DE1720776A1 - Process for the production of epoxy resin foams - Google Patents

Description

15th January 1968 Dr.Stk / sch

5614
Process for the production of epoxy resin foams

The curing of epoxy resins with Lewis acids such as boron fluoride, Tin tetrachloride, antimony pentachloride and aluminum chloride or acids such as phosphoric acid and benzene-1,3-disulfonic acid are known. Curing is carried out in the presence of low-boiling solvents as a blowing agent, foams are obtained, as is also known.

Epoxy resin foams made with Lewis acids as catalysts however, show undesirable properties such as shrinkage and cracking. When curing low-viscosity epoxy resins with orthophosphoric acid as well as in foam production under Addition of a propellant and pore regulator to the epoxy resin is one complete mixing of the resin component with orthophosphoric acid difficult because of the hardening that is beginning. On the other hand is the crosslinking of the resin is incomplete, so that larger proportions can be extracted on low molecular weight product.

Furthermore, the copolymerization of epoxy resins with cyclic ethers such as oxiranes, oxacyelobutane and their derivatives! Tetrahydrofuran and isotonic known / The mixed polymerisation, however, does not lead to valuable hardening products with the use of all Lewis catalysts or phosphoric acid and polyphosphorus . Härfc.r. _109β 30 / 192δ

A method for the production of foams has now been drrch

Hardening of epoxy compounds with more than one Kpoxidgruppt irr Molecule in the presence of liquid propellants, ggi ". Pore regulator: and / or lactones or cycli scV.e- copolyraerisable with epoxy resins; Ethers found, characterized in that PluorphospliorsKnre as hardener possibly mixed with acidic. Phosphorus compounds is used.

Epoxy resins are compounds with more than one epoxy group understood in the molecule. It is generally advantageous that 3 the epoxy resins contain no more than 10 epoxy groups per molecule. Examples of suitable epoxy resins are reaction products From epiohlorohydrin and polyhydric alcohols and especially with mono- and polynuclear, polyhydric phenols. Furthermore can oil and polyglycidic esters can also be used. Suitable for foaming there are also compounds that are produced by the epoxidation of olefins and polyolefins, Dienes, cyclic dienes and diolefinically unsaturated carboxylic acid esters can be obtained. Telomeres and cotelomeres, which contain olycidyl ether and / o <äer oloid ester groups are used. will. The use of unsetting products is preferred 2,2-Diphenylolpropane with EpiohlorhydrLn. Mainly become foaming at Paumtemperifcur liquid epoxy resins advises epoxy equivalents of 100 - "500 used. However, solid or epoxy resins can also be used are used with higher epoxy equivalents, provided that they are due to the addition of blowing agents, reactive thinners or comonomers. can be obtained liquid «

When Pl ^ orphosphorsäure is a readily available! Long live acid. Representations such as those made from phosphorus pentoxide and aqueous hydrofluoric acid, phosphorus oxyfluoride and orthophosphoric acid, from metaphosphoric acid and hydrogen fluoride, orthophosphoric acid and difluorophosphoric acid are described in the literature. The preparation of fluorophosphoric acid by reacting 65 to 75% aqueous hexafluorophosphoric acid with pyrophosphoric acid and of polyphosphoric acid with hydrogen fluoride, ... for which, however, no protection is sought has proven to be advantageous.

FluorphosphorsHure can do that with pore regulators and * Preibmlttel. mingled Epoxldhar * can be added directly. Ea is sweeker, however they together with not polymerizable with epoxy resins. Complexing agents zuzyeetzet ·.

1O803O / 192S

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! Aig n "r> he n1 <r * 't nit epoxy copolymer rl trollable Los.ungs- or grain rr ierungsrlt tel own look ither as DiSthyläther, diisopropyl ether, dioxane, Kt hylenglykoldiirethylather, Di äthy glycol di methyl Mther, Diäthylenp; ! lykoldiäthyläi ago, ketones such as acetone, Methyläthylkelon, Methylisobuty ketone, Fster as "ethyl and ^ thylformiat, ^Kethyl: 'thyl-, butyl and P'.enylaootat, Glykolmonoacetat, oxalic Scu ^•: crnGteinsäure liätliyJester or Aili-pinnäurrdi ethyl ester.

ReKonders beneficial, it 1st However Fluorp ^ .oFphorsäure einr.nsetzen as Lösunr in monomers copolymerizable with the epoxy resin · copolymerize such as cyclic ethers and lactones or as a solution in compounds which react under rpoxidhar ζ ^ t nlyaddi lon with the ⁵ such as ilkylprosnhonsMuren, rhosphoric acid monoFtern or aromatic polyhydroxylve rhi ^. dun heels wi ρ ^p 1 Rphenole ^ '^ ovolaker "

a?; esei.7: 1 are like P-propi olacton, '' -Methyl - 1-prorl olactor ¹ , 4 -! «pi -. * iyl-r - propi olac + or., ^, '- I 'nmpthy] - "- prop?> lac: fon, 4-' ¹ TI cfilormrt.hy] -" - proni olact on, ^ ¹ , ^ -Ήί 3- (tric-hlor_methy]} -? -prori olp.cton "Fif-ButyroTad on, ^ -Valero! Act on, P- ^ ethyl -J-valc ^ olaoton, fv'opomefryl-, tfonoäthyl-, mononropyi-, monoisorropyl- etc. to '■" nnooodeoyl - ^ - caprolactone, dialkyl - ^ - oiiDrolac tone, in which the (Jen HkylKruppen are on the same or different carbon atoms, but not both rm £ -Yo \\ 1 enstof fatom, TrI alkyl - ^ .- caprolac tone, 1n ■ which- two or three carbon atones 1 m Lactonrinr sutist jf ¹ 1 ert are, ^ ikoxy - ^ - caprolactone -like methoxy- and "^ .hoxy - ^ - ca per lac tone, cycloalkyl-, aryl- and aralkyl - ^ - caprolactone like cyclohexyl -, Phenyl - and Benzyl - ^ "- caprolactone. Lactones with more than f> carbon atoms in the ^ inf such as u -natolactone and" ^ -caprilactone can also be used.

■ Μ ρ Monomerei-, in the fluorophosphorus acid pelöst and the propellant and epoxy resin containing pore regulators can be added, proved ' ^ -Caprolactone is particularly popular.

Also come with as reactive solvents for the catalyst Epoxy resins copolymerizable cyclic ethers such as propylene oxide, Eplchlorhydrin, Ihenylglycidyl ether, Oxacycl obutane, "^ -Methyl-oxacyclobutane, ^, '- Di methyl-oxacycl obutane, ^,' ■ -Bis- (chloromethyte V-oxacyclobutane and tetrahydrofuran.

109830/1925

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In addition to the alkyl esters of the polyphosphoric acid derivatives mentioned, their Alkyl groups have 1 Ms 10 carbon atoms, are linear or branched and can be substituted by halogen, are also aryl esters, such as phenyl, methylphenyl, chlorophenyl and 1,3,5-tribromophenyl esters used.

Furthermore, reaction products of the neutral and acidic polyphosphoric acid esters can also be used with aliphatic and cycloaliphatic diols, Triols, polyether diols and polyhydric phenols such as resorcinol and polyhydric, polycyclic phenols such as 4,4'-dioxide / phenylmethane or 4,4'-dioxydiphenyl ^ jS-propane can be used.

The mentioned phosphorus compounds, which together with the fluorophosphoric acid can be used, up to equivalent amounts based on w on the epoxy resin, i.e. a hydroxy equivalent of the phosphorus compound to an equivalent epoxy. It has, however, in terms of The foam properties have proven advantageous to use lower than equivalent amounts of the abovementioned phosphorus compounds, preferably 0.2-0.6 hydroxyl equivalents per epoxy equivalent.

The ones in the trade, are! lohe called monofluorophosphoric acid Acid "which, according to the elemental analysis, corresponds to the empirical formula PPO (OH) ρ, also contains small amounts according to nuclear magnetic resonance measurements Orthophosphoric acid and difliorphosphoric acid.

The cell structure of those produced with the catalyst according to the invention Foam is essentially determined by the content of Orthophosphoric acid determined. So if you use a $ 20 Igen Open-celled solution of monofluorophosphoric acid in orthophosphoric acid Foam obtained, with ^ O to 100 ^ lger Monof luorphosphorsäu, re. the lines are largely closed. The GesohlossenzelllRkelt, - takes with stony concentration of fluorophosphorus sauce In Orthpr. phosphoric acid "to. ■. ..

Of course, the Laetpne and cyclic. Ether together with the phosphorus compounds as a solution medium for phosphoric acid can be used. _:. .- ,. · ....

Finally, the soap can also be used as novolaks. known conversion products of monovalent or polyvalent, mononuclear polynuclear

109830/1925 .adowgihal; ' '

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Phenols with formaldehyde are added. .. ..>

The foaming of the epoxy resins takes place in a known manner by adding easily evaporating halogenated hydrocarbons or hydrocarbons such as mono ^ luortrichloromethane, mono-fluorodichloromethane, l,?,? - trichlorotrifluoromethane, Ι, Ρ-dichlorotetrafluoroethane, ^ ethylrnci'il. The propellant is generally used in amounts of T> to ⁷ ; 0 wt .- ^, based on the epoxy resin. For ore πίπη- ^'1:. Very uniform pore foam 1st is also advantageous pore regulators such as silicone oils add. Furthermore, fillers, dyes, plasticizers or flame retardants can be added to the mixture to be foamed.

^ F For foam production, for example, the mixture of resin, propellant and silicone oil is stirred with the reactive solvent containing the catalyst. However, the catalyst components to which the pore regulator and blowing agent have been added can also be mixed with the liquid oxide resin. The mixing can be batch catfish using suitable stirrer or continuously performed on Scbaummaschinen, wherein the "pritz- or mixing operations sur ^ irschäumuni" can be worked from predetermined ormen ^w. The pot life of the foam mixture depends in each case on the epoxy resin used, the catalyst concentration and the selected initial temperature of the individual components.

The mixture can be stirred for 10 to 10 seconds sufficient for thorough homogenization.

The components to be mixed can have the same or different temperatures from ^F > to h ^ ° " _t, preferably ^Ί " to " ¹ ^ ⁰ H. The foaming is normally finished in 10 to 60 seconds and the foam after? 0 seconds Don't stick it for a few minutes.

The anpal to be provided according to the method according to the invention is distinguished by its easy workability and that it is preserved. ficha'ume have good mechanical K1genscha ⁿ Len and a ^ e Kerir tendency to rubbing interior of putting down Lm foam. Furthermore , the fluorophosphoric acid gives the foam self-lashing properties

109830 / 19.25

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720776

The required foams supplied; as

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Me "tr; (Sem Talfretiaen BelKplelen genaiiRten parts telle * The product used as epoxy resin is a di ^ lyeidiylether of the Λ _$ Λ '-Moxi-dipftenyl ~ ί?» Γ-proparrs with the Fpaxid'äqiiiv & lent IQO and etner Vlsfco> sit & t from -IlFOD cP at F ^ - ⁰ C. The ίΐΐΐΙσοποΊ used is a UCC commercial product with the designation ^T. ^ L.

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TOOC parts of epoxy resin are mixed with 10 parts of silicone oil and 150 parts of chlorofluoromethane. The viscosity of the mixture is 1100 cp at.? 5 ° Π. Then 28 parts of fluorophoric acid and 1? Parts of orthophosphoric acid dissolved in 50 parts ■ £ -caprolactone and cooled to 5 ⁰ C P. This catalyst solution is within L ^c seconds by means of an impeller with the blowing agent and ^p orenregler containing Fpoxidharz stirred until homogeneous and poured to verechäumende mixture immediately into a mold. The foam is highly increased within 50 seconds, and after 11 minutes non-tackiness rei .. It is a colorless, homogeneous fine-pored and tough foam body having a density of "obtained ⁷ O g / l. Its compression strength is 1.6 kg / cm" which Heat resistance after waiting (DIN-Nortn hV ^ 2k) QO ⁰ C. The cells are 76 * closed.

The fluorophosphoric acid / orthophosphoric acid fish used as a catalyst was prepared by reacting pyrophosphoric acid with aqueous hexafluorophosphoric acid in a weight ratio of Pq / ¹ ? Difluorophosphoric acid.

Example P

Fri viird procedure described in Example 1, but al ε hardener ELRE lüEunr: from ^ - "3 parts Pluorphosphorsäure and 75 Great Orthophopphorsä'ure in l ^r> 0 ^ parts caprolactone elnresetzt The Steipreit betrfigt 0 Secunder The Cchaurrkörner is..?. ^after; ί0 second kleb ^ rei Its compressive strength betrKgf tei ^ r / l ν κ · - ^ t 'for a full of "enzel lj gor Schaumstof ^r Sustainer i.er....

Example 2.

FJS 'is moved vip irr Example 1 except that as the catalyst a τ ofui'c: Pl of parts Fluorptosphorsä'ure and 0 parts of ortho'. Used phosphoric acid in 5 ^"1 share Vinylprosrhonnnuro The P ^ ^o piece GGtir, ness of fchaumst of fee is at ^ 5 v / \ 1 kg / cm 'The time "On 5-1 r _{ j -m' ί«

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Example 4

1000 parts of epoxy resin are mixed with 10 parts of silicone oil and V) Q parts of Tri ^ luorcMormetiian. Then 100 parts of a Prienol / Porraaldel ycä-FondenRationsprotJukter-:; ^r i ^ O parts ^ f- ^ aprolacton rcelöst and mixed with *> 0 g of a winoror.-iEn ^ orsaure / nrt'haphosphoT'sättregemlsehes im GeW -.- Ve rh .. '30Λ - 0. The catalyst solution is mixed within 1 \> seconds. Tilt the epoxy resin component and into a fort! given. The frothing starts immediately and within a minute the S'ir-aum has reached its full height. It will be a zn S? 'i closed-cell foam body of the density ^{x (:} μ, / \. and with a Druckfestipkelt of 2, f k ^ / cm ".

The phenol '^ orrr-aldehyde condensate ion product became durably acidic catalyped conversion of phenol with formaldehyde ir. mol ratio 5: 1 manufactured. The excess phenol was Jm Vacuum aDdestiitiert.

The used P] nor- / Orth-Trrt o ^ nhoräure-KIöchunt; was made by VSmsetv.v.nr of. Poly.n'h- ^ FDhoräure with 10 wt .- ^ ^1? iu - '> hydrogen produced. '

Example £. '...

Tn f '/ S' parts epoxy resin of the example ^i! '; - ^: -' ^J - ^: s parts r "hermolecular epoxy resin , which was produced by non-retr-.unK of 4, ^ t '-dioxide! phenyl-ii-pronane rt> it lnichlorohydrin, and a fichmel / point before * Y ^ 0 "nd has an epoxy equivalent of 500» Cooling down to Hr ₁ ⁰ C the Tr'nunr with ^ O f? if- ^ aorolic-ton diluted and at? 5 ° C r1t 'τα parts SiIiconcM and I ¹ V / Tt-; Len Trichlorofluor- ■, rrethan veririsiert »Then P ^ parts of phosphoric acid in ^l '? _f ! Share ^ -oaOroTact'on dissolved, ^{cooled to 0} ^ ⁰ C and rrittefs a? rat nellrüiirerf) irner ^ alb of 15 seconds mi'i the 'Vre Ibmiitel and pore regulator contained Γ T) Oy i dharz verm' -R.cht and E: n? place in a form i ^r egonsen. Mach \ no . "Seconds the Tchaun has reached his vniTp m'Yo ^ v- ^r \> l 1st racb v / .eite ^ pp ^r 0 seconds without a knee dr-rckfoptlgkeit of l / i lfg / cir 'einr-r density of? .8 r / l "89 ^' geschiopsene cells and a heat .'- forrr'bestKn '] i ^ Celtic after waiting of <> 1 ^O C.

1 09830 / t 92 6 bath

Claims (1)

- 4 * 0 - Claims - ■ t) Process 'for the production of epoxy haraßehauTfjtof fen dr.ro ·: HMs of epoxy compounds with rrehr as e-ir «' · ^r 'poyj <i -η-φρ in the molecule in the presence of liquid'"re'hnfii tr a i, nd gg '~. pore regulators and / or lactones or with jp oxide ¹ -ar., en οτρτ ^τ γ-riwriei erbaren cyclic ethers, dfulur-oh geV ^ ir: * ■ ^: or r.et. that' ■ as hardener fluorophosphoric acid-p, ρκΓ. in Kor * ty! nn. * _ i or. ml + F'i'iff phosphorus compounds ,. used v / i.rd. 2) Method according to claim 1, characterized in that gekenrj ' ⁷ ei?' ■ ^r ", dn ° PhnrphosphorsSure dissolved in '.onorr.eren die τ; γ der:' ό- jc i; i ^v : ^ r: · ο λμ>.!.; / - merisleren like cyclisßhe fither and lactones od ^ r alr> Γ ^ν 'εητ ·. · ir compounds, which under polyarid it lon with the i'.p>xid'.ar. ~ "ΐ: νί < ! 'ΐ such as alkylphosphonaic acid, phosphoric acidic acid, o ^ vj; ·· r r- rTirr aromatic polyhydroxy]: compounds, use ¹ · we-d. 5). Procedure according to. Claims 1 and 2, characterized in ; κ, * ker. "Kf; i ·:; ^ e *, ^ -Caprolactone as CoaiöFio ^ ereE: is used. • AD ORJGINAL 10 9 8 3 0/1925