BE579422A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



  "Intermolecular complexes of alkyd resins and epoxy resins and their manufacturing process".



   The present invention relates to intermolecular alkyd-epoxy complexes, derived from alkyd compounds and epoxy derivatives of unsaturated compounds, to the compositions formed therewith and their mixtures with various materials, to the methods of making these complexes. This invention relates more particularly to resinous complexes of epoxy resins, which can be diluted indefinitely in water (apparently water soluble), forming films and plastics, in the form of. an intermolecular arrangement of a modified resinous alkyd product and a compound derived from an epoxidized fatty acid, such as epoxy linseed oil or other epoxidized product derived from a fatty oil.



  This invention also relates to a process for the manufacture of these compounds in the form of a water-soluble system, and the products they allow to be obtained.



   The products of this invention are preferably used as vehicles in the coating compositions; they can be diluted with water, and they can form improved varnishes, paints and enamels.



  The preferred compositions of this invention polymerize into films possessing excellent adhesion, excellent internal cohesion (evidenced by

 <Desc / Clms Page number 2>

 flexibility), excellent tenacity, with a beautiful gloss and superior resistance to water, alkalines and chemicals, and it does not turn yellow significantly and its color does not tarnish by excessive aging. .



   The non-flammable vehicles constituting the products of this invention are particularly useful in cases where the coatings are factory applied and the use of conventional coating compositions results in fire hazards, and where regulations require the evacuation of harmful vapors.

   To get the
 EMI2.1
 For best results, the products of this invention are baked to polymerize the finished films, but baking is not required in all of the snacks. duction The present invention proposes to provide: - improved constituents for inducing compositions which appear to be soluble in water and which can therefore be diluted infinitely with water, said compositions and said constituents that can be used
Without danger of fire, and which give tenacious, durable and flexible films, exhibiting excellent resistance to water, alkaline substances, acids, excellent tenacity and resistant to weathering, abrasion, and repeated cycles of freezing and thawing,

   and very resistant to yellowing and retaining their color well when pigmented; methods of making such coating composition constituents and coating compositions; - complex resinous epoxy compositions based on oil, stable and soluble in water, containing a reactive epoxy group, and which can be diluted with water to apply them as a film, then dry and polymerize to make films insoluble in water; - epoxy fatty compounds, containing complexes, pigmented in white and soluble in water, in association with resinous products, and capable of being cooked to form the finished films;

   
In order to achieve these objects as well as related objects, the invention comprises the characteristics described in more detail in what follows and which are specific to it, the following description setting out in detail certain examples of forms of implementation. work serving as examples of the invention and improvements, these examples not being

 <Desc / Clms Page number 3>

 however, given only as an indication of the various ways in which the principle of the invention can be carried out.



   To manufacture intermolecular complexes of the alkyd resins modified with fatty acids described and epoxy compounds containing internal oxygen in oxirane form, and the compositions for coating of the present invention, the treatment comprises the following two operational stages: - Part 1 : In this part of the treatment, an alkyd resin modified with an oil is formed, containing a mono acid, an acid or a polybasic anhydride and a polyol in which a second polybasic anhydride is reacted with the monoacid complex. - polyacid-polyol having already reacted, so as to obtain a resinous half ester modified by an oil.

   These complexes all have a high acid number, between about 80 and 120 after the final reaction, with retention of a carboxyl group, e or more carboxyl groups which react with the epoxy groups.



    - Part 2: the second part of the treatment, reacting the resinous half-ester complex modified with an oil, after cooling and dilution with a mutual solvent miscible with water, with a long-chain fatty compound comprising internal oxygen of the oxyran type. This reaction is not continued until its completion, but is stopped by adding a neutral inhibitor and stabilizer, such as ammonia or an amine, preferably an alkyl amine, in which the alkyl radical comprises from 1 to 5 carbon atoms, for example triethylamine.

   In addition, in this part of the reaction, care is taken not to allow the reaction between the complex of Part 1 and the epoxy complex to go to completion, and, for this purpose, little can be added. in the desired proportions the epoxy compound and the inhibitor and neutralizing compound, while stirring and cooling well, because the reaction is exothermic. Periodic determinations of the acid number of the reacting mass and determinations of the clarity of the samples (once completely neutralized and diluted with water), as in the examples given elsewhere in this description, allow adequate control to be carried out.

   In. this part 2,

 <Desc / Clms Page number 4>

 the temperature should not be allowed to exceed about 93 ° C, and should preferably be maintained between 52 and 63 C for preferred reagents, as will be shown by examples.



   The end product of the reactions of parts 1 and 2 is an intermolecular complex of a long chain fatty compound, epoxidized, and a half ester of the oil-modified alkyd resin type existing as an oil-modified alkyd resin. 'a product neutralized by an amine of half an alkyd ester and an epoxidized long chain fatty substance, having partially reacted, contained in water and in an organic solvent miscible with the water. In the products finally obtained the viscosity normally depends on the proportion of liquid to solids. The preferred resulting viscosity is between 10 and about 30 stored for about 46% NV (non-volatile matter). The pH is approximately 7.2 to 9 and the color, according to the Gardner scale, is approximately 1 to 4.



   The products of the invention are mainly used as vehicles, for paints and enamels, which can be diluted by adding water, before or after direct grinding of the pigments in these products, and with or without the subsequent addition of a additional amount of water, for thinning, if desired or necessary, for film application. Films formed with the preferred water soluble vehicles can be polymerized at temperatures between 65 and 149 C, in 10 to 60 minutes or more. At lower temperatures, it is necessary to polymerize for a longer time.



  The preferred cooking program is to cook between
 EMI4.1
 é / 121 and 149g C, for 30 minutes. As discussed below, tough, high gloss films are obtained with excellent resistance to chemicals. As will be shown hereinafter in examples, still other resinous and compatible components can be incorporated.



   Residual reactive nuclei of the complex remain blocked by the inhibitor-neutralizer, during storage and even in finished paint or enamel.



  However, upon application as a film, and upon heating, the inhibitor-neutralizing agent is driven off and the final reaction occurs in situ in the film. The reaction includes a reaction between nuclei

 <Desc / Clms Page number 5>

 half-ester and the epoxy compound, resulting in the formation of the desired film, having the characteristics mentioned above. All this happens without the risk of fire.



   As explained, the base resin is a modified alkyd resin. In order to avoid yellowing, the modification is carried out with saturated fatty acids.



   The following examples further illustrate how to make the products of this invention, but it is understood that these examples are given for explanatory purposes only, and should not be construed as limiting the present invention.



   Example I
 EMI5.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Pelargonic <SEP> <SEP> 210
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 224
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> <SEP> phthalic anhydride <SEP> 285
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> (optional) <SEP> 1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 63
<tb>
<tb>
<tb>
<tb> (optional)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> F. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 188
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> G.

   <SEP> Ether <SEP> monobutyl <SEP> of <SEP> ethylene <SEP> 312
<tb>
<tb>
<tb>
<tb> glycol
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1283
<tb>
 
 EMI5.2
 
<tb> Viscosity <SEP> 80 <SEP> stokes
<tb>
<tb> No <SEP> volatile <SEP> 69%
<tb>
<tb> <SEP> acid index <SEP> 94 <SEP> (on <SEP> not <SEP> volatile)
<tb>
 
 EMI5.3
 
<tb> PART <SEP> 2 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> Alkyd <SEP> <SEP> of <SEP> base <SEP> of <SEP> ester
<tb>
<tb>
<tb>
<tb> Part <SEP> 1 <SEP> 250
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Triethylamine <SEP> 23.5
<tb>
<tb>
<tb>
<tb> B. <SEP> Epoxidized <SEP> Linseed <SEP> Oil <SEP>
<tb>
<tb>
<tb> (at <SEP> 8.5 <SEP>% <SEP> oxygen <SEP> in <SEP> form <SEP> oxyran) <SEP> 68.8
<tb>
<tb>
<tb>
<tb> C.

