DK153888B - PROCEDURE FOR THE PREPARATION OF THIXOTROPIC SOLUTIONS OF UNSATURED POLYESTER RESIN - Google Patents
PROCEDURE FOR THE PREPARATION OF THIXOTROPIC SOLUTIONS OF UNSATURED POLYESTER RESIN Download PDFInfo
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- DK153888B DK153888B DK125879A DK125879A DK153888B DK 153888 B DK153888 B DK 153888B DK 125879 A DK125879 A DK 125879A DK 125879 A DK125879 A DK 125879A DK 153888 B DK153888 B DK 153888B
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
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Description
DK 153888 BDK 153888 B
Ved fremstilling af emner af forstærkede umættede polyesterharpikser er det i mange tilfælde ønskeligt eller nødvendigt, at de anvendte harpiksopløsninger i deres strømningsforhold udviser en mere eller mindre stærk thixotrop karakter. Derved 5 opnås, at de lag, der er anbragt på lodrette eller skrå flader, ikke løber af. Dette gælder især for lam i nerharpikser og fi η 1agsharpikser (sidstnævnte betegnes også ge1coatharpikser eller topcoatharpikser), som påføres i lagtykkelser mellem 300 og 600 pm. Endvidere anvendes thixotrope harpikser, når der 10 skal opnås bestemte farvevirkninger, således som det er tilfældet ved knapfremst i 11 ing og lignende.In preparing articles of reinforced unsaturated polyester resins, it is in many cases desirable or necessary that the resin solutions used in their flow conditions exhibit a more or less strong thixotropic character. Thereby 5 is achieved that the layers arranged on vertical or inclined surfaces do not run off. This is especially true for lambs in lower resins and five-layer resins (the latter also referred to as gelcoat resins or topcoat resins), which are applied in layer thicknesses between 300 and 600 µm. Furthermore, thixotropic resins are used when certain color effects are to be obtained, as is the case with button advances in 11 and the like.
Thixotroperi ngen af umættede polyesterharpiksopløsninger sker med organiske forbindelser eller med uorganiske fyldstoffer, 15 såsom højdisperse kieselsyrer og lignende mineralske stoffer.The thixotropy of unsaturated polyester resin solutions occurs with organic compounds or with inorganic fillers, such as high-dispersed silica and similar mineral substances.
De nævnte tilsætningsstoffer dispergeres ved hjælp af hurtigtgående blandere, valser, ælteapparater og lignende i opløsningen af polyesterharpiksen i coplymer i serbare monomere, idet der til 1 ami nerharpi ksen anvendes 0,5 til 1,5 vægt-% og til 20 fi η 1agsharpikser 2 til 3 vægt%.The said additives are dispersed by means of fast-moving mixers, rollers, kneading machines and the like in the solution of the polyester resin in copolymer in visible monomers, using 1 to 1 resin, 0.5 to 1.5% by weight, and to 20 µl 1-layer resins 2 to 3% by weight.
De hidtil praktiserede fremgangsmåder, således som de er beskrevet i standardværket af Peter H. Selden "G 1 asfaserver-stårkte Kunsttoffe" Springer Verlag Berling 1967, har dog en 25 række ulemper, som især ved fremstilling af store mængder th·*-xotrope polyesterharpiksopløsninger har både økonomiske cr tekniske følger:However, the methods practiced so far, as described in the standard work of Peter H. Selden "G 1 asphaserver-strengthened Kunsttoffe" Springer Verlag Berling 1967, have, however, a number of disadvantages, particularly in the preparation of large quantities of th · * xotropic polyester resin solutions. has both financial cr technical consequences:
Styrol og lignende monomere, hvori disse polyesterharpikser er 30 opløst udviser på grund af deres vidtgående apolære karakter en dårlig dispergeringsevne for thixotroper ingsmid1 et. For at opnå den ønskede virkning er det derfor nødvendigt at anvende apparater, der udviser en høj dispergeringsydelse eller at anvende større mængder thixotroperingsmiddel.Styrol and similar monomers in which these polyester resins are dissolved exhibit a poor dispersibility of the thixotropic agent because of their wide apolar nature. Therefore, to achieve the desired effect, it is necessary to use apparatus which exhibit a high dispersion performance or to use larger amounts of thixotropic agent.
Den i US patentskrift nr. 3.632.545 beskrevne fremgangsmåde til thixotropering af umættede polyestere, ved hvilken der i opløsningen af harpiksen i den copolymeriserbare monomer udar- 35The process disclosed in U.S. Patent No. 3,632,545 for thixotroping of unsaturated polyesters in which the solution of the resin in the copolymerizable monomer is prepared
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2 bejdes et med diethylenglycol forbehandlet mikrokrystal1insk silikat, kan ikke overvinde denne ulempe. Desuden bliver holdbarsegenskaberne af de deraf fremstillede materialer påvirket negativt af det i polyesteren tilbageblevne polære disperge-5 ringsmiddel.Det samme gælder for den i tysk offentliggørelsesskrift nr. 2,622.913 beskrevne fremgangsmåde, ved hvilken po-lyesterharpiksopløsningen blandes med en asbest, der er oplukket med en vandig sæbeopløsning eller med en organisk væske, såsom toluen eller styren. Også denne oplukning sker i nærvæ-10 relse af polære dispergeringsmi dier.2, a microcrystalline silicate pretreated with diethylene glycol cannot overcome this disadvantage. In addition, the retaining properties of the resulting materials are adversely affected by the polar dispersant remaining in the polyester. The same is true of the method disclosed in German Publication No. 2,622,913 in which the polyester resin solution is mixed with an asbestos which is sealed with an asbestos. aqueous soap solution or with an organic liquid such as toluene or styrene. This opening up also occurs in the presence of polar dispersants.
US patentskrift nr. 4.081.496 beskriver ligeledes en fremgangsmåde, ved hvilken thixotroperingsmidlet indføres sammen med den reaktionsdygtige monomere i polyesterharpiksen ved 15 hjælp af et befugtningsmiddelU.S. Patent No. 4,081,496 also discloses a method by which the thixotroping agent is introduced together with the reactive monomer into the polyester resin by a wetting agent
For det andet må der ved den hidtil sædvanligt anvendte metode til indarbejdning af thixotroperingsmidlet i polyesterharpiks-opløsningen manipuleres store harpiksmængder, hvilket er en u-20 lempe både af økonomiske grunde og af arbejdshygiejniske grunde på grund af de monomere, som fordamper, og det nødvendiggør ligeledes komplicerede apparatur.Secondly, in the hitherto commonly used method of incorporating the thixotroping agent into the polyester resin solution, large amounts of resin must be manipulated, which is a disadvantage both for economic and occupational hygiene reasons due to the monomers which evaporate and necessitate likewise complicated apparatus.
En yderligere ulempe ved den sædvanlige fremgangsmåde ligger i 25 den varmebe1astning, som polyesterharpiksen udsættes for ved indarbejdning af thixotroperingsmidler. Derved skades som bekendt lagerstabiliteten af denne harpiksopløsm'ng væsentligt.A further disadvantage of the conventional method lies in the heat load to which the polyester resin is exposed by incorporation of thixotroping agents. Thus, as is well known, the storage stability of this resin solution is significantly damaged.
Det er den foreliggende opfindelses opgave at undgå de nævnte 30 ulemper og dermed at fremstille også store mængder thixotrope opløsninger af umættede polyesterharpikser, således som de anvendes til fremst i’1 ing af laminater og finlag. Anvende 1 sesområder for finlagsharpikser er f.eks. bådebygn i ng, f remst i 11 i ng af facadeplader, indre belægning af beholdere og bygning af 35 anlæg, især hvor der kræves kemisk holdbarhed.It is the object of the present invention to avoid the above-mentioned drawbacks and thus to also produce large amounts of thixotropic solutions of unsaturated polyester resins, as they are used primarily in laminates and fine layers. Use 1 viewing areas for fine-layer resins are e.g. boat building in ng, removed in 11 in of facade panels, interior coating of containers and building of 35 plants, especially where chemical durability is required.
Denne opgave løses ved, at man indarbejder thixotroperingsmidlet allerede under fremstillingen af polyesterharpiksen, nem-This task is solved by incorporating the thixotroping agent already during the manufacture of the polyester resin, easily
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3 lig ved anvendelse af en koncentreret pasta af thixotrope-ringsmidlet i et eller flere af de anvendte flydende eller let smeltelige råstoffer, der benyttes til harpiksfremstillingen.3 equals the use of a concentrated paste of the thixotroping agent in one or more of the liquid or easily digestible raw materials used for the resin preparation.
Til dette formål kan der især anvendes forskellige glycoler på 5 grund af deres polaritet og gunstige dispergeringsegenskaber.In particular, various glycols can be used for this purpose because of their polarity and favorable dispersion properties.
Den foreliggende fremgangsmåde til fremstilling af thixotrope opløsninger af umættede polyesterharpikser i copolymer i serbare monomere er ejendommelig ved, at man fremstiller en pasta af 10 et thixotroperingsmiddel ved dispergering af 3-30 vægtdele af et temperaturbestandigt thixotroperingsmiddel i 70-97 vægtdele at et eller flere af de flydende eller ved smeltning flydende-gjorte udgangsmater i a 1 er, der anvendes til fremstillingen af polyesterharpiksen, og tilsætter denne pasta i en mængde, der 15 medfører den ønskede thixotropi af polyesterharpiksopløsningen, til udgangsmaterialerne til dannelse af den umættede polyesterharpiks, hvorefter der forestres, og hvorpå den copolyme-riserbare monomer tilsættes.The present process for preparing thixotropic solutions of unsaturated polyester resins in copolymer in visible monomers is characterized by preparing a paste of a thixotropic agent by dispersing from 3 to 30 parts by weight of a temperature resistant thixotroping agent in 70-97 parts by weight. the liquid or melt-liquefied starting materials ia 1 are used in the preparation of the polyester resin and adding this paste in an amount which results in the desired thixotropy of the polyester resin solution to the starting materials to form the unsaturated polyester resin and then esterifying it; and to which the copolymerizable monomer is added.
20 Det er klart, at fremgangsmåden ifølge opfindelsen kun er anvendelig ved anvendelse af thixotroperingsmidler, der ikke ændres kemisk, selv ved temperaturer på 150-250°C. Denne egenskab opfyldes af de for det meste anvendte uorganiske thioxo-troperingsmidler. Også organiske stoffer tåler denne tempera-25 tur i mange tilfælde uden viaere, hvis de foreligger i en smelte og/eller opløsning, således som dette er tilfældet ved harpiks fremstillingen.It is to be understood that the process of the invention is only applicable to the use of thixotropic agents which do not change chemically, even at temperatures of 150-250 ° C. This property is met by the mostly inorganic thioxo-tropic agents used. Also, in many instances, organic matter can withstand this temperature without passing, if present in a melt and / or solution, as is the case in the resin preparation.
Fortrinsvis anvendes uorganiske thixotroperingsmiIder, såsom 30 pyrogene eller fældede syntetiske kolloide kieselsyrer, bento-niter, bestemte kaolintyper, modificerede asbesttyper eller smekt i t typer.Preferably, inorganic thixotroping agents such as 30 pyrogenic or precipitated synthetic colloidal silicas, bentonites, particular kaolin types, modified asbestos types, or smear in t types are used.
Umættede po1yesterharpikser fremstilles i almindelighed ved 35 polyforestring af polycarbonsyrer eller polycarbonsyreanhydri -der med polyoler, i almindelighed glycoler, idet der eventuelt også kan medanvendes monofunktionelle syrer eller alkoholen.Unsaturated polyester resins are generally prepared by polyesterification of polycarboxylic acids or polycarboxylic anhydrides with polyols, generally glycols, optionally monofunctional acids or the alcohol may also be used.
En af polyesterens bestanddele er ethylenisk umættet, i almin-One of the constituents of the polyester is ethylenically unsaturated, generally
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4 delighed polycarbonsyren. Typisk umættede polyesterharpikser fremstilles af dicarbonsyrer, såsom phthalsyre, phthalsyrean-hydrid, adipinsyre, ravsyre, tetrahydrophthalsyre eller -anhy-drid, tetrabromphthalsyre eller -anhydrid, maleinsyre eller 5 -anhydrid eller fumarsyre. Eksempler på typiske glycoler er ethylenglycol, propylenglycol, butylenglycol, neopentylglycol, diethylenglycol, dipropylenglycol, polyethylenglycol og poly-propylenglycol eller diol-diethere af diphenoler, f.eks. bis-phenol A. Lejlighedsvis anvendes til fremstilling af polyeste-10 ren også trivalente eller højere polyoler, såsom trimethylol-ethan, trimethylolpropan eller pentaerythriol. I almindelighed benyttes et ringe støkiometrisk glycoloverskud til fremstillingen af den umættede polyester.4 parts polycarboxylic acid. Typically unsaturated polyester resins are prepared from dicarboxylic acids such as phthalic acid, phthalic anhydride, adipic acid, succinic acid, tetrahydrophthalic acid or anhydride, tetrabromophthalic acid or anhydride, maleic acid or 5-anhydride or fumaric acid. Examples of typical glycols are ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol or diol dieters of diphenols, e.g. bis-phenol A. Occasionally, for the production of the polyester, trivalent or higher polyols such as trimethylol-ethane, trimethylolpropane or pentaerythriol are also used. Generally, a small stoichiometric glycol excess is used to prepare the unsaturated polyester.
15 Forestringen sker ved azeotropmetoden eller smeltekondensationsmetoden. Efter færdigfremst i 11 i ng sættes harpiksen for det meste til inhibitorholdige copolymeri serbare monomere, i -det man' lader harpikssmelten flyde til, og idet der omhyggeligt må sørges for, at en maksimal temperatur overholdes.The esterification occurs by the azeotrope method or the melt condensation method. After completion in 11 µg, the resin is mostly added to inhibitor-containing copolymerizable monomers, in which the resin melt is allowed to flow and care must be taken to ensure that a maximum temperature is observed.
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Som dispergeringsmedium til fremgangsmåden ifølge opfindelsen kan anvendes alle flydende råstoffer, som benyttes ved polyesterfremstilling. Desuden kan med ringe teknisk besvær også anvendes de faste råstoffer, hvis smeltepunkt ikke ligger for 25 højt, til fremstilling af thixotroperingsmiddelpastaen. Af disse råstoffer, fortrinsvis de flydende eller let smeltelige glycoler, fremstilles en thixotroperingsmiddelpasta, der indeholder 3-30 vægt% af thixotroperingsmidlet. Denne pasta sættes til reaktionsmaterialet i et omfang svarende til det tilstræb-30 te indhold af thixotroperingsmiddel i slutproduktet. Fremstillingen polyesterharpiksen sker så i nærværelse af thixotroperingsmidlet på sædvanlig måde. Overraskende opstår der ingen aflejringer på reaktorvæggene ved denne fremgangsmåde, uagtet der på grund af de høje temperaturer {indtil 280°C) også kunne 35 være sket afblanding og dermed aflejring af thixotroperingsmiddel. Rensningen af reaktoren eller opløsningsmiddelbeholderen bereder derfor heller ingen vanske 1 igheder. ner sker heller ingen misfarvning af produktet.As a dispersing medium for the process according to the invention, all liquid raw materials used in polyester production can be used. In addition, with little technical difficulty, the solid raw materials, the melting point of which is not too high, can also be used to make the thixotropic paste. Of these raw materials, preferably the liquid or easily digestible glycols, a thixotropic paste containing 3 to 30% by weight of the thixotropic agent is prepared. This paste is added to the reaction material to an extent corresponding to the desired thixotroping agent content in the final product. The polyester resin preparation is then carried out in the presence of the thixotroping agent in the usual manner. Surprisingly, no deposits on the reactor walls occur in this process, despite the fact that due to the high temperatures (up to 280 ° C), mixing and thus deposition of thixotroping agent could have occurred. The purification of the reactor or the solvent tank therefore does not produce any problems. nor does it discolor the product.
