SE202424C1

SE202424C1 -

Info

Publication number: SE202424C1
Authority: SE
Publication date: 1965-01-01

Description

Uppfinnare: K Raichle och H Rudolph Prioritet begard frau den 9 rnaj 1963 (Forbundsrepubliken Tyskland) Polyesterformmassor pa basis av omattade polyestrar och clamed sampolymeriserbara monomera foreningar ha vid lagring, sarskilt vid forhojd temperatur, en benagenhet att gelatinera i fOrtid. Det ar kant att stabilisera polyesterformmassorna mot denna gelatinering i Reid genom tillsats av olika inhibitorer, exempelvis av fenoler, sasom hydrokinon, tart butylpyroksatekol och 4-etylpyrokatekol, kinoner, sasom p-bensokinon och 2,5- di-tert.-butylbensokinon, vissa aromatiska aminer, aminsalter och kvartara fosfonium- och arsoniumsalter. Inventors: K Raichle and H Rudolph Priority requested from 9 January 1963 (Federal Republic of Germany) Polyester molding compositions based on unsaturated polyesters and clamed copolymerizable monomeric compounds have a tendency to gelatinize prematurely during storage, especially at elevated temperatures. It is possible to stabilize the polyester molding compositions against this gelatinization in Reid by adding various inhibitors, for example of phenols, such as hydroquinone, tart butylpyroxate carbon and 4-ethylpyrocatechol, quinones, such as β-benzoquinone and 2,5-di-tert-butylbenzoquinone, certain aromatic amines, amine salts and quaternary phosphonium and arsonium salts.

Den stabiliserande verkan av de namnda inhibitorerna forbattras ytterligare eller overtraffas, vilket likaledes är tidigare kant, genom losliga koppar-(II)-foreningar, sarskilt kopparsalter av organiska syror, sasom koppar-(II)-naftenat. Koppar-(H)-foreningarna ha emellertid den oldgenheten, att de aro intensivt fargade och redan i en mangd, som annu icke pa langt nar är tillracklig for en verksam stabilisering av polyesterformmassorna, fororsaka gronaktigt bruna till gronaktigt bla missfargningar av de i och for sig farg- lOsaDen med stigande kopparkon- eentration kande missfargningen av formmassorna ar redan vid en mangd av foga mer an 1 del koppar per miljon delar formmassa sa kraftig, att en i och for sig onskvard tillsats av annu storre kopparmangd i praktiken ar i det narmaste ombjlig pa grund av den darmed forbundna, icke godtagbara missfargningen. The stabilizing effect of the said inhibitors is further improved or exceeded, which is likewise earlier edge, by soluble copper (II) compounds, in particular copper salts of organic acids, such as copper (II) naphthenate. However, the copper (H) compounds have the antiquity that they are intensely colored and already in an amount which is not yet sufficient for an effective stabilization of the polyester molding compositions, cause greenish brown to greenish, among other things discolorations of the The discolouration of the molding compounds with increasing copper concentration is already so strong in a quantity of more than 1 part copper per million parts of molding compound that an in itself undesirable addition of an even larger amount of copper is in practice almost obsolete due to the associated, unacceptable discoloration.

For undvikande av dessa olagenheter ligger det nara till hands att ersatta de fargade koppar-(II)- foreningarna med farglosa koppar-(I)-foreningar, sasom koppar-(I)-halogenider. Det är emellertid Dupl. kl. 39 b: 22/06; 39 c: 16 svart att fordela dessa foreningar likformigt i formmassorna, enar exempelvis koppar-(I)-jodid är fullstandigt oloslig i formmassor, medan vid anvandning av koppar-(I)-bromid och koppar-(I)- klorid en storre mangd losningsformedlare ar erforderlig, fOr att man skall mojliggora en tillrackligt hastig och likformig upplosning ay kopparfOreningen i formmassan. Den darvid erforderliga mangden losningsformedlare, sasom acetonitril eller dimetylformamid, ár emellertid sit stor, att den ofta forsamrar egenskaperna av de hardade produkter, som framstallts ay dessa formmassor. Man har dessutom redan foreslagit framstallning av formmassor, som innehalla koppar-(I)-klorid, genom att man tillsatter koppar-(I)-kloriden till de f Or framstallning av den omattade polyestern anvanda utgangsfOreningarna f Ore polykondensationen. Eftersom emellertid koppar-(I)-klorid är mycket instabil vid de for polykondensationen erforderliga hoga omsattningstemperaturerna, oxideras namnda klorid vid detta arbetssatt latt till fOreningar av tvavard koppar genom foreningar, som verka oxiderande, sit att aven i data fall fargade produkter erhallas. To avoid these imperfections, it is obvious to replace the colored copper (II) compounds with colorless copper (I) compounds, such as copper (I) halides. However, it is Dupl. at 39 b: 22/06; 39 c: 16 black to distribute these compounds uniformly in the molding compositions, for example copper (I) iodide is completely insoluble in molding compositions, while when using copper (I) bromide and copper (I) chloride a larger amount Solution intermediates are required to enable a sufficiently rapid and uniform dissolution of the copper compound in the molding composition. However, the amount of release agent required, such as acetonitrile or dimethylformamide, is so great that it often degrades the properties of the cured products produced in these molding compositions. In addition, it has already been proposed to prepare molding compositions containing copper (I) chloride by adding the copper (I) chloride to the starting compounds for the preparation of the unsaturated polyester using the starting compounds for the polycondensation. However, since copper (I) chloride is very unstable at the high conversion temperatures required for the polycondensation, said chloride in this process is easily oxidized to compounds of dihydric copper by compounds which have an oxidizing effect, since in data cases even colored products are obtained.

