NO132153B - - Google Patents

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Publication number
NO132153B
NO132153B NO4849/70A NO484970A NO132153B NO 132153 B NO132153 B NO 132153B NO 4849/70 A NO4849/70 A NO 4849/70A NO 484970 A NO484970 A NO 484970A NO 132153 B NO132153 B NO 132153B
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Norway
Prior art keywords
unsaturated
impregnated
resin
chelate
reinforcing material
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NO4849/70A
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Norwegian (no)
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NO132153C (en
Inventor
B Nilsson
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Asea Ab
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Publication of NO132153B publication Critical patent/NO132153B/no
Publication of NO132153C publication Critical patent/NO132153C/no

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/68—Unsaturated polyesters
    • C08G18/683—Unsaturated polyesters containing cyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Description

Impregnerte, arkformige armeringsmaterialer, f.eks. impregnert glassfibermatte, anvendes i stor utstrekning for fremstilling av produkter av armert plast. Som regel anvendes en umettet esterharpiks som impregneringsmiddel i slike impregnerte armeringsmaterialer. Ved siden av en umettet alkyd inneholder den umettede esterharpiks en umettet monomerforbindelse, f.eks. styren. Det impregnerte, arkformige armeringsmateriale inneholder i alminnelighet all den harpiks som er nodvendig for tilvirkning av plastpro-duktet, og det foretaes derfor ingen tilsetning av harpiks ved denne tilvirkning. Som eksempel på plastprodukter som ofte fremstilles med anvendelse av slike impregnerte armeringsmaterialer, Impregnated sheet-like reinforcement materials, e.g. impregnated glass fiber mat, is used to a large extent for the production of products made of reinforced plastic. As a rule, an unsaturated ester resin is used as impregnating agent in such impregnated reinforcement materials. Alongside an unsaturated alkyd, the unsaturated ester resin contains an unsaturated monomer compound, e.g. styrene. The impregnated, sheet-like reinforcing material generally contains all the resin that is necessary for the production of the plastic product, and no resin is therefore added during this production. As an example of plastic products that are often produced using such impregnated reinforcement materials,

kan nevnes storre gjenstander av glassfiberarmert esterplast, f.eks. plane plater, korrugerte plater, transportkasser, båter, bildeler, mention can be made of larger objects made of glass fiber reinforced ester plastic, e.g. flat sheets, corrugated sheets, transport boxes, boats, car parts,

dessuten laminat med andre arkformige materialer som armering, som papir, overflatebelegningsskikt, hvori det arkformige materiale ofte utgjores av papir. also laminate with other sheet-like materials as reinforcement, such as paper, surface coating layer, in which the sheet-like material is often made of paper.

Det er kjent at egenskapene til en umettet esterharpiks kan modifiseres ved tilsetning av et flerverdig isocyanat. Det er også kjent å anvende en slik tilsetning til en umettet esterharpiks i de i innledningen beskrevne impregnerte, arkformige armeringsmaterialer for å gjore disse klebefrie og dermed lettere å hånd-tere ved fremstilling av plastprodukter. It is known that the properties of an unsaturated ester resin can be modified by adding a polyhydric isocyanate. It is also known to use such an addition to an unsaturated ester resin in the impregnated, sheet-like reinforcing materials described in the introduction to make them non-sticky and thus easier to handle when manufacturing plastic products.

Det er også kjent at en tilsetning av et titanchelat, som titanacetylacetonat, til bl.a. varmtherdnende alkydharpikser, poly-urethanharpikser og epoxyharpikser i enkelte tilfeller kan ned-sette den nodvendige herdetid for harpiksene. It is also known that an addition of a titanium chelate, such as titanium acetylacetonate, to e.g. thermosetting alkyd resins, polyurethane resins and epoxy resins in some cases can reduce the necessary curing time for the resins.

Tidligere kjente impregnerte armeringsmaterialer som inneholder umettede esterharpikser sammen med flerverdige isocyanater og som er lagringsbestandige, kan bare herdes ved forhoyet temperatur. Detterer selvfølgelig en stor ulempe spesielt i forbindelse med fremstilling av store gjenstander av armert plast, som storre plater, båter og bildeler.etc., fordi det da må anvendes formverk-toy med oppvarmingsanordninger. Previously known impregnated reinforcing materials which contain unsaturated ester resins together with polyvalent isocyanates and which are storage-resistant, can only be cured at an elevated temperature. This of course presents a major disadvantage, especially in connection with the production of large objects made of reinforced plastic, such as large plates, boats and car parts, etc., because molding tools with heating devices must then be used.

Det har ifolge oppfinnelsen vist seg mulig å fremstille gjenstander av armert plast uten varmetilfbrsel ved anvendelse av arkformige armeringsmaterialer impregnert med en harpiks bestående av en umettet esterharpiks sammen med et flerverdig isocyanat. According to the invention, it has proved possible to produce reinforced plastic objects without the application of heat by using sheet-shaped reinforcing materials impregnated with a resin consisting of an unsaturated ester resin together with a multivalent isocyanate.

Oppfinnelsen angår en fremgangsmåte ved fremstilling av en gjenstand bestående av armert harpiks, ved formning av gjenstanden fra et arkformig armeringsmateriale som er impregnert med en uherdet impregneringsharpiks bestående av en umettet alkyd med hydroxylgrupper, en umettet monomer og et flerverdig isocyanat hvorved det flerverdige isocyanat eventuelt i det minste delvis er omsatt med den umettede alkyds hydroxylgrupper og det til impregneringsharpiksen er tilsatt en akselerator for polymeriseringsreaksjoner mellom umettede grupper, idet en katalysator for polymeriseringsreaksjoner mellom umettede grupper fordeles over en overflate på det impregnerte, arkformige armeringsmateriale ved anvendelsen av dette for formning av den armerte gjenstand og harpiksen i den formede gjenstand bringes til å herde, og fremgangsmåten er sær-preget ved at det til impregneringsharpiksen dessuten er tilsatt The invention relates to a method for the production of an object consisting of reinforced resin, by forming the object from a sheet-shaped reinforcing material which is impregnated with an uncured impregnation resin consisting of an unsaturated alkyd with hydroxyl groups, an unsaturated monomer and a polyvalent isocyanate, whereby the polyvalent isocyanate optionally in the smallest is partially reacted with the hydroxyl groups of the unsaturated alkyd and an accelerator for polymerization reactions between unsaturated groups is added to the impregnation resin, a catalyst for polymerization reactions between unsaturated groups being distributed over a surface of the impregnated, sheet-like reinforcing material when using this for shaping the reinforced object and the resin in the shaped object are brought to harden, and the method is characterized by the fact that it is also added to the impregnation resin

et metallchelatj hvorved impregneringsharpiksen bringes til å a metal chelate whereby the impregnation resin is brought to

herde uten tilfor sel av varme. harden without the addition of heat.

Armeringsmaterialet er av vanlig type og kan bestå av glassfibermatte, glassfibervev, matter, filter og vever av andre fiberformige materialer, som asbest, bomull og fibre av termoplaster, som polyethylenglycolterefthalat og acrylnitril. Dessuten kan papir anvendes på samme måte som glimmerprodukter, f.eks. en selv-bærende glimmerfolie. The reinforcing material is of the usual type and can consist of fiberglass mat, fiberglass fabric, mats, filters and fabrics of other fibrous materials, such as asbestos, cotton and fibers of thermoplastics, such as polyethylene glycol terephthalate and acrylonitrile. Furthermore, paper can be used in the same way as mica products, e.g. a self-supporting mica foil.

Impregneringsharpiksen kan inneholde fyllmiddel som kan være pulverformig eller fiberformig. Det pulverformige fyllmiddel kan være av en slik type som er vanlig anvendt i pressmasser, som f.eks. kritt, kaolin, dolomitt, glimmermel, kvartsmel, teglstensmel, skifermel, talkum, bariumsulfat og polyethen- og polyvinylklorid-pulver etc. Det fiberformige fyllmiddel kan likeledes være av en type som er vanlig anvendt i pressmasser, som f.eks. korte fibre av glass, asbest og bomull, sisalfibre og syntetiske organiske fibre med hoyt smeltepunkt, som polyethylenglycolterefthalatfibre og acrylnitrilfibre. The impregnation resin may contain filler which may be powdery or fibrous. The powdery filler can be of a type that is commonly used in press materials, such as e.g. chalk, kaolin, dolomite, mica flour, quartz flour, brick flour, slate flour, talc, barium sulphate and polyethylene and polyvinyl chloride powder etc. The fibrous filler can likewise be of a type that is commonly used in pressing compounds, such as e.g. short fibers of glass, asbestos and cotton, sisal fibers and synthetic organic fibers with a high melting point, such as polyethylene glycol terephthalate fibers and acrylonitrile fibers.

Den umettede alkyd kan være av vanlig type. Den kan fremstilles på vanlig måte ved forestring av umettede og mettede tobasiske carboxylsyrer eller tilsvarende anhydrider med en ekvivalent mengde eller et lite overskudd av toverdig alkohol. Som eksempel på for dette anvendbare umettede syrer kan nevnes maleinsyre, fumarsyre og itaconsyre som sådanne eller i form av anhydrider. Eksempler på anvendbare mettede syrer er forst og fremst adipinsyre, ravsyre, fthalsyre, isofthalsyre, tetra- og hexahydrofthalsyre, tetraklor-fthalsyre og hexaklorendomethylentetrahydrofthalsyre som sådanne eller i form av anhydrider. Som eksempler på egnede toverdige alkoholer kan nevnes glycoler, som ethylenglycol, propylenglycol og butylenglycol, og dessuten polyglycoler, som diethylenglycol, triethylenglycol og dipropylenglycol, og bl.a. en alkohol med The unsaturated alkyd may be of the usual type. It can be prepared in the usual way by esterification of unsaturated and saturated dibasic carboxylic acids or corresponding anhydrides with an equivalent amount or a small excess of dihydric alcohol. Examples of unsaturated acids that can be used for this purpose include maleic acid, fumaric acid and itaconic acid as such or in the form of anhydrides. Examples of usable saturated acids are primarily adipic acid, succinic acid, phthalic acid, isophthalic acid, tetra- and hexahydrophthalic acid, tetrachlorophthalic acid and hexachloroendomethylenetetrahydrophthalic acid as such or in the form of anhydrides. Examples of suitable dihydric alcohols include glycols, such as ethylene glycol, propylene glycol and butylene glycol, and also polyglycols, such as diethylene glycol, triethylene glycol and dipropylene glycol, and i.a. an alcohol with

formelen the formula

hvor R er et alkylen- where R is an alkylene-

radikal med 2-3 carbonatomer, A er et 2-alkylidenradikal med 1-4 carbonatomer, hver m og n er minst 1, og den aritmetiske gjennom-snittsverdi for rn og n ikke er over 3. I enkelte tilfeller kan en del av den toverdige alkohol erstattes med en flerverdig alkohol, som glycerol eller pentaerytritol. Det foretaes av og til en tilsetning av mono-, tri- og tetrafunksjonelle alkoholer, på samme måte radical with 2-3 carbon atoms, A is a 2-alkylidene radical with 1-4 carbon atoms, each m and n is at least 1, and the arithmetic average value for rn and n does not exceed 3. In some cases, part of the dihydric alcohol is replaced with a polyhydric alcohol, such as glycerol or pentaerythritol. Mono-, tri- and tetra-functional alcohols are occasionally added in the same way

som slike syrer, for å oppnå spesielle virkninger. such as such acids, to achieve special effects.

Monomermengden i impregneringsharpiksen kan fordelaktig være 15-60 % av den samlede vekt av umettet alkyd og monomer. Mono-meren #an utgjores av bl.a. styren, o-klorstyren, p-klorstyren, vinyltoluen, divinylbenzen og av blandinger av methylmetacrylat og styren. The amount of monomer in the impregnation resin can advantageously be 15-60% of the total weight of unsaturated alkyd and monomer. The monomer #an is made up of, among other things styrene, o-chlorostyrene, p-chlorostyrene, vinyltoluene, divinylbenzene and of mixtures of methyl methacrylate and styrene.

Som eksempler på egnede isocyanater kan nevnes toluylen -2 , h-diisocyanat, toluylen-2,6-diisocyanat, dimerisext toluylen-2 ,4-diisocyanat, difenylmetan-4,4'-diisocyanat, naf thylen-1,5-diiso-cyanat, trifenylmethan-<1>+,4', ^"-triisocyanat og hexamethylen-1,6-diisocyanat. Examples of suitable isocyanates include toluylene-2, h-diisocyanate, toluylene-2,6-diisocyanate, dimerext toluylene-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthylene-1,5-diiso- cyanate, triphenylmethane-<1>+,4',^"-triisocyanate and hexamethylene-1,6-diisocyanate.

Mengden av flerverdig isocyanat i det impregnerte, arkformige armeringsmateriale er med fordel 1-30, fortrinnsvis 2-15, vekt% av den samlede vekt av umettet alkyd, umettet monomer og flerverdig isocyanat. The quantity of multivalent isocyanate in the impregnated, sheet-like reinforcing material is advantageously 1-30, preferably 2-15, weight% of the total weight of unsaturated alkyd, unsaturated monomer and polyvalent isocyanate.

Det er gunstig at av det impregnerte, arkformige armeringsmaterialets samlede vekt utgjores ca. 10-90 % av den samlede vekt av umettet alkyd, den umettede monomer og isocyanatet, ca. 10-90 % It is advantageous that the total weight of the impregnated, sheet-like reinforcement material is made up of approx. 10-90% of the total weight of unsaturated alkyd, the unsaturated monomer and the isocyanate, approx. 10-90%

av det arkformige armeringsmateriale, ca. 0-60 % av den samlede vekt av pulverformige og/eller fiberformige fyllmidler og 0-20 % of the sheet-shaped reinforcing material, approx. 0-60% of the total weight of powdery and/or fibrous fillers and 0-20%

av i den umettede esterharpiks oppløselige tilsetningsmidler av vanlig type, f.eks. dibutylfthalat, polystyren, klorparaffin og farge-stoffer . of additives of the usual type soluble in the unsaturated ester resin, e.g. dibutyl phthalate, polystyrene, chloroparaffin and dyes.

Dessuten kan det impregnerte, arkformige armeringsmateriale inneholde forskjellige tilsetningsmidler, som stabilisatorer, f.eks. hydrokinon, og slippmidler, f.eks. sinkstearat, og dekkende pig-menter, som titandioxyd, jernoxyd, antimontrioxyd og sinksulfid. In addition, the impregnated, sheet-like reinforcing material can contain various additives, such as stabilizers, e.g. hydroquinone, and release agents, e.g. zinc stearate, and covering pigments, such as titanium dioxide, iron oxide, antimony trioxide and zinc sulphide.

Akseleratoren for polymeriseringsreaksjoner mellom umettede grupper kan bl.a. utgjores av koboltnafthenat, magnesium-, tinn-, jernoctoater og -nafthenater, fenylfosfinsyre og dimethylanilin. Akseleratormengden er med fordel 0,1-3 % av den samlede vekt av The accelerator for polymerization reactions between unsaturated groups can, among other things, consists of cobalt naphthenate, magnesium, tin, iron octoates and naphthenates, phenylphosphinic acid and dimethylaniline. The amount of accelerator is advantageously 0.1-3% of the total weight of

alkyd og monomer...' alkyd and monomer...'

Med metallchelat menes metallforbindelser som er oppbygd av et metall og en ligand med flere "klor',' dvs. en ligand inneholdende mer enn en atomgruppe med affinitet overfor metallet. Slike ligander er f.eks. 2 ,!+-pentadion, aceteddikester , malonsyremethylester og o-amino-fenol. Metallet kan bestå av ett eller flere av metallene titan, By metal chelate is meant metal compounds that are made up of a metal and a ligand with several "chlorines", i.e. a ligand containing more than one atomic group with affinity towards the metal. Such ligands are, for example, 2,!+-pentadione, acetdiester, malonic acid methyl ester and o-amino-phenol The metal may consist of one or more of the metals titanium,

aluminium, krom og jern. aluminium, chrome and iron.

Eksempler på slike forbindelser som med fordel kan anvendes ifolge oppfinnelsen, er diisopropylbis-2,4-pentandiontitanat som i alminnelighet kalles titanacétylacetonat, Ti (C^H,-^^ <*> (C^H^O^, aceteddikesteraluminat, Al ( C^ E^ O^)^, ferroacetylacetonat, Examples of such compounds which can be advantageously used according to the invention are diisopropylbis-2,4-pentanedione titanate, which is commonly called titanium acetylacetonate, Ti (C^H,-^^ <*> (C^H^O^, aceteddikesteraluminate, Al ( C^ E^ O^)^, ferroacetylacetonate,

Fe (C^Hr^^ °§ o-aminof enolkromat, Cr (C^HyON)^. Innholdet Fe (C^Hr^^ °§ o-aminophenol chromate, Cr (C^HyON)^. The content

av metallchelat er med fordel 1-10, fortrinnsvis 2-5, prosent av den samlede vekt av alkyd, monomer og isocyanat. Titanacétylacetonat er spesielt foretrukket. of metal chelate is advantageously 1-10, preferably 2-5, percent of the total weight of alkyd, monomer and isocyanate. Titanium acetylacetonate is particularly preferred.

Katalysatoren for polymeriseringsreaksjoner.kan bl.a. bestå The catalyst for polymerization reactions can i.a. consist

av cyclohexanonperoxyd, methylethylketonperoxyd og benzoylperoxyd. Den tilforte katalysatormengde ved fremstillingen av den formede gjenstand avpasses med fordel til 0,1-8 % av den samlede vekt av alkyd og monomer. For å lette fordelingen av katalysatoren over armeringsmaterialets overflate og dens inntrengning i impregneringsharpiksen opploses den med fordel i en flytende, umettet monomer-for'bindelse av den ovenfor foreslåtte type, f. eks. styren, hvorved monomermengden avpasses slik at den sammen med den i impregneringsharpiksen forekommende mengde vil utgjore en for den herdede harpiks egnet mengde. Ved opplosning av katalysatoren i en flytende monomer kan den påfores f.eks. ved pensling eller sprøyting. of cyclohexanone peroxide, methyl ethyl ketone peroxide and benzoyl peroxide. The amount of catalyst added during the production of the shaped article is advantageously adjusted to 0.1-8% of the total weight of alkyd and monomer. In order to facilitate the distribution of the catalyst over the surface of the reinforcement material and its penetration into the impregnation resin, it is advantageously dissolved in a liquid, unsaturated monomer compound of the type suggested above, e.g. styrene, whereby the amount of monomer is adjusted so that, together with the amount present in the impregnation resin, it will constitute a suitable amount for the cured resin. By dissolving the catalyst in a liquid monomer, it can be applied, e.g. by brushing or spraying.

Ifolge en foretrukken måte for fremstilling av det impregnerte armeringsmateriale tilfores den umettede alkyd, den umettede monomer, det flerverdige isocyanat, akseleratoren, metallchelatet eventuelle fyllmidler og eventuelle andre tilsetningsmidler til armeringsmaterialet uten at den umettede alkyd og isocyanatet får tid til å reagere eller i vesentlig grad å reagere med hverandre, According to a preferred way of producing the impregnated reinforcing material, the unsaturated alkyd, the unsaturated monomer, the polyvalent isocyanate, the accelerator, the metal chelate, any fillers and any other additives are added to the reinforcing material without the unsaturated alkyd and the isocyanate having time to react or to a significant extent to react with each other,

og isocyanatet og alkyd omsettes derefter med hverandre i det impregnerte armeringsmateriale, f.eks. ved lagring av det impregnerte armeringsmateriale 1 noen tid ved værelsetemperatur. Derved kan det oppnåes at det impregnerte armeringsmateriale blir klebefritt for det anvendes for fremstilling av formede gjenstander. Innen alkyden og isocyanatet har reagert eller i vesentlig grad har r.eagert, har bindemidlet en lav viskositet som muliggjor en homogen innblanding av eventuelle fyllmidler og andre bestanddeler og en effektiv impregnering av det arkformige armeringsmateriale. Ved efterfolgende lagring eller tilsvarende behandling reagerer aikydens hydroxylgrupper med isocyanatet, hvorved impregneringsharpiksens viskositet and the isocyanate and alkyd are then reacted with each other in the impregnated reinforcing material, e.g. by storing the impregnated reinforcing material 1 for some time at room temperature. Thereby, it can be achieved that the impregnated reinforcement material becomes adhesive-free because it is used for the production of shaped objects. Before the alkyd and the isocyanate have reacted or have reacted to a significant extent, the binder has a low viscosity which enables a homogeneous mixing of any fillers and other components and an effective impregnation of the sheet-shaped reinforcing material. During subsequent storage or similar treatment, the aikyde's hydroxyl groups react with the isocyanate, whereby the impregnation resin's viscosity

oker slik at det impregnerte armeringsmateriale blir klebefritt-increase so that the impregnated reinforcement material becomes adhesive-free

Oppfinnelsen er nærmere forklart ved de utforelsesformer derav som er beskrevet i de folgende eksempler. The invention is explained in more detail by the embodiments thereof which are described in the following examples.

Eksempel 1 Example 1

En egnet harpiks for impregnering av et armeringsmateriale kan fremstilles på folgende måte: A suitable resin for impregnation of a reinforcing material can be produced in the following way:

En blanding av 5 mol maleinsyreanhydrid, 2 mol fthaisyreanhydrid og A mixture of 5 moles of maleic anhydride, 2 moles of phthalic anhydride and

8 mol ethylenglycol oppvarmes til 150°C. Temperaturen okes suksessivt til 190°C og holdes på denne verdi inntil syretallet er ca. 30 mg KOH/g.. Reaksjonsblandingen avkjoles til 100°C og opploses efter tilsetning av 0,1 vektprosent hydrokinon i monostyren. Styrentil-setningen utgjor 25 % av den samlede vekt av umettet alkyd og styren. 8 mol of ethylene glycol is heated to 150°C. The temperature is successively increased to 190°C and held at this value until the acid number is approx. 30 mg KOH/g.. The reaction mixture is cooled to 100°C and dissolved after the addition of 0.1% by weight of hydroquinone in monostyrene. The styrene addition makes up 25% of the total weight of unsaturated alkyd and styrene.

En forblanding fremstilles fra de folgende bestanddeler ved blanding i f.eks. et vanlig propellblandeapparat: A premix is prepared from the following components by mixing in e.g. a common propeller mixer:

45 vektdeler av den ovenfor beskrevne umettede esterharpiks 45 parts by weight of the unsaturated ester resin described above

Forst tilsettes toluylendii so cyana t til esterharpiksen, og straks efter sammenblandingen av disse tilsettes de ovrige bestanddeler. 2 glassfibermatter med en overflatevekt av 450 g/m fores mellom to til ca. 60°C oppvarmede valser med en innbyrdes avstand av ca. 2,5 mm. Glassfibermatten består av ca. 50 mm lange glassf iberkhipper: bundet First, toluylendii so cyanate is added to the ester resin, and immediately after the mixing of these, the other components are added. 2 fiberglass mats with a surface weight of 450 g/m are lined between two to approx. 60°C heated rollers with a mutual distance of approx. 2.5 mm. The fiberglass mat consists of approx. 50 mm long glass fiber hips: tied

til hverandre med et bindemiddel, f.eks. i det vesentlige bestående av polyvinylacetat eller en polyesterharpiks. Tynne folier av f.eks. polyethen loper mellom glassfibermattene og valsene. Forblandingen av umettet esterharpiks og tilsetningsmiddel blir straks eller i lopet av ca. 1 time efter fremstillingen tilsatt mellom glassfiber - mattene som impregneres av forblandingen ved foringen mellom valsene. Det oppnåes derved et glassinnhold av ca. 30 vektprosent. 'Den impregnerte glassmatte rulles opp og lagres innpakket i en diffusjons-tett folie av f.eks. polyethylenglycolterefthalat eller aluminium i 3 dogn ved 40°C. Det på denne måte oppnådde produkt er da klebefritt, og polyethenfoliene kan derfor fjernes. to each other with a binder, e.g. essentially consisting of polyvinyl acetate or a polyester resin. Thin foils of e.g. polyethylene runs between the fiberglass mats and the rollers. The premix of unsaturated ester resin and additive is immediately or in the course of approx. 1 hour after production added between glass fiber - the mats that are impregnated by the premix at the lining between the rollers. A glass content of approx. 30 percent by weight. 'The impregnated glass mat is rolled up and stored wrapped in a diffusion-proof foil of e.g. polyethylene glycol terephthalate or aluminum for 3 days at 40°C. The product obtained in this way is then adhesive-free, and the polyethylene foils can therefore be removed.

Matten kan anvendes for fremstilling av forskjellige formede gjenstander, hvorved en polymeriseringskatalysator fordeles over overflaten efterat matten er blitt anbragt i formen, på en slik måte at katalysatoren effektivt kan trenge inn i mattens impregneringsharpiks. Fremstilling av f.eks. et laminat kan gjores på folgende måte: Ett lag av den beskrevne impregnerte matte plaseres på et underlag, f.eks. på et plant pressebord i en presse. På den ene eller begge sider av matten eller på pressebordets overflate pensles eller sproytes en katalysatorblanding inneholdende 15 vektprosent cyclohexanonperoxyd og 85 vektprosent styren i en slik samlet mengde at innholdet av peroxyd blir 2 % av den samlede vekt av alkyd og styren (samlet mengde, omfattende den i katalysatorblandingen forekommende). Over det forste mattelag plasseres ennu et lag som på den ene eller begge sider er forsynt med eller blir forsynt med samme mengde katalysatorblanding som angitt ovenfor. For eventuelt ytterligere påforfe lag av impregnert glassfibermatte gåes det frem på samme måte. Lagene presses derefter sammen mellom pressebordets og pressens ovre presseoverflate. Herdingen foregår i lbpet av et par timer ved værelsetemperatur. The mat can be used for the production of various shaped objects, whereby a polymerization catalyst is distributed over the surface after the mat has been placed in the mold, in such a way that the catalyst can effectively penetrate the mat's impregnation resin. Production of e.g. a laminate can be made in the following way: One layer of the described impregnated mat is placed on a substrate, e.g. on a flat press table in a press. On one or both sides of the mat or on the surface of the press table, a catalyst mixture containing 15% by weight of cyclohexanone peroxide and 85% by weight of styrene is brushed or sprayed in such a total amount that the peroxide content is 2% of the total weight of alkyd and styrene (total amount, including that present in the catalyst mixture). Above the first mat layer, another layer is placed which on one or both sides is provided with or will be provided with the same amount of catalyst mixture as indicated above. For any additional layers of impregnated fiberglass mat, proceed in the same way. The layers are then pressed together between the upper press surface of the press table and the press. Curing takes place over the course of a couple of hours at room temperature.

Eksempel 2 Example 2

En egnet harpiks for forimpregnering av et armeringsmateriale kan fremstilles på folgende måte: En blanding av 3 mol isofthalsyre og 7 mol propylenglycol oppvarmes til en temperatur av 190°C som opprettholdes inntil syretallet er 40 mg KOH/g. Reaksjonsblandingen avkjoles til 150°C, og 3 mol fumarsyre tilsettes. Forestringen fortsettes under gradvis oking av temperaturen til 1200°C. Denne temperatur opprettholdes inntil syretallet er 50 mg KOH/g, hvorefter 0,1 vektprosent hydrokinon tilsettes. Reaksjonsblandingen avkjoles til 120° C og fortynnes med styren i en mengde av 40 %, basert på den samlede vekt av umettet alkyd og styren. A suitable resin for pre-impregnation of a reinforcing material can be prepared as follows: A mixture of 3 mol of isophthalic acid and 7 mol of propylene glycol is heated to a temperature of 190°C which is maintained until the acid number is 40 mg KOH/g. The reaction mixture is cooled to 150°C, and 3 moles of fumaric acid are added. Esterification is continued while gradually increasing the temperature to 1200°C. This temperature is maintained until the acid value is 50 mg KOH/g, after which 0.1% by weight of hydroquinone is added. The reaction mixture is cooled to 120° C. and diluted with styrene in an amount of 40%, based on the combined weight of unsaturated alkyd and styrene.

En forblanding fremstilles av de folgende bestanddeler på samme måte som angitt i eksempel 1: A premix is prepared from the following components in the same way as stated in example 1:

En glassfiberduk av vanlig type med overflatevekten 340 <g>/m<2 >impregneres med den ovenforrangitte harpiksblanding. Impregneringen kan f.eks. utfores ved at glassduken får lope gjennom et bad av harpiksblandingen og at overskudd av harpiksen presses ut mellom valser. Et glassfiberinnhold av ca. 60-65 vektprosent er egnet. A fiberglass cloth of the usual type with a surface weight of 340 <g>/m<2> is impregnated with the above-ranked resin mixture. The impregnation can e.g. is carried out by allowing the glass cloth to run through a bath of the resin mixture and the excess resin being squeezed out between rollers. A glass fiber content of approx. 60-65 percent by weight is suitable.

Ved opprullingen av den impregnerte duk spoles en tynn folie, f.eks. polyethenfolie, mellom lagene. Den impregnerte duk lagres i dif-fus jonstett folie ved 40°C i 4 dogn. Duken blir da klebefri slik at polyethenfolien kan fjernes. Duken er egnet, anordnet i flere skikt, for anvendelse ved pressing av f.eks. laminater. Duken kan også med fordel anvendes som overflatebelegningsmateriale for spon-plater, skumplast, finer eller andre underlag. Derved anbringes ett eller flere lag av duken på et underlag, og katalysatorblandingen fordeles over hvert lags overflate på samme måte som beskrevet i eksempel 1. Katalysatorblandingen kan bestå av inntil 15 vektprosent methylethylketonperoxyd opplost i styren. For hvert lag av duken .anvendes en så stor mengde katalysatorblanding at peroxydinn-holdet blir 4 % av den samlede vekt av alkyd og den samlede mengde styren. When rolling up the impregnated cloth, a thin foil, e.g. polythene foil, between the layers. The impregnated cloth is stored in diffusion-proof foil at 40°C for 4 days. The cloth then becomes non-sticky so that the polyethylene foil can be removed. The cloth is suitable, arranged in several layers, for use when pressing e.g. laminates. The cloth can also be advantageously used as a surface coating material for chipboard, foam plastic, veneer or other substrates. Thereby, one or more layers of the cloth are placed on a substrate, and the catalyst mixture is distributed over the surface of each layer in the same way as described in example 1. The catalyst mixture can consist of up to 15% by weight of methyl ethyl ketone peroxide dissolved in styrene. For each layer of the cloth, such a large amount of catalyst mixture is used that the peroxide content is 4% of the total weight of alkyd and the total amount of styrene.

Eksempel Example

Et papir med en gramvekt av 150 g/m 2 impregneres med en harpiksblanding av den i eksempel 2 angitte type, men med den for-skjell at akseleratoren består av koboltnafthenat i samme mengde og at titanchelatet i eksempel 2 erstattes med den samme mengde aluminiumacetylacetonat. A paper with a gram weight of 150 g/m 2 is impregnated with a resin mixture of the type specified in example 2, but with the difference that the accelerator consists of cobalt naphthenate in the same amount and that the titanium chelate in example 2 is replaced with the same amount of aluminum acetylacetonate.

Det impregnerte papir kan anvendes bl.a. som overflatebelegningsmateriale for f.eks. de i eksempel 2 angitte underlag. Som katalysatorblanding ved fremstilling av de formede gjenstander kan en hvilken som helst av de i eksemplene 1 og 2 angitte blandinger anvendes. The impregnated paper can be used i.a. as surface coating material for e.g. the substrates specified in example 2. Any of the mixtures indicated in examples 1 and 2 can be used as a catalyst mixture in the production of the shaped articles.

Eksempel 4 Example 4

En egnet harpiks for impregnering av et armeringsmateriale kan fremstilles på folgende måte: En blanding av 6 mol maleinsyreanhydrid, 2 mol hexaklorendomethylentetrahydrofthalsyre og 9 mol diethylenglycol oppvarmes til 190°C. Efter at syretallet er sunket til 40 mg KOH/g, avkjoles den dan-nede umettede alkyd til 150°C og fortynnes med styren i en mengde av 30 %, basert på den samlede vekt av umettet alkyd og styren. A suitable resin for impregnation of a reinforcing material can be prepared as follows: A mixture of 6 mol maleic anhydride, 2 mol hexachloroendomethylenetetrahydrophthalic acid and 9 mol diethylene glycol is heated to 190°C. After the acid number is reduced to 40 mg KOH/g, the unsaturated alkyd formed is cooled to 150°C and diluted with styrene in an amount of 30%, based on the combined weight of unsaturated alkyd and styrene.

De folgende bestanddeler blir derefter blandet: The following ingredients are then mixed:

Den oppnådde blanding anvendes for impregnering av en glassfibermatte på den i eksempel 1 angitte måte. Den impregnerte matte anvendes derefter for fremstilling av et laminat på lignende måte som angitt i eksempel 1. The resulting mixture is used for impregnating a glass fiber mat in the manner indicated in example 1. The impregnated mat is then used to produce a laminate in a similar way as stated in example 1.

De impregnerte, arkformige materialer kan ikke bare anvendes for fremstilling av plane produkter av laminattypen som nærmere beskrevet i de ovenstående eksempler. De kan selvfølgelig også anvendes for fremstilling av korrugerte plater og for fremstilling av gjenstander med en hvilken som helst form, hvorved det impregnerte, arkformige materiale"plaseres i den angjeldende form i ett eller flere lag og i forbindelse dermed tilsettes en polymeriseringskatalysator. ' The impregnated, sheet-like materials cannot only be used for the production of flat products of the laminate type as described in more detail in the above examples. They can of course also be used for the production of corrugated sheets and for the production of objects of any shape, whereby the impregnated, sheet-like material is "placed in the relevant form in one or more layers and in connection with this a polymerization catalyst is added.'

Claims (6)

1. Fremgangsmåte ved fremstilling av en gjenstand bestående av armert harpiks, ved formning av gjenstanden fra et arkformig armeringsmateriale som er impregnert med en uherdet impregneringsharpiks bestående av en umettet alkyd med hydroxylgrupper, en umettet monomer og et flerverdig isocyanat, hvorved det flerverdige isocyanat eventuelt i det minste delvis er omsatt med den umettede alkyds hydroxylgrupper og det til impregneringsharpiksen er tilsatt en akselerator for polymeriseringsreaksjoner mellom umettede grupper, idet en katalysator for polymeriseringsreaksjoner mellom umettede grupper fordeles over en overflate på det impregnerte, arkformige armeringsmateriale ved anvendelsen av dette for formning av den armerte gjenstand og harpiksen i den formede gjenstand bringes til å herde, karakterisert ved at det til impregneringsharpiksen dessuten er tilsatt et metallchelat, hvorved impregneringsharpiksen bringes til å herde uten tilfjrsel av varme.1. Method for the production of an object consisting of reinforced resin, by forming the object from a sheet-shaped reinforcing material which is impregnated with an uncured impregnation resin consisting of an unsaturated alkyd with hydroxyl groups, an unsaturated monomer and a polyvalent isocyanate, whereby the polyvalent isocyanate optionally in the smallest is partially reacted with the hydroxyl groups of the unsaturated alkyd and an accelerator for polymerization reactions between unsaturated groups is added to the impregnation resin, a catalyst for polymerization reactions between unsaturated groups being distributed over a surface of the impregnated, sheet-like reinforcing material when using this for shaping the reinforced object and the resin in the shaped object is brought to harden, characterized in that a metal chelate is also added to the impregnation resin, whereby the impregnation resin is brought to harden without the application of heat. 2. Fremgangsmåte ifolge krav 1,karakterisert ved at det som chelat anvendes et titanchelat.2. Method according to claim 1, characterized in that a titanium chelate is used as chelate. 3.. Fremgangsmåte ifolge krav 1 eller 2, karakterisert ved at det som chelat anvendes titanacetylacetonat. <>>+. 3.. Method according to claim 1 or 2, characterized in that titanium acetylacetonate is used as chelate. <>>+. Arkformig armeringsmateriale for fremstilling av en gjenstand ved fremgangsmåten ifolge krav 1, impregnert med en uherdet impregneringsharpiks bestående av en umettet alkyd med hydroxylgrupper, en umettet monomer og et flerverdig isocyanat, hvorved det flerverdige isocyanat eventuelt i det minste delvis er omsatt med den umettede alkyds hydroxylgrupper og det til impregneringsharpiksen er tilsatt en akselerator for polymeriseringsreaksjoner mellom umettede grupper, karakterisert ved at det til impregneringsharpiksen dessuten er tilsatt et metallchelat0Sheet-shaped reinforcing material for the production of an object by the method according to claim 1, impregnated with an uncured impregnation resin consisting of an unsaturated alkyd with hydroxyl groups, an unsaturated monomer and a polyhydric isocyanate, whereby the polyhydric isocyanate is possibly at least partially reacted with the hydroxyl groups of the unsaturated alkyd and an accelerator for polymerization reactions between unsaturated groups is added to the impregnation resin, characterized in that a metal chelate is also added to the impregnation resin 5. Armeringsmateriale ifolge krav 4, karakterisert ved at chelatet utgjores av et titanchelat.5. Reinforcing material according to claim 4, characterized in that the chelate consists of a titanium chelate. 6. Armeringsmateriale ifolge krav h eller 4, karakterisert ved at chelatet utgjores av titanacetylacetonat,,6. Reinforcement material according to claim h or 4, characterized in that the chelate consists of titanium acetylacetonate,,
NO4849/70A 1969-12-19 1970-12-17 NO132153C (en)

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