WO2023104076A1 - 一种聚碳酸酯组合物及其塑料和制备方法 - Google Patents

一种聚碳酸酯组合物及其塑料和制备方法 Download PDF

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WO2023104076A1
WO2023104076A1 PCT/CN2022/137176 CN2022137176W WO2023104076A1 WO 2023104076 A1 WO2023104076 A1 WO 2023104076A1 CN 2022137176 W CN2022137176 W CN 2022137176W WO 2023104076 A1 WO2023104076 A1 WO 2023104076A1
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polycarbonate composition
plastic containing
composition according
ppcp
ppc
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English (en)
French (fr)
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李洪国
王勋林
张俊玲
王波
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山东联欣环保科技有限公司
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Publication of WO2023104076A1 publication Critical patent/WO2023104076A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

Definitions

  • the present invention relates to the technical field described in IPC classification number C08L 69/00 (2006.01), be specifically related to a kind of polycarbonate composition and its plastics and preparation method.
  • Patent CN201410662371.6 A polymethylethylene carbonate composition and its preparation method prepared by melt blending polymethylethylene carbonate matrix, thermoplastic polyurethane and polyvinyl alcohol to form a modified material and then mixing it with additives The composition has good tensile strength and elongation at break.
  • Patent CN201210283571.1 A degradable polymethylethylene carbonate-based composite material and its preparation method The material prepared by mixing and modifying polymethylethylene carbonate and polyvinyl formal has high mechanical strength and machinability sex.
  • one of the objectives of the present invention is to provide a polycarbonate composition with high stability and mechanical properties.
  • the invention provides a polycarbonate composition, comprising the following raw materials: PPCP and PPC, wherein the mass ratio of PPCP and PPC is (1-99):(99-1).
  • the number average molecular weight of the PPCP is 1.0-1.5*10 5 .
  • the M w /M n of the PPCP is 1.8-2.1.
  • the number average molecular weight of the PPC is 2.0-2.5*10 5 .
  • the M w /M n of the PPC is 2.5-3.0.
  • the present invention also provides a plastic containing a polycarbonate composition.
  • the raw materials include 90-120 parts of the polycarbonate composition described in the technical solution, 1-3 parts of ester compounds, and block oligomers. 0.2-0.6 parts, 5-15 parts of pigments and fillers, 0.1-0.3 parts of antistatic agent and 0.5-2 parts of isocyanate compounds.
  • the polycarbonate composition is a pretreated polycarbonate composition
  • the pretreatment includes: mixing the polycarbonate composition and a solvent, heating and stirring, and filtering and drying in sequence.
  • the solvent includes at least one of ethanol, acetone, toluene, ethyl acetate, methylene chloride and isopropanol;
  • the mass ratio of the polycarbonate composition to the solvent is 1:(6-8).
  • the solvent includes isopropanol and propanol with a mass ratio of (25-35):(65-75).
  • the temperature of the heating and stirring is 50-60°C, and the time is 5-8h.
  • the ester compounds include at least one of sulfonate compounds, phthalate compounds, cinnamate compounds, citrate compounds, adipate compounds and laurate compounds kind.
  • the ester compounds include citrate compounds and adipate compounds in a mass ratio of (1.5-2.5):(4-7).
  • the molecular weight of the adipate ester compound is 3000-4000.
  • the weight average molecular weight of the block oligomer is 2500-3500.
  • the pigments and fillers include stearate, carbonate, silicon dioxide, titanium dioxide, montmorillonite, attapulgite, vermiculite, starch, wood fiber, wood powder, graphene oxide, metal oxide and At least one of nanocrystalline cellulose.
  • the pigment and filler include heavy calcium carbonate, graphene oxide and nanocrystalline cellulose in a mass ratio of (2.5-3.5):(2.5-3.5):1.
  • the average particle diameter of the heavy calcium carbonate is 2000-3000 mesh
  • the particle size of the graphene oxide is 190-320nm.
  • the flame retardant includes at least one of magnesium hydroxide, aluminum hydroxide and halogen flame retardants.
  • the isocyanate compound includes at least one of 4,4-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, hexamethylene isocyanate and triallyl isocyanate.
  • the present invention also provides the preparation method of the plastic containing the polycarbonate composition described in the above technical scheme, comprising the following steps: pre-mixing PPCP and PPC to obtain the polycarbonate composition, then adding other raw materials and mixing them uniformly, putting Extrude and granulate in a twin-screw extruder to obtain the plastic containing the polycarbonate composition.
  • the following steps are included: pre-dry PPCP and PPC at 55-70°C for 3-5 hours, then mix in a high-speed mixer for 3-7 minutes, add the remaining raw materials in turn, continue to stir and mix for 2-5 minutes, and then pre-mix
  • the mixture is fed into a twin-screw extruder, extruded and granulated at 100°C-170°C to obtain the polycarbonate-containing composition.
  • the invention provides a polycarbonate composition, comprising the following raw materials: PPCP and PPC, wherein the mass ratio of PPCP and PPC is (1-99):(99-1).
  • the present invention also provides a plastic containing a polycarbonate composition.
  • the raw materials include 90-120 parts of the polycarbonate composition described in the technical solution, 1-3 parts of ester compounds, and block oligomers. 0.2-0.6 parts, 5-15 parts of pigments and fillers, 0.1-0.3 parts of antistatic agent and 0.5-2 parts of isocyanate compounds.
  • the invention provides a polycarbonate composition, comprising the following raw materials: PPCP and PPC, wherein the mass ratio of PPCP and PPC is (1-99):(99-1).
  • the number average molecular weight of the PPCP is preferably 1-1.5*10 5 , and M w /M n is preferably 1.8-2.1.
  • the number average molecular weight of the PPC is preferably 2-2.5*10 5
  • the M w /M n is preferably 2.5-3.0.
  • the polycarbonate composition is preferably subjected to a pretreatment process, and the pretreatment preferably includes the following steps: uniformly mixing the polycarbonate composition with a solvent, heating and stirring, and filtering and drying.
  • the mass ratio of the polycarbonate composition to the solvent is preferably 1:(6-8).
  • the solvent preferably includes at least one of ethanol, acetone, toluene, ethyl acetate, methylene chloride and isopropanol, more preferably includes isopropanol and acetone, and the mass ratio of the isopropanol to acetone is Preferred are (25-35): (65-75).
  • the temperature of the heating and stirring is preferably 50-60°C, and the time is preferably 5-8h.
  • PPCP and PPC significantly improved their stability and mechanical properties when the number average molecular weight and molecular weight distribution were constant, but the actual improvement results were quite different from expectations.
  • the present invention surprisingly finds that the mechanical properties and thermal stability of PPCP and PPC can be further improved by pretreatment. It is speculated that the molecular chains of the pretreated PPCP and PPC can be closely arranged in a certain spatial order, which can effectively promote the growth of crystals in the system, make the crystals evenly distributed, effectively increase the glass transition temperature, and then improve its stability. sex and mechanical properties.
  • the mass ratio of the PPCP and PPC is preferably (30-70):(30-70).
  • One of the objectives of the present invention is to provide a plastic containing polycarbonate composition, in parts by mass, the plastic raw material comprises 90-120 parts of polycarbonate composition, 1-3 parts of ester compound, embedding 0.2-0.6 parts of segmented oligomers, 5-15 parts of pigments and fillers, 0.1-0.3 parts of antistatic agents and 0.5-2 parts of isocyanate compounds.
  • the ester compounds preferably include sulfonate compounds, phthalate compounds, cinnamate compounds, citrate compounds, adipate compounds and laurate compounds. At least one of, more preferably including citrate compounds and adipate compounds; the mass ratio of the citrate compounds and adipate compounds is preferably (1.5-2.5): (4-7).
  • the molecular weight of the adipate compound is preferably 3000-4000.
  • the viscosity of the adipate compound at 25° C. is preferably 2500-3500 cps.
  • the weight average molecular weight of the block oligomer is preferably 2500-3500.
  • the block oligomers are preferably 1,3,5-triazine and N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4- Block oligomers formed by the reaction of piperidine amines.
  • the pigments and fillers preferably include stearate, carbonate, silicon dioxide, titanium dioxide, montmorillonite, attapulgite, vermiculite, starch, wood fiber, wood powder, graphene oxide, metal At least one of oxide compound and nano-microcrystalline cellulose, more preferably including heavy calcium carbonate, graphene oxide and nano-microcrystalline cellulose; the quality of said heavy calcium carbonate, graphene oxide and nano-microcrystalline cellulose The ratio is preferably (2.5-3.5):(2.5-3.5):1.
  • the average particle diameter of the ground calcium carbonate is preferably 2000-3000 mesh.
  • the particle size of the graphene oxide is preferably 190-320nm.
  • the present invention found that adding fillers such as carbonates to the polycarbonate composition can effectively enhance its thermal stability compared with the pure polycarbonate composition, but it will also lead to a decrease in the barrier performance of the material.
  • the present invention finds that the use of heavy calcium carbonate, graphene oxide, and nano-microcrystalline cellulose as pigments and fillers can effectively avoid excessive decline in barrier performance. It is speculated that different pigments and fillers are interlaced in the system, which makes the penetration path complicated, hinders the diffusion of external molecules in the material, and reduces the transmittance.
  • the flame retardant preferably includes at least one of magnesium hydroxide, aluminum hydroxide and a halogen flame retardant.
  • the flame retardant is preferably magnesium hydroxide.
  • the isocyanate compound preferably includes at least one of 4,4-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, hexamethylene isocyanate and triallyl isocyanate; more preferably Triallyl isocyanate.
  • the third object of the present invention is to provide a method for preparing plastics containing polycarbonate compositions, comprising the following steps: pre-mixing PPCP and PPC to obtain polycarbonate compositions, then adding other raw materials and mixing them uniformly, putting them into Extrude and granulate in a twin-screw extruder to obtain the plastic containing the polycarbonate composition.
  • the preparation method of the plastic containing polycarbonate composition preferably comprises the following steps: PPCP and PPC are pre-dried at 55-70°C for 3-5h, and then mixed in a high-speed mixer for 3-7min , add the remaining raw materials in sequence, continue to stir and mix for 2-5 minutes, then put the premix into a twin-screw extruder, extrude and granulate at 100°C-170°C to obtain the plastic containing the polycarbonate composition.
  • the present invention not only effectively enhances its thermodynamic properties by adding different types and contents of fillers to plastics, but also effectively hinders the diffusion of external molecules in the material, reduces the transmittance, and improves its gas barrier properties and resistance Static.
  • a polycarbonate composition comprises the following raw materials: PPCP and PPC, wherein the mass ratio of PPCP/PPC is 30:70.
  • the PPCP (propylene glycol phthalate-propylene carbonate copolymer) has a number average molecular weight of 1.3 ⁇ 10 5 and a Mw/Mn of 1.91.
  • the number average molecular weight of the PPC (polymethylethylene carbonate) is 2.3 ⁇ 10 5 , and M w /M n is 2.76.
  • a plastic containing polycarbonate composition in parts by mass, said plastic raw material includes 100 parts of polycarbonate composition, 2 parts of ester compound, 0.4 part of block oligomer, 10 parts of pigment and filler, 0.25 part of antistatic agent Parts, 1.5 parts of isocyanate compounds.
  • the polycarbonate composition undergoes a pretreatment process before being added, and the pretreatment includes the following steps: uniformly mixing the polycarbonate composition with a solvent, heating and stirring, filtering and drying.
  • the mass ratio of the polycarbonate composition to the solvent is 1:7.
  • the solvent includes isopropanol and acetone, and the mass ratio of the isopropanol to acetone is 30:70.
  • the heating and stirring temperature is 55°C, and the stirring time is 6h.
  • the ester compounds include citrate compounds and adipate compounds.
  • the mass ratio of the citrate compound and the adipate compound is 2:5.
  • the citrate compound is acetyl triethyl citrate.
  • the molecular weight of the adipate ester compound is 3000-4000, and the viscosity at 25° C. is 2500-3500 cps.
  • the adipate ester compound was purchased from Shenzhen Zhonglian Rubber Co., Ltd., model: PN-1050.
  • the weight average molecular weight of the block oligomer is 2600-3400.
  • the block oligomer is generated by the reaction of 1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine Block oligomer (CAS No.: 192268-64-7). Purchased from Shanghai Puzhan Industrial Co., Ltd., model: CHIMASSORB 2020.
  • the pigments and fillers are heavy calcium carbonate, graphene oxide and nano-microcrystalline cellulose. Described heavy calcium carbonate, the mass ratio of graphene oxide and zinc oxide is 3:3:1.
  • the average particle size of the heavy calcium carbonate is 2500 mesh, purchased from Guangxi Hezhou Xinye Trading Co., Ltd.
  • the graphene oxide is aminated graphene oxide, PEG-modified graphene oxide, purchased from Jiangsu Xianfeng Nano Material Technology Co., Ltd., with a size of 190-320nm, and the nano-microcrystalline cellulose is purchased from Angxing New Carbon Material Changzhou Ltd.
  • the flame retardant is magnesium hydroxide.
  • the flame retardant was purchased from Weifang Haililong Magnesium Industry Co., Ltd., model: H1411.
  • the antistatic agent was purchased from Shandong Juli Antistatic Technology Co., Ltd., model: JL-1.
  • the isocyanate compound is triallyl isocyanate.
  • a method for preparing plastics containing a polycarbonate composition comprising the steps of: pre-drying PPCP and PPC at 60°C for 4 hours, then mixing them in a high-speed mixer for 5 minutes, adding the remaining raw materials in sequence, continuing to stir and mix them for 3 minutes, and then Put the premix into a twin-screw extruder, extrude and granulate at 165°C.
  • a plastic containing a polycarbonate composition the specific implementation is the same as in Example 1, except that the mass ratio of the PPCP/PPC is 70:30.
  • a plastic containing a polycarbonate composition the specific implementation is the same as in Example 1, except that the mass ratio of the PPCP/PPC is 40:60.
  • a plastic containing a polycarbonate composition the specific implementation is the same as in Example 1, except that the mass ratio of the PPCP/PPC is 50:50.
  • a polycarbonate composition comprises the following raw materials: PPCP and PPC, wherein the mass ratio of PPCP/PPC is 30:70.
  • the number average molecular weight of the PPCP (propylene glycol phthalate-propylene carbonate copolymer) is 1.3*10 5 , and Mw/Mn is 1.91.
  • the number average molecular weight of the PPC (polymethylethylene carbonate) is 2.3*10 5 , and the Mw/Mn is 2.76.
  • a plastic containing polycarbonate composition in parts by mass, said plastic comprises 100 parts of polycarbonate composition, 2 parts of ester compound, 0.4 part of block oligomer, 10 parts of pigment and filler, 0.25 part of antistatic agent Parts, 1.5 parts of isocyanate compounds.
  • the ester compounds include citrate compounds and adipate compounds.
  • the mass ratio of the citrate compound and the adipate compound is 2:5.
  • the citrate compound is acetyl triethyl citrate.
  • the molecular weight of the adipate ester compound is 3000-4000, and the viscosity at 25° C. is 2500-3500 cps.
  • the adipate ester compound was purchased from Shenzhen Zhonglian Rubber Co., Ltd., model: PN-1050.
  • the weight average molecular weight of the block oligomer is 2600-3400.
  • the block oligomer is generated by the reaction of 1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine Block oligomer (CAS No.: 192268-64-7). Purchased from Shanghai Puzhan Industrial Co., Ltd., model: CHIMASSORB 2020.
  • the pigments and fillers are heavy calcium carbonate, graphene oxide and nano-microcrystalline cellulose. Described heavy calcium carbonate, the mass ratio of graphene oxide and zinc oxide is 3:3:1.
  • the average particle size of the heavy calcium carbonate is 2500 mesh, purchased from Guangxi Hezhou Xinye Trading Co., Ltd.
  • the graphene oxide is aminated graphene oxide, PEG-modified graphene oxide, purchased from Jiangsu Xianfeng Nano Material Technology Co., Ltd., with a size of 190-320nm, and the nano-microcrystalline cellulose is purchased from Angxing New Carbon Material Changzhou Ltd.
  • the flame retardant is magnesium hydroxide.
  • the flame retardant was purchased from Weifang Haililong Magnesium Industry Co., Ltd., model: H1411.
  • the antistatic agent was purchased from Shandong Juli Antistatic Technology Co., Ltd., model: JL-1.
  • the isocyanate compound is triallyl isocyanate (CAS number: 101-37-1).
  • a method for preparing plastics containing a polycarbonate composition comprising the steps of: pre-drying PPCP and PPC at 60°C for 4 hours, then mixing them in a high-speed mixer for 5 minutes, adding the remaining raw materials in sequence, continuing to stir and mix them for 3 minutes, and then Put the premix into a twin-screw extruder, extrude and granulate at 135°C.
  • a plastic containing a polycarbonate composition the specific implementation is the same as in Example 1, except that the mass ratio of the ground calcium carbonate, graphene oxide, and nanocrystalline cellulose is 3:10:1.
  • Biodegradability test According to GB/T19277, carry out a 60-day compulsory composting test.
  • Barrier performance test Carry out water vapor transmission coefficient and oxygen transmission coefficient tests according to GB/T26253 and GB/T19789.

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  • Polymers & Plastics (AREA)
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Abstract

本发明涉及C08L69/00，具体涉及一种聚碳酸酯组合物及其塑料和制备方法。包括以下原料：PPCP和PPC，其中，PPCP和PPC的质量比为(1-99):(99-1)。本发明制备的材料不仅能够在保证优异的力学性能和可降解性的同时，进一步提高其阻隔性和热稳定性等性能，使制备的材料综合性能更加。

Description

一种聚碳酸酯组合物及其塑料和制备方法
本申请要求于2021年12月07日提交中国专利局、申请号为CN202111483956.8、发明名称为“一种聚碳酸酯组合物及其塑料和制备方法”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IPC分类号C08L 69/00(2006.01)所述的技术领域，具体涉及一种聚碳酸酯组合物及其塑料和制备方法。
背景技术
工业化技术的发展使得各种产品的制备和消耗速度加快，二氧化碳排放量不断增多，不仅导致国内外能源价格的升高，而且与现今追求的绿色可持续化发展的观念不符，因此对二氧化碳利用成为解决问题的关键之一。以CO 2为原料合成聚碳酸酯环境友好型材料，加强对CO 2利用，为绿色可持续化发展提供了一条新的道路。
专利CN201410662371.6一种聚甲基乙撑碳酸酯组合物及其制备方法通过聚甲基乙撑碳酸酯基体，热塑性聚氨酯和聚乙烯醇熔融共混组成改性材料然后与助剂混合制备得到的组合物具有良好的拉伸强度和断裂伸长率。
专利CN201210283571.1一种可降解聚甲基乙撑碳酸酯基复合材料及其制备方法通过聚甲基乙撑碳酸酯和聚乙烯缩甲醛混合改性制备的材料具有较高的机械强度和可加工性。
但现有技术中聚甲基乙撑碳酸酯与体系中各种原料的相容性较差，对其力学性能的改良有限，无法充分满足客户要求。
发明内容
为了解决上述技术问题，本发明的目的之一在于提供了一种聚碳酸酯组合物，所述聚碳酸酯组合物具有较高的稳定性和力学性能。
本发明提供了一种聚碳酸酯组合物，包括以下原料：PPCP和PPC，其中，PPCP和PPC的质量比为(1-99):(99-1)。
优选的，所述PPCP的数均分子量为1.0-1.5*10 5。
优选的，所述PPCP的M w/M n为1.8-2.1。
优选的，所述PPC的数均分子量为2.0-2.5*10 5。
优选的，所述PPC的M w/M n为2.5-3.0。
本发明还提供了一种含有聚碳酸酯组合物的塑料，按质量份计，原料包括上述技术方案所述的聚碳酸酯组合物90-120份、酯类化合物1-3份、嵌段齐聚物0.2-0.6份、颜填料5-15份、抗静电剂0.1-0.3份和异氰酸酯类化合物0.5-2份。
优选的，所述聚碳酸酯组合物为经过预处理的聚碳酯组合物；
所述预处理包括：将聚碳酸酯组合物和溶剂混合，依次进行加热搅拌和过滤烘干。
优选的，所述溶剂包括乙醇、丙酮、甲苯、乙酸乙酯、二氯甲烷和异丙醇中的至少一种；
所述聚碳酸酯组合物和溶剂的质量比为1:(6-8)。
优选的，所述溶剂包括质量比为(25-35)：(65-75)的异丙醇和丙醇。
优选的，所述加热搅拌的温度为50-60℃，时间为5-8h。
优选的，所述酯类化合物包括磺酸酯类化合物、邻苯酸酯类化合物、肉桂酸酯类化合物、柠檬酸酯类化合物、己二酸酯类化合物和月桂酸酯类化合物中的至少一种。
优选的，所述酯类化合物包括质量比为(1.5-2.5)：(4-7)的柠檬酸酯类化合物和己二酸酯类化合物。
优选的，所述己二酸酯类化合物的分子量为3000-4000。
优选的，所述嵌段齐聚物的重均分子量为2500-3500。
优选的，所述颜填料包括硬脂酸盐、碳酸盐、二氧化硅、二氧化钛、蒙脱土、凹凸棒石、蛭石、淀粉、木纤维、木粉、氧化石墨烯、金属氧化物和纳米微晶纤维素中的至少一种。
优选的，所述颜填料包括质量比为(2.5-3.5)：(2.5-3.5)：1的重质碳酸钙、氧化石墨烯和纳米微晶纤维素。
优选的，所述重质碳酸钙的平均粒径为2000-3000目；
所述氧化石墨烯的粒径为190-320nm。
优选的，所述阻燃剂包括氢氧化镁、氢氧化铝和卤素阻燃剂中的至少一种。
优选的，所述异氰酸酯类化合物包括4,4-二苯甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基异氰酸酯和异氰酸三烯丙酯中的至少一种。
本发明还提供了上述技术方案所述的含有聚碳酸酯组合物的塑料的制备方法，包括以下步骤：将PPCP和PPC预先混合得到聚碳酸酯组合物，然后加入其它原料混合均匀后，放入双螺杆挤出机中挤出造粒，得到所述含有聚碳酸酯组合物的塑料。
优选的，包括以下步骤：将PPCP和PPC预先在55-70℃下干燥3-5h，然后在高速混合机中混合3-7min，依次加入剩余原料，继续搅拌混合2-5min，然后将预混物加入双螺杆挤出机中，在100℃-170℃下挤出造粒，得到所述含有聚碳酸酯组合物。
本发明提供了一种聚碳酸酯组合物，包括以下原料：PPCP和PPC，其中，PPCP和PPC的质量比为(1-99):(99-1)。
本发明还提供了一种含有聚碳酸酯组合物的塑料，按质量份计，原料包括上述技术方案所述的聚碳酸酯组合物90-120份、酯类化合物1-3份、嵌段齐聚物0.2-0.6份、颜填料5-15份、抗静电剂0.1-0.3份和异氰酸酯类化合物0.5-2份。
本发明通过对材料中PPCP，PPC等各原料进行种类和比例的限定，不仅能够在保证优异的力学性能和可降解性的同时，进一步提高其阻隔性，抗静电性，热稳定性，耐油性等性能，使制备的材料综合性能更加，尤其适用于医学包装技术领域。
具体实施方式
本发明提供了一种聚碳酸酯组合物，包括以下原料：PPCP和PPC，其中，PPCP和PPC的质量比为(1-99):(99-1)。
在本发明中，所述PPCP的数均分子量优选为1-1.5*10 5，M w/M n优选为1.8-2.1。
在本发明中，所述PPC的数均分子量优选为2-2.5*10 5，M w/M n优选 为2.5-3.0。
在本发明中，所述聚碳酸酯组合物优选经过了预处理过程，所述预处理优选包括以下步骤：将聚碳酸酯组合物与溶剂混合均匀，加热搅拌，过滤烘干即可。在本发明中，所述聚碳酸酯组合物和溶剂的质量比优选为1：(6-8)。在本发明中，所述溶剂优选包括乙醇、丙酮、甲苯、乙酸乙酯、二氯甲烷和异丙醇中的至少一种，更优选包括异丙醇和丙酮，所述异丙醇和丙酮的质量比优选为(25-35)：(65-75)。在本发明中，所述加热搅拌的温度优选为50-60℃，时间优选为5-8h。
研究发现PPCP和PPC在数均分子量和分子量分布一定的情况下显著提高其稳定性和力学性能，但实际提高的结果与预期相差较大。本发明意外研究发现通过对PPCP和PPC进行预处理可以进一步提高其力学性能和热稳定性。推测是由于经过与预处理的PPCP和PPC在体系内分子链能够按一定的空间次序进行紧密排列，有效促进体系内晶体的生长，使晶体分布均匀，有效提高玻璃化转变温度，进而提高其稳定性和力学性能。
在本发明中，所述PPCP和PPC的质量比优选为(30-70):(30-70)。
本发明的目的之一在于提供了一种含聚碳酸酯组合物的塑料，按质量份计，所述塑料原料包括聚碳酸酯组合物为90-120份、酯类化合物1-3份、嵌段齐聚物0.2-0.6份、颜填料5-15份、抗静电剂0.1-0.3份和异氰酸酯类化合物0.5-2份。
在本发明中，所述酯类化合物优选包括磺酸酯类化合物、邻苯酸酯类化合物、肉桂酸酯类化合物、柠檬酸酯类化合物、己二酸酯类化合物和月桂酸酯类化合物中的至少一种，更优选包括柠檬酸酯类化合物和己二酸酯类化合物；所述柠檬酸酯类化合物和己二酸酯类化合物的质量比优选为(1.5-2.5)：(4-7)。
在本发明中，所述己二酸酯类化合物的分子量优选为3000-4000。
在本发明中，所述己二酸酯类化合物在25℃下的粘度优选为2500-3500cps。
在本发明中，所述嵌段齐聚物的重均分子量优选为2500-3500。
在本发明中，所述嵌段齐聚物优选为1,3,5-三嗪和N-丁基-1-丁胺和 N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应生成的嵌段齐聚物。
在本发明中，所述颜填料优选包括硬脂酸盐、碳酸盐、二氧化硅、二氧化钛、蒙脱土、凹凸棒石、蛭石、淀粉、木纤维、木粉、氧化石墨烯、金属氧化物和纳米微晶纤维素中的至少一种，更优选包括重质碳酸钙、氧化石墨烯和纳米微晶纤维素；所述重质碳酸钙、氧化石墨烯和纳米微晶纤维素的质量比优选的为(2.5-3.5)：(2.5-3.5)：1。
在本发明中，所述重质碳酸钙的平均粒径优选为2000-3000目。
在本发明中，所述氧化石墨烯的粒径优选为190-320nm。
本发明研究发现采用碳酸盐等填料加入到聚碳酸酯组合物中较纯聚碳酸酯组合物能够有效增强其热稳定性，但也会导致材料的阻隔性能下降。本发明意外研究发现通过采用重质碳酸钙，氧化石墨烯，纳米微晶纤维素作为颜填料可以有效避免阻隔性能下降过多。推测是由于不同的颜填料在体系中交错存在，使得穿透路径复杂，阻碍外界分子在材料中扩散，降低了透过率，当重质碳酸钙、氧化石墨烯和纳米微晶纤维素的质量比为(2.5-3.5)：(2.5-3.5)：1时不仅可以有效保证其热稳定性和阻隔性能，而且还能进一步提高材料的抗静电性，扩大材料的使用范围。
在本发明中，所述阻燃剂优选包括氢氧化镁、氢氧化铝和卤素阻燃剂中的至少一种。
在本发明中，所述阻燃剂优选为氢氧化镁。
在本发明中，所述异氰酸酯类化合物优选包括4,4-二苯甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基异氰酸酯和异氰酸三烯丙酯的至少一种；更优选为异氰酸三烯丙酯。
本发明的目的之三在于提供了一种含聚碳酸酯组合物的塑料的制备方法，包括以下步骤：将PPCP和PPC预先混合得到聚碳酸酯组合物，然后加入其它原料混合均匀后，放入双螺杆挤出机中挤出造粒，得到所述含聚碳酸酯组合物的塑料。
在本发明中，所述含聚碳酸酯组合物的塑料的制备方法，优选包括以下步骤：将PPCP和PPC预先在55-70℃下干燥3-5h，然后在高速混合机中混合3-7min，依次加入剩余原料，继续搅拌混合2-5min，然后将预混 物加入双螺杆挤出机中，在100℃-170℃下挤出造粒，得到所述含聚碳酸酯组合物的塑料。
有益效果：
1)本发明通过对PPCP和PPC的分子量和分子量分布进行限定，并对聚碳酸酯组合物进行预处理，有效改善了体系内的结晶能力，促进玻璃化转变温度提高，有效提高材料的力学性能和热力学稳定性(玻璃化温度高达50℃)等性能，
2)本发明通过采用不同种类和含量的填料添加到塑料中，不仅有效增强了其热力学性能，而且能够有效阻碍外界分子在材料中扩散，降低了透过率，改善了其气体阻隔性和抗静电性。
3)本发明通过对材料中PPCP，PPC等各原料进行种类和比例的限定，不仅能够在保证优异的力学性能和可降解性的同时，进一步提高其阻隔性，抗静电性，热稳定性，耐油性等性能，使制备的材料综合性能更加，尤其适用于医学包装技术领域。
实施例1
一种聚碳酸酯组合物，包括以下原料：PPCP和PPC，其中PPCP/PPC的质量比为30:70。
所述PPCP(邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物)的数均分子量为1.3×10 5，Mw/Mn为1.91。
所述PPC(聚甲基乙撑碳酸酯)的数均分子量为2.3×10 5，M w/M n为2.76。
一种含聚碳酸酯组合物的塑料，按质量份计，所述塑料原料包括聚碳酸酯组合物100份，酯类化合物2份，嵌段齐聚物0.4份，颜填料10份，抗静电剂0.25份，异氰酸酯类化合物1.5份。
所述聚碳酸酯组合物在加入前经过预处理过程，所述预处理包括以下步骤：将聚碳酸酯组合物与溶剂混合均匀，加热搅拌，过滤烘干即可。所述聚碳酸酯组合物和溶剂的质量比为1：7。所述溶剂包括异丙醇和丙酮，所述异丙醇和丙酮的质量比为30：70。所述加热搅拌温度为55℃，搅拌 时间为6h。
所述酯类化合物包括柠檬酸酯类化合物和己二酸酯类化合物。所述柠檬酸酯类化合物和己二酸酯类化合物的质量比为2：5。所述柠檬酸酯类化合物为乙酰柠檬酸三乙酯。所述己二酸酯类化合物的分子量为3000-4000，在25℃下的粘度为2500-3500cps。所述己二酸酯类化合物购自深圳市众联橡胶有限公司，型号:PN-1050。
所述嵌段齐聚物的重均分子量为2600-3400。所述嵌段齐聚物为1,3,5-三嗪和N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应生成的嵌段齐聚物(CAS号：192268-64-7)。购自上海璞展实业有限公司，型号：CHIMASSORB 2020。
所述颜填料为重质碳酸钙，氧化石墨烯和纳米微晶纤维素。所述重质碳酸钙，氧化石墨烯和氧化锌的质量比为3:3:1。所述重质碳酸钙的平均粒径为2500目，购自广西贺州市鑫业贸易有限公司。所述氧化石墨烯为氨基氧化石墨烯，PEG修饰氧化氧化石墨烯，购自江苏先丰纳米材料科技有限公司，尺寸为190-320nm，所述纳米微晶纤维素购自昂星新型碳材料常州有限公司。
所述阻燃剂为氢氧化镁。所述阻燃剂为经表面处理后的氢氧化镁，所述阻燃剂的平均粒径为D50＝1.0-1.5um。所述阻燃剂购自潍坊海利隆镁业有限公司，型号：H1411。
所述抗静电剂购自山东聚力防静电科技有限公司，型号：JL-1。
所述异氰酸酯类化合物为异氰酸三烯丙酯。
一种含聚碳酸酯组合物的塑料的制备方法，包括以下步骤：将PPCP和PPC预先在60℃下干燥4h，然后在高速混合机中混合5min，依次加入剩余原料，继续搅拌混合3min，然后将预混物加入双螺杆挤出机中，在165℃下挤出造粒即得。
实施例2
一种含聚碳酸酯组合物的塑料，具体实施方式同实施例1，不同之处在于所述PPCP/PPC的质量比为70:30。
实施例3
一种含聚碳酸酯组合物的塑料，具体实施方式同实施例1，不同之处在于所述PPCP/PPC的质量比为40:60。
实施例4
一种含聚碳酸酯组合物的塑料，具体实施方式同实施例1，不同之处在于所述PPCP/PPC的质量比为50:50。
对比例1
一种聚碳酸酯组合物，包括以下原料：PPCP和PPC，其中PPCP/PPC的质量比为30:70。
所述PPCP(邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物)的数均分子量为1.3*10 5，Mw/Mn为1.91。
所述PPC(聚甲基乙撑碳酸酯)的数均分子量为2.3*10 5，Mw/Mn为2.76。
一种含聚碳酸酯组合物的塑料，按质量份计，所述塑料包括聚碳酸酯组合物为100份，酯类化合物2份，嵌段齐聚物0.4份，颜填料10份，抗静电剂0.25份，异氰酸酯类化合物1.5份。
所述酯类化合物包括柠檬酸酯类化合物和己二酸酯类化合物。所述柠檬酸酯类化合物和己二酸酯类化合物的质量比为2：5。所述柠檬酸酯类化合物为乙酰柠檬酸三乙酯。所述己二酸酯类化合物的分子量为3000-4000，在25℃下的粘度为2500-3500cps。所述己二酸酯类化合物购自深圳市众联橡胶有限公司，型号:PN-1050。
所述嵌段齐聚物的重均分子量为2600-3400。所述嵌段齐聚物为1,3,5-三嗪和N-丁基-1-丁胺和N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应生成的嵌段齐聚物(CAS号：192268-64-7)。购自上海璞展实业有限公司，型号：CHIMASSORB 2020。
所述颜填料为重质碳酸钙，氧化石墨烯和纳米微晶纤维素。所述重质碳酸钙，氧化石墨烯和氧化锌的质量比为3:3:1。所述重质碳酸钙的平均粒径为2500目，购自广西贺州市鑫业贸易有限公司。所述氧化石墨烯为氨基氧化石墨烯，PEG修饰氧化氧化石墨烯，购自江苏先丰纳米材料科技有限公司，尺寸为190-320nm，所述纳米微晶纤维素购自昂星新型碳材 料常州有限公司。
所述阻燃剂为氢氧化镁。所述阻燃剂为经表面处理后的氢氧化镁，所述阻燃剂的平均粒径为D50＝1.0-1.5um。所述阻燃剂购自潍坊海利隆镁业有限公司，型号：H1411。
所述抗静电剂购自山东聚力防静电科技有限公司，型号：JL-1。
所述异氰酸酯类化合物为异氰酸三烯丙酯(CAS号：101-37-1)。
一种含聚碳酸酯组合物的塑料的制备方法，包括以下步骤：将PPCP和PPC预先在60℃下干燥4h，然后在高速混合机中混合5min，依次加入剩余原料，继续搅拌混合3min，然后将预混物加入双螺杆挤出机中，在135℃下挤出造粒即得。
对比例2
一种含聚碳酸酯组合物的塑料，具体实施方式同实施例1，不同之处在于所述重质碳酸钙，氧化石墨烯，纳米微晶纤维素的质量比为3：10：1。
测试
1.力学性能测试：按照GB/T1040测试拉伸强度；
2.生物降解性测试：按照GB/T19277进行60天强制堆肥测试。
3.阻隔性能测试：按照GB/T26253和GB/T19789进行水蒸气透过系数和氧气透过系数测试。
表1 性能测试结果
Figure PCTCN2022137176-appb-000001
Figure PCTCN2022137176-appb-000002

Claims (21)

  1. 一种聚碳酸酯组合物，其特征在于，包括以下原料：PPCP和PPC，其中，PPCP和PPC的质量比为(1-99):(99-1)。
  2. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述PPCP的数均分子量为1.0×10 5-1.5×10 5。
  3. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，所述PPCP的M w/M n为1.8-2.1。
  4. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述PPC的数均分子量为2.0×10 5-2.5×10 5。
  5. 根据权利要求4所述的聚碳酸酯组合物，其特征在于，所述PPC的M w/M n为2.5-3.0。
  6. 一种含有聚碳酸酯组合物的塑料，其特征在于，按质量份计，原料包括权利要求1-5任一项所述的聚碳酸酯组合物90-120份、酯类化合物1-3份、嵌段齐聚物0.2-0.6份、颜填料5-15份、抗静电剂0.1-0.3份和异氰酸酯类化合物0.5-2份。
  7. 如权利要求6所述的含有聚碳酸酯组合物的塑料，其特征在于，所述聚碳酸酯组合物为经过预处理的聚碳酯组合物；
    所述预处理包括：将聚碳酸酯组合物和溶剂混合，依次进行加热搅拌和过滤烘干。
  8. 如权利要求7所述的含有聚碳酸酯组合物的塑料，其特征在于，所述溶剂包括乙醇、丙酮、甲苯、乙酸乙酯、二氯甲烷和异丙醇中的至少一种；
    所述聚碳酸酯组合物和溶剂的质量比为1:(6-8)。
  9. 如权利要求8所述的含有聚碳酸酯组合物的塑料，其特征在于，所述溶剂包括质量比为(25-35)：(65-75)的异丙醇和丙醇。
  10. 如权利要求7～9任一项所述的含有聚碳酸酯组合物的塑料，其特征在于，所述加热搅拌的温度为50-60℃，时间为5-8h。
  11. 根据权利要求6所述的含有聚碳酸酯组合物的塑料，其特征在于， 所述酯类化合物包括磺酸酯类化合物、邻苯酸酯类化合物、肉桂酸酯类化合物、柠檬酸酯类化合物、己二酸酯类化合物和月桂酸酯类化合物中的至少一种。
  12. 根据权利要求11所述的含有聚碳酸酯组合物的塑料，其特征在于，所述酯类化合物包括质量比为(1.5-2.5)：(4-7)的柠檬酸酯类化合物和己二酸酯类化合物。
  13. 根据权利要求11或12所述的含有聚碳酸酯组合物的塑料，其特征在于，所述己二酸酯类化合物的分子量为3000-4000。
  14. 根据权利要求6所述的含有聚碳酸酯组合物的塑料，其特征在于，所述嵌段齐聚物的重均分子量为2500-3500。
  15. 根据权利要求6所述的含有聚碳酸酯组合物的塑料，其特征在于，所述颜填料包括硬脂酸盐、碳酸盐、二氧化硅、二氧化钛、蒙脱土、凹凸棒石、蛭石、淀粉、木纤维、木粉、氧化石墨烯、金属氧化物和纳米微晶纤维素中的至少一种。
  16. 根据权利要求15所述的含有聚碳酸酯组合物的塑料，其特征在于，所述颜填料包括质量比为(2.5-3.5)：(2.5-3.5)：1的重质碳酸钙、氧化石墨烯和纳米微晶纤维素。
  17. 根据权利要求16所述的含有聚碳酸酯组合物的塑料，其特征在于，所述重质碳酸钙的平均粒径为2000-3000目；
    所述氧化石墨烯的粒径为190-320nm。
  18. 根据权利要求6所述的含有聚碳酸酯组合物的塑料，其特征在于，所述阻燃剂包括氢氧化镁、氢氧化铝和卤素阻燃剂中的至少一种。
  19. 根据权利要求6所述的含有聚碳酸酯组合物的塑料，其特征在于，所述异氰酸酯类化合物包括4,4-二苯甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、六亚甲基异氰酸酯和异氰酸三烯丙酯中的至少一种。
  20. 权利要求6-19任一项所述的含有聚碳酸酯组合物的塑料的制备方法，包括以下步骤：将PPCP和PPC预先混合得到聚碳酸酯组合物，然后加入其它原料混合均匀，得到预混物；将所述预混物放入双螺杆挤出机中挤出造粒，得到所述含有聚碳酸酯组合物的塑料。
  21. 根据权利要求20所述的制备方法，其特征在于，包括以下步骤：将PPCP和PPC预先在55-70℃下干燥3-5h，然后在高速混合机中混合3-7min，依次加入剩余原料，继续搅拌混合2-5min，然后将预混物加入双螺杆挤出机中，在100℃-170℃下挤出造粒，得到所述含有聚碳酸酯组合物。
PCT/CN2022/137176 2021-12-07 2022-12-07 一种聚碳酸酯组合物及其塑料和制备方法 WO2023104076A1 (zh)

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