WO2022217942A1 - 用于饰品铸造的熔模精密铸造模料及其制备方法 - Google Patents

用于饰品铸造的熔模精密铸造模料及其制备方法 Download PDF

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Publication number
WO2022217942A1
WO2022217942A1 PCT/CN2021/135165 CN2021135165W WO2022217942A1 WO 2022217942 A1 WO2022217942 A1 WO 2022217942A1 CN 2021135165 W CN2021135165 W CN 2021135165W WO 2022217942 A1 WO2022217942 A1 WO 2022217942A1
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WIPO (PCT)
Prior art keywords
toughening agent
wax
casting mold
mold material
modified
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PCT/CN2021/135165
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English (en)
French (fr)
Inventor
蔡卓弟
谭世芝
徐勇军
陈炎丰
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东莞理工学院
东莞市化工学会
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Publication of WO2022217942A1 publication Critical patent/WO2022217942A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives

Definitions

  • the invention relates to the technical field of investment precision casting, in particular to investment precision casting moulding materials for jewelry casting and a preparation method thereof.
  • Investment casting also known as "lost wax casting”
  • Lost wax casting can be traced back to 4,000 years ago in the casting field and has been used for centuries. It is an advanced near-net-shape production process.
  • the biggest advantage of investment casting is that due to the high dimensional accuracy and surface finish of investment castings, machining work can be reduced, but a little machining allowance can be left on the parts with higher requirements.
  • an investment precision casting mold material for jewelry casting which has good fluidity, high impact strength, strong toughness and moderate hardness, and can be widely used in various high toughness requirements. Especially in the investment casting field of jewelry casting with high toughness requirements at low temperature.
  • An investment precision casting mold material for jewelry casting which, in mass percentage, comprises the following components: 25%-45% microcrystalline wax, 15%-25% paraffin wax, 1%-3% natural wax , 25%-35% of petroleum resin, 1%-7% of EVA and 1%-5% of modified toughening agent, the total content of each component is 100%; Toughening agent, graft modifier, initiator and antioxidant are blended and grafted.
  • the mass of the graft modifier is 1 wt % to 3 wt % of the mass of the toughening agent.
  • the mass of the initiator is 0.15wt%-0.25wt% of the mass of the toughening agent.
  • the mass of the antioxidant is 0.1 wt % to 0.25 wt % of the mass of the toughening agent.
  • the toughening agent is a combination of two or three of polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer.
  • the toughening agent is prepared by blending polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer in a mass ratio of 2:2:1.
  • the graft modifier is maleic anhydride.
  • the initiator is dicumyl peroxide.
  • the antioxidant is antioxidant 1010.
  • the microcrystalline wax is one or more combinations of 70#, 75#, and 80# microcrystalline waxes.
  • the paraffin wax is one or more combinations of 58#, 60#, 62#, 64# fully refined or semi-refined paraffin wax.
  • the natural wax is one or more combinations of carnauba wax, candelilla wax, montan wax, beeswax, Sichuan wax, and ozokerite wax.
  • the petroleum resin is one or more combinations of C9 petroleum resin, C5/C9 copolymerized petroleum resin, C9 hydrogenated petroleum resin, C5 petroleum resin, and C5 hydrogenated petroleum resin.
  • the EVA is an ethylene-vinyl acetate copolymer, and its VA content is 15%-30%.
  • a preparation method of an investment precision casting mold material for jewelry casting comprising the following steps.
  • modified toughening agent the toughening agent, graft modifier, initiator and antioxidant are evenly mixed under a high-speed mixer for graft modification to obtain a graft; the graft is purified to remove excess After the auxiliary agent, a modified toughening agent is obtained.
  • Preparation of basic wax/modified toughening agent composite material adding paraffin wax and microcrystalline wax to the reaction kettle, heating and melting; then adding modified toughening agent and EVA to make it evenly dispersed in the matrix of paraffin wax and microcrystalline wax, The composite material of base wax/modified toughening agent can be obtained.
  • Preparation of investment casting mold material adding natural wax and petroleum resin to the composite material of basic wax/modified toughening agent, continuing to heat, mixing and stirring evenly, and cooling to obtain investment precision casting mold material.
  • the step of preparing the modified toughening agent specifically includes the following steps.
  • graft-modified toughening agent First, the toughening agent, graft-modifying agent, initiator and antioxidant are melted and mixed uniformly in a high-speed mixer, and then extruded into a twin-screw extruder after mixing. , to obtain a graft-modified toughening agent.
  • Preparation of purified modified toughening agent heat and mix the graft modified toughening agent and xylene solution, and reflux for 2 hours; filter the refluxed solution into an acetone solution through a nickel mesh while hot, and purify the modified toughening agent to The form of white floc floats in the acetone solution; the white precipitate is filtered and placed in a vacuum drying oven to dry to obtain a purified modified toughening agent.
  • the twin-screw extruder has six temperature zones, and the temperatures of each temperature zone are 170°C, 180°C, 190°C, 195°C, 195°C, and 195°C, respectively.
  • the screw speed of the twin-screw extruder is 200 rmp.
  • the ratio of the graft-modified toughening agent to the xylene solution is 4:100.
  • paraffin wax, microcrystalline wax, EVA and modified toughening agent are used as the basic composite material of the investment casting mold material, supplemented by natural wax, petroleum resin and other materials, so that the mold material has good fluidity and relatively high impact strength.
  • Large, strong toughness, moderate hardness can be widely used in various high toughness requirements, especially in the investment casting field of jewelry casting with high toughness requirements at low temperature.
  • Excellent performance and low cost make investment casting mold material have broad market prospects and meet the requirements of today's market.
  • the present application provides an investment precision casting mold material for jewelry casting, which, in terms of mass percentage, includes the following components: 25%-45% microcrystalline wax, 15%-25% paraffin wax, 1%-3% Natural wax, 25%-35% petroleum resin, 1%-7% EVA and 1%-5% modified toughening agent, the total content of each component is 100%; wherein, the modified toughening The agent is obtained by blending and grafting of toughening agent, graft modifier, initiator and antioxidant.
