polyester compositions is, however, neither considered such is still mentioned as a component for polyester masses.
Die deutsche Patentschrift 1 014254 betrifft Klebstoffe auf der Grundlage von Mischungen aus ungesättigten Polyestern und polymerisationsfähigen Acryl-oder Methacrylestern sowie Härtungskatalysatoren, wobei es ausschlaggebend ist, daß diese Klebstoffe mit den Polyestern verträgliche Polyvinyläther enthalten. German patent specification 1 014254 relates to adhesives based on of mixtures of unsaturated polyesters and polymerizable acrylic or Methacrylic esters and curing catalysts, it being crucial that these Adhesives that contain polyvinyl ethers compatible with the polyesters.
Der gemäß der vorliegenden Erfindung zu verwendende Acrylsäure-tert.-butylester wird dabei nicht erwähnt.The acrylic acid tert-butyl ester to be used according to the present invention is not mentioned.
Die deutsche Auslegeschrift 1 123 419 betrifft ein spezielles Verfahren zum Verkleben von Metallen, wobei unter anderem Klebstoffe verwendet werden, die in der oben zitierten deutschen Patentschrift 1 014254 beschrieben sind. Der Gegenstand der vorliegenden Erfindung wird von der deutschen Auslegeschrift indessen nicht getroffen. The German Auslegeschrift 1 123 419 concerns a special procedure for bonding metals, whereby, among other things, adhesives are used that are described in the German patent specification 1 014254 cited above. The object However, the present invention is not addressed by the German patent application met.
Die Teile und Prozente in den Beispielen und Vergleichsversuchen beziehen sich-wenn nicht anders vermerkt-auf das Gewicht. The parts and percentages in the examples and comparative experiments refer to weight unless otherwise noted.
Beispiele und Vergleichsversuche A. Ein Polyester der Säurezahl 40 aus Maleinsäureanhydrid, Phthalsäureanhydrid und Propandiol- (1, 2) im Molverhältnis 2 : 1 : 3,2 wird in drei Portionen zu je 63 Teilen aufgeteilt. Die einzelnen Portionen werden mit 0,01 Teil Hydrochinon und 37 Teilen verschiedener, in der Tabelle angegebener Monomerer bzw. Examples and comparative experiments A. A polyester with an acid number of 40 from maleic anhydride, phthalic anhydride and propanediol- (1, 2) in a molar ratio 2: 1: 3.2 is divided into three portions of 63 parts each. The individual servings are with 0.01 part of hydroquinone and 37 parts of various, given in the table Monomeric resp.
Monomerengemische homogen vermischt. Es werden die Brechungsindizes (n20°) der drei so erhaltenen Polyestermassen gemessen.Mixtures of monomers mixed homogeneously. It will be the indices of refraction (n20 °) of the three polyester compositions obtained in this way.
Jede der drei Polyestermassen wird in zwei gleiche Teile (a und b ; je 50 Teile) aufgeteilt. Die einzelnen Teilmengen werden mit je 0,2 Teilen einer 1 Obigen Kobaltnaphthenatlösung in Styrol innig verrührt, wonach den Teilmengen a je 0,75 Teile, den Teilmengen b je 2 Teile einer 50°/Oigen Cyclohexanonperoxydaufschlämmung in Dibutylphthalat zugesetzt werden. Each of the three polyester masses is divided into two equal parts (a and b ; 50 parts each). The individual subsets are 0.2 parts each 1 Above cobalt naphthenate solution in styrene thoroughly stirred, after which the partial amounts a 0.75 parts each, the partial amounts b each 2 parts of a 50% strength cyclohexanone peroxide suspension in dibutyl phthalate can be added.
Die Teilmengen a werden zur Herstellung von Formteilen in Reagenzgläser gegossen, 10 Stunden bei Raumtemperatur belassen und dann 15 Stunden bei 120°C getempert. Die Brechungsindizes (n o) der so erhaltenen Formteile werden gemessen. The subsets a are used for the production of molded parts in test tubes poured, left at room temperature for 10 hours and then tempered at 120 ° C. for 15 hours. The refractive indices (n o) of the molded parts thus obtained are measured.
An den Teilmengen b werden in Reagenzgläsern von 18 mm Durchmesser die folgenden Werte bestimmt : a) Gelierzeiten : Zeiten vom Einrühren der Peroxydaufschlämmung in die 25° C warmen, Kobaltnaphthenatlösung enthaltenden Massen bis zum Erreichen einer Temperatur von 30°C. The subsets b are placed in test tubes with a diameter of 18 mm the following values are determined: a) Gel times: times from stirring in the peroxide slurry into the 25 ° C warm, cobalt naphthenate solution containing masses until it is reached a temperature of 30 ° C.
