Untitled record

Process for producing ionic units of rubber and nano-polymer formulations

Process for the production of rubber ionomers and polymer nanocomposites

Full description

Background of the invention

The invention relates to an environmentally friendly, energy efficient process for preparing water and solvent-free rubber ionomers and/or polymer nanocomposites comprising said rubber ionomers. .

The term “rubber” as used herein generally means and includes co-polymers of C4-C7 isolefins, conjugated dienes C4-C14 and optionally other co-polymerizable monomers, unless otherwise defined. The term “brominated rubber” as used herein generally means and includes rubbers containing bromine covalently bound to a rubber polymer unless otherwise defined. An alternative and preferred example of rubber is rubber produced by the co-polymerization of isobutylene and isoprene (IIR). Its brominated analogue is referred to as brominated analogue isobutylene and isoprene (BIIR).

It has been shown that treatment with BIIR and other bromine-bound rubbers with nitrogen and/or phosphorus-based nucleophiles leads to the generation of ionic units with beneficial physical and chemical properties, which depend on their initial isoprene content (see EP 1 922 361 A, EP 1 913 077 A, Parent, J. S.; . S.; Penciu, A.; Guillen-CasteUanos, SA; Liskova, A.; Whitney, R. A. Macromolecules 37, 7477-7483, 2004).

The mentioned ionic units are often used to prepare nano-polymer formulations, which are obtained when incorporating nanosized fillers into the ionomer matrix. Hybrid materials reinforced with sheet-like fillers with high and/or pure organically modified bulk represent the most widely studied class of polymer nanocomposites. Strong interfacial interactions between dispersed layers and the ionic unit fabric lead to enhanced mechanical and barrier properties over conventional composites. Among the many areas of research of polymer nanocomposites, the tire industry has become particularly interested in high-volume fillers. Existing studies have shown that adding a high percentage of filler material to tire inner liner formulations increases oxygen impermeability by up to 40% (see, for example, US Patents 7,019,063, European Patents 1,942,136, US Patents 7,501,460, and US Patents 7,514,491). ).

Maximizing the high aspect ratio of fillers to their highest possible levels requires correct morphology, which makes the choice of both ionomer and filler sensitive. Inserting an ionic unit into platelet galleries, delamination and exfoliation of the platelets and anisotropic alignment of the plates in the fabric of the ionic unit must be achieved. To complete at least the lining and peeling, it is useful to establish a chemical link between the ionic unit fabric and the filler surface.

Ionic units, particularly butyl ionomers, used to prepare polymer nanostructures are typically prepared in a multi-step method involving slurry polymerization, solution bromination, isolation of the brominated rubber, and a subsequent kneading reaction to form the ionic units and compositions. Nano.

In a conventional slurry process, for example, to produce bromobutyl rubber (BIIR), isobutylene and isoprene monomers are first polymerized in a polar halohydrocarbon medium, such as methyl chloride, with an aluminum initiating system. Typically, either aluminum trichloride (AlCl3) or ethyl aluminum dichloride (EtAlCl3). Butyl rubber does not dissolve appreciably in this polar medium, but exists as suspended particles and so the process is often referred to as a slurry process. The remaining monomers and polymerization medium are then stripped from the steam of the butyl rubber, before being dissolved in a bromination medium, typically a non-polar medium such as hexane. Only recently, a method for using a common solvent system was described in International Patent 006983/2010a.

Brominated rubbers are typically produced by contacting a solution of non-brominated rubber in an alkane with bromine in an agitated vessel. The solution is generally referred to as cement. The unreacted bromine and hydrogen bromide formed as a byproduct are neutralized by adding a caustic soda solution. Additives can also be incorporated at this stage. The resulting solution is then steam stripped to remove the solution, thus coagulating the rubber into a solid product. The solid product is generally recovered as a 5 to 12% slurry in water. Stabilizers and/or antioxidants are added to the brominated rubber immediately prior to recovery. The brominated rubber is then finished using mechanical drying equipment in a process similar to that used for regular (unbrominated) rubber; However, due to the greater reactivity of the brominated product, less severe conditions are used. The isolated dry brominated rubbers are then used to prepare ionic units and nanostructures by reacting with nucleophiles and mixing with fillers, which is usually carried out by kneaders.

The previously mentioned processes of coagulation, steam stripping and kneading suffer from very high energy consumption. A large amount of steam is necessary not only to evaporate the solvent but also to heat and maintain the full water content of the stripping drums at a high temperature. Adding additional steam is also necessary to strip residual amounts of solvent by reducing the partial pressure of the solvent in the stripping drum.

The above processes also use a large amount of water because the concentration of brominated rubbers in the slurry after coagulation is generally only 5% to 20% for brominated rubbers. All water must be removed from the waste water of these slurry components. While the effluent contains sodium salts from neutralization, reworking and recycling the effluent to remove sodium salts is not economically viable because the salt concentration is very low.

The brominated rubber fraction is separated from the bulk water mechanically using sieve trays or simple screens. Brominated rubber still contains approximately 30 to 50% water after this separation. Further mechanical drying is then performed using extruders that knead the product and excrete the water. The disadvantage of this mechanical drying process is that the water is contaminated with small rubber particles, which are not caught again by the sieves, which leads to the liquid waste needing additional treatment.

The mechanical dewatering mentioned above may also reduce the moisture content to approximately 5 to 15%. Then additional thermal drying stages are required. The rubber is then heated to 150 to 200 degrees Celsius under pressure in a single screw or twin screw extruder. A plate is installed to maintain pressure. When the rubber is pushed through the die plate, the water in the rubber is evaporated and open porous crumbs are formed. Then a cutting device cuts the fragment into small pieces. The crumbs are transferred to a convective dryer where residual moisture is removed by hot air. After this drying, brominated rubber generally has a moisture content of 0.1 to 0.7%.

The above processes for drying brominated rubber are complex and require extensive equipment. Moreover, process parameters must be carefully monitored to avoid heat and shear stress, which will accelerate the degradation of brominated rubber. In addition to this, the subsequent formation of ionic units by the reaction of brominated rubbers with nucleophiles such as nucleophiles that carry phosphorus and nitrogen and the intercalation and lining of sufficient filler material in the fabric of the ionic unit requires a very high input of mechanical energy.

Many other special processes have been developed to isolate elastomeric polymers by removing water and volatile organic solvents from concrete. An extrusion device releases gas into a vacuum with or without the use of devices to create microbubbles in concrete that are accepted in practical applications as a more important technology. However, the energy requirements of these prior art processes are very high.

US Patent 5,283,021A1 describes a two-step process for removing solvent from an elastomeric polymer solution. Thus, the polymer solution is directly heated by heating fluid and sprayed under vacuum. During this spraying, the solvent is evaporated, thus forming a fraction which is then fed to an extruder to release additional gas. However, fracture formation at this stage is undesirable.

General description of the invention

In light of the foregoing, the object of the invention herein is to provide an environmentally and economically desirable, energy efficient and continuous process for the preparation of rubber ionic units and polymeric nanocomposites.

This objective is solved by a process for preparing rubberized ionic units comprising at least the steps:

A) Feeding

A concentrated fluid (L) containing at least one rubber bound to bromine and at least one volatile compound

A nucleophile contains at least one nitrogen and/or phosphorus.

The extruder unit includes at least:

An extruder degassing section comprising at least a conveying section, at least one vent port, and one or more vapor lines,

accumulating section and

outlet section,

And

b) At least partial reaction of brominated rubbers or brominated rubbers with a nucleophile containing nitrogen and/or phosphorus or nucleophiles containing nitrogen and/or phosphorus inside the extrusion unit, through which rubber ionomers (ION) are formed. Removal of volatile compounds at least partially through vent ports and steam lines.

The scope of the invention includes any possible combination of definitions, standards and explanations set forth herein either generally or within areas of preference.

Another aspect of the invention relates to a process for preparing polymeric nanocomposites comprising at least the steps:

A*) Feeding

A concentrated fluid (L) containing at least one bromine-bound rubber and at least one volatile compound

At least one nucleophile contains nitrogen and/or phosphorus.

and at least one filler material

In an extruder unit comprising at least

Gas release section of an extrusion device comprising at least one conveying section and at least one vent with one or more steam lines,

Assembling department

director section,

And

b) Reaction of brominated rubbers or brominated rubbers with nucleophiles containing nitrogen and/or phosphorus or nucleophiles containing nitrogen and/or phosphorus, through which rubber ionic units (ION) are formed.

Formation of polymeric nanostructures by reaction

Brominated rubber or rubbers combined with bromine and a nucleophile containing nitrogen and/or phosphorus or nucleophiles containing nitrogen and/or phosphorus and/or

Inflatable ionic modules (ION)

With at least one filler material

Thus, the previously mentioned reaction and formation are carried out at least partially within the extrusion device unit, through which the volatile compounds are removed at least partially through the ventilation outlets and steam lines.