   <SEP> Water <SEP> 181.7
<tb>
<tb>
<tb>
<tb>
<tb> 524.0
<tb>
 
 EMI5.4
 
<tb> Viscosity <SEP> 17.3 <SEP> stokes'
<tb>
<tb> No <SEP> volatile <SEP> 46 <SEP>%
<tb>
<tb> hH <SEP> 8.33
<tb>
<tb> color <SEP> (Gardner) <SEP> 2-3
<tb>
 

 <Desc / Clms Page number 6>

 Example II
 EMI6.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> -weight
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> <SEP> fatty acids <SEP> of <SEP> coconut <SEP> 190
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 200
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> <SEP> phthalic anhydride <SEP> 285
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> (optional)
<tb>
<tb>
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether. <SEP> of <SEP> diethylene <SEP> glycol <SEP> 63
<tb>
<tb>
<tb>
<tb> (optional)
<tb>
<tb>
<tb>
<tb>
<tb> F.

   <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 188
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> G. <SEP> Ether <SEP> monobutyl <SEP> of <SEP> ethylene <SEP> glycol <SEP> 315
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1242
<tb>
 
 EMI6.2
 
<tb> Viscosity <SEP> 75 <SEP> stokes
<tb> No <SEP> volatile <SEP> 68 <SEP>% <SEP>
<tb>
<tb> <SEP> acid index <SEP> 104 <SEP> (on <SEP> not <SEP> volatile)
<tb>
 
 EMI6.3
 
<tb> Part <SEP> 2 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb> Alkyd <SEP> <SEP> of <SEP> base <SEP> of <SEP> ester
<tb>
<tb>
<tb> part <SEP> 1 <SEP> 250
<tb>
<tb> A. <SEP> triethylamine <SEP> 24.8
<tb>
<tb>
<tb> B. <SEP> Epoxidized <SEP> Linseed <SEP> <SEP> <SEP> oil (at <SEP> 8% <SEP> oxygen
<tb>
<tb> in <SEP> form <SEP> oxyran) <SEP> 60
<tb>
<tb>
<tb> C.

   <SEP> Water <SEP> 166.5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 501.3
<tb>
 
 EMI6.4
 
<tb> Viscosity <SEP> 21 <SEP> stokes
<tb>
<tb> No <SEP> volatile <SEP> 46.5 <SEP>% <SEP>
<tb>
<tb> pH <SEP> 8.5 <SEP> '<SEP>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 3
<tb>
 
In each of the above examples, components (A), (B), (C), (D) and (E), of part 1, are mixed and reacted to form the ester d alkyd by a conventional method of esterification of alkyds. The process consists essentially in mixing and heating in the usual manner, between 177 and 204 ° C., the compounds (A) to (E), until the desired acid number is obtained.

   Acid number determinations are carried out according to the classic Gardner test method at given time intervals on samples of the reaction products. Maleic anhydride is preferably used, but it can be dispensed with if desired. In its place, but less preferably, other mono and diacids unsaturated in alpha-beta can be used. Preferably, an inert, water-miscible solvent such as ether (E) is used. We can however

 <Desc / Clms Page number 7>

 change from this solvent, in some cases, or replace it with another non-reactive solvent.



   After the acid number, determined by conventional test methods, has dropped to about 70 to 90, the reaction mixture is cooled. 135 C, or less, and tetrachlorophthalic anhydride (F) is added.



  The temperature is raised again to 177-190 ° C. and maintained for about 15 to 30 minutes, to form a partial ester or half ester of the prepared alkyd and tetrachlorophthalic acid, with retention of an acid. - Residual content equivalent to at least one carboxyl group.



  Once the elm half-ester is finished, the fatty oil-modified alkyd resin is cooled to 121 ° C. or less, the water-miscible solvent (G) is added while stirring, and then cooled to 'below about 54 ° C.



   The components of Part 2 are then added to the tetrachlorophthalic half-ester of Part 1, and preferably as follows: approximately one third of the triethylamine (A), inhibitor and stabilizer is added. , and mixed to prepare the half ester with the addition of the epoxy component (B) which is then added.

   In varian
 EMI7.1
 During this, the inhibitor may first be mixed, in an approximate proportion, as indicated, with the reaction compound. then this mixture produces sufficient reaction and then add this mixture to the product of the reaction of Part 1 while stirring. to lower the index The addition of the epoxy component B causes an acid rise in temperature due to an exothermic reaction, 6 to 12 points in- and this temperature is maintained between 60 and 63g C approximately, ron , and preferably about 8-10 points, as could be determined approximately by a method of normally measuring samples from time to time.

   Another method of measurement, to determine the clarity and the final term of the reaction, is as follows:
About 50 g of the complex are taken, the content of non-volatile compounds and the acid number of which are known.



  This sample contains part of the amine used as an inhibitor and stabilizer. The acidity is further neutralized to a pH of 7.8 with an additional amount of the same amine. The non-volatiles content of the amine neutralized sample is reduced to 15% by addition of water. Excessive opacity of this solution indicates that it is necessary to continue the reaction.



  If the opacity of the 15% solution is such that a newspaper can be read through a thickness of about 38 mm, the preparation reaction is considered to be substantially complete.

 <Desc / Clms Page number 8>

 



   By the time the desired clarity is reached, as shown in the sample. When tested, the supplement of the amine is added to stop the reaction. Then the vehicle is diluted with water (C), about 5-10 minutes after the last addition of the amine.



   It has been found that the alkyd resin-epoxy complexes of Examples 1 and 2 can be used immediately or they can be stored for later use.



  In order to use them as a vehicle for paints and enamels, pigments are easily ground in these complexes using conventional paint grinding plants. The pigmented product can be stored for a long time and indefinitely without affecting its properties as a coating.



   As indicated, the above alkyd resin-epoxy complexes, diluted with water, are preferably used as a vehicle for varnishes, paints and enamels, in which the vehicle is easier to incorporate.
 EMI8.1
 pigment or coloring matter, as in the case of Example 'WI4 It has been found that the water-soluble alkyd resin-epoxy complexes, when properly polymerized, are essentially colorless or clear. like water, and resist yellowing, when overheated, better than Lor-Isly expected. This property makes these vehicles useful for making emaus used on refrigerators, washing machines, stoves, appliances. sanitary facilities, etc ...



   Below are other examples of alkyd-epoxy resin complexes, soluble in water:
Example III
 EMI8.2
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> Components
<tb>
<tb>
<tb>
<tb> A. <SEP> Oil <SEP> fatty acids <SEP> <SEP> from <SEP> tall <SEP> 105
<tb>
<tb> (at <SEP> low <SEP> content <SEP> in <SEP> resin)
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 80
<tb>
<tb>
<tb> C. <SEP> Phthalic anhydride <SEP> <SEP> 110
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> 1.6
<tb>
<tb>
<tb> E. <SEP> Diethyl ether <SEP> from <SEP> diethylene <SEP> glycol <SEP> 24
<tb>
<tb>
<tb>
<tb> F. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 72
<tb>
<tb>
<tb> G.

   <SEP> Monobutyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 128
<tb>
 
This complex is made as set forth in the present description.



   The oil-based epoxy resin complex is made, which can be infinitely diluted or dissolved in water, by controlled addition of the [following components,

 <Desc / Clms Page number 9>

 Constituting an addition to the reaction product of Part 1 of the mixture, namely:
 EMI9.1
 
<tb> Part <SEP> 2 <SEP> Parts <SEP> in <SEP> "weight
<tb>
<tb>
<tb> A. <SEP> Epoxidized <SEP> Linseed <SEP> Oil <SEP> <SEP> 73
<tb>
<tb> (at <SEP> 8.3 <SEP>% <SEP> of oxyrane)
<tb>
<tb>
<tb> B. <SEP> Triethylamine <SEP> 62
<tb>
<tb>
<tb> C. <SEP> Water <SEP> (from <SEP> tap) <SEP> 320
<tb>
 
This addition is carried out as described.



   The compositions are made as described and the mixture is reacted as indicated.