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Dispergeringen af thixotroperingsmidlet sker meget let, hvorved det er muligt at anvende mindre komplicerede apparater, f.eks. også hurtigtløbende propelrøreværker. Ved fremgangsmåden ifølge opfindelsen anvendes som befugtnings- og opløs-5 ningsmidler for thixotroperingspastaen sådanne produkter, som indgår som råstoffer til den påfølgende syntese af den umættede polyesterharpiks. Under syntesen sker der en yderligere homogenisering af thixotroperingsmidlet i den opstående harpiks, hvorved virkningen forøges yderligere. Dispergeringsprocessen 10 sker altså i en enkelt arbejdsgang, de fremkomne mængder er meget.mindre, hvilket betyder et væsentligt mindre brug af tid og apparatur. Mængden af massen, som skal forarbejdes, ligger i næsten alle tilfælde under 10% af den mængde, som måtte gå igennem apparaterne ved den sædvanlige fremgangsmåde.The dispersion of the thixotroping agent is very easy, making it possible to use less complicated apparatus, e.g. also fast-running propeller stirrers. In the process of the invention, as wetting and solvents for the thixotroping paste, such products are used as raw materials for the subsequent synthesis of the unsaturated polyester resin. During the synthesis, a further homogenization of the thixotroping agent occurs in the resin which rises, thereby further increasing the effect. Thus, the dispersion process 10 takes place in a single operation, the quantities obtained are very small, which means a significantly less use of time and apparatus. The amount of pulp to be processed is in almost all cases less than 10% of the amount which may pass through the apparatus by the usual process.
15 0 ispergeri ngen sker i fravær af de toksiske og forholdsvis flygtige monomere, hvorved der kan spares komplicerede beskyttelsesindretninger. Ligeledes er den ved dispergeringen eventuelt optrædende varme uden indflydelse på slutproduktet. Pa-20 staerne kan naturligvis også lagres i længere tid og med mindre hensyntagen til omgivelsernes temperatur end det ville være muligt med en pasta på basis af en polyesterharpiksopløs-ning i monomer.15 0 ispergerisation occurs in the absence of the toxic and relatively volatile monomers, thereby saving complicated protective devices. Likewise, the heat generated by the dispersion may be unaffected by the final product. Of course, the pastes can also be stored for a longer time and with less regard for the ambient temperature than would be possible with a paste based on a polyester resin solution in monomer.
25 Overraskende opnås som en yderligere virkning, især ved anvendelse af højdispers kieselsyre, en forkortelse af reaktionstiden på indtil 50%, hvilket igen fører til en bedre udnyttelse af reaktorkapaciteten.Surprisingly, as a further effect, especially when using high-dispersion silica, a shortening of the reaction time of up to 50% is achieved, which in turn leads to better utilization of the reactor capacity.
30 I kraft af den gode og ensartede oplukning af thixotroperingsmidlet i det polære dispergeringsmedium kan der i det færdige produkt iagttages en væsentlig forøgelse af ensartetheden af thixotroperingsstyrken. I kraft af den store dispersitet kan mængden af thixotroperingsmidlet, som kræves for at opnå en 35 bestemt virkning, også i mange tilfælde nedsættes, hvilket i-gen giver en forbedring af emnernes kemiske modstandsdygtighed og holdbarhed over for vejrliget. Denne virkning kunne heller ikke forudses af fagmanden, da man snarere skulle antage, atDue to the good and uniform absorption of the thixotroping agent in the polar dispersing medium, a substantial increase in the uniformity of the thixotropic strength can be observed in the finished product. Due to the large dispersion, the amount of thixotroping agent required to achieve a particular effect can also be reduced in many cases, which in turn provides an improvement in the chemical resistance and durability of the articles. This effect could also not be foreseen by one of ordinary skill in the art, since one would rather assume that
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6 der kunne optræde forstyrrelser i thixotroperingsforholdene som følge af det ved forestringen opståede reaktionsvand på grund af vandets udprægede evne til dannelse af H-broer.6 which could cause disturbances in the thixotroping conditions due to the reaction water that occurred during the esterification due to the water's pronounced ability to form H bridges.
5 Da den færdige polyesterharpiksopløsning desuden ikke er udsat for nogen yderligere termisk belastning, forøges slutproduktets lagerstabilitet.Furthermore, since the finished polyester resin solution is not subjected to any additional thermal loading, the storage stability of the final product is increased.
Da. f.eks. glycol pastaer ved samme mængde thixotroperingsmid-10 del er væsentligt mere lavviskose end tilsvarende pastaer på basis af polyesterharpiksopløsninger, kan de ved fremgangsmåden ifølge opfindelsen anvendte pastaer benyttes væsentligt mere koncentrerede. På den anden side er indstilling af en konstant pastaviskositet væsentligt simplere, hvilket sparer 15 omstillingstid til dispergeringsmaskiner med tvangsgennemløb (kolloidmøller, ultraturrax, ultralyddispergatorer).As. eg. glycol pastes at the same amount of thixotroping agent are substantially more viscous than similar pastes based on polyester resin solutions, the pastes used in the process of the invention can be used significantly more concentrated. On the other hand, setting a constant paste viscosity is significantly simpler, saving 15 conversion time for forced-flow dispersers (colloid mills, ultraturrax, ultrasonic dispersers).
Ved anvendelse af faste polyesterråstoffer til dispergering af thixotroperingsmidlet arbejdes i en smelte. Lagringen af "thi-20 xotroperingspastaen" sker så fortrinsvis i brudt tilstand, hvorved fyldning af reaktoren forenkles.Using solid polyester raw materials to disperse the thixotroping agent is worked in a melt. The "thi-20 xotroping paste" is then stored preferably in a broken state, thereby simplifying filling of the reactor.
De følgende eksempler tjener til nærmere belysning af opfindelsen .The following examples serve to illustrate the invention.
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Fremstilling af thixotroperingspastaer Pasta APreparation of Thixotroping Pasta Pasta A
30 I 220 g propylenglycol dispergeres ved hjælp af et tandskive-røreværk (dissolver) 55 g af en højdispers syntetisk kieselsy-re med en specifik overflade ifølge BET på 380 ± 30 m2 pr. g, en middelstørrelse af primærpartiklerne på 4 nm og et Si02~ indhold på 99,8%.In 220 g of propylene glycol, 55 g of a high-dispersed synthetic silica with a specific surface area according to BET of 380 ± 30 m2 per dispersion is dispersed by means of a dental disc stirrer (dissolver). g, an average size of the primary particles of 4 nm and a SiO 2 content of 99.8%.
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Pasta BPasta B.
En propylenglycolpasta med samme sammensætning som pasta A fremstilles i et sædvanligt hurtigtgående propelrøreværk (om-5 drejningstal 2000-2500 omdrejninger pr. minut).A propylene glycol paste of the same composition as paste A is produced in a conventional fast-moving propeller stirrer (about 5 rpm 2000-2500 rpm).
Pasta CPasta C
164 g neopentylglycol smeltes ved ca. 120°C og dispergeres i 10 et tandskiverøreværk med 36 g af et thixotroperingsmiddel på basis af en oplukket Chrysoti 1 asbest med en specifik overflade BET på ca. 50 m2 pr. g og hovedbestanddelene Si02 (44%) og MgO (38%). Thixotroperingsmiddelmængden i pastaen er 18 vægt%.164 g of neopentyl glycol are melted at approx. 120 ° C and dispersed in a dental disc stirrer with 36 g of a thixotropic agent on the basis of an opaque Chrysoti 1 asbestos with a specific surface BET of approx. 50 m2 per g and the major constituents SiO 2 (44%) and MgO (38%). The amount of thixotroping agent in the paste is 18% by weight.
15 På samme måde kan også anvendes f.eks. TCD-alkohol D (ved mindst 50-60°C) eller propylenglycoldietheren af bisphenol A (ved mindst 70-90°C). (TCD-alkohol D = tricyklodecandiol).Similarly, e.g. TCD alcohol D (at least 50-60 ° C) or the propylene glycol diether of bisphenol A (at least 70-90 ° C). (TCD alcohol D = tricyclodecanediol).
Eksempel 1 20 a) Thixotropering ifølge kendt teknik (1aminerharpikstype) 143 g propylenglycol (1,88 mol) forestres med 118,5 g phthal-syreanhydrid (0,8 mol) og 98 g maleinsyreanhydrid (1 mol) på 25 sædvanlig måde ved azeotropmetoden til et syretal på 40-45 mg KOH pr. g. Harpiksen fortyndes med styren til et indhold af fast stof på 60% og stabiliseres med 85 ppm hydrochinon.Example 1 a) Thixotroping of the prior art (1 amine resin type) 143 g of propylene glycol (1.88 mole) is esterified with 118.5 g of phthalic anhydride (0.8 mole) and 98 g of maleic anhydride (1 mole) in the usual manner by the azeotrope method. to an acid number of 40-45 mg KOH per day. g. The resin is diluted with styrene to a solids content of 60% and stabilized with 85 ppm hydroquinone.
Derefter dispergeres i harpiksopløsningen 1 vægt% af den i pa-30 sta A anvendte højdisperse kieselsyre ved hjælp af et tandskiverøreværk .Then, in the resin solution, 1% by weight of the high-dispersed silica used in step A is dispersed by means of a dental disc stirrer.
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Fremgangsmåde ifølge opfindelsen b) Thixotropering med pasta AProcess according to the invention b) Thixotroping with paste A
5 Analogt med 1 a) fremstilles en umættet polyesterharpiks, idet der i stedet for den der anførte propylenglycol anvendes en blanding af 27,5 g pasta A (0,29 mol propylenglycol) og 121 g propylenglycol (1,59 mol).Analogously to 1 a), an unsaturated polyester resin is prepared, using a mixture of 27.5 g of paste A (0.29 mol of propylene glycol) and 121 g of propylene glycol (1.59 mol) instead of the aforementioned propylene glycol.
10 c) Thixotropering med pasta BC) Thixotroping with paste B
Der gås frem som under punkt 1 b), men i stedet for pasta A anvendes den samme mængde pasta B.Proceed as under point 1 (b), but instead of paste A, the same amount of paste B. is used.
15 Dataene for de forskellige forsøg er sammenfattet i tabel 1.15 The data for the different experiments are summarized in Table 1.
Eksempel 2 a) Thixotropering ifølge kendt teknik (finlagsharpikstype) 20 135,4 g neopentylglycol (1,3 mol) forestres med 99,7 g iso-phthalsyre (0,6 mol) og 58,8 g maleinsyreanhydrid (0,6 mol) på sædvanlig måde ved azeotropmetoden til et syretal på 15-20 mg Κ0Η pr. g. Harpiksen fortyndes med styren til et indhold af 25 fast stof på 60% og inhiberes med 500 ppm hydrochinon. Harpiksopløsningen bliver i en dissolver forarbejdet med 3 vægt% (beregnet på harpiksopløsningen) af det i pasta C anvendte thixotroperingsmiddel.Example 2 (a) Thixotroping of Prior Art (Fine Layer Resin Type) 135.4 g of neopentyl glycol (1.3 mole) is esterified with 99.7 g of isophthalic acid (0.6 mole) and 58.8 g of maleic anhydride (0.6 mole) in the usual way by the azeotrope method to an acid number of 15-20 mg Κ0Η per g. The resin is diluted with styrene to a content of 25% solids and inhibited with 500 ppm hydroquinone. The resin solution is processed in a dissolver at 3% by weight (based on the resin solution) of the thixotropic agent used in paste C.
30 b) Thixotropering ved fremgangsmåden ifølge opfindelsen 62 g pasta C (0,5 mol neopentylglycol), 83,4 g neopentylglycol (0,8 mol), 99,7 g isophthalsyre (0,6 mol) og 58,8 g maleinsyreanhydrid (0,6 mol) forestres i overensstemmelse med 2 35 a), opløses i styren og inhiberes.B) Thixotroping by the method of the invention 62 g of paste C (0.5 mole of neopentyl glycol), 83.4 g of neopentyl glycol (0.8 mole), 99.7 g of isophthalic acid (0.6 mole) and 58.8 g of maleic anhydride ( 0.6 mol) is esterified in accordance with 2 a), dissolved in styrene and inhibited.
