WO2023274190A1 - Melt-blown polypropylene composition, method for improving strength of melt-blown polypropylene composition, and application of melt-blown polypropylene composition - Google Patents

Melt-blown polypropylene composition, method for improving strength of melt-blown polypropylene composition, and application of melt-blown polypropylene composition Download PDF

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Publication number
WO2023274190A1
WO2023274190A1 PCT/CN2022/101752 CN2022101752W WO2023274190A1 WO 2023274190 A1 WO2023274190 A1 WO 2023274190A1 CN 2022101752 W CN2022101752 W CN 2022101752W WO 2023274190 A1 WO2023274190 A1 WO 2023274190A1
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melt
polypropylene
blown
blown polypropylene
polypropylene composition
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PCT/CN2022/101752
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French (fr)
Chinese (zh)
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唐宇航
钱志军
郭唐华
陈平绪
叶南飚
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金发科技股份有限公司
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Publication of WO2023274190A1 publication Critical patent/WO2023274190A1/en

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Definitions

  • the invention relates to the technical field of polypropylene modification processing, more specifically, to a melt-blown polypropylene composition and a method and application for improving the strength of the melt-blown polypropylene composition.
  • Polypropylene melt-blown material is used as the raw material for the core layer of the mask, and the quality of the polypropylene melt-blown material determines the quality of the mask.
  • the hydrogen adjustment method that is, the advanced catalyst system is used, the polymerization process is strictly controlled, and hydrogen is used as a molecular weight regulator to improve the fluidity of the product.
  • the degradation method that is, the polypropylene is degraded by peroxide to improve the fluidity of the polypropylene.
  • the degradation method has been widely used due to its simple production process and easy conversion between different brands of products.
  • melt-blown polypropylene composition If some elastomers or tougheners are directly added to the melt-blown polypropylene composition, other properties of the melt-blown cloth will be reduced.
  • the purpose of toughness, but part of the residual peroxide in this method may have a cross-linking reaction with the ethylene-octene copolymer, resulting in a brittle melt-blown cloth that is easily pulled off.
  • the invention provides a method for improving the strength of the melt-blown polypropylene composition.
  • Another object of the present invention is to provide said meltblown polypropylene composition.
  • Another object of the present invention is to provide applications of the meltblown polypropylene composition.
  • a method for improving the strength of a melt-blown polypropylene composition comprising the steps of:
  • step S2 Steam heating the particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition
  • the steam heating temperature in step S2 is 80-110°C.
  • the additives include but are not limited to electret agents, nucleating agents, degradation agents and antioxidants, calculated by weight, 80-100 parts of polypropylene; 0.2-0.6 parts of electret agents; 0.1-0.8 parts of nucleating agents; 0.2-0.5 parts of degradation agent; 0.2-0.6 parts of antioxidant.
  • the steam heating temperature in step S2 is lower than 80°C, which cannot achieve the purpose of improving crystallization. If the temperature is higher than 110°C, the polypropylene resin will become soft and cannot be used if it exceeds the heat distortion temperature of polypropylene.
  • the present invention can reduce the content of volatile organic compounds (VOC) through the low pressure separation system and the steam heating step.
  • the volatile matter (VOC) in the melt-blown polypropylene composition continuously diffuses into the hot steam; at the same time, the hot steam can also penetrate the pores of the melt-blown polypropylene composition and will adhere to the inside of the polypropylene pellets.
  • the volatile organic compounds (VOC) are carried out into the vapor phase, and then the purpose of removing the volatile organic compounds (VOC) in the polypropylene pellets is achieved by steam scheduling.
  • the function of the low-pressure separation system of the present invention is to reduce the air pressure by increasing the free volume space between the screw barrel and the screw at the back section of the extruder on the one hand; At 0.4 ⁇ 0.8MPa.
  • the steam heating temperature in step S2 has an important influence on the crystallization of polypropylene.
  • the inventors found that when the steam temperature is 85-105°C, the crystallization is higher and the strength is better. Therefore, it is more preferable that the steam heating in step S3 The temperature is 85-105°C.
  • the steam heating time in step S2 is 60-120 minutes.
  • the outlet pressure of the steam heated by the steam in step S2 is 1.05-2.0 MPa.
  • the vacuum degree in the low-pressure separation system in step S1 is 0.4-0.8 MPa.
  • the melt-blown polypropylene melt mixture can be obtained by conventional preparation methods, for example, directly blending polypropylene and other additives, or it can be prepared in parts by first making masterbatches and then blending.
  • melt-blown polypropylene melt mixture in step S1 is prepared by the following method:
  • step M2 Mix the masterbatch, polypropylene, nucleating agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a melt-blown polypropylene melt mixture.
  • the polypropylene in the M1 and The weight ratio of polypropylene in M2 is (0.1-0.2):1.
  • the present invention adds a degradation agent and an electret agent to make a masterbatch.
  • This method can make the degradation agent and the electret agent more uniformly dispersed in the melt-blown composition, so that the subsequent The electret effect of the melt-blown cloth prepared by using the composition is better, and at the same time, uneven dispersion of the electret agent and easy plugging of the spinneret holes are avoided.
  • the melt-blown polypropylene melt mixture in step S1 is prepared by the following method:
  • step M2 Mix the masterbatch, polypropylene, nucleating agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a melt-blown polypropylene melt mixture.
  • the polypropylene in the M1 and The weight ratio of polypropylene in M2 is (0.1-0.2):1.
  • a melt-blown polypropylene composition comprising polypropylene, electret agent, nucleating agent, degradation agent, antioxidant;
  • the strength of the meltblown polypropylene composition is greater than 25N under the conditions that the meltblown cloth sample size is 25cm ⁇ 5cm, the clamping distance is 10cm, the tensile rate is 100mm/min and the pretension is 200cN.
  • the melt-blown polypropylene composition includes the following components calculated in parts by weight: 80-100 parts of polypropylene; 0.2-0.6 parts of electret agent; 0.1-0.8 parts of nucleating agent; 0.2-0.5 parts of degradation agent parts; antioxidant 0.2 to 0.6 parts.
  • the degradation agent is 2.5-dimethyl-2.5-bis(tert-butylperoxy)hexane, dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxide One or more of amyl peroxide, bis(1,1-dimethylpropyl) peroxide, and dicumyl peroxide.
  • the antioxidant is a phenolic antioxidant and/or a phosphite antioxidant.
  • the nucleating agent is an aryl phosphate ester salt nucleating agent and/or a sorbitol nucleating agent.
