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`CERTIFICATION
`
`This is to certify that the attached translation is, to the best of my knowledge and belief, a true
`
`and accurate translation from German into English of the attached European Patent Application
`
`No.0 374 709 A2.
`
`WEE“
`Kristin Santizo, Senior Project Manager _
`Geotext Translations, Inc.
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`Sworn to and subscribed before me
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`SNF Exhibit 1006, Page 1 0f18
`
`SNF Exhibit 1006, Page 1 of 18
`
`

`

`Europaisches Patentamt
`
`9 European Patent Office
`
`Office européen des brevets
`
`(11) Publication number:
`
`0 374 709
`
`A2
`
`(12)
`
`(21)
`(22)
`
`EUROPEAN PATENT APPLICATION
`
`Application number: 89123007.0
`Filing date: 13l12l1989
`
`(51) Int. Cl.5:
`
`COSF 2/10, C08F 2/00,
`A61 L 15,24’ A61 L 15,60
`
`
`(30) Priority: 20,12,88 AT 3090/88
`
`(73) Patent holder: Chemie Linz Gesellschaft ”Lb-H.
`St. Peter-Strasse 25
`
`(43) Date of publication of application:
`27/06/90 Patent Office Journal 90/26
`
`(84) Contracting States mentioned:
`AT BE CH DE ES FR GB GR IT Ll LU NL SE
`
`
`
`A-4021 Linz (AT)
`
`(72)
`
`Inventor: P'eh’ Stefan, Dr.
`F°'5tha“55tra_ss° 393
`A-4060 Leondmg (AT)
`Inventor: Willert, Gerhard
`Bodendorf 52
`
`A-4223 Katsdorf (AT)
`Inventor: Kloimstein, Engelbert
`Schiferplatz 22
`A-4070 Eferding (AT)
`Inventor: Haslauer, Gerold
`Anastasius-Grfln Strasse 20
`
`A-4020 Linz (AT)
`
`(74) Representative: Kunz, Ekkehard, Dr.
`Chemie Holding AG Patentwesen St.
`
`Peter-Strasse 25
`A-4021 Linz (AT)
`
`
`
`(54) Process for the continuous preparation of liquid-absorbing, cross-linked polymers.
`
`(57) Process for continuous preparation of liquid-absorbing, cross—linked polymers, wherein a release liquid is also
`used during the polymerisation process.
`
`EP0374709A2
`
`Xerox Copy Centre
`
`SNF Exhibit 1006, Page 2 0f18
`
`SNF Exhibit 1006, Page 2 of 18
`
`

`

`EP 0 374 709 A2
`
`Process for the continuous preparation of liquid-absorbing, cross-linked polymers
`
`The invention relates to a process for continuous preparation of liquidsabsorbing, cross-linked polymers, wherein
`a release liquid is also used during the polymerization process.
`in DE-OS 34 32 690 by free radical solution
`Liquid-absorbing polymers, as they are prepared, for example,
`polymerization of acrylic monomers, are mainly used as desiccants and absorbents for absorbent sanitary products,
`and as soil improvers in agriculture, in particular, in arid areas.
`The solution polymerization of polar monomers such as acrylic acid, acrylamide or their derivatives leads
`relatively quickly‘ to gelatinous or elastic gelatinous products in an aqueous solution with or without a crosslinker.
`Even at relatively low monomer concentrations, for example, below 10%, a hydrated, tough or tough—elastic gel that
`poses problems during its production and processing is formed in a mostly free—radicaI-initiated reaction.
`in
`particular, the single hydrogel-forming block that is produced during polymerization adheres to the reactor wall by
`adhesive forces, thereby hindering or making its further transfer and removal as part of a continuous polymerization
`difficult. The pressurized monomer solution that forcibly makes its way through the tight hydrogel block is especially
`dangerous. On the one hand, this results in a non-uniform, unevenly polymerized polymer that is mixed with the
`monomer solution and is rendered unusable; it must be disposed of as waste. On the other, such a penetration
`forces the termination of the polymerization process and requires a labor—, cost-, energy— and time-intensive restart of
`the polymerization. For this reason, it is mentioned, for example in DE—AS 12 18 157 that the polymerization is only
`possible in batches in an aqueous medium. Continuous polymerization had required considerable additional
`expense, such as the incorporation of a rotating agitator in the reactor, for example in DE-OS 34 32 690. In DE-OS
`35 37 276, a reactor with built~in kneading and conveying elements that are arranged on a shaft is used. However,
`the disadvantage of using such kneading, mixing and conveying elements is that a mechanically strongly degraded
`product with low gel strength and viscosity is obtained due to the shear forces occurring.
`The object of the invention was to provide a process in which these disadvantages do not occur and in which the
`hydrogel that is formed in the course of the continuous polymerization can be easily transported further in the reactor
`and discharged, without leading to fixation or adherence of the hydrogel to the reactor wall, monomer penetrations or
`degradation reactions. The object has been solved by adding an immiscible or partially miscible release liquid
`parallel to the supply of the aqueous monomer solution into the reactor. It is particularly surprising that the release
`liquid migrates to the reactor wall
`in the course of the polymerization and forms a separating and sliding layer
`between the reactor wall and the polymer block. This allows free sliding of the block polymer on the reactor wall,
`without adherence or fixation, thus enabling easy discharge of the polymer block from the reactor.
`The present invention relates to a process for the continuous production of liquid-absorbing, crosslinked, water-
`insoluble polymers by polymerization of water-soluble monomers, which contain one or more double bonds or
`mixtures thereof, which is characterized in that an aqueous solution of monomersand an immiscible or partially
`miscible release liquid are simultaneously fed to the reactor at its inlet, wherein the release liquid’is distributed
`automatically between the reactor wall and the polymer phase during the polymerization, and the resulting polymers
`are discharged together with the release liquid at the reactor outlet. For example, monomers from the group of the
`mono-functional vinyl or acrylic monomers, such as vinyl pyrrolidone, acrylamides or amides of methacrylic acid,
`such as methacrylamide, N—alkyl (C1—C4) and N dialkyl (C1—C4) methacrylamides such as N-methyl methacrylamide,
`N,N'—dimethyl methacrylamide,
`N-tert— butyl methacrylamide, N-butyl methacrylamide,
`N, N'-dimethyl
`methacrylamide,
`aminoalkyl
`(C1—C4) methacrylamides,
`in
`their
`neutral
`or quaternized form,
`such
`as
`dimethylaminomethyl
`methacrylamide,
`dimethylaminoethyl
`methacrylamide,
`trimethylammoniumpropyl
`methacrylamidochloride, methacrylic acid and its alkali and ammonium salts, and methacrylic acid hydroxyalkyl ester
`(C1-C4), such as hydroxy ethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid aminoalkyl ester in their
`neutral or quaternized form, such as dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, trimethyl
`ammonium methyl methacryloyl methyl sulphate, dimethyl ammonium alkyl methacryloyl chloride, sulphonic acids
`such as vinyl sulphonic acid, acrylamidomethyl propane sulphonic acid, sulphoethyl methacrylate and their water—
`soluble salts could be used as water-soluble monomers with a double bond. Acrylic acid and their salts and acrylic
`acid derivatives and their salts are preferred.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`SNF Exhibit 1006, Page 3 0f18
`
`SNF Exhibit 1006, Page 3 of 18
`
`

`

`EP 0 374 709 A2
`
`Monomers with two or more double bonds are usually added as a crosslinker to these monomers with a double
`bond, typically in amounts of 001—1 mol. %, based on the total quantity of monomers. However, it is also possible to
`polymerize the bi- or multifunctional monomers as such. Examples of bi- or multifunctional monomers are N,N'-C1-
`C6, alkylenes or C5 acrylene bisacryl or bis-methacryl compounds, such as N,N'— methylene-bis-methacrylamide,
`N,N'-ethylene-bis—methacrylamide,
`N,N'-propylene-bis-methacrylamide,
`C,—C,—alkylene—bis-acrylates
`or
`bis—
`methacrylate, such as ethylene-bis-methacrylate, propylene-bis—methacrylate, di—, tri- and tetra-allyl compounds, for
`example, diallyl maleate, diallyl tartrate, tetrallyloxy ethane, allylvinyl compounds, such as allylvinyl maleate, allyl
`acrylate, allyl methacrylate, allyl methacrylamide or polyalkyl glycol bis—acrylate or bis-methylacrylate, such as
`diethylene glycol bis—methacrylate,
`triethylene glycol bis—methacrylate,
`tetraethylene glycol bis—methacrylate,
`trimethylol propane di— and tri-acrylates, glycerol di- and tri-acrylates, divinyl others, such as polyethylene glycol
`divinyl ether, diethylene glycol divinyl ether, glycidyl ethers, such as bis-phenol diglycidyl ether.
`Suitable release liquids are all
`immiscible or partially miscible aqueous solutions of liquid compounds or
`solutions of solid compounds in immiscible or partially miscible aqueous solutions of organic solvents, for example,
`non—ionic surfactants. Liquids or solutions that are not miscible with water are preferably used. Compounds with an
`HLB (hydrophilic-lipophilic balance) of up to 17 prove to be especially suitable as release liquids. The HLB value
`allows the classification of surfactants with respect to their hydrophilic and lipophilic properties, wherein a low HLB
`value characterizes strongly lipophilic and a high HLB value strongly hydrophilic properties. The HLB value can be
`determined, for example, according to Kirk~Othmer, Encyclopaedia of Chemical Technology, Vol. 8, 3.. ed., pages
`910 - 917 or Ullmann's Encyclopaedia of Industrial Chemistry, Vol. 22, 4'h ed, pages 488 - 490.
`fatty acid
`For example, polyalkylene oxides,
`fatty acid esters,
`resin acid esters,
`fatty acid amides,
`hydroxylamines, polyalkylene oxide block copolymers, silicones and waxes may be used as release liquids.
`Examples of polyalkylene oxides are alcohol ethowlates, such as diethylene glycol monolaurate (HLB 6.5) and
`polyethylene glycol dilaurate (HLB 6.3), alkylphenol ethoxylates, such as nonylphenol ethoxylates with 4-25 ethylene
`oxide units (HLB 7.5 — 17; Arkopals N-4O to N-250 from Hoechst); octylphenol ethoxylates (HLB 7.8) and polyalkylene
`glycols. Examples of fatty acid and resin acid esters are polyethylene oxide fatty acid esters or polyethylene oxide
`abietic acid esters, such as polyethylene oxide stearic acid monoesters (HLB 8); glycerol fatty acid esters or oils and
`fats and mono and diglycerides, such as glycerol monostearate (HLB 3.8); sorbitan or isosorbide fatty acid esters,
`such as sorbitan monostearate (HLB 4.7), sorbitan mono palmitate (HLB 6.7); ethoxylated sorbitan or isosorbitan
`fatty acid esters, such as: polyethylene oxide sorbitan monooleate (HLB 10); ethoxylated natural fats or oils or
`waxes, such as polyethylene oxide vegetable oil esters (HLB 13.3); fatty acid glycol esters or fatty acid diethylene
`glycol esters or fatty acid polyethylene glycol esters, such as propylene glycol monostearate (HLB 3.4); fatty acid
`alkyl esters, such as butyl stearate and butyl oleate. Examples of fatty acid amides or fatty acid hydroxylamines are
`monoethanolamine or diethanolamine condensates, such as triethanolamine oleate (HLB 12); polyethylene oxide
`fatty acid amides such as polyethylene oxide fatty acid amide (HLB 13.9). Examples of polyalkylene oxide block
`copolymers are polyethylene oxide/polypropylene oxide copolymers, e.g. Pluroni0® 10500 (BASF). Examples of
`silicone or silicone oils are: polydimethyl siloxanes. Examples of waxes are: Fischer—Tropsch hard paraffin waxes,
`microcrystalline waxes, acid and ester waxes. Butyl stearate, butyl oleate or silicone oils are particularly preferably
`used as a release liquid.
`'
`The quantity of the release liquid used is in the range of about 0.001 to 1 wt.—%, based on the weight of the
`monomer solution used. Preferably, about 0.01 to 0.8 wt. % release liquid is used.
`At the start of the polymerization, usual initiators, for example, inorganic or organic peroxide or azo compounds are
`used. Examples of the inorganic peroxide initiators are alkali metal persulphates or ammonium persulphate,
`optionally as redox initiators in combination with a reducing agent such as ammonium bisulphite. For example tert-
`butyl hydroperoxide may be used as the organic peroxide initiator, while 4,4‘-azobis (4—cyanovaleric acid) or 2,2-
`azobis (2—amidinopropane) hydrochloride may be used as azo compounds. The initiators can be used separately or
`in combination. Particularly preferred is a redox initiator consisting of ammonium persulphate and sodium hydrogen
`sulphite, and azo compounds such as 2,2-azobis (2—amidinopropane) hydrochloride. These polymerization initiators
`are preferably used in the form of aqueous solutions. But they can also be used in dilution with a suitable solvent.
`The amount of initiator is about 0.001 to 5 wt. %, preferably about 0.003 to 2 wt.% in solid form, based on the total
`amount of the monomers used.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`4o
`
`45
`
`50
`
`SNF Exhibit 1006, Page 4 0f18
`
`SNF Exhibit 1006, Page 4 of 18
`
`

`

`EP 0 374 709 A2
`
`The polymerization can be performed in vertical or horizontal reactors, which preferably have a cylindrical cross—
`section and whose inner wall
`is preferably lined with plastics, e.g. polyolefines, such as polyethylene or
`polypropylene, fluorinated polyolefins, polyesters or polyvinyl compounds such as PVC or polymethyl methacrylate.
`The internal diameter of the reactor is preferably about 10 to 500 mm.
`Monomer solution, polymerization initiator, release liquid and, optionally, other usual additives are added at one
`end of the reactor, which was first washed, for example with N2 in the absence of oxygen for the preparation of the
`polymers according to the invention. The reactor is also under an inert gas atmosphere during the polymerisation.
`When passing through the reactor, the solution polymerises exothermally to a highly viscous, gelatinous polymer
`block. The reaction is performed adiabatically as far as possible, wherein the temperature rises in the reactor due to
`the released heat of polymerisation and the polymerisation is carried out as a function of the used monomer, the
`monomer concentration and the initiator system at a temperature range of about -10 to +120 °C. The starting
`temperature is preferably between 0 and 40 °C, the monomer concentration in the range of about 2 to 50 wt. %,
`particularly preferably 15 to 50 wt. %.
`In the course of polymer formation, the release liquid migrates to the reactor wall, where it gets distributed and
`forms a film between the reactor inner wall and the gelatinous polymer block, on which the polymer block slides to
`the reactor outlet without significant friction. The sliding conditions can be optimized further by selecting a suitable
`release liquid, depending on the process conditions, the type of polymer, the design, position, and inner lining of the
`reactor. The polymer block is transferred to the reactor outlet by means of either gravity, by its own weight or by
`pressure at the reactor inlet, for example by the pressure at which the starting materials are pumped into the reactor,
`or by an overpressure of the inert gas. Transport by means of the pump pressure or gas pressure occurs especially
`in horizontal reactors and in stationary reactors at a reaction sequence from bottom to top.
`A vertical, cylindrical tubular reactor is preferably used, wherein the monomer solution, initiator and release liquid are
`continuously fed into the upper end of the reactor, for example by means of pumps.
`During the passage through the reactor, the monomers polymerize to form a highly viscous, gelatinous polymer
`block, wherein the release liquid between the reactor inner wall and the polymer block is distributed to form a sliding
`film on which the polymer block slides along and is continuously discharged at the end of the reactor, for example
`using a pair of rollers. The gelatinous polymer block sliding on the slide film and reactor wall simultaneously ensures
`sealing of the reactor to the outside and prevents the penetration of monomers and low viscosity, partially
`polymerized oligomers on the product side of the reactor. The release liquid is discharged along with the polymers.
`When using a stationary reactor with an inner diameter greater than about 100 mm, the polymer block slides
`downwards under its own weight.
`The dwell time while passing through the reactor is usually 15—180 minutes, depending on the monomer, the initiator
`and the temperature, wherein a yield of at least 90% is achieved. The rate of passage through the reactor is
`generally at a range of about 1 to 32 m/h, wherein there the advantages of the invention, in particular, the distribution
`of the release liquid to the interface between the reactor inner wall and the polymergel, combined with a smooth
`transport of the polymer block are not adversely affected even at higher speeds.
`'
`
`10
`
`15
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`20
`
`25
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`30
`
`35
`
`@9191;
`
`4o
`
`
`Preparation of the monomer solution
`
`In a BOO—litre agitator with a pH meter, thermometer and nitrogen purge line, 226 kg of a 50% acrylamide
`aqueous solution (AA), 86.6 kg of a 50% aqueous solution of acrylamidomethyl propane sulphonic acid potassium
`(AMPS—K), 37.97 g of methylene bis-acrylamide (MBA) and 28.35 g of Trilon C (ethylene diamine tetraacetic acid,
`BASF) were taken and mixed with 275 kg of deionized water and homogenized by stirring at room temperature.
`Subsequently, the pH is adjusted to 4.9 using HCl 1:1 and purged with nitrogen in the agitator. The monomer
`concentration was 26.5%.
`
`45
`
`SNF Exhibit 1006, Page 5 0f18
`
`SNF Exhibit 1006, Page 5 of 18
`
`

`

`EP 0 374 709 A2
`
`Preparation of the initiator solution
`
`1500 ml of water, 27.16 g of azobis (2—amidinopropane) hydrochloride (V—5O® from Wako, Japan) were added to
`a 2—litre supply reservoir, and homogenized. Subsequently, 0.87 g sodium bisulphite dissolved in 250 ml of water and
`1.76 g of ammonium persulphate dissolved in 250 ml water were added and the solution was homogenized.
`
`Polymerization
`
`The polymerization was carried out in a vertical, Teflon-coated metal tube with a diameter of 200 mm and a
`height of 4 m. The monomer solution (60 kg/h) and the initiator solution (2.4 kg/h) were homogeneously mixed by
`tangentially injecting into a mixing head, and supplied continuously to the reactor. The release liquid (2.2 ml/h of butyl
`stearate, equivalent to an amount of 0.0036 wt. %, based on the monomer solution used) was added via an inlet pipe
`at the reactor top. Nitrogen was passed into the reactor via an inlet pipe and removed out of it via a discharge pipe.
`In the initial phase, the reactor was sealed at the bottom with a dummy disc and reopened after the start of
`polymerization. This allows easy discharge of the resulting rubbery, easily deformable polymer at the bottom of the
`reactor, supported by a roller.
`in the course of the polymerization, the viscosity of the solution increased rapidly following an induction period.
`The temperature profile was indicated by measuring points integrated into the reactor:
`
`0 m
`
`From the mixing head
`
`
`
`“ u
`
`“
`
`“
`
`“
`
`"
`
`0.5 m
`
`1 m
`
`1.5 m
`
`2 m
`
`2.5 m
`
`4m
`
`The dwell time in the reactor was 2 hours. Polymer was continuously discharged at a flow rate of 62.4 kg/h and
`at a temperature of 80 °C.
`
`Comparative example C1
`
`The polymerization was carried out similar to example 1, with the difference that no release liquid was added.
`After the start of polymerization and opening of the dummy disc, the polymer had to be discharged by force. Due to
`the absence of the release liquid, there was an uneven discharge of the gel, wherein deformation and strain of the
`gel was observed. Depending on this, the monomer solution flow could flow at the interface between the gel and the
`wall. After 1 hour of discharge, there was penetration of low—viscosity monomer solution at the bottom of the reactor,
`after which the polymerization had to be stopped.
`
`Examples 2 to 12
`
`A polymer gel was prepared similar to example 1, with the difference that the release liquids shown in table 1
`and the inner coatings of the tubular reactor were used during the polymerization.
`
`SNF Exhibit 1006, Page 6 0f18
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`10
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`30
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`SNF Exhibit 1006, Page 6 of 18
`
`

`

`
`
`EP 0 374 709 A2
`
`Table 1:
`
`Example
`
`Release liquid
`
`Reactor coating
`
`Discharge
`
`
`
`
`
`0.0036 wt.% Butyl stearate
`
`Teflon
`
`0.7 wt.% Butyl stearate
`
`-
`
`0.4 wt.% Butyl stearate
`
`—
`
`0.8 wt.% Butyl stearate
`—
`
`0.8 wt.% Butyl stearate
`
`_
`
`Polyethylene
`
`Polyethylene
`
`Polypropylene
`
`Polypropylene
`
`PVC
`PVC
`
`Polymethyl methacrylate
`
`Polymethyl methacrylate
`
`0.8 wt.% lsododecanol ethoxylate
`
`0.8 wt.% Nonylphenol ethoxylate
`
`Teflon
`
`Teflon
`
`0.2 wt.% Dimethyl polysiloxane
`
`Polypropylene
`
`+
`
`+
`
`—
`
`+
`
`-
`
`+
`-
`
`+
`
`_
`
`+
`
`+
`
`+
`
`1
`
`2
`
`3
`
`4
`
`5
`
`6
`7
`
`8
`
`g
`
`10
`
`11
`
`12
`
`
`
`+ Uniform gel discharge at the bottom of the reactor due to its own weight; no adhesion to the reactor wall.
`- Product adheres to the reactor due to the high adhesion forces and cannot be removed from the cylindrical
`
`reactor(e.g. tension or pressure), without the application of external force; uneven product flow.
`
`* Tegeloxan® 100, TH. Goldschmidt
`
`5
`
`Examgles 13 and 14
`
`10
`
`A polymer was prepared similar to example 1, except that 0.8 wt.% nonyl phenol ethoxylate was used as the
`
`release liquid, and the monomer concentrations listed in table 2 were used. Furthermore, the amount of initiator,
`starting temperature and dwell time in the reactor are given in table 2. Discharge of the polymer gel was smooth; it
`did not stick to the inner reactor wall.
`
`
`
`15
`
`20
`
`Table 2:
`
`
`
`Discharge
`
`
`lnItIal
`temperature
`
`
`Monomer
`initiator
`
`Example
`
`
`
`
`
`
`(kg/h)
`2.4
`1.8
`9.6
`
`Example 15 to 21
`
`A polymer was prepared similar to example 1, except that 0.1 wt.% butyl stearate was used as release liquid,
`and the monomers listed in table 3 were used. The amounts of the monomers are in mol.%, based on the total
`amount of monomers with a double bond, the amounts of the initiators are indicated in moles of initiator per 1 million
`moles of monomer (mpmm). Furthermore. the absorption capacities of the obtained polymers are listed in table 3.
`The absorption capacity was measured by sprinkling 1 g of a polymer, dried for 48 h at 40°C in a drying oven, onto a
`09% aqueous NaCl solution, and determining the weight of the swollen polymer gel after complete swelling and
`draining on a sieve for 25 minutes.
`
`SNF Exhibit 1006, Page 7 0f18
`
`SNF Exhibit 1006, Page 7 of 18
`
`

`

`EP 0 374 709 A2
`
`The polymers obtained were not stuck in the reactor and could be discharged easily.
`
`Table 3
`
`
`
`
`
`
`
`V—50
`
`
`641
`
`Sulphite
`
`(9/9)
`
`Monomers
`DMM—HCI
`AS—Na
`MBA
`
`
`
`0.16
`‘
`‘
`50
`
`
`
`10
`
`
` nitiators Absorption capacity
`
`
`
`
`(mpmm)
`
` Peroxide
`49.3
`
`
`TAT
`
`VP
`
`
`
`
`
`
`
`
`
`
`
`641
`
`
`
`147.9
`78.8
`641
`
`
`
`
`
`|
`641
`148
`79
`641
`985
`592
`|
`
`
`
`5O
`
`38
`29
`30
`19
`49
`
`30
`45
`
`The following abbreviations are used for the monomers in table 3:
`AA
`Acrylamide
`AMPS—K
`Acrylamidomethyl propane sulphonic acid potassium
`AS
`Acrylic acid
`AS-Na
`Sodium acrylate
`MBA
`Methylene bisacrylamide
`TAT
`Tris—acryloylperhydro—s-triazine
`VP
`Vinyl pyrrolidone
`DAA
`Diacetone acrylamide
`DMM
`Dimethyl aminoethyl methacrylate
`DMM- HCI
`Dimethylaminoethyl methacrylate hydrochloride
`
`Claims
`liquid-absorbing, crosslinked, water—insoluble polymers by
`the continuous preparation of
`1.
`Process for
`polymerization of water-soluble monomers which contain one or more double bonds or of mixtures thereof,
`characterized in that a reactor is fed simultaneously at the inlet with an aqueous solution of the monomers and a
`release liquid which is immiscible or only partially miscible with this solution, and the release liquid becomes
`independently distributed in the course of the polymerization between the inner wall of the reactor and the polymer
`phase, and the resulting polymers are discharged together with the release liquid at the reactor outlet.
`2.
`Process according to Claim 1, characterized in that the release liquid is immiscible with the aqueous monomer
`solution.
`
`3.
`
`4.
`
`Process according to Claim 2, characterized in that the release liquid added is butyl stearate, butyloleate or
`silicone oil.
`
`Process according to one of Claims 1 to 3, characterized in that 0.01 to 0.8% by weight of release liquid, relative
`to the weight of monomer solution used, is added.
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`SNF Exhibit 1006, Page 8 of 18
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`SNF Exhibit 1006, Page 8 of 18
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`

`

`EP 0 374 709 A2
`
`Process according to one of Claims 1
`thereof, or derivatives thereof.
`
`to 4, characterized in that the monomers used are acrylic acid, salts
`
`Process according to one of Claims 1 to 5, characterized in that the monomer solution and release liquid are
`continuously introduced at the top of a vertical cylindrical tubular reactor, the monomers are polymerized as they
`pass through the tubular reactor in a downwards direction to form a highly viscous, gel-like polymer mass, the
`release liquid becoming distributed between the inner wall of the reactor and the polymer mass, and the polymer
`mass with the release liquid are continuously withdrawn at the base of the tubular reactor.
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`SNF Exhibit 1006, Page 9 0f18
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`SNF Exhibit 1006, Page 9 of 18
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`

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`SNF Exhibit 1006, Page 10 0f18
`
`SNF Exhibit 1006, Page 10 of 18
`
`

`

`9
`
`Européilsches Patentamt
`
`European Patent Office
`
`Office européen des brevets
`
`® Ver'dffentllchungsnummer:
`
`0 374 709
`
`A2
`
`®
`
`EUROPAISCHE PATENTANMELDUNG
`
`® Anmeldenummer: 89123007.0
`
`® Anmeldetag: 13.12.89
`
`@
`
`lnt.CI.5:C08F 2/10, C08F 2/00,
`A61L 15/24, A61L 15/60
`
`@ Priorltét: 20.12.88 AT 3090/88
`
`Veriiffentlichungstag' der Ame/dung:
`27.06.90 Patentblatt 90/26
`
`Benannte Vertragsst'aaten:
`AT BE CH DE ES FR GB GRIT LI LU NL SE
`
`
`
`®
`
`Anmelder: Chemle Linz Gesellschaft m.b.H.
`SLPeter~Strasse 25
`A-4021 LInz(AT)
`
`@
`
`Erfinder: Pleh, Stefan, Dr.
`Forsthausstrasse 39a
`
`A-4060 Leonding(AT)
`Erfinder: Willert, Gerhard
`Bodendorf 52
`A-4223 Katsdorf(AT)
`Erfinder: Kloimstein, Engelbert
`Schlferplatz 22
`A4070 Eferding(AT)
`Erfinder: Haslauer, Gerald
`Anastasius-Grfin Strasse 20
`
`A-4020 Llnz(AT)
`
`Vertreter: Kunz, Ekkehard, Dr.
`Chemie Holding AG Patentwesen St.
`Peter-Strasse 26
`
`11-4021, Llnz(AT)
`
`@ Verfahren zur kontinuierllchen Herstellung von fl'Lissigkeitsabsorblerenden, vernetzten Polymeren.
`
`@ Verfahren zur konfinuierlichen Herstellung von flusslgke/tsabsorbierenden, vernetzten Polymeren, bel dem
`wéhrend der Polymerlsatlon eine TrennflUssigkeit mitverwendet wird.
`
`EP0374709A2
`
`_Xerox Copy Cenlve
`
`SNF Exhibit 1006, Page 11 0f18
`
`SNF Exhibit 1006, Page 11 of 18
`
`

