NO140472B - PROCEDURE FOR THE PRODUCTION OF FIRE-PROFESSIONAL PHENOL-FORMAL HYDIC ROCK FOAM - Google Patents

PROCEDURE FOR THE PRODUCTION OF FIRE-PROFESSIONAL PHENOL-FORMAL HYDIC ROCK FOAM Download PDF

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Publication number
NO140472B
NO140472B NO159568A NO159568A NO140472B NO 140472 B NO140472 B NO 140472B NO 159568 A NO159568 A NO 159568A NO 159568 A NO159568 A NO 159568A NO 140472 B NO140472 B NO 140472B
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formaldehyde
phenol
fire
production
compound
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NO159568A
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Norwegian (no)
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NO140472C (en
Inventor
Daniel Hanton
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Saint Gobain
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Publication of NO140472B publication Critical patent/NO140472B/en
Publication of NO140472C publication Critical patent/NO140472C/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2361/10Phenol-formaldehyde condensates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers

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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)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Fireproofing Substances (AREA)

Description

Foreliggende oppfinnelse angår en fremgangsmåte for fremstilling av brannsikre fenolformaldehydharpiksskum omfattende oppskumming av en vandig oppløsning av fenolformaldehydharpiks som er tilsatt et driv-middel, en vannoppløselig overflateaktiv silikonolje, som er stabil i oppløsning, samt en nitrogenholdig organisk forbindelse som under innvirkning av varme, frigjør en gassblanding som ikke underholder forbrenning. The present invention relates to a method for the production of fire-resistant phenol-formaldehyde resin foam comprising foaming of an aqueous solution of phenol-formaldehyde resin to which a propellant has been added, a water-soluble surface-active silicone oil, which is stable in solution, and a nitrogen-containing organic compound which, under the influence of heat, releases a gas mixture that does not support combustion.

Det er kjent at oppskummede fenolharpikser med høy isola-sjonsevne, befridd for vann og syrekatalysator ved avdamping, har den ulempe at materialene når de utsettes for påvirkning av ild over lengre tid og ilden deretter opphører, vil fortsette å bryte sammen uten flamme, hvilket fører til fullstendig forkulling av materialets cellestruktur. It is known that foamed phenolic resins with high insulating properties, freed from water and acid catalyst by evaporation, have the disadvantage that when the materials are exposed to the influence of fire for a long time and the fire then ceases, they will continue to break down without flame, which leads to complete charring of the material's cellular structure.

I fenolharpikser anvendt for fremstilling av skum med In phenolic resins used for the production of foam with

stor egenvekt er det likeledes kjent å innføre nitrogenforbindelser, slik som spesielt urea, og ammoniakksalter. Man kan iakt-ta to faser under denne fremstilling: 1) Varmeutvikling p.g.a. kondensasjon mellom fenol og formaldehyd, og 2). over en viss temperatur reagerer nitrogenforbindelsene voldsomt med det overskudd av formaldehyd som ikke har bundet seg til fenolen, og i nærvær av syrekatalysator får man en meget rask herding av harpiksmassen. large specific gravity, it is also known to introduce nitrogen compounds, such as urea in particular, and ammonia salts. Two phases can be observed during this production: 1) Heat development due to condensation between phenol and formaldehyde, and 2). above a certain temperature, the nitrogen compounds react violently with the excess of formaldehyde that has not bound to the phenol, and in the presence of an acid catalyst you get a very rapid hardening of the resin mass.

Det er imidlertid umulig å kontrollere reaksjonen, og dette gir opphav til celleprodukter med heterogen struktur, However, it is impossible to control the reaction, and this gives rise to cell products with a heterogeneous structure,

dvs. med store porer som ofte oppviser større hulrom. Fremfor alt er fordelingen av materialet ujevn, og volumvekten (tilsyne-latende egenvekt) varierer betraktelig innenfor produktet, i.e. with large pores that often exhibit larger cavities. Above all, the distribution of the material is uneven, and the volume weight (apparent specific gravity) varies considerably within the product,

hvilket gir det dårligere isolasjonsegenskaper og gjør det mindre sterkt og mindre motstandsdyktig mot varmepåvirkning og brann. which gives it poorer insulation properties and makes it less strong and less resistant to heat and fire.

Foreliggende oppfinnelse har til hensikt å motvirke de ovenfor beskrevne mangler og har således til hensikt å tilveie-bringe en fremgangsmåte for fremstilling av fenolformaldehydharpiksskum med spesielt stor holdfasthet og motstandsevne mot påvirkning av ild, med homogen struktur og med jevne celledimen-sjoner samt gode mekaniske egenskaper. The present invention aims to counteract the above-described shortcomings and thus aims to provide a method for the production of phenol-formaldehyde resin foam with particularly high holding strength and resistance to the influence of fire, with a homogeneous structure and with uniform cell dimensions as well as good mechanical properties .

Oppfinnelsen angår således en fremgangsmåte for fremstilling av brannsikre fenolformaldehydharpiksskum, omfattende oppskumming av en vandig oppløsning av fenolformadehydharpiks som er tilsatt et driv-middel, en vannoppløselig overflateaktiv silikonolje som er stabil i oppløsning, og en nitrogenholdig organisk forbindelse som under påvirkning av varme frigjør en gassblanding som ikke underholder forbrenning, og fremgangsmåten karak-teriseres ved at det som nitrogenholdig forbindelse anvendes en amino-organisk forbindelse partielt kondensert med formaldehyd eller kokondensert med fenol og formaldehyd, hvorved den i det vesentlige er indifferent overfor fritt formaldehyd og stabil ved den temperatur der drivmidlet aktiveres. The invention thus relates to a method for the production of fire-resistant phenol formaldehyde resin foam, comprising foaming of an aqueous solution of phenol formaldehyde resin to which a propellant has been added, a water-soluble surface-active silicone oil which is stable in solution, and a nitrogen-containing organic compound which, under the influence of heat, releases a gas mixture which does not support combustion, and the method is characterized by the use as a nitrogen-containing compound of an amino-organic compound partially condensed with formaldehyde or co-condensed with phenol and formaldehyde, whereby it is essentially indifferent to free formaldehyde and stable at the temperature at which the propellant is activated.

Nevnte nitrogenholdige forbindelse deltar i dannelsen av Said nitrogenous compound participates in the formation of

den sammensatte polymer. the composite polymer.

Nitrogenforbindelsene kan velges blant partielt konden-serte aminoplaster. Spesielt kan man benytte reaksjonsproduk-ter fra omsetning av formaldehyd med urea, melamin, dicyandiamid eller generelt et hvilket som helst annet amin. The nitrogen compounds can be chosen from partially condensed aminoplasts. In particular, reaction products from the reaction of formaldehyde with urea, melamine, dicyandiamide or generally any other amine can be used.

Nitrogenderivater som innføres i fenolharpiksen for oppskumming kan med fordel være: 1) kondensater mellom fenol, formaldehyd og en organisk Nitrogen derivatives that are introduced into the phenolic resin for foaming can advantageously be: 1) condensates between phenol, formaldehyde and an organic

nitrogenforbindelse som urea, melamin eller dicyandiamid, nitrogen compound such as urea, melamine or dicyandiamide,

2) kondensater mellom formaldehyd og en organisk nitrogenforbindelse som urea, dicyandiamid eller melamin, 3) kokondensater mellom formaldehyd og en organisk nitrogenforbindelse som f.eks. de ovenfor nevnte. 2) condensates between formaldehyde and an organic nitrogen compound such as urea, dicyandiamide or melamine, 3) cocondensates between formaldehyde and an organic nitrogen compound such as e.g. those mentioned above.

På grunn av disse nitrogenforbindelsers lave reaktivitet, er det mulig å kontrollere herdereaksjonen i oppskummingsperio-den, og på denne måte lettvint regulere skummets volumvekt (for å kunne oppnå produkter med høy tetthet på mellom 30 og 200 kg/m (, og for å kunne oppnå jevn porestørrelse under forbedring av de mekaniske egenskaper hos det ferdige produkt, særlig trykkfastheten. De fenolskumplaster som er fremstilt i henhold til oppfinnelsens fremgangsmåte, har utmerket holdfasthet og motstandsevne mot varme og ild. Due to the low reactivity of these nitrogen compounds, it is possible to control the curing reaction during the foaming period, and in this way easily regulate the volume weight of the foam (to be able to obtain products with a high density of between 30 and 200 kg/m (, and to be able to achieve a uniform pore size while improving the mechanical properties of the finished product, especially the compressive strength.The phenolic foam plastics produced according to the method of the invention have excellent holding strength and resistance to heat and fire.

Under påvirkning av varme dekomponerer nitrogenforbindelsene under avgivelse av en gassblanding som hovedsakelig består av ammoniakk, karbondioksyd og nitrogen, hvilket skaper en inert atmosfære hvor forbrenningen ikke kan underholdes. Nitrogenforbindelsene velges også slik at de avgir en maksimal gassmengde i de tilfelle hvor den ferdigherdede fenolharpiks i seg selv vil kunne brenne. Under the influence of heat, the nitrogen compounds decompose, emitting a gas mixture consisting mainly of ammonia, carbon dioxide and nitrogen, which creates an inert atmosphere where combustion cannot be entertained. The nitrogen compounds are also chosen so that they give off a maximum amount of gas in cases where the fully cured phenolic resin itself will be able to burn.

Som harpikser av ovenstående type, kan man f.eks. bruke de nedenstående som er fremstilt ved kondensasjon under base-katalyse mellom en fenol og formaldehyd i vandig oppløsning eller i form av polymer. As resins of the above type, one can e.g. use those below which are produced by condensation under base catalysis between a phenol and formaldehyde in aqueous solution or in the form of a polymer.

Harpiks 1 Resin 1

Harpiks 2 Harpiks 3 Harpiks 4 Resin 2 Resin 3 Resin 4

Ved fremgangsmåten ifølge oppfinnelsen tilsetter man til en fenolharpiks, som f.eks. harpiks 1 i vandig oppløsning, følgende: 1) et skummiddel eller drivmiddel som kan være en væske med lavt kokepunkt, f.eks. et alifatisk hydrokarbon eller halogen-derivater av slike hydrokarboner, 2) et mineralsk fyllstoff som talkum, silisiumdioksyd, kisel-gur, asbest, glimmer osv., In the method according to the invention, one adds to a phenolic resin, which e.g. resin 1 in aqueous solution, the following: 1) a foaming agent or propellant which can be a liquid with a low boiling point, e.g. an aliphatic hydrocarbon or halogen derivatives of such hydrocarbons, 2) a mineral filler such as talc, silicon dioxide, diatomaceous earth, asbestos, mica, etc.,

3) en nitrogenforbindelse av ovenstående type, 3) a nitrogen compound of the above type,

4) et herdemiddel som kan være en mineralsk eller organisk syre. 4) a curing agent which can be a mineral or organic acid.

Dette fremkaller en eksoterm polymerisering av harpiksen, og den avgitte varmemengde er tilstrekkelig til å fordampe drivmidlet som ekspanderer massen. This induces an exothermic polymerization of the resin, and the amount of heat given off is sufficient to vaporize the propellant which expands the mass.

Likeledes tilsettes i henhold til oppfinnelsen til en blanding av harpiks og drivmiddel, en silikonolje med overflateaktiv virkning, og spesielt benyttes silikonoljer av typen sili-konglykolkopolymerer, vannoppløselige og stabile i oppløsning, Similarly, according to the invention, a silicone oil with surface-active effect is added to a mixture of resin and propellant, and in particular silicone oils of the silicone-glycol copolymer type are used, which are water-soluble and stable in solution,

som angitt i søkerens franske patent nr. 1.462.228. En av de ovenstående nitrogenforbindelser tilsettes deretter til blandingen. as set forth in Applicant's French Patent No. 1,462,228. One of the above nitrogen compounds is then added to the mixture.

Gjennomføringen av fremgangsmåten skjer på i og for seg kjent måte ved hjelp av en skovl eller en anordning som sam- The method is carried out in a manner known per se by means of a shovel or a device which

tidig sørger for å dosere og blande bestanddelene, samt utmater dem kontinuerlig. early ensures that the ingredients are dosed and mixed, as well as continuously dispensed.

100 kg tørr fenolharpiks er fremstilt ut fra følgende vektforhold mellom bestanddelene: 100 kg of dry phenolic resin is produced from the following weight ratio between the components:

Oppfinnelsen skal illustreres nærmere ved de følgende eksempler. The invention shall be illustrated in more detail by the following examples.

Eksempel 1 Example 1

kondensat AX: kondensasjonsprodukt av 1 mol dicyandiamid og 2,1 mol formaldehyd. Eksempel 2 Eksempel 3 condensate AX: condensation product of 1 mol of dicyandiamide and 2.1 mol of formaldehyde. Example 2 Example 3

Kondensat AX: kondensasjonsprodukt av 1 mol dicayndiamid og 2,1 Condensate AX: condensation product of 1 mol of dicaynediamide and 2.1

mol formaldehyd. moles of formaldehyde.

Kondensat B : kondensasjonsprodukt av 1 mol fenol, 2,3 mol for-moldehyd og dicyandiamid (25 vekt-% av fenolen). Condensate B: condensation product of 1 mol of phenol, 2.3 mol of formaldehyde and dicyandiamide (25% by weight of the phenol).

Ved oppfinnelsens fremgangsmåte oppnås særlig følgende fordeler: In particular, the following advantages are achieved by the method of the invention:

- en forbedring av skumplastens volumvekt som kan ligge - an improvement in the volume weight of the foam plastic that can lie

3 3

mellom 30 og 200 kg/m , between 30 and 200 kg/m,

- en perfekt jevnhet i porestørrelse, - a perfect uniformity in pore size,

- gode mekaniske egenskaper, særlig trykkfasthet, - good mechanical properties, especially compressive strength,

- fremragende motstandsevne mot ild: ifølge prøve ASTM D 1692-59T klassifiseres de fremstilte skumtyper som selv-slukk- - excellent resistance to fire: according to test ASTM D 1692-59T, the manufactured foam types are classified as self-extinguishing

ende. end.

Det er nødvendig å dampbehandle skumplasten for å befri It is necessary to steam the foam to free

den for gjenværende vann og fjerne gjenværende syre for å hindre at plasten blir korroderende. Denne operasjon beregnes vanlig- it for residual water and remove residual acid to prevent the plastic from corroding. This operation is usually calculated-

vis av dampbehandlingstemperaturen (omkring 100°C) fordi risi- show the steam treatment temperature (around 100°C) because risi-

koen for forkulling er stor. Skummet som oppnås ved fremgangsmåten ifølge oppfinnelsen, har mye større varmemotstand og kan tørke ved høyere temperaturer (omkring 120°C), hvilket nedset- the cow for charring is large. The foam obtained by the method according to the invention has much greater heat resistance and can dry at higher temperatures (around 120°C), which reduces

ter oppholdstiden i behandlingskammeret betydelig. significantly reduces the length of stay in the treatment chamber.

Claims (4)

1. Fremgangsmåte for fremstilling av brannsikre fenolformaldehydharpiksskum, omfattende oppskumming av en vandig opp-løsning av fenolformaldehydharpiks som er tilsatt et driv-1. Process for the production of fire-resistant phenol formaldehyde resin foam, comprising foaming of an aqueous solution of phenol formaldehyde resin to which a propellant has been added middel, en vannoppløselig overflateaktiv silikonolje som er stabil i oppløsning, og en nitrogenholdig organisk forbindelse som under innvirkning av varme frigjør en gassblanding som ikke underholder forbrenning, karakterisert ved at det som nitrogenholdig forbindelse anvendes en aminoorganisk forbindelse partielt kondensert med formaldehyd eller kokondensert med fenol og formaldehyd, hvorved den i det vesentlige er indifferent overfor fritt formaldehyd og stabil ved den temperatur der drivmidlet aktiveres. agent, a water-soluble surface-active silicone oil which is stable in solution, and a nitrogen-containing organic compound which, under the influence of heat, releases a gas mixture which does not support combustion, characterized in that the nitrogen-containing compound is an amino-organic compound partially condensed with formaldehyde or co-condensed with phenol and formaldehyde, whereby it is essentially indifferent to free formaldehyde and stable at the temperature at which the propellant is activated. 2. Fremgangsmåte som angitt i krav 1, karakterisert ved at det som nitrogenholdig forbindelse anvendes en delvis kondensert aminoplast. 2. Method as stated in claim 1, characterized in that a partially condensed aminoplast is used as nitrogenous compound. 3. Fremgangsmåte som angitt i krav 1, karakterisert ved at det som nitrogenholdig forbindelse anvendes et kondensat mellom formaldehyd og urea, dicyandiamid eller melamin. 3. Method as stated in claim 1, characterized in that a condensate between formaldehyde and urea, dicyandiamide or melamine is used as the nitrogenous compound. 4. Fremgangsmåte som angitt i krav 1, karakterisert ved at det som nitrogenholdig forbindelse anvendes et kokondensat mellom fenol, formaldehyd og urea, dicyandiamid eller melamin.4. Method as stated in claim 1, characterized in that a cocondensate between phenol, formaldehyde and urea, dicyandiamide or melamine is used as nitrogenous compound.
NO159568A 1967-05-30 1968-04-25 PROCEDURE FOR THE PRODUCTION OF FIRE-PROFESSIONAL PHENOL-FORMAL HYDIC ROCK FOAM NO140472C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR108436A FR1532540A (en) 1967-05-30 1967-05-30 Fire resistant phenolic resin foams

Publications (2)

Publication Number Publication Date
NO140472B true NO140472B (en) 1979-05-28
NO140472C NO140472C (en) 1979-09-05

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Application Number Title Priority Date Filing Date
NO159568A NO140472C (en) 1967-05-30 1968-04-25 PROCEDURE FOR THE PRODUCTION OF FIRE-PROFESSIONAL PHENOL-FORMAL HYDIC ROCK FOAM

Country Status (11)

Country Link
AT (1) AT288034B (en)
BE (1) BE715792A (en)
CH (1) CH491161A (en)
DK (1) DK135811B (en)
ES (1) ES354281A1 (en)
FR (1) FR1532540A (en)
GB (1) GB1201105A (en)
LU (1) LU56167A1 (en)
NL (1) NL164074C (en)
NO (1) NO140472C (en)
SE (1) SE361322B (en)

Also Published As

Publication number Publication date
NO140472C (en) 1979-09-05
LU56167A1 (en) 1969-03-20
NL164074B (en) 1980-06-16
DK135811B (en) 1977-06-27
SE361322B (en) 1973-10-29
DK135811C (en) 1977-11-28
NL164074C (en) 1980-11-17
CH491161A (en) 1970-05-31
DE1769471B2 (en) 1976-03-04
FR1532540A (en) 1968-07-12
DE1769471A1 (en) 1971-07-08
AT288034B (en) 1971-02-25
ES354281A1 (en) 1969-11-01
GB1201105A (en) 1970-08-05
BE715792A (en) 1968-11-28
NL6807562A (en) 1968-12-02

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