WO2007134550A1 - A method for preparing nylon microsphere and the same - Google Patents

A method for preparing nylon microsphere and the same Download PDF

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Publication number
WO2007134550A1
WO2007134550A1 PCT/CN2007/070038 CN2007070038W WO2007134550A1 WO 2007134550 A1 WO2007134550 A1 WO 2007134550A1 CN 2007070038 W CN2007070038 W CN 2007070038W WO 2007134550 A1 WO2007134550 A1 WO 2007134550A1
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Prior art keywords
radical
monomer
nylon
lactam
polymer
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PCT/CN2007/070038
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English (en)
French (fr)
Inventor
Aihua Pei
Tingxiu Xie
Guisheng Yang
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Shanghai Genius Advanced Material Co., Ltd.
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Priority to BRPI0711874-0A priority Critical patent/BRPI0711874B1/pt
Priority to KR1020087030159A priority patent/KR101408574B1/ko
Priority to JP2009511325A priority patent/JP5059104B2/ja
Priority to CA2652997A priority patent/CA2652997C/en
Priority to EP07721661.2A priority patent/EP2022809B1/en
Priority to AU2007252124A priority patent/AU2007252124B2/en
Publication of WO2007134550A1 publication Critical patent/WO2007134550A1/zh
Priority to US12/269,428 priority patent/US8048967B2/en

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    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/46—Post-polymerisation treatment
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • This invention relates to a method of making nylon microspheres and nylon microspheres. More specifically, the present invention relates to a process for preparing high molecular weight nylon microspheres of controlled particle size, and nylon microspheres having a high molecular weight and a controlled particle size. Background technique
  • Nylon has high strength, high wear resistance, high chemical resistance, good resistance to deformation and aging, and has a wide range of applications in engineering plastics.
  • the molecular weight of the nylon synthesized by the anionic ring-opening polymerization method is much higher than that of the nylon synthesized by the polycondensation method, and thus has more advantages in application.
  • Nylon granules have broad application prospects in coatings, rotational molding materials and extrusion molding materials.
  • Conventional preparation methods of nylon granules include: solution precipitation method, emulsion method, direct polymerization method and mechanical pulverization method (low temperature, slicing method and jet pulverization method).
  • the above preparation methods generally have the defects of complicated technology, high cost and energy consumption, irregular shape of the granular powder, large particle size and wide distribution range, which brings great difficulties to practical applications.
  • Patent WO03097228 proposes a process for the preparation of polyamide particles by interfacial polycondensation.
  • the above two preparation methods are complicated in process, require a large amount of solvent and dispersant, and are not suitable for industrialization.
  • Patent CN1624025 a method for blending polyamide pellets and water-soluble polymer, synthesizing polyamide as dispersed phase, water-soluble polymer as continuous phase blend, and then removing water-soluble polymer with water to obtain polyamide powder is proposed.
  • this method is advantageous for industrial production, the raw material used is polyamide powder, and the preparation of the polyamide powder requires a large amount of energy consumption. Summary of invention
  • Still another object of the present invention is to provide a nylon microsphere having a high molecular weight and a controlled particle size.
  • a method of preparing a nylon microsphere characterized in that The method includes the following steps (1), (2), and (3) or includes the following steps ( ⁇ ), (2), and (3):
  • the radical polymer is soluble in the lactam monomer; the radically polymerizable monomer is selected from those formed by a free radical polymer capable of dissolving in the One or more monomers of the lactam monomer.
  • the free-radically polymerizable monomer is one or more selected from the group consisting of acrylate, methacrylate, acrylamide, acrylonitrile, styrene, methyl styrene, vinyl Pyrrolidone, vinyl acetate, divinylbenzene, and derivatives thereof; the radical polymer is a homopolymer of one of the above monomers or a copolymer of two or more monomers.
  • the radically polymerizable monomer is used in an amount of 5 to 80% by weight, based on the radical polymerizable monomer and the lactam monomer.
  • the radical polymer is used in an amount of 5 to 80% by weight based on the total weight of the radical polymer and the lactam monomer.
  • the radically polymerizable monomer is used in an amount of 10 to 50% by weight, based on the total weight of the radical polymerizable monomer and the lactam monomer; in the step ( ⁇ ) The radical polymer is used in an amount of 10 to 50% by weight based on the total weight of the radical polymer and the lactam monomer.
  • the lactam monomer is one or more selected from the group consisting of C 4 -C 12 lactams; when the lactam monomer is one, the polyamide is the lactam single A homopolymer of a body; when the lactam monomers are two or more, the polyamide is a copolymer of these lactam monomers.
  • the free radical polymerization of step (1) is carried out in the range of from 60 to 150 °C.
  • the anionic ring opening polymerization of step (2) is carried out in the range of from 120 to 250 °C.
  • the anionic ring opening polymerization process of the lactam monomer is selected from the group consisting of a static casting process or a reactive extrusion process.
  • the radical initiator is one or more selected from the group consisting of an azo initiator, an organic peroxy initiator, and an oil-soluble oxidation-reduction. Initiating system; the free radical initiator is present in an amount of from 0.05 to 5% by weight based on the total weight of the free radical polymerizable monomer and the lactam monomer.
  • the initiator is selected from the group consisting of a lactam metal compound, an alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkali metal alkoxide or an alkali metal carbonate.
  • the activator is one or more selected from the group consisting of substituted or unsubstituted isocyanates, acetyl caprolactams, acid chlorides or acid anhydrides.
  • the initiator is one or more selected from the group consisting of sodium, sodium, potassium, lithium, NaH, LiH, NaOH, KOH or Na 2 CO 3 .
  • the particle size of the nylon microspheres is controlled by adjusting the ratio of the amount of free radical polymer to lactam monomer.
  • the free radical polymer removed by dissolution in step (3) is recovered, and the recovered radical polymer is mixed with the molten lactam monomer to provide the freedom described in the step ( ⁇ ).
  • the mixture of the base polymer and the lactam monomer continues to produce nylon microspheres by carrying out steps (2) and (3).
  • a nylon microsphere characterized in that the weight average molecular weight of the nylon is in the range of 10,000 to 300,000, and the particle diameter of the nylon microsphere is in the range of 0.1 to 500 ⁇ m.
  • the nylon has a weight average molecular weight in the range of 10,000 to 80,000 and the nylon microspheres have a particle diameter in the range of 0.5 to 100 ⁇ m.
  • the nylon has a weight average molecular weight in the range of 25,000 to 60,000, and the nylon microspheres have a particle diameter in the range of 1 to 50 ⁇ m.
  • the nylon is a monomer of the amide 4 -c 12 c is selected from a homopolymer or a copolymer of two or more monomers.
