DK155435B - WATER-I RESIN EMULSION BASED ON A THERMOUS POLYESTER TO USE IN THE PREPARATION OF CONCRETE REPLACEMENT PRODUCTS BASED ON A HYDRAULIC BINDING AGENT - Google Patents
WATER-I RESIN EMULSION BASED ON A THERMOUS POLYESTER TO USE IN THE PREPARATION OF CONCRETE REPLACEMENT PRODUCTS BASED ON A HYDRAULIC BINDING AGENT Download PDFInfo
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Den foreliggende opfindelse angår vand-i-harpiks-emulsion på basis af en thermohærdende polyester til brug ved fremstillingen af betonerstatningsprodukter baseret på et hydraulisk bindemiddel, hvilken emulsion opnås ved at blande vand med en blanding, der i det 5 væsentlige består af en umættet polyesterharpiks og en umættet monomer. En sådan emulsion kan anvendes til fremstilling af hærde-lige blandinger indeholdende et afbindingsmiddel, som afbinder ved hydrati sering, f.eks. brændt gips og Portland cement.The present invention relates to water-in-resin emulsion based on a thermosetting polyester for use in the manufacture of concrete replacement products based on a hydraulic binder, which emulsion is obtained by mixing water with a mixture consisting essentially of an unsaturated polyester resin and an unsaturated monomer. Such an emulsion can be used to prepare hardenable compositions containing a debonding agent which is bound by hydration, e.g. roasted plaster and Portland cement.
10 Beton hidrørende fra Portland cement er gennem mange år blevet anvendt i bygningsindustrien. Betons anvendelighed i denne industri skyldes dets høje trykstyrke. Imidlertid har den meget lav trækstyrke og bøjningsstyrke og er også modtagelig for syreangreb. På grund af hulrummene i betonen er den også tilbøjelig til at smuldre, 15 når den udsættes for frysning/optøning.10 Concrete derived from Portland cement has been used in the building industry for many years. The usefulness of concrete in this industry is due to its high compressive strength. However, it has very low tensile and bending strength and is also susceptible to acid attack. Due to the cavities in the concrete, it is also prone to crumbling when exposed to freezing / thawing.
I forsøg på at forbedre betons egenskaber og derved udstrække dets anvendelsesområde er der blevet inkorporeret forskellige harpikser i beton på en række måder. Således har man f.eks. blandet emulsioner 20 af termoplasti ske polymerer i betonmaterialet under blanding, eller, hvis betonmaterialet har en struktur med tilstrækkelig porøsitet i afbundet tilstand, har man imprægneret den afbundne beton med den termoplasti ske polymer. Disse sammensætninger har forbedret betonegenskaberne ved normale omgivelsestemperaturer. Når de udsættes for 25 særligt høje temperaturer som ved brand, smelter de imidlertid og mister følgelig deres styrke. Derfor har disse materialer ikke vundet almindelig udbredelse inden for bygni'ngsindustrien.In trying to improve the properties of concrete and thereby extend its scope, various resins have been incorporated in concrete in a number of ways. Thus, e.g. mixed emulsions 20 of thermoplastic polymers in the concrete material during mixing, or, if the concrete material has a structure with sufficient porosity in the bound state, the bound concrete has been impregnated with the thermoplastic polymer. These compositions have improved the concrete properties at normal ambient temperatures. However, when exposed to 25 particularly high temperatures such as fire, they melt and consequently lose their strength. Therefore, these materials have not gained widespread use in the construction industry.
Forbedrede egenskaber ville opnås for en betonsammensætning, som 30 omfattede en termohærdende harpiks i stedet for en termoplastisk harpiks som følge af, at en termohærdende harpiks ikke smelter. Der er blevet gjort forskellige forsøg på at inkorporere termohærdende harpikser eller mere præcist tværbundne harpikser i betonsammensætninger. Således angår beskrivelsen til australsk patent nr. 426.171 35 en tør cementsammensætning indeholdende en hydraulisk cement, et polyvalent metalsalt af en vand-redispergerbar additionspolymer indeholdende enheder hidrørende fra en a/TJ-monoethylenisk umættet carboxyl syremonomer, et kompleksdannelsesmiddel og en trimethylolal-kan. Tilsætning af vand til den tørre blandingImproved properties would be obtained for a concrete composition which included a thermosetting resin instead of a thermoplastic resin due to a thermosetting resin not melting. Various attempts have been made to incorporate thermosetting resins or, more precisely, crosslinked resins into concrete compositions. Thus, the specification of Australian Patent No. 426,171 35 relates to a dry cement composition containing a hydraulic cement, a polyvalent metal salt of a water redispersible addition polymer containing units derived from an α / TJ monoethylenically unsaturated carboxylic acid monomer, a complexing agent and a trimethylol alkane. Adding water to the dry mixture
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2 resulterer i hydrati sering af additionspolymeren og kompleksbinding af de polyvalente metalioner, hvorved en kondensationsreaktion mellem additionspolymeren og trimethylolal kanen får mulighed for at finde sted samtidig med en hydrati sering af cementen.2 results in hydration of the addition polymer and complex bonding of the polyvalent metal ions, thereby allowing a condensation reaction between the addition polymer and the trimethylolal can occur simultaneously with a hydration of the cement.
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Fra beskrivelsen til USA-patent nr. 3.437.619 kendes en tør blanding omfattende en umættet polyesterharpiks, styrenmonomer, Portland cement, en baseaktiveret harpiks-dispergerbar initiator og en virksom mængde af en inhibitor. Ved tilsætning af vand aktiverer de 10 hydroxyl ioner, som leveres af cementen, katalysatoren, som derefter initierer en additionspolymerisationsreaktion mellem den umættede polyester og styrenet. Skønt polyesterharpikstørblåndinger har en fordel fremfor emulsioner i form af reducerede transportomkostninger, udlignes denne fordel hyppigt af prisen på tørringsmidler, 15 hvilket er tilfældet for den sammensætning, som er beskrevet i beskrivelsen til australsk patent nr. 426.171, og problemet med at undgå afbinding under transport og opbevaring resulterende i for tidlig afbinding og deraf følgende spild. Brugen af inhibitorer som beskrevet i beskrivelsen til USA-patent nr. 3.437.619 til hindring 20 af for tidlig afbinding er også en ulempe som følge af, at sådanne kan hindre og ofte forsinke additionspolymerisationen i at forløbe under andet end ideale omstændigheder. Således ville der være fordele at opnå med et system, som omfatter cement, fyldstof og en emulsion dannet ved at blande vand med en tværbi ndelig polymer og et 25 tværbindingsmiddel, hvori vandet til hærdning af cementen leveres af emulsionen, Et sådant system kendes fra beskrivelsen til USA-patent nr. 3.310.511, som beskriver en epoxyharpiksemulsion, som kan inkorporeres i en betonblanding og hærdes af en amin ved hjælp af en kondensationspolymerisationsreaktion. Imidlertid er epoxyharpikser 30 meget dyre, og der opnås således en økonomisk fordel ved at benytte et billigere tværbindel igt system. Umættede polyesterharpikser, som kan tværbindes med en umættet monomer, er blevet anvendt i nogen tid ved fremstillingen af fiberglasforstærkede polyesterharpikser.From the disclosure of U.S. Patent No. 3,437,619, a dry blend comprising an unsaturated polyester resin, styrene monomer, Portland cement, a base-activated resin dispersible initiator and an effective amount of an inhibitor is known. Upon addition of water, the 10 hydroxyl ions supplied by the cement activate the catalyst, which then initiates an addition polymerization reaction between the unsaturated polyester and the styrene. Although polyester resin blends have an advantage over emulsions in the form of reduced transport costs, this advantage is frequently offset by the cost of desiccants, which is the case for the composition disclosed in the Australian Patent Specification No. 426,171 and the problem of avoiding bonding during transport. and storage resulting in premature untying and resulting wastage. The use of inhibitors as described in U.S. Patent No. 3,437,619 to prevent premature unbinding is also a disadvantage as such can prevent and often delay the addition polymerization to proceed under other than ideal circumstances. Thus, there would be advantages to be obtained with a system comprising cement, filler and an emulsion formed by mixing water with a cross-linkable polymer and a cross-linking agent in which the water for curing the cement is supplied by the emulsion. to U.S. Patent No. 3,310,511, which discloses an epoxy resin emulsion which can be incorporated into a concrete mixture and cured by an amine by a condensation polymerization reaction. However, epoxy resins 30 are very expensive, thus obtaining an economic advantage by using a less expensive crosslinkable system. Unsaturated polyester resins which can be crosslinked with an unsaturated monomer have been used for some time in the production of fiberglass reinforced polyester resins.
35 Copolymeriserbare blandinger af en umættet polyester og en umættet monomer anvendes imidlertid ikke normalt som vandige emulsioner.However, copolymerizable mixtures of an unsaturated polyester and an unsaturated monomer are not normally used as aqueous emulsions.
Ikke desto mindre beskriver USA-patent nr. 3.256.219 vand-i-harpiksemulsioner, hvori den vandige fase forbliver dispergeret, selv under og efter additionspolymerisationen af den umættedeNevertheless, U.S. Patent No. 3,256,219 discloses water-in-resin emulsions in which the aqueous phase remains dispersed even during and after the addition polymerization of the unsaturated
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3 polyester med den umættede monomer. På den anden side er der ingen antydning af, at de i denne patentbeskrivelse omhandlede emulsioner forbliver stabile efter tilsætning af et afbindingsmiddel, som størkner ved hydrati sering.3 polyester with the unsaturated monomer. On the other hand, there is no suggestion that the emulsions referred to in this patent description remain stable after the addition of a dehydrating agent which solidifies by hydration.
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Beskrivelsen til italiensk patent nr. 585.721 omhandler polyesterharpikser indeholdende et fyldstof i form af hydraulisk cement.The specification for Italian Patent No. 585,721 discloses polyester resins containing a filler in the form of hydraulic cement.
Sådanne fyldte polyesterharpikser fremstilles ved at frembringe en tør blanding af umættet polyester, umættet monomer, fri 10 radikal initiator, promotor og ikke-ionisk emulgeringsmiddel. De forskellige komponenter tilsættes fortrinsvis en efter en til polyesterharpiksen, idet der foretages en intens og nøjagtig blanding og homogenisering efter hver tilsætning. Vand iblandes til slut i den tørre blanding.Such filled polyester resins are prepared by producing a dry mixture of unsaturated polyester, unsaturated monomer, free radical initiator, promoter and nonionic emulsifier. Preferably, the various components are added one by one to the polyester resin, with intense and accurate mixing and homogenization after each addition. Water is finally mixed into the dry mixture.
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Vandet hydrati serer cementen. Hydrati seringsvarmen fremskynder den additionspolymerisationsreaktion mellem den umættede monomer og den umættede polyester, der initieres af initiatoren, og emulgeringsmidlet letter dispersionen af vand og dermed cement i 20 blandingen. Dette patenskrift beskriver således fremstillingen af en præmix omfattende et fyldstof i form af hydraulisk afbindende cement, en tør blanding af en umættet polyester, en umættet monomer, en fri radikal initiator, en promotor og et ikke-ionisk emulgeringsmiddel, hvortil der afslutningsvis tilsættes vand, hvorved afbin-25 dingen tilvejebringes og det tilstræbte produkt dannes. I dette patentskrift er der således ikke tale om at frembringe en vand- i-harpiks-emulsion, der er ingen forståelse for de fordele, der kan opnås ved anvendelsen af en sådan vand-i-harpiks-emulsion i form af optimale egenskaber hos de produkter, der fremstilles hermed, og der 30 er følgelig heller ingen anvisninger på, hvorledes man frembringer en stabil emulsion af vand i en blanding af umættet polyester og umættet monomer, som forbliver stabil, også efter, at der er tilsat et hydraulisk afbindende bindemiddel, f.eks. i form af cement.The water hydrates the cement. The hydration heat speeds up the addition polymerization reaction between the unsaturated monomer and the unsaturated polyester initiated by the initiator, and the emulsifier facilitates the dispersion of water and thus cement in the mixture. Thus, this patent describes the preparation of a premix comprising a filler in the form of hydraulically bonding cement, a dry blend of an unsaturated polyester, an unsaturated monomer, a free radical initiator, a promoter and a nonionic emulsifier to which water is finally added. thereby providing the unbinding and forming the desired product. Thus, in this patent, it is not a matter of producing a water-in-resin emulsion, which is beyond comprehension of the advantages which can be obtained from the use of such water-in-resin emulsion in the form of optimal properties of the products made therewith, and consequently, there is also no instructions on how to produce a stable emulsion of water in a mixture of unsaturated polyester and unsaturated monomer which remains stable even after the addition of a hydraulically binding binder, eg. in the form of cement.
35 Fra tysk offentliggørerelsesskrift nr. 2.628.718 kendes præfabrikerede byggeelementer (færdigbyggedele) fremstillet ved formgivning af puzzolangranulat-beton. Den benyttede puzzolangranulat-beton fremstilles ved at fremstille:35 From German publication specification No. 2,628,718, prefabricated building elements (finished parts) known from the design of puzzol granular concrete are known. The used pozzolanegranate concrete is prepared by making:
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4 a) en blanding af puzzolangranulat, der befugtes ved neddykning i vand og derpå afvandes, og brændt cement i en mængde på ca. 25 vol umen-% af puzzolanen, og 5 b) en emulsion af polyesterharpiks og vand, hvor vandet udgør 50 vægt-% af polyesterharpiksen, hvortil der afslutningsvis sættes en katalysator og en accelerator, hvorefter blandingen og emulsionen sammenblandes i sådanne mængde-10 forhold, at der for hvert kg puzzolangranulat er i det mindste 70 g polyesterharpiks, og den færdigblandede beton afvandes for overskydende vand og udhældes i forme.4 (a) a mixture of pozzolanegranate, which is wetted by immersion in water and then dewatered, and burnt cement in an amount of approx. 25 vol umen% of the pozzolan and 5 b) an emulsion of polyester resin and water, the water constituting 50% by weight of the polyester resin, to which is finally added a catalyst and an accelerator, after which the mixture and the emulsion are mixed in such proportions. that for every kg of pozzolan granulate there is at least 70 g of polyester resin and the pre-mixed concrete is dewatered for excess water and poured into molds.
I dette tyske patentskrift er der en forståelse for de fordele, der 15 kan opnås ved at benytte en stabil emulsion af polyesterharpiks og vand, som ikke forstyrres ved tilsætningen af mineralske tilsætningsstoffer, idet der herved vil opstå et heterogent produkt. Det anføres, at hvis der benyttes traditionelle tilsætningsstoffer, såsom sten og andre mineralske tilsætningsstoffer, kan den frem-20 bragte emulsion ikke opretholdes uforstyrret, med mindre bestemte blandingsforhold ikke overskrides, hvorved den fremstillede beton imidlertid bliver uforholdsmæssig dyr. Det tyske patentskrift angiver som løsning på dette problem, at der som tilslagsmateriale til betonen kun benyttes puzzolangranulat eller tilsvarende materi -25 aler. Det tyske patentskrift giver således ingen anvisninger på, hvorledes der kan tilvejebringes en stabil emulsion af vand og polyesterharpiks, som forbliver stabil ved tilsætning af et hydraulisk afbindende bindemiddel, og som kan benyttes med tilslag af almindelige, billige tilslagsmaterialer, såsom sten, grus og sand.In this German patent, there is an understanding of the advantages that can be obtained by using a stable emulsion of polyester resin and water which is not disturbed by the addition of mineral additives, thereby creating a heterogeneous product. It is stated that if traditional additives such as stones and other mineral additives are used, the emulsion produced cannot be maintained undisturbed unless certain mixing ratios are not exceeded, however, the concrete produced becomes disproportionately expensive. The German patent specification states as a solution to this problem that only additives for the concrete are used as puzzol granules or similar materials -25 ales. Thus, the German patent does not give directions on how to provide a stable emulsion of water and polyester resin, which remains stable by the addition of a hydraulically bonding binder, and which can be used with the addition of ordinary, low-cost additives, such as stone, gravel and sand. .
30 Det tyske patentskrift giver heller ingen anvisninger på, hvorledes der kan tilvejebringes en emulsion af vand og polyesterharpiks med et sådant vandindhold, at det ved betonblandingens fremstilling netop opfylder behovet for den til hydrati seringen af det benyttede hydraulisk afbindende bindemiddel nødvendige vandmængde, d.v.s. som 35 ikke nødvendiggør, at tilslagsmaterialet skal befugtes forud, eller at den færdigblandede beton skal afvandes inden udhældningen i forme.30 The German patent also does not give instructions on how to provide an emulsion of water and polyester resin with a water content such that, in the preparation of the concrete mixture, it meets precisely the need for the hydration of the hydraulically-binding binder used, i.e. which does not require the aggregate to be wetted in advance or the pre-mixed concrete to be dewatered before pouring into molds.
Den foreliggende opfindelse har til formål at tilvejebringe enThe present invention has for its object to provide one
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5 stabil emulsion af vand og harpiks til brug ved fremstillingen af produkter omfattende et hydraulisk afbindende bindemiddel, hvilken emulsion forbliver stabil ved tilsætning af det hydraulisk afbindende bindemiddel og kan benyttes med tilslag af almindelige 5 tilslagsmaterialer, såsom sten, grus og sand.5 stable emulsion of water and resin for use in the manufacture of products comprising a hydraulically bonding binder, which emulsion remains stable upon addition of the hydraulically bonding binder and may be used with additions of common 5 aggregate materials such as stone, gravel and sand.
Opfindelsen har endvidere til formål at tilvejebringe en stabil emulsion af vand og harpiks, der kan benyttes i stedet for vand ved fremstillingen af sædvanlige betonmaterialer, d.v.s. uden at der til 10 en blanding af cement, grus og/eller sten og sand skal tilsættes ekstra vand eller at materialerne skal befugtes forud, og samtidig uden at der forekommer vandudtrædning, som skal fjernes.The invention further aims to provide a stable emulsion of water and resin which can be used in place of water in the manufacture of conventional concrete materials, i.e. without the addition of a mixture of cement, gravel and / or stone and sand to additional water or the materials to be wetted beforehand, and at the same time without any water withdrawal to be removed.
Endelig har opfindelsen til formål at tilvejebringe en stabil 15 emulsion af vand og harpiks, hvilken emulsion er så stabil, at den kan forsendes, f.eks. i beholdere.Finally, the object of the invention is to provide a stable emulsion of water and resin which is emulsion so stable that it can be dispatched, e.g. in containers.
Disse formål opnås med en vand-i-harpiks-emulsion af den i indledningen til krav 1 omtalte art, hvilken emulsion er ejendommelig ved, 20 1) at polyesterharpiksen har en molekylvægt på fra 3100 til 3600 og er blevet fremstillet ved en polykondensationsreaktion mellem polyhydroxy- og polycarboxylforbindelser eller derivater deraf, hvor kondensationsreaktionen har fået lov til at forløbe, indtil polyes-25 teren har et syretal på ikke over 25, og hvor polyhydroxyforbindel-serne har været til stede i et overskud i forhold til det støkiometrisk krævede, idet mindst én af forbindelserne eller derivaterne er umættet, 30 2) at blandingen af polyesterharpiks og monomer ikke indeholder mere end 30 vægtprocent monomer, og 3) at emulsionen indeholder fra 35 til 60 vægtprocent vand baseret på vægten af emulsionen.These objects are achieved with a water-in-resin emulsion of the kind referred to in the preamble of claim 1, which emulsion is characterized in that the polyester resin has a molecular weight of from 3100 to 3600 and has been prepared by a polycondensation reaction between polyhydroxy and polycarboxyl compounds or derivatives thereof, wherein the condensation reaction has been allowed to proceed until the polyester has an acid number of not more than 25 and the polyhydroxy compounds have been present in excess of the stoichiometric requirement, with at least one of the compounds or derivatives is unsaturated, 2) that the mixture of polyester resin and monomer does not contain more than 30% by weight of monomer, and 3) that the emulsion contains from 35 to 60% by weight of water based on the weight of the emulsion.
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Ved anvendelse af emulsionen blander man emulsionen med et afbindingsmiddel af en type, som afbinder ved hydratisering under dannelse af en hærdelig blanding, sætter en additionspolymerisationsreaktion mellem den umættede polyester og den umættede monomer i gang,Using the emulsion, the emulsion is mixed with a debonding agent of a type which binds by hydration to form a curable mixture, initiating an addition polymerization reaction between the unsaturated polyester and the unsaturated monomer.
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6 og lader den hærdel ige blanding hærde, hvorved der dannes et produkt, hvori der af emulsionen tilvejebringes tilstrækkelig meget vand til at muliggøre, at hydrati seri ngen finder sted.6 and curing the curable mixture to form a product in which the emulsion provides enough water to allow the hydration to take place.
5 Det må bemærkes, at betegnelsen emulsionsbrydning heri anvendes i den normale betydning, d.v.s. brydning af en emulsion under dannelse af to separate væskelag, et vandigt lag og et organisk lag. Skønt afbindingsmidlet optager vand fra emulsionen, og emulsionen derfor -forudsat, at der er tilstrækkeligt meget afbindingsmiddel til stede 10 - med tiden vil ophøre med at eksistere, nedbrydes emulsionen alligevel på intet tidspunkt i to separate væskelag efter tilsætning af afbindingsmidlet. .It should be noted that the term emulsion breakage herein is used in the normal sense, i.e. breaking an emulsion to form two separate liquid layers, an aqueous layer and an organic layer. Although the binder absorbs water from the emulsion and therefore the emulsion, assuming that sufficient binder is present 10 - will eventually cease to exist, the emulsion never breaks down into two separate liquid layers after addition of the binder. .
Emulsionen indeholder fortrinsvis fra 35 til 65 vægtprocent vand og 15 er en vand-i-harpiks-emulsion. Afbindingsmidlet kan være hydraulisk cement, brændt gips eller en blanding af kalk og hydraulisk cement. Afbindingsmidlet er fortrinsvis en Portland cement.The emulsion preferably contains from 35 to 65% by weight water and 15 is a water-in-resin emulsion. The binder may be hydraulic cement, burnt plaster or a mixture of lime and hydraulic cement. The binder is preferably a Portland cement.
Stabiliteten af emulsionen i nærvær af afbindingsmidlet påvirkes af 20 indholdet af umættet monomer i blandingen, forholdet mellem reaktanterne anvendt ved fremstilling af den umættede polyester og molekylvægten af de således anvendte reaktanter.The stability of the emulsion in the presence of the binder is influenced by the content of unsaturated monomer in the mixture, the ratio of the reactants used in preparing the unsaturated polyester to the molecular weight of the reactants thus used.
Det har vist sig, at emulsioner baseret på blandinger af umættet 25 polyester og monomer indeholdende over 30 vægtprocent umættet monomer baseret på vægten af blandingen er ustabile. Blandingen af umættet polyester og umættet monomer omfatter derfor ikke over 30 vægtprocent af den umættede monomer baseret på vægten af blandingen.It has been found that emulsions based on mixtures of unsaturated polyester and monomer containing over 30% by weight of unsaturated monomer based on the weight of the mixture are unstable. The mixture of unsaturated polyester and unsaturated monomer therefore does not comprise more than 30% by weight of the unsaturated monomer based on the weight of the mixture.
Mol forhol det mellem umættede og mættede komponenter, som 30 polyesterharpiksen er opbygget af, ligger fortrinsvis mellem 0,8 og 1,75 og navnlig mellem 1,35 og 1,4.The molar ratio between unsaturated and saturated components on which the polyester resin is composed is preferably between 0.8 and 1.75, and most preferably between 1.35 and 1.4.
De polyvalente alkoholer og de polycarboxylsyrer, der benyttes ved fremstilling af de umættede polyestere har fortrinsvis høje mole-35 kylvægte, d.v.s. mellem 100 og 1000, og er fortrinsvis ikke polymere af egen årsag, såsom polyetherpolyoler eller polyesterpolyoler.The polyhydric alcohols and polycarboxylic acids used in the preparation of the unsaturated polyesters preferably have high molecular weights, i.e. between 100 and 1000, and are preferably not polymers for their own reasons, such as polyether polyols or polyester polyols.
Egnede polyoler er ethylenglycol, trimethylpentandiol og neopentyl glycol. En polyethylenglycol kan imidlertid også benyttes.Suitable polyols are ethylene glycol, trimethylpentanediol and neopentyl glycol. However, a polyethylene glycol may also be used.
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Den samlede mængde af al kohol komponenterne er fortrinsvis over 2-5 mol procent over de støkiometriske krav. Den foretrukne molekylvægt af den umættede polyester ligger mellem 3.100 og 3.600.The total amount of all the alcohol components is preferably above 2-5 mole percent above the stoichiometric requirements. The preferred molecular weight of the unsaturated polyester is between 3,100 and 3,600.
5 Ved fremstillingen af polyesteren forløber kondensationspolymerisationsreaktionen, indtil polyesteren har et syretal på 25 eller derunder.In the preparation of the polyester, the condensation polymerization reaction proceeds until the polyester has an acid number of 25 or less.
Den umættede polyester eller den umættede monomer indeholder for-10 trinsvis substituentatomer i form af brom eller chlor for at forbedre flammeresistensegenskaberne af genstande fremstillet ved fremgangsmåden ifølge den foreliggende opfindelse. Således anvendes tetrabromphthalsyreanhydrid fortrinsvis som en af reaktanterne ved fremstilling af de umættede polyestere, som skal inkorporeres i 15 emulsionerne ifølge den foreliggende opfindelse.The unsaturated polyester or unsaturated monomer preferably contains 10 substituent atoms in the form of bromine or chlorine to improve the flame resistance properties of articles made by the process of the present invention. Thus, tetrabromophthalic anhydride is preferably used as one of the reactants in the preparation of the unsaturated polyesters to be incorporated into the emulsions of the present invention.
Den umættede monomer kan være en vinyl monomer, f.eks. styren, methylmetharcrylat, di allylphthalatmonomer, tri allylcyanuratmonomer eller blandinger heraf.The unsaturated monomer may be a vinyl monomer, e.g. styrene, methyl methacrylate, di allyl phthalate monomer, tri allyl cyanurate monomer or mixtures thereof.
2020
Additionspolymerisationsreaktionen initieres fortrinsvis af en fri radikal-initiator. Additionspolymerisationsreaktionen kan gennemføres ved en varm- eller koldpolymerisationsproces. Det er muligt at fremstille en harpiks med to initiatortilsætningsstoffer, hvoraf det 25 ene åbner mulighed for partiel polymerisation ved omgivelsestemperaturen, og et andet katalysatortilsætningsstof, som vil tilvejebringe den fuldstændige og endelige polymerisation i et varmt tryksystem. Denne fremgangsmåde med to tilsætningsstoffer gør det muligt at levere en mørtel i forkvældede ruller. En egnet initiator 30 til initiering ved lave temperaturer er di benzoyl peroxid, som aktiveres af en kobberforbindelse. De foretrukne i ni ti atorer er imdlertid methyl ethylketonperoxid og butylperbenzoat. Andre egnede initiatorer er de organiske hydroperoxider og hydrogenperoxid. Det er også mulig at benytte fri radikal-initiatorer, som aktiveres af 35 ultraviolet lys. Alternativt kan additionspolymerisationsprocessen initieres af stråling med høj energi.The addition polymerization reaction is preferably initiated by a free radical initiator. The addition polymerization reaction can be carried out by a hot or cold polymerization process. It is possible to prepare a resin with two initiator additives, one of which allows for partial polymerization at ambient temperature, and another catalyst additive which will provide the complete and final polymerization in a hot pressure system. This two-additive process makes it possible to deliver a mortar in swollen rolls. A suitable initiator 30 for low temperature initiation is di benzoyl peroxide which is activated by a copper compound. The preferred in nine ten atoms, however, are methyl ethyl ketone peroxide and butyl perbenzoate. Other suitable initiators are the organic hydroperoxides and hydrogen peroxide. It is also possible to use free radical initiators which are activated by 35 ultraviolet light. Alternatively, the addition polymerization process can be initiated by high energy radiation.
Når afbindingsmidlet og initiatoren tilsættes emulsionen og blandes med denne, gennemtrænger afbindingsmidlet emulsionen ogWhen the binder and initiator are added to the emulsion and mixed with it, the binder penetrates the emulsion and
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8 hydrati seres af vandet. Hvis den anvendte initiator er af den varmeaktiverende type, aktiverer den varme, som dannes ved hydrati-sering af cemtenten, initiatoren efter 10-15 minutter. Den aktiverede initiator initierer derefter en additionspolymerisationsreaktion 5 mellem den umættede polyester og den umættede monomer. Hydrati seringsvarmen fremmer additionspolymerisationshastigheden resulterende i hurtig afbinding af blandingen af emulsion og afbindingsmiddel. Initialafbinding finder sædvanligvis sted inden for 30 minutter.8 are hydrated by the water. If the initiator used is of the heat activating type, the heat generated by hydrating the cemt tent activates the initiator after 10-15 minutes. The activated initiator then initiates an addition polymerization reaction 5 between the unsaturated polyester and the unsaturated monomer. The heat of hydration promotes the rate of addition polymerization resulting in rapid degradation of the mixture of emulsion and stripping agent. Initial bonding usually takes place within 30 minutes.
Hvis en lavtemperatur-i ni ti ator imidlertid sættes til en blanding af 10 emulsionen og aggregatet, begynder blandingen ikke at afbinde i flere timer. I praksis tilsættes afbindingsmidlet således fortrinsvis til emulsionen på brugsstedet. Hvis stedet på den anden side ikke ligger meget langt fra blandingsanlægget, kan initiatoren tilsættes i blandingsanlægget, og afbindingsmidlet iblandes på 15 stedet.However, if a low temperature in ten atoms is added to a mixture of the emulsion and the aggregate, the mixture does not begin to decompose for several hours. Thus, in practice, the binder is preferably added to the emulsion at the site of use. If, on the other hand, the site is not very far from the mixing plant, the initiator may be added in the mixing plant and the binder added at the site.
Naturligvis kan en hvilken som helst hensigtsmæssig form for forstærkning inkorporeres i siutproduktet inden dets afbinding, såsom fiberglas eller stål. Korte fiberglasstykker, der indføres i mate-20 rialet under fremstillingen, har vist sig at være ganske tilfredsstillende. Dannelsen af emulsionen af umættet polyester og umættet monomer er betydningsfuld for fremstillingen af tilfredsstillende materialer. Emulsionen kan fremstilles ved at blande den umættede polyester, den umættede monomer og vand i et hurtigtgående blande-25 apparat, som er i stand til at bringe den dispergerede fase på partikelform med en partikelstørrelse lig med eller noget mindre end 25 mi kron. Den umættede polyesterharpiks er således, at den kan emulgeres med op til 60 vægtprocent vand, uden at emulsionsbrydning finder sted ved tilsætning af afbindingsmidlet. For at fremstille 30 sådanne stabile emulsioner er det muligt at benytte små mængder emulgeringsmiddel, f.eks. et ikke-ionisk eller anionisk emulgeringsmiddel, men det er ikke nødvendigt. For at sikre stabiliteten af emulsionen ved transport og opbevaring kan det være nødvendigt at tilsætte stabilisatorer, såsom titandioxid (rutil), en emulsion af 35 en vinyl i sk eller acrylisk additionspolymer (1 vægtprocent af den umættede polyester plus den umættede monomer). Et fyldstof kan være calciumcarbonat eller calciumsilikat.Of course, any suitable form of reinforcement can be incorporated into the sieve product prior to its bonding, such as fiberglass or steel. Short fiberglass pieces introduced into the material during manufacture have been found to be quite satisfactory. The formation of the emulsion of unsaturated polyester and unsaturated monomer is important for the preparation of satisfactory materials. The emulsion can be prepared by mixing the unsaturated polyester, the unsaturated monomer and water in a fast-moving mixing apparatus capable of bringing the dispersed phase in particulate form with a particle size equal to or slightly less than 25 ml. The unsaturated polyester resin is such that it can be emulsified with up to 60% by weight of water, without emulsion breaking taking place by the addition of the binder. To prepare 30 such stable emulsions, it is possible to use small amounts of emulsifier, e.g. a nonionic or anionic emulsifier, but it is not necessary. To ensure the stability of the emulsion during transport and storage, it may be necessary to add stabilizers such as titanium dioxide (rutile), an emulsion of a vinyl in sk or acrylic addition polymer (1% by weight of the unsaturated polyester plus the unsaturated monomer). A filler may be calcium carbonate or calcium silicate.
Opfindelsen vil blive beskrevet nærmere i forbindelse med 9The invention will be further described in connection with 9
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nedenstående eksempler, af hvilke eksempel 1-6 belyser fremstilling af polyestere, 7-11 belyser blandinger af polyester og umættet monomer, eksempel 12, 14, 16 og 18 belyser emulsioner ifølge opfindelsen og eksempel 13, 15, 17 og 19-21 belyser anvendelse af 5 emulsionerne: EKSEMPEL 1Examples below, of which Examples 1-6 illustrate the preparation of polyesters, 7-11 illustrate mixtures of polyester and unsaturated monomer, Examples 12, 14, 16 and 18 illustrate emulsions of the invention and Examples 13, 15, 17 and 19-21 illustrate application of the 5 emulsions: EXAMPLE 1
En umættet polyester med en syre af høj molekylvægt fremstilledes af 10 følgende komponenter: 269 vægtdele ethylenglycol 382 vægtdele tetrabromphthalsyreanhydrid (MW = 463,7) 284 vægtdele maleinsyreanhydrid eller fumarsyre 15 149 vægtdele phthalsyreanhydrid.A high molecular weight unsaturated polyester was prepared from the following 10 components: 269 parts by weight of ethylene glycol 382 parts by weight of tetrabromophthalic anhydride (MW = 463.7) 284 parts by weight of maleic anhydride or fumaric acid 149 149 parts by weight of phthalic anhydride.
En blanding af ovenstående komponenter frembragtes og opvarmedes i en reaktionsbeholder under kontinuerlig omrøring og med en strøm af inert gas fejende gennem og over blandingen. Opvarmning gennemførtes 20 som følger: (a) først til 170°C i en time, (b) derefter til 185°C i 30 minutter, og (c) derefter til 190°C i 7 timer.A mixture of the above components is produced and heated in a reaction vessel with continuous stirring and with a stream of inert gas sweeping through and over the mixture. Heating was carried out as follows: (a) first to 170 ° C for one hour, (b) then to 185 ° C for 30 minutes, and (c) then to 190 ° C for 7 hours.
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Reaktionen mellem komponenterne afsluttedes, da et syretal på under 20 var opnået, og den fremkomne polymer afkøledes derefter.The reaction between the components was terminated when an acid number of less than 20 was obtained and the resulting polymer was then cooled.
EKSEMPEL 2 30EXAMPLE 2 30
Fremgangsmåden ifølge eksempel 1 fulgtes med undtagelse af, at komponenter, hvoraf polyesteren skulle dannes, omfattede følgende: 467 vægtdele trimethylpentandiol (MW = 146,15) 35 15 vægtdele pentaerythritol 98 vægtdele maleinsyreanhydrid, hvor komponenterne således indbefattede en glycol med høj mol kyl vægt.The procedure of Example 1 was followed except that components from which the polyester was to be formed included the following: 467 parts by weight trimethylpentanediol (MW = 146.15) 35 parts by weight pentaerythritol 98 parts by weight maleic anhydride, the components thus including a high mole cool weight glycol.
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EKSEMPEL 3EXAMPLE 3
Fremgangsmåden ifølge eksempel 1 fulgtes, dog under med anvendelse af følgende komponenter: 5 394 vægtdele trimethylpentandiol (MW = 146,15) 430 vægtdele tetrabromphthalsyreanhydrid (MW = 463,7) 41 vægtdele pentaerythritol 186 dele maleinsyreanhydrid eller fumarsyre.The procedure of Example 1 was followed, however, using the following components: 5,394 parts by weight of trimethylpentanediol (MW = 146.15) 430 parts by weight of tetrabromophthalic anhydride (MW = 463.7) 41 parts by weight of pentaerythritol 186 parts of maleic anhydride or fumaric acid.
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Komponenterne omfattede således en glycol og en syre med høj molekylvægt.Thus, the components included a high molecular weight glycol and an acid.
EKSEMPEL 4 15EXAMPLE 4 15
Fremgangsmåden ifølge eksempel 1 fulgtes, idet der dog anvendtes følgende komponenter: 250 vægtdele ethylenglycol 20 382 vægtdele tetrabromphthalsyreanhydrid 224 vægtdele maleinsyreanhydrid eller fumarsyre 149 vægtdele phthalsyreanhydrid • 19 vægtdele 2,2-bis(methylallylether)-l-butanol.The procedure of Example 1 was followed, however, using the following components: 250 parts by weight of ethylene glycol 20,382 parts by weight of tetrabromophthalic anhydride 224 parts by weight of maleic anhydride or fumaric acid 149 parts by weight of phthalic anhydride • 19 parts by weight of 2,2-bis (methyl allyl ether) -1-butanol.
25 Den substituerede butanol tilsattes ved esterificeringsreaktionens afslutning.The substituted butanol was added at the end of the esterification reaction.
EKSEMPEL 5 30 Fremgangsmåden ifølge eksempel 1 fulgtes med undtagelse af, at der dog anvendtes følgende komponenter: 467 vægtdele trimethylpentandiol 15 vægtdele pentaerythritol 35 98 vægtdele maleinsyreanhydrid 10 vægtdele 2,2-bis(methylallylether)-l-butanol.EXAMPLE 5 30 The procedure of Example 1 was followed except that, however, the following components were used: 467 parts by weight trimethylpentanediol 15 parts by weight pentaerythritol 35 98 parts by weight maleic anhydride 10 parts by weight 2,2-bis (methyl allyl ether) -1-butanol.
Den substituerede butanol tilsattes igen ved esterificeringsreaktionens afslutning.The substituted butanol was added again at the end of the esterification reaction.
EKSEMPEL 6 11EXAMPLE 6 11
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Fremgangsmåden ifølge eksempel 1 fulgtes, idet der dog anvendtes følgende komponenter: 5 394 vægtdele trimethylpentandiol 430 vægtdele tetrabromphthalsyreanhydrid 41 vægtdele pentaerythritol 186 vægtdele maleinsyreanhydrid eller fumarsyre 10 8 vægtdele 2,2-bis(methylallylether)-l-butanol.The procedure of Example 1 was followed, however, using the following components: 5,394 parts by weight of trimethylpentanediol 430 parts by weight of tetrabromophthalic anhydride 41 parts by weight of pentaerythritol 186 parts by weight of maleic anhydride or fumaric acid 10 parts by weight of 2,2-bis (methyl allyl ether) -1-butanol.
Den substituerede butanol tilsattes igen ved esterificeringsreakti-onens afslutning.The substituted butanol was again added at the end of the esterification reaction.
15 EKSEMPEL 7EXAMPLE 7
Polyesterne ifølge eksemplerne 1-6 blandedes hver for sig med henholdsvis 290 vægtdele, 200 vægtdele, 280 vægtdele, 290 vægtdele, 200 vægtdele og 280 vægtdele monomer i form af styren under dannelse 20 af en blanding af umættet polyester og umættet monomer.The polyesters of Examples 1-6 were mixed separately with 290 parts by weight, 200 parts by weight, 280 parts by weight, 290 parts by weight, 200 parts by weight and 280 parts by weight in the form of styrene to form a mixture of unsaturated polyester and unsaturated monomer.
EKSEMPEL 8EXAMPLE 8
Polyesterne ifølge eksemplerne 1-6 blandedes hver for sig henholds-25 vis med 290 vægtdele, 200 vægtdele 280 vægtdele, 290 vægtdele, 200 vægtdele og 280 vægtdele monomer i form af methylmethacrylat under dannelse af en blanding af umættet polyester og umættet monomer.The polyesters of Examples 1-6, respectively, were mixed together with 290 parts by weight, 200 parts by weight 280 parts by weight, 290 parts by weight, 200 parts by weight and 280 parts by weight in the form of methyl methacrylate to form a mixture of unsaturated polyester and unsaturated monomer.
EKSEMPEL 9 30EXAMPLE 9 30
Polyesterne ifølge eksemplerne 1-6 blandedes hver for sig med 290 vægtdele, 200 vægtdele, 280 vægtdele, 290 vægtdele, 200 vægtdele og 280 vægtdele monomer i form af en 50/50 blanding (på vægtbasis) af styren og methylmethacrylat under dannelse af en blanding af en 35 umættet polyester og en umættet monomer.The polyesters of Examples 1-6 were mixed separately with 290 parts by weight, 200 parts by weight, 280 parts by weight, 290 parts by weight, and 200 parts by weight of monomer in the form of a 50/50 weight (by weight) mixture of styrene and methyl methacrylate to form a mixture of an unsaturated polyester and an unsaturated monomer.
EKSEMPEL 10EXAMPLE 10
Polyesterne ifølge eksemplerne 1-6 blandedes hver for sig medThe polyesters of Examples 1-6 were mixed together separately
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12 henholdsvis 710 vægtdele, 490 vægtdele, 690 vægtdele, 710 vægtdele, 490 vægtdele og 690 vægtdele diallylphthalatmonomer under dannelse af en blanding af umættet polyester og umættet monomer, som kan tværbindes ved høj temperatur.12, 710 parts by weight, 490 parts by weight, 690 parts by weight, 710 parts by weight, 490 parts by weight and 690 parts by weight of diallyl phthalate monomer to form a mixture of unsaturated polyester and unsaturated monomer which can be crosslinked at high temperature.
5 EKSEMPEL 11EXAMPLE 11
Polyesterne ifølge eksemplerne 1-6 blandedes hver for sig med henholdsvis 710 vægtdele, 490 vægtdele, 690 vægtdele, 710 vægtdele, 10 490 vægtdele og 690 vægtdele af en 50/50 blanding (molbasis) af styren og triallylcyanuratmonomer under dannelse af en blanding af umættet polyester og umættet monomer.The polyesters of Examples 1-6 were mixed separately with 710 parts by weight, 490 parts by weight, 690 parts by weight, 710 parts by weight, 10 490 parts by weight and 690 parts by weight of a 50/50 mixture (molar basis) of styrene and triallyl cyanurate monomer to form a mixture of unsaturated polyester and unsaturated monomer.
EKSEMPEL 12 15EXAMPLE 12 15
Blandingerne ifølge eksemplerne 7-11 fremstilledes som emulsioner ved blanding af følgende komponenter: 500 vægtdele blanding 20 3 vægtdele aktivator i form af coboltoctanat 300 vægtdele vand.The mixtures of Examples 7-11 were prepared as emulsions by mixing the following components: 500 parts by weight of mixture 20 3 parts by weight of activator in the form of cobalt octanate 300 parts by weight of water.
Blandingen gennemførtes under anvendelse af et hurtigtgående blan-deapparat, idet blandingshastigheden var tilstrækkelig til, at stort 25 set hele den dispergerede fase forekom på parti kel form med en partikelstørrelse lig med eller mindre end 25 mi kron.The mixing was carried out using a fast-moving mixing apparatus, the mixing speed being sufficient to cause substantially all of the dispersed phase to be in particulate form with a particle size equal to or less than 25 ml of crown.
EKSEMPEL 13 30 Cementprodukter fremstilledes ved blanding i et standardcementblan-deapparat af komponenter i følgende vægtforhold: 803 vægtdele af emulsionen ifølge eksempel 12 500 vægtdele Portland cement 35 5 vægtdele kiselmel 3300 vægtdele sand 2700 vægtdele grus 5 vægtdele katalysator i form af methyl ethylketonperoxid.Example 13 30 Cement products were prepared by mixing in a standard cement mixer of components in the following weight ratios: 803 parts by weight of the emulsion of Example 12,500 parts by weight Portland cement 35 5 parts by weight of silica 3300 parts by weight of sand 2700 parts by weight of gravel 5 parts by weight of catalyst in the form of methyl ethyl ketone peroxide.
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Blandingen hældtes i en form mellem to plader af glasfibermåtter og o pressedes med et tryk på 2,5 kg/cm , indtil hærdning havde fundet sted. Der fremkom plader med særdeles gode mekaniske egenskaber og gode antikorrosionsegenskaber.The mixture was poured into a mold between two sheets of fiberglass mats and pressed at a pressure of 2.5 kg / cm until curing had taken place. Sheets with very good mechanical properties and good anti-corrosion properties were obtained.
5 EKSEMPEL 14EXAMPLE 14
Blandingerne ifølge eksemplerne 8 og 9 til dannedes til emulsioner ved blanding af komponenterne som følger: 10 500 vægtdele harpiks 300 vægtdele vand.The mixtures of Examples 8 and 9 were formed into emulsions by mixing the components as follows: 10,500 parts by weight of resin 300 parts by weight of water.
Blandingen gennemførtes under anvendelse af et hurtigtgående blan-15 deapparat, hvor blandehastigheden var tilstrækkelig til, at stort set hele mængden af harpiks forekom på parti kel form med en partikelstørrelse lig med eller mindre end 25 mi kron.The mixing was carried out using a fast-moving mixing apparatus where the mixing speed was sufficient to cause almost the entire amount of resin to be in particulate form with a particle size equal to or less than 25 ml of crown.
EKSEMPEL 15 20EXAMPLE 15
Der fremstilledes cementprodukter ved i et standardcementblandeappa-rat at blande komponenter som følger: 800 vægtdele af emulsionen ifølge eksempel 14 25 500 vægtdele Portland cement 10 vægtdele katalysator (tert.-butylperbenzoat) 3300 vægtdele sand 2700 vægtdele grus.Cement products were prepared by mixing in a standard cement mixer components as follows: 800 parts by weight of the emulsion of Example 14 25,500 parts by weight Portland cement 10 parts by weight of catalyst (tert-butyl perbenzoate) 3300 parts by weight of sand 2700 parts by weight of gravel.
30 Blandingerne hældtes i forme mellem to ark glasfibermåtte, pressedesThe mixtures were poured into molds between two sheets of fiberglass mat, pressed
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med et tryk på 4,5 kg/cm , opvarmedes i 5 minutter til 99°C og blev derefter udtaget af formen. Der fremkom plader med særdeles gode mekaniske egenskaber, god kemisk bestandighed og forbedret lystæthed. En svejseflamme virkende på overfladen af en på denne 35 måde fremstillet plade i 30 minutter gav kun en sværtningseffekt på overfladen, men der skete ingen antændelse.at a pressure of 4.5 kg / cm, warmed to 99 ° C for 5 minutes and then removed from the mold. Sheets with very good mechanical properties, good chemical resistance and improved light density were obtained. A welding flame acting on the surface of a plate made in this way for 30 minutes only produced a surface blackening effect, but no ignition occurred.
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14 EKSEMPEL 16EXAMPLE 16
Blandingerne ifølge eksemplerne 7-9 tildannedes til emulsioner ved 5 blanding af komponenter som følger: 500 vægtdele blanding 3 vægtdele aktivator i form af coboltoctanat 500 vægtdele vand.The mixtures of Examples 7-9 were prepared for emulsions by mixing 5 components as follows: 500 parts by weight mixing 3 parts by weight activator in the form of cobalt octanate 500 parts by weight of water.
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Blandingen gennemførtes under anvendelse af et hurtigtgående blan-deapparat, idet blandingshastigheden var tilstrækkelig til, at stort set hele den dispergerede fase forekom på parti kel form med en partikelstørrelse lig med eller mindre end 25 mi kron.The mixing was carried out using a fast-moving mixing apparatus, the mixing speed being sufficient for virtually the entire dispersed phase to occur in particulate form with a particle size equal to or less than 25 ml of crown.
15 EKSEMPEL 17EXAMPLE 17
Der fremstilledes pudsematerialer ved i et standardcementblandeap-parat at blande komponenter som følger: 20 1003 vægtdele af emulsionen ifølge eksempel 16 500 vægtdele brændt gips 5 vægtdele kisel mel 3300 vægtdele sand 25 2700 vægtdele grus 5 vægtdele katalysator i form af methyl ethylketonperoxid.Plaster materials were prepared by mixing components in a standard cement mixer as follows: 20 1003 parts by weight of the emulsion of Example 16,500 parts by weight of burnt drywall 5 parts by weight of silicon flour 3300 parts by weight of sand 25 2700 parts by weight of gravel 5 parts by weight of catalyst in the form of methyl ethyl ketone peroxide.
De fremkomne blandinger hældtes i forme mellem to plader af gi asfi-bermåtte og pressedes ved et tryk på 3 kg/cm .The resulting mixtures were poured into molds between two sheets of g ash mat and pressed at a pressure of 3 kg / cm.
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De fremkomne plader havde mekaniske styrkeegenskaber svarende til plader fremstillet med cement men var mange gange stærkere end en standardgipsplade.The resulting sheets had mechanical strength properties similar to sheets made with cement but were many times stronger than a standard gypsum board.
35 EKSEMPEL 18EXAMPLE 18
Blandingerne ifølge eksemplerne 7-9 tildannedes til emulsioner ved blanding af komponenter som følger:The mixtures of Examples 7-9 were formed into emulsions by mixing components as follows:
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15 500 vægtdele blanding 500 vægtdele vand.15 500 parts by weight of mixture 500 parts by weight of water.
Blandingen gennemførtes under anvendelse af et hurtigtgående blan-5 deapparat, idet blandingshastigheden var tilstrækkelig til, at stort set hele den dispergerede fase forekom på parti kel form med en partikelstørrelse lig med eller mindre end 25 mi kron.The mixing was carried out using a fast-moving mixing apparatus, the mixing speed being sufficient for virtually the entire dispersed phase to occur in particulate form with a particle size equal to or less than 25 ml of crown.
EKSEMPEL 19 10EXAMPLE 19 10
Gipsmaterialer fremstilledes ved blanding i et standardcementblan-deapparat af komponenter som følger: 1000 vægtdele af emulsionen ifølge eksempel 18 15 5oo vægtdele brændt gips 10 vægtdele katalysator (tert.-butylperbenzoat) 3300 vægtdele sand 2700 vægtdele grus.Plaster materials were prepared by mixing in a standard cement blender apparatus of components as follows: 1000 parts by weight of the emulsion of Example 18 15 50 parts by weight of burnt drywall 10 parts by weight of catalyst (tert-butyl perbenzoate) 3300 parts by weight of sand and 2700 parts by weight of gravel.
20 De fremkomne blandinger hældtes i forme mellem to plader af gi asfi- 2 bermåtte og pressedes med et tryk på 3 kg/cm .The resulting mixtures were poured into molds between two sheets of g asphalt mat and pressed at a pressure of 3 kg / cm.
De fremkomne plader udviste mekaniske styrkeegenskaber svarende til plader fremstillet med cement, men var mange gange stærkere end en 25 standardgipsplade.The resulting sheets exhibited mechanical strength properties similar to sheets made of cement, but were many times stronger than a standard plasterboard.
EKSEMPEL 20EXAMPLE 20
Cementprodukter fremstilledes ved banding i et standardcementblan= 30 deapparat af komponenter som følger: 800 vægtdele af emulsionen ifølge eksempel 14 500 vægtdele kalk 5 vægtdele kisel mel 35 3300 vægtdele sand 2700 vægtdele grus 5 vægtdele katalysator i form af methyl ethylketonperoxid Blandingerne hældtes i en form mellem to plader af glasfibermåtte ogCement products were prepared by banding in a standard cement blend = 30 apparatus of components as follows: 800 parts by weight of the emulsion of Example 14,500 parts by weight of lime 5 parts of silica flour 35,300 parts by weight of sand 2700 parts by weight of gravel 5 parts by weight of catalyst in the form of methyl ethyl ketone peroxide The mixtures were poured into a mold between two sheets of fiberglass mat and
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16 o pressedes med et tryk på 2,5 kg/cm , indtil hærdning havde fundet sted. Der fremkom plader med en meget høj mekanisk styrke og gode anti korrosionsegenskaber.16 o was pressed at a pressure of 2.5 kg / cm until curing had taken place. Sheets with a very high mechanical strength and good anti-corrosion properties were obtained.
5 EKSEMPEL 21EXAMPLE 21
Cementprodukter fremstilledes ved blanding i et standardcementblan-deapparat af komponenter som følger: 10 800 vægtdele af emulsionen ifølge eksempel 14 500 vægtdele af en 50/50-blånding (vægtbasis) af kalk og Portland cement 5 vægtdele kiselmel 3300 vægtdele sand 15 2700 vægtdele grus 5 vægtdele katalysator i form af methyl ethylketonperoxid.Cement products were prepared by mixing in a standard cement mixer of components as follows: 10,800 parts by weight of the emulsion of Example 14,500 parts by weight of a 50/50 blend (weight basis) of lime and Portland cement 5 parts by weight of silica flour 3300 parts by weight of sand 15 2700 parts by weight of gravel 5 parts by weight of catalyst in the form of methyl ethyl ketone peroxide.
Blandingerne hældtes i en form mellem to plader af glasfibermåtte og pressedes med et tryk på 2,5 kg/cm , indtil hærdning havde fundet 20 sted. Resultaterne var plader med en meget høj mekanisk styrke og gode anti korrosionsegenskaber.The mixtures were poured into a mold between two sheets of fiberglass mat and pressed at a pressure of 2.5 kg / cm until curing had taken place. The results were sheets with a very high mechanical strength and good anti-corrosion properties.
Produkter fremstillet ud fra emulsionerne ifølge opfindelsen kan let tilvejebringes med styrkeegenskaber, der er langt bedre end sædvan-25 lig betons styrkeegenskaber. F.eks. sammenlignes afprøvninger udført på et produkt ifølge eksempel 13 i nedenstående tabel med egenskaberne for sædvanlig beton og med egenskaberne af en harpiks-sandblånding af kendt type.Products made from the emulsions of the invention can easily be provided with strength properties that are far superior to conventional concrete strength properties. Eg. For example, tests performed on a product of Example 13 in the following table are compared with the properties of ordinary concrete and with the properties of a resin-sand blend of known type.
30 Produkt ifølgeProduct according to
Harpiks/ den foreliggende- _Beton sand_de opfindelseResin / The Present-Concrete True Invention
Massefylde 2,4 2,1 1,9 35 Trykstyrke kg/cm2 300 1200 1780 Bøjningsstyrke kg/cm2 70 1300 1300Density 2.4 2.1 1.9 35 Compressive strength kg / cm2 300 1200 1780 Flexural strength kg / cm2 70 1300 1300
Trækstyrke kg/cm2 30 430 500Tensile strength kg / cm2 30 430 500
Slagstyrke kg/cm/cm2 0,4 10 8,2Impact strength kg / cm / cm2 0.4 10 8.2
Eksotermt maksimum 30/40°C 120°C 75/80°CExothermic maximum 30/40 ° C 120 ° C 75/80 ° C
DK 155435 BDK 155435 B
1717
De produkter, som fremkommer under anvendelse af de tre polyestere ifølge eksemplerne 1-3, er næsten helt vandtætte, hvilket er af betydning for materialer anvendt til fremstilling af byggeplader og lignende elementer. Polyesterne ifølge eksempel 3 har vist sig at 5 være ufølsomme over for temperaturer i det midste i området fra -60°C til 135°C og over for gentagne varmechok inden for samme temperaturområde. Produktet kan også indrettes til at udvise ringe tørringssvind under afbindingen, idet tørringssvind på under 1 mm/meter let kan opnås.The products obtained using the three polyesters of Examples 1-3 are almost completely waterproof, which is of importance for materials used in the manufacture of building boards and similar elements. The polyesters of Example 3 have been found to be insensitive to mid-temperature temperatures ranging from -60 ° C to 135 ° C and to repeated heat shocks within the same temperature range. The product can also be arranged to exhibit slight drying shrinkage during the bonding, drying shrinkage of less than 1 mm / meter can be easily obtained.
1010
Sammenlignende afprøvning af styrkeegenskaber for produkter fremstillet ifølge opfindelsen, ifølge italiensk patentskrift nr.Comparative testing of the strength properties of products made according to the invention, according to Italian Patent No.
585.721 og ifølge tysk offentliggørelsesskrift nr. 2.628.718 efter 100 timers afbinding i terningformer gav følgende resultater: 15585,721 and according to German publication no. 2,628,718 after 100 hours of dicing in dice forms gave the following results: 15
Prøve nr.Sample no.
1_2_31_2_3
Ifølge opfindelsen (jfr. eksempel 21) 69,6 MPa 67,8 MPa 65,6 MPa Ifølge italiensk patent nr.According to the invention (cf. Example 21) 69.6 MPa 67.8 MPa 65.6 MPa According to Italian patent no.
20 585.721, side 2-3 34,2 MPa 30 MPa 29 MPa20 585.721, pages 2-3 34.2 MPa 30 MPa 29 MPa
Ifølge tysk offentliggørelses- skrift nr. 2.628.718 21,8 MPaAccording to German Publication No. 2,628,718 21.8 MPa
Det fremgår med ønskelig tydelighed af ovenstående tabel, at pro-25 dukter fremstillet under anvendelse af emulsionen ifølge opfindelsen er overlegne i forhold til både de, der fremstilles ifølge det italienske patentskrift og de, der fremstilles ifølge det tyske offentliggørelsesskri ft.It is desirable, from the above table, that products made using the emulsion of the invention are superior to both those made in the Italian patent and those produced in the German publication.
30 3530 35
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK147577A DK155435C (en) | 1977-04-01 | 1977-04-01 | WATER-I RESIN EMULSION BASED ON A THERMOUS POLYESTER TO USE IN THE PREPARATION OF CONCRETE REPLACEMENT PRODUCTS BASED ON A HYDRAULIC BINDING AGENT |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK147577A DK155435C (en) | 1977-04-01 | 1977-04-01 | WATER-I RESIN EMULSION BASED ON A THERMOUS POLYESTER TO USE IN THE PREPARATION OF CONCRETE REPLACEMENT PRODUCTS BASED ON A HYDRAULIC BINDING AGENT |
| DK147577 | 1977-04-01 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK147577A DK147577A (en) | 1978-10-02 |
| DK155435B true DK155435B (en) | 1989-04-10 |
| DK155435C DK155435C (en) | 1989-10-16 |
Family
ID=8105217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK147577A DK155435C (en) | 1977-04-01 | 1977-04-01 | WATER-I RESIN EMULSION BASED ON A THERMOUS POLYESTER TO USE IN THE PREPARATION OF CONCRETE REPLACEMENT PRODUCTS BASED ON A HYDRAULIC BINDING AGENT |
Country Status (1)
| Country | Link |
|---|---|
| DK (1) | DK155435C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2628718A1 (en) * | 1975-06-26 | 1977-01-13 | Christian Germain Luois Dussel | MIXED CONCRETE MADE OF PLASTIC AND CEMENT FOR THE PRODUCTION OF PRE-FABRICATED COMPONENTS |
-
1977
- 1977-04-01 DK DK147577A patent/DK155435C/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2628718A1 (en) * | 1975-06-26 | 1977-01-13 | Christian Germain Luois Dussel | MIXED CONCRETE MADE OF PLASTIC AND CEMENT FOR THE PRODUCTION OF PRE-FABRICATED COMPONENTS |
Also Published As
| Publication number | Publication date |
|---|---|
| DK147577A (en) | 1978-10-02 |
| DK155435C (en) | 1989-10-16 |
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