CA1278135C - Resin solutions for cements and coating compositions, process for their preparation and their use - Google Patents
Resin solutions for cements and coating compositions, process for their preparation and their useInfo
- Publication number
- CA1278135C CA1278135C CA000496800A CA496800A CA1278135C CA 1278135 C CA1278135 C CA 1278135C CA 000496800 A CA000496800 A CA 000496800A CA 496800 A CA496800 A CA 496800A CA 1278135 C CA1278135 C CA 1278135C
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- Canada
- Prior art keywords
- resin
- epoxy
- cements
- resin solution
- coating compositions
- 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.)
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Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
Abstract
Abstract of the disclosure:
Resin solution for cements and coating compositions based on a reaction product of epoxy resins having more than one epoxy group in the molecule and furfuryl alcohol alone or in mixture with other furan derivatives dissolved in reactive diluents and process for its preparation. These resin solutions are used for preparing cements and coat-ing compositions by mixing the resin solution immediately before use with A) at least one filler and B) at least one curing agent or a mixture of A) and B), the weight ratio of the solution to the sum of components A) and 8) being 1:(0.5-7), preferably 1:(1-4).
Resin solution for cements and coating compositions based on a reaction product of epoxy resins having more than one epoxy group in the molecule and furfuryl alcohol alone or in mixture with other furan derivatives dissolved in reactive diluents and process for its preparation. These resin solutions are used for preparing cements and coat-ing compositions by mixing the resin solution immediately before use with A) at least one filler and B) at least one curing agent or a mixture of A) and B), the weight ratio of the solution to the sum of components A) and 8) being 1:(0.5-7), preferably 1:(1-4).
Description
HOECHST AKTIENGESELLSCHAFT HOE 84/F 289 Dr.K~St Resin solutions for cements and coating compositions, process for their preDaratiOn and their use .. .. . _ . ...
It is known to use polycondensates of furfuryl alcohol as binders for acid-curing cements. The second main com-ponent of these cements are fil lers to which acids or acid-eliminatlng substances are admixed as curing catalysts which can effect curing ~;thout suprJly of heat.
It is also known from ~erman Patent 2,926,053 to react furfuryl alcohol with a hydroxymethyl-containing alkyl-phenol resol based on bifunctional alkylphenols at ele-vated temperature and ~o dissolve the reaction Droduct inat least one reactive diluent from the group consist-ina of benzyl alcohol, low-molecular ePoxy compounds, furfurol, difuryl ether, furfuryl aLcohol to avoid the otherwise considerable shrinkage of furan cements. The addition of lo~-molecular epoxy compounds does not affect the elastic behavior of the cured Droducts, but they have a certain sensitivity to some aggressive, organic solvents which in practice are of ;mDortance for a number of cases~ such as ketones, chlorinated and aromat;c hydro-carbons, and esters~
The presence of furfuryL alcohol in Dlastic cements com-posed of 1.5 - 1.6X by weight of furfuryl alcohol, 14 -16X by weight of furan-epoxy binder, 2.8 -3.2X by wei~ht o-f polyethylenepolyamine and mineral f;llers ;s said by another publ;cation (Sov;et Patent 619,464) on the one hand to increase the strength of these cements and on the other ~o reduce shrinkage. Such a material f;nds util;ty in the construct;on ;ndustry for produc;ng corrosion-resistant coatings and as chemically resistant ma'terial for floor coverings~ Ho~ever, the shrinkage, be;ng 0.75%, is relatively high.
These crosslinked products are l;ke~ise not su;table for preparing cement resins or cements which are subject to high chem-ical stresses, since, owing to their amine conten-t, they inhibi-t the acid catalysts required for curing the cement and, moreover, in the crosslinked s-tate are not sufEiciently acid- and alkali-resistant.
German Ausleyeschrift 1,113,565 discloses the reaction of epoxy resins with furfuryl alcohol in the presence of Friedel-CraEts compounds, metal fluorobora-tes or boron -trifluoride as catalysts. However, this method produces only cured plastics such as casts but not storable resin solu-tions.
U.S. Patent 4,100,31~ proposes the use of a synthetic resin solution as a coating agent for tar-impregnated coal bodies which comprises crosslinking furan compounds, for example a mix-ture of equal parts of furfurol and furfuryl alcohol, diethyl sulfate as catalyst and epoxy resins. Crosslinking is effected at temperatures between 100 and 135C, which is not suitable for preparing cements if only for that reason, since these have to be crosslinked at room temperature or at least in the vicinity of room temperature.
It is further known to modify furan resins in diverse ways. For instance, furfurol can be reacted with phenol to give novolaks w~ich serve for preparing phenolic resin compression molding compositions. However, these resins are not suitable for preparing cements if only because of their excessively high , . . . . .
ntrlnslc VlSCOSlty.
It is also known -to modify condensates of furfuryl alcohol with urea and formaldehyde and to use these , ~
. Ir ~
~,~t~ ~3~
- 2a - 23221-4230 polycondensates as core binders. But even the known inclusion of phenol in this modification does not alter the inadequate chemical resistance and low thermal resistance of these polycondensates, which is generally necessary in the preparation of core binders.
., ~ , ..
