CA1134973A - High ortho etherified resole resins - Google Patents
High ortho etherified resole resinsInfo
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- CA1134973A CA1134973A CA000330970A CA330970A CA1134973A CA 1134973 A CA1134973 A CA 1134973A CA 000330970 A CA000330970 A CA 000330970A CA 330970 A CA330970 A CA 330970A CA 1134973 A CA1134973 A CA 1134973A
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- phenol
- resole
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- 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
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
-
- 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
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
-
- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
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- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE This invention relates to high ortho etherified resole resins. The resole resins are prepared by re-acting under acidic conditions phenol with formalde-hyde in the presence of a divalent electropositive metal. The resole resins are then etherified with an alcohol and dehydrated to less than 1 percent water. The novel high ortho etherified resole resins are useful in coating, bonding and adhesive compositions. Such resoles are readily curable with coreactive resins providing chemical and solvent resistance.
Description
~3~973 HIGH ORTHO ET~ERIFIED RESOLE RESI~S
BACKGROUND OF THE INVENTION
The field of the present invention is compositions based on high ortho alkoxymethyl and aralkoxymethyl etherified phenol-formaldehyde resins.
Phenolic ethers have been described in Xirk-Othmer "En-cyclopedia of Chemical Technology", 2nd Edition, Vol. 8 (1965), :
pages 165-175 in which the phenolic aromatic hydroxyl is ether-ified as an aryl ether. In the case of -the resole ethers which are c.haracteri2ed by having the methylol group ortho and para to the free aromatic hydroxyl etherified, relatively little prior art is known. The state of known prior art i5 set forth in U.s.P. 2,454,153, u.S.P. 3,630,977 and U.S.P. 3,650,996 which :
disclose the utility of ethers derived from methylol derivatives of difunctional phenols. The ethers described have the disad~
vantage of having only two reactive sites and, hence, are not self-curable and their chemical and solvent resistance is im-paired. In U.S.P. 3,485,797 there are disclosed resole resin containing internal benzylic ether linkages only as contrasted to the present invention having both internal benzylic ether and alkoxymethyl or aralkoxymethyl ether linkages.
It is the obJective of the present inventicn then to provide novel resole resins characteri2ed by having either ar-: -alkoxymethyl and alkoxymethyl ether groups incorporated in their ~25 ~ resole structure. The resoles are also characterized by having ;~
:, ortho-ortho and ortho-para functionality capable of being cured -': ~ ' , . -':
~ - 2 ~
~3~73 at elevated temperatures yet having great storage s-tability at temperatures of about 20-25C.
Another objective is to provide said resole resins that have high compatibility and reactivit;y with coreacting resins such as alkyds, epoxies, polyvinyl formals and butryals.
Finally, it is an objective to provide methods of pre-paring said novel etherified resole resins.
SUMMARY OF THE INVENTION
The phenol resole ethers described herein are resinous mixtures of monomeric, dimeric and higher condensation products of phenol and formaldehyde, modified by etherification with monohydric alcohols and further modified by formation of di-benzyl ethers.
The monomer species are as shown below~
OH OH
~ CH20B ~r where R-H, CH3, c2H5~ C3H7, C4Hg, etc-The dimeric species are primarily as folows:
0~ O~I
ROCR2--~_CR20 C1~2 --~CR20R
RO-CR2_~ CH2 ~CX20R
.
~3~73 06-12-053g OH
1 ROCH2 ~ ~ CH2 ~ OH
~he higher condensation products may be represented as ~ollows:
OH OH OH
l~C112-0 C}~2~-l~c~2~c~2o~
m n Complex mixtures of this type are best described in terms of numbsr average structure as shown in "NMR of Phenolic Resins"
of J. Poly Science 3:1079-1106 (1965) by Woodbrey, Higginbottom and Culbertson. In the case o~ the etherified resole being de-~;~ scribed here, the ~ollowing termino~ogy is used:
RA ~ aromatic protons per phenolic ring ;
,j AM - methylol grou~s per phenolic ring REB ~ benzylether bridges per phenolic ring : RME - alkoxymethyl or aralkoxymethyl ethers n - a~erage number of rings per molecule ,: Mn _ number average molecular weight ::
.
'.
' 1~ _ ` ~3~73 ., .
06-12-053~
The structures given above clearly show that the methylol groups are preponderantly ortho to the phenolic hydroxyl and as .;~ .
a result the alkoxymeth~1 ethers and dibenzyl ethers are so oriented. The methylene bridges, on the other hand, are both ortho-ortho and ortho-para but rarely para-para.
Process_~or Preparation Phenol and formaldehyde are heated together in an aqueous system in the presence of an ortho directing catalyst such as the oxide, hydroxide or organic acid salt o~ a divalent electropositive metal such as Zn+~, Mg++, Mn~+, Ca~t and Co~* or mixtures thereof. ~ith the pH in the range oP 4 to 7 the mix-ture is heated to ôO-100C., until the formaldehyde is essen-tially all combined. A monohydric aliphatic alcohol is then added and the mixture heated at 65 to 100C., until the desired degree of etherification and condensation has taken place. The resin is then dehydrated under reduced pressure to remove excess alcohol and water to yield a viscous syrup essentially free of , solvents.
These novel phenolic compositions are characteri~ed by ~ 20 unusual and valuable properties. The compositions are stable at ; room temperature for long periods oP time yet are capable oP
!
~ being cured rapidly at elevated temperatures. They are near 100 ,.
percent reactive solids yet are still Pluid at room temperature.
Solubility in organic solvents, particularly hydrocarbons, is greatly enhanced over conventional reeoles. Compatibility with co-reactants such as alkyds, epoxies, polyvinyl formals and polyvinylbutyrals is also greatly improved.
Although it is possible to prepare resole ethers employ-ing the more expensive substituted phenols such as paratertiary-:~ . ..
. ~ .
,: .
, ,; .
. .
~ = 5 -~ `-~ ~L345~73 , butylphenol, these in turn being di~unctional in terms of a phenolic cure, produce only linear polymers with little or no crosslinking. Resins based on such substituted phenols thus re-quire the addition of a more highly ~unctional resin or core-actant to produce a crosslinked system. r~he present resins de-rived from phenol, meta-substituted phenols or mixtures of phenol and substituted phenols other than meta-substituted phenols pro-" vide ortho and para activity and provide highly crosslinkable sys-tems when cured and an improvement in properties such as ;10 hardness, gloss, chemical and solvent resistance.
The present invention then relates to:
A high ortho etherified resole resin coating composition s comprising a high ortho etherified resole resin and about l to 95% by weight o~ a coreactive resin, said high ortho etheri~ied ~,15 resole resin being characterized by:
,~ A. having a reacted formaldehyde to phenol mol ratio of l.lO to 2.0, said formaldehyde react-ing with said phenol, ~orming methylol groups taking a final orientation of about 90% to 100%
~ 20 in the ortho position, :
.,j .
~ B. having said phenol selected from the group con- :
,.. .
'~, sisting of phenol, meta-substituted phenols and mixtures of phenol and substituted phenols, C. having condensed phenol-aldehyde linkages wherein ~ 25 25.to 90% of said linkages are benzyl ether `. linkages having a final orientation essentially~'. in the ortho position and lO to 75% are methylene ~-linkages taking a final orientation of about 70 to 90% in the ortho position and about lO to 30%
~:~
: ' `.` `
~3~373 o6 12-0539 in the para position, D. having an average degree of polymerization of less than 4.0, and E. having said methylol groups partially ether-ified with monohydric a,lcohols.
The present invention also relates to a process for pre-paring a high ortho etherified resole resin by first reacting said phenol and said formaldehyde in an aqueous reaction mixture under reflux at about 80C. to 100C., in the present of a di-valent electropositive metal ion while maintaining a pH in the range between about 4 to 7 wherein said pH is controlled by add-ing sufficient amounts of an organic acid and thereafter ether-ifying said resole resin with a monohydric alcohol at a tempera-ture of 65C. to 100C., and dehydrating the resulting aqueous solution to a water content of less than about 1 weight percent and an alcohol content of less than about 5 percent.
The above is a preferred process. The etherified resole resin can also be prepared by adding all of the reactants in-cluding the alcohol in the initial reaction mixture and carrying out the methylolation and etherification and resin advancement simultaneously. It is preferred to carry out the methylolation as a separate step without alcohol present as the alcohol tends to retard methylolation. It is also possible to methylolate under alkaline conditions using, e.g., Ca++ and Mg++ ions at a : 25 pH above 7 and obtain high ortho orientation of the methylol groups follo~ed by acidification to a range of 4 to 7 with etherification. This method requires careful control of catalyst concentration, temperature and time of reaction to prevent para orientation and resin advancement through methylene bridge forma-.
~3~3 tion.
D~SCRIPTIO~ OF ~HE PREFE~RED EMB DIMENTS
The following exa~ples are set forth to illustrate more clearly the principles and practice o~ the present in~ention to one skilled in the ar-t and are not intended to be restrictive but merely illustrative of the invention hereln contained.
Phenols used in this invention consist primarily of7 phenol and meta substituted phenols in whlch three active sites are available. Other substituted phenols substituted in the ortho or para position may be used in part with phenol to modify the properties but are not used exclusively. Formaldehyde is the preferred aldehyde and may be employed in a variety of forms, formalin 30 to 60 percent concentration or paraform. Alcohols used are monohydric alcohols and may be primary and secondary alcohols containing 1 to 12 carbon atoms and one -OH group. The ::
resole resins are etherified with said alcohols incorporating in amounts of about 0.05 to 0.50, preferably 0.20 to 0.40 as methylol ether groups per phenolic group in the form of alkoxy methyl ethers or aralkoxy methyl ethers.
~XAMPLX 1 Preparation of a methylated etherified high ortho phenol-formaldehyde resole. Phenol, 700 parts and 50 percent formalin, 670 parts, are added to a stirred reactor along with 14 parts of zinc oxide and 14 parts acetic acid. The mixture is heated to reflux and after two hours is cooled to 50C., and dehydrated at ~ -29" Hg vacuum to remove 330 parts of water. Methanol, 700 parts, is then added and the mixture refluxed at 75C., for five hours.
Uethanol and ~ater are removed (300 parts) by atmospheric dis-tillation until the temperature reaches 83C., then held an , , additional six hours. The product i8 then vacuum dehydrated at 29" Hg vacuum to an end temperature of 83C., to yield a syrup which had an ASTM solids of 78 percent. Yield was approximately 1000 parts. Analysis of the final product by proton magnetic resonance gave the following number average structure: 0.28 methoxymethyl groups per phenolic nucleus, 0.40 methylols, 0.22 methylene bridges and 0.19 benzyl ether bridges.