) Maximaltemperaturen : Die während der Härtung der Massen erreichten Maximaltemperaturen. y) Härtezeiten : Zeiten vom Einrühren der Peroxydaufschlämmung in die 25°C warmen, Kobaltnaphthenat enthaltenden Massen bis zum Erreichen der Maximaltemperaturen. ) Maximum temperatures: those reached during the curing of the masses Maximum temperatures. y) Setting times: times from stirring in the peroxide slurry into the 25 ° C warm, cobalt naphthenate-containing masses until the maximum temperatures are reached.
Die gemessenen Werte sind in der folgenden Tabelle wiedergegeben
(St = Styrol, MM = Methacrylsäuremethylester, AtB = Acrylsäure-tert.-butylester).
Je 100 Teile der drei Polyestermassen werden mit je 0,3 Teilen einer 10°/Oigen Kobaltnaphthenatlösung in Styrol und 3 Teilen einer 50°/oigen Cyclohexanonperoxydaufschlämmung in Dibutylphthalat innig verrührt, in Reagenzgläser gegossen, 10 Stunden bei Raumtemperatur belassen und dann 15 Stunden bei 120° C getempert. Die Brechungsindizes (h o) der so erhaltenen Formteile werden gemessen. Every 100 parts of the three polyester masses are 0.3 parts each 10% cobalt naphthenate solution in styrene and 3 parts of a 50% cyclohexanone peroxide suspension intimately stirred in dibutyl phthalate, poured into test tubes, 10 hours at room temperature left and then tempered at 120 ° C for 15 hours. The refractive indices (h o) of the Moldings thus obtained are measured.
Die gemessenen Werte sind in der folgenden Tabelle wiedergegeben
(AnB = Acrylsäure-n-butylester, AiB = Acrylsäure-iso-butylester, AtB = Acrylsäure-tert.-butylester).
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE628723D BE628723A (en) | 1962-02-22 | ||
| DEB66052A DE1178592B (en) | 1962-02-22 | 1962-02-22 | Manufacture of molded parts from polyester molding compounds |
| GB696863A GB1026975A (en) | 1962-02-22 | 1963-02-21 | Curable polyester resins and cured shaped articles made therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB66052A DE1178592B (en) | 1962-02-22 | 1962-02-22 | Manufacture of molded parts from polyester molding compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1178592B true DE1178592B (en) | 1964-09-24 |
Family
ID=6974993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB66052A Pending DE1178592B (en) | 1962-02-22 | 1962-02-22 | Manufacture of molded parts from polyester molding compounds |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE628723A (en) |
| DE (1) | DE1178592B (en) |
| GB (1) | GB1026975A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3391224A (en) * | 1967-08-17 | 1968-07-02 | American Cyanamid Co | Mar-resistant polyester resins for ophthalmic lenses |
| FR2980695B1 (en) | 2011-09-30 | 2015-04-10 | Oreal | FOAM COLORING COMPOSITION COMPRISING ETHYLENE OXIDE POLYCONDENSATE AND PROPYLENE OXIDE |
| CN103781459A (en) | 2011-09-30 | 2014-05-07 | 莱雅公司 | Foam dye composition comprising at least one particular oxyethylenated nonionic surfactant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642410A (en) * | 1947-02-24 | 1953-06-16 | Libbey Owens Ford Glass Co | Polymerization in the presence of organic hydroperoxide and metal salt drier |
| DE1014254B (en) * | 1956-04-19 | 1957-08-22 | Degussa | Adhesive based on mixtures of unsaturated polyesters and polymerizable acrylic or methacrylic esters as well as curing catalysts |
| DE1123419B (en) * | 1960-09-27 | 1962-02-08 | Degussa | Method for bonding metals |
-
0
- BE BE628723D patent/BE628723A/xx unknown
-
1962
- 1962-02-22 DE DEB66052A patent/DE1178592B/en active Pending
-
1963
- 1963-02-21 GB GB696863A patent/GB1026975A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642410A (en) * | 1947-02-24 | 1953-06-16 | Libbey Owens Ford Glass Co | Polymerization in the presence of organic hydroperoxide and metal salt drier |
| DE1014254B (en) * | 1956-04-19 | 1957-08-22 | Degussa | Adhesive based on mixtures of unsaturated polyesters and polymerizable acrylic or methacrylic esters as well as curing catalysts |
| DE1123419B (en) * | 1960-09-27 | 1962-02-08 | Degussa | Method for bonding metals |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1026975A (en) | 1966-04-20 |
| BE628723A (en) |
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