Reducing the resistance of the fluidity of the polyolefin, the method of its production (options) and composition based on it

 

(57) Abstract:

Offered soluble in hydrocarbons, reducing the resistance of the fluidity of the suspension, and how it is obtained. The method aims to obtain reduce resistance to the flow of product that is easy to transport, not dangerous, easy to handle and provides a significant increase in our ability to reduce drag yield compared to existing industrial products. Preferably, the suspension was essentially no solvent. 4 C. and 6 C.p. f-crystals, 7 tab., 2 Il.

Background of the invention

The present invention relates to the production and application of non-crystalline, high molecular weight, soluble in hydrocarbons and reduce the resistance to the flow of polymers.

More specifically the invention relates to a method for having a high activity, not dangerous, easy to transport and easy to handle suspension reduces the resistance to the flow of polymers having improved performance.

It is known that some polymers that are soluble in oil, can cure various substances in the presence of catalysis of the materials by various means. These polymers, when dissolved in the hydrocarbon fluid flowing through a pipeline, greatly reduce turbulent flow and lower "resistance", thereby reducing the power required to move a given volume of fluid, or, conversely, to move larger volumes of fluid at a given power. In addition, the diluted solution having a high molecular weight polymers in solvents, such as hydrocarbons, are useful flow characteristics, unusual for a well-known crystalline, substantially insoluble, forming artifacts polymers, like polyethylene and polypropylene. In particular, these are soluble in the hydrocarbon materials for their effectiveness are called reducing resistance to agents and anti-fog agents. Anti-fog agent is a polymer which, when dissolved in the hydrocarbon contributes to a significant increase of the droplet size of the environment and thereby reducing the Flammability of fuel sprays, caused by a shift with high wind speed, as the one that takes place during the destruction of the fuel element originating from the blow, as if the plane crash.

One significant feature of trazom, passing through the pump, the heavy construction of the pipelines or the like, where there is turbulent flow, can push the polymer and reduce its effectiveness. Therefore, it is important to place these polymers in the current hydrocarbon in a form that takes certain desirable properties.

The polymer should be placed in a form adequate for easy transport and convenient treatment, without unusual or unusual equipment, as pumping stations can often be in remote and inaccessible places. The polymer must also be in a form that dissolves quickly transported hydrocarbon, so as polymers to dissolve slightly reduce resistance to fluidity. The polymer must also be harmless, given the primary goal of the flow of hydrocarbon. For example, in the case of crude oil flowing through the pipeline may be permitted large quantities of water and dirt, than in the finished pipe product as diesel fuel or gasoline, which are intended ultimately for consumption in internal combustion engines or the like.

At the present time has developed a number of different solutions to the problem p is uchesti polymers. When using these polymers form very dilute solutions (in the range of from about 100 parts of polymer per million of hydrocarbons), which are effective in reducing the resistance of fluidity or fog effect. Conventional production method consists in the preparation of dilute solutions of the polymer in an inert solvent such as kerosene or other solvent substance, as described in U.S. patent 4433123, in the name of Mack. Mack used a solution having a high molecular weight polymer suitable for use as a reducing resistance fluidity agent, in the production by the polymerization of alpha-olefin in a hydrocarbon solvent. The whole mixture containing polyolefin, solvent and catalyst particles, is used without separation for formation of dilute solutions of the polymer in crude oil or other hydrocarbon. However, the drawback of this approach is to use a solvent, which is a dangerous factor in shipping and handling. In addition, the product forms a gel-like solution that requires equipment for discharge under pressure and which becomes extremely viscous and causes difficulties in handling them in polarisavenue methods of polymerization in solution established the need to complete the reaction when the content of the polymer is not more than 20% by weight of the total contents of the reactor, in order to obtain polymers of high molecular weight in an effective form, as described in U.S. patent 4415714, 4493903 and 4945142.

Another solution is to obtain polymers in the form of solids, as described in U.S. patent 4340076 name Weitzen, which shows that having a high molecular weight polymer quickly dissolves in the solvent when the polymer was very finely ground at cryogenic temperatures, and the resulting polymer particles were injected into the solvent at a temperature below the glass transition temperature of the polymer. You can easily obtain the concentration of the polymer is below 15 percent, although to reduce the resistance of the fluidity required only a few parts per million. All three issued O'mara U.S. patents 4720397, 4826728 and 4837249 described finely chopped or granulated polymer in an inert atmosphere at a temperature below the glass transition temperature of the polymer in the presence of a separating agent for formation of a multilayer coating, which maintains an inert atmosphere adjacent to the polymer particles after grinding. The patent indicates that the grinding should be carried out necessarily in an inert atmosphere using a refrigerant, Kalo 35 mesh. This method requires the particles to dissolve in the hydrocarbon solvent is contained in an inert atmosphere without contact with water or oxygen.

Thus, you must have either an impervious coating of the particles, which prevents the contact of the particles with air or water to dissolve, or to dissolve the substances, the entire system must be kept in an inert atmosphere. This method is inconvenient, especially in remote areas of the pipeline.

In the most successful solution to the problem: use the entire reaction mixture of the polymerization process containing polymer with a high molecular weight, dissolved in a polymerization solvent as hexane, heptane or kerosene, at a concentration in the range of 2-3 percent to at most about 12 percent. Although this substance has proved difficult to pump the pump in cold weather, now it is the most economical usage of the product polymer reaction as substances that reduce resistance to fluidity.

All production methods or the methods known up to the present time, for polymers that are suitable for the reduction of the resistance of recuces edstone in crude oil, requires the entry of particles in a liquid, or, in the alternative, the preliminary dissolution of solids in liquids, and discharge liquid into the current hydrocarbon. Either method requires additional equipment that is not usually used in places of pipeline and pumping stations, and also requires significant investments in transport equipment. For example, in U.S. patent 4340076 you want to work with the source of liquid nitrogen. The present production method, using the entire polymerization mixture containing the solvent, is inconvenient, because the polymer solution must be transported as a hazardous material and stored in high-pressure cylinders. The product is a viscous polymer solution, which makes transportation in low temperature also inconvenient. Restriction on the content of polymer in the 10-15 percent in modern production methods also means that with respect to the contents of the active polymer significant costs are for delivery.

Prior art

In the art there are descriptions of polymers that reduce resistance to fluidity. Normal, but not be the friction of flow or resistance to being pumped by the pump through the pipeline fluid by adding minor amounts of high molecular weight non-crystalline polymer. In U.S. patent 3884252 describes the use of polymer lumps in the quality of the material, reducing the resistance of fluidity. These materials are extremely viscoelastic and not suitable for the formation being formed by casting or pneumothorax products. At all other use of them but reduce the resistance of flow is unknown. The same properties that make these materials are extremely effective as reducing resistance additives that make manipulating them is extremely difficult, as they have a strong tendency to cold fluidity or re-agglomeration.

Well-known General tendency nesecito polymer material to cold flow and re-agglomeration. There were many attempts to eliminate the disadvantages inherent in the cold creep of solid substances in polymers. Typical, but not exhaustive example of such technology is U.S. patent 3791913, when the elastomeric granules surface was overidealize at a small depth in order to save devulcanizing internal portion of the polymer in the bag of the cured material. In U.S. patent 4147677 described method of making freely the current finely ground powder neutralizating which reduces the resistance of the fluidity of the polymer in an inert, under normal conditions the liquid media to be added to the fluids flowing in pipelines, reaching dissolve effect with a staggered arrangement by changing the particle size of the polymer. Also described the suspension with surface-active agents. In U.S. patent 4340076 shows how the dissolution of high molecular weight hydrocarbon polymer in liquid hydrocarbons by breaking the polymer into individual particles and the contact of these materials at temperatures close to cryogenic, liquid hydrocarbons to more rapid dissolution of the polymer. In U.S. patent 4584244 says about grinding at cryogenic temperatures to reduce the resistance of polymers in liquid nitrogen with aluminum oxide to obtain a free current, crisp, solid, reducing the resistance of the fluidity of the composition.

U.S. patents 4720397, 4826728 and 4837249 issued by O'mara et al., relate to methods and compositions associated with rapidly dissolving polymer composition or polymer, grinding at cryogenic temperatures below the glass transition temperature, and at a time when the surface of suzerandall in an inert atmosphere, coating material coating, which maintains an inert atmosphere, the global resistance of the fluidity of the polymer, which are divided into particles and placed in a solvent with a low boiling point, which can be mixed with water, together with surface-active substances for the formation of the emulsion, the solvent of the emulsion is removed.

In the patent Canada 901727 described method for continuous polymerization. The method uses two rolls of sheet material, which is formed in the shell, with azagermatranes, but rolled edge. The liquid polymerization mixture is placed in a cavity formed by the joining of the two sheets. The method is suitable for the formation of compounds with the polymerized oxygen function, as esters, acetals, ketals, esters. Shell remains up until not complete the polymerization, and then recovering the plastic sheet and restored a long strip of the polymerized polymer.

In U.S. patent 5244937 said crushed at cryogenic temperature polymers that reduce the resistance of flow can suspendibility in water, using a thickener, and location in the current hydrocarbons as suspension.

Therefore, the aim of the present invention is to eliminate the disadvantages of the prior level of the initial weight, soluble in hydrocarbon polyolefin polymer, which is useful for improving the flow of hydrocarbons in pipelines. Other objectives will become apparent to experts in the course descriptions.

Brief description of the invention

The present invention relates to a method of polymerization in bulk for fast obtain soluble in oil, reducing the resistance of the fluidity of the polymer and the polymerized in the mass of the polymer is disintegrated to a particle and suspendered in water to create a very solid product with a low viscosity. The reaction product further contains additives that are required during production or as necessary to impart specific properties.

Advantages of the method and product of the present invention in comparison with the currently available industrial products that reduce the resistance of flow include a viscosity low enough to flow under the action of gravity to the suction of the fuel pump, and eliminating the use of high-pressure cylinders, which increase transportation costs. In addition, the material contains a significantly higher concentration of the polymer volume, which reduces the cost of natisa. The material of the present invention in form, appearance, and behavior is very similar to latex paint. There is no need to include any significant amounts of solvents or hydrocarbons to reduce hazards manipulation and the influence of the external environment.

Substances that reduce the resistance of flow of the present invention is produced by polymerization in mass olefinic monomers to education having extremely high molecular weight polymer, with grinding of polymers at cryogenic temperatures down to fine powder and mixing the powder with water and additives to obtain a stable suspension. Although the processes of polymerization in mass can be used solvents, it is preferable that the reaction and the product were as much as possible free from solvent, providing essentially the polymerization process and the product, reducing the resistance to flow, without solvent. Under normal conditions the contents of the polymerization reactor in the mass will be equal to at least 80% polymer by weight. Reactive olefins are usually fully polymerized (above 95% of the content of the polymer by weight), although the reactor may be subject to change in viscosity by adding neh conditions will contain at least 80% of the total contents of the reactor, preferably 90% of the full contents of the reactor. Most preferred option performed with the reactor containing at least 95% of the reactive olefins by weight.

More specifically the present invention relates to polymerization in the mass of alpha-olefins containing from 2 to 30 carbon atoms, where the polymerization mass is carried out at temperatures above 0oF [ABOUT 17.8 MLNoC], with the removal of sufficient heat of reaction with the formation of essentially non-crystalline, soluble in hydrocarbon polymer with an extremely high molecular weight, having a characteristic viscosity (IV) at least 25 deciliters per gram (DL/g). Preferably, the polymerization mass was held in the reaction vessel containing barrier plastics. The reaction vessel is consumed with the final product during the grinding and crushing at the cryogenic temperature of the obtained product and the reaction shell. Where polymerization is carried out using catalysts, requiring the exclusion of oxygen and water barrier plastics are barrier polymers, which under normal conditions are layers to prevent passage to the laid between the layers is very effective impervious water barrier polymers, as the polyethylene, polypropylene or polybutylene in order to provide the necessary reaction membrane or the reaction vessel to obtain having an extremely high molecular weight polyolefins and with the possibility of continuing the reaction essentially to completion by preventing deactivation of the catalyst with water or oxygen.

Significant feature of the present invention is that the containers, which carry out the reaction, give a size to provide a minimum cross-sectional area to dissipate large heat of reaction, and the reactor, accepted or expended, had the smallest size 9 " [22.86 cm]. The advantage of the present invention, use of spent reactor is in processing in that the polymer of the reaction product is sticky and when education is sintered. In the preferred method according to the present invention the reactor is removable and is consumed with the polymer at the end-use, excluding leading to cost the requirement of obtaining, cleaning and preservation of conventional reactors.

Detailed description of the invention

The present invention includes a method of receiving starimage in hydrocarbon, having extremely high molecular weight polymer, which reduces the resistance of fluidity. The polymer is produced by polymerization in mass of olefins containing from 2 to 30 carbon atoms, in the presence of a polymerization catalyst under polymerization conditions with removal of the heat of reaction sufficient to obtain a polymer having a characteristic viscosity (IV) at least 25 of deciliters per gram (DL/g). For the extremely high molecular weights determination procedure (IV) was modified using chetyrehstolbovoi shear viscometer with dilution, and measurement at 0.05 grams (g) of polymer per 100 milliliters (ml) of hexane solvent at 25oC and shear rate 300 s-1where the results of high shear bulb not used.

Discovered that the polymerization mass is capable of producing non-crystalline polymers with such a high molecular weight. Decrease the resistance to creep up to now has been considered that it is necessary to keep the concentration of monomers is low (below 20% by weight of the total monomer content) polymerization in solution in order to obtain the molecular weight, can effectively reduce soprotivleniyah temperature, in accordance with the requirements of production. For U.S. patent 4384089 required to spend a significant part of the reaction at low temperatures, the monomer is cooled.

Pre-conventional polimerization in solution were made of solid polymers with subsequent removal of the solvent prior to grinding. Attempted polymerization in mass as the decision related to the production of a polymer essentially no solvent, for grinding, in order to avoid this stage of solvent removal. It was expected that the polymerization in mass eliminates the stage of solvent removal, and it was expected that due to the achieved temperatures and lower molecular weights will require additional polymer to obtain an equivalent reduction of the resistance of fluidity. Obtain a polymer with a higher molecular weight polymerization in mass is not expected in view of the prior art. Polymerization in mass contains cases where the conversion of the monomer is not complete, and the occasions when solvent is added to change the reaction kinetics.

In the description and the formula of the present invention, the term "polymerization in bulk" means that the environment polymerization contains the main obrany conditions react all reactive olefins. The reaction medium under normal conditions contains at least 80% of the reactive olefins by weight, and under normal conditions, these olefins fully react, the resulting polymer is at least 80% by weight from the full contents of the reactor. Preferably, the olefins contained at least 90% by weight, most preferably 95% by weight from the reaction medium.

Discovered that even if you get a lower molecular weight by increasing the concentration of monomers in polymerization in solution, this result does not extend to very high concentrations of monomers, as by polymerization in mass. Polymerization in bulk of alphaolefins as 1-the mission is probably different kinetics. Found that ultra-high molecular weight gain at relatively high temperatures and at high monomer concentrations, in contrast to conventional methods for the production of substances that reduce resistance to fluidity. These consisting of polyolefin ultra-high molecular weight substances that reduce the resistance of flow is much larger (molecular weight) than the best available molecular weight, obtained by polymerization of the situation in the mass can be carried out, starting at a temperature of about room temperature and subjected to a thermal increase in the 60oF [15,6oC] upon receipt of the polymer with the molecular weight is too high for conventional measurement of the characteristic viscosity. In a preferred embodiment, the polymers of the present invention are used in the form of finely ground, essentially non-crystalline, having ultra-high molecular weight, soluble in hydrocarbon polyolefin suitable for improving the flow of hydrocarbons, including:

(a) combining at least one olefin containing from 2 to 40 carbon atoms capable of polymerization to form non-crystalline, having ultra-high molecular weight polyolefin, the polymerization catalyst in a thin impermeable organic polymer reaction shell, able essentially to prevent the penetration of oxygen and water in the reaction shell, and the shell shall be of such size and shape to facilitate high thermal conductivity from the contents of the reaction membrane to the external environment,

(b) polymerization of olefin to obtain a non-crystalline, having ultra-high molecular weight pagliaccio at a temperature suitable for non-crystalline, having ultra-high molecular weight polyolefin for a time sufficient to obtain such a polymer,

(C) cooling the obtained polymer and the shell to cryogenic temperature, and

(g) grinding the reaction membrane and the obtained polymer until finely ground state at cryogenic temperature below the glass transition temperature of the polymer.

The term "essentially" as used in the description and the formula of the present invention, means that the reaction shell is able to prevent sufficient oxygen and water to give a polymerization carried out, and that through the reaction membrane can in fact be insignificant amount of water and oxygen.

It is recognized that during polymerization in mass, the problem is to remove large heat of reaction, since reaching temperatures may rise by 500oF [260oC] to about 580oF [304,4oC]. As indicated in the issued Mack'y U.S. patent 4358572, the molecular weight of the final product is very sensitive to the temperature of the polymerization reaction. Changing the initial temperature of 10oF [5,6oC] can modify Horace, the material is ultra-high molecular weight can be obtained without cooling source material or cooling the reaction mixture to a low temperature. The reaction of the present invention optionally may begin at room temperature and the temperature rise is kept to approximately the 60oF [15,6oC], to obtain a polymer of ultra-high molecular weight, which is unexpected in view of the results obtained by polymerization in solution, where the source materials and reagents must be cooled to keep the temperature rise as low as possible level in order to maximize molecular weight. In systems with solutions temperature rise increases with the concentration of the reagent with a significant loss of molecular weight in the resulting polymer. However, at levels of about 100% of the monomer observed in polymerization in mass, although there is a greater temperature increase than in systems with solutions, polymers with lower molecular weight substantially does not occur, which is extremely surprising.

However, when polymerization in the mass it is necessary to control the increase of heat in order to get value out of fluidity. It is determined that there is a maximum size of the reaction shell, above which the heat of reaction can be removed faster than it is formed in the reaction. When the polymerization using the above olefins, the maximum thickness of the assessment is approximately 9 " [22.86 cm]. However, in order to keep the temperature low enough around the reaction vessel to obtain a polymer of ultra-high molecular weight, it is preferable to design the reaction shell as the smaller sizes. It was found that the reaction vessels must be of such form that the maximum surface area was exposed to the cooling medium in order to obtain ultra-high molecular weight.

The reaction shell

Estimated polymer bottles and bags, and found that they are effective vessels for the polymerization reaction, the reaction shells). However, the resulting polymer is very sticky to the walls of such reaction vessels, and therefore in the formation of substances that reduce the resistance of flow of the present invention the polymeric reaction vessels are crushed together with the final product. Of course, you can wire owiny snails or reactions in a single layer of polymer reactors (bottles or bags). Although it can be used all types of reactors described in a preferred embodiment of the present invention are the most effective devices used at the present time.

Polymerization in bulk according to the present invention can be carried out using any catalyst for polymerization of olefins, but it is preferable to conduct the reaction in the presence of catalysts of the Ziegler-Natta. It is well known that these catalysts are sensitive to oxygen and water. Accordingly, the reaction shell should be made of barrier polymers that are able to exclude air and water from the reaction mixture during the reaction. These barrier polymers are crystalline and insoluble in hydrocarbons, and reducing the resistance of the fluidity of non-crystalline polymers are soluble at ambient conditions, for example, crude oil and refined fuel. In such barrier polymers may occur crosslinking.

The present invention has been illustrated with the use of bottles and bags, containing from five to seven layers, with the contents waterproof polyolefin like polypropylene, polyethylene, polybutylene, binder and polyethylene, polypropylene or polybutylene. Most preferably used as an additional layer of polyethylene terephthalate for additional strengthening of the reactor at high temperatures. The ethylene vinyl alcohol copolymer is excellent oxygen barrier, but poor water barrier, then as polyethylene, polypropylene, polybutylene and the like are excellent water barriers, but allow the passage of oxygen. Since these barrier substances do not have a good mutual adhesion, polymer, designed for bonding to both layers, is placed between these substances. Examples of the binder polymer are jointly extrudable adhesive polymers sold under the trademark BYNEL" by the DuPont Company.

Ethylene vinyl alcohol, in addition, has a better oxygen barrier properties when it is dry, and the location of the layer of ethylene vinyl alcohol inside a water-resistant outer polyolefin substances improves its effectiveness as an oxygen barrier. The purpose polyolefin layer adjacent to the reaction mixture, is to protect the catalyst from the functional groups on the copolymer of ethylene vinyl alcohol.

Catalysts

Used catalysts of the Ziegler-Natta can be any of the catalysts described in this area. Particularly suitable substances are substances described in U.S. patents 4945142, 4358572, 4371455, 4415714, 4333123, 4493903 and 4493904. Of interest is the fact that it was discovered that, to some extent, the concentration of the catalyst, which is optimal depends on the size of the reaction vessel is larger vessels. Cooling may to some extent compensate for the differences in the concentrations of catalyst. In systems of polymerization in bulk catalysts are usually used in a concentration of 3500 of moles of monomer per mole of the halide of the transition metal in the catalyst, although the relationship may vary from just 500/1 to whole 10000/1 and more. The concentration of the catalyst affects the reaction rate and temperature, and molecular weight.

Test characteristic viscosity

When using such catalysts in polymerization in weight can be obtained by appropriate transformation of more than 95% of polymer by weight, the content of polymer in the reactor is at least 80%, preferably at least 90%, most preferably 95% by weight non-crystalline reducing the resistance to the flow of polymer to the total weight of the contents of the reactor. This result directly contradicts the known data about the polymerized in a solution of the polymer, reducing the resistance of fluidity. The molecular weight of the product is so high that the methods of measurement of the characteristic viscosity, used to measure existing products may not be used to measure the resulting polymer. Pala polymerized in the mass of the polymer tends to clog the capillary tube. Characteristic viscosity is used as an indirect measure of molecular weight, because of extremely high molecular weight of these substances makes unreliable the usual methods of determination of molecular weight. Accordingly, the characteristic strength shall be determined for the polymerized in bulk polymers using 4-bulb shear dilution viscometer Cannon Ubbelohde and revised the procedure for adaptation to extremely high molecular weight (0.05 g of polymer in 100 mm hexane solvent at 25oC). The characteristic viscosity are calculated for each of the last three flasks (flask with a high shear rate is not taken into account due to excessive shear dilution) and visualized on a graph as a function of the average shear rate. The graph is then used to obtain the characteristic viscosity at shear rate 300 s-1(procedure B). Typical values of the polymerized in bulk polymers ranges from 27 to 31 DL per gram.

As shown in the table. 1, the results of the characteristic viscosity is almost 1.5 times higher for procedure B. All samples were polymerized in a solution of the polyolefin.

AK is impossible to form a solution, which may be tested.

The polymers obtained according to the present invention is extremely effective against the polymerized in solution substances used in industry at the present time, containing the solvent, as shown in the examples.

The monomers

The present invention may be implemented with a variety of monomers and mixtures of monomers. You only need to present the monomers with molecular weights high enough (the content of carbon atoms higher than about 4) to obtain a polymer, which ultimately is essentially non-crystalline and soluble in the hydrocarbon. A significant number of monomers with a lower content of carbon atoms as ethylene or propylene, will ultimately produce a more crystalline product, which is less soluble in the current hydrocarbons. However, these substances may be present creating any advantages for certain decision problems in specific systems current hydrocarbons. Thus, for achieving high molecular weights and dissolution in the current hydrocarbon quite suitable from 5 to 50 mole percent of C2-C4-monomer.

The person who SUB> C6C8C10C12C14C16and things like that. A mixture of monomers apparently react at least as fast as the individual monomers, the resulting copolymers apparently have a lower degree of crystallinity than the homopolymers, due to the use of different monomers. The lack of crystallinity is extremely beneficial when dissolved substances in the current hydrocarbon, with the resulting increase in the reduction of the resistance of fluidity. Although mentioned monomers with an even number of carbon atoms because of their availability, there is no technical reason to avoid adding monomers with an odd number of carbon atoms, if any.

For reactions that are incomplete, removal of unreacted monomer is the best that can be done by vacuum drying and/or vacuum drying of deposition according to well known methods. However, it is preferable that the reaction mass is held essentially to completion and to the stage of drying to remove monomer and/or solvent was absent whenever possible, for economic reasons.

Reaction

In practice the kata is the period of time sufficient to increase the viscosity of the reagents, sufficient for suspension of the catalyst, and then placed in a cold environment to continue the reaction. Cold environment is usually maintained at a temperature of from about 0oF [ABOUT 17.8 MLNoC] up to approximately 80oF [26,7oC], giving the reaction can proceed at a relatively constant rate, with the removal of heat and the formation of polymers with ultra-high molecular weight. Can be obtained the conversion of more than 95 percent, although achieving such levels of transformation can take several days.

The suspension

At the completion of the polymerization in the weight of the entire reaction vessel can be reduced at cryogenic temperatures or for regulatory purposes can be cut, and the cut particles are then sieved at cryogenic temperatures in the cold mill. Easier and more economical to grind at cryogenic temperatures using liquid nitrogen to freeze the substance below the glass transition temperature of polymers. During this grinding at cryogenic temperatures is usually added to cover the agent, sometimes referred to as a separating agent to prevent adhesion Dre suitable covering agents are aluminum oxide, calcined clay, talc, carbon black, calcium stearate, magnesium stearate. The level of the covering agent can vary depending on the covering agent, but can reach up to approximately 30 to 35 percent by weight of the polymer. Can be used a mixture of covering agents, and they can be desirable to create a stable suspension.

After cryogenic grinding substance suspendered in water or in aqueous-alcoholic solution. Effective alcohols are alcohols which are soluble in water in the proportions used, as ethanol, propanol, isopropanol, butanol, Isobutanol and glycols as ethylene glycol and propylene glycol. Can also be used a mixture of alcohols. You only need to use the alcohols formed the continuous phase with water and any suitable zagustiteleyj agents and surface-active substances.

In order to obtain a satisfactory industrial product, it is necessary to obtain a stable suspension. Sustainability can be achieved by increasing the viscosity of the aqueous phase, but it is necessary that the viscosity of the final suspension was low enough to flow under gravity to the injection pump to enter the TV water polymers. Such water-soluble polymers represented by carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl diatomaceous earth and nstantaneous resin, but not only them.

Surfactants are typically used in the production of stable, but do not play a decisive role. Can be added surfactants, which reduce flocculation and increase the levels of solids.

Can be used a large number of surfactants or combinations of surfactants. Preferred surfactants are non-ionic surfactants and anionic surfactants.

If necessary, can be used biocides and anti-foam additives to prevent bacterial growth in suspension mixture and to prevent foaming during the formation and pumping pump the suspension. Typical, but not exhaustive examples of the antifoaming materials provide an Antifoam agent, a trademark of Dow Corning, Midland, Michigan, USA, and "Bubble Breaker products", trademark of Witco Chemical Company, division of organic matter.

Typical, but not ow Chemical Company", and Proxel BD" brand Corporation ICI Americas Inc.".

The present invention is described in more detail with reference to the following examples in which all parts and percentages are by weight, unless otherwise indicated. Examples are provided only to illustrate the present invention and not limit it.

Example 1

A suspension of the catalyst prepared by combining 0.40 g TiCI3AA in the solvent (the solvent is selected sufficient for mixing TiCI3AA) together with the promoter - debutalbum ether, as described by U.S. patent 4416714, Mack. The mixture is stirred for 30 minutes and add socializaton - aluminiuim. A suspension of the catalyst is then stirred for 30 minutes.

Layered barrier bottle of 40 ounces (1,18 l) fill 1000 g of mission and socializaton - aluminiumgie to purge with nitrogen and drying. The catalyst is introduced into the bottle to activate the polymerization reaction. Each bottle is shaken for 5 to 10 seconds, then placed in a rotating pipe to continue stirring for about 3 minutes. When the bottle comes out of the cylinder, the reaction is continued until the point where the mission thickens so that the catalyst is deposited. Batujaya environment and leave to settle for about two weeks to complete the polymerization.

Catalytic activation

TiCl3AA - 0.40 g (2.0 mmol)

suspended in approximately 40 ml solvent (solvent chosen sufficient for mixing TiCl3)

Disutility ether is 0.38 ml (2.2 mmol)

stirred for 30 minutes,

Diisobutyl aluminium chloride (25% in heptane) to 4.0 ml (4.0 mmol)

stirred for 30 minutes.

The reaction in bottles with a capacity of 40 ounces (1,18 l) for polymerization

The mission - 1000,0 grams

Diisobutyl aluminium chloride (25% in heptane) to 10.0 ml

The catalyst of the above composition to 4.0 ml

This catalyst is generally the conversion of about 95% for a polymer with a characteristic viscosity of 28 DL/g

Example 2

Prepare a second catalyst with the following composition and method of preparation:

TiCl3AA - 0.40 g (2.0 mmol)

suspended in approximately 40 ml solvent, such as hexane (solvent is selected sufficient for mixing TiCl3)

Disutility ether is 0.38 ml (2.2 mmol)

stirred for 30 minutes,

Diisobutyl aluminium chloride (25% in heptane) to 4.0 ml (4.0 mmol)

stirred for 20 minutes,

Polyethylene siloxane (PMMS) - 2.0 ml (2.0 mmol is as in example 1.

Example 3

It is possible to prepare the catalyst as in examples 1 or 2, using other esters in the composition of the catalytic activation. Disutility ether may be replaced by any of the following: benzyl ether, n-propyl ether, isopropyl ether, methyltetrazolyl ether and diethyl ether. Mack in the patent 4416714 experimentally showed that these promoters increase the characteristic viscosity of the obtained polymers with decreasing speed. In systems of polymerization in mass according to the present invention, the speed decreases slightly, and these substances will create effective polymers for reducing the resistance of fluidity.

Example 4

Repeat the preparation of the catalysts of examples 1 and 2 using the catalyst described in U.S. patent 4493903 using TiCl3AA 1.13, camphor-modified TiCl3. Instead ether take phosphate catalytic modifier. The resulting polymer has a characteristic viscosity comparable with that given in example 1, and is an effective substance that reduces the resistance of fluidity. Use following receipt of the catalyst:

TiCl3AA (Type 1.13) - 0.40 g (2.0 mmol)

suspended the project for TiCl3)

Triphenylphosphine - of 0.45 ml (0.3 mmol)

stirred for 30 minutes,

Diisobutyl aluminium chloride (25% in heptane) to 4.0 ml

stirred for 30 minutes.

Example 5

Using a process similar to that described in example 1, get the polymerized in the mass of the substance in numerous bottles. Cover shoot bottles and bottles cut to pieces in the middle about 1/2 inch (13 mm) in diameter for ease of manipulation. Then the pieces are crushed at the cryogenic temperature of liquid nitrogen together with the reaction vessels to get free of the current, finely ground powder in the presence of a separating agent with calcium stearate.

Crushed at cryogenic temperatures freely current powder and separating agent, allow to warm to ambient conditions in the ambient atmosphere. The heated particles are then suspended to form a suspension. The final suspension contains:

86 grams of the crushed powder (30% solids loaded in suspension),

1 gram means "Dowicil 75", a trademark of the Dow Chemical Company", selling it as a biocide,

5 grams "Antifoam 1410", trademark defoaming means based on silicone arbide"),

1.2 grams of hydroxyethyl cellulose.

The mixture is mixed at high speed for 20 minutes and get a steady, latokartano suspension.

In the following examples are valid data reduction resistance fluidity. These data were obtained from odnotumbovogo [2.54 cm] test circuit, and pipelines with different diameters. Taken into account the difference in resistance lowering turnover, and for reducing the resistance of a known substance, and for reducing the resistance of the substance of the present invention, between the data path and data industrial pipelines. The reason for this is that the difference in diameter of the pipeline affects the limit Virk'a set of theoretical reduction of the resistance of the yield that can be achieved. For completeness of the information specified article "Drag Reduction Fundamentals", by P. S. Virk, AIChE Journal, so 21, N 4, July, 1975, is hereby incorporated into this description by reference. This article gives a complete overview on the question of lowering the resistance of the yield stress in a turbulent flow, using dilute solutions of polymers. Strictly speaking, this article describes three modes for fully turbulent flow in the pipeline rubbable the resistance point, where the ratio of the friction factor to the Reynolds number is the same as for solvent.

(2) the Second mode is the reduction of the resistance of fluidity, in which the coefficient of friction depends on the nature of the solution of polymer concentration and polymer molecular weight.

(3) the Third mode is the asymptotic regime the maximum possible reduction of the resistance of flow is described as a universal rule that depends only on the Reynolds number and regardless of the properties and concentrations of additives.

Using the equations given in the above article, you can calculate the maximum possible reduction of the resistance of the flow for this situation, trends, using equation Virk'a and an iterative calculation. For illustration in these examples, listed below, odnoralova [2.54 cm] contour with diesel fuel at a flow rate of 10.5 gallons per minute [41,54 DM3/min] maximum asymptote reduce drag yield according to equation Virk'a is about 65 percent. In contrast, during the 18-inch [45.72 cm] pipe with a Reynolds number of approximately 200,000 asymptote minimize resistance Virk'a is 85 procamera 12,25 inches [31,12 cm] length of 29.3 miles [47154 m], the raw crude oil 28,4oAPI [American petroleum Institute] (Alaska North Slope or ANS and the 38oAPI West Texas Intermediate or WTI). Normal pipeline capacity ranges from 3600 to 4400 barrels [from 572,353 to 699,543 m3] per hour (national Department of standardization), depending on the crude oil and the ambient temperature. Described polymer slurry is pumped into the pipeline with constant levels of ppm (parts per million, a decrease of the creep resistance was monitored throughout all of 29.3 miles. The results are shown in table. 2.

Example 7

The same pipeline, which is described in example 6, is used in field testing of conventional, commercially available, reducing the resistance of the yield of polymer obtained by polymerization in solution and containing about 7.1% active polymer ("CDRM", trademark Corporation Conoco Speciality Products Inc."). A substance that reduces the resistance to flow, is placed in the pipeline at constant levels of ppm (parts per million and reduced resistance to yield control to the pipeline length of 29.3 miles. The results are shown in table. 3.

Although the polymerized in the mass of the polymer is cut, crushed at cryogenic temperatures and premesis and with the polymerized in the polymer solution, used in industry, the polymerized in bulk polymer has the best performance (Fig. 1). Regarding the content of the active polymer polymerized in the mass of the suspended substance that reduces the resistance of flow provides a greater reduction in the creep resistance than currently available industrial chemicals reduce the resistance of flow tested as the polymerized in a solution of the reaction products. To produce the solution of the polymers, which were dried (solvent removed), chopped at cryogenic temperatures, suspended and entered, you will see a big loss of efficiency reduce drag fluidity. The comparison is shown in Fig. 2.

In Fig. 1 and 2 "CDR102M" is a trademark of "Conoco Speciality Products Inc. ". BPDR means of the polymerized in the mass of a substance that reduces the resistance of fluidity. PPD means of precipitated and ground at cryogenic temperatures M. All graphs built on a comparative basis with the active polymer. The results show that even after they are subjected to mechanical shear, after mixing mixing and use in colder, more viscous crude non-industrial products. Product ("CDR102M"), deposited from solution, grinding at cryogenic temperatures and suspendiruemye in water in the same way as the polymerized in the mass of the polymer of the present invention shows significantly lower reduced resistance to creep under the conditions of Fig. 1 and 2.

Example 8

The circulating speed of 10.5 gallons [41,54 m3] at the moment in odnoralova [2.54 cm] streaming circuit of diesel oil number 2 is used to provide comparisons between "CDR102M", trademark Corporation Conoco Speciality Products, and polymerized in the mass of the polymer of the present invention, where "CDR102M is polymerized in a solution of a polyolefin with a concentration of about 10% polymer to dissolve and physically is in the form of a viscous gel (here referred to as gel). The compared samples are normal polydecene industrial production, with the following characteristic viscosity:

Method a: gel 15,6 DL/g in weight -- .

Method B: gel 23,2 DL/g, and the weight of 27.8 DL/g

Testing reduces the resistance of the fluidity of the gel polymerized in the mass of a substance that reduces the resistance of fluidity, pre ranim concentrations. Reduced resistance to fluidity is determined by measuring the pressure drop in 100 feet [30,48 m] from the place of discharge calculation formula

Reduced resistance to fluidity in %

where P is the difference between the initial pressure without substance that lowers resistance to stress (P), and pressure with a substance that reduces the resistance of fluidity.

In Fig. 2 shows that the deposition and grinding at cryogenic temperatures degrade the polymer. One grinding at cryogenic temperatures also affects the polymer, but not to such an extent. The effectiveness of lowering the resistance of the fluidity of the powder obtained by grinding at cryogenic temperatures polymerized in the polymer mass, compared to the unground polymerized in the mass of the polymer and with modern industrial gel in the table. 4.

Higher levels reduce drag for crushed at cryogenic temperatures of the powder compared with the same source material is the same for samples within the accuracy of the experiment.

On the data table. 4 concentration of active polymer to reduce the resistance of the fluidity of the target levels were interpositives by using correlat active polymer.

Polymerized in the mass of the polymer approaches the asymptote Virk'a short test interval. Differences between polymers explicitly hidden at high concentrations because of the approach to the asymptote Virk'a. This effect at high concentrations is true only in the short laboratory test circuits, where the worsening slightly.

In industrial pipelines asymptote Virk'a is never really achieved, because in normal turbulent flow at distances that has commercial value, there is a deterioration of the polymer. However, due to its higher molecular weight polymerized in the mass of polymer can be achieved in pipelines a higher level of reduction of the resistance of flow than is possible with polymers, polymerized in solution. Higher molecular weight polymerized in the mass of the substance that lowers the resistance of flow is manifested in a higher characteristic viscosities and higher levels of resistance reduce turnover.

Example 9

The trial was conducted in 26-inch [66.04 cm] pipeline transporting 26,000 barrels [4133,662 m3] per hour (national Department of standardization) of crude oil with it resistance to creep, with the schedule of assumed values of resistance reduce turnover. Estimated values are based on more than 15 years of experience and correlate with the properties of oil, the flow rate and pipe diameter. The active polymer was polydecene and polymerized in a solution of a substance that reduces the resistance of fluidity, and polymerized in the mass of the substance that reduces the resistance of flow polymerized in consumable containers, as described in the present invention, then cut, crushed at cryogenic temperatures in the presence of calcium stearate and suspended in water. The trial was conducted to demonstrate the feasibility of closing the intermediate pumping station using polymerized in the polymer mass. Polymerized in the polymer solution was "CDR 102M" sold by the Corporation Conoco Speciality Products.

It should be borne in mind that the polymerized in the mass of polymer produced significantly better performance (concentration of polymer and expected results) than polymerized in the polymer solution, which does not reach the anticipated levels (see tab. 6).

Example 10

The test described in example 9, vannoy) crude oil with low sulfur content. These results are reported under the same conditions as in example 9 (see tab. 7).

Relative concentrations of the polymer in parts per million, the data show a significant increase for polymerized in the polymer mass, even after grinding at cryogenic temperatures and suspension as described in the present invention.

Although both polymer exceeded the expected decrease in the resistance point, obviously, polymerized in the mass of polymer was better with regard to the content of the polymer. Although certain embodiments of the present invention, and details are given for illustration of the invention, specialists in the art will understand that various changes and modifications without deviating from the essence or scope of the invention.

1. The method of obtaining essentially non-crystalline, high molecular weight, soluble in hydrocarbon polyolefins suitable for improving the flow of hydrocarbons by pipelines, including polymerization to levels of at least 90% by weight of the total weight of the contents of the reactor at least one olefin containing from 2 to 40 carbon atoms, in the presence of a catalyst political viscosity (IV) at least 25 DL per gram, where the characteristic viscosity is determined by measuring through Tahkovuori shear dilution viscometer at 0.05 g of polymer per 100 ml of hexane solvent at 25oC and shear rate 300 s-1.

2. The method according to p. 1, in which the polymerization reaction mass is carried out in the reactor with the least amount of not more than nine inches (22.86 cm).

3. The method according to p. 2, in which the catalyst is a catalyst of Ziegler-Natta olefin polymerization.

4. The method according to p. 3, in which the catalyst and the reactants are in contact at a temperature of from 0oC to about 40oC.

5. The method of obtaining finely ground, essentially non-crystalline, having ultra-high molecular weight, soluble in hydrocarbon polyolefin, which is suitable for improving the flow of hydrocarbons in pipelines, including

a) combining at least one olefin containing 2 to 40 carbon atoms, with a catalyst for polymerization with essentially complete absence of oxygen and water impermeable reaction shell of organic polymers that are able to essentially prevent the passage of oxygen and water, and the shell has such a environment,

b) polymerization of olefin removal from reactive polyolefin in the reaction shell of heat sufficient to maintain the reaction at a temperature suitable for obtaining a non-crystalline, having ultra-high molecular weight polyolefin for a time sufficient to obtain such a polymer with at least 90% by weight of the total weight of the contents of the reactor,

C) cooling the obtained polymer and the shell to cryogenic temperatures,

d) grinding the reaction membrane and the obtained polymer until finely ground state at cryogenic temperature below the glass transition temperature reduces the resistance of the fluidity of the polymer.

6. The method according to p. 5, in which crushed at cryogenic temperature, the product (g) together with a water soluble polymeric thickener and suspenders substance selected from the group consisting of water and water-alcohol mixtures, under conditions of agitation to obtain a stable, not agglomerated suspensions.

7. Finely ground, essentially non-crystalline, having ultra-high molecular weight, soluble in hydrocarbons, reducing the resistance of the fluidity of the polyolefin containing Russiaa

a) combining at least one 1-olefin containing 2 to 40 carbon atoms, with a catalyst for polymerization with essentially complete absence of oxygen and water impermeable reaction shell of organic polymers that are able to essentially prevent the passage of oxygen and water, and the reaction shell is of such size and shape to remove the heat of reaction from the shell polymerization reactions in the external environment,

b) carrying out polymerization in the mass of the olefin to be removed from the polymerization reaction in the reaction shell of organic polymers of heat sufficient to maintain the polymerization reaction at a temperature suitable for obtaining a non-crystalline, having ultra-high molecular weight polyolefin, with the level of conversion of at least 90% of the content of the reactor from full weight of the contents of the reactor and for a time sufficient to obtain such a polymer,

C) cooling the obtained polymer and the reaction shell of organic polymers to cryogenic temperatures,

d) grinding the reaction shell of organic polymers, and obtained by polymerization in the mass of non-crystalline, having a height which is below the glass transition temperature reduces the resistance of the fluidity of the polymer.

8. Reducing the resistance of the fluidity of the polyolefin under item 7, in which the catalyst for polymerization is a polymerization catalyst of Ziegler-Natta and in which the organic polymer forming reaction membrane is a multilayer containing crystalline polyolefin on each side of the oxygen barrier polymer and in which the reaction temperature is maintained in the range from about -10oF (-23,3oC) up to about 150oF (65,6oC).

9. Reducing the resistance of the fluidity of the composition, including

a) having a high molecular weight, essentially non-crystalline polyolefin obtained by polymerization of at least one olefin containing 2 to 40 carbon atoms,

b) at least one crystalline, insoluble in hydrocarbons, aqueous barrier and/or oxygen barrier polymer, suspended in

in) suspendresume substance selected from the group consisting of water and water-alcohol mixtures containing suspendisse agent.

10. Composition under item 9, which is a water barrier polymer and which is the oxygen barrier polymer is a different polymers.

Priority points:

 

Same patents:

The invention relates to a catalyst for polymerization of olefins on the media containing the product of the interaction metallocene component (b) and alyuminiiorganicheskikh connection to media (A) obtained by reacting at least one alyuminiiorganicheskikh connection with dry media under inert conditions with subsequent hydrolysis of the resulting suspension by adding water

The invention relates to a method for producing alpha-olefins of high molecular weight polymers in solution by polymerization of ethylene or mixtures of ethylene and at least one higher olefin C3-C12in the presence of a coordination catalyst, consisting of two components: the first contains Ti, Mg, Al, and the second mixture alkylamine and alkoxyalkane, when heated to 180-320oC, and the formation of the first and second catalyst components and their mixing is carried out in the stream at a temperature lower than the 30oC

The invention relates to a spherical solid components of catalysts for the polymerization of olefins, comprising deposited on dihalogenide magnesium in an activated form of a compound of titanium, containing at least one link with a titanium halide and one OR group with the specified group OR is linked to an atom of titanium in such quantities that the molar ratio OR/Ti is greater than or equal to 0.5

The invention relates to a catalytic system comprising the transition metal compounds of groups IV-B of the Periodic table of elements and activator, as well as to the composition using this catalytic system for obtaining polyolefins, in particular polyethylene, polypropylene and copolymers of ethylene -- olefin

The invention relates to a method of producing catalyst type catalyst of the Ziegler-Natta having granular media

The invention relates to a catalytic system used for the stereospecific polymerization of alpha-olefins, in particular propylene and polypropylene obtained in the presence of catalytic systems

The invention relates to a catalyst on the carrier for the polymerization of olefins, the method of its production and the use of such catalyst in the polymerization of olefins

The invention relates to a method of gas-phase polymerization of olefins of the formula CH2= СНR, where R is hydrogen, alkyl or aryl with 1 to 8 carbon atoms

The invention relates to a method of gas-phase polymerization used for polymerization of the monomers in the reactor in the fluidized bed operating in condensing variation by using a metallocene catalyst, where the recirculated stream comprising liquid and gas phase, is introduced into the reactor such that the weight percentage of liquid in terms of the total weight of the recycle stream exceeds 2.0 wt.% this recirculating flow includes increasing the dew point of the component in excess of 2.0 mol.%

The invention relates to the technology of synthetic polymeric materials, in particular to a method of producing polyisobutylene or copolymers of isobutylene, and may find application in petrochemical industry

The invention relates to the technology of synthetic polymeric materials, in particular to a method of producing polyisobutylene or copolymers of isobutylene, and may find application in petrochemical industry

The invention relates to a spherical solid components of catalysts for the polymerization of olefins, comprising deposited on dihalogenide magnesium in an activated form of a compound of titanium, containing at least one link with a titanium halide and one OR group with the specified group OR is linked to an atom of titanium in such quantities that the molar ratio OR/Ti is greater than or equal to 0.5

The invention relates to a catalyst intended for use in polymerization by Ziegler and containing ORGANOMETALLIC compound and complex (transition metalloidal)

The invention relates to copolymers of ethylene and to methods of copolymerization, these methods use at least one homogeneous catalyst polymerization and at least one heterogeneous catalyst polymerization in separate reactors connected in series or in parallel

The invention relates to a method of gas-phase polymerization used for polymerization of the monomers in the reactor in the fluidized bed operating in condensing variation by using a metallocene catalyst, where the recirculated stream comprising liquid and gas phase, is introduced into the reactor such that the weight percentage of liquid in terms of the total weight of the recycle stream exceeds 2.0 wt.% this recirculating flow includes increasing the dew point of the component in excess of 2.0 mol.%
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