Det har nu visat sig, att de namnda olagenheterna kunna undvikas och att utmarkt lagringsbestandiga losliga kopparforeningar sasom stabilisatorer innehallande, i det narmaste icke fargade polyesterformmassor kunna erhallas, om man for stabiliseringen av formmassorna anvander komplexforeningar av koppar(I)-klorid och/eller koppar-(I)-bromid med neutrala fosforsyrlighetsestrar. It has now been found that the above-mentioned imperfections can be avoided and that excellently storage-resistant loose copper compounds such as stabilizers containing almost non-colored polyester molding compositions can be obtained if complex compounds of copper (I) chloride and / or copper are used for the stabilization of the molding compositions. - (I) -bromide with neutral phosphoric acid esters.

Komplexforeningarna kunna sattas direkt till polyesterformmassorna yid rum.stemperatur eller 2 mattligt forhojd temperatur. De 'Elsa sig utan speciella svarigheter i formmassorna och orsaka icke ens i jamfOrelsevis stora mangder nagra storande missfargningar. For en tillraeklig stabilisering ãr det i allmanhet tillrackligt att forsatta polyesterformmassorna med kopparforeningarna i en sadan mangd, att formmassorna komma att innehalla upp till ungefar 50 delar koppar per miljon delar formmassa. The complex compounds can be added directly to the polyester molding compositions at room temperature or at a slightly elevated temperature. They 'Elsa themselves without special responsibilities in the mold masses and do not even in comparatively large quantities cause any major discolorations. For a sufficient stabilization, it is generally sufficient to continue the polyester molding compositions with the copper compounds in such an amount that the molding compositions will contain up to about 50 parts of copper per million parts of molding compound.

Sasom exempel pa enligt uppfinningen anyandbara komplexforeningar kunna namnas komplexen av koppar-(I)-klorid och koppar-(I)-bromid med trietylfosfit, 2,2',2"-trikloretylfosfit, tripropylfosfit, trifenylfosfit osv., vilka exempelvis beskrivas I Gmelins Handbuch der anorganischen Chemie, system nr 60, del B, upplaga 1, pp 251 och 365. Examples of complex compounds according to the invention which may be mentioned are the complexes of copper (I) chloride and copper (I) bromide with triethyl phosphite, 2,2 ', 2 "-trichlorethyl phosphite, tripropyl phosphite, triphenyl phosphite, etc., which are described, for example, in Gmelins Handbuch der inorganischen Chemie, system nr 60, del B, upplaga 1, pp 251 och 365.

Ornattade polyestrar, vilkas losningar i monomera, sampolymeriserbara foreningar kunna stabiliseras med fOrdel enligt uppfinningen, utgora alla de emattade polyestrar i den sedvanliga bemarkelsen, sarskilt sadana, som innehalla a,flomattade dikarbonsyror, eventuellt innehallande radikaler av andra karbonsyror saval som speciellt flervarda alkoholer. Non-wet polyesters, the solutions of which in monomeric, copolymerizable compounds can be stabilized with advantage according to the invention, constitute all the emitted polyesters in the usual market, in particular those containing a, flattened dicarboxylic acids, optionally containing radicals of other carboxylic acids or special alcohols.

Sasom exempel pa for uppbyggnad av polyesterhartserna lampliga karbonsyror kunna namnas: maleinsyra, fumarsyra, itakonsyra, mesakonsyra, citrakonsyra, barnstenssyra, glutarsyra, adipinsyra, ftalsyra, tetraklorftalsyra, hexaklorendometylentetrabydroftalsyra, trimellitsyra, bensoesyra, linoljefettsyra och ricinoljefettsyra. Examples of carboxylic acids suitable for the construction of polyester resins are: maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, tetrachlorophthalic acid, hexachloroomethylenetetrabydrophthalic acid, trimethyloleic acid and trimellic acid.

