WO2023093705A1 - 一种基于原位增容与扩链的再生材料及其制备方法 - Google Patents

一种基于原位增容与扩链的再生材料及其制备方法 Download PDF

Info

Publication number
WO2023093705A1
WO2023093705A1 PCT/CN2022/133450 CN2022133450W WO2023093705A1 WO 2023093705 A1 WO2023093705 A1 WO 2023093705A1 CN 2022133450 W CN2022133450 W CN 2022133450W WO 2023093705 A1 WO2023093705 A1 WO 2023093705A1
Authority
WO
WIPO (PCT)
Prior art keywords
waste
chain extension
hips
recycled
situ
Prior art date
Application number
PCT/CN2022/133450
Other languages
English (en)
French (fr)
Inventor
符永高
曹诺
胡嘉琦
王玲
万超
Original Assignee
中国电器科学研究院股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国电器科学研究院股份有限公司 filed Critical 中国电器科学研究院股份有限公司
Priority to US18/274,467 priority Critical patent/US20240317986A1/en
Publication of WO2023093705A1 publication Critical patent/WO2023093705A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/484—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with two shafts provided with screws, e.g. one screw being shorter than the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B29K2025/04—Polymers of styrene
    • B29K2025/06—PS, i.e. polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0014—Catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0077—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0089—Impact strength or toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention belongs to the technical field of recycled materials, and in particular relates to a recycled material based on in-situ expansion and chain extension and a preparation method thereof.
  • High impact polystyrene As a polystyrene material with excellent cost performance and significantly improved toughness, high impact polystyrene (HIPS) is widely used in various industries including packaging, electronic and electrical products, and automobiles. However, after long-term service, it will age and degrade due to the effects of light, heat, and oxygen. While causing molecular chain scission, active groups such as hydroxyl and carboxyl groups will be produced, accompanied by changes in the microscopic phase structure. The performance of the aged waste HIPS is lower than that of the new material. If the performance is not improved through modification, its overall application range will be severely limited.
  • polypropylene has the advantages of low density, non-toxicity, low price, and easy processing, but it also has disadvantages such as low rigidity and notch sensitivity. After aging, the waste PP will also break or rearrange its molecular structure to form hydroxyl, carboxyl and other groups, resulting in a comprehensive decline in macroscopic properties.
  • the alloying of polymer materials can integrate the superior properties of various matrix materials and realize high-value applications, so it is also an important research and application direction.
  • the preparation of polymer alloys from waste materials has a cost advantage, but it is necessary to effectively restore the properties of waste substrates and improve the compatibility between the substrates in order to prepare recycled alloy materials with balanced properties and market demand.
  • waste HIPS and waste PP are used to prepare polymer alloys. If active groups such as hydroxyl and carboxyl groups generated after aging of waste HIPS and waste PP can be fully utilized, the two matrix materials can be repaired through in-situ chain extension. While comprehensively improving its comprehensive performance, the in-situ generated compatibilizer can effectively improve the compatibility of waste HIPS and waste PP, and a recycled alloy material with excellent comprehensive performance will be obtained. Due to the extensive use of waste materials, this material not only has the advantage of cost performance, but also has environmental protection properties, and has a wide application prospect.
  • the purpose of the present invention is to provide a regenerated material based on in-situ expansion and chain extension.
  • the regenerated material uses waste HIPS and waste PP as raw materials, and uses two types of chemical modifiers in stages, respectively through grafting and Chain extension reaction to realize in-situ capacity expansion and chain extension repair, so that waste HIPS and waste PP can be directly modified in situ to prepare recycled HIPS/PP alloy materials with excellent comprehensive performance.
  • waste HIPS and waste PP can be directly modified in situ to prepare recycled HIPS/PP alloy materials with excellent comprehensive performance.
  • Under the premise of making full use of waste resources also reflects the high-value attributes.
  • the purpose of the present invention is also to provide a method for preparing the above-mentioned recycled material based on in-situ compatibilization and chain extension.
  • a recycled material based on in-situ expansion and chain extension which is mainly made of the following raw materials with the following mass proportions:
  • Waste HIPS 30 ⁇ 70
  • Waste PP 30 ⁇ 70
  • Alkylation reaction catalyst 0.1 ⁇ 0.4;
  • Macromolecular chain extender 2-8.
  • the raw materials of recycled materials based on in-situ expansion and chain extension mainly include waste HIPS and waste PP, which are originally incompatible matrix phases.
  • waste HIPS and waste PP which are originally incompatible matrix phases.
  • HIPS-g-PP and HIPS-g-POE grafts are generated, and the grafts can play a good role in the waste HIPS components and waste PP components in the blend.
  • the waste HIPS is waste HIPS (waste high-impact polystyrene) which is crushed and homogenized to obtain flakes.
  • the waste PP is waste PP (waste polypropylene) which is crushed and homogenized to obtain flakes.
  • the POE is virgin ethylene-octene copolymer elastomer.
  • the alkylation reaction catalyst is anhydrous aluminum chloride.
  • the co-catalyst is styrene.