  • the present invention further improves various properties of the investment casting mold material, and the obtained investment casting mold material has low viscosity, good fluidity, small shrinkage, strong toughness and moderate hardness. , Strong resistance to high and low temperature deformation, can be widely used in various high toughness requirements, especially in the investment casting field of jewelry casting with high toughness requirements at low temperature.
  • the graft modifier is maleic anhydride
  • the initiator is dicumyl peroxide
  • the antioxidant is antioxidant 1010
  • the quality of the graft modifier is 1wt of the toughening agent. %-3wt%
  • the mass of the initiator is 0.15wt%-0.25wt% of the mass of the toughening agent
  • the mass of the antioxidant is 0.1wt%-0.25wt% of the mass of the toughening agent.
  • the toughening agent is a combination of two or three of polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer.
  • Jewelry casting is different from ordinary investment casting. Due to the complex shape of jewelry products and the existence of various small corners, in addition to the performance requirements of high dimensional accuracy and high surface quality, it is also necessary to have good deformation resistance of the mold material. Ability and resilience. Polypropylene, ethylene-propylene-diene terpolymer and ethylene-ethylene-octene copolymer are widely used raw materials in the fields of engineering plastics, rubber, and thermoplastic elastomers. The raw materials are readily available and relatively inexpensive.
  • the toughening agent is prepared by blending polypropylene and ethylene-ethylene-octene copolymer.
  • the addition of polypropylene enhances the tensile strength, rigidity and chemical resistance of the mold material; and the ethylene-propylene-diene terpolymer contains a large amount of ethylene and propylene, so it has good low-temperature performance;
  • There are no polar substituents in the molecular structure of rubber the molecular cohesion energy is low, and the molecular chain can maintain flexibility in a wide range, second only to natural rubber and butadiene rubber, and can still be maintained at low temperatures.
  • the toughening agent is prepared by blending polypropylene, ethylene-ethylene-octene copolymer and propylene-diene terpolymer in a mass ratio of 2:2:1.
  • Ethylene-ethylene-octene copolymer has good compatibility with polypropylene, ethylene-propylene-diene terpolymer, and ethylene-ethylene-octene copolymer can be used as a compatibilizer to improve the compatibility of composite materials. It can not only synergize with polypropylene to enhance the tensile strength and other properties of the molding compound, but also synergize with the ethylene-propylene-diene terpolymer to enhance the flexibility of the molding compound.
  • the polarity of the composite material is given, the intermolecular force increases, and the bonding strength, product toughness, impact resistance, low temperature resistance and heat resistance of the composite material and other materials are further improved.
  • Various properties are improved, and the compatibility of the graft-modified composite material with paraffin wax, microcrystalline wax and other basic waxes is improved, so that the reaction conditions are milder.
  • the paraffin wax is one or more combinations of 58#, 60#, 62#, 64# fully refined or semi-refined paraffin wax;
  • the microcrystalline wax is 70#, 75#, 80# microcrystalline wax One or more combinations of waxes.
  • Paraffin wax and microcrystalline wax are by-products of crude oil cracking, and are widely used materials in investment casting. Their low price, low viscosity, low surface tension, low melting point and high heat of fusion enhance the fluidity and Capability of rheological properties of injection temperature.
  • microcrystalline wax endows the mold material with certain strength and toughness. Therefore, using the mixture of paraffin wax and microcrystalline wax as the basic wax of the investment casting mold material can provide a better foundation for the investment casting mold material. performance.
  • the natural wax is one or more combinations of carnauba wax, candelilla wax, montan wax, beeswax, Sichuan wax, and ozokerite;
  • the petroleum resin is C9 petroleum resin, C5/C9 copolymer
  • One or more combinations of petroleum resin, C9 hydrogenated petroleum resin, C5 petroleum resin, C5 hydrogenated petroleum resin, the softening point is 90 °C-100 °C;
  • EVA is ethylene-vinyl acetate copolymer, and its VA content is 15%- 30%, the melting point is 75°C-90°C.
  • the present application also provides a method for preparing an investment precision casting mold material for jewelry casting, which includes the following steps.
  • modified toughening agent the toughening agent, graft modifier, initiator and antioxidant are evenly mixed under a high-speed mixer for graft modification to obtain a graft; the graft is purified to remove excess After the auxiliary agent, a modified toughening agent is obtained.
  • Preparation of basic wax/modified toughening agent composite material add paraffin wax and microcrystalline wax to the reaction kettle, heat and melt, and the heating reaction temperature is 150°C-160°C; then add modified toughening agent and EVA to make it evenly dispersed In the matrix of paraffin wax and microcrystalline wax, the composite material of base wax/modified toughening agent can be obtained.
  • Preparation of investment casting mold material add natural wax and petroleum resin to the composite material of basic wax/modified toughening agent, continue to heat, mix and stir evenly, and the heating reaction temperature is 120°C-130°C, and the investment mold can be obtained after cooling Precision casting mould material.
  • the steps of preparing the modified toughening agent specifically include the following steps.
  • graft-modified toughening agent First, the toughening agent, graft-modifying agent, initiator and antioxidant are melted and mixed uniformly in a high-speed mixer, and then extruded into a twin-screw extruder after mixing. , to obtain a graft-modified toughening agent.
  • modified toughening agent Preparation and purification of modified toughening agent:
  • the graft modified toughening agent and xylene solution are heated and mixed in a ratio of 4:100, and refluxed for 2 hours; the refluxed solution is filtered through a nickel mesh into an acetone solution while hot, and purified
  • the modified toughening agent floats in the acetone solution in the form of white flocs; the white precipitate is filtered and placed in a vacuum drying oven to dry to obtain a purified modified toughening agent.