Preparation of a Butylated Etherified High Ortho Phenol-Formaldehyde Resole Phenol 600 parts, and 574 parts, 50 percent formalin were charged to a stirred reactor and 2l~ parts zinc oxide and 36 parts acetic acid added. The mixture was refluxed for 2 hours at 100-102C., -~hen 600 parts n-Butanol added. The mixture was refluxed at 95 to 100C., for 3-1/2 hours while the water was being re-moved by azeotropic distillation. Excess butanol was then re-moved by vacuum distillation to an end temperature of 90C., at 29.6" Hg vacuum. This yielded 942 parts of a viscous syrup of 88.9 percent ASTM solids. Analysis of the final product by pro-ton magnetic resonance gave the following number average struc-ture: 0.32 methylol groups per phenolic nucleus, 0.27 butox~-methyl groups, 0.32 methylene bridges and 0.27 benzyl ether bridges.
Preparation of a Butylated Etherified High Ortho Phenol-Formaldehyde Resole Phenol 600 parts and 574 parts, 50 percen-t formalin were charged to a stirred reactor and 6 parts zinc oxide and 9 parts acetic acid added. The mixture was refluxed 2 hours at 100-102C., then 600 parts n-Butanol added. Refluxed at 95-100C., . , . : . , ~ . ,, ~:
~3~3 n~-l2-0539 for 3 hours while the water was being removed by azeotropic dis-tillation. Excess butanol was then remo~ed by vacuum distilla-tion to an end temperature of 90C. at 29.6" Hg vacuum. This yielded 885 parts of viscous syrup of 71 percent solids. Proton magnetic resonance analysis gave the following number average structure: o.66 methylol groups per phenolic nucleuS, 0.14 butoxymethyl groups, 0.11 methylene bridges and 0.20 benzyl ether bridges.
Mixed Phenol Etherified Resole Resin Phenol 540 parts, p~nonylphenol, 140.4 parts and 574 parts, 50 percent formalin were charged to a stirred reactor and 12 parts zinc oxide and 18 parts acetic acid added. The mixture was refluxed 2 hours at 100-102C., then 600 parts n-butanol added. Refluxed at 95-100C., for 3 hours while the water was being removed by azeotropic distillation. Excess butanol was then remo~ed by vacuum distillation to give 1005 parts of a vis-cous syrup of 80 percent ASTM solids with a viscosity of 8000 cps. Proton magnetic resonance analysis gave the following number average structure: 0.53 methylol groups per phenolic nucleus, 0.28 butoxymethyl groups, 0.18 methylene bridges and 0.24 benzyl ether bridges.
Synthesis of a Styrene Substituted Phenol and a Butylated Etherified Resole Resin Phenol 600 parts, H2S04 1.8 parts are charged to a stirred reactor and heated to 80C. Styrene, 180 parts is added ;~
slowly over a period of 30 minutes holding the temperature at 115C. After the addition is complete the temperature is held :, " : `
at 110-115C. an additional 30 min. then cooled to 50C. and 15 parts zinc oxide and 12 parts acetic acid are added. Formalin (50%) 574 parts are added and the mixture heated to reflux. The mixture is refluxed at 100-102C. for 2 hours then 600 parts bu-tanol and 24 parts xylol are added. The mixture i5 again broughtto reflux at 95C. and water removed azeotropically over a period of 3 hrs. Excess butanol was then removed by vacuum distillation to yield 1111 parts of a viscous syrup of 80.5% ASTM solids and a viscosity of 7000 cps.
Preparation of Stable Aqueous Emulsions by Butylated Etherified Phenolic Resole Resin of Ex. 5, 50.5 parts was added slowly to 200 parts of an aqueous solution containing ~ parts hydroxyethyl cellulose and 1 part Aerosol OT' with intense agitation in a Waring*Blender.
A smooth homogeneous emulsion formed immediately and which re-mained stable for over two months. ~ `
EXAMPL~ 7 Chemically Resistant Coating Varnish Composition Based on Butylated Etherified Phenolic Resole A mixture of 32 parts butylated phenolic resole of Ex 2, 3.2 parts polyvinyl formal resin (Formvar 15/95 "E" commercially available from the Monsanto Co. St. Louis, Mo. under the Trade-mark Formvar), 15.9 parts furfuraldehyde and 15.9 parts 70% iso-propanol are stirred together until the Formvar has completely dissolved. The mixture is then catalyzed with 1.2% H3PO4 based on total resin content. Sheet steel is coated wi-th the above formulation then baked 12 min. at 400F. The cured film is tough with extremely good chemical resistance.
The substituted phenols are preferably meta substituted * Trademark ~3~3~3 n~-12-0539 phenols to insure ortho and para activity for rapid curing.
Substituted phenols having ortho and para substitution are functional when used with phenol to insure ortho and para acti-vity. Such phenols can be used in combination with phenol or mixtures wherein the substituted phenols is present in the mix-ture in amounts up to about 50 percent by weight of the mixed phenols.
The meta substituted phenol having at least one attached radical selected from the group consisting of alkyl, aryl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, carbocylic, halogen and mixtures thereo~.
The substituted phenols useful in the resins of this in-vention are all phenols that have at least one reactive position open in the ortho or para position. Phenol and such substituted phenols or their mixtures can be used. Substituted phenol-s in--clude all phenols having at least one attached radical selected from the group consisting of alkyl, aryl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, carbocylic, halogen and mixtures thereof.
Examples of substituted phenols include: phenols sub-stituted with straight and branched chain alkyl radicals having 1 to 16 carbon atoms, e.g., cresol, isopropylphenol, 2,3-xylenol, 3,5-xylenol, 3,~-xylenol, 2,6-xylenol, mono and disubstituted butyl, amyl, octyl, nonyl, decyl and dodecyl phenols; aryl sub-stituted phenols, e.g., phenyl phenol and naphthyl phenol;
cycloalkyl phenols, e.g., terphenylphenols, e.g., using limonene~
pinene 3 methadiene, cyclohexyl and cyclopentyl; cycloalkenyl phenols, e.g., cyclopentenyl, dicyclopentadieneyl and metha-cyclopentadieneyl phenols; alkenyl phenols, e.g., allylphenol, ~3~73 butenylphenol, pentenylphenol, hexenylphenol; alkaryl phenols, e.g., tolylphenol, xylylphenol, propylphenylphenol; aralkyl phenols, e.g., benzyl, phenethyl, alphamethyl, phenyethyl, indyl and cumyl phenols bisphenol A, bisphenol F, halophenols, e.g., chlorophenols, bromophenols, 2,4-dichlorophenol, 2,6, dichloro-phenol, etc.
The substituted phenols can be prepared under Friedel-Craft conditions as disclosed in U.S.P. 3,637.429. When phenols selected from the group of phenol, meta substituted phenol and a mixture of phenol and at least one substituted phenol are re-acted with aldehydes using a high aldehyde-phenol ratio under acid conditions in the presence of an organic acid salt of a di-valent metal ion high ortho phenol-aldehyde resole resins are formed.
The particular catalysts used were selected from a group consisting of an oxide, or hydroxide or organic acid salt of a divalent electropositive metal ion. -Divalent electropositive metals of oxides or hydroxides or organic acid salts employed in accordance with the invention are calcium (Ca++), barium (Ba++), strontium (Sr++), magnesium (Mg++), zinc (Zn++), manganous (Mn+~), manganese, cadmium (Cd~+), cobaltous (Co++), cobalt and plumbous (Pb++) lead. Preferred metals are magnesium (Mg++), zinc (Zn++) and manganous (Mn++), manganese and cobalt (Co+f).
When an organic acid salt is employed, it is preferred that it be a salt of an aliphatic monocarboxylic acid such as formic acid or acetic acid, however, the salt can also be derived ~ -from an aliphatic hydroxycarboxylic acid such as lactic acid, or the salt can be derived from aromatic carboxylic acids such as - 13 ~
1~3f~'73 benzoic acid or dicarboxylic acids such as adipic and succinic.
Typical salts useful for the purpose of the invention are cadmium formate, zinc acetate, magnesium acetate, manganese acetate, lead acetate and zinc benzoate.
~he organic acid is selected such that the salt ~ormed with the divalent electropositive metal is soluble in catalytic amounts in the reacting mixture. The organic acids described above also form soluble organic salts in situ with the metal ox-ides and hydroxides. Regardless of theory, the divalent metal ions provided by the oxides~ hydroxides or salts are provided in soluble form to direct the condensation of the formaldehyde with the phenol giving a high ortho orientation. The organic acid is used in sufficient quantities to insure the solubility o~ the metal ion and maintain the pH in the range of about pH4 to pH7.
In general the amount of oxide or hydroxide or salt, calculated as a percentage based on the amount of phenol, is within the range of 0.1 to 10 percent, the preferred amount being within the range of 1.0 to 5.0 percent.
The high ortho etherified phenol formaldehyde resins of this invention differ from prlor art conventionally alkaline catalyzed resole resins in that they have a final orientation of 90 to 100 percent in the ortho position and in addition the con-densed phenol linkages are characterized by having about 25 per-cent to 90 percent dibenzyl ether structures. In contrast~
alkaline catalyzed resoles have about 0 percent to 5 percent ben7yl ether linkages and significantly less than 80 percent substitution in the ortho position.
The resins of this invention are further characterized by having a relatively low degree of condensation or polymeriza-.' - 14--_ 4~73 tion, e.i., less than 4 and are capable of giving a cure rate of less than 30 minutes, preferably less than 20 minutes at 150C. 5 to a fully crosslinked polymer.
Certain high ortho resole resins are known, however, they differ from the present invention in that the phenol-formaldehyde reactions taught are only those for the ortho position with no para reactions and have degrees of polymerization greater than 4.
Such resins are de~icient in that they are extremely slow curing and in fact need external curing reagents to effect thermosetting properties such as the use of acids, hexa or isocyanates for cur-ing such resins.
Further, since there are no reacting groups in the para position they can only provide high molecular weight resins with a degree of polymerization oP greater than 4 giving slow or neglieible cure rates for the resulting polymers.
This lack of thermosetting character is overcome by the present invention by controlling the formaldehyde to phenol re-action to give 10 to 30 percent para orientation in methylene bridge formation essential for chain branching and true thermo-setting characteristics. The further effect of having appreci-able amounts of para orientation is that the thermosetting characteristics are obtained without the addition of external catalysts and with resins having a low degree of polymerization, e.l., having a DP of less than 4. This para activity also allows for the use of various substituted phenols, in particular ortho substituted phenols in admixture with phenol and within the scope of this invention.