   Example IV
 EMI9.2
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> <SEP> components: <SEP>
<tb>
<tb>
<tb> A. <SEP> Soy <SEP> fatty <SEP> <SEP> <SEP> <SEP> 406
<tb>
<tb>
<tb> B. <SEP> Pentaerythritol <SEP> 312
<tb>
<tb>
<tb> C. <SEP> Phthalic anhydride <SEP> <SEP> 425
<tb>
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> -4
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 94
<tb>
<tb>
<tb> F. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 281
<tb>
<tb>
<tb> G. <SEP> Monobutyl <SEP> ether <SEP> of <SEP> ethylene <SEP> gly- <SEP> 500
<tb>
<tb> col
<tb>
 
React and fabricate as described.



   The modified alkyd base made in Part 1 is then ready for the production of the water soluble epoxy resin complex formed in Part 2, which consists of a partial reduction of an epoxy oil with the product of the reaction of Part 1, as follows:

   
 EMI9.3
 
<tb> Part <SEP> 2. <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Base <SEP> of ester <SEP> alkyd <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 345
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Triethylamine <SEP> 32.5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (at <SEP> 8.3 <SEP>% <SEP> 50
<tb>
<tb>
<tb>
<tb>
<tb> of oxyrance)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Water <SEP> 204
<tb>
 This product is made as described.

   
 EMI9.4
 
<tb> Viscosity <SEP> 10.3 <SEP> stokes
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 47 <SEP>% <SEP>
<tb>
<tb> pH <SEP> 8.4
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 5
<tb>
 

 <Desc / Clms Page number 10>

   This water-soluble epoxy complex is preferably pigmented, but it can be used in bulk or clear, heat-cured topcoat.



  Otherwise, if desired, the composition is applicable, like other analogous complexes, in the plastic hot-molding industry, or as a water-soluble adhesive product in the sterile industry. in other techniques and, in each of these cases, it is heat polymerized to bring it to a water insoluble state.



   Further examples illustrating various reaction components applicable in the manufacture of water-soluble epoxy resin complexes, and half-ester alkyd and epoxidized oil compositions will be found in the following. These epoxy complexes, as well as others already described, are also components for plastics, adhesives and other compositions, including vehicles for varnishes, paints and enamels as described herein:

   
Example V
 EMI10.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> A. <SEP> <SEP> fatty acids <SEP> from <SEP> lin <SEP> 330
<tb>
<tb>
<tb> B. <SEP> Glycerol <SEP> 280
<tb>
<tb>
<tb> C. <SEP> Phthalic anhydride <SEP> <SEP> 425
<tb>
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> 5
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 97
<tb>
<tb>
<tb> F. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 280
<tb>
<tb>
<tb> G. <SEP> Monoethyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 460
<tb>
 
Viscosity 125 stokes
Non-volatile matter 70%
Acid number 91 (on non-volatile materials) Part 2.
 EMI10.2
 
<tb>



  A. <SEP> resin <SEP> alkyd <SEP> of <SEP> base <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 345
<tb> B. <SEP> Triethylamine <SEP> 33
<tb>
<tb> C. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (at <SEP> 8.3% <SEP> of oxyran) <SEP> 72.5
<tb>
<tb> D. <SEP> Water <SEP> 228
<tb>
 
 EMI10.3
 
<tb> Viscosity <SEP> 25 <SEP> stores
<tb>
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 47 <SEP>% <SEP>
<tb>
<tb>
<tb> pH <SEP> 8.2
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 4
<tb>
 

 <Desc / Clms Page number 11>

 Example VI
 EMI11.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Oil <SEP> fatty acid <SEP> <SEP> from <SEP> tall <SEP> 367
<tb>
<tb>
<tb>
<tb> B. <SEP> Trimethylolethanol <SEP> 162
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> Sorbitol <SEP> 140
<tb>
<tb>
<tb>
<tb>
<tb> D.

   <SEP> Phthalic anhydride <SEP> <SEP> 425
<tb>
<tb>
<tb>
<tb> E. <SEP> Maleic anhydride <SEP>
<tb>
<tb>
<tb>
<tb> F. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 94
<tb>
<tb>
<tb>
<tb>
<tb> G. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 280
<tb>
<tb>
<tb>
<tb> H. <SEP> Monobutyl <SEP> ethylene <SEP> <SEP> ether <SEP> glycol <SEP> 480
<tb>
 
Viscosity 100 stokes
Non-volatile matter 69.1%
Acid number 87 (on non-volatile matter) Part 2
 EMI11.2
 
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 345
<tb>
<tb> B. <SEP> Dimethylethanolamine <SEP> 31
<tb>
<tb>
<tb> C. <SEP> Soybean <SEP> <SEP> <SEP> epoxidized <SEP> oil (6.2% <SEP> in <SEP> oxyran) <SEP> 67.5
<tb>
<tb>
<tb> D.

   <SEP> Water <SEP> 228.7
<tb>
 
 EMI11.3
 
<tb> Viscosity <SEP> 22 <SEP> stokes
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 46 <SEP>%
<tb>
<tb> pH <SEP> 8.0
<tb>
<tb> Color <SEP> (Gardner) <SEP> 3+
<tb>
 Example VII
 EMI11.4
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> A. <SEP> Soy <SEP> fatty <SEP> <SEP> <SEP> <SEP> 120
<tb>
<tb> B. <SEP> Mono-pentaerythritol <SEP> 58
<tb>
<tb> C. <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 170
<tb>
<tb> D. <SEP> Monobutyl <SEP> ethylene <SEP> <SEP> ether <SEP> glycol <SEP> 45
<tb>
 
Viscosity 22 stokes
Non-volatile matter 77.5%
Acid number 88.7 (on non-volatile matter) Part 2
 EMI11.5
 
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 312
<tb>
<tb> B. <SEP> Dimethylethanolamine <SEP> 31
<tb>
<tb> C.

   <SEP> Soybean <SEP> <SEP> <SEP> epoxidized <SEP> oil (6.2% <SEP> in <SEP> oxyran) <SEP> 70
<tb> D. <SEP> Water <SEP> 267
<tb>
 
 EMI11.6
 
<tb> Viscosity <SEP> 10 <SEP> stokes
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 46 <SEP>%
<tb>
<tb>
<tb> pH <SEP> 8.5
<tb>
<tb> Color <SEP> (Gardner) <SEP> 6
<tb>
 

 <Desc / Clms Page number 12>

 Example VIII
 EMI12.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb> A. <SEP> Castor oil <SEP> fatty acids <SEP> <SEP> <SEP>
<tb>
<tb>
<tb> dehydrated <SEP> 365
<tb>
<tb>
<tb> B. <SEP> krono-p <SEP> e-nt <SEP> erythritol <SEP> 310
<tb>
<tb>
<tb>
<tb> C. <SEP> Phthalic anhydride <SEP> <SEP> 485
<tb>
<tb> D. <SEP> Melic anhydride <SEP> <SEP> 3
<tb>
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 94
<tb>
<tb>
<tb> F.

   <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 165
<tb>
<tb>
<tb> G. <SEP> Monobutyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 490
<tb>
 Viscosity 215 stokes Non-volatile matter 69% Acid number 89.8 (on non-volatile matter) Part 2.
 EMI12.2
 
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base <SEP> of <SEP> the <SEP> Parie <SEP> 1 <SEP> 250
<tb>
<tb> B. <SEP> Triethylamine <SEP> 24
<tb>
<tb> C. <SEP> <SEP> Linseed <SEP> oil <SEP> epoxidized <SEP> (at <SEP> 8.3% <SEP> of oxyrane) <SEP> 36
<tb>
<tb> D.

   <SEP> Water <SEP> 143
<tb>
 
 EMI12.3
 
<tb> Viscosity <SEP> 18 <SEP> stokes
<tb>
<tb>
<tb> Non-volatile <SEP> <SEP> <SEP> 46.5%
<tb>
<tb>
<tb>
<tb>
<tb> pH <SEP> 7.4
<tb>
<tb>
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 3+
<tb>
 
The method of making each water-soluble half-ester alkyd resin and the addition reaction with the latter of an epoxidized fatty oil, are the same as in Example III above, in. except Part 1 of Example VII.



   In Part 1 of Example VII there is described a variant of the batch process of adding excess tetrachlorophthalic anhydride in place of phthalic anhydride. In the preferred process, this eliminates cooling before adding dibasic anhydride. The reaction conditions and temperature are similar, with the difference that the reaction time is reduced by about 1 hour.



  However, with the excess tetrachlorophthalic anhydride used, there will be both diester and half ester formation; the viscosity adjustment is more uncertain and it is found that the compositions are more unstable and that they are subject to gelation during

 <Desc / Clms Page number 13>

 of the reaction, if great care is not taken to prevent overheating. In general, it can be stated that the preferred method of this invention is to apply the procedure of Part 1 of Examples I to IV.



   Example IX Part 1
An alkali-refined soybean oil alcoholysis product is first made by mixing 226 parts of soybean oil and 54 parts of monpentaehythmritol and 0.10 part by weight of sodium hydroxide. lithium, and heating the mixture for half an hour at 232 C. The following components are added to the above product:
 EMI13.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> <SEP> phthalic anhydride <SEP> 285
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 112
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> Maleic anhydride <SEP> <SEP> 1.5
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 63
<tb>
 
 EMI13.2
 B.

   Tetrachlorophthalic anhydride, 188
 EMI13.3
 
<tb> F. <SEP> Monobutyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 300
<tb>
 
The above reaction product is made as described in Examples 1 to 3. This consists essentially of first treating the product of the alcoholic soybean oil, with components (A), (B), (C) and (D), as in an alkyd manufacture, as described, after which component (E) is added, the mixture is heated to 177-1880 C, and the process is continued. react until having an acid number of about 86. The reaction mixture is then cooled to about 1210 ° C. and part (F) is added.

   The constants of this composition are as follows:
Viscosity 83 stokes
Non-volatile matter 69.3%
Color (Gardner) 5+
Acid number 102 (on non-volatile materials)

 <Desc / Clms Page number 14>

 
 EMI14.1
 
<tb> Part <SEP> 2 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base, <SEP> Part <SEP> 1 <SEP> 250
<tb>
<tb>
<tb> B. <SEP> Triétbylamine <SEP> 25
<tb>
<tb>
<tb> C. <SEP> Epoxidized <SEP> Linseed <SEP> Oil <SEP> <SEP> (8.3%) <SEP> 60.7
<tb>
<tb>
<tb>
<tb> D. <SEP> Water <SEP> 173.3
<tb>
 
The treatment of Part 2 is the same as that described above, essentially half an hour at 63 C, and it gives a complex of water-soluble resin, of an epoxidized long fatty chain compound, derived from an oil or an oil-based substance.

   The constants of the product. final are the following:
Viscosity 7.5 stokes pH 7.6
Infinitely soluble in water.



   Example X
 EMI14.2
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> A. <SEP> Oil <SEP> fatty acids <SEP> <SEP> from <SEP> tall <SEP> 130
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 100
<tb>
<tb>
<tb> C. <SEP> Phthalic anhydride <SEP> <SEP> 135
<tb>
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> 2
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 30
<tb>
<tb>
<tb> F. <SEP> Chlorendic anhydride <SEP> <SEP> II)
<tb>
<tb>
<tb> G.

   <SEP> Monobutyl <SEP> ethylene <SEP> <SEP> ether <SEP> glycol <SEP> 124
<tb>
 
 EMI14.3
 
<tb> Viscosity <SEP> 240 <SEP> stokes
<tb>
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 76 <SEP>% <SEP>
<tb>
<tb>
<tb> <SEP> acid index <SEP> 91.2 <SEP> (on <SEP> materials
<tb>
<tb>
<tb> -non <SEP> volatiles)
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 3-4
<tb>
 Part 2
 EMI14.4
 
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base, <SEP> Part <SEP> 1 <SEP> 230
<tb>
<tb> B. <SEP> Triethylamine <SEP> 24
<tb> C. <SEP> Epoxidized <SEP> Linseed <SEP> Oil <SEP>
<tb>
<tb> (Oxyrane <SEP> index <SEP> 8.3%) <SEP> 61
<tb>
<tb> D.

   <SEP> Water <SEP> 200
<tb>
 
 EMI14.5
 
<tb> Viscosity <SEP> 14 <SEP> stokes
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 46 <SEP>% <SEP>
<tb>
<tb> pH <SEP> 7.8
<tb>
 
The above product is made in the manner already described and this product is a further example of the epoxidized, water-soluble oil-based resin complex described herein.



   Below are other examples of a modification:

 <Desc / Clms Page number 15>

 Example XI
 EMI15.1
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb> A. <SEP> Oil <SEP> fatty acids <SEP> <SEP> from <SEP> tall <SEP> 112
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 102
<tb>
<tb>
<tb>
<tb> C. <SEP> <SEP> phthalic anhydride <SEP> 143
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> 1
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> from <SEP> diethyl <SEP> ethylene
<tb>
<tb>
<tb> glycol <SEP> 30
<tb>
<tb> F. <SEP> Monochlorophthalic anhydride <SEP> <SEP> b5
<tb>
<tb>
<tb> G.

   <SEP> Monobutyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 150
<tb>
 
(A), (B), (C), (D) and (E) are reacted in the usual manner, as described, until the acid number is 75, and add (F) to 135 ° C. The mixture is heated to 17-1882-C for 30 minutes, cooled to 93 C and added (G).



   The results of the analysis of the product obtained are as follows:
Viscosity 190 stokes
Non-volatile matter 68.5%
Acid number 105 (on non-volatile materials)
 EMI15.2
 
<tb> Part <SEP> 2 <SEP> Parts <SEP> in <SEP> -weight
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base, Part <SEP> 1 <SEP> 200
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Triethylamine <SEP> 5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (index
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> d'oxyrane <SEP> 8,3) <SEP> 49
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Triethylamine <SEP> 17
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> E. <SEP> Water <SEP> 137
<tb>
 
The components (A), (B) and (C) are reacted as explained;

   the temperature is maintained at 52 ° C. for an hour and a half, then (D) is added while cooling. After 5 to 10 minutes, add (E) while stirring well. The product features are as follows:
 EMI15.3
 
<tb> Viscosity <SEP> 9.9 <SEP> stokes
<tb>
<tb>
<tb> pH <SEP> 7.3
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2-3
<tb>
 Example XII
 EMI15.4
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> -weight
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Pelargonic <SEP> <SEP> 190
<tb>
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritel <SEP> 220
<tb>
<tb>
<tb>
<tb> C. <SEP> <SEP> phthalic anhydride <SEP> 285
<tb>
<tb>
<tb>
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> 1
<tb>
<tb>
<tb>
<tb> E. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 63
<tb>
<tb>
<tb>
<tb>
<tb> F.

   <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 188
<tb>
<tb>
<tb>
<tb> G. <SEP> Monobutyl <SEP> ethylene <SEP> <SEP> ether <SEP> glycol <SEP> 285
<tb>
 

 <Desc / Clms Page number 16>

 
React from (A) to (E) in the usual way, as discussed, between 177 and 1999 C, until the acid number is 80, cool to 135 C and we add (F). The mixture is again heated to 177-1889 C for half an hour, cooled to 93 C and added (G). The product features are as follows:
 EMI16.1
 
<tb> Viscosity <SEP> 117 <SEP> stokes
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 1-2
<tb>
<tb>
<tb> <SEP> acid index <SEP> 103 <SEP> (on <SEP> materials <SEP> no
<tb>
<tb>
<tb> volatiles)
<tb>
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 68.8 <SEP>%.
<tb>
 



   Alternatively, other inhibitors, of a less preferred nature for some compositions, can be used to make water soluble alkyd epoxy resins.



   Variants which are in no way limiting, showing the use of ammonia and various amines as stabilizing agents will be found below:
 EMI16.2
 
<tb> Part <SEP> 2a <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb> A. <SEP> Resin <SEP> alkyd <SEP> of <SEP> base, <SEP> Part <SEP> 1 <SEP> 250
<tb>
<tb>
<tb> B. <SEP> Ammonia <SEP> to <SEP> 28 <SEP> on. <SEP> 3.9
<tb>
<tb>
<tb> C. <SEP> Epoxidized <SEP> Linseed <SEP> Oil <SEP> <SEP> 70
<tb>
<tb> (<SEP> to <SEP> 8.3 <SEP>% <SEP> of oxyrane)
<tb>
<tb>
<tb>
<tb> D. <SEP> Ammonia <SEP> to <SEP> 28 <SEP>% <SEP> 11
<tb>
<tb>
<tb> E. <SEP> Water <SEP> 197
<tb>
 
Components (A), (B) and (C) were reacted as explained and the temperature was maintained at 52 for one hour. Then (D) is added while cooling.



  After 10 minutes, add (E) while stirring well. Examination of the product gives the following results:
 EMI16.3
 
<tb> Viscosity <SEP> 28 <SEP> stokes
<tb>
<tb>
<tb> pH <SEP> 7.75
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2 <SEP> +
<tb>
 Part 2b
 EMI16.4
 
<tb> A. <SEP> Resin <SEP> of <SEP> the <SEP> part <SEP> 1 <SEP> 250
<tb>
<tb> B. <SEP> N-methyl <SEP> morpholine <SEP>. <SEP> 6.5 <SEP>
<tb>
<tb> C. <SEP> <SEP> Linseed <SEP> oil <SEP> epoxidized <SEP> (at <SEP> 8.0% <SEP> of oxyrane) <SEP> 70
<tb>
<tb> D. <SEP> N-methyl <SEP> morpholine <SEP> 18.4
<tb>
<tb> E. <SEP> Water <SEP> 187.6
<tb>
 
Components (A), (B) and (C) are reacted at 52 ° C. for one hour, then (D) is added with cooling. After 10 minutes, add (E) while stirring well.

 <Desc / Clms Page number 17>

 



  Examination of the product gives the following results:
 EMI17.1
 
<tb> Viscosity <SEP> 14 <SEP> stokes
<tb>
<tb> pH <SEP> 6.5
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2
<tb>
 PART 2c
 EMI17.2
 
<tb> A. <SEP> Resin <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 250
<tb>
<tb>
<tb> B. <SEP> Diethylethanolamine <SEP> 7.5
<tb>
<tb>
<tb>
<tb> C. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (at <SEP> 8.5 <SEP>% <SEP> 7
<tb>
<tb>
<tb>
<tb> of oxyrane)
<tb>
<tb>
<tb>
<tb> D. <SEP> Diethylethanolamine <SEP> 21.3
<tb>
<tb>
<tb>
<tb> E. <SEP> Water <SEP> 183.6
<tb>
 
The process is the same as in part 2 b.



  Examination of the product gives the following results:
 EMI17.3
 
<tb> Viscosity <SEP> 13 <SEP> stokes
<tb>
<tb> pH <SEP> 7.7
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2
<tb>
 Part 2d
 EMI17.4
 
<tb> A. <SEP> Resin <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 250
<tb>
<tb>
<tb>
<tb> B. <SEP> Dimethylethanol <SEP> amine <SEP> 8
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (at <SEP> 8.3 <SEP>% <SEP> 70
<tb>
<tb>
<tb> of oxyrane)
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Dimethylethanol <SEP> amine <SEP> 23
<tb>
<tb>
<tb>
<tb>
<tb> E. <SEP> Water <SEP> 181
<tb>
 
The process is the same as in Part 2b.



  Product analysis gives the following results:
 EMI17.5
 
<tb> Viscosity <SEP> 13 <SEP> stokes
<tb>
<tb>
<tb> pH <SEP> 8.2
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2+
<tb>
 Example XIII
 EMI17.6
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> A. <SEP> Pelargonic <SEP> <SEP> 190
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 165
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C. <SEP> Ethylene <SEP> glycol <SEP> 50
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> D. <SEP> Tetrahydrophthalic anhydride <SEP> <SEP> 290
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> E. <SEP> Maleic anhydride <SEP> <SEP> 1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> F. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 63
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> G.

   <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 188
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> H. <SEP> Monobutyl <SEP> ethylene <SEP> <SEP> ether <SEP> glycol <SEP> 295
<tb>
 
This production is carried out as explained in Example 1; it generally consists of a conventional alkyd esterification for components (A) to (F), esterified between 183 and 2049-C until the acid number is 75 The alkyd is then cooled to 135 C, (G) is added and the mixture is heated to 188 C to form the half ester of the alkyd which is cooled to 93 C by adding -1 'ether (H).

 <Desc / Clms Page number 18>

 



  Product analysis gives the following results:
 EMI18.1
 
<tb> Non-volatile <SEP> <SEP> materials <SEP> 69.7 <SEP>% <SEP>
<tb>
<tb>
<tb> Viscosity <SEP> 26.5 <SEP> stokes
<tb>
<tb>
<tb> Color <SEP> (Gardner) <SEP> 1-2
<tb>
<tb>
<tb> <SEP> acid index <SEP> 88 <SEP> (on <SEP> materials
<tb>
<tb>
<tb> no <SEP> volatile <SEP>) <SEP>
<tb>
 Part 2.
 EMI18.2
 
<tb>



  A. <SEP> Product <SEP> of <SEP> the <SEP> part <SEP> 1 <SEP> 250
<tb>
<tb> B. <SEP> Epoxidized <SEP> Linseed <SEP> <SEP> <SEP> <SEP> 61
<tb> C. <SEP> Triethylamine <SEP> 21.7
<tb>
<tb> D. <SEP> Water <SEP> 178.3
<tb>
 
The reaction product of Part 2 is made in the manner indicated above, which generally consists of charging component (A) and 25% of component (C) into a reactor, heating to 52 ° C. , add (B) and maintain the temperature at 52 ° C for one hour.

   The remainder of (C) is then added and, after 10 minutes, the water (D) is added while mixing well and re-mixing.
 EMI18.3
 cooling. Analysis of the product gives the following results:
 EMI18.4
 
<tb> Non volatile <SEP> <SEP> materials <SEP> 4b <SEP>%
<tb> Viscosity <SEP> 5,2 <SEP> stores
<tb> pH <SEP> 7.5
<tb> Color <SEP> (Gardner) <SEP> 2-
<tb>
 Example XIV
 EMI18.5
 
<tb> Part <SEP> 1 <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb> A. <SEP> Oil <SEP> fatty <SEP> <SEP> from <SEP> tall <SEP> (poor <SEP> 270
<tb> in <SEP> resin)
<tb>
<tb> B. <SEP> Monopentaerythritol <SEP> 210
<tb>
 
 EMI18.6
 C.-Tetrahydrophta anhydride? ic 290
 EMI18.7
 
<tb> D. <SEP> Maleic anhydride <SEP> <SEP> - <SEP> 1.5 <SEP>
<tb> e. <SEP> Diethyl <SEP> ether <SEP> of <SEP> diethylene <SEP> glycol <SEP> 64
<tb>
<tb>
<tb> F.

   <SEP> Tetrachlorophthalic anhydride <SEP> <SEP> 188
<tb>
<tb> G. <SEP> Monobutyl <SEP> ether <SEP> of <SEP> ethylene <SEP> glycol <SEP> 340
<tb>
 
A modified alkyd ester is made using the above components as described in Example 13. This manufacture generally consists of a conventional alkyd esterification of components (A) a between 182 and 204 C, until the acid number is 78.