  • the electret is one or more of tourmaline powder, fluoropolymer, fatty acid with 6 to 20 carbon atoms or its salt, natural wax or N,N'-ethylene bisstearamide kind.
  • the fluoropolymers include but not limited to polytetrafluoroethylene, hexafluoropropylene, and tetrafluoroethylene copolymers.
  • the polypropylene has a melt index of 10-70 g/10 min at 230° C. and 2.16 kg.
  • an antibacterial agent can be added, and the antibacterial agent is selected from one or more of inorganic nano-silver, copper or zinc, and oxides, such as Ag/ZnO nanocomposite antibacterial agent.
  • the melt-blown polypropylene composition is prepared by the following method: S1.
  • S1 The melt-blown polypropylene melt mixture mixed with polypropylene, electret, nucleating agent, degradation agent, and antioxidant is transported to a low-pressure separation system In, extruding and granulating;
  • step S2 Steam heating the particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition
  • the steam heating temperature in step S2 is 80-110°C.
  • a melt-blown cloth for masks is made from the melt-blown polypropylene composition.
  • the meltblown cloth for masks obtained by the above preparation method has high filtration performance, low VOC, high strength and low resistance performance.
  • the present invention provides a method for improving the strength of the melt-blown polypropylene composition.
  • the inventors found that under steam heating conditions, the polypropylene chain accelerates thermal movement, and annealing and crystallization will occur, thereby further improving the strength of the melt-blown polypropylene composition. .
  • the tensile strength and breaking strength of the filter cloth (unit weight: 25-28g/100cm 2 ) prepared by using the meltblown polypropylene is greater than 25N.
  • the meltblown polypropylene prepared by the above preparation method also has low odor, low resistance and high filtration efficiency.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field unless otherwise specified.
  • Polypropylene Homopolypropylene 320H, melt index 32 ⁇ 5g/10min Sinopec Sales Co., Ltd.;
  • Antibacterial agent BM-102TG, Japan Fuji;
  • Degradant Enox 101, Jiangsu Qiangsheng Functional Chemicals Co., Ltd.;
  • Antioxidant Antioxidant 1010, Sanfeng Chemical Co., Ltd.
  • the present embodiment provides a method for improving the strength of the melt-blown polypropylene composition, comprising the steps of:
  • step M2 Mix the masterbatch, polypropylene, nucleating agent, antibacterial agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a molten mixture.
  • the polypropylene in M1 and M2 The weight ratio of polypropylene in is 0.1:1;
  • step S2 The particles obtained in step S1 are heated with steam, the heating temperature is 105° C., and the heating time is 120 minutes, and then dried to obtain a melt-blown polypropylene composition.
  • melt-blown polypropylene composition 100 parts of polypropylene; 0.5 parts of degradation agent; 0.6 parts of electret agent; 0.5 parts of antibacterial agent; 0.8 parts of nucleating agent;
  • Examples 11 to 14 provide a series of methods for increasing the strength of the melt-blown polypropylene composition.
  • the preparation method and formulation are the same as those in Example 1, and the difference lies in the parameters in Table 2.
  • comparative example 1 provides a kind of preparation method of melt-blown polypropylene composition, comprises the steps:
  • step S1 Mix the masterbatch, polypropylene, nucleating agent, antibacterial agent and antioxidant obtained in step S1 until uniform, and the mixture is melted, sheared and kneaded,
  • Comparative Example 3 The formula and preparation method of Comparative Example 3 are the same as those of Example 1, the difference being that the steam temperature in step S2 is 115°C.
  • the testing items are standard melt mass flow rate (GB/T 3682 230°C, 2.16Kg), ash content (ISO 3451 850°C, 2H), volatile matter (ISO 787 105°C).
  • the odor level test is carried out according to PV3900-2000: take 20g of the sample and place it in a 1L non-odor sealed bottle, heat it in an oven at 80°C for 2 hours, take it out, and when it cools down to 65°C, it will be measured by 5 odor evaluators. Each tester evaluates the smell, and the final average is the test result.
  • VOC test The total volatile organic compound content of the melt-blown polypropylene composition is tested according to the public standard PV3341-1996, and the headspace-gas chromatography (HS-GC) method is used for testing. The test conditions are 120°C and constant temperature 5H.
  • HS-GC headspace-gas chromatography
  • Filtration efficiency test standard The polypropylene melt-blown material produced in the examples and comparative examples is produced under the same melt-blown electret process to produce a melt-blown cloth with a grammage of 25 ⁇ 2g/ cm2 , using GB/T2626-2018
  • the salt spray method of respiratory protective equipment (a method of testing the filter performance of masks by using NaCl or equivalent halides as aerosol particles, the results refer to the PFE results and resistance), specific parameters: the test flow rate is 85L/min.
  • melt flow rate, ash content, volatile matter and moisture of the above polypropylene composition all meet the standards for polypropylene melt-blown special materials.
  • Comparative Example 1 without steam heating, it can be seen that its strength is only 12N. In Comparative Example 2, the temperature of steam heating is lower than 80°C, which cannot improve the strength. In Comparative Example 3, when the temperature of steam heating is higher than 110°C, polypropylene If it becomes soft, melt-blown cloth cannot be prepared, and there is no relevant test data.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Filtering Materials (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Disclosed in the present invention are a melt-blown polypropylene composition, a method for improving the strength of the melt-blown polypropylene composition, and an application of the melt-blown polypropylene composition. The method for improving the strength of the melt-blown polypropylene composition comprises the following steps: S1, conveying, into a low-pressure separation system, a melt-blown polypropylene melt mixture formed by mixing a polypropylene raw material and an additive, and performing extrusion and granulation; and S2, performing steam heating on particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition, the temperature of steam heating in step S2 being 80-110°C. The melt-blown polypropylene obtained by the method is low in odor, low in resistance, high in filtering efficiency, and high in strength.

Description

熔喷聚丙烯组合物及其提高熔喷聚丙烯组合物强度的方法和应用Melt-blown polypropylene composition and method and application thereof for increasing strength of melt-blown polypropylene composition 技术领域technical field
本发明涉及聚丙烯改性加工技术领域，更具体地，涉及一种熔喷聚丙烯组合物及其提高熔喷聚丙烯组合物强度的方法和应用。The invention relates to the technical field of polypropylene modification processing, more specifically, to a melt-blown polypropylene composition and a method and application for improving the strength of the melt-blown polypropylene composition.
背景技术Background technique
2020年年初，“COVID-19”病毒开始蔓延全球，口罩成为了最重要的防疫物资，因此，医用口罩及民用口罩的需求量剧烈增长。聚丙烯熔喷料作为口罩核心层的原料，聚丙烯熔喷料的品质好坏决定了口罩的质量。现有制备高流动性聚丙烯材料的方法主要有两种，一种是氢调法，即采用先进的催化剂体系，严格控制聚合工艺，用氢气作为分子量调节剂，来达到提高产品的流动性，但该方法由于生产过程中要加入大量的氢气造成成型设备与工艺的过于繁杂；另一种是降解法，即采用过氧化物对聚丙烯进行降解处理来提高聚丙烯的流动性。降解法由于生产工艺简单、容易实现不同牌号产品之间的转换，因此得到了较为广泛的应用，虽然在挤压造粒过程中加入过氧化物降解剂来制备高流动性聚丙烯材料不影响聚合装置连续化稳定生产，但由于过氧化物的分布不均和残留会导致产品的拉伸性能差、生产出的熔喷布易撕裂，熔喷布放置一段时间明显出现发脆等现象；另外由于降解剂本来具有低分子高气味的特点及降解的过程，给改性后的熔喷组合物材料带来大量刺激性气味的低分子物质，该类物质的残留严重影响容熔喷布在口罩方面的应用。At the beginning of 2020, the "COVID-19" virus began to spread around the world, and masks became the most important anti-epidemic materials. Therefore, the demand for medical masks and civilian masks increased sharply. Polypropylene melt-blown material is used as the raw material for the core layer of the mask, and the quality of the polypropylene melt-blown material determines the quality of the mask. There are two main methods for preparing high-fluidity polypropylene materials, one is the hydrogen adjustment method, that is, the advanced catalyst system is used, the polymerization process is strictly controlled, and hydrogen is used as a molecular weight regulator to improve the fluidity of the product. However, in this method, a large amount of hydrogen must be added in the production process, which causes the molding equipment and process to be too complicated; the other is the degradation method, that is, the polypropylene is degraded by peroxide to improve the fluidity of the polypropylene. The degradation method has been widely used due to its simple production process and easy conversion between different brands of products. Although the addition of peroxide degradation agents in the extrusion granulation process to prepare high-fluidity polypropylene materials does not affect the polymerization The continuous and stable production of the device, but the uneven distribution and residue of peroxide will lead to poor tensile properties of the product, the produced melt-blown cloth is easy to tear, and the melt-blown cloth is obviously brittle after being placed for a period of time; in addition Since the degradation agent originally has the characteristics of low molecular weight and high odor and the degradation process, it brings a large amount of low-molecular substances with pungent odor to the modified melt-blown composition material, and the residue of such substances seriously affects the capacity of the melt-blown cloth on the mask. aspects of application.
若在熔喷聚丙烯组合物中直接加入一些弹性体或者增韧剂会降低熔喷布的其他性能，例如中国专利(CN112194850A)为了提高拉伸性能，添加了乙烯-辛烯共聚物达到柔软增韧的目的，但该方法部分残留的过氧化物可能与乙烯-辛烯共聚物产生交联反应，导致熔喷布较脆而极易被拉扯断。If some elastomers or tougheners are directly added to the melt-blown polypropylene composition, other properties of the melt-blown cloth will be reduced. The purpose of toughness, but part of the residual peroxide in this method may have a cross-linking reaction with the ethylene-octene copolymer, resulting in a brittle melt-blown cloth that is easily pulled off.
发明内容Contents of the invention
本发明为克服熔喷聚丙烯组合物强度不足的缺陷，提供一种提高熔喷聚丙烯组合物强度的方法。In order to overcome the defect of insufficient strength of the melt-blown polypropylene composition, the invention provides a method for improving the strength of the melt-blown polypropylene composition.
本发明的另一目的在于提供所述熔喷聚丙烯组合物。Another object of the present invention is to provide said meltblown polypropylene composition.
本发明的另一目的在于提供所述熔喷聚丙烯组合物的应用。Another object of the present invention is to provide applications of the meltblown polypropylene composition.
为实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种提高熔喷聚丙烯组合物强度的方法，包括如下步骤：A method for improving the strength of a melt-blown polypropylene composition, comprising the steps of:
S1.将由聚丙烯原料、添加剂混合成的熔喷聚丙烯熔融混合物输送至低压分离***中，进行挤出、造粒；S1. Transport the melt-blown polypropylene melt mixture mixed with polypropylene raw materials and additives to a low-pressure separation system for extrusion and granulation;
S2.将步骤S1得到的粒子进行蒸汽加热，然后再通过烘干即得熔喷聚丙烯组合物；S2. Steam heating the particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition;
步骤S2中所述蒸汽加热的温度为80～110℃。The steam heating temperature in step S2 is 80-110°C.
所述添加剂包括但不限于驻极剂、成核剂、降解剂和抗氧剂，按重量份计算，聚丙烯80～100份；驻极剂0.2～0.6份；成核剂0.1～0.8份；降解剂0.2～0.5份；抗氧剂0.2～0.6份。The additives include but are not limited to electret agents, nucleating agents, degradation agents and antioxidants, calculated by weight, 80-100 parts of polypropylene; 0.2-0.6 parts of electret agents; 0.1-0.8 parts of nucleating agents; 0.2-0.5 parts of degradation agent; 0.2-0.6 parts of antioxidant.
发明人经过大量研究发现，在蒸汽加热条件下，聚丙烯链加速热运动，发生退火结晶现象，结晶进一步提高，熔喷聚丙烯组合物的强度得到增强。After a lot of research, the inventor found that under steam heating conditions, polypropylene chains accelerate thermal movement, annealing crystallization occurs, crystallization is further improved, and the strength of the melt-blown polypropylene composition is enhanced.
步骤S2中所述蒸汽加热的温度低于80℃，不能实现提高结晶的目的，温度若大于110℃，超过了聚丙烯热变形温度，聚丙烯树脂***，不能使用。The steam heating temperature in step S2 is lower than 80°C, which cannot achieve the purpose of improving crystallization. If the temperature is higher than 110°C, the polypropylene resin will become soft and cannot be used if it exceeds the heat distortion temperature of polypropylene.
另外，本发明通过低压分离***和蒸汽加热步骤能够降低挥发性有机物(VOC)的含量。其中在蒸汽加热过程中熔喷聚丙烯组合物中的挥发分(VOC)不断向热蒸汽中扩散；同时热蒸汽还可以穿透熔喷聚丙烯组合物的气孔，将附着在聚丙烯颗粒料内部的挥发性有机物(VOC)携带出来进入汽相，然后通过蒸汽定排来达到脱除聚丙烯颗粒料中挥发性有机物(VOC)的目的。In addition, the present invention can reduce the content of volatile organic compounds (VOC) through the low pressure separation system and the steam heating step. During the steam heating process, the volatile matter (VOC) in the melt-blown polypropylene composition continuously diffuses into the hot steam; at the same time, the hot steam can also penetrate the pores of the melt-blown polypropylene composition and will adhere to the inside of the polypropylene pellets. The volatile organic compounds (VOC) are carried out into the vapor phase, and then the purpose of removing the volatile organic compounds (VOC) in the polypropylene pellets is achieved by steam scheduling.
本发明所述低压分离***的作用一方面通过在挤出机的后段增加螺筒与螺杆之间的自由体积空间，从而降低气压；另一方面通过抽真空装备，抽取易挥发物，真空度在0.4～0.8MPa。The function of the low-pressure separation system of the present invention is to reduce the air pressure by increasing the free volume space between the screw barrel and the screw at the back section of the extruder on the one hand; At 0.4 ~ 0.8MPa.
步骤S2中的蒸汽加热温度对聚丙烯结晶有重要影响，发明人发现，当蒸汽温度在85～105℃时，结晶更高，强度更好，因此更优选地，步骤S3中所述蒸汽加热的温度为85～105℃。The steam heating temperature in step S2 has an important influence on the crystallization of polypropylene. The inventors found that when the steam temperature is 85-105°C, the crystallization is higher and the strength is better. Therefore, it is more preferable that the steam heating in step S3 The temperature is 85-105°C.
优选地，步骤S2中所述蒸汽加热的时间为60～120min。Preferably, the steam heating time in step S2 is 60-120 minutes.
优选地点，步骤S2中所述蒸汽加热的加热蒸汽出口压力为1.05～2.0MPa。Preferably, the outlet pressure of the steam heated by the steam in step S2 is 1.05-2.0 MPa.
优选地，步骤S1中所述低压分离***中的真空度为0.4～0.8MPa。Preferably, the vacuum degree in the low-pressure separation system in step S1 is 0.4-0.8 MPa.
所述熔喷聚丙烯熔融混合物可以通过常规的制备方法得到，例如，将聚丙烯以及其他助剂直接共混得到，也可以分部制备，先制成母粒，然后再共混得到。The melt-blown polypropylene melt mixture can be obtained by conventional preparation methods, for example, directly blending polypropylene and other additives, or it can be prepared in parts by first making masterbatches and then blending.
优选地，步骤S1中熔喷聚丙烯熔融混合物通过下述方法制备得到：Preferably, the melt-blown polypropylene melt mixture in step S1 is prepared by the following method:
将驻极剂、降解剂、聚丙烯、成核剂与抗氧剂混合至均匀，将混合物熔融、剪切和混炼得到熔喷聚丙烯熔融混合物；mixing electret agent, degradation agent, polypropylene, nucleating agent and antioxidant until uniform, melting, shearing and kneading the mixture to obtain a melt-blown polypropylene melt mixture;
或者，M1.将驻极剂、降解剂与聚丙烯混合至均匀，然后挤出、水冷、拉条、造粒和烘干得到母粒；Or, M1. mix the electret, degradation agent and polypropylene until uniform, then extrude, water-cool, draw, granulate and dry to obtain the masterbatch;
M2.再将步骤M1得到的母粒、聚丙烯、成核剂与抗氧剂混合至均匀，将混合物熔融、剪切和混炼得到熔喷聚丙烯熔融混合物，所述M1中的聚丙烯与M2中的聚丙烯重量份比为(0.1～0.2)：1。M2. Mix the masterbatch, polypropylene, nucleating agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a melt-blown polypropylene melt mixture. The polypropylene in the M1 and The weight ratio of polypropylene in M2 is (0.1-0.2):1.
本发明在制备熔喷聚丙烯组合物的过程中添加降解剂、驻极剂制成母粒的方式，该方法能使降解剂、驻极剂更均匀的分散在熔喷组合物中，这样后续使用该组合物制备的熔喷布的驻极效果更好，同时避免了驻极剂分散不均并导致并易堵喷丝孔。更优选地，步骤S1中熔喷聚丙烯熔融混合物通过下述方法制备得到：In the process of preparing the melt-blown polypropylene composition, the present invention adds a degradation agent and an electret agent to make a masterbatch. This method can make the degradation agent and the electret agent more uniformly dispersed in the melt-blown composition, so that the subsequent The electret effect of the melt-blown cloth prepared by using the composition is better, and at the same time, uneven dispersion of the electret agent and easy plugging of the spinneret holes are avoided. More preferably, the melt-blown polypropylene melt mixture in step S1 is prepared by the following method:
M1.将驻极剂、降解剂与聚丙烯混合至均匀，然后挤出、水冷、拉条、造粒和烘干得到母粒；M1. Mix electret agent, degradant and polypropylene until uniform, then extrude, water-cool, draw, granulate and dry to obtain masterbatch;
M2.再将步骤M1得到的母粒、聚丙烯、成核剂与抗氧剂混合至均匀，将混合物熔融、剪切和混炼得到熔喷聚丙烯熔融混合物，所述M1中的聚丙烯与M2中的聚丙烯重量份比为(0.1～0.2)：1。M2. Mix the masterbatch, polypropylene, nucleating agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a melt-blown polypropylene melt mixture. The polypropylene in the M1 and The weight ratio of polypropylene in M2 is (0.1-0.2):1.
一种熔喷聚丙烯组合物，包括聚丙烯、驻极剂、成核剂、降解剂、抗氧剂；A melt-blown polypropylene composition, comprising polypropylene, electret agent, nucleating agent, degradation agent, antioxidant;
所述熔喷聚丙烯组合物的强度在熔喷布试样大小为25cm×5cm、夹持距离为10cm、拉伸速率为100mm/min和预加张力为200cN的条件下强度大于25N。The strength of the meltblown polypropylene composition is greater than 25N under the conditions that the meltblown cloth sample size is 25cm×5cm, the clamping distance is 10cm, the tensile rate is 100mm/min and the pretension is 200cN.
优选地，所述熔喷聚丙烯组合物，包括如下按重量份计算的组分，聚丙烯80～100份；驻极剂0.2～0.6份；成核剂0.1～0.8份；降解剂0.2～0.5份；抗氧剂0.2～0.6份。Preferably, the melt-blown polypropylene composition includes the following components calculated in parts by weight: 80-100 parts of polypropylene; 0.2-0.6 parts of electret agent; 0.1-0.8 parts of nucleating agent; 0.2-0.5 parts of degradation agent parts; antioxidant 0.2 to 0.6 parts.
优选地，所述降解剂为2.5-二甲基-2.5-双(叔丁基过氧基)己烷、双叔丁基过氧化二异丙基苯、二叔丁基过氧化物、二叔戊基过氧化物、二(1,1-二甲基丙基)过氧化物、过氧化二异丙苯中的一种或多种。Preferably, the degradation agent is 2.5-dimethyl-2.5-bis(tert-butylperoxy)hexane, dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxide One or more of amyl peroxide, bis(1,1-dimethylpropyl) peroxide, and dicumyl peroxide.
优选地，所述抗氧剂为酚类抗氧剂和/或亚磷酸酯类抗氧剂。Preferably, the antioxidant is a phenolic antioxidant and/or a phosphite antioxidant.
优选地，所述成核剂为芳基磷酸酯盐类成核剂和/或山梨醇类成核剂。Preferably, the nucleating agent is an aryl phosphate ester salt nucleating agent and/or a sorbitol nucleating agent.
优选地，所述驻极剂为电气石粉、含氟聚合物、碳原子数为6～20的脂肪酸或其盐、天然蜡或N,N’-乙撑双硬脂酰胺中的一种或多种。Preferably, the electret is one or more of tourmaline powder, fluoropolymer, fatty acid with 6 to 20 carbon atoms or its salt, natural wax or N,N'-ethylene bisstearamide kind.
所述含氟聚合物包括但不限于聚四氟乙烯、六氟丙烯、四氟乙烯共聚物。The fluoropolymers include but not limited to polytetrafluoroethylene, hexafluoropropylene, and tetrafluoroethylene copolymers.
优选地，所述聚丙烯在230℃、2.16kg下熔融指数为10～70g/10min。Preferably, the polypropylene has a melt index of 10-70 g/10 min at 230° C. and 2.16 kg.
优先地，为了进一步提高抗菌效果，可以加入抗菌剂，所述抗菌剂选择无机的纳米银、铜或锌以及氧化物的一种或多种，例如Ag/ZnO纳米复合抗菌剂。Preferably, in order to further improve the antibacterial effect, an antibacterial agent can be added, and the antibacterial agent is selected from one or more of inorganic nano-silver, copper or zinc, and oxides, such as Ag/ZnO nanocomposite antibacterial agent.
优选地，所述熔喷聚丙烯组合物通过如下方法制备：S1.将由聚丙烯、驻极剂、成核剂、降解剂、抗氧剂混合成的熔喷聚丙烯熔融混合物输送至低压分离***中，进行挤出、造粒；Preferably, the melt-blown polypropylene composition is prepared by the following method: S1. The melt-blown polypropylene melt mixture mixed with polypropylene, electret, nucleating agent, degradation agent, and antioxidant is transported to a low-pressure separation system In, extruding and granulating;
S2.将步骤S1得到的粒子进行蒸汽加热，然后再通过烘干即得熔喷聚丙烯组合物；S2. Steam heating the particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition;
步骤S2中所述蒸汽加热的温度为80～110℃。The steam heating temperature in step S2 is 80-110°C.
一种口罩用熔喷布，由所述熔喷聚丙烯组合物制成。A melt-blown cloth for masks is made from the melt-blown polypropylene composition.
通过上述制备方法得到的口罩用熔喷布具有高过滤性能，低VOC、高强度和低阻力性能。The meltblown cloth for masks obtained by the above preparation method has high filtration performance, low VOC, high strength and low resistance performance.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
本发明提供了一种提高熔喷聚丙烯组合物强度的方法，发明人发现，在蒸汽加热条件下，聚丙烯链加速热运动，会发生退火结晶现象，进一步提高熔喷聚丙烯组合物的强度。采用所述熔喷聚丙烯制备滤布(单位克重：25～28g/100cm 2)的拉伸强度断裂强度大于25N。通过上述制备方法制备得到的熔喷聚丙烯还具有低气味、低阻力、高过滤效率。 The present invention provides a method for improving the strength of the melt-blown polypropylene composition. The inventors found that under steam heating conditions, the polypropylene chain accelerates thermal movement, and annealing and crystallization will occur, thereby further improving the strength of the melt-blown polypropylene composition. . The tensile strength and breaking strength of the filter cloth (unit weight: 25-28g/100cm 2 ) prepared by using the meltblown polypropylene is greater than 25N. The meltblown polypropylene prepared by the above preparation method also has low odor, low resistance and high filtration efficiency.
具体实施方式detailed description
下面将对本发明实施例中的技术方案进行清楚、完整地描述，但本发明的实施方式不限于此。The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the implementation manners of the present invention are not limited thereto.
本发明所采用的试剂、方法和设备，如无特殊说明，均为本技术领域常规试剂、方法和设备。The reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field unless otherwise specified.
以下实施例及对比例中采用的原料如下：The raw materials adopted in the following examples and comparative examples are as follows:
聚丙烯：均聚聚丙烯320H，熔融指数32±5g/10min中国石化销售有限公司；Polypropylene: Homopolypropylene 320H, melt index 32±5g/10min Sinopec Sales Co., Ltd.;
驻极剂：12500目的电气石粉末，隆川钻井材料厂提供；Electret: 12500 mesh tourmaline powder, provided by Longchuan Drilling Material Factory;
抗菌剂：BM-102TG，日本富士；Antibacterial agent: BM-102TG, Japan Fuji;
成核剂：NA-98，呈和科技股份有限公司；Nucleating agent: NA-98, Chenghe Technology Co., Ltd.;
降解剂：Enox 101，江苏强盛功能化学股份有限公司；Degradant: Enox 101, Jiangsu Qiangsheng Functional Chemicals Co., Ltd.;
抗氧剂：抗氧剂1010，三丰化工有限公司。Antioxidant: Antioxidant 1010, Sanfeng Chemical Co., Ltd.
实施例1Example 1
本实施例提供一种提高熔喷聚丙烯组合物强度的方法，包括如下步骤：The present embodiment provides a method for improving the strength of the melt-blown polypropylene composition, comprising the steps of:
M1.将驻极剂、降解剂与聚丙烯混合至均匀，然后挤出、水冷、拉条、造粒和烘干得到母粒；M1. Mix electret agent, degradant and polypropylene until uniform, then extrude, water-cool, draw, granulate and dry to obtain masterbatch;
M2.将步骤M1所得的母粒、聚丙烯、成核剂、抗菌剂与抗氧剂混合至均匀，将混合物熔融、剪切和混练作用得到熔融混合物，所述M1中的聚丙烯与M2中的聚丙烯重量份比为0.1：1；M2. Mix the masterbatch, polypropylene, nucleating agent, antibacterial agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a molten mixture. The polypropylene in M1 and M2 The weight ratio of polypropylene in is 0.1:1;
S1.将熔融混合物输送至低压分离***中进行小分子气体和熔体进行分离，然后将脱挥后的熔体挤出造粒，低压分离***中的气压为0.5MPa；S1. Transport the molten mixture to the low-pressure separation system to separate the small molecular gas from the melt, and then extrude the devolatilized melt to granulate. The air pressure in the low-pressure separation system is 0.5MPa;
S2.将步骤S1得到的粒子进行蒸汽加热，加热温度为105℃，加热时间为120min，然后再通过烘干即得熔喷聚丙烯组合物。S2. The particles obtained in step S1 are heated with steam, the heating temperature is 105° C., and the heating time is 120 minutes, and then dried to obtain a melt-blown polypropylene composition.
所述熔喷聚丙烯组合物中，聚丙烯100份；降解剂0.5份；驻极剂0.6份；抗菌剂0.5份；成核剂0.8份；抗氧剂0.2份。In the melt-blown polypropylene composition, 100 parts of polypropylene; 0.5 parts of degradation agent; 0.6 parts of electret agent; 0.5 parts of antibacterial agent; 0.8 parts of nucleating agent;
实施例2～10Embodiment 2-10
实施例2～10的制备方法和配方同实施例1，其区别在于表1。The preparation method and formula of embodiment 2～10 are the same as embodiment 1, and its difference is in table 1.
表1 实施例2～10的参数The parameter of table 1 embodiment 2～10
Figure PCTCN2022101752-appb-000001
Figure PCTCN2022101752-appb-000001
实施例11～14Examples 11-14
实施例11～14提供一系列提高熔喷聚丙烯组合物强度的方法，制备方法和配方同实施例1，其区别在于表2的参数。Examples 11 to 14 provide a series of methods for increasing the strength of the melt-blown polypropylene composition. The preparation method and formulation are the same as those in Example 1, and the difference lies in the parameters in Table 2.
表2 实施例11～14的参数The parameter of table 2 embodiment 11～14
Figure PCTCN2022101752-appb-000002
Figure PCTCN2022101752-appb-000002
对比例1Comparative example 1
对比例1的配方同实施例1，对比例1提供一种熔喷聚丙烯组合物的制备方法，包括如下步骤：The formula of comparative example 1 is the same as embodiment 1, and comparative example 1 provides a kind of preparation method of melt-blown polypropylene composition, comprises the steps:
M1.将驻极剂、降解剂与聚丙烯混合至均匀，然后挤出、水冷、拉条、造粒和烘干得到母粒；M1. Mix electret agent, degradant and polypropylene until uniform, then extrude, water-cool, draw, granulate and dry to obtain masterbatch;
M2.将步骤S1所得的母粒、聚丙烯、成核剂、抗菌剂与抗氧剂混合至均匀，将混合物熔融、剪切和混练作用，M2. Mix the masterbatch, polypropylene, nucleating agent, antibacterial agent and antioxidant obtained in step S1 until uniform, and the mixture is melted, sheared and kneaded,
S1.将熔融混合物输送至低压分离***中进行小分子气体和熔体进行分离，然后将脱挥后的熔体挤出造粒，低压分离***中的气压为0.5MPa。S1. Transport the molten mixture to the low-pressure separation system to separate the small molecule gas from the melt, and then extrude the devolatilized melt to granulate. The air pressure in the low-pressure separation system is 0.5MPa.
对比例2Comparative example 2
对比例2的配方和制备方法同实施例1，其区别在于，步骤S2中的蒸汽温度为75℃。The formula and preparation method of Comparative Example 2 are the same as those of Example 1, the difference being that the steam temperature in step S2 is 75°C.
对比例3Comparative example 3
对比例3的配方和制备方法同实施例1，其区别在于，步骤S2中的蒸汽温度为115℃。The formula and preparation method of Comparative Example 3 are the same as those of Example 1, the difference being that the steam temperature in step S2 is 115°C.
上述实施例和对比例均通过下述的性能测试：Above-mentioned embodiment and comparative example all pass through following performance test:
1.按照GB/T 30923-2014塑料聚丙烯熔喷专用料标准执行1. According to the standard of GB/T 30923-2014 special material for plastic polypropylene melt blown
检测项目为标准中熔体质量流动速率(GB/T 3682 230℃，2.16Kg)、灰分(ISO 3451 850℃，2H)、挥发份(ISO 787 105℃)。The testing items are standard melt mass flow rate (GB/T 3682 230°C, 2.16Kg), ash content (ISO 3451 850°C, 2H), volatile matter (ISO 787 105°C).
2.熔喷聚丙烯组合物气味等级、VOC测试评价2. Odor level and VOC test evaluation of melt-blown polypropylene composition
气味等级测试按PV3900-2000进行测试：取20g的样品置于1L没有气味密封的瓶子里，经过80℃烘箱中加热2h后取出，当冷却至65℃时随即由5位气味评测员开始测定。每个测试者对气味作出评估，最后的平均值即为检测结果。评判标准共分六个等级：1＝无异味，2＝稍有气味，3＝有味道但不刺激，4＝有刺激气味，5＝强烈的刺激气味，6＝无法忍受的味道。The odor level test is carried out according to PV3900-2000: take 20g of the sample and place it in a 1L non-odor sealed bottle, heat it in an oven at 80°C for 2 hours, take it out, and when it cools down to 65°C, it will be measured by 5 odor evaluators. Each tester evaluates the smell, and the final average is the test result. The judging criteria are divided into six grades: 1=no peculiar smell, 2=slight smell, 3=taste but not irritating, 4=pungent smell, 5=strong pungent smell, 6=unbearable taste.
VOC测试：熔喷聚丙烯组合物总挥发性有机化合物含量按照大众标准PV3341-1996测试，采用顶空-气相色谱(HS-GC)法测试，测试条件为120℃，恒温5H。VOC test: The total volatile organic compound content of the melt-blown polypropylene composition is tested according to the public standard PV3341-1996, and the headspace-gas chromatography (HS-GC) method is used for testing. The test conditions are 120°C and constant temperature 5H.
3.强度及滤效测试3. Strength and filter efficiency test
强度测试标准：将实施例和对比例生产出的聚丙烯熔喷料，在同一熔喷驻极工艺下生产出克重为25±2g/cm 2的熔喷布，将生产出的熔喷布放置48h，测试熔喷布的强度。参照GB3923-1983《织物断裂强力和断裂伸长的测定条样法》，采用YG065型电子织物强力仪测试非织造布的纵向拉伸性能，熔喷布试样大小为25cm×5cm，夹持距离为10cm，拉伸速率为100mm/min，预加张力为200cN，每种非织造布测试5组数据，取其平均值。 Strength test standard: The polypropylene melt-blown material produced in the examples and comparative examples was produced under the same melt-blown electret process to produce a melt-blown cloth with a grammage of 25±2g/ cm2 , and the produced melt-blown cloth Leave it for 48 hours to test the strength of the melt blown cloth. Referring to GB3923-1983 "Strip Method for Determination of Fabric Breaking Strength and Elongation at Break", YG065 electronic fabric strength tester is used to test the longitudinal tensile properties of nonwoven fabrics. The sample size of meltblown fabric is 25cm×5cm, and the clamping distance It is 10cm, the tensile rate is 100mm/min, and the pre-tension is 200cN. Each nonwoven fabric is tested for 5 sets of data, and the average value is taken.
滤效测试标准：将实施例和对比例生产出的聚丙烯熔喷料，在同一熔喷驻极工艺下生产出克重为25±2g/cm 2的熔喷布，采用GB/T2626-2018呼吸防护用品的盐雾法(以NaCl或等同卤化物作为气溶胶颗粒物来检测口罩过滤性能的方法，结果参考PFE结果与阻力)，具体参数：试验流量为85L/min。 Filtration efficiency test standard: The polypropylene melt-blown material produced in the examples and comparative examples is produced under the same melt-blown electret process to produce a melt-blown cloth with a grammage of 25±2g/ cm2 , using GB/T2626-2018 The salt spray method of respiratory protective equipment (a method of testing the filter performance of masks by using NaCl or equivalent halides as aerosol particles, the results refer to the PFE results and resistance), specific parameters: the test flow rate is 85L/min.
4.抗菌性能效果测试4. Antibacterial performance test
参考GB/T 20944.3-2008《织物品抗菌性能的评价第三部分：振荡法》，测试上述得到的熔喷网布对大肠杆菌的抑菌率，将样品和对照样品(纯棉)裁切为5×5mm的碎片，各取0.75g加入70ml浓度为0.03mol/mL的PBS缓冲液中，加入大肠杆菌菌液，测试振荡18h后的抑菌率，Y＝(Wt-Qt)/Wt，其中Wt为对照样处理18h的活菌浓度(CFU/mL)；Qt为测试样处理18h的活菌浓度(CFU/mL)。Referring to GB/T 20944.3-2008 "Evaluation of Antibacterial Properties of Fabrics Part III: Oscillating Method", test the antibacterial rate of the above-mentioned melt-blown mesh against Escherichia coli, and cut the samples and control samples (pure cotton) into 5 × 5mm fragments, each take 0.75g and add 70ml of PBS buffer solution with a concentration of 0.03mol/mL, add Escherichia coli bacterial liquid, test the bacteriostatic rate after shaking for 18h, Y=(Wt-Qt)/Wt, where Wt is the concentration of viable bacteria (CFU/mL) of the control sample treated for 18 hours; Qt is the concentration of viable bacteria (CFU/mL) of the test sample treated for 18 hours.
表2 实施例和对比例的数据The data of table 2 embodiment and comparative example
Figure PCTCN2022101752-appb-000003
Figure PCTCN2022101752-appb-000003
Figure PCTCN2022101752-appb-000004
Figure PCTCN2022101752-appb-000004
上述聚丙烯组合物的熔体流动速率、灰分、挥发分和水分都符合聚丙烯熔喷专用料标准。The melt flow rate, ash content, volatile matter and moisture of the above polypropylene composition all meet the standards for polypropylene melt-blown special materials.
从实施例1～5看，蒸汽加热的温度为85～105℃时，强度的效果更好。Seen from Examples 1-5, when the temperature of steam heating is 85-105° C., the effect of strength is better.
从实施例1和6～8看，蒸汽加热的时间在60～120min时效果更好，超过120min效果变化不大。From Examples 1 and 6-8, the effect of steam heating is better when the time of steam heating is 60-120min, and the effect does not change much beyond 120min.
对比例1中不经过蒸汽加热，可以看出其强度只有12N，对比例2中蒸汽加热的温度低于80℃，不能提高强度，对比例3中蒸汽加热的温度高于110℃时，聚丙烯***，不能制备得到熔喷布，没有相关测试数据。In Comparative Example 1 without steam heating, it can be seen that its strength is only 12N. In Comparative Example 2, the temperature of steam heating is lower than 80°C, which cannot improve the strength. In Comparative Example 3, when the temperature of steam heating is higher than 110°C, polypropylene If it becomes soft, melt-blown cloth cannot be prepared, and there is no relevant test data.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

  1. 一种提高熔喷聚丙烯组合物强度的方法，其特征在于，包括如下步骤：A method for improving the strength of a melt-blown polypropylene composition, comprising the steps of:
    S1.将由聚丙烯原料、添加剂混合成的熔喷聚丙烯熔融混合物输送至低压分离***中，进行挤出、造粒；S1. Transport the melt-blown polypropylene melt mixture mixed with polypropylene raw materials and additives to a low-pressure separation system for extrusion and granulation;
    S2.将步骤S1得到的粒子进行蒸汽加热，然后再通过烘干即得熔喷聚丙烯组合物；S2. Steam heating the particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition;
    步骤S2中所述蒸汽加热的温度为80～110℃。The steam heating temperature in step S2 is 80-110°C.
  2. 根据权利要求1所述方法，其特征在于，步骤S2中所述蒸汽加热的温度为85～105℃。The method according to claim 1, characterized in that the steam heating temperature in step S2 is 85-105°C.
  3. 根据权利要求1所述方法，其特征在于，步骤S2中所述蒸汽加热的时间为60～120min。The method according to claim 1, characterized in that the steam heating time in step S2 is 60-120 minutes.
  4. 根据权利要求1所述方法，其特征在于，步骤S2中所述蒸汽加热的的蒸气压为1.05～2.0MPa。The method according to claim 1, characterized in that the vapor pressure of the steam heating in step S2 is 1.05-2.0 MPa.
  5. 根据权利要求1所述方法，其特征在于，步骤S1中所述低压分离***中的真空度为0.4～0.8MPa。The method according to claim 1, characterized in that the degree of vacuum in the low-pressure separation system in step S1 is 0.4-0.8 MPa.
  6. 根据权利要求1所述方法，其特征在于，步骤S1中熔喷聚丙烯熔融混合物通过下述方法制备得到：The method according to claim 1, wherein the melt-blown polypropylene melt mixture is prepared by the following method in step S1:
    将驻极剂、降解剂、聚丙烯、成核剂与抗氧剂混合至均匀，将混合物熔融、剪切和混炼得到熔喷聚丙烯熔融混合物；mixing electret agent, degradation agent, polypropylene, nucleating agent and antioxidant until uniform, melting, shearing and kneading the mixture to obtain a melt-blown polypropylene melt mixture;
    或者，M1.将驻极剂、降解剂与聚丙烯混合至均匀，然后挤出、水冷、拉条、造粒和烘干得到母粒；Or, M1. mix the electret, degradation agent and polypropylene until uniform, then extrude, water-cool, draw, granulate and dry to obtain the masterbatch;
    M2.再将步骤M1得到的母粒、聚丙烯、成核剂与抗氧剂混合至均匀，将混合物熔融、剪切和混炼得到熔喷聚丙烯熔融混合物，所述M1中的聚丙烯与M2中的聚丙烯重量份比为(0.1～0.2)：1。M2. Mix the masterbatch, polypropylene, nucleating agent and antioxidant obtained in step M1 until uniform, and melt, shear and knead the mixture to obtain a melt-blown polypropylene melt mixture. The polypropylene in the M1 and The weight ratio of polypropylene in M2 is (0.1-0.2):1.
  7. 根据权利要求6所述方法，其特征在于，步骤S1中熔喷聚丙烯熔融混合物通过下述方法制备得到：The method according to claim 6, characterized in that, in the step S1, the melt-blown polypropylene melt mixture is prepared by the following method:
    M1.将驻极剂、降解剂与聚丙烯混合至均匀，然后挤出、水冷、拉条、造粒和烘干得到母粒；M1. Mix electret agent, degradant and polypropylene until uniform, then extrude, water-cool, draw, granulate and dry to obtain masterbatch;
    M2.将步骤M1得到的母粒、聚丙烯、成核剂与抗氧剂混合至均匀，将混合物熔融、剪切和混练得到熔喷聚丙烯熔融混合物，所述M1中的聚丙烯与M2中 的聚丙烯重量份比为(0.1～0.2)：1。M2. Mix the masterbatch, polypropylene, nucleating agent and antioxidant obtained in step M1 until uniform, melt, shear and knead the mixture to obtain a melt-blown polypropylene melt mixture, the polypropylene in M1 and M2 The weight ratio of polypropylene is (0.1-0.2):1.
  8. 一种熔喷聚丙烯组合物，其特征在于，包括聚丙烯、驻极剂、成核剂、降解剂、抗氧剂；A melt-blown polypropylene composition, characterized in that, comprises polypropylene, electret agent, nucleating agent, degradation agent, antioxidant;
    所述熔喷聚丙烯组合物的强度在熔喷布试样大小为25cm×5cm、夹持距离为10cm、拉伸速率为100mm/min和预加张力为200cN的条件下强度大于25N。The strength of the meltblown polypropylene composition is greater than 25N under the conditions that the meltblown cloth sample size is 25cm×5cm, the clamping distance is 10cm, the tensile rate is 100mm/min and the pretension is 200cN.
  9. 根据权利要求8所述熔喷聚丙烯组合物，其特征在于，所述熔喷聚丙烯组合物通过如下方法制备：S1.将由聚丙烯、驻极剂、成核剂、降解剂、抗氧剂混合成的熔喷聚丙烯熔融混合物输送至低压分离***中，进行挤出、造粒；According to the described melt-blown polypropylene composition of claim 8, it is characterized in that, described melt-blown polypropylene composition is prepared by the following method: S1. will be made of polypropylene, electret, nucleating agent, degradation agent, antioxidant The mixed melt-blown polypropylene melt mixture is transported to the low-pressure separation system for extrusion and granulation;
    S2.将步骤S1得到的粒子进行蒸汽加热，然后再通过烘干即得熔喷聚丙烯组合物；S2. Steam heating the particles obtained in step S1, and then drying to obtain the melt-blown polypropylene composition;
    步骤S2中所述蒸汽加热的温度为80～110℃。The steam heating temperature in step S2 is 80-110°C.
  10. 一种口罩用熔喷布，其特征在于，由含有权利要求8或9所述熔喷聚丙烯组合物制成。A kind of melt-blown cloth for mouth mask, is characterized in that, is made by containing the described melt-blown polypropylene composition of claim 8 or 9.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288897A (en) * 1962-05-18 1966-11-29 Montedison Spa Dyeable materials
US5204037A (en) * 1991-01-25 1993-04-20 Idemitsu Petrochemical Co., Ltd. Process for production of polypropylene sheets or films
CN102127218A (en) * 2010-12-16 2011-07-20 金发科技股份有限公司 Device and method for purifying high-temperature-resistant resin
CN111531839A (en) * 2020-05-26 2020-08-14 金发科技股份有限公司 Method and device for assisting polymer extrusion blending by liquid additive and application
CN112194850A (en) * 2020-10-10 2021-01-08 浙江佳华精化股份有限公司 Low-odor, high-toughness and high-electret polypropylene melt-spraying material and preparation method thereof
CN113480801A (en) * 2021-06-28 2021-10-08 金发科技股份有限公司 Melt-blown polypropylene composition, method for improving strength of melt-blown polypropylene composition and application of melt-blown polypropylene composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288897A (en) * 1962-05-18 1966-11-29 Montedison Spa Dyeable materials
US5204037A (en) * 1991-01-25 1993-04-20 Idemitsu Petrochemical Co., Ltd. Process for production of polypropylene sheets or films
CN102127218A (en) * 2010-12-16 2011-07-20 金发科技股份有限公司 Device and method for purifying high-temperature-resistant resin
CN111531839A (en) * 2020-05-26 2020-08-14 金发科技股份有限公司 Method and device for assisting polymer extrusion blending by liquid additive and application
CN112194850A (en) * 2020-10-10 2021-01-08 浙江佳华精化股份有限公司 Low-odor, high-toughness and high-electret polypropylene melt-spraying material and preparation method thereof
CN113480801A (en) * 2021-06-28 2021-10-08 金发科技股份有限公司 Melt-blown polypropylene composition, method for improving strength of melt-blown polypropylene composition and application of melt-blown polypropylene composition

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