`

`EP 0 374 709 A2
`
`‘ Verfahren zur kontlnuierlichen Hersteliung von fliissigkeitsabsorbierenden, vernetzten Pplymeren
`
`Die Erfindung betrifit ein Verfahren zur kontlnuierlich Herstellung von flI'.'Isslgkeitsabsorbierenden..
`vernetzten Polymeren bei dem wéhrend der Polymerisation eine Trennflfisslgkeit miiverwendet wird.
`Fllissigkeitsabsorbierende Polymers, wie sie beispielsweise in der DE-OS 34 32 690 durch radikalische
`Ldsungspolymerisation von Acrylmonomeren hergestellt werden', kommen vorwiegend fUr saugf'eihige Hy-
`gieneartikel, als Trocknungs- und Wasserrilckhaltemittel sowle in der Landwlrtschaft als Bodenverbesse-
`rungsmittel vor allem in‘Trockengebieten zum Elnsatz.
`Die. Lésungspolymerisation von polaren Monomeren, wie 2.3. Acrylséure. Acrylamid oder deren
`Derivaten, fiihrt in wéBriger Lb'sung sowohl ohne als auch mit Vernetzer realtiv schneil zu gelartigen bzw.
`elastischegelartigen Produkten. Bereits bei relativ nledrigen Monomer-Konzentrationen. beispielswelse von
`unter 10 %, bildet sich in einem meist radikalisch initiierten Reaktionsverlauf ein wassergequollenes. zéhes
`bzw. z'a'h-elastisches Gel, dasbei seiner Herstellung und Auiarbeiiung Probleme aufwirft. Vor allem haitet
`der wéhrend der Polymerlsation entstehende. einen einzigen Hydrogelkifirper bildende Block durch Adhéi-
`sionskrfiite an der Reaktorwand, wodurch seine Welterfdrderung und Entnahme lm Zuge einer kontinuierll~
`Chen Polymerlsation erschwert bzw. verhindert wird. Besonders gef'eihrlich sind dabei Durchbrilche von
`nachdrUckender Monomerib‘sung lnfolge erzwungener Kanalbildung durch den festsitzenden Hydrogelblock.
`Dadurch wird einerseits eln uneinheitliches. mit Monomerldsung vermischtes. ungleichméflig polymerisier-
`tes und deshalb unbrauchbares Polymer erhalten. das als Abfall entsorgt werden muB. Andererseits
`erzwingt ein derartiger Durchbruch den Abbruch des Polymerisationsprozesses und erfordert ein erneutes
`arbeits-, kosten-, en'ergie-und zeitlntenslves Anfahren der Polymerlsatlon. Aus diesem Grund wird beispiels-
`weise in der DE-AS 12 18 157 angeffihrt. daB die Polymerisation in wéiBrigem Medium nur diskontinuierlich
`mdglich ist. Die kontinuierliche Polymerisation eriorderte bisher beiréchtlichen zus'étzlichen Aufwand. wie
`2.3. in der DE-OS 34 32 690 den Einbau von rotierenden R'Lihrerwellen In den Reaktor. Auch in der DE-OS
`
`35 37 276 wird eln Fleaktor mit elngebauten. auf einer Welle angeordneten Kneter- und Fb‘rderelementen
`verwendet. Bel Verwendung derartiger .Kneter-, RUhr- und Ftirderelemente ergibt sich ailerdings der
`Nachiell, da‘B aufgrund der auftretenden Scherkre'fie ein mechanisch stark degradiertes Produkt mit geringer
`Gelfestigkeit'und Viskositét erhalten wlrd.
`Die Aufgabe der En‘indung lag nun darin. ein Verfahren‘ zu linden. bei dem dlese Nachteile nicht
`auftreten und bei dem das im Verlauf der kontinuierlichen. Polymerisation entstehende Hydrogel Ieicht im
`Reaktor weitertransportlert und ausgetragen werclen kann, ohne dafl es Zum Ankleben und Festsitzen an der
`Reaktorwand, zu Monomerdurchbriichen b‘zw. Abbaureaktionen kommt. Die Aufgabe konnte dadurch gelb‘st