  The alkyd is then cooled to 135 C, then component (F) is added and the mixture is heated to 1909 C, to form the half-ester with a residual acidity which is determined as already mentioned. indicated. The modified alkyd is then cooled to 93 ° C., (G) is added and the mixture is thoroughly mixed until a homogeneous solution is obtained. The modified alkyd ester has the following characteristics:

   

 <Desc / Clms Page number 19>

 
 EMI19.1
 
<tb> Non-volatile <SEP> <SEP> <SEP> 70.5 <SEP>%
<tb>
<tb> Viscosity <SEP> 63.5 <SEP> stokes
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2-3
<tb>
<tb> Index <SEP> of aciue <SEP> (on <SEP> materials <SEP> no <SEP> 88
<tb>
<tb> volatiles)
<tb>
 Part 2
 EMI19.2
 
<tb> A. <SEP> Product <SEP> of <SEP> the <SEP> Part <SEP> 1 <SEP> 250
<tb>
<tb> B. <SEP> Epoxidized <SEP> flaxseed <SEP> oil <SEP> <SEP> (at <SEP> 8.5% <SEP> of oxyrane) <SEP> 61
<tb>
<tb> C. <SEP> Dimethylethanol <SEP> amine <SEP> 19.5
<tb>
<tb> D. <SEP> Water <SEP> @ <SEP> 185.5
<tb>
 
 EMI19.3
 The alkyd-epoxy complex is made in the same manner as in part 2 of Example 13.

   The vehicle complex gave the following results for the examination:
 EMI19.4
 
<tb> Viscosity <SEP> 15 <SEP> stokes
<tb>
<tb> pH <SEP> 7.6
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2
<tb>
<tb> Non-volatile <SEP> <SEP> materials <SEP> 46 <SEP>% <SEP>
<tb>
   Example XV
In this example, a modified alkyd ester of Example 12 is made, and modified with an epoxidized long chain fatty acid ester. The components forming part 2 of the above compositions comprise 250 parts of the modified alkyd base of Example 12.71 parts of the epoxy ester of pentaerythritol and flaxseed fatty acid (8.5% flax). oxyran), 24 parts triethylamine and 197 parts water.

   This epoxy modified alkyd-ester complex, which can be diluted indefinitely with water, is made in the same manner as described in Examples 14 and 15.



  Examination of the vehicle complex gives the following results:
 EMI19.5
 
<tb> viscosity <SEP> 17.5 <SEP> stokes
<tb>
<tb> pH <SEP> 8.3
<tb>
<tb> Color <SEP> (Gardner) <SEP> 2 <SEP> +
<tb>
<tb> Non-volatile <SEP> <SEP> <SEP> 46%
<tb>
 
This epoxidized ester is an example of epoxidized esters of the nature described for making compositions and products as made and considered herein.



  Components of Part 1
Base oil components incorporated in alkyd resins are examples of long chain fatty acids and esters, saturated and unsaturated, derived from oils.

 <Desc / Clms Page number 20>

 fats of vegetable, animal and marine origin, the fatty chain of which comprises 6 to 26 carbon atoms. The oils used to make the alkyd resin can be alcoholysed preferably in the presence of a catalyst, with a polyalcohol, before proceeding with the addition of the diacide, which is generally phthalic anhydride. Alternatively, fatty acids can also be used in the synthesis of alkyd resins.

   Mention may be made, as types of saturated or unsaturated acids, but without this list being exhaustive, for example those of cottonseed, corn, rapeseed, soybean, carthane, castor, castor oil, dehyarate, flax, coconut, Menhaden, sardines, whale, cod, tallow, bacon etc ...



  The acids useful for the manufacture of alkyd resins, generally derived from these oils, include the following acids: caproic, caprylic, capric, lauric, myristic, palmitic, stearic, behenic, oleic, erucian, linoleic, linolenic, arachidonic and clupanodonic. Other acids include tall oil acids and pelargonic acid. These acids can be modified, for example with benzoic acid, and the like.



   The amount of fatty oil or fatty acid used in the alkyd can be varied. The alkyd resin is generally codified for at 'it contains between 10 and 40% and, preferably, between 20 and 30% oil.



   Examples of polyols which can be used are trimethyldlethane, pentaerythritol, polypentaerythritols, glycol, diethylene glycol, butanediol, glycerol, sorbitol, and the like. The amounts of such polyols used can vary from about 10% shortage to about 10% excess, relative to the chemically equivalent amount of the total combined acid components listed in Part 1 of the Examples. However, the preferred amount of polyol is that which is chemically equivalent to the total acidity.



    Although there remains an excess of acidity in the alkyd ester or in the finished resinous product, it is preferred to use at least the theoretical amount of polyol, to obtain with the diacid clear and soluble products in the acid. 'water,

 <Desc / Clms Page number 21>

 having the half-ester structure, and the best results in terms of gloss and water resistance of polymerized films.



   The acid entering into the composition of the alkyd resin can be any of those known in the art. However, phthalic anhydride is preferred in the initial esterification of the alkyd, to achieve better color retention, and for reasons of economy. Because a considerable amount of the diacid exists as a diester in the terminated alkyd, this form is incapable of reacting with the epoxidized oil as a base. However, it is believed that part of the phthalic element is in the half-ester form and therefore reacts with the epoxidized oil. Its main role is that of a resinous component.



   The carboxide groups of the alkyd obtained in part 1 of the examples act as a solubilizing agent and a bonding agent between the alkyd resin and the epoxidized oil serving as a base product. The added diacid compounds, which react with the alkyd, are the anhydrides. phthalic, hexahydrophthalic, tetrahydrophthalic, mono-chlorophthalic, chlorendic, and others.



  They are reacted with the bulk of the alkyd esther after the first major portion of the alkyd esterification reaction is complete. This adduct reacts with the epoxy compound to form the alkyd-epoxy intermolecular complex. Preference is given to this modification of the alkyd with these diacid anhydrides to achieve maximum reactivity with the epoxy compounds used in Part 2 of the Examples.



  Thus, the oxyran equivalent of the epoxidized oil as the base product may be found in excess of the free carbonyl groups of the base alkyd.



   The water-miscible solvent, such as ethylene glycol monobutyl ether, is also a solvent for half-ester and oil resins, epoxidized oil and the reaction product. This solvent considerably lowers the viscosity of the oil-based resin and facilitates manufacture during the final operations of neutralization and mixing with pigments.

 <Desc / Clms Page number 22>

 solvent also increases water tolerance and helps maintain vehicle clarity. As other examples of solvents having a high flash point, there may be mentioned monomethyl ether and monoethyl ether of ethylene glycol, and the monometh, yl-, monoethyl-, and monobutyl ethers of diethylene glycol.

   The amounts in which they are used are not critical, but large amounts tend to give low viscosity to the finished vehicles and improve reaction conditions. The preferred amount is about 13 to 15% in the finished vehicle at 46% non-volatiles.



  Other water-miscible solvents with a lower flash point, such as denatured alcohol, and the like can be used, with proper control of the temperatures of manufacture and addition.



  Components of part 2
The volatile amine which is a base acts as a stabilizer or inhibitor for the reaction between the half esters and the epoxy component. The ene is volatile and it disappears during cooking to allow residual acidity to subsequently react with the epoxidized oil compound. However, although preference is given to such products as triethyl amine, dimethylethanol amine, N-methyl morpholine, in order to obtain clear compositions and to produce films with a stable color, it is possible to use , in some cases, other inhibitor stabilizers such as ammonia, monoethanol amine, diethanol amine, morpholine, dipro-
 EMI22.1
 pyl amine and di-4.sopropy1 amine, etc.

   Dimethyl ether nol-amine also gives good results. Ammonia and many other less volatile amines, including caustic soda, and similar neutralizing or inhibiting agents, either tending to discolor the films, or do not form a suitable film when cooked by steaming. moderate temperature from 93 to 149 C.



  The preferred amount of volatile amine used is the stoichiometric equivalent sufficient to neutralize the acidity of the carrier consisting of the alkyd resin-epoxy complex.



   The epoxidized oils and compounds useful in the present invention can be made by any

 <Desc / Clms Page number 23>

 of the processes described in US Patents 2485,160 of October 18, 1949 and 2,813,878 of November 19, 1957 and disclosed by RITTER Jr. et al. in US Pat. No. 2,771 472 of November 20, 1956 and by SWERN in US Pat. No. 2,569,502 of October 2, 1951. The epoxy compounds are preferably alkaline refined before being reacted in the treatment described herein. These oils are essentially those which contain unsaturation, as discussed in connection with the base oils for alkyd resins of Part 1 of the Examples.

   These unsaturated oils and their fatty acids can be previously converted into other esters by alcoholysis or by esterification with aliphatic and aromatic mono or polyalcohols, saturated or unsaturated, substituted or unsubstituted, before or after the process. epoxidation. It is furthermore possible to use fatty esters with epoxidized long chains, for example epoxy-stearyl acetate, epoxy-stearyl epoxy-stearate, butyl epoxy-stearate,. octyl epoxy-behenate, methyl di-epoxy-stearate, di- (epoxy-lauryl) adipate, propyl triepoxy-stearate, allyl epoxy-stearate, and others ...



   Although the epoxidized oils and the esters mentioned above are of animal, vegetable and marine origin, it is not excluded to use synthetic epoxy esters or those derived from petroleum.



   The general definition of the oxyran compounds useful in the present invention is as follows: they are essentially long-chain compounds, comprising or not comprising substituents, containing from 8 to 26 carbon atoms in the fatty chain, comprising at least one internal oxyran group per chain, and with or without additional oxyran groups in the substituted radical.



   Preferred oxyran compounds are epoxidized glyceride oils comprising 5 to 12% oxygen in oxyran form. Of this group, an oil with 8.0 and 9.5% oxyran is particularly preferred. It follows from this that the base oil for the epoxidation should preferably have an iodine value of at least 150. This category includes: linseed oil, purified soybean oil , safflower oil, and certain fish oils. However, preference is given to linseed oil.

 <Desc / Clms Page number 24>

 



   The end uses and properties of the finished products of the invention are determined by various factors among which one can consider: 1 The degree of mono-acid modification (oil length or modification) of the alkyae resin of the part. 1 aes examples; 2. The weight ratio of alkyd resin to epoxidized oil from part 2 of the examples; 3. and the content of oxyran and the structure of the epoxidized oil of part 2 of the examples.



   The hardness of the films and their general qualities after baking of the final products improves as the oxyran content of the epoxidized oil increases, with the amount and type of alkya resin remaining constant. Conversely, it is possible to obtain hard or soft, plastic or sticky films, when the oxyran content decreases from the preferred oxyran content, which is 8 to 9.5%, up to. About 4%. If the oxyran content of the epoxidized oil is kept constant and the percentage of oil or the mono-acid modification of the alkyd resin increases, the film becomes softer.

   Therefore, for a given set of desired final properties, the weight ratio of the base acid alkyd ester or base resin to the base component of the epoxidized oil, or the change in alkyd and the content. oxyran of the epoxy component, are all important and interrelated.



   In general, films can be obtained with substantially equivalent properties by combining: 1. two parts of a short alkyd resin modified with 20 to 25% monoacid, with one part of a 1 inch oil. epoxy (8 to 8.5% or more as oxyran), and 2, six parts of a longer alkyd resin
 EMI24.1
 modified iléµÎXàÉÎ ÎÉ / ÎÉ ÎÉ Epoxidized linseed oil (8 to 8.5% or more as oxyran).



  -The above proportions are within the preferred limits for obtaining the desired film-forming properties of the products mentioned in the present description. Ratios different from those given above will give a wider range of products ranging from soft plastics, compositions

 <Desc / Clms Page number 25>

 sticky, even hard, crumbly and brittle products.



   These improved vehicles of the present invention, Examples I to XV, can be used as clear oven varnishes if desired. In this application, they give a very nice shine and their color is very stable, they are very resistant to water and alkaline agents, to chemical agents, and they adhere very tenaciously, while at the same time. being very hard and very flexible after cooking. As the diluent is water, there is no risk of fire or smoke in their application.



   The alkyd-epoxy resin complexes are compatible with other resinous compositions soluble in water or capable of dispersing in water. We can still vary them. film-forming characteristics and the final film-forming properties, so that they are more or less soft or hard and more or less shiny or matt. In general, less shine and smoothness are obtained when the components are not fully compatible.



   The following table lists some representative types soluble in water and which gold can disperse in water, of resinous products compatible with the alkyd resin-epoxy complexes of the invention.
 EMI25.1
 
<tb> Type <SEP> of <SEP> resin <SEP> Name <SEP> Manufacturer
<tb>
<tb> commercial
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Phenol-formaldehyde <SEP> Admire <SEP> PL-64 <SEP> ADM
<tb>
<tb>
<tb>
<tb> Type <SEP> silicone <SEP> Silicone <SEP> R-64 <SEP> Union <SEP> Carbide
<tb>
<tb>
<tb>
<tb> Melamine-formaldehyde <SEP> Cymel <SEP> 7273-7 <SEP> American
<tb>
<tb>
<tb>
<tb> Cyanamid <SEP> C
<tb>
<tb>
<tb>
<tb> Melamine-formaldehyde <SEP> Resimene <SEP> 881 <SEP> Monsanto
<tb>
<tb>
<tb> butylated <SEP> ..

   <SEP> 882
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 883
<tb>
<tb>
<tb>
<tb> Butadiene-styrene <SEP> Dow <SEP> Latex <SEP> 566 <SEP> Dow
<tb>
<tb>
<tb>
<tb> Emulsion <SEP> acrylic <SEP> Rhoplex <SEP> B-85 <SEP> Rohm <SEP> & <SEP> Haas
<tb>
 
The following example illustrates a particular composition of the water soluble complexes of the present invention in combination with a preferred melamine-formaldehyde resin which is water soluble or dispersible in water. water.

 <Desc / Clms Page number 26>

 



  Example XVI Part 1 Part by weight A. A water-soluble alkyd-epoxy resin complex selected from Examples X to XII 100 B. A water-soluble melamine-formaldehyde resin, and preferably "Cymel" "7273-7 (75% non-volatile) (American Cyanamid) 5.0
The melamine-formaldehyde resin is simply mixed with the alkyd-epoxy resin complex in the proportion of about 2 to 10 parts per 100 parts of the vehicle. The water-soluble melamine resin, added even in small amounts, promotes lowering the viscosity of the complex in solution when diluted with water, and improves the color stability of the films after baking.

   As the weight of melamine resin is increased, the hardness of the film and its resistance to chemicals increase, but the adhesion and flexibility of the finished products decreases. It is believed that, upon baking, the melamine resin reacts with the alkyd-epoxy resin complex.



   In Example XVI, it is possible to replace the melamine-formaldehyde with the compounds which are soluble in water, or which can be dispersed in water, listed above, or else they can be mixed in any other way with the complexes. soluble epoxy resins to form modified compositions with them.



   The water soluble alkyd resin-epoxy complexes described above can be used as vehicles and mixed directly with pigment and diluted with water to provide high gloss, oven enameled topcoats. This is what the following example of a cooking mixture shows, giving a nice shine:

   
Example XVII
 EMI26.1
 
<tb> Parts <SEP> in <SEP> weight
<tb>
<tb> Oxide <SEP> of <SEP> titanium <SEP> '(Rutile <SEP> not <SEP> chalky) <SEP> 195
<tb>
<tb> Vehicle <SEP> of <SEP> Example <SEP> III <SEP> (47% <SEP> of <SEP> materials
<tb>
<tb> non <SEP> volatile) <SEP> 472
<tb>
<tb>
<tb> Water <SEP> 333
<tb>
 

 <Desc / Clms Page number 27>

 
 EMI27.1
 
<tb> Concentration <SEP> in <SEP> volume <SEP> of <SEP> pigment <SEP> 18, <SEP>%
<tb> <SEP> non <SEP> volatile <SEP> elements of the <SEP> vehicle <SEP> 27.6 <SEP>% <SEP>
<tb>
<tb> Consistency <SEP> (in <SEP> units <SEP> Krebs) <SEP> 75-85
<tb>
<tb> Total <SEP> solids <SEP> <SEP> 41.7 <SEP>%
<tb>
<tb> Ratio <SEP> pigment / binder <SEP> 0.9 / 1.0
<tb>
 
The titanium oxide serving as pigment is ground to a paste, in a suitable grinder,

   and about a quarter to a third of the vehicle of Example III, then the remainder of the vehicle of Example III is mixed. The product is then diluted with water. This gives an enamel which bakes giving a very shiny, hard, tenacious, and extremely resistant film after 30 minutes of baking at 1212 C. The shine indicated by the Gardner apparatus at 60 is 90.