In general, to produce a high ortho resole intermediate resin for use in this invention, a phenol or mixture of phenols , , ' ,~ , , ,, ", "~ " " ,~ " , ,,. ,, . " ~ :, are reacted under acid aqueous liquid phase conditions with from about 1.1 to 2.8 mols of formaldehyde per mol o~ phenol (pre~er-ably from 1.1 to 2.0 mols formaldehyde per mol of phenol) pro-viding a reacted formaldehyde to phenol ratio of 1.1 to 2.0, preferably 1.25 to 2.0, in the presence of a catalyst selected ~rom the group consisting of an oxide or hydroxide or organic acid salt of a divalent electropositive metal. Said group is at least partially soluble in the reacting mixture having an organic acid present in such amount that the reacting mixture is main-tained between pH4 and pH7.
This reaction mixture is then heated to temperatures offrom about 80 to 100C., for a time sufficient to substantially react most of the formaldehyde and thereby produce a desired high ortho resole intermediate product. Times of from about 2 to~4 hours are typical. Aqueous liquid phase preparation conditions are used.
~ he high ortho phenol formaldehyde resole resin inter-mediate is then etherified with a monohydric alcohol at a pH of 4 to 7 at a temperature of 65 to lOO~C., followed by dehydration the resulting aqueous soIution to a water content of less than about 1 percent by weight and an alcohol content of less than 5 percent by weight forming a high ortho etherified phenol-form aldehyde resole resin o~ the present invention.
The alkoxymethyl or aralkoxymethyl ether and benzyl ~ ether content and the degree of advancement are readily controll-able, so that one can optimihe such an etherified resole resin ~
~or use in a particular application. For purposes of this in- -vention, a high ortho etherified phenol-formaldehyde resole resin or resole can be regarded as being the reaction product of the i , , ...
,:: , . - ..... : ... : . ~ . .
~3~3 above-described phenol and formaldehyde and alcohol under the aqueous acid catalyzed conditions as described herein which product can be thermoset by heat alone without the use of a cur-ing catalyst. In general, the etherified resole as made usually ranges from 5 to 100,000 cps as a liquid or varnish.
In making the etherified resole resin of this invention such an etherified resole is dehydra-ted, preferably under heat and reduced pressure, to a water con-tent of less than 1 percent and an alcohol content of less than 5 percent ~based on total re-sole weight). When the resulting water content is under about 1 weight percent, there is produced a single-phased, clear light-colored, high solids, viscous etherified resole resin varnish.
In any given instance, its total solids content, (residual) ~ater content, and viscosity depend upon the amount of phenol aldehyde product present, the mol ratio of formaldehyde to phenol, speci-fic type and amount of methylolation catalyst, conditions and re-actants used to substitut-e the phenol, me~hylolation temperature, ~-degree of etherification, degree of advancement and the like.
After such dehydration, the resulting etherified resole ~`
resin or varnish can be dissolved in a relatively volatile, inert ~ -organic solvent medium i~ desired having properties as defined ~ -below. While the organic liquid used has properties as indicated below, it will be appreciated that such liquid can comprise mi~- `~
tures of different organic liquids. Preferred liquids are lower ~ -~
25 alkanols (such as ethanol, me~hanol and propanol) and lower ket- ~ -ones (such as acetone or methyl ethyl Ketone). The term "lower"
refers to less than 7 carbon atoms per molecule as used herein.
Aromatic and aliphatic (including cycloaliphatic) hydrocarbons can also be employed as solvents for a given resin, including ~L~3~73 06~12-0539 benzene, toluene, xylene, naphthalene, nonene, petroleum frac~
tions, etc. Preferably, the total water content of a varnish of the invention is below about 1 weight percent, however, with proper solvent can tolerate from about 0.5 to 30 percent water.
Those skilled in the art will appreciate that care should preferably be taken to use an organic liquid system in which high ortho etherified phenolic resole resins are completely soluble as well as any wa-ter present. Adding, for exam~le, a ketone or an ether-ester solvent like butyl Cellosolve*will generally improve the water tolerance (ability to dissolve water) of a solvent system.
These varnishes are characteristically light colored, one-phase, clear liquid solutions, each having a viscosity rang-ing from about 5 to 100,000 centipoises. The exact viscosity of a given varnish depends upon many chemical process and product variables. For impregnating applications, viscosities of from about 100 to 1000 centipoise-s are preferred.
The total reactive solids content of a given varnish product can be as high as about 99 weight percent and as low as about 20 weight percent or even lower, but preferred reactive solids contents usually fall in the range of from about 25 to 85 weight percent. The varnishes of this invention are of lower viscosity and can be advanced (e.g., crosslinked as by heating to produce larger molecules) to a greater extent without forming precipitates from the organic solvent phase than is the case o~
corresponding alkaline resole products. -~
When used for impregnation and reinforcing purposes, the liquid resole resin varnishes of this invention are useful for impregnating cellulosic paper, asbestos paper, and other non-*~Trademark 1~34~73 woven sheet structures as well as woven fabrics (cotton, glass fibers, nylon etc.), etc. Impregnation can be accomplished by any convenient means, including dipping, coating, spraying, mix-ing, or the like. The so-impregnated material is dried to lower the volatiles content and then heated to adv~nce the resin to the proper degree for the intended use. The etherifiéd resole var-nishes of this invention are useful in the preparation of lamin-ates, such as those made from such impreenated sheet materials~
Such laminates are used in electrical applications as supports or as insulation for conductive elements. The laminates are gener-ally manufactured in a sheet or block form which is then punched or otherwise machined to provide desired configurations for a particular end use.
The etherified resole varnishes of this invention are also useful in the manufacture of cloth laminates, and automotive oil filters. A suitable oil filter media, for example, is pre-pared by impregnating with a varnish of this invention, cellu-losic fiber paper modified with a synthetic fiber (polyester, or the like) and having a thickness of from about 5 to 20 mils.
Sufficient etherified resole varnish resin of this invention is used to obtain an impregnated sheet member having a cured resin content of about 15 to 25 percent, based on the weight of the paper. After such paper is so impregnated, it is heated to ad-vance the resin to a so-called B-stage, and then is corrugated or pleated to form the filter element. ~he filter element is then assembled with the end use filter container and heated to 250F. to 350F., for from 5 to 20 minutes to cure the resin.
When cured, the product has good flexibility and low tendency to crack during use.
~3~3 06-l2-ns.~s In eeneral, a varnish of the present invention can be used to make rein~orced plastics.
The varnishes o~ this invention coraprise:
A. from about 30 to 99 weight percent o~
reactive solids o~ a high ortho ether-i~ied phenol-formaldehyde resole resin, B. from about 0.5 to 30 weight percent of dissolved water, C. the balance up to 100 weight percent o~
any giverl varnish being an organic liquid which:
1. is substantially inert (as respects such resin and water),
BACKGROUND OF THE INVENTION
The field of the present invention is compositions based on high ortho alkoxymethyl and aralkoxymethyl etherified phenol-formaldehyde resins.
Phenolic ethers have been described in Xirk-Othmer "En-cyclopedia of Chemical Technology", 2nd Edition, Vol. 8 (1965), :
pages 165-175 in which the phenolic aromatic hydroxyl is ether-ified as an aryl ether. In the case of -the resole ethers which are c.haracteri2ed by having the methylol group ortho and para to the free aromatic hydroxyl etherified, relatively little prior art is known. The state of known prior art i5 set forth in U.s.P. 2,454,153, u.S.P. 3,630,977 and U.S.P. 3,650,996 which :
disclose the utility of ethers derived from methylol derivatives of difunctional phenols. The ethers described have the disad~
vantage of having only two reactive sites and, hence, are not self-curable and their chemical and solvent resistance is im-paired. In U.S.P. 3,485,797 there are disclosed resole resin containing internal benzylic ether linkages only as contrasted to the present invention having both internal benzylic ether and alkoxymethyl or aralkoxymethyl ether linkages.
It is the obJective of the present inventicn then to provide novel resole resins characteri2ed by having either ar-: -alkoxymethyl and alkoxymethyl ether groups incorporated in their ~25 ~ resole structure. The resoles are also characterized by having ;~
:, ortho-ortho and ortho-para functionality capable of being cured -': ~ ' , . -':
~ - 2 ~
~3~73 at elevated temperatures yet having great storage s-tability at temperatures of about 20-25C.
Another objective is to provide said resole resins that have high compatibility and reactivit;y with coreacting resins such as alkyds, epoxies, polyvinyl formals and butryals.
Finally, it is an objective to provide methods of pre-paring said novel etherified resole resins.
SUMMARY OF THE INVENTION
The phenol resole ethers described herein are resinous mixtures of monomeric, dimeric and higher condensation products of phenol and formaldehyde, modified by etherification with monohydric alcohols and further modified by formation of di-benzyl ethers.
The monomer species are as shown below~
OH OH
~ CH20B ~r where R-H, CH3, c2H5~ C3H7, C4Hg, etc-The dimeric species are primarily as folows:
0~ O~I
ROCR2--~_CR20 C1~2 --~CR20R
RO-CR2_~ CH2 ~CX20R
.
~3~73 06-12-053g OH
1 ROCH2 ~ ~ CH2 ~ OH
~he higher condensation products may be represented as ~ollows:
OH OH OH
l~C112-0 C}~2~-l~c~2~c~2o~
m n Complex mixtures of this type are best described in terms of numbsr average structure as shown in "NMR of Phenolic Resins"
of J. Poly Science 3:1079-1106 (1965) by Woodbrey, Higginbottom and Culbertson. In the case o~ the etherified resole being de-~;~ scribed here, the ~ollowing termino~ogy is used:
RA ~ aromatic protons per phenolic ring ;
,j AM - methylol grou~s per phenolic ring REB ~ benzylether bridges per phenolic ring : RME - alkoxymethyl or aralkoxymethyl ethers n - a~erage number of rings per molecule ,: Mn _ number average molecular weight ::
.
'.
' 1~ _ ` ~3~73 ., .
06-12-053~
The structures given above clearly show that the methylol groups are preponderantly ortho to the phenolic hydroxyl and as .;~ .
a result the alkoxymeth~1 ethers and dibenzyl ethers are so oriented. The methylene bridges, on the other hand, are both ortho-ortho and ortho-para but rarely para-para.
Process_~or Preparation Phenol and formaldehyde are heated together in an aqueous system in the presence of an ortho directing catalyst such as the oxide, hydroxide or organic acid salt o~ a divalent electropositive metal such as Zn+~, Mg++, Mn~+, Ca~t and Co~* or mixtures thereof. ~ith the pH in the range oP 4 to 7 the mix-ture is heated to ôO-100C., until the formaldehyde is essen-tially all combined. A monohydric aliphatic alcohol is then added and the mixture heated at 65 to 100C., until the desired degree of etherification and condensation has taken place. The resin is then dehydrated under reduced pressure to remove excess alcohol and water to yield a viscous syrup essentially free of , solvents.