In one embodiment of the invention, a concentrated fluid (L) is obtained which is fed to an extruder unit for the preparation of rubber ionic units or polymer nanocomposites by steps

1) Treat the fluid (F) in at least one concentrator unit comprising at least a heater, a gas release vessel (4) and a steam line, whereby the fluid (F) is heated, and the hot fluid (G) is fed to the gas release vessel Where a portion of the volatile compounds is removed through the steam line to obtain a concentrated fluid (H),

2) Reheating the concentrated fluid (H) from step 1) in at least one reheating unit to obtain the concentrated fluid (L).

In one embodiment of the invention the nucleophiles and/or fillers, which are finally fed into the extruder unit are already added to the fluid (F).

In one embodiment of the invention, the concentrated fluid (L) is free-flowing; in the context of this invention, the term “free-flowing” means a viscosity in the range 500 to 50,000,000 MPa*s, preferably 5,000 to 30,000,000. MPa*s and the best is 10,000 MPa*s to 300,000 MPa*s.

Unless otherwise stated, viscosity values for fluids refer to zero shear viscosity estimated inductively from measurements at a given temperature using a Haake Rheostress RS 150 viscosimeter or a coneplate type rotational rheometer for viscous samples. Very viscuous samples. Extrapolation is performed by taking a second-class polynomial to invert a graph of shear stress versus shear rate resulting from the measurements. The linear portion of the polynomial reflects the slope when the shear rate equals zero and therefore the shear viscosity equals zero. In the context of this invention, the term “effectively free of volatile compounds” means that the total concentration of volatile compounds is less than 1 weight%, preferably less than 0.5 weight% based on the mass of the ionic unit of the rubber or polymeric nanostructure.

In the context of this invention, the term “forming polymeric nanocomposites” includes intercalation, lining and exfoliation of filler particles in the rubber ionic unit, i.e. establishing an interaction between the ionic unit and the surface of the filler material.

In the context of this invention, the terms “at least partially reacting” and “at least partial formation” within the extruder unit mean, without wishing to be associated with any theory, that the reaction is normally induced and carried out by the input of mechanical and/or mechanical energy. Thermal through an extrusion device. However, it is clear to the person skilled in the art that, on the basis of the reactivity of the nucleophiles and the brominated rubber used, the reaction can also be initiated already when the concentrated fluid L or any preceding fluid is mixed with the nucleophile.

In one embodiment, at least 20%, preferably at least 50%, of the ionic unit and/or nanocomposition composition in the extruder unit is calculated on the specified compound or functional group.

In another embodiment, at least 80%, preferably at least 95% or 100% composition of the ionic unit and/or nanocomposition is performed in the extruder unit calculated on the specified compound or functional group.

Polymeric nanoformulations (NCs) can also generally be formed in situ in the presence of bromine-bound rubber, nucleophile and filler within the extruder unit.

Specifically, the term “virtually free of volatile compounds” means substantially free of water and substantially free of volatile organic compounds.

Ionic modules and polymer nanostructures are considered to be virtually water-free if the residual water concentration is less than 0.5 wt% (preferably less than 0.25 wt%) and preferably less than 0.1 wt% based on the mass of the polymer.

In the context of this invention, the term “volatile organic compounds” means organic compounds having a boiling point of less than 250°C at standard pressure.

Elastomer ionic units or polymeric nano-formulations are considered to be substantially free of volatile organic compound, if the residual concentration of said volatile organic compound is less than 0.75 weight%, preferably less than 0.25 weight%, preferable less than 0.1 weight% based on the mass of the polymer. The volatile organic compounds mentioned are usually the solvents used in polymerization or subsequent processing steps such as the bromination step, and include hydrocarbons such as hexanes and pentanes.

As used herein, the term brominated rubber includes bromobutyl rubbers, brominated terpolymers such as those described in U.S. Pat. 6,960,632 and Kaszas et al., Rubber Chemistry and Technology, 2001, 75, 155 Where para-methylstyrene is added to the mixed feed of butyl polymerizations (feeding methyl chloride, isobutylene and isoprene mixed feed, with mixtures of aluminum trichloride/water as initiator), which It results in a high molecular weight polymer with up to 10 mol% of styrenic groups randomly integrated along the polymer chain. It was found that the incorporation of para-methylstearin is uniform along the molecular weight distribution due to the similar reactivity with isobutylene. Isoprene moieties within butyl terpolymers can be bonded to bromine by conventional methods. Alternatively, the brominated terpolymer may comprise an isomonoolefin C4-C7, such as isobutylene, and a comonomer, such as para-alkylstyrene, preferably para-methylstearene. The previously mentioned copolymers available commercially under the trade name 3035,3433,3745 EXXPRO, when brominated, some of the alkyl substituent groups present in the styrene monomer units contain benzylic bromide formed by the bromination of the polymer. The preferred brominated rubbers are bromobutyl rubbers.

In the context of this invention, butyl rubber refers to a copolymer of isobutene (2-methylbuta-1,3-diene) and isoprene (2-methylbuta-1,3-diene). On a molar basis, the isoprene content in the polymer is between 0.001% and 20, preferably between 0.1 and 10 mol% and most preferably between 1.8 and 2.3 mol%. Butyl rubber consists of linear polyisobutene chains with randomly distributed isoprene units. Isoprene units insert unsaturated positions in the polymer chain to allow vulcanization. The average molecular weight of the butyl rubber molecules Mw is usually between 50,000 and 1,000,000 g/mol, preferably between 300,000 and 1,000,000 g/mol.

Bromobutyl rubbers also contain a certain amount of bromine covalently bound to the butyl rubber molecules. The amount of covalently bound bromine is usually in the range above 0-8 weight% with respect to the total mass of the polymer. Bromobutyl rubber may also contain additives, for example 0.0001 to 4 phr (phr = parts per hundred rubber weight), epoxidized soy bean oil (ESBO), 0.0001 to 5 phr calcium stearate. stearate and 0.0001 to 0.5 phr antioxidants. Other additives may also be used, depending on the application of the bromobutyl rubber product, i.e. fillers or colorants.

In the case of bromobutyl rubber, the typical bromine content in the product is 1.5 to 2.5 weight%, preferably 1.6 to 2.0 weight%.

As used herein, the term “nucleophile” refers to a compound with a lone electron pair on nitrogen or phosphorus that is capable of forming a covalent bond to form phosphonium or ammonium ions.

The preferred nucleophiles containing nitrogen and/or phosphorus are those of formula I.

AR1 R2 R3 (I)

where

A indicates nitrogen or phosphorus

R1, R2 and R3 are independent of each other and are chosen from the group consisting of alkyl C1-C20, arylalkyl -C6-C20 or aryl aryl -C5-C14.

C1-C18 alkyl radical refers to a straight-chain, cyclic, branched or unbranched alkyl radical that may also optionally be substituted to form alcohols, ethers, carboxylic acids, nitriles, and ethoxylated amines. Ethoxylated amines, acrylates, esters and ionic units of ammonium ionomer. The example applies to the alkyl moiety of the arylalkyl radical -C6-C15.

Aryl-C5-C14 refers not only to carbocyclic radicals but also to heteroaromatic radicals, which have zero, one, two or three carbon atoms in each aromatic ring, but at least one carbon atom in the radical as a whole. It is replaced by a heteroatom selected from the group nitrogen, sulfur or oxygen.

Alkoxy refers to a straight-chain alkoxy radical, cyclic, branched, or unbranched.

The preferred nucleophiles of formula (I) are those where two or three of the remaining R1, R2 and R3 are identical.

The most preferred nucleophiles with formula (I) are:

Trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-butylphosphine tri -n-butyl-phosphine, triphenylphosphine, 2-dimethylaminoethanol, dimethylaminoethylacrylate, dimethylaminoethylacrylate dimethylaminomethylacrylate, N-methylamino-bis-2-propanol N-methylamino-bis-2-propanol, n-ethylamino-bis-2-propanol N-ethylamino-bis-2-propanol, dimethyaminoethylmethacrylate, 1 - 1-dimethylamino-2-propanol, 2-(isopropylamino)ethanol, 3-dimethylamino-1-propanol, N-methyldiethanolamine -methyldiethanolamine, 2-(diethylamino)ethanol, 2- Dimethylamino-2-methyl-1-propanol, 2-[2-(dimethylamino)-ethoxy]ethanol 2-[2-(dimethylamino)-ethoxy]ethanol, 4- (Dimethylamino)-1-butanol 4-(dimethylamino)-1-butanol, N-ethyldiethanolamine, triethanolamine, tripropanolamine, aminolauric acid, betaine, 3- 3-diethylamino-1-propanol, 3-(diethylamino)-2,1-propanediol 3-(diethylamino)-1,2-propanediol, 2-{[2-(dimethylamino)ethyl]methylamino}ethanol 2-{[2-(dimethylamino)ethyl]methylamino}ethanol, 4-dimethylamino- 2-Butyn-1-ol 4-diethylamino-2-butyn-1-ol, 2-(diisopropylamino)ethanol, 2-(diisopropylamino)ethanol, N-butyldiethanolamine, N-butyldiethanolamine Amine N-tert-butyldiethanolamine, 2-(methylphenylamino)ethanol, 3-(dimethylamino)benzyl alcohol alcohol, 2-[4-(dimethylamino)phenyl]ethanol 2-[4-(dimethylamino)phenyl]ethanol, 2-(N-ethylanilino)ethanol 2-(N-ethylanilino)ethanol, N-benzyl-N - N-benzyl-N-methylethanolamine, N-phenyldiethanolamine, 2-(dibutylamino)ethanol, 2-(N-ethyl-N-meta-toluidino) 2-(N-ethyl-Nm-toluidino)ethanol, 2,2-(4-methylphenylimino)diethanol 2,2′-(4-methylphenylimino)diethanol, tert[2-(2-methoxyethoxy) Ethyl]amine tris[2-(2-methoxyethoxy)ethyl]amine, 3-(dibenzylamino)-1-propanol, dimethyl hydrogenated or mixtures of nucleophiles mentioned previously.

Where nucleophiles react preferentially with the allylic or benzylic bromide functional group of bromobutyl elastomers, the resulting monomeric moiety is typically a repeating unit derived from allylic or benzylic bromide. The total content of the monoionic moiety in the rubber ionic unit therefore does not exceed the starting amount of allylic or benzylic bromide in the brominated rubber; However, residual allylic or benzylic bromides and/or several remaining olefins may be present. According to the present invention the resulting rubber ionic unit may also be a mixture of a single-ion moiety bound to a polymer and an allylic or benzylic bromide such that the total molar amount of the mono-ionic moiety and the functional group of the allylic and/or benzylic halide are in the range of 0.05. to 20.0%, more preferably 0.2 to 1.0 mol% and even more preferably 0.5 to 0.8 mol% with residual polyolefin being in the range 0.2 to 5 mol% and more preferably 0.5 to 0.8 mol%. Residual allylic or benzylic bromides may be present in amounts from 0.1 mol% up to an amount not exceeding the original allylic or benzylic bromide content of the brominated rubber used to produce the rubber ionomer. Residual polyolefin may be present in an amount from 0.1 mol% up to an amount not exceeding the original polyolefin content of the non-brominated rubber used to produce brominated rubber. Typically, the residual multiolefin content of the rubber ionic unit is at least 0.4 mol%, preferably at least 0.6 mol%, more preferably at least 1.0 mol%, more preferably at least 2.0 mol%, still more preferable 3.0 mol% on Least, preferably more also at least 4.0 mol%.

As used herein, the term “filler” includes particles of a mineral, such as, for example, silica, silicate clay (such as, for example, bentonite), gypsum, alumina, titanium dioxide , talc and the like, in addition to mixtures thereof in quantities from 1 to 80 phr.

Other examples of suitable filler materials include:

Highly dispersable silicas, prepared for example by precipitation of silicate solutions or flame hydrolysis of silicon halides, with specific surface areas from 5 to 1000, preferably 20 to 400 m2/g (surface area). , especially according to the theory of Bernauer, Emmett and Taylor, BET Brunauer, Emmett and Teller theory), with particle sizes starting from 10 to 400 nm; Silica compounds may also optionally exist in the form of oxides mixed with other metal oxides such as zirconium, Zirconium Zr; Zinc Zn zinc, Ba Barium, Ca Calcium, Mg Magnesium, Al Aluminum, Ti Titanium

Synthetic silicate compounds, such as aluminum silicate and alkaline earth metal silicate;

Magnesium silicate or calcium silicate, with BET surface areas from 20 to 400 m2/g and primary particle diameters from 10 to 400 nm;

Natural silica compounds, kaolin and silica exist in nature;

Natural clays, such as montmorillonite and other clays found in nature;

Organophilically modified clays such as organophilically modified clays (eg Cloisite Nanoclays available from Southern Clay Products) and other naturally occurring organic clays;

Glass fibers and glass fiber products (matting, extrudates) or glass microspheres;

metal oxides, such as zinc oxide, calcium oxide, magnesium oxide and aluminum oxide;

Metal carbonates, such as magnesium carbonate, calcium carbonate, and zinc carbonate;

Metal hydroxides, for example aluminum hydroxide and magnesium hydroxide

Or combinations of the previously mentioned fillers.

In an embodiment of the invention, the filler materials are selected from a group of high-yield filler materials.

As used here, the term “high aspect ratio” means an aspect ratio of at least 3:1, where the aspect ratio is defined as the ratio of the mean diameter of a circle to the average thickness of the plate. The aspect ratio of the filling materials formed in the form of a needle or fiber is the ratio of length to diameter.

Fillers may include acircular or nonisometric materials with a flat or needle-like structure. The preferred high aspect ratio fillers have an aspect ratio of at least 3:1, more preferably 7:1, and even more preferably from 7:1 to 250:1. Fillers according to the present invention have an average particle size in the range from 0.001 to 100 microns, preferably between 0.005 and 50 microns and more preferably between 0.01 and 10 microns.

A suitable filler has a BET surface area, measured according to DIN (Deutsche Industrie Norm) 66131, from 5 to 200 square meters per gram.

In a preferred embodiment, the high aspect ratio fillers are selected from the group consisting of nanoclays, preferably organically modified nanoclay. The present invention is not limited to special nanoclay; However, natural powdered smectite clays, such as sodium or calcium montmorillonite, or synthetic clays such as hydrotalcite and laponite are preferred as starting materials. Organically modified montmorillonite nanoclays are particularly preferred. Clays are preferably modified by substituting a transition metal rather than an onium ion, as is known in the art, to provide a surfactant functional group for the clay that helps spread the clay within the generally hydrophobic polymer environment. The preferred onium ions are phosphorus-based (eg, phosphonium ions) and nitrogen-based (eg, ammonium ions) and contain functional groups with 2 to 20 carbon atoms (eg, NR4+-). MMT).

Clay types are preferably supplied with particle sizes on the nanometer scale, more preferably less than 25 m in size, more preferably 1 to 50 m, more preferably 1 to 30 m, more preferably 2 to 20 m. .

In addition to silica, the preferred nanoclays may also contain some alumina. Nanoclays may contain from 0.1 to 10 wt% alumina, preferably 0.5 to 5 wt% alumina, more preferably 1 to 3 wt% alumina.

Examples of preferred commercially available organically modified nanoclays suitable for use as high-percentage fillers according to the present invention are those sold under the trade names Cloisite clays 10A, 20A, 6A, 15A, 30B, or 25A and Nanomer 1.44P, 1.44PS, and 1.34TCN. . Other examples of high aspect ratio fillers include Polyfil 80, Mistron Vapor, Mistron HAR, Mistron CB as well as hydrotalcite clays such as Perkalite LD, or Perkalite F100.

High-percentage fillers are found in polymeric nanoformulations in amounts from 1 to 80 phr, more preferably 2 to 20 phr, even more preferable 4 to 20 phr.

Brief explanation of the drawings

The subject matter of the invention will be explained in more detail by means of schematic drawings which:

Figures 1 and 2 each show an extrusion device unit that includes three extruder gas release sections, three collecting sections and one outlet section, where one extruder gas release section is a backward degassing section.

Figure 3 shows an extrusion device unit that includes three extrusion device gas release sections, three collecting sections, a side feeder, and one outlet section, where the extrusion device gas release section is one rear gas release section.

Figure 4 shows a single-stage concentrator unit that includes a pressure regulation device, a reheating unit, an extrusion unit that includes a pressure regulating device, four extruder gas release sections, four collection sections, a side feeder, and an outlet section. One, wherein the extruder gas release section is one back gas release section.

Figure 5 shows an extruder unit comprising a pressure regulating device, four extruder gas release sections, four collecting sections, a side feeder and one outlet section, where one extruder gas release section is a back gas release section.

Figure 6 shows an extruder unit comprising a pressure regulating device, four extruder gas release sections, four collecting sections, two side feeders in different extruder gas release sections and one outlet section, where one extruder gas release section is a back gas release section.

Figure 7 shows a single-stage prewashing unit, a single-stage concentrator, a reheater unit and an extruder unit that includes a pressure regulating device, four extruder gas release sections, four collection sections, an optional side feeder and one outlet section, where The gas release section of one extruder shall be a rear gas release section.

Detailed description

A basic and representative embodiment of process steps a) and b) and a suitable device for performing said process steps are shown in Figure 1. A basic and representative embodiment of process steps a) and b*) and a suitable device for performing said process steps are shown in Figure 2.

In step a), concentrated fluid L and a nucleophile containing at least one nitrogen and/or phosphorus (NUC) are fed to the extruder at feeding point 12.

In step A*), concentrated fluid L, a nucleophile containing at least one nitrogen and/or phosphorus (NUC) and a filler (NF) are fed to the extruder unit at feed point 12.

The extruder unit may include one or more extruders connected in series. At least one of such extruders includes an extruder gas release section comprising at least one transfer section and at least one vent with one or more steam lines, a collection section and an outlet section. If more than one extruder is used, only the last one usually includes an outlet section as previously defined.

Suitable extruder types include single-screw and multiscrew extruders incorporating any number of barrels and other types of screw elements and conveying kneaders. Possible embodiments of multi-screw extruders are twin-screw extruders, ring extruders or planetary roller extruders, with twin-screw extruders and rotary roller extruders being preferred.

Single-screw extruders include those with an axial oscillating screw. Twin-screw extruders are, for example, counter-rotating intermeshing, counter-rotating non-intermeshing, co-rotating intermeshing and co-rotating non-intermeshing, Co-rotating twin screw extruders are preferred.

In one embodiment of the invention the extruders may be either heated through the barrels to a temperature of up to 300°C or cooled.

In a preferred embodiment, the extrusion device includes means for operating separate zones independently of each other at low temperatures such that the zones are either heated, unheated, or cooled. In another preferred embodiment the extruder for each conveying section includes at least one separate zone, which can be operated independently at different temperatures.

Preferred extruder materials must be non-corrosive and must largely prevent the liquid concentrate (NUC), elastomeric ionic units (ION) or polymeric nanostructures (NC) from being contaminated with metal or metal ions. Preferred extruder materials include nitrided steel, duplex steel, stainless steel, nickel-based alloys, composite materials such as sintered metals, hot isostatic pressed materials, Wear resistant materials such as Stellite, coated metals with coatings made of for example ceramics, titanium nitride, chromium nitride and diamonds Diamond like carbon (DLC).

Transport sections 16A, 16B and 16C are open to ventilation ports 13, 15A and 15B. In conveyor sections 16a, 16b and 16c a portion of the solvent is evaporated and separated from the reheated concentrated fluid L. The vapors are removed through the ventilation ports 13, 15a and 15b through vapor lines 13-1, 15-1a and 15-1b.

In a preferred embodiment of the invention, the concentrated fluid (L) is injected into the first extrusion device gas release section of the extrusion device unit, where the extruder gas release section includes one or more rear vent ports in a reverse direction, each of them connected to a vapor line.

The advantage of the rear vent ports is that the volatile compounds present in the concentrated fluid L undergo sudden and rapid evaporation, affecting at least partially the separation of the brominated rubber, nucleophiles and optionally the rubber on the one hand and the volatile compounds on the other hand, the vapors emitted through the rear vent ports in The opposite direction. In general, from about 20 to about 99 weight% of the volatile compounds present in the fluid L are removed through upstream vents.

Whereas the vaporization of volatile compounds has a tendency to bring the concentrated fluid L, nucleophiles (NUC), rubbery ionic units (IONs) or polymeric nanostructures (NC) toward the ventilation ports, in a preferred embodiment of the invention the ventilation ports 15 are designed to prevent the substance, particularly the concentrated fluid L, Nucleophiles (NUC), rubbery ionic units (ION) or polymeric nanostructures (NC) from exiting the ventilation ports.

Suitable means to accomplish this purpose are stuffer srews, which are installed on the ventilation outlets and move any material back into the extruder, or rollers or belts, which are applied inside the ventilation outlets to push the deposited material back into the extrusion device. As an alternative or in addition to the above, ventilation port covers can also be applied, which reduce or prevent adhesion of the material to the surface. Suitable coatings include DLC, Ethylene-Tetrafluoroethylene (ETFE), Polytetrafluoroethylene (PTFE) and Nickel-Alloys. However, applying embalming screws to the ventilation ports is preferred.

The pressure at ventilation ports 13, 15a and 15b is for example between 1 hPa and 2,000 hPa, preferably between 5 hPa and 900 hPa.

Steam lines may and preferably be connected to a condensing system.

In general, the purpose of the condensing system is to collect volatile compounds removed by venting through steam lines and typically includes a condenser and a vacuum pump. Any condensation system known in the art can be used to affect the recovery of volatile compounds.

In general, it is preferable to recycle condensed volatile compounds, optionally after layer separation to separate the volatile organic compounds from water, in the process of preparing liquid concentrate L.

The conveying section 16c terminates with an assembly section 20. The purpose of the assembly is to assert a certain pressure level at the ventilation port 15b and to introduce mechanical energy into the material to facilitate the vaporization of volatile compounds. The assembly section 20 may include any means that allows the material to be assembled. They can be designed to include for example kneading or throttling elements, blister discs or mold plates.

Examples of throttling elements are conical or cylindrical flow paths or other throttling means.

Applying kneading elements, blistering discs or mold plates within the assembly section is preferable, kneading elements are also more preferable. Examples of kneading elements include kneading blocks, which can be designed as double or triple kneading blocks for flighted forward, backward, or fast-moving neutral; Single or dual fast-moving screw mixing elements with grooves, single or triple flighted tooth mixing elements, blister plates and dual or triple flighted eccentric discs. The kneading elements can be assembled in any combination on the screw shafts of the extruder, especially co-rotating twin-screw or reverse-rotating twin-screw extruders.

A typical assembly section includes from 2 to 10 kneading blocks, often terminating in a back-transport type kneading element. For mixing a stripping agent, tooth type elements or screw elements with recesses may be used.

The eccentric tablets are preferably applied in the final section of the extruder, where the product P is highly viscous and largely free of volatile compounds.

For rotary drum extruders, dough elements such as tooth-shaped rollers or rollers with grooves and clearances are preferred.

In general, an extruder unit may include one or more conveying sections and one or more assembly sections, the number being limited only by constructional constraints. The typical number of conveyor sections and assembly sections is 1 to 30, preferably 2 to 20 and more preferably 3 to 15.

The final assembly section 20 is typically aligned to form a product plug at the extruder outlet, preventing ambient air from entering the extruder.

Passing from the transport section 16a to the collection section 20 and also to the outlet section 22 the concentrated fluid L reacts with nucleophiles (NUC) to form ionic units (step b) or, if at least one filler is also present to form nanostructures (NC) wherein Conversion from concentrated fluid L to products (ION or NC).

The outlet section 22 typically includes means for allowing the ionic rubber units (IONs) or polymeric nanocomposites (NCs) to exit the extrusion device and optionally but preferably processing equipment. Examples of suitable processing equipment include a combination of plates and die cutters; Mold plates and underwater pelletizing media; Crusher-forming factors such as screw elements with teeth and holes; A device for improving air flow which may be designed as cylinders with holes in them, by which the product is compressed from the outside of the cylinder into the inside, and by which a rotating knife inside the cylinder cuts the product into pieces; Fixed knives are placed at the end plate of the extruder, where they cause rotation Screw rotation is a cutting process, which is preferably applied when working with single screw, co-rotating and rotary cylinder extruders.

To reduce mechanical and thermal stress on the product, in a preferred embodiment of the invention, the processing equipment is combined with cooling means.

Cooling means include any means that allows the removal of heat from the product. Examples of cooling methods include pneumatic crumb conveyers with convective air cooling, vibrating crumb conveyers with convective air cooling, vibrating crumb conveyer with cooled contact surfaces, and a belt conveyer. With convection air cooling, a belt converter with cooled belts, water spraying on the hot crumbs at the exit of the extrusion device, and as previously mentioned pelletizing methods. pelletizing means underwater, where water acts as a coolant.

The ionic rubber units (IONs) or polymeric nanoformulations (NC) may then be further processed for final packaging and shipping.

The resulting polymeric nanocomposites may also be processed according to B*, for example using conventional processing systems such as sulfur, resin and peroxide in a subsequent step C*).

The preferred treatment system is sulfur-based. A typical sulfur-based treatment system includes: (1) a metal oxide, (2) elemental sulfur, and (3) at least one sulfur-based accelerator. The use of metal oxides as a component in a curing system is well known in the field. A suitable metal oxide is zinc oxide, which is typically used in an amount of about 1 to about 10, preferably about 2 to about 5, parts by weight per hundred parts by weight of butyl polymer in nanosynthesis. Elemental sulfur, including component (2) of the preferred curing system, is usually used in amounts from about 0.2 to about 10 parts by weight per hundred parts by weight of the butyl polymer in the composition. Suitable sulfur-based accelerators (component (3) of the preferred treatment system) are typically used in quantities of about 0.5 to about 3 parts by weight, per hundred parts by weight of the butyl polymer in the composition. Unlimited examples of useful sulfur-based accelerators may be selected from thiuram sulfides such as tetramethyl thioram disulfide (TMTD), thiocarbamates such as zinc dimethyl dithiocarbamate (ZDC), and thiazyl and benzothiazyl compounds such as Mercaptobenzothiazyl disulfide (MBTS). Preferably, the sulfur based accelerator is mercaptobenzothiazyl disulfide.

