CN1191496A - Polymerization process, apparatus and polymer - Google Patents

Abstract

A process for producing a substantially dry polymer particle powder. A mixture of polymerization reagents is formed from a mixture of at least one monomer source and a solvent selected from the group consisting essentially of water and organic solvents and an initiator source. The mixture of polymerization reagents is sprayed into a heated, controlled atmosphere, forming droplets of the mixture which are allowed to fall through the heated, controlled atmosphere for a sufficient period of time to obtain a desired degree of polymerization. The solvent is continuously evacuated from the atmosphere during the polymerization process.

Description

A kind of polymerization, equipment and polymer

The present invention relates to a kind of polymer that is used to produce the injection polymerization and the equipment of dried polymer and the novel physical characteristic is arranged.More particularly, the present invention relates to a kind ofly in controlled atmospher, what produce the polymer beads that comprises desired granularity, shape and density continuously from the monomer source of liquid state is the polymerization of the polymer beads powder done basically.

By progressively polymerization and chain polymerization method can synthetic polymer be known in this area.The chain polymerization method is to cause by the active group that one or more compounds produced that is called as initator.Usually, monomer demonstrates in various degree selectivity to the type of the reaction center that produces chain polymerization.Though speed difference, some monomers demonstrate high selectivity between anion and cationic initiator, and many monomers will carry out the polymerization that free-radical initiator causes.In the presence of free-radical initiator, the example of type that will aggregate into the monomer of heavy polymer comprises: ethene; 1, the 3-alkadienes; Styrene; Alkenyl halide; Vinyl ester; Esters of acrylic acid; Methyl acrylic ester; Acrylonitrile; Methacrylonitrile; Methyl acrylic ester; Acrylonitrile; Methacrylonitrile; Acrylamide; Methacrylamide; The N-VCz; The N-vinyl pyrrolidone.

Substantially, the polymerization situation that free radical causes, or homogeneous polymerization or heterogeneous polymerization, this is homogeneous phase or heterogeneous deciding by the initial action mixture.But because polymer insoluble in reaction medium, when polymerization was carried out, some homogeneous reaction systems can become the heterogeneous reaction system.Usually, body and solution polymerization process are homogeneous polymerization process, and suspension polymerization and emulsion polymerization are the heterogeneous polymerization methods.All monomers can carry out polymerization by any in the various polymerizations, still, consider from industrial point of view, and people usually find, the polymerization of concrete monomer is preferably undertaken by one or both of said method.

The integral body of pure monomer or polymerisation in bulk provide polymerization the simplest and that contamination of products is minimum.But because the characteristic of free radical chain polymerization, polymerisation in bulk is restive.Mass polymerization is the height heat release, and relates to high activation energy, and the tendency of oriented gel effect.These characteristics make the difficulties in dispersion of heat, therefore, during bulk polymerisation process, control temperature strictly.Moreover than low-conversion the time, the viscosity of reaction system promptly increases, and therefore requires to use well-designed mixing plant.Local " focus " occurs, and can occur destroying, the polymeric articles of degraded and variable color, and because the chain between polymer molecule shifts, can generate wide molecular weight distribution.Under opposite extreme situations, the unsteered acceleration of polymerization rate is also arranged, can be directed at and produce catastrophic danger away from reaction type.

Can overcome many shortcomings of polymerisation in bulk by the monomer polymerization in solvent (polymerisation in solution).The solvent that can be water plays a kind of dilution, and helps the transfer of polymerization reaction heat.Solvent may be to be easy to stir, and has therefore just reduced the viscosity of reactant mixture.Though the heat control ratio body of solution polymerization process or mass polymerization is easy, removes the difficulty of desolvating if having in polymerization process and in polymerization process subsequently, the purity of polymer may be affected so.

The heterogeneous polymerization method is widely used for controlling some problems of usually relevant with homogeneous polymerization process thermal viscosity.Precipitation polymerization method is a kind of heterogeneous polymerization method, and it begins as homogeneous polymerization process, but changes into heterogeneous polymerization afterwards.Be created on polymer insoluble in the reaction medium at monomer whole or in solution (aqueous solution, but be organic solution sometimes) usually polymerization.Precipitation polymerization can be thought powder or bead polymerization, because generate and obtained last polymeric articles in polymerization process.Employed initator is dissolved in initial reaction medium in precipitation polymerization method, and along with proceeding of reaction, monomer absorbs and enters polymer beads.

Suspension polymerization is also referred to as beading or bead polymerization, is to be undertaken by monomer (decentralized photo) is suspended in the water (continuous phase) as droplet (50-500 μ m diameter).The ratio of water and monomer is generally about 1 in many polymerization processes: 1-4: change in 1 the scope.Because there are, are also referred to as the existence of dispersant or surfactant in effect of stirring and suspension stabilizer, the monomer droplet that changes into polymer beads basically is not coalescent.Stabilizing agent can be water miscible polymer or water-insoluble inorganic powder.The general employed amount of suspension stabilizer is less than the water amount of 0.1% (wt).In suspension polymerization,, just can not keep two-phase suspension system if do not stir.

The suspension polymerisation initator is dissolved in the monomer droplet, and is called oil-soluble initiator.In the presence of the water-soluble stabilizing agent of high concentration, suspension polymerisation is used to produce the dispersion like latex of small size particle.This suspension polymerisation can be called dispersin polymerization.Anti-microsuspension polymerization comprises that organic solvent is as continuous phase pure or that be dissolved in the water-soluble monomer in the water.Anti-dispersion refers to and comprises the system of organic solvent as the dissolved monomer initator continuous phase that produces insoluble polymer.

Emulsion polymerisation comprises emulsion form, i.e. the polymerization of the monomer of the dispersion of colloidal state.The type that emulsion polymerisation is carried out in polymerization with aspect the littler particle diameter, the kind of the initator that adopted and the molecular weight of polymer determine these aspects different with suspension polymerisation by response parameter.To most polymerization, there is opposite relation between polymerization rate and polymer molecular weight.Do not change the molecular weight that polymerization rate can significantly reduce polymer by using chain-transferring agent.By reducing initiator concentration, or only come to improve molecular weight widely by reducing polymerization rate by reducing reaction temperature.

Emulsion polymerisation allows to improve polymer molecular weight and does not reduce polymerization rate.Emulsion polymerisation has the advantage that can obtain HMW and this two aspect of high reaction rate simultaneously.Decentralized medium is water normally, and various components utilize emulsifying agent to be dispersed in the water.Other component comprises monomer, decentralized medium and water soluble starter.Generally the amount with 1-5% (wt) is used surfactant in emulsion polymerisation.The ratio of water and monomer is generally in the scope of 70/30-40/60 (wt/wt).

The polymerization of above-mentioned discussion comprises the dry polymer that is generated, isolating polymer in the employed organic solvent from method, or the additional step of recovery organic solvent.Add these steps and require in the preparation finished product, to increase energy and time, therefore improved the cost of the polymer of being produced.But, use the polymer that these known methods produce generally to produce with piece dough subsequent drying, must grind or with some method fragmentation up to the polymeric articles that obtains using.By grinding or grinding broken polymeric articles to produce the dust that floats in a large number into environment, influenced in polymer dust and the personnel's that around dust, work health.

So people still have a kind of needs to the equipment of the method that can produce dried polymer particles nodular powder and this method of enforcement, like this, just do not need dry and grind the polymeric articles of being produced.People also need a kind of polymerization that can be used for continuing finishing the polymer of polymerization immediately that is used to produce.

At last, people need easily a kind of and accurately control the method for production polymer of granularity, shape and the density of polymer.For example, employed polymer beads is that smooth surface is favourable, and for example, under the situation of fiber optic cables, this is a particular importance.The most general fiber optic cables are subject to the erosion of water in telecommunications.But, in fiber optic cables, owing to be to use super-absorbent polymer problematic around the clad of " soft " of every fiber.The clad of " softness " is easy to scratch, and this has just changed the index of refraction of clad, so changed the ability of fibre light guide.Test verified, produce with the superabsorbers of known method production clad very trickle scratch be to result from the influence of rough surface of polymer beads, described polymer beads be solid cross-linked polymer from above-mentioned production method preparation as described above through grind, grind or and the fine powder of chopping obtain.The fiber optic cables deflection for example is wrapped on the spool when then the spool that twines being installed when fiber optic cables, and the scratch of cover surface all can take place at any time.

Some polymerization usually requires in certain matrix or is having on the particle of nuclear to carry out.For example, United States Patent (USP) discloses a kind of method that is used to make hydrophilic polymer for No. 4135043.The polymer that is generated applies with the monomer of similar type in advance, generates a coating on polymer seeds.After this, the seed of coating carries out heat treated, so that coating is carried out polymerization thereon.The additional production step that such polymerization also requires as mentioned above to be adopted.

The example of the shortcoming of present polymerization is the known method that is used to produce the polymer that absorbs water.These methods can be categorized into the method that comprises aqueous systems or heterogeneous system.Be used to produce these polymer aqueous systems and generally generate semi-solid block material, must be from wherein removing moisture in the strong drying steps of energy.For example, in No. 4295987, United States Patent (USP), the monomer mixture of polymerization must be with excessive methanol dehydration, and the solid of firm (for example dry in vacuum drying oven) of generation grinds to form the particle or the powder of the size that requires then.

Also more known method of producing continuously these polymer in Aquo System is addressed as describing in No. 4525527, United States Patent (USP), in this article the full content of this piece patent documentation is introduced reference.Substantially, that piece patent documentation has been described the heating monomer solution, when flowing on the conveyer belt of mixture at transporter, initator is injected add initator on the mixture.Polymerisation is exothermic reaction, helps to remove to anhydrate, and generates " the solid polymer of the low water content of doing ", and above-mentioned solid polymer water content is 8-15%.By grinding solid polymer is made powder then.

Multi-phase polymerization process is included in the polymerization of the aqueous reaction mixture in the inert organic solvents, removes from polymerizate subsequently and desolvates.These known for a long time methods are discontinuous methods, and have found the typical example of these methods in No. 4446261, United States Patent (USP), and this paper introduces reference with the full content of this piece document.That piece patent has been described by aqueous solution monomer and the crosslinking agent in a hydrocarbon and halogenated aromatic are prepared polymeric beads, carries out the polymerization of monomer then when adding water soluble starter.As described in that piece patent, remove dealkylation and pass through heating under reduced pressure, dry residual polymer beads by decompression distillation.

Other example of these methods is found in following United States Patent (USP): moisture 3,661,815 3,669,103 4,071,650 41,674,644,286,082 4,295,987 4,342,858 43,519,224,389,513 4,401,795 4,525,527 45,529,384,612,250 4,618,631 4,654,393 4703067 heterogeneous 4,059,552 4,093,776 4,340,706 44,462,614,459,396 4666975 moisture/heterogeneous 4,062,817 4654039

Therefore the feature of these two types of methods all is to have to have increased the shortcoming of producing these polymer costs, and the requirement of the method for improving the polymer that is used to produce these and other is arranged.For example, moisture and heterogeneous this discontinuous method of two types all require the drying steps of polymer.

Producing polymer by known polymerization methods, is size, shape and the density that is difficult to the polymer beads produced by experience control about another shortcoming of the polymer that absorbs water particularly.For example just known to the applicant, the water-absorbing polymer particles of smooth outer surface was pre-unknown before this.Appear is that at least some are used to produce the heterogeneous method generation sphere of these polymer (for example referring to United States Patent (USP) 4,446,261 5 hurdles, 39,48 and 60 go) or annular (referring to No. 4,342,858 six hurdles of United States Patent (USP) 57 row of above-mentioned introducing) particle, but the applicant does not have can find to have any this particle of smooth surface.And the feature of all known particles is coarse surfaces, or the surface as described in the above-mentioned listed United States Patent (USP) No. 4342858 (six hurdle 56-58 are capable), resemble the annulation of the high surface of the collapse sphere of 2-5 micron protrusion " in its surface with ".

Wait and the capable place of a hurdle 18-56 of No. 4625001, United States Patent (USP) discloses some other shortcoming at two hurdles of No. 4093776, United States Patent (USP), 56 row, this paper is with these two pieces of patent documentation full contents introducing references.

So the purpose of this invention is to provide a kind of size, shape and the density that can control polymer beads easily and accurately novelty polymer and be used to produce the method and apparatus of this polymer.

Another object of the present invention provides the degree of cross linking and the novel polymeric of water content and the method and apparatus of this polymer of production in a kind of polymer beads that can conveniently accurately make.

Another purpose of the present invention provides a kind of polymer of the novelty that does not generate and produces the method and apparatus of this polymer on the matrix of seed that forms as polymer or nuclear or precursor.

A further object of the present invention provides a kind of method and apparatus that is used for producing polymer, and it has been eliminated and produces high-viscous solution, gel or the pie that these polymer produce by known method and handle intrinsic difficulty.

Also purpose of the present invention is to have eliminated the grinding of the needed semi-solid bulk polymer of the known method feature that is used to characterize the preparation polymer, the step that grinds and shred.

Another purpose of the present invention is to have got rid of to be used for producing the known method employed organic solvent of recovery of polymer or the expensive step of medium.

Another object of the present invention provides a kind of method and apparatus of producing polymer of the expensively drying steps of having got rid of the many known methods that are used to produce polymer.

An object of the present invention is to provide a kind of polymerization, this method allows polymerisation, polymer particles particle size, polymer beads shape and the water content of the polymer beads powder produced is easy to control.

An object of the present invention is to provide the method and apparatus of the polymer beads powder that a kind of fluid source production of using selected monomer does basically.

Other purpose of the present invention and advantage are from the comment of the following detailed of some embodiment preferred of the present invention's proposition, and those skilled in the art will be clearer.

The invention provides a kind of normal pressure chain polymerization method.This method comprises that at least a monomer source of preparation is added in first mixture to generate second mixture of polymerization reactant with first mixture that selects a kind of solvent in Free water, organic solvent and their the mixture composition group with the initator source.Crosslinking agent, nertralizer or other reactant also can be added in first reactant.The mixture of polymerization reactant sprays in the controlled atmospher of heating.At a closed container, for example keep the controlled atmospher of heating in reative cell.The mixture result who sprays into forms droplet, and the experience free-falling obtains during the desired degree of polymerization time enough by the controlled atmospher of heating.During polymerization process, emptying solvent continuously from the controlled atmospher of heating.

The mixture of polymerization reactant preferably sprays into reative cell at the top of reative cell.The height of reative cell is preferably about 30.48 meters of about 3.65-.The pressure of reative cell preferably is lower than the atmospheric pressure of environment.The force value of wishing is the about 50790N/m of about 338.6- ², be lower than environment atmospheric pressure.And reative cell preferably is heated to about 23.8 ℃-Yue 148.8 ℃ temperature during polymerisation.

Before the initator source added first mixture, further preferred first mixture maintained temperature desired and pressure.Second mixture also is preferably maintained in the range of from about the temperature between 26.6 ℃ and about 93.3 ℃.

In the preferred embodiment of polymerization of the present invention, second mixture of reactant is to spray in the atmosphere by one or several nozzle.Produce the basic polymer beads powder of doing by polymerisation.Polymer beads is defined as the basic product of doing like powder herein.The basic meaning of doing is not agglomeration of particle or clings together, and powder can flow freely.Method of the present invention can the production granularity be about 20 microns-Yue 125000 microns polymer beads.But when at similar pressure, when preparing under temperature and other the parameter, the size of the polymer beads in the powder, shape and density will very even all, and this will discussion more fully in detailed description of the present invention.

By increasing or reduce the size of nozzle bore, can change the size of the polymer beads of being produced.In a preferred method, the mixture of polymerization reactant sprays in the controlled atmospher of pressure for the pressure between about 517KPa and about 13.7MPa of heating.The polymer beads powder of doing can reclaim, and keeps adding the atmosphere of thermal control simultaneously.

Monomer source can be the aqueous solution, slurries or the emulsion of selected monomer.Preferred solvent is a water.The crosslinking agent source can be the aqueous solution, liquid slurry or the emulsion of selected crosslinking agent equally, and solvent is a water.

The monomer source that uses method of the present invention can carry out polymerization comprises not functionalized alkene and functionalized alkene, includes but not limited to acrylic acid, vinyl, dienes, phenylethylene, propylene class, vinyl-based, methyl acrylic ester, acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide and olefine.

The present invention also provides a kind of polymerization that contains the polymerizing acrylic acid thing that is used to produce.This method comprises preparation part acrylic acid aqueous mixture that neutralizes, and polymerization initiator is added to aqueous mixture generates second mixture of polymerization reactant and the second above-mentioned mixture is sprayed into several steps in the controlled atmospher of heating.Mixture spray into the droplet that the result forms above-mentioned second mixture, and make the controlled atmospher of its landing by heating, obtain enough time durations of the degree of polymerization that requires, so just generated the polymerizing acrylic acid thing that part neutralizes that contains of nodular powder form.

The present invention also provides the polymer of producing by the inventive method.

The invention provides a kind of equipment of radical polymerization.This equipment comprises that the height that a reative cell, adds the device of thermal reaction chamber, above-mentioned reative cell is preferably about 30.48 meters of about 3.65-, the device of the above-mentioned reative cell internal pressure of control, the device that is connected and is used to receive one or several nozzle in monomer source and initator source and is used for mixture is sprayed into reactor top with charge pipe.The mixture result who sprays into reative cell forms droplet, makes its landing by reative cell, obtains during the desired degree of polymerization time enough.Mixture preferably sprays into the reative cell that pressure is positioned at the about 13.7MPa of about 517KPa-.

Pressure in the reative cell is preferably kept and is lower than environmental pressure.Desirable force value comprises the about 50790N/m of about 338.6- ², be lower than environment atmospheric pressure.And in polymerization process, reative cell further preferably is heated to about 23.8 ℃-Yue 148.8 ℃ temperature.

Equipment further comprises from above-mentioned reative cell bottom polymer discharge, keeps the device of interior heating of reative cell and pressure simultaneously.The device of polymer discharge comprises the groove that is positioned at the reative cell bottom, in the bottom of groove first conveying worm is installed, be used for polymer is shifted out reative cell, a feed bin enters the polymer of first conveying worm deposition, and in the bottom of feed bin second conveying worm is installed.

Equipment preferably further comprises the device of the temperature of the monomer that is used to control in the charge pipe and initiator mixture.Before equipment also is preferably included in monomer and initator and sprays into reative cell, be used for device with its mixing.

Also be provided with by from above-mentioned reative cell, get rid of the device of the unconverted monomer of gaseous state with the purging with nitrogen gas reative cell.For monomer source is provided with the container that separates with the initator source.Also be that crosslinking agent source and other reactant are provided with container.When the cross-linked polymer structures that is produced when being desirable, before the mixture in monomer source and initator source is sprayed into reative cell, crosslinking agent is added in the mixture in monomer source and initator source.

The polymer that uses present device to produce is that never functionalized alkene and functional olefines carries out polymerization, and these alkene include but not limited to acrylic acid, vinyl, dienes, phenylethylene, propylene class, vinyl-based, methyl acrylic ester, acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide and olefine.

Produce polymer by the radical polymerization method, described method comprises at least a monomer source of preparation and is selected from first mixture of being made of a kind of solvent in the group basically water and organic solvent, the initator source is added in first mixture second mixture that generates polymerization reactant, then second mixture is sprayed into several steps in the controlled atmospher of heating.Keep the controlled atmospher of heating in a closed container or reative cell, the height of described reative cell is preferably about 3.65-30.48 rice.Second mixture preferably sprays at the top of reative cell.

Before adding the initator source, first mixture preferably maintains desired temperature and pressure.Second mixture also preferably maintains the temperature between about 26.6 ℃ and about 93.3 ℃.Second mixture of reactant sprays in the atmosphere that adds thermal control through one or several nozzle, and the result generates droplet, and makes its landing by adding the atmosphere of thermal control, obtains the sufficiently long time durations of the desired degree of polymerization.During polymerization process, solvent and unconverted monomer be emptying continuously from atmosphere.The polymer that is produced reclaims for dried nodular powder and from reative cell, keeps the heating controlled atmospher in the reative cell simultaneously.The particle diameter of polymer is about 2-125000 micron.Can change the size of the polymer beads of being produced by the aperture that increases or reduce nozzle.Second mixture of polymerization reactant preferably sprays in the heating controlled atmospher of pressure between about 517KPa and about 13.7MPa.

In a preferred embodiment, atmosphere is maintained at about 23.8 ℃-Yue 148.8 ℃ temperature.Controlled atmospher also preferably maintains the about 50790N/m of about 338.6- ²Decompression under.Be lower than environment atmospheric pressure.

When crosslinked polymer architecture was produced in hope, crosslinking agent can add first mixture.Nertralizer also can add first mixture.When crosslinking agent added the polyblend of reactant, monomer source can be water-soluble unsaturation monomer, and the result generates water absorbent polymer.

Monomer source can be the aqueous solution, slurries or the emulsion of selected monomer.Preferred solvent is a water.The crosslinking agent source can be that the aqueous solution, slurries or emulsion and the solvent of selected crosslinking agent is water equally.

Monomer source can be not functionalized alkene or functionalized alkene, include but not limited to acrylic acid, or be selected from mainly by vinyl, dienes, phenylethylene, propylene class, vinyl-based, ester class, esters of acrylic acid, methyl acrylic ester, acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide and olefine and form compound in the group.

Produce by moisture free radical polymerization method and to contain the polymerizing acrylic acid thing, described method comprises the mixture that preparation is acrylic acid aqueous, and polymerization initiator is added the several steps that aqueous mixture generates second mixture of polymerization reactant and second mixture sprayed into the controlled atmospher of heating.Spray into the mixture result and generate the droplet of second mixture.The second mixture droplet landing that sprays into obtains during the time enough of the desired degree of polymerization by heating controlled atmospher.What so just generated the particle powder shape contains the polymerizing acrylic acid thing.The polymer that makes is pulverous water absorbent polymer of doing basically, and for example particle diameter is less than about 100 microns.

The unforeseen advantage of the polymer of producing according to method of the present invention is that the particle of producing has smooth surface, makes these polymer have some new purposes, particularly water absorbent polymer and has some new purposes.For example, the short circuit that in communication cable, is produced by water erosion for the protection conductor, known use water absorbent polymer is favourable.

Fig. 1 is the schematic diagram according to the equipment of the present invention's drafting.

Fig. 2 is the cutaway view of the equipment of Fig. 1 along the 2-2 line.

At first with reference to figure 1, it shows the general equipment of representing with label 10 by the present invention's drafting.Briefly, equipment 10 be by reative cell or other closed container 12, the device 14 that is used for adding thermal reaction chamber 12, the pressure apparatus that is used to reduce reative cell 12 be vavuum pump 16, be connected with charge pipe 20 be used for receiving the nozzle 18 of monomers and initiator mixture from mixture source 22 and 28 separately, what generally represent with label 26 is feed bin shape and screw propulsion feeder system, be used for getting rid of the polymer beads powder of doing that is produced at reative cell 12, keep the device of the decompression state in the reative cell 12 to form simultaneously from the bottom of reative cell 12.The height of reative cell 12 is preferably about 30.48 meters of about 3.65-.

In more detail, equipment 10 comprises the several materials source or the several vessels of monomer 22, initator 28, and preferably includes the 3rd container 24 in crosslinking agent source.When the composition of crosslinking agent or crosslinking agent is needed generation cross-linked polymer structures, for example during the polymer of Xi Shui acrylic acid series, crosslinking agent or its composition will be added in monomer and the initiator mixture.For other monomer (to copolymerization process), water, nertralizer, stabilizing agent, (chain) transfer agent, solvent or other reactant all is provided with other container (not shown), preferably each container is all controlled temperature separately.

The aqueous solution of container 22,24 and each each reactant of can packing into of 28 and/or solution, suspension or the emulsion of organic solvent so valve 30,32 and 34 preferably is set respectively, are used under the influence of pump 36 flow of each reactant in the control container.Pipe 20 can be selected to be exerted pressure by each container 22,24 and 28.Pipe 20 be provided with label 44 being used for of representing the mixture moisture and/or organic solvent with reactant mix, with the equally distributed device between monomer, initator and other reactant of assurance reactant mixture.Mixing arrangement 44 is the many known form in this area, the groove or the baffle system of for example online spiral or conveying worm, grinding machine, band stirring vane.Mouth 38 also is set on the housing of mixing arrangement, is used to add the reactant of any other type.

Because the polymerization of monomer begins immediately when initator and monomer mixing, exothermic reaction is carried out rapidly, utilize the degree of polymerization of the temperature control monomer of mixture in the charge pipe 20, and when adding crosslinking agent, also be used for controlling the degree of cross linking (not depicting scale among Fig. 1) of polymer architecture.For this reason, be provided for controlling the device of mixture temperature in the charge pipe 20, represent with label 42.Temperature control equipment 42 can be the combination of water-bath shape, refrigerating coil, heat-proof device, heating element heater and refrigerating coil, or is used for known any other device of temperature control, and this characteristic by that be aggregated and/or crosslinked monomer is determined.Operative installations 42 mainly is to reduce the heat that exothermic polymerization reaction produced.The polymerization rate that has stoped monomer source at the low temperature of pipe 20 reaction mixture.

In an embodiment preferred, pipe 20 is provided with a purity nitrogen air chamber 45, and chamber 45 adds nitrogen by the pipe 46 that valve 48 is set thereon, passes through the mixture of purge reactant here with nitrogen stream.Measuring pump 40 in charge pipe 20 provides the pressure of mixture of reactant and the control of flow rate.

During polymerisation, the pressure of atmosphere in the control reative cell 12.The pressure of the atmosphere in the reative cell 12 is reduced to relevant environmental pressure by vavuum pump 16, in the present invention through managing 50 from reative cell 12 discharges atmosphere wherein.Air inlet at pipe 50 is provided with filter 52, is inhaled into vavuum pump 16 with the little drop and grain that prevents polymerization single polymerization monomer.Filter 52 preferably is provided with one from reative cell 12 outside accessible filter frames, is beneficial to the periodic replacing of filter element (not illustrating).

In order to produce than being lower than the finer and close polymer beads of being produced under the atmospheric pressure of polymer architecture, the pressure of the atmosphere in the reative cell 12 also can be brought up to more than the environment atmospheric pressure.

Band air intake of flow control valve 56 or the top that outlet 54 is arranged on reative cell 12 are used to make surrounding air to enter reative cell 12, with blowing pipe 50 and pump 16 and/or in case of emergency close.Be not when utilizing air intake pipe 54 as an exhaust outlet, nitrogen also can in this case, be provided for regaining the blowing pipe 55 of nitrogen by purge atmosphere wherein in the atmosphere of pipe 54 introducing reative cells 12.In addition, filter 57 prevents that polymer beads is inhaled into pipe 55.Reative cell 12 is gone back setting device 62, for the cleaning hand-hole, is used to get rid of unconverted monomer, or in device 26 irregular workings of getting rid of particle in emergency circumstances, gets rid of the particle of the polymerization of doing from its bottom.Heater 14 is parallel resistor heating element heaters, and gas burner or steam pipe are schematically represented to be driven by the general pipe 60 from power supply, vapor source or source of the gas (not shown) with label 58.

Set device 26 is used for getting rid of polymer from the bottom of reative cell 12, keeps wherein heat and atmosphere simultaneously.Device 26 can be any device known to those skilled in the art.For example, as shown in Figure 1, be the V-type groove 64 that forms two limits that tilt, 66 formation of reative cell 12.In the bottom of reative cell 12, install first and advance feeder, spiral conveyer or other continuous conveyor system 68, polymer beads is shifted out reative cell 12, leave feed bin 70 in.Feed bin 70 is provided with second and advances feeder, and spiral conveyer or other continuous conveyor system 72 are installed in the feed bin bottom, will shift out feed bin 70 with the polymer that first auger 68 leaves in here, enter hopper, bag or storage/collection container 74.First auger 68 and second auger 72 are driven by motor 76 and 78 respectively, or are driven by a motor and conveyor roll system (not illustrating).

The dry polymeric particle 80 that accumulates in the bottom of reative cell 12 has covered the section port 82 of reative cell 12 bottoms, when first transporter 68 moves into feed bins 70 with the polymer beads 80 that accumulates, keeps the decompression state in the reative cell 12.First auger that cylinder 84 covering reative cells 12 and feed bin are 70 flows into reative cell 12 to stop surrounding air, by the lid 86 sealing feed bins 70 at the feed bin top.Part 88 in feed bin 70 bottoms allows to wait to shift out the polymer beads that feed bin 70 enters hopper 74 and is accumulated in the feed bin 70.In the same manner, the polymer beads 80 of accumulation covers the base section 82 of reative cell 12, and the base section 88 that the polymer beads 90 of accumulation covers in the feed bin 70 stops from flowing into air here.

Such as explained below, the polymer beads 80 of polymerization and the crosslinked bottom accumulation that occurs in reative cell 12 be basic do and condition that low water capacity is such under, when the polymer beads 80 of accumulation shifts out reative cell 12, be the polymer particles burl cake that prevents to do, stoping wet surrounding air is necessary near the polymer beads 80 of accumulation.The those skilled in the art who has known this open benefit will think, for the polymer 80 of getting rid of the accumulation of doing from the bottom of reative cell 12 does not destroy the vacuum of reative cell 12 bottoms, can utilize other device.For example, industrial available gravity filling, intermittently topple over suction apparatus and all can be advantageously used in this purpose.

As shown in Figure 2, charge pipe 20 enters reative cell 12, and stops on the loop 94 that is provided with many nozzles 18.Single nozzle selectively uses.Nozzle 18 preferably is screwed into the screw thread 96 that forms every a segment distance around loop 94, so that nozzle 18 is dismantled easily, cleans and/or changes.(do not go out) in another preferred embodiment, the loop 94 on charge pipe 20 is positioned at the outside at reative cell 12 tops.This back one embodiment is to frequent replacing nozzle 18, for example by changing nozzle 18 to change the diameter advantageous particularly of polymer drops.

If require large diameter polymer beads, at the mixture of pipe in 20 under lower pressure, the about 2.06MPa of for example about 517KPa-, by the nozzle 18 than large diameter hole is arranged, for example number is that 16 nozzles spray into reative cell 12.If wish to produce the more ball of minor diameter, it is high like that the pressure in pipe 20 is increased to the about 13.7MPa of about 1.03MPa-with pump 40, makes mixture be atomized into littler size particles.If require littler particle, if or require under lower expulsion pressure, to produce the more particle of minor diameter, so, just with the nozzle of small-bore more, for example number is that 64 nozzle replaces nozzle 18.

Now, explain the method for continuous production polymer of the present invention with reference to the accompanying drawings.Described method is included in the blender 44 mixes monomer source in water or in the organic solvent, preparation liquid monomer source.The liquid monomer source can selectively make from the known monomer source of those skilled in that art.The preferred moisture monomer source of monomer.Initator, crosslinking agent, additional water, nertralizer and/or other reactant can add in the monomer source of blender 44.In the preferred embodiment of the inventive method, employed monomer, initator and other reactant will be dissolved in employed water or the organic solvent, preparation liquid monomer source.But monomer, initator and other reactant are preferably water-soluble.The initator source that suits to use with selected monomer will be that those skilled in the art are known.

Before mixture began to spray into reative cell 12, initator preferably added from the downstream of monomer source immediately, reduced by the prepolymerization of monomer and stopped up pipe 20 or nozzle 18 contingent things.Though initator preferably is added to monomer source, some monomer can carry out from initiated polymerization, does not therefore just need to use initator.But rate of polymerization and degree are to use initator to promote.

Should be pointed out that by using stirring of adding pipe 20 Dian Chu downstreams at initator or guaranteeing that initator and aqueous mixture fully mix favourable with the similar second mixing arrangement (not shown) of mixing arrangement 44.

Should be understood that 14 heating of reative cell 12 usefulness heaters, according to the monomer source controlled atmospher pressure that is aggregated.Making selected monomer carry out polymerization under desirable pressure is that those skilled in the art are known.Keep atmosphere under reduced pressure with vavuum pump 16.But by using the pressure gas bleeder valve controlled atmospher link to each other with the pressure return pump under positive pressure.But, before spraying into mixture, can be by force (forcing) pump or other known device of those skilled in the art in the built-in pressure of attentioning of reative cell.

The mixture of monomer and/or reactant sprays into the controlled atmospher of heating, generates the droplet of this mixture thus.The landing of this droplet is obtained by reative cell during the time enough of desired monomer polymerization degree and under the situation of having added crosslinking agent, and the monomer of polymerization carries out crosslinked, generates the particle of polymer.The polymer beads that is generated can be straight chain, side chain or crosslinked polymer, and this depends on the composition that sprays into mixture.

When the droplet of the mixture of monomer and/or reactant from the nozzle landing during by reative cell, along with the carrying out of polymerisation, water that links with polyblend and/or solvent evaporate continuously or volatilize.In reative cell 12, exist under the preferred decompression situation, water that interrelates with mixture and/or solvent since the existence of heat and decompression evaporate continuously or volatilize.During polymerisation, steam vavuum pump 16 emptyings.In addition, be under the situation of malleation at reative cell 12, water that interrelates with mixture and/or solvent are owing to the heat in the reative cell evaporates.

Because the polymer beads that the result produced of polymerisation is essentially dried powder 80.The granularity of the dried granular polymer of being produced is about 2 microns so little so big up to 125000 microns (about 1/8 inches) by this method.The granularity of polymer beads will depend on existing and/or pressure, the temperature of being utilized and other parameter that will more discuss fully hereinafter in polymerization process.But when producing under similar condition, the granularity of polymer, shape and density are all more even.Get rid of the bottom be collected in reative cell 12 the whereabouts polymer beads 80, the pressure in the reative cell of continuous control simultaneously.Since the eliminating of polymer beads, atmosphere will maintain require under the pressure so that the desired polymerisation of selecting.

In a particularly preferred scheme, method of the present invention additionally comprises the bottom that allows the polymer beads 80 of whereabouts of q.s accumulate in reative cell 12.The polymer beads of building up forms abundant heated particle, keeps atmosphere in the reative cell in the quantity of desired temperature energy needed with reduction.

Atmosphere in the reative cell 12 preferably is heated to the temperature between about 23.8 ℃-Yue 148.8 ℃.Have been found that the temperature between about 82.2 ℃ and about 110 ℃ is preferred especially.Though can make polymer beads being lower than under 37.8 ℃ the temperature, if keep low water or solvent and low levels of residual monomers, the pressure in just will reative cell 12 reduce greatly.

When crosslinking agent adds mixture, the reaction that the polymerisation that takes place by reative cell 12 and cross-linking reaction are heat release because droplet falls.In case desired temperature reaches and polymerisation/cross-linking reaction is carried out continuously.Just less from the outer heat of heater 14 required supplies.Therefore, for example substantially exceed the temperature that surpasses 37.8 ℃ and just can keep, and do not lose the efficient of method.The further raising of the efficient of the inventive method is the preservation of the heat of most of particle 80 of gathering in reative cell 12 bottoms.

The pressure of atmosphere does not need to drop to ambient air and depresses producing polymer beads in reative cell 12, or is elevated to ambient air and presses, still, and pressure even the less subnormal atmospheric pressure of reduction (about 101580N/m ²) the unpolymerized levels of residual monomers that makes the water content of the polymer of being produced and do not participate in polymerization and/or cross-linking reaction reduces unevenly.Therefore, polymerization process preferably is to carry out under the condition that reduces pressure in reative cell.

About method of the present invention, the preferred about 50790N/m of about 338.6-that uses ²Reduce pressure.To certain particle, water content and/or levels of residual monomers are directly proofreaied and correct with the temperature and pressure that keeps the atmosphere in the reative cell 12.Usually, because the rising of temperature, pressure is along with the minimizing littler gradually with respect to environmental pressure, and the content of residual monomer and/or water or solvent can remain on the percentage of low level.Otherwise, because the pressure of atmosphere along with little by little lower temperature, can keep the low percentage of residual monomer and/or water or solvent with respect to the reduction of environmental pressure in reative cell 12.

In addition, polymerisation can improve in reative cell 12 under the condition of pressure and carries out.For implementing the present invention, can use the pressure in the reative cell to bring up to about 2psi from about environmental pressure.Usually, along with the rising of temperature, the percentage of residual monomer and/or water or solvent can remain on the low value of hope owing to be lower than the less gradually increase of pressure of environmental pressure relatively.Otherwise because the increase of the relative environmental pressure of pressure of the atmosphere in the reative cell 12, and temperature is along with being elevated to higher temperature gradually, and the low percentage of residual monomer and/or water or quantity of solvent just can keep.

The shape of polymer beads also is subjected to the influence of the pressure under the environmental pressure in the reative cell.The variation of pressure make production from sphere to more erose polymer beads.Be lower than under the more low-pressure of environmental pressure, polymer beads will be less uniform shape, and more rough edge or seemingly laminar outward appearance are arranged.When reducing pressure near environmental pressure, for example polymer beads becomes more like spherical than observing the polymer beads of being produced when being lower than ambient atmosphere pressure 15 inches of mercury.Improve the pressure of reative cell, can be than under low atmospheric pressure conditions, producing more smooth finer and close polymer drops.

Droplet falls by having determined the height of reative cell during the atmosphere required time in the reative cell 12.Usually, under preferred temperature of institute and controlled pressure, be the emptying of the residual monomer of realizing the desired degree of polymerization, crosslinked and water/solvent and many monomers/crosslinking agent mixture, need the about 5-60 fall time of second.Experiment shows that in order to realize the needed degree of polymerization, the reative cell height must be enough to allow the sufficient reative cell landing time.

The diameter parts of the droplet that time durations by reative cell 12 (being the reative cell height therefore) also sprays with nozzle 18 that allows droplet to fall is relevant.The nozzle 18 of large aperture 98 is produced large diameter droplet, therefore can increase the fall time of the reative cell of droplet, the pressure of atmosphere reduces and can increase in the reative cell 12, some combination that temperature can improve or these three parameters change can realize, so that obtain the evaporation of the desired degree of polymerization and water/solvent in the whole process that particle generates.Under the situation of major diameter droplet very, require to compare 67720N/m ²High pressure reduces, and temperature is more than 101.7 ℃, and reative cell fall time is 20 seconds or longer, to obtain the desired degree of polymerization and evaporation of liquid.

Other changeable influence of producing polymer by the inventive method is the pressure that the mixture of monomer and initator and/or crosslinking agent sprays into the controlled atmospher of reative cell 12 heating.In general, when the pressure of spray mixture increased, the size of droplet reduced, and required the fall time in reative cell, the aperture 98 of the reducing of temperature and the pressure in reative cell 12, nozzle 18, or their some combination changes thereupon.Obtained satisfied result between expulsion pressure is for about 517KPa and about 13.7MPa, the pressure between about 698.3KPa and about 1.20MPa has been represented particularly preferred embodiment of the inventive method.Spray mixture and reduction temperature can stop the polymerization of monomer before mixture sprays into reative cell under the pressure of charge pipe.So the pressure in temperature in the reduction charge pipe and the raising charge pipe combines and introduces initator immediately and just got rid of any prepolymerization of monomer in the charge pipe basically before mixture sprays into reative cell.

The final variable influence of each parameter to the inventive method and pressure, temperature and the fall time of carrying out the inventive method is the character of monomer, initator, crosslinking agent and other reactant of the polymerization that requires.About monomer, it is meant can be by any organic molecule of covalent bond and other organic molecule and/or self-polymerization formation chain.Many polymer can also be crosslinked.Though not that intended method of the present invention is following monomer,, the example of listing below that some monomer will be provided comprises functionalized and/or not functionalized alkene, according to method of the present invention, in many cases, they can polymerization and crosslinked.

(a) as the unsaturation monomer of No. 4446261 disclosed water miscible olefinics of United States Patent (USP) of the Yamasaki that introduces in the above etc.: acrylic acid, methacrylic acid, the salt of acrylic acid and methacrylic acid, acrylamide, Methacrylamide, the acrylamide that N-replaces, the Methacrylamide that N-replaces, 2-acryloyl group ethane-sulfonic acid, 2-methacryl ethane-sulfonic acid, the salt of 2-acryloyl group ethane-sulfonic acid and 2-methacryl ethane-sulfonic acid, styrene sulfonic acid and salt thereof, acrylic acid 2-hydroxyl ethyl ester and methacrylic acid 2-hydroxyl ethyl ester;

(b) at No. 2810716 disclosed monomers of United States Patent (USP) of Markus: methacrylaldehyde, the allylidene diacetate esters, acrylonitrile, acrylic acid and methacrylate (comprise methyl methacrylate, EMA, fumaric acid, fumaric acid-methyl esters, dimethyl fumarate, fumaric acid-ethyl ester, DEF, maleic anhydride, maleic acid, maleic acid-methyl esters, dimethyl maleate, maleic acid-ethyl ester, diethyl maleate, the dimethylated methylene phenyl malonic ester, the diethyl methylene malonate, itaconic acid, itaconic acid-methyl esters, dimethyl itaconate, itaconic acid-ethyl ester, diethyl itaconate, atropic acid, atropic acid methyl esters and atropic acid ethyl ester), chloracrylic acid and ester thereof, bromopropene acid and ester thereof, iodopropylene acid and ester thereof, adjacent-, between-and p-methylstyrene, fluorobenzene ethene and chlorostyrene, alpha-sulfo acrylic acid and salt thereof and ester, α-An Jibingxisuan and salt thereof and ester, N-methyl and N, N '-DMAA, acrylic acid and methacrylic anhydride, methyl vinyl ketone, the methylol vinyl ketone, adjacent-and p-methoxystyrene, ethylene glycol-maleate, the ethohexadiol fumarate, N-vinyl methylacetamide, vinylacetate, vinyl butyrate, the vinyl benzoic acid ester, vinylquinoline and vinylpyridine such as 2-vinylpyridine, 4-vinylpridine, 2-methyl-5-vinylpyrine, 2-vinyl-5-ethylpyridine, the N-vinyl pyrrolidone, cyclopentadiene, N-vinyl phthalimide, N-vinyl succinimide, N-vinyl acetamide and N-vinyl-diacetayl amide;

(c) disclosed monomer in No. 2956046, the United States Patent (USP) of Glavis etc.: undersaturated monomer hydrochlorate, for example the salt of their quaternary ammonium salt and amine salt and ammonia, alkali metal and alkaline-earth metal comprises propenoic acid beta-hydroxy ethyl trimethyl ammonium, acrylic acid benzyltrimethylammon.um, amine salt, acrylic acid-first ammonium and acrylic acid two and trimethylammonium;

(d) monomer described in No. 3220960, the United States Patent (USP) of Wichterle etc.: methacrylic acid methyl amino ethyl ester, methacrylic acid piperidino ethyl ester, methacrylic acid morpholino ethyl ester, methacrylyl glycolic acid (glycolic acid), glycol, glycerine and polyalcohol, two aklylene glycols and PAG-methacrylate and corresponding acrylate;

(e) monomer of in No. 3229769, the United States Patent (USP) of Bashaw etc., describing: the alkylaryl and the aromatic polymer of the sulfonation of crosslinked water-fast water-swellable basically, the polyvinyl toluene salt of for example crosslinked kayexalate and sulfonation, the alkaryl of this sulfonation and aromatic hydrocarbons material and acrylonitrile, the alkyl acrylonitrile, acrylate and methacrylate, the cross-linked copolymer of crosslinked polyvinyl alcohol and the copolymer of polyacrylamide and polyacrylamide, the for example cross-linked copolymer of acrylamide and acrylic acid or acrylamide and acrylic acid monovalent salt and crosslinked heterocyclic monomer, for example polyvinyl morpholino ketone (morphollinone), poly--5-methyl-N-vinyl-2-oxazolidone and PVP (pyrrolidene);

(f) monomer described in No. 3664343, the United States Patent (USP) of Assarsson: water-fast hydrophilic poly-(oxirane) polymer, be by water-soluble poly-(oxirane) polymer stand the ionising radiation preparation (this base polymer is the homopolymers of oxirane and oxirane and one or several alkylene oxide such as propylene oxide, styrene oxide and 1,2-butylene oxide, 2, the copolymer of 3-butylene oxide and isobutylene oxygen, all these is described as No. 3127371,3214387,3275998,3275199 and 3399149, United States Patent (USP).)；

(g) monomer described in No. 3926891, the United States Patent (USP) of Gross etc.: acrylic acid and alkyl methacrylate, for example methyl acrylate, ethyl acrylate, propyl acrylate, Hexyl 2-propenoate, butyl methacrylate, hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, decyl-octyl methacrylate and Ω hydroxy alkyl acrylate, for example 2-hydroxy ethyl methacrylate, hydroxymethyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxyl butylacrylic acid ester;

(h) ethene, 1,3-dienes, styrene, alkenyl halide, vinyl esters, acrylate, methacrylate, acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide, N-VCz, N-vinyl pyrrolidone, propylene and

(i) olefine, acetate vinyl acetate

Certainly, know those skilled in the art of this open benefit, will with reference to the monomer of whole monomers of this piece specification and the careful consideration of claims for example maleic acid and styrene copolymerisation generate at industrial useful copolymer, graft polymers, block polymer.For example the example of this analog copolymer can wait at two hurdles of No. 4057521, United States Patent (USP), 66 row and find.By the situation of method of the present invention about the selection that is used for the concrete combination of polymerization and crosslinked monomer, crosslinking agent and initator, selection about the combination of monomer is that those skilled in the art is known, be not component part of the present invention, so further describing of this combined polymerization there is no need.

Similarly, method of the present invention utilizes a large amount of crosslinking agents favourable about employed concrete monomer or multiple monomer without limits.These crosslinking agents be included in the aqueous solution can with any organic compound of organic polymer reaction, generally comprise the compound that has two polymerizable double bonds at least, have a polymerizable double bond and at least one at least and contain the monomer of acid or the compound of the functional group of polymer reaction, the compound of at least two functional groups and acidiferous monomer or polymer reaction and can generate the polyvalent metal compounds of ionization cross-bond.Nonrestrictive some of these crosslinking agents enumerated comprise:

-polyethylene base class, for example product of divinylbenzene, divinyl toluene, divinyl acid anhydrides, divinylsulfone, divinyl benzene sulfonate and their alkyl or halogen replacement;

-unsaturated monobasic or polybasic carboxylic acid and polyalcohol be the polyester of ethylene glycol, trimethylolpropane, glycerine and polyoxyethylene glycol for example;

-bisacrylamide, for example, N, N '-methylene-bisacrylamide and N, N '-di-2-ethylhexylphosphine oxide Methacrylamide;

The carbamyl ester that-PIC and hydroxyl monomer reaction obtain;

Two, three or four esters of-acrylic or methacrylic acid;

The polyenoid propyl diester of-polycarboxylic acids, for example diallyl phthalate and, diallyl adipate;

The ester of one allyl ester of-one by one unsaturated or polycarboxylic acid and polyalcohol, for example divinyl ether of the acrylic acid of polyethylene glycol-allyl ether, allyl acrylate, diallyl glycol ether and ethylene triols (ethylene tri-) or diethylene glycol (DEG);

-two or triallylamine, N, N '-diallyl alkene acid amides, diallyl Methacrylamide;

One N hydroxymethyl acrylamide, the N-methylol methacrylamide;

The ethylene oxidic ester of-acrylic acid and methacrylic acid, poly-ethylene glycol diacrylate, poly dimethyl acrylic acid glycol ester;

-hexadiene the class that replaces, for example 2,5-dimethyl-3,4-dihydroxy-1,5-hexadiene and 2,5-dimethyl-2,4-hexadiene;

Undersaturated list of-olefinic or polycarboxylic acid, acrylic acid for example, methacrylic acid, crotonic acid, iso-crotonic acid, angelic acid, tiglic acid, senecioic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, teraconic acid, citraconic acid, mesaconic acid and glutaconate;

-glyoxal (glycxal);

-polyalcohol, ethylene glycol and many halogen alkanol for example, for example, and 1,3-dichloroisopropanol and 1,3-dibromo isopropyl alcohol;

-polyamines class, for example Alkylenediamine (ethylenediamine), polyalkylenepolyamines class, the diacrylate and the dimethylacrylate of triethanolamine diacrylate and dimethylacrylate, triethanolamine triacrylate and trimethyl acrylic ester and two hydroxyl acetamides;

-polyepoxide and halogen epoxyalkane, for example chloropropylene oxide, epibromohydrin, 2-methyl epichlorohydrin and epiiodohydrin;

-poly epihydric alcohol ethers and polyalcohol poly epihydric alcohol ethers, for example ethylene glycol, diethylene glycol (DEG) and propylene glycol diglycidylether, glycerine triglycidyl ether, glycerine diglycidyl ether and polyethyleneglycol diglycidylether, tartaric acid diacrylate and trimethyl acrylic ester, triethylene glycol diacrylate and dimethylacrylate, ethylene glycol dimethacrylate and propylene glycol diacrylate;

-oxide;

-hydroxide;

The salt of weak acid of-alkaline-earth metal (calcium, magnesium) and zinc, strontium and barium (for example carbonate, acetate), for example calcium oxide and zinc diacetate and

The multivalent metal salt of-acrylic acid and methacrylic acid.

About employed initator, method of the present invention does not plan to limit equally.Can produce free radical by the various methodologies of heat well known by persons skilled in the art, photochemistry and redox (OR).The benefit that initator is selected also is well known by persons skilled in the art.Suitable polymerization initiator well-known in the art comprises:

-per-compound class (sodium, the mistake of potassium and ammonium (two) sulfate), hydrogen peroxide, the peroxide of decoyl and benzene, cumene hydroperoxide, acetyl peroxide, tert-butyl diperoxy phthalic acid ester (diterphthlae), the tert-butyl perbenzoate, peracetic acid sodium, the tert-butyl hydroperoxides, SODIUM PERCARBONATE and general redox initiator system for example are by peroxide and reducing agent for example sodium sulfite or ammonium sulfite or sodium hydrogensulfite or ammonium bisulfite, the system that the reducing agent combination of L-ascorbic acid or ferrous salt is generated;

The combination of-peroxide and reducing agent;

-tetraphenyl amber dintrile, four-right-anisyl amber dintrile; With

-azo initiator, for example azodiisobutyronitrile (AIBN), 4-tert-butyl azo-4 '-cyano group-4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-amidino groups-propane)-hydrogen chlorate.

The mixture of one or more of common these initators of use.

By the following unrestricted example with reference to the crosslinked water absorbent polymer of the preparation of method as mentioned above, the present invention just can more in depth understand.

Embodiment 1

Cross (two) sodium sulphate and 2 in following ratio (all being parts by weight) preparation initator, 2 '-azo two (2-amidine propane HCl (ABAH) (Polyscienes, Inc.Wamington, PA) and the aqueous solution of ascorbic acid:

Initator water is crossed (two) sodium sulphate 0.650 12.346ABAH 0.975 12.021 ascorbic acid 0.013 12.983

Use other reactant in following ratio:

Water 29.7%

(Catalog 42.61% for acrylic acid

No.14723-0，Aldrich

Chemical company, Milwaukee, WI)

Triallylamine (Catalg No.

T4500-4, Aldrich chemicals 0.30%

Company, Milwaukee, WI)

Caustic soda 22.12%

Ascorbic acid solution 1.05%

ABAH solution 2.11%

Cross (two) metabisulfite solution 2.11%

Water is mixed with acrylic acid and remain on 10 ℃, add triallylamine then.Add caustic soda to remain under 40 ℃ the temperature with enough slow speed, make its temperature drop to 7 ℃ then, and remain on and add ascorbic acid and ABAH solution under this temperature.The aqueous mixture that generates after 4-5 minute, added (two) sodium sulphate with purging with nitrogen gas.This mixture mixed for 30 seconds under 37.8 ℃ temperature.Mixture sprays into the reative cell of building by technology of the present invention, high about 4.57 meters of reative cell, and atmosphere pressures wherein is lower than environmental pressure, is about 33860N/m ², and be heated to about 107.2 ℃.The suction spherical polymer particles of making is smooth surface, and diameter is the about 100 μ m of about 50-, and water content is about 2%.

Embodiment 2

By using the following ratio of reactant, improve embodiment 1 described method: water 26.00% acrylic acid (referring to embodiment 1) 44.85% triallylamine (referring to embodiment 1) 0.31% caustic soda 23.29% ascorbic acid solution 1.11%ABAH solution 2.22% is crossed (two) metabisulfite solution 2.22%

Except the temperature of reative cell 12 be pressure in 65.6 ℃ and the reative cell 12 be not reduced to be lower than under the environmental pressure, all technological parameters are all identical with embodiment 1.Though the spherical polymer particles of preparation is smooth surface and can effectively absorbs water that water content is about 8%.When using potassium hydroxide to replace caustic soda to repeat, productive rate descends about 50%.

Embodiment 3

Improve embodiment 1 described method by omitting the initator ascorbic acid.The productive rate of the spheric granules of the smooth surface that makes is approximately identical with embodiment's 1, but water content is about 4%.

Seemingly pulverous particle that polymerization production of the present invention is done does not need drying, grinding, pulverizing and/or other method, and just can produce particle diameter is the suitable particle that directly uses of 2-125000 micron.But the present invention uses the liquid monomer source, produces the basic polymer beads of doing, and does not rely on base material and begins thereon to form.

Method and apparatus described herein also can be used for preparing continuously soap and washing agent.Produce that soap or detergent raw material mix and/or homogenizing after, handle, just as known to those skilled in the art, prepare the liquid mixture of the compound of soap-or washing agent-make.Then this liquid mixture is sprayed into according to above-mentioned reative cell.Can utilize soap well known by persons skilled in the art and washing agent standard recipe, Powdered soap or washing agent that preparation is done basically.

The preparation of soap or washing agent does not require the temperature in the charge pipe that reduces said method and equipment.But liquid mixture will experience the pressure in the charge pipe and the condition of above-mentioned injection and reative cell.The pressure and temperature that changes aforesaid reative cell will produce with produce by prepared washing agent of monomer polymerization and soap in analog result.

The method and apparatus of Miao Shuing can also be used to prepare several new polymeric articles herein.Have been found that up front by changing the operating parameter of equipment, be not only the size and the density that change product, and can change the shape and the physical property of product.More particularly, when equipment during in lower pressure and higher temperature operation, in polymerization process, the water in the mixture droplet or other solvent discharge fiercely.Consequently obtained the basic polymeric articles of doing that irregular inflated configuration is arranged as the puffed rice shaped polymer.The novelty that it is believed that this product is its an irregular inflated configuration, low-density and under the situation of water absorbent polymer, owing to increased the surface area of polymer, has just improved the ability of suction or urine.And, in known method, make the desired additional processing of like product without spray-drying or picture, just can make product with these features.

With known product do not have the identical degree of irregularity of their shapes because these known product are by pulverizing and the mechanical means of chopping bulk polymer material is made.Therefore, known erose polymer has less surface area and higher density is arranged usually.The known method that is used for preparing erose polymeric articles be the U.S. that is entitled as " at the polymer composition of the employed formation hydrogel of absorbent structure " that on April 19th, 1988 was presented to Brandt etc. again reissue patent described in No. 32649 those and be presented to those methods described in No. 4625001, the United States Patent (USP) that is entitled as " continuous producing method of cross-linked polymer " of Tsubakimoto etc. on November 25th, 1986.These patents are incorporated herein reference.

The colored copolymer product of the new product of other that makes from method and apparatus described herein for doing basically is used for powder coated.In order to obtain this product, this method further comprises the step that second monomer is added the step of first mixture and pigment is added first mixture.The mixture of the homogenizing equipment that sprays into forms the mixture droplet then, and this mixture droplet carries out polymerization in the free-falling process.The product that this method obtains is the basic curable copolymer of doing of colored ray, is used for the application facet of powder coated, and copolymer product does not need the chemistry or the mechanical treatment that add.

The production that is used as the copolymer of adhesive in powder coated is that the United States Patent (USP) that is entitled as " with the crosslinkable copolymer of free radical method " that was presented to Kempter etc. on January 16th, 1996 is described for No. 5484850.This piece patent is incorporated herein reference.As described in the Kempter patent, the copolymer that is used for the powder coated application facet generally requires several manufacturing steps in their production.Monomer reactant at first aggregates into copolymer.In order to introduce additive, this copolymer is dispersed or dissolved in emulsion or the solution then by various known method.At last, with the dry copolymer compositions of traditional method.In a step of method and apparatus as herein described, from the homogeneous mixture of monomer and various additives, make the basic painted copolymer of doing.

Term as used herein " controlled atmospher " is the inner case of description equipment and the reaction condition of polymerization process.For example, " controlled atmospher " to refer to be static atmosphere basically.In equipment or near the polymerization process gas any flowed or motion should reduce to minimum carrying out; Should the free-falling of influential polymerization droplet flow or disturbance exists.When droplet such as common described landing during by equipment, describing more accurately is the free-falling of picture experience, and this is preferred only by gravity effect.

The above-mentioned example that person of skill in the art will appreciate that of knowing this open benefit proposes with way of example, is used for the purpose in accordance with the requirement of patent regulation, and these examples are intended scope of the present invention not.Equally, about equipment 10, people will recognize and can make amendment to each included structural detail of that equipment, and these elements are realized its attempt result's the mode of action in the not change equipment.All such modifications all are intended to fall in the scope of following claims.

Claims (65)

1. a polymerization equipment comprises:

One reative cell;

Heat the device of above-mentioned reative cell;

Control the device of above-mentioned reative cell internal pressure;

One or several nozzle that is connected with the charge pipe that is used to receive the monomer source and the mixture in initator source; With

Mixture is sprayed into the device at the top of reative cell, and therefore the result of above-mentioned injection forms the droplet of said mixture, during described droplet experience freely falls and obtains the time enough of the desired degree of polymerization by reative cell.

2. by the equipment of claim 1, further comprise from the bottom of above-mentioned reative cell and get rid of polymer, keep the heating of reative cell and the device of pressure simultaneously.

3. press the equipment of claim 2, the device of wherein getting rid of polymer comprises the groove that is positioned at the reative cell bottom, first auger conveyor is installed in the bottom of above-mentioned groove, be used for shifting out polymer from reative cell, feed bin enters the polymer that above-mentioned first auger conveyor is deposited, and second auger conveyor is installed in the bottom of above-mentioned feed bin, is used for polymer is shifted out above-mentioned feed bin.

4. by each equipment of aforementioned claim, further comprise the device of monomer and initiator mixture temperature in the control charge pipe.

5. by each equipment of aforementioned claim, the mixture that further comprises monomer and initator before the said nozzle ejection, the device that monomer and initator are mixed.

6. by each equipment of aforementioned claim, further comprise the device of getting rid of unconverted monomer from above-mentioned reative cell.

7. by each equipment of aforementioned claim, further comprise the device of mixture in the above-mentioned charge pipe of purge.

8. by the equipment of claim 7, wherein the bubbling device of charge pipe comprises the device with the purging with nitrogen gas charge pipe.

9. by each equipment of aforementioned claim, further comprise the device of the above-mentioned reative cell of purge.

10. by the equipment of claim 9, wherein the bubbling device of reative cell comprises the device with the purging with nitrogen gas reative cell.

11. by each equipment of aforementioned claim, wherein the height of above-mentioned reative cell is about 30.48 meters of about 3.65-.

12., further comprise the independently container in above-mentioned monomer source and above-mentioned initator source by each equipment of aforementioned claim.

13. the equipment by claim 12 further comprises the crosslinking agent source container.

14. by the equipment of claim 13, wherein before the mixture in monomer source and initator source is sprayed into above-mentioned reative cell, above-mentioned crosslinking agent source is connected with the device that is suitable for the crosslinking agent source is added to the monomer source and the said mixture in initator source.

15. by each equipment of aforementioned claim, wherein mixture is the above-mentioned reative cell that sprays into the about 13.7MPa of the about 517KPa-of pressure.

16., the pressure that keeps in the reative cell device less than environmental pressure is set wherein by each equipment of aforementioned claim.

17. by the equipment of claim 16, it is the about 50790N/m of about 338.6-that wherein above-mentioned device keeps the pressure in the reative cell ²Be lower than environmental pressure.

18. by each equipment of aforementioned claim, wherein above-mentioned reative cell is to be heated to about 23.8 ℃-Yue 176.7 ℃ temperature.

19., the device that increases or reduce the size of each nozzle is set wherein by each equipment of aforementioned claim.

20. by each the equipment of claim 1-18, wherein in use, monomer source is functionalized or not functionalized alkene.

21. by each equipment of claim 1-18, wherein in use, monomer source is an acrylic acid.

22. each equipment by claim 1-18, wherein in use, above-mentioned monomer source is to be selected from the compound of being made of group ethene, alkadienes, styrene, propylene, vinyl-based, acrylate, methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylic acid amino and olefine.

23. an equipment of producing washing agent continuously comprises:

One reative cell;

Heat the device of above-mentioned reative cell;

Control the device of above-mentioned reative cell internal pressure;

One or several nozzle that is connected with the charge pipe that is used to receive the detergent raw material mixture; With

Mixture is sprayed into reactor top, and therefore the result of above-mentioned injection just forms the droplet of said mixture, and these droplet free-fallings have obtained enough time durations of the basic detergent powder of doing by reative cell.

24. a polymerization, the method comprising the steps of:

(a) at least a monomer source of preparation and first mixture that selects a kind of solvent of Free water, organic solvent and their mixture composition group;

(b) the initator source is added first mixture, generate second mixture;

(c) second mixture is sprayed into the atmosphere of basic static state of the pressure control of heating, above-mentioned injection result has formed the droplet of above-mentioned second mixture; With

(d) the second mixture droplet of above-mentioned injection is fallen by the static basically atmosphere of heating, obtained enough time durations of the degree of polymerization that requires.

25., wherein in airtight container or reative cell, keep the atmosphere of the basic static state of heating by the polymerization of claim 24.

26. by the polymerization of claim 25, wherein above-mentioned second mixture is in the top jet of container or reative cell.

27. by the polymerization of claim 25 or 26, the wherein about 3.65-30.48 rice of the height of said vesse or reative cell.

28. by each the polymerization of claim 24-27, wherein above-mentioned second mixture is to spray into atmosphere by one or several nozzle.

29., wherein be by increasing or reduce the size of the polymer beads that size Selection is produced of nozzle bore by each the polymerization of claim 24-28.

30. by each the polymerization of claim 24-29, this method further comprises nertralizer is added first mixture.

31. by each the polymerization of claim 24-30, wherein above-mentioned solvent emptying continuously in polymerization process.

32. by each the polymerization of claim 24-31, the wherein basic polymer powder of doing is because the result of polymerization process makes.

33. by the polymerization of claim 32, wherein reclaim the powder of doing, keep the atmosphere of the basic static state of heating simultaneously.

34. by the polymerization of claim 32 or 33, the dry polymeric powder of wherein being produced comprises the polymer of suction.

35. by the polymerization of claim 32 or 33, the dry polymeric powder of wherein being produced comprises the polymer that is suitable for the powder coated use.

36, by the polymerization of claim 32 or 33, the dry polymeric powder of wherein being produced comprises the low-density polymer of irregular inflated configuration.

37. by each the polymerization of claim 24-37, wherein above-mentioned atmosphere is about 23.8 ℃-Yue 176.7 ℃ temperature.

38. by each the polymerization of claim 24-37, wherein above-mentioned basic static atmosphere is reduced atmosphere.

39. by each the polymerization of claim 24-38, wherein above-mentioned basic static atmosphere is malleation atmosphere.

40. by the polymerization of claim 38, wherein the controlled atmospher of the basic static state of above-mentioned heating is to be maintained at about the about 50790N/m of 388.6- ²Pressure under, be lower than environmental pressure.

41. by each the polymerization of claim 24-40, wherein above-mentioned second mixture is the atmosphere that sprays into the basic static state of the heating of pressure between about 517KPa and about 13.7MPa.

42. by each the polymerization of claim 24-41, wherein monomer source is that monomer and solvent are the aqueous solution of water.

43. by each the polymerization of claim 24-41, wherein monomer source is that selected monomer and solvent are a kind of moisture emulsion of water.

44. each polymerization by claim 24-43 wherein before the initator source adds above-mentioned first mixture, cools off above-mentioned first mixture.

45. by each polymerization of claim 24-44, this method further comprises crosslinking agent is added first mixture.

46. by the polymerization of claim 45, wherein the crosslinking agent source is that selected crosslinking agent and solvent are the aqueous solution of water.

47. by the polymerization of claim 45, wherein crosslinked Li Yuan is that selected crosslinking agent and solvent are the aqueous emulsions of water.

48. by each the polymerization of claim 24-47, wherein monomer source is water miscible unsaturated monomer.

49. by each polymerization of claim 24-48, wherein monomer source is not functionalized alkene.

50. by each polymerization of claim 24-48, wherein monomer source is a functional olefines.

51. by each polymerization of claim 24-48, wherein monomer source is an acrylic acid.

52. by each polymerization of claim 24-48, wherein above-mentioned monomer source is to be selected from the group of being made up of ethene, alkadienes, styrene, propylene, vinyl-based, acrylate, methacrylate, acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide and olefine.

53. by each polymerization of claim 24-27, wherein first mixture cools off first mixture before add in the initator source.

54. each polymerization by claim 24-53 further comprises nertralizer is added first mixture.

55. by each polymerization of claim 24-54, wherein second mixture is under the temperature that remains between 26.6 ℃ and about 93.3 ℃.

56. the polymerization that a production contains acrylate copolymer comprises step:

(a) acrylic acid aqueous mixture of preparation part neutralization;

(b) polymerization initiator is added aqueous mixture, generate second mixture and

(c) above-mentioned second mixture is sprayed into the basic static atmosphere of pressure control of heating, above-mentioned injection result has formed the droplet of above-mentioned second mixture; With

(d) the above-mentioned droplet of second mixture of injection is fallen by heating, Jing Tai atmosphere has obtained enough time durations of the degree of polymerization that requires basically, so has generated and contain part acrylic acid particle powder shaped polymer that neutralizes.

57. one kind preparation is as the method for powder coated application copolymer continuously, described method comprises step:

(a) prepare the liquefied mixture of two or more monomers;

(b) liquefied mixture of homogenizing pigment and monomer;

(c) the static basically atmosphere of pressure control that liquefied mixture is sprayed into heating, the result of above-mentioned injection forms the droplet of mixture; With

(d) make the basically static atmosphere of the mixture droplet whereabouts of injection, obtained generating enough time durations of the basic copolymer of doing that can be used for the powder coated application by heating.

58. a method for preparing irregular inflated configuration polymer continuously, the method comprising the steps of:

(a) prepare the liquid mixture of one or more monomers;

(b) liquid mixture is sprayed into the basic reduced atmosphere of the pressure control of heating, the result of above-mentioned injection forms the droplet of mixture;

(c) make the fall atmosphere of the basic static state by heating of the droplet of the mixture of injection, obtain generating during the time enough of low-density polymeric of the basic irregular inflated configuration of doing.

59. the method for a continuous preparing washing agent comprises step:

(a) liquid mixture of preparing washing agent raw material;

(b) liquid mixture is sprayed into the basic static atmosphere of the pressure control of heating, above-mentioned injection result forms the droplet of mixture; With

(c) the above-mentioned droplet of the mixture of injection is fallen by the basic static atmosphere of heating, obtain forming during the time enough of the basic detergent powder of doing.

60. the polymeric articles of producing by each method of claim 24-58.

61. contained acrylate copolymer by what moisture radical polymerization method produced, described radical polymerization method comprises step:

(a) acrylic acid aqueous mixture of preparation part neutralization;

(b) polymerization initiator is added to aqueous mixture, generates second mixture of polymerization reactant;

(c) above-mentioned second mixture is sprayed into the atmosphere of the basic static state of heating, the result of above-mentioned injection forms the droplet of above-mentioned second mixture; With

(d) the above-mentioned droplet of second mixture of injection is fallen by the static basically atmosphere of heating, obtained during the time enough of the degree of polymerization that requires.

62. by the polymer of claim 61, the above-mentioned polymer of wherein being produced is the polymer of suction.

63. by the polymer of claim 61, the above-mentioned polymer of wherein being produced is to be used for the copolymer that powder coated is used.

64. by the polymer of claim 61, the above-mentioned polymer of wherein being produced is the low-density polymeric of an irregular inflated configuration.

65 each polymer by claim 61-64, the above-mentioned polymer of wherein being produced is a particulate powder, granularity is less than about 100 microns.

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