   The film's hold is exceptional compared to that of all other enamels and oven primer, diluted with water. It is also possible to remove the product with water, if it is done immediately, and there are no problems with fumes or fire hazards.



   This example relates to only one of many known pigments and coloring agents of a common nature which can be mixed with the various modified alkyd resin-oil-based epoxy complexes described herein. A preferred pigmented vehicle is obtained by modifying a complex of Examples 1, 2, and 3 into the preferred composition of Example XIII, and preparing a pigmented composition, as shown in Example XVII.



   The preferred water-soluble vehicles which are the subject of the invention exhibit excellent vehicle stability, which allows the pigment to be ground directly therein without the need to add other stabilizers or wetting agents. , and it follows that the formulas of enamels and paints are very simple. Water soluble solutions readily wet pigments and shorten mixing time to 25% of that usually required, and add 2-4 times the amount of pigment normally added in the process. mixed.



   Further, when the vehicles are mixed with iron oxide, silicates, and the like, excellent printing coatings and the like are obtained which adhere to steel surfaces and the like, often difficult to coat. . For example, as indicated below,

 <Desc / Clms Page number 28>

 compositions for printing coatings:

   
Example XVIII
Formula for printing.
 EMI28.1
 
<tb> Part <SEP> 1 <SEP>% <SEP> in <SEP> weight
<tb>
<tb>
<tb> Oxide <SEP> of <SEP> iron <SEP> brown <SEP> metallic <SEP> 5.33
<tb>
<tb>
<tb> Lithopnne <SEP> 5.33
<tb>
<tb>
<tb> Kaolin <SEP> 2.71
<tb>
<tb>
<tb> Silica <SEP> 2.71
<tb>
<tb>
<tb> Complex <SEP> of <SEP> resin, <SEP> soluble <SEP> in <SEP> water
<tb>
<tb> (from <SEP> preference <SEP> to <SEP> 46% <SEP> of <SEP> materials <SEP> not <SEP> 15.99 <SEP>.

   <SEP>
<tb>
<tb> volatiles)
<tb>
<tb>
<tb> Water <SEP> 7.38
<tb>
<tb>
<tb>
<tb>
<tb> Part <SEP> 2 <SEP>% <SEP> in <SEP> weight
<tb>
<tb>
<tb>
<tb> Complex <SEP> of <SEP> resin <SEP> soluble <SEP> in <SEP> water <SEP> 31.98
<tb>
<tb>
<tb> (from <SEP> preference <SEP> to <SEP> 46% <SEP> of <SEP> materials <SEP> no
<tb>
<tb> volatiles)
<tb>
<tb>
<tb>
<tb> Water <SEP> 28.57
<tb>
 
 EMI28.2
 9 The components of Part 1 are introduced into a conventional ball mill, and ground for 24g to 40 hours. The components of part 2 can then be mixed with part 1 by stirring, or by adding them to the ball mill. The proportion of non-volatile solids can vary.

   However, for practical reasons of manufacture, the range of non-volatile compounds indicated generally in the complexes of which the composition has been given, is the best from the point of view of the qualities of flow during the manufacture, handling, and to produce pigmented film-forming compositions.



   Numerous variations and modifications can be made to the terms of the implementation described, without thereby departing from the scope of the invention.


    

Claims (1)

SUMMARY A. As new industrial products: 1. A resinous product comprising an epoxy oil-based complex derived from an alkyd ester and an epoxy compound having an internal oxyran group. 2. - An aqueous solution of an epoxy resin complex based on fatty oil. 3.- An oil-based epoxy resin complex, in combination with an aqueous solution of a residual product. <Desc / Clms Page number 29> neux different. 4. - An aqueous solution of an oil-based epoxy resin complex, in combination with a melamine resin. 5. - An aqueous solution containing an inter-molecular complex of an alkyd ester and an epoxy compound. 6. - A combination of an epoxy complex based on oil, an alkyd ester and a modifying agent for this complex. 7. - A reaction product consisting of an intermolecular complex of an oil-based product derived from an unsaturated fatty oil source comprising a fatty chain radical of 8 to 26 carbon atoms, and containing l oxygen in oxyran form, and an alkyd ester. 8- A water soluble resinous composition, derived from an alkyd esterification product, modified with a compound of a polyacid having residual acidity and present in the form of a half ester soluble in water, and a partially reacted oxyran compound, the composition being present in a water-miscible solvent and having a residual acid number of between about 40 and 120, and an inhibitor temporarily preventing that the reaction between the residual acidity of the modified alkyd esterification product and the oxyran compound is complete; oxyran compound is derived from an epoxidized fatty oil product with a fatty chain of 8 to 26 carbon atoms, and the inhibitor is a volatile organic amine present in an amount capable of stopping the reaction. 9.- A water-soluble vehicle for baking finishing coatings, comprising a water-soluble product of esterification of a fatty acid comprising a fatty chain derived from a fatty oil% 6 to 26 atoms of carbon and a polyol which is reacted in combination with a compound of a diacid and present as a half ester with residual acidity, a partially reacted oxyran compound, a volatile inhibitor to maintain the an epoxy compound in its partial reaction state, and a water-miscible solvent; the fatty acid is derived from linseed oil, soybean, tall oil, dehydrated castor oil and the oxyran compound is derived from an epoxy product based on fatty oil. long chain with several internal oxyran groups. <Desc / Clms Page number 30> 10.- A pigmented coating composition, shiny, insoluble in water and resistant to alkali agents, consisting of the reaction product of a water-soluble alkyd ester and an oxy compound - long chain rane, derived from an unsaturated fatty oil comprising from 8 to 26 carbon atoms in the fatty radical. This coating composition can comprise a melamine resin. B. A method of making an epoxidized oil resin complex in the form of a modified intermolecular alkyd-oxyran compound, characterized by the following; separately or in combinations. II.- A long chain fatty acid, derived from a fatty oil, is reacted with a resin-forming compound; a reactive diacid anhydride is added; the mixture is heated to give a reactive composition which is a half ester with residual acidity; the composition based on the half-ester is cooled; a solvent is added; stirred and an epoxy compound is added to the cooled composition; a partial reaction is carried out between the epoxy compound and said half-ester composition, and a partially reacted resinous alkyd-epoxy complex is obtained. 12. - The partial reaction is stopped after a chosen reduction in the acid number, by adding a neutralizing inhibitor. C. Process for the manufacture of an epoxy compound derived from a fatty oil and soluble in water, usable as a vehicle for paints and enamels, characterized by the following points, or in combination. : -13.- A reactive composition is first produced consisting of a half-ester of a long-chain aliphatic compound, modified with a polyol and derived from a fatty oil source, and the diacid product is resinified with a reaction temperature of between 182 and 204 C approximately; an acid number of the order of 40 to 120 approximately is obtained for the composition based on the half ester; the reaction product is cooled to about 121 ° C.; a solvent miscible with water is added; an epoxidized compound containing internal oxygen in oxyran form is added to said first composition; reacting the epoxy compound with said reactive half-ester composition; a decreased acid number is obtained and an inhibitor is added to temporarily stop the reaction in the water soluble phase. <Desc / Clms Page number 31> 14. - At least part of a reaction inhibitor is added to said first reactive composition, before adding said epoxy compound. D. As a new industrial product, a composition based on epoxy resin, forming films, containing melamine resin as an agent for stabilizing the color of the cured film.