These novel phenolic compositions are characteri~ed by ~ 20 unusual and valuable properties. The compositions are stable at ; room temperature for long periods oP time yet are capable oP
!
~ being cured rapidly at elevated temperatures. They are near 100 ,.
percent reactive solids yet are still Pluid at room temperature.
Solubility in organic solvents, particularly hydrocarbons, is greatly enhanced over conventional reeoles. Compatibility with co-reactants such as alkyds, epoxies, polyvinyl formals and polyvinylbutyrals is also greatly improved.
Although it is possible to prepare resole ethers employ-ing the more expensive substituted phenols such as paratertiary-:~ . ..
. ~ .
,: .
, ,; .
. .
~ = 5 -~ `-~ ~L345~73 , butylphenol, these in turn being di~unctional in terms of a phenolic cure, produce only linear polymers with little or no crosslinking. Resins based on such substituted phenols thus re-quire the addition of a more highly ~unctional resin or core-actant to produce a crosslinked system. r~he present resins de-rived from phenol, meta-substituted phenols or mixtures of phenol and substituted phenols other than meta-substituted phenols pro-" vide ortho and para activity and provide highly crosslinkable sys-tems when cured and an improvement in properties such as ;10 hardness, gloss, chemical and solvent resistance.
The present invention then relates to:
A high ortho etherified resole resin coating composition s comprising a high ortho etherified resole resin and about l to 95% by weight o~ a coreactive resin, said high ortho etheri~ied ~,15 resole resin being characterized by:
,~ A. having a reacted formaldehyde to phenol mol ratio of l.lO to 2.0, said formaldehyde react-ing with said phenol, ~orming methylol groups taking a final orientation of about 90% to 100%
~ 20 in the ortho position, :
.,j .
~ B. having said phenol selected from the group con- :
,.. .
'~, sisting of phenol, meta-substituted phenols and mixtures of phenol and substituted phenols, C. having condensed phenol-aldehyde linkages wherein ~ 25 25.to 90% of said linkages are benzyl ether `. linkages having a final orientation essentially~'. in the ortho position and lO to 75% are methylene ~-linkages taking a final orientation of about 70 to 90% in the ortho position and about lO to 30%
~:~
: ' `.` `
~3~373 o6 12-0539 in the para position, D. having an average degree of polymerization of less than 4.0, and E. having said methylol groups partially ether-ified with monohydric a,lcohols.
The present invention also relates to a process for pre-paring a high ortho etherified resole resin by first reacting said phenol and said formaldehyde in an aqueous reaction mixture under reflux at about 80C. to 100C., in the present of a di-valent electropositive metal ion while maintaining a pH in the range between about 4 to 7 wherein said pH is controlled by add-ing sufficient amounts of an organic acid and thereafter ether-ifying said resole resin with a monohydric alcohol at a tempera-ture of 65C. to 100C., and dehydrating the resulting aqueous solution to a water content of less than about 1 weight percent and an alcohol content of less than about 5 percent.
The above is a preferred process. The etherified resole resin can also be prepared by adding all of the reactants in-cluding the alcohol in the initial reaction mixture and carrying out the methylolation and etherification and resin advancement simultaneously. It is preferred to carry out the methylolation as a separate step without alcohol present as the alcohol tends to retard methylolation. It is also possible to methylolate under alkaline conditions using, e.g., Ca++ and Mg++ ions at a : 25 pH above 7 and obtain high ortho orientation of the methylol groups follo~ed by acidification to a range of 4 to 7 with etherification. This method requires careful control of catalyst concentration, temperature and time of reaction to prevent para orientation and resin advancement through methylene bridge forma-.
~3~3 tion.
D~SCRIPTIO~ OF ~HE PREFE~RED EMB DIMENTS
The following exa~ples are set forth to illustrate more clearly the principles and practice o~ the present in~ention to one skilled in the ar-t and are not intended to be restrictive but merely illustrative of the invention hereln contained.
Phenols used in this invention consist primarily of7 phenol and meta substituted phenols in whlch three active sites are available. Other substituted phenols substituted in the ortho or para position may be used in part with phenol to modify the properties but are not used exclusively. Formaldehyde is the preferred aldehyde and may be employed in a variety of forms, formalin 30 to 60 percent concentration or paraform. Alcohols used are monohydric alcohols and may be primary and secondary alcohols containing 1 to 12 carbon atoms and one -OH group. The ::
resole resins are etherified with said alcohols incorporating in amounts of about 0.05 to 0.50, preferably 0.20 to 0.40 as methylol ether groups per phenolic group in the form of alkoxy methyl ethers or aralkoxy methyl ethers.
~XAMPLX 1 Preparation of a methylated etherified high ortho phenol-formaldehyde resole. Phenol, 700 parts and 50 percent formalin, 670 parts, are added to a stirred reactor along with 14 parts of zinc oxide and 14 parts acetic acid. The mixture is heated to reflux and after two hours is cooled to 50C., and dehydrated at ~ -29" Hg vacuum to remove 330 parts of water. Methanol, 700 parts, is then added and the mixture refluxed at 75C., for five hours.
Uethanol and ~ater are removed (300 parts) by atmospheric dis-tillation until the temperature reaches 83C., then held an , , additional six hours. The product i8 then vacuum dehydrated at 29" Hg vacuum to an end temperature of 83C., to yield a syrup which had an ASTM solids of 78 percent. Yield was approximately 1000 parts. Analysis of the final product by proton magnetic resonance gave the following number average structure: 0.28 methoxymethyl groups per phenolic nucleus, 0.40 methylols, 0.22 methylene bridges and 0.19 benzyl ether bridges.
Preparation of a Butylated Etherified High Ortho Phenol-Formaldehyde Resole Phenol 600 parts, and 574 parts, 50 percent formalin were charged to a stirred reactor and 2l~ parts zinc oxide and 36 parts acetic acid added. The mixture was refluxed for 2 hours at 100-102C., -~hen 600 parts n-Butanol added. The mixture was refluxed at 95 to 100C., for 3-1/2 hours while the water was being re-moved by azeotropic distillation. Excess butanol was then re-moved by vacuum distillation to an end temperature of 90C., at 29.6" Hg vacuum. This yielded 942 parts of a viscous syrup of 88.9 percent ASTM solids. Analysis of the final product by pro-ton magnetic resonance gave the following number average struc-ture: 0.32 methylol groups per phenolic nucleus, 0.27 butox~-methyl groups, 0.32 methylene bridges and 0.27 benzyl ether bridges.
Preparation of a Butylated Etherified High Ortho Phenol-Formaldehyde Resole Phenol 600 parts and 574 parts, 50 percen-t formalin were charged to a stirred reactor and 6 parts zinc oxide and 9 parts acetic acid added. The mixture was refluxed 2 hours at 100-102C., then 600 parts n-Butanol added. Refluxed at 95-100C., . , . : . , ~ . ,, ~:
~3~3 n~-l2-0539 for 3 hours while the water was being removed by azeotropic dis-tillation. Excess butanol was then remo~ed by vacuum distilla-tion to an end temperature of 90C. at 29.6" Hg vacuum. This yielded 885 parts of viscous syrup of 71 percent solids. Proton magnetic resonance analysis gave the following number average structure: o.66 methylol groups per phenolic nucleuS, 0.14 butoxymethyl groups, 0.11 methylene bridges and 0.20 benzyl ether bridges.
Mixed Phenol Etherified Resole Resin Phenol 540 parts, p~nonylphenol, 140.4 parts and 574 parts, 50 percent formalin were charged to a stirred reactor and 12 parts zinc oxide and 18 parts acetic acid added. The mixture was refluxed 2 hours at 100-102C., then 600 parts n-butanol added. Refluxed at 95-100C., for 3 hours while the water was being removed by azeotropic distillation. Excess butanol was then remo~ed by vacuum distillation to give 1005 parts of a vis-cous syrup of 80 percent ASTM solids with a viscosity of 8000 cps. Proton magnetic resonance analysis gave the following number average structure: 0.53 methylol groups per phenolic nucleus, 0.28 butoxymethyl groups, 0.18 methylene bridges and 0.24 benzyl ether bridges.
Synthesis of a Styrene Substituted Phenol and a Butylated Etherified Resole Resin Phenol 600 parts, H2S04 1.8 parts are charged to a stirred reactor and heated to 80C. Styrene, 180 parts is added ;~
slowly over a period of 30 minutes holding the temperature at 115C. After the addition is complete the temperature is held :, " : `
at 110-115C. an additional 30 min. then cooled to 50C. and 15 parts zinc oxide and 12 parts acetic acid are added. Formalin (50%) 574 parts are added and the mixture heated to reflux. The mixture is refluxed at 100-102C. for 2 hours then 600 parts bu-tanol and 24 parts xylol are added. The mixture i5 again broughtto reflux at 95C. and water removed azeotropically over a period of 3 hrs. Excess butanol was then removed by vacuum distillation to yield 1111 parts of a viscous syrup of 80.5% ASTM solids and a viscosity of 7000 cps.
Preparation of Stable Aqueous Emulsions by Butylated Etherified Phenolic Resole Resin of Ex. 5, 50.5 parts was added slowly to 200 parts of an aqueous solution containing ~ parts hydroxyethyl cellulose and 1 part Aerosol OT' with intense agitation in a Waring*Blender.
A smooth homogeneous emulsion formed immediately and which re-mained stable for over two months. ~ `
EXAMPL~ 7 Chemically Resistant Coating Varnish Composition Based on Butylated Etherified Phenolic Resole A mixture of 32 parts butylated phenolic resole of Ex 2, 3.2 parts polyvinyl formal resin (Formvar 15/95 "E" commercially available from the Monsanto Co. St. Louis, Mo. under the Trade-mark Formvar), 15.9 parts furfuraldehyde and 15.9 parts 70% iso-propanol are stirred together until the Formvar has completely dissolved. The mixture is then catalyzed with 1.2% H3PO4 based on total resin content. Sheet steel is coated wi-th the above formulation then baked 12 min. at 400F. The cured film is tough with extremely good chemical resistance.
The substituted phenols are preferably meta substituted * Trademark ~3~3~3 n~-12-0539 phenols to insure ortho and para activity for rapid curing.
Substituted phenols having ortho and para substitution are functional when used with phenol to insure ortho and para acti-vity. Such phenols can be used in combination with phenol or mixtures wherein the substituted phenols is present in the mix-ture in amounts up to about 50 percent by weight of the mixed phenols.
The meta substituted phenol having at least one attached radical selected from the group consisting of alkyl, aryl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, carbocylic, halogen and mixtures thereo~.
