DE2758493A1 - Polyether-epoxy! resin reaction prods. with phosphoric acid - for prepn. of water-dilutable coating compsns. - Google Patents

Abstract

Prepn. of acid resins capable of dilution with water after neutralising with a base, is effected by reaction of H3PO4 with a polyether-epoxy resin (EI) consisting of a diglycidyl ether of formula (a) or a mono-glycidyl ether of formula (q) (where Q is n is 0-40, r is 0, 1 or 2 R1 is H, methyl or ethyl R2 is Br, Cl, 1-4C alkyl or alkenyl, R3 is 1-4C alkylene or alkenylene, C(CF3)2, CO, SO2, S, O or a direct bond, R4 is as R2, R20 is H or 1-12c alkyl). Sufficient H3PO4 (or substance forming this by hydrolysis) is used to give >=0.3 and OH gps. per oxirane gp. in the product. Used for formation of hydrophobic films and coatings on various substrates by painting, spraying, dipping, powder coating, etc. followed by removal of water and base and hardening of the residue, e.g. by storing.

Description

This invention relates to a composition or

Binding of acids that can be diluted with water and neutralized with base Resins that can be converted into hydrophobic hardened resins of high effectiveness, a process for the production of such a composition or compound and the use of these products.

The composition of the invention is a mixture of one with Base-neutralized reaction product of H3PO4 with a polyether epoxide Formula (a) or (q) defined in claim 1 and optionally different ones other types of mono- or polyfunctional epoxies.

In the preferred method of the invention, a polyether epoxy is used E 1 and optionally another epoxide E 2 with a source of orthophosphoric acid reacted and the product obtained with a base, preferably a volatile base, neutralized. The invention also includes a method in which separately produced Epoxy E 1 and E 2 reaction products can be combined with phosphoric acid0 If the Base is a volatile base, like ammonia or a volatile amine, can do that with Water diluted neutralized resin into a hardened one that is insensitive to water Resin by evaporating the water, heating to split the ammonium salt groups and stripping off the ammonia or amine and converting hardness. Here you can common hardeners that are able to work with acidic and / or alcoholic To react hydroxyl groups are added to the uncured resin. Under "Volatile" is understood here to mean that a substance is caused by heating at ambient pressure in can be removed to such an extent that it does not contain any impermissible harmful effects on the curing speed or the properties of the hardened resin.

The ammonia or amine that is present during or after the evaporation of the Water from the uncured resin can be driven off in a conventional manner recovered as such or as a non-volatile salt with an acid.

A preferred process for preparing the water-dilutable compositions or compounds according to the invention provides that (i) orthophosphoric acid is reacted with (7) a polyether-epoxy resin E1 consisting essentially of a diglycidyl ether of the formula or a monoglycidyl ether of the formula where Q is independent for each occurrence is, n is an integer from 0 to 40, r is independently for each occurrence O, 1 or 2, R1 is H, methyl or ethyl, R5 is-Br, -Cl or a C1-C4 alkyl or alkenyl group, R3 a C1-C4 alkylene or alkenylene group '-C (CF3) 2-, -CO-, -S02-, -S-, -0- or a valence bond, R -Br, -C1 or a C1-C4 alkyl- or alkenyl group and R50 is H or an alkyl group of 1-12 carbon atoms, and this reaction is carried out by contacting E1 with a source of orthophosphoric acid using 0-25 molar parts of water per mole of H 3P04 from the source for this material until the proportion of oxirane groups in E1 is at least sufficiently converted to render the resulting product dilutable with water when brought into contact with a base, the amount of which is included in this source as such is ortho -Phosphoric acid or orthophosphoric acid obtainable therefrom by hydrolysis is such that about 0, 3 or more acidic hydroxyl groups per oxirane group are obtained and (ii) that the reaction product obtained is brought into contact with at least so much of a base that it can be diluted with water.

An advantageous embodiment of the invention is characterized in that that in addition another vicinal epoxide ES, other than one of the formula (a) or (q) which has an epoxy equivalent weight of 90-2000 with the source of orthophosphoric acid is reacted and is brought into contact with a base in the same way, like the polyether epoxy resin El, The invention also includes one A resin mixture, which is produced by the reaction of the phosphoric acid and the epoxy El and optionally the epoxy E2 is formed, this composition being dilutable with water is when it is neutralized with a base.

The invention also includes the product that can be diluted with water, the obtained by contacting the resinous product with a base.

A preferred embodiment of the invention are aqueous dispersions of the neutralized product of the ZL composition according to the invention.

The neutralized epoxy / acid reaction product of the present invention can be more precisely defined as a water-dilutable phosphate resinous composition or compound containing the following components: (a) Resin molecules that are derived from conversion to 1,2-glycol or beta-hydroxyphosphoric monoester groups of Oxirane groups of an El epoxide of the formulas (a) and (q) already defined, where the mean epoxy equivalent weight of the epoxy molecules that make up the resin molecules derive is 172 to 5,500, (b) 0 to 85 parts by weight of ortho-phosphoric acid per 100 parts by weight of the resin molecules, (c) one or more bases, in one such Amount, and at least the P-OH shares in the molecules that can be derived from E1 and E2 to convert into the salt state, thereby making the molecules dispersible in water to make, and if necessary (d) other molecules that are derived from conversion to 1,2-glycol or beta-hydroxyphosphoric monoester groups of Oxirane groups of the epoxide E2, a different vicinal epoxide than the epoxides of the Formulas (a) and (q), where the epoxide E2 has an epoxide equivalent weight of 90 to 2000 has, and the molar ratio of the molecules derivable from El to the itself of molecules derivable from E2 is 0.1 to 100, the ratio of Glycol to monoester groups on each type of these molecules ranging from 0 to 18 lies.

In a preferred composition of this type, those molecules are which are not derived from epoxides of formula (a) or (q), derivable from E2 epoxides of the given definition, those with methylol or lower alkoxymethyl groups contain substituted benzene rings (i.e., R-O-CH2 groups, where R is an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms is).

In another preferred composition according to the invention are which are not derived from an El-derived molecule from an E2 epoxide, which consists of Epoxinovolaanolekfflen.

The already mentioned basic component of the compositions according to of the invention is preferably volatile in nature.

"Water-dilutable" is understood here to mean that a product is a after it forms a substantially homogeneous solution or dispersion Amount of water has been diluted, the resulting dispersed product being does not settle or otherwise deleteriously at such a rate changes that the dispersion is unusable for the use of coatings.

The mixtures which form the compositions according to the invention, can be made in two ways.

The E 1 and E 2 epoxides can be shared with the source of the phosphoric acid are reacted or the reaction products obtained by separate reaction of the epoxides can before or after neutralization with the same or different bases be mixed.

The last mentioned method of making the compositions is another embodiment of the invention. The invention thus encompasses also combining separately prepared EI / H3P04 and E2 / H3P04 reaction products and a sufficient amount of a base to make the combination dispersible in water close.

The following embodiments of the invention are particularly preferred for the use of the compositions according to the invention as coating materials: 1. The product of the above process in which El is a diglycidyl ether of the formula (a) which is derived from an adductive polymerization of bisphenol-A with a diglycidyl ether of bisphenol-A, i.e. where R is CH3-C-CH3 and r is O.

2. A product of embodiment 1., which by neutralization with Ammonia or an amine has been made dilutable with water.

3. The neutralized product of embodiment 2. after dilution with water to a resin content of 50% by weight or less.

4. A thermoset resin coating made from the water-diluted product of embodiment 3 ..

5. The product of the process already generally defined, in which El has an epoxy equivalent weight of less than 3200.

6. The embodiment of the method generally defined above, in which the general ratio of acidic hydroxyl groups to oxirane groups in the Range from 0.4 to 1.0.

7. The embodiment of the above method in which the amount of the H3PO4 fed to the reaction is 1 part by weight or less per 100 parts by weight E1 is.

8. The embodiment of the method generally defined above, in which the phosphoric acid to the reaction mixture as 70 to 90 percent by weight aqueous H3PO4 is added.

The fourth embodiment relating to the cured resin can be found in FIG obtained a zçässiges composition according to the invention, in which the with water diluted, neutralized epoxy / M3 PO4 reaction product the only resinous Component is or from similar compositions in which other water-dispersible Resins, reactive diluents and / or hardening agents are present.

In either case, hardening can be accelerated by known means such as chemicals, ultrasound, heat, high-energy waves or particle radiation.

The E1-type epoxides of formula (a) can also be characterized as resins. A few of the lower epoxides, such as the diglycidyl ether of bisphenol-A, are available as pure, crystalline solids. Most epoxies of the "DGBEA" type are generally not available as pure compounds as a result of the methods used in practice for production. For example, the commercial product "DER" - 331 is a less expensive form of the diglycidyl ether of bisphenl-A, and this product is obtained by a two-stage reaction of epichlorohydrin with bisphenl-A. The product of this reaction contains not only the desired dieter, but also in small amounts by-products such as The presence of impurities of this type and in the amounts occurring generally has no adverse effect on the properties of the products according to the invention.

Any epoxide of formula (a) that has an epoxide equivalent weight of less than 5 500 can with a phenol of the type already defined in in such an amount that the epoxy is converted into a resin with an epoxy equivalent weight of not higher than 5 500 is converted and a corresponding proportion of product molecules which correspond to the formula (p).

The reaction is usually carried out by making the El epoxy or epoxides in the medium, if one is used, is dissolved and the source of the acid material and possibly as much water as this Material is required or to obtain the desired product composition, combines and the mixture at a predetermined temperature (and optionally Pressure) as long as heated under reflux until the desired oxirane conversion has taken place. The reaction mixture is cooled with the selected base neutralized, diluted with water (often in the same amount as the weight of the existing solids) and freed from volatile components.

As a source for the phosphoric acid can be used for the El / acid reaction become: 100% ortho * phosphoric acid, the hemihydrate 2 H3P04 / H20 and aqueous solutions, containing at least 18% by weight of H3P04 (one mole of H3PO4 per 25 moles of water), different condensed phosphoric acids (polymers or partial anhydrides), for example pyrophosphoric acid and triphosphoric acid.

If the acid material is in condensed form, it should be sufficient Water is available in a stage prior to the hardening of the resinous end product must be made to ensure that there is no significant proportion of P-O-P bonds remains in the cured resin.

Usually, aqueous phosphoric acid solutions, especially 70 up to 90% preferred. When a phosphoric acid in condensed form as a source for which phosphoric acid is used depends on the stage at which the P-O-P hydrolysis takes place is carried out, depending on whether a reduction in the water content during the Response is desired.

If a source of condensed phosphoric acid is completely considered H3P04 should be used in the reaction, sufficient time should be allowed to achieve complete P-O-P hydrolysis.

The spoxide / acid reaction can with the starting materials as such be carried out, but an inert diluent is preferred as the reaction medium used. Examples of suitable solvents are in decreasing order Prefer the following solvents: 1. Mixtures of acetone with methylene chloride containing 25 percent by weight or less of methylene chloride, 2. ketones, such as acetone and methyl ethyl ketone, 3. cyclic ethers, such as dioxane, 4. linear Ethers, such as glycol ethers, 5. esters, such as lower alkyl acetates, 6. mixtures of lower alkyl acetates Alcohols and chlorinated hydrocarbons, such as methylene chloride, 7. low Alcohols and 8. chlorinated hydrocarbons such as methylene chloride.

The parameters that primarily affect the dilutability with water des Determine neutralized E 1 / acid reaction product are the epoxide equivalent weight of the E 1 epoxy, the P-O-H to oxirane ratio, the water to P-O-H / H3PO4 / ratio, the solubility of water in the reaction medium, the temperature and the contact time.

In order to be dilutable with water after neutralization, it has to be Reaction product contain a minimum content of phosphorus monoester groups and this requires an upper limit of 5500 for the epoxy equivalent weight of the E 1 Epoxy and a lower limit of 0.3 for the ratio of P-OH groups (the provided by the acid source) to oxirane groups. It is also for the dilutability with water is essential that the ratio of glycol groups (from the addition of water to oxirane groups or the hydrolysis of phosphodiester groups) to phosphorus monoester groups is not higher than 18 to 1.

This in turn shows that the molar ratio of water to M3PO4 in the starting materials is not higher than 25 to 1.

