DE1745791A1 - Method and device for the production of polyester resins - Google Patents

Description

Y / HL Case 1

PATINTANWAtTE 17AR791

dr. w. Schalk dipl-ing. Peter Wirth

DI PL.-I NG. G. E. M. DAN N EN BERG · DR. V. SCHMI ED-KOWARZIK

FRANKFURT AM MAIN . . _Λ ,,

r. _{oM> IieM1I (HllMll} , "." 4.1.1 *

AIiCIIER-DAHIEIb-MIDLAlID COMPANY

700 Investors Building Minneapolis, Hennepin, left Iinnesota / UGA.

Method and device for the production of polyester resins

The i.rfinduri; relates to and includes the manufacture of improved polyester resins, including alkyd resins, and the products made therefrom. In particular, the invention is concerned with improved, in particular 2Ui :; _iescj: .ic'itcii and coating g ^ee do ^ne 't' ^en preparations made from riiciib- ^ oiled polyester resins, including AlKydhurzen, i.iouirisiertan Al; ydnarzeu ud _o l., which, among other advantages, a better pourability, higher iPirte, toughness , cheiäjclie ./ideratandsfuhigkeit, permanent juiciness and desüerte Aata hardening times and in which the luolecular- ^ ev / i-rr-Vertfiilun ;;., · apparently proportionalOniariiliiiij ^ leichlichkeit; iat and the components with a ear high and very low ^ olukul -.- 'i'tiewicht only in unobjectionable! .. narrow vori.ando.i. .; ind. The invention .; also includes the devices used to provide the unnamed Pro \ u3ite.

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The invention uufaiüt AuCN improved V ^ ^ rii.uvea for iierstellunj of said polyester and Ai lydharüprodukte, starting from the Ausgaii ^ produlzteii. The χιΓί Lndun ^, from further encounters also improved to Seduce Ui /./ imJlun _o polyester and Alkydprodukten in those old improved properties by this ii- a large Men _c e of an inert solvent with or without Verriii ^ eruiig of bäurewertes ( SV /.) Treated v / ground. Ii ζ reference to the Z'oEieniclatur should under the pressure used in the application "polyester resin" and also Alicyd resins, modified ..i, -: ydnirze and polyester-like ür-.rze, as they ru.ciisT.ei.e .- ^ i.oc ;: öjnje ^ eberi v / erden, Liitverst-nder, v / earth. The iiu & är "c,: o"Polytii; terrio.rz "and" Alkydharz "kö; Ue: - · ulso ;: eoai.el:, n ± se L-.:.atzt vieratn, and neither of them ocludes the anüor & i - for the a ^ nnzeic: iu: .. from.

It is be ^ ui. :: ^, ia- Polyes jeriir.ri; -rr Ij ^ r ^^ e vüseaxliG-.e hens nieaermolelcul ^ re I ^J oIy ".ex-i3; ite ^ ο" .vie .. acii rolyr.erijaui: higher l.olekularge.7ic /: tes enthalccn. ZIt rAeuevuz ·! '- * Λ ^: ΐ "~ ιΐι polymers cause the" iC-i-fccriJkeiV -ier lilmt · v / l-ii'e ^ c · the hardening and beeiritrüciiti ^ -eii the J; .er ^ tfti ^ lceit, hardness, toughness, chemical viiders "ca: - * _i .cnf" .iii / -. ei't and aiviere Eigenjchaftei'i the Piliie. i «s has been sciion c.ari - .. ιΐ 'hin ^ ev / ieben, dai,' -veiin these Niederiaolelailaren fractions could be removed, the riarzfilL.e also dry faster in the air v / because then ice in the sticky; l: eit ba './ any material of lower molecular weight ₍ je * .: ichtii vorhunien be

008816/1811

• AD OWGiNAL

and; -with it also the hardness, toughness, criei. »i. ^r 3che resistors and3fähigkeit and durability improved γ / were ground, '/ ground the portions with lower. llole / .ular ^ ev / ot removed, ao the treated films also harden faster, and they are harder, tougher, more durable and also more chemically resistant.

The usual polyester resins contain some yo: -ochi; molecular polymers which, due to the complex nature of the polymer structure, high viscosity, incompatibility, erin (; en Ql .uz, _L : eri ::, je Farbaniii ^ ue and jeri.'iijes? -. ie.:-/perlauben ud ^ l. • verui-nuciieii. './erde.i diene fraction «., nehr hüiien molecule r, .ev: ichtea eiiofex-ni, εο be Polyeaterh ^ GCT; .. it jerin.jor ^ v 7i3: .oii; ^it: t, i _t verbecserter Yertr -liciikoit and li.juiic rliei * uov.'it;vorbe;; - nerteu Uj!. .i: z, verbesaerter Parbaniii-h .-. e and verbeatjei ' Atv iiij'.t ^ i «and other advantages.

it is also 3chon liin _t; EMI · -a '.- i: worier, eel ?, f ^ ILU both the fraction of low molecular · rtje-vichts as a fraction I Ie h;. Molecular weights may possibly digest polyester resin away, olnie duii ..itrbei wlüireud the ^ eJ.Mndlun ^ · ei.ie ielierunj, the following improvements are expected faster hardening {cDwoLl through 'Jrc-okne; i in the air as well as through Lr'.värmeii, harder films, ziih-ire "' ilr.:e, depressed _o ere Filrue, draerhafwere Piiiie, resin? lower Yiakcsite ^{: :} t, toler

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IAD OAlOINAL

Resins as well as resins of higher gloss, improved flowability, improved color pick-up and other advantages result.