The substituted phenols useful in the resins of this in-vention are all phenols that have at least one reactive position open in the ortho or para position. Phenol and such substituted phenols or their mixtures can be used. Substituted phenol-s in--clude all phenols having at least one attached radical selected from the group consisting of alkyl, aryl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, carbocylic, halogen and mixtures thereof.
Examples of substituted phenols include: phenols sub-stituted with straight and branched chain alkyl radicals having 1 to 16 carbon atoms, e.g., cresol, isopropylphenol, 2,3-xylenol, 3,5-xylenol, 3,~-xylenol, 2,6-xylenol, mono and disubstituted butyl, amyl, octyl, nonyl, decyl and dodecyl phenols; aryl sub-stituted phenols, e.g., phenyl phenol and naphthyl phenol;
cycloalkyl phenols, e.g., terphenylphenols, e.g., using limonene~
pinene 3 methadiene, cyclohexyl and cyclopentyl; cycloalkenyl phenols, e.g., cyclopentenyl, dicyclopentadieneyl and metha-cyclopentadieneyl phenols; alkenyl phenols, e.g., allylphenol, ~3~73 butenylphenol, pentenylphenol, hexenylphenol; alkaryl phenols, e.g., tolylphenol, xylylphenol, propylphenylphenol; aralkyl phenols, e.g., benzyl, phenethyl, alphamethyl, phenyethyl, indyl and cumyl phenols bisphenol A, bisphenol F, halophenols, e.g., chlorophenols, bromophenols, 2,4-dichlorophenol, 2,6, dichloro-phenol, etc.
The substituted phenols can be prepared under Friedel-Craft conditions as disclosed in U.S.P. 3,637.429. When phenols selected from the group of phenol, meta substituted phenol and a mixture of phenol and at least one substituted phenol are re-acted with aldehydes using a high aldehyde-phenol ratio under acid conditions in the presence of an organic acid salt of a di-valent metal ion high ortho phenol-aldehyde resole resins are formed.
The particular catalysts used were selected from a group consisting of an oxide, or hydroxide or organic acid salt of a divalent electropositive metal ion. -Divalent electropositive metals of oxides or hydroxides or organic acid salts employed in accordance with the invention are calcium (Ca++), barium (Ba++), strontium (Sr++), magnesium (Mg++), zinc (Zn++), manganous (Mn+~), manganese, cadmium (Cd~+), cobaltous (Co++), cobalt and plumbous (Pb++) lead. Preferred metals are magnesium (Mg++), zinc (Zn++) and manganous (Mn++), manganese and cobalt (Co+f).
When an organic acid salt is employed, it is preferred that it be a salt of an aliphatic monocarboxylic acid such as formic acid or acetic acid, however, the salt can also be derived ~ -from an aliphatic hydroxycarboxylic acid such as lactic acid, or the salt can be derived from aromatic carboxylic acids such as - 13 ~
1~3f~'73 benzoic acid or dicarboxylic acids such as adipic and succinic.
Typical salts useful for the purpose of the invention are cadmium formate, zinc acetate, magnesium acetate, manganese acetate, lead acetate and zinc benzoate.
~he organic acid is selected such that the salt ~ormed with the divalent electropositive metal is soluble in catalytic amounts in the reacting mixture. The organic acids described above also form soluble organic salts in situ with the metal ox-ides and hydroxides. Regardless of theory, the divalent metal ions provided by the oxides~ hydroxides or salts are provided in soluble form to direct the condensation of the formaldehyde with the phenol giving a high ortho orientation. The organic acid is used in sufficient quantities to insure the solubility o~ the metal ion and maintain the pH in the range of about pH4 to pH7.
In general the amount of oxide or hydroxide or salt, calculated as a percentage based on the amount of phenol, is within the range of 0.1 to 10 percent, the preferred amount being within the range of 1.0 to 5.0 percent.
The high ortho etherified phenol formaldehyde resins of this invention differ from prlor art conventionally alkaline catalyzed resole resins in that they have a final orientation of 90 to 100 percent in the ortho position and in addition the con-densed phenol linkages are characterized by having about 25 per-cent to 90 percent dibenzyl ether structures. In contrast~
alkaline catalyzed resoles have about 0 percent to 5 percent ben7yl ether linkages and significantly less than 80 percent substitution in the ortho position.
The resins of this invention are further characterized by having a relatively low degree of condensation or polymeriza-.' - 14--_ 4~73 tion, e.i., less than 4 and are capable of giving a cure rate of less than 30 minutes, preferably less than 20 minutes at 150C. 5 to a fully crosslinked polymer.
Certain high ortho resole resins are known, however, they differ from the present invention in that the phenol-formaldehyde reactions taught are only those for the ortho position with no para reactions and have degrees of polymerization greater than 4.
Such resins are de~icient in that they are extremely slow curing and in fact need external curing reagents to effect thermosetting properties such as the use of acids, hexa or isocyanates for cur-ing such resins.
Further, since there are no reacting groups in the para position they can only provide high molecular weight resins with a degree of polymerization oP greater than 4 giving slow or neglieible cure rates for the resulting polymers.
This lack of thermosetting character is overcome by the present invention by controlling the formaldehyde to phenol re-action to give 10 to 30 percent para orientation in methylene bridge formation essential for chain branching and true thermo-setting characteristics. The further effect of having appreci-able amounts of para orientation is that the thermosetting characteristics are obtained without the addition of external catalysts and with resins having a low degree of polymerization, e.l., having a DP of less than 4. This para activity also allows for the use of various substituted phenols, in particular ortho substituted phenols in admixture with phenol and within the scope of this invention.
In general, to produce a high ortho resole intermediate resin for use in this invention, a phenol or mixture of phenols , , ' ,~ , , ,, ", "~ " " ,~ " , ,,. ,, . " ~ :, are reacted under acid aqueous liquid phase conditions with from about 1.1 to 2.8 mols of formaldehyde per mol o~ phenol (pre~er-ably from 1.1 to 2.0 mols formaldehyde per mol of phenol) pro-viding a reacted formaldehyde to phenol ratio of 1.1 to 2.0, preferably 1.25 to 2.0, in the presence of a catalyst selected ~rom the group consisting of an oxide or hydroxide or organic acid salt of a divalent electropositive metal. Said group is at least partially soluble in the reacting mixture having an organic acid present in such amount that the reacting mixture is main-tained between pH4 and pH7.
This reaction mixture is then heated to temperatures offrom about 80 to 100C., for a time sufficient to substantially react most of the formaldehyde and thereby produce a desired high ortho resole intermediate product. Times of from about 2 to~4 hours are typical. Aqueous liquid phase preparation conditions are used.
~ he high ortho phenol formaldehyde resole resin inter-mediate is then etherified with a monohydric alcohol at a pH of 4 to 7 at a temperature of 65 to lOO~C., followed by dehydration the resulting aqueous soIution to a water content of less than about 1 percent by weight and an alcohol content of less than 5 percent by weight forming a high ortho etherified phenol-form aldehyde resole resin o~ the present invention.
The alkoxymethyl or aralkoxymethyl ether and benzyl ~ ether content and the degree of advancement are readily controll-able, so that one can optimihe such an etherified resole resin ~
~or use in a particular application. For purposes of this in- -vention, a high ortho etherified phenol-formaldehyde resole resin or resole can be regarded as being the reaction product of the i , , ...
,:: , . - ..... : ... : . ~ . .
~3~3 above-described phenol and formaldehyde and alcohol under the aqueous acid catalyzed conditions as described herein which product can be thermoset by heat alone without the use of a cur-ing catalyst. In general, the etherified resole as made usually ranges from 5 to 100,000 cps as a liquid or varnish.
In making the etherified resole resin of this invention such an etherified resole is dehydra-ted, preferably under heat and reduced pressure, to a water con-tent of less than 1 percent and an alcohol content of less than 5 percent ~based on total re-sole weight). When the resulting water content is under about 1 weight percent, there is produced a single-phased, clear light-colored, high solids, viscous etherified resole resin varnish.
In any given instance, its total solids content, (residual) ~ater content, and viscosity depend upon the amount of phenol aldehyde product present, the mol ratio of formaldehyde to phenol, speci-fic type and amount of methylolation catalyst, conditions and re-actants used to substitut-e the phenol, me~hylolation temperature, ~-degree of etherification, degree of advancement and the like.
After such dehydration, the resulting etherified resole ~`
resin or varnish can be dissolved in a relatively volatile, inert ~ -organic solvent medium i~ desired having properties as defined ~ -below. While the organic liquid used has properties as indicated below, it will be appreciated that such liquid can comprise mi~- `~
tures of different organic liquids. Preferred liquids are lower ~ -~
25 alkanols (such as ethanol, me~hanol and propanol) and lower ket- ~ -ones (such as acetone or methyl ethyl Ketone). The term "lower"
refers to less than 7 carbon atoms per molecule as used herein.
Aromatic and aliphatic (including cycloaliphatic) hydrocarbons can also be employed as solvents for a given resin, including ~L~3~73 06~12-0539 benzene, toluene, xylene, naphthalene, nonene, petroleum frac~
tions, etc. Preferably, the total water content of a varnish of the invention is below about 1 weight percent, however, with proper solvent can tolerate from about 0.5 to 30 percent water.
Those skilled in the art will appreciate that care should preferably be taken to use an organic liquid system in which high ortho etherified phenolic resole resins are completely soluble as well as any wa-ter present. Adding, for exam~le, a ketone or an ether-ester solvent like butyl Cellosolve*will generally improve the water tolerance (ability to dissolve water) of a solvent system.
These varnishes are characteristically light colored, one-phase, clear liquid solutions, each having a viscosity rang-ing from about 5 to 100,000 centipoises. The exact viscosity of a given varnish depends upon many chemical process and product variables. For impregnating applications, viscosities of from about 100 to 1000 centipoise-s are preferred.
The total reactive solids content of a given varnish product can be as high as about 99 weight percent and as low as about 20 weight percent or even lower, but preferred reactive solids contents usually fall in the range of from about 25 to 85 weight percent. The varnishes of this invention are of lower viscosity and can be advanced (e.g., crosslinked as by heating to produce larger molecules) to a greater extent without forming precipitates from the organic solvent phase than is the case o~
corresponding alkaline resole products. -~
When used for impregnation and reinforcing purposes, the liquid resole resin varnishes of this invention are useful for impregnating cellulosic paper, asbestos paper, and other non-*~Trademark 1~34~73 woven sheet structures as well as woven fabrics (cotton, glass fibers, nylon etc.), etc. Impregnation can be accomplished by any convenient means, including dipping, coating, spraying, mix-ing, or the like. The so-impregnated material is dried to lower the volatiles content and then heated to adv~nce the resin to the proper degree for the intended use. The etherifiéd resole var-nishes of this invention are useful in the preparation of lamin-ates, such as those made from such impreenated sheet materials~
Such laminates are used in electrical applications as supports or as insulation for conductive elements. The laminates are gener-ally manufactured in a sheet or block form which is then punched or otherwise machined to provide desired configurations for a particular end use.