The cured article may contain other auxiliary products for rubber, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti-aging agents, stabilizers heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, materials to increase Tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, and hexanetriol , etc., which are well-known in the rubber industry. Rubber acids are used in conventional quantities that depend, among other things, on the intended use. The treated material may also contain metallic and/or non-metallic fillers. Typical amounts are from 0.1 to 50 wt%, based on rubber.

More information on vulcanizers may be found in Encyclopedia of Polymer Science and Engineering, Vol. 17, s. 666 et seq. (Vulcanization).

The elastomeric units generated according to steps a) and b) and the treated and untreated nanocomposites generated according to steps a*), b*) and c*) may be used as part of a frame including, but not limited to, an inner liner, tread, wall Sidewall, adhesive, as part of thermoplastic elastomer, footwear, storage membranes, protective clothing, pharmaceutical stoppers, linings, barrier coatings.

In general, an increased feed rate of concentrated fluid L at feed point 12 requires a corresponding increase in extruder screw speed. Moreover, the screw speed determines the retention time of the concentrated fluid L. Therefore, the screw speed, feed rate and extruder diameter usually depend on each other. The extrusion is typically operated in such a way that the dimensionless throughput is set to V/(n*d3), where V is the volume flow rate, n is the screw speed expressed in revolutions per minute, and d is the effective diameter of the extruder. Preferably about 0.01 to about 0.2 to about 0.015 to about 0.1. The maximum and minimum feed rates and screw speeds of the extruder are determined by, for example, the size of the extruder, the physical properties of the brominated rubber contained in the fluid L and the target values for the remaining volatile compounds. Due to these properties, however, operating parameters may be determined by an expert in the field through some preliminary experimentation.

In one embodiment of the invention the extruder is operated at a feed rate of 1 to 25,000, preferably 1 to 6,000 kilograms per hour.

Generally, the removal of gases from an extruder may be aided by the addition of a stripping agent that is removed along with other volatile compounds. Although the stripper may be added anywhere in the extruder, it is preferable to add it in one or more assembly sections. In a more preferred embodiment a stripping agent is added in one or more assembly sections except the last section (20).

Suitable stripping agents are materials that are inert to concentrated fluid (L), nucleophiles (NUC), while being applicable to filler (NF) and/or products (ION or NC)) and have a vapor pressure higher than 100 hPa at 100° percentage.

In the context of the invention, the term “inert” means that the stripping agent does not or does not actually react with the polymers contained in the liquid concentrate L, nucleophiles (NUC), while being applicable to the filler material (NF), and/or products (ION or NC ). Suitable stripping agents are nitrogen, carbon dioxide, noble gases, propane, butane, water and a mixture of the aforementioned substances, where carbon dioxide is preferred. The amount of stripping agent may be 0.0001 to 10, preferably 0.001 to 5 and more preferably 0.1 to 2 wt% based on the amount of rubber ionic unit (ION) or nanopolymer (NC) composition produced in the outlet section.

The invention also relates to the use of a suitable device to complete the process in accordance with the invention. Accordingly, the invention also includes the use of a device comprising at least:

One extrusion device unit includes at least one feed point (12), at least one extruder degassing section (16), at least one collecting section (20) and at least one outlet section (22), where each device degassing section includes Additional (16) extrusion on at least one vent (15) connected to a steam line (15-1)

To prepare rubber ionomers and/or polymer nanocomposites

Another embodiment of the invention is shown in Figure 3. Figure 3 shows another flow chart and a suitable device for completing the process according to the invention, which includes an extrusion device unit that includes three sections for removing gas from the extrusion device, including three transport sections 16a, 16b and 16c, each of which is connected to a ventilation hole 13, 15a and 15b and a steam line 13- 1, 15-1a and 15-1b, three collecting sections 18a, 18b and 20 terminate the transport sections 16a, 16b and 16c and an outlet section 22. In addition, the extruder unit additionally includes a side feeder 19.

Generally, the extruder unit may include one or more side feeders, which may be located anywhere in the extruder, preferably near the feed point or outlet section 22. Side feeders are suitable for adding additives to the polymer and especially for the alternative or additional addition of nucleophiles. and/or filler materials.

Generally, nucleophiles, where fillers are applicable, can be added to

To fluid F, G or H or

To the concentrated fluid L, that is, before feeding the fluid L to the extrusion device or

Any place inside the extruder unit before the outlet section, as it is preferable to complete this using a side feeder.

Where nucleophiles and fillers are fed to the extruder unit to prepare nanopolymer formulations, the addition of nucleophiles and fillers may be affected independently of each other. However, it is preferable to add the filler simultaneously with or after the nucleophile in the same direction.

Fillers may be added as a solid eg via an embalming nail or in the form of a paste, slurry or suspension eg via a liquid pump.

Nucleophiles may be added, depending on their state of aggregation, as a liquid (melt), a solid or as a solution.

The liquid used for preparing the aforementioned pastes, slurries, suspensions or solutions shall preferably have the same or similar composition as the volatile compounds that are part of the liquid L

The addition of nucleophiles and fillers through a side feeder is shown in Figure 5.

The addition of nucleophiles and fillers through different side feeders in different transport sections is shown in Figure 6.

The addition of nucleophiles at different locations (NUC1, NUC2 and NUC3) is shown in Figure 7.

Examples of additives, particularly for rubber ionic units and/or polymeric nanoformulations, include stabilizing agents, acid scavengers such as ESBO (epoxy soybean oil), stearates such as calcium stearate, antioxidants and the like. Examples of suitable antioxidants include sterically hindered phenols such as butylhydroxytoluenes and derivatives such as Irganox 1010 and 1076, amines, mercapto-benzimidazoles, certain phosphites and the like.

In particular, bromobutyl rubbers, ionic units and nanoformulations derived from them are mixed with additives, for example 0.0001 to 4 phr epoxidized soybean oil (ESBO), 0.0001 to 5 phr calcium stearate and 0.0001 to 0.5 phr antioxidants (phr = parts per hundred rubber by weight of rubber). Other additives are also applicable, depending on the application of the butyl rubber product, i.e. fillers or colours.

Another embodiment of the invention is shown in Figure 4. Figure 4 shows another flow chart and an apparatus suitable for completing the process according to the invention including steps 1) and 2 and comprising a concentrating unit with pump 1, a heater 2, a degassing vessel 4, a steam line 4-1 and a pump 4-2, a reheating unit comprising A heater 6 and an extrusion device unit comprising four sections for releasing gas from the extruder having four conveying sections 16a, 16b, 16c and 16d, each of which is connected to a ventilation hole 13, 15a, 15b and 15c and steam lines 13-1, 15-1a, 15-1b and 15- 1C, four assembly sections 18A, 18B, 18C and 20 terminate transportation sections 16A, 16B, 16C and 16D and exit section 22. In addition, the extruder unit additionally includes a side feeder 19.

In step 1) fluid F containing at least one brominated rubber and at least one volatile compound is conveyed via pump 1 to heater 2, where fluid F is heated.

Fluid F, also called concrete, contains, for example, from 3 to 50 weight% of brominated rubber, and from 60 to 97 weight% volatile compounds, especially solvent or solvent and water, to which the previously mentioned components are added in amounts of up to 90 to 100, Preferably 95 to 100 weight% of the total volume of fluid F.

The solvent is preferably chosen from a group of linear or branched alkanes with between 4 and 10 carbon atoms. The most preferred solvents are n-pentane, iso-pentane, n-hexane, cyclo-hexane, iso-hexane, methyl-cyclopentane, methyl- methyl-cyclohexane and n-heptane, as well as mixtures of these alkanes.

In a preferred embodiment of the invention, fluid F contains from 3 to 40 weight% of brominated rubber and from 60 to 95 weight% of volatile organic compounds, in particular a solvent, and from 0.5 to 20 weight% of water, wherein the aforementioned components are previously added in up to 95 to 100 wt% of the total volume of fluid F.

Fluid F is usually obtained from bromination treatments or other processing steps. Fluids F containing water are usually obtained after neutralization following bromination processes.

Fluid F entering the heater typically and preferably has a temperature of 10°C to 100°C, preferably 30°C to 80°C. The fluid viscosity F is for example in the range from 100 MPa* s to 25,000 MPa* s, preferably in the range from 500 MPa* s to 5,000 MPa* s.

The heater may be any device capable of raising the temperature of the fluid F. In a preferred embodiment, heater 2 is a heat exchanger. The heating medium is chosen from the group consisting of steam, heating oil, or hot pressurized water. The heat exchanger, for example, is a shell-and-tube type, where the fluid F is inside the tubes and the heating medium is on the shell side. Special inserts may be applied in the pipes to enhance heat transfer. Another type of heat exchanger may also be used, in which the fluid F is outside the heat exchanger tubes. The advantage of the previously mentioned types of heat exchangers is avoiding misdistribution and ease of maintenance, in addition to good heat transfer. The mentioned heat exchangers are well known and commercially available. In a less favorable embodiment plate type heat exchangers may also be applied.

Upon heating, the heated fluid G is obtained. Heated fluid G has a higher temperature than fluid F, preferably 100 to 200°C, most preferably 110°C to 190°C and most preferably 120°C to 175°C. The heated fluid G is then further transferred to a degassing vessel 4. In the degassing vessel, the volatile compounds are at least partially vaporized. The vapors are separated and removed from the heated fluid G by vacuum line 4-1. The pressure in the degassing vessel 4 is for example in the range from 100 hPa to 4,000 hPa, preferably in the range from 200 hPa and 2,000 hPa and more preferably in the range from 230 to 1,100 hPa.

The removed vapors are preferably condensed via the vacuum line 4-1 and recycled in the fluid preparation process F. After degassing and separation, a concentrated fluid H is obtained, which is removed from the degassing vessel 4 via a pump 4-2 .

The degassing vessel may generally be a flash evaporator or other device typically used to remove volatile compounds while having short retention times.

In a preferred embodiment of the invention, the degassing vessel is designed in the form of a cyclone to aid further separation of vapor from the heated fluid G. In another preferred embodiment of the invention, the degassing vessel has a conical or at least torisperical shaped bottom, to allow the vessel to be emptied completely or to to a big limit.

The pump 4-2 is preferably connected directly to the outlet of the degassing vessel 4. In general, the connection segment between the pump and the vessel is preferably as short as possible.

Due to the high viscosity of the concentrated fluid H at this stage, the pump inlet is preferably designed with a large inlet, which reduces the pressure drop at the inlet.

Pump 4-2 may be selected from the group consisting of positive displacement type pumps, gear pumps, piston pumps, membrane pumps, screw type pumps, extruder type pumps extruder type pumps such as reversible screw type extruders, single or dual co-rotating screw type extruders, or kneader type pumps. Positive displacement type pumps and gear pumps are preferred, but gear pumps are even more preferred.

In another preferred embodiment the pump 4-2 includes a combination of an extruder or kneader and a gear pump wherein the gear pump is fed from the kneader or kneader.

The amount of volatile compounds removed in this step 1) is, for example, dependent on the temperature of the fluid G and the pressure in the degassing vessel 4. In a preferred embodiment of the invention the fluid temperature G and pressure in the degassing vessel 4 are chosen such that the concentrated fluid H is preferably free flowing as previously determined and comprising, for example, from 10 to 60, preferably from 25 to 60 wt.% rubber combined with bromine and from about 40 to about 90, and preferably from 40 to 75 wt.%, volatile compounds wherein the aforementioned components are added a non-volatile polymer, a volatile organic compound and water in an amount of up to 90 to 100 wt.%, preferably 95 to 100 wt. % of total mass of fluid H.

In a preferred embodiment where the feedstock fluid F comprises water, fluid H for example comprises from 10 to 60, preferably from 25 to 60 wt% brominated rubber, from about 25 to about 90, preferably from 25 to 75 weight% volatile organic compounds, particularly a solvent, and about 0.5 to about 15 weight% water, to which the above-mentioned components are added a non-volatile polymer, a volatile organic compound and water in an amount of up to 90 to 100 weight%, preferably 95 to 100 weight% of the total volume of fluid H.

The temperature of the concentrated fluid H is lower than that of the heated fluid G and is for example in the range from 15 to 100°C, preferably in the range from 30 to 100°C. The concentrated fluid H is preferably free-flowing as previously determined.

In step 2), the concentrated fluid H produced in step a) is then passed through a reheating unit 6 to obtain a reheated concentrated fluid L. In a preferred embodiment the reheating unit includes a heat exchanger, where the same description applies including preferences with respect to Using heating media and types of heat exchanger as previously described for heat exchanger 2.

The temperature of the reheated concentrate fluid L is higher than that of the concentrated fluid L and is for example in the range 50°C to 200°C, preferably in the range 90°C to 180°C. The reheated concentrated fluid L is preferably free-flowing as previously defined.

In one embodiment of the invention the nucleophiles (NUC) may actually be added to the fluid F as shown in Figure 7 (NUC(1)). However, adding the nucleophile to the concentrated fluid L or elsewhere within the extruder before the outlet section is preferable.

In a preferred embodiment of the step of the invention 1) it is repeated at least once, preferably one or two times. The advantage of the repeating step is that the total energy consumption to produce the fluid L can be significantly reduced due to improved operation parameter and easier operation per unit concentration. Repeat step 1) Preferably, the appropriate number of concentrating units are connected in sequence.

In a preferred embodiment of the invention the concentrator, reheater or extruder unit may be independently of each other equipped with one or more pressure regulating devices which permit very precise operation of the units under previously specified conditions.

Pressure regulating devices may be active or passive, with active pressure regulation devices being preferred. Examples of positive pressure regulators include control valves such as a relief valve. Examples of passive pressure regulators include nozzles, dies, or orifice plates. Suitable valves can be selected from ball, piston, gate or needle valves.

In the case of a passive pressure monitoring device, it is preferable to calculate an opening to create a certain pressure drop. The calculation is based on the viscosity of the fluid at that point and the throughput. Anyone who is an expert in the field can perform this calculation.

Active pressure control devices are typically controlled by measuring pressure against the direction of the device. For example, pressure is measured and compared to the specified value. Then the pressure control device is adjusted according to a recognized equation.

Instead the pressure drop across the device is measured instead of the absolute pressure upstream from the pressure control device. The valve position is adjusted manually, electrically, pneumatically or hydraulically. Valve control location, ie: adjustment

To set point pressure mode, it can for example be operated manually or from any automated process control system.

In another aspect of the invention it relates to the use of a tool as described above which also includes

One concentrating unit includes a heater (2) in communication with the degassing vessel (4), where the bottom of the degassing vessel (4) is in communication with the pump (4.2) and the top of the degassing vessel (4) in communication with the Minimum one steam line (4.1)

One heating unit (6) in connection with the pump (4.2) of the concentrator and a feed point (12) on the extruder unit and optionally

One or more pressure regulating devices

Within the context of this invention, the expression "in communication" includes direct or indirect communications, where indirect communications may be achieved, for example, by means of tubes. The expression "in communication" also includes the choice between units or means within communication units as well or arranged means.

Another embodiment of the invention has additional pressure controls for example shown in Figures 4, 5, 6 and 7. The hot liquid pressure G is under the control of the pressure controller 3 (Figure 4), the concentrated liquid pressure L enters the extruder under the control of the pressure controller 7 (Figures 4, 5, 6 and 7).

There is also a significant reduction of residual hydrophilic compounds or water or both that can be usefully achieved by preparing liquid F in the process of removing hydrophilic compounds and optionally water from a crude fluid A containing at least a non-bromined rubber. At least one volatile organic compound, one or more hydrophilic compounds and optionally hydrophilicity include at least one step

Before i) treating the raw liquid (a) in at least one pre-washing unit including at least a separating apparatus (26), wherein the liquid (a) is mixed with water to obtain an organic phase (28) comprising a non-volatile polymer initially Volatile organic compounds and an aqueous phase (27) include primarily water and hydrophilic compounds, wherein the organic phase (28) is separated from the aqueous phase (27) in a separator (26) and is further used as liquid F, where at least part of the aqueous phase (27) is removed. ) from the separator (liquid C).

Within the context of this invention the expression “hydrophilic compounds” denotes volatile compounds and non-volatile compounds that are at least partially soluble in water. Examples include inorganic salts, particularly residues of catalysts used for the polymerization reaction, eg aluminum salts, iron salts, transition metals, or others, and inorganic bromide products, in particular, from bromine addition reactions and subsequent modifications.

A typical embodiment of step before i) is illustrated using Figure 7.

In the step before i) a raw liquid containing at least one non-volatile polymer, at least one volatile compound and at least one hydrophilic compound is fed to the mixing section 30 of the separator 26, equipped with a mixer 32 and passed through the separating wall 34 To a stabilizing section, where the mixture is separated into an aqueous phase 27 and an organic phase 28, where the separation is supported by coalesce 29. A portion of the aqueous phase 27 is removed from the separator 26 as liquid C, which typically removes the remaining fresh water E and is recycled via the recirculation line 38 by operating a recirculation pump 36 back to the mixing section 30. The organic phase 28 It is removed and subjected to subsequent process steps as Liquid F.

Generally, coalescer in the preparatory washing step is helpful, but not mandatory. It helps collect and coalesce droplets and directs them to the phase junction, where they lead to typically shorter residence times. Suitable examples of coalescers include structured or unstructured packings. Organized connection, for example, flat plates, flat vanes, roof-shaped vanes and vanes with holes in the vertical direction. Vanes or plates may be placed parallel to the main flow direction or with a slope. Irregular splicing, for example wire mesh, making splicing of rings, spheres, cylinders, irregularly shaped geometries, and weirs such as distributor plates, which have openings or slits, vertical plates covering part of the flow path. the main. Bonding can be made from any technically practical material, for example: metals, glass, ceramics, coated metals, metals and polymeric materials such as PTFE, ETFE, polyethylene (PE), polyether ether. polyetheretherketone (PEEK), polypropylene (PP), polyamide (PA) and polyvinylidenfluoride (PVDF).

In a preferred embodiment of the invention step before i) is repeated at least once, preferably once.

In a preferred embodiment of the invention wherein the separation is performed at temperatures greater than 40°C. The upper limit depends on the polymer and construction of the separation device. Typically the upper limit is 125 m.

In a more preferable embodiment of the invention where the separation is performed at temperatures from 40 to 110 C from preferably at temperatures from 80 to 110 C.

Depending on the composition of the liquid and the boiling points of its components, the separator may be designed to operate under pressure.

In general, the efficiency of the pre-wash step increases with increasing temperature.

In another embodiment of the invention, the organic phase 28 leaving the separator may be preparatively heated to facilitate the free flow of fluid F. This purpose may also be accomplished by a heater, which heats the exchangers as shown for heater 2 above.

For example, liquid A resulting from the bromination process of butyl rubber typically contains inorganic bromide levels of 3,000 to 5,000 parts per million calculated per mass of bromobutyl rubber. Upon performance of the preparatory step i) this level can go from less than 500 ppm, from preferably to less than 300 ppm and to a greater degree from preferably to less than 100 ppm.

It was also found that performing the step before i) allows for a significant reduction in the water content of Liquid F compared to Liquid A, which contributes to a much lower energy consumption for the subsequent processing steps.

In another embodiment, liquid A is obtained by a process including at least the following steps

I) Providing a reaction medium including

A common aliphatic medium comprising at least 50% by weight of an aliphatic hydrocarbon or more having a boiling point in the range of 45°C to 80°C at a pressure of 1013 hPa, and

The monomer mixture includes at least one monoolefin monomer, at least one monoolefin monomer and either not or at least one polymerizable monomer in a mass ratio of the monomer mixture to the common aliphatic intermediate from 40:60 to 95:5, Preferably from 50:50 to 85:15 and more preferably from 61:39 to 80:20;

II) polymerization of the monomer mixture within the reaction medium to form a rubber solution comprising a rubber polymer dissolved at least substantially in a medium including a common aliphatic medium, and the remaining monomers of the monomer mixture;

III) Separation of the remaining monomers from the monomer mixture from the rubber solution to form a separate rubber solution including the rubber polymer and the aliphatic co-intermediate,

IV) Addition of bromine, rubber polymer into the separated rubber solution to obtain raw liquid A, the solution includes bromine-added rubber and common aliphatic intermediate,

As used herein the expression “at least substantially soluble” means at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight and to a greater extent preferably at least 95% by weight of rubber polymers acquired in accordance with For step II) melt in the middle. A process like this is known from International Patent 006983/2010, incorporated herein in its entirety.

Examples

Analytical methods

Water content of fluids: The sample was placed in a centrifuge and spun for 5 minutes at 4000 rpm at room temperature. Then collect the water at the bottom of the vial and weigh.

Total volatiles concentration: A rubber sample cut into 2-2 millimeter pieces. Approximately 30 grams of rubber pieces are placed in alumina crucible powder. Weight of crucible and rubber powder. The powder includes the rubber sample and is then placed in a vacuum oven at a vacuum pressure level of 130 hPa for 60 minutes at a temperature of 105 °C. After drying, the powder is placed in the exsiccator and cooled for 30 minutes. Then I weighed the powder again. Weight loss is determined.

Residual solvent concentration in products: The concentration of remaining solvent in the product is determined by headspace gas chromatography. A portion (0.5 +- 0.005 g) of the sample is weighed, placed in a headspace vial, and the amount of solvent (1,2 dichlorobenzene, or ODCB) added is measured. The vial is closed and shaken until the rubber dissolves. The flask is heated until the VOCs are distributed in the equilibrium between the sample and the gas phase in the flask (headspace). Aliquot headspace gas is injected into the carrier gas stream, where it transports the sample to the chromatographic column. Known composition standards are used for GC grading. Toluene is added to the solvent for use as an internal standard.

Residual water concentration in products: The concentration of total volatiles is the sum of water, solvents and monomers. As the monomer concentration is typically less than 0.0005 wt%, the water content can be determined by subtracting the solvent concentration from the total volatiles concentration.

Solvent concentration in liquids: Solvent concentration in liquids is measured using gas chromatography. The internal standard was isooctane. The sample is diluted with toluene and then injected into a gas chromatograph. Gas chromatograph performed on HP 6890 chromatograph, with the following specifications:

- Column type DB-5 from J&W, length 60 metres, diameter 0.23 mm, film thickness 1.0 metres.

- Make a temporary injector temp. : 250 m

- Make a temporary detector temp. : 350 m

- Carrier gas: Helium

- Detector column pressure: 96 kPa

- Detector: FID

Fluid viscosity: Viscosity is measured in a cone plate type rotary rheometer. All viscosities given refer to zero shear viscosity.

Ionomer content: Ionic unit content measured by: 1H and 31P NMR spectroscopy.

Viscosity of solids: Viscosity is measured using a Mooney viscometer of rotating disc type. Viscosity is measured using a large rotor at 125°C with one minute pre-heat time and eight minutes before measurement (ml (1+8) @ 125°C).

Oxygen permeability: Oxygen permeability measured using a Mocon Ox-tran model 2/61 permeability tester at 40 m. Rubber samples for permeability testing are mounted in a standard sulfur curing formulation frame and processed into thin sheets at 160 m.

Example 1: Concentration and Extrusion

the tool

The tool used for the examples was similar to the one shown in Figure 4. A piston pump was used to pump fluid (F) to the heater (2). The heater (2) was a single tube in a tube type heat exchanger. The inner tube is equipped with a Kenics static mixer, the diameter of the internal pipe is 15 mm. The tube is heated by a shell tube. The heating medium is heated oil (Marlotherm). A pressure relief valve (3) is installed before the degassing vessel (4), an upstream pressure that automatically controls the valve to the set point value. This setting point is chosen to boil in the hot liquid (G). The hot liquid (G) is fed to the degassing vessel (4) from the top. The conical outlet of the degassing vessel (4) is equipped with a pump (4.2), which is an extruder type pump and gear pump assembly. In step ii), the concentrated liquid H acquired from step i) was then passed through the recirculation unit (6) which was a single tube in a tube type heat exchanger. The internal pipe diameter is 20 mm. The internal pipe is equipped with an SMX static mixer. Heating is accomplished by a tube using heating oil (Marlotherm) as the heating medium.

In step a) the concentrated liquid L and the nucleophile compound are mixed and fed to the extruder unit. The extruder unit is a twin mixed roll extruder with a coil diameter of 32mm and a screw length of 1260mm. The extruder unit also includes a hose as a pressure control device (7, see Figure 7) upstream, the feed point (12), the extruder, three extruder gas removal sections, where the feed point (12) is placed in the first extruder gas removal section, where the extruder gas removal section The first consists of a carrying section (16A), a rear vent port (13) that connects to a steam line (13.1) in the upstream direction, and where the extruder unit includes the removal of repellent gas. They are also divided into a whole, including a carrying section 16B and 16C), a vent outlet (15 A and 15B), where the vent ports (15A and 15B) are each connected to a steam line (15.1A and 15.1B), and where each The carrying sections (16a, 16b and 16c) are terminated by a collecting section (18a, 18b and 20) where the extruder unit also includes an outlet section (22).

Each of the sections, especially the bearing sections can be heated independently throughout the extruder barrel in order to control the temperature of the rubber A in the extruder.

The rear vent port (13) connects to the condenser via a first steam line (13.1). The condenser is a foil type heat exchanger and is also connected to a liquid ring vacuum pump. The other steam lines (15.1a and 15.1b) connect to a condensing system including a screw type dry running vacuum pump.

The first assembly section (18a) is made of blocks, the second assembly section (18b) is made of blocks and holds an element. Both assembly sections (18A and 18B) are designed to allow injection of the separation agent.

A sight glass is installed in the relief port (15.1b) to allow observation of load behavior and product properties in the load section (16c).

The kneading zone (20) and the dividing outlet (22) are combined into one functional section. The collecting section area is composed of chip mold and forming rubber hose formed into crumb rubber in the outlet section.

Prepare liquid F

A crude butyl rubber solution was taken from a commercial production plant, allowed the solution several hours and the organic phase to separate from the aqueous phase. The organic phase is then used to perform experiments as a liquid (F). Liquid (F) content of (a) 25 or (b) 20 wt% rubber, 70 wt% hexanes and (a) 5 or (b) 5 wt% water based on 100 wt% of these three components.

Bromobutyl rubber, soluble in liquid (F), has the following properties: Mooney (mL 1+8, 125 m) from 28 to 36, bound bromine content from 1.6 to 2.0 wt.%.

The viscosity of the fluid F at 60 m was 1,760 mPa*s for (b).

Example 2

Liquid F as described above for (b) is used as raw material (Liquid F). The production capacity of liquid F lay is 10kg/h, which corresponds to about 2.0kg/h of bromobutyl rubber.

The heating temperature of the heater (2) is set to 155°C, the pressure in the separating vessel (4) to 475 hPa. The temperature of the reheater heating medium (6) was set at 156°C, and the pressure in the rear vent port (13) was 475 hPa.

25% by weight triphenylphosphine solution is added to the liquid L in an amount of 0.32 kg/hour. The temperature of the extruder barrel is set at 150°C.

The pressure in the second and third relief port (15A and 15B) is reduced to 11 hPa. No separation agent is fed to the collecting section (18b). The resulting rubber is an ionic unit that appears white to pale orange and is permanently drawn into and kneaded by screw shafts. In the outlet section (22) a rubber ionic unit is produced.

The final product is collected in the outlet section and analyzed to determine hexane and total volatile matter concentration. The total volatile matter content of the rubber ionic unit is typically under 2 wt%, the hexane content under 1 wt% and the water content under 1 wt%. The resulting ionic unit rubber is dried and analyzed by 1H and 31P NMR to confirm the ionic unit content. Example 3 Liquid F as described above for (b) is used as a raw material. The production capacity of liquid F is 10 kg/hour. The heating temperature of the heater (2) is set to 155°C, the pressure in the separator vessel (4) to 475 hPa. The temperature of the reheater heating medium (6) is set at 156°C, the pressure in the rear vent port (13) is 475 hPa. The temperature of the extruder barrel is 150°C. The pressure in the second and third relief port (15A and 15B) is reduced to 11 hPa.

Add 25 wt% of a solution of triphenylphosphine (0.08 kg/h) and nanoclay (Cloisite 15a, 0.4 kg/h) to the liquid L. The resulting polymer nanocomposites appear as white to pale orange and are permanently drawn into and kneaded by making roll columns. In the outlet section (22) polymer nanocomposites are produced.

The total volatile content of polymer nanocomposites is typically under 2 wt%, hexane content under 1 wt% and water content under 1 wt%. The resulting ionic unit rubber is analyzed by: 1H and 31P NMR to confirm the ionic unit content. Nanoclay exfoliation is confirmed by X-ray diffraction analysis.

Examples 4 and 5

Examples 3 and 4 are repeated using a 30 wt% solution of commercially available bromobutyl rubber (BB 2030 Lanxess Inc.) as liquid L i.e. without a previous concentration step. The results obtained are comparable to those obtained for Examples 2 and 3. The formation of a rubbery ionic unit product and polymer nanocomposites is observed in both cases.

Examples 6 to 10

Liquid F as described above for (a) is used as a raw material (Liquid F). The production capacity of Liquid F is 4 kg/h, which corresponds to about 1.0 kg/h of bromobutyl rubber.

The heating temperature of the heater (2) is set to 155°C, the pressure in the separator vessel (4) to 475 hPa. The temperature of the reheater heating medium (6) is set at 156°C, the pressure in the rear vent port (13) is 475 hPa.

A 7.5 wt% triphenylphosphine solution is added to the liquid L in an amount of 0.0 to 0.8 kg/h. The temperature of the extruder barrel is set at 150°C.

The pressure in the second and third relief outlets (15A and 15B) is reduced to 11 hPa. No separation agent is fed to the collecting section (18b). The resulting rubber appears pale orange in color and is permanently drawn into and kneaded by making coil columns. In the outlet section (22) a rubber ionic unit is produced.

The final product is collected in the outlet section and analyzed to determine hexane and total volatile matter concentration. The total volatile matter content of a rubber ionic unit is typically under 2 wt%, the hexane content under 1 wt% and the water content under 1 wt%. The resulting ionic unit rubber is dried and analyzed by 1H and 31P NMR to confirm ionic unit content.

Examples 11-15

Liquid F as described above for (a) is used as a raw material. The production capacity of liquid F is 4kg/hour. The heating temperature of the heater (2) is set to 155°C, the pressure in the separator vessel (4) to 475 hPa. The temperature of the reheater heating medium (6) is set at 156°C, the pressure in the rear vent port (13) is 475 hPa. The temperature of the extruder barrel is 150°C. The pressure in the second and third relief port (15A and 15B) is reduced to 11 hPa.

A 7.5 wt% solution of triphenylphosphine (0.0 to 0.8 kg/h) and Nanoclay (NanomerTM I.44P, 0.1 kg/h) are added to the liquid L. The resulting polymer nanocomposites appear orange-tan in color and are permanently drawn into and kneaded in columns. The scroll. In the outlet section (22) polymer nanocomposites are produced.

The total volatile matter content of polymer nanocomposites is typically below 2 wt%, the hexane content below 1 wt% and the water content below 1 wt%. The resulting rubber ionic unit is analyzed by 1H and 31P NMR to confirm the ionic unit content. Nanoclay exfoliation confirmed by X-ray diffraction analysis.

The results of examples 6 through 15 are given in Table 1

Example

formula (phr)

BB2030

100

100

100

100

100

100

100

100

100

100

Triphenylphosphine (TPP)

Nanomere I.44P

Total

100

101

102

104

106

110

111

112

114

116

Process parameters

BB2030 cement concentration (wt%)

25,0

25,0

25,0

25,0

25,0

25,0

25,0

25,0

25,0

25,0

Cement BB2030(kg/h)

4,0

4,0

4,0

4,0

4,0

4,0

4,0

4,0

4,0

4,0

Rubber production rate (kg/hour)

1,0

1,0

1,0

1,0

1,0

1,0

1,0

1,0

1,0

1,0

TPP solution concentration (wt%)

7,5

7،5

7،5

7،5

7،5

7،5

7،5

7،5

7،5

7،5

TPP solution(kg/h)

0,0

0,13

0,27

0,53

0,80

0,00

0,13

0,27

0,53

0,80

Extruder temperature (°C)

150

150

150

150

140

110

110

110

120

120

Fuse temperature (°C)

155

165

160

160

160

135

135

145

145

150

Analysis results

Ionic unit content (mol%)

0,00

0,05

0,08

0,11

0,30

0,00

0,07

0,12

0,38

0,22

Mooney viscosity (ML(1+8)at 125 C)

34,6

43,0

59,1

63,1

59,8

45,8

73,7

82,0

72,4

72,1

Oxygen permeability at (cm3.mm/m2.day)

180,0

164,6

151,4

149,2

139,1

138,0

Reduction in oxygen permeability versus control

0,0

8,5

15,9

17,1

22,7

23,3

Table 1 describes only the preferred embodiment and other features and features of the invention will be explained to experts in the art. Variants or equivalents of described elements that operate in the same manner may be substituted without affecting the manner in which the invention operates. All minor groups of features described are intended by the inventor to be protected by the following claims.

The reference numbers inquired above are summarized below:

1 pump pump

2 Heater

3 Pressure control device

4 Degassing vessel

4.1, vapor line

4.2, pump

6 reheating unit

7 Pressure control device

12 feeding point

13 Rear vent port (upstream)

13.1 Vapor line

15, 15A, 15B, 15B, 15C vent port (downstream)

15.1, 15.1a, 15.1b, 15.1c vapor line

16, 16a, 16b, 16c, 16d Conveying section (downstream)

18, 18a, 18b, 18c accumulating section

19, 19a, 19b Side feeder

20 Last accumulating section

22 outlet section

26 separating vessel

27 aqueous phase

28 Organic phase

29 merge coalescer

30 mixing section

32 mixer mixer

34 Separating wall

36 recirculation pump

38 recirculation line

A crude fluid A

C waste water

E fresh water

F fluid F

G heated fluid H

Concentrated fluid H

Rubber ion Ionic unit rubber ionomer

L concentrated fluid L

NC polymer nanocomposites

NF filler

NUC, NUC 1, NUC 2, NUC 3 is a nucleophilic compound