  • FIG. 1 is a scanning electron microscope (SEM) photograph of a nylon 6 microsphere obtained in Example 1 of the present invention, at a magnification of 100 times. Detailed description of the invention
  • a major feature of the present invention is the preparation of a polymer alloy of a free radical polymer/polyamide by continuous in-situ polymerization by free radical polymerization and anionic ring opening polymerization, respectively.
  • This system utilizes lactam as a solvent for the radical polymerizable monomer, and the radical polymerization monomer and the lactam monomer are separately polymerized in situ by continuous solution radical polymerization and anion ring-opening polymerization to obtain an alloy of the two.
  • many free radical polymers do not themselves dissolve in the lactam monomer, so the polymer alloy of the free radical polymer/polyamide cannot be obtained by in situ anionic ring opening polymerization.
  • the radical polymer/lactam monomer mixture obtained by radical polymerization is a transparent and stable system, and the presence of the radical polymer does not affect the anion of the lactam monomer. Ring opening polymerization.
  • Another major feature of the present invention is also that the key to the present invention is the use of spherical nylon particles having a substantially regular shape.
  • high levels of polymer are present in the form of a continuous phase, while low levels of polymer are present in the form of a dispersed phase.
  • Reverse rotation means a state in which a low content of a polymer is a continuous phase and a high content of a polymer is a dispersed phase.
  • polyamide (nylon;) is the structure of the dispersed phase.
  • the polyamide exists in a spherical state due to factors such as viscosity and interfacial tension, and the radical polymer exists between the ball of the polyamide phase and the gap between the balls.
  • the polyamide phase exists in a state of a regular spherical shape.
  • the nylon microspheres having a regular spherical shape can be obtained by dissolving the radical polymer in a suitable organic solvent, washing and drying.
  • the size of the nylon microspheres can be controlled by adjusting the ratio of the amount of free radical polymer to lactam monomer.
  • the ratio of the amount of the radical polymer to the lactam monomer is small, the size of the obtained nylon microspheres is large.
  • the ratio of the amount of the radical polymer to the lactam monomer increases, the size of the obtained nylon microsphere becomes small.
  • the concentration of the initiator and the activator (based on the lactam) is low, and the obtained nylon has a large molecular weight; and as the concentration of the initiator and the activator increases, the molecular weight of the obtained nylon becomes smaller. . Therefore, by adjusting the concentration of the initiator and the activator in the lactam polymerization process, the molecular weight of the nylon microspheres can be controlled.
  • a mixture of a radical polymer and a lactam monomer can be obtained by one of two methods: (1) dispersing a radically polymerizable monomer in a molten lactam In the monomer, a radical initiator is added to carry out radical polymerization of the radical polymerizable monomer to obtain a mixture of the radical polymer and the lactam monomer; or ( ⁇ ) to provide a radical polymer and a molten lactam single a mixture of bodies.
  • a mixture of a free radical polymer and a lactam monomer can be prepared in situ (for example, step (1) can also be formed by mixing an existing free radical polymer with a molten lactam monomer (for example, step ( ) .
  • the nylon microspheres are prepared in a continuous manner, wherein a mixture of the free radical polymer and the lactam monomer is first obtained by free radical polymerization as shown in step (1), and then the steps are carried out.
  • the radical polymerization in the step (1) is preferably carried out at a temperature of from 60 to 150 °C.
  • the polymerization time is usually from 4 to 72 hours, depending on the type and amount of the radical monomer.
  • the solvent used for dissolving and removing the radical polymer in the step (3) is a solvent capable of dissolving the radical polymer but not dissolving the nylon, such as but not limited to: acetone, tetrahydrofuran (THF), Water, toluene, xylene, methyl ethyl ketone, ethyl acetate, propionitrile or a mixed solvent thereof.
  • acetone tetrahydrofuran
  • Water toluene
  • xylene methyl ethyl ketone
  • ethyl acetate ethyl acetate
  • propionitrile or a mixed solvent thereof.
  • One skilled in the art can readily select a suitable solvent for dissolving and removing the free radical polymer to obtain nylon microspheres.
  • the method of the invention has the following main advantages:
  • the production process is simple and easy to operate, and the energy consumption and production cost are low;
  • Some of the reagents used can be recycled, for example, a solvent for dissolving and removing the radical polymer can be recycled, and the dissolved radical polymer can also be recycled;
  • the particle diameter of the nylon microsphere can be effectively controlled within the range of 0.1 to 500 ⁇ m.
  • effective control of the molecular weight of the nylon microspheres can be achieved, for example, the molecular weight can be controlled in the range of 10,000 to 300,000, preferably, the weight average molecular weight of the nylon is in the range of 10,000 to 80,000, and the particle diameter of the nylon microspheres is In the range of 0.5-100 microns. More preferably, the weight average molecular weight of the nylon is in the range of 25,000 to 60,000, and the particle diameter of the nylon microsphere is in the range of 1 to 50 ⁇ m.
  • nylon microspheres having a regular spherical shape can be obtained. More preferably, the particle size and molecular weight of the resulting nylon microspheres can be controlled by adjusting the content of the free radical polymer.
  • the nylon microspheres of the present invention can be used as a powder coating, a rotational molding, an extrusion molding raw material, and the like.
  • Methyl methacrylate ( ⁇ ) (25% by weight;) was mixed with molten caprolactam, stirred at 80 ° C with constant temperature, and 0.2% by weight of azobisisobutyronitrile (AIBN;) was added for radical polymerization for 24 hours.
  • AIBN azobisisobutyronitrile
  • the mixture system was warmed to 160-180 ° C and evacuated for 20 minutes to remove residual MMA monomer and water.
  • 4% by weight of sodium caprolactam and 0.4% by weight of 2,4-toluene diisocyanate (TDI) were added, mixed uniformly, and statically cast, and the mold temperature was controlled at 160-180 °C.
  • the obtained polymethyl methacrylate (PMMA) / monomer cast nylon 6 (MCPA6) polymer alloy was coarsely pulverized, and then ruthenium was dissolved in acetone, and dried by filtration to obtain a desired nylon 6 microsphere.
  • the molecular weight of the obtained nylon 6 microsphere gel chromatography (GPC) method was measured, and the volume average particle diameter was measured by a laser diffraction method.
  • the results are shown in Table 1.
  • a scanning electron microscope (SEM) photograph of the nylon 6 microspheres prepared in this example is shown in FIG. As can be seen from Fig. 1, spherical nylon particles having a regular shape can be obtained by the method of the present invention.
  • Example 2 A scanning electron microscope (SEM) photograph of the nylon 6 microspheres prepared in this example is shown in FIG. As can be seen from Fig. 1, spherical nylon particles having a regular shape can be obtained by the method of the present invention.