The etherified resole varnishes of this invention are also useful in the manufacture of cloth laminates, and automotive oil filters. A suitable oil filter media, for example, is pre-pared by impregnating with a varnish of this invention, cellu-losic fiber paper modified with a synthetic fiber (polyester, or the like) and having a thickness of from about 5 to 20 mils.
Sufficient etherified resole varnish resin of this invention is used to obtain an impregnated sheet member having a cured resin content of about 15 to 25 percent, based on the weight of the paper. After such paper is so impregnated, it is heated to ad-vance the resin to a so-called B-stage, and then is corrugated or pleated to form the filter element. ~he filter element is then assembled with the end use filter container and heated to 250F. to 350F., for from 5 to 20 minutes to cure the resin.
When cured, the product has good flexibility and low tendency to crack during use.
~3~3 06-l2-ns.~s In eeneral, a varnish of the present invention can be used to make rein~orced plastics.
The varnishes o~ this invention coraprise:
A. from about 30 to 99 weight percent o~
reactive solids o~ a high ortho ether-i~ied phenol-formaldehyde resole resin, B. from about 0.5 to 30 weight percent of dissolved water, C. the balance up to 100 weight percent o~
any giverl varnish being an organic liquid which:
1. is substantially inert (as respects such resin and water),
2. evaporates below about 200C., at atmospheric pressures, and
3. is a mutual solvent for said resole resin and said water (i~ present), the amount of said organic liquid being present in any given varnish being such as to maintain both said resole resin and said water in dis- ;~
solved form.
The etheriried resole resin used in this invention ~ur~
ther has a relatively low molecular weight and has an alcohQl solubility such that a 60 weight percent solution thereof can be prepared in alcohol. Such alcohol solution characteristically ~-has a viscosity not; greater than about 2000 centipoises, and pre~erably this viscosity lies in the range ~rom about 100 to 1000 centipoises.
~L3~73 ~6-12-0539-The etherif'ied resole resin of the present invention can be emulsi~ied and used as stable aqueous emulsions for coatings, laminating, bonding, etc. The solicLs contents range ~rom about 20 to 50 percent of` reactive solids by weight o~ emulsion. Con-ventional nonionic emulsi~iers can be used, e.g., hydroxy ethylcellulose, partially hydrolyzed polyvinyl acetates having 15 to 30 percent polyvinyl alcohol content.
The etheri~ied resole resins o~ the present invention can be used as coatings or components of' coatings. A typical f'ormu-lation is shown in Example 7. Such coreactant resins can in-clude f'or example, alkyds, epoxies, polyvinyl f`ormals, polyvinyl butyrals, polyvinyl acetate and polyesters. The etheri~ied re-sole resin as prepared can be classed as a varnish having small amounts of phenol and alcohol, depending on the reactive solids content, having an alcohol content on the order of` 1 to 5 per-cent. The etheri~ied resole resins of` the present invention are f'luid at room temperature and, hence, can be used as high solid varnishes as compared to conventional resoles which have cured solids in the range of' 50-65 percent in solvents and cannot be used as varnishes with high solids because they become too vis-cous and lack thermal stability.
The monohydric alcohols used in etherif'ying the high ortho resoles have been defined above and include alkyl or ali-phatic alcohols and can be primary and secondary alcohols con-taining 1 to 12 carbons and one -OH group, ~or example, methyl, ethyl, propyl, butyl isobutyl, secondary butyl, amyl alcohols, etc. The aralkyl alcohols may be primary and secondary alcohols containing 1 to 12 carbon atoms and one -OH group, e.g., benzyl, phenethyl, e.g., l-phenethyl and 2-phenethyl, etc. Unsaturated .1 ~ . ` , ~L~3~ 73 monohydric alcohols can be used such as allyl and cinnamic alcohol.
The high ortho etherified resole coating compositions comprise a high ortho etherified resole resin and about 1 to 95% by weight of a coreactive resin, said high ortho etheri~ied resole resin being characterized by:
A. having a reacted formaldehyde to phenol mol ratio of 1.10 to 2.0, said formalde-hyde reacting with said phenol, forming methylol group0 taking a final orienta-tion oP about 90% to 100% in the ortho position, B. having said phenol selected ~rom the group consisting of phenol, meta-substi-tuted phenols and mixtures of phenol and .-substituted phenols, ; C. having condensed phenol-aldehyde linkages wherein 25 to 90% of said linkages are ~, : benzyl ether linkages having a ~inal orientation essentially in the ortho position and 10 to 75% are methylene link- ~ ~;
ages taking a ~inal orientation o~ about ~ -70 to 90% in the ortho position and about - 10 to 30% in the para position, .
D. having an average degree of polymerization of less than 4.0, and E. having said methylol groups partially ether-ified with monohydric alcohols, said ether-i~ied resoles being prepared by first reacting -..
~; - 22 -. . ~ ~ . , ; , . . .
said phenol and said formaldehyde in an aqueous reaction rnixture under reflux at about 80C. to 100C., :in the presence of a divalent electropositive metal ion, while maintaining the pH in the range of about 4 to 7, wherein said p~ is controlled by having a sufficient amount of an organic acid present, forming said resole in said reaction mixture, etherifying said resole with a monohydric alcohol at a temperature of 65 to 100C. in said reaction mixture and dehydrating the resultant a~ueous reaction mixture to a water content of less than about 1 wei~ht percent and an alcohol content of less than about 5% by weight providing an etherified high ortho resole resin as a single phase clear liquid varnish.
The coating composition can f`urther contain a solvent for said resole resin and said coreactive resin. Said solvent is selected from the group-consisting of lower alkanols, lower . '';' ketones or aromatic and aliphatic hydrocarbons. These solvents ~ -cPn be those that are disclosed herein as solvents for the ~ -etherified resole resins. The preferred solvents are lower al-kanols (such as ethanol), methanol and propanol) and lower ket-ones (such as acetone or methyl ethyl Ketone). The term "lower"
refers to less than 7 carbon atoms per molecule as used herein.
Aromatic and aliphatic (including cycloaliphatic) hydrocarbons can also be employed as solvents for a given resin, including benzene, toluene, ~tylene, naphthalene, nonene, petroleum ~rac-~ ' _ 23 -~.3'.~3 tions, etc. Preferably, the total water content of a composi~
tion of the invention is below about 1 weight percent, however, witb proper solvent can tolerate from about 0.5 to 30 percent water.
Thoseskilled in the art wil:L appreciate that care should preferably be taken to use an organ:ic liquid system in which high ortho etherified phenolic reso:le resins and the coreactive resins are completely soluble as well as any water present.
Adding, for example, a ketone or an ether-ester solvent like butyl Cellosolve*will generally improve the water tolerance (ability to dissolve water) of a solvent system.
The etherified resole resins are low molecular resins having a degree of polymerization of less than 4, hence, exist as clear li~uid varnishes which are curable to a high solids coatings that can be cured and dried as high solids coatings, i.e., 80 to 98% active ingredients.
The coreactive resins are also low molecular resins that have functional groups which can inter-crosslink with the ether-ified resole resin. These resins are generally oligomeric in -nature, hence, are soluble in the resole varni-sh or in a mutual solvent for both resins. Such low molecular ~eight resins have no gel fraction and are commonly called A-type or green resins having high percentages of active ingredients that will cure to a high solids coating having an excellent balance of physical and chemical properties. Such coreactive resins are of such low molecular weight that they are not film forming as coatings un- ~
til crosslinked by the etherified resole. The coreactive resin ~`
molecular weights are about 10,000 or less preferably 1000 or less, e.g. 200 to 1000 but have about 80 to 98% of active coat-* l~ad~nark. :
- ~ :! - ' :
_ 24 -.. . .. . I
3~3 ing forming components for high solids, thermosettin~ baked coatings. ~he coreactive resins are present in the coating com-position in amounts of 1 to 95% by weight of the coatine compo-sition preferably in amounts of about 30 to 70% by r,reight in high solids coating or about 15 to 35% by weight in relative low solids coatings having 40 to 60~ solvent.
~ he coreactive functional groups on the coreactive resin can be selected from the group consistlng of hydroxyl, carboxyl, acetal, amide, keto, methylol, isocynate and alkoxymethyl groups or mixtures thereof as contained in commercial, alkyd, epoxy, polyvinyl formals, polyvinyl butryals, polyvinyl acetate, poly-vinyl alcohol, polyesters, polyamides, polyurethanes and poly-ether resins. Polyacrylates can be used based on polymers or copolymers having a vinyl monomer containing a hydroxyl group, e.g. hydroxy alkyl esters of B-ethylenically unsaturated monocarboxylic acid, methacrylic acid, ethacrylic acid, e.g., 2-hydroxy ethyl acrylate.
The compositions can be cured thermally or with the aid of an acid catalyst, e.g. sulfonic acids such as paratoluene sulfonic, benzene sulfonic, etc. phosphoric, oxalic, succinic;
lactic-, benzoic, acetic acid, etc. which are less corrosive acids. Generally such acids can be used in amounts of about 0.01 to 3% by weight based on the total resin conten-t of the composition. ~he etherified resole component of the present invention generally has a pH of about 4 yo 7, hence, will enable thermal curing, however, additional acid will accelerate curing in the pH range of 4 to 7.
-. .: : , , . ~, ~ :. .
~L~3~"3~3 C-0~-12-053~
Co tln~ Test_ A butylated etherified phenolic resole similar to Example 2 containing 15% combined b~tanol and 82. 5d ASTI~ solids (ASTM Test D-115-55~ uas formulated with a number of coreactive resins. One and tuo mil coatings were cast on Bonderized*steel panels. The panels were baked at 3C)0F. for 30 minutes and tr.e coatings evaluated for gloss, hardness solvent (I~EK-methyle-thyl ketone) and water resistance ~s tested by water emersion at 25C. for 96 hours.
~ormulation:
5 grams ~utylated Resole of Exemple 2 5 grams acrylic polymer having hydroxyl functionality 78% solids in methyl n-amyl ketone Supplied by Rohm and Haas as AT-~OO*
0.2 gr-ams paratoluenesulfonic acid The above formulation at 80% total solids (ASTM) witk 11% free solvent was cast as a 2 mil film and b~ed 30 minutes ~- ;
at 300~. to give a clear glossy coating light y~llow in color.
Pencil hardness W2S 2H, MEK resistznce wzs excellent. The above formulation was reduced to 50% solids (ASTM) with butanol and czst and cured in the same m2nner to yield a 1 mil coating ~ith excellent ~loss , hardness of 6H (?encil hardness) excellent MEK and water resist2nce.