  • the twin-screw extruder has six temperature zones, and the temperatures of each temperature zone are 170°C, 180°C, 190°C, 195°C, 195°C, and 195°C, respectively;
  • the screw speed is 200rmp.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 15% of 64# paraffin, 39% of 75# microcrystalline wax, and 1% of modified toughening agent , 7% EVA, 35% C9 hydrogenated petroleum resin, 2% beeswax and 1% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • modified toughening agent physical pre-blending of polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer in a mass ratio of 2:2:1;
  • the toughening agent, maleic anhydride, dicumyl peroxide and antioxidant 1010 are added to the high-speed mixer in a mass ratio of 100:2:0.25:0.2, and are melted and mixed uniformly under the high-speed mixer; Extrude into granules in an extruder to obtain a graft-modified toughening agent; heat and mix the graft-modified toughening agent and xylene solution at a ratio of 4:100, and reflux for 2 hours; Filter the excess acetone solution through a nickel mesh while it is still hot, purify the modified toughening agent and float in the acetone solution in the form of white flocs, filter the white precipitate, and place it in a vacuum drying oven to dry; modified toughening agent.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 20.5% of 64# paraffin, 39% of 75# microcrystalline wax, and 1.5% of modified toughening agent , 6% EVA, 35% C9 hydrogenated petroleum tree, 2% carnauba wax and 1% montan wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • modified toughening agent physical pre-blending of polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer in a mass ratio of 2:2:1;
  • the toughening agent, maleic anhydride, dicumyl peroxide and antioxidant 1010 are added to the high-speed mixer in a mass ratio of 100:1:0.15:0.1, and are melted and mixed uniformly under the high-speed mixer; Extrude into granules in an extruder to obtain a graft-modified toughening agent; heat and mix the graft-modified toughening agent and xylene solution at a ratio of 4:100, and reflux for 2 hours; Filter the excess acetone solution through a nickel mesh while it is still hot, purify the modified toughening agent and float in the acetone solution in the form of white flocs, filter the white precipitate, and place it in a vacuum drying oven to dry; modified toughening agent.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 20.5% of 64# paraffin, 37.5% of 70# microcrystalline wax, and 2% of modified toughening agent , 6% EVA, 20% C9 hydrogenated petroleum resin, 12% C9 petroleum resin and 2.5% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • modified toughening agent physical pre-blending of polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer in a mass ratio of 2:2:1; Toughening agent, maleic anhydride, dicumyl peroxide and antioxidant 1010 are added to the high-speed mixer in a mass ratio of 100:3:0.25:0.25, and are melted and mixed uniformly under the high-speed mixer; Extrude into granules in an extruder to obtain a graft-modified toughening agent; heat and mix the graft-modified toughening agent and xylene solution at a ratio of 4:100, and reflux for 2 hours; Filter the excess acetone solution through a nickel mesh while it is still hot, purify the modified toughening agent and float in the acetone solution in the form of white flocs, filter the white precipitate, and place it in a vacuum drying oven to dry; modified toughening agent.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 20% of 62# paraffin, 40% of 70# microcrystalline wax, and 2.5% of modified toughening agent , 5% EVA, 30% C9 hydrogenated petroleum resin, 2% beeswax and 0.5% candelilla wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • modified toughening agent physical pre-blending of polypropylene, ethylene-ethylene-octene copolymer, and propylene-diene terpolymer in a mass ratio of 2:2:1;
  • the toughening agent, maleic anhydride, dicumyl peroxide and antioxidant 1010 are added to the high-speed mixer in a mass ratio of 100:2:0.2:0.15, and are melted and mixed uniformly under the high-speed mixer;
  • Extrude into granules in an extruder to obtain a graft-modified toughening agent; heat and mix the graft-modified toughening agent and xylene solution at a ratio of 4:100, and reflux for 2 hours; Filter the excess acetone solution through a nickel mesh while it is still hot, purify the modified toughening agent and float in the acetone solution in the form of white flocs, filter the white precipitate, and place it in a vacuum drying oven to dry; modified toughening agent.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 21% of 62# paraffin, 40% of 70# microcrystalline wax, and 3% of modified toughening agent , 4% EVA, 20% C9 hydrogenated petroleum resin, 10% C5 hydrogenated petroleum resin and 2% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • modified toughening agent physical pre-blending of polypropylene, ethylene-ethylene-octene copolymer and propylene-diene terpolymer in a mass ratio of 2:2:1; Maleic anhydride, dicumyl peroxide and antioxidant 1010 were added to the high-speed mixer in a mass ratio of 100:2.5:0.25:0.2, and melted and mixed uniformly under the high-speed mixer; extruding into granules to obtain a graft-modified toughening agent; heating and mixing the graft-modified toughening agent and xylene solution at a ratio of 4:100, and refluxing for 2 hours; passing the refluxed solution while hot The nickel mesh is filtered into the excess acetone solution, the purified modified toughener floats in the acetone solution in the form of white flocs, the white precipitate is filtered, and it is placed in a vacuum drying oven to dry; the purified modified toughener can be obtained.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 25% of 62# paraffin, 39% of 70# microcrystalline wax, and 3.5% of modified toughening agent , 3% EVA, 30% C9 hydrogenated petroleum resin and 2% candelilla wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • the purified modified toughening agent floats in the acetone solution in the form of white flocs, and the white precipitate is filtered and placed in a vacuum drying oven to dry; the purified modified toughening agent can be obtained.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 25% of 62# paraffin, 39.5% of 70# microcrystalline wax, and 4% of modified toughening agent , 2% EVA, 28% C9 hydrogenated petroleum resin and 1.5% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • Granulate to obtain a graft-modified toughening agent; heat and mix the graft-modified toughening agent and xylene solution at a ratio of 4:100, and reflux for 2 hours; filter the refluxed solution through a nickel mesh while it is still hot.
  • the purified modified toughening agent floats in the acetone solution in the form of white flocs, and the white precipitate is filtered and placed in a vacuum drying oven to dry; the purified modified toughening agent can be obtained.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 25% of 64# paraffin, 43.5% of 75# microcrystalline wax, and 4.5% of modified toughening agent , 1% EVA, 35% C9 hydrogenated petroleum resin and 1% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • Granulate to obtain a graft-modified toughening agent; heat and mix the graft-modified toughening agent and xylene solution at a ratio of 4:100, and reflux for 2 hours; filter the refluxed solution through a nickel mesh while it is still hot.