  • the macromolecular chain extender is high impact polystyrene grafted glycidyl methacrylate (HIPS-g-GMA).
  • the above-mentioned preparation method of recycled materials based on in-situ expansion and chain extension includes the following steps: waste HIPS, waste PP, POE, alkylation reaction
  • the catalyst and co-catalyst are mixed according to the above dosage relationship to obtain the mixed material, which is fed into the mixed material from the main feeding device of the twin-screw extruder and melted.
  • Add the macromolecular chain extender according to the above dosage relationship blend with the molten mixture, extrude, pull, cool, and pelletize to obtain the recycled HIPS/PP alloy material based on in-situ expansion and chain extension.
  • the processing temperature range of the twin-screw extruder is 175-235°C.
  • processing temperatures of the eight zones of the twin-screw extruder are: 180°C, 180°C, 185°C, 185°C, 235°C, 235°C, 230°C, 230°C.
  • the Friedel-Crafts alkylation reaction is used to generate HIPS-g-PP and HIPS-g-POE grafts in situ in a molten state, and the grafts It can play a very good compatibilizing effect on the waste HIPS component and waste PP component in the blend; in the last four processing zones of the extruder, it introduces a macromolecular chain extender to make it mix with the waste HIPS And active groups such as hydroxyl groups generated on the aging chain of waste PP, in-situ chain extension reaction occurs under extrusion conditions to achieve chain scission growth.
  • the processing temperature of the fourth zone of the rear section and the fourth zone of the front section is actively improved, and its main purpose is to have two points: firstly, the catalyst for the alkylation reaction can be activated by the sudden increase in the processing temperature of the fifth zone. Rapid volatilization and removal, avoiding chain scission competition reaction at high temperature, and other side reactions that may occur after the introduction of macromolecular chain extenders in the later stage. On the other hand, a higher temperature is also conducive to the effective chain extension reaction within a limited retention time to achieve the actual effect of chain extension repair.
  • the present invention adopts the same matrix type macromolecular chain extender, which can extend the chain and improve the aging structure of the waste HIPS phase.
  • the use of POE can also improve the aging interface structure of the waste PP phase and significantly Improve the most obvious impact resistance of the waste PP phase due to aging deterioration. Therefore, although the two matrix phases of the recycled alloy material prepared by the present invention are both aging waste materials, their respective main chain continuity and microscopic order The properties have been repaired, and the compatibility between the two phases has also been guaranteed, so the overall performance of the recycled alloy is excellent;
  • the recycled material based on in-situ expansion and chain extension provided in this example is mainly made of the following raw materials in proportion by mass:
  • Macromolecular chain extender 6.
  • waste HIPS is waste HIPS (waste high-impact polystyrene) that is crushed and homogenized to obtain flakes
  • waste PP is waste PP (waste polypropylene) that is crushed and homogenized to obtain flakes
  • POE is ethylene-octene Alkene copolymerized elastomer new material
  • the catalyst for the alkylation reaction is anhydrous aluminum chloride
  • the co-catalyst is styrene
  • the macromolecular chain extender is high-impact polystyrene grafted glycidyl methacrylate (HIPS-g- GMA).
  • the method for preparing recycled materials based on in-situ compatibilization and chain extension includes the following steps: mixing waste HIPS, waste PP, POE, alkylation reaction catalyst, and co-catalyst according to the above-mentioned dosage relationship to obtain a mixed material.
  • the main feeding device of the extruder adds the mixed material to melt, the screw speed is controlled to 40rpm, and the macromolecular chain extender is added from the fifth processing zone of the twin-screw extruder according to the above-mentioned dosage relationship, blended with the melted mixed material, and extruded Extraction, traction, cooling, pelletizing, that is, the recycled alloy material is obtained.
  • the processing temperatures of the eight zones of the twin-screw extruder are: 180°C, 180°C, 185°C, 185°C, 235°C, 235°C, 230°C, 230°C.
  • the recycled material based on in-situ expansion and chain extension provided in this example is mainly made of the following raw materials in proportion by mass:
  • Macromolecular chain extender 4.
  • composition is with embodiment 1.
  • the method for preparing recycled materials based on in-situ compatibilization and chain extension includes the following steps: mixing waste HIPS, waste PP, POE, alkylation reaction catalyst, and co-catalyst according to the above-mentioned dosage relationship to obtain a mixed material.
  • the main feeding device of the extruder adds the mixed material to melt, the screw speed is controlled to 60rpm, and the macromolecular chain extender is added from the fifth processing zone of the twin-screw extruder according to the above-mentioned dosage relationship, blended with the melted mixed material, and extruded Extraction, traction, cooling, pelletizing, that is, the recycled alloy material is obtained.
  • the temperature of the eight processing zones of the twin-screw extruder is set as follows: 175°C, 175°C, 180°C, 185°C, 225°C, 225°C, 225°C, 230°C.
  • the recycled material based on in-situ expansion and chain extension provided in this example is mainly made of the following raw materials in proportion by mass:
  • HIPS-based macromolecular chain extender 8.
  • composition is with embodiment 1.
  • the method for preparing recycled materials based on in-situ compatