BE595757A - - Google Patents

Description

       

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  "Diolefin copolymers."
The present invention relates to the preparation of copolymers of conjugated diolefins and of ethylenically unsaturated copolymerizable compounds, which can be used as drying oils in paints, varnishes and enamels, and to the preparation of improved drying oils and to paint vehicles prepared in accordance with the invention. means of these copolymers.



   In accordance with the invention, the syn-
 EMI1.1
 thetics vii copolyzing butadiene, 1'3ôojitvüv, taiâ vi3. methyl butadiene, piperylene, methyl pentadiene or others

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 Conjugated diolefins containing from 4 to 6 carbon atoms per molecule, with lesser amounts of ethylenically unsaturated monomers, copolymerizable therewith, for example with 5 to 30% of styrene, of styrenes having alkyl groups substituted on the ring, for example para methyl styrene, dimethyl or diethyl styrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl isobutyl ether, methyl vinyl ketone and isopropenyl methyl ketone,

   and preferably with styrene or ring-substituted alkyl styrenes. The copolymerization is carried out in the presence of metallic sodium and preferably in a solvent.



   In accordance with a preferred embodiment of the invention, copolymers which can be used as drying oils are obtained by copolymerizing in a reaction diluent 60 to 90 parts of butadiene-193 - with 40 to 10 parts of styrene, from preferably about 75 to 85 parts of the first and 25 to 15 parts of the second, at a temperature of 20 to 100 C, preferably below the melting point of the catalyst or between 65 and 85 C. Temperatures around the lower part of the above range are generally more suitable for batch polymerizations, and temperatures near the upper end of the range are particularly suitable for continuous operation.

   As the polymerization catalyst, about 0.1 to 10 parts, preferably about 1 to 3 parts, of a finely dispersed metallic sodium catalyst are used, in the presence, if desired, of various polymerization modifiers which tend. to promote the reaction and give colorless products with drying rates which can be reproduced more exactly.

   As a reaction diluent, it is good to use, for example, heavy gasoline with a boiling point range of 90 to 120 0 or straight-run mineral spirits, such as Varsol (range of boiling points). boiling points 150 to 200 * 0), hydrocarbons iner

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 your diluents, such as butane, xylene, benzene, to: luene, cyclohexane or the like, individually or mixed with each other. To be suitable for the intended polymerization reaction: here the diluents should have a boiling point range between about -15 and 200 C.

   The diluents are generally used in an amount ranging from 50 to 500, preferably 200 to 300 parts per 100 parts of monomers.



   Instead of using inert diluents, it is also possible to use modifying diluents, such as butene-2 or other low boiling olefins which modify the reaction by copolymerization, limiting and completion of the chain. Different ethers, containing more than two carbon atoms per molecule, such as diethyl ether, diisopropyl ether, dioxane, vinyl ethyl ether, vinyl isopropyl ether.

   vinyl isobutyl ether, anisole, phenetole and other ethers of various types are also suitable as diluents and they are particularly useful as co-diluents to ensure the formation of colorless products when used in amounts ranging from about 10 to 35 parts per 100 of monomers, with the amount indicated above of inert diluents such as solvent gasoline pè dioxane, and its various methyl and ethyl homologues which are particularly preferred.

   When choosing the ether co-diluent, it is particularly good to choose an ether having a boiling point at least 10 ° C below the lower limit of the boiling range of the diluent hydrocarbon; thus, when using Varsol, it is preferable to use co-diluents based on ether boiling at approximately 25 to 140 ° C., in order to be able to easily recover them from the polymerized reaction mixture.



   In particular, it is good to add the styrene monomer to the reaction mixture after the polymerization of the

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 butadiene has started. By proceeding in this way the start-up period is very appreciably reduced, and the polymer obtained does not contain any gel and has the desired low viscosity, unlike the more viscous product obtained when the styrene monomer is present from the start in the reaction mixture.



   In particular, when a coarse dispersion of sodium is used as the catalyst, it is also advantageous to use about 1 to 50%, preferably 10 to 20% based on the amount of sodium, of an aliphatic alcohol C1 to This * Secondary and tertiary alcohols, especially isopropanol or tertiary butanol are preferable. These alcohols promote polymerization and, depending on the degree of dispersion of the catalyst, they have a more or less pronounced effect on the intrinsic viscosity of the resulting product.

   The reaction time and the start-up period also vary depending on the degree of dispersion of the catalyst and the reaction temperature, the reaction time being about 40 hours, with a coarse catalyst, and a temperature of about 50 C, up to about 15 minutes at a temperature of about 100 ° C. with catalyst particles with a diameter of less than 100 microns. Although sodium is preferable, analogous catalysts such as potassium, sodium hydride and various sodium alloys are also of interest. Agitation of the reaction mixture during synthesis increases the efficiency of the catalyst.

   Conversions of 50 to 100% of the monomers can be achieved fairly quickly in both continuous and discontinuous polymerizations, although the catalyst requirements are two or three times greater in continuous operation than in discontinuous operation, for the same conversion.



  The destruction of the catalyst is effectively ensured,? at the end of the reaction, adding to the apparatus a moderate excess of alcohol, for example 100% excess of isopropanol on the

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 sodium base, and stirring at reaction temperature for about another half hour. After destruction of the residual sodium with alcohol, the crude product containing the alcoholate, excess alcohol and other solid impurities is cooled, neutralized with solid carbon dioxide, glacial acetic acid or the like. preferably anhydrous acid which does not act on the polymer and the neutralized product is then filtered with a filter aid such as silica gel, arbile, charcoal or the like.



   In the preferred variant, the clear colorless filtrate is then fractionated off so as to remove first the alcohol-hydrocarbon azeotropes, then the dioxane-hydrocarbon azeotropes. Finally, if the polymerization has been carried out in a relatively large amount of diluting hydrocarbons such that the resulting polymer solution is too dilute to serve as a varnish or as a dmail base, it is good to distill off a solution. additional amount of hydrocarbons until a product is obtained containing about 50% of non-volatile matter which constitutes the polymerized drying oil.

   The resulting product, which is a solution of drying oil polymerized in a suitable solvent hydrocarbon such as solvent gasoline or mineral spirits, is a colorless and clear varnish composition, with a viscosity of between 0.5 and 5. poises approximately, at 50% non-volatile matter. The Staudingr molecular weight of the non-volatile or polymerized components of the product generally falls between 2000 and 5000, corresponding to an intrinsic viscosity of about 0.15 to 0.3. If desired, the viscosity of the product can easily be increased between or above these limits: 3 by heating to temperatures between 200 and 300 C, for example 220 to 260 C.

   These clear varnish compositions can be brushed, poured or sprayed, which give good clear coats by air drying or baking, in particular when siccatives are added.

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 ) usual such as naphthenates or octoates of cobalt, lead or m @@ ganesis.



   However, while drying oils of the type described above give a good varnish, they are poor wetting vehicles for pigments and they give film-forming enamels which lack gloss, scratch when brushing and in which pigments tend to agglomerate. Furthermore, a particularly troublesome fact is that, under apparently identical conditions, products are obtained whose gloss and wetting power are entirely different, ranging from very poor quality to suitable quality.

   It has been found that wetting agents, such as linoleic acid, aromatic sulphonates or diamines such as octadecyl diethenyl diamine, as well as polar or non-polar solvents, such as acetone or various alcohols do not remedy , effectively to these drawbacks when added to drying oils.



     According to another characteristic of the invention, improved drying oils are obtained j. suitable for the preparation of enamels, by reacting the copolymerized synthetic oils, described above, with 0.01 to 10% of a monoethylenically unsaturated compound, containing one or more elements or groups not containing hydrocarbons and the ethylenic bond of which is capable of reacting with the methylene groups neighboring the double bonds of the oily polymer, or with a compound containing a thiol group capable of reacting with the double bond of the oily polymer.



   Although the reaction mechanism by which these two types of compounds combine with the polymer is chemically different, the final modifying effectiveness of the two types of compounds is analogous and depends on their ability to impart polar characteristics to the polymer. oily hydrocarbons.

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   As suitable ethylenic modifiers, there may be mentioned unsaturated dibasic acids such as maleic acid, chlormalealic acid or ketraconic acid, acrylonitrile, [alpha] -methacrylonitrile, [alpha] -chloracrylonitrile, methyl acrylate, butyl acrylate, methyl methacrylate, vinyl acetate, vinyl methyl ketone, cinnamaldehyde, etc.



   As suitable compounds containing a thiol group, there may be mentioned thioglcolic acid, mercaptoptopionic acid SH, (CH2) 2COOH, thiosalicylic acid SH, C6H4, COOH, and the corresponding esters, aldehydes and ketones. Methyl or ethyl esters, such as ethyl thioglycolate, are particularly suitable.



   This treatment with unsaturated dicarbonic acid or anhydride is preferably carried out by adding 0.1 to 2.5% and preferably 0.05 to 0.5% of the modifier, preferably maleic anhydride, to monomeric hydrocarbons, before or during the synthesis of the drying oil, or a similar and even more efficient result can be obtained by adding the indicated amount of maleic anhydride to the finished polymer and heating the mixture to temperatures from 50 to 250 C, preferably from 180 to 220 C. The reaction time required for this additional treatment varies from 15 minutes to 2 hours depending on the temperature used.

   In particular, it can be noted that the above stated amount of maleic acid is very critical, since amounts exceeding 1% maleic anhydride based on the monomers cause a serious retardation of the drying rate of the product. resulting which, bier. that not fading too much with freshly treated oil, becomes very pronounced if the treated oil is left to stand for a few days or weeks in cans before applying it as a protective coating. Drying oils treated with more than 2.5% dry so slowly that they are unusable for all practical applications unless they are specially reprocessed or combined.

   When using the

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 Other ethylenic compounds, the monomers are preferably reacted with 0.05 to 10% of the modifier, preferably under conditions giving a product containing from 0.05 to 0.5% of the modifier. The operation can be carried out by adding the modifying agent to the finished polymer and heating the mixture to 50 to 250 C, temperatures between 180 and 200 C being preferable, especially when the modification treatment is carried out without a catalyst. . Advantageously, a peroxide catalyst can also be used, in an amount ranging from about 0.1 to 2% based on the polymer, in order to accelerate the reaction between the siccative herril and the ethylenically unsaturated modifier.

   Suitable catalysts for peorxyde that may be mentioned are benzoyl peroxide, hy-
 EMI8.1
 tertiary butyl droperoxide, peracetic acid, cumene oxide, etc. Tertiary butyl peroxide is preferred since it ultimately leaves a volatile residue which can be removed from the product more easily than like residues of other catalysts.



   The other thiol modifiers, such as thioglycolic acid, add to the polymer quite easily and quantitatively, and in this case a peroxide catalyst is generally not used, since the low gain in the polymerization. Reaction speed is often offset by the fact of an annoying reduction in clarity due to the formation of insoluble biaulfide compounds by oxidation of thiol compounds.



   The practical reaction time for this additional treatment varies from about 15 minutes to 2 hours, depending on the presence or absence of catalysts, as well as the temperature employed. However, in the case of ethylenically unsaturated modifiers, such as acrylonitrile, it has been found
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 that: tl ::. e in the condi "tlons plus -.fa7orablss ¯¯¯ l 'Elc, ent qus mm \ Rns I.; js coit # j-ons': -es plus, .favorable,: VV :: : n 1 ë.tô.u.1 modifier does not combine with the polymer. In this case, the excess modifier that has not reacted can be separated from the oil.

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 it and recycled or it can be left in the product without noticeably harming it.



   The copolymers prepared in the above manner can be used as an addition for vegetable oils so as to accelerate their setting on heating without adversely affecting the drying rate or the film-forming properties of the product.



   When cooking vegetable oils such as linseed oil in the usual way so as to increase their viscosity, it takes a reaction time of about 12 hours to achieve the change in temperatures. required for this purpose are of the order of 295-305 C and the usual heating is therefore generally accompanied by undesirable browning of the treated oil, as well as an appreciable loss of material due to prolonged cooking. Previous attempts have been made to increase the low production rate and to reduce the degradation of the resulting oil.

   These previous tests have focused on the use of monomeric reagents such as styrene, butadiene, cyclopentadiene or catalysts such as oxygen or litharge, but the use of any of these materials. ., will cause varying degrees, high loss or adversely affect the drying rate, color or some other property of the final product. Consequently, the improvement in the cooking speed was obtained only at the cost of a serious sacrifice which could not always be made depending on the vegetable oil used and the end use envisaged for it.



   It has been found that the synthetic oily polymers according to the invention have a surprisingly beneficial accelerating effect on the cooking rate of vegetable drying oils without causing loss of color and often actually improving hardness and other properties. .



   Drying or semi-drying vegetable oils

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 to which the present invention is applicable include linseed oil, soybean oil, rapeseed oil, tung oil, cottonseed oil, perilla oil, ilticia oil. , grain oil, dehydrated castor oil, fish oil, sunflower oil, saffron oil and other vegetable oils containing a substantial proportion of glycerides of linoleic acids and / or linolenic.



   In accordance with this characteristic of the invention, the rate of cooking of the drying or semi-drying vegetable oils is accelerated by adding thereto approximately 2 to 25%, preferably approximately 5 to 15%, of an oily copolymer. and then cooking the mixture substantially in the absence of oxygen at a temperature of about 230 to 330 C, preferably 265 to 300 C, until the cooked oil has reached the desired consistency.

   Instead of applying the invention to the cooking of vegetable oils alone, it can also be applied advantageously to the cooking of oleoresinous varnishes containing a vegetable oil and approximately 10 to 70% of a resin such as an ester-gum. , various oil-soluble hydrocarbon resins, modified phenolics or phenolics, esters and rosins treated with maleic acid and natural resins.

   The main advantage of this feature of the invention lies in the fact that one can give body to vegetable oils by heating them, which is essentially a phenomenon of polarization, in a shorter time and / or at lower temperature, so that cooking loss, as well as browning of the valuable product charge, is minimized. It follows from the foregoing that this characteristic of the invention gives significant savings in heat, time and material, without in any way harming the properties of the final product.



   It has been found that a substantial preponderance of vegetable oil over synthetic copolymer is desirable

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 regarding the cooking speed. At the same time, however, it has been found that whether the proportion is reversed, for example by reacting about 70 parts of the oily copolymer with 30 part? of dehydrated castor oil at 295 ° C. for 80 minutes, the varnishes prepared with the resulting base product have excellent wettability of metallic and glass surfaces.

   This is absolutely surprising given that in the absence of the vegetable oil, the siccative oils obtained by synthesis from butadiene tend to run and slip in small streams, leaving a discontinuous film. when applied to metal or glass.



   It has also been noted that the drying rate of enamel compositions prepared with drying oils according to the invention gradually decreases when the compositions have been left for a certain time in containers, under conditions analogous to storage in store, which often goes on sale for periods of up to a year or more, before the packaged product reaches the end consumer.

   It has been established that this reduction in the drying rate is due to the fact that all the pigments normally used in combination with the drying oils consisting only of hydrocarbons, more or less eagerly absorb the metal soap driers initially added to the synthetic composition. enamel to regulate its drying speed and, whereas it was previously known in the paint and varnish industry that certain pigments have a tendency to absorb the driers of enamels containing various varnishes with vegetable drying oil , the assertion of the siccative seems to be of a very different nature and much more pronounced with, consequently, more disadvantages, in the presence of synthetic siccative oils,

   probably due to the relative ability of synthetic siccativ oils to adequately wet the pigments therein.

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   In most cases, when these glazes are stored or allowed to stand at room temperature (24-25'0), they show only little loss of drying properties.



  If they are stored under conditions permitting temperature. rature to approach or exceed 50 C, they depreciate at a much faster rate. Since many warehouses get very hot in sunny summer weather, the reduction in the drying rate caused by this hot storage can become a problem if not corrected. It is generally considered essential that the enamels air dry within four to six hours to come to a dust free condition in order to be acceptable as a high quality commodity *.

   Thus, products prepared with hydrocarbon-drying oils require a process of stabilizing the initial drying rate to ensure their reputation as quality enamels.



   In the attempts made previously to remedy this drawback and thus stabilize the drying rate of synthetic enamels, it has been found that various wetting agents of the hydrocarbon sulfonate type, fatty acids, as well as a certain number of complex amines , which have been tried, were not effective.



   It has been found according to the invention that the addition of calcium oxide to such enamels and paints prepared with synthetic drying oils gives a satisfactory drying rate and that paint compositions could not be recommended as quality products. not containing this addition, even after storage for relatively short periods under conditions which could not be considered abnormal.



   In accordance with another feature of the invention, improved mixtures of enamels and paint are prepared using these. copolymeric drying oils incorporating

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 in the enamel a small amount, preferably 2.5 to 10% by weight of the copolymer oil, of calcium oxide.



   The following examples illustrate the present invention. All parts and percentages given below are given by weight, unless otherwise indicated.



  EXAMPLE 1
Operation A
A styrene butadiene drying oil was prepared from the above charge:
 EMI13.1
 
<tb>
<tb> Parties
<tb> Butadiene <SEP> 1.3 <SEP> 80
<tb> Styrene <SEP> 20
<tb> Varsol <SEP> (1) <SEP> 200
<tb> Dioxane <SEP> 40
<tb> Isopropanol <SEP> 0.2
<tb> Sodium <SEP> (2) <SEP> 1.5
<tb>
 (1) Straight-run mineral spirits; API density, 49; flash point 41 C; boiling range 150 to 200 C; solvent power, 33-37 Kauri-butanol value (reference scale: benzene-K.B. value 100, n-heptane K.B. value 25.4) (2) Dispersed to a particle size of 10 to 50 microns? using an Eppenbach Homo-mixer
This charge was polymerized at 5000 in a two liter autoclave fitted with a mechanical stirrer.

   A complete conversion was obtained in four and a half hours. The catalyst was destroyed and removed from the resulting crude product. The product was finished so that it contained 50% non-volatile material, as mentioned above. The resulting product had a viscosity of 0.9 poise and its non-volatile part had an average molecular weight of about 3000.



   Operation B
By repeating operation A with the same load and in

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 Under conditions as identical as possible, a final product was obtained having a viscosity of 1.2 poises with 50% non-volatile material.



   Operations C to F
By doing still other analogous operations, products were obtained having viscosities such as those shown in Table I. Operation E, in which pn obtained a product having a fairly high viscosity, differed from ether as a diluent, to instead of the dioxane of the others because 350 parts of dietyl were used and this change resulted in a start-up period of about three hours. It has been found to be generally correct that long start-up periods result in products having a very significantly higher final viscosity than when the start-up period is short.

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    TABLE I Quality of the enamel
 EMI15.1
 
<tb> Email <SEP> Isosity <SEP> Factor <SEP> Gloss <SEP> Gloss <SEP> Equalization, <SEP> Speed <SEP> of <SEP> drying <SEP> (hours)
<tb> (Operation <SEP> n) <SEP> of <SEP> oil <SEP> of <SEP> paste <SEP> (film <SEP> (film <SEP> absence <SEP> of <SEP> taken <SEP> to <SEP> No <SEP> sticky
<tb> (poise) <SEP> (gr <SEP> oil <SEP> pouring) <SEP> applied <SEP> marks <SEP> of the <SEP> touching <SEP> sticky
<tb> (poise) <SEP> p.

   <SEP> 100 <SEP> gr <SEP> to the <SEP> pin- <SEP> brush <SEP> touch
<tb> pigment) <SEP> ceau)
<tb> A <SEP> 0.9 <SEP> 121.5 <SEP> flat <SEP> shell <SEP> bad <SEP> 4-6 <SEP> <24
egg <tb>
<tb> B <SEP> 1.2 <SEP> 122.5 <SEP> excellent <SEP> excellent <SEP> excellent <SEP> 4-6 <SEP> <24
<tb> C <SEP> 0.5 <SEP> 142 <SEP> flat, <SEP> gra- <SEP> good <SEP> bad <SEP> 4-6 <SEP>> 24 <SEP> <<SEP> 48
<tb> null
<tb> D <SEP> 0.8 <SEP> 154.7 <SEP> flat <SEP> good <SEP> bad <SEP> 4-6 <SEP> <24
<tb> E <SEP> 7 <SEP> 172 <SEP> shell <SEP> excellent <SEP> excellent <SEP> 4-6 <SEP>> 24
egg <tb>
<tb> F <SEP> 1 <SEP> 111 <SEP> good,

   <SEP> stony <SEP> good <SEP> bad <SEP> 4 <SEP> <24
<tb>
 

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All of the above-described drying oil products / protectors gave excellent coatings when applied as a clear varnish to steel, wood and other ordinary surfaces. Films containing usual small amounts of drier, such as 0.05% cobalt, 0.05% manganese, and 0.5% lead, in the form of naphthenates, applied by dripping or brushing the clear varnish , had good drying rates because they generally set to the touch in two to four hours and were no longer tacky in 10 to 24 hours.



  The resulting dry films were hard, smooth, shiny, unaffected by water, grease, and caustics, and were only slightly discolored by the soap.



   The value of the drying oils in question was determined on a laboratory pigment mill, cooled with water and having three consecutive rolls rotating at different speeds, the first roll being the slowest and the third the fastest. According to the usual practice, the paste of oil and pigments is placed between the first and the second rotating cylinder, between which it is crushed and entrained. It is understood that the desire in the industry for the ratio of oil to pigments, also known as "paste factor", to be as low as possible, in order to obtain the fastest mill throughput. possible.

   Once the paste is made, it is then quickly diluted to the desired consistency, simply by mixing in additional amounts of oil. The formula used in this enamel assessment was
 EMI16.1
 
<tb>
<tb> Synthetic <SEP> drying <SEP> oil <SEP> (50% <SEP> of <SEP> products <SEP> not
<tb> Synthetic <SEP> drying <SEP> oil <SEP> (50% <SEP> of <SEP> products <SEP> not
<tb> volatiles <SEP> in <SEP> of <SEP> Varsol) <SEP> 200 <SEP> gr
<tb> CO <SEP> (2) <SEP> 0.05%
<tb> Mn <SEP> (2) <SEP> 0.05%
<tb> Pb <SEP> (2) <SEP> 0.5%
<tb>
   (1) R6 10 pure or Ti (2) Drying agents in the form of naphthenates

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The enamels were applied to steel panels both by casting and by brushing and the resulting dry enamel films shine observed,

   as well as the presence or absence of marks due to pine @ eau. These figures, together with the paste factor of each of the drying oils tested, have been given in Table 1 from which it can be seen that the synthetic drying oils prepared as above are of poor quality. vehicles for enamels, as they give an unduly high paste factor and drying oils with poor, irregular gloss and poor leveling.



   When drying oils obtained in accordance with Example 1 were used for the preparation of enamels by incorporating therein pigments such as titanium oxide, the results were not satisfactory, both because that an unduly high amount of oil was required in the pigment mill to give a homogeneous smooth paste, and due to the lack of gloss and poor leveling, which could not be adjusted, films made with the resulting glazes.



  Example 2 below shows the improvement obtained by treating the copolymer oils with the various modifiers such as maleic anhydride, ethylenic unsaturated compounds or thiol compounds. The products were evaluated as stated in Example 1 above.



    EXAMPLE 2
Operation M
The finished drying oil obtained in operation A of Example 1, containing 50% non-volatile matter and a viscosity of 0.9 poise, was subjected to a subsequent treatment consisting of subjecting the oil to reflux. at 175 ° C. for 2 hours, in the presence of 0.1% maleic anhydride. The resulting oily product was perfectly clear and had the clarity of water. Its satisfactory viscosity and drying speed were much the same as that of the original oil but it had much better characteristics.

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 of wetting and equalization than this.

   The titanium oxide enamels prepared from the oil treated using the formula given above gave coatings with excellent gloss.



   Operation N
When one part of the treated oil obtained in operation M was mixed with four parts of the untreated oil obtained in operation A of Example 1, thereby obtaining an oil having an average content in maleic anhydride of 0.02%, the mixture retained to a great extent all the advantages of the oil treated with undiluted maleic anhydride, indicating that surprisingly a small amount was sufficient. maleic anhydride for the applications of the invention.



   Operation 0
In this case, the drying oil completed from operation A was subjected to a subsequent treatment which consisted in subjecting the oil to reflux at 175 ° C. for two hours in the presence of 1% maleic anhydride. The resulting clear, water-white product had a paste factor of 37.2 which is about as good as that of the best natural drying oils and represents a very significant improvement over the. untreated oil which had a paste factor of 121.5. The drying speed, the leveling, the gloss of the enamel and all the other important characteristics of the treated oil were very satisfactory.



   Operation P
When one part of the treated oil obtained in step 0 was mixed with three parts of the untreated oil from step A, thereby giving an oil having an average maleic anhydride content of 0.25% , the mixture had substantially the same favorable properties as the oil

 <Desc / Clms Page number 19>

 of operation 0 except a slight increase in the dough factor from 37 to 41.



   Operation Q
It has been found that it is possible to further improve the pulp factor by increasing the concentration of malelque anhydride. However, as shown in Table 11, this increase in the maleic anhydride content increases the difficulty of completing the reaction of the anhydride with the oil, and the uncombined residual anhydride tends to have an adverse effect on the rate. drying of the product.



   Operation R
Instead of incorporating maleic anhydride into the oil in a separate subsequent operation, it is possible to achieve a similar improvement by adding a suitable amount of maleic anhydride to the reaction mixture when the synthesis is to be made. oil. This variant is described below.



   Operation A was recommended except that in the present case isopropyl alcohol was not used and instead 0.25 µm of maleic anhydride was added to the polymerizable feed material according to specification. invention. The start-up period was increased to about 5 hours, and the total polymerization time at 60 ° C was about 18 hours, to achieve a 100% conversion. When the mixture resulting from the reaction was completed as stated above and reduced to a content of 50% non-volatile material, a drying oil was obtained having a viscosity of about 8, 8 poises, but slightly discolored and a little cloudy.

   When this product was used to prepare glazes with the above formula and process, a satisfactory paste factor was obtained for films having excellent gloss and leveling characteristics, as shown in Table II. The drying speed of the

 <Desc / Clms Page number 20>

   mail was satisfactory, being at the beginning the same as with the unmodified drying oils obtained in operations A to F.



  A to F.



  Operation S By repeating operation R but this time adding 1.5% part of maleic anhydride to the raw material, the reaction time was further increased to bring it to about 20 hours. The finished drying oil had a viscosity of about 11 poises and a non-volatile content of 50%, relatively high viscosities being characteristic of long start-up periods. The oil was still slightly cloudy and discolored. This product wetted pigments very well giving enamel films having excellent properties, as in operation R, and the enamel prepared from this drying oil had a satisfactory drying rate.



  Operation T By repeating operation R once more, but this time adding 3% maleic anhydride to the polymerizable material, only a conversion of 7% was obtained and the amount of drying oil obtained was insufficient for allow an assessment.



  Incidentally, it has been observed in the course of the present research that, even in the absence of maleic anhydride, the gloss and the leveling of an unsatisfactory drying oil can be improved somewhat, simply by heating to a temperature between 120 and 200 C for a period of about one and a half to five hours, in the appreciable absence of air or oxygen, without increasing the viscosity of the oil. This is represented by operation U of Table II. However, this heat treatment does not improve the paste factor of the oil in a manner similar to that obtained by the treatment with maleic anhydride.

   AT

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   ---------------------------- temperatures above 200 C and especially 250 C, this heat treatment causes the oil to take body, a phenomenon that can be used if one wishes to have oils of greater viscosity.



   All results are summarized in Table II.

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    TABLE II Quality of the enamel
 EMI22.1
 
<tb> Email <SEP> Anhydride <SEP> Viscosity <SEP> Factor <SEP> of <SEP> paste <SEP> Gloss <SEP> Gloss <SEP> Equalization <SEP> Speed <SEP> of <SEP> drying <SEP > (hours)
<tb> (opera- <SEP> maleic <SEP> from <SEP> oil <SEP> (gr <SEP> oil <SEP> p. <SEP> 100 <SEP> (film- <SEP> (film < SEP> (absence <SEP> of <SEP> Socket <SEP> to <SEP> No <SEP> sticky
<tb> tion <SEP> maleic <SEP> (poises) <SEP> gr <SEP> pigment) <SEP> the <SEP> neck- <SEP> to the <SEP> brush) <SEP> marks <SEP> of the < SEP> touch
<tb>
 
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 ') ¯¯ Q, u) ¯¯¯¯¯¯¯¯ ##########
 EMI22.3
 
<tb> N <SEP> 0.02 <SEP> (b) <SEP> 1 <SEP> 86 <SEP> excellent <SEP> excellent <SEP> excellent <SEP> 6 <SEP> <24
<tb>
 
 EMI22.4
 rat 0.1 (b) 1;

   '; 0 "" "2-4 <24
 EMI22.5
 
<tb> P <SEP> 0.25 <SEP> (b) <SEP> 1 <SEP> 41 <SEP> "<SEP>" <SEP> "<SEP> 6 <SEP> <24
<tb> 0 <SEP> 1 <SEP> (b) <SEP> 1 <SEP> 37.2 <SEP> "<SEP>" <SEP> "<SEP> 6 <SEP> <24
<tb> Q <SEP> 2 <SEP> (b) <SEP> 1 <SEP> 36.5 <SEP> "<SEP>" <SEP> "<SEP> 24 <SEP>> 24
<tb> R <SEP> 0.25 <SEP> (a) <SEP> 8.8 <SEP> 67 <SEP> "<SEP>" <SEP> "<SEP> 6 <SEP> (d) <SEP > <24 <SEP> (d)
<tb> S <SEP> 1,5 <SEP> (a) <SEP> 11 <SEP> 47 <SEP> "<SEP>" <SEP> "<SEP> 6 <SEP> (d) <SEP> < 24 <SEP> (d)
<tb> T <SEP> 3 <SEP> (a) <SEP> - <SEP> - <SEP> - <SEP> U <SEP> nothing <SEP> (c) <SEP> 1 <SEP> 94.3 <SEP> excellent <SEP> excellent <SEP> excellent <SEP> 4 <SEP> 24
<tb> (a) <SEP> anhydride <SEP> added <SEP> to <SEP> the <SEP> material <SEP> monomer
<tb> (b) <SEP> anhydride <SEP> having <SEP> reacted <SEP> with <SEP> drying <SEP> oil <SEP> completed
<tb> (c)

   <SEP> thermal <SEP> treatment <SEP> of <SEP> drying oil <SEP> <SEP> completed <SEP> for <SEP> 2 <SEP> hours <SEP> to <SEP> 145 C
<tb> (d) <SEP> after <SEP> billing
<tb>
 

 <Desc / Clms Page number 23>

 
Steps R to T show that a satisfactory modification of the synthetic drying oil can be obtained by directly adding maleic anhydride to the material being treated and thus eliminating a separate post-synthetic treatment. However, it should be remembered that the seemingly simplified one-step process, involving the addition of anhydri, - de to the raw material, results in a substantial increase in the reduction time required and results in a relatively high viscosity product as well as somewhat inferior in color and clarity.

   In general, therefore, it has been found that the variant of the treatment with post-synthesis is much more advantageous and it is recommended to carry out the modification of adding the anhydride to the raw material only when an operation is preferred. in a single phase, even at the expense of increasing the total reaction time and some decrease in product quality.



   Coating compositions can be prepared from the oils according to the invention, so as to meet varying requirements. In particular, they easily accept all types of tones, as well as organic and mineral pigments such as titanium oxide, chreme green, lead black, minium, toluidine and lithol reds, blues. iron and phthalocyanine, chromium and hansa yellows. Depending on the type of pigments used and the end use envisaged, the concentration of the pigment can vary in different enamels between: - very distant limits, for example between 5 and 75% based on the weight of the non-volatile polymer constituents of the base drying oil.

   For example, carbon black is generally used in concentrations ranging from 6 to 10%, titanium dioxide from 40 to 60% and lead pigments in even higher concentrations. Obviously, when preparing the initial paste, concentrations of up to 300 parts of pigments per 100 parts

 <Desc / Clms Page number 24>

 drying oil are common.



  EXAMPLE 3
100 parts of the oily product containing 50% of non-volatile matter were mixed in mineral spirits obtained by direct distillation and obtained as was said above in operation A (oil viscosity 0.9 poise), with two parts acrylonitrile and 0.35 part t-butyl hydroperoxide catalyst, then the mixture was refluxed for 6 hours at 70 ° C. The treated oil had a viscosity of 1 poise.



   When this product has been used for the preparation of enamels according to the method and formula given above, advantageously low paste factor has been obtained and films having excellent gloss and leveling characteristics, such as shows Table II. The enamel drying speed was good. It should be noted in particular that the paste factor of the modified oil has been reduced by about half that of the unmodified original oil (operation A).



  EXAMPLE 4
In this operation, the ingredients and conditions of the reaction were the same as in Example 3 above, except that the amount of acrylonitrile added was brought to four parts.



   From Table III below, it can still be seen that, due to the increase in the nitrile content, the resulting modified polymer was characterized by a paste factor which was significantly better even than that obtained in the same. Example 3, but in most other respects the two modified oils were approximately equivalent. The viscosity of the treated oil was 1.2 poise.



    EXAMPLE
100 parts of the oil described in Examples 3 and 4 above were mixed with four parts of acryonitrile and

 <Desc / Clms Page number 25>

 0.35 part of t-butyl hydroperoxide catalyst and the mixture was refluxed for 22 hours at 90 ° C. The results shown in Table II show that the paste factor of the resulting modified oil was further improved over the result of Example 4, probably due to the fact that the more severe reaction conditions cause a more extensive reaction between the oil and the acrylonitrile. The oil took a lot of body during this treatment, as shown by the final viscosity of 5.5 poise of the product obtained.



  EXAMPLE 6
This time 100 parts of the oil described in Example 3 above were mixed with 2 parts of acrylonitrile and heated in a closed reaction apparatus for 3 hours at 200 ° C., in the absence of catalyst. The resulting modified oil had an even better paste factor than the oils obtained in any of the preceding examples, indicating that acrylonitrila reacts strongly with the hydrocarbon oil, even in the absence of a catalyst, provided that The duration and / or the temperature of the reaction is suitably increased.

   At the same time, however, it was observed that, unlike in the previous examples where the modifying treatment was carried out in the presence of peroxide catalyst, the drying rate of the resulting oil was not. accelerated in this example.



    EXAMPLE 7 to 17
Still other reaction conditions and modifiers were used to improve the synthetic drying oil from Operation A, as shown in Table III, from which it can be seen that a small amount of a wide variety of mercapto and ethylenically unsaturated compounds, having a strongly polar group such as a nitrile group, a carboxyl group, an ester group, an aldehyde group and the like, can react effectively with a synthetic butadiene drying oil, in such a manner. to improve its properties

 <Desc / Clms Page number 26>

 tees of paste factor, enamel gloss and the like.

   And, although with the exception of thioglycolic acid derivatives, a substantial amount of the added modifier remains uncombined in the oil at the end of the reaction, it has been found, by means of the tests shown herein, that the unexpected effective improvement in paste factor and similar properties is not due to the unreacted part of the modifier present in the oil, but only to the combined part, even if this is only one small fraction of the modifier initially added.



   The results are summarized in Table III below.

 <Desc / Clms Page number 27>

 



    TABLE III Quality of the enamel
 EMI27.1
 
<tb> Email <SEP> Viscosity <SEP> Added <SEP> modifier <SEP> Factor <SEP> of <SEP> Gloss <SEP> Equalization <SEP> Speed <SEP> of <SEP> drying <SEP> (arm)
<tb> of <SEP> hui- <SEP> pte (gr <SEP> hui <SEP> Pell <SEP> cule <SEP> ellicule <SEP> (absence <SEP> of
<tb> (exem- <SEP> of <SEP> processed <SEP> the <SEP> for <SEP> 100 <SEP> Film <SEP> Film <SEP> marks <SEP> at <SEP> Taken <SEP> at <SEP> tou- <SEP> No <SEP> sticky
<tb> ple <SEP> n) <SEP> (poises) <SEP> gr <SEP> pigment) <SEP> casting <SEP> with <SEP> brush <SEP> brush) <SEP> dear
<tb> 3 <SEP> 1 <SEP> acrylonitrile <SEP> 2% <SEP> (a) <SEP> 62.3 <SEP> excell.

   <SEP> excels <SEP> excels <SEP> 2-4 <SEP> 6
<tb> 4 <SEP> 1,2 <SEP> "<SEP> 4% <SEP> (a) <SEP> 52,2 <SEP>" <SEP> "<SEP>" <SEP> 2-4 < SEP> 6
<tb> 5 <SEP> 5.5 <SEP> "<SEP> 4% <SEP> (<SEP> c <SEP>) <SEP> 47.2 <SEP>" <SEP> "<SEP>" < SEP> 2-4 <SEP> 6
<tb> 6 <SEP> 1.3 <SEP> "<SEP> 2% <SEP> (b) <SEP> 38.1 <SEP>" <SEP> "<SEP>" <SEP> 6 <SEP> 20-24
<tb> 7 <SEP> 1.2 <SEP> "<SEP> 0.25% <SEP> (b) <SEP> 57 <SEP>" <SEP> "<SEP>" <SEP> 6-8 < SEP> 24
<tb> 8 <SEP> 1.1 <SEP> '<SEP> 0.75% <SEP> (b) <SEP> 53.8 <SEP> "<SEP>" <SEP> "<SEP> 6- 8 <SEP> 24
<tb> 9 <SEP> 1.3 <SEP> cinnamaldehyde <SEP> 2% <SEP> (b) <SEP> 64 <SEP> "<SEP>" <SEP> "<SEP> 6 <SEP> 24
<tb> 10 <SEP> 1,2 <SEP> methyl <SEP> acrylate <SEP> 5% <SEP> (a) <SEP> 66.1 <SEP> "<SEP>" <SEP> "<SEP> 2-4 <SEP> 6
<tb> 11 <SEP> 1,3 <SEP> butyl <SEP> acrylate <SEP> 2% <SEP> (b) <SEP> 53,

  4 <SEP> "<SEP>" <SEP> "<SEP> 6 <SEP> 24
<tb> 12 <SEP> 1,2 <SEP> vinyl <SEP> acetate <SEP> 2% <SEP> (b) <SEP> 68 <SEP> '<SEP> "<SEP>" <SEP> "< SEP> 6 <SEP> 20-24
<tb> 13 <SEP> 1 <SEP> SH, CH2COOH <SEP> 0.5% <SEP> (d) <SEP> 35 <SEP> good <SEP> good <SEP> good <SEP> 8 <SEP> 20-24
<tb> 14 <SEP> 1 <SEP> SH, CH2COOH <SEP> 0.25% <SEP> (d) <SEP> 50 <SEP> "<SEP>" <SEP> "<SEP> 6-8 < SEP> <24
<tb> 15 <SEP> 1 <SEP> SH, CH2COOH <SEP> 0.1% <SEP> (d) <SEP> 53.8 <SEP> "<SEP>" <SEP> "<SEP> 6- 8 <SEP> <24
<tb> 16 <SEP> 1 <SEP> SH, CH2COOEt. <SEP> 0.5% <SEP> (d) <SEP> 44 <SEP> "<SEP>" <SEP> "<SEP> 8 <SEP> 20-24,
<tb> 17 <SEP> 1.5 <SEP> SH, CH2COOEt. <SEP> 2% <SEP> (b) <SEP> 49 <SEP> excella. <SEP> - <SEP> excell. <SEP> 2 <SEP> 8
<tb> ic
<tb> (a) <SEP> reacted <SEP> for <SEP> 6 <SEP> hours <SEP> at <SEP> 70 C, <SEP> catalyst <SEP>:

   <SEP> hydroperoxide <SEP> t-butyl, <SEP> 0.7% <SEP> of the <SEP> polymer
<tb> (b) <SEP> "<SEP> 3 <SEP> to <SEP> 200 C, <SEP> not <SEP> from <SEP> ique
<tb> (c) <SEP> "<SEP> 22 <SEP>" <SEP> to <SEP> 90 C, <SEP> catalyst <SEP> hydroperoxide <SEP> t-butyl, <SEP> 0.7% <SEP> of the <SEP> polymer
<tb> (d) <SEP> "<SEP> 0.5 <SEP>" <SEP> to <SEP> 160 C, <SEP> not <SEP> of <SEP> catalyst.
<tb>
 

 <Desc / Clms Page number 28>

      



   Operations A through F of Example 1, listed in Table 1, show that all untreated synthetic drying oils have a pulp factor of 111 and above, whereas in the industry, generally speci? values between 20 and 90, preferably between 20 and 50. Additionally, with the exception of enamel B and to some extent enamel E, untreated enamels gave dried films which exhibited a gloss. unsatisfactory and poor equalization. The excellent characteristics of the dry films obtained from the enamel B could not be explained and they could not be obtained again in other operations, despite the repeated and painful efforts made. in order to repeat exactly all the conditions used in the synthesis of the oil used in operation B.

   This shows that it is not possible to obtain a product of comparable quality by carefully controlling the synthesis of the unmodified drying oil. At the same time, operation E shows that in this case a glossy film was obtained which could be satisfactorily evened out with a brush, although the cast film was dull as an eggshell, and one can explain This difference in behavior is that, under certain unknown conditions, excessive agglomeration of the pigments can be prevented by an expenditure of sufficient energy to apply the enamel to the surface.



   As opposed to the unsatisfactory and irregular results of operations A to F, operations M to S of Example 3 summarized in Table II and the results of Examples 3 to 17 listed in Table III show that the oils treated with the modifiers according to the present invention possess excellent pigment wetting power and give dried enamel films having excellent gloss and leveling characteristics, whether maleic acid is incorporated into the oily polymer at the same time. Classes

 <Desc / Clms Page number 29>

 of the initial synthesis or in a subsequent treatment of the finished drying oil.



   Coating compositions can be prepared from the oils according to the invention, so as to meet varying requirements. In particular, they easily accept all types of tone as well as organic and inorganic pigments such as titanium oxide, chromium green, carbon black, minium, toluidine and lithol red, iron and phthalocyanine, and chromium and hansa yellows. Depending on the type of pigment used and the intended end use, the concentration of the pigment in different enamels can be varied between wide limits, for example between 5 and 75% based on the weight of the polymerized non-volatile constituents of the oil. basic siccative.

   For example, carbon black is generally used in concentrations ranging from 6 to 10%, titanium dioxide in concentrations of 40 to 60% and lead pigments in even higher amounts. The compositions can be diluted or mixed with suitable hydrocarbon solvents, boiling between about 80 and 200 C, solvents which can be of the type used as diluents of the reaction in the synthesis of the above oil, or with others. solvents such as xylene, different solvent essences, mixed aromatic products from the range of benzene and xylene, white oils, solvents known under the name of "Solvesso", etc.



   Furthermore, while the treated oily products by themselves give protective coatings with well balanced properties, they can be further modified by mixing them with other drying oils such as linseed oil, oil. tung, soybean oil or other unsaturated vegetable oils. Often it is also advantageous to prepare a main mass of synthetic drying oil, treated with a relatively large amount of maleic anhydride, up to 5 or even 10%, and then as in

 <Desc / Clms Page number 30>

 operations N and 0, to cut the main mass with an additional quantity of drying oil, so as to give a drying oil having an average content of maleic anhydride of less than 1%.

   The drying oil used to cut the main mass can conveniently be a synthetic polymer or copolymer of butadiene not treated with maleic anhydride, for example a butadiene and styrene drying oil, as has been mentioned above. high, or the oil may be of natural origin. In this connection, the treated oil can be cut with untreated oil, so as to obtain a mixture having a total content of combined anhydria and it has been found that these mixtures have approximately the same properties as if one had. initially reacts all of the oil with the desired amount of anhydride.

   When desired, the products of the invention can also be mixed with different resins such as rosin and gum ester, so as to obtain protective coatings having special characteristics.



     EXAMPLE 18
In this example; the accelerating effect of butadiene and styrene copolymer oil was tested on an oleoresinous varnish containing alkali-refined soybean oil and a hydrocarbon resin prepared by copolymerization. - tion of 50 parts of butadiene and 50 parts of xylene, at -15, with an aluminum chloride catalyst.
 EMI30.1
 
<tb>
<tb>



  Formulas <SEP> Operation <SEP> Operation
<tb> 1, <SEP> gr <SEP> 2, <SEP> gr
<tb> Hydrocarbon <SEP> resin <SEP> 150 <SEP> 150
<tb> Refined <SEP> soybean <SEP> <SEP> to <SEP> alkali <SEP> 232 <SEP> 232
<tb>
 Butadiene and styrene oil (1) (prepared as described in operation A added to the mixture of soybean oil and resin in the form of a solution containing 2 g of straight-run mineral spirits) "38 , 2 - (1) 10% by weight based on soybean oil and resin.

 <Desc / Clms Page number 31>

 



   The above reagents were heated to 295 ° C in an aluminum boiler, under a layer of nitrogen, with stirring and holding at this temperature until the processing time of a thin film of the base varnish. on a plate heated to 200 C was reduced to 60 seconds. Then, the basic wernis was quickly cooled to 230 ° C and mixed with an equal weight of straight run mineral spirits.
 EMI31.1
 
<tb>
<tb>



  Results <SEP> Operation <SEP> 1 <SEP> Opera-
<tb>
 
 EMI31.2
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯ tion 2
 EMI31.3
 
<tb>
<tb> Cooking <SEP> duration <SEP>, <SEP> hours <SEP> 11.42 <SEP> 5.52
<tb> Loss <SEP> at <SEP> the <SEP> cooking, <SEP>% <SEP> in <SEP> weight <SEP> 16 <SEP> 11
<tb> Viscosity, <SEP> poises <SEP> 4 <SEP> 2.4
<tb> Color <SEP> (Gardner) <SEP> 14 <SEP> 12-13
<tb>
 
It is also noted that the curing time required for the accelerated varnish is only half the time required to effect the polymerization of the control varnish to a state characterized by a comparable processing time. Further, due to the shorter cooking time, the amount of the valuable oil lost during cooking appears to have been reduced by about a third.

   The color of the accelerated baked varnish was even lighter than that of the non-accelerated varnish.



   To show that the accelerated baked varnish had approximately the same processing time or the same drying speed as the more viscous product obtained by baking the non-accelerated varnish, the products of operations 9 and 10 were mixed with a siccative containing 0, 5% lead naphthenate and 0.05% manganese naphthenate and coated with tin plates which were tested.

 <Desc / Clms Page number 32>

 Air drying speed
 EMI32.1
 
<tb>
<tb> ¯¯¯¯Hours¯¯¯¯¯¯¯¯¯¯¯¯.
<tb>



  Sample <SEP> 1 <SEP> 2 <SEP> 4 <SEP> 6 <SEP> 24
<tb> Operation <SEP> 1 <SEP> 7 <SEP> 3 <SEP> 1 <SEP> 1 <SEP> 0
<tb> Operation <SEP> 2 <SEP> 6 <SEP> 3 <SEP> 2 <SEP> 1 <SEP> 0
<tb> * Scale <SEP>: <SEP> 9 <SEP> - <SEP> wet
<tb>
 
6 - taken to the touch
3 - dust free
0 - without viscosity
The properties of the air dried and baked films prepared from each of the varnishes were also compared:

  
Resistance of the 'Film * to
 EMI32.2
 
<tb>
<tb> Sample <SEP> Water <SEP> Soap <SEP> Grease <SEP> NaOH <SEP> Hardness <SEP> Flexibility
<tb> test <SEP> of
<tb> folding
<tb>
 
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 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯ ¯¯¯ ¯¯¯¯ ¯¯¯ ¯¯¯ to 180
 EMI32.4
 
<tb>
<tb> Dried <SEP> in <SEP> air, <SEP> 1 <SEP> week
<tb> Operation <SEP> 1 <SEP> 5 <SEP> 4 <SEP> 0 <SEP> 0 <SEP> good <SEP> not <SEP> assigned
<tb> Operation <SEP> 2 <SEP> 3 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> "<SEP>"
<tb> Cooked <SEP> 1 <SEP> hour <SEP> to <SEP> 12000
<tb> Operation <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> "
<tb> Operation <SEP> 2 <SEP> .0 <SEP> 0 <SEP> 0 <SEP> 4 <SEP> "
<tb>
   *Ladder :

     0 - not assigned
1- 3 - discolored
4- 6 - softened and less adherent
7-8 - pinholes or bulb
9 - film removed
The above results show that the two varnishes have approximately equal properties and that air-dried films from accelerated varnish have somewhat higher water and soap resistance than air-dried films made. of ordinary varnish, while films baked from ordinary varnish have a better

 <Desc / Clms Page number 33>

 alkali resistance than baked films made from accelerated varnish.



    EXAMPLE 19
We examined the drying rate of various glazes made with synthetic drying oils, mainly of hydrocarbon origin: a, when they were freshly prepared; b, after accelerated aging in closed containers at 60 C, and c, after aging in closed containers at room temperature.



   The enamel used here consisted of 200 gr of Varsol (mineral spirits of direct distillation boiling at 150 to 200 C); 200 g of a copolymer oil of butadiene and styrene (ratio of monomers 80/20), viscosity of about 1 poise at a non-volatile matter content of 50%; 200 gr of titanium dioxide pigment (rutile type, ground for enamel); 10 g of drier containing 10% lead and 1% manganese (in the form of naphthenates); 5 g of siccative containing 2% of cohalt (in the form of naphthenate); 10 gr of calcium oxide (powder).



   The polymer was prepared by the method of Example 1 and modified with about 0.2% maleic anhydride as stated above in Example 3, giving a 50% solution of copolymer oil in mineral spirits.



   The enamel was prepared by adding a sufficient amount of titanium dioxide-calcium oxide copolymer solution in the proportion desired to make a paste, after which the paste was ground to the particle size. suitable for enamel, on an ordinary three-roll pigment mill. Finally, the stock paste was reduced with the remainder of the polymer solution and dissolved.

 <Desc / Clms Page number 34>

 persé the siccatives indicated. Other colored enamels were prepared in the same way with variations allowing the quantity of pigments necessary to obtain a practical covering power.



   The advantageous effects of the invention are indicated by the figures in Table IV below.



   It has been found that the addition of calcium oxide supports a satisfactory drying rate for:. Enamels and paints based on synthetic hydrocarbon oils. Without this stabilizing action, they could not be recommended as constituting a quality product after storage for a relatively short time, under conditions which are not necessarily abnormal.



   In most of the examples, comparisons were made between products not comprising calcium oxide, representative of the previous procedure, and samples stabilized with calcium oxide according to the method of the invention. . After aging for a short time of 10 to 14 days or up to 210 days, the comparison samples did not dry to a dust free state within 6 hours. On the other hand, samples which had been stabilized with calcium oxide retained their satisfactory drying speed and became dust free in 6 hours or less.

   Some samples showed a slight decrease in drying speed, even in the presence of calcium oxide, but they still maintained the necessary equalization. There have been some small reductions in drying rate, even by storage at room temperature, without the aid of the invention, but the degree is not dangerous. Obviously, the initial concentration of the drier must be sufficient to promote the initial rate of drying, with or without the stabilizing effect of the calcium oxide.

 <Desc / Clms Page number 35>

 



    TABLE IV Effect of calcium oxide on the stability of the siccatives of hydrocarbon oil-based enamels, during aging (1)
 EMI35.1
 
<tb> Echan- <SEP> u.r.r. <SEP> Drying agent <SEP> uau <SEP> dies <SEP> of <SEP> se- <SEP> Days <SEP> of <SEP> Temp. <SEP> Hours <SEP> of <SEP> Days <SEP> of <SEP> Tempetillon <SEP> (2) <SEP> n <SEP> (3) <SEP>% <SEP> (4)

   <SEP> chage <SEP> initial <SEP> aged- <SEP> C <SEP> drying <SEP> aged- <SEP> erased
<tb> '2 <SEP> 4 <SEP> 6 <SEP> 24 <SEP> sement <SEP> 2 <SEP> 4 <SEP> 6 <SEP> 24 <SEP> sement <SEP> C
<tb> 1-1 <SEP> 50% <SEP> 5 <SEP> 0 <SEP> 6 <SEP> 3 <SEP> 0 <SEP> 0 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 0 <SEP> 94 <SEP> 60
<tb> 1-2 <SEP> 50 <SEP> 5 <SEP> 5 <SEP> 6 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 94 <SEP> 60
<tb> 2-1 <SEP> 40 <SEP> 4 <SEP> 0 <SEP> 7 <SEP> 4 <SEP> 1 <SEP> 1 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 0 <SEP> 90 <SEP> 60
<tb> 2-2 <SEP> 40 <SEP> 6 <SEP> 0 <SEP> 8 <SEP> 4 <SEP> 1 <SEP> 1 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 4 <SEP> 0 <SEP> 90 <SEP> 60
<tb> 2-3 <SEP> 50 <SEP> 6 <SEP> 0 <SEP> 8 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 14 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 5 <SEP> 0 <SEP> 90 <SEP> 60
<tb> 2-4 <SEP> 50 <SEP> 6

  <SEP> 5 <SEP> 8 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 14 <SEP> 60 <SEP> 7 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 90 <SEP > 60
<tb> 2-5 <SEP> 50 <SEP> 6 <SEP> 3 <SEP> 7 <SEP> 6 <SEP> 2 <SEP> 0 <SEP> 15 <SEP> 60 <SEP> 8 <SEP> 6 <SEP> 1 <SEP> 0 <SEP> 90 <SEP> 60
<tb> 3-1 <SEP> 50 <SEP> 5 <SEP> 5 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 25 <SEP> 60 <SEP> 7 <SEP> 4 <SEP> 3 <SEP> 0 <SEP> 60 <SEP> 60
<tb> 3-2 <SEP> 50 <SEP> 5 <SEP> (a) <SEP> 7 <SEP> 7 <SEP> 4 <SEP> 0 <SEP> 25 <SEP> 60 <SEP> 8 <SEP > 7 <SEP> 7 <SEP> 0 <SEP> 60 <SEP> 60
<tb> 4-1 <SEP> 50 <SEP> 5 <SEP> 5 <SEP> 6 <SEP> 1 <SEP> 0 <SEP> 0 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 3 <SEP> 0 <SEP> 94 <SEP> 60
<tb> 4-2 <SEP> 50 <SEP> 5 <SEP> (b)

   <SEP> 6 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 1 <SEP> 94 <SEP> 60
<tb> 4-3 <SEP> 50 <SEP> 5 <SEP> c <SEP> 6 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 2 <SEP> 94 <SEP> 60
<tb> 4-4 <SEP> 50 <SEP> 5 <SEP> d <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 13 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 60 <SEP> 60
<tb> 4-5 <SEP> 50 <SEP> 6 <SEP> e <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 0 <SEP> 11 <SEP> 60 <SEP> 8 <SEP>? <SEP> 7 <SEP> 0 <SEP> 33 <SEP> 60
<tb> 5-1 <SEP> 50 <SEP> 5 <SEP> 5 <SEP> 6 <SEP> 2 <SEP> 0 <SEP> 0 <SEP> 10 <SEP> 60 <SEP> 8 <SEP> 3 <SEP> 1 <SEP> 0 <SEP> 94 <SEP> 60
<tb> 5-2 <SEP> 50 <SEP> 5 <SEP> 0 <SEP> 8 <SEP> 4 <SEP> 3 <SEP> 0 <SEP> 14 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 5 <SEP> 0 <SEP> 60 <SEP> 60
<tb> 5-3 <SEP> 50 <SEP> 5 <SEP> 3 <SEP> 8 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 14 <SEP> 60 <SEP> 7 <SEP> 3 <SEP> 2 <SEP> 0 <SEP>

  60 <SEP> 60
<tb> 5-4 <SEP> 50 <SEP> 5 <SEP> 1.5 <SEP> 8 <SEP> 4 <SEP> 2 <SEP> 0 <SEP> 14 <SEP> 60 <SEP> 7 <SEP > 5 <SEP> 4 <SEP> 0 <SEP> 60 <SEP> 60
<tb> 5-5 <SEP> 50 <SEP> 5 <SEP> 0.75 <SEP> 8 <SEP> 4 <SEP> 2 <SEP> 0 <SEP> 14 <SEP> 60 <SEP> 7 <SEP > 5 <SEP> 3 <SEP> 0 <SEP> 60 <SEP> 60
<tb> 6-1 <SEP> 31 <SEP> 6 <SEP> 0 <SEP> 7 <SEP> 6 <SEP> 5 <SEP> 0 <SEP> 3 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 2 <SEP> 25 <SEP> 60
<tb> 6-2 <SEP> 25 <SEP> 5 <SEP> 3 <SEP> 8 <SEP> 6 <SEP> 2 <SEP> 0 <SEP> 11 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 5 <SEP> 0 <SEP> 90 <SEP> 60
<tb>
   (1) Code for the determination of the drying rates: 9-wet, 8-very sticky, 7-filmy sticky just to the finger, 6-taken to the touch, 3-noticeably viscous, mans dust-free, 0-non-viscous.



  (2) C.P.P., concentration by weight of pigment in% of total non-volatile matter.



  (3) Drying index: 4: 0.4% Pb, 0.04% Mn and 0.04% Co in terms of metal in the form of soap or naphthenate based on the drying polymer present; 5: 0.5% Pb, 0.05% lin, 0.05% Co; 6: 0.6% Pb, 0.06% Mn, 0.06% Co.



  (4)% CaO based on the amount of polymeric drier present.

 <Desc / Clms Page number 36>

 



    TABLE IV (continued)
 EMI36.1
 
<tb> Exchange- <SEP> Hours <SEP> of <SEP> Days <SEP> of <SEP> Temp. <SEP> Hours <SEP> of <SEP> Days <SEP> of <SEP> Temp. <SEP> Hours <SEP> of <SEP> Days <SEP> of <SEP> Temp. <SEP> Time <SEP> of <SEP> Days <SEP> of <SEP> TemP.Hours
<tb> ticon <SEP> drying <SEP> aged- <SEP> C <SEP> drying <SEP> aged- <SEP> C <SEP> drying <SEP> aged- <SEP> C <SEP> drying <SEP> aging- <SEP> C <SEP> of <SEP> sess <SEP> sement <SEP> sement <SEP> sement <SEP> drying
<tb> 2 <SEP> 4 <SEP> 6 <SEP> 24 <SEP> 2 <SEP> 4 <SEP> 6 <SEP> 24 <SEP> 2 <SEP> 4 <SEP> 6 <SEP> 24 <SEP > 2 <SEP> 4 <SEP> 6 <SEP> 24 <SEP> 2 <SEP> 4 <SEP> 6 <SEP> 24
<tb> White <SEP> enamels <SEP> to <SEP> dioxide <SEP> of <SEP> titana
<tb> 1-1 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 1 <SEP> 180 <SEP> 60 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 1 <SEP> 10 <SEP> 25 <SEP> 7

  <SEP> 4 <SEP> 2 <SEP> 0 <SEP> 94 <SEP> 25 <SEP> 8 <SEP> 6 <SEP> 4 <SEP> 0 <SEP> 180 <SEP> 25 <SEP> 8 <SEP > 6 <SEP> 3 <SEP> 0
<tb> 1-2 <SEP> 8 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 180 <SEP> 60 <SEP>? <SEP> 4 <SEP> 1 <SEP> 0 <SEP> 10 <SEP> 25 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 94 <SEP> 25 <SEP> 8 <SEP > 3 <SEP> 3 <SEP> 0 <SEP> 180 <SEP> 25 <SEP> 7 <SEP> 4 <SEP> 1 <SEP> 0
<tb> 2-1 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 2 <SEP> 180 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 3 <SEP> 10 <SEP> 25 <SEP> 7 <SEP> 5 <SEP> 3 <SEP> 0 <SEP> 90 <SEP> 25 <SEP> 8 <SEP> 7 <SEP> 6 <SEP> 0 <SEP> 180 <SEP > 25 <SEP> 7 <SEP> 7 <SEP> 7 <SEP>
<tb> 2-2 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 0 <SEP> 180 <SEP> 60 <SEP>? <SEP>? <SEP> 6 <SEP> 0 <SEP> 10 <SEP> 25 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 90 <SEP> 25 <SEP> 8 <SEP> 6 <SEP > 4 <SEP> 0 <SEP> 180 <SEP> 25 <SEP> 7 <SEP> 7 <SEP> 5 <SEP> 0
<tb> 2-3 <SEP> 8 <SEP>? <SEP>? <SEP> 0

  <SEP> 149 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 0 <SEP> 14 <SEP> 25 <SEP> 6 <SEP> 4 <SEP> 2 <SEP> 0 <SEP > 90 <SEP> 25 <SEP> 7 <SEP> 5 <SEP> 3 <SEP> 0 <SEP> 149 <SEP> 25 <SEP> 6 <SEP> 2 <SEP> 1 <SEP> 0
<tb> 2-4 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 149 <SEP> 60 <SEP> 7 <SEP> 6 <SEP> 2 <SEP> 0 <SEP> 14 <SEP> 25 <SEP> 6 <SEP> 3 <SEP> 1 <SEP> 0 <SEP> 90 <SEP> 25 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 149 <SEP > 25 <SEP> 7 <SEP> 2 <SEP> 1 <SEP> 0
<tb> 2-5 <SEP> 7 <SEP> 6 <SEP> 3 <SEP> 0 <SEP> 149 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 2 <SEP> 0 <SEP> 210 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 2 <SEP> 0- <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP>
<tb> 3-1 <SEP> 6 <SEP> 6 <SEP> 3 <SEP> 0 <SEP> 210 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 2 <SEP> 0 <SEP> 25 <SEP> 25 <SEP> 6 <SEP> 3 <SEP> 1 <SEP> 0 <SEP> 60 <SEP> 25 <SEP> 7 <SEP> 4 <SEP> 2 <SEP> 0 <SEP> 210 <SEP >