'-;:
", , * Trademark ~6 `~ ' .. ` ':
~ - 26 - ~
~ ~ 3 ~ L.~7 3 Formulation:
6.1 grams Butylated Resole of Example 2 82% s.oli.ds lO.0 grams Aroplaz** 1855-M30 (50% soli.ds ;n Xyloll 3.9 grams n ~utanol 0.2 grams paratoluenesul:Eonic acid The a~ove formulat.ion at 5Q% total solids was cast and baked 30' at 300F., to give a l mi.l coating of good gloss and a 2H pencil hardness. Aroplaz** is an alkyd medium soya oil alkyd supplied by Ashland Chemical Company.
Formulation:
6.1 grams Butylated Resole of Example 2 82% solids 5.0 grams EP-5801*/**, (96-87% solids) :
0.2 grams paratoluenesulfonic acid :
The 91~ soIids solution of the above formulation was : 20 clear and of low viscosi.ty. A 2 mil film was cast and gives a clear glossy coating after baking 30' @ 300F. The film was ,~
relatively soft with a pencil hardness of H. A one mil coating : ~' prepared from a 50% solut:ion-was hard, (pencil hardness 6~I) and '~
had moderate MEK and water resistance.
:~ 25 * EP 5801 (,trademark~ i.s a low viscosity (600 cps.~ oli.gomeric polyester at 96-98% solids supplied by DuPont. This material is hydroxyl terminated and as in the present invention provides ' soft, high solids coatings.
**,Trademarks ~ .
~ - 27 -EX~PLÆ _ Formulation:
5.0 grams Butylated Resole of Example 2 5.0 grams EP-5803* (90~ solIds~
The above formulation at 86% solids gave a hard glossy coating when cast as a 2 mil film then baked 30' @ 300F.
Solvent Resistance was excellent having a hardness of 3H. A
one mil film cast from a 50~ solution in butanol and baked 30' @ 3Q0F. gave a coating ~ith pencil hardness 6H, excellent solvent and water resistance.
* EP 5803 (trademark) is a medium viscosity (9000 cps.) oligomeric, hydroxyl terminated polyester supplied by DuPont. As used in the present invention it provides hard coatings. This material can be used in conjunction with EP-5801 (trademark~ to provide cured high solids coatings of any desired hardness.
~ - 28 -. ,.~. .... .. . . .. .... ... . .. .. . ... ... ... . .
solved form.
The etheriried resole resin used in this invention ~ur~
ther has a relatively low molecular weight and has an alcohQl solubility such that a 60 weight percent solution thereof can be prepared in alcohol. Such alcohol solution characteristically ~-has a viscosity not; greater than about 2000 centipoises, and pre~erably this viscosity lies in the range ~rom about 100 to 1000 centipoises.
~L3~73 ~6-12-0539-The etherif'ied resole resin of the present invention can be emulsi~ied and used as stable aqueous emulsions for coatings, laminating, bonding, etc. The solicLs contents range ~rom about 20 to 50 percent of` reactive solids by weight o~ emulsion. Con-ventional nonionic emulsi~iers can be used, e.g., hydroxy ethylcellulose, partially hydrolyzed polyvinyl acetates having 15 to 30 percent polyvinyl alcohol content.
The etheri~ied resole resins o~ the present invention can be used as coatings or components of' coatings. A typical f'ormu-lation is shown in Example 7. Such coreactant resins can in-clude f'or example, alkyds, epoxies, polyvinyl f`ormals, polyvinyl butyrals, polyvinyl acetate and polyesters. The etheri~ied re-sole resin as prepared can be classed as a varnish having small amounts of phenol and alcohol, depending on the reactive solids content, having an alcohol content on the order of` 1 to 5 per-cent. The etheri~ied resole resins of` the present invention are f'luid at room temperature and, hence, can be used as high solid varnishes as compared to conventional resoles which have cured solids in the range of' 50-65 percent in solvents and cannot be used as varnishes with high solids because they become too vis-cous and lack thermal stability.
The monohydric alcohols used in etherif'ying the high ortho resoles have been defined above and include alkyl or ali-phatic alcohols and can be primary and secondary alcohols con-taining 1 to 12 carbons and one -OH group, ~or example, methyl, ethyl, propyl, butyl isobutyl, secondary butyl, amyl alcohols, etc. The aralkyl alcohols may be primary and secondary alcohols containing 1 to 12 carbon atoms and one -OH group, e.g., benzyl, phenethyl, e.g., l-phenethyl and 2-phenethyl, etc. Unsaturated .1 ~ . ` , ~L~3~ 73 monohydric alcohols can be used such as allyl and cinnamic alcohol.
The high ortho etherified resole coating compositions comprise a high ortho etherified resole resin and about 1 to 95% by weight of a coreactive resin, said high ortho etheri~ied resole resin being characterized by:
A. having a reacted formaldehyde to phenol mol ratio of 1.10 to 2.0, said formalde-hyde reacting with said phenol, forming methylol group0 taking a final orienta-tion oP about 90% to 100% in the ortho position, B. having said phenol selected ~rom the group consisting of phenol, meta-substi-tuted phenols and mixtures of phenol and .-substituted phenols, ; C. having condensed phenol-aldehyde linkages wherein 25 to 90% of said linkages are ~, : benzyl ether linkages having a ~inal orientation essentially in the ortho position and 10 to 75% are methylene link- ~ ~;
ages taking a ~inal orientation o~ about ~ -70 to 90% in the ortho position and about - 10 to 30% in the para position, .
D. having an average degree of polymerization of less than 4.0, and E. having said methylol groups partially ether-ified with monohydric alcohols, said ether-i~ied resoles being prepared by first reacting -..
~; - 22 -. . ~ ~ . , ; , . . .
said phenol and said formaldehyde in an aqueous reaction rnixture under reflux at about 80C. to 100C., :in the presence of a divalent electropositive metal ion, while maintaining the pH in the range of about 4 to 7, wherein said p~ is controlled by having a sufficient amount of an organic acid present, forming said resole in said reaction mixture, etherifying said resole with a monohydric alcohol at a temperature of 65 to 100C. in said reaction mixture and dehydrating the resultant a~ueous reaction mixture to a water content of less than about 1 wei~ht percent and an alcohol content of less than about 5% by weight providing an etherified high ortho resole resin as a single phase clear liquid varnish.
The coating composition can f`urther contain a solvent for said resole resin and said coreactive resin. Said solvent is selected from the group-consisting of lower alkanols, lower . '';' ketones or aromatic and aliphatic hydrocarbons. These solvents ~ -cPn be those that are disclosed herein as solvents for the ~ -etherified resole resins. The preferred solvents are lower al-kanols (such as ethanol), methanol and propanol) and lower ket-ones (such as acetone or methyl ethyl Ketone). The term "lower"
refers to less than 7 carbon atoms per molecule as used herein.
Aromatic and aliphatic (including cycloaliphatic) hydrocarbons can also be employed as solvents for a given resin, including benzene, toluene, ~tylene, naphthalene, nonene, petroleum ~rac-~ ' _ 23 -~.3'.~3 tions, etc. Preferably, the total water content of a composi~
tion of the invention is below about 1 weight percent, however, witb proper solvent can tolerate from about 0.5 to 30 percent water.
Thoseskilled in the art wil:L appreciate that care should preferably be taken to use an organ:ic liquid system in which high ortho etherified phenolic reso:le resins and the coreactive resins are completely soluble as well as any water present.
Adding, for example, a ketone or an ether-ester solvent like butyl Cellosolve*will generally improve the water tolerance (ability to dissolve water) of a solvent system.
The etherified resole resins are low molecular resins having a degree of polymerization of less than 4, hence, exist as clear li~uid varnishes which are curable to a high solids coatings that can be cured and dried as high solids coatings, i.e., 80 to 98% active ingredients.
The coreactive resins are also low molecular resins that have functional groups which can inter-crosslink with the ether-ified resole resin. These resins are generally oligomeric in -nature, hence, are soluble in the resole varni-sh or in a mutual solvent for both resins. Such low molecular ~eight resins have no gel fraction and are commonly called A-type or green resins having high percentages of active ingredients that will cure to a high solids coating having an excellent balance of physical and chemical properties. Such coreactive resins are of such low molecular weight that they are not film forming as coatings un- ~
til crosslinked by the etherified resole. The coreactive resin ~`
molecular weights are about 10,000 or less preferably 1000 or less, e.g. 200 to 1000 but have about 80 to 98% of active coat-* l~ad~nark. :
- ~ :! - ' :
_ 24 -.. . .. . I
3~3 ing forming components for high solids, thermosettin~ baked coatings. ~he coreactive resins are present in the coating com-position in amounts of 1 to 95% by weight of the coatine compo-sition preferably in amounts of about 30 to 70% by r,reight in high solids coating or about 15 to 35% by weight in relative low solids coatings having 40 to 60~ solvent.
~ he coreactive functional groups on the coreactive resin can be selected from the group consistlng of hydroxyl, carboxyl, acetal, amide, keto, methylol, isocynate and alkoxymethyl groups or mixtures thereof as contained in commercial, alkyd, epoxy, polyvinyl formals, polyvinyl butryals, polyvinyl acetate, poly-vinyl alcohol, polyesters, polyamides, polyurethanes and poly-ether resins. Polyacrylates can be used based on polymers or copolymers having a vinyl monomer containing a hydroxyl group, e.g. hydroxy alkyl esters of B-ethylenically unsaturated monocarboxylic acid, methacrylic acid, ethacrylic acid, e.g., 2-hydroxy ethyl acrylate.
The compositions can be cured thermally or with the aid of an acid catalyst, e.g. sulfonic acids such as paratoluene sulfonic, benzene sulfonic, etc. phosphoric, oxalic, succinic;
lactic-, benzoic, acetic acid, etc. which are less corrosive acids. Generally such acids can be used in amounts of about 0.01 to 3% by weight based on the total resin conten-t of the composition. ~he etherified resole component of the present invention generally has a pH of about 4 yo 7, hence, will enable thermal curing, however, additional acid will accelerate curing in the pH range of 4 to 7.
-. .: : , , . ~, ~ :. .
~L~3~"3~3 C-0~-12-053~
Co tln~ Test_ A butylated etherified phenolic resole similar to Example 2 containing 15% combined b~tanol and 82. 5d ASTI~ solids (ASTM Test D-115-55~ uas formulated with a number of coreactive resins. One and tuo mil coatings were cast on Bonderized*steel panels. The panels were baked at 3C)0F. for 30 minutes and tr.e coatings evaluated for gloss, hardness solvent (I~EK-methyle-thyl ketone) and water resistance ~s tested by water emersion at 25C. for 96 hours.
~ormulation:
5 grams ~utylated Resole of Exemple 2 5 grams acrylic polymer having hydroxyl functionality 78% solids in methyl n-amyl ketone Supplied by Rohm and Haas as AT-~OO*
0.2 gr-ams paratoluenesulfonic acid The above formulation at 80% total solids (ASTM) witk 11% free solvent was cast as a 2 mil film and b~ed 30 minutes ~- ;
at 300~. to give a clear glossy coating light y~llow in color.
Pencil hardness W2S 2H, MEK resistznce wzs excellent. The above formulation was reduced to 50% solids (ASTM) with butanol and czst and cured in the same m2nner to yield a 1 mil coating ~ith excellent ~loss , hardness of 6H (?encil hardness) excellent MEK and water resist2nce.
'-;:
", , * Trademark ~6 `~ ' .. ` ':
~ - 26 - ~
~ ~ 3 ~ L.~7 3 Formulation:
6.1 grams Butylated Resole of Example 2 82% s.oli.ds lO.0 grams Aroplaz** 1855-M30 (50% soli.ds ;n Xyloll 3.9 grams n ~utanol 0.2 grams paratoluenesul:Eonic acid The a~ove formulat.ion at 5Q% total solids was cast and baked 30' at 300F., to give a l mi.l coating of good gloss and a 2H pencil hardness. Aroplaz** is an alkyd medium soya oil alkyd supplied by Ashland Chemical Company.
Formulation:
6.1 grams Butylated Resole of Example 2 82% solids 5.0 grams EP-5801*/**, (96-87% solids) :
0.2 grams paratoluenesulfonic acid :
The 91~ soIids solution of the above formulation was : 20 clear and of low viscosi.ty. A 2 mil film was cast and gives a clear glossy coating after baking 30' @ 300F. The film was ,~
relatively soft with a pencil hardness of H. A one mil coating : ~' prepared from a 50% solut:ion-was hard, (pencil hardness 6~I) and '~
had moderate MEK and water resistance.
:~ 25 * EP 5801 (,trademark~ i.s a low viscosity (600 cps.~ oli.gomeric polyester at 96-98% solids supplied by DuPont. This material is hydroxyl terminated and as in the present invention provides ' soft, high solids coatings.
**,Trademarks ~ .
~ - 27 -EX~PLÆ _ Formulation:
5.0 grams Butylated Resole of Example 2 5.0 grams EP-5803* (90~ solIds~
The above formulation at 86% solids gave a hard glossy coating when cast as a 2 mil film then baked 30' @ 300F.
Solvent Resistance was excellent having a hardness of 3H. A
one mil film cast from a 50~ solution in butanol and baked 30' @ 3Q0F. gave a coating ~ith pencil hardness 6H, excellent solvent and water resistance.
* EP 5803 (trademark) is a medium viscosity (9000 cps.) oligomeric, hydroxyl terminated polyester supplied by DuPont. As used in the present invention it provides hard coatings. This material can be used in conjunction with EP-5801 (trademark~ to provide cured high solids coatings of any desired hardness.
~ - 28 -. ,.~. .... .. . . .. .... ... . .. .. . ... ... ... . .
Claims (15)
1. A high ortho etherified resole resin coating compo-sition comprising a high ortho etherified resole resin and about 1 to 95% by weight of a coreactive resin, said high ortho ether-ified resole resin being characterized by:
A. having a reacted formaldehyde to phenol mol ratio of 1.10 to 2.0, said formalde-hyde reacting with said phenol, forming methylol groups taking a final orienta-tion of about 90% to 100% in the ortho position, B. having said phenol selected from the group consisting of phenol, meta-substi-tuted phenols and mixtures of phenol and substituted phenols, C. having condensed phenol-aldehyde linkages wherein 25 to 90% of said linkages are benzyl ether linkages having a final orientation essentially in the ortho position and 10 to 75% are methylene linkages taking a final orientation of about 70 to 90% in the ortho position and about 10 to 30% in the para position, D. having an average degree of polymerization of less than 4.0, and E. having said methylol groups partially etherified with monohydric alcohols, said etherified resoles being prepared by first reacting said phenol and said formalde-hyde in an aqueous reaction mixture under reflux at about 80°C. to 100°C. in the presence of a divalent electropositive metal ion, while maintaining the pH in the range of about 4 to 7, wherein said pH is controlled by having a sufficient amount of an organic acid present, forming said resole in said reaction mixture, etherifying said resole with a monohydric alcohol at a temperature of 65 to 100°C., in said reaction mixture and dehydrating the resultant aqueous reaction mixture to a water content of less than about 1 weight percent and an alcohol content of less than about 5% by weight providing an ether-ified high ortho resole resin as a single phase clear liquid varnish.
A. having a reacted formaldehyde to phenol mol ratio of 1.10 to 2.0, said formalde-hyde reacting with said phenol, forming methylol groups taking a final orienta-tion of about 90% to 100% in the ortho position, B. having said phenol selected from the group consisting of phenol, meta-substi-tuted phenols and mixtures of phenol and substituted phenols, C. having condensed phenol-aldehyde linkages wherein 25 to 90% of said linkages are benzyl ether linkages having a final orientation essentially in the ortho position and 10 to 75% are methylene linkages taking a final orientation of about 70 to 90% in the ortho position and about 10 to 30% in the para position, D. having an average degree of polymerization of less than 4.0, and E. having said methylol groups partially etherified with monohydric alcohols, said etherified resoles being prepared by first reacting said phenol and said formalde-hyde in an aqueous reaction mixture under reflux at about 80°C. to 100°C. in the presence of a divalent electropositive metal ion, while maintaining the pH in the range of about 4 to 7, wherein said pH is controlled by having a sufficient amount of an organic acid present, forming said resole in said reaction mixture, etherifying said resole with a monohydric alcohol at a temperature of 65 to 100°C., in said reaction mixture and dehydrating the resultant aqueous reaction mixture to a water content of less than about 1 weight percent and an alcohol content of less than about 5% by weight providing an ether-ified high ortho resole resin as a single phase clear liquid varnish.
2. A coating composition of Claim 1, said composition additionally containing a solvent for said resole and said co-reactive resin.
3. A coating composition of Claim 2 wherein said sol-vent is selected from the group consisting of lower alkanols, lower ketones or aromatic and aliphatic hydrocarbons.
4. A coating composition of Claim 3 wherein said sol-vent is a solvent selected from the group consisting of ethanol, methanol, propanol, acetone, methyl ethyl ketone, benzene, tolu-ene, xylene, naphthalene, nonene and petroleum fractions.
5. A composition of Claim 1 wherein said coreactive resin contains coreactive functional groups selected from the group consisting of hydroxyl, carboxyl, amide, keto, methylol, isocyanate, alkoxymethyl, acetal or mixtures thereof.
6. A composition of Claim 1 wherein said coreactive resin is selected from the group consisting of alkyds, epoxy, polyvinyl formal, polyvinyl butyral, polyester, polyvinyl ace-tate, polyvinyl alcohol, polyamide, polyurethane, polyether, polyacrylate and mixtures thereof.
7. A composition of Claim 1 wherein said coreactive resin is a low molecular weight resin having a molecular weight of less than about 10,000 and about 80 to 98% of coating form-ing oligomeric components.
8. A coating composition of Claim 1 having present a catalyst to cure said composition.
9. A coating composition of Claim 8 wherein said catalyst is an acid selected from the group consisting of sulfonic, phosphoric, oxalic, acetic, adipic, succinic, lactic, benzoic or mixtures thereof.
10. A coating composition of Claim 1 wherein said meta substituted phenol is a phenol having at least one attached radical selected from the group consisting of alkyl, aryl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, carbo-cyclic, halogen and mixtures thereof.
11. A coating composition of Claim 1 wherein said sub-stituted phenol is a phenol substituted with a material se-lected from the group consisting of indenes, vinylidene aro-matics, cyclopentadienes, dicyclopentadienes, nonenes, octenes, terpenes and mixtures thereof.
12. A composition of Claim 1 wherein said divalent electropositive metal ion is provided by a compound selected from the group consisting of oxides, hydroxides and organic acid salts of such metal ions, and wherein said resole resins are prepared in the presence of said compounds wherein the amount of said compound is within the range of about 0.1 to 10.0 weight percent based on the weight of said phenols.
13. A composition of Claim 1 wherein said divalent electropositive metal ion is selected from the group consisting of zinc (Zn++), cobalt (Co++), magnesium (Mg++), manganese (Mn++) and calcium (Ca++) or mixtures thereof.
14. A composition of Claim 1 wherein the monohydric alcohol is selected from the group consisting of alkyl and aralkyl.
15. A composition of Claim 1 wherein said alcohol is incorporated in amounts of about 0.05 to 0.50 methylol ether groups per phenolic group.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US920,597 | 1978-06-29 | ||
| US05/920,597 US4157324A (en) | 1977-01-31 | 1978-06-29 | High ortho etherified resole resins admixed with coreactive resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134973A true CA1134973A (en) | 1982-11-02 |
Family
ID=25444031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000330970A Expired CA1134973A (en) | 1978-06-29 | 1979-06-28 | High ortho etherified resole resins |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU527966B2 (en) |
| CA (1) | CA1134973A (en) |
| GB (1) | GB2025998B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2538757B1 (en) * | 1982-12-30 | 1986-05-16 | Charbonnages Ste Chimique | LAMINATE MATERIALS WITH IMPROVED FINISH LAYER |
| DE3412095A1 (en) * | 1984-03-31 | 1985-10-17 | Hoechst Ag, 6230 Frankfurt | MIXTURE FOR THE PRODUCTION OF ACID-RESISTANT SEALS AND IMPREGNATIONS, METHOD FOR THE PRODUCTION AND THEIR USE |
| WO2016069572A1 (en) * | 2014-10-27 | 2016-05-06 | Eastman Chemical Company | Resole phenolic resins curable with functional polyesters |
| US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
| US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
| US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
| US20160340471A1 (en) | 2015-05-19 | 2016-11-24 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
| US20170088665A1 (en) | 2015-09-25 | 2017-03-30 | Eastman Chemical Company | POLYMERS CONTAINING CYCLOBUTANEDIOL AND 2,2 BIS(HYDROXYMETHYL) AlKYLCARBOXYLIC ACID |
| US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
| US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
-
1979
- 1979-06-28 GB GB7922601A patent/GB2025998B/en not_active Expired
- 1979-06-28 AU AU48497/79A patent/AU527966B2/en not_active Ceased
- 1979-06-28 CA CA000330970A patent/CA1134973A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU527966B2 (en) | 1983-03-31 |
| GB2025998B (en) | 1982-10-20 |
| AU4849779A (en) | 1980-01-03 |
| GB2025998A (en) | 1980-01-30 |
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