WO2023072194A1 - 一种聚丙烯微球及其制备方法、3d打印原料和用途 - Google Patents

一种聚丙烯微球及其制备方法、3d打印原料和用途 Download PDF

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WO2023072194A1
WO2023072194A1 PCT/CN2022/127943 CN2022127943W WO2023072194A1 WO 2023072194 A1 WO2023072194 A1 WO 2023072194A1 CN 2022127943 W CN2022127943 W CN 2022127943W WO 2023072194 A1 WO2023072194 A1 WO 2023072194A1
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polypropylene
compound
microsphere
magnesium
product
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English (en)
French (fr)
Inventor
凌永泰
刘建叶
周俊领
徐耀辉
刘涛
张师军
夏先知
吕明福
刘月祥
张恒源
李威莅
陈龙
赵瑾
高富堂
任春红
谢吉嘉
谭扬
杨睿
马长友
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to EP22886069.8A priority Critical patent/EP4424725A4/en
Priority to KR1020247017596A priority patent/KR20240091045A/ko
Priority to JP2024525712A priority patent/JP2024541265A/ja
Priority to US18/705,485 priority patent/US20250236753A1/en
Publication of WO2023072194A1 publication Critical patent/WO2023072194A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/10—Homopolymers or copolymers of propene
    • C09D123/14—Copolymers of propene
    • C09D123/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/18—Bulk density
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/27—Amount of comonomer in wt% or mol%
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

  • the present invention claims the priority of the Chinese patent application entitled “A Polypropylene Microspheres Synthesized by Polymerization” and the application number CN202111258205.6 filed on October 27, 2021, the entire content of which is incorporated herein by reference middle.
  • the invention relates to the technical field of polypropylene materials, in particular to a polypropylene microsphere, a preparation method thereof, a 3D printing raw material and its application.
  • 3D printing also known as "additive manufacturing” is a kind of rapid prototyping technology. It uses 3D printers to use materials such as metal powder or plastic according to the digital blueprint, and prints the materials layer by layer. Item crafting. This technology can realize product production anytime, anywhere and on demand, and has applications in daily necessities such as footwear, construction, automobile industry, aerospace, medical treatment, education and other fields. This emerging technology is gradually changing human life, and its prospects are promising by all walks of life. "Time” magazine listed 3D printing as the first of the “Ten Fastest Growing Industries in the United States”. The British “Economist” magazine believes that 3D printing will promote the third industrial revolution.
  • SLS technology is a rapid prototyping technology, which is currently the most widely used and most promising technology in additive manufacturing technology, showing a rapid development trend in recent years.
  • SLS technology is a technology in which the computer first scans the three-dimensional entity, and then irradiates the material powder pre-spread on the workbench or parts through high-intensity laser, and selectively melts and sinters it layer by layer, thereby realizing layer-by-layer molding. .
  • SLS technology has a high degree of design flexibility, can manufacture accurate models and prototypes, can form parts with reliable structures and can be used directly, and shorten the production cycle and simplify the process, so it is especially suitable for the development of new products.
  • pulverization methods such as cryogenic pulverization methods
  • cryogenic pulverization methods are usually used to prepare powder materials suitable for SLS.
  • CN104031319A discloses a polypropylene powder obtained by cryogenic pulverization.
  • this method not only requires special equipment, but also the surface of the prepared powder raw material particles is rough, the particle size is not uniform, and the shape is irregular, which is not conducive to the formation of the sintered compact and affects the performance of the compact.
  • polyamide powder raw materials such as polyamide powder.
  • polyamide is usually dissolved in a suitable solvent, the material is evenly distributed in the solvent by stirring, and the powder is precipitated by cooling.
  • CN103374223A discloses a precipitation polymer powder based on AABB-type polyamide obtained by reprecipitating polyamide obtained by polycondensation of diamine and dicarboxylic acid.
  • an alcoholic solvent is used in the reprecipitation process.
  • this method needs to use a large amount of organic solvents, and the yield and efficiency are low, which does not have environmental and economic advantages.
  • the polymer is polypropylene
  • general polymer particle preparation methods such as emulsion polymerization, soap-free emulsion polymerization, microemulsion polymerization, miniemulsion polymerization, suspension polymerization, dispersion Polymerization, precipitation polymerization and seed polymerization, etc.
  • the low-temperature brittleness of the material can only be used to crush it into micron-sized powders under low temperature conditions.
  • the crushing of polyolefins often requires relatively high-cost liquid nitrogen cryogenic treatment for crushing. Poor powder form, irregular shape, poor fluidity.
  • polymer particles need to be powdered layer by layer and then sintered layer by layer.
  • Polypropylene foam material has the advantages of low density, high specific strength, good thermal stability, excellent impact resistance, green production raw materials and process, easy recycling and recycling, etc. It can be used as cushioning, shock absorption, sound insulation, heat insulation, etc. Functional Materials.
  • the common polypropylene foam materials can be mainly divided into four types: autoclave pressure foam, molded foam, extrusion foam and injection foam according to different processing techniques.
  • autoclave expanded polypropylene (EPP) beads and moldings have the most significant advantage of free formability. EPP beads can be molded to obtain Foamed products with complex geometric shapes and high three-dimensional dimensional accuracy.
  • Polypropylene expanded particle molded products have good rigidity and better impact resistance than polystyrene, and compared with polystyrene foam, which is difficult to recycle, polypropylene foam is an environmentally friendly material with high thermal deformation It can be used in some high-temperature fields. It has good energy absorption characteristics and excellent pressure resistance and energy absorption performance. It has good stability in size and shape recovery. The product can withstand multiple continuous impacts and deflections without permanent deformation. The foamed products have low density and are easy to recycle and reuse. The products are non-toxic and do not produce toxic substances when burned. These excellent properties make it widely used, and its applications in packaging, automobiles, construction and other fields have been continuously expanded. It is especially suitable for high-end applications such as automotive interior and exterior decoration, cold chain logistics, and electronic product packaging.
  • the foaming raw material should choose polypropylene microparticles with regular shape (preferably approximately spherical) and smaller particle size.
  • the foamed beads prepared by relatively regular spherical micro-particles are also approximately spherical, and are easy to pack tightly during the molding process, and are not easy to form larger pores.
  • the preparation of expanded polypropylene particles also requires the use of relatively high-cost liquid nitrogen cryogenic treatment for crushing.
  • the powder is poor in shape, irregular in shape, and poor in fluidity, which makes the particles prone to bridging during transportation, resulting in poor production. Stable, and such pulverized particles often lead to uneven foaming, rough surface, and whitening.
  • the smaller the PP microparticles the smaller the foamed beads are, which is conducive to the transportation of EPP beads in the process pipeline of the molding equipment, reduces clogging, and can be packed tightly in the mold cavity. Therefore, the bonding effect between the beads is better during molding, the amount of steam used is lower, and the mechanical properties and thermal insulation properties of the product are better.
  • the small particle size is conducive to the preparation of products with thin walls and complex structures, and the surface of the products is smoother and smoother.
  • the crystallization distribution of polypropylene prepared by using ZN catalysts tends to have a large dispersion, which is reflected in the DSC test results.
  • the molecular weight distribution of the former is relatively narrow, which often makes the processing performance of its products poor, and the molecular weight distribution of the products obtained by the former is relatively wide, which is more conducive to improving the rigidity and toughness balance of the resin.
  • the present invention proposes a polypropylene microsphere and a preparation method thereof.
  • a polypropylene microsphere comprises 0.2wt% to 10wt% of structural units derived from ethylene and 90wt% to 99.8wt% of structures derived from propylene The unit, wherein the melting endothermic curve of polypropylene microspheres is obtained by differential scanning calorimetry (DSC), and the half-maximum width (Wm) of the melting endothermic curve of polypropylene microspheres is 4-10°C.
  • DSC differential scanning calorimetry
  • Wm half-maximum width
  • the half-peak width of the melting endotherm curve of the polypropylene microspheres is 5-8°C.
  • the molecular weight distribution (Mw/Mn) of the polypropylene microspheres is 4-9.
  • the molecular weight distribution of the polypropylene microspheres is 5, 6, 7, 8, or any value between any two points above.
  • the polypropylene microspheres have a bulk density of 0.20 g/cm 3 to 0.50 g/cm 3 , preferably 0.32 g/cm 3 to 0.48 g/cm 3 .
  • the angle of repose of the polypropylene microspheres is 10°-23°, preferably 13°-20°.
  • the isotactic index of the polypropylene microspheres is 60%-94%, preferably 64%-90%.
  • the ash content of the polypropylene microspheres is 0.005%-0.04%.
  • the ash content of the polypropylene microspheres is 0.01%, 0.015%, 0.02%, 0.025%, 0.03%, 0.035%, or any value between any two points above.
  • the melt index of the polypropylene microspheres is 3-160 g/10 min, preferably 15-100 g/10 min.
  • the endothermic effect is characterized by a raised peak (enthalpy increase).
  • DSC uses a Perkin-Elmer DSC-7 differential scanning calorimeter, heats the sample at 10°C/min to 200°C, keeps it for 5 minutes, then lowers it to 50°C at 10°C/min, keeps it at 50°C for 1 minute, and then heats it at 10°C. °C/min and then increased to 200 °C.
  • the DSC schematic diagram is shown in Figure 2.
  • the ordinate of the DSC result is the dH/dt heat flow rate, and the abscissa is the temperature (T).
  • Tm represents the melting point of the test sample and Tfm represents the temperature at which the melting peak connects to the baseline.
  • the polymer microspheres with a narrower half-peak width obtained in the present invention can significantly improve the expansion ratio and uniformity of EPP beads during autoclave foaming and molding, and can be molded at a lower temperature, reducing the cost of EPP beads.
  • the energy consumption during molding can speed up the production cycle of EPP bead molding, thereby effectively reducing the production cost of EPP beads and moldings.
  • the EPP bead molded body prepared with the beads has better appearance quality, and is especially beneficial to the preparation of thin-walled or complex-shaped EPP molded body products.
  • the average particle diameter of the polypropylene microspheres is 50 ⁇ m to 200 ⁇ m; preferably, the average particle diameter of the polypropylene microspheres is 60 ⁇ m to 160 ⁇ m; most preferably, the average particle diameter of the polypropylene microspheres is 80 ⁇ m ⁇ 120 ⁇ m.
  • the aspect ratio of the polypropylene microspheres is 0.9-1.1; preferably, the aspect ratio of the polypropylene microspheres is 0.95-1.05; most preferably, the aspect ratio of the polypropylene microspheres is 1.
  • the polypropylene microspheres are prepared by direct copolymerization.
  • a method for preparing the above-mentioned polypropylene microspheres comprising: in the presence of an olefin polymerization catalyst system, copolymerizing olefins containing propylene to obtain polypropylene microspheres.
  • the olefin polymerization catalyst system comprises the following components or the reaction product of the following components: catalyst, alkylaluminum compound and optionally added or not added external electron donor compound.
  • the alkylaluminum compound may be various alkylaluminum compounds commonly used in the field of olefin polymerization, which can be used as cocatalysts for Ziegler-Natta catalysts.
  • the alkylaluminum compound can be, but not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, monohydrogen diethylaluminum, monohydrogen diisobutylaluminum , at least one of diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride.
  • the external electron donor compound may be various external electron donor compounds commonly used in the field of olefin polymerization that can be used as cocatalysts for Ziegler-Natta catalysts.
  • the external electron donor compound can be but not limited to trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethyl Oxysilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Ethylisopropyldimethoxysilane, Propylisopropyldimethoxysilane, Diisopropyldimethylsilane Oxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyl Dimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-but
  • the external electron donor compound can be dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane At least one of methyl tert-butyldimethoxysilane and tetramethoxysilane.
  • the catalyst includes a magnesium-containing compound support, a titanium compound and an internal electron donor compound.
  • the molar ratio of the titanium compound to the magnesium-containing compound carrier and the internal electron donor compound is (37-255):(2-15):1, preferably (67-235):(4-12 ):1.
