CA1246782A - Acid-curable mixture for low-shrinkage furan cements and a process for its preparation - Google Patents
Acid-curable mixture for low-shrinkage furan cements and a process for its preparationInfo
- Publication number
- CA1246782A CA1246782A CA000472716A CA472716A CA1246782A CA 1246782 A CA1246782 A CA 1246782A CA 000472716 A CA000472716 A CA 000472716A CA 472716 A CA472716 A CA 472716A CA 1246782 A CA1246782 A CA 1246782A
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- phenol
- resin
- furfuryl alcohol
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
- C08G16/0256—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds containing oxygen in the ring
- C08G16/0262—Furfuryl alcohol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/34—Filling pastes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dental Preparations (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Saccharide Compounds (AREA)
- Dc Digital Transmission (AREA)
Abstract
Abstract of the disclosure:
1. Acid-curable mixture for low-shrinkage cements which is based on a reaction product of furfuryl alcohol with a resol having at least 0.5 hydroxymethyl group per phenolic hydroxyl group, and which contains A), as the binder, the reaction product of furfuryl alcohol and the resol on the basis of a) at least one trifunctional phenol or a mixture of this phenol a) with b) alkylphenols and/
or aralkylphenols, each having 3 to 20 carbon atoms in the alkyl radical, or an arylphenol, each mixture b), based on the sum of the phenols a) and b), more than 0.4 mole of furfuryl alcohol having been reacted per hydroxymethyl group, and B) at least one reactive diluent in a ratio by weight of (0.4 to 1.5):1 to the resin A).
This solution is mixed, preferably immediately before use, uith C) at least one filler and D) at least one cur-ing agent, the ratio by weight between the sum of the components A) and B) and that of the components C) and D) being 1:(1 to 7), preferably 1:(1.5 to 5). The result-ing cements have a very low shrinkage and are extremely resistant to chemicals.
1. Acid-curable mixture for low-shrinkage cements which is based on a reaction product of furfuryl alcohol with a resol having at least 0.5 hydroxymethyl group per phenolic hydroxyl group, and which contains A), as the binder, the reaction product of furfuryl alcohol and the resol on the basis of a) at least one trifunctional phenol or a mixture of this phenol a) with b) alkylphenols and/
or aralkylphenols, each having 3 to 20 carbon atoms in the alkyl radical, or an arylphenol, each mixture b), based on the sum of the phenols a) and b), more than 0.4 mole of furfuryl alcohol having been reacted per hydroxymethyl group, and B) at least one reactive diluent in a ratio by weight of (0.4 to 1.5):1 to the resin A).
This solution is mixed, preferably immediately before use, uith C) at least one filler and D) at least one cur-ing agent, the ratio by weight between the sum of the components A) and B) and that of the components C) and D) being 1:(1 to 7), preferably 1:(1.5 to 5). The result-ing cements have a very low shrinkage and are extremely resistant to chemicals.
Description
1246~82 ,, `, ~ he invention relates to acid-curable mixtures for low-shr~nkage cements containing furan resins ~ the bin-der. In the speci~ication the terms ~bifunctional" and "trifunctional phenol" respectively correspond to "phenol having 2 (and 3) reactive positions in the nucleus respec-tively.
6erman Offenlegungssehrift 2,926,053 discloses lou-shrinkage, acid-curing mixtures for eements contain-~ng~ as the binder~ a reaction product of furfuryl alco-hol uith a resol, containin~ hydroxymethyl ~roups, basedon bifunctional alkylphenols or aralkylphenols having 3 to 20 carbon atoms in the alkyl radical, if appropriate as oixture uith a minor proportion of unsubstituted phenol or diphenol propane, at least 75X of the reactlve hydrogen atoms 1n tho nucleus of the substituted resol being subst1tuted by reaction ~ith formaldehyde and more than 0.5 nole of furfuryl alcohol having been reacted per hydroxymethyl group, and the reaction product being dis-solved ~n at le-st one reactive thinner belonging to the group co~pris1ng benzyl alcohol, lou-molecular epoxide conpounds, furfurol, d1furyl ether or furfuryl alcohol.
The resins obtained in accordance uith this teaching con-stitute valuable binders for cements, but exhibit a cer-tain sensit1vity touards a fe~ corrosive organic solvents ~hich re of importance in practice for a number of cases, such as ketones, chlorinated and aromatic hydrocarbons and e~ters.
~ t is also knoun from 6erman Offenlegungsschrift 3,028,974 to obtain, from a phenol compound, an aldehyde and furturyl alcohol, resins uhich have been prepared under ~ubstantially anhydrous conditions in the presence of a metal catalyst. These resins, uhich are suitable for the preparation of foundry cores and foundry mo~ds, cannot, ho~ever, be used for the preparation of o-~nts because they do not crossLink under the conditions customary in the techno~ogy of cements.
The invention relates to an acid-curable mixture for low-~hrinkage cements based on a reaction product of furfuryl alcohol with a resol carrying at lea~t 0.5 hy-droxymethyl group per phenolic hydroxyl, which mixture contains A) as binder, the reaction product oi furfuryl alco-hol and the resol based on a) at least one trifunctional phenol or a mixture oi this phenol a) with b) alkylphenols and/or aralkylphenols having in each case 3 to 20 carbon atoms in the alkyl radical or an arylphenol, each mixture containing up to 70, preierably up to 60, mole % of the substituted phenols b), based on the sum of the phenols a) and b), more than 0.4 mole of fur~uryl alcohol having been reacted per hydroxymethyl group, and B) at least one reactive diluent in a ratio by weight oi (0.4 to 1.5):1 to the resin A.
One embodiment of the invention envisages that the mlxture of A) and B) also contains, in addition:
C) at least one iiller and D) at least one curing agent, the ratio by weight bet-ween the sum oi the components A) and B) and that of the components C) and D) beinB 1:(1 to 7), preierably 1:(1.5 to 5).
The mixtures, prepared in accordance with the in-vention, ior cements displag very advantageous propertiesin respe¢t oi the stability on storage, resistance to chemlcals and heat reeistance o~ the cured products. In addition, the cements have a very low shrinkage and, when the ~ubsequent shrinkage is determined in accordance with ASTM C 358, display lower values compared with the cements oi German Patent No. 2,926,053, which, ior their part, already have a very low shrinkage. In addition, they have a good pot liie and a shortened curing time and are nevertheless extremely resistant to chemicals. Their im-proved resistance to corrosive solvents, such as acetone,chloroform, toluene, bu tyl acetate and others, should be pointed out particularly.
" i246q8~
Trifunctional phenols which can be used, in each ca8e on their own or aB a mixture, are m-cresol, m-ethyl-phenol or 3,5-dimethylphenol, but it i8 preferable to use unBub8titut8d phenol.
~he alkylphenols which c~n, ii desired, be u8ed conco~itantl~ in the Ik~lphenol resol are bifunctional It is possible to use p-ra-~ono-lkylphenols or ortho-mono-lk~lphenols, such as o-propylphenol, o-isopropyl-phenol, o-n-but~lphenol~ o-sec -but~lphenol, o-tert -butyl-phenol, o-isononylphenol, p-n-butylphenol, p-tert -butyl-phenol~ p-n-hexylphenol~ p-eyelohexylphenol, p-isooctyl-phenol, p-isononylpheno( and p-isododecylphenol, and also rylphenols, such ~s o-phenylphenol or p-phenylphenol, but prefer~bly aralkylphenols, such ~s the o- ~nd p-sub-stitution products of styrene or other vinyl--ro~atic com-pounds, such s ~-nethylstyrene and vinyltoluene, together uith phenol, in e-ch e--e on thelr o~n or as mixture ~he alkyl radieals e-n be line-r, branched or eyclic and can cont-1n ~ to 20, preter-bly ~ to 12, carbon toms The phenol comPonent can ~Iso cont-in oinor mounts of ~ore highly ~Ikyl~ted phcnols, sueh as di~lkylphenols and/
or tr~lkylphenols ~prov~ded th~t these phenols still con-t~in ~t least one position ~v~ ble for the reaction ~ith form~ldehyde) or polyhydric phenols, for ex~mple diphenyl-olproPane, specitic~lly in t proportion of up to 30 mole X.~t is possible to use ~IkylphenoLs, tor example also in the form ot mixture-, uch as are obtained in the alk~-lation of phenol ~ith uns~turated eompounds, for example ~Ikylenes having 3 to 20 earbon toms.
3o The8e eub~tituted bifun¢tiona1 phenol8 are pre~erably employed a8 a mixture w1th unsubst1tuted phcnol, lt being poss1ble for the content Or the substituted pheno1s to be up to 70, preferab1y up to 60, mole %, and the optimum achievable properties being at contents Or the substituted phenols oi 20 to 60, preferably 30 to 55, mole ~.
124678~
The scope of the invention Hlso includes a process ior the preparation of the mixture, according to the in-vention, for cements, which comprises reacting iurfuryl alcohol at an elevated temperature with a resol contain-ing at least 0.5 hydro~ymethyl groups per phenolic hydroxylgroup~ and iB based on a phenol selectea ~rom the group consisting of a) at least one trifunctional phenol, b) an alkglphenol, c) an aralkylphenol, having in each case 3 to 20 carDon atoms in the alkyl radical, d) an arylphenol or a combination thereof, the combinations containing up to 70 mole ~ of the eubstituted phenols b) to d), based on the sum oi the phenols a) to d) and wherein more than 0.4 mole Or furruryl alcohol having been reacted per hydro~y-methyl group, di~solving the reaction product in a reac-ti~e diluent in a ratio by welght oi (0.4 to 1.5);1to the re~ln A) and mi~ing thie ~olution, preferably ; lmmealately before u~e, with a ~lller and a curin~ agent, the ratlo between the weight Or the components A) and B) and that Or the components C) and D) belng 1:(1 to 7), pre~erably 1:(1.5 to 5).
In general, the resin solution A) and B) has a solids content Or 30 to 80, preferably 45 to 65, % by weight.
~ he noditied furan resins A) are enployed in solu-tion in cU~ton-rr reactive diluents, such s benzyl alco-hol, lo~-~olecular epox~de conpounds, such s phenyl gly-c1dyl ether or d1phenylolpropane diglycidyl ether, but, above all, 1n tur~n eonPounds~ such as furfurol, difuryl ether and, preter~bly, furfuryl ~Icohols. ~his diluent can be present, for exanple, as an excess conponent aris-lng fron the react10n ~ith the resol. ~he reactive dil-uents re eeployed in a ratio by ~ei~ht of ~0.4 to 1.5):1, preferably ~0.~ to 1.1):1 to the resin A).
Ex-~ples of fillers ~hi ch can bc used are ground ninerals, b-rytes, ~uart~ po~der and, preferably, po~dered coke or po~dered graphite, for example in the forn of artificial graphite.
124~782 The curing agents used can ~e a) acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, sulfonic cids, such as suLfamic acid, ~onosulfonic and disulfonic cids of benzene, toluene or xylene and also naphthalenedisulfonic acid, and/or b) substances uhich spl;t off acids, sueh as suLfochlorides of the sul-fonic acids nentioned under a), for example toluenesul-fochloride or ben2enesulfochloride, alkyl esters of these sulfonic acids or acid sulfuric acid esters, and/or c) ~o acid salts of sulfuric ocid or phosphoric acid, prefer-abl~ the eodium sal~ thereo~ in each case on their own or ~8 a mi~ture. Their proportion i8, as a rule, 0.1 ta 3, pre~erably 0.2 to 2.0, equivalent~, based on phenolic hy-dro~yl group~.
~he resol containing hydroxymethyl groups uhich 1s used 5 the starting matcrial is prepared from the phenolic resin component and more than 0 5 mole, prefer-ably more than 1 mole~ of formaldehyde per phenol group under conditions uhich substantially avoid the formation of higher condensates In ~eneral, the furan-modified phenolic resins thus obtained have a viscosity of 50 to 10,000, preferably 200 to Z,OOO, mPa s/20C ~oder-te reaction tenperatures betueen 20 nd 80C, preferably betueen 30 and 60C, nd a rel-tively high concentra-tion of cat~lyst, for example 5 to 100, prefer-bly 10 to 50 and especially 15 to 30, equivalent X, in each case basod on the phenolic OH groups, are suitable for this react10n. Examples of suit-ble cat-lysts for this reac-tion ~re bases, such as alkali mctal hydroxides, alkaline ~ earth metal hydroxides, tertiary amines and quaternary ammonium bases. After the condensation reaction, the c~talyst is neutr-lized, for example vith org-nic or in-or~anic acids, nd the salt formed is removed by extrac-tion by uashing ; 35 The temperature up to which the products of cur-ing are stable is about 300C In the reaction of the phenolic resin uith furfuryl alcohol, it is advantageous ~24678 to choose as lou a reaction temPerature as possible. In general, the reaction takes place at an elevated tempera-ture, for example 100 to 170C, preferablr up to 150C, u~th the s1multaneous removal of ~ater for~ed in the re~c-tion. The re-ction sets in at about 100 to 120C. The ~ater can be re~oved by ~eans of a distillation column;
the ~ater is preferabLy removed by azeotropic distilla-t~on in the presence of an entraining agent. Entraining gents uhich can be used are aromatic hydrocarbons, such 10 as toluene or xylene, or aliphatic hydrocarbons or other uater-immiscible substances, for example the same sub-stances uhich are used as solvents in the preparation of the resin. If relatively high-boiling entraining agents are used, it is important to reduce the reaction tempera-15 ture to the desired range by applying a reduced pressure.The reaction betueen furfuryl alcohol and the resol can also be c-rried out in the melt according to another em-bodiment, but reaction in solvents is preferable.
It is possible to carry out an acid-catalyzed 20 reaction of the phenols uith formaldehyde to give novo-laks pr10r to the reaction leading to hydroxymethyl com-pounds, provided that not more than 0 7, preferably not more than 0.5, mole of formaldehyde is used per mole of phenols. The novolak thus formed should then be reacted 25 uith further formaldehyde in a econd st~ge, under the abovcmentioned condit10ns, to g1ve the resol.
The further reactlon according to the invention can prefer-bly be c-rrled out using more than 0.8 ~ole of furfuryl lcohol, but can, in particular, also be carried 30 out in the presence of an excess of furfuryl alcohol, 1.e. more than 1 mole of furfuryl alcohol is employed per hydroxymethyl group. The excess furfuryl alcohol can remain in the resin as a reactive diluent.
The ratios can be so chosen that the excess of 35 furfuryl alcohol is sufficiently large to dilute the resin ade~uately after the reaction and, if relevant, after the removal of the entrain1ng gent Houever, it ;s also possible to dd the re~ctive solvents later The stability on storage of the resin solution nd also of a mixture uith the fillers ~lone 1s virtually unli~ited. The preparation of the cementis preferably carried out immediately before u~e b~ ixing the furan resin solution uith the filler and the cataly~t or a ~ix-ture thcreof or, if a mixture of resin solution and filler 15 employed, by mixing this ~ith the e-talyst ~nd~ if necessary, a further filler In the examples belou parts re parts by ueight and X is percent by ~eight Examp les 1-) PrcParation of thc res1n ~styrene-uodificd resin h-ving a ~olar ratio of 1 phenol : 0.4 styrene : 1 7 for-maldehyde) 376 parts of phenol ucre ~elted 1n reaction ve~el equiPped uith stirring app~ratu~ a thermo~eter, metering apparatus, a ~ater ~eparator, a reflux conden-~er and a device for dist1llation under reduced pressure, 0 7 p-rt of concentrated sulfur1c acid uas added, and the mixture vas he-ted to 100C 166 parts of ~tyrene uere ~etered in as alloucd by thc exother~ic react1On, the temPeraturc rising to 140C. ~hen all the ~tyrene had been addcd~ the m~xture uas kept at 140C for a further 1 25 hour and u~s thcn coolcd to 60C. 120 parts ot 33X
¦ ~trength ~odtum hydroxide olution uere added durin~ the coolin~. ~hen temper-ture ot 60C had been reached, 162 part~ of aqueous 37X ~trength formaldehyde solution and 158.4 parts of 91X strength paraformaldehydc uerc added ~s a~lo~ed b~ the exothermic reaction~ in thc cour~c of one hour, and the m1xture u~s rcacted at 60C until thc content of free formaldehyde uas 0 6X, uhich required bout
6erman Offenlegungssehrift 2,926,053 discloses lou-shrinkage, acid-curing mixtures for eements contain-~ng~ as the binder~ a reaction product of furfuryl alco-hol uith a resol, containin~ hydroxymethyl ~roups, basedon bifunctional alkylphenols or aralkylphenols having 3 to 20 carbon atoms in the alkyl radical, if appropriate as oixture uith a minor proportion of unsubstituted phenol or diphenol propane, at least 75X of the reactlve hydrogen atoms 1n tho nucleus of the substituted resol being subst1tuted by reaction ~ith formaldehyde and more than 0.5 nole of furfuryl alcohol having been reacted per hydroxymethyl group, and the reaction product being dis-solved ~n at le-st one reactive thinner belonging to the group co~pris1ng benzyl alcohol, lou-molecular epoxide conpounds, furfurol, d1furyl ether or furfuryl alcohol.
The resins obtained in accordance uith this teaching con-stitute valuable binders for cements, but exhibit a cer-tain sensit1vity touards a fe~ corrosive organic solvents ~hich re of importance in practice for a number of cases, such as ketones, chlorinated and aromatic hydrocarbons and e~ters.
~ t is also knoun from 6erman Offenlegungsschrift 3,028,974 to obtain, from a phenol compound, an aldehyde and furturyl alcohol, resins uhich have been prepared under ~ubstantially anhydrous conditions in the presence of a metal catalyst. These resins, uhich are suitable for the preparation of foundry cores and foundry mo~ds, cannot, ho~ever, be used for the preparation of o-~nts because they do not crossLink under the conditions customary in the techno~ogy of cements.
The invention relates to an acid-curable mixture for low-~hrinkage cements based on a reaction product of furfuryl alcohol with a resol carrying at lea~t 0.5 hy-droxymethyl group per phenolic hydroxyl, which mixture contains A) as binder, the reaction product oi furfuryl alco-hol and the resol based on a) at least one trifunctional phenol or a mixture oi this phenol a) with b) alkylphenols and/or aralkylphenols having in each case 3 to 20 carbon atoms in the alkyl radical or an arylphenol, each mixture containing up to 70, preierably up to 60, mole % of the substituted phenols b), based on the sum of the phenols a) and b), more than 0.4 mole of fur~uryl alcohol having been reacted per hydroxymethyl group, and B) at least one reactive diluent in a ratio by weight oi (0.4 to 1.5):1 to the resin A.
One embodiment of the invention envisages that the mlxture of A) and B) also contains, in addition:
C) at least one iiller and D) at least one curing agent, the ratio by weight bet-ween the sum oi the components A) and B) and that of the components C) and D) beinB 1:(1 to 7), preierably 1:(1.5 to 5).
The mixtures, prepared in accordance with the in-vention, ior cements displag very advantageous propertiesin respe¢t oi the stability on storage, resistance to chemlcals and heat reeistance o~ the cured products. In addition, the cements have a very low shrinkage and, when the ~ubsequent shrinkage is determined in accordance with ASTM C 358, display lower values compared with the cements oi German Patent No. 2,926,053, which, ior their part, already have a very low shrinkage. In addition, they have a good pot liie and a shortened curing time and are nevertheless extremely resistant to chemicals. Their im-proved resistance to corrosive solvents, such as acetone,chloroform, toluene, bu tyl acetate and others, should be pointed out particularly.
" i246q8~
Trifunctional phenols which can be used, in each ca8e on their own or aB a mixture, are m-cresol, m-ethyl-phenol or 3,5-dimethylphenol, but it i8 preferable to use unBub8titut8d phenol.
~he alkylphenols which c~n, ii desired, be u8ed conco~itantl~ in the Ik~lphenol resol are bifunctional It is possible to use p-ra-~ono-lkylphenols or ortho-mono-lk~lphenols, such as o-propylphenol, o-isopropyl-phenol, o-n-but~lphenol~ o-sec -but~lphenol, o-tert -butyl-phenol, o-isononylphenol, p-n-butylphenol, p-tert -butyl-phenol~ p-n-hexylphenol~ p-eyelohexylphenol, p-isooctyl-phenol, p-isononylpheno( and p-isododecylphenol, and also rylphenols, such ~s o-phenylphenol or p-phenylphenol, but prefer~bly aralkylphenols, such ~s the o- ~nd p-sub-stitution products of styrene or other vinyl--ro~atic com-pounds, such s ~-nethylstyrene and vinyltoluene, together uith phenol, in e-ch e--e on thelr o~n or as mixture ~he alkyl radieals e-n be line-r, branched or eyclic and can cont-1n ~ to 20, preter-bly ~ to 12, carbon toms The phenol comPonent can ~Iso cont-in oinor mounts of ~ore highly ~Ikyl~ted phcnols, sueh as di~lkylphenols and/
or tr~lkylphenols ~prov~ded th~t these phenols still con-t~in ~t least one position ~v~ ble for the reaction ~ith form~ldehyde) or polyhydric phenols, for ex~mple diphenyl-olproPane, specitic~lly in t proportion of up to 30 mole X.~t is possible to use ~IkylphenoLs, tor example also in the form ot mixture-, uch as are obtained in the alk~-lation of phenol ~ith uns~turated eompounds, for example ~Ikylenes having 3 to 20 earbon toms.
3o The8e eub~tituted bifun¢tiona1 phenol8 are pre~erably employed a8 a mixture w1th unsubst1tuted phcnol, lt being poss1ble for the content Or the substituted pheno1s to be up to 70, preferab1y up to 60, mole %, and the optimum achievable properties being at contents Or the substituted phenols oi 20 to 60, preferably 30 to 55, mole ~.
124678~
The scope of the invention Hlso includes a process ior the preparation of the mixture, according to the in-vention, for cements, which comprises reacting iurfuryl alcohol at an elevated temperature with a resol contain-ing at least 0.5 hydro~ymethyl groups per phenolic hydroxylgroup~ and iB based on a phenol selectea ~rom the group consisting of a) at least one trifunctional phenol, b) an alkglphenol, c) an aralkylphenol, having in each case 3 to 20 carDon atoms in the alkyl radical, d) an arylphenol or a combination thereof, the combinations containing up to 70 mole ~ of the eubstituted phenols b) to d), based on the sum oi the phenols a) to d) and wherein more than 0.4 mole Or furruryl alcohol having been reacted per hydro~y-methyl group, di~solving the reaction product in a reac-ti~e diluent in a ratio by welght oi (0.4 to 1.5);1to the re~ln A) and mi~ing thie ~olution, preferably ; lmmealately before u~e, with a ~lller and a curin~ agent, the ratlo between the weight Or the components A) and B) and that Or the components C) and D) belng 1:(1 to 7), pre~erably 1:(1.5 to 5).
In general, the resin solution A) and B) has a solids content Or 30 to 80, preferably 45 to 65, % by weight.
~ he noditied furan resins A) are enployed in solu-tion in cU~ton-rr reactive diluents, such s benzyl alco-hol, lo~-~olecular epox~de conpounds, such s phenyl gly-c1dyl ether or d1phenylolpropane diglycidyl ether, but, above all, 1n tur~n eonPounds~ such as furfurol, difuryl ether and, preter~bly, furfuryl ~Icohols. ~his diluent can be present, for exanple, as an excess conponent aris-lng fron the react10n ~ith the resol. ~he reactive dil-uents re eeployed in a ratio by ~ei~ht of ~0.4 to 1.5):1, preferably ~0.~ to 1.1):1 to the resin A).
Ex-~ples of fillers ~hi ch can bc used are ground ninerals, b-rytes, ~uart~ po~der and, preferably, po~dered coke or po~dered graphite, for example in the forn of artificial graphite.
124~782 The curing agents used can ~e a) acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, oxalic acid, sulfonic cids, such as suLfamic acid, ~onosulfonic and disulfonic cids of benzene, toluene or xylene and also naphthalenedisulfonic acid, and/or b) substances uhich spl;t off acids, sueh as suLfochlorides of the sul-fonic acids nentioned under a), for example toluenesul-fochloride or ben2enesulfochloride, alkyl esters of these sulfonic acids or acid sulfuric acid esters, and/or c) ~o acid salts of sulfuric ocid or phosphoric acid, prefer-abl~ the eodium sal~ thereo~ in each case on their own or ~8 a mi~ture. Their proportion i8, as a rule, 0.1 ta 3, pre~erably 0.2 to 2.0, equivalent~, based on phenolic hy-dro~yl group~.
~he resol containing hydroxymethyl groups uhich 1s used 5 the starting matcrial is prepared from the phenolic resin component and more than 0 5 mole, prefer-ably more than 1 mole~ of formaldehyde per phenol group under conditions uhich substantially avoid the formation of higher condensates In ~eneral, the furan-modified phenolic resins thus obtained have a viscosity of 50 to 10,000, preferably 200 to Z,OOO, mPa s/20C ~oder-te reaction tenperatures betueen 20 nd 80C, preferably betueen 30 and 60C, nd a rel-tively high concentra-tion of cat~lyst, for example 5 to 100, prefer-bly 10 to 50 and especially 15 to 30, equivalent X, in each case basod on the phenolic OH groups, are suitable for this react10n. Examples of suit-ble cat-lysts for this reac-tion ~re bases, such as alkali mctal hydroxides, alkaline ~ earth metal hydroxides, tertiary amines and quaternary ammonium bases. After the condensation reaction, the c~talyst is neutr-lized, for example vith org-nic or in-or~anic acids, nd the salt formed is removed by extrac-tion by uashing ; 35 The temperature up to which the products of cur-ing are stable is about 300C In the reaction of the phenolic resin uith furfuryl alcohol, it is advantageous ~24678 to choose as lou a reaction temPerature as possible. In general, the reaction takes place at an elevated tempera-ture, for example 100 to 170C, preferablr up to 150C, u~th the s1multaneous removal of ~ater for~ed in the re~c-tion. The re-ction sets in at about 100 to 120C. The ~ater can be re~oved by ~eans of a distillation column;
the ~ater is preferabLy removed by azeotropic distilla-t~on in the presence of an entraining agent. Entraining gents uhich can be used are aromatic hydrocarbons, such 10 as toluene or xylene, or aliphatic hydrocarbons or other uater-immiscible substances, for example the same sub-stances uhich are used as solvents in the preparation of the resin. If relatively high-boiling entraining agents are used, it is important to reduce the reaction tempera-15 ture to the desired range by applying a reduced pressure.The reaction betueen furfuryl alcohol and the resol can also be c-rried out in the melt according to another em-bodiment, but reaction in solvents is preferable.
It is possible to carry out an acid-catalyzed 20 reaction of the phenols uith formaldehyde to give novo-laks pr10r to the reaction leading to hydroxymethyl com-pounds, provided that not more than 0 7, preferably not more than 0.5, mole of formaldehyde is used per mole of phenols. The novolak thus formed should then be reacted 25 uith further formaldehyde in a econd st~ge, under the abovcmentioned condit10ns, to g1ve the resol.
The further reactlon according to the invention can prefer-bly be c-rrled out using more than 0.8 ~ole of furfuryl lcohol, but can, in particular, also be carried 30 out in the presence of an excess of furfuryl alcohol, 1.e. more than 1 mole of furfuryl alcohol is employed per hydroxymethyl group. The excess furfuryl alcohol can remain in the resin as a reactive diluent.
The ratios can be so chosen that the excess of 35 furfuryl alcohol is sufficiently large to dilute the resin ade~uately after the reaction and, if relevant, after the removal of the entrain1ng gent Houever, it ;s also possible to dd the re~ctive solvents later The stability on storage of the resin solution nd also of a mixture uith the fillers ~lone 1s virtually unli~ited. The preparation of the cementis preferably carried out immediately before u~e b~ ixing the furan resin solution uith the filler and the cataly~t or a ~ix-ture thcreof or, if a mixture of resin solution and filler 15 employed, by mixing this ~ith the e-talyst ~nd~ if necessary, a further filler In the examples belou parts re parts by ueight and X is percent by ~eight Examp les 1-) PrcParation of thc res1n ~styrene-uodificd resin h-ving a ~olar ratio of 1 phenol : 0.4 styrene : 1 7 for-maldehyde) 376 parts of phenol ucre ~elted 1n reaction ve~el equiPped uith stirring app~ratu~ a thermo~eter, metering apparatus, a ~ater ~eparator, a reflux conden-~er and a device for dist1llation under reduced pressure, 0 7 p-rt of concentrated sulfur1c acid uas added, and the mixture vas he-ted to 100C 166 parts of ~tyrene uere ~etered in as alloucd by thc exother~ic react1On, the temPeraturc rising to 140C. ~hen all the ~tyrene had been addcd~ the m~xture uas kept at 140C for a further 1 25 hour and u~s thcn coolcd to 60C. 120 parts ot 33X
¦ ~trength ~odtum hydroxide olution uere added durin~ the coolin~. ~hen temper-ture ot 60C had been reached, 162 part~ of aqueous 37X ~trength formaldehyde solution and 158.4 parts of 91X strength paraformaldehydc uerc added ~s a~lo~ed b~ the exothermic reaction~ in thc cour~c of one hour, and the m1xture u~s rcacted at 60C until thc content of free formaldehyde uas 0 6X, uhich required bout
2 hours. The p~ u-s ad~usted to a value of 5.4 by means of 189 p-rts of 25X strength sulfuric acid, 100 parts of toluene uere stirred belo~ the surface and the aqueous phase uas then re~oved by suction. 784 parts of furfuryl alcohol uere dded to the resin remaining in the flask and ~Z4678Z
recycle distillat;on ~as begun During the recycle dis-tillation the temperature rose to 135 to 138C 255 ml of ~n ~queous phase ~ere removed ~fter cooling to 110C, the entr~ining gent uas distil~ed off under a pressure of tO0 mbar, and the ~ixturc uas then diluted uith 930 parts of furfury~ alcohol The furan resin solution pro-duced t2000 parts) had a residue of 50 2X ~one hour/170C) and a viscosit~ of 1025 mPa.s/20C.
1b~ Preparation of the cement For testin~ the propertiès of the cement,a cement po~der ~as prepared from 93 parts o~ ooke dhst, 2 ~s of oxalic acid, 1 part of crystalline phosphoric acid and 4 parts of toLuenesulfochloride, and 100 parts thereof ~ere mixed ~ith 50 parts of the resin solution to give a cement. The o~Ynt had a pot ~ife of 30 minutes and, after 24 hours at room temperature, reached a Shore hardness D of 55. ~fter 48 hours, the Shore hardness increased to 63 ~ee tabLe).
1c) Phys~cal test1ng.
In order to determine its resistance to solvents and chemicals, cylindrical elements having a he~ght of 25 mm and a di-meter of 25 mm uere prepared from theo~Ent and these elenents uere stored for 8 days at room tempera-ture; ~fter this time~, the test specimens uere resistant to boil1ng 70X strength sulfuric acid, boiling concentra-ted hydrochloric acid, concentrated phosphoric acid at 130C, concentrated and dilute sodium hydroxide solution and other alkali solutions. Resistance to eolvents wa~
tested b~ ~toring test specimen ior 8 da~ at room tem-perature and then boiling them for 5 2 8 hours in acetone,chloroiorm, toluene, but~l acetate and water. The changes ln weight of the test specimens can be seen from the table.
The subsequent shrinkage was measured b~ a method based on ~STM C 358 by storing cylindrical test specimens 100 mm long and 25 mm in diameter for 8 days at room temperature and measuring the change in their length The change in i 124~78Z
-- 10 _ length uas 0 1929X after 60 days and 0.207X after 120 days 2a) Preparation of the resin - ~styrene-modified resin having a molar ratio of 1 phenol : 0 5 styrene : 1 75 for-maldehyde). As in Example 1, 376 p-rts of phenol, 0 7 P-rt of concentrated sulfuric cid, 208 p-rts of styrene, 12û p-rts of 33X strength sodium hydroxide solut1On, 162 parts of 37X strength queous formaldehrde solution and 164.8 parts of 91X strength paraformaldehyde uerc reac-ted, the m1xture uas diluted uith toluene~ freed from the ~queous phase and sub~ected to recycle d1stillotion u1th 784 parts of furfuryl alcohol ~in the course of uhich 210 ml of ~ater ~ere removed) and the residue ~-s freed from the entraining gent nd diluted uith 8û0 p-rts of fur-furyl alcohol. This gave 2100 p-rts of a 5û.3X strength res1n solut1On (residue 1 hourl170C) having a viscosity of 550 ~P~.s120C.
2b) Preparat1On of the oement In order to test the properties of theonE~t, 50 parts of the resin solution uere m1xed u1th 100 parts of theo~nt po~der from Example 1. Theo~Ent had a pot life of 35 minutes and, after 24 hours at room temperature, developed a Shore hardness D of 35; after 48 hours the Shore hardness D ~-s 58. The beh-vior touards acids and alkallne-olutions corresPonded exactly to that of the resin from Example 1. Ihe Ib#~Ynt shr~qe, determ1ned as in Ex~mpîe 1, ~-s 0.16X ~fter 60 d-ys and 0.1754X fter 120 days. ~he resistance to solvents can be scen from the table 3o Compar1sons ComPar1son la). Prep~r~tion of the res1n - ~styrene-modified resin h-ving a mol~r ratio of 1 phenol : 1 sty-rene : 1.625 form~ldehyde 1n accordanee uith 6erman Patent 35 No. 2,926,053).
124~782 1 1 _ 376 p~rts of phenol, 0.7 part~ o~ concentr~ted sul-~uric acid, 416 parts oi ~tyrene, ~20 parts of 33% strength sodium hydro~ide solution, 162 parts of 37% strength aqueous formaldehyde solution ~nd 148 partn o~ 91~ strength paraiormaldehyde were re~cted as in E~am~le 1.
~ ftor a react10n tine at ~0C of 3 112 hours, thc fornaldehyde content uas 1.S6X; the reaction ~as dis-cont1nued t th1s po1nt br dding 189 parts of 25X strength sulfur1c ~c1d. After 140 parts of toluene had been added, the a~ueous phase ~a~ separated off~ 784 parts of furfuryl alcohol ~ere added and the nixture ~as subjected to re-cycle d1st111-t10n ~s 1n Exaople 1. 200 nl of aqueous phase ~ere renoved. ~fter the entra1n1ng agent had been renoved br d1~t111-tion, the residue uas d11uted uith 880 part~ of furfuryl Icohol. Y1eld 2150 parts, residue 50X
~1 hour/170C), v1~co~1tr 340 nP- -/200C.
Conpar1~on 1b). Prepar-tion of the o~nt and physical te~t1ng.
The propert1es of the o~Ent uere tested by mixing 50 p~rt~ of the res1n solution fron Conparison 1a and 100 P~rts of the o~Ent pouder froo Example 1. ~he o~nt had a pot life of 70 n1nutes and, fter 24 hours, h-d a Shore ~ hardness D of 5. After 48 hour~, the Shore hardness D
; ~a~ 45. ~he r~ tance to ac1d~and a~ellne solutions uas ~1n11-r to th-t of the cements obtained u1th the resin ~olut10n~ fron Ex~nple 1 nd 2. ~e~ting the resistance to solvents~ uh1ch ~as carried out as above, and the results of ~h1ch rc shoun 1n the table, gave differences uhich 1n ~o~e c-~es uere cons1derable.
~ Compar1son 2-). Prep~r~t10n of the resin - Cstrrene-nodified re-~n having a nol~r r-tio of 1 phenol : 0 4 str-rene ~ S fornaldehyde, based on 6ernan Offenlegungs-schrift 3,028,974).
188 parts of phenol ~ere reacted as in Example 1 ~1th 83 parts of styrene in the presence of 0.35 part of coneentrated sulfuric cid, nd the mixture ~as cooled to 90C, 28 5 p-rts of zinc octoate solut10n ~1n ~h1te lZ46782 sp~rit) hav~ng a content of 8X of zinc and 109 parts of 91X strength p~r-formaldehyde vere added at this te~pera-ture and stirring uas carried out at this tenperature for t8 hours until the fornaldehyde content uas OX. 180 parts of to~uene and 392 parts of furfuryl alcohol uere then added nd the nixture vas subjected to rec~cle distilla-t10n up to a naxi~un temperature of 170C In the course of th1s 78 n~ of n aqueous phase vere re-oved. After the entrain1ng agent h-d been separated off under a pressure 10 ot 100 b-r, the solution uas djusted to a residue content of 49.5X ~1 hour~170C) by neans of 314 parts of furfuryl alcohol. Viscosity 130 ~Pa s/20C; yield 1005 9 Co~par1~on 2b). Prepar-tion of the o~nt nd physical test1ng.
The properties of the o~Ent ~ere tested by n1xing SO p~rts of the r~in solut10n fron Co~par1son 2a ~ith 100 p~rts of the o~Ent pouder fron Ex~nple 1. Only fter 7 da~ ~a~ there a sl1ght 1ncre-se 1n the trength of the o~Ent conpos1t10n; even at this po1nt 1n t1me the Shore 20 hardne~ D uas 0. ~he o~Ent did not cross~ink.
Conpar1~on 3a). Prepar-tion of the resin - ~styrene-~od1f1ed resin hav1ng a nol~r ratio of 1 phenol : 0 4 sty-rene : 1.65 forn-ldehyde 1n accord-nce ~ith 6ernan Offen-legungsschrift 3~0Z8,974).
Conpar1~on 2 ~as repeated using onlr 14.3 p-rts of zinc oetoate~ 1n order to reduce the poss1bl~ h-rnful effect of the zinc octoate. ~fter react10n at 70t for 22 hours, the fornaldehyde content ~as 1.7X. Reaction uith furfuryl alcohol and vorking up as in Ex~mple 2 gave, 30 after diLut10n to 51.3X, 1009 parts of res~n solution hav~ng a v1~cosity of 230 ~Pa s/20C.
Co~Par1son 3 b~. ~esting the propert1es of the cement.
~ hen the properties of the o~nt ~ere tested, no crosslinking took place even after 7 days, s in Exanple 2 ~' ~246782 >~ .
UO~ C~
--~ .
O _ , E
~n ~ ,0, Q N O g I I ~_ I I I I I I I O
E ~ :~
L N `O
' O ~ ~ O
~ O O _ O ~
0 00 ~0~
0 0 ~ O
O ~ O
~1 In o r~ + I I I I o o 'O ~O 'O V~ O
~1 ~ N ~
~ ~ O . O ~ O
.0 ~ _ N
& _ ~ o ~0 ~ ~ I ~ ~ I I I I O O
EE ~
o O
. C O C
~ O ~ >~ ~1 ~ .C O ~ I~
c L) ~ m :~
_ _ L L .
recycle distillat;on ~as begun During the recycle dis-tillation the temperature rose to 135 to 138C 255 ml of ~n ~queous phase ~ere removed ~fter cooling to 110C, the entr~ining gent uas distil~ed off under a pressure of tO0 mbar, and the ~ixturc uas then diluted uith 930 parts of furfury~ alcohol The furan resin solution pro-duced t2000 parts) had a residue of 50 2X ~one hour/170C) and a viscosit~ of 1025 mPa.s/20C.
1b~ Preparation of the cement For testin~ the propertiès of the cement,a cement po~der ~as prepared from 93 parts o~ ooke dhst, 2 ~s of oxalic acid, 1 part of crystalline phosphoric acid and 4 parts of toLuenesulfochloride, and 100 parts thereof ~ere mixed ~ith 50 parts of the resin solution to give a cement. The o~Ynt had a pot ~ife of 30 minutes and, after 24 hours at room temperature, reached a Shore hardness D of 55. ~fter 48 hours, the Shore hardness increased to 63 ~ee tabLe).
1c) Phys~cal test1ng.
In order to determine its resistance to solvents and chemicals, cylindrical elements having a he~ght of 25 mm and a di-meter of 25 mm uere prepared from theo~Ent and these elenents uere stored for 8 days at room tempera-ture; ~fter this time~, the test specimens uere resistant to boil1ng 70X strength sulfuric acid, boiling concentra-ted hydrochloric acid, concentrated phosphoric acid at 130C, concentrated and dilute sodium hydroxide solution and other alkali solutions. Resistance to eolvents wa~
tested b~ ~toring test specimen ior 8 da~ at room tem-perature and then boiling them for 5 2 8 hours in acetone,chloroiorm, toluene, but~l acetate and water. The changes ln weight of the test specimens can be seen from the table.
The subsequent shrinkage was measured b~ a method based on ~STM C 358 by storing cylindrical test specimens 100 mm long and 25 mm in diameter for 8 days at room temperature and measuring the change in their length The change in i 124~78Z
-- 10 _ length uas 0 1929X after 60 days and 0.207X after 120 days 2a) Preparation of the resin - ~styrene-modified resin having a molar ratio of 1 phenol : 0 5 styrene : 1 75 for-maldehyde). As in Example 1, 376 p-rts of phenol, 0 7 P-rt of concentrated sulfuric cid, 208 p-rts of styrene, 12û p-rts of 33X strength sodium hydroxide solut1On, 162 parts of 37X strength queous formaldehrde solution and 164.8 parts of 91X strength paraformaldehyde uerc reac-ted, the m1xture uas diluted uith toluene~ freed from the ~queous phase and sub~ected to recycle d1stillotion u1th 784 parts of furfuryl alcohol ~in the course of uhich 210 ml of ~ater ~ere removed) and the residue ~-s freed from the entraining gent nd diluted uith 8û0 p-rts of fur-furyl alcohol. This gave 2100 p-rts of a 5û.3X strength res1n solut1On (residue 1 hourl170C) having a viscosity of 550 ~P~.s120C.
2b) Preparat1On of the oement In order to test the properties of theonE~t, 50 parts of the resin solution uere m1xed u1th 100 parts of theo~nt po~der from Example 1. Theo~Ent had a pot life of 35 minutes and, after 24 hours at room temperature, developed a Shore hardness D of 35; after 48 hours the Shore hardness D ~-s 58. The beh-vior touards acids and alkallne-olutions corresPonded exactly to that of the resin from Example 1. Ihe Ib#~Ynt shr~qe, determ1ned as in Ex~mpîe 1, ~-s 0.16X ~fter 60 d-ys and 0.1754X fter 120 days. ~he resistance to solvents can be scen from the table 3o Compar1sons ComPar1son la). Prep~r~tion of the res1n - ~styrene-modified resin h-ving a mol~r ratio of 1 phenol : 1 sty-rene : 1.625 form~ldehyde 1n accordanee uith 6erman Patent 35 No. 2,926,053).
124~782 1 1 _ 376 p~rts of phenol, 0.7 part~ o~ concentr~ted sul-~uric acid, 416 parts oi ~tyrene, ~20 parts of 33% strength sodium hydro~ide solution, 162 parts of 37% strength aqueous formaldehyde solution ~nd 148 partn o~ 91~ strength paraiormaldehyde were re~cted as in E~am~le 1.
~ ftor a react10n tine at ~0C of 3 112 hours, thc fornaldehyde content uas 1.S6X; the reaction ~as dis-cont1nued t th1s po1nt br dding 189 parts of 25X strength sulfur1c ~c1d. After 140 parts of toluene had been added, the a~ueous phase ~a~ separated off~ 784 parts of furfuryl alcohol ~ere added and the nixture ~as subjected to re-cycle d1st111-t10n ~s 1n Exaople 1. 200 nl of aqueous phase ~ere renoved. ~fter the entra1n1ng agent had been renoved br d1~t111-tion, the residue uas d11uted uith 880 part~ of furfuryl Icohol. Y1eld 2150 parts, residue 50X
~1 hour/170C), v1~co~1tr 340 nP- -/200C.
Conpar1~on 1b). Prepar-tion of the o~nt and physical te~t1ng.
The propert1es of the o~Ent uere tested by mixing 50 p~rt~ of the res1n solution fron Conparison 1a and 100 P~rts of the o~Ent pouder froo Example 1. ~he o~nt had a pot life of 70 n1nutes and, fter 24 hours, h-d a Shore ~ hardness D of 5. After 48 hour~, the Shore hardness D
; ~a~ 45. ~he r~ tance to ac1d~and a~ellne solutions uas ~1n11-r to th-t of the cements obtained u1th the resin ~olut10n~ fron Ex~nple 1 nd 2. ~e~ting the resistance to solvents~ uh1ch ~as carried out as above, and the results of ~h1ch rc shoun 1n the table, gave differences uhich 1n ~o~e c-~es uere cons1derable.
~ Compar1son 2-). Prep~r~t10n of the resin - Cstrrene-nodified re-~n having a nol~r r-tio of 1 phenol : 0 4 str-rene ~ S fornaldehyde, based on 6ernan Offenlegungs-schrift 3,028,974).
188 parts of phenol ~ere reacted as in Example 1 ~1th 83 parts of styrene in the presence of 0.35 part of coneentrated sulfuric cid, nd the mixture ~as cooled to 90C, 28 5 p-rts of zinc octoate solut10n ~1n ~h1te lZ46782 sp~rit) hav~ng a content of 8X of zinc and 109 parts of 91X strength p~r-formaldehyde vere added at this te~pera-ture and stirring uas carried out at this tenperature for t8 hours until the fornaldehyde content uas OX. 180 parts of to~uene and 392 parts of furfuryl alcohol uere then added nd the nixture vas subjected to rec~cle distilla-t10n up to a naxi~un temperature of 170C In the course of th1s 78 n~ of n aqueous phase vere re-oved. After the entrain1ng agent h-d been separated off under a pressure 10 ot 100 b-r, the solution uas djusted to a residue content of 49.5X ~1 hour~170C) by neans of 314 parts of furfuryl alcohol. Viscosity 130 ~Pa s/20C; yield 1005 9 Co~par1~on 2b). Prepar-tion of the o~nt nd physical test1ng.
The properties of the o~Ent ~ere tested by n1xing SO p~rts of the r~in solut10n fron Co~par1son 2a ~ith 100 p~rts of the o~Ent pouder fron Ex~nple 1. Only fter 7 da~ ~a~ there a sl1ght 1ncre-se 1n the trength of the o~Ent conpos1t10n; even at this po1nt 1n t1me the Shore 20 hardne~ D uas 0. ~he o~Ent did not cross~ink.
Conpar1~on 3a). Prepar-tion of the resin - ~styrene-~od1f1ed resin hav1ng a nol~r ratio of 1 phenol : 0 4 sty-rene : 1.65 forn-ldehyde 1n accord-nce ~ith 6ernan Offen-legungsschrift 3~0Z8,974).
Conpar1~on 2 ~as repeated using onlr 14.3 p-rts of zinc oetoate~ 1n order to reduce the poss1bl~ h-rnful effect of the zinc octoate. ~fter react10n at 70t for 22 hours, the fornaldehyde content ~as 1.7X. Reaction uith furfuryl alcohol and vorking up as in Ex~mple 2 gave, 30 after diLut10n to 51.3X, 1009 parts of res~n solution hav~ng a v1~cosity of 230 ~Pa s/20C.
Co~Par1son 3 b~. ~esting the propert1es of the cement.
~ hen the properties of the o~nt ~ere tested, no crosslinking took place even after 7 days, s in Exanple 2 ~' ~246782 >~ .
UO~ C~
--~ .
O _ , E
~n ~ ,0, Q N O g I I ~_ I I I I I I I O
E ~ :~
L N `O
' O ~ ~ O
~ O O _ O ~
0 00 ~0~
0 0 ~ O
O ~ O
~1 In o r~ + I I I I o o 'O ~O 'O V~ O
~1 ~ N ~
~ ~ O . O ~ O
.0 ~ _ N
& _ ~ o ~0 ~ ~ I ~ ~ I I I I O O
EE ~
o O
. C O C
~ O ~ >~ ~1 ~ .C O ~ I~
c L) ~ m :~
_ _ L L .
3 3 c c , ~
~J oo C
~ ~ o _ ~ C C
., ~ , ....
O ~ c a- o 0 . .
,a) , ~ ~ ., ~ ~ _ ~ ~ ETJ ~ _ ~ L L ~
_ ~ L ~ L O O
O ~ C ~ .. Y -- C ~ ' ~O ~J
_ O ~
c ' , .. c ~ L, ~
I~ .~ ~ ~- o
~J oo C
~ ~ o _ ~ C C
., ~ , ....
O ~ c a- o 0 . .
,a) , ~ ~ ., ~ ~ _ ~ ~ ETJ ~ _ ~ L L ~
_ ~ L ~ L O O
O ~ C ~ .. Y -- C ~ ' ~O ~J
_ O ~
c ' , .. c ~ L, ~
I~ .~ ~ ~- o
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An acid-curing mixture for low-shrinkage cements based on a furan-modified phenolic resin which contains A) as binder, the reaction product of furfuryl alco-hol and a resol, having at least 0.5 hydroxymethyl groups per phenolic hydroxyl group, based on a phenol selected from the group consisting of a) at least one trifunctional phenol, b) an alkylphenol, c) an aralkylphenol, having in each case 3 to 20 carbon atoms in the alkyl radical, d) an arylphenol or a combination thereof, the combinations containing up to 70 mole % of the substituted phenols b) to d), based on the sum of the phenols a) to d), and where-in in said reaction product more than 0.4 mole of furfuryl alcohol having been reacted per hydroxymethyl group, and B) at least one reactive diluent in a ratio by weight of (0.4 to 1.5):1 to the resin A).
2. A mixture as claimed in claim 1, which also con-tains, in addition, C) at least one filler and D) at least one curing agent, the ratio by weight bet-ween the sum of the components A) and B) and that of the components C) and D) being 1:(1 to 7).
3. A mixture as claimed in claim 1 having at least one of the characteristics that the alkyl radical in the alkyl-phenols has 4 to 12 carbon atoms, that the alkyl radical in the aralkylphenols has 4 to 12 carbon atoms, that the tri-functional phenol is unsubstituted phenol, that more than 0.8 mole of furfuryl alcohol has been reacted per hydroxy-methyl group and that the reactive diluent is a furan com-pound.
4. A mixture as claimed in claim 1 or 2 or 3, wherein the furan-modified phenolic resin has a viscosity of 50 to 10,000 mPa.s/20°C.
5. A mixture as claimed in claim 1 or 2 or 3, wherein the resin contains a substitution product formed from phenol and vinyl-aromatic hydrocarbons as the aralkylphenol.
6. A mixture as claimed in claim 2 or 3, wherein the curing component D) is an acid substance, present in a pro-portion of 0.1 to 3 equivalents, based on phenolic OH
groups.
groups.
7. A mixture as claimed in claim 2 or 3, wherein the filler C) is present in the form of coke, artificial gra-phite, quartz or barium sulfate.
8. a process for the preparation of a mixture for low-shrinkage cements, which comprises reacting at an ele-vated temperature A) furfuryl alcohol with a resol con-taining at least 0.5 hydroxymethyl groups per phenolic group and is based on a phenol selected from the group consisting of a) at least one trifunctional phenol, b) an alkylphenol, c) an aralkylphenol, having in each case 3 to 20 carbon atoms in the alkyl radical, d) an arylphenol or a combination thereof, the combinations containing up to 70 mole % of the substituted phenols b) to d), based on the sum of the phenols a) to d) and wherein more than 0.4 mole of furfuryl alcohol having been reacted per hydroxy-methyl group, dissolving the reaction product A) in a reac-tive diluent B) in a ratio by weight of (0.4 to 1.5):1 to the resin A) and mixing this solution with a filler C) and a curing agent D), the ratio of the weight of the compo-nents A) and B) to that of the components C) and D) being 1:(1 to 7).
9. The process as claimed in claim 8, wherein the reaction of furfuryl alcohol with the resol is carried out at temperatures from 100 to 170°C and the solution of the resin in the reactive diluent has a solid resin con-tent of 30 to 80 % by weieht.
10. The process as claimed in claim 8, wherein the filler C) is added in the form of a mixture with the cur-ing agent D).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843402359 DE3402359A1 (en) | 1984-01-25 | 1984-01-25 | ACID-HARDENING MIXTURE FOR LOW-SHRINKAGE FURANITES AND METHOD FOR THE PRODUCTION THEREOF |
| DEP3402359.3 | 1984-01-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246782A true CA1246782A (en) | 1988-12-13 |
Family
ID=6225774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000472716A Expired CA1246782A (en) | 1984-01-25 | 1985-01-24 | Acid-curable mixture for low-shrinkage furan cements and a process for its preparation |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0152760B1 (en) |
| JP (1) | JPH0699618B2 (en) |
| AT (1) | ATE43134T1 (en) |
| AU (1) | AU572948B2 (en) |
| CA (1) | CA1246782A (en) |
| CS (1) | CS254981B2 (en) |
| DE (2) | DE3402359A1 (en) |
| ES (1) | ES8601284A1 (en) |
| ZA (1) | ZA85560B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4100159A1 (en) * | 1991-01-03 | 1992-07-09 | Cta Industriemontage Gmbh Berl | Gel for phenol-cresol- and xylenol-resinous cements - contg. sulphuric acid and/or p-toluene sulphonic acid hydrate, silicic acid and water, esp. for ceramic tiles |
| DE4243797C2 (en) * | 1992-12-23 | 1997-01-30 | Hoechst Ag | Curable phenolic resin-modified furan resins as binders for putties and coating compositions with improved thermal stability, processes for their production and their use |
| DE4338835A1 (en) * | 1993-11-13 | 1995-05-18 | Hoechst Ag | Low-emission resole for putty |
| JP5886675B2 (en) * | 2012-04-05 | 2016-03-16 | 積水化学工業株式会社 | Lining material for existing pipe rehabilitation, its manufacturing method, and existing pipe rehabilitation method using the same |
| RU2571908C2 (en) * | 2014-02-14 | 2015-12-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Костромской государственный технологический университет" | Glue for manufacturing chipboards |
| RU2726232C1 (en) * | 2019-12-05 | 2020-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный лесотехнический университет имени С.М. Кирова" | Adhesive for making wood-particle boards and boards based on annual plants wastes |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE498688A (en) * | 1949-10-17 | |||
| GB777458A (en) * | 1954-02-26 | 1957-06-26 | Ici Ltd | Improvements in and relating to corrosion-resistant resinous cements |
| CH373182A (en) * | 1954-11-19 | 1963-11-15 | Hoechst Ag | Process for the production of hardened, alkali and acid-resistant coatings, putties and seals |
| DE1014319B (en) * | 1954-12-30 | 1957-08-22 | Hoechst Ag | Process for the production of highly crosslinked phenolic, cresol or xylenol resins |
| DE1494099A1 (en) * | 1962-10-05 | 1969-04-17 | Hefele Dr Josef | Process to increase the chemical resistance of synthetic resin compounds |
| US3312650A (en) * | 1964-05-20 | 1967-04-04 | Borden Co | Binder composition (1) condensate of phenol, furfuryl alcohol and formaldehyde and (2) additional furfuryl alcohol |
| US4051301A (en) * | 1975-10-16 | 1977-09-27 | Cpc International Inc. | Furan-phenolic resin coated sand for collapsible foundry molds |
| US4048103A (en) * | 1976-02-09 | 1977-09-13 | Minnesota Mining And Manufacturing Company | Composition based on phenolic resin, polyisocyanate, and petroleum oil |
| DE2926053C2 (en) * | 1979-06-28 | 1982-04-08 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of resin solutions for putty and their use |
-
1984
- 1984-01-25 DE DE19843402359 patent/DE3402359A1/en not_active Withdrawn
-
1985
- 1985-01-16 DE DE8585100366T patent/DE3570243D1/en not_active Expired
- 1985-01-16 EP EP85100366A patent/EP0152760B1/en not_active Expired
- 1985-01-16 AT AT85100366T patent/ATE43134T1/en not_active IP Right Cessation
- 1985-01-23 ES ES539774A patent/ES8601284A1/en not_active Expired
- 1985-01-24 CS CS85495A patent/CS254981B2/en unknown
- 1985-01-24 ZA ZA85560A patent/ZA85560B/en unknown
- 1985-01-24 AU AU38063/85A patent/AU572948B2/en not_active Ceased
- 1985-01-24 CA CA000472716A patent/CA1246782A/en not_active Expired
- 1985-01-24 JP JP60010008A patent/JPH0699618B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699618B2 (en) | 1994-12-07 |
| ES539774A0 (en) | 1985-11-16 |
| AU3806385A (en) | 1985-08-01 |
| ZA85560B (en) | 1985-10-30 |
| ES8601284A1 (en) | 1985-11-16 |
| EP0152760B1 (en) | 1989-05-17 |
| EP0152760A2 (en) | 1985-08-28 |
| CS49585A2 (en) | 1987-07-16 |
| CS254981B2 (en) | 1988-02-15 |
| DE3402359A1 (en) | 1985-08-01 |
| JPS60170653A (en) | 1985-09-04 |
| EP0152760A3 (en) | 1987-01-21 |
| DE3570243D1 (en) | 1989-06-22 |
| AU572948B2 (en) | 1988-05-19 |
| ATE43134T1 (en) | 1989-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1246782A (en) | Acid-curable mixture for low-shrinkage furan cements and a process for its preparation | |
| CN105308091A (en) | Epoxy compound, epoxy resin, curable compound, cured product thereof, semiconductor sealing material, and printed circuit board | |
| CN103119029A (en) | Novel compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility | |
| US3988386A (en) | Synthetic resins | |
| US3674732A (en) | Rosin modified phenolic resins and method of preparing same | |
| US2744882A (en) | Unsymmetrical diphenylol methanes | |
| CA1150888A (en) | Low-shrinkage, acid-hardening mixtures of furan cements and process for the preparation thereof | |
| DE69008122T2 (en) | PHENOLNOVOLAK RESIN, THE HARDENING PRODUCT AND METHOD FOR THE PRODUCTION THEREOF. | |
| CN106694794B (en) | Triethylamine cold core box binder | |
| US4102866A (en) | Method of making glycidyl ethers of novolak resins | |
| DE102004057671B4 (en) | Phenol-formaldehyde resins and process for their preparation | |
| DE1770929C2 (en) | Process for the production of epoxidized phenolic resins | |
| CN107150103B (en) | Mold molding set, mold molding sand composition, and method for producing same | |
| US2986550A (en) | Polynuclear epoxide resin | |
| US4268648A (en) | Resol resins prepared using butanol and tri-alkali metal phosphate | |
| US4245083A (en) | Phenolic formaldehyde-salicylic acid condensation products | |
| CA1078873A (en) | Polyhydroxy phenols and method for preparing the same | |
| US5478908A (en) | Low-contaminant resols for cements | |
| AT155968B (en) | Process for the production of synthetic resins. | |
| KR101828095B1 (en) | Novel polynuclear poly(phenol) compound | |
| US4259473A (en) | Process for making self-curing or curable materials from coal hydrogenation distillate residues | |
| US2462636A (en) | Aldehyde-(phenol-phenol ether reaction products) reaction products and methods for producing them | |
| DE2647851B2 (en) | Process for coating metals | |
| DE2254379C3 (en) | Process for the manufacture of novolaks | |
| DE2542209B2 (en) | BINDERS FOR MOLDING SAND |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |