The allocation method (co)polymer coagulation

 

(57) Abstract:

Describes how the allocation of (co)polymers by steam coagulation, obtained from butadiene, isoprene and/or styrene, in which (a) (co)polymers are mixed with the steam pressure in the range from 3 to 12 bar abs. and temperature in the range from 120 to 200C in the contactor, and (C) thus obtained mixture was fed into the coagulator, operating at a temperature in the range from 90 to 120C. and at a pressure of from 1.0 to 2.5 bar abs. The method differs in that stage (C) is carried out in the presence of polyvinyl alcohol as a dispersant. The technical result - the exception of education coarse polymer particles. 4 C.p. f-crystals.

The invention relates to a method for selection of polymer coagulation. More specifically, the invention relates to improvements in the method of coagulation ferry, the allocation of block and statistical copolymers derived from mainly of diene with conjugated double bonds and/or predominantly moulinrouge aromatic compounds.

Application of methods of coagulation ferry to highlight statistical and block copolymers from solution of the above copolymer in an organic solvent after the reaction of anionic polymerization by Vasami, initiated organic compound containing an alkaline metal, or through the agent, giving the proton, in the case of fully sequentially obtained block copolymer, or a binder in the case of the first received intermediate the diblock copolymer, in principle known, for example, from a European patent application N 0413403. From the above of a European patent application and, in particular, rows 7, 8 and 54-56 on page 6 it is known that adhesive from random copolymers or block copolymers of moulinrouge aromatic compounds and diene with conjugated double bonds and solvent, comprising a significant part of cyclopentane can be handled by steam coagulation.

Typically, however, the disadvantage of this method, particularly when it was used for the block copolymers obtained from monovillage aromatic compounds and diene with conjugated double bonds, and having a relatively low viscosity, was the formation of large agglomerates and strong contamination of the reactor and/or the allocation of block copolymers that occur with very low productivity and, therefore, will entail additional costs when removing. On the other hand, the average pregnant low viscosity and/or the relatively high content of poly (mono) vinyl aromatic compounds, require much higher capital costs due to the need for expensive additional equipment.

Specialists in this field it is clear that the need for block-copolymers derived from predominantly moulinrouge aromatic compounds and mainly of diene with conjugated double bonds, having a relatively low viscosity and intended for use in modern industry, such as adhesives, pressure-sensitive, still growing, while on the other hand, required the allocation of a block copolymer by coagulation with a lower cost, i.e., higher productivity, and reduce cleaning time due to avoid or reduce pollution.

Therefore, the aim of the present invention is the provision of an improved method of selection (co) polymer coagulation, and such copolymers, which are mainly derived from the diene with conjugated double bonds and/or predominantly moulinrouge aromatic compounds.

It should be understood that the term "allocation method (copolymers by coagulation, which is used throughout the present description, the coverage is mixed with an immiscible liquid, in which the polymer is essentially insoluble, while simultaneously applying heat to remove a significant part of the organic solvent by means of a hot fluid, for example steam, or heated inert gas, for example nitrogen.

Of all the options cues polymer using coagulation ferry is the most preferred.

In the research and eksperimentirovaniya was unexpectedly found an improved way.

Accordingly, the present invention relates to a method of allocating coagulation co(polymers), and such copolymers, which are obtained mainly of diene with conjugated double bonds and/or predominantly moulinrouge aromatic compounds by coagulation of the adhesive containing - (polymer), in the presence of a dispersant polyvinyl alcohol.

The present invention preferably relates to a method of selection (co)polymers using coagulation steam, and more preferably to a method for allocation of block copolymers using coagulation vapor comprising at least one block derived primarily from diene with conjugated double bonds, tx2">

Polyvinyl alcohol used in the method of the present invention has srednevekovoy molecular weight in the range from 200 to 200,000, and preferably from 3000 to 30000 and may have an average degree of hydrolysis in the range of from 25 to 98% and preferably from 60 to 90%.

Polyvinyl alcohol is added in quantities of from 10 to 10,000 ppm relative to the weight of coagulation of water and preferably from 25 to 1000 ppm, and most preferably in an amount of from 40 to 100 parts per million.

In accordance with a preferred variant of the present invention, polyvinyl alcohol is introduced into the contactor through a small stream of water, but should take into account that in accordance with other options PVA (polyvinyl alcohol) may be introduced into the contactor with pre-prepared adhesive.

It has been unexpectedly found that the use of polyvinyl alcohol as a dispersant during the implementation of the allocation method coagulation, and in particular during the allocation method using coagulation steam block copolymers containing at least one block predominantly diene with conjugated double bonds and at least one block preimushestvennogo reactor block copolymer, with low viscosity, while the concentration of the block copolymer in suspension may rise significantly, such as from 1 wt.% up to 4.5 wt.%, when using 50 parts per million polyvinyl alcohol in water coagulation.

Use as a dispersant poly (vinyl alcohol) will allow to obtain high concentrations of block copolymer in aqueous suspensions, higher productivity and less time cleaning a contaminated reactor.

The term "predominantly" used in the description means that the specific monomer can be used in essentially pure form or may be intentionally mixed with certain specific small amounts of co monomer (< 20 wt.%), which may have a structure similar to that of the main monomer component of the link block, or different from it. For example, the main component of 1,3-butadiene may be mixed with minor quantities of other conjugated dienes, such as isoprene 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene or 2,3-dimethyl-1,3-pentadiene or mixtures thereof, or with the co monomer differing patterns, such as monovinyl aromatic compound. The main component of monovinylacetylene-methylstyrene; 3.5-diethylstil, 4-n-propertywala, 2,4,6-trimethylstyrene; 4-vinylstyrene, 4-methylstyrene, 3,5-diphenylethanol, 1-vinylnaphthalene; 3-ethyl-1-vinylnaphthalene; phenyl-1-vinyl-naphthalene, or mixtures thereof, or mixed with isoprene, butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene or 2,3-dimethyl-1,3-pentadiene or mixtures thereof. Link block copolymer derived from such monomer mixtures may be essentially disordered or cone-shaped structure.

In any case, the basic Monomeric component one particular part of the block is preferably mixed with the main monomer component other link unit, for example butadiene mixed with styrene.

You should take into account that the method of the present invention is applicable to co(polymer) adhesives, the polymer which may preferably consist of mainly polydiene with conjugated double bonds, or of a copolymer of a diene with conjugated double bonds and moulinrouge aromatic compounds. More preferably the method is used for separation of block copolymers, which have linked poly(mono)vinylaromatic content in the range from 15 to 90 wt.% and in particular from 25 to 85 wt.%.1)nX, where component A is predominantly a block of polystyrene having an average molecular weight in the range from 5000 to 30000, B is predominantly block of polyisoprene and/or polybutadiene block, which may not necessarily be selectively gidrirovanny and has an average molecular weight in the range from 30000 to 70000, B1primarily represents branch, Rubezhnoe, Ukraine and/or polybutadiene link block having an average molecular weight ranging from 15,000 to 35,000, which may not necessarily be selectively gidrirovanie, X is the residue not containing halogen binder, and n> 3, the total molecular weight is in the range of from 50000 to 300000, and the content of the bound styrene in the block copolymer is in the range from 10 to 50 wt.% relative to the weight of the entire block copolymer.

More specifically, the average molecular weight of block B mentioned triblock copolymers ABA is in the range of 30,000 to 50,000, while the average molecular weight of block A is in the range from 8000 to 25000, abshot 10 to 30 wt.%.

Note that the triblock-copolymer ABA or the main product of the radial block copolymer (AB)1)nX may be accompanied by varying the amount of diblock copolymer AB1that is the inevitable result of the reaction of a combination of previously received "live" block copolymers AB1with the binder to obtain due to the efficiency of the combination < 95%, (AB1)nX or ABA, or who intentionally get together with a fully sequentially polymerized triblock copolymer, or which is added to such a triblock-copolymer in order to adapt the technology for the production of hot melt adhesives. Such present diblock copolymers can have an average molecular weight of from 40000 to 80000.

It was found that the method of the present invention can be successfully used for the (co) polymer adhesives with a wide variety of inert organic solvents in which the preliminary polymerization. More specifically, it was found that the method can be successfully used for adhesives, including block copolymers, containing pure blocks of styrene and units of butadiene and/or isoprene.

The solvent is usually possible to choose and the residents, selected from linear or branched alkanes having from 5 to 7 carbon atoms, such as n-hexane, isopentane or n-pentane.

The method of the present invention is usually used by mixing glue with water vapor pressure in the range from 3 to 12 bar and a temperature in the range from 120 to 200oC contactor, and the mixture is then fed into the coagulator, which usually operates at a temperature in the range from 90 to 120oC and at a pressure of from 1.0 to 2.5 bar, while a large part of the solvent quickly evaporated under vacuum and condense.

The resulting suspension rubber usually contains from 3 to 5 wt.% polymer and, in particular, elastomer and about 5 wt.% residual solvent in the polymer, which is then removed during one or more stages of distillation under vacuum, which is carried out at a temperature of from 95 to 105oC and a pressure of from 1 to 1.5 bar up until the solvent content will amount to 0.2 wt.% or less.

Typically, the residence time in each vessel, intended for distillation under vacuum, is from 20 to 40 minutes.

In fact, for example, from U.S. patent N 4154923 known method of dehydrating aqueous slurry of granules of the polymer, and in particular pellets floor is Ziya insoluble organic party in destabilizing, having a molecular weight of at least 200, source of soluble compounds containing ionogenic solubilizing group, in a quantity sufficient to flocculation and to facilitate dewatering of suspensions and

(b) dewatering the thus treated suspension by means of physical separation from her water at a temperature of at least 50oC with the formation of soft sludge granules of polymer essentially containing no stabilizer dispersion of polyvinyl alcohol.

However, experts in this field know that the use of polyvinyl alcohol is disadvantageous, because the polymer suspension containing a polyvinyl alcohol, require allocation of additional polymer phase deposition with a stabilizer to obtain a polymer not containing polyvinyl alcohol. Therefore, experts in the field may not be advisable to apply it when the allocation of coagulation.

The invention will also be illustrated with the help of the following examples, which, however, do not limit the scope of its application.

Example 1

1500 g Cariflex TR-III2 loaded in a 25 liter reactor made of stainless steel, equipped with a mixer and add the and made stirring for 12 hours. The resulting solution was transferred into a vessel and kept under stirring under a nitrogen pressure of 4 bar.

100 l of coagulation vessel equipped with a stirrer, downloaded 30 liters of demineralized water. Then added 1.616 g of polyvinyl alcohol having an average molecular mass (Mwin the range of 9000 g/mol to 10,000 g/mole and an average degree of hydrolysis of 80%. The aqueous solution was stirred while heating to 110oC vapor pressure (1,4 bar).

Glue containing Cariflex TR-III2 and hydrocarbon solvents, mixed with steam, high pressure (10 bar 185oC) in the contactor. This mixture is then Inuktitut in coagulator at this speed, so you can get a steady stream of distillate consisting of water and a hydrocarbon solvent. The contents of the coagulation vessel was unloaded and assembled. The wet polymer was dried with hot air having a temperature of approximately 45oC for 8 hours. Received 1480 fine white polymer crumb.

Coagulation Cariflex TR-III without the addition of polyvinyl alcohol which was carried out under conditions similar to those described above, have led to large agglomerates and heavy pollution coagulation vessel.wstage -1 35000 g/mol, the content of the polystyrene 70 wt.%) and added 6 liters (4.7 kg) isopentane. The resulting solution was kept under stirring under a nitrogen pressure of 4 bar.

100-liter coagulation vessel downloaded 30 liters of demineralized water. Then he added 1.50 g of polyvinyl alcohol having an average molecular mass (Mwin the range of 9000 g/mol to 10,000 g/mole and an average degree of hydrolysis of 80%.

The aqueous solution was stirred under heating by injection of high pressure steam to a temperature in the range from 95 to 100oC for about 30 minutes.

Adhesive containing a thermoplastic elastomer and a hydrocarbon solvent, is mixed with steam high pressure (10 bar 185oC) in the contactor. This mixture is then Inuktitut in coagulator at this speed, to get a steady stream of distillate consisting of water and a hydrocarbon solvent. Simultaneously to the mixture, consisting of high-pressure steam and the polymer solution was added an aqueous solution containing 0.7 wt.% the above polyvinyl alcohol at a rate of 10 ml/min the Contents of the coagulation vessel was unloaded and assembled. Wet polim is approximately 700 g of a white polymer crumb.

Coagulation experienced above thermoplastic elastomer (10 wt. % in cyclohexane, diluted SBS, Mwstage -1 35000 g/mol, the content of the polystyrene 70 wt.%) without the addition of polyvinyl alcohol which was carried out under conditions similar to those described above, resulted in the formation of very large agglomerates, leading to the problems associated with unloading of the coagulator and with the stage of drying.

1. The allocation method (co)polymers by steam coagulation, obtained from butadiene, isoprene and/or styrene, in which (a) the adhesive of the copolymer is mixed with the steam pressure 3 - 12 bar abs. and a temperature of 120 - 200oC contactor and (b) thus obtained mixture was fed into the coagulator, operating at a temperature of 90 - 120oC and at a pressure of 1.0 - 2.5 bar abs., characterized in that to prevent the formation of coarse polymeric particles in stage (b) is conducted in the presence of polyvinyl alcohol as a dispersant.

2. The method according to p. 1, characterized in that the block copolymers containing at least one block predominantly diene with conjugated double bonds and at least one block predominantly moulinrouge aromatic compounds and having a low viscosity, Vineet srednevekovoy molecular weight of 3000 - 30000.

4. The method according to PP.1 to 3, characterized in that the polyvinyl alcohol has an average degree of hydrolysis of 60 to 90%.

5. The method according to PP.1 to 3, characterized in that the polyvinyl alcohol is added in the amount of 40 - 100 hours in a million.

 

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