  • Methyl methacrylate (MMA) (20% by weight;) was mixed with molten octanolacide, stirred at 100 ° C with constant temperature, and 0.3% by weight of cumene hydroperoxide was added thereto, and radical polymerization was carried out for 20 hours.
  • the mixture system was maintained at 120-140 ° C and evacuated for 20 minutes to remove residual MMA monomer and water. 4% by weight of sodium caprolactam and 0.4% by weight of TDI were added, mixed uniformly, and statically cast, and the mold temperature was controlled at 120-160 °C.
  • the resulting polymethyl methacrylate (PMMA) / monomer cast nylon 8 (MCPA8) polymer alloy was coarsely crushed, then dissolved in acetone and filtered to dryness to obtain the desired nylon 8 microspheres.
  • the obtained nylon 8 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • the system was warmed to 130-150 ° C and evacuated for 20 minutes to remove residual styrene monomer and water.
  • PS polystyrene
  • MCPA6 / 8 monomer cast nylon 6 / 8
  • the obtained polymer alloy was dissolved in tetrahydrofuran (THF) to remove PS, and dried by filtration to obtain the desired nylon 6/8 microspheres.
  • the obtained nylon 6/8 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • Styrene (10% by weight;) was mixed with molten caprolactam, stirred at a constant temperature of 60 ° C, and 0.2 wt% of AIBN was added to initiate styrene radical polymerization, and polymerization was carried out for 24 hours.
  • the system was heated to 100-140 ° C and evacuated for 20 minutes to remove residual styrene monomer and water. Add 4 weights / ( ⁇ 11, 0.4 weight ° / ( ⁇ 01, evenly mixed, static casting, mold temperature control at 160 ⁇ 180 ° C.
  • Vinylpyrrolidone (10% by weight;) was mixed with molten butyrolactam, stirred at 80 ° C with constant temperature, and 0.3% by weight of AIBN was added to initiate radical polymerization, and radical polymerization was carried out for 24 hours.
  • the temperature of the system was raised to about 180 ° C and evacuated for 30 minutes to remove residual vinylpyrrolidone monomer and water.
  • the resulting polyvinylpyrrolidone (; PVP) / monomer cast nylon 4 (MCPA4) polymer alloy was coarsely crushed, then PVP was dissolved in water, and dried by filtration to obtain the desired nylon 4 microspheres.
  • the obtained nylon 4 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • PVP polyvinylpyrrolidone
  • MCPA4 monomer cast nylon 4
  • Methylstyrene (50% by weight;) was mixed with molten decanolacide, stirred at 100 ° C with constant temperature, and 0.3% by weight of AIBN was added to initiate methyl styrene radical polymerization, and polymerization was carried out for 24 hours.
  • the temperature of the system was maintained at 160-170 ° C and evacuated for 30 minutes to remove residual methyl styrene monomer and water.
  • the resulting polymethylstyrene (PMS)/monomer cast nylon 10 (MCPA10) polymer alloy was coarsely crushed, then PMS was dissolved in toluene, and dried by filtration to obtain the desired nylon 10 microspheres.
  • the obtained nylon 10 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • the temperature of the system was maintained at 150 ° C - 170 ° C and evacuated for 20 minutes to remove residual acrylonitrile monomer and water. Add 2% by weight of sodium caprolactam, 0.2 weight ° / ⁇ ⁇ 01, mix evenly, static casting, The mold temperature is controlled at 160-190 °C.
  • the resulting polyacrylonitrile (PAN) / monomer cast nylon 12 (MCPA12) polymer alloy was coarsely crushed, then PAN was dissolved in propionitrile and filtered to dryness to obtain the desired nylon 12 microspheres.
  • the obtained nylon 12 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • Polystyrene (PS) PS of Model 666D purchased from Yanshan Petrochemical Co., Ltd., having a molecular weight of 260,000 X 15% by weight;
  • molten caprolactam were mixed and stirred at 120 ° C with constant temperature.
  • the mixture system was heated to 160-180 ° C, 4% by weight of sodium caprolactam, 0.4% by weight of 2,4-toluene diisocyanate (TDI) was added, uniformly mixed, and statically cast, and the mold temperature was controlled at 160-180 °C.
  • TDI 2,4-toluene diisocyanate
  • the obtained polystyrene (PS) / monomer cast nylon 6 (MCPA6) polymer alloy was coarsely pulverized, and then PS was dissolved in toluene, and dried by filtration to obtain a desired nylon 6 microsphere.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • Methyl methacrylate (15% by weight;) and molten caprolactam were mixed, stirred at 90 ° C with constant temperature, and 0.4% by weight of dibenzoyl peroxide (BPO) was added to initiate radical polymerization, and the reaction was carried out for 24 hours.
  • BPO dibenzoyl peroxide
  • the system was warmed to 150-180 ° C and evacuated for 20 minutes to remove residual monomer and water.
  • the above system was introduced into a reaction extruder, and 4% by weight of sodium caprolactam was added, and 0.4 weight/( ⁇ 01) was subjected to reaction extrusion, and the temperature was controlled at 250 °C.
  • the obtained polymer alloy of polymethyl methacrylate (PMM A) / nylon 6 (P A6) was dissolved in acetone to dissolve PMMA, and dried to obtain a desired nylon 6 microsphere.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel permeation chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel permeation chromatography
  • Styrene (40% by weight;) and molten caprolactam were mixed, stirred at 80 ° C under constant temperature, and 0.3% by weight of AIBN was added to initiate styrene radical polymerization, and polymerization was carried out for 24 hours.
  • the system was warmed to 100-120 ° C and evacuated for 20 minutes to remove residual styrene monomer and water.
  • the above system was introduced into a reaction extruder, and 2% by weight of sodium caprolactam and 0.2% by weight of butyl 01 were added for reaction extrusion, and the reaction temperature was controlled at 250 °C.
  • the obtained polymer alloy of polystyrene (PS) / nylon 6 (PA6) was dissolved in THF with THF and dried to obtain the desired nylon 6 microspheres.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • Vinylpyrrolidone (25% by weight;) and molten caprolactam were mixed, stirred at 90 ° C under constant temperature, and 0.3% by weight of 8?0 was added to initiate radical polymerization, and polymerization was carried out for 24 hours.
  • the system was warmed to 120-140 ° C and evacuated for 20 minutes to remove residual vinylpyrrolidone monomer and water.
  • the above system was introduced into a reaction extruder, and 2% by weight of sodium caprolactam and 0.2% by weight of acetyl chloride were added to carry out reactive extrusion, and the reaction temperature was controlled at 230 °C.
  • polyvinylpyrrolidone (PVP)/nylon 6 (PA6) polymer alloy was dissolved in water with PVP and filtered to dryness to obtain the desired nylon 6 microspheres.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • Vinylpyrrolidone (40% by weight;) and molten octanolacide were mixed, stirred at 120 ° C with constant temperature, and 0.3% by weight of cumene hydroperoxide was added to carry out radical polymerization for 24 hours.
  • the system was heated to 120 ° C to 180 ° C and evacuated for 20 minutes to remove residual vinylpyrrolidone monomer and water.
  • the above system was introduced into a reaction extruder, and 2% by weight of sodium carbonate and 0.2% by weight of butyl 01 were added to carry out reactive extrusion, and the reaction temperature was controlled at 250 °C.
  • polyvinylpyrrolidone (PVP)/nylon 8 (PA8) polymer alloy was dissolved in water with PVP and filtered to dryness to obtain the desired nylon 8 microspheres.
  • the obtained nylon 8 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • the system was heated to 150 ° C to 180 ° C and evacuated for 20 minutes to leave monomer and water.
  • the above system was introduced into a reaction extruder, and 2% by weight of sodium caprolactam and 0.2% by weight of butyl 01 were added to carry out reactive extrusion, and the reaction temperature was controlled at 250 °C.
  • the resulting polyacrylamide (P AM)/nylon 12 (PA12) polymer alloy dissolved PVP in water and was filtered to dryness to give the desired nylon 12 microspheres.
  • the obtained nylon 12 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • PMMAX Polymethyl methacrylate (PMMAX was purchased from Shanghai Pen Chemical Co., Ltd., model 255, molecular weight of 122,000) (20% by weight;) and molten caprolactam were mixed and stirred at 80 ° C with constant temperature.
  • the mixture system was heated to 160-180 ° C, and 4% by weight of sodium caprolactam and 0.4% by weight of TDI were added to carry out reactive extrusion, and the reaction temperature was controlled at 250 °C.
  • the obtained polymer alloy of polymethyl methacrylate (PMMA) / nylon 6 (PA6) was coarsely pulverized, and then PMMA was dissolved in acetone, and dried by filtration to obtain a desired nylon 6 microsphere.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and the volume average particle diameter was measured by a laser diffraction method. The results are shown in Table 1.
  • GPC gel chromatography
  • the obtained polymer alloy was coarsely crushed, the styrene-methylstyrene copolymer was dissolved in water, and dried by filtration to obtain a desired nylon 6 microsphere.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.
  • Example 16 Styrene (5 wt%;) and molten caprolactam were mixed, stirred at 100 ° C under constant temperature, and 0.04 wt% AIBN was added to initiate radical polymerization to obtain a polystyrene/caprolactam solution, and 0.2 wt% was added to the mixed solution.
  • / ⁇ 011 and 2% by weight of 1101 (hexamethylene diisocyanate) were then polymerized in a mold, and the reaction temperature was controlled at 240 °C.
  • the obtained polymer alloy was coarsely crushed, polystyrene was dissolved in water, and dried by filtration to obtain a desired nylon 6 microsphere.
  • the obtained nylon 6 microspheres were measured for molecular weight by a gel chromatography (GPC) method, and their volume average particle diameters were measured by a laser diffraction method. The results are shown in Table 1.

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Description

一种尼龙微球的制备方法和尼龙微球 技术领域
本发明涉及制备尼龙微球的方法以及尼龙微球。 更具体地说， 本发明涉及 制备粒径可控的高分子量尼龙微球的方法， 以及具有高分子量和受控粒径的尼 龙微球。 背景技术
尼龙具有高强度、 高耐磨性、 高耐化学性及良好的抗变形性和抗老化性， 在工程塑料方面具有广泛的应用。 阴离子开环聚合法合成的尼龙的分子量与缩 聚法合成的尼龙的分子量相比要高得多， 因此在应用上具有更多优势。
尼龙颗粒在涂料、 滚塑成型原料和挤出成型原料等方面都有着广泛的应用 前景。 尼龙颗粒的传统制备方法包括： 溶液沉淀法， 乳液法， 直接聚合法和机 械粉碎法 (低温、 切片法和气流粉碎法)等。 但是上述制备方法都普遍存在技术 复杂、 成本和能耗高、 颗粒粉体形状不规则、 粒径大且分布范围宽等缺陷， 给 实际应用带来了很大的困难。
在专利 EP1636292中， 提出了利用乳液聚合的方法制备聚酰胺球形粒子。 专利 WO03097228提出了通过界面缩聚的方法制备聚酰胺粒子的方法。 但上述 两种制备方法工艺复杂， 需要大量的溶剂和分散剂， 不适合工业化。
专利 CN1624025中， 提出了利用聚酰胺粒料和水溶性聚合物共混， 合成聚 酰胺为分散相， 水溶性聚合物为连续相共混物， 然后用水除去水溶性聚合物得 到聚酰胺粉的方法。 这种方法虽然有利于工业化生产， 但其所用原料为聚酰胺 粉， 而聚酰胺粉的制备需要大量的能耗。 发明概述
本发明的一个目的是提供一种工艺简单、 能大规模工业化生产的制备尼龙 微球的方法。
本发明还有一个目的是提供一种具有高分子量和受控粒径的尼龙微球。 在本发明的第一方面， 提供了一种尼龙微球的制备方法， 其特征在于， 该方 法包括以下步骤 (1)、 （2)和 (3)或者包括以下步骤 (Γ)、 （2)和 (3):
(1) 将可自由基聚合的单体分散在熔融的内酰胺单体中， 加入自由基引发 剂， 进行可自由基聚合单体的自由基聚合， 得到自由基聚合物与内酰胺单体的 混合物； 或者
(1') 提供自由基聚合物与熔融的内酰胺单体的混合物； 以及
(2) 向除去了残留的可自由基聚合单体和水的步骤 (1)所得混合物或者向步 骤 (Γ)提供的混合物中加入用于内酰胺单体阴离子开环聚合的引发剂和活化剂， 进行内酰胺的阴离子开环聚合， 得到自由基聚合物 /聚酰胺的聚合物合金； 和
(3) 将步骤 (2)得到的聚合物合金中的自由基聚合物通过溶解除去， 得到尼 龙微球。
在一个优选的实施方案中， 所述自由基聚合物能溶解于所述内酰胺单体； 所述可自由基聚合的单体是选自那些其所形成的自由基聚合物能溶解于所述 内酰胺单体的一种或多种单体。
更优选是， 所述可自由基聚合的单体是选自以下单体的一种或多种： 丙烯 酸酯、 甲基丙烯酸酯、 丙烯酰胺、 丙烯腈、 苯乙烯、 甲基苯乙烯、 乙烯基吡咯 烷酮、 醋酸乙烯酯、 二乙烯基苯、 及其衍生物； 所述自由基聚合物是上述一种 单体的均聚物或者两种或多种单体的共聚物。
在一个优选的实施方案中， 在步骤 (1)中， 所述可自由基聚合的单体的用量 为 5-80重量％， 以所述可自由基聚合的单体和所述内酰胺单体的总重量计； 在 步骤 ( 中， 所述自由基聚合物的用量为 5-80 重量％， 以所述自由基聚合物和 所述内酰胺单体的总重量计。
更优选是， 所述可自由基聚合的单体的用量为 10-50重量％， 以所述可自 由基聚合的单体和所述内酰胺单体的总重量计； 在步骤 (Γ)中， 所述自由基聚合 物的用量为 10-50重量％， 以所述自由基聚合物和所述内酰胺单体的总重量计。
在一个优选的实施方案中， 所述内酰胺单体是选自 C4-C12内酰胺的一种或 多种； 当内酰胺单体为一种时， 所述聚酰胺是该内酰胺单体的均聚物； 当内酰 胺单体是两种或两种以上时， 所述聚酰胺是这些内酰胺单体的共聚物。
在一个优选的实施方案中，步骤 (1)的自由基聚合反应在 60-150°C的范围内 进行。 在一个优选的实施方案中， 步骤 (2)的阴离子开环聚合反应在 120-250°C的 范围内进行。
在一个优选的实施方案中， 所述内酰胺单体的阴离子开环聚合方法选自静 态浇铸法或反应挤出法。
在一个优选的实施方案中， 在步骤 (1)中， 所述自由基引发剂是选自以下的 一种或多种： 偶氮类引发剂、 有机过氧类引发剂和油溶性氧化-还原引发体系； 所述自由基引发剂的含量为 0.05-5重量％， 以所述可自由基聚合的单体和所述 内酰胺单体的总重量计。
在一个优选的实施方案中， 在步骤 (2)中， 所述引发剂是选自内酰胺金属化 合物、 碱金属、 碱金属氢化物、 碱金属氢氧化物、 碱金属醇盐或碱金属碳酸盐 的一种或多种；所述活化剂是选自取代或未取代的异氰酸酯、 乙酰基己内酰胺、 酰氯或酸酐中的一种或多种。
更优选是， 引发剂是选自己内酰胺钠、 钠、 钾、 锂、 NaH、 LiH、 NaOH、 KOH或 Na2CO3的一种或多种。
在一个优选的实施方案中， 通过调节自由基聚合物与内酰胺单体的用量比 值来控制尼龙微球的粒径尺寸。
在一个优选的实施方案中， 对步骤 (3)中通过溶解除去的自由基聚合物进行 回收， 回收得到的自由基聚合物与熔融的内酰胺单体混合， 提供步骤 (Γ)所述的 自由基聚合物和内酰胺单体的混合物，继续通过进行步骤 (2)和 (3)来制备尼龙微 球。
在本发明的第二方面， 提供了一种尼龙微球， 其特征在于， 尼龙的重均分子 量在 10,000-300,000的范围内， 尼龙微球的粒径在 0.1-500微米的范围内。
优选地， 尼龙的重均分子量在 10,000-80,000 的范围内， 尼龙微球的粒径在 0.5-100微米的范围内。
更优选地， 尼龙的重均分子量在 25,000-60,000的范围内， 尼龙微球的粒径在 1-50微米的范围内。
在一个优选的实施方案中， 所述尼龙是选自 c4-c12内酰胺的一种单体的均聚 物或者两种或多种单体的共聚物。 附图说明
图 1是本发明实施例 1制得的尼龙 6微球的扫描电子显微镜 (SEM)照片， 放大倍数为 100倍。 发明的详细说明
与现有技术相比， 本发明的一大特点是利用连续原位聚合， 分别通过自由 基聚合和阴离子开环聚合， 制备自由基聚合物 /聚酰胺的聚合物合金。 该体系利 用内酰胺作为自由基聚合单体的溶剂， 通过连续进行的溶液自由基聚合和阴离 子开环聚合， 使自由基聚合单体和内酰胺单体分别原位聚合而得到两者的合 金。 实际上， 不少自由基聚合物本身并不溶解于内酰胺单体中， 所以无法通过 原位阴离子开环聚合的方法得到自由基聚合物 /聚酰胺的聚合物合金。而通过本 发明的方法，经自由基聚合后得到的自由基聚合物 /内酰胺单体的混合物则是一 种透明稳定的体系， 并且自由基聚合物的存在并不影响内酰胺单体的阴离子开 环聚合。