Mængden af thixotroperingsmiddel er 2,6 vægt% beregnet på harpiksopløsningen.The amount of thixotroping agent is 2.6% by weight based on the resin solution.
DK 153888 BDK 153888 B
99
Dataene er sammenfattet i tabel 1.The data are summarized in Table 1.
5 10 15 20 25 30 355 10 15 20 25 30 35
,0 DK 153888 B, 0 DK 153888 B
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XX
LULU
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT294578 | 1978-04-25 | ||
| AT294578A AT353011B (en) | 1978-04-25 | 1978-04-25 | PROCESS FOR PRODUCING THIXOTROPIC SOLUTIONS OF UNSATATURATED POLYESTER RESIN SOLUTIONS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK125879A DK125879A (en) | 1979-10-26 |
| DK153888B true DK153888B (en) | 1988-09-19 |
| DK153888C DK153888C (en) | 1989-01-30 |
Family
ID=3542826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK125879A DK153888C (en) | 1978-04-25 | 1979-03-28 | PROCEDURE FOR THE PREPARATION OF THIXOTROPIC SOLUTIONS OF UNSATURED POLYESTER RESIN |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0004869B1 (en) |
| AT (1) | AT353011B (en) |
| DE (1) | DE2963391D1 (en) |
| DK (1) | DK153888C (en) |
| HU (1) | HU180545B (en) |
| PL (1) | PL115742B1 (en) |
| YU (1) | YU95979A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632545A (en) * | 1969-05-13 | 1972-01-04 | Fmc Corp | Thixotropic agents for liquid resin systems |
| DE2622913A1 (en) * | 1975-05-21 | 1976-12-09 | British Industrial Plastics | HEAT-RESIN COMPOSITES WITH A RESIN-LIKE MATERIAL BASED ON UNSATED POLYESTER |
| US4081496A (en) * | 1977-06-27 | 1978-03-28 | N L Industries, Inc. | Thixotropic polyester compositions containing an organophilic clay gellant |
-
1978
- 1978-04-25 AT AT294578A patent/AT353011B/en not_active IP Right Cessation
-
1979
- 1979-03-15 EP EP19790100783 patent/EP0004869B1/en not_active Expired
- 1979-03-15 DE DE7979100783T patent/DE2963391D1/en not_active Expired
- 1979-03-28 DK DK125879A patent/DK153888C/en active
- 1979-04-23 HU HUVI001245 patent/HU180545B/en unknown
- 1979-04-23 YU YU95979A patent/YU95979A/en unknown
- 1979-04-23 PL PL21509779A patent/PL115742B1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632545A (en) * | 1969-05-13 | 1972-01-04 | Fmc Corp | Thixotropic agents for liquid resin systems |
| DE2622913A1 (en) * | 1975-05-21 | 1976-12-09 | British Industrial Plastics | HEAT-RESIN COMPOSITES WITH A RESIN-LIKE MATERIAL BASED ON UNSATED POLYESTER |
| US4081496A (en) * | 1977-06-27 | 1978-03-28 | N L Industries, Inc. | Thixotropic polyester compositions containing an organophilic clay gellant |
Also Published As
| Publication number | Publication date |
|---|---|
| AT353011B (en) | 1979-10-25 |
| DK125879A (en) | 1979-10-26 |
| EP0004869A1 (en) | 1979-10-31 |
| PL115742B1 (en) | 1981-04-30 |
| DK153888C (en) | 1989-01-30 |
| EP0004869B1 (en) | 1982-07-28 |
| YU95979A (en) | 1982-10-31 |
| HU180545B (en) | 1983-03-28 |
| ATA294578A (en) | 1979-03-15 |
| PL215097A1 (en) | 1980-02-25 |
| DE2963391D1 (en) | 1982-09-16 |
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