The extent to which the water enters the reaction does not depend only on the ratio of water to acid, but also on the activity of the water from, in turn, both on the nature of the solvent for the reaction as also depends on the temperature. As a general rule, the activity of the Water lower in poor solvents for water and at low temperatures is.

The addition of P-OH to oxirane groups appears to proceed fairly rapidly in less polar solvents and in such solvents it is possible to form P'-dihydroxyphosphodiester groups to a substantial extent, at least in the first stages of implementation. If water is absent or has low activity in the solvent, the oxiranes can be converted predominantly to such diester groups and the E1 molecules can be linked by the diester groups to such an extent that gelation occurs.

The diester groups easily become "glycol" and monoester groups hydrolyzes and as a result are not an essential component of the end product that is formed from the reaction of mixtures in which the activity of Water is essential. In addition, the more polar solvents show through Acid catalyzed addition of water to the oxirane groups very effectively with the Compete for P-OH attachment.

Both the addition reaction and the hydrolysis reaction take place naturally faster at higher temperatures, so that shorter contact times are required, a desired degree of oxirane conversion or a certain state of equilibrium to reach.

If the activity of the existing water is much higher at a As the temperature is higher, the proportion of "glycol" groups in the product can be adjusted accordingly increase.

As a result the direct conversion of the oxirane to glycol groups is generally free H3PO4 is present in the reaction product even if the P-OH to oxirane ratio in the starting materials was less than 1. The presence of free acid (as a basic salt) in the neutralized product usually has no significant detrimental effect on dispersibility of the product in water. As a result, it can be a water-dispersible product in some cases can be obtained even if the quantity of the source for the acid, used in the reaction was as high as 85 parts by weight of H3P04 100 parts by weight derived from El Marz molecules in the product. However, such high acid contents lead to poor hydrolytic stability of the hardened coatings. Of course, the high acid levels can get through Extraction can be reduced to a tolerable level, this extraction being preferred takes place before the neutralization of the product. It has been found that the Dilutability with water of the El / acid product due to the nature of the solvent is influenced that is present during the neutralization and that from the with Water diluted reaction mixture is driven off. That for the formation of a Product of the desired composition is not the most suitable solvent absolutely the best medium for the preparation of the aqueous dispersion. The reaction mixture but can before (or even after) the neutralization and dilution with water of the existing volatile solvent are freed and instead of this driven off A more suitable solvent can be added to the solvent. For the last mentioned purpose, methyl ethyl ketone has proven to be particularly suitable. Alternatively Acetone has been used as a solvent in a mixture with smaller amounts of methylene chloride shown to be very useful for both the reaction and the dispersion stage.

Preferred ratios of the starting materials and conditions for the E 1 / acid reaction are as follows: Acid source = aqueous 70 to 90% H3P04 Amount of acid source such that 0.8 to 1.2 P-OH are present per oxirane; Reaction temperature 110 to 130 0C and contact time 3 to 6 hours. To have to Of course elevated pressures are used which are at least the autogenous pressure of the reaction mixture correspond when temperatures are above the boiling point of the solvent Atmospheric pressure can be used. For example, temperatures up to like iso0c can be used.

These reaction conditions can also generally be used for the Implementation of E 2 epoxides with sources of phosphoric acid for the production of with Use water-dilutable neutralized products. They can also be used for the joint reactions of E 1 and E 2 epoxides with phosphoric acid sources, such as H3P04. If the epoxies E 1 or E 2 tend to polymerize or substituted with reactive groups such as methylol or lower alkoxymethyl groups are, it is advantageous to work at lower reaction temperatures or to moderate the government in another way.

It is of interest that most of the E 2 epoxies required for a May be used, have significantly lower epoxy equivalent weights, as the most important E 1 epoxides in the context of this invention, for which the mean value of n in the formulas (a) and (q) is 9 or more. So it won't always be be necessary within the aforementioned limits of the ratios for the E 1 / acid reaction and products stay when an E 2 epoxy is used alone will. In general, however, the best dispersions of E 2 products or obtained from mixed E 1 and E 2 products within these limits.

The base component of the neutralized mixed E 1 and E 2 acid reaction products consists essentially of one or more volatile bases. These bases are volatile components and dissociate from the acid (free acid or phosphoric ester P-OH) when heating the salt-like product to a temperature that is equal to or lower than the required curing temperature, but higher than the maximum Is the boiler temperature when the volatile components are driven off.

Ammonia and amines and examples of such volatile bases. the preferred bases are amines, in particular those of the formula bR3 where R is H, methyl or ethyl is in each case independent of one another, with the exception that no more as an R is H. The most preferred base is triethylamine.

In order to explain the invention more completely, further Details of preferred E1 and E2 epoxies are given below.

Preferred epoxies E 1 are those in which Q every time is, i.e. E 1 is preferably a nominal difunctional epoxide of the formula or a nominal monofunctional monoepoxide, which is derived therefrom by 1: 1 addition with a phenol of the formula forms, where R2, r and R20 have the meaning already defined.

E 1 are preferred epoxides of the formulas below in which Q essentially each time either is.

Most preferred are E 1 epoxides in which Q is essentially every occurrence is.

Epoxies of this type are commercially available and are currently preferred Epoxy type of this type is the product "DER # - 667" or equivalent DGEBA resins, for which n in the formula (a) is within the range of 10 to 13, respectively Epoxy equivalent weights from 1500 to 2000.

The most commonly used resins of this type are "DGEBA" diglycidyl ether / bisphenol A resins, i.e. polyether epoxides which are derived from the polymeric addition of bisphenol A with the diglycidyl ether of bisphenol A. The diglycidyl ether can be prepared by reacting 2 molecules of epichlorohydrin with one molecule of bisphenol A in the presence of a base, such as sodium hydroxide. Classically, however, the last-mentioned reaction is carried out in such a way that the diethermolecules formed react in situ with bisphenol molecules to give DGEBA resins.

In the latter case, the reaction product tends to be a mixture consisting predominantly of polymeric compounds of different molecular weights, the individual products having different values of n, so that these compounds can ideally be represented by the following formula: By incorporating a certain proportion of monofunctional epoxy compounds, such mixtures show an average epoxy functionality of slightly less than 2.

The epoxy equivalent weights in the later examples of the preceding Epoxy type are generally slightly higher than the theoretical values of the nominal Connections for the reasons given.

There is no limitation in practicing the invention to the use of one type of E-1 epoxy or to the use of such Epoxides where all R1, R2, R3 or R20 groups are the same in the molecule. There can be two or more different E 1 epoxides in a single reaction product be combined with phosphoric acid. Similarly, a given E 1 can be epoxy as many different R1 groups (H, -CH3 or -c2M5), R2 or R4 groups (-Br, -C1 or -CH3), R3 groups (C1 - C4 alkyl or alkylene, -S02- or -0-) or R20 Contain groups (H or Cl - salt alkyl), as is synthetically possible in to incorporate a single molecule.

For example, polyether diepoxides can be produced by Using an epichlorohydrin and methylepichlorohydrin instead of either Chlorohydrin alone, using well-known synthetic methods such as them for example, described in Handbook of Epoxy Resins, (ch 2) Lee and Neville; McGraw-Hill (1967). Similarly, mixtures of different bisphenols can be used used in well known procedures to combine a single bisphenol with epichlorohydrin or to react with a diglycidyl ether of the same or a different bisphenol.

At most a few of the commercially available resins of the "DGEBA" type derive from bisphenols other than bisphenol A, the bisphenols with Bromine or chlorine can be substituted. Also used instead of epichlorohydrin hardly any other chlorohydrin used.

Therefore, the commercially available resins of the DGEBA type are those of the preceding general formula for E 1, in which R1 is H, n either 0 or 2 and R2 is Br or C1 and R3 is (CH3) 2C #.

Examples of such commercially available DGEBA resins used in the invention preferred are manufactured and sold by The Dow Chemical Company.

These commercially available resins are detailed in the table below characterizes: Table A Theoretical viscosity value of n cp at 25 ° C accordingly, or designation M = 2x EÄG EÄG (Duran F) C p DERR - 332 0 172-6 4000-5000 - 331 0 186-92 11000-14000 - 5422 0 330-80 (51-61 °) - 337 ~ 0.5 230-50 semi-solid - 660 ~ 2 425-75 (65-74) - 661 2-3 475-575 (70-80) - 662 3-4 575-700 (80-90) - 664 5-6 875-975 (95-105) - 667 10-13 1600-2000 (113-123) - 668 13-23 2000-3500 (120-140) - 669 23-38 3500-5500 (135-155) - 684 ~ 90 <~ 3000 1 epoxy equivalent weight 2 produced using tetrabromo-bisphenol-A 3 molecular weight The epoxy functionality of DGEBA resins is generally lower than the theoretical value of 2 and the actual values of n for the above resins are consequently lower than that theoretical values for the molecular weights corresponding to twice those given Epoxy equivalent weights.

According to Lee and Neville (loc cit), there is a typical DGEBA resin with an epoxy equivalent weight of about 190 (theoretical value of n = O) from about 88% molecules where n = 0, 10% n = 1 and 2% n = 2. It was found in a similar way that a typical higher molecular weight DGEBA, as it is for the production of coatings from solutions and has an epoxy equivalent weight of about 540 (theoretical Value n »2) has the following composition:> 50% n = 3-5; about 15Z n-2; 15% n-l and 20% n = 4.

Examples of bisphenols from which the E 1 epoxides of the general formula (a) can be prepared are: mononuclear dihydric phenols binuclear bisphenols Bisphenol F Bisphenol A Dichlorobisphenol A Tetrabromobisphenol A Additional examples of bisphenols are given in Tables I and II from: The Chemistry of Phenolic Resins; RW Martin, pages 64-79, Wiley &Sons; NY, NY (1956).

El epoxides of the type of formula (q) can be easily prepared by capping corresponding epoxides of formula (a) with 1 or more phenols Produce R2 20, where R², r and R20 have the meaning already defined. This type of capping is well known in epoxy chemistry. It has been found that the wettability of the resin can be varied in such a way that better wetting of a particular type of substrate is achieved.

It is evident to the person skilled in the art that epoxides of the formula E 1 (q) only valid for the disguised products as a medium or general structure are. This means that even if the phenol and the type (a) epoxide are in equimolar Ratios are implemented, some of the product molecules are not blocked and in other molecules both oxirane groups have reacted. The epoxy and the phenol can also be converted in a ratio other than 1: 1 as long as the epoxy equivalent of the product does not rise above 5500.

Suitable E2 epoxides in the present invention are vicinal Epoxides of a constitution other than those of formulas (a) and (q), the epoxide equivalent weights in the range from 90 to 200 and obtained by reaction with orthophosphoric acid and subsequent neutralization with a base in the water-dispersible product can be converted. On the basis of this information, it is easy for a person skilled in the art to whether the epoxies under consideration meet this requirement.

Examples of suitable E 2 epoxides are mono- to penta-functional epoxides of the following type: (b) a methylol- or alkoxymethyl-substituted phenylglycidyl ether of the following formula in which Y is H or C1 - C4 alkyl or alkenyl group, each YO-CH2 group is either in the ortho or para position to the glycidyloxy group, x is 1, 2 or 3, p is 0 or 1 and a is 1 or 2 , R1 is independently H, methyl or ethyl for each occurrence, R5 is a C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl, phenoxy, -Br, C1 group or a Is a group in which YO is 1 or 2, Y and R1 have the meaning already defined, T is a C1-C4 alkylene or alkenylene group, \ C (CF3) 2, -SO2-, -S-, -0 - or a valence bond, R6 is -Br, -C1 or a C1 -C12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl or phenoxy group and t is 0 or 1, with the proviso that (x + a) cannot exceed 4 and (x + y) is 2 to 4; (c) a methylol or alkoxymethyl substituted (2,3-epoxy) propylbenzene of the formula in which b is 1 to 3, d is 0 to 1, R7 is C1-C12 alkyl or is, Y 'is H or a C1 - C4 alkyl or alkenyl group, R1 is H, methyl or ethyl, with the proviso that (b + d) cannot exceed the value 3; (d) Di- and trioxides of acyclic or cyclic, C4-C28 hydrocarbons or esters with 2 or 3 non-aromatic, carbon-carbon double bonds and optionally a -Br, -C1 or -F or a hydroxy substituent; (e) epoxy ethers of the formulas R8-O-R9, where each R8 and R9 is the same or a different monovalent radical which is obtained by removing hydrogen from a C3-C12 aliphatic, alicyclic or phenalkylene oxide; (f) 2,3-epoxypropyl halides, alcohols or esters of the formula in the A Cl-, -Br, -OH or in which R1 is -H, -CM3 or C2H5 and R21 is a C1-C15 hydrocarbon group.