本发明的另一大特点也是本发明的关键在于利用相反转制得形状规整的 球形尼龙微粒。 一般来说， 在两种聚合物的合金体系中， 高含量的聚合物以连 续相形式存在， 而低含量的聚合物以分散相形式存在。 "相反转" 是指低含量 的聚合物为连续相而高含量的聚合物为分散相的状态。 本发明的发明人经过大 量研究后发现，本发明的自由基聚合物 /聚酰胺的聚合物合金体系在自由基聚合 物的含量极低时就开始出现相反转， 从而形成自由基聚合物为连续相、 聚酰胺 (尼龙;)为分散相的结构。 在相反转过程中， 由于粘度、 界面张力等因素的影响， 聚酰胺以球形状态存在， 而自由基聚合物则存在于聚酰胺相的球与球的夹缝之 间。 在这种特殊的相结构中， 聚酰胺相以规整球形的状态存在。 通过将自由基 聚合物溶解于合适的有机溶剂中， 再进行洗涤、 干燥， 可以制得具有规整球形 的尼龙微球。
本发明还有一个特点是可以通过调节自由基聚合物与内酰胺单体的用量 比值来控制尼龙微球的尺寸。 当自由基聚合物与内酰胺单体的用量比值较小 时， 得到的尼龙微球的尺寸较大。 随着自由基聚合物与内酰胺单体的用量比值 增加， 所得尼龙微球的尺寸变小。 由此， 通过调节聚合物合金中各组分的比例 即可以得到不同粒径大小和分布的尼龙微球， 从而实现对尼龙微球尺寸的控 制。 另外， 在内酰胺聚合过程中， 引发剂和活化剂 （以内酰胺为基准） 的浓度 低， 所得到的尼龙分子量大； 而随着引发剂和活化剂的浓度增加， 所得到的尼 龙分子量变小。 因此通过调节内酰胺聚合过程中引发剂和活化剂的浓度， 能够 实现对尼龙微球分子量的调控。
在本发明的制备尼龙微球的方法中， 自由基聚合物与内酰胺单体的混合物 可以通过以下两种方式之一获得： （1)将可自由基聚合的单体分散在熔融的内 酰胺单体中， 加入自由基引发剂， 进行可自由基聚合单体的自由基聚合， 得到 自由基聚合物与内酰胺单体的混合物；或者 (Γ)提供自由基聚合物与熔融的内酰 胺单体的混合物。 也就是说， 自由基聚合物与内酰胺单体的混合物可以现场制 备得到 (例如步骤 (1 ， 也可以使用现成的自由基聚合物与熔融的内酰胺单体通 过混合形成 (；例如步骤 ( )。
在一个优选的实施方案中， 以连续方式制备尼龙微球， 其中， 先按步骤 (1) 所示通过自由基聚合制得自由基聚合物与内酰胺单体的混合物， 然后实施步骤
(2)和 (3)， 制得尼龙微球。 并且， 在步骤 (3)中被除去的溶解在溶剂中的自由基 聚合物可以回收使用，用于在接下来的生产工艺中按照步骤 ( 所示与熔融的内 酰胺单体直接混合， 获得自由基聚合物和内酰胺单体的混合物， 然后再实施步 骤 (2)和 (3)。
在本发明的制备方法中，步骤 (1)中的自由基聚合反应优选是在 60-150°C的 温度范围内进行。 聚合反应的时间通常为 4-72个小时， 随自由基单体的种类和 用量而异。
在本发明的制备方法中， 用于步骤 (3)中溶解除去自由基聚合物的溶剂是那 些能溶解自由基聚合物但不溶解尼龙的溶剂， 例如但不限于： 丙酮、 四氢呋喃 (THF), 水、 甲苯、 二甲苯、 丁酮、 醋酸乙酯、 丙腈或它们混合溶剂。 本领域 技术人员能够容易地选择合适的溶剂用于溶解除去自由基聚合物， 得到尼龙微 球。 本发明的方法主要具有以下优点：
(1) 生产工艺简单易操作， 能耗和生产成本低； (2) 所用的一些试剂可以回收利用， 例如用于溶解除去自由基聚合物的溶 剂可回收利用， 而且， 溶解的自由基聚合物也可以回收利用；
(3) 利用本发明的技术， 不仅能够得到具有规整球形的尼龙微球， 而且能 够实现对尼龙微球的球粒径的有效控制， 例如可以将粒径有效地控制在 0.1-500μηι 的范围内。 此外， 还能够实现对尼龙微球的分子量的有效控制， 例 如可以将分子量控制在 10,000-300,000 的范围， 优选地， 尼龙的重均分子量在 10,000-80,000的范围内， 尼龙微球的粒径在 0.5-100微米的范围内。 更优选地， 尼 龙的重均分子量在 25,000-60,000的范围内，尼龙微球的粒径在 1-50微米的范围内。
利用本发明的方法， 可以制得具有规整球形的尼龙微球。 更好的是， 可以 通过调节自由基聚合物的含量来控制所得尼龙微球的粒径和分子量。
本发明的尼龙微球能够用作粉末涂料、 滚塑成型、 挤出成型原料等。
下面结合具体实施例， 进一步阐述本发明。 应理解， 这些实施例仅用于说 明本发明而不用于限制本发明的范围。 下列实施例中未注明具体条件的实验方 法， 通常按照常规条件， 或按照制造厂商所建议的条件进行。 除非另外说明， 否则所有的份数为重量份， 所有的百分比为重量百分比。 实施例 1
甲基丙烯酸甲酯 (ΜΜΑ) (25 重量％；)和熔融的己内酰胺混合， 80°C恒温搅 拌， 加入 0.2重量％的偶氮二异丁腈 (AIBN；)， 进行自由基聚合反应 24小时。
将混合物体系升温至 160-180°C， 抽真空 20分钟以除残留的 MMA单体和 水。 加入 4重量％己内酰胺钠、 0.4重量％的 2,4-甲苯二异氰酸酯 (TDI)， 混合均 匀， 进行静态浇铸， 模温控制在 160-180°C。
对所得的聚甲基丙烯酸甲酯 (； PMMA)/单体浇铸尼龙 6(MCPA6)的聚合物合 金进行粗粉碎， 然后用丙酮溶解 ΡΜΜΑ, 过滤干燥， 得到所需的尼龙 6微球。 对所得的尼龙 6微球凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体 积平均粒径， 结果见表 1。本实施例制得的尼龙 6微球的扫描电子显微镜 (SEM) 照片如图 1所示。 由图 1可知， 通过本发明方法能够制得形状规整的球形尼龙 微粒。 实施例 2
甲基丙烯酸甲酯 (MMA) (20重量％；)和熔融的辛内酰胺混合， 100°C恒温搅 拌， 加入 0.3重量％的异丙苯过氧化氢， 进行自由基聚合反应 20小时。
将混合物体系保持在 120-140°C，抽真空 20分钟除残留的 MMA单体和水。 加入 4重量％己内酰胺钠、 0.4重量％的 TDI， 混合均匀， 进行静态浇铸， 模温 控制在 120-160 °C。
对所得聚甲基丙烯酸甲酯 (； PMMA)/单体浇铸尼龙 8(MCPA8)的聚合物合金 进行粗破碎， 然后用丙酮溶解 ΡΜΜΑ, 过滤干燥， 得到所需的尼龙 8微球。 对 所得的尼龙 8 微球用凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体 积平均粒径， 结果见表 1。 实施例 3
苯乙烯 (10 重量％；)和熔融己内酰胺和辛内酰胺 (；质量比 1: 1)混合， 120°C恒 温搅拌， 加入 0.2重量％异丙苯过氧化氢， 进行自由基聚合反应 20个小时。
将体系升温至 130-150°C， 抽真空 20分钟以除苯乙烯残留单体和水。 加入 4重量％己内酰胺钠和 0.4重量°/<^01， 混合均匀， 进行静态浇铸， 模温控制在 140〜180°C， 得到聚苯乙烯 (PS)/单体浇铸尼龙 6/8(MCPA6/8)的聚合物合金。
对所得聚合物合金用四氢呋喃 (THF)溶解掉 PS， 过滤干燥， 得到所需的尼 龙 6/8微球。 对所得的尼龙 6/8微球用凝胶色谱 (； GPC)法测定其分子量， 用激光 衍射法测定其体积平均粒径， 结果见表 1。 实施例 4
苯乙烯 (10重量％；)和熔融的己内酰胺混合， 60°C恒温搅拌， 加入 0.2重量 %AIBN引发苯乙烯自由基聚合， 聚合反应进行 24个小时。
将体系升温至 100-140°C， 抽真空 20分钟以除去苯乙烯残留单体和水。 加 入 4重量°/(^ 11、 0.4重量°/(^01， 混合均匀， 进行静态浇铸， 模温控制在 160〜 180°C。
所得的聚苯乙烯 (PS)/单体浇铸尼龙 6 (MCPA6)的聚合物合金用 THF溶解 掉 PS，过滤干燥，得到所需的尼龙 6微球。对所得的尼龙 6微球用凝胶色谱 (GPC) 法测定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 5
乙烯基吡咯烷酮 (10 重量％；)和熔融的丁内酰胺混合， 80°C恒温搅拌， 加入 0.3重量％AIBN引发自由基聚合， 自由基聚合反应进行 24个小时。
将体系温度升高至 180°C左右，抽真空 30分钟以除去残留乙烯基吡咯烷酮 单体和水。 加入 2重量％10)11、 0.2重量°/(^01， 混合均匀， 进行浇铸， 模温控 制在 140〜160°C。
所得聚乙烯基吡咯烷酮 (； PVP)/单体浇铸尼龙 4(MCPA4)的聚合物合金进行 粗破碎， 然后， 用水溶解掉 PVP， 过滤干燥， 得到所需的尼龙 4微球。 对所得 的尼龙 4微球用凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体积平 均粒径， 结果见表 1。 实施例 6
甲基苯乙烯 (50重量％；)和熔融的癸内酰胺混合， 100°C恒温搅拌， 加入 0.3 重量％AIBN引发甲基苯乙烯自由基聚合， 聚合反应进行 24个小时。
将体系的温度保持在 160-170°C， 抽真空 30分钟以除去甲基苯乙烯残留单 体和水。加入 2 重量％己内酰胺钠、 0.2 重量°/<^01， 混合均匀， 进行静态浇铸， 模温控制在 160-180°C。
所得聚甲基苯乙烯 (PMS)/单体浇铸尼龙 10(MCPA10)的聚合物合金进行粗 破碎， 然后， 用甲苯溶解掉 PMS， 过滤干燥， 得到所需的尼龙 10微球。 对所 得的尼龙 10微球用凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体积 平均粒径， 结果见表 1。 实施例 7
丙烯腈 (35重量％；)和熔融的十二内酰胺混合， 150°C恒温搅拌， 加入 0.5重 量％过氧化二异丙苯引发剂， 进行自由基聚合反应 12个小时。
将体系的温度保持在 150°C -170°C， 抽真空 20分钟以除去丙烯腈残留单体 和水。 加入 2重量％己内酰胺钠、 0.2重量°/<^01， 混合均匀， 进行静态浇铸， 模温控制在 160-190°C。
所得聚丙烯腈 (PAN)/单体浇铸尼龙 12(MCPA12)的聚合物合金进行粗破 碎， 然后， 用丙腈溶解掉 PAN, 过滤干燥， 得到所需的尼龙 12微球。 对所得 的尼龙 12微球用凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体积平 均粒径， 结果见表 1。 实施例 8
将聚苯乙烯 (PS)(购自燕山石化公司的型号为 666D 的 PS, 分子量为 26 万 X15重量％；)和熔融的己内酰胺混合， 120°C恒温搅拌。
将混合物体系升温至 160-180°C， 加入 4重量％己内酰胺钠、 0.4重量％的 2,4-甲苯二异氰酸酯 (TDI)， 混合均匀， 进行静态浇铸， 模温控制在 160-180°C。
对所得的聚苯乙烯 (PS)/单体浇铸尼龙 6(MCPA6)的聚合物合金进行粗粉 碎， 然后用甲苯溶解 PS， 过滤干燥， 得到所需的尼龙 6微球。 对所得的尼龙 6 微球用凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 9
将甲基丙烯酸甲酯 (15 重量％；)和熔融的己内酰胺混合， 90°C恒温搅拌， 加 入 0.4重量％过氧化二苯甲酰 (； BPO)引发自由基聚合， 反应进行 24个小时。
将体系升温至 150-180°C， 抽真空 20分钟以除去残留单体和水。 上述体系 引入反应挤出机中，加入 4 重量％己内酰胺钠、 0.4 重量°/(^01，进行反应挤出， 温度控制在 250°C。
对所得的聚甲基丙烯酸甲酯 (PMM A)/尼龙 6(P A6)的聚合物合金用丙酮溶 解掉 PMMA， 进行干燥， 得到所需的尼龙 6微球。 对所得的尼龙 6微球用凝胶 色谱 (GPC)法测定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 10
将苯乙烯 (40 重量％；)和熔融的己内酰胺混合， 80°C恒温搅拌， 加入 0.3重 量％AIBN以引发苯乙烯自由基聚合， 聚合反应进行 24个小时。 将体系升温至 100-120°C， 抽真空 20分钟以除去苯乙烯残留单体和水。 上 述体系引入反应挤出机中， 加入 2 重量％己内酰胺钠、 0.2重量％丁01， 进行反 应挤出， 反应温度控制在 250°C。
对所得的聚苯乙烯 (PS)/尼龙 6(PA6)的聚合物合金用 THF溶解掉 PS， 进行 干燥， 得到所需的尼龙 6微球。 对所得的尼龙 6微球用凝胶色谱 (GPC)法测定 其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 11
将乙烯基吡咯烷酮 （25重量％；)和熔融的己内酰胺混合， 90°C恒温搅拌， 加 入 0.3重量％8?0以引发自由基聚合， 聚合反应进行 24个小时。
将体系升温至 120-140°C， 抽真空 20分钟以除去残留乙烯基吡咯烷酮单体 和水。 上述体系引入反应挤出机中， 加入 2 重量％己内酰胺钠、 0.2重量％乙酰 氯， 进行反应挤出， 反应温度控制在 230°C。
所得聚乙烯基吡咯烷酮 (； PVP)/尼龙 6(PA6)的聚合物合金用水溶解掉 PVP， 过滤干燥， 得到所需的尼龙 6微球。 对所得的尼龙 6微球用凝胶色谱 (GPC)法 测定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 12
将乙烯基吡咯烷酮 （40 重量％；)和熔融的辛内酰胺混合， 120°C恒温搅拌， 加入 0.3重量％异丙苯过氧化氢， 进行自由基聚合反应 24个小时。
将体系升温至 120°C〜180°C， 抽真空 20分钟以除去残留乙烯基吡咯烷酮 单体和水。上述体系引入反应挤出机中， 加入 2 重量％碳酸钠、 0.2重量％丁01， 进行反应挤出， 反应温度控制在 250°C。
所得聚乙烯基吡咯烷酮 (； PVP)/尼龙 8(PA8)的聚合物合金用水溶解掉 PVP， 过滤干燥， 得到所需的尼龙 8微球。 对所得的尼龙 8微球用凝胶色谱 (GPC)法 测定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 13
将丙烯酰胺 (80 重量％；)和熔融的十二内酰胺混合， 150°C恒温搅拌， 加入 0.2重量％的氢过氧化物进行自由基聚合反应 6个小时。
将体系升温至 150°C〜180°C， 抽真空 20分钟以残留单体和水。 上述体系 引入反应挤出机中， 加入 2重量％己内酰胺钠、 0.2重量％丁01， 进行反应挤出， 反应温度控制在 250°C。
所得聚丙烯酰胺 (P AM)/尼龙 12(PA12)的聚合物合金用水溶解掉 PVP，过滤 干燥， 得到所需的尼龙 12微球。 对所得的尼龙 12微球用凝胶色谱 (GPC)法测 定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 14
将聚甲基丙烯酸甲酯 (PMMAX购自上海笔化公司的型号为 255的 ΡΜΜΑ, 分子量为 12.2万 )(20重量％；)和熔融的己内酰胺混合， 80°C恒温搅拌。
将混合物体系升温至 160-180°C， 加入 4重量％己内酰胺钠、 0.4重量％的 TDI， 进行反应挤出， 反应温度控制在 250°C。
对所得的聚甲基丙烯酸甲酯 (PMMA)/尼龙 6(PA6)的聚合物合金进行粗粉 碎， 然后用丙酮溶解 PMMA， 过滤干燥， 得到所需的尼龙 6微球。 对所得的尼 龙 6微球用凝胶色谱 (GPC)法测定其分子量， 用激光衍射法测定其体积平均粒 径， 结果见表 1。 实施例 15
将苯乙烯和甲基苯乙烯的混合物 (40重量％， 其中苯乙烯为 30重量％、 甲 基苯乙烯为 10重量％；)和熔融的己内酰胺混合， 在 100°C恒温搅拌， 加入 0.05 重量％AIBN引发自由基聚合， 得到苯乙烯 -甲基苯乙烯共聚物 /己内酰胺溶液。
在此混合溶液中加入 5重量°/<^ (：1和 2重量％乙酰基己内酰胺， 然后在反 应型双螺杆挤出机中进行反应挤出， 反应温度控制在 240°C。
对所得的聚合物合金进行粗破碎， 用水溶解掉苯乙烯-甲基苯乙烯共聚物， 过滤干燥， 得到所需的尼龙 6微球。 对所得的尼龙 6微球用凝胶色谱 (GPC)法 测定其分子量， 用激光衍射法测定其体积平均粒径， 结果见表 1。 实施例 16 将苯乙烯 (5重量％；)和熔融的己内酰胺混合， 在 100°C恒温搅拌， 加入 0.04 重量％AIBN， 引发自由基聚合， 得到聚苯乙烯 /己内酰胺溶液， 在此混合溶液 中加入 0.2重量°/<^ 011和 2重量％1101(；己二异氰酸酯)， 然后在模具中聚合， 反应温度控制在 240°C。
对所得的聚合物合金粗破碎， 用水溶解掉聚苯乙烯， 过滤干燥， 得到所需 的尼龙 6微球。 对所得的尼龙 6微球用凝胶色谱 (GPC)法测定其分子量， 用激 光衍射法测定其体积平均粒径， 结果见表 1。
表 1
Figure imgf000014_0001

Claims

权 利 要 求 书
1. 一种尼龙微球的制备方法， 其特征在于， 该方法包括以下步骤 (1)、（2)和 (3) 或者包括以下步骤 (1')、 （2)和 (3):
(1) 将可自由基聚合的单体分散在熔融的内酰胺单体中， 加入自由基引发 剂， 进行可自由基聚合单体的自由基聚合， 得到自由基聚合物与内酰胺单体的 混合物； 或者
(1') 提供自由基聚合物与熔融的内酰胺单体的混合物； 以及
(2) 向除去了残留的可自由基聚合单体和水的步骤 (1)所得混合物或者向步 骤 (Γ)提供的混合物中加入用于内酰胺单体阴离子开环聚合的引发剂和活化剂， 进行内酰胺的阴离子开环聚合， 得到自由基聚合物 /聚酰胺的聚合物合金； 和
(3) 将步骤 (2)得到的聚合物合金中的自由基聚合物通过溶解除去， 得到尼 龙微球。
2. 如权利要求 1所述的方法， 其特征在于， 所述自由基聚合物能溶解于所 述内酰胺单体； 所述可自由基聚合的单体是选自那些其所形成的自由基聚合物 能溶解于所述内酰胺单体的一种或多种单体。
3. 如权利要求 1所述的方法， 其特征在于， 在步骤 (1)中， 所述可自由基聚 合的单体的用量为 5-80重量％， 以所述可自由基聚合的单体和所述内酰胺单体 的总重量计； 在步骤 ( 中， 所述自由基聚合物的用量为 5-80 重量％， 以所述 自由基聚合物和所述内酰胺单体的总重量计。
4. 如权利要求 1所述的方法， 其特征在于， 所述内酰胺单体是选自 C4-C12 内酰胺的一种或多种； 当内酰胺单体为一种时， 所述聚酰胺是该内酰胺单体的 均聚物； 当内酰胺单体是两种或两种以上时， 所述聚酰胺是这些内酰胺单体的 共聚物。
5. 如权利要求 1 所述的方法， 其特征在于， 步骤 (1)的自由基聚合反应在 60- 150 °C的范围内进行； 和 /或 步骤 (2)的阴离子开环聚合反应在 120-250°C的范围内进行； 和 /或
所述内酰胺单体的阴离子开环聚合方法选自静态浇铸法或反应挤出法。
6. 如权利要求 1所述的方法， 其特征在于， 在步骤 (1)中， 所述自由基引发 剂是选自以下的一种或多种： 偶氮类引发剂、 有机过氧类引发剂和油溶性氧化 -还原引发体系； 所述自由基引发剂的含量为 0.05-5重量％， 以所述可自由基聚 合的单体和所述内酰胺单体的总重量计； 和 /或
在步骤 (2)中， 所述引发剂是选自内酰胺金属化合物、 碱金属、 碱金属氢化 物、 碱金属氢氧化物、 碱金属醇盐或碱金属碳酸盐的一种或多种； 所述活化剂 是选自取代或未取代的异氰酸酯、 乙酰基己内酰胺、 酰氯或酸酐中的一种或多 种。
7. 如权利要求 1所述的方法， 其特征在于， 通过调节自由基聚合物与内酰 胺单体的用量比值来控制尼龙微球的粒径尺寸。
8. 如权利要求 1所述的方法， 其特征在于， 对步骤 (3)中通过溶解除去的自由 基聚合物进行回收， 回收得到的自由基聚合物与熔融的内酰胺单体混合， 提供 步骤 ( 所述的自由基聚合物和内酰胺单体的混合物，继续通过进行步骤 (2)和 (3) 来制备尼龙微球。
9. 一种尼龙微球， 其特征在于， 尼龙的重均分子量在 10,000-300,000的范围 内， 尼龙微球的粒径在 0.1-500微米的范围内。
10. 如权利要求 9所述的尼龙微球，其特征在于，所述尼龙是选自 C4-C12内酰 胺的一种单体的均聚物或者两种或多种单体的共聚物。
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