CN107090134B - A kind of preparation method of drag reducer slurries - Google Patents
A kind of preparation method of drag reducer slurries Download PDFInfo
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Abstract
The present invention relates to the compositions fields of high-molecular compound, disclose a kind of preparation method of drag reducer slurries, this method is included in silicone oil, slurry polymerization is carried out to 'alpha '-olefin monomers, obtains drag reducer polymer suspension, wherein, this method further include: be separated by solid-liquid separation obtained drag reducer polymer suspension, lower layer's silicone oil phase is isolated, upper layer solid elastomers are mutually crushed, and mixes, disperse with the lotion containing density adjuster, interleaving agent and surfactant and alcoholic solvent.After obtained drag reducer polymer suspension is separated by solid-liquid separation by method of the invention, the part silicone oil isolated can be back to use in polymerization reaction, on the one hand reduce the amount for the silicone oil that polymerization reaction uses, and on the other hand reduce the viscosity of polymer suspension.Upper layer solid elastomers containing a small amount of silicone oil are mutually crushed, and mixed with the lotion containing density adjuster, interleaving agent and surfactant and alcoholic solvent, the form dispersed prepares polymer slurries, the phase stability of system is further increased, product is made to be easier to be filled into pipeline.
Description
Technical field
The present invention relates to the compositions fields of high-molecular compound, more particularly, to a kind of preparation of drag reducer slurries
Method.
Background technique
Drag reducer is a kind of chemical agent for reducing fluid flow resistance, to the energy-saving of the realization defeated process of fluid hose and is mentioned
High pipeline throughput rate is of great significance.
For the drag reduction of crude oil and product transportation process, the polymer of drag-reduction effect most preferably alpha-olefin, alkene
It is 2-30, the preferably alpha-olefin of 8-14 containing carbon number.In the case where usage amount very little, the alpha-olefine polymers of long-chain
Reach higher drag-reduction effect, drag-reduction effect increases, usual alpha-olefines polymerization with the increase of alpha-olefine polymers molecular weight
The molecular weight for closing object will reach 106More than.
Alpha-olefine polymers can use single alkene homopolymerization, can also be copolymerized using different alkene.The polymerization side of early stage
The method that formula mostly uses polymerisation in solution, and the product of polymerisation in solution is directly applied to oil pipeline, but due to polymerizate sheet
The content of body large viscosity, polymer is lower, therefore, brings very big difficulty to transporting and using.The 1990s mid-term,
Bulk polymerization is developed.This method substantially increases the conversion ratio of monomer and the molecular weight of polymer, the property of drag reducer
It can be greatly enhanced, but what bulk polymerization obtained is rubber-like drag reducer polymer solid, it is necessary to pass through low-temperature grinding
And the in the mixed solvent of water or water and alcohol is distributed to together with other additives, slurries are made and are just easy to use, this process claims
For the post-processing of drag reducer.Low-temperature grinding not only consumes a large amount of liquid nitrogen, but also equipment needs the pre-cooling of long period, operates numerous
It is trivial, there is injury from low temperature to operator and has the danger for causing asphyxia.
Slurry polymerization is a kind of completely new drag reducer synthetic method, i.e., alpha-olefin is dispersed in the poor solvents such as silicone oil,
Carry out slurry polymerization under the action of catalyst, obtain being suspended in the drag reducing agent slurries in silicone oil, and may be directly applied to crude oil and
Transportation of product oil through pipeline drag reduction simplifies production technology to eliminate last handling process.Molecular weight can be obtained close to originally in slurry polymerization
The poly alpha olefin of body polymerization, while the post-processing link such as eliminate low-temperature grinding.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of new drag reducer slurries.
It was found by the inventors of the present invention that the drag reducer slurries directly obtained using slurry polymerization, on the one hand due to silicone oil sheet
The viscosity of body is larger, and (silicone oil viscosity is in 100mm2/ s or more), cause the viscosity of final slurries higher, is brought to pipeline filling tired
Difficulty, on the other hand, the price of silicone oil is higher, containing more silicone oil in slurries, increases the cost of drag reducing agent product.Therefore, it sends out
Bright people attempts to first pass through a part of silicone oil separation in the polymer suspension for obtaining polymerization, will then isolate containing few
The polymer of part silicone oil is crushed and is mixed with the lotion containing density adjuster, interleaving agent and surfactant and alcoholic solvent
Splitting or integrating dissipates, so as to obtain the better slurry system of phase stability after slurry polymerization.
To achieve the goals above, the present invention provides a kind of preparation method of drag reducer slurries, this method is included in silicon
In oil, slurry polymerization is carried out to 'alpha '-olefin monomers, obtains drag reducer polymer suspension, wherein this method further include: will obtain
Drag reducer polymer suspension be separated by solid-liquid separation, isolate lower layer's silicone oil phase, upper layer solid elastomers mutually crushed, and with
Contain the mixing of the lotion of density adjuster, interleaving agent and surfactant and alcoholic solvent, dispersion.
Using advantage of this approach is that, after obtained drag reducer polymer suspension is separated by solid-liquid separation, isolate
Part silicone oil can be back to use in polymerization reaction, on the one hand reduce the amount for the silicone oil that polymerization reaction uses, on the other hand drop
The low viscosity of polymer suspension.In addition, by mutually being crushed containing the upper layer solid elastomers of a small amount of silicone oil, and with contain density
The mixing of the lotion of regulator, interleaving agent and surfactant and alcoholic solvent, the form dispersed prepare polymer slurries, not only can
The viscosity of system is enough greatly reduced, also further increases the phase stability of system, product is made to be easier to be filled into pipeline.And
And the price of the alcoholic solvent due to containing in lotion is the half of silicone oil price, in the premise of same polymer content
Under, reduce the cost of slurry polymerization final products.
The present inventor first configures the lotion emulsified it has furthermore been found that under preferable case under strong stirring, then
The polymer of crushing is mixed with the lotion under the mixing dispersion condition more mitigated, is dispersed, can be further improved
The phase stability of the solid elastomers arrived, density adjuster, interleaving agent, the surfactant contained in the especially described lotion are
The group timesharing that the present invention preferably limits, can be better achieved goal of the invention of the invention.In addition, using the polymer that will be crushed
The form that particle mixes with lotion, disperses prepares polymer syrup liquid system, and it is preferably high boiling to prepare alcoholic solvent used by lotion
Point alcoholic solvent, the storing stability for the polymer slurries being prepared are more preferable.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the present invention, the preparation method of the drag reducer slurries is included in silicone oil, carries out slurry to 'alpha '-olefin monomers
Polymerization, obtains drag reducer polymer suspension, wherein this method further include: carries out obtained drag reducer polymer suspension
Be separated by solid-liquid separation, isolate lower layer's silicone oil phase, upper layer solid elastomers mutually crushed, and with containing density adjuster, interleaving agent and
The mixing of the lotion of surfactant and alcoholic solvent, dispersion.
According to the present invention, although if the upper layer solid elastomers phase particle of crushing is mixed with lotion, it is fully dispersed i.e.
Goal of the invention of the invention may be implemented, however, it is preferred in the case of, the weight of upper layer the solid elastomers phase particle and lotion of crushing
Amount is than being 1:1-3, further preferably 1:1.2-2.
According to the present invention, the condition that the upper layer solid elastomers phase particle of crushing is mixed with lotion is generally included into mixing
Temperature and mixed time, mixed temperature to the impact effect of the dispersion effect of the upper layer solid elastomers phase particle of crushing not
Obviously, it is generally the case that mixed temperature can be room temperature, as long as the mixed time guarantees the upper layer solid elastic of the crushing
Body phase particle is fully dispersed, for example, can be 10-60min, further preferred 20-40min.In order to mix, disperse more
To be abundant, the mixing carries out under stiring, and the revolving speed of stirring is 50-3000r/min, preferably 1000-2000r/min.Its
In, the room temperature is also referred to as room temperature or general temperature, can be generally defined as 15-30 DEG C, preferably 15-25 DEG C.
According to the present invention, the method that the upper layer solid elastomers containing a small amount of silicone oil mutually crush can be used into this field skill
Method well known to art personnel carries out, for example, can be smashed using cutter, under preferable case, and powder that the condition of crushing makes
The granular size of broken upper layer solid elastomers phase is preferably less than or equal to 200 μm less than or equal to 500 μm.If described
The particle of upper layer solid elastomers phase is spherical shape, and the granular size refers to the diameter of particle, if elliposoidal, the particle
Size refers to the long axis of particle, and if irregular property, the granular size refers to the maximum distance between particle both ends.
According to the present invention, the lotion is by mixing density adjuster, interleaving agent and surfactant and alcoholic solvent
It is made after conjunction, under preferable case, in order to further ensure the fully emulsified and homogeneity of lotion, and in order to realize more
Good phase stablizing effect, the preparation method of the lotion includes: under stiring, at room temperature, first by alcoholic solvent and Auto-regulating System of Density of Heavy Medium
Agent and surfactant mixing, then at 50-70 DEG C, obtained mixture is mixed with interleaving agent.Wherein, the room temperature
Also referred to as room temperature or general temperature, can be generally defined as 15-30 DEG C, preferably 15-25 DEG C.
The present invention is to by the incorporation time of alcoholic solvent and density adjuster and surfactant and the mixture that will be obtained
There is no particular limitation with the incorporation time of interleaving agent, and the above-mentioned time mixed twice is preferably greater than 5min, more preferably greater than
30min。
Further preferably, the revolving speed of the stirring is 1000-10000r/min, preferably 3000-8000r/min r/
min。
According to the present invention, in order to which goal of the invention of the invention is better achieved, by the upper layer solid elastomers phase of crushing
Stirring rate when grain is mixed with lotion is less than the stirring rate in the preparation of lotion.
According to the present invention, the density adjuster is selected from hexylene glycol, butyl, propylene glycol monomethyl ether and ethylene glycol first
One of ether is a variety of.
According to the present invention, based on the total weight of lotion, the dosage of the density adjuster is 5-30 weight %, preferably
For 10-20 weight %.
According to the present invention, the surfactant is selected from alkyl phenol polyoxyethylene ether and/or fatty alcohol polyoxyethylene ether.Its
In, the carbon atom number of alkyl is each independently 5-10 in the alkyl phenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether,
Preferably nonyl or octyl.The repetitive unit of oxy alkylene in the alkyl phenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether
Number, i.e. ,-(CH2CH2O)nMiddle n value is generally 5-30, preferably 10-20.The carbon of fatty alcohol in the fatty alcohol polyoxyethylene ether
Atomicity is 10-20, preferably 12-18.
According to the present invention, based on the total weight of lotion, the dosage of the surfactant is 0.5-2 weight %, excellent
It is selected as 0.9-2 weight %.
According to the present invention, the interleaving agent can be the various interleaving agents that can be used for drag reducer slurries, under preferable case, institute
It states interleaving agent and is selected from one of stearate, stearmide and ethylenebis kemanide S or a variety of.Wherein, the tristearin
Hydrochlorate can be various stearate commonly used in the art, one be preferably selected from calcium stearate, magnesium stearate and zinc stearate
Kind is a variety of.
According to the present invention, based on the total weight of lotion, the dosage of the interleaving agent is 5-15 weight %, preferably 6-
13 weight %.
According to the present invention, the alcoholic solvent can replace silicone oil play the role of dispersed polymeres, at the same by polymer with
Form containing the mixing of the lotion of density adjuster, interleaving agent and surfactant and alcoholic solvent, dispersion prepares polymer syrup
Liquid ensure that the polymer can be stablized in silicone oil, alcohol solvent system without split-phase.Wherein, the alcoholic solvent can be height
The alcoholic solvent of boiling point can specifically be selected from one of hexanol, enanthol, n-octyl alcohol, sec-octyl alcohol and isooctanol or a variety of.
According to the present invention, based on the total weight of lotion, the dosage of alcoholic solvent is 55-85 weight %, preferably 65-80
Weight %.
According to the present invention, the method for the separation of solid and liquid can be used and can be separated well known to a person skilled in the art various
The method of lower layer's silicon layer, for example, one of the methods of natural subsidence, filters pressing, centrifugation and vacuum filtration or a variety of.
According to the present invention, silicone oil is the polysiloxanes of liquid, usually linear structure, can be the poly- silicon oxygen of homopolymerization type
Alkane is also possible to the polysiloxanes of copoly type.It should be understood that silicone oil is primarily as reaction dissolvent in method of the invention
It is used with dispersing agent, those skilled in the art can select suitable silicone oil according to basic common sense.Preferable silicone oil is molecule
With a silicon oxygen chain, one of alkyl that the group being connected with silicon atom in chain is hydrogen and carbon atom number is 1-8 or a variety of,
It such as can be selected from dimethicone, diethyl silicone oil, diphenyl silicone oil, hydrogen methyl-silicone oil, hydrogen ethyl silicon oil, hydrogen phenyl silicone oil, first
One of base phenyl silicone oil and ethyl phenyl silicone oil are a variety of.Silicone oil 25 DEG C viscosity can -5000 centipoise of 5 centipoise it
Between, more preferably between -2000 centipoise of 10 centipoise.
According to the present invention, the 'alpha '-olefin monomers include all 'alpha '-olefin monomers that can be used for drag reducer.Preferable case
Under, at least one of the line style linear alpha-olefin that the 'alpha '-olefin monomers are 6-18 selected from carbon atom number, further preferred
In the case of, the 'alpha '-olefin monomers are selected from one of line style linear alpha-olefin that carbon atom number is 8-14 or a variety of.
In the present invention, the ratio of silicone oil and alpha-olefin can change in a wider scope.In order to obtain more preferably drag reduction
The mass ratio of effect, silicone oil and alpha-olefin is preferably 0.5-20:1, more preferably 1-3.5:1.
During carrying out slurry polymerization as dispersing agent using silicone oil, existing coordination catalysis body is still can be used in polymerization reaction
System, and completed under known polymerizing condition.Slurry polymerization system generally uses Ziegler-Natta catalyst system, can also be with
Using single-site catalyzed system, such as metallocene catalysis system and non-luxuriant catalyst system.Above-mentioned three kinds of catalyst systems, especially
Ziegler-Natta catalyst system, there is numerous descriptions in the prior art, and the present invention repeats no more this.The slurry polymerization
It carries out under anhydrous, anaerobic conditions.
For slurry polymerization field, controlling polymer particle size in slurry polymerization is basic common sense, and the present invention is to this
Also it repeats no more.The granularity of poly alpha olefin is not particularly limited in the present invention, as long as can finally form more stable suspension
?.Generally the granularity of poly alpha olefin is controlled at 500 microns hereinafter, control is in 200 microns or less better effects.
The drag reducer slurries that the method according to the invention is prepared can be directly used as drag reducer.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
The present invention will be described in detail by way of examples below.
Solid elastomers in the phase of upper layer are practical to refer to poly alpha olefin, the content of elastomer can by by upper layer mutually with pressing
Filter filters and removes silicone oil with the method that solvent washes repeatedly, and weighing calculates the content of elastomer.
In following embodiment, the 'alpha '-olefin monomers, silicone oil, density adjuster, interleaving agent and surfactant and alcohol
Solvent can be commercially available.
In following embodiment, state of the observation drag reducer slurries standing after 20 days.And it measures drag reducer slurries and stands 20 days
Serum viscosity (viscosity uses II Pro rotary viscosity measuring of Brook-Field DV-) afterwards, and measure drag reducer slurry obtained
The intrinsic viscosity and drag reducing efficiency of liquid sample:
The drag-reduction effect evaluation criterion of drag reducer is using SY/T6578-2003 " in oil pipe drag reduction agent drag-reduction effect room
Test method ", wherein drag reducing efficiency calculation formula are as follows:
△P0--- when not adding and subtracting resist, measure the pressure loss at straight pipe both ends
△PDR--- after drag reducer is added, measure the pressure loss at straight pipe both ends.
The measuring method of intrinsic viscosity are as follows: using Cannon Ubbelohbe (Ubbelohde) four arena shearing thin liquid viscosimeter and
For this ultra high molecular weight of adaptation, modified method (0.05g polymer/100ml hexane solvent, 25 DEG C) measures polymer
Intrinsic viscosity.The spy of each in three bulbs (since shear shinning effect is excessive, high-rate of shear bulb is disregarded) after calculating
Property viscosity, and the function construction as average shear rate, then, being obtained by the curve in shear rate is 300 seconds-1Under spy
Property viscosity.
In following embodiment and comparative example, the room temperature refers to 25 DEG C.
Embodiment 1
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Polymerization catalyst used is prepared as follows: by 2.0 grams of magnesium ethylate particulate carrier (particle diameter 40-50
Micron), toluene 30ml be added in reaction flask after being uniformly dispersed, cool the temperature to -10 DEG C, 10ml (6.0mol) TiCl be added4, stop
It stays 0.5 hour, is warming up to 80 DEG C of addition 0.6ml (0.39mol) diisobutyl phthalates, it is small to be warming up to 110 DEG C of reactions 2
When, it settles, filtering, toluene heat washes twice (each 20ml), secondary load titanium, and 5ml (3.0mmol) TiCl is added4With 30ml first
Benzene reacts 1 hour, settles, and filtering, hexane washs 4 times, obtains catalyst solid constituent after 72 DEG C of dryings.The matter of titanium in catalyst
Measuring percentage composition is 2.87%.
By the 1- octene 35g through molecular sieve refinement treatment (being purchased from ACROS Reagent Company) and through molecular sieve refinement treatment
Dimethicone 65g (being purchased from Beijing Ding Ye Trade Co., Ltd., 25 DEG C of viscosity is 300 centipoises) mixing, in anhydrous, anaerobic item
Under part, the cyclohexylmethyl dimethoxysilane of triisobutylaluminum toluene solution and 0.3mL1.0M that 2.5mL1.1M is added is molten
Liquid, in the case where -7 DEG C, pressure are 0.1MPa, after ten minutes, 70mg polymerization catalyst is added, in -7 DEG C, pressure 0.1MPa in stirring
Under, be stirred to react 6 hours, obtain poly alpha olefin/dimethicone slurries 100g, wherein containing polymer 30g (poly alpha olefin
Granularity is 200 microns or less).
Using the method for vacuum filtration by the silicone oil removal in the polymer slurries, the silicone oil of bottom precipitation is isolated
62.5g, in remaining 37.5g elastomer phase, polymer content accounts for 80 weight %, and is crushed with pulper, is crushed
The polymer 37.5g (polymer beads size be 200 μm of <) containing 20 weight % silicone oil.
Lotion preparation: at room temperature, sec-octyl alcohol 63.4g is taken, hexylene glycol 7.2g, surfactant NP101.4g mixing rise
Temperature is kept for 60-70 DEG C to 60 DEG C, and stearmide 8g, the mechanical stirring 30min under the revolving speed of 5000r/min is added, and cooling obtains
Latex A.
At room temperature, it takes above-mentioned 37.5g to contain the polymer of 20 weight % silicone oil, is added in above-mentioned 60g latex A,
Mechanical stirring 30min obtains polymer slurries A under the revolving speed of 2000r/min.
Storage stability and mobility and drag reducing efficiency are shown in Table 1.Reuse silicone oil and fresh silicone oil Contrast on effect are shown in Table 2.
Embodiment 2
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike:
Lotion preparation: at room temperature, isooctanol 63.7g is taken, propylene glycol monomethyl ether 7.2g, surfactant NP151.1g are mixed
It closes, is warming up to 60 DEG C, kept for 60-70 DEG C, stearmide 8g is added, mechanical stirring 30min, cold under the revolving speed of 5000r/min
But lotion B is obtained.
At room temperature, 37.5g obtained contains the polymer of 20 weight % silicone oil in Example 1, is added to above-mentioned 60g
In lotion B, mechanical stirring 30min obtains polymer slurries B under the revolving speed of 2000r/min.Storage stability and mobility
1 is shown in Table with drag reducing efficiency.
Embodiment 3
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike:
Lotion preparation: at room temperature, enanthol 64.08g is taken, butyl 7.2g, surfactant A EO91.08g are mixed
It closes, is warming up to 60 DEG C, kept for 60-70 DEG C, stearmide 8g is added, mechanical stirring 30min, cold under the revolving speed of 5000r/min
But lotion C is obtained.
At room temperature, 37.5g obtained contains the polymer of 20 weight % silicone oil in Example 1, is added to above-mentioned 60g
In lotion C, mechanical stirring 30min obtains polymer slurries C under the revolving speed of 2000r/min.Storage stability and mobility
1 is shown in Table with drag reducing efficiency.
Embodiment 4
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike:
At room temperature, 37.5g obtained contains the polymer of 20 weight % silicone oil in Example 1, is added to 37.5g cream
In liquid A, mechanical stirring 30min obtains polymer slurries E under the revolving speed of 2000r/min.Storage stability and mobility and
Drag reducing efficiency is shown in Table 1.
Embodiment 5
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike:
At room temperature, 37.5g obtained contains the polymer of 20 weight % silicone oil in Example 1, is added to 75g lotion
In A, mechanical stirring 30min obtains polymer slurries F under the revolving speed of 2000r/min.Storage stability and mobility and subtract
Resistance rate is shown in Table 1.
Embodiment 6
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike:
Lotion preparation: at room temperature, sec-octyl alcohol 52g, hexylene glycol 16.4g, surfactant NP101.6g mixing, heating are taken
It to 60 DEG C, is kept for 60-70 DEG C, stearmide 10g, the mechanical stirring 30min under the revolving speed of 8000r/min is added, cooling obtains
Lotion G.
At room temperature, it takes above-mentioned 37.5g to contain the polymer of 20 weight % silicone oil, is added in above-mentioned 60g lotion G,
Mechanical stirring 30min obtains polymer slurries G under the revolving speed of 1500r/min.Storage stability and mobility and drag reducing efficiency are shown in
Table 1.
Embodiment 7
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike:
Lotion preparation: at room temperature, sec-octyl alcohol 58.8g is taken, hexylene glycol 14.8g, surfactant NP100.8g mixing rise
Temperature is kept for 60-70 DEG C to 60 DEG C, and ethylenebis kemanide S 5.6g, the mechanical stirring under the revolving speed of 4000r/min is added
30min, cooling obtain lotion H.
At room temperature, it takes above-mentioned 37.5g to contain the polymer of 20 weight % silicone oil, is added in above-mentioned 60g lotion H,
Mechanical stirring 30min obtains polymer slurries H under the revolving speed of 2000r/min.Storage stability and mobility and drag reducing efficiency are shown in
Table 1.
Embodiment 8
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike, when carrying out slurry polymerization, using reuse
Silicone oil.Obtain polymer slurries I.Storage stability and mobility and drag reducing efficiency are shown in Table 1.Reuse silicone oil and fresh silicone oil effect
Comparison is shown in Table 2.
Embodiment 9
The present embodiment is used to illustrate the preparation of drag reducer slurries provided by the invention.
Drag reducer slurries are prepared according to the method for embodiment 1, unlike, speed of agitator when preparing lotion is 1000r/
Min, speed of agitator when preparing polymer slurries is 1000r/min, obtains polymer slurries K.Storage stability and flowing
Property and drag reducing efficiency are shown in Table 1.
Comparative example 1
Drag reducer slurries are prepared as described in Example 2, unlike, 37.5g obtained contains 20 weights in Example 1
The polymer of % silicone oil is measured, isooctanol 63.7g, propylene glycol monomethyl ether 7.2g, surfactant NP151.1g, stearmide is added
8g, the mechanical stirring 30min under the revolving speed of 5000r/min obtain polymer syrup liquid product D.Storage stability and mobility
1 is shown in Table with drag reducing efficiency.
Table 1
Table 2
| Sample | Intrinsic viscosity/(dL/g) | Drag reducing efficiency/% |
| A | 11.7 | 40.3 |
| I | 11.5 | 39.2 |
According to the data in table 1 it is found that compared with comparative example, the drag reducer slurries that are prepared using method of the invention
After placing 45 days, there is not solvent precipitation phenomenon, resistance reducing performance is preferable.From the data comparison result of embodiment 9 and embodiment 1
Known to, it is preferable that stirring rate when mixing the upper layer solid elastomers phase particle of crushing with lotion is less than the system in lotion
When stirring rate when standby, the serum viscosity of obtained drag reducer slurries is smaller, and resistance reducing performance is more preferable.And use comparative example 1
The drag reducer slurry viscosity that method obtains is larger, and slurries cannot stablize placement, thus illustrates, using method of the invention pass through by
After polymerizeing the part silicone oil separation in obtained slurries, and contain density adjuster, surfactant, alcoholic solvent and interleaving agent
Lotion mixing dispersion method preparation drag reducer slurries system stability it is good.In addition, can from the data in table 2
Out, the silicone oil after separation is back to the preparation of polymer again, the drag reducing efficiency and the fresh silicon of use of obtained drag reducer slurries
The situation of oil is suitable, thus greatly reduces production cost.
Claims (25)
1. a kind of preparation method of drag reducer slurries, this method comprises: slurry polymerization is carried out to 'alpha '-olefin monomers in silicone oil,
Obtain drag reducer polymer suspension, which is characterized in that this method further include: carry out obtained drag reducer polymer suspension
Be separated by solid-liquid separation, isolate lower layer's silicone oil phase, upper layer solid elastomers mutually crushed, and with containing density adjuster, interleaving agent and
The mixing of the lotion of surfactant and alcoholic solvent, dispersion.
2. according to the method described in claim 1, wherein, the upper layer solid elastomers phase particle of crushing and the weight ratio of lotion are
1:1-3。
3. according to the method described in claim 2, wherein, the upper layer solid elastomers phase particle of crushing and the weight ratio of lotion are
1:1.2-2。
4. method described in any one of -3 according to claim 1, wherein by the upper layer solid elastomers phase particle of crushing with
Lotion mixing condition include: mixing temperature be room temperature, the mixed time be 10-60min, it is described mixing under stiring into
Row, the revolving speed of stirring are 50-3000r/min.
5. the revolving speed of the stirring is according to the method described in claim 4, wherein, the mixed time is 20-40min
1000-2000r/min。
6. method described in any one of -3 according to claim 1, wherein the particle of the upper layer solid elastomers phase of crushing is big
Small is less than or equal to 500 μm.
7. according to the method described in claim 6, wherein, the granular size of the upper layer solid elastomers phase of crushing is to be less than or wait
In 200 μm.
8. according to the method described in claim 1, wherein, the preparation method of the lotion include: under stiring, at room temperature,
First alcoholic solvent is mixed with density adjuster and surfactant, then at 50-70 DEG C, by obtained mixture and interleaving agent
Mixing；The revolving speed of stirring is 1000-10000r/min.
9. according to the method described in claim 8, wherein, the revolving speed of the stirring is 3000-8000r/min.
10. according to the method described in claim 8, wherein, the density adjuster is selected from hexylene glycol, butyl, third
One of glycol methyl ether and ethylene glycol monomethyl ether are a variety of.
11. the method according to any one of claim 8-10, wherein described close based on the total weight of lotion
The dosage for spending regulator is 5-30 weight %.
12. according to the method for claim 11, wherein based on the total weight of lotion, the use of the density adjuster
Amount is 10-20 weight %.
13. according to the method described in claim 8, wherein, the surfactant is selected from alkyl phenol polyoxyethylene ether and/or rouge
Fat alcohol polyoxyethylene ether, wherein the carbon atom number of alkyl is 5-10, and the number of repeat unit of oxy alkylene is 5-30, the carbon of fatty alcohol
Atomicity is 10-20.
14. according to the method for claim 13, wherein the alkyl is nonyl or octyl, the repetition list of the oxy alkylene
First number is 10-20, and the carbon atom number of the fatty alcohol is 12-18.
15. the method according to any one of claim 8,9,13 and 14, wherein based on the total weight of lotion,
The dosage of the surfactant is 0.5-2 weight %.
16. according to the method for claim 15, wherein based on the total weight of lotion, the use of the surfactant
Amount is 0.9-2 weight %.
17. according to the method described in claim 8, wherein, the alcoholic solvent is selected from hexanol, enanthol, n-octyl alcohol, sec-octyl alcohol and different
One of octanol is a variety of.
18. the method according to claim 8 or 17, wherein based on the total weight of lotion, the dosage of alcoholic solvent is
55-85 weight %.
19. according to the method for claim 18, wherein based on the total weight of lotion, the dosage of alcoholic solvent is 65-80
Weight %.
20. according to the method described in claim 8, wherein, the interleaving agent is selected from calcium, the stearate of magnesium or zinc, stearoyl
One of amine and ethylenebis kemanide S are a variety of.
21. the method according to claim 8 or 20, wherein based on the total weight of lotion, the dosage of the interleaving agent
For 5-15 weight %.
22. according to the method for claim 21, wherein based on the total weight of lotion, the dosage of the interleaving agent is
6-13 weight %.
23. according to the method described in claim 1, wherein, the method for the separation of solid and liquid is natural subsidence or centrifugation.
24. according to the method described in claim 1, wherein, the mass ratio of silicone oil and 'alpha '-olefin monomers is 0.5-20:1.
25. according to the method for claim 24, wherein the mass ratio of silicone oil and 'alpha '-olefin monomers is 1-3.5:1.
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| CN116463053B (en) * | 2023-04-12 | 2024-07-02 | 西北工业大学 | Organosilicon high-molecular drag reducer coating, slow-release surface preparation method and application |
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