(g) Glycol monoether of the formula and glycol dieters in which R1 is -H, -CH3 or -C2H5, R10 is -H or -CH3, X is -H, -CH3 or -C2H5, g is 1, 2 or 3 and h is an integer from 2 to 10; (h) diglycidyl ethers or esters of the formula wherein R¹² is a divalent hydrocarbon radical of 2 to 20 carbon atoms, R1 is -H, -CH3 or -C2H5, and i and j are independently 0 or 1; (i) Mono- or diglycidyl ethers of the formulas (j) mono-, di- or trigylcidyl ethers of glycerol; (k) trifunctional aromatic epoxides of the formulas in which Z 12 is R C1-C2 alkoxy, C1-C6 alkyl or C2-C6 alkenyl, R 3 is H, C1-C12 alkyl or C2-C12 alkenyl, R C1-C8 is alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl, this group being in the ortho or para position to those Z-CH2 moieties on the benzene ring to which this group is attached, R1 has the meaning already defined and R15 is a C1-C4 alkylene or alkenylene group or -SO2; 2 (1) tetraglycidyl ether of the formula in R16 a C1 to C6, divalent aliphatic hydrocarbon radical, -C (CF3) 2, -S02-, -S-, -O- or a valence bond (m) tri- to pentafunctional epoxy novolaks of the formula in which p is 1 to 3, R17 is independently for each occurrence H or -CH3, R is an alkylene group having 1 to 4 carbon atoms is; (n) methylol-substituted, oligomeric monoepoxides of the formula in which u is 0? 1, 2 or 3, R1 is independently H, methyl or ethyl for each occurrence and R is independently for each occurrence C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, phenalkyl or alkylphenyl; (o) epoxidized triglycerides of unsaturated fatty acids with up to 18 carbon atoms and (p) one to one adducts of substituted phenols with diglycidyl ethers of substituted bisphenols of the formula in which R1, R2, R3 and r have the meaning already defined in formula (a), Y, R5 and p have the meaning already defined in formula (b), v is 1, 2 or 3 and w is independently 0 for each occurrence , Is 1 or 2.

Examples of specific E2 epoxies of types (d) to (m) and (o) are the following compounds: type epoxy (d) butadiene diepoxide, lime dioxide, linalo oil dioxide, 4-vinylcyclohexene dioxide and trivinylbenzene trioxide.

(Compare also Example 13) (e) diglycidyl ether, 4,4'-divinyldiphenyl ether dioxide, Bis (2,3-epoxycyclopentyl) ether and the glycidyl ether of 3,4-epoxy-1-butanol.

(f) glycidol, epibromohydrin, 2-methylepichlorohydrin, glycidyl benzoate and glycidyl methacrylate.

(g) The monoglycidyl ether of ethylene glycol and the bis (2-methylglycidyl) ether of tripropylene glycol.

(h) ethylene glycol diglycidyl ether, 2-butene-1,4-diol, diglycidyl ether and the bis (2-ethylglycidyl) ether of 1,1-dimethylol-3-cyclohexene.

(i) 2-Glycidyloxymethyl-5-hydroxymethyl-tetrahydrofuran and the bisC2-methylglycidyl) ether of 2,6-dioxanediol.

(k) 1,3,5-tris (glycidyloxy) benzene, 2,6-diglycidylphenylglycidyl ether, tris (4-glycidyloxyphenyl) methane, 2,2 ', 4'-tris (2-methylglycidyloxy) diphenyl and (1) 2,2 ', 4,4'-tetrakis (glycidyloxy) diphenylmethane.

(m) (The pentaglycidyl ether of the condensation product of 5 molecules of phenol with 4 molecules of acetone.) (O) Epoxy molecules of this type form the reactive component of epoxidized soybean oil.

Corresponding products are available commercially (for example FLEXOLQ -EPO; Union Carbide Corp.).

This is an epoxidized mixture of triglycerides from C14 to C18 fatty acids. The distribution of saturated and unsaturated fatty acids are in the oil before epoxidation as follows: fatty acid formula wt.% number of CnC myristic C14H2802 0.1 0 Palmitin C16H3202 8.0 0 Stearin C18H3602 4.0 0 Arachin C20H4002 0.6 0 Myristolein C14H2602 0.1 1 Palmitolein C16H3002 0.2 1 Olein C18H3402 28.0 1 Linole C18H3202 54.0 2 linoles C18H3002 5.0 3 The theoretical epoxy equivalent weight for the epoxidation of all double bonds in the oil is 210.

Types (b), (c), (d), (g), (m), (n), (o) and (p) are among the E2 epoxides listed above are preferred.

Within this group, types (b), (c), (n) and (p) are special preferred as they are methylol or low Alkoxymethyl substituents that contain the E1 / E2-H3PO4 product blends that contain them by heat make it hardenable very quickly.

Epoxies of types (d), (g), and (o) provide an improvement in this regard the film formation, the adhesion of the dry film and / or the flexibility of the hardened film. An epoxy of type (m) improves film formation and adhesion of the cured film and solvent resistance, but lowers flexibility of the cured film.

The most preferred E2 epoxides correspond to formula (b), in which Y is H or -CH3, x = z, p = 1 and R5 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms.

Examples of epoxides of formula (b) which can be used in the process of the invention are those methylol-substituted glycidyloxybenzene compounds which can be prepared from the following known methylol-substituted phenols and bisphenols by known methods, for example according to US Pat. No. 3,859 255, columns 5 to 7: Q = Br, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or nonyl; A specific methylol-substituted mononuclear diepoxide of the formula (b) is disclosed in US Pat. No. 3,929,315 and has the following formula Specific binuclear diepoxides of type (b) are the commercially available "APOGEN" R resins, from Schaefer Chemicals, Inc., PO Box 132, Riverton, New Jersey: Mixed glycidyl ethers of mono-, di-, and trimethylol phenol can be prepared by epoxidizing corresponding allyl ethers such as are commercially available as "METHYLON" R - Resin 75108 from General Electric Company. (For the epoxidation process, reference is made to US Pat. No. 2,965,607.) These mixed ethers are representative of mononuclear monoepoxides having 1 to 3 methylol groups as substituents of type (b).

Examples of E2 epoxides of the formula (c) are: These products are obtained by the epoxidation process of Example XII of US Pat. No. 2,965,607 from the corresponding starting materials l-allyl-2,4,6-trimethylolbenzene (US Pat. No. 3,9 06,126) and l-allyl-2-methoxy-3 , 5-dimethylolbenzene (U.S. Patent 2,7 07,715).

Some or all of those present in the epoxypropylbenzene compounds Methylol groups of this type or in the glycidyl ethers which are methylol-substituted from these Phenols can be derived into the corresponding alkoxymethyl groups by well-known ones Process for the production of benzyl ethers can be converted.

Epoxides of formula (r,) can be substituted as oligomers of methylol Phenylglycidyl ethers are considered.

You can do it by simply warming the named ethers to a Produce a temperature of, for example, about 1650C, with the methylol groups with the oxirane groups react at a satisfactory rate. The temperature is maintained until the epoxy equivalent weight of the resin is the desired value of u corresponds to.

The specific oligomer at which in the formula (n) is the mean value of u is about 1.5, R is H and R is t-butyl has an epoxide equivalent weight of about 940 and is made by heating the appropriate monomer for about 2.3 hours received on 165OC.

Some or all of the remaining methylol groups in such oligomers can of course be converted to alkoxymethyl groups by known procedures to obtain an E2 type epoxy.

Examples of epoxides of the formula (p) are: These epoxides can be prepared in a known manner by reacting the corresponding 4-alkyl-2,6-dimethylolphenols and diglycidyl ethers of the bis-A type diphenols in the presence of a catalyst such as ethyl triphenylphosphonium acetate.

One is not limited to one in practicing the invention Compound of the type E2 epoxies or epoxides in which all Y, R R R3, R6, Z and the like groups in the molecule are the same.

There can be two or more E2 epoxies of any or all of the foregoing Formulas (b) to (p) combined in a single reaction product with phosphoric acid will. A given epoxide can contain various types of said substituents contained, as is possible from the synthetic side, in a single one To accommodate molecule of the given formulas.

When the blends of the present invention are produced by the coreaction of a source of phosphoric acid with an El and an E2 epoxy the response can be in two ways. The El and E2 epoxies can mixed and then brought into contact with the acid, or you can first let one and then the other of the two epoxies react.

It might be expected that the second type of process would be the end product Molecules results that contain E1 and E2 residues that have phosphodiester groups are connected.

In general, however, this is only the case when water is essentially is excluded from the mixture and any remaining after the first reaction free acid has been removed before the second epoxy was added. aside from that Such diester groups tend to hydrolyze when the reaction product is mixed with water is brought into contact.

In general it is advantageous to use the acid with the E1 and E2 epoxides to react one after the other.

When this happens, different reaction temperatures can be used for the successive conversion of the two types of epoxies can be used. In the As a rule, the E2 epoxy is more reactive and is therefore best introduced first after the El epoxy has been at least partially converted.

As a source of the phosphoric acid can be used for the implementation become: 100% orthophosphoric acid, the hemihydrate 2 H3PO4 / H20 and aqueous solutions, containing at least 18% by weight of H3PO4 (one mole of H3PO4 per 25 moles of water), various condensed phosphoric acids (polymers or partial anhydrides), for example pyrophosphoric acid and triphosphoric acid.

If the acid material is in condensed form, it should be sufficient Water is available in a stage prior to the hardening of the resinous end product to ensure that there is no significant amount of P-O-P compounds remains in the cured resin.

Usually, aqueous phosphoric acid solutions, especially 70 up to 90% preferred. When a phosphoric acid in condensed form as a source for which phosphoric acid is used depends on the stage at which the P-O-P hydrolysis occurs is carried out, depending on whether a reduction in the water content during the Response is desired.

If a source of condensed phosphoric acid is completely considered H3PO4 should be used in the reaction, sufficient time should be allowed to achieve complete P-O-P hydrolysis.

The rate at which the oxirane groups in the El / H3P04 reaction are converted and the structure of the products obtained naturally depend on such Parameters such as the ratio of water to acid, ratio of acid to oxirane, Nature of the solvent, temperature and contact time.

It was found that the implementation is generally more than just an addition of P-OH to oxirane groups. If no special measures taken to ensure the absence of water in the reaction mixture, the product will generally contain substantial proportions of molecules at least one oxirane group has been converted into an alpha, beta-dihydroxy group, i.e., a "glycol" group. This is obviously not only due to the H + -catalyzed Addition of water to oxiranes, but also to the hydrolysis of phosphodiester groups. As a result of the final reaction, some free phosphoric acid generally becomes be present in the reaction product even if the amount of acid used is such that there is essentially less than one P-OH group per oxirane group is available.

Obviously the presence of water has a greater impact on the composition of the epoxy / H3P04 reaction product than previously assumed became.

The introduction of water into the reaction mixture can be achieved by using 100% phosphoric acid should be avoided as the only source of acid. It was however found that the esterification of the secondary alcohol groups in Epoxides of the DGEBA type appear to be carried out to a lesser extent. Because water when this reaction arises, measures should be taken to avoid any saturated food To trap or remove water if interested in low ratios from glycol to get ester groups in the product. The easiest way to do this is to by having at least some of a material as a source of the phosphoric acid P-O-P groups are used, such as pyrophosphoric acid or polyphosphoric acid, together with 100% phosphoric acid. The esterification of the alcoholic hydroxyl groups and the formation of water is also minimized in that the reaction occurs at relative low temperatures such as 60 - 800C.

Optionally, a suitable source may be phosphoric acid with P-O-P groups can be produced in situ by pre-reacting pyrophosphoric acid with less Water as required to convert all of the P-O-P groups.

Although the presence of phosphorous monoester groups in salty Condition essential for the dilutability of the E1 / H3PO4 reaction product with water is, it is not necessary that a high proportion of the oxirane groups in the El Product exist as ester groups instead of glycol groups. In contrast to "esterification" products from DER-667 in which the number ratio of glycol ester groups is as high as 18.3 to 1 have been found to be water-dilutable products that are after result in suitable coatings for hardening (cf.