  • R 1 is a C 1 -C 10 alkyl group
  • R 2 and R 3 are the same or different, each independently being H, a C 1 -C 10 alkyl group or a C 1 -C 10 haloalkyl group substituted by 1 to 10 halogen atoms;
  • R 4 is a C 1 -C 10 haloalkyl group substituted by at least one halogen atom or a C 6 -C 20 haloaryl group substituted by at least one halogen atom;
  • R 5 is C 1 -C 5 alkyl
  • X is fluorine, chlorine, bromine or iodine; preferably, X is chlorine or bromine;
  • the internal electron donor compound is selected from at least one of carboxylic acid esters, alcohol esters, ethers, ketones, nitriles, amines and silanes, preferably monovalent or polyvalent aliphatic carboxylic acid esters, monovalent or polyvalent aromatic At least one of family carboxylic acid esters, glycol esters and dibasic ethers.
  • the diol ester may be a diol carboxylate.
  • the internal electron donor compound is at least one of dibasic ethers, and the dibasic ether structure is shown in formula (III):
  • R 21 and R 22 are each independently selected from hydrogen, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 arane R 21 and R 22 may be optionally bonded to form a ring; R 23 and R 24 are each independently a C 1 -C 10 alkyl group.
  • the internal electron donor compound may be selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2 -Butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl- 1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxy Propane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl- 1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropan
  • the general formula of the titanium compound is Ti(OR 6 ) 4-b X' b , wherein R 6 is a C 1 -C 14 aliphatic hydrocarbon group, X' is F, Cl or Br, and b is 1 An integer of ⁇ 4.
  • the titanium compound is preferably titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium chloride, triethoxychloride at least one of titanium oxide, diethoxytitanium dichloride and ethoxytitanium chloride.
  • the preparation method of the magnesium-containing compound carrier comprises the following steps:
  • X is selected from fluorine, chlorine, bromine or iodine
  • Y is selected from fluorine, chlorine, bromine, iodine, C 1-6 alkyl, C 1-6 alkoxy, C 6-14 aryl or C 6-14 aryloxy.
  • X" is selected from chlorine or bromine
  • Y is selected from chlorine, bromine, C 1-5 alkyl, C 1-5 alkoxy, C 6-10 aryl or C 6-10 aryloxy
  • Y is selected from C 1-6 alkyl, C 1-6 alkoxy
  • the alkyl and the alkoxy are linear or branched alkyl and alkoxy groups
  • the C 1-6 alkyl group refers to an alkyl group with 1 to 6 carbon atoms, for example including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , tert-butyl, n-pentyl, isopentyl, etc.
  • the C 1-6 alkoxy group refers to an alkoxy group with 1 to 6 carbon atoms, for example including but not limited to methoxy, ethoxy base, n-propoxy, isopropoxy, n-butoxy, sec-butoxy
  • the C 6-14 aryl refers to an aryl group having 6 to 14 carbon atoms, for example including but not limited to phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethyl Phenyl, p-ethylphenyl, naphthyl, etc.
  • the C 6-14 aryloxy group refers to an aryloxy group with 6 to 14 carbon atoms, for example including but not limited to phenoxy, naphthyloxy, o-methylphenoxy, o-ethylphenoxy base, m-methylphenoxy, etc.
  • the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride, preferably magnesium chloride.
  • R 7 is a C 1-10 alkyl group.
  • R 8 and R 9 are each independently selected from H, C 1-10 alkyl, C 1-10 haloalkyl substituted by 1 to 10 halogen atoms; preferably, R 8 and R 9 are each independently It is selected from H, C 1-5 alkyl, and C 1-5 haloalkyl substituted by 1 to 10 halogen atoms.
  • the oxirane compound is selected from ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorobutane, epoxybromopropane and epoxybromobutane at least one of . .
  • R 10 is selected from C 1-10 halogenated alkyl substituted by at least one halogen atom or C 6-20 halogenated aromatic substituted by at least one halogen atom base.
  • the halohydrin can be monohalohydrin or polyhalohydrin, preferably chlorohydrin, bromohydrin or iodohydrin, such as 2,2,2-trichloroethanol, 2,2-dichloroethanol , 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1-hexanol, 3-bromo-1-propanol, 5-chloro-1-pentanol, 4-chloro-1-butanol , 2-chlorocyclohexanol, 1,2-dichloroethanol, 1,3-dichloropropanol, 1,4-dichlorobutanol or 2-iodoethanol, etc.
  • chlorohydrin bromohydrin or iodohydrin
  • bromohydrin or iodohydrin such as 2,2,2-trichloroethanol, 2,2-dichloroethanol , 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1
  • R 10 is selected from C 1-10 haloalkyl substituted by at least two halogen atoms or A C 6-20 halogenated aryl group substituted by at least two halogen atoms, and the halogen atom is selected from at least one of chlorine atom, bromine atom and iodine atom.
  • the halogenated alcohol is selected from 2,2,2-trichloroethanol, 2,2-dichloroethanol, 1,2-dichloroethanol, 1,3-dichloropropanol, 1,4-dichloroethanol at least one of chlorobutanol.
  • R 11 is a C 1-5 alkyl group.
  • the second alcohol compound is ethanol, methanol, n-propanol, isopropanol, n-butanol or isobutanol.
  • R 11 is a C 1-2 alkyl group, that is, the second alcohol Compounds are methanol and/or ethanol.
  • the amount of the halogenated alcohol is 0.05-6.5 mol, and the amount of the second alcohol compound is 5-100 mol.
  • the obtained catalyst carrier will form a cohesive mass, and subsequent operations cannot be performed.
  • the amount of the first alcohol compound is 1-30 mol, and the amount of the oxirane compound is 1-10 mol.
  • the amount of the first alcohol compound is 6-22 mol
  • the amount of the oxirane compound is 2-6 mol
  • the amount of the halogenated alcohol is 1-22 mol. 5 mol
  • the amount of the second alcohol compound is 8-80 mol, more preferably 31-50 mol.
  • the trace amount of water carried in the above-mentioned reactants will also participate in the reaction of forming the spherical carrier, therefore, the prepared spherical carrier may contain trace amounts of water from the reaction raw materials and reaction medium. Water, those skilled in the art should not be construed as limiting the present invention.
  • the first contact in S1 is carried out under the condition of stirring, and the conditions of the first contact include: the temperature is 80-120°C, and the time is 0.5-5h; preferably, in S1, the The conditions for the first contact include: the temperature is 80-100° C., and the time is 0.5-3 hours.
  • the present invention has no particular limitation on the specific operation method of the emulsification, and methods known to those skilled in the art can be used.
  • low-speed shear or high-speed shear is used for emulsification.
  • the stirring rate of the low-speed shear is 400-800 rpm.
  • the high-speed shearing method is well known to those skilled in the art, for example, the high-speed stirring speed disclosed in CN1330086A is used to carry out.
  • the emulsification operation can also be carried out with reference to the methods disclosed in the following patent applications, such as CN1580136A discloses that the solution containing liquid magnesium halide compound is rotated and dispersed in a high-gravity bed (rotating speed is 100-3000rpm); another example is CN1463990A It is disclosed that the solution containing the liquid magnesium halide adduct is output in an emulsifier at a speed of 1500-8000 rpm; and as disclosed in US6020279A, the solution containing the liquid magnesium halide adduct is emulsified by spraying.
  • the conditions of the second contact include: the temperature is 50-120°C, and the time is 20-60min; preferably, the conditions of the second contact include: the temperature is 80-100°C, the time is 20-60min. 20-50 minutes.
  • the second product is washed with an inert solvent and then subjected to the second alcohol compound with the general formula R 10 OH and the second alcohol compound with the general formula R 11 OH.
  • the inert solvent is selected from at least one of pentane, hexane, heptane, petroleum ether and gasoline.
  • the present invention is not particularly limited to the specific conditions of the third contact in S3, as long as the halohydrin containing the general formula R 10 OH, the second alcohol compound with the general formula R 11 OH and the It only needs that the second product can be sufficiently contacted to form a fluid.
  • the conditions of the third contact include: under stirring conditions, the temperature is 0-120°C, and the time is 0.5-6h.
  • the present invention has no particular limitation on the specific method of the third contact in S3, the halohydrin and the second alcohol compound can be mixed and contacted with the second component synchronously, or the The halohydrin and the second alcohol compound are sequentially contacted with the second component respectively.
  • the conditions of the spray drying can adopt the existing conditions that can form the catalyst carrier for olefin polymerization, but in order to obtain a catalyst carrier with better performance, according to the present invention
  • the spray drying is implemented in a sprayer with an atomizing nozzle, the atomizing nozzle contains a material conduit and a nozzle head, and the third product is led to the nozzle through the material conduit In the head, and spray through the nozzle head into the tower body containing the inert medium of the sprayer for curing.
  • the temperature of the third product in the material conduit is between 0°C and 80°C, and the temperature of the third product in the nozzle head is 80-180°C; more preferably, the third product The temperature of the three products in the nozzle head is 120-180°C.
  • the spray drying conditions include: a temperature of 60-200°C, more preferably 90-150°C.
  • the spray drying temperature refers to the temperature of the inert medium in the spray machine.
  • the inert medium may include a protective gas medium and/or an inert liquid medium
  • the type of the protective gas medium is not particularly limited, for example, it may be nitrogen or an inert gas medium such as helium , can also be other suitable gases such as carbon dioxide, etc.
  • the inert liquid medium is a variety of commonly used liquid media in the art that do not chemically interact with reactants and reaction products, preferably the inert liquid medium is silicone oil and/or inert liquid Hydrocarbon solvent; more preferably, the inert liquid medium is selected from kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil At least one of, more preferably white oil.
  • the amount of the inert liquid medium in the sprayer can be selected according to the amount of magnesium halide with the general formula MgX"Y, preferably 0.8-10L, more preferably 2-8L.
  • the preparation method described in the present invention also includes conventional post-processing means in the field such as solid-liquid separation, washing, drying, etc., and the present invention is not particularly limited thereto.
  • the solid-liquid separation can adopt various existing methods capable of separating the solid phase and the liquid phase, such as suction filtration, pressure filtration, or centrifugal separation.
  • the solid-liquid separation method is a pressure filtration method.
  • there is no special limitation on the conditions of the pressure filtration there is no special limitation on the conditions of the pressure filtration, and the separation of the solid phase and the liquid phase shall be achieved as fully as possible.
  • Described washing can adopt the method well-known to those skilled in the art that the solid phase product that obtains is washed, for example can adopt inert hydrocarbon solvent (such as pentane, hexane, heptane, sherwood oil and gasoline) to obtain solid phase product Perform a wash.
  • inert hydrocarbon solvent such as pentane, hexane, heptane, sherwood oil and gasoline
  • the present invention is not particularly limited to the specific conditions of the drying, for example, the drying temperature can be 20-70°C, the drying time can be 0.5-10h, and the drying can be carried out under normal pressure or reduced pressure .
  • the composition of the catalyst is not particularly limited, and may be the composition of an existing catalyst for olefin polymerization in the art, but in order to obtain a catalyst suitable for olefin polymerization, especially propylene polymerization Catalyst; preferably, the catalyst contains the carrier, titanium halide compound and electron donor compound.
  • the titanium halide compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetra-n-butoxytitanium, tetraethoxytitanium, monochlorotri-n-butoxytitanium, dichlorodi At least one of n-butoxytitanium, trichloro-n-butoxytitanium, monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride; preferably
  • the electron donor compound is selected from at least one of diisobutyl phthalate, diol carboxylate, and phosphoric acid ester.
  • the present invention has no special limitation on the content of each component in the catalyst, and those skilled in the art can make reasonable adjustments and designs according to actual needs.
  • the average particle diameter of the magnesium-containing compound carrier is 2-100 microns, and the particle size distribution is less than 2; preferably, the average particle diameter of the magnesium-containing compound carrier is 2-19 microns, and the particle size distribution is 0.6 to 1.6.
  • the average particle diameter of the magnesium-containing compound carrier is 2 to 10 microns.
  • the diameter distribution is 0.6 ⁇ 1.
  • the catalyst has the characteristic of "morphological replication" in the process of catalyzing the polymerization of propylene.
  • spherical catalysts do not necessarily obtain spherical polymers, spherical polymers can generally only be prepared from spherical catalysts. of.
  • the particle size of the polymer obtained by the catalyst with smaller particle size is generally smaller, and the structure and morphology of the catalyst itself play an important role in the morphology of the polymer. Good catalyst structure and morphology are conducive to reducing the friction between polymers, etc., so that the angle of repose of the final polymer is reduced, which is beneficial to the production and transportation of polymers.
  • a 3D printing raw material comprising: the above-mentioned polypropylene microspheres and/or the polypropylene microspheres prepared according to the above-mentioned preparation method.
  • SLS Selective Laser Sintering
  • the present invention includes the following beneficial effects:
  • the half peak width of the existing ordinary polypropylene microspheres is relatively wide, but the half peak width of the polypropylene microspheres of the present invention is only 4-10°C, which is narrower than the existing ones, which shows that the crystallization of the obtained polypropylene microspheres
  • the sequence distribution is relatively uniform. When used in 3D printing, it can improve the uniformity of polymer particle melting and fusion, which can make the 3D printing fused uniform product performance better, and improve the structural strength and surface properties of the sintered sample; at the same time, the present invention is relatively
  • the polypropylene microspheres prepared by the metallocene catalyst have a wider molecular weight distribution, so that the obtained sintered product has a better balance of rigidity and toughness.
  • the average particle size of the polypropylene microspheres of the present invention is less than 160 microns, which can be directly used for 3D printing without secondary processing; the angle of repose of the polypropylene microspheres of the present invention is less than 23°, which has better fluidity and is easier to print when printing.
  • the powder spreading is more uniform; the ethylene content of the polypropylene microspheres of the present invention is greater than 0.2 wt%, and they do not warp during the 3D printing process.
  • the polypropylene microsphere of the present invention presents good spherical shape, regular particles, good fluidity, and has great industrial application prospect.
  • the specific surface of the catalyst is large and the polymerization activity is good.
  • the use of alkylaluminum can be reduced, and a smaller amount of triethylaluminum is used to combine with cyclohexylmethyl Dimethoxysilane, catalyst, hydrogen and propylene monomer are mixed and reacted to obtain polypropylene microspheres, the ash content of the obtained polymer microspheres is further reduced and there is basically no abnormality.
  • spherical polymers are obtained by direct polymerization through the characteristics of "morphological replication" of the catalyst; due to the good characteristics of the structure and morphology of the catalyst, the friction between the obtained polymers is small, The angle of repose of the polymer is small, which is beneficial to the production and transportation of the polymer.
  • the polypropylene microspheres provided by the present invention are obtained by direct polymerization in a reactor, which avoids post-processing procedures and saves costs.
  • Fig. 1 is the electron micrograph of the obtained polypropylene powder of embodiment 1-1.
  • Figure 2 is a schematic diagram of DSC.
  • the average particle diameter and particle size distribution of the magnesium-containing compound carrier are measured using a Masters Sizer2000 particle size analyzer (manufactured by Malvern Instruments Ltd).
  • the apparent morphology of the polypropylene powder is observed by an XL-30 field emission electron microscope produced by FEI Company of the United States.
  • the structure and composition of the magnesium-containing compound carrier adopts the AVANCE 300 nuclear magnetic resonance spectrometer of the Swiss Bruker Company to carry out 1H-NMR tests on the carrier, and adopts the PY-2020iD cracker of the Fronteerlab Company and the Thermo Fisher Company's
  • the carrier was tested by TraceGC Ultra chromatograph and DSDII mass spectrometer.
  • DSC detection adopts the method specified in "GBT 19466 Plastic Differential Scanning Calorimetry (DSC)" to measure.
  • the half-peak width detected by DSC refers to the absolute value of the temperature difference between two points where the straight line crosses the two sides of the peak and the straight line parallel to the baseline is drawn through the midpoint of the peak height.
  • the test method of the molecular weight distribution index Mw/Mn of the polypropylene powder is determined by the method specified in GB/T36214-2018.
  • the copolymerization activity of the catalyst is evaluated by the ratio of the weight of the product obtained after polymerization to the weight of the amount of catalyst used.
  • the bulk density of polypropylene powder is measured by the method specified in GB/T 1636-2008.
  • the ash content of polypropylene powder is determined by the method specified in GB_T 9345.1-2008.
  • the specific surface area of the polypropylene powder is tested with a POREMASTER GT60 mercury porosimeter.
  • the angle of repose of polypropylene powder adopts the method that GB/T 11986-1989 stipulates to measure.
  • the aspect ratio of the polypropylene powder refers to the ratio of the long axis in the particle projection to its average short axis.
  • the ethylene content of the polypropylene powder is measured by a Fourier transform infrared spectrometer, and the sample is prepared by a hot-pressing film method.
  • the tensile strength of the spline is measured by the method specified in GB/T 1040.2-2006.
  • the surface smoothness adopts a comparison method: compare the surface to be tested with a standard product, and then evaluate the roughness of the surface to be tested after comparing by visual, tactile or other methods. Scored by 5 staff members, the standard product is 10 points, and then the average score is taken.
  • 1,3-Dichloropropanol was purchased from Bailingwei Company;
  • Diisobutyl phthalate was purchased from Bailingwei Company;
  • Titanium tetrachloride was purchased from Bailingwei Company;
  • Triethylaluminum was purchased from Bailingwei Company;
  • Cyclohexylmethyldimethoxysilane was purchased from Bailingwei Company.
  • the emulsification was performed under stirring at 600 rpm during the preparation of the catalyst carrier.
  • ⁇ i is the heat flow rate difference between T i+1 temperature and T i temperature.
  • the average particle diameter (D50) of the catalyst spherical carrier Z1 is 4 microns, and the particle size distribution ((D90-D10)/D50) is 0.9.
  • the particles of the catalyst spherical carrier Z1 are relatively regular in shape, smooth in surface, basically spherical in shape, relatively concentrated in particle size distribution, and basically free of irregular particles.
  • the copolymerized polypropylene powder obtained in Example 1-1 showed a good spherical shape ( FIG. 1 ) when viewed from an electron microscope, and there were basically no irregularities.
  • This example adopts the method provided in Example 1-1 to prepare polypropylene, except that the volume of hydrogen used is different, and the rest are the same.
  • the polypropylene powder exhibits a good spherical shape when viewed from an electron microscope, and there is basically no abnormal shape.
  • the conditions of the second contact include: the temperature is 90° C., and the time is 30 minutes;
  • the average particle diameter (D50) of the catalyst spherical carrier Z2 is 4 microns, and the particle size distribution ((D90-D10)/D50) is 0.8.
  • the particle shape of the spherical carrier Z2 for olefin polymerization catalyst is relatively regular, the surface is smooth, basically spherical, the particle size distribution is relatively concentrated, and there are basically no abnormal-shaped particles.
  • Polypropylene was prepared in a manner similar to that of Example 1-1, except that in step S1, the types of catalyst supports used were different, and the rest were the same as in Example 1-1.
  • the catalyst C2 was spherical in shape by electron microscope observation. After testing, the average particle diameter (D50) of the catalyst C2 was 4 microns, and the particle size distribution ((D90-D10)/D50) was 0.8.
  • the obtained polypropylene powder has a good particle shape, and exhibits a good spherical shape when viewed from an electron microscope, and there is basically no abnormal shape.
  • This example adopts the method provided in Example 2-1 to prepare polypropylene, except that the volume of hydrogen used is different, and the rest are the same.
  • the polypropylene powder exhibits a good spherical shape when viewed from an electron microscope, and there is basically no abnormal shape.
  • the conditions of the second contact include: the temperature is 90° C., and the time is 30 minutes;
  • the average particle diameter (D50) of the catalyst spherical carrier Z3 is 5 microns, and the particle size distribution ((D90-D10)/D50) is 0.8.
  • the particles of the catalyst spherical carrier Z3 are relatively regular in shape, smooth in surface, basically spherical in shape, relatively concentrated in particle size distribution, and basically free of irregular particles.
  • Catalyst polymerization is the same as in Example 2-1, except that Z3 is substituted for Z2.
  • the polypropylene powder exhibits a good spherical shape when viewed from an electron microscope, and there is basically no abnormal shape.
  • This example adopts the method provided in Example 3-1 to prepare polypropylene, except that the volume of hydrogen used is different, and the rest are the same.
  • the polypropylene powder exhibits a good spherical shape when viewed from an electron microscope, and there is basically no abnormal shape.
  • This example adopts the method provided in Example 1-1 to prepare polypropylene, the difference is: in addition to adding 0.25 mmol of triethylaluminum, 0.01 mmol of cyclohexylmethyldimethoxysilane is also added at the same time, and the others are the same Example 1-1, obtaining polypropylene powder.
  • the polypropylene powder exhibits a good spherical shape when viewed from an electron microscope, and there is basically no abnormal shape. Comparative Preparation Example 3
  • the average particle diameter (D50) of the catalyst carrier DZ3 for olefin polymerization is 3 microns, and the particle size distribution ((D90-D10)/D50) is 0.8.
  • Polypropylene was prepared in a manner similar to Example 1-1, except that in the preparation of the catalyst for olefin polymerization, 2-isopropyl-2-isoamyl-1 was replaced by diisobutyl phthalate , 3-dimethoxypropane, the rest are the same as.
  • Polypropylene was prepared in a manner similar to Comparative Example 1, except that in the preparation of polypropylene copolymer microspheres, the volume of hydrogen used was different, which was 6.5 NL, and the rest were the same as Comparative Example 1.
  • Polypropylene was prepared in a manner similar to that of Example 1-1, except that DZ3 was used instead of Z1, and the rest were the same.
  • Polypropylene was prepared in a manner similar to that of Example 1-1, except that no ethylene was added during polymerization.
  • the magnesium halide adduct MgXY mR1OH is prepared according to the method disclosed in Example 1 of CN1718595, specifically as follows:
  • the mixed solution into a high-gravity rotating bed for dispersion, and introduce the dispersed mixed solution into a hexane medium that has been cooled to -35°C under stirring conditions.
  • the amount of hexane used is 1200 L, and dispersed into small droplets
  • the magnesium chloride/alcohol adduct melt is cooled and solidified into spherical solid particles.
  • the solid particulate matter was filtered out from the suspension obtained after quenching, and the particulate matter was washed at room temperature with hexane, the amount of hexane was 100 L/time, washed 5 times in total, and vacuumized at 60° C. to obtain a solid.
  • the average particle diameter (D50) of the magnesium halide adduct is 52 microns, and the particle size distribution ((D90-D10)/D50) is 1.1.
  • the electron microscope was used to observe the morphology of the particles, and it was found that the particle shape of the magnesium halide adduct was relatively regular, the surface was relatively smooth, and the particle size distribution was relatively concentrated.
  • the structural formula of the magnesium halide adduct D5 was determined by GC, NMR and elemental analysis to be: MgCl 2 ⁇ 2.5C 2 H 5 OH.
  • the random copolymerized polypropylene pellets prepared by commercial DDC401 catalyst were crushed after cryogenic cooling with liquid nitrogen.
  • the polypropylene microspheres of the present invention have a wider molecular weight distribution and a narrower half-width, and the obtained polypropylene microspheres have a relatively uniform crystal sequence distribution, and when used for 3D printing, the particles melt evenly , The resulting product has good performance. And a wider molecular weight distribution can also endow the product with a better rigidity-toughness balance.
  • the copolymerized polypropylene powder prepared by the catalyst provided by the present invention has a good spherical shape, good fluidity, small angle of repose, good tensile properties of 3D printed parts, and good smoothness of the objects. Due to the smaller angle of repose, the effect of powder spreading is good, which is beneficial to reduce the space defects in the printing process. It also has a large specific surface area, and has a good fusion effect with antioxidants, which greatly reduces the local degradation of polypropylene during laser sintering. .
  • the ethylene-propylene copolymer product of the present invention has a narrower DSC measurement half-peak width, has a more uniform copolymer crystal composition, improves the uniformity of melting and fusion of polymer particles, and improves the structural strength and surface properties of sintered samples.
  • the compressive strength of the foamed molding is measured according to the method of GB/T8813-2008 for the determination of the compression properties of rigid foamed plastics, and the bending strength of the foamed molding is measured according to the method of GB/T8812-2007 for the determination of the bending properties of rigid foamed plastics Measurement;
  • Test method of expansion ratio of foamed beads use the density accessory YDK01 of the German Satorius CPA225D balance, and use the drainage method to obtain the density of the foamed beads of the polypropylene composition, according to the national standard GB/T1033.1-2008, ISO1183-1:2012 The method measurement is described in .
  • 200g copolymerized polypropylene microspheres are placed in the autoclave, 0.2g antioxidant 1010, dispersion medium (deionized water) 1000g, 1g surfactant (sodium dodecylbenzenesulfonate), dispersant (kaolin) 1g Add and mix with 0.02g of dispersion enhancer (aluminum sulfate); then fill in low-pressure carbon dioxide to replace the air in the kettle, then fill in high-pressure carbon dioxide, raise the temperature of the autoclave to 138°C, control the pressure to 6MPa, and swell and penetrate for 30 minutes.
  • dispersion medium deionized water
  • 1g surfactant sodium dodecylbenzenesulfonate
  • dispersant kaolin
  • the different foamed beads obtained by the foaming process described above were molded with a molding machine under a certain steam pressure for a certain period of time, and then the obtained molded body was aged at a temperature of 100°C and a pressure of standard atmospheric pressure for 24 hours. Hours, the foamed bead molded body is obtained.

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Abstract

本发明提供了一种聚丙烯微球及其制备方法、3D打印原料和用途，属于聚丙烯材料技术领域。所述聚丙烯微球包括0.2wt％～10wt％的衍生自乙烯的结构单元和90wt％～99.8wt％的衍生自丙烯的结构单元，其中，通过差示扫描量热仪(DSC)获得聚丙烯微球熔融吸热曲线，所述聚丙烯微球熔融吸热曲线的半峰宽(Wm)为4～10℃。本发明聚丙烯微球的结晶序列分布比较均一，用于3D打印时，能够使得3D打印熔融均匀制品性能好，极具工业应用前景。

Description

一种聚丙烯微球及其制备方法、3D打印原料和用途
相关申请的交叉引用
本发明要求享有2021年10月27日提交的名称为“一种聚合合成的聚丙烯微球”，申请号为CN202111258205.6的中国专利申请的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本发明涉及聚丙烯材料技术领域，具体涉及一种聚丙烯微球及其制备方法、3D打印原料和用途。
背景技术
3D打印，也称“增材制造”，是快速成型技术的一种，其使用3D打印机按照数字蓝图使用金属粉末或塑料等材料，通过逐层打印的方式把材料一层层叠在一起，最终完成物品制作。该技术可实现了随时、随地、按需进行产品生产，在生活用品如鞋类、建筑业、汽车工业，航空航天、医疗、教育等领域都有应用。这项新兴技术正在逐步改变人类的生活，前景被各行各业看好。《时代》周刊将3D打印列为“美国十大增长极快的工业”之首。英国的《经济学人》杂志认为3D打印将推动第三次工业革命。
选择性激光烧结(Selective Laser Sintering,SLS)技术是一种快速成型技术，是目前增材制造技术中应用最广泛且最具市场前景的技术，近年来呈现出快速发展的趋势。SLS技术是由计算机首先对三维实体进行扫描，然后通过高强度激光照射预先在工作台或零部件上铺上的材料粉末，将其选择性地逐层地熔融烧结，进而实现逐层成型的技术。SLS技术具有高度的设计柔性，能够制造出精确的模型和原型，可以成型具有可靠结构的并可以直接使用的零部件，并且缩短生产周期，简化工艺，因此特别适合于新产品的开发。
理论上，能够用于SLS技术的成型材料种类较为广泛，例如聚合物、石蜡、金属、陶瓷以及它们的复合材料。然而，成型材料的性能、性状是SLS技术烧结成功的一个重要因素，它直接影响成型件的成型速度、精度，以及物理、化学性能及其综合性能。目前，能够直接应用于SLS技术并成功制造出尺寸误差小、表面规整、孔隙率低的模塑品的聚合物粉末原料在市场上鲜见。因此，亟待开发 和改善适用于SLS技术的聚合物种类及其相应的固体粉末原料。
现有技术中，通常采用粉碎法，如深冷粉碎法来制备适合于SLS的粉末原料。例如，在CN104031319A中公开了一种用深冷粉碎法得到的聚丙烯粉末。但是，这种方法不仅需要特定设备，而且制备得到的粉末原料颗粒表面较粗糙、粒径不够均匀、形状不规则，不利于烧结成型体的形成，并影响成型体的性能。
另外，还存在沉淀法来制备聚合物粉末原料，例如聚酰胺粉末。在该方法中，通常将聚酰胺溶解于合适的溶剂中，通过搅拌使物料在溶剂中均匀分布并冷却析出粉末沉淀。例如，CN103374223A公开了一种以AABB-型聚酰胺为基础的沉淀聚合物粉末，其通过对二胺和二羧酸的缩聚作用获得的聚酰胺进行再沉淀而获得。在该专利描述的方法中，在再沉淀过程中采用醇类溶剂。但是，这种方法需要使用大量有机溶剂，并且产率和效率均较低，不具备环保和经济优势。
当聚合物是聚丙烯时，由于聚丙烯的生产特性，无法使用一般的聚合物微粒制备方法如乳液聚合法、无皂乳液聚合法、微乳液聚合法、细乳液聚合法、悬浮聚合法、分散聚合法、沉淀聚合法和种子聚合法等。只能利用材料的低温脆性，在低温条件下将其粉碎成微米级的粉末，但是聚烯烃的粉碎往往需要采取成本相对较高的液氮深冷处理方式来进行粉碎，最为不足的是粉碎得到的粉末形态差，为不规则形状，流动性差。在SLS技术烧结时，聚合物微粒需要进行逐层铺粉后逐层烧结，而使用这种不规则形状流动性差微粒时，铺粉非常困难，导致打印无法进行。聚合物的结晶组成越均一，聚合物的熔体流动速率指数越高，在打印时有利于熔融均匀，越有利于打印件的结构稳定性。因此急需一种流动性好，形态好的聚丙烯微球以满足实际需要。
聚丙烯发泡材料具有密度低、比强度高、热稳定性好、抗冲击性能优异、生产原料和过程绿色环保、易回收循环利用等优点，可用作缓冲、减震、隔音、隔热等功能材料。目前常见的聚丙烯发泡材料根据加工工艺不同，主要可分为釜压发泡、模压发泡、挤出发泡和注塑发泡四种。而釜压发泡聚丙烯(Expanded polypropylene,EPP)珠粒及成型体除了具备聚丙烯发泡材料共有优点外，其最显著优势在于自由成型性，可将EPP珠粒经模塑成型从而得到具有复杂几何形状和三维尺寸精度高的发泡制品。聚丙烯发泡粒子模塑制品刚性好，抗冲击性能优于聚苯乙烯，而且与聚苯乙烯泡沫的难回收性相比，聚丙烯泡沫是一种环境友好的材料，有较高的热变形温度，可以在一些高温领域中应用，具有很好的吸收能量特性和优异的抗压吸能性能，尺寸形状恢复稳定性好，制品能够承受多次连续 撞击和挠曲而不产生永久形变，发泡制品的密度低，易回收再利用，制品无毒且燃烧不产生有毒物质。这些优良特性使得其应用非常广泛，在包装、汽车、建筑等领域的应用不断得到拓展。特别适合在汽车内外饰、冷链物流和电子产品包装等高端领域应用。
对于EPP珠粒来说，模内二次成型性能是非常重要的。这就要求发泡原料要选择具有规则的形状(最好近似为球形)和较小的粒径的聚丙烯微颗粒。较规则的球状微颗粒所制备的发泡珠粒也近似为球状，在成型加工中易于紧密堆积，不易形成较大的孔隙。聚丙烯发泡粒子的制备同样也需要使用成本相对较高的液氮深冷处理方式来进行粉碎，粉末形态差，为不规则形状，流动性差，使颗粒在输送时容易产生架桥，导致生产不稳定，而且这种粉碎颗粒往往会导致发泡不均匀，表面比较粗糙，产生发白现象。相同膨胀倍率下，PP微颗粒越小，发泡后的珠粒就越小，有利于EPP珠粒在成型设备的工艺管道中的输送，减少堵塞现象，并能够在模腔内堆积紧密。从而成型时珠粒之间粘结效果更好，使用的蒸汽量更低，制品的力学性能和保温性能更佳。此外，小的粒径有利于制备薄壁、结构复杂的制品，制品的表面也更光滑平整。
常规的牵条切粒和水下切粒通常难以制备得到0.5mm粒径以下的粒子，且长径比偏高。如果想得到平均粒径在0.5mm以下的微颗粒，往往需要使用成本相对较高的液氮深冷处理方式来进行粉碎，粉末形态差，为不规则形状，流动性差，使颗粒在输送时容易产生架桥，导致生产不稳定，而且这种粉碎颗粒往往会导致发泡不均匀，表面比较粗糙，产生发白现象。
使用ZN催化剂制备的聚丙烯的结晶分布往往存在较大的分散性，这在DSC测试结果上反映出其半峰宽比较宽，而使用茂金属催化剂制备的聚丙烯的结晶分布较为均匀，但是后者的分子量分布较窄，这往往使得其产品加工性能较差，前者所得产品的分子量分布较宽，更有利于提高树脂的刚韧平衡性。
所以，开发一种流动性好、形态好、可用于3D打印和发泡材料的聚丙烯微球制备方法具有重要的现实意义。
发明内容
为了解决现有技术中聚丙烯微球存在结晶序列分布均一性较差，用于3D打印时熔融均匀制品性不良的技术问题，本发明提出了一种聚丙烯微球及其制备方法。
根据本发明的第一方面，提供了一种聚丙烯微球，所述聚丙烯微球包括0.2wt％～10wt％的衍生自乙烯的结构单元和90wt％～99.8wt％的衍生自丙烯的结构单元，其中，通过差示扫描量热仪(DSC)获得聚丙烯微球熔融吸热曲线，所述聚丙烯微球熔融吸热曲线的半峰宽(Wm)为4～10℃。
可选地，所述聚丙烯微球熔融吸热曲线的半峰宽为5～8℃。
可选地，所述聚丙烯微球的分子量分布(Mw/Mn)为4～9。
可选地，所述聚丙烯微球的分子量分布为5、6、7、8，或为上述任意两点间的任意值。
可选地，所述聚丙烯微球的堆密度为0.20g/cm 3～0.50g/cm 3，优选为0.32g/cm 3～0.48g/cm 3。
可选地，所述聚丙烯微球的休止角为10°～23°，优选为13°～20°。
可选地，所述聚丙烯微球的等规指数为60％～94％，优选为64％～90％。
可选地，所述聚丙烯微球的灰分为0.005％～0.04％。
可选地，所述聚丙烯微球的灰分为0.01％、0.015％、0.02％、0.025％、0.03％、0.035％，或为上述任意两点间的任意值。
可选地，所述聚丙烯微球的熔融指数为3～160g/10min，优选为15～100g/10min。
可选地，进行DSC测试时，DSC结果满足以下特征：λi＝(dH/dt) i+1-(dH/dt) i，λi≮0(i满足T m<T i<T fm)，其中，纵坐标为热流率dH/dt，横坐标为温度T。
DSC测试所得熔融吸热曲线中，吸热效应用凸起的峰值来表征(热焓增加)。
DSC采用Perkin-Elmer DSC-7型差示扫描量热仪，以10℃/min加热试样至200℃，保持5min，然后以10℃/min降至50℃，在50℃保持1min后以10℃/min再升至200℃。DSC示意图如图2所示，DSC结果纵坐标为dH/dt热流率，横坐标为温度(T)，吸热效应用凸起的峰值来表征(热焓增加)，升温曲线以第二次升温的曲线作为结果(通常都是采用第二次升温曲线，目的是为了消除测试样品的热历史)。如通常表示一样，T m表示测试样品的熔点，T fm表示熔融峰与基线相连的位置的温度。
本发明所得具有更窄半峰宽的聚合物微球在进行釜压发泡与成型时，可以显著提高EPP珠粒的发泡倍率和均匀性，可以在更低的温度成型，降低EPP珠粒成型时的能耗，加快EPP珠粒成型的生产周期，从而有效降低EPP珠粒及成型体的生产成本。且以该珠粒制备的EPP珠粒成型体具有更优秀的外观质量，尤其有利于制备薄壁或形状复杂的EPP成型体产品。
可选地，所述聚丙烯微球的平均粒径为50μm～200μm；优选地，所述聚丙烯微球的平均粒径为60μm～160μm；最优选地，聚丙烯微球的平均粒径为80μm～120μm。
可选地，所述聚丙烯微球的长径比为0.9～1.1；优选地，所述聚丙烯微球的长径比为0.95～1.05；最优选地，聚丙烯微球的长径比为1。
作为本发明的具体实施方式，所述聚丙烯微球通过直接共聚制得。
根据本发明的第二方面，提供了一种上述聚丙烯微球的制备方法，包括：在烯烃聚合催化剂体系存在下，使含丙烯的烯烃进行共聚得到聚丙烯微球。
可选地，所述烯烃聚合催化剂体系包含以下组分或以下组分的反应产物：催化剂、烷基铝化合物和任选加入或不加入的外给电子体化合物。
所述烷基铝化合物可以为烯烃聚合领域常用的各种能够用作齐格勒-纳塔型催化剂的助催化剂的烷基铝化合物。
可选地，所述烷基铝化合物可以但不限于是三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氢二乙基铝、一氢二异丁基铝、一氯二乙基铝、一氯二异丁基铝、倍半乙基氯化铝和二氯乙基铝中的至少一种。
所述外给电子体化合物可以为烯烃聚合领域常用的各种能够用作齐格勒-纳塔型催化剂的助催化剂的外给电子体化合物。
可选地，所述外给电子体化合物可以但不限于是三甲基甲氧基硅烷、三甲基乙氧基硅烷、三甲基苯氧基三乙基甲氧基硅烷、三乙基乙氧基硅烷、二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、乙基异丙基二甲氧基硅烷、丙基异丙基二甲氧基硅烷、二异丙基二甲氧基硅烷、二异丁基二甲氧基硅烷、异丙基异丁基二甲氧基硅烷、二叔丁基二甲氧基硅烷、叔丁基甲基二甲氧基硅烷、叔丁基乙基二甲氧基硅烷、叔丁基丙基二甲氧基硅烷、叔丁基异丙基二甲氧基硅烷、叔丁基丁基二甲氧基硅烷、叔丁基异丁基二甲氧基硅烷、叔丁基(仲丁基)二甲氧基硅烷、叔丁基戊基二甲氧基硅烷、叔丁基壬基二甲氧基硅烷、叔丁基己基二甲氧基硅烷、叔丁基庚基二甲氧基硅烷、叔丁基辛基二甲氧基硅烷、叔丁基癸基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷、环己基甲基二甲氧基硅烷、环己基乙基二甲氧基硅烷、环己基丙基二甲氧基硅烷、环己基异丁基二甲氧基硅烷、二环己基二甲氧基硅烷、环己基叔丁基二甲氧基硅烷、环戊基甲基二甲氧基硅烷、环戊基乙基二甲氧基硅烷、环戊基丙基二甲氧基硅烷、环戊基叔丁基二甲氧基硅烷、二环戊基二甲氧基硅烷、环戊基环己基二甲氧基硅烷、双(2-甲基环戊基)二甲氧基硅烷、二苯基二 甲氧基硅烷、二苯基二乙氧基硅烷、苯基三乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、丙基三甲氧基硅烷、异丙基三甲氧基硅烷、丁基三甲氧基硅烷、丁基三乙氧基硅烷、异丁基三甲氧基硅烷、叔丁基三甲氧基硅烷、仲丁基三甲氧基硅烷、戊基三甲氧基硅烷、异戊基三甲氧基硅烷、环戊基三甲氧基硅烷、环己基三甲氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、正丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-2-乙基哌啶基二甲氧基硅烷和(1,1,1-三氟-2-丙基)-甲基二甲氧基硅烷中的至少一种。更优选地，所述外给电子体化合物可以为二环戊基二甲氧基硅烷、二异丙基二甲氧基硅烷、二异丁基二甲氧基硅烷、环己基甲基二甲氧基硅烷、甲基叔丁基二甲氧基硅烷和四甲氧基硅烷中的至少一种。
可选地，所述催化剂包括含镁的化合物载体、钛化合物和内给电子体化合物。
可选地，所述钛化合物与含镁的化合物载体、内给电子体化合物的摩尔比为(37～255):(2～15):1，优选为(67～235):(4～12):1。
可选地，所述含镁的化合物载体的结构如式(I)所示；
Figure PCTCN2022127943-appb-000001
式(I)中，R 1为C 1-C 10的烷基；
R 2和R 3相同或不相同，各自独立地为H、C 1-C 10的烷基或由1～10个卤素原子取代的C 1-C 10的卤代烷基；
R 4为由至少一个卤素原子取代的C 1-C 10的卤代烷基或由至少一个卤素原子取代的C 6-C 20的卤代芳香基；
R 5为C 1-C 5的烷基；
X为氟、氯、溴或碘；优选地，X为氯或溴；
m为0.1～1.9，n为0.1～1.9，且m+n＝2；优选地，m为0.8～1.2，n为0.8～1.2；
0<q<0.2；0<a<0.1；优选地，0.005≤q≤0.2；0.001<a<0.05。
可选地，所述内给电子体化合物选自羧酸酯、醇酯、醚、酮、腈、胺和硅烷 中的至少一种，优选为一元或多元脂肪族羧酸酯、一元或多元芳香族羧酸酯、二元醇酯和二元醚中的至少一种。
可选地，所述二元醇酯可为羧酸二醇酯。
可选地，所述内给电子体化合物为二元醚中的至少一种，所述二元醚结构如式(Ⅲ)所示：
Figure PCTCN2022127943-appb-000002
其中，R 21和R 22各自独立地选自氢、C 1-C 20的烷基、C 3-C 20的环烷基、C 6-C 20的芳基、C 7-C 20的芳烷基或C 7-C 20的烷芳基，R 21和R 22之间可任选地键接成环；R 23和R 24各自独立地为C 1-C 10的烷基。
具体地，所述内给电子体化合物可选自2-(2-乙基己基)-1,3-二甲氧基丙烷、2-异丙基-1,3-二甲氧基丙烷、2-丁基-1,3-二甲氧基丙烷、2-仲丁基-1,3-二甲氧基丙烷、2-环己基-1,3-二甲氧基丙烷、2-苯基-1,3-二甲氧基丙烷、2-(2-苯基乙基)-1,3-二甲氧基丙烷、2-(2-环己基乙基)-1,3-二甲氧基丙烷、2-(对-氯苯基)-1,3-二甲氧基丙烷、2-(二苯基甲基)-1,3-二甲氧基丙烷、2,2-二环己基-1,3-二甲氧基丙烷、2,2-二环戊基-1,3-二甲氧基丙烷、2,2-二乙基-1,3-二甲氧基丙烷、2,2-二丙基-1,3-二甲氧基丙烷、2,2-二异丙基-1,3-二甲氧基丙烷、2,2-二丁基-1,3-二甲氧基丙烷、2-甲基-2-丙基-1,3-二甲氧基丙烷、2-甲基-2-苄基-1,3-二甲氧基丙烷、2-甲基-2-乙基-1,3-二甲氧基丙烷、2-甲基-2-异丙基-1,3-二甲氧基丙烷、2-甲基-2-苯基-1,3-二甲氧基丙烷、2-甲基-2-环己基-1,3-二甲氧基丙烷、2,2-双(2-环己基乙基)-1,3-二甲氧基丙烷、2-甲基-2-异丁基-1,3-二甲氧基丙烷、2-甲基-2-(2-乙基己基)-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷、2,2-二苯基-1,3-二甲氧基丙烷、2,2-二苄基-1,3-二甲氧基丙烷、2,2-双(环己基甲基)-1,3-二甲氧基丙烷、2-异丁基-2-异丙基-1,3-二甲氧基丙烷、2-(1-甲基丁基)-2-异丙基-1,3-二甲氧基丙烷、2-异丙基-2-异戊基-1,3-二甲氧基丙烷、2-苯基-2-异丙基-1,3-二甲氧基丙烷、2-苯基-2-仲-丁基-1,3-二甲氧基丙烷、2-苄基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-仲-丁基-1,3-二甲氧基丙烷、2-环己基-2-异丙基-1,3-二甲氧基丙烷、2-环己基-2-仲-丁基-1,3-二甲氧基丙烷、2-异丙基-2-仲-丁基 -1,3-二甲氧基丙烷、2-环己基-2-环己基甲基-1,3-二甲氧基丙烷和9,9-二甲氧基甲基芴中的至少一种。
可选地，所述钛化合物的通式为Ti(OR 6) 4-bX' b，其中，R 6为C 1-C 14的脂肪烃基，X'为F、Cl或Br，b为1～4的整数。
所述钛化合物优选为四氯化钛、四溴化钛、四氟化钛、三丁氧基氯化钛、二丁氧基二氯化钛、丁氧基氯化钛、三乙氧基氯化钛、二乙氧基二氯化钛和乙氧基氯化钛中的至少一种。
可选地，所述含镁的化合物载体的制备方法包括以下步骤：
S1：将通式为MgX"Y的卤化镁和通式为R 7OH的第一醇类化合物进行第一次接触和乳化，得到第一产物；
S2：将具有式(II)所示结构的环氧乙烷类化合物与第一产物进行第二接触，得到第二产物；
S3：将含有通式为R 10OH的卤代醇、通式为R 11OH的第二醇类化合物与第二产物进行第三接触，得到第三产物；
S4：将第三产物进行喷雾干燥，得到含镁的化合物载体。
可选地，作为本发明的具体实施方式，所述S1中，所述通式MgX"Y中，X"选自氟、氯、溴或碘；Y选自氟、氯、溴、碘、C 1-6的烷基、C 1-6的烷氧基、C 6-14的芳基或C 6-14的芳氧基。
优选地，X"选自氯或溴，Y选自氯、溴、C 1-5的烷基、C 1-5的烷氧基、C 6-10的芳基或C 6-10的芳氧基。当Y选自C 1-6的烷基、C 1-6的烷氧基时，所述烷基和所述烷氧基为直链的或支链的烷基和烷氧基基团；所述C 1-6的烷基指具有1～6个碳原子的烷基基团，例如包括但不限于甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基等；所述C 1-6的烷氧基指具有1～6个碳原子的烷氧基基团，例如包括但不限于甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基、正戊氧基、异戊氧基等。
所述C 6-14的芳基指具有6～14个碳原子的芳基基团，例如包括但不限于苯基、邻甲苯基、间甲苯基、对甲苯基、邻乙苯基、间乙苯基、对乙苯基、萘基等。
所述C 6-14的芳氧基指具有6～14个碳原子的芳氧基基团，例如包括但不限于苯氧基、萘氧基、邻甲基苯氧基、邻乙基苯氧基、间甲基苯氧基等。
可选地，所述卤化镁选自氯化镁、溴化镁、氯化苯氧基镁、氯化异丙氧基镁和氯化正丁氧基镁中的至少一种，优选为氯化镁。
可选地，所述式R 7OH中，R 7为C 1-10的烷基。
可选地，所述S2中，所述环氧乙烷类化合物的结构式如式(II)所示，
Figure PCTCN2022127943-appb-000003
其中，R 8和R 9各自独立地选自H、C 1-10的烷基、由1～10个卤素原子取代的C 1-10的卤代烷基；优选地，R 8和R 9各自独立地选自H、C 1-5的烷基、由1～10个卤素原子取代的C 1-5的卤代烷基。
可选地，所述环氧乙烷类化合物选自环氧乙烷、环氧丙烷、环氧丁烷、环氧氯丙烷、环氧氯丁烷、环氧溴丙烷和环氧溴丁烷中的至少一种。。
可选地，所述S3中，所述式R 10OH中，R 10选自由至少一个卤素原子取代的C 1-10的卤代烷基或由至少一个卤素原子取代的C 6-20的卤代芳香基。
所述卤代醇可以为单卤代醇或多卤代醇，优选为氯代醇、溴代醇或碘代醇，例如为2,2,2-三氯乙醇、2,2-二氯乙醇、2-氯乙醇、3-氯-1-丙醇、6-氯-1-己醇、3-溴-1-丙醇、5-氯-1-戊醇、4-氯-1-丁醇、2-氯环己醇、1,2-二氯乙醇、1,3-二氯丙醇、1,4-二氯丁醇或2-碘乙醇等。
但是，为了能够获得性能更好的催化剂载体，根据本发明再一种优选的具体实施方式，在式R 10OH中，R 10选自由至少两个卤素原子取代的C 1-10的卤代烷基或由至少两个卤素原子取代的C 6-20的卤代芳香基，且所述卤素原子选自氯原子、溴原子和碘原子中的至少一种。
优选地，所述卤代醇选自2,2,2-三氯乙醇、2,2-二氯乙醇、1,2-二氯乙醇、1,3-二氯丙醇、1,4-二氯丁醇中的至少一种。
可选地，所述式R 11OH中，R 11为C 1-5的烷基。
本发明中，所述第二醇类化合物为乙醇、甲醇、正丙醇、异丙醇、正丁醇或异丁醇。但是，为了能够获得性能更好的催化剂载体，根据本发明又一种优选的具体实施方式，在式R 11OH中，R 11为C 1-2的烷基，也即所述第二醇类化合物为甲醇和/或乙醇。
可选地，相对于1mol所述卤化镁，所述卤代醇的用量为0.05～6.5mol，所述第二醇类化合物的用量为5～100mol。
卤代醇化合物的用量过大时，所得催化剂载体发粘结块，无法进行后续操作。
可选地，相对于1mol所述卤化镁，所述第一醇类化合物的用量为1～30mol，所述环氧乙烷类化合物的用量为1～10mol。
优选地，相对于1mol所述卤化镁，所述第一醇类化合物的用量为6～22mol，所述环氧乙烷类化合物的用量为2～6mol，所述卤代醇的用量为1～5mol，所述第二醇类化合物的用量为8～80mol，更优选为31～50mol。
需要说明的是，上述各反应物中携带的微量水也会参与形成所述球形载体的反应中，因此，制备得到的所述球形载体中可能会含有来自于反应原料和反应介质所带的微量水，本领域技术人员不应理解为对本发明的限制。
可选地，所述S1中所述第一接触在搅拌的条件下进行，所述第一接触的条件包括：温度为80～120℃，时间为0.5～5h；优选地，在S1中，所述第一接触的条件包括：温度为80～100℃，时间为0.5～3h。
在S1中，本发明对所述乳化的具体操作方法没有特别限制，可以采用本领域技术人员公知的方法进行。例如采用低速剪切或高速剪切进行乳化。优选地，采用低速剪切时，所述低速剪切的搅拌速率为400～800rpm。所述高速剪切的方法为本领域技术人员所公知，例如采用CN1330086A公开的高速搅拌速度进行。此外，还可以参照以下专利申请公开的方法进行所述乳化操作，如CN1580136A公开的将含有液态卤化镁化合物的溶液在超重力床中进行旋转分散(旋转的速度为100-3000rpm)；再如CN1463990A公开的将含有液态卤化镁加合物的溶液在乳化机中以1500～8000rpm的速度输出；又如US6020279A公开的通过喷雾法将含有液态卤化镁加合物的溶液乳化。
可选地，在S2中，所述第二接触的条件包括：温度为50～120℃，时间为20～60min；优选地，所述第二接触的条件包括：温度为80～100℃，时间为20～50min。
可选地，在S3中还包括，将所述第二产物使用惰性溶剂洗涤后再与含有通式为R 10OH的卤代醇、通式为R 11OH的第二醇类化合物进行所述第三接触；优选地，所述惰性溶剂选自戊烷、己烷、庚烷、石油醚和汽油中的至少一种。
本发明对S3中的所述第三接触的具体条件没有特别限制，只要能够使得所述含有通式为R 10OH的卤代醇、通式为R 11OH的第二醇类化合物与所述第二产物能够充分接触形成流体即可。但是为了能够具有更好性能的催化剂载体；优选地，在S3中，所述第三接触的条件包括：在搅拌的条件下进行，温度为0～120℃，时间为0.5～6h。
本发明对S3中的所述第三接触的具体方式没有特别限制，可以将所述卤代 醇和所述第二醇类化合物两者混合同步与所述第二组分进行接触，也可以将所述卤代醇和所述第二醇类化合物分别依次与所述第二组分进行接触。
作为本发明的具体实施方式，所述S4中，所述喷雾干燥的条件可以采用现有的能够形成用于烯烃聚合的催化剂载体的条件，但是为了能够得到性能更好的催化剂载体，根据本发明一种优选的具体实施方式，所述喷雾干燥在具有雾化喷嘴的喷雾机中实施，所述雾化喷嘴含有物料导管和喷嘴头，所述第三产物通过所述物料导管引至所述喷嘴头中，并且通过所述喷嘴头喷射至喷雾机的含有惰性介质的塔体内进行固化。优选地，所述第三产物在所述物料导管中的温度为0℃至80℃之间，并且所述第三产物在所述喷嘴头中的温度为80～180℃；更加优选所述第三产物在所述喷嘴头中的温度为120～180℃。
可选地，在S4中，所述喷雾干燥的条件包括：温度为60～200℃，更优选为90～150℃。本发明中，所述喷雾干燥的温度指的是所述喷雾机中的惰性介质的温度。
作为本发明的具体实施方式，所述惰性介质可以包括保护气体介质和/或惰性液体介质，对所述保护气体介质的种类没有特别的限定，例如可以为氮气也可以为惰性气体介质如氦气，也可以是其它适宜气体如二氧化碳等；所述惰性液体介质为本领域常用的各种不与反应物和反应产物发生化学作用的液体介质，优选所述惰性液体介质为硅油和/或惰性液体烃类溶剂；更优选地，所述惰性液体介质选自煤油、石蜡油、凡士林油、白油、甲基硅油、乙基硅油、甲基乙基硅油、苯基硅油和甲基苯基硅油中的至少一种，更进一步优选为白油。
作为本发明的具体实施方式，所述喷雾机中的惰性液体介质的用量可以根据通式为MgX"Y的卤化镁的用量来选择，优选为0.8～10L，更优选为2～8L。
作为本发明的具体实施方式，在本发明所述的制备方法中，还包括本领域常规的如固液分离、洗涤、干燥等后处理手段，本发明对此没有特别限制。所述固液分离可以采用现有的各种能够实现固相与液相分离的方法，例如抽滤、压滤或离心分离等，优选情况下，所述固液分离的方法为压滤法。本发明对压滤的条件没有特别地限定，以尽可能充分地实现固相与液相的分离为准。所述洗涤可以采用本领域技术人员公知的方法将得到的固相产物进行洗涤，例如可以采用惰性烃类溶剂(如戊烷、己烷、庚烷、石油醚和汽油)对得到的固相产物进行洗涤。本发明对于所述干燥的具体条件没有特别限定，例如所述干燥的温度可以为20～70℃，所述干燥的时间可以为0.5～10h，所述干燥可以在常压或减压条件下进 行。
作为本发明的具体实施方式，对所述催化剂的组成没有特别限制，可以为本领域现有的用于烯烃聚合的催化剂的组成，但是为了能够得到适于用于烯烃聚合，特别是丙烯聚合的催化剂；优选地，所述催化剂中含有所述载体、卤化钛化合物和给电子体化合物。优选地，所述卤化钛化合物选自四氯化钛、四溴化钛、四碘化钛、四正丁氧基钛、四乙氧基钛、一氯三正丁氧基钛、二氯二正丁氧基钛、三氯一正丁氧基钛、一氯三乙氧基钛、二氯二乙氧基钛、三氯一乙氧基钛和三氯化钛中的至少一种；优选地，所述给电子体化合物选自邻苯二甲酸二异丁酯、羧酸二醇酯、磷酸酯中的至少一种。同时，本发明对所述催化剂中的各组分的含量没有特别限制，本领域技术人员可以根据实际需要进行合理的调节设计。
可选地，所述含镁的化合物载体的平均颗粒直径为2～100微米，粒径分布小于2；优选地，所述含镁的化合物载体的平均颗粒直径为2～19微米，粒径分布为0.6～1.6。
为了使采用含有含镁的化合物载体的催化剂用于烯烃聚合时，得到具有更高堆积密度的烯烃聚合物，进一步优选地，所述含镁的化合物载体的平均颗粒直径为2～10微米，粒径分布为0.6～1。
本发明的聚丙烯微球制备方法中，催化剂在催化丙烯聚合过程中具有“形貌复制”的特性，虽然球形催化剂不一定得到球形聚合物，但是球形聚合物一般只能是由球形催化剂制备得到的。粒径越小的催化剂得到的聚合物的粒径也一般更小，而且催化剂本身的结构和形貌对聚合物的形态起重要的作用。良好的催化剂结构和形貌有利于降低聚合物之间的摩擦力等，使最终聚合物的休止角减少，从而有利于聚合物的生产和传输。
根据本发明的第三方面，提供了一种3D打印原料，包括：上述聚丙烯微球和/或根据上述制备方法制得的聚丙烯微球。
根据本发明的第四方面，提供了一种上述聚丙烯微球或根据上述制备方法制得的聚丙烯微球在用于3D打印的用途，尤其用于激光烧结打印，最优选地，用于选择性激光烧结(Selective Laser Sintering,SLS)的用途。
与现有技术相比，本发明包括以下有益效果：
1、现有普通聚丙烯微球的半峰宽较宽，而本发明聚丙烯微球的半峰宽仅为4～10℃，比现有更窄，这说明得到的聚丙烯微球的结晶序列分布比较均一，用于3D打印时，可改善聚合物颗粒熔融与融合的均匀性，能够使得3D打印熔融均 匀制品性能好，提升了烧结试样的结构强度和表面性能；同时，本发明相对于茂金属催化剂制得的聚丙烯微球具有更宽的分子量分布，使得所得的烧结制品具有更好的刚韧平衡性。
2、本发明聚丙烯微球的平均粒径小于160微米，可直接用于3D打印，无需二次加工；本发明聚丙烯微球的休止角小于23°，具有更好的流动性，打印时铺粉更加均匀；本发明聚丙烯微球的乙烯含量大于0.2wt％，在3D打印过程中不翘曲。本发明聚丙烯微球呈现良好的球形形貌，颗粒规整，流动性好，极具工业应用前景。
3、本发明的聚丙烯微球制备方法，催化剂的比表面大且聚合活性好，同时由于催化剂的特性，可以减少烷基铝的使用，采用更少量的三乙基铝，与环己基甲基二甲氧基硅烷、催化剂、氢气和丙烯单体混合反应得到聚丙烯微球，使所得聚合物微球的灰分进一步降低且基本无异形料的出现。
4、本发明聚丙烯微球制备方法中，通过催化剂的“形貌复制”的特性直接聚合得到球形聚合物；由于催化剂的结构和形貌的良好特性使所得聚合物之间的摩擦力小，聚合物的休止角小，有利于聚合物的生产和传输。
5、本发明提供的聚丙烯微球是由反应器直接聚合得到的，避免了后期加工流程，节省了成本。
附图说明
图1为实施例1-1所得聚丙烯粉料的电子显微镜图。
图2为DSC示意图。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但并不构成对本发明的任何限制。
本发明中，含镁的化合物载体的平均颗粒直径和粒径分布采用Masters Sizer2000粒度仪(由Malvern Instruments Ltd生产制造)进行测定。
本发明中，聚丙烯粉料的表观形貌通过美国FEI公司生产的XL-30型场发射电子显微镜观察。
本发明中，含镁的化合物载体的结构及组成，采用瑞士Bruker公司的AVANCE 300核磁共振谱仪，对载体进行1H-NMR测试，以及采用Fronteerlab 公司的PY-2020iD型裂解器、Thermo Fisher公司的TraceGC Ultra型色谱仪和DSDⅡ型质谱仪对载体进行测试得到。
本发明中，DSC检测采用《GBT 19466塑料差示扫描量热法(DSC)》规定的方法进行测定。其中，DSC检测的半峰宽是指通过峰高的中点作平行于基线的直线，此直线与峰两侧相交两点之间的温度差绝对值。
本发明中，聚丙烯粉料的分子量分布指数Mw/Mn的测试方法采用GB/T36214-2018规定的方法进行测定。
本发明中，催化剂共聚活性通过聚合后所得产物的重量与催化剂用量重量的比值进行评测。
本发明中，聚丙烯粉料的堆密度采用GB/T 1636-2008规定的方法进行测定。
本发明中，聚丙烯粉料的灰分测定采用GB_T 9345.1-2008规定的方法进行测定。
本发明中，聚丙烯粉料的比表面积采用POREMASTER GT60型压汞仪进行测试。
本发明中，聚丙烯粉料的休止角采用GB/T 11986-1989规定的方法进行测定。
本发明中，聚丙烯粉料的长径比是指颗粒投影中长轴与其平均短轴之比。
本发明中，聚丙烯粉料的乙烯含量采用傅里叶变换红外光谱仪测定乙烯含量，热压薄膜法制备试样。
本发明中，样条的拉伸强度采用GB/T 1040.2-2006规定的方法进行测定。
本发明中，表面光滑度采用比较法：将被测表面与标准品相比较，通过视觉、触感或其它方法进行比较后，对被测表面的粗糙度作出评定。由5个工作人员进行评分，标准品为10分，然后取平均得分。
得分 评价
1-2 很差
3-4 差
5-6 一般
7-8 好
9-10 良好
本发明中，在没有特别说明的情况下，所用原料均为市售品：
1,3-二氯丙醇购自百灵威公司；
环氧氯丙烷购自百灵威公司；
邻苯二甲酸二异丁酯购自百灵威公司；
四氯化钛购自百灵威公司；
三乙基铝购自百灵威公司；
环己基甲基二甲氧基硅烷购自百灵威公司。
本发明各实施例和对比例中，没有特别说明的情况下，在催化剂载体的制备过程中，乳化均是通过在600rpm的搅拌下进行的。
DSC采用Perkin-Elmer DSC-7型差示扫描量热仪，以10℃/min加热试样至200℃，保持5min，然后以10℃/min降至50℃，在50℃保持1min后以10℃/min再升至200℃；在二次升温测试结果中使用公式λi＝(dH/dt) i+1-(dH/dt) i计算λi≮0(i满足T m<T i<T fm时)，所得结果如果有小于0，则λi≮0为否，反之，如果所计算的值均不小于0，则λ i≮0为是。λi为T i+1温度时与T i温度时的热流率差值。
实施例1-1
1)含镁的化合物载体的制备
S1：在0.6L的反应釜中，依次加入0.08mol氯化镁、1.7mol乙醇(第一醇类化合物)，在搅拌下升温至90℃，恒温反应1h进行第一接触，然后进行乳化，得到第一产物；
S2：将所述第一产物与0.48mol的环氧氯丙烷进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
S3：将所述第二产物压滤后，与2.5mol乙醇(第二醇类化合物)和0.35mol的1,3-二氯丙醇(卤代醇)充分混合搅拌进行第三接触形成流体，得到第三产物；
S4：使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中进行喷雾干燥，所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，获得催化剂球形载体Z1。
经测试，所述催化剂球形载体Z1的平均颗粒直径(D50)为4微米，粒径分布((D90-D10)/D50)为0.9。
经观测，所述催化剂球形载体Z1的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z1的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共得到11.8g催化剂球形载体Z1。
2)烯烃聚合用催化剂的制备
S1：在300mL的反应瓶中，加入100mL的四氯化钛，冷却至零下20℃，将8克的由实施例1得到的催化剂球形载体Z1加入其中，并在零下20℃下搅拌30min，得到第一产物；
S2：将S1得到的第一产物缓慢升温至110℃，在升温过程中加入1.5mL的2-异丙基-2-异戊基-1,3-二甲氧基丙烷，在110℃下维持30min后，滤去液体，得到第二产物；
S3：将S2得到的第二产物用四氯化钛洗涤2次，再用己烷洗3次，干燥，得到烯烃聚合用催化剂C1。
3)聚丙烯共聚物微球的制备
在一个5L的不锈钢高压反应釜中，在氮气保护气氛下，加入0.25mmol的三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、10mL的无水己烷、10mg的催化剂C1、1.5L(标准体积)的氢气和2L的液体丙烯单体，通入乙烯，升温至70℃，在该温度下反应40min，然后降温、放压、出料、干燥，得到共聚的聚丙烯粉料。
实施例1-1得到的共聚的聚丙烯粉料从电子显微镜观看呈现良好的球形形态(图1)，基本不存在异形料。
实施例1-2
本实施例采用实施例1-1提供的方法制备聚丙烯，不同的是：使用的氢气的体积不同，其余均相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
该聚丙烯粉料从电子显微镜观看呈现良好的球形形态，基本不存在异形料。
实施例2-1
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.4mol乙醇(第一醇类化合物)，在搅拌下升温至90℃，恒温反应1.5h进行第一接触，然后通过进行乳化，得到第一产物；
(2)将所述第一产物与0.35mol环氧氯丙烷进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
(3)将所述第二产物压滤后，与2.5mol乙醇(第二醇类化合物)和0.25mol的1,3-二氯丙醇(卤代醇)充分混合搅拌进行第三接触形成流体，得到第三产物；
(4)使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中进行喷雾干燥，所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，得到催化剂球形载体Z2。
经测试，所述催化剂球形载体Z2的平均颗粒直径(D50)为4微米，粒径分布((D90-D10)/D50)为0.8。
经观测，烯烃聚合用催化剂球形载体Z2的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z2的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共得到11.9g的所述催化剂球形载体Z2。
采用与实施例1-1相似的方式制备聚丙烯，不同的是：在步骤S1中，使用的催化剂载体的种类不同，其余均与实施例1-1中相同。
具体的：用相同重量的实施例2-1制备得到的所述催化剂球形载体Z2代替所述催化剂球形载体Z1，得到烯烃聚合用催化剂C2；
经测试，通过电子显微镜观察，催化剂C2呈球形。经测试，催化剂C2的平均颗粒直径(D50)为4微米，粒径分布((D90-D10)/D50)为0.8。
所得聚丙烯粉料颗粒形态好，从电子显微镜观看呈现良好的球形形态，基本不存在异形料。
实施例2-2
本实施例采用实施例2-1提供的方法制备聚丙烯，不同的是：使用的氢气的体积不同，其余均相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
该聚丙烯粉料从电子显微镜观看呈现良好的球形形态，基本不存在异形料。
实施例3-1
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.4mol乙醇(第一醇类化合物)，在搅拌下升温至90℃，恒温反应1.5h进行第一接触，然后进行乳化，得到第一产物；
(2)将所述第一产物与0.35mol环氧氯丙烷，进行第二接触，得到第二产物，所述第二接触的条件包括：温度为90℃，时间为30min；
(3)将所述第二产物压滤后与2.5mol乙醇(第二醇类化合物)和0.1mol的1,3-二氯丙醇(卤代醇)，搅拌至进行第三接触形成流体，得到第三产物；
(4)使用含有喷嘴头和物料导管的喷雾机B-290将所述第三产物喷入喷雾机塔内100℃的循环氮气中，所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，得到催化剂球形载体Z3。
经测试，所述催化剂球形载体Z3的平均颗粒直径(D50)为5微米，粒径分布((D90-D10)/D50)为0.8。
经观测，所述催化剂球形载体Z3的颗粒形态比较规整，表面光滑，基本上都是球形的，颗粒尺寸分布比较集中，且基本上没有异形粒子存在。
在制备所述催化剂球形载体Z3的过程中，所述喷雾机的喷嘴头处没有发生堵塞现象，共得到12.0g的所述催化剂球形载体Z3。
催化剂聚合同实施例2-1，除了Z3替代Z2。
该聚丙烯粉料从电子显微镜观看呈现良好的球形形态，基本不存在异形料。
实施例3-2
本实施例采用实施例3-1提供的方法制备聚丙烯，不同的是：使用的氢气的体积不同，其余均相同。
具体的：1.5L(标准体积)的氢气替换为6.5L(标准体积)的氢气，得到聚丙烯粉料。
该聚丙烯粉料从电子显微镜观看呈现良好的球形形态，基本不存在异形料。
实施例4
本实施例采用实施例1-1提供的方法制备聚丙烯，不同的是：除了加入0.25mmol的三乙基铝以外，同时还加入0.01mmol的环己基甲基二甲氧基硅烷，其它都同实施例1-1，得到聚丙烯粉料。
该聚丙烯粉料从电子显微镜观看呈现良好的球形形态，基本不存在异形料。对比制备例3
(1)在0.6L的反应釜中，加入0.08mol氯化镁、1.7mol乙醇，在搅拌下升 温至90℃，恒温反应1h后，加入0.48mol环氧氯丙烷在90℃下反应30min，得到第一产物；
(2)将所述第一产物压滤后，加入2.5mol乙醇进行搅拌至形成流态混合物；
(3)使用含有喷嘴头和物料导管的喷雾机将所述流态混合物喷入100℃的循环氮气中，以及所述第三产物在所述物料导管中的温度为15℃，在所述喷嘴头中的温度为120℃，得到烯烃聚合用催化剂载体DZ3。
所述烯烃聚合用催化剂载体DZ3的平均颗粒直径(D50)为3微米，粒径分布((D90-D10)/D50)为0.8。
对比例1
采用与实施例1-1相似的方式制备聚丙烯，不同的是：在烯烃聚合用催化剂的制备中，以邻苯二甲酸二异丁酯代替2-异丙基-2-异戊基-1,3-二甲氧基丙烷，其余均与相同。
对比例2
采用与对比例1相似的方式制备聚丙烯，不同的是：在聚丙烯共聚物微球的制备中，使用的氢气的体积不同，为6.5NL，其余均与对比例1相同。
对比例3
采用与实施例1-1相似的方式制备聚丙烯，不同的是：以DZ3代替Z1，其余均相同。
对比例4
采用与实施例1-1相似的方式制备聚丙烯，不同的是：聚合时不加乙烯。
对比例5
(1)卤化镁加合物MgXY·mR1OH按照CN1718595中实施例1公开的方法制备得到，具体如下：
在带搅拌的150L的反应器中，将10kg无水氯化镁和12.6kg乙醇加入60L粘度为30厘泊(20℃)的白油中，在125℃下反应2小时。然后将得到的熔融加合物与白油的混合液转移到已预热至125℃的甲基硅油介质中；甲基硅油的粘 度为300厘泊(20℃)，甲基硅油的用量为120L；以200转/分的转速搅拌10-30分钟，得到混合液。将所述混合液引入超重力旋转床进行分散，并在搅拌条件下、将分散后的混合液引入预先降温至-35℃的己烷介质中，己烷的用量为1200L，分散为小液滴的氯化镁/醇加合物熔体被冷却固化，成为球形固体颗粒。从急冷后所得的悬浮液中过滤出固态颗粒物，用己烷在室温下洗涤该颗粒物，己烷用量为100L/次，共洗涤5次，在60℃下抽真空得到固体。
所述卤化镁加合物的平均颗粒直径(D50)为52微米，粒径分布((D90-D10)/D50)为1.1。采用电子显微镜观察粒子的形貌发现，卤化镁加合物的颗粒形态比较规整，表面较为光滑，颗粒尺寸分布比较集中。
经气质、核磁及元素分析确定卤化镁加合物D5的结构式为：MgCl 2·2.5C 2H 5OH。
以D5替代Z1其余与实施例1-1相同。
对比例6
在聚丙烯共聚物微球的制备中使用的氢气的体积不同，为6.5NL，其余均与对比例5相同。
对比例7
使用商业化DDC401催化剂制备的无规共聚聚丙烯粒料，经液氮深冷后粉碎。
表1
Figure PCTCN2022127943-appb-000004
Figure PCTCN2022127943-appb-000005
*无法流动；**无法靠重力落下
表2
  半峰宽(℃) 分子量分布 长径比
实施例1-1 7.2 7.0 1
实施例1-2 7.0 6.9 1
实施例2-1 7.2 6.8 1
实施例2-2 7.0 6.8 1
实施例3-1 7.2 6.6 1
实施例3-2 7.0 6.5 1
实施例4 8.0 5.8 1
对比例1 16.1 - -
对比例2 15.6 - -
对比例3 - 5.8 1
对比例4 - 5.5 1
对比例5 16.3 5.6 1.06
对比例6 16.0 5.4 1.07
对比例7 16.2 - 1.8
由上述表2内容可知，本发明聚丙烯微球具有更宽的分子量分布，且其半峰宽更窄，所得的聚丙烯微球的结晶序列分布比较均一，用于3D打印时，颗粒熔 融均匀，所得制品性能好。且更宽的分子量分布还可以赋予产品更好的刚韧平衡性。
测试例1：激光烧结3D打印
将5mg抗氧剂1010溶于100ml己烷加入一定量上述实施例或对比例所述的聚丙烯粉料，混合均匀后抽干干燥，在选择性激光烧结打印机中，将一定量上述的聚丙烯粉料加入，调节参数：工作温度130～132℃、激光功率40W、扫描速度1500mm·s -1、扫描间距0.1mm，打印样条，然后对样条的力学性能进行测试，具体结果见表3。
表3
  聚合物形状 拉伸强度/MPa 表面光滑度
实施例1-1 球形 33.9 良好
实施例1-2 球形 29.3 良好
实施例2-1 球形 31.0 良好
实施例2-2 球形 27.3 良好
实施例3-1 球形 28.7 好
实施例3-2 球形 25.2 好
实施例4 球形 30.1 良好
对比例1 球形 无法打印 -
对比例2 球形 无法打印 -
对比例3 球形 16.8 差
对比例4 球形 无法打印 -
对比例5 球形 无法打印 -
对比例6 球形 无法打印 -
对比例7 不规则颗粒形 无法打印 -
综上，本发明提供的催化剂所制备的共聚聚丙烯粉料呈现良好的球形形态，流动性好，休止角小，3D打印制件拉伸性能好，物件光滑度好。由于有更小的休止角，铺粉效果好，有利于减少打印过程的空间缺陷，还具有较大的比表面积，与抗氧剂融合效果较好，大大减少了聚丙烯在激光烧结过程局部降解。本发明乙丙共聚产品拥有更窄的DSC测量半峰宽，具有更加均一的共聚物结晶组成，改善了聚合物颗粒熔融与融合的均匀性，使烧结试样的结构强度和表面性能得到提升。
测试例2：釜压发泡珠粒
1、发泡成型体的压缩强度按硬质泡沫塑料压缩性能的测定GB/T8813-2008的方法测量，发泡成型体的弯曲强度按硬质泡沫塑料弯曲性能的测定GB/T8812-2007的方法测量；
2、发泡珠粒的倍率测试方法：使用德国SatoriusCPA225D天平的密度附件YDK01，利用排水法得到聚丙烯组合物发泡珠粒的密度，按照国标GB/T1033.1-2008，ISO1183-1:2012中介绍方法测量。得到的聚丙烯组合物发泡材料的发泡倍率用公式计算：b＝ρ1/ρ2，其中，b为发泡倍率，ρ1为二元无规共聚聚丙烯基础树脂的密度，ρ2为发泡材料的表观密度。
将200g共聚聚丙烯微球置于高压釜内，0.2g抗氧剂1010，分散介质(去离子水)1000g，1g表面活性剂(十二烷基苯磺酸钠)、分散剂(高岭土)1g和分散增强剂(硫酸铝)0.02g加入混合；再充入低压二氧化碳将釜中空气置换干净，再充入高压二氧化碳，升高高压釜温度至138℃，压力控制为6MPa，溶胀渗透30分钟。然后快速卸压至表压为0，卸压速率控制为10MPa/s，并将釜内料放至5℃冷水中，干燥。将前文所述发泡工艺得到的不同发泡珠粒使用模塑成型机在一定蒸汽压力一定时间下模压成型，随后将所获成型体在温度为100℃、压力为标准大气压的条件下熟化24小时，即得到发泡珠粒成型体。
发泡珠粒的发泡倍率、模塑成型的蒸汽压力与成型时间如表4所示。
表4
Figure PCTCN2022127943-appb-000006
Figure PCTCN2022127943-appb-000007
从表4中数据可以看出，本发明的聚合物共聚微球用于发泡时不仅发泡倍率更高，而且所需要的蒸汽压力更低，成型时间更短。更低的蒸汽压力不仅有利于节约能源，降低成本，还有助于减少工艺的风险。更短的成型时间意味着更高的生产效率，对于提高利润，增加生产收入很有意义。
应当注意的是，在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (15)

  1. 一种聚丙烯微球，其特征在于，所述聚丙烯微球包括0.2wt％～10wt％的衍生自乙烯的结构单元和90wt％～99.8wt％的衍生自丙烯的结构单元，其中，通过差示扫描量热仪获得聚丙烯微球熔融吸热曲线，所述聚丙烯微球熔融吸热曲线的半峰宽为4～10℃。
  2. 根据权利要求1所述的聚丙烯微球，其特征在于，所述聚丙烯微球熔融吸热曲线的半峰宽为5～8℃。
  3. 根据权利要求1或2所述的聚丙烯微球，其特征在于，所述聚丙烯微球的分子量分布为4～9。
  4. 根据权利要求1-3任一项所述的聚丙烯微球，其特征在于，所述聚丙烯微球的堆密度为0.20g/cm 3～0.50g/cm 3，优选为0.32g/cm 3～0.48g/cm 3；
    和/或，休止角为10°～23°，优选为13°～20°；
    和/或，等规指数为60％～94％，优选为64％～90％；
    和/或，灰分为0.005％～0.04％；
    和/或，熔融指数为3～160g/10min，优选为15～100g/10min。
  5. 根据权利要求1-4任一项所述的聚丙烯微球，其特征在于，进行DSC测试时，DSC结果满足以下特征：λi＝(dH/dt) i+1-(dH/dt) i，λi≮0(i满足T m<T i<T fm)，其中，纵坐标为热流率dH/dt，横坐标为温度T。
  6. 根据权利要求1-5任一项所述的聚丙烯微球，其特征在于，所述聚丙烯微球的平均粒径为50μm～200μm；优选地，所述聚丙烯微球的平均粒径为60μm～160μm；更优选地，所述聚丙烯微球的平均粒径为80μm～120μm。
  7. 根据权利要求1-6任一项所述的聚丙烯微球，其特征在于，所述聚丙烯微球的长径比为0.9～1.1；优选地，所述聚丙烯微球的长径比为0.95～1.05；更优选地，所述聚丙烯微球的长径比为1。
  8. 一种根据权利要求1-7任一项所述聚丙烯微球的制备方法，其特征在于，该制备方法包括：在烯烃聚合催化剂体系存在下，使含丙烯的烯烃进行共聚得到聚丙烯微球。
  9. 根据权利要求8所述的制备方法，其特征在于，所述烯烃聚合催化剂体系包含以下组分或以下组分的反应产物：催化剂、烷基铝化合物和任选加入或不加入的外给电子体化合物；
    和/或，所述催化剂包括：含镁的化合物载体、钛化合物和内给电子体化合 物；
    和/或，所述钛化合物与含镁的化合物载体、内给电子体化合物的摩尔比为(37～255):(2～15):1，优选为(67～235):(4～12):1。
  10. 根据权利要求9所述的制备方法，其特征在于，所述含镁的化合物载体的结构如式(I)所示；
    Figure PCTCN2022127943-appb-100001
    式(I)中，R 1为C 1-C 10的烷基；
    R 2和R 3相同或不相同，各自独立地为H、C 1-C 10的烷基或由1～10个卤素原子取代的C 1-C 10的卤代烷基；
    R 4为由至少一个卤素原子取代的C 1-C 10的卤代烷基或由至少一个卤素原子取代的C 6-C 20的卤代芳香基；
    R 5为C 1-C 5的烷基；
    X为氟、氯、溴或碘；
    m为0.1～1.9，n为0.1～1.9，且m+n＝2；优选地，m为0.8～1.2，n为0.8～1.2；
    0<q<0.2；0<a<0.1；优选地，0.005≤q≤0.2；0.001<a<0.05；
    和/或，所述内给电子体化合物选自羧酸酯、醇酯、醚、酮、腈、胺和硅烷中的至少一种，优选为一元或多元脂肪族羧酸酯、一元或多元芳香族羧酸酯、二元醇酯和二元醚中的至少一种；
    和/或，所述钛化合物的通式为：Ti(OR 6) 4-bX' b；
    其中，R 6为C 1-C 14的脂肪烃基；
    X'为F、Cl或Br；
    b为1～4的整数；
    优选地，所述钛化合物选自四氯化钛、四溴化钛、四氟化钛、三丁氧基氯化钛、二丁氧基二氯化钛、丁氧基氯化钛、三乙氧基氯化钛、二乙氧基二氯化钛和乙氧基氯化钛中的至少一种。
  11. 根据权利要求9或10所述的制备方法，其特征在于，所述含镁的化合物载体的制备方法包括以下步骤：
    S1：将通式为MgX"Y的卤化镁和通式为R 7OH的第一醇类化合物进行第一次接触和乳化，得到第一产物；其中，
    通式MgX"Y中，X"选自氟、氯、溴、碘中的任意一种；Y选自氟、氯、溴、碘、C 1-6的烷基、C 1-6的烷氧基、C 6-14的芳基、C 6-14的芳氧基中的任意一种；
    式R 7OH中，R 7为C 1-10的烷基；
    S2：将具有式(II)所示结构的环氧乙烷类化合物与第一产物进行第二接触，得到第二产物；其中，
    S2中，所述环氧乙烷类化合物的结构式如式(II)所示，
    Figure PCTCN2022127943-appb-100002
    其中，R 8和R 9各自独立地选自H、C 1-10的烷基、由1～10个卤素原子取代的C 1-10的卤代烷基；
    S3：将通式为R 10OH的卤代醇和通式为R 11OH的第二醇类化合物与第二产物进行第三接触，得到第三产物；
    式R 10OH中，R 10选自由至少一个卤素原子取代的C 1-10的卤代烷基、由至少一个卤素原子取代的C 6-20的卤代芳香基；
    式R 11OH中，R 11为C 1-5的烷基；
    S4：将第三产物进行喷雾干燥，得到含镁的化合物载体。
  12. 根据权利要求11所述的制备方法，其特征在于，相对于1mol所述卤化镁，所述第一醇类化合物的用量为1～30mol，所述环氧乙烷类化合物的用量为1～10mol，所述卤代醇的用量为0.05～6.5mol，所述第二醇类化合物的用量为5～100mol；优选地，相对于1mol所述卤化镁，所述第一醇类化合物的用量为6～22mol，所述环氧乙烷类化合物的用量为2～6mol，所述卤代醇的用量为1～5mol，所述第二醇类化合物的用量为8～80mol；更优选地，相对于1mol所述卤化镁，所述第二醇类化合物的用量为31～50mol。
  13. 根据权利要求9-12任一项所述的制备方法，其特征在于，所述含镁的化合物载体的平均颗粒直径为2～100微米，粒径分布小于2；优选地，所述含镁的化合物载体的平均颗粒直径为2～19微米，粒径分布为0.6～1.6；更优选地，所述含镁的化合物载体的平均颗粒直径为2～10微米，粒径分布为0.6～1。
  14. 一种3D打印原料，其特征在于，所述3D打印原料包括：权利要求1-7任一项所述的聚丙烯微球和/或权利要求8-13任一项所述制备方法制得的聚丙烯微球。
  15. 一种权利要求1-7任一项所述的聚丙烯微球或权利要求8-13任一项所述制备方法制得的聚丙烯微球在用于3D打印的用途，尤其用于激光烧结打印，最优选地，用于选择性激光烧结的用途。
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KR20240091045A (ko) 2024-06-21
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