Sasom exempel pa lampliga alkoholer kunna namnas: etylenglykol, dietylenglykol, propan-, butan- och hexandiol, trimetylolpropan, pentaerytritol, butanol och tetrahydrofurfurylalkohol. Examples of suitable alcohols are: ethylene glycol, diethylene glycol, propane, butane and hexanediol, trimethylolpropane, pentaerythritol, butanol and tetrahydrofurfuryl alcohol.

Enligt uppfinningen kan man med fordel stabilisera exempelvis aven lufttorkande formmassor, vilka fOrutom radikalerna av a,p-omattade dikarbonsyror innehalla fi,y-omattade eterradikaler, varvid det kan vara fraga om bestandsdelar i polyestern, exempelvis enligt den tyska patentskriften 1 024 654, eller om en bestandsdel i andra blandningskomponenter, exempelvis enligt den tyska patentskriften 1 067 210 och 1 081 222, eller om omattade polyestrar, sem innehalla eventuellt inkondenserade tertiara aromatiska aminer enligt den tyska patentskriften 919 431. According to the invention, it is advantageous to stabilize, for example, air-drying molding compositions which, in addition to the radicals of α, β-unsaturated dicarboxylic acids, contain free-γ-unsaturated ether radicals, which may be constituents of the polyester, for example according to German Patent Specification 1,024,654, or on a constituent of other blending components, for example according to German Pat. Nos. 1,067,210 and 1,081,222, or on unsaturated polyesters containing optionally uncondensed tertiary aromatic amines according to German Pat. No. 919,431.

Med sampolymeriserbara monomera foreningar skall forstas de Mom polyesterhartstekniken sadvanliga omattade sampolymeriserbara foreningarna med eventuellt i a-stallning substituerade vinylgrupper eller i p-stallning sub stituerade allylgrupper, t. ex. styren, vinyltoluen, divinylbensen, vinylacetat, akrylsyra och dess estrar, akrylnitril, metakrylsyra och dess motsvarande derivat saval som allylestrar, t. ex. allylacetat, allylakrylat, ftalsyradiallylester, triallylfosfat och triallylcyanurat. By copolymerizable monomeric compounds is meant the conventional polyester resin technique of the unsaturated copolymerizable compounds with optionally substituted in the α-position vinyl groups or in the position-substituted allyl groups, e.g. styrene, vinyltoluene, divinylbenzene, vinyl acetate, acrylic acid and its esters, acrylonitrile, methacrylic acid and its corresponding derivatives saval as allyl esters, e.g. allyl acetate, allyl acrylate, phthalic acid diallyl ester, triallyl phosphate and triallyl cyanurate.

De med anvandning av kopparforeningarna enligt uppfinningen stabiliserade polyesterformmas sorna kunna i ovrigt aven dessutom innehalla andra vanliga inhibitorer. The polyester molding compositions stabilized by the use of the copper compounds according to the invention may also also contain other common inhibitors.

Uppfinningen askadliggores narmare medelst foljande exempel, van i temperaturangivelserna avse Celsiusgrader. The invention is further illustrated by the following examples, used in the temperature indications for degrees Celsius.

Exempel 1. En genom kondensation av 152 viktdelar maleinsyraanhydrid, 141 viktdelar ftalsyraanhydrid och 195 viktdelar propandio1-1,2 framstalld, med 0,045 viktdelar hydrokinon forsatt omattad polyester med syratalet 47 loses i styren till en 65 %-ig losning. Olika prover av den erhallna polyesterformmassan forses med en kopparhalt om 2 delar per miljon genom tillsats av koppar(II)-naftenat (prov A) resp. enligt uppfinningen genom tillsats av [CuCl P(0C21-1)3] (prov B). Egenskaperna av de erhallna formmassorna anges i foljande tabell I tillsammans med egenskaperna av den ursprungliga polyesterformmassan (prov C), som icke innehaller flagon koppar. Example 1. A polyhydric anhydride, 141 parts by weight of phthalic anhydride and 195 parts by weight of propanediol-1-1.2 prepared by condensation of 152 parts by weight of unsalted polyester with the acid number 47 are dissolved in styrene to a 65% solution. Different samples of the obtained polyester molding compound are provided with a copper content of 2 parts per million by adding copper (II) naphthenate (sample A) resp. according to the invention by adding [CuCl P (OC21-1) 3] (sample B). The properties of the moldings obtained are given in the following Table I together with the properties of the original polyester mold (Sample C), which do not contain flake copper.

Tabell I. Table I.