Example 11). This result is extremely surprising and very beneficial for using the compositions according to the invention for Covering food containers. A consequence of this behavior is in it too see that the phosphoric acid and the base used for salt formation are so small Quantities can be used, e.g. as little as 0.75 g H3PO4 per 100 g DER -667, that the cost of the end product is much lower than it would otherwise be would. Another consequence is that if a volatile base is used the amount of base released before or during curing is so low that the problem of their recovery is correspondingly small. Another very important one The consequence is that the amount retained in the cured coatings volatile base is essentially zero, e.g., in the range of 50 parts to one Billion parts up to undetectable quantities.

The amount of water provided for the acid / epoxy reaction can be between 0 to 25 molecules of water for one molecule of H3PO4 vary from the source of this acid. Amounts of water greater than about 2-4 moles per mole of acid generally add an inhomogeneous reaction mixture, if not a good solvent for water is added. The presence of water in relatively high proportions does not necessarily lead to such low ratios of phosphoric ester to glycol groups in the reaction product, than could be expected. Ester to glycol ratios as high as 1 to 2.3 are below with a water to acid mole ratio in the range of 25 to 1 Using DER-667 as the epoxide and acetone as the reaction medium.

The resins obtained as the reaction product are generally with Water is diluted, and it is usually advantageous to use water in the reaction mixture before the solvent is removed. For this reason arise through the presence of relatively large amounts of water during the reaction is not particularly significant Problems.

It has been found that longer response times are essential to get high oxirane conversions at higher water concentrations. For the Economics of the process but it is very advantageous that one is able is to recover solvents that have a substantial water content. It is therefore advisable to use the optimum water content for each individual El epoxy to determine. No great experimental effort is required and in the Appropriate methods are disclosed in examples.

The amount of acid introduced into the reaction mixture by the acid source should be such that about 0.3 or more acid hydroxyls (bound to phosphorus Hydroxyl groups) per oxirane group in the E1 epoxide used as starting material available. However, the amount of acid below 1/3 mol of H3PO4 is preferred per equivalent weight of El, i.e. below an acidic hydroxyl group per oxirane group, causing a substantial decrease in the water resistance of the cured Products is avoided. If as El epoxy DER-667 or an equivalent DGEBA epoxy is used, it is very preferred that no more than 1 part by weight of H3PO4 per 100 parts by weight of El epoxy are present.

There can be larger amounts of acid to the point at which the Reaction mixture is undesirably inhomogeneous, can be used. The usage of more than a sufficient amount of H3PO4 to produce about 4 acidic hydroxyl groups per Giving oxirane groups can trap so much free phosphoric acid or the corresponding salt lead to an undesirable effect on the properties of the uncured or the cured resin occurs, thereby removing at least part of the excess acid, preferably before introducing the base is required.

The reaction between the epoxide and the acid can be in the absence a reaction medium such as a solvent. But how already has been set out, the use of a reaction medium can be essential to to ensure the homogeneity of the reaction mixture when the amounts of water and / or H3PO4 are relatively high compared to the amount of epoxy.

Better results are obtained when the reaction mixture is homogeneous is, and it is generally advantageous to use a reaction medium in each case use.

Suitable media for the reaction are in the process of the present invention Invention of inert materials, the mixture with the starting materials, a solution or form a dispersion that is fluid at the reaction temperature used. The term "inert" is understood to mean that the medium is not disadvantageous Way reacts with any material present in such a way that a Objective of the invention cannot be achieved.

Preferred media are inert organic compounds or mixtures of which, which are liquid at normal temperatures, have a boiling point below 150 ° C and solvents for epoxides and the source of phosphoric acid. The solvents should also be able to dissolve enough water to ensure that the desired ratio of dissolved water to acid (or oxirane groups) is achieved. Examples of such media are dioxane, glycol ethers, lower alkyl acetates, Methyl ethyl ketone, acetone, ethanol, isopropanol and methylene chloride in a mixture with one of the solvents mentioned above. The alcohols listed explain "inert" Solvents that are not adversely reactive in an unacceptable manner. They are especially useful as additives when there is a tendency in their absence to precipitate, such as when aqueous H3PO4 turns into a dilute solution one tablespoon of resin is placed in a medium that consists only of dichloromethane.

The nature of the reaction medium affects both the rate of the reaction as well as the composition of the reaction product. As a general rule it can be noted that the rate of oxirane conversion by P-OH addition and the Proportion of diester groups in the reaction mixture is higher if a bad one Solvent for water is used as the reaction medium.

At a temperature of about 600C, the nonsolvents or poor solvents for water favor the formation of higher polymer chains consisting of El epoxy residues, which are interconnected by diester groups according to the following schematic formula are connected. For example, if DER R -667 is converted into a 100% CH2C12 at 600C with 1% of its weight of H3PO4 (as 85% aqueous H3PO4), the reaction mixture gels in about 4 hours. The chemical activity of water in a solvent such as dichloromethane does not appear to be high enough under these conditions to result in substantial hydrolysis of oxirane or ester groups. A gel of the last-mentioned type could, however, be taken up in a solvent that is more miscible with water and hydrolyzed to a readily usable product which contains approximately equal proportions of glycol and monoester groups.

If the reaction medium also, for example, up to 25% by weight of a Solvent for water that is miscible with CH2C12, such as acetone, is diester formation at 600C is still the predominant reaction, but it is resulting product not a gel. The activity is at a temperature of 115 - 1200C of the water contained in H3PO4 in a medium of 75% by weight CH2C12 and 25% by weight Acetone is essential. The diester formation does not proceed as far and it does hydrolysis of all diester groups formed takes place. As much as that The proportion of acetone is increased further, the formation of diesters decreases and the monoester content of finished product increases. The direct accumulation of water to oxirane groups is obviously the predominant reaction at 115-12OOC, however, the ratio of glycol to monoester groups decreases to the extent that in which the proportion of acetone in the CH2C12 / acetone mixture increases.

The nature of the medium in which the neutralized reaction product is also essential.

In this context it is important that the medium that works best is suitable for the preparation of a particular reaction product, not necessarily also is the medium that has the most stable dispersion of the highest solids content of the neutralized product in water.

Tests have shown that although higher monoester contents in the previously discussed reactions of an El epoxide with 85% H3PO4 in acetone alone instead of being obtained in acetone / CH2C12 solutions, the presence of small amounts of dichloromethane for the dispersibility of the neutralized product useful is when water is added and the organic medium is removed. It was also found that generally product particles formed when the liquid fractions arise from the neutralized reaction product, a smaller one A tendency to show agglomeration when they result from solutions in dioxane or in particular Derive methyl ethyl ketone. Such solvents can therefore with special Advantage as media for the production of the neutralized acid / epoxy products be used, which in itself is heavier to disperse in water are.

When extractive removal of excess phosphoric acid in a stage before neutralization is considered, one can of course Appropriate amounts of a suitable solvent that is not miscible with water and does not tend to emulsify therein, include in the reaction medium.

Also solvents that are sensitive to bases, such as acetone, should be removed first if more than stoichiometrically required Amount of base used to bring about neutralization.

Mixtures of two or more solvents are available in some cases preferably to a medium with the desired combination of solvency and a initial or azeotropic boiling point (reflux temperature).

Suitable reaction temperatures vary between the lowest Temperature at which the addition of P-OH to oxirane groups of the El epoxy with occurs at a reasonable rate, up to temperatures as high as that at which firstly, harmful reactions (such as the reaction between the alcoholic reaction medium and phosphoric acid) occur to an undesirable extent, or secondly, excessively high vapor pressures occur. Temperatures are within the range of 50 -1500C generally suitable, the preferred temperatures being 70-1350C. Temperatures between 100 and 125 ° C. are particularly preferred and very particularly preferably between 110 and 1200C The relationship between the Temperature and the solvent effects is discussed in the previous discussion Reaction media have already been treated.

The pressure is only an important parameter of the implementation, if this is carried out at elevated pressures. At least an autogenous print of the Reaction mixture is required when the reaction temperatures are above Boiling point of the reaction medium under normal conditions. The reaction can can of course also be carried out below normal pressure.

The contact time is an essential parameter in the process according to the invention only insofar as the reaction generally proceeds is left to less than 1%, and preferably less than 0.5%, of the original existing oxirane groups are consumed.

It is only necessary to convert as much of the epoxy as is required is to obtain a reaction product which essentially has the character of the has higher converted epoxy / acid products according to the invention. That is, the epoxy conversion need only be essentially complete.

The run in accordance with well-known laws Rates of the various reactions at elevated reaction temperatures faster, so that shorter contact times are required at such temperatures.

As a general rule, a longer contact time leads to a higher degree of diester hydrolysis.

In most cases, contact times of around 1 hour (for Temperatures near 1500C) to about 24 hours (at temperatures of 60 - 700C) bring good results. Usually it will be an essentially complete one Conversion of an El epoxy to a product that can be diluted with water in the neutralized state is, by a contact time of 3 to 6 hours at a temperature of 125 - 1000C reached.

The reactions of the epoxides with the source of orthophosphoric acid and with the water that may be present in the usual apparatus carried out.

The first stage of implementation is usually dissolution of the epoxide or epoxides in the reaction medium or in a component of the Medium that is the best solvent for the epoxy. In the case of higher molecular weight Epoxides El are at least dissolved in most solvents ordinary temperatures somewhat slow, so that usually a stirring treatment the mixture of resin and solvent for a period of about 8 hours or longer is required.

The source of the acid, which is usually 85% aqueous H3P04 can be dissolved in one or more components of the reaction medium beforehand or diluted with it to facilitate mixing with the epoxy solution. It is usually easier to introduce the acid into the epoxy solution than the other way around. It is not necessary to add the starting materials gradually and / or at low temperatures bring together if not a very reactive epoxy (usually the E2 epoxy) in the Implementation is used. An example of a very reactive El epoxy is the diglycidyl ether of bisphenol A.

In the case of the presence of highly reactive epoxies it is it is desirable to start at the lowest possible temperature, so that the reaction proceeds at the desired rate. Thereby and dilution can minimize the reactions that lead to gelation will. It is also possible with simultaneous or successive reactions Mix the starting materials as carefully as possible before putting them into practice come. In addition, precooling, mixing and stirring of the starting materials and if necessary of the medium at a low temperature ((50C for example) for a period of time possible up to a day or longer. After this is done, the mixture should be to be left standing so that it warms up slowly and any favoring one sudden exothermic reaction is avoided. After the reactive epoxies have been converted to a large extent, i.e. after the oxirane content is sufficient has been lowered, the reaction mixture can be heated to a higher temperature to bring them to an end more quickly. Temperatures above 150 ° C should but in general during the implementation and also during the subsequent Removal of the solvent can be avoided.

Usually, the starting materials are preferably added with stirring the desired reaction temperature in an appropriately designed reaction vessel warmed that for example a reflux condenser, a pressure seal and has similar facilities. The contents of the vessel is as long as one held at a suitable temperature until sufficient conversion of the oxirane groups occurred to a water-dilutable product after the addition of a base to surrender.

The reaction mixture is cooled, neutralized, diluted with water and freed from volatile materials. If a reaction medium is higher than If water contains or consists of boiling solvents, the addition of Water can be delayed until the higher-boiling solvents are replaced by lower-boiling ones Solvents have been replaced, which in turn are then driven off after the water has been added.

In general, it is desirable to gradually reduce the water under good Add stirring to avoid coagulation of the neutralized resin.

The reaction product of H3P04, and the El and / or E2 resin can with a base are neutralized, so that a water-dilutable neutralized Product is created. Depending on factors known to those skilled in the art, is complete neutralization is not necessary in all cases. This means, that the acid / epoxide reaction product only has to be neutralized with so much base, as is required that the salt-like ester P-OH groups to a dilutability lead with water. In general, however, it is advantageous that at least one equivalent Base per phosphate ester group exists, and this will be the This is the rule when the acid number of the product is relatively low. In the other In extreme cases, sufficient base is provided to remove all acidic hydrogens in the Neutralize acid / epoxy reaction product (including any free H3PO4).

Examples of suitable types of bases used in the invention are as follows: A. Alkali hydroxides, such as lithium, sodium and potassium hydroxide. These bases can be molded (e.g. from surface-active materials) with resins of unhardened salts are used, or where the existing reactive Groups (secondary alcoholic hydroxyl groups) cause hardening.

B. Oxides or hydroxides of alkaline earths, such as beryllium or calcium, which form phosphates or acid phosphates with measurable solubilities in water. In this case too, hardening with such salts requires the presence of those mentioned reactive groups. The salts can be used as water-dispersible sealants or primer on unfired ceramic items that are subsequently baked, be used.

C. Oxides or hydroxides of other metals, such as copper and iron, which form phosphates or acidic phosphates that have a measurable solubility in water as such or as hydrates or complexes with ammonia.

D. ammonia or ammonium hydroxide.

E. Organic bases. This class of bases is very preferred and includes types of the following compounds: a. Choline and guanidine; b. aliphatic mono- and polyfunctional amines, such as methylamine, n-butylamine, diethylamine, triethylamine, Diethylenetriamine, n-hexylamine, ethylenediamine, allylamine; c. Cycloaliphatic amines, such as cyclohexylamine and cycloheptylamine; d. aromatic amines such as aniline, N, N-dimethylaniline, Diaminobenzenes and the like; e. heterocyclic amines, such as ethyleneimine, piperazine, Morpholine, pyrrolidine, pyridine and hexamethyleneimine, and f. Alkanolamines and alkylalkanolamines, such as ethanolamine, dimethylaminoethanol, diethylaminoethanol, diisopropanolamine, triisopropanolamine, 4-hydroxy-n-butylamine, 2-dimethylamino-2-methyl-1-propanol, and the like.

For all compounds of classes a-f, those are compounds preferably those from the neutralized resin dispersions during or after boiling The water can be removed by heating to temperatures that are lower than those for producing satisfactory cure rates.

Those organic bases of the classes are particularly preferred b and f, which are removed by heating to temperatures below about 1500C can. This is generally possible with bases that boil at 760 mm Hg of less than 1500C.

Most of the last-mentioned bases are amines of the formula ONLY 3 preferred in which each R is independently H, Methyl or ethyl with the proviso that no more than one R is H. In the order of decreasing Preferring factors such as curing time, including time to Carrying out deneutralization and amine removal, and the viscosity in the case driving off the volatiles from the neutralized reaction mixture the most preferred specific amines are triethylamine, dimethylamine, trimethylamine and diethylamine. Triethylamine is among these amines not only because of the above mentioned factors are particularly preferred, but also because established such amounts as may remain in the cured coating, not easily leached by water. This also applies to such increased Temperatures such as those encountered when handling canned food.

Furthermore, alkanolamines of the formula R2N-CH2-CH2-OH are very preferred, in which R 'is H, methyl or ethyl, or independently thereof H, ethyl or 2-hydroxyethyl is.

In order of decreasing preference, these include alkanolamines N, N-dimethylethanolamine, N-methylethanolamine, ethanolamine and diethanolamine.

Triethanolamine is apparently for the neutralization of higher molecular weight Acid / El epoxy reaction products according to the invention are not very suitable. THE @ DER 4 reaction mixtures, which are neutralized with triethanolamine, diluted with water and freed from volatiles to a solids content of about 50% gave no dispersions. But triethanolamine does not cause any problems if it in hexamethoxymethylmelamine (CYMELR 303) is included and for coating formulations with the dispersions according to this invention.

It was also found that higher molecular weight El / acid products, which are made with dimethylaminomethylpropanol, neutralized, only form good dispersions if the amount of H3P04 used for the acid / epoxy reaction is greater than about one part per 100 parts of the resin (DER 667).

Mixtures of any of the foregoing amines and alkanolamines can of course also be used for special applications, if they offer advantages. Similarly, 3P04 can be prepared separately with H El and E2 reaction products neutralized with different bases and then combined will. On the other hand, it is also possible to combine such products first and then neutralize them with the same base.

The neutralization is usually carried out by the Acid / epoxy reaction mixture including any solvent used diluted with enough water to make a dispersion that will stir well leaves and then adds the base. You can also proceed in reverse. When out of the epoxy / Acid reaction miqcOunR ~ no acid has been removed.

A very useful method is simply to get two Equivalent base, for example two moles of an amine (for each mole for the reaction H3P04 used) admits 100%. However, the amount of base required can be due to the previously determined acidity can be determined. Alternatively, pH paper can be used or a device to measure the pH is used to terminate the addition of base will. Another possibility is to simply add the base in portions stirring well until the appearance and behavior of the dispersion on stirring changes conspicuously in a known manner in such a way that the desired degree of neutralization is reached. In general, however, a certain pH value is used as the end point of the neutralization determined beforehand and then adjusted during the neutralization, this pH value usually between 6 and 10, preferably between 6.5 and 9. Because the speed of neutralization decreases to the extent that the number of non-neutralized, acidic hydroxyls fall, enough time should be allowed after each base addition, to ensure that an apparent endpoint is also the actual endpoint is. Usually no pH shift should be detectable after one hour.

If the neutralized product cannot be used without transport as little water as possible should be used for its production, so that the transport costs are as low as possible. Before applying to the The substrate to be coated is neutralized and freed from volatile components Material should therefore usually be diluted with more water to a consistency it depends on the amount of additives or hardeners, which must also be dissolved, the type of application, the desired viscosity and the thickness of the desired coating. In general, it is preferred to use aqueous dispersions with a solids content of 50% and there are no difficulties has been observed upon further dilution of such dispersions with water. the Energy costs for the evaporation of water are of course different point to be considered. Usually this is used as a diluent Water added at a relatively slow rate with good agitation be to the formation of a quasi-permanent mixture of two discrete liquid Phases to avoid. In some cases, however, the reverse addition is also or the addition "all at once" is possible.

Stripping off the neutralized mixture becomes more common Way carried out at a pressure that depends on the normal boiling point of the solvent. However, care should be taken to avoid excess Boiler temperatures are avoided during stripping, so that no undesirable Hydrolysis of ester groups occurs. The occurrence of such undesirable boiler temperatures is most likely during the latter stages of the abortion, in particular when relatively high water-miscible solvents are in the reaction medium have been used. In such cases, the propulsion speed should be slow can be used or you can also use other aids, such as the addition a solvent that, with the water-miscible solvent, produces an azep ;; 4pgs çich forms.

In an alternative embodiment, one can neutralize the Convert the reaction product into a powder, for example by spray drying, which is subsequently dissolved in water or directly on substrates by known working methods can be applied for coating with powders.

Aqueous solutions of the neutralized reaction products can be used different substrates by known working methods, such as spraying, dipping, application rate applied with a roller, brush and the like.

The removal of water from the resulting aqueous films takes place in a known manner, for example by passing through a heated air stream of controlled temperature and moisture content, passing the film through a zone of reduced pressure, heating and the like. When the salt groups in the neutralized reaction product are of such a nature that they pass through Rapidly decompose when heated and the base released during decomposition is volatile all or a substantial part of the base can be removed during the removal of the water can also be removed.

Any base remaining in the film can be removed after the water has been removed can be eliminated by further heating under normal pressure or reduced pressure. The removed base will usually be recovered, for example by condensation or by washing with acid.

As stated earlier, curing of the resin after Removal of the water and the base in usual way. If an additional chemical hardener is to be used, this can be used Agents can be added before or after the removal of the water. In general The simplest and most economical method of hardening is simply that Application of heat, as in baking, to create a crosslinking between the reactive To bring about groups of deneutralized coating mass, as between the secondary Hydroxyl groups, P-OH groups and any other groups. As an additional hardener can ureas, melamines and phenols and their condensation products with formaldehyde or other aldehydes can be used.

Procedure for characterizing the products 1. Titration of the acids The relative amount of added phosphoric acid found in the product mixture as Free acid, occurring as monoester groups and as diester groups, can be as follows be determined: a sufficiently large sample of the reaction mixture is taken, thus about one milliequivalent (meq) solids (based on the acid present) in 35 ml of a solvent composed of 66.7% by weight of 2-butanone, 16.65% by weight of methanol and 16.65 % By weight of water is dissolved.

The solution is made with about 0.3 N-methanolic tetrabutylammonium hydroxide using an automatic titration device (Metrohm / Herisau) up to a second kink in the resulting conductivity versus the volume of the Titrant titrated.

There are 10 ml of water and 10 ml of a 10% aqueous CaCl2 solution are added and the reaction is allowed to proceed for about 10 minutes, with the entire Phosphorus mono- and diester groups are converted into neutral calcium salt groups. The free phosphoric acid is converted into the single acid phosphate with the formula CaHPO4 converted. All calcium-containing products fail and there can be a third kink can be observed in the titration curve without interference from the second Monoester proton enters, after neutralization of the proton in the CaHPO4 with further quaternary hydroxide. The amount of base required to make the first kink is the one by the only acidic proton of the diester and by the first Protons of the monoester group and the free acid is consumed. The additional Amount of base needed to bring about the second kink is that which is consumed by the second (last) proton in the monoester groups and the second proton in the free acid. The extra amount of base needed is used to bring about the last kink in the curve, is only made by the last Proton of the calcium salt derived from the free acid is consumed. if the total volumes of base solution required to complete the consecutive To bring about kinks vl, v2 and v3, apply to the relative amounts of existing Phosphate as mono- and diester groups and the free acid use the following equations: free H3PO4. v3 - v2 monoester = 2v2 - v1 - V3 diester = 2v1 - v2 The proportion of consumed Epoxy groups appear in the product as glycol groups as a result of the hydrolysis reactions occur is calculable from the following relationship, assuming that the The only conversion products of glycol, monoester or diester groups are: MA% eg = 100- (% m + 2 (% d) e0 - ep In this formula the general symbols have the following Meaning: ep = equivalent of epoxide as such present in the product (usually zero) e0 P equivalent of epoxide added to the reaction mixture e = equivalent of epoxide converted in glycol groups g MA = mol H3PO4 added to the reaction mixture m m - mol% added Acid occurring as a monoester% d - mol of Z added acid occurring as a diester 2. Titration of the oxirane groups It has been found that the standard method for Determination of oxirane groups is suitable and in all cases and in all examples could be used.

A 25% solution of tetramethylammonium bromide in glacial acetic acid is used for this used and against crystal violet with a 0.1 n solution of perchloric acid back-titrated in glacial acetic acid.

3. Viscosity measurements As an indicator of the crosslinking and / or the changes in molecular weight became the viscosities of some reaction mixtures determined in the examples by the well-known Gardner method.

Example 1 Solubilization of the commercial resin DERR-667 by Reaction with 65% or 75% M 3P04 and neutralization with triethylamine. Epoxy equivalent weight = c 2000; 3H / oxirane.

A.

The resin is dissolved in the same amount by weight of dioxane and the Solution is at room temperature with 75% H3PO4 in the weight ratio acid / Resin (13.26 / 200 g) mixed so that there is 3.0 equivalents of M per equivalent of oxirane are. A sample of the mixture obtained (number 0) is immediately "quenched" (stored at low temperature) as an analytical control sample. Other parts of the mix are placed in seven consecutively numbered containers and placed in an oven of 700 introduced.

These containers are removed from the oven in the order they are numbered after the lapse of certain times indicated in the table below are removed and rapidly cooled to allow the reaction to proceed further to prevent.

Samples of these treated materials are then titrated to their oxirane content (epoxy equivalent weight = EÄG) H3PO4, phosphorus monoester and Determine phosphodiester. The Gardner viscosity of each reaction mixture is also determined and also the dispersibility in water, after neutralization investigated with triethylamine.

B.

Experiment A is repeated, but 15.3 g of the 65% phosphoric acid are used used so that 3 acidic hydroxyl groups (3 equivalents of H) per equivalent of the Resin can be obtained.

The results of experiments A and B are in the table below I summarized.

Table I A * -1 A-2 A-3 A-4 A-5 A-6 A-7 B ** - 1 B-2 B-3 B-4 B-5 B-7 Reaction 1/2 1 - 3 4 5 6 1/2 1 1 - 3 4 6 time 70 ° C, h 1/2 1/2% oxirane 27.4 45.6 75.3 86.5 94.0 98.1 62.8 75.8 87.9 93.9 94.1 95.4 consumed visc. 77 144 259 331 293 173 160 78 133 164 135 118 106 yarn, sec.