`warden, dal! gleichzeitig mit der ZufUhrung der Monomerldsung in den Heaktor auch eine mit dieser nicht
`mischbare Trennfliisslgkelt zugefflhrt wird. Es ist dabei besonders ‘Liberraschend. dafi die Trennflijssigkeit
`im Verlauf der Polymerisation an die Fleaktorwand wandert und dort eine Trenna und Gleitschicht zwischen
`’ Reaktorwand und Polymerblock bildet._ Dadurch wird eln freles Gleiten des Polymerblockes an der
`Fleaktorwand, ohne Kleben oder Festsitzen und damit auch ein leichter Austrag des Polymerblockes aus
`‘dem Reaktor ermb‘glicht.
`‘
`Gegenstand der vorliegenden Erfindung ist demnach eln Verfahren zur kentinulerllchen Herstellung von
`flUsslgkeitsbsorbierenden, vernetzten, wasserunlfislichen Polymeren durch Polymerisalion von wasserldsll-
`chen Monomeren, die eine oder mehrere Doppelbindungen enthalten, Oder von deren Gemischen, das
`dadurch gekennzeichnet ist. dell elnem Reaktor glelchzeitig mit einer wéiBrigen Ldsung der Monomeren
`eine mit dieser Léisung unmlschbare bzw. teilweise mischbare Trennfliissigkeit am Fleaktoreingang zuge-
`fUhrt wird, wobel sich die TrennflUslgkelt im Verlauf der Polymerisa‘tion selbst’cindig zwischen Reaktorinnen-
`wand und Polymerphase vertellt, und die entstandenen Polymeren gemeinsam mit der Trennflijssigkelt am
`Fleaktorausgang ausgetragen warden. Als wasserlb‘sllche Monomere mit einer Dopp‘elbindung k6nnen
`belspielsweise Monomers aus der Gruppe der monofunktionellen Vinyl- oder Acrylmonorneren, beispiels-
`weise Vinylpyrrolidon Acrylséureamide oder Melhacrylsfiureamide ((Meth)acrylsfiureamide) wie z. B. (Math)-
`acrylamld, N-Alkyl (C1'C4) und N-D-ialkyl
`(CI -C.I) (meth)acrylamide wie 23. N--Methy| (meth)acrylamid
`N,NDimethyl(meth)acrylamid, N-tert Butyl-(meth)acrylamid. N--Butyl(meth)acrylamid. N,N--Dimethyl(meth)-
`acrylamid, Aminoalkyl (01 -CI) (meth)acrylamide in ihrer neutraleri bzw.
`in ihrer quartemisierten Form wie
`2.5. Dimethylaminomethyl(meth)acrylamid, Dimethylaminoethyl(meth)a¢rylamid, Trimethylammoniumpropyl-
`(meth)acrylamidochlorid,
`(Meth)acrylsfiure
`und
`deren Alkali-und Ammoniumsalze,
`und
`(Math)-
`acryls‘aiurehydroxyalkylester
`((31 -CI) wie 2.8. Hydroxyethyl(meth)acrylat. Hydroxypropyl(meth)acrylat.
`(Meth)acryls§ureamlnoalkylester
`in
`ihrer neutralen
`bzw.
`in
`ihrer quartemisierten
`Form wie 2.8.
`Dimethylaminoethylimeth)acrylat. Dimeihylarnlnopropmeethlacrylat,
`Trimethylammoniummeihyl(meth)-
`acryloylmethylsulfat, Dimethyiammoniumalkyl(meth)acryloylchlorid. Sulfonséuren wie Vlnylsulfons‘aiure.
`
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`2
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`SNF Exhibit 1006, Page 12 0f18
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`SNF Exhibit 1006, Page 12 of 18
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`EP 0 374 709'A2
`
`AcrylamidomethylpropansuIfons'a‘ure. Suifoethyl(meth)acrylat und deren wasserldsliche Salze verwendet
`werden. Bevorzugt sind Acrylsé'ure und deren Salze sowie Acrylsia'urederivate und deren Salze.
`Diese Monomeren mit einer Doppelbindung warden zumeist Monomere mit zwei oder mehreren Doppelbin-
`dungen als Vernelzer zugesetzt. Ublicher