  • the purified modified toughening agent floats in the acetone solution in the form of white flocs, and the white precipitate is filtered and placed in a vacuum drying oven to dry; the purified modified toughening agent can be obtained.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 16.5% of 62# paraffin, 45% of 70# microcrystalline wax, and 5% of modified toughening agent , 2% EVA, 30% C9 hydrogenated petroleum resin and 1.5% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • the purified modified toughening agent floats in the acetone solution in the form of white flocs, and the white precipitate is filtered and placed in a vacuum drying oven to dry; the purified modified toughening agent can be obtained.
  • the investment casting mold material for jewelry casting of this embodiment in terms of mass percentage, includes the following components: 15% of 64# paraffin, 40% of 75# microcrystalline wax, 7% of EVA, 35% of EVA C9 hydrogenated petroleum resin, 2% beeswax and 1% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • the investment casting mold material for jewelry casting in this embodiment in terms of mass percentage, includes the following components: 25% 62# paraffin wax, 39.5% 70# microcrystalline wax, and 4% toughening agent blend material, 2% EVA, 28% C9 hydrogenated petroleum resin and 1.5% carnauba wax.
  • the method for preparing the investment casting mold material of the present embodiment includes the following steps.
  • the investment casting mold material prepared in Example 1 has a softening point of 71.9/°C, a penetration of 0.76 at 25°C and 0.1mm, a viscosity of 179.17mPa.s, and an impact strength of 2.12KJ/m 2 , the tensile strength is 2.23MPa, and the melt flow rate is 36.5g/min at 60°C.
  • the investment casting mold material prepared in Example 2 has a softening point of 72.3° C., a penetration of 0.74 at 25° C. and 0.1 mm, a viscosity of 162.48 mPa.s, and an impact strength of 2.25KJ/m 2 , the tensile strength is 2.32MPa, and the melt flow rate is 38.8g/min at 60°C.
  • the investment casting mold material prepared in Example 3 has a softening point of 72.5° C., a penetration of 0.71 at 25° C. and 0.1 mm, a viscosity of 156.25 mPa.s, and an impact strength of 2.36 KJ/m 2 .
  • the tensile strength was 2.39 MPa and the melt flow rate was 40.3 g/min at 60°C.
  • the investment casting mold material prepared in Example 4 has a softening point of 71.8° C., a penetration of 0.69 at 25° C. and 0.1 mm, a viscosity of 141.38 mPa.s, and an impact strength of 2.53 KJ/m 2 .
  • the tensile strength was 2.43 MPa and the melt flow rate was 41.8 g/min at 60°C.
  • the investment casting mold material prepared in Example 5 has a softening point of 72.1° C., a penetration of 0.67 at 25° C. and 0.1 mm, a viscosity of 133.88 mPa.s, and an impact strength of 2.67 KJ/m 2 .
  • the tensile strength was 2.50 MPa and the melt flow rate was 43.2 g/min at 60°C.
  • the investment casting mold material prepared in Example 6 has a softening point of 71.9° C., a penetration of 0.66 at 25° C. and 0.1 mm, a viscosity of 125.06 mPa.s, and an impact strength of 2.81 KJ/m 2 .
  • the tensile strength was 2.54 MPa and the melt flow rate was 44.3 g/min at 60°C.
  • the investment casting mold material prepared in Example 7 has a softening point of 72.4° C., a penetration of 0.64 at 25° C. and 0.1 mm, a viscosity of 119.63 mPa.s, and an impact strength of 2.97 KJ/m 2 .
  • the tensile strength was 2.63 MPa and the melt flow rate was 43.9 g/min at 60°C.
  • the investment casting mold material prepared in Example 8 has a softening point of 72.1° C., a penetration of 0.62 at 25° C. and 0.1 mm, a viscosity of 113.98 mPa.s, and an impact strength of 2.85 KJ/m 2 .
  • the tensile strength was 2.67 MPa and the melt flow rate was 43.6 g/min at 60°C.
  • the investment casting mold material prepared in Example 9 has a softening point of 72.3° C., a penetration of 0.61 at 25° C. and 0.1 mm, a viscosity of 118.54 mPa.s, and an impact strength of 2.88 KJ/m 2 .
  • the tensile strength was 2.77 MPa and the melt flow rate was 41.41 g/min at 60°C.
  • the investment casting mold material prepared in Comparative Example 1 has a softening point of 71.8° C., a penetration of 0.86 at 25° C. and 0.1 mm, a viscosity of 230.79 mPa.s, and an impact strength of 1.27 KJ/m 2 .
  • the tensile strength was 1.39 MPa and the melt flow rate was 24.3 g/min at 60°C.
  • the investment casting mold material prepared in Comparative Example 2 has a softening point of 72.3° C., a penetration of 0.75 at 25° C. and 0.1 mm, a viscosity of 190.31 mPa.s, and an impact strength of 1.93 KJ/m 2 .
  • the tensile strength was 2.08 MPa and the melt flow rate was 33.1 g/min at 60°C.
  • the modified toughener has a certain degree of improvement in various performance parameters of the investment casting mold material, with low viscosity, good toughness, moderate softening point and hardness, and impact resistance.
  • the strength and tensile strength are large, which can well meet the actual production and writing needs, and have high market competitiveness.

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Abstract

本发明涉及一种用于饰品铸造的熔模精密铸造模料及其制备方法，先将增韧剂、接枝改性剂、引发剂和抗氧化剂共混接枝制得改性增韧剂：再将25%-45%的微晶蜡、15%-25%的石蜡、1%-7%的EVA与1%-5%的改性增韧剂混合，制得基础蜡/改性增韧剂复合材料；最后混合1%-3%的天然蜡和25%-35%的石油树脂，制得熔模精密铸造模料。

Description

用于饰品铸造的熔模精密铸造模料及其制备方法
相关申请的交叉引用
本申请要求于2021 年04月16日提交中国专利局、申请号为“202110411349.4”、发明名称为“用于饰品铸造的熔模精密铸造模料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及熔模精密铸造技术领域，特别是用于饰品铸造的熔模精密铸造模料及其制备方法。
 背景技术
熔模精密铸造，又称为“失蜡铸造”，在铸造领域可以追溯到4000年前，至今已经应用了几个世纪了，是一种先进的近净成形生产工艺。熔模铸造最大的优点就是由于熔模铸件有着很高的尺寸精度和表面光洁度，所以可减少机械加工工作，只是在零件上要求较高的部位留少许加工余量即可。
 技术问题
但随着科技的不断进步，人们对金属首饰以及很多非金属工艺品的要求也越来越高，这些工件制备的复杂程度也随之加强。产品形状复杂程度的大大提高以及对尺寸精度和表面质量的提高，对精密铸造模料的各项性能也有了更高的要求，特别在模料的韧性方面，市面上普通的精密铸造模料已不能很好的满足首饰件的尺寸和精度的需求。
 技术解决方案
根据本申请的各种实施例，提供一种用于饰品铸造的熔模精密铸造模料，流动性好、抗冲击强度较大、韧性强、硬度适中，可广泛应用于各种高韧性要求，特别是在低温下高韧性要求的饰品铸造的熔模精密铸造领域。
一种用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%-45%的微晶蜡、15%-25%的石蜡、1%-3%的天然蜡、25%-35%的石油树脂、1%-7%的EVA及1%-5%的改性增韧剂，各组分总含量为100%；其中，所述改性增韧剂由增韧剂、接枝改性剂、引发剂和抗氧化剂共混接枝制得。
在其中一个实施例中，所述接枝改性剂的质量为所述增韧剂质量的1wt%-3wt%。
在其中一个实施例中，所述引发剂的质量为所述增韧剂质量的0.15wt%-0.25wt%。
在其中一个实施例中，所述抗氧化剂的质量为所述增韧剂质量的0.1wt%-0.25wt%。
在其中一个实施例中，所述增韧剂为聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物的两种或三种组合。
在其中一个实施例中，所述增韧剂由聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1共混制得。
在其中一个实施例中，所述接枝改性剂为马来酸酐。
在其中一个实施例中，所述引发剂为过氧化二异丙苯。
在其中一个实施例中，所述抗氧化剂为抗氧化剂1010。
在其中一个实施例中，所述微晶蜡为70#、75#、80#微晶蜡的一种或多种组合。
在其中一个实施例中，所述石蜡为58#、60#、62#、64#全精炼或半精炼石蜡的一种或多种组合。
在其中一个实施例中，所述天然蜡为巴西棕榈蜡、小烛树蜡、褐煤蜡、蜂蜡、川蜡、地蜡的一种或多种组合。
在其中一个实施例中，所述石油树脂为C9石油树脂、C5/C9共聚石油树脂、C9氢化石油树脂、C5石油树脂、C5氢化石油树脂的一种或多种组合.
在其中一个实施例中，所述EVA为乙烯-醋酸乙烯共聚物，其VA含量为15%-30%。
根据本申请的各种实施例，还提供一种用于饰品铸造的熔模精密铸造模料的制备方法，通过对增韧剂进行接枝改性，进一步提高了熔模精密铸造模料的各项性能。
一种用于饰品铸造的熔模精密铸造模料的制备方法，包括如下步骤。
制备改性增韧剂：将增韧剂、接枝改性剂、引发剂和抗氧化剂在高速混合机下混合均匀进行接枝改性，得到接枝物；将接枝物进行纯化去除多余的助剂后得到改性增韧剂。
制备基础蜡/改性增韧剂复合材料：于反应釜中加入石蜡和微晶蜡，加热熔融；再加入改性增韧剂和EVA，使其均匀分散于石蜡和微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
制备熔模精密铸造模料：于基础蜡/改性增韧剂的复合材料中加入天然蜡和石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
在其中一个实施例中，所述制备改性增韧剂的步骤，具体包括如下步骤。
制备接枝改性增韧剂：首先将增韧剂、接枝改性剂、引发剂和抗氧化剂在高速混合机下熔融混合均匀，混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂。
制备纯化改性增韧剂：将接枝改性增韧剂与二甲苯溶液加热混合，回流2小时；将回流后的溶液趁热通过镍网过滤到丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中；过滤白色沉淀，并将其放置于真空干燥箱干燥，即可得到纯化改性增韧剂。
在其中一个实施例中，所述双螺杆挤出机具有六个温区，各个温区的温度分别为170℃、180℃、190℃、195℃、195℃、195℃。
在其中一个实施例中，所述双螺杆挤出机的螺杆转速为200rmp。
在其中一个实施例中，所述接枝改性增韧剂与所述二甲苯溶液的比例为4:100。
 有益效果
本申请以石蜡、微晶蜡、EVA和改性增韧剂作为熔模精密铸造模料的基础复合材料，辅以天然蜡、石油树脂等材料，使得模料的流动性好、抗冲击强度较大、韧性强、硬度适中，可广泛应用于各种高韧性要求，特别是在低温下高韧性要求的饰品铸造的熔模精密铸造领域。优异的性能和低廉的成本使得熔模精密铸造模料具备广阔的市场前景，满足当今市场的要求。
 附图说明
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。
 本发明的实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
本申请提供一种用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%-45%的微晶蜡、15%-25%的石蜡、1%-3%的天然蜡、25%-35%的石油树脂、1%-7%的EVA及1%-5%的改性增韧剂，各组分总含量为100%；其中，所述改性增韧剂由增韧剂、接枝改性剂、引发剂和抗氧化剂共混接枝制得。
本发明通过对增韧剂进行接枝改性，进一步提高了熔模精密铸造模料的各项性能，得到的熔模精密铸造模料粘度低、流动性好、收缩小、韧性强、硬度适中、抗高低温变形性强，可广泛应用于各种高韧性要求，特别是在低温下高韧性要求的饰品铸造的熔模精密铸造领域。
在一个或多个实施例中，接枝改性剂为马来酸酐，引发剂为过氧化二异丙苯，抗氧化剂为抗氧化剂1010；接枝改性剂的质量为增韧剂质量的1wt%-3wt%，引发剂的质量为增韧剂质量的0.15wt%-0.25wt%，抗氧化剂的质量为增韧剂质量的0.1wt%-0.25wt%。
在一个或多个实施例中，增韧剂为聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯- 二烯三元共聚物的两种或三种组合。
饰品铸造区别于普通的熔模精密铸造，由于首饰件产品形状复杂，存在各种细小的边角，在高尺寸精度和高表面质量的性能要求的同时，还需要模料具体较好的耐变形能力和韧性。而聚丙烯、乙烯-丙烯-二烯三元共聚物和乙烯-乙烯-辛烯共聚物是目前工程塑料、橡胶、热塑性弹性体领域中使用十分广泛的原材料，原料易得且价格相对低廉。
增韧剂由聚丙烯和乙烯-乙烯-辛烯共聚物共混制得。聚丙烯的加入，增强了模料的拉伸强度、刚性和耐化学性；而乙烯-丙烯-二烯三元共聚物中含有大量乙烯和丙烯成分，所以具有良好的低温性能；而由于乙丙橡胶分子结构中无极性取代基，分子内聚能低，分子链可在较宽范围内保持柔韧性，仅次于天然橡胶和顺丁橡胶，并在低温下仍能保持。
增韧剂由聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比 2:2:1共混制得。乙烯-乙烯-辛烯共聚物与聚丙烯、乙烯-丙烯-二烯三元共聚物的相容性较好，乙烯-乙烯-辛烯共聚物可作为相容剂提高复合材料的相容性，既能与聚丙烯协同增强模料的拉伸强度等性能，也能与乙烯-丙烯-二烯三元共聚物协同增强模料的柔韧性。通过对复合材料进行接枝改性，赋予了复合材料极性，分子间作用力增大，进一步改善复合材料与其它材料的结合强度、产品韧性、抗冲击性、耐低温性及耐热性等各项性能，且提高接枝改性后的复合材料与石蜡，微晶蜡等基础蜡的相容性，使得反应的条件更加温和。
在一个或多个实施例中，石蜡为58#、60#、62#、64#全精炼或半精炼石蜡的一种或多种组合；微晶蜡为70#、75#、80#微晶蜡的一种或多种组合。
石蜡和微晶蜡是原油裂解产生的副产品，是目前熔模铸造中广泛被使用的材料，其价格低廉、低粘度、低表面张力、低熔点和高熔化热，增强了模料的流动性和注射温度的流变性能的能力。
而微晶蜡对于相比于石蜡，赋予了模料一定的强度和韧性，因此以石蜡和微晶蜡的混合物作为熔模铸造模料的基础蜡可为熔模铸造模料提供较好的基础性能。
在一个或多个实施例中，天然蜡为巴西棕榈蜡、小烛树蜡、褐煤蜡、蜂蜡、川蜡、地蜡的一种或多种组合；石油树脂为C9石油树脂、C5/C9共聚石油树脂、 C9氢化石油树脂、C5石油树脂、C5氢化石油树脂的一种或多种组合，其软化点为90℃-100℃；EVA为乙烯-醋酸乙烯共聚物，其VA含量为15%-30%，熔点为75℃-90℃。
除此之外，本申请还提供了一种用于饰品铸造的熔模精密铸造模料的制备方法，包括如下步骤。
制备改性增韧剂：将增韧剂、接枝改性剂、引发剂和抗氧化剂在高速混合机下混合均匀进行接枝改性，得到接枝物；将接枝物进行纯化去除多余的助剂后得到改性增韧剂。
制备基础蜡/改性增韧剂复合材料：于反应釜中加入石蜡和微晶蜡，加热熔融，加热反应温度为150℃-160℃；再加入改性增韧剂和EVA，使其均匀分散于石蜡和微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
制备熔模精密铸造模料：于基础蜡/改性增韧剂的复合材料中加入天然蜡和石油树脂，继续加热混合搅拌均匀，加热反应温度120℃-130℃，冷却后即可得到熔模精密铸造模料。
制备改性增韧剂的步骤，具体包括如下步骤。
制备接枝改性增韧剂：首先将增韧剂、接枝改性剂、引发剂和抗氧化剂在高速混合机下熔融混合均匀，混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂。
制备纯化改性增韧剂：按4:100的比例将接枝改性增韧剂与二甲苯溶液加热混合，回流2小时；将回流后的溶液趁热通过镍网过滤到丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中；过滤白色沉淀，并将其放置于真空干燥箱干燥，即可得到纯化改性增韧剂。
在一个或多个实施例中，双螺杆挤出机具有六个温区，各个温区的温度分别170℃、180℃、190℃、195℃、195℃、195℃；双螺杆挤出机的螺杆转速为200rmp。
以下为实施例说明。
实施例1：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：15%的64#石蜡、39%的75#微晶蜡、1%的改性增韧剂、7%的EVA、35%的C9加氢石油树脂、2%的蜂蜡及1%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）制备改性增韧剂：将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:2:0.25:0.2加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的64#石蜡和75#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于64#石蜡和75#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的蜂蜡、巴西棕榈蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例2：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：20.5%的64#石蜡、39%的75#微晶蜡、1.5%的改性增韧剂、6%的EVA、35%的C9加氢石油树、2%的巴西棕榈蜡及1%的褐煤蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）制备改性增韧剂：将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:1:0.15:0.1加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的64#石蜡和75#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于64#石蜡和75#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的巴西棕榈蜡、褐煤蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例3：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：20.5%的64#石蜡、37.5%的70#微晶蜡、2%的改性增韧剂、6%的EVA、20%的C9加氢石油树脂、12%的C9石油树脂及2.5%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）制备改性增韧剂：将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:3:0.25:0.25加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的64#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于64#石蜡和70#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的巴西棕榈蜡、C9加氢石油树脂和C9石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例4：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：20%的62#石蜡、40%的70#微晶蜡、2.5%的改性增韧剂、5%的EVA、30%的C9加氢石油树脂、2%的蜂蜡及0.5%的小烛树蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）制备改性增韧剂：将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:2:0.2:0.15加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的62#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于62#石蜡和70#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的蜂蜡、小烛树蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例5：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：21%的62#石蜡、40%的70#微晶蜡、3%的改性增韧剂、4%的EVA、20%的C9加氢石油树脂、10%的C5加氢石油树脂及2%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
制备改性增韧剂：将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:2.5:0.25:0.2加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的62#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于62#石蜡和70#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的巴西棕榈蜡、C9加氢石油树脂和C5加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例6：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%的62#石蜡、39%的70#微晶蜡、3.5%的改性增韧剂、3%的EVA、30%的C9加氢石油树脂及2%的小烛树蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:2:0.15:0.2加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的62#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于62#石蜡和70#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的小烛树蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例7：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%的62#石蜡、39.5%的70#微晶蜡、4%的改性增韧剂、2%的EVA、28%的C9加氢石油树脂及1.5%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:2:0.25:0.25加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的62#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于62#石蜡和70#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的巴西棕榈蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例8：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%的64#石蜡、43.5%的75#微晶蜡、4.5%的改性增韧剂、1%的EVA、35%的C9加氢石油树脂及1%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:3:0.25:0.25加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的64#石蜡和75#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于64#石蜡和75#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的巴西棕榈蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
实施例9：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：16.5%的62#石蜡、45%的70#微晶蜡、5%的改性增韧剂、2%的EVA、30%的C9加氢石油树脂及1.5%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）将聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1进行物理预共混；再将共混增韧剂与马来酸酐、过氧化二异丙苯和抗氧化剂1010按质量比为100:2:0.25:0.2加入到高速混合机中，在高速混合机下熔融混合均匀；混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；将接枝改性增韧剂与二甲苯溶液按4:100的比例加热混合，回流2小时；并将回流后的溶液趁热通过镍网过滤到过量的丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中，过滤白色沉淀，并将其放置于真空干燥箱干燥；即可得到纯化的改性增韧剂。
（2）制备基础蜡/改性增韧剂复合材料：于反应釜中加入定量的62#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的改性增韧剂和EVA，使其均匀分散于62#石蜡和70#微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料。
（3）制制备熔模精密铸造模料：降温至130℃，于基础蜡/改性增韧剂的复合材料中加入定量的巴西棕榈蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
 
对比例1：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分： 15%的64#石蜡、40%的75#微晶蜡、7%的EVA、35%的C9加氢石油树脂、2%的蜂蜡及1%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）制备基础蜡/增韧剂复合材料：于反应釜中加入定量的64#石蜡和75#微晶蜡，升温至150℃，加热熔融；再加入定量的EVA，使其均匀分散于64#石蜡和75#微晶蜡的基体中，即可得到基础蜡/增韧剂的复合材料。
（2）制备熔模精密铸造模料：降温至130℃，于基础蜡/增韧剂的复合材料中加入定量的蜂蜡、巴西棕榈蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
对比例2：
本实施例的用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%的62#石蜡、39.5%的70#微晶蜡、4%的增韧剂共混物、2%的EVA、28%的C9加氢石油树脂及1.5%的巴西棕榈蜡。
制备本实施例的熔模精密铸造模料的方法包括如下步骤。
（1）制备基础蜡/增韧剂复合材料：于反应釜中加入定量的62#石蜡和70#微晶蜡，升温至150℃，加热熔融；再加入定量的增韧剂共混物和EVA，使其均匀分散于62#石蜡和70#微晶蜡的基体中，即可得到基础蜡/增韧剂的复合材料。
（2）制备熔模精密铸造模料：降温至130℃，于基础蜡/增韧剂的复合材料中加入定量的巴西棕榈蜡和C9加氢石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
对本发明的实施例1~9和对比例1~2进行性能测试，其结果如下所示。
实施例1制得的熔模精密铸造模料，其软化点为71.9/℃，针入度在25℃、0.1mm时为0.76，粘度为179.17mPa.s，抗冲击强度为2.12KJ/m 2，拉伸强度为2.23MPa，熔体流动速率在60℃时为36.5g/min。
实施例2制得的熔模精密铸造模料，其软化点为72.3℃，针入度在25℃、0.1mm时为0.74，粘度为162.48mPa.s，，抗冲击强度为2.25KJ/m 2，拉伸强度为2.32MPa，熔体流动速率在60℃时为38.8g/min。
实施例3制得的熔模精密铸造模料，其软化点为72.5℃，针入度在25℃、0.1mm时为0.71，粘度为156.25mPa.s，抗冲击强度为2.36KJ/m 2，拉伸强度为2.39MPa，熔体流动速率在60℃时为40.3g/min。
实施例4制得的熔模精密铸造模料，其软化点为71.8℃，针入度在25℃、0.1mm时为0.69，粘度为141.38mPa.s，抗冲击强度为2.53KJ/m 2，拉伸强度为2.43MPa，熔体流动速率在60℃时为41.8g/min。
实施例5制得的熔模精密铸造模料，其软化点为72.1℃，针入度在25℃、0.1mm时为0.67，粘度为133.88mPa.s，抗冲击强度为2.67KJ/m 2，拉伸强度为2.50MPa，熔体流动速率在60℃时为43.2g/min。
实施例6制得的熔模精密铸造模料，其软化点为71.9℃，针入度在25℃、0.1mm时为0.66，粘度为125.06mPa.s，抗冲击强度为2.81KJ/m 2，拉伸强度为2.54MPa，熔体流动速率在60℃时为44.3g/min。
实施例7制得的熔模精密铸造模料，其软化点为72.4℃，针入度在25℃、0.1mm时为0.64，粘度为119.63mPa.s，抗冲击强度为2.97KJ/m 2，拉伸强度为2.63MPa，熔体流动速率在60℃时为43.9g/min。
实施例8制得的熔模精密铸造模料，其软化点为72.1℃，针入度在25℃、0.1mm时为0.62，粘度为113.98mPa.s，抗冲击强度为2.85KJ/m 2，拉伸强度为2.67MPa，熔体流动速率在60℃时为43.6g/min。
实施例9制得的熔模精密铸造模料，其软化点为72.3℃，针入度在25℃、0.1mm时为0.61，粘度为118.54mPa.s，抗冲击强度为2.88KJ/m 2，拉伸强度为2.77MPa，熔体流动速率在60℃时为41.41g/min。
对比例1制得的熔模精密铸造模料，其软化点为71.8℃，针入度在25℃、0.1mm时为0.86，粘度为230.79mPa.s，抗冲击强度为1.27KJ/m 2，拉伸强度为1.39MPa，熔体流动速率在60℃时为24.3g/min。
对比例2制得的熔模精密铸造模料，其软化点为72.3℃，针入度在25℃、0.1mm时为0.75，粘度为190.31mPa.s，抗冲击强度为1.93KJ/m 2，拉伸强度为2.08MPa，熔体流动速率在60℃时为33.1g/min。
由上述的性能测试结果可以看出，改性增韧剂对于熔模精密铸造模料的各项性能参数指标都有一定程度的提升，其粘度低、韧性好、软化点和硬度适中、抗冲击强度和拉伸强度较大，能够很好的满足实际生产写需求，具备较高的市场竞争力。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的一种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (19)

  1. 一种用于饰品铸造的熔模精密铸造模料，以质量百分比计，包括如下组分：25%-45%的微晶蜡、15%-25%的石蜡、1%-3%的天然蜡、25%-35%的石油树脂、1%-7%的EVA及1%-5%的改性增韧剂，各组分总含量为100%；
    其中，所述改性增韧剂由增韧剂、接枝改性剂、引发剂和抗氧化剂共混接枝制得。
  2. 根据权利要求1所述的熔模精密铸造模料，所述接枝改性剂的质量为所述增韧剂质量的1wt%-3wt%。
  3. 根据权利要求1所述的熔模精密铸造模料，所述引发剂的质量为所述增韧剂质量的0.15wt%-0.25wt%。
  4. 根据权利要求1所述的熔模精密铸造模料，所述抗氧化剂的质量为所述增韧剂质量的0.1wt%-0.25wt%。
  5. 根据权利要求1所述的熔模精密铸造模料，所述增韧剂为聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物的两种或三种组合。
  6. 根据权利要求5所述的熔模精密铸造模料，所述增韧剂由聚丙烯、乙烯-乙烯-辛烯共聚物、丙烯-二烯三元共聚物按质量比2:2:1共混制得。
  7. 根据权利要求1所述的熔模精密铸造模料，所述接枝改性剂为马来酸酐。
  8. 根据权利要求1所述的熔模精密铸造模料，所述引发剂为过氧化二异丙苯。
  9. 根据权利要求1所述的熔模精密铸造模料，所述抗氧化剂为抗氧化剂1010。
  10. 根据权利要求1所述的熔模精密铸造模料，所述微晶蜡为70#、75#、80#微晶蜡的一种或多种组合。
  11. 根据权利要求1所述的熔模精密铸造模料，所述石蜡为58#、60#、62#、64#全精炼或半精炼石蜡的一种或多种组合。
  12. 根据权利要求1所述的熔模精密铸造模料，所述天然蜡为巴西棕榈蜡、小烛树蜡、褐煤蜡、蜂蜡、川蜡、地蜡的一种或多种组合。
  13. 根据权利要求1所述的熔模精密铸造模料，所述石油树脂为C9石油树脂、C5/C9共聚石油树脂、C9氢化石油树脂、C5石油树脂、C5氢化石油树脂的一种或多种组合。
  14. 根据权利要求1所述的熔模精密铸造模料，所述EVA为乙烯-醋酸乙烯共聚物，其VA含量为15%-30%。
  15. 一种用于饰品铸造的熔模精密铸造模料的制备方法，包括如下步骤：
    制备改性增韧剂：将增韧剂、接枝改性剂、引发剂和抗氧化剂在高速混合机下混合均匀进行接枝改性，得到接枝物；将接枝物进行纯化去除多余的助剂后得到改性增韧剂；
    制备基础蜡/改性增韧剂复合材料：于反应釜中加入石蜡和微晶蜡，加热熔融；再加入改性增韧剂和EVA，使其均匀分散于石蜡和微晶蜡的基体中，即可得到基础蜡/改性增韧剂的复合材料；
    制备熔模精密铸造模料：于基础蜡/改性增韧剂的复合材料中加入天然蜡和石油树脂，继续加热混合搅拌均匀，冷却后即可得到熔模精密铸造模料。
  16. 根据权利要求15所述的方法，所述制备改性增韧剂的步骤，具体包括如下步骤：
    制备接枝改性增韧剂：首先将增韧剂、接枝改性剂、引发剂和抗氧化剂在高速混合机下熔融混合均匀，混合完成后在双螺杆挤出机中进行挤出成粒，得到接枝改性增韧剂；
    制备纯化改性增韧剂：将接枝改性增韧剂与二甲苯溶液加热混合，回流2小时；将回流后的溶液趁热通过镍网过滤到丙酮溶液中，纯化改性增韧剂以白色絮状物的形式漂浮于丙酮溶液中；过滤白色沉淀，并将其放置于真空干燥箱干燥，即可得到纯化改性增韧剂。
  17. 根据权利要求16所述的方法，所述双螺杆挤出机具有六个温区，各个温区的温度分别为170℃、180℃、190℃、195℃、195℃、195℃。
  18. 根据权利要求17所述的方法，所述双螺杆挤出机的螺杆转速为200rmp。
  19. 根据权利要求16所述的方法，所述接枝改性增韧剂与所述二甲苯溶液的比例为4:100。
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