A Formmassans gronak- farglosfarglos farg*tigt far- gad Lagringsbe40 dagar 40 dagar 12 dagar bestandighet vid 60° * Skikttjocldek 3 cm. A Form mass green-colorless colorless * tightly colored Storage 40 days 40 days 12 days durability at 60 ° * Layer thickness 3 cm.

Exempel 2. En genom kondensation av 882 viktdelar maleinsyraanhydrid, 1332 viktdelar ftalsyraanhydrid, 1098 viktdelar etylenglykol och 963 viktdelar trimetylolpropandiallyleter i narvaro av 0,43 viktdelar hydrokinon framstalld omattad polyester med syratalet 23 loses i styren till en 50 %-ig losning. Olika prover av den erhallna polyesterformmassan ges en kopparhalt av 20 delar per miljon genom tillsats av koppar-(II)- naftenat (prov A) rasp. enligt uppfinningen genom tillsats av [CuBr • P(0061-1)3] (prov B). Egenskaperna hos den erhallna formmassan anges i foljande tabell II tillsammans med egenskaperna av den ursprungliga polyesterformmassan (prov C), som icke innehaller nagon koppar. Example 2. A condensation of 882 parts by weight of maleic anhydride, 1332 parts by weight of phthalic anhydride, 1098 parts by weight of ethylene glycol and 963 parts by weight of trimethylolpropanedial ether in the presence of 0.43 parts by weight of hydroquinone produced by unsaturated polyester with acid number 23 is dissolved in styrene to a 50% solution. Various samples of the resulting polyester molding composition are given a copper content of 20 parts per million by the addition of copper (II) naphthenate (sample A) rasp. according to the invention by adding [CuBr • P (0061-1) 3] (sample B). The properties of the molding composition obtained are given in the following Table II together with the properties of the original polyester molding composition (Sample C), which does not contain any copper.

Tabell II. Table II.

A Formmassans intensivt farglosfarglos farg*gronfar- gad Lagringsb e7,5 dagar 7,5 dagar 2,5 dagar standighet vid 80° * Skikttjocklek 3 cm. A Intensively colorless colorless color of the molding compound * green-colored Storage b e 7.5 days 7.5 days 2.5 days durability at 80 ° * Layer thickness 3 cm.

Exempel 3. Enligt exempel 1 1 den tyska patentskriften 919 431 kondenserar man under vanliga betingelser 73 viktdelar adipinsyra, 98 viktdelar 3 maleinsyraanhydrid, 74 viktdelar ftalsyraanhydrid och 125 viktdelar glykol, tills 50 % av den teoretiska mangden vatten avdestillerat. Darefter tillsatter man 7,5 delar dioxietylanilin och kondenserar vid 200° tills nagot vatten icke langre overdestillerar. Resten av vattnet avdestilleras i vakuum vid 15 mm och 200°. Efter avkylning till 160° tillsatter man 0,25 viktdelar hydrokinon och efter fortsatt avkylning till 110° tillsatter man 140 viktdelar styren. Example 3. According to Example 1 of German Pat. Then add 7.5 parts of dioxyethylaniline and condense at 200 ° until some water no longer over-distills. The rest of the water is distilled off in vacuo at 15 mm and 200 °. After cooling to 160 °, 0.25 parts by weight of hydroquinone are added and after further cooling to 110 °, 140 parts by weight of styrene are added.

Olika prover av den erhallna polyesterformmassan forses med en kopparhalt av 25 delar per miljon genom tillsats av koppar-(H)-naftenat (pray A) resp. enligt uppfinningen genom tillsats av [CuCI P(0C41-19)3] (pray B). Egenskaperna av de erhallna formmassorna anges i tabell III tillsammans med egenskaperna hos den ursprungliga polyesterformmassan (prov C), som joke innehaller nagon koppar. Various samples of the obtained polyester molding composition are provided with a copper content of 25 parts per million by adding copper (H) -naphthenate (pray A) resp. according to the invention by the addition of [CuCl P (OC41-19) 3] (pray B). The properties of the resulting molding compositions are given in Table III together with the properties of the original polyester molding composition (sample C), which joke contains some copper.

Tabell III. Table III.

A Formmassans intensivt svagt gul- svagt gul- faregronfar- aktig aktig gad Lagringsbe- 24 timmar 27 timmar 10 timmar standighet vid 100° * Skikttjacklek 3 cm. A Forming compound intensively faint yellow- faintly yellow- danger- greenish-like-like storage Storage 24 hours 27 hours 10 hours durability at 100 ° * Layer jacket 3 cm.

Claims

Claims: Curable, unsaturated polyester molding compositions, stabilized by a content of copper compounds, characterized in that they, like copper compounds, contain complex compounds of copper (I) chloride and / or copper (I) bromide and neutral phosphoric acid esters. Request publications: