CN114515554A - Preparation method of poly alpha-olefin drag-reducing high-molecular polymer microcapsule - Google Patents
Preparation method of poly alpha-olefin drag-reducing high-molecular polymer microcapsule Download PDFInfo
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- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 100
- 239000003094 microcapsule Substances 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 17
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- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007764 o/w emulsion Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
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- 238000001914 filtration Methods 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229920006158 high molecular weight polymer Polymers 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
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- 239000003638 chemical reducing agent Substances 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
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- HHXYJYBYNZMZKX-UHFFFAOYSA-N 3,4:15,16-diepoxy-7-oxo-13(16),14-clerodadien-20,12-olide-(3alpha,4alpha)-form Natural products C12CCC3C4(C)CCCC(C)(C)C4CCC3(C)C1(C)CCC1C2(C)CCC1C(=C)C HHXYJYBYNZMZKX-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Abstract
The invention discloses a preparation method of a poly-alpha-olefin drag-reducing high-molecular polymer microcapsule, which comprises the following steps: cooling the poly-alpha-olefin to below the glass transition temperature, crushing to obtain blocky particles, mixing the blocky particles with a grinding aid, and grinding to obtain poly-alpha-olefin powder; dissolving a surfactant in deionized water, and adding polyalcohol to serve as a water phase; mixing poly alpha-olefin powder with isocyanate reaction monomer to obtain an oil phase; adding the oil phase into the water phase to form a suspension, stirring and dispersing uniformly, heating to 50-80 ℃ to form an oil-in-water emulsion, and keeping the temperature unchanged for reacting for 30-60 min; and cooling to room temperature after the reaction is finished, filtering and drying to obtain the poly alpha-olefin drag-reducing high molecular polymer microcapsule. The method has the advantages of mild reaction conditions, simple and safe operation process, low requirement on production equipment and easy realization of industrial production; the prepared microcapsule has stable drag reduction performance and can be stored at normal temperature, thereby reducing the transportation cost.
Description
Technical Field
The invention belongs to the technical field of petrochemical products, and particularly relates to a preparation method of a poly alpha-olefin drag-reducing high-molecular polymer microcapsule.
Background
As is well known, pipelines are one of five transportation modes (railway, road, waterway, aviation, pipeline) in the world, and most of oil and gas produced around the world are transported by pipelines. However, due to the unique physical and chemical properties of petroleum, such as high viscosity, narrow transportation temperature range, oil-water mixing, etc., the petroleum pipeline transportation has high requirements, and particularly, the high-pressure transportation of crude oil is easy to form a high-Reynolds-number turbulent phenomenon, consumes a large amount of transportation energy, and increases the transportation cost. To address the above problems, Drag Reducing Agents (DRAs) are now commonly used in petroleum pipeline transportation to eliminate or reduce the effects of turbulence during transportation.
At present, the drag reducer high polymer commonly used for petroleum pipeline transportation is poly-alpha-olefin, the drag reducer high polymer is a long chain high polymer, and is formed by randomly copolymerizing more than 3 long chain alpha-olefin monomers, and the molecular weight is more than 600 ten thousand. Because of strong van der waals force between groups in the poly-alpha-olefin and mutual entanglement of flexible long chains, the high polymer does not have crystallinity and is in a viscoelastic state at normal temperature, and the poly-alpha-olefin needs to be processed to be in a fluid state when being injected into a pipeline. The common treatment method comprises the following steps: firstly, poly alpha-olefin is crushed into powder with certain fineness under the condition of low temperature, and then the crushed poly alpha-olefin is dispersed into a dispersing agent added with an additive while the crushed poly alpha-olefin is cold, so that petroleum drag reduction polymer slurry is formed. However, due to the surface properties and physical characteristics of the drag reducing polymer particles, the resulting drag reducing agents are unstable and tend to agglomerate during storage and transportation, making them unusable, especially in order to reduce transportation costs, and it has been difficult to successfully attempt to produce drag reducing polymer particles that can be stored at ambient temperatures. Thus, modifying the surface properties of the drag reducing polymer particles is the fundamental approach to solving the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of a poly-alpha-olefin anti-drag high molecular polymer microcapsule, which has the advantages of mild reaction conditions, simple and safe operation process, low requirement on production equipment and easy realization of industrial production; the prepared microcapsule has stable drag reduction performance and can be stored at normal temperature, thereby reducing the transportation cost.
In order to realize the purpose, the invention adopts the technical scheme that: a preparation method of a poly alpha-olefin drag reduction high molecular polymer microcapsule comprises the following steps:
(1) cooling the poly-alpha-olefin to below the glass transition temperature, crushing to obtain blocky particles, mixing the blocky particles with a grinding aid, and grinding into poly-alpha-olefin powder;
(2) dissolving a surfactant in deionized water, and adding polyalcohol to serve as a water phase; mixing poly alpha-olefin powder with isocyanate reaction monomer to obtain an oil phase; the adding amount of the surfactant is 0.5 percent of the mass of the deionized water, the adding amount of the poly alpha-olefin powder is 10 percent of the mass of the deionized water, the adding total amount of the polyol and the isocyanate is 20 percent of the mass of the poly alpha-olefin, and the molar ratio of the isocyanate to the polyol is (1-1.5): 1;
(3) adding the oil phase into the water phase to form a suspension, uniformly stirring and dispersing, heating to 50-80 ℃ to form an oil-in-water emulsion, and keeping the temperature unchanged for reaction for 30-60 min; and cooling to room temperature after the reaction is finished, filtering and drying to obtain the poly alpha-olefin drag-reducing high molecular polymer microcapsule.
Preferably, in the step (1), the poly-alpha-olefin has a viscosity average molecular weight of 100 ten thousand or more, and the synthetic monomer is an alpha-olefin having 6 to 20 carbon atoms.
Preferably, in the step (2), the polyalcohol is glycerol or 1, 4-butanediol; the isocyanate is diphenylmethane-4, 4' diisocyanate or polymethylene polyphenyl isocyanate.
Preferably, in the step (2), the surfactant is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Preferably, in the step (1), the grinding aid is calcium stearate, and the mass of the grinding aid is 20-30% of that of the poly alpha-olefin.
Preferably, in the step (1), the particle size of the polyalphaolefin powder is 1000um or less.
Preferably, in step (1), the poly-alpha-olefin is cooled in a liquid nitrogen environment.
Preferably, in the step (3), the drying process is as follows: drying at 50 deg.C to constant weight, or naturally drying in air to constant weight.
The traditional interfacial polymerization method for preparing the microcapsule is to add an oil phase capsule core into a water phase to form an oil-in-water emulsion and then add an isocyanate reaction monomer. The invention adopts an interfacial polymerization method to prepare the poly-alpha-olefin microcapsules, the interfacial polymerization method is to dissolve two reaction monomers in two different solvents respectively, the two solvents are mutually incompatible, and when one solution is dispersed in the other solution, the polymerization reaction is carried out at the interface of the two solutions to form the microcapsules. The invention mixes the capsule core poly alpha-olefin and oil soluble isocyanate reaction monomer as oil phase to be added into water phase to form oil-in-water emulsion. The method specifically comprises the following steps: in the oil-in-water emulsion system, diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl isocyanate (PAPI) are oil-soluble and dispersed around oil-phase poly-alpha-olefin, polyol is dissolved in water phase, and during stirring, an isocyanate monomer and a polyol monomer are subjected to polymerization reaction on the surface of the poly-alpha-olefin, namely an oil-water interface according to a certain molar ratio to generate a layer of polyurethane film, so that the poly-alpha-olefin is coated to form a micro-capsule structure; the thickness of the capsule wall can be effectively controlled by controlling the monomer concentration, the amount of monomer adsorbed, the contact time, and the like.
Compared with the prior art, the invention has the following advantages:
(1) the surface property of the poly-alpha-olefin is changed by coating a layer of polyurethane film on the surface of the poly-alpha-olefin, so that the problem that the poly-alpha-olefin is easy to bond at normal temperature is solved, and the poly-alpha-olefin is stored at normal temperature and is easy to inject into a pipeline for use;
(2) the poly-alpha-olefin exists in the form of particles, the particles can be mutually dispersed, and the performance is stable; the method has the advantages of easily available raw materials, mild reaction conditions, simple and safe operation process, low requirement on production equipment and easy realization of industrial production;
(3) the poly alpha-olefin microcapsule prepared by the invention has better dispersion effect, less empty shells are formed in the preparation process, and the oil-soluble isocyanate reaction monomer is compactly attached to the surface of the poly alpha-olefin, so that the loss of the poly alpha-olefin is avoided. The method is favorable for the poly-alpha-olefin to be solid at normal temperature and to be changed into liquid oil drops after being heated and melted.
Drawings
FIG. 1 is a DSC plot of the polyalphaolefin used in the examples;
FIG. 2 is an SEM image of polyalphaolefin used in examples, wherein (a) is an SEM image of the overall microstructure of the polyalphaolefin and (b) is an SEM image of a partially enlarged microstructure;
FIG. 3 is a photograph of the macro-morphology of the poly-alpha-olefin used in the examples;
FIG. 4 is an infrared spectrum of a poly-alpha-olefin drag-reducing high molecular weight polymer microcapsule prepared in the first example;
FIG. 5 is an SEM image of a polyalphaolefin drag reducing polymeric microcapsule prepared according to the first example, wherein (a) is an SEM image of an overall micro-morphology and (b) is an SEM image of a partially enlarged micro-morphology;
FIG. 6 is a photo of the macro-morphology of the poly α -olefin drag reducing high molecular weight polymer microcapsule prepared in the first example;
FIG. 7 is an IR spectrum of a poly α olefin drag reducing high molecular weight polymer microcapsule prepared in example two;
FIG. 8 is an SEM image of a polyalphaolefin drag reducing polymeric microcapsule prepared in example two, wherein (a) is an SEM image of an overall micro-morphology and (b) is an SEM image of a partially enlarged micro-morphology;
FIG. 9 is a photo of the macro-morphology of the poly α -olefin drag reducing high molecular weight polymer microcapsules prepared in example two;
FIG. 10 is a thermogravimetric analysis of the bulk of the polyalphaolefin used in the examples and the polyalphaolefin drag reducing high molecular weight polymer microcapsules prepared in examples one and two.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Meanwhile, the experimental methods described in the following embodiments are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The viscosity average molecular weight of the polyalphaolefin used in the examples was 100 or more ten thousand (the synthetic monomer used in the experiment was an alpha-olefin having 8 carbon atoms), and the DSC curve thereof is shown in FIG. 1, from which it can be seen that the glass transition temperature thereof was-51.2 ℃; the microscopic and macroscopic morphologies of the block poly-alpha-olefin are respectively shown in fig. 2 and fig. 3, and it can be seen from the figures that the surface of the block poly-alpha-olefin is smooth, the particles are mutually adhered and can not be dispersed, and the block poly-alpha-olefin is a viscoelastic body at normal temperature, and the adhesion aggregation can not be dispersed.
Example one
A preparation method of a poly alpha-olefin drag reduction high molecular polymer microcapsule comprises the following steps:
(1) cooling 100g of poly alpha-olefin in a viscoelastic state in liquid nitrogen for 2h to below a glass transition temperature, crushing to obtain blocky particles, mixing the blocky particles with 30g of grinding aid calcium stearate, and screening out poly alpha-olefin powder with the particle size of less than 20 meshes (the particle size is 1000um) after grinding;
(2) adding 100mL of deionized water into a three-neck flask, adding 0.5g of sodium dodecyl sulfate, starting magnetic stirring, keeping the stirring speed at 500r/min, adding 0.4g of glycerol (4.3mmol), and dissolving to obtain a water phase; 10g of poly-alpha-olefin powder was mixed thoroughly with 1.6g (6.39mmol) of diphenylmethane-4, 4' -diisocyanate (MDI) in a 100ml beaker to give an oil phase; the molar ratio between isocyanate and polyol is 1.5: 1;
(3) adding the oil phase into the water phase to form a suspension, uniformly stirring and dispersing, heating to 50 ℃ to form an oil-in-water emulsion, keeping the stirring speed, keeping the temperature unchanged, reacting for 30min, naturally cooling to room temperature, performing suction filtration, and naturally drying the obtained solid in the air to constant weight to obtain the poly-alpha-olefin drag-reducing high-molecular polymer microcapsule.
The infrared spectrum of the poly alpha-olefin drag-reducing high molecular polymer microcapsule prepared in this example is shown in FIG. 4, and as can be seen from FIG. 4, it is 2300-1900cm-1Stretching vibration of double bond N ═ C ═ O does not occur in the range, which shows that-NCO in diphenylmethane diisocyanate (MDI) completely participates in the reaction; at 3650 and 3560cm-1No O-H stretching vibration absorption peak exists in the range, which indicates that-OH in the glycerol has completely reacted; at 3400cm-1And 720cm-1There are N-H absorption peak of extension vibration and absorption peak of bending vibration in surface, 1412cm-11306cm C-N stretching vibration absorption peak at-NHCOO--1C-O-C asymmetric stretching vibration absorption peak with-COOR, 1641cm-1And C ═ O stretching vibration characteristic absorption peak appears. In summary, the two reaction monomers, which are based on MDI and glycerol, have reacted completely and a polyurethane coating is formed.
The surface micro-morphology of the poly-alpha-olefin drag reduction high molecular polymer microcapsule prepared in this example is shown in fig. 5, and the left and right images are respectively the whole surface morphology and the local enlarged micro-morphology, and it can be seen from fig. 5 that the poly-alpha-olefin exists in the form of particles, and the particles can be mutually dispersed. Covering a layer of polyurethane coating material on the surface of the poly alpha-olefin to form a microcapsule structure; the macroscopic morphology is shown in fig. 6, and as can be seen from fig. 6, the obtained poly alpha-olefin microcapsules have a good dispersion effect, can be stored at normal temperature, and have uniform particle size and no adhesion phenomenon.
Example two
A preparation method of a poly alpha-olefin drag reduction high molecular polymer microcapsule comprises the following steps:
(1) cooling 100g of poly alpha-olefin in a viscoelastic state in liquid nitrogen for 2h to below a glass transition temperature, crushing to obtain blocky particles, mixing the blocky particles with 20g of grinding aid calcium stearate, and screening out poly alpha-olefin powder with the particle size of less than 20 meshes (the particle size is 1000um) after grinding;
(2) adding 100mL of deionized water into a three-neck flask, adding 0.5g of sodium dodecyl sulfate, starting magnetic stirring, keeping the stirring speed at 500r/min, adding 1.23g of 1, 4-butanediol (6.1mmol), and dissolving to obtain a water phase; 10g of poly-alpha-olefin powder was thoroughly mixed with 1.53g (6.12mmol) of polymethylene polyphenyl isocyanate (PAPI) in a 100ml beaker to give an oil phase; the molar ratio between isocyanate and polyol is 1: 1;
(3) adding the oil phase into the water phase to form a suspension, stirring and dispersing uniformly, heating to 80 ℃ to form an oil-in-water emulsion, keeping the stirring speed, keeping the temperature unchanged, reacting for 60min, naturally cooling to room temperature, performing suction filtration, and drying the obtained solid at 50 ℃ to constant weight to obtain the poly-alpha-olefin drag-reducing high-molecular polymer microcapsule.
The infrared spectrum of the poly alpha-olefin drag-reducing high molecular polymer microcapsule prepared in this example is shown in FIG. 7, and it can be seen from FIG. 7 that the infrared spectrum is at 2300-1900cm-1Stretching vibration of double bond N ═ C ═ O does not occur in the range, which shows that-NCO in polymethylene polyphenyl isocyanate (PAPI) is completely involved in the reaction; at 3392cm-1And 720cm-1Has an N-H stretching vibration absorption peak and an in-plane bending vibration absorption peak at 1410cm-11307cm, C-N stretching vibration absorption peak at-NHCOO--1C-O-C asymmetric stretching vibration absorption peak with-COOR, 1717cm-1The C ═ O stretching vibration characteristic absorption peak of-NHCOO-appears nearby, and the absorption intensity is large. In summary, the two reaction monomers, which are derived from PAPI and 1, 4-butanediol, have reacted completely and a polyurethane coating material is formed.
The surface micro-morphology of the poly-alpha-olefin drag reduction high molecular polymer microcapsule prepared in this example is shown in fig. 8, and the left and right images are respectively the whole surface morphology and the local enlarged micro-morphology, and it can be seen from fig. 8 that the poly-alpha-olefin exists in the form of particles, and the particles can be mutually dispersed. Covering a layer of polyurethane coating material on the surface of the poly alpha-olefin to form a microcapsule structure; the macroscopic morphology is shown in fig. 9, and as can be seen from fig. 9, the obtained poly-alpha-olefin microcapsules have good dispersion effect, can be stored at normal temperature, have uniform particle size, and do not have adhesion phenomenon.
Thermogravimetric analysis of the uncoated poly-alpha-olefin and the poly-alpha-olefin drag-reducing high molecular polymer microcapsules prepared in the first and second examples is shown in fig. 10, and it is apparent from the graph that the thermal decomposition temperature and the weight residue of the two coated poly-alpha-olefin microcapsules are higher than those of the uncoated poly-alpha-olefin, which indicates that the thermal stability of the poly-alpha-olefin is improved by the two microcapsules, wherein the poly-alpha-olefin microcapsule prepared in the first example has the highest thermal decomposition temperature and the best thermal stability.
Claims (8)
1. A preparation method of a poly alpha-olefin drag reduction high molecular polymer microcapsule is characterized by comprising the following steps:
(1) cooling the poly-alpha-olefin to below the glass transition temperature, crushing to obtain blocky particles, mixing the blocky particles with a grinding aid, and grinding to obtain poly-alpha-olefin powder;
(2) dissolving a surfactant in deionized water, and adding polyalcohol to serve as a water phase; mixing poly alpha-olefin powder with isocyanate reaction monomer to obtain an oil phase; the adding amount of the surfactant is 0.5 percent of the mass of the deionized water, the adding amount of the poly alpha-olefin powder is 10 percent of the mass of the deionized water, the adding total amount of the polyol and the isocyanate is 20 percent of the mass of the poly alpha-olefin, and the molar ratio of the isocyanate to the polyol is (1-1.5): 1;
(3) adding the oil phase into the water phase to form a suspension, uniformly stirring and dispersing, heating to 50-80 ℃ to form an oil-in-water emulsion, and keeping the temperature unchanged for reaction for 30-60 min; and cooling to room temperature after the reaction is finished, filtering and drying to obtain the poly alpha-olefin drag-reducing high molecular polymer microcapsule.
2. The method for preparing poly alpha-olefin drag-reducing high molecular polymer microcapsule according to claim 2, characterized in that in step (1), the viscosity average molecular weight of the poly alpha-olefin is more than 100 ten thousand, and the synthetic monomer is alpha-olefin with carbon number of 8.
3. The method for preparing the poly-alpha-olefin drag-reducing high molecular polymer microcapsule according to claim 1 or 2, characterized in that in the step (2), the polyalcohol is glycerol or 1, 4-butanediol; the isocyanate is diphenylmethane-4, 4' diisocyanate or polymethylene polyphenyl isocyanate.
4. The method for preparing poly alpha-olefin drag reducing high molecular polymer microcapsule according to claim 1 or 2, characterized in that in step (2), the surfactant is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
5. The preparation method of the polyalphaolefin drag reduction high molecular polymer microcapsule according to claim 1 or 2, wherein in the step (1), the grinding aid is calcium stearate, and the mass of the grinding aid is 20-30% of that of the polyalphaolefin.
6. The method for preparing poly-alpha-olefin drag reducing high molecular polymer microcapsules of claim 1 or 2, wherein in step (1), the particle size of poly-alpha-olefin powder is below 1000 um.
7. The method for preparing poly-alpha-olefin drag reducing high molecular polymer microcapsule according to claim 1 or 2, characterized in that in step (1), poly-alpha-olefin is cooled in liquid nitrogen environment.
8. The method for preparing the poly-alpha-olefin drag-reducing high molecular polymer microcapsule according to claim 1 or 2, wherein in the step (3), the drying process is as follows: drying at 50 deg.C to constant weight, or naturally drying in air to constant weight.
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Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3516941A (en) * | 1966-07-25 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsules and process of making |
| GB1375142A (en) * | 1972-03-06 | 1974-11-27 | ||
| US4409201A (en) * | 1980-05-31 | 1983-10-11 | Hoechst Aktiengesellschaft | Pressure-resistant microcapsules with a polyamide shell and a polyurethane-polyurea inner mass and process for their manufacture |
| EP0391556A1 (en) * | 1989-03-15 | 1990-10-10 | The Mead Corporation | Method for producing microcapsules |
| US6126872A (en) * | 1998-01-27 | 2000-10-03 | Baker Hughes Incorporated | Microencapsulated drag reducing agents |
| WO2001096011A1 (en) * | 2000-06-12 | 2001-12-20 | Mcmaster University | Encapsulation process using isocyanate moieties |
| US20030065054A1 (en) * | 2001-09-28 | 2003-04-03 | Smith Kenneth W. | Drag-reducing polymer suspensions |
| US20040195711A1 (en) * | 2003-03-26 | 2004-10-07 | Masaki Hayashi | Microcapsules and processes for producing the same |
| WO2007110383A1 (en) * | 2006-03-28 | 2007-10-04 | Basf Se | Encapsulation of lipophilic active substances |
| CN101418077A (en) * | 2007-10-25 | 2009-04-29 | 中国石油天然气股份有限公司 | Method for preparing polyolefin cladding oil pipe drag reduction polymer microcapsule powder |
| US20090209679A1 (en) * | 2008-02-14 | 2009-08-20 | Conocophillips Company | Core-shell flow improver |
| CN102453260A (en) * | 2010-10-28 | 2012-05-16 | 中国石油天然气股份有限公司 | Preparation method of alpha-olefin anti-drag polymer solid-phase storage-stable particle |
| US20130196071A1 (en) * | 2012-02-01 | 2013-08-01 | Nanyang Technological University | Microencapsulation of reactive diisocyanates and the application to self-healing anticorrosion coatings |
| CN106481986A (en) * | 2016-10-17 | 2017-03-08 | 西安石油大学 | Polyalphaolefin drag reducing agent microcapsule and preparation method thereof |
| US20170073610A1 (en) * | 2014-05-15 | 2017-03-16 | The George Washington University | Microencapsulation of chemical additives |
| US20170113200A1 (en) * | 2015-10-27 | 2017-04-27 | Encapsys,LLC | Encapsulation |
| CN107787351A (en) * | 2015-06-30 | 2018-03-09 | 陶氏环球技术有限责任公司 | Coating for controlled release |
| JP2019150783A (en) * | 2018-03-05 | 2019-09-12 | 富士フイルム株式会社 | Manufacturing method of microcapsule and manufacturing method of microcapsule-containing composition |
| US20200236928A1 (en) * | 2019-01-30 | 2020-07-30 | Monsanto Technology Llc | Microencapsulated acetamide herbicides |
| US20200268623A1 (en) * | 2017-11-15 | 2020-08-27 | Firmenich Sa | Microcapsules with improved deposition |
-
2022
- 2022-01-18 CN CN202210054978.0A patent/CN114515554A/en active Pending
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3516941A (en) * | 1966-07-25 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsules and process of making |
| GB1375142A (en) * | 1972-03-06 | 1974-11-27 | ||
| US3875074A (en) * | 1972-03-06 | 1975-04-01 | Champion Int Corp | Formation of microcapsules by interfacial cross-linking of emulsifier, and microcapsules produced thereby |
| US4409201A (en) * | 1980-05-31 | 1983-10-11 | Hoechst Aktiengesellschaft | Pressure-resistant microcapsules with a polyamide shell and a polyurethane-polyurea inner mass and process for their manufacture |
| EP0391556A1 (en) * | 1989-03-15 | 1990-10-10 | The Mead Corporation | Method for producing microcapsules |
| US6126872A (en) * | 1998-01-27 | 2000-10-03 | Baker Hughes Incorporated | Microencapsulated drag reducing agents |
| WO2001096011A1 (en) * | 2000-06-12 | 2001-12-20 | Mcmaster University | Encapsulation process using isocyanate moieties |
| US20030065054A1 (en) * | 2001-09-28 | 2003-04-03 | Smith Kenneth W. | Drag-reducing polymer suspensions |
| US20040195711A1 (en) * | 2003-03-26 | 2004-10-07 | Masaki Hayashi | Microcapsules and processes for producing the same |
| WO2007110383A1 (en) * | 2006-03-28 | 2007-10-04 | Basf Se | Encapsulation of lipophilic active substances |
| CN101418077A (en) * | 2007-10-25 | 2009-04-29 | 中国石油天然气股份有限公司 | Method for preparing polyolefin cladding oil pipe drag reduction polymer microcapsule powder |
| US20090209679A1 (en) * | 2008-02-14 | 2009-08-20 | Conocophillips Company | Core-shell flow improver |
| CN102453260A (en) * | 2010-10-28 | 2012-05-16 | 中国石油天然气股份有限公司 | Preparation method of alpha-olefin anti-drag polymer solid-phase storage-stable particle |
| US20130196071A1 (en) * | 2012-02-01 | 2013-08-01 | Nanyang Technological University | Microencapsulation of reactive diisocyanates and the application to self-healing anticorrosion coatings |
| US20170073610A1 (en) * | 2014-05-15 | 2017-03-16 | The George Washington University | Microencapsulation of chemical additives |
| CN107787351A (en) * | 2015-06-30 | 2018-03-09 | 陶氏环球技术有限责任公司 | Coating for controlled release |
| US20170113200A1 (en) * | 2015-10-27 | 2017-04-27 | Encapsys,LLC | Encapsulation |
| CN106481986A (en) * | 2016-10-17 | 2017-03-08 | 西安石油大学 | Polyalphaolefin drag reducing agent microcapsule and preparation method thereof |
| US20200268623A1 (en) * | 2017-11-15 | 2020-08-27 | Firmenich Sa | Microcapsules with improved deposition |
| JP2019150783A (en) * | 2018-03-05 | 2019-09-12 | 富士フイルム株式会社 | Manufacturing method of microcapsule and manufacturing method of microcapsule-containing composition |
| US20200236928A1 (en) * | 2019-01-30 | 2020-07-30 | Monsanto Technology Llc | Microencapsulated acetamide herbicides |
Non-Patent Citations (2)
| Title |
|---|
| BING LI 等: ""Preparation of microencapsulated α-olefin drag reducing polymer used in oil pipeline transportation"", 《PETROLEUM SCIENCE》 * |
| 董桂霖等: "聚氨酯材料包覆聚α-烯烃微胶囊的制备研究", 《材料工程》 * |
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