DE1963763A1 - Process and equipment for the production of synthetic resins for the paint industry with continuous technology - Google Patents

Description

Tiszai Vegyi Kombinat in Tiszaszederkeny, Hungary

PROCEED]! AND RESIN PRODUCTION EQUIPMENT FOR THE PAINT INDUSTRY WITH CONTINUOUS TECHNOLOGY

The invention relates to a method and a device for the production of synthetic resins for the laok industry continuous technology »

With the development of the varnish and paint industry, eich advances the manufacture of iaoke and paints in a more traditional way Boiled linseed oil base more and more in the direction of Kunnt. resin base.

The paint binder system expanded with numerous new types of synthetic resins. From the standpoint of the manufacturing process and technology, these types of kunat resin can be classified into the following main types » 1189/1 old. / Kn *

009836/2048

1. Polymerized oils and synthetic resins,

2. polycondensation resins and laoke,

3. Adducts.

The group of polymerisation synthetic resins includes those types of synthetic resin that are made up of so-called monomer units polymerize to synthetic resins with a lower or higher molecular weight. Among these are from the standpoint of Lacquer industry, which polymerize with heat, vegetable oils (stand oil), the vinyl polish diners and copolymers are the most important.

The vegetable oils containing unsaturated fatty acids (linseed oil, wood oil, castor oil) polymerize at 290 to 300 ⁰ C to form highly viscous paints (so-called stand oils) and form an important basic substance in the paint industry,

The thermal polymerization can be completed at the temperature mentioned in the course of 8 to 10 hours. The implementation the reaction of the approach at high temperature is however from a technological point of view, because of the fire and Risk of explosion extremely difficult "

A specially designed autoclave is required for such types of paint. The stand oil production, which works with discontinuous technology, is difficult to control, especially towards the end of the reaction, since the reaction can only be set under strong cooling, the technological implementation of which is laborious The most important are the acrylate polymers, the vinyl acetate-based polymers or their copolymers. Their production is possible in the novel Eiiirichtungen in which the polymer ionstemperatur is varied between 120 and 18O ⁰ C.

A larger group of synthetic resins for the paint industry form the so-called polycondensation synthetic resins.

Among these are those with vegetable oil or with fatty acids modified glyptal resins (alkyd resins), the saturated and unsaturated polyesters, the epoxy resins, etc. the most important,

009836/2048

Those made from polyalcohols and polycarboxylic acids and polyesters modified with vegetable fatty acids can be sold separately under the name alkyd resins Group.

From a technological point of view, three types of production are known for their production »

a) Single-stage alkyd resin production.

b) Alkyd resin production with alcohol.

c) Alkyd resin production with acidolysis.

It is characteristic of all three technologies that in the course of the reaction polyaddition, polycondensation and Polymerization phases are to be distinguished. Ala side reaction also unavoidably takes place transesterification and / or dehydration,

Different technological methods can be used to control and accelerate these reactions will. In the discontinuously functioning reactors, however, the individual stages in time and space

are nicht.getrennt, and the temperature of the reaction is comparable _n

changes / between 120 and 300 C «

The polyesters containing unsaturated dicarboxylic acids polymerize when dissolved in vinyl monomers to form so-called synthetic resins with 100 # solids content and belong to the group of modern synthetic resin lacquers. Find in the course of the reaction Polyaddition and polycondensation processes take place, which are adversely affected by the oxygen in the air, which is why the construction of the apparatus from the traditional construction used in the paint industry to the one used for synthetic resin- device serving different positions. The water is removed by azeotropic distillation.

The reaction temperature varies between 180 and 220 ⁰ C. The resin is conveniently dissolved under 7O ⁰ C in vinyl monomers.

The synthetic resins formed as a result of the Diels-Alder reaction of abietic acid, linoleic acid, maleic acid ranked in the group of so-called adducts.

From a technological point of view, it is for their manufacture It is characterized by the fact that the adduct formation is followed by esterification in order to reduce the acid number of the synthetic resins.

- 3 -

009836/2048

like synthetic resins are, for example, the maleinate resins, the maleinate oils. The temperature of manufacture changes between 160 and 26O ⁰ C.

The production of the synthetic resins belonging to the three types can therefore be carried out due to the different temperature and pressure conditions as well as the deviating reaction line are not carried out in the same facilities.

In the course of the development of the lacquer and paint industry, the synthetic resin factories endeavored to develop special facilities for synthetic resin production, for which a discontinuous, batch-like production is characteristic. In order to meet the increasing demand, the volume of the reactors was increased. In the field of synthetic resin manufacture, devices with a capacity of 1 to 2 nr are used instead of devices of 3 to 6 Tcr , even the manufacture of devices with a capacity of 15 to 20 nr is planned. Even in this case, only a performance of 600 to 800 kg / hour can be achieved.

The manufacture of such devices is extreme costly, its automation cannot be solved easily, its operation is cumbersome and insecure, it exists the risk of gel and scrap formation.

Having knowledge of the aforementioned technological and economic problems in the manufacture of plastic resins for the paint industry is the development of a continuous method and the construction of a suitable one Facility essential for the paint industry,

According to the invention, for the purpose of continuous production of synthetic resins for the paint industry in the Weiae, the homogenized and preheated mixture of starting materials is continuously fed to the top floor of a reactor consisting of at least six floors Overflows located at the bottom, in the form of a 0.5 to 1 »5 mm thick film, with gradually increasing temperature gradients and at temperatures between 120 and 30O ⁰ C duroh. the reactor, then it is cooled back on the lowest reactor floor, and the finished resin is poured into a

- 4 009836/2048

196376

holder for the dissolving process, being transported into the reactor possibly in those at high temperature Reactor space continuously or discontinuously in countercurrent with the reaction mixture xylene and / or an inert gas initiated, since the reaction mixture located on the individual trays is kept stirring and since then possibly introduced Xylene in the form of an azeotropic xylene-water Gemisehea im upper part of the reactor is discharged as steam.

The xylene is advantageously introduced into the reaction chamber with the highest temperature in order to lower the temperature of the finished resin. Based on the total weight of the resin formed, about 5% xylene is added.

In the case of producing stand oil stand oil the homogenized components are conducted at about 16O ⁰ C in the reactor and during the initiating, placed in the reactor at 260 to 290 ⁰ C, ns any of an inert gas in counter-current in response.

In the case of the preparation of alkyd resins which homogenized the reaction components are fed at about 140 ⁰ C in the reactor, and the reactor is maintained at about 18O ⁰ C a polyaddition reaction at a temperature bia 260 ⁰ C, a polycondensation reaction, and finally at a temperature up to 27O ⁰ C undertook a polymerization reaction, with xylene being introduced in countercurrent.

In the case of the production of polyesters, the homogenized reaction components are ^{introduced into the reactor at about 120 °} C., then brought into reaction at the individual floors of the reactor at temperatures between 160 and 200 ^° C., with xylene being introduced in countercurrent.

The device used according to the invention for continuous » The natural production of paint industry resins can be characterized in that the reactor consists of at least 6, consists of vertically arranged floors, the reactor is surrounded by a cylindrical shell and a heatable jacket, the reactor 1st with a serving to introduce the raw material mixture Pipeline, at its top floor with a steam exhaust Line, at its lowest base with a line suitable for emptying the finished synthetic resin.

009836/2048

equips, at the level of the lower floor there is a line serving to introduce liquid or gas to the individual floors mounted on a common axis, the stirrer of the top and bottom trays fluge If and the rest are bell-shaped; the latter divide the individual floors into two parts, above that of the individual The stirrer located at the bottom is expediently a centrifugal disk attached to distribute the flowing liquid, the individual floors are covered with overflows, for the film-like penetration of the individual Soils located liquid are suitable.

The reaction system visible in FIG. 1 is more continuous for implementation when fed continuously Synthetic resin production suitable; We give its operation in the following ant

In the container 1, which is provided with a stirrer, the quantities of substances specified in the recipe are mixed with the help of the Puir ·· ■

14 introduced and the technological requirement accordingly - heated generally to 120 ⁰ C. The homogeneous substance mixture is continuously fed into the homogenizing container 2. This container is used to store the raw material mixtures and to keep them at a constant temperature. With the gear pump 3, the speed of which can be changed, the homogeneous substance mixture is continuously conveyed into the reactor 4 at the speed specified in the technological regulation.

The construction of the reactor 4 is illustrated in FIG. Daa on the floor 16 of the reactor consisting of 6 floor systems (reactor floor no. 1) through the line

15 synthetic resin mixture is heated to 160 to 220 ⁰ C, then the substance flows through the flow tube 25 to the bottom 17 (reactor bottom no. 2). The agitator 22 of the bottom 16 makes it possible that the substance does not heat up too much at the reactor wall and that the direction of the flow remains favorable, the agitator 23 of the bottoms 17 »18, 19, 20 and 21 (reactor bottoms no. 3, 4 and 5) divides the reaction space into two parts and thereby determines the flow direction of the substance in the system. From the

BATH ORIGINAL

009836/2048

It can be seen from FIG. 2 that xylene is introduced in countercurrent through line 27, with that during formation of the polycondensation products the water of reaction as an azeotropic one Mixture can be distilled from the system. With the continuous supply of xylene it can be ensured that the film-like flowing synthetic resin melt is intimately mixed with the xylene vapor, and the azeotropic mixture then through the one located at the top of the bottom 16 Steam line 29 and passes through the condenser 6 into the container 5 for xylene-water separation 5. Di supplying the xylene The device works continuously as the water and xylene vapors are in the form of a condenser Separate liquid. The xylene flows back into the system and the water can be continuous or discontinuous removed. Above the stirrer located on the individual floors is a distribution of the flowing through Reaction mixture suitable centrifugal disk 24 arranged. The stirrers 22 and 23 are mounted on a common axis. It is thus ensured in the reactor 4 that the polycondensation synthetic resins or the semi-products in the system flow through from floor to floor and that formed in the reaction Water is removed in countercurrent. In the case of the production of polymerization resins, the Addition of xylene, since the polymerization in solvent mediiii takes place. The end product arrives on the path of the bottom 21 provided with the overflow 28 through the line 8a into the container 8 or 9 to dissolve the synthetic resin which has been formed and which can be operated discontinuously. In this container, the necessary solvent is supplied through the line 8a and through the addition of the synthetic resin the paint can be produced with the desired solids content will. The synthetic resins are generally used in a solution of up to 75% or are placed on the market. The resin dissolving container is provided with a capacitor 10 and a dephlegmator 12. These prevent aromatic hydrocarbons and other solvents from escaping from the system. From the The finished resin solution is pumped into containers 8 and 9

009836/2048

11, possibly removed by the filter 13. The on Fig. 1 Gichtbare container 7 is used to dose the xylene from the. the loss of xylene can be replaced if necessary. Of the Reactor 4 is a continuous facility for Runat resin production both for the production of polymeric synthetic resins as well as polyadducts and polycondensation resins suitable. The examples relate to a reactor with a capacity of 100 liters.

Example 1. Production of stand oil

Starting materials: linseed oil 970.0 kg

Maleic anhydride 30.0 "

Sodium thiosulfate 0.1 "

1000.1 kg

These starting materials are brought into the container 1, which has no longer had a stirrer, ^{heated to 160 °} C. and transferred to the homogenizing container 2. In this, the substance mixture is kept at 160 ° C. and fed into the reactor 4 at a rate of 10 kg / hour. Inert gas (eg nitrogen) is metered in countercurrent through the reactor. The homogeneous batch of the introduced substances is warmed up to 260 ° C. on the bottom 16 and the temperature is kept constant. The effluent from the bottom 16 mixture is heated on the floor 17 to 290 ⁰ C and also kept on the trays 18 and 19 at this temperature, on the ground 20 is the temperature at 260 ° C lowered to the bottom 21, the temperature is 220 ° C set. After the temperature equilibrium ratios have settled,] in the continuous reactor with 10 k / i / hour output a product lir-rgeetollt wo ^ don, which has a viscosity of 1200 βοίπηκϊ "» (P ¹ Oi d 4) HufvfiMt, Von rl »in Ρΐ'Ίπι;'l iHrörnt · 1 · ιη V <* v t j (·:' - r | {-f5if <s «M"'' ¹ Jj -.-'-, 'η' f, Tejnj »n. . a1 ii »ίι <'? ίί ^{(H: ä} Hlfoi ^ (3 ππΊ Ή V';. f ■ <■ -} di? ^'1 J = _^1:; -ί- ■ -... · t υ "-j- '?;« rrc.dn'. S '- ^ - "«;f.' ■ ". · ->": j »_Tuiir KUi 1,.""'·'

Example 2 Acrylate copolymer synthetic resin paints 193.0 kg Production of Methoxyethacrylate 193.0 kg Output st offeι Butyl acrylate 46.8 kg Methacrylic acid 308.0 kg Xylene 247.0 kg Butyl acetate 5.7 kg Benzoyl peroxide 87.0 kg Butyl alcohol 0.027 kf? Diethylaniline

1080.527 kg

These substances are brought into the container 1 provided with a stirrer, ^{heated to 50 °} C. and transferred to the homogenizing container 2. Here the temperature is kept at a constant value (50 ^° C.) ₁ so that no polymerization takes place here. With the gear pump 3, the speed of which can be changed, the homogeneous batch is fed to the bottom 16 of the continuous reactor 4. Dieeem on the bottom of the mixture is warmed to 120 ⁰ C and at this temperature the mixture flows to the ground 17, where its temperature is set at 16O ⁰ C.

The floors 18 and 19 are also operated at the same temperature. On the bottom 20, the temperature of the Kunstharzlackeeauf is lowered 12O ⁰ C, then adjusted to the bottom 21 to 90 ⁰ C. With this temperature gradient, a synthetic resin lacquer is produced which has a viscosity of 150 to 200 seconds (Ford 4 *) and it is cooled ^{to 50 to 60 ° C. in the containers 8 and 9.} The production takes place in an inert gas atmosphere, addition of xylene j.at is superfluous, as the solvent circulation is ensured by the amount of xylene fed in. The synthetic resin paint produced in this way is suitable for the production of θ ^ combustible paint systems; the heat stability, the color fastness, the hardness and the elasticity of the coatings prepared from these are better than those of the usual products.

009836/2048

Example 3 19B3763

Manufacture of alkyd resins

Auegangetoffei castor oil 315.0 kg

Distilled tall oil fats Hurö 315.0 kg Pentaerythritol 15? »4 kg

Phthalic anhydride 225.0 kg Albertolic acid 75.0 kg

total 1087.4 kg

The batch is weighed into the container 1 equipped with a stirrer and heated to 140 ⁰ C. The homogenized batch is transferred to the storage container 2 and kept at this temperature. The substance is fed to the plate 16 of the continuous reactor 4 P with a gear pump 3. The feed rate is 20 kg / hour.

In the production of alkyd resins, a distinction is made between four reaction zones whose operation and temperature gradient are different. The plate 16 is the so-called. Polyadditions _r . zone where the supplied substance is heated ^{to 180 ° C.} In the polyaddition zone, the agitator is designed in a two-way manner that the incoming substance warms up as a result of the heat transfer from the wall surface and rises through the overflow next to the agitator. flows. The floors 17, 18 and 19 form the so-called. Polycondensation zone where the resin is held at 26O ⁰ C. In the case of these soils, when testing the fc process, one finds that the degree of polycondensation increases progressively downwards, while the amount of water formed in the reaction decreases. The degree of polycondenation depends on the equilibrium constant and the water content. It also follows from this that an alkyd resin with a corresponding degree of condensation can only be produced with complete removal of the water.

Purely removing the water is done through the pipe Jfylene introduced into the reaction space. Daa xylene met a double task ι

a) it partially reduces the viscosity of the alkyd resin and thereby enables the easy removal of the reaction wafer, -> -

- - .10 -. / BATH

098 387 20 48

Id) "on the other hand, it ensures an azeotropic xylene water Distillation, with the xylene flowing upwards with the am specially designed agitator, draining alkyd resin film comes into intimate contact in the counter flow and the reaction water with it. __.-- ■ .-

Bach. At the end of the polycondensation, the viscosity of the alkyd resin does not reach the corresponding level, which is why it is necessary to polymerize the unsaturated fatty acids. The Polymeriaationareaktion runs on your floor 20, where the temperature is increased to 270 ⁰ C for the purpose of leveling the reaction rate. At this temperature the viscosity of the synthetic resin in 50% white spirit reaches the viscosity value of 200 to 250 seconds (measured on the Ford 4 funnel) . The bottom 21 is in the alkyd resins the so-called "cooling zone in which the reaction" - cooled product to 22O ⁰ C and held at that temperature where the reaction stops, ie practically finished.

Sum up! there is thus the continuous reactor in the case of alkyd resin production from four main zones, polyaddition reactions taking place in the first zone, in the second zone - which consists of three floors, the polycondensation reactions take place, the penultimate floor is necessary for the end of the polymerisation reaction and the last tray is used for cooling back. Example 4

Manufacture of unsaturated polyesters Starting materials: soybean oil 44.0 kg

epoxidized fatty acid 270.0 kg

Ethylene glycol 326.0 kg

Phthalic anhydride 296.0. kg

Maleic anhydride 392.0 kg

Hydroquinone. _< _ _w _JlijLJ5 £ L ~

insRoeamti 1328.4 FCP:

The specified raw materials or are weighed into container 1, which is equipped with a stirrer. up to 120 C ^! f! i raf. and in the LagerbehlO ter 2 über'HJMrI-, bei difm ^ r Tajnpöv _i? for v {irC> the Subfitana with the i ^ ihiü'nd] ■ »- ■; ..; *: ■ '}, Λ ^ ν ^ η ΠνοΙ;: ^ ;! :) -> ■ ·. γ

Π it ti Π '■' · '■ · / *? «-'' ■ ·' -

_{t can} be changed and fed into the continuous reactor 4 at a rate of 30 kg / hour. Similar to the case of the alkyd resin, xylene is introduced through line 27 to the bottom 21 and the xylene-water mixture is continuously removed from the product. On the bottom 16, the temperature to 16O ⁰ C is set on the trays 17, 18 and 19, however, to 220 ⁰ C.

The floors 20 and 21 serve for the cooling back of the polycondensates and the temperature is adjusted to about 14O ⁰ C.

The finished unsaturated polyester resin flows into the dissolving container 8 or 9, where the synthetic resin is dissolved in styrene monomers.

Example 5

Manufacture of maleinate resin

Starting materials »spruce resin 867.0 kg

Pentaerythritol 177.0 kg

Maleic anhydride 60.0 kg

total ι 1104.0 kg

In the container 1, the spruce resin c * is melted urch heating to 120 ⁰ C in the first stage, and the necessary. Amount of maleic anhydride and pentaerythritol is added. At this temperature the batch is in a liquid state and in this state it enters the homogenizing container 2. With the pump 3, the substance is fed to the bottom 16 of the continuous reactor 4 at a speed of 20 kg / hour, where it is heated to 220.degree warmed up on the floor 17 overflows. The temperature of the synthetic resin is increased to 260 ^° C. on the floor 17 and is also maintained at this temperature on the floors 18 and 19. Xylene is added to the bottom 19 to remove the water. The bottom and 21 serve to cool down the synthetic resin and in this case it is not advisable ^{to lower the temperature on the bottom 21 below 20O 0} C, since the melting point of the resin is high. In this case, the synthetic resin is expediently emptied onto a base that serves to solidify or, if necessary, dissolved in the containers 8 or 9 * The base 16 is used for the course of the polyaddition reactions. On the floors

- 12 -

009836/2048

17> 18 and 19 the weathering reactions take place with the applied polyalcohols.

The advantages of making synthetic resins for the Laok industry with continuous technology can be in are summarized below.

1. The volume ratio of the resin production reactor and its related performance becomes improved. In the case of discontinuous and continuous Reactors with the same power is the volume continuous apparatus significantly smaller. The manufacturing cost the apparatus bind but with the grb'aae dea built-in Volume proportional.

2 » In the case of the continuous technology, the reaction time is shorter, which is related to the more effective removal of the by-products arising in the case of polycondensation resins. The total surface of the liquid surfaces in the cascade stage is larger in relation to the volume, the resin that overflows from the upper to the lower stage as a thin film ensures a particularly good possibility for the removal of gases and vapors, this is also done by flushing the apparatus JXylene vapor promoted to a high degree.

As a result, the color number of the synthetic resins is better and the product is lighter.

3. The energy balance is continuous in the case of Technology cheaper. In contrast to the discontinuous Technology, the energy required for heating up and cooling down the device is superfluous, this one reaches a third of the total energy requirement. In the case of the continuous reactor according to the invention, the Heat introduction on the wall of the device. For avoiding from local overheating and for ensuring homogeneity A simple agitator is sufficient. In all stages, the agitation can be solved with a single agitator » In the case of the discontinuous technology, very intensive stirring is required because of the large Kunatharzmaose. the The surface of the resin mass is not uniform due to the turbulent movement and the synthetic resin burns on the upper part

- 13 -

009836/2048

of the coat, so the production of a light-colored Synthetic resin with the discontinuous technology difficult, the activation of frequent breaks and the Wash out the apparatus is necessary,

4. In the continuously operating apparatus is the reaction rate almost constant in the individual stages in contrast to the discontinuous apparatus in which the Processes run at a time-varying speed, for which time-varying amounts of energy are required are.

In such cases, for example, regulating the heat output is cumbersome. The resulting from the regulation Errors affect the response time and the quality of the product.

5. In the continuously operating reactors can the different types of reactions are spatially separated, and for increasing the speed of these reactions different options are available, In the case of continuous technology, calibration offers the possibility of changing the speeds at the same time to cause various reactions (e.g. the alkyd resins can be used at the end of the reaction at high temperature without Risk of gelation being polymerized). That’s why the products more evenly, the molecular weight distribution of the Products is cheaper and the film properties of the Resin-made paints get better.

6. In the case of continuous technology, that is Possibility of more complete control, the degree of instrumentation more satisfactory, less work required.

- 14

Claims (6)

PATENT CLAIMS 1. A method for the continuous production of synthetic resins for the paint industry, characterized in that the homogenized and preheated mixture of the starting materials is continuously fed to the top floor reactor consisting of at least 6 floors, then the reaction mixture is gravitationally due to the individual Bottoms located overflows, expediently in the form of a 0.5 to 1.5 mm thick film, with gradually increasing temperature gradients, at temperatures between and 300 ⁰ C passed through the reactor, then is cooled back on the lowest reactor floor, and the finished resin is conveyed into a device for dissolving, with xylene or an inert gas being introduced continuously or discontinuously in countercurrent with the reaction mixture into the reactor, if necessary in the reaction space at high temperature, the reaction mixture at the individual trays being kept stirring and the possibly introduced xylene in F. orm of an azeotropic xylene-water mixture in the upper part of the reactor is discharged as steam. 2. The method according to claim 1, characterized in that the xylene is expediently in the reaction space is initiated at the highest temperature. 3. The method according to claim 1, characterized in that calculated on the total weight of the resin formed about 5% xylene are added. 4. The method according to claim 1 for the production of stand oil, characterized geke η η ze ichne t that the homogenized Stand oil components at around 160 C in the reactor passed and there at temperatures between 260 and 290 G, with the introduction of any one carried out in countercurrent Inert gases are brought into reaction. 5. The method according to claim 1 for the production of alkyd resins, characterized ge ke η ηζ e ic h η et that the homogenized Reaktioriskomponanten of the alkyd resin are passed at about 180 ⁰ C in the reactor, at about 180 ⁰ C 'a polyaddition reaction is carried out, a Polyicoridenaationereaktion takes place at a temperature up to 26O ⁰ C - 15 - 00983.6 / 2048 and being introduced in counter-current with the re nude ions ge mi sch xylene at a temperature up to 27O ⁰ C, a Polymeriaationareaktion. 6. The method of claim 1 for the preparation of polyester resins, characterized geke nnze ichne t that the homogenized Polyesterrreaktionskomponenten conducted at about 120 ⁰ C in the reactor, be brought to the individual plates of the reactor at about 160 to 220 ⁰ C in the reaction, wherein xylene is introduced in countercurrent 7 Reactor for the continuous production of synthetic resins for the paint industry according to claims 1 to 6, marked by the fact that the reactor (4) at least six vertically arranged, with a cylindrisohen floors (16, 1 ?, 18, 19 »20, 2l): further characterized by a pipeline accommodated at the top floor of the reactor (15), a steam line (29) placed at the top floor of the reactor and at the bottom floor of the reactor one line suitable for emptying the finished resin. (28), at the bottom one for the introduction of liquid or Gas suitable line (27) »the individual floors are provided with a Rüirenm mounted on a common axis, whereby the stirrer of the top and bottom trays wing-shaped (22) and the other are bell-shaped (23), the latter stirrer dividing the trays into two parts, above the one on the individual Stirrer located in the bottom is a for distributing the The reaction mixture flowing through a suitable centrifugal disk (24) is arranged, and the individual floors are with Provide overflows that are suitable for the film-like flow of the reaction liquid. - 16 - 009836/2048 Blank page