L3~
Nor does the kno~n reaction of furfuryl alcohol ~;th ~he-nols or wi~h resorcinol lead to suitable resins for ce-ments or coa~ing compositions, but to resins which are use-ful only as binders for glues, compression moLding com-positions or paints. Nor does the reaction bet~een hydroxy-benzyl alcohol and furfuryl alcohol produce any useful ce-ment resin. When such polycondensates are mixed ~ith a filler ~hich contains acid catalys~s a violent polycon-densation reaction occurs. The cured product thus obtained undergoes shr;nkage and moreover lacks resistance to alkali.
German Offenlegungsschrift 2,750,70~ describes the pre-paration of reaction products of hydroxyaromatic com-pounds, formaldehyde and furfuryl alcohol, ~herein the furfuryl alcohol can if desired also be used in such an excess that ;t acts as a solvent. Furthermore, the reac-tion product can be cured ~ith acid catalysts. These known, furfuryL alcohol modified resol resins are said by this publication to be used ~ith other monomers such as isocyanates, to give flame-retardant compact moldings, but preferably foam materials. The preparation of cements is not mentioned.
The furan resins customarily used to date in the prepara-tton of acid-curing cements produce cements having very high chemical resistance. In particular, the furan cements are highly alkali-res;stant. On the other hand, disadvantages of furan cements are their relatively high brittleness, ~hich rules out their use for certain a~plica-tions, for example for cementing machine components but in particular their use in coating composit;ons, ~ith uhich the present invention is more specifically concerned. The t~f~ modulus of elasticity of the cured cements is ~.2 to 2.0 ~' -~ 35 106 N/cm2. This relatively high modulus of elasticity of the previously used furan resin cements is disadvan-tageous owing to the attendant brittleness. The brittle-ness can have the effect that, in acid-resistant ceramic slab pav;ng laid ~ith furan resin cement, detachment from ~7;~
the ground and cracks can easily arise ~hen the different thermaL expansion coefficients of cemen~, ceramic materi-als and ground become active as a result of temPerature cycles or changes. This is because the lower the modulus of ~lasticity of the cement, the more sensitive the sys-tem comprising cement, ceramic mater;al and ground is to cracking and detachment on change in temperature. The cement is then less brittle and consequently larger deformations are possible ~ithout cracking and detach-ment occurring. The heat resistance of the previoLIslyused furan resin cements ~as in general about 200 to 210C.
The same relationships also apply to coating comoositions.
Owing to the disadvantages ment;oned, the use of these furan resins for cements or coating compositions have t5 previously not been described. It ;s therefore desirable to have cements and coating compositions which are free of these disadvantages described.
The invention~ then, relates to resin solutions for cements and coating compositions and to a process for their preparaeion ~herein ePoxy resins are dissolved in furfuryl alcohol alone or in mixture ~ith other furan derivatives and are reacted at temperatures bet~een 20 and 200C, preferably bet~een 40 and 140C, in the pre-sence of catalysts and ~herein, if desired, the catalystis neutralized after the reaction and the reaction mixture has reactive diluents added to ;t.
Surprisingly, the cements prepared according to the inven-tion not only have a long storage life but also have all the ~avorable properties of furan resin cements, an excel-lent chemical stability and a thermal stability up to temperatures of 3Z0C. In addition, the cements shrink very little. Moreover, they combine a high use l;fe ~ith a shorter curing time and are nonetheless highly resist-ant to chem;cals.
The epoxy resins used can be any ePOXy resin ~hich con-7~ ~3~
tains more than one epoxy group per molecuLe, for examole those ~hich are prepared by reacting epihalogenohydrins ~ith polyhydric alcohols or polyglycol ethers or by epoxi-dation of double bonds, for example by epoxidation of unsaturated fatty oils or unsaturated hydrocarbons~ for examDle dicyclopentadiene, butadiene and so on. Prefer-ence is given to epoxy resins ~hich are obtained from aiphenylalkanes or higher polyphenylolalkanes such as novolaks and epihaloaenohydrins or dihalogenohydr;ns, -10 preferably epichlorohydrin. Their ePoxy eouivalen~ ~eight is in general 150 to 200û, preferably 170 to 1200.
The ePoxy resins are reacted ~ith furfuryl alcohol or in mixture with other furan der;vatives by dissolving the epoxy resins, for exanDle in furfuryl alcohol, and react-ing ~hem at temoeratures between 20^ and 200~, prefer-ably be~ween 40C and 140 C, in the presence of catalysts until the epoxy grouDs have been converted. Co~Pleteness of conversion can be monitored by deternining the eDoxy Z0 content of the reaction batch or by determining the resi-due on drying.
While, if acid catalysts are used~ they need to be neut-ralized after the reaction, such a neutralization is not Z5 always necessary if basic ca~alysts are used.
Possible catalysts for the reaction of the eDoxy resins with furfuryl alcohoL are strong mineral acids, alkylsul-fonic acids or arylsulfonic acids. Ho~ever, it is pre-ferable to use basic catalysts. Suitable catalysts arein particular the hydrox;des of the alkaLi metals, for example also ;n the form of their aqueous solutions.
It is like~ise possible to use as catalysts tertiary alkyl'amines having 1-6, preferably up to 4, carbon atoms , in the alkyl radical, such as trimethylamine, tr;ethyl-amine, tert.-butylami'ne and so on. It is also possible to use those tr;alkyls wh;ch add;t;onally have primary or secondary am;no functions, for example dimethylaminopro-7~35 pylamine. If these amines, uhich are incorporated into the epoxy resin via their primary and/or secondary amino groups, are used, it is necessary to ensure that their amount is only so low as not to impair the subsequent acid curing. If the am;ne catalysts are used in a larger amount, their removal from the reaction mixture, for example by salt formation, is however ;n general always advisable.