H2O disp. *** no yes yes yes yes yes yes no no yes yes yes yes free acid % - 51.7 47.9 42.8 47.5 55.2 51.0 54.0 54.9 49.7 53.2 53.1 53.0 monoesters% - 41.2 45.6 50.1 47.9 41.0 46.8 41.7 40.5 45.5 42.9 44.9 44.6 diester% - 0.71 6.7 7.1 4.6 3.9 2.2 4.3 4.6 4.9 4.0 2.0 2.4% oxirane - 8.2 21.5 25.6 39.1 49.1 47.9 19.9 34.4 37.0 45.8 48.0 48.2 needs to be indicated as glycol groups footnotes: * 75 % H3PO4 ** 65% H3PO4 *** dispersible Example 2 Solubilization of DER 664 by reaction with 85% or 99% H3P04 in dioxane under reflux cooling and neutralization with triethylamine.

EÄG = v1000; H / oxirane ratio = 3: 1.

A.

25 g (0.025 equivalents) of the epoxy resin characterized above was dissolved in dioxane. To the solution was added 25 g (about 0.076 equivalents) of a 10 % solution of 100% H3PO4 (probably only 99% because of the absorption of some moisture when handling) in dioxane. The mixture was taking Heated reflux cooling to 1010C, heated under reflux cooling for three hours and then cooled to room temperature. The acid number of the reaction mixture was 124.05 (compared to 102 corresponding to the theoretical addition of an oxirane group per H3PO4 molecule).

No unreacted epoxy could be found.

The reaction mixture was extracted with 50 ml of water and the acid content the extract was found to be 0.013 equivalents by titration with dilute KOM.

The raffinate required three grams (0.03 equivalents) of triethylamine for neutralization. The total acid consumption for the reaction was then 0.076- (0.013 + 0.030) = 0.033 equivalents or 0.033 / 0.025 = 1.32 equivalents of H + per oxirane.

B.

Experiment 1 was repeated, but 25 ml of a dioxane solution were used, the 2.94 g (0.076 equivalents) of 85% H3PO4 instead of the acidic solution from experiment A contained. The acid number of the reaction mixture was lower (108), the acid content of the extract and raffinate were 0.009 and 0.035, respectively, and those during the reaction acid consumed was again 0.033 equivalents.

Both raffinates A and B gave after stripping the remainder Dioxane slightly cloudy but stable aqueous dispersions with a solids content of 41%.

Example 3 Influence of the EÄG and the H / oxirane ratio on the Solubilization of DGEBA-type epoxy resins when reacted with 85% H3PO4.

Four resins of this type with different EÄG between 190 and 2000 were reacted separately at 750 in dioxane with such amounts of 85% H3PO4, that there were 0.5 to 3.0 equivalents of H + per oxirane. The dispersibility each reaction mixture as such and after neutralization with triethylamine and solvent stripping was checked. The results are in the following Table II compiled. From these results it can be seen that so low H + to oxirane ratios such as 0.5 generally for purposes of this invention are not suitable.

The results also show that ratios above about 1.0 For the dispersibility of only such resins, the EÄG values are essential greater than about 1000.

Table II Resin DERR-331 DERR-661 DERR-664 DERR-667 EÄG 190 500 1000 2000 eq. Acid / epoxy * 0.5 1.0 1.5 3.0 0.5 1.0 1.5 3.0 0.5 1.0 1.5 3.0 0.5 1.0 1.5 3.0% acid (85%) 9.3 17.0 23.5 38.1 4.15 7.97 11.5 20.9 1.91 3.75 5.5 10.4 0.96 1.9 2.84 5.5 Time at 75 ° C 1 h 3 h 3 h 7 h Dispersibility in H2O ** G + + + G - - - V - - - V - - -a) Resin + dioxane G + + + G + + + V + + + V -? + b) resin + Dioxane + amine G + + + G + + + V + + + V? ? + c) resin + amine + water, (without dioxane) * P-OH / oxirane ratio ** V = very viscous G = gelled + = dispersible - = not dispersible? = Borderline case Example 4 Solubilization of DERR - 667 by reaction with a condensed phosphoric acid as acid source (8 P-OM per oxirane).

A solution of 100 g (0.05 equivalents) of said resin in 200 g of dioxane was slowly stirred into a solution of 17.8 g (0.1 mol) of pyrophosphoric acid (Equivalent to 0.2 mol of H3PO4) are run in in an equal amount by weight, with the temperature of the reaction mixture was kept at 80 to 1000C. In about 0.5 A soft gel had formed for hours. After adding a further 270 g of dioxane the gel partially dissolved and the resulting mixture could be stirred. After a further reaction for 3 hours, no unreacted epoxide could be detected (in the continuous liquid phase). The titration of a sample of the Gel phase (dissolved in a mixed solvent; 17% H20, 17% methanol and 66% methyl ethyl ketone) showed that it consisted essentially of the resin in which the oxirane groups had been converted to phosphodiester groups.

The reaction mixture was converted into a homogeneous liquid, by adding 10 g (0.56 mol) of water and stirring the system for 3 hours was heated.

The titration of the finished solution showed that all diester groups and P-O-P bonds had been hydrolyzed.

As a determination of the amount of free phosphoric acid by titration was not well possible, an aliquot of the reaction mixture was repeated extracted with water and the combined extracts titrated. It became the Calculated proportion of the oxirane groups converted into phosphorus monoester groups to be 71.4%, from the difference between the amount of H 3 PO4 added (as H4P207) and the free acidity in the aqueous extracts. The percentage of converted into glycol groups Oxirane groups then resulted from the difference to 28.6% and the numerical ratio from glycol to monoester groups in the finished product to 0.4.

Although the continuous liquid phase that coincides with the Gel had arisen that was not worked up separately, became the titration curve concluded for this phase that only about 10 Z or less of the difference from the epoxy the derivative product it contained was diester and the remainder was monoester was.

Dispersions were made from the final reaction mixture, which had not been completely freed from H3P04 by extraction with water. The samples were neutralized to a pH of 7.5 - 8.0 with triethylamine, freed of volatile components and treated with water to a non-volatile content Components diluted by 16% by weight. The unextracted sample gave a viscous one cloudy white dispersion showing good film-forming properties. The extracted Sample gave a thin aqueous, clear and blue dispersion, its film-forming ability but was not good.

Example 5 Use of the neutralized reaction product from DERR - 667 with H3PO4 as a dispersant for a DGEBA epoxy with an epoxy equivalent weight up to ~ 13,000.

A.

It became a DER R - 667 / H3P04 product with a "high" ester content made by adding the appropriate epoxy resin with an epoxy equivalent weight of about 1550 with one mole (6 phr) H3PO4 (as 99% aqueous H3PO4) per equivalent Epoxide was reacted in methyl ethyl ketone at 800C for 15 hours. There was no unreacted epoxide and the ratio of glycol to ester was 34/66 = 1 / 1.94. This product was successively mixed with smaller amounts of a DER - 684 solution (40 % By weight solids in "MEK") and each of the resulting mixtures was mixed with two equivalents of triethylamine, diluted with 25 "phr" of methylene chloride and diluted mixed with 100 parts of water to 100 parts of the total resins. Those of the volatile Fractionated emulsion-like products contained 50% by weight total solids and were tested as dispersions.

The results are shown in Table III.

Table III Dispersibility in Water of Mixtures of DERR - 684 and DER - 667/6 "phr" H3PO4 reaction product "phr" "phr" dispersion quality DER - 684 PO4 60 2.0 granular dispersion, settles on the when standing from 50 2.6 Borderline of acceptability, slight settling 40 3.1 at the borderline of acceptability, little settling 20 4.1 good dispersion, no settling B.

680 g of a 40% solution of the commercially available resin DERR - 684 "MEK" were heated to 780 ° C. for 24 hours with 3.72 g of pyrophosphoric acid and the required amount Amount (0.38 g) of water to convert them to 100% H3PO4 (~ 1.5 phr). The epoxy equivalent weight the resin never rose above 50,000 (about 74% oxirane conversion) and that neutralized end product gave no dispersion with water. When using of the product with the epoxy equivalent weight of 50,000 instead of DERR - 684 in the above blends of Part A, dispersibility was found to be somewhat inferior observed.

The dispersed mixtures obtained in Experiment A represent contents at DER '- - 684 of 50 phr and less an excellent and superior embodiment of the invention. For those skilled in the art, the merits of such products are with respect to of the properties of cured coatings based on the presence of a DGEBA resin component with an (average) molecular weight of about 26,000 are.

Furthermore, the rather slow conversion speed of the Oxirane in experiment B to recognize that most or all of the oxirane groups aton DERR-684 are present as such in the 684 dispersions prepared in this way. It was not to be expected that the latter groups would be unlimited for one Period in the presence of both water and acid hydrolyzed amine phosphate groups would not be converted even though the DERR - 684 is dispersed and not dissolved is. Aqueous dispersions of mixtures of neutralized DER - 684 (as such or reacted with H3PO4) and DERR - 667 / H3PO4 reaction products are new Compositions of excellent properties.

Example 6 Reduction of the free acid content of a reaction product of a DGEBA resin with a high epoxy equivalent with about 6 phr H3PO4 for improvement the dispersibility.

A 95 g (0.0198 equivalent) solution of DERR - 669 (epoxy equivalent weight 4800) and 5.88 ¢ 85% H3PO4 (0.051 mol H3PO4, 7.73 P-OH per oxirane) in '% EK " was heated to 80 ° C. under reflux for 15 hours. The reaction mixture was cooled and samples were taken for analysis. The following values were determined: unreacted oxirane content = none oxirane converted into phosphorus monoesters = 40 Z oxirane converted to glycol = 60% ratio of glycol / ester = 3/2 free H3PO4 in the product, 4.31 g or 4.27% by weight of the non-volatile components present.

The reaction mixture was divided. Part was with triethylamine neutralized to a pH of 7, diluted with water and removed from volatiles freed by aborting these parts. The remaining material was none stable dispersion.

A second part was made with enough water (an equal volume of water) mixed to precipitate the polymer.

The liquid phase was decanted and the precipitate increased with more Treated water, which was then also decanted. The polymer was made in MEK and samples were taken from the solution for analysis.

It was found that 30% of the free acid was obtained by washing had been removed. The H3PO4 present made up about 3% by weight of the resinous product the end. After neutralizing the product with triethylamine to pH 7, dilute with water and rubbing off the MEK, it became a persistent, opaque, non-granular dispersion (50 Z Solids).

Example 7 Influence of the substituent on those used to cap the DGEBA Resin used phenol on the wettability of a substrate.

DER to - 664 was separated with 0.5 molecular fractions of each Phenol, p-t-butylphenol and p-nonylphenol reacted per equivalent of oxirane. One gram - Mol of the phenol starting material, 0.3 g of ethyl triphenylphosphonium acetate (A-1 catalyst) and 15 ml of xylene was added to 250 g (0.13 g mole) of molten DE 664 at one temperature of about 1200C and the mixture was heated to 2000C while stirring kept at this temperature with reflux cooling until the epowid equivalent weight roughly equal to the sum of the molecular weight of the phenol and twice the original Resin equivalent weight. The xylene was driven off from what was left The product was sampled and the remainder of the capped resin obtained was mixed with an equal amount of 21EK with stirring.

The resulting solution was refluxed and there were 0.5 mol of H3PO4 (as 85% aqueous acid) undiluted with the same amount by weight MEK mixed drop by drop. The refluxing was continued, until the epoxy equivalent weight was about 60,000 or remained constant. The solution was cooled, neutralized with 1 mol of triethylamine and diluted.

The diluted mixture was reduced from the volatiles Pressure released at 700C until no more tEK passed. That of volatile components freed product was a persistent aqueous dispersion that was about 50 wt: solids contained. Portions of this dispersion were mixed with water to make 30, 35 or 40 weight percent solids diluted.

It became the Brookfield RVT viscosities of each of the four dispersions (12, total) using a # 4 spindle at 100 rpm. Further The surface tension was determined using a Fisher surface tensiomat measured on a wire circle with a diameter of 5.990 cm (mean value in each case of 5 measurements).

The wetting capabilities of the various dispersions for three Types of substrates were assessed by adding a small amount of each dispersion was placed on the same substrate, after which at the same time in parallel with a No. 18 wire rod this dispersion sample was distributed and the properties of the obtained Filmstrip has been observed, particularly the expansion or shrinkage, Fish eyes, uniformity and those known in English as "crawling" and conding Properties. Based on these visual observations, ratings were given, where 1 was the best and 3 the worst.

The pH values of all dispersions were examined and they were in the range of 8.45 to 8.55. The results of the surface tension viscosity test and the wettability are summarized in Table IV below. Tabel IV substrate% solid viscosity cp surface tension relative wettability fabrics dynes / cm of resin capped with NP (1) BP (2) P (3) in NP BP P NP BP P Disp.

Aluminum 30 13 12 11 46 50.8 46 1 3 3 (CH2Cl2- 50% "beads" "beads" cleaned) Area covered 35 20 20 20 46.5 50 54 1 2 3 "wets" "slight" severe crawl " crawl "40 39 30 30 50.8 50 53.3 1 2 3" wets "" mode- "severe rate crawl" crawl "untinned Steel (cleaned 40 39 30 30 50.8 53.3 1 2 3 nigt) "crawl" "puddles" "large beads" cold rolled 30 13 12 11 46 50.8 53.3 1 2 3 steel "slight" "mode-" more crawl " (not crawl "rate cleans) crawl" footnotes: (1) nonylphenyl (2) t-butylphenol (3) phenol From the results in Table IV it can be seen that the wettability decreases when in the formula (q) R20 from the nonyl radical via the t-butyl residue drops to H, the differences being greatest with a solids content from 35 to 40% on a cleaned aluminum substrate and are the least pronounced at 30% solids on uncleaned cold rolled steel. These effects roughly agree with the slightly higher viscosities and lower surface tensions the dispersion of the product with the nonylphenol residue.

Example 8 Successive coreaction of orthophosphoric acid with a diglycidyl ether of the formula (a) with n in the range from 10 to 13 and one Epoxy equivalent weight of 1600-2000 and one substituted with methylol groups Phenylglycidyl ether of an E2 epoxide (epoxide equivalent weight = 720; 0.935 P-OH / Oxirane).

31.75 kg of the diglycidyl ether characterized above dissolved in 45.36 kg of methylene chloride and 9.07 kg of isopropyl alcohol, with reflux cooling Heated for 2 hours and reacted for 24 hours at 41100 with 2.27 kB of 85% E3P04. Of the Oxirane content on a solids basis was less than 0.1%. 13.61 kg of the glycidyl ether 1,6-bis (methylol) -4-tert-butylphenol were then reacted at 41,100 for 23 hours. The oxirane content was less than 0.1X / acid number 14.5. 79 kg of distilled water and 36.29 kg of riethylamine were then stirred in.

After the solvents were driven off, the remaining Dispersion had a Ph of 8.5 and showed excellent durability and outstanding Solution features, i.e. no settling, low opacity and none Grain formation. There were coatings on aluminum test strips with a content of non-volatile Ingredients of 20 wt% in water using a # 10 wire wound Stick applied without pretreatment of the surfaces of the test strips. It was good wetting, excellent flow and complete curing in 8 minutes at 19300 or in 5 minutes at 20400 or in 3 minutes at 227 ° C. The chemical resistance of the films was excellent as the coating was generally Survived 50 double rubs with acetone. Even with non-galvanized steel coupons excellent wetting was observed. There could be no tarnishing of the coating for neither surface type after 30 minutes immersion in boiling water Water can be determined. The above curing times were avoided when 1% para-toluenesulfonic acid on a solids basis in the dispersions diluted with water was added, and no impairment of the film properties was found became.

Examples 9 to 12 Influence of neutralization with various amines of the successive co-reaction product on the viscosity, curing rates and film properties.

As in Example 8, an acid / El / E2 product was made in a two-stage process Esterification established (epoxy equivalent weight El + E2 = 720; 1.32 P-OH / oxirane). In the first Stage were 700 g (0.2 g - mole) DER R - 667 in 1000 g of methylene chloride and 200 g of "IPA" heated under reflux for 2.5 hours and reacted with 70 g of 85% H3Po4 at 410C (acid number 95, oxirane content less than 0.2%).

In the second stage, 300 g (1.13 g - mol) of the glycidyl ether of 1,6-bis-methylol-4-t-butylphenol at 410C for 16.5 hours (oxirane content less than 0.1 wt%; Acid number 70). 2150 g of distilled water were stirred in and the obtained homogeneous dispersion was divided into four equal portions and used in the following examples.

Example 9 To 100 g of the acidic product dispersion described above 27 g of trimethylamine were added. After driving off the volatile components the pH was 7.4.

Coatings were made as in Example 8, and these coatings had essentially the same properties as those of Example 8.

Example 10 To 1000 g of the dispersion x * 7 described above 34 g of a 50:50 (parts by weight) blend of triethylamine and dimethylaminoethanol given. Before the volatiles were driven off, the p71 was 9. The obtained one The mixture was a highly viscous gel from which, however, the solvent was easily driven off could be. The dispersion that was driven off was not very viscous and gave coatings at the same solids content which differed from those of the example 9 differentiated as follows: curing at 2040C required 3 instead of 5 minutes; the Coatings had less tendency to dry before curing; there was none Difference in the influence of 1% p-toluenesulphonic acid on the hardening and viscosity the dispersion diluted with water was higher.

Example 11 To 1000 g of the dispersion characterized above were given 0 g of dimethylaminoethanol. A very viscous gel resulted from but the volatile components could easily be driven off. The received Dispersion was diluted with water to a solids content of 20 7e. Coatings, which were prepared as in Example 9 differed in the following ways: slower curing (5 minutes at 2040C instead of 3 minutes); Acetone resistance a little less; almost no tendency to dry before curing; much higher viscosity and 1% p-toluenesulfonic acid was less effective in accelerating hardening.

Example 12 To 1000 g of the dispersion characterized above 35.5 g of diethylaminoethanol were added. A very viscous gel was obtained, but from which the volatile components could easily be driven off. Afterwards was the dispersion obtained was still quite viscous and became for this reason diluted to a solids content of 15% (instead of 20%) with water. Made from it Coatings showed the following differences compared to the coatings of Example 9: a lot higher solution viscosity; no tendency to dry out before hardening; slower ones Hardening (7 grooves at 2040C instead of 5 minutes) and no improvement in the effect of 1% paratoluene sulfonic acid on the cure rate.

The comparison of Examples 8 and 9 shows that trimethylamine and Triethyl is generally equivalent for the neutralization of the co-reaction product are. Similarly, there is no significant difference according to the examples 11 and 12 between N, N-dimethylethanolamine and N, N-diethyl homologues. The comparison of Examples 8 and 9 and 10 shows that a 1: 1 mixture of triethylamine and N, N-dimethylethanolamine a faster curing rate without a catalyst, a higher dispersion viscosity and a lower tendency to dry the uncured Films results. However, it can be seen from Examples 11 and 12 that the use of either N, N-dimethyl- and N, N-diethylethanolamine, generally worse Brings results, with the exception of a further reduction in the tendency to dehydration.

Example 13 Reverse sequential reaction in ethanol one substituted monofunctional E2 epoxy of type (b) and a bisphenol-F resin (E1 with H3PO4); Epoxy equivalent weight = 284; 1.15 P-OH / oxirane; Electrically separable product.

11.25 g (0.096 g - mol) of an 84% strength aqueous H3PO4 were added to a Mixture of 50 .thanol-B and 38.75 g (0.0965 g - mol) of the glycidyl ether of 2,6-dimethylol-4-nonylphenol given at room temperature. A slightly exothermic reaction was observed. A mixture of 5 g of Sthanol-B and 31.8 g (0.0965 g-mole) of an experimental Resin (nominally: the diglycidyl ether of bisphenol-F) was then added. this led to an exothermic reaction at which the temperature of the finished mixture rose to around 1000C. The reaction mixture was allowed to cool and at room temperature stored over the weekend.

67 g of the product (89% non-volatile components) were 33 g Stirred water and the dispersion obtained was adjusted to a pH of 6.0 with 5.6 g Diethylamine neutralized.

The addition of 10 g of ethanol and 18.4 g of additional water resulted a dispersion containing 50% by weight of non-volatile components.

The dispersion was used to make a film on an untinned To apply sheet steel by electrical deposition. There were two steel coupons with the dimensions 4.1 x 10.2 cm at a distance of 5.1 cm at a depth of 7.6 cn immersed in the dispersion and it became a direct current of a voltage of 100 volts is applied between the two electrodes. The amperage fell within 30 seconds from an initial value of 150 milliamps to a value of 50 Milliamps. The anode was from a cohesive coating of the resin covered.

After curing for 15 minutes at 1750C, the film obtained showed a good resistance to boiling water.

A film of the dispersion was applied to an uncleaned untinned Steel coupon opened and showed excellent wetting. After the shepherd for 10 minutes at 1850C the film was resistant to acetone and showed excellent results Resistance to boiling water and when bending into a curve with a No cracks occurred in a radius of 2.5 cm.

After diluting part of the dispersion with tiasser to one The diluted dispersion had a non-volatile component content of 5 Gei such as the properties and appearance of a solution. Films of this dilute dispersion are excellent on aluminum and cold rolled steel deposited. After curing for 10 minutes at 1750C, they showed excellent Resistance to acetone and a "50 inch pounds" reverse impact strength.

Example 14 Simultaneous coreaction of a 1-epoxy (DEP2- 667) and an E2 epoxy of type (rn) with phosphoric acid (epoxy equivalent 2,465; 0.85 P-OH / oxirane).

420 g (0.26 g - mole) DERR - 667 was dissolved in 900 g of methylene chloride and 180 g of isopropanol dissolved. 180 g (0.286 g - Ciol) (1 equivalent) a heat-fluidized (approx. 80 to 100 ° C) epoxy novolak (DENR - 438 von Dow) were stirred in and then 82 g of S% H3PO4 were added.

The mixture was kept at room temperature for one hour and was then refluxed (410) and refluxed for 16 hours implemented. At this point the epoxy equivalent weight (solids basis) was 49,000 (% oxirane - 43 x 100/4900 = 0.09 1%) and the acid number was 53,800 g distilled water were stirred in and the resulting dispersion was divided into two shared equal parts.

One part was made with 50 g of 25% aqueous NaOH and the other part neutralized with 30.5 g of triethylamine.

The part neutralized with caustic soda was only slightly less volatile Freed fractions, leaving a product with a solids content of more than 15% by weight was created. Both of the volatile, steep products were included Water easy to dilute into stable, homogeneous and grain-free dispersions.

The novolak resin had an epoxy equivalent weight of about 180, one Epoxy functionality of about 3.5 and was a polyglycidyl ether of a phenol-formaldehyde novolac.

Dependence of the dilutability with water on the product composition Gel permeation chromatography has shown that at most very small amounts to oxirane groups through reactions other than reaction with water or P-OH Groups are consumed and that in essence no Trieste groups develop. Likewise, at most small amounts of polyfunctional diesters are formed (Esters in which one epoxy molecule is attached to more than one other epoxy molecule is bound), if the reaction medium is not about 75% by weight or contains more dichloromethane as a solvent.

The values given in the previous examples show that that the formation of glycol groups is not only due to the hydrolysis of oxirane groups is based. The hydrolysis of ester groups (phosphodiester groups) also progresses in to a limited extent, but is more significant at higher reaction temperatures and if more dilute t13P04 is used.

In addition, the direct esterification of alcoholic hydroxyl groups, which are present as such in the epoxide 1 or which result from the P-OH / oxirane addition form little influence on the total content of phosphorus monoester groups in the finished product (in the level after a reaction time of about 3 to 6 Hours).

It is particularly surprising that the solubilization (dilutability with water) such resins as DEnv R - 667 can be achieved through a reaction can, in which up to about 95% of the oxirane groups in glycol groups instead of in acidic, salt-forming groups are converted. The DGEBA resins are already regarding of the alcoholic hydroxyl groups are polyfunctional, but are nonetheless. pronounced hydrophobic. It could not be expected that the transformation would be from an oxirane group per molecule into a glycol group in such a remarkable way entire would change the hydrophobic character of the molecule.

In addition, it was to be assumed that the conversion of the remaining oxirane groups (averaged a little less than one per molecule) alpha-hydroxyphosphoronic monoester groups sufficient salt (neutralized) groups for solubilization result in irde. Nevertheless, it has been shown that the oxirane groups in the resins are almost completely converted to glycol and (mono) ester groups, and that even at an average Content of substantially less than one monoester group per molecule that differs from El resins with equivalent weights up to about 3200 dissipative neutralized products can be diluted with water. It is even more surprising that DGEBA found resins with epoxy equivalent weights as high as 5500 water dispersible by the method of the present invention can be made.