The fractionation of alkyd resins is unsatisfactory, however, since good fractionation processes for polyester and alkyd resins are not available and in any case the use of fractionation as a measure to improve polyester and alkyd resins is an uneconomical process. Insofar as fractionation attempts have already been carried out, it has been determined! that the low molecular weight fractions (with a molecular weight of about 2000 or less) are watery and fluid, dry only slowly and remain sticky, and that the high molecular weight fractions (of about 10,000) are gelatinous, cannot be mixed with solvents and the high molecular weight Viscosity and incompatibility as well as the low gloss, the low flowability and ) ! the low acceptance of farts and the like.

The invention therefore aims to provide a solution esterification process and apparatus, among them Using improved polyester resins, including alkyd resins, can be made.

Another object of the invention is to provide a fermented solution esterification process and an apparatus for its manufacture

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of polyester resins, including alkyd resins, according to which the resins are made from the starting materials produced and / or under heat and pressure in the presence of a solvent in a certain ratio is used, converted and a solvent is used that is neutral to the resins, but those so prepared or converted in the solvent Able to dissolve resins, and the invention also relates to the products thus obtained.

Another object of the invention is to provide a method of additional treatment according to the conventional one Process produced, non-gelled polyester resin solutions with the application of heat and pressure and without gelling or causing a substantial increase in esterification or a decrease in acid value modified and improved « will.

The invention further aims to provide improved apparatus and methods for the manufacture of Polyester resins, including alkyd resins, with the application of which gelation of the resin in "the" Resin deposits are prevented, namely at acid values and under boiling conditions under which such gelation would normally occur, and the invention also includes the products thus obtained.

The invention is illustrated below with reference to the drawing

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schematieoh the preferred embodiment of the method and the apparatus and according to which it is operated under reflux, the reaction chamber under pressure and the. Condenser operated under normal pressure, and the return of the solvent to the reaction vessel is effected at approximately constant speed to all during the reaction process in the reaction system The times to maintain the desired amount of solvent are described in more detail by a few examples.

In the present invention, the polyester resin is used in a certain amount of a selective solvent either formed or transformed, which dissolves the resin thus formed, but does not enter into the reaction. The reaction for the formation of the resin can be carried out from the beginning in the specific and required amount of solvent or the resin may be partially formed or made in a non-gelled state and then by treatment in a specific L'Ienge solvent solution further implemented for its we * i> fee- »e * t improvement will.

In order to carry out the invention, it must be determined that the solvent for use in making the improved products are as follows Have properties:

1. The solvent must, calculated on the weight of the total commitment, in a very specific amount of about 30 to about 70 # and a sufficient one

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Have the ability to react to the polyester resin during of the process and as the end product in solution.

2. The solvent must be neutral with respect to the reactants and conditions.

3. ^I1 Ur dl · carrying out the process is to have the solvent tlnen Siedebereioh up to about 205 ⁰ C and gate ways consist of the same solvent,

the product diluted with the * e for its natural use will.

4. The neutral liquid organic solvent must only have a low solution content for water, to facilitate the removal of leaking water.

Solvents with a boiling range not above about 205 ⁰ C are mostly used for the production of τοη coatings. If higher-boiling solvents are used, they must be removed and a lower-boiling solvent replaced, since the high-boiling solvents delay the hardening of the alkyd resin pilms under normal drying conditions. In this respect, however, it has been found that the higher-boiling solvents can only be removed with difficulty, if not impossible, from the alkyd resin in exchange for another solvent. One of the difficulties encountered here is that the resin often gels during the removal of the solvent, or that the resin-like preparation contains gel particles which cannot be filtered off and is indicated by 009616/1811

17457ii

then the connection between the applied films is disturbed. It follows that the alkyd resins before use All coating compounds must not be in a gel state at any time.

According to the present invention, several processes have now been developed in which a solution esterification for Use comes, and "in particular for the production of the alkyd resins according to the invention. These processes can, for example ™ can be divided as follows

1. The polyester resin is tone beginning in dea Solvent produced

Under these conditions, the components of the polyester, such as dlt fatty acid, the Pelyel UjU the polybasic acids together old one so dimensioned (critical) amount of a solvent in dark tones used to ensure that the solvent is always in Merigin Von

·. ■ · *> ■

' About 30 to about 700 of the total charge, inclusive of the solvent, with about 40 to about 65ji being preferred for better effect. The esterification reaction of the polyester may under reflux conditions and using appropriate measures for the removal of the water at about 205 - 26O ⁰ C are performed with a temperature of about 232 - 255 ° is preferred. If a solvent is used which meets the above conditions, then one must work under pressure

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1745731

azeotropic process can be used. A preferred embodiment of one that can be used for this purpose Printing device is shown in the newspaper and is described in more detail below. The use of reflux is to accomplish the polyester conversion not always necessary, of course, but reflux will accelerate the reaction, and preferably are therefore reflux conditions in the treatment preferably such that the percentage of solvent in the reaction zone remains practically constant. If water is formed during the esterification reaction, certain measures must be taken to remove it will. After this procedure, the resin is processed under the above-mentioned conditions to the desired ones Final values for acid value and viscosity - processed. After the desired acid levels have been reached, the resin is cooled and adjusted to the desired percentage adjusted to solids in the desired solvent, which is preferably from the same solvent that has been used in the solution esterification reaction.

Various embodiments of azeotropically operating printing devices can be used to carry out the method to be used. With one execution * ferm of the device are the autoclave or the reaction vessel (which are equipped with a suitable stirring device

009818/1811

the condenser and the separator (water separator) are all connected and locked, to prevent vapors from escaping into the atmosphere. Under these conditions, the water and solvent escaping from the reaction mixture are condensed in the condenser, and they then flow into the separator, in which the water separates out, while the solvent is fed back into the reaction mixture by incline or with the use of a circulation pump · In one of such a device, the reaction takes place in the j

essentially in the same way as a normal cooking or Fusion cook under solvent reflux at atmospheric pressure, with the only difference that the The reaction device is closed and the pressure is increased »

In the preferred embodiment of the device, the As illustrated in the drawing, only the reaction vessel is pressurized. While processing will a mixture of solvent and water vapor is continuously driven off through a throttle valve, compressed in a condenser and boiled in a separator. By a suitable pump is then used to return the liquid solvent to the reaction mixture. This pump must the solvent against the pressure in the reaction vessel ' return, TBd si · must therefore be implemented so that it also pumps against the developed Druok · By suitable Control devices can be the pump and the throttle valve

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be adjusted so that the same amount of solvent is returned to the reaction vessel as it is through the throttle valve is removed. This device is the preferred one.

If the amount of solvent used during processing is greater than is desired in the final resin, so some of the solvent can be removed either under vacuum, or at atmospheric pressure, or by stripping while the resin solution is at the temperature of the esterification reaction. On the other hand, can But no solvents can also be added to the resin solution in order to produce a Harelöeung as the end product j has a lower solids content than during the - production stage »The solvent can duroh any j appropriate measures are added «by hiring '. · The solids content duroh any suitable measures can thus finally resin products with the desired Solids content can be produced.

2. Alcohol se of the triglyceride component

of the resin as a preliminary stage of the polyesterification reaction.

In this procedure, the triglyceride oil component the polyester resin such as soybean oil, linseed oil, saffron oil and the like, and a desired natural or synthetic one Polyol in the presence of a suitable catalyst at about

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. «J ', j

• i -

232 - 260 * 0

u «.in ·

ttil ftf »Hi

After alcoholy has ended, like i ^ lltu feitgeetellt will be, the Ub ^ i || in Btaifl de Aniatiii β ο like dai inert Esterification does not occur the butt above beeohrieben, weitir

5. Procedure »according to which φ fti * kti $ formation you polyestirhare ·· iI ia way carried out wifd, atMff nlöh% point out, to wilehe» · 1 * ι öeliemni lifttfitt.

SW / Y

i?

* i,

Haoh this Working while, and tin 41 · response time suffered beeohleunigen was feitgeitlllt _t 111, the ImH medium for Löiunge-Vereitirung'fiioht Echia ie ". High reaction vegetarian du ftioht-gllierten Aniatses be zugeeetsi ,, lof «Al became Tiel» ehjr da | The main part of the volatility dii folyeii under normal conditions is carried out <the inert solvent is set in the position, on aiia the usual V ^ ffahriaii wine to the! Cell eohon carried out or almost as soon as q $ t termination without & elieruÄg progress the reaction then in the critical amount of solvent is continued to flow.

. '' ■■ *

According to the invention, it has been found that the polyether haree which according to Method 1 above, and

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ORIGINAL INSPECTED

- ■ «■■ -. ■■";

1741711

_j ά1βΒ · 1ΐ5 · η Jplytiterprajtfrt / tt, which are manufactured according to the above Vtrfahrtft a and 3, are almost equivalent. The color, the speed of movement, the durability and the absolute durability, etc., are almost j

ι the same for a hair, since "after any one of the Driving eats, however, likes the viscosity to a certain extent be somewhat boiled.

4. Solution modification of polyester resins.

Another process for the production of non-gelled polyester resins of certain composition and properties is that the Harae are heated in an inert solvent of the type and amount specified above. In this way, one or more of the properties of the resin are changed and thus its range of general uses is improved. According to the invention, finished and technically usable polyester resins are thus diluted with a solvent of the type and amount mentioned above and heated under pressure in a sealed reaction vessel, then cooled and then filtered. In this way, a reduction in viscosity is achieved without any- ^! a significant change in acid value. In addition, the flow and hardness properties of the common laoc preparations and the like made from them are improved.

Solvents which are used according to the invention with good results are coating solvents with

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1745781

A rating range of et ** 61-215 0, such as Ilr »le _t lacquer,! aphtha, petroleum distillates (such as mineral spirit, white epirits), solvent naphtha, trichlorethylene, haphthene and the like.

Other useful solvents, which are also bit good, Results that can be used are aromatic solvents such as xylene, toluene, benzene, chlorobenzene and various petroleum solvents that contain a larger amount containing aromatic compounds commonly used in top and coating compositions. These inert liquid organic As is known in the art of painting, solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons and chlorinated aliphatic and aromatic Hydrocarbons.

It has been found that the amount of inert solvent has a certain influence on the final viscosity of the resin produced and has a certain interaction with it. As it is from the following cited examples, the viscosity of the final resin increases when the tightness of the inert Solvent between the limit values of about 30 to about 7Ο? * »of the total in the heaktionzone Material decreases. However, within these limit values, the final properties of the resin films do not change significantly. -lioh. If less than about 3054 solvents are present in the heating zone, little benefit is obtained, while if more than 7-9 solvents are used

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γ · ■ .-

- 15 -

become, in the preserved parts of the gate no particular increase '

j is to be released. When driving should therefore, among other things,

in the application "non-gelled products ι described

IU obtained a critical amount of about 30 The about 70 ^,

■ ÜUBunga means are used. '|

Wha furthermore the modified polyester approaches according to the invention are concerned, ao the usual fatty acids, fatty acid esters and fatty oils as well as synthetic λ- compounds with carbon chains, which contain aliphatic and alioyolic groups with 4-26 carbon atoms and in structure, for example, correspond to synthetic acids and acids and inabeeoftdere from vegetable liohen and

animal oil wells and the like are obtained, used and

be used to modify the alkyd resins discussed. Typical sources are, for example, soy "linseed, saffron, tung, coconut, yalnul" rape, perilla, sunflower, Hizinus, battBiwolleat> t _t tuna, sardines, herrings, tall oil acids and the like, and those made from substituted or unsubstituted long-chain lengths In addition, any of the polyols normally used in polyester and alkydane ethers can be used usual two-component

Acids or anhydrides are used, such as phthalic acid, ι

i phthalic anhydride, isophthalic anhydride, sharkic acid

anhydride, "." 'uaarscnire, .. ipic acid, sebacic acid, dimers 009816/1811

• AD

Acids, etc. Monobasic acidic modifiers can also be used, such as pelargonic acid, cyölohexanoarboxylic acid, Benzoic acid, p-tert. Butylbenzoic acid or resin. Tribasic acids or anhydrides, such as trimelitic acid - anhydride, can also be used.

According to the invention it was also found that the solution esterification process enables the production and processing of polyester resins without gelation, which, if they are produced by a conventional azeotropic solvent or melt process, would be obtained in gels. The theory of gelation is that a gelled resin except molecules of low and medium molecular weights · a considerable amount verrietet strong contains · * I.Ioleküle. These highly crosslinked molecules in solvents * * eo] -that the more soluble molecules in its structure eingeeöhloi sen are gel-like insoluble and by nature a. From the solution-fitting according to the invention * · "'"'

process is believed that in dieiem dit such hoohvernetzter molecular arrangements verhi | l changed, is by allowing precise control of Ansaht '' networking 'polyester resin Ansätee of which is known to gel under certain conditions, for example when they are cooked for so long as to reduce the acid number to a certain value * can be clogged to much lower acid values if the polyether reaction is carried out according to the solution fermentation method of the present invention.

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-H-

The polyester resins so produced in accordance with the present invention have certain desirable viscosity-solids interactions and are generally characterized by excellent flow properties, very fast setting properties, hardness, flexible films, good adhesion, good chemical resistance, excellent durability and the like. Certain batches can even be produced with exceptionally good properties, which heretofore could not be achieved with conventional polyester resins, and in each case improvements in one or more properties can be observed. It was partly found that alkyd and polyester resin formulations which, if prepared in conventional manner to a low acid number, would give gels or near gels, ungelled resins with improved best film-forming properties and improved films obtained therefrom when made in accordance with the present invention.

V / ith the present invention a polyester approach used which would gel under λ conventional processing, so must the inert solvent may be added before the üelierung occurs. However, it is practically immaterial when the inert solvent is added, provided that it is added before the resin gels. The polyester resin Jcunn aloo heated almost until the time of elimination and then the solvent was added, which immediately prevents gel formation. Such up close

. 009816/1811

IAD ORIGINAL

however, processing performed on gelation is not recommended because it may cause gelation to occur before it can be stopped. However, if you work carefully, the resin can be boiled almost to the gelling point. If, however, the solvent is not added early enough or not mixed in quickly enough, the pail can occur that the resin further boils off to an insoluble gel before this. Solvent has completely got into the circle and has had the opportunity to make use of its beneficial influence. For this reason, ea is therefore zveclaiiui, - ,, the polyester resin approaches only bi3 to one: states etv / a 5 bic 10 points above the V / ertes to process, with v.'elciiem the gelation occurs when the same resin is prepared in ilblicner way, and then add ά & α inert solvents. The resin solution will then continue without

gel-free gelation takes place up to the desired point in the inert solvent, as described, processed.

It was found that the procedure and the techniques In particular, alkyd resins can be used, which are intermolecular with up to about 70 Gev /.'/ ί of a fatty acid component that have been modified from animal or vegetable and synthetic. Oils or lutes and acids obtained from such sources are diluted. The claimed mode of operation also applies to Λ1- "yd / tarze, the are essentially unmodified or oil-free, and sometimes referred to as polyester. JJ3.3 procedure

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OWGINAL

Can also be applied to all alkyd and polyester resins that have been intermolecularly modified with up to 95 % Pettsfiurekoinponenten, but no significant improvements were observed in the properties or found with known test methods when the resin was intermolecularly modified with more than about 70%. "S fatty acid" components are modified and then further processed as described in the application.

The device illustrated in the drawing and suitable for carrying out the method measures according to the invention contains a system which can be operated either as a closed or open system. It consists essentially of an autoclave or a reaction vessel 10, which contains a suitable (not illustrated) stirring device and is connected by a steam line 11 to a condenser 12, so / ie a condensate return line 13, a condensate and water trap 14 and a Solvent return purape 19 with nasty %

loosened IcJsunga-return lines 15,16,17 and 18 and others: ·! * Plushness lines and KontroXl- and controls as described in more detail below. Dat: The reaction vessel itself is equipped with a liicht-illustrated inlet port for the feed and a Abzuösleitun ^ provided through a valve can be closed and opened.

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The line 11 is connected to a regulating steam flow Valve 25 is provided, through which the line 11 can also be closed when the reaction vessel 10 falls below the reaction pressure should be used. The condenser is provided with a valve 26 that allows the condenser system to work at atmospheric pressure and also to remove it the non-condensable and harmful discoloration of the resins "causing gases from the device enables.

The condensate return line 13 is provided with a sight glass 35 and a flow regulating valve 35 *, through which the condensate from the condenser 12 is fed to the separator H through the gradient. A branch line 28, 29 equipped with a flow control valve 27 is also connected to the pipe 13, and the line 29 is connected to a discharge line controlled by a valve 57, which can be used to ^:

»To be deducted from the system, as described below b · -

is written. . . ^s

The line 28 is near the bottom to the separator H connected so that the / \ contained in the solvent

• ·

with recirculated water separates more easily and. * accumulates at the bottom of the separator 14. The accumulated in the separator Water can be withdrawn from this by actuating the valve 31 through the line 30, what

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can be determined through a (not illustrated) glass. The Soheider 14 is provided with a drain line 15 through which the solvent can be drawn off after the reaction vessel 10. The line 15 is connected to the reaction vessel 10 by the line 16, which enables the solvent condensate to flow back when the valves 37 and 60 are opened due to the gradient. However, a return against the pressure in the reaction vessel 10 via the lines 17 and 18, opening the valves 17 ′, 18 and 36 and starting up a suitable pressure pump 19, is also provided. When the pressure pump 19 is used, the valve 37 is closed, | A secondary guard equipped with a valve 34 is also provided on the line 18, through which solvent can be fed to the reaction vessel 10 if necessary. _;

• i

The separator 14 is also available with a pressure equalization line 40 ^! through which the head of the Soheider is connected to the condenser 12 just below the gas discharge valve 26. The line 40 can be opened and closed through the valve 38.

In order to enable a coordinated regulation of the outgoing β and its return after the heating vessel 10, a branch line 43 is arranged in the vicinity of the valve 25, in which control valves 41 and 42 regulating the flow and in the pressure vessel are arranged «Lven1iil 44

009818/1011 * <

Original inspected

are provided. Since "Br * 0ka ^ m? Mti ^ 44" 4? 4 'tt • unification with the solvent level 1 "SoheideirU by the Sohwlmmer 46, the Ilüeeig · keitsdruolc in the line 47 is controlled by actuating the · control valve s 48 , since · is duroh line 4 $ a "^ angesohioeeen a non-veraneohauliohte source of fluid pressure" Derartigj | _ateuerventile are tekannt and therefore brauohen closer nioht here be _B cribed.

The hot cooling coil system and their. Iempe "f ^ 3fi1i # ttiTy tung 33 from known" · Auführun "and Imifytmk " ifefr a more detailed description of their effects "

Furthermore, a discharge line 54 with valve 55 is provided on the reaction vessel, through which samples of the converted polyester can be drawn off, as will be described in more detail below .

The invention is completed by 4i · napÄet |

explained in de? | ej | _t fQfy * niihta |

«The parts of the iaipoMnten ier aneätee #« wioÄdivided mean-

«He invention

Polyesters and alkyds with a high acid number to form liquid excess

*
egelöeungen with liquid-solid contents and

Acid values are converted at which the polymers would normally consist of irreversible and insoluble gels. The manufacture of strongly acidic polyester and alkyd materials is known in the art. However, in order to especially connect short, medium and
to explain long 01- and acid type, for which the bevoraugte method is particularly applicable to ^e ν gestures ftachatehend described but both f drive whose Anaätze and their Herstellungaver-.

Example 1.

The following jo ja Jl :: ^ ttsäure- alkyd resin sät ζ formed,
if it has been processed according to the above procedural measures, if it has a value of J> C - 35, it is irreversible
and insoluble gel.
The approach consisted of the following components:

Soy fatty acid 725 parts by weight

Glyoerin 332 ""

Pentaerythritol 196 ""

Phthalic Anhydride 932 ""

After the present process, this alkyd resin was used
first prepared by conventional boiling of the batch to an acid value of about 40 to 5P, then diluted with 4000 parts (ie 65>) solvent (xylene)) and then

009816/1811

ORIGINAL INSPECTED

teaed in the reaction vessel 10, pat

I would also have learning activities from the start and the diluent can then be reacted. ' _v ! "· Y

Then the reaction vessel 10 with the above had been impressed »was the Scheider 14 with the Xylene solvents at the level of the result 15 The solution agent condensation tea is filled. Then it was felt

waeeer duroh a (nioht-veraneohauliohten) heat exchanger in the condenser Ht geaohiokt. Thereupon "lit valves were closed, with the exception of the valves 25" of the Aualafiventile 26 and 38 tia $ dee valves "27 / '

After the device had been adjusted as indicated, the heating length 32 was heated and the temperature control device 35 was adjusted so that the usual reaction condition of 232 - 249 ⁰ O was reached. was obtained. The (non-veraneoJUutfMit) stirrer in the heating vessel 10 was then started. 'At about 138 ⁰ O dae töeungeeittel began aue abeudeetillieren the Reaktiehegemiech, and ee was offtut by dae valve 26, the air aue the device displaces · The Dtetillation of Löeungemittel duroh deeeen Anetuamlung in Sichtglae 35 was observed * The air and other niohtkondeneierbare Gaee be ready after kureer distillation

also displaced from the reaction vessel 10. Dae open vent valve 38

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- as ί

enables free drainage of the condensate duroh the lines 13 »29 and 20 to the separator 14, where the valve 35 is closed and the valve 37 is open.

After the cleaning mentioned, the reaction vessel was closed by opening the valve 25. The heating of the reaction vessel was then continued, was reached until the gewünsohte React ions temperamental door of 232 ■ "249 ^0C. At this temperature the pressure in the reaction vessel was about 7-9 kg / o ». After the reaction temperature of about 238 ° had been reached, the two valves 41 and 42 and also the valves 27, 17 ', 18' and 36 were opened. The solvent distilled off from the reaction vessel 10 hit the Soheider 14 up to the level above the line 15 and flowed off via the lines 1 and 17. At this point, as a result of d || attached IltUsigkeitsspiegel im Soheidi # 'U ^ | {l Tfntil 48. operated by the float 46, u «j | 1iputv * ^ 1 ^^ 4 | Ktit einule ^ th and the pressure control valve 44 ''m ^ bf ^ lilgan * on this Weiae the valve 44 aUtoa ^ || ^ | t ^^ j ^ tpt ^ llt | - .; ujtt in the device «in öleiohgewioll ^« wi <p «tt 4e» during the reaction

the 3qhfide4

> ·· ■ -rf

and the

wrinkled to normal · » plant the

At this point in time the * the solvent condtmat au «

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i.f

INSPECTED '' '

and it against the pressure generated in the reaction vessel into the Reaction vessel 10 to be pushed back. This recycle condition is continued to maintain the solvent in the reaction vessel at a relatively constant percentage. Sas solvent is used also as azeotropes, in that water is supplied to the separator 14. In suitable intervals the water was withdrawn from the separator 14 through the exhaust pipe 30.

With the progress of reaction, 10 samples were taken from time to time from the reaction vessel and the acid value determined by Ubllohe analysis', the acid value glue in the solution with 3 »5 dropped, the pressurizing pump were stopped 19, the valves 27 and 36 are closed and the Valve opened to allow the solvent distillate to be withdrawn through line 58 into a sump not shown. After about 2000 parts of Jylene- solvent had been distilled off to obtain a solution containing about 50% non-volatile substances, the valves 41 and 42 were closed, the temperature control device 33 switched over and cooling liquid was forced through the heat exchanger 32. After cooling, the product was drawn off through valve 60 and filtered, and it could now be used immediately or in a drum or the like. get saved.

Thus, the reflux conditions were explained, for example, by a relatively constant percentage

009816/1811 __

ORIGINAL INSPECTED

of solvent in the range that is desirable for the conversion of an alkyd material of high acidity into a non-gelled hair with a lower acid number bit improved physical properties. Reflux procedures can also be applied to changes in the reaction temperature, which also necessitate changes in pressure and in the reaction time. The Lösungβ- like feittel mark AUOH after the initial esterification züge- '"• tit and the formation of the resin then, as described above, MLI desolate without removing dsr nioht-condensable that | be out ttt · the device" u Bnde, for Manufacture of overexposure masses, as well as color carriers and the like, is »sweeping to remove the non-condensable gauges from the hard places * so that healer shades are obtained«

The following example reraneoha illustrates the manufacture of the dee Horses ft | e example 1, where tea starting hares is produced under reflux conditions and a solvent.

Example 2.

In Example 1, the alkyd hair was first produced and then converted after the addition of the solvent. she Beetandteile of the resin batch of Example 1 were with

009816/1811

ORIGINAL INSPECTED

All the solvent is put into the reaction vessel and the entire reaction is carried out in one operation Use of the described azeotropic printing process brought to the end. Although this procedure is not preferred, it becomes the two- or multi-step Avoided working the preferred method. This one-step procedure requires about twice as much Response time, even when carried out at higher temperatures. This time factor makes besides others Factors this way of working is more expensive and is less for the implementation of the method.8 in technical systems expedient.

The final constants of the alkyd resins prepared according to Examples 1 and 2 were, according to analysis, the following:

N.P. (non-c-frichtige substances) 50

viscosity 15-25 stokee

S.W. (Acid substances) 6-10

Color (Gardner) 5-8

Solvent xylene.

Below are some of the advantages of the alkyd resin materials which were prepared by the procedure of Examples 1 and 2 are illustrated. To 90 g samples of each of the converted Resin solutions with 506 N.P. were 10 g xylene, 0.32 ecm of a 6 year old cobalt naphthenate solution, 0.65 ecm

009816/1811

a 24 $ solution of lead naphthenate and 0.47 com of a 4 $ solution of gallium naphthenate added to catalyze the drying of the films made from the resin solutions. The films were drawn down on glass to a thickness of 0.0381 mm. These films air dried to tack free in 5 minutes as measured by the 500 g Zapon test. In 1 hour the Bward hardness was 16 $ and after 1 saga 32j5. Films 0.0381 thick were also cast on glass and heated and cured at 149 ° C for 15 minutes. The Sward hardness was 48 ^ς / ί. By comparison, it was found that the air ^r irockenzeit and the Sward hardness of these alkyd resins prepared according to Examples 1 and 2 were much better than that made the relatively slow-drying and softer alkyd resins as the starting materials of Example 1, but after the usual Working method were cooked almost to their gelling point. The hardened resin films were also very resistant to chemical solvents, damage and abrasion.

Heretofore, in order to obtain these film properties, it has been considered necessary to use those initially produced Polyester or alkyd resins with hard resins such as phenolic resins, urea and amine resins, nitrocellulose lacquers, Vinyl resins, or modify them with reactive ones to further polymerize monomeric vinyl compounds and the like. However, it is known that resins modified in this way

• 009816/1811

- 30 - ·

17457 * 1

usually do not have good resistance to solvents and damage

To further illustrate the benefits of solvent processing of alkyd resin approaches are obtained, the following examples are also given.

Example 3.

An alkyd resin was made from the following approach »

Soy fatty acids 415.5 parts ethylene glycol 93.4 ^M

Pentaerythritol 166.8

Phthalic anhydride 376.8 ··.

The starting materials were all in the reaction vessel inserted and at 205 - 221 ⁰ C esterified with liquation Xiirloi-IHlckflu2 * in the manner described in Example 2 for the preparation of Ausganga ^ .l ^ dharzes. The physical properties of the resin were as follows

<fi Ν.Γ. - 60

Viscosity TV ■,

S.W. 6-10 (on solids)

Color ^l -7 max.

solvent xylene. ν

This product is available as a slow drying commercial praukt usable.

009816/1811

■ AD

Example 3a.

Dae above Kara was stripped with xylene as solvent at 60 <i nlaht-flüohtige substances (KP), washed the solution heated to about 158 ⁰ O, and the reaction apparatus as described in Example 1 _f of the non-kondenaierbaren gases. NaOH cleaning the mixture in a sealed reaction vessel was heated to about 205-232 ⁰ G tmd heated for about 1 hour kept at that temperature, without an apparent change took place in the acid number. The combined Vfirkung of heat, the transit "and stirring the solution, however, a new resin is eriial- \ th, which, compared with the original physical values, the following physical values comprises:

1> Hf 60

Yiskositat H-P

S.W. 6-10

Color - 7 nax.

Solvent xylene.

The only apparent change was * a comparison i (ringerung the Tiekosität without gelling. Were however,

on top of this treated hair coating masses of the usual anaesthetics so were the flowability and applicability substantially superior to those of the coating compositions prepared according to Example 3, and they also had j better drying properties, as indicated in table 1 has been.

009816 / 18J1

• AD 0 "UOJNAL

422.3 Parts 70.5 H 198.1
382.4 H
•

Example 4.

Another resin formulation is given below, the after normal processing it gelled at an acid value of about 10. The approach consisted of the following Fabrics:

So 1 afatty acid ethylene glycol pentaerythritol phthalic anhydride

This alkyd resin was made by your usual cooking process made until the acid value was about 15-20, and then diluted with xylene to 40% non-volatile matter and finally according to the procedure described in Example 1 under pressure to an acid value below 10 further processed. The physical properties of the resin carrier obtained were as follows

ψ Η.Ϊ 60

Viscosity U-W

Color 7 max.

S.tf. 6-10

Solvent xylene.

■ ■ ■. '' ■ ^ 3eiepiel 5.

An additional alkyd resin preparation was made from the following Fabrics made "

00981S / 1811

So ¹ ^ fatty acids 420j 9

Ethylene glycol 52.6

Pentaerythritol 206.4

Phthalic anhydride 387.5.

The first stage of the preparation of this alkyd resin was carried out by a conventional method and shortly before the selection stopped at an acid value of 40.

This approach has been made by usual cooking to a low level Acid number processed further, as it is suitable for use in varnish, Ladt and color carriers, so gelled this resin has an acid number of about 20-25. However, this produced non-gelie.rte alkyd resin with xylene as a solvent to a content of 50yj non-volatile οtopen blended and placed in the reaction vessel for treatment according to the conversion process described in Example 1 used. so the physical properties of the finished liquid product were the filling ones:

^c / i IT.I ¹ . 60 ..... ...

viscosity. X + 1/2

Color 6

J. \ 7. . ., 10 _;

.Solvent xylene.

The end of the table illustrates ver The iJigGiioCiiaften of the above-described nich'ü-uagev / aiidelten and u / agöv / all product of example 5 and the niciitunewandelteii and converted products of the examples

and

0 0 9 816/1811 '' "" '' 'iad original

. ■ ■■ '· .-. ■ i:

Kara

3 Äüsgarigshalz

3a converted
resin

kittiöciön (l

3/4

4 non-converted 4 hours 4 converted

10-15 min.

5 non-converted 3 hours

5 converted

5-8 back

'· ■? ■

18 20

^; 22nd

2ä

16

20th

(1) Time to blue the fOOg zapon tea! IIen.Q04? S COi

... (Μ ^ .ϊΐι, Ifo _; ASA 1.5 mil naEneer? Ilm _A on Griaeplatte.

■■ '(Da ^ iji ^ iSA can from ir ^ MdOlnÜ'ÜDiiehen skin-

There are connecting agents that are usually added y / ird, but also v / eg can be omitted).

(2) 15 / j butylated Llel ^ iin-Pormaldehydnarz-GismilSla hardens 1.5 rail wet? Ilm 30 min. At 94 ⁰ O.

The non-uma'ewandelte ^ & ^rz e.-4er f Qegenv / ar ^ t v.qx \, iaainh ^ rzen as a result

Resins

sp ^ e ^ - |., and ,,. ^ ₅₉ ^ iyd ^ n

-f S 3 .ζ «·, ·. ■:? (· ■ 1T

ti · Λ y Jj?>

16/1811

OWGlNAL

Example 6. ί

• i

This hard was produced as in Example 4, with the ^;

Difference that during the pressurized aseotropic reflux process naphtha instead of ■ Xylene was used and the pressure obtained was 8-9.5 kg / cm. The proportion of non-volatile substances during 4 processing was 45? T. After processing has been kela solvent distilled off. The properties of the obtained hardnesses were the following:

+ Vf 45

Viscosity · 35-45 stokes

-tar «6-10 *;

color 6 '

Solvent V.U. and P naphtha.

lelapiel 7.

Blesee Hare was prepared as in Example 4, with sjkstelle το »IyIeI eder layktlu. Lacquered χ ine (mineral spirits) were used as a solution and * the obtained ' Druok was 4-6 kg / cm. The properties of the kid's product were as follows

+ ».F. 45 I.

Viscosity 40-45 stokes

S.W. 6-10

Color 6

Solvent mineral spirits.

009816/181 *

ORIGINAL INSPECTED

The device described enables the use of pressure in the reaction vessel and atmospheric or negative pressure in the condenser and the separator, as well as precise control of the flow ratio and the return of solvent to the reaction vessel. In this way, the risk of using flammable coating agents under pressure in the condenser part of the device is avoided, which is also an advantageous feature of the method according to the invention for the production of the improved resins.

009816/1811

Claims (1)

-Jf- T745791 Patent claims 1) Process for the production of polyester resins, according to which polybasic acid and polyhydric alcohol components which form polyesters are reacted with one another, characterized in that the reaction up to an end point, which is normally behind the gel formation, in the presence of a neutral organic solvent, the amount of 30 -. is 70 wt ^ of the entire Reaktionsgemiüches \ continued and a solution of a nieht-gelled polyester resin is produced having an acid value which is below that at which gelation would normally occur. 2) Seductive nac, claim 1, characterized in that a solvent with a boiling range not significantly above 205 ° C is used and the treatment mixture containing the solvent is heated to superatmospheric pressure. i 3) Method according to claim 1 and 2, characterized in that the components forming the polyester initially up to to a higher acidic value than that which indicates normal gelation corresponds, are reacted, then the solvent is added and the reaction is continued. 00981 6/1811 - 38 *: ■ '■ ■ ζ ~; 17457Ö1. 4) Process according to claim 1 and 2, characterized » that the components forming the polyester are initially converted to a higher acid value than the normal gelation point in the presence of an amount of the solvent of about 5-10% by weight of the entire reaction mixture are, then the rest dee solvent added and the anschliei3end Heaktion is continued. 5) Method nu.cn claims 1-4, characterized in that that the reaction mixture containing the solution heated to supernatural pressure and mixed with the solvent an azeotropic reflux is carried out, the solvent from the esterification water carried by it separated and the solvent to the reaction vessel in such a way that it is practical a constant percentage of solvent in de ^ genisch maintained v / ird. β) method nccn claim 5, characterized in that? so worked v.'ird that the polyester resin obtained a Acid fourth from 3-15. 7) Method according to claims 1-6, characterized in that that the polyester resin produced consists of an alkyd resin, that is modified with a carboxylic acid material that 4-26 carbon atoms per lithium molecule «? reveals. 8) Method nr ^ ch claims 1-6, thereby jeke / .i 009816/1811 ■ AD OWQtNAL Π45791 that the polyester resin produced consists of an alkyd resin is that modified by a -Langkettigee PettCl-llaterlal has been. 9) A method according to claim 7 or 8, characterized in that the reaction in the presence of the DALI Lösun _<: cuitteis biue is at a temperature in the range done at 260 G · 10) Method according to claims 3 and any one of claims 7-9 » characterized in that the components forming the alkyd resin are reacted with one another until the 5 - 10 units above the value. the 0eXi «? t || g nomi & irweiae would occur ·, and 4 $ ψ muMimmkkgeeetzt is. '^; fbw.i iI «laer solution of a non-Elier acid value below that values · Above enter 4 # t a selection occur ·. ·· \ _vie, v / elc-.e ... ei-.e 'Jelie: · .. t aiu more neutral. . r; ■ _.- nisöh »n solution Binifb ·! in a range of 30 - 70 The polyester resin is reacted further to a point which is normally beyond its gelling acid value. 12) The method according to Anspruoh 11, characterized in that the Polyeeterliarzlösung on Uteratniouphliriuchen pressure heated and läit d'in a solvent fcseotroyischer 009816/1811 ■ AD CWGfNAL Reflux is carried out, the solvent from the entrained therewith separated and esterification dae · solvent is fed to the reaction mixture in an amount such again that a substantially constant percentage is maintained of solvent in the mixture. 13) Hach deiii method of the preceding claims produced quick-drying Älkydharz-ÜberzugiJiuasae, characterized in that it is present in non-gelled liquid form P, an acid value of 3-10 (prepared for the pests) and a viscosity of 15-35 Stokee has a non-volatile content of 40-70 and the named alkyd preparation can dry tack-free in the air after a 500 g Zapon test in a time of 5-20 minutes and a Sward hardness of 16-48 is obtained in 1 hour . 1 <1) Alkyd resin coating composition according to claim 13, characterized in that it contains an alkyd resin which has been modified with up to r 70> ί a long chain oil material. 15) quick-drying non-gelled alkyd resin coating liquid produced according to the method of one of the preceding claims with a low acid value, which means that the alkyd resin contains a reaction product of a polybasic acid and a polybasic alcohol which chemically does not more than 009816/1811 “AD OKGINAL the 70 $ of a modifier Sj / from an animal, vegetable or fishul or alkyd and polyester-forming monobasic and polybasic acids and anhydrides, is connected and the mass is an inert solvent for the alkyd resin in an amount of 30-70 (iev /, ^ the mentioned! .lasse contains. 16) Quick-drying alkyd resin Überzugmas.äe m..oli claim 15, characterized in that it is a desiccant contains. | 17) Quick-drying alkyd resin coating composition according to claim 15 and 16, characterized in that they are a pigment contains. 18) Quick-drying alkyd resin coating wet according to claim 15, 16 or 17, characterized in that a dried PiIm the coating carrier mass has a Sward hardness of 10 - -48 owns. 19) Device for carrying out the method of claim i 1 - 12 out consisting catch from a pressure vessel as ileaktionsgefäß, eineiu Lösunjsmittelkondensator, an up and Jclicidejef.'lß for lösun ^ umittelkondensat, a pump far the liüc'cführung of the solvent to the reaction vessel , Lines through which the condenser, separator and pump are connected to the reaction vessel, and control and kojitrüllvorrichtunjen in the lines, through - / calibrate ^1. Reaction vessel under pressure conditions and the 009816/1811 BATH »- 42 - Condenser whined under normal atmospheric pressure can be, oowle a line for the return of the Solvent in the reaction vessel against the.in this prevailing pressure, so that during the production of the resin in the factory, the reaction chamber to superatmospheric Pressure can be maintained, a relatively constant amount of gaseous, stripping solvent under practically normal atmospheric conditions condensed and a recycle of solvent against the pressure in the reaction vessel is maintained. The patent attorney 009816/1811