It is also possible to use in addit;on to furfuryl alco hol other furan der;vat;ves such as furfurol, hydroxome-thylfurfurol, difuryl ether and others. These comoounds can be present from the start during the reaction or can be mixed in afterwards, an excess act;ng as a reactive diluent.
The ;nvention also relates to the use of the res;n solu-tions prepared according to the invention for cements and coating compositions by mixing the resin solution immedi-ately before use ~ith A. at least one filler and ~ . at least one curing agent, the weight ratio of the resin solution to the sum of com-ponents A and B being 1:tû.5 to 7), preferably 1:(1 to 4).
The resin solutions used generally have a solid res;n con-tent of 10 to 75, preferably 25 to 70, in par~icular 45to 55, Z by weight of sol;ds content.
The modified furan resins are in accordance with the claimed use generally used in reactive diluents, the ueight ratio of diluent to solid resin (A) being tO.4 to 1.5):1, preferably tO.6 to 1.1):1. Diluents are for example benzyl alcohol, low-molecular eDoxy compounds such as diglyc;dyl ether, diphenylolpro~ane d;glycidyl ether, but in particular furfurol, difuryl ether, prefer-ably furfuryl alcohol. The latter and the furan compo-nents can already be present in excess from the start as early as the reaction ~ith the epoxy compounds. The storability of the resin solutions is practically unlimi-_ 7 _ ~.27B13~
~ed. Their viscosi~ies are in general between 50 and20,000, preferably 100 and 15,000, mPa.s~20C.
As filter A) in the preparation of the cements it is pos-sible to use rock flours such as clay and chamotte, barium sulfate, quartz flour and preferably coke flour or graDhite flour, for example artificial graphite.
As curing agent B) for curing the cements it is possible to use acid and/or acid-forming substances, for example (a) inorganic or organic ac;ds, such as sulfuric acid, hydrochloric acid, phosphoric acid, usually in aqueous solution, oxalic acid, sulfonic acids, such as amidosul-fonic acid, monosulfonic and disulfonic acids of benzene, toluene, xylene, and also naphthalenedisulfonic acids and/or (b) acid-eliminating substances such as sulfo-chlorides of the sulfonic acids mentioned in ta)O for example toluene- or benzene-sulfochloride, alkyl esters of these sulfonic acids or acid sulfate esters and/or (c~
acid salts of sulfuric acid or phosphoric acid, prefer-ably their sodium salts. It also is possible to use adducts of urea and aromatic sulfonic acids individually or in mixture with the above resins. The curing agent accounts of 4 to 12, preferably 6 to 8, X by ~eight of the filler/curing agent mixture.
; The cements arc prepared by mixing the solution of the furan resin with a filler A) and catalyst or curing agent B) immediately before use. In general, a mixture of fil-ler and curing substance, the so-called cemen~ flour, is prepared in advance and is added to the furan resin solu-tion. the cement obta;ned is then a~plied in conven-tional manner onto or bet~een the materials to be cemen-ted. The cement is rated on the basis of the properties of the furan resin; the'properties of the cement after mixing the furan resin ~ith the cement flour; the course of curing; and the chemical and physical propert;es of the end product. The furan resin used should have a low 3~
degree of condensa~ion and thus posses a low viscosity, so as to be free-flowing and give good ~etting of the filler. If n~cessary, the reactive diluent content needs to be set so as to ensure processability. Along storage life is a further prerequisite for opti~al use. The degree of condensation should increase only insign;-ficantly during storage, since an excessive increase in viscosity ~ould lead to poorer ~etting of the filler and hence to processing faults.
The cement is prepared immediately before use. After the filler has been mixed with the furan res;n, the action of the catalyst brings about an immediate enlargement of the furan resin molecule. The pot l;~e, i.e. the time bet-~een mixing and loss of processable consistency, should n general amount to 30 minutes to 2 hours, so as toensure comfortabLe processing. After processing, it is desirable for the cement to be cured at room temp~rature in as short a time as possible and to become resistan~ ~o chemicals and solvents.
In the examples ~hich follow, parts and Zages are by weight.
Examples 1 a) Preparation of the res;n 1425 parts of an epoxy resin based on diphenylolpropane and epichlorohydrin and having an average epoxy equ;valent weight of 4Z5 were dissolved in 2,013 parts of furfuryl al-cohol ;n a reaction vessel equ;pped w;th a stirrer and athermometer and the solution was brought to a temperature of 60C. After addition of 25.5 parts of 33X strength aqueous sodium hydrox;de solution, the batch ~as heated to ~00C and ~as st;rred at that temperature for 4 hours.
The resin solution had a residue tl h/170C) of 49.3%
and a v;scosity of 1250 mPa.stZ0C. The alkal; cata-lyst contained there;n kas neutral;zed ~ith 19.1 parts of ' ' ' ' ' ' .
~B~;~5 _ 9 _ 80X strength lactic acid, producing a solution having a viscosity of 1200 mPa~s/2ûC.
Application ~esting 1 b) Preparation of cement: for th;s test a rement flour (1ûO parts) was prepared from 93 parts of carbon, 6 part~
of a r- naphthalenesulfonic acidturea adduct and 1 part of p-toluenesulfonic acid and was mixed with 6Q parts of the resin solution (1 a~. The cement preDared therefrom had a pot life at 20C of 75 minutes and after 24 hours had attained a Shore D hardness value of 45.
Chemical test 1 c) To determine the chemical resistance, cylindrical bodies measuring 25 mm in both height and diameter were ~repared from the cement and ~ere store.d at 20C for 8 days. After that period the test sDecimens ~ere resistant to boilin~ 70% strength sulfuric ac;d, boiling concentrated hydrochloric acid and concentrated and dilute sodium hydroxide. solution.
Physical tests 1 d) The linear shrinkage was measured on cylindrical test specimens ~hich measured 25 mm in diameter and 90 mm in Z5 length and to the ends of which measurement marks made of glass have been attached. The overall leng~h, including the measurement marks, ~as 100 mm. The test ~as carried out in line with the ASTM method C 358. The first mea-surement of the length was carried out 24 hours after preparing the test speciment and uas used as the starting value. Within a period of observation of 94 days the shrinkage at room temperature amounted to 0.18X.
Determination of the modulus of elasticity of flexure _ _ (see table).
2 a~ Preparation of the resin As in Example 1~ 1,425 parts of an epoxy resin based on - 1o diphenylolproDane and epichlorohydrin and having an aver-age epoxy equivalent ~eight of 950 ~ere dissolved in 1,714 parts of furfuryl alcohol; 25~5 parts of 33X strength sod-ium hydroxide solution were added at 60C and the tem~-erature ~as then raised to 100C. After stirring at thattemperature for 4 hours the resin had a residue of 49.5 (1 hour/170C) and a viscosity of 13,50û mPa.s~
After neutral;zation with 19.1 parts of 80X strength lac-tic acid the v;scosity droPPed to 12,500 mPa.s.
Application testing 2 b) Preparation of the cement For the test, a cement flour (100 parts) was prepared from ~3 parts of carbon and 6 parts of! -naphthalenesul-fonic acid/urea adduct and one part of p-toluenesulfonic acid and was mixed ~ith 75 par~s of resin solution 2 a~
as in ExamDle 1. The cement prepared therefrom had a pot life at 20C of 80 minutes and after 24 hours had a Shore D hardness value of 60.
Chemical test 2 c) To determine the chemical resistance, cylindrical bodies measuring 25 mm in both height and diameter ~ere prepared from the cement and ~ere stored at 20C for 8 days. After that period the test specimens ~ere resis-tant to boiling 70X strength sulfuric ac;d, boiling con-centrated hydrochloric acid and concentrated and dilute 3û sodium hydroxide soLut;on.
Physical tests 2 d) The linear shrinkage was measured as in Example 1 d).
Within a period of observation of 94 days the shrinkage at 20C amounted to 0.2X.
Dçtermination of the modulus of elasticity of flexure on test specimens 10 x 15 ~ ~D
~ x a mD l e 1 E x a mo l e Z__ Modulws of elasticity (10 N/mm2) after 8 days at 20C 0.44 V.52 5 after 28 days at 20C 0.63 o.~a af~er 28 days at Z0C
plus 16 hours at 90C 0.59 0.58
It is known to use polycondensates of furfuryl alcohol as binders for acid-curing cements. The second main com-ponent of these cements are fil lers to which acids or acid-eliminatlng substances are admixed as curing catalysts which can effect curing ~;thout suprJly of heat.
It is also known from ~erman Patent 2,926,053 to react furfuryl alcohol with a hydroxymethyl-containing alkyl-phenol resol based on bifunctional alkylphenols at ele-vated temperature and ~o dissolve the reaction Droduct inat least one reactive diluent from the group consist-ina of benzyl alcohol, low-molecular ePoxy compounds, furfurol, difuryl ether, furfuryl aLcohol to avoid the otherwise considerable shrinkage of furan cements. The addition of lo~-molecular epoxy compounds does not affect the elastic behavior of the cured Droducts, but they have a certain sensitivity to some aggressive, organic solvents which in practice are of ;mDortance for a number of cases~ such as ketones, chlorinated and aromat;c hydro-carbons, and esters~
The presence of furfuryL alcohol in Dlastic cements com-posed of 1.5 - 1.6X by weight of furfuryl alcohol, 14 -16X by weight of furan-epoxy binder, 2.8 -3.2X by wei~ht o-f polyethylenepolyamine and mineral f;llers ;s said by another publ;cation (Sov;et Patent 619,464) on the one hand to increase the strength of these cements and on the other ~o reduce shrinkage. Such a material f;nds util;ty in the construct;on ;ndustry for produc;ng corrosion-resistant coatings and as chemically resistant ma'terial for floor coverings~ Ho~ever, the shrinkage, be;ng 0.75%, is relatively high.
These crosslinked products are l;ke~ise not su;table for preparing cement resins or cements which are subject to high chem-ical stresses, since, owing to their amine conten-t, they inhibi-t the acid catalysts required for curing the cement and, moreover, in the crosslinked s-tate are not sufEiciently acid- and alkali-resistant.
German Ausleyeschrift 1,113,565 discloses the reaction of epoxy resins with furfuryl alcohol in the presence of Friedel-CraEts compounds, metal fluorobora-tes or boron -trifluoride as catalysts. However, this method produces only cured plastics such as casts but not storable resin solu-tions.
U.S. Patent 4,100,31~ proposes the use of a synthetic resin solution as a coating agent for tar-impregnated coal bodies which comprises crosslinking furan compounds, for example a mix-ture of equal parts of furfurol and furfuryl alcohol, diethyl sulfate as catalyst and epoxy resins. Crosslinking is effected at temperatures between 100 and 135C, which is not suitable for preparing cements if only for that reason, since these have to be crosslinked at room temperature or at least in the vicinity of room temperature.
It is further known to modify furan resins in diverse ways. For instance, furfurol can be reacted with phenol to give novolaks w~ich serve for preparing phenolic resin compression molding compositions. However, these resins are not suitable for preparing cements if only because of their excessively high , . . . . .
ntrlnslc VlSCOSlty.
It is also known -to modify condensates of furfuryl alcohol with urea and formaldehyde and to use these , ~
. Ir ~
~,~t~ ~3~
- 2a - 23221-4230 polycondensates as core binders. But even the known inclusion of phenol in this modification does not alter the inadequate chemical resistance and low thermal resistance of these polycondensates, which is generally necessary in the preparation of core binders.
., ~ , ..
L3~
Nor does the kno~n reaction of furfuryl alcohol ~;th ~he-nols or wi~h resorcinol lead to suitable resins for ce-ments or coa~ing compositions, but to resins which are use-ful only as binders for glues, compression moLding com-positions or paints. Nor does the reaction bet~een hydroxy-benzyl alcohol and furfuryl alcohol produce any useful ce-ment resin. When such polycondensates are mixed ~ith a filler ~hich contains acid catalys~s a violent polycon-densation reaction occurs. The cured product thus obtained undergoes shr;nkage and moreover lacks resistance to alkali.
German Offenlegungsschrift 2,750,70~ describes the pre-paration of reaction products of hydroxyaromatic com-pounds, formaldehyde and furfuryl alcohol, ~herein the furfuryl alcohol can if desired also be used in such an excess that ;t acts as a solvent. Furthermore, the reac-tion product can be cured ~ith acid catalysts. These known, furfuryL alcohol modified resol resins are said by this publication to be used ~ith other monomers such as isocyanates, to give flame-retardant compact moldings, but preferably foam materials. The preparation of cements is not mentioned.
The furan resins customarily used to date in the prepara-tton of acid-curing cements produce cements having very high chemical resistance. In particular, the furan cements are highly alkali-res;stant. On the other hand, disadvantages of furan cements are their relatively high brittleness, ~hich rules out their use for certain a~plica-tions, for example for cementing machine components but in particular their use in coating composit;ons, ~ith uhich the present invention is more specifically concerned. The t~f~ modulus of elasticity of the cured cements is ~.2 to 2.0 ~' -~ 35 106 N/cm2. This relatively high modulus of elasticity of the previously used furan resin cements is disadvan-tageous owing to the attendant brittleness. The brittle-ness can have the effect that, in acid-resistant ceramic slab pav;ng laid ~ith furan resin cement, detachment from ~7;~
the ground and cracks can easily arise ~hen the different thermaL expansion coefficients of cemen~, ceramic materi-als and ground become active as a result of temPerature cycles or changes. This is because the lower the modulus of ~lasticity of the cement, the more sensitive the sys-tem comprising cement, ceramic mater;al and ground is to cracking and detachment on change in temperature. The cement is then less brittle and consequently larger deformations are possible ~ithout cracking and detach-ment occurring. The heat resistance of the previoLIslyused furan resin cements ~as in general about 200 to 210C.
The same relationships also apply to coating comoositions.
Owing to the disadvantages ment;oned, the use of these furan resins for cements or coating compositions have t5 previously not been described. It ;s therefore desirable to have cements and coating compositions which are free of these disadvantages described.
The invention~ then, relates to resin solutions for cements and coating compositions and to a process for their preparaeion ~herein ePoxy resins are dissolved in furfuryl alcohol alone or in mixture ~ith other furan derivatives and are reacted at temperatures bet~een 20 and 200C, preferably bet~een 40 and 140C, in the pre-sence of catalysts and ~herein, if desired, the catalystis neutralized after the reaction and the reaction mixture has reactive diluents added to ;t.
Surprisingly, the cements prepared according to the inven-tion not only have a long storage life but also have all the ~avorable properties of furan resin cements, an excel-lent chemical stability and a thermal stability up to temperatures of 3Z0C. In addition, the cements shrink very little. Moreover, they combine a high use l;fe ~ith a shorter curing time and are nonetheless highly resist-ant to chem;cals.
The epoxy resins used can be any ePOXy resin ~hich con-7~ ~3~
tains more than one epoxy group per molecuLe, for examole those ~hich are prepared by reacting epihalogenohydrins ~ith polyhydric alcohols or polyglycol ethers or by epoxi-dation of double bonds, for example by epoxidation of unsaturated fatty oils or unsaturated hydrocarbons~ for examDle dicyclopentadiene, butadiene and so on. Prefer-ence is given to epoxy resins ~hich are obtained from aiphenylalkanes or higher polyphenylolalkanes such as novolaks and epihaloaenohydrins or dihalogenohydr;ns, -10 preferably epichlorohydrin. Their ePoxy eouivalen~ ~eight is in general 150 to 200û, preferably 170 to 1200.
The ePoxy resins are reacted ~ith furfuryl alcohol or in mixture with other furan der;vatives by dissolving the epoxy resins, for exanDle in furfuryl alcohol, and react-ing ~hem at temoeratures between 20^ and 200~, prefer-ably be~ween 40C and 140 C, in the presence of catalysts until the epoxy grouDs have been converted. Co~Pleteness of conversion can be monitored by deternining the eDoxy Z0 content of the reaction batch or by determining the resi-due on drying.
While, if acid catalysts are used~ they need to be neut-ralized after the reaction, such a neutralization is not Z5 always necessary if basic ca~alysts are used.
Possible catalysts for the reaction of the eDoxy resins with furfuryl alcohoL are strong mineral acids, alkylsul-fonic acids or arylsulfonic acids. Ho~ever, it is pre-ferable to use basic catalysts. Suitable catalysts arein particular the hydrox;des of the alkaLi metals, for example also ;n the form of their aqueous solutions.
It is like~ise possible to use as catalysts tertiary alkyl'amines having 1-6, preferably up to 4, carbon atoms , in the alkyl radical, such as trimethylamine, tr;ethyl-amine, tert.-butylami'ne and so on. It is also possible to use those tr;alkyls wh;ch add;t;onally have primary or secondary am;no functions, for example dimethylaminopro-7~35 pylamine. If these amines, uhich are incorporated into the epoxy resin via their primary and/or secondary amino groups, are used, it is necessary to ensure that their amount is only so low as not to impair the subsequent acid curing. If the am;ne catalysts are used in a larger amount, their removal from the reaction mixture, for example by salt formation, is however ;n general always advisable.
It is also possible to use in addit;on to furfuryl alco hol other furan der;vat;ves such as furfurol, hydroxome-thylfurfurol, difuryl ether and others. These comoounds can be present from the start during the reaction or can be mixed in afterwards, an excess act;ng as a reactive diluent.
The ;nvention also relates to the use of the res;n solu-tions prepared according to the invention for cements and coating compositions by mixing the resin solution immedi-ately before use ~ith A. at least one filler and ~ . at least one curing agent, the weight ratio of the resin solution to the sum of com-ponents A and B being 1:tû.5 to 7), preferably 1:(1 to 4).
The resin solutions used generally have a solid res;n con-tent of 10 to 75, preferably 25 to 70, in par~icular 45to 55, Z by weight of sol;ds content.
The modified furan resins are in accordance with the claimed use generally used in reactive diluents, the ueight ratio of diluent to solid resin (A) being tO.4 to 1.5):1, preferably tO.6 to 1.1):1. Diluents are for example benzyl alcohol, low-molecular eDoxy compounds such as diglyc;dyl ether, diphenylolpro~ane d;glycidyl ether, but in particular furfurol, difuryl ether, prefer-ably furfuryl alcohol. The latter and the furan compo-nents can already be present in excess from the start as early as the reaction ~ith the epoxy compounds. The storability of the resin solutions is practically unlimi-_ 7 _ ~.27B13~
~ed. Their viscosi~ies are in general between 50 and20,000, preferably 100 and 15,000, mPa.s~20C.
As filter A) in the preparation of the cements it is pos-sible to use rock flours such as clay and chamotte, barium sulfate, quartz flour and preferably coke flour or graDhite flour, for example artificial graphite.
As curing agent B) for curing the cements it is possible to use acid and/or acid-forming substances, for example (a) inorganic or organic ac;ds, such as sulfuric acid, hydrochloric acid, phosphoric acid, usually in aqueous solution, oxalic acid, sulfonic acids, such as amidosul-fonic acid, monosulfonic and disulfonic acids of benzene, toluene, xylene, and also naphthalenedisulfonic acids and/or (b) acid-eliminating substances such as sulfo-chlorides of the sulfonic acids mentioned in ta)O for example toluene- or benzene-sulfochloride, alkyl esters of these sulfonic acids or acid sulfate esters and/or (c~
acid salts of sulfuric acid or phosphoric acid, prefer-ably their sodium salts. It also is possible to use adducts of urea and aromatic sulfonic acids individually or in mixture with the above resins. The curing agent accounts of 4 to 12, preferably 6 to 8, X by ~eight of the filler/curing agent mixture.
; The cements arc prepared by mixing the solution of the furan resin with a filler A) and catalyst or curing agent B) immediately before use. In general, a mixture of fil-ler and curing substance, the so-called cemen~ flour, is prepared in advance and is added to the furan resin solu-tion. the cement obta;ned is then a~plied in conven-tional manner onto or bet~een the materials to be cemen-ted. The cement is rated on the basis of the properties of the furan resin; the'properties of the cement after mixing the furan resin ~ith the cement flour; the course of curing; and the chemical and physical propert;es of the end product. The furan resin used should have a low 3~
degree of condensa~ion and thus posses a low viscosity, so as to be free-flowing and give good ~etting of the filler. If n~cessary, the reactive diluent content needs to be set so as to ensure processability. Along storage life is a further prerequisite for opti~al use. The degree of condensation should increase only insign;-ficantly during storage, since an excessive increase in viscosity ~ould lead to poorer ~etting of the filler and hence to processing faults.
The cement is prepared immediately before use. After the filler has been mixed with the furan res;n, the action of the catalyst brings about an immediate enlargement of the furan resin molecule. The pot l;~e, i.e. the time bet-~een mixing and loss of processable consistency, should n general amount to 30 minutes to 2 hours, so as toensure comfortabLe processing. After processing, it is desirable for the cement to be cured at room temp~rature in as short a time as possible and to become resistan~ ~o chemicals and solvents.
In the examples ~hich follow, parts and Zages are by weight.
Examples 1 a) Preparation of the res;n 1425 parts of an epoxy resin based on diphenylolpropane and epichlorohydrin and having an average epoxy equ;valent weight of 4Z5 were dissolved in 2,013 parts of furfuryl al-cohol ;n a reaction vessel equ;pped w;th a stirrer and athermometer and the solution was brought to a temperature of 60C. After addition of 25.5 parts of 33X strength aqueous sodium hydrox;de solution, the batch ~as heated to ~00C and ~as st;rred at that temperature for 4 hours.
The resin solution had a residue tl h/170C) of 49.3%
and a v;scosity of 1250 mPa.stZ0C. The alkal; cata-lyst contained there;n kas neutral;zed ~ith 19.1 parts of ' ' ' ' ' ' .
~B~;~5 _ 9 _ 80X strength lactic acid, producing a solution having a viscosity of 1200 mPa~s/2ûC.
Application ~esting 1 b) Preparation of cement: for th;s test a rement flour (1ûO parts) was prepared from 93 parts of carbon, 6 part~
of a r- naphthalenesulfonic acidturea adduct and 1 part of p-toluenesulfonic acid and was mixed with 6Q parts of the resin solution (1 a~. The cement preDared therefrom had a pot life at 20C of 75 minutes and after 24 hours had attained a Shore D hardness value of 45.
Chemical test 1 c) To determine the chemical resistance, cylindrical bodies measuring 25 mm in both height and diameter were ~repared from the cement and ~ere store.d at 20C for 8 days. After that period the test sDecimens ~ere resistant to boilin~ 70% strength sulfuric ac;d, boiling concentrated hydrochloric acid and concentrated and dilute sodium hydroxide. solution.
Physical tests 1 d) The linear shrinkage was measured on cylindrical test specimens ~hich measured 25 mm in diameter and 90 mm in Z5 length and to the ends of which measurement marks made of glass have been attached. The overall leng~h, including the measurement marks, ~as 100 mm. The test ~as carried out in line with the ASTM method C 358. The first mea-surement of the length was carried out 24 hours after preparing the test speciment and uas used as the starting value. Within a period of observation of 94 days the shrinkage at room temperature amounted to 0.18X.
Determination of the modulus of elasticity of flexure _ _ (see table).
2 a~ Preparation of the resin As in Example 1~ 1,425 parts of an epoxy resin based on - 1o diphenylolproDane and epichlorohydrin and having an aver-age epoxy equivalent ~eight of 950 ~ere dissolved in 1,714 parts of furfuryl alcohol; 25~5 parts of 33X strength sod-ium hydroxide solution were added at 60C and the tem~-erature ~as then raised to 100C. After stirring at thattemperature for 4 hours the resin had a residue of 49.5 (1 hour/170C) and a viscosity of 13,50û mPa.s~
After neutral;zation with 19.1 parts of 80X strength lac-tic acid the v;scosity droPPed to 12,500 mPa.s.
Application testing 2 b) Preparation of the cement For the test, a cement flour (100 parts) was prepared from ~3 parts of carbon and 6 parts of! -naphthalenesul-fonic acid/urea adduct and one part of p-toluenesulfonic acid and was mixed ~ith 75 par~s of resin solution 2 a~
as in ExamDle 1. The cement prepared therefrom had a pot life at 20C of 80 minutes and after 24 hours had a Shore D hardness value of 60.
Chemical test 2 c) To determine the chemical resistance, cylindrical bodies measuring 25 mm in both height and diameter ~ere prepared from the cement and ~ere stored at 20C for 8 days. After that period the test specimens ~ere resis-tant to boiling 70X strength sulfuric ac;d, boiling con-centrated hydrochloric acid and concentrated and dilute 3û sodium hydroxide soLut;on.
Physical tests 2 d) The linear shrinkage was measured as in Example 1 d).
Within a period of observation of 94 days the shrinkage at 20C amounted to 0.2X.
Dçtermination of the modulus of elasticity of flexure on test specimens 10 x 15 ~ ~D
~ x a mD l e 1 E x a mo l e Z__ Modulws of elasticity (10 N/mm2) after 8 days at 20C 0.44 V.52 5 after 28 days at 20C 0.63 o.~a af~er 28 days at Z0C
plus 16 hours at 90C 0.59 0.58
Claims (16)
1. A resin solution for cements and coating composi-tions based on a reaction product of epoxy resins with more than one epoxy group in the molecule and furfuryl alcohol alone or in mixture with other furan derivatives dissolved in reactive diluents.
2. A resin solution as claimed in claim 1, wherein all the epoxy groups of the epoxy resin are reacted with furfuryl alcohol or other furan derivatives.
3. A resin solution as claimed in claim 1, wherein the weight ratio of reactive diluents to solid resin A
is (0.4 to 1.5) : 1.
is (0.4 to 1.5) : 1.
4. A resin solution as claimed in claim 1 or 2 or 3, wherein the resin solution has viscosities between 50 and 20,000 mPa,s/20°C and the epoxy resins used have an epoxy equivalent weight of 150 to 2000.
5. A resin solution as claimed in claim 1 or 2 or 3, wherein the furan derivatives used are furfurol, hydroxy-methylfurfurol or difuryl ether.
6. A process for preparing resin solutions for cements and coating compositions, which comprises dissolving epoxy resins having more than one epoxy group in the molecule in furfuryl alcohol alone or in mixture with other furan derivatives and reacting them at temperatures between 20 and 200°C in the presence of acid or basic catalysts.
7. Process as claimed in claim 6, wherein the cata-lyst is neutralized after the reaction and reactive di-luents are added in addition to the reaction mixture.
8. Process as claimed in claim 6, wherein the reac-tion temperature is 40 to 140°C.
9. Process as claimed in claim 6, wherein all the epoxy groups of the epoxy resin are reacted with furfuryl alcohol or other furan derivatives.
10. Process as claimed in claim 6 or 7 or 8, wherein the weight ratio of reactive diluents to solid resin A
is (0.4 to 1.5) : 1.
is (0.4 to 1.5) : 1.
11. Process as claimed in claim 6 or 7 or 8, wherein the epoxy resins used have an epoxy equivalent weight of 150 to 2000 and the resin solution obtained has viscosities between 50 and 20,000 mPa.s/20°C.
12. Process as claimed in claim 6 or 7 or 8, wherein the furan derivatives used are furfurol, hydroxymethylfurfurol or difuryl ether.
13. Cements and coating compositions in which the resin solution as claimed in claim 1 is mixed immediately before use with A) at least one filler and B) at least one curing agent or a mixture of A) and B), the weight ratio of the solution to the sum of components A) and B) being 1 : (0.5 - 7).
14. Cement and coating compositions as claimed in claim 13, wherein component A) is rock flour, barium sulfate, quartz, coke or graphite flour.
15. Cement and coating compositions as claimed in claim 13, wherein component B) is an acid, an acid-forming substance or both.
16. Cement and coating compositions as claimed in claim 13, 14 or 15, wherein the resin solution has a solid resin content of 10 to 75 % by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843444281 DE3444281A1 (en) | 1984-12-05 | 1984-12-05 | RESIN SOLUTIONS FOR KITTS AND COATING MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DEP3444281.2 | 1984-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1278135C true CA1278135C (en) | 1990-12-18 |
Family
ID=6251921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000496800A Expired - Fee Related CA1278135C (en) | 1984-12-05 | 1985-12-04 | Resin solutions for cements and coating compositions, process for their preparation and their use |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4804722A (en) |
| EP (1) | EP0184106B1 (en) |
| AT (1) | ATE64927T1 (en) |
| CA (1) | CA1278135C (en) |
| DE (2) | DE3444281A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5610317A (en) | 1985-09-05 | 1997-03-11 | The Boeing Company | Multiple chemically functional end cap monomers |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| 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 |
| DE4421623A1 (en) * | 1994-06-21 | 1996-01-04 | Thera Ges Fuer Patente | Multi-component, cationically curing epoxy materials and their use as well as processes for producing hardened materials |
| CN104277546A (en) * | 2014-10-30 | 2015-01-14 | 成都优品涂料有限公司 | UV wood lacquer jelly-type transparent earth-invigorating putty and preparation method thereof |
| CN113248959B (en) * | 2021-05-18 | 2022-07-12 | 深圳优易材料科技有限公司 | High-temperature-wear-resistant anticorrosive paint and preparation method and application thereof |
| SE545414C2 (en) * | 2021-12-21 | 2023-09-05 | Stora Enso Oyj | Process for the preparation of a bonding resin |
| CN114380560B (en) * | 2022-02-08 | 2022-12-30 | 华创建筑设计有限公司 | C50 high-strength resin concrete and preparation process thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL120506C (en) * | 1958-03-27 | 1900-01-01 | ||
| NL132481C (en) * | 1962-03-30 | 1900-01-01 | ||
| US3491041A (en) * | 1966-10-25 | 1970-01-20 | Esb Inc | Modified furfuryl alcohol coating resin |
| CH587879A5 (en) * | 1973-11-09 | 1977-05-13 | Possessio Verwaltungs Ag | |
| US4267236A (en) * | 1979-08-09 | 1981-05-12 | Ignatius Metil | Alloys of epoxy and homopolymers of furfuryl alcohol |
| DE3446842A1 (en) * | 1984-03-27 | 1985-10-31 | Amcor Ltd., Tel Aviv | LIQUID FILTER DEVICE |
-
1984
- 1984-12-05 DE DE19843444281 patent/DE3444281A1/en not_active Withdrawn
-
1985
- 1985-11-26 EP EP85114947A patent/EP0184106B1/en not_active Expired - Lifetime
- 1985-11-26 DE DE8585114947T patent/DE3583381D1/en not_active Expired - Fee Related
- 1985-11-26 AT AT85114947T patent/ATE64927T1/en not_active IP Right Cessation
- 1985-12-04 CA CA000496800A patent/CA1278135C/en not_active Expired - Fee Related
-
1987
- 1987-08-13 US US07/085,074 patent/US4804722A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3583381D1 (en) | 1991-08-08 |
| EP0184106A3 (en) | 1987-04-29 |
| EP0184106B1 (en) | 1991-07-03 |
| US4804722A (en) | 1989-02-14 |
| DE3444281A1 (en) | 1986-06-05 |
| ATE64927T1 (en) | 1991-07-15 |
| EP0184106A2 (en) | 1986-06-11 |
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