  25 <SEP> 7 <SEP> 4 <SEP> 1 <SEP> 0
<tb> 3-2 <SEP> 6 <SEP> 6 <SEP> 6 <SEP> 0 <SEP> 210 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 0 <SEP> 25 <SEP> 25 <SEP> 7 <SEP> 6 <SEP> 3 <SEP> 0 <SEP> 60 <SEP> 25 <SEP> 7 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 210 <SEP > 25 <SEP> 8 <SEP>? <SEP>? <SEP> 0
<tb> 4-1 <SEP> 7 <SEP> 5 <SEP> 5 <SEP> 0 <SEP> 180 <SEP> 60 <SEP> 6 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 10 <SEP> 25 <SEP> 7 <SEP> 4 <SEP> 1 <SEP> 0 <SEP> 94 <SEP> 25 <SEP> 8 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 180 <SEP > 25 <SEP> 8 <SEP> 3 <SEP> 1 <SEP> 0
<tb> 4-2 <SEP> 7 <SEP> 7 <SEP>? <SEP> P <SEP> 180 <SEP> 60 <SEP> 6 <SEP> 6 <SEP> 5 <SEP> 3 <SEP> 10 <SEP> 25 <SEP> 7 <SEP> 5 <SEP> 4 <SEP > 0 <SEP> 94 <SEP> 25 <SEP> 8 <SEP> 6 <SEP> 3 <SEP> 0 <SEP> 180 <SEP> 25 <SEP> 8 <SEP> 7 <SEP> 5 <SEP> 0
<tb> 4-3 <SEP> 8 <SEP> 8 <SEP> 7 <SEP> 3 <SEP> 180 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 10 <SEP> 25 <SEP> 7 <SEP> 4

  <SEP> 3 <SEP> c <SEP> 94 <SEP> 25 <SEP> 8 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 180 <SEP> 25 <SEP> 8 <SEP> 7 <SEP > 5 <SEP> 0
<tb> 4-4 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 6 <SEP>) 89 <SEP> 60 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 13 <SEP> 25 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 5 <SEP> 60 <SEP> 25 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 89 < SEP> 25 <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 6
<tb> 4-5 <SEP> 8 <SEP> 7 <SEP> 6 <SEP> 0 <SEP> chrome <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 11 <SEP> 25 <SEP> 7 <SEP> 7 <SEP> 3 <SEP> 0 <SEP> 33 <SEP> 25 <SEP> 7 <SEP> 3 <SEP> 1 <SEP> 0- <SEP> - < SEP> - <SEP> - <SEP> - <SEP> -
<tb> 5-1 <SEP> 8 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 180 <SEP> 60 <SEP> 7 <SEP> 2 <SEP> 0 <SEP> 0 <SEP> 10 <SEP> 25 <SEP> 6 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 94 <SEP> 25 <SEP> 8 <SEP> 2 <SEP> 1 <SEP> 0 <SEP> 180 <SEP > 25 <SEP> 8 <SEP> 2 <SEP> 1 <SEP> 0
<tb> 5-2 <SEP>? <SEP> 7 <SEP> 6 <SEP> 0 <SEP> 90 <SEP>

  60 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 1 <SEP> 14 <SEP> 25 <SEP> 7 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 60 <SEP> 25 < SEP> 6 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 90 <SEP> 25 <SEP> 7 <SEP> 5 <SEP> 3 <SEP> 0
<tb> 5-3 <SEP> 6 <SEP> 3 <SEP> 1 <SEP> 0 <SEP> 90 <SEP> 60 <SEP> 7 <SEP> 6 <SEP> 4 <SEP> 0 <SEP> 14 <SEP> 25 <SEP> 6 <SEP> 1 <SEP> 1 <SEP> 0 <SEP> 60 <SEP> 25 <SEP> 6 <SEP> 1 <SEP> 1 <SEP> 0 <SEP> 90 <SEP > 25 <SEP> 8 <SEP> 4 <SEP> 2 <SEP> 0
<tb> 5-4 <SEP> 7 <SEP> 5 <SEP> 4 <SEP> 0 <SEP> 90 <SEP> 60 <SEP> 7 <SEP> 6 <SEP> 5 <SEP> 1 <SEP> 14 <SEP> 25 <SEP> 6 <SEP> 2 <SEP> 1 <SEP> C <SEP> 60 <SEP> 25 <SEP> 7 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 90 <SEP > 25 <SEP> 7 <SEP> 5 <SEP> 4 <SEP> 0
<tb> 5-5 <SEP> 7 <SEP> 6 <SEP> 5 <SEP> 0 <SEP> 90 <SEP> 60 <SEP> 7 <SEP> 6 <SEP> 5 <SEP> 1 <SEP> 14 <SEP> 25 <SEP> 7 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 60 <SEP> 25 <SEP> 6 <SEP> 3 <SEP> 2 <SEP> 0 <SEP> 90 <SEP > 25 <SEP> 7 <SEP> 5

  <SEP> 4 <SEP> 0
<tb> Emals <SEP> to <SEP> green <SEP> of <SEP> chrome
<tb> 6.-1 <SEP> 8 <SEP> 7 <SEP> 7 <SEP> 1 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> -
<tb> 6-2 <SEP> 7 <SEP> 7 <SEP> 3 <SEP> 0 <SEP> 124 <SEP> 60 <SEP> 8 <SEP> 7 <SEP> 5 <SEP> 0 <SEP> 11 <SEP> 25 <SEP> 7 <SEP> 5 <SEP> 2 <SEP> 0 <SEP> 90 <SEP> 25 <SEP> 7 <SEP> 6 <SEP> 2 <SEP> 0 <SEP> 124 <SEP > 25 <SEP> 8 <SEP> 8 <SEP> 3 <SEP> 0
<tb>
   (a) 0.5% Ca as naphthenate, instead of calcium oxide b) 7.25% zinc oxide, instead of calcium oxide c) 3.6% magnesium oxide , instead of calcium oxide d) 5% of calcium hydrate, instead of calcium oxide e) 15% of barium oxide replacing about 5% of calcium oxide.

 <Desc / Clms Page number 37>

 



   The first two examples are typical. The unstabilized 1-1 sample dries to a tack-free state in 6 hours, when fresh, but after aging for 10 days at 60 C, the time has extended well beyond the desirable range of 6. hours. Sample 1-2, stabilized with calcium oxide, dried almost dust-free in 4 hours and almost no sticking in 6 hours, after being stored in closed containers for 180 days at 60 C.

   Samples 3-2, 4-2, 4-3, 4-4 and 4-5, containing calcium naphthenate, zinc oxide, magnesium oxide, hydra Calcium and barium oxide, respectively, show the relatively poor efficacy of these compounds as stabilizers under the conditions of the invention. Chromium yellow enamels show the effect of varying amounts of calcium oxide. It can be seen that the most effective concentration is between about 2-5 and 10, preferably between 3 and 5% calcium oxide based on the drying polymer present in the enamel.



   It can be seen from the foregoing that it has been found that calcium oxide is a surprisingly effective and unique material capable of stabilizing the drying rate of enamels containing a siccative based on a varnish. synthetic, primarily hydrocarbon in nature.

   Although the invention has been described in the case of enamels containing an almost complete varnish free of oxygen, prepared by the ex-sodium polymerization of monomers consisting entirely of hydrocarbons and which, therefore, represents the type of synthetic varnish most likely to lose its drying speed, it is understood that a similar advantageous result can be obtained with glazes of a slightly more pronounced polar nature, although the need for stabilization of the drier gradually decreases when the polar nature of the base enamel becomes more pronounced.



   It is also of course also understood that while we have not described here

 <Desc / Clms Page number 38>

 invention that in the case of some typical pigments it is about as effective with other pigments, such as toluidine red, lithol red, iron phthalocyanine blues, hansa yellow, minium , carbon black, etc. Depending on the type of pigment used and the subsequent use envisioned, the concentration of the pigment may vary, in the different enamels between distant limits, for example between 5 and 75% based on the weight of the non-volatile polymer constituents of the base varnish. . For example, carbon black is generally used in concentrations ranging from 6 to 10%, titanium dioxide from 35 to 70% and lead pigments in even higher concentrations by weight.

   Further, in preparing the initial paste, concentrations of up to 300 parts of pigment per 100 parts of base varnish are not abnormal.



   Likewise, although the invention has been described in the case of certain particular, common compositions of siccatives, it is also possible to use other known siccatives, individually or in admixture with each other, in the form of organic acid soaps. , oil soluble, heavy metal. As suitable siccatives, mention may be made of heavy metal soaps of octanoic acid, stearic or oleic acid, for example copper octoate, cobalt stearate or manganese oleate.



   In addition, the new compositions can be diluted or mixed with suitable hydrocarbon solvents, such as xylene, various gasolines-solvents, mixed aromatics from the range of benzene and xylene, white oils, etc.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

CLAIMS 1. A process for preparing copolymers of diolefins and ethylenically unsaturated monomers corolymerizable therewith suitable for use as drying oils, comprising polymerizing a mixture comprising <Desc / Clms Page number 39> 60 to 90%, preferably 75 to 85%, of a conjugated diolefin containing 4 to 6 carbon atoms per molecule, and 40 to 10%, preferably 15 to 25% of an ethylenically unsaturated monomer, copolymerizable with the diolefin, at a temperature between 20 and 100 C in the presence of metallic sodium as catalyst and of a diluent. 2. A process according to claim 1, wherein the temperature is below the melting point of the catalyst and is preferably between 65 and 8500, 3. A process according to claims 1 or 2, wherein the amount of catalyst is 0.1 10%, preferably 13% by weight of the olefin mixture. 4. A process according to any one of claims 1 to 3, wherein the diluent is a bydrocarburized solvent having a boiling point range of -15 to 200 C, such as heavy gasoline having a range. boiling points, ranging from 90 to 120 C, or straight-run mineral spirits boiling in the range 1,500 to 20,000. 5. A process according to any one of claims 1 to 4, wherein the amount of diluent used is 50 to 500 parts, preferably 200 to 300 parts, per 100 parts of polymerization mixture. 6. A process according to any one of claims 1 to 5, wherein the conjugated diolefin is 1-3 butadiene, isoprene, 1-3 dimethyl butadiene, p erylidene or methyl pentadiene. 7. A process according to any one of claims 1 to 6, wherein the ethylenically unsaturated monomer copolymerizable with the diolefin is styrene, an alkyl styrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl isobutyl ether, methyl vinyl ketone, or isopropenyl methyl ketone. 8. A variant of the process according to any one <Desc / Clms Page number 40> of claims 1 to 7, wherein a diluent capable of modifying the properties of a product is used instead of all or part of the inert diluents. 9. A process according to claim 8, wherein the modifier diluent consists of diethyl ether, diisopropyl ether, dioxane, vinyl ethyl ether, vinyl isopropyl ether, vinyl isobutyl ether, l. anisole or phenetole. 10. A process according to claims 8 or 9, wherein the amount of the modifying diluent used is 10 to 35 parts per 100 parts of the olefinic reaction mixture. 11. A process according to any one of claims 8 to 10, wherein the modifying diluent has a boiling point which is at least 10 ° C below the lower boiling limit of the inert diluent used. 12. A process according to any preceding claim, wherein the conjugated diolefin is 1-3 butadiene and the ethylenically unsaturated compound is styrene. 13. A process for the preparation of synthetic drying oils according to the process of any one of the preceding claims, which comprises copolymerizing 80 parts of butadiene 1-3 with 20 parts of styrene in the presence of 1.5 parts of metallic sodium. subdivided and 200 parts of an inert hydrocarbon solvent boiling between 150 and 200 C, 40 parts of dioxane and 0.2 part of isopropanol. 14. A process for preparing oily copolymers as claimed in any one of claims 1 to 13, wherein the finished copolymer is given body by heating it to a temperature of 200 to 300 C, preferably 2200 to 260. vs. 15. A process for the preparation of oil-based copolymers <Desc / Clms Page number 41> They are suitable for use as drying oils as claimed in any one of claims 1 to 13, wherein the copolymer produced is further reacted with a modifying agent comprising an unsaturated ethylene compound. EMI41.1 only, containing one or more non-hydrocarbon elements or groups and capable of reacting with the unsaturated groups of the copolymer, or a compound containing a thiol group. 16. A process according to claim 15, wherein the ethylenically unsaturated modifier containing one or more non-hydrocarbon elements or groups is an unsaturated dicarboxylic acid or an anhydride of such an acid. 17. A process according to claim 15, wherein the ethylenically unsaturated modifier containing one or more non-hydrocarbon elements or groups is maleic anhydride, chloromaleic anhydride or citraconic anhydride. 18. A process according to any one of claims 15 to 17, wherein maleic anhydride is used as a modifying agent in an amount between 0.01 and 2.5%, preferably 0.05 to 0.5%. by weight of the copolymer. 19. A process according to claim 15, wherein the ethylenically unsaturated modifier is acrylonitrile, methacrylonitrile, chlorjacrylonitrile, methyl acrylate, butyl acrylate, methyl methacrylate, acetate. vinyl, vinyl methyl ketone or cinnamaldehyde. 20. A process according to claim 15, wherein the modifying agent containing the thiol group is thioglycolic acid, mercaptopropionic acid or thiosalicylic acid, or a corresponding anhydride or aldehyde ester or a ketone thereof. body. 21. A process according to claim 19 or 20, wherein the amount of the modifying agent used is <Desc / Clms Page number 42> 0.1 to 10% by weight of the copolymer. 22. A following process. any of claims 15 to 21, wherein the processing is carried out under conditions such that the final product contains 0.05 to 0.5% by weight of the modifying agent. 23. A process according to any one of claims 15 to 22, wherein the treatment with the modifying agent is carried out by heating the mixture of the finished polymer and the modifying agent to a temperature between 50 and 250 C, preferably 180 to 220 C. 24. A process according to any one of claims 15 to 23, wherein the reaction is also carried out in the presence of 0.1 to 2% by weight, based on the polymer, of a peroxide catalyst. for example, benzoyl peroxide, tertiary butyl hydroperoxide, peracetic acid or cumene hydroperoxide. 25. An oily copolymer containing 60 to 90 parts per 100 by weight of a conjugated diolefin containing 4 to 6 carbon atoms in the molecule, and 40 to 10 parts per 100 by weight of an ethylenically unsaturated compound, this copolymer re having a molecular weight between 200d and 5000. 26. An oily copolymer comprising 75 to 85 parts per 100 by weight of a conjugated diolefin containing 4 to 6 carbon atoms per molecule, and 15 to 25 parts per 100 by weight of an ethylenically unsaturated compound, this copolymer having a molecular weight between 2000 and 5000. 27. An oily copolymer according to claims 25 or 26, wherein the conjugated diolefin is 1-3 butadiene, isoprene, 1-3 dimethyl butadiene, peryylene or methyl pentadiene. 28. An oily copolymer according to any one of claims 25 to 27, wherein the ethylethyl unsaturated compound is styrene, an alkyl styrene, acrylonitrile, methylacrylonitrile, methyl acrylate, methyl methacrylate. , vinyl isobutyl ether, methyl vinyl <Desc / Clms Page number 43> EMI43.1 ketone: or isopropenyl methyl ketone. 29. An oily copolymer of a conjugated diolefin containing 4 to 6 carbon atoms per molecule and a EMI43.2 an ethylenically unsaturated compound when prepared by the process of any one of claims 1 to 13. 30. An oily copolymer of a conjugated diolefin containing 4 to 6 carbon atoms per molecule and an ethylenically unsaturated compound, modified by addition of an ethylenically unsaturated compound containing one or more non-hydrocarbon elements or groups or a compound of thiol, as prepared by the process of. any one of claims 15 to 23. 31. An oily copolymer according to any one of claims 25 to 30, wherein the conjugated diolefin is butadiene and the ethylenically unsaturated compound is styrene. 32. An oily copolymer according to any one of claims 25 to 29, thickened by heating to a temperature between 200 and 300 C, preferably between 220 and 260 C. 33. A process for preparing a varnish or a paint or an enamel base, comprising dissolving a copolymer oil according to any one of claims 25 to 32, in an unsaturated drying oil, preferably a vegetable drying oil. 34. A process according to claim 33, wherein the solution of copolymeric oil in drying oil is further treated by heating to a temperature of between 230 and 330 C, preferably between 265 and 300 C, to cook it. . 35. A process according to claims 33 or 34, wherein the amount of polymer oil added to the drying oil is 2 to 25%, preferably 5 to 15% by weight of. <Desc / Clms Page number 44> this drying oil. 36. A process according to claims 33 or 34, wherein the 70 parts by weight of the copolymer oil is added to the 30 parts by weight of the drying oil. 37. A process according to any one of claims 33 to 36, wherein the drying oil is linseed oil, soybean oil, rapeseed oil, coconut oil. tung, cottonseed oil, perilla oil, oil EMI44.1 ost3'a, grain oil op, dehydrated castor oil, fish oil, sunflower oil or saffron oil. 38. A process according to any one of claims 33 to 37, wherein a soluble ester resin or gum is also added to the mixture. varnish 39. A paint or enamel base, comprising !, a solution of a copolymer oil according to any one; of claims 25 to 32, dissolved in a drying oil. 40. A varnish or paint or enamel base, according to claim 39, in which the drying oil is linseed oil, soybean oil, rapeseed oil, coconut oil. tung, cottonseed oil, perilla oil, orticla oil, grain oil, dehydrated castor oil, fish oil, oil of sunflower or saffron oil. 41. A varnish or paint or enamel base according to claims 9 or 40, in which the amount of the oily copolymer is 2 to 25%, preferably 5 to 15% by weight of the mixture. 42. A varnish or paint or enamel base according to claims 39 or 40, comprising 70 parts by weight of copolymer oil and 30 parts by weight of the drying oil. 43. The following varnish or paint or enamel base <Desc / Clms Page number 45> any one of claims: 39 to 42, wherein the mixture has been baked by heating to a temperature between 200 and 300 C, preferably between 265 and 300 C. a varnish or paint or enamel base according to any one of claims 39 to 43, in which the mixture also contains a soluble ester resin or gum. 45. A varnish or paint or enamel base, comprising a copolymer oil according to any one of claims 25 to 32, dissolved in an inert hydrocarbon solvent boiling between 80 and 200 C, in the proportion of 20 to 300 parts of the copolymer oil per 100 parts of the solvent. 46. A varnish or paint or enamel base according to claim 45, having a viscosity of 0.5 to 5 poises. 47. A varnish or: 1.paint or enamel base according to claims 46 or 47, in which a soluble ester resin or gum is also added. 48. An enamel comprising a liquid base according to any one of claims 44 to 47, together with 5 to 300 parts by weight of pigment per 100 parts by weight of liquid base. 49. An enamel according to claim 48, in which metal siccatives are also added. 50. An enamel comprising about 100 parts of titanium oxide pigment, about 100 parts of gasoline; minerals boiling between 150 and 200 C, about 100 parts of a sodium copolymeric drying oil composed of about 80 parts of combined butadiene, 20 parts of combined styrene and 0.05 to 0.5 part of combined maleic anhydride and having an intrinsic viscosity of about 0.2, and 0.05 to 1% of at least one naphthenate drier selected from the group comprising lead, cobalt, and manganese. 51. A cmail comprising about 5 to 300 parts of pigment per 100 parts of liquid base having a viscous <Desc / Clms Page number 46> Cosity of about 0.5 to 5 poises, this liquid base consisting essentially of 20 to 80% of an oily sodium polymer composed of 75 to 85 parts of combined butadiene, 25 to 15 parts of combined styrene and 0, 05 to 0.5 part of acrylonitrile combined, and dissolved in an inert hydrocarbon solvent boiling between about 80 and 200 C. 52. A process for improving the storage properties of enamels according to any one of claims 48 to 50, wherein 2.5 to 10% by weight of calcium oxide relative to the weight of the mixture is added to the mixture. copolymer oil. 53. An enamel according to any one of claims 48 to 50, also containing 2.5 to 10% by weight of finely divided calcium oxide, based on the copolymer oil.