The reaction product obtained in the invention retains its essence Character even if it additionally contains phosphodiester groups that derive from the reaction of a molecule of phosphoric acid with one oxirane group in two different epoxy molecules, in such close proximity that these groups take up to 10% of the available phosphorus. At certain levels of the process according to the invention, higher proportions of diester groups can be present but such groups tend to hydrolyze to monoester and glycol groups.

This hydrolysis reaction generally also takes place at room temperature continued as long as water is present, so that at most very few diester groups remain.

Since the neutralization is generally carried out in the presence of water then the content of diester groups in the bar is at most very low, if there are any.

When an acid / epoxy reaction product that is a relatively large amount Contains free phosphoric acid, is neutralized, in particular with an inorganic one Base, the amount of salt derived from the free acid can be such be that the dispersibility of the salt-like resin in the water that actually is a sole, becomes French. For the expert, however, there are obvious ones Measures to avoid this problem and in any case will reduce the amount of base be in the neutralized product at least the sum of the base, which by the Free acid is consumed and which is required to convert as much P-OH into to convert the salt-like state that the resin molecules are dispersible in water are.

Example 5 shows that the invention also includes products which differ from epoxides of the DGEBA type with equivalent weights as high as 13 000! derive.

That means that resins of this type like DER too - 684, which do not contain any Water dilutable products when reacted with phosphoric acid and neutralization can nevertheless be codispersed in water (as such or esterified Resins) with (neutralized) reaction products according to the invention.

Further tests show that products that differ from DGEBA Derive resins with equivalent weights lower than DER - 667, not as dispersants are suitable for DERR - 684. However, essentially all are neutralized products according to the invention capable of substantial proportions of unreacted DGEBA Molecules of at least as high an epoxide equivalent weight as that derived from it dispersing dissipative neutralized products. Neutralized products after of the invention in which up to about 54% of the initial oxirane groups are absent converted, can be dispersed in water and give well usable Coatings. Assuming a statistical distribution of unreacted Oxirane groups in the resin molecules can be seen that a substantial proportion of the molecules all of their original oxirane groups unchanged in such products contains.

The compositions or compounds according to the invention can consequently additionally contain molecules of the formula (a) in which both oxirane groups are intact or one of them is intact and the other by a glycol or beta-hydroxyphosphomonoester group is replaced. The average molecular weight of these molecules is no more than about 10 times the average molecular weight of the molecules of formula (a) in which both oxiranes are replaced by glycol or beta-hydroxy ester groups have been replaced. (The ratio of epoxy equivalent weights for DER - / - 684 and DERV d - 667 is 13000/1550 or 8 4).

The proportion of such oxirane-containing molecules can be such that-about is one oxirane group per glycol or ester group in the composition. This means, that the number of oxirane groups can be as high as the total number of glycol and beta-hydroxyphosphomonoester groups.

The E2-type resins, which are derived from epoxies of formulas (b) to (p) derive are of great advantage for the practical implementation of the invention. Those epoxides in which R5 is an alkyl radical having 3 to 10 carbon atoms are particularly advantageous for the production of resins derived from E2 epoxies. Most preferred among the latter are those compounds in which p 1 and R5 is t-butyl or n-nonyl. Epoxies of this type give the mixed El and E2 resin dispersions have a better ability to wet hydrophobic substrates, such as aluminum substrates that are not oil-free.

The diglycidyl ether of 2,6,2 ', 6'-tetra (methoxymethyl) bisphenol-A is a preferred alkoxymethyl-substituted epoxide of formula (1) for preparation of dispersions of E2 resins.

The relative proportions of those derived from E1 and E2 epoxides Resins can be used within wider limits depending on the properties desired of the end product and its use, for example as a hardened tcr coating, sealant, surfactant or primer, will vary. In most applications an end product will be required whose properties are essentially the same of a resin derived from an -EI epoxy and the molar ratio of As a result, El to E2 epoxy will have a value up to about 100. In other In some cases, the E1 epoxy can do more as a modifier of the main epoxy component serve and the molar ratio of differing from El and E2 epoxies Derivative compounds in the final product can have a value up to about 0.1. In Cases in which the E2 epoxy or a low molecular weight El epoxy has a certain Any monomeric unit undergoes oligomerization during reaction with the acid in the oligomer as a single molecule when determining the El / E2 ratio viewed.

The content of free (unesterified) phosphoric acid in the mixed Products can also vary within wide limits, for example from 0 to about 85 parts by weight per 100 parts by weight of the molecules derived from epoxides. In general, however, a proportion of "free" acid of more than about 5% by weight is undesirable, if increased fire resistance is not desired or there is a desire, a significant amount of a dissociable base in a strongly acidic environment to be given off when heated. The content of the "free" acid is preferably 1 part by weight or less H3PO4 per 100 parts of molecules derived from epoxides.

Claims (10)

PROCESS FOR THE PRODUCTION OF WATER DILUTABLE, BASE-NEUTRALIZED ACID RESINS AND COMPOSITIONS OF SUCH RESINS Patent claims: 1.) Process for the production of water-dilutable, base-neutralized acidic resins which can be converted into hydrophobic hardened resins of high effectiveness, characterized in that (i) orthophosphoric acid is reacted with (1) a polyether-epoxy resin El consisting essentially of a diglycidyl ether of the formula or a monoglycidyl ether of the formula where Q is independent for each occurrence is, ñ is an integer from 0 to 40, r is independently for each occurrence O, 1 or 2, R1 is H, methyl or ethyl, R2 is-Br, -C1 or a C1C4 alkyl or alkenyl group, R3 is a C1C4 Alkylene or alkenylene group -C (CF3) 2-, -CO-, -SO2-, -S-, -0- or a valence bond, R4 is-Br, -C1 or a C1-C4 alkyl or alkenyl group and R20 is H or an alkyl group of 1-12 carbon atoms, and this reaction is carried out by contacting E1 with a source of orthophosphoric acid using 0-25 molar parts of water per mole of H3PO4 from the source Material until the proportion of oxirane groups in El is at least sufficiently converted to make the resulting product dilutable with water when it is brought into contact with a base, the amount of orthophosphoric acid included in this source as such or from it by hydrolysis available orthophosphoric acid is such that about 0.3 od er more acidic hydroxyl groups per oxirane group can be obtained and (ii) that the reaction product obtained is brought into contact with at least so much of a base that it can be diluted with water. 2.) Method according to claim 1, characterized in that in addition another vicinal epoxide E2, other than one of the formula (a) or (q), the one Has epoxy equivalent weight of 90-2000, with the source of orthophosphoric acid is reacted and is brought into contact with a base in the same way, like the polyether epoxy resin El, being the molar ratio of the epoxides E1 for E2 is 0.1 to 100. 3.) Process according to claim 1 or 2, characterized in that dioxane, Methyl ethyl ketone, acetone or a mixture of dichloromethane and acetone, the 25th Contains% by weight or less dichloromethane as a medium for the conversion of the phosphoric acid with the epoxy being used. 4.) The method according to claim 1 or 2, characterized in that the Base is an amine of the formula NR3, where each R is independently H, methyl or ethyl is. 5.) Process according to claim 2, characterized in that E2 is one or more compounds of the formulas (b) to C): (b) a methylol- or alkoxymethyl-substituted phenylglycidyl ether of the formula in which Y is H or C1-C4 alkyl or alkenyl, each YOCH2 group is either ortho or para to the glycidyloxy group, x is 1, 2 or 3, p is 0 or 1 and a is 1 or 2, R1 independently each time H, methyl or ethyl, R5 is a Cl-Cl2 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl, phenoxy, -Br, -Cl or a Is a group in which y is 0, 1 or 2, Y and R have the meaning already defined, T is a C1-C4 alkylene or alkenylene group, -C (CF3) -2, -SO2-, -S-, - 0 or a valence bond, R6 is -Br, -Cl or C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl or phenoxy group and t is 0 or 1, with the proviso that (x + a) 4 is not and (x + y) is 2 to 4, (c) a methylol or alkoxymethyl substituted (2,3-epoxy) propylbenzene of the formula in which b is 1 to 3, d O od R7 C1-C12 alkyl or Y 'is H or C1 to C4 alkyl or alkenyl, R1 is H, methyl or ethyl, with the proviso that (b + d) does not exceed 3; (d) Di- and trioxides of acyclic or cyclic, C4-C23 hydrocarbons or esters with 2 or 3 non-aromatic, carbon-carbon double bonds and optionally a -Br, -C1 or -F or hydroxyl substituent; (e) epoxy ethers of the formula R8-0-R9, in which R8 and R9 are identical or different monovalent radicals which are obtained by removing one hydrogen from an aliphatic, alicyclic or phenalkylene oxide; (f) 2,3-epoxypropyl halides, alcohols or esters of the formula in the A -Cl, -Br, -OH or R1 is -H, -CH3 or -C2H5 and R21 is a C1-C15 hydrocarbon group; (g) Glycol monoether of the formula and glycol dieters of the formula in which R1 is -H, -CH3 or -C2H5, R10 is -H or -CH3, X is -H, -CH3 or -C2H5, g is 1, 2 or 3 and h is an integer from 2 to 10; (h) diglycidyl ethers or esters of the formula in which R is a divalent hydrocarbon radical having 2 to 20 carbon atoms, R1 is -H, -CH3 or -C2H5 and i and j are independently O or 1; (i) Mono- or digylcidyl ethers of the formulas (j) mono-, di-, or triglycidyl ethers of glycerol; (k) Trifunctional aromatic epoxides of the formulas in which R12 is Cl-C2 alkoxy, C1-C6 alkyl or C2-C6 alkenyl, R¹³ is H, C1-C12 alkyl or C2-C12 alkenyl, R14 C1-C8 alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl in ortho- or para- Position to those Z-CH2 portions on the benzene ring to which this group is attached, R1 has the meaning already defined and R15 is a C1-C4 alkylene or alkenylene group or -SO2-; (1) Tetraglycidyl ether of the formula in R16 a C1 to C6 divalent aliphatic hydrocarbon radical, -SO2-, -S-, -0- or a valence bond and Z is (m) tri- or pentafunctional epoxy novolaks of the formula wherein p is 1 to 3, R17 is independently for each occurrence H or -CH3, R is an alkylene group having 1 to 4 carbon atoms and (n) methylol-substituted, oligomeric monoepoxides in which u is 0, 1, 2 or 3, R1 is independently H, methyl or ethyl for each occurrence and R19 is independently C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, phenalkyl or alkylphenyl for each occurrence; (o) epoxidized triglycerides of unsaturated fatty acids with up to 18 carbon atoms each and C) one to one adducts of substituted phenols with diglycidyl ethers of substituted bisphenols of the formula in which R¹, R², R³ and r have the meanings already defined for formula (a), Y, R5 and p have the meanings given for formula (b), v is 1, 2 or 3 and w is independent for each occurrence Is 0, 1 or 2. 6.) A water-dilutable phosphate resinous composition containing Ca) resin molecules, which are derived from the conversion into 1,2-glycol- or beta-Hydroypho sphormonoestergruppe n of the oxirane groups of an El epoxide Formulas (a) and (q) of claim 1, wherein the mean epoxy equivalent weight the epoxy molecules from which the resin molecules are derived is 172 to 5 500, (b) 0 to 85 parts by weight of orthophosphoric acid per 100 parts by weight of the resin molecules, (c) a base in an amount sufficient to contain at least the P-OH fractions in the resin molecules in the salt state, thereby the molecules to make dispersible in water. 7.) Composition according to claim 6, characterized in that it contains other molecules derived from conversion to 1,2-glycol or beta-hydroxyphosphoronic monoester groups of the oxirane groups of epoxy E2, another vicinal epoxide than the epoxides of formulas (a) and (q), the epoxide E2 being a Has epoxy equivalent weight of 90 to 2000, and the molar ratio of which is different from El derivable molecules to the molecules derivable from E2 at 0.1 to 100 lies. 8.) Composition according to claim 6 or 7, characterized that the numerical ratio of glycol to monoester groups in each type of molecule is from 0 to 18. 9.) Use of the composition according to claim 7 or 8 for the preparation of films or of coatings on a substrate. 10.) Use according to claim 9 with simultaneous dehydration, Salt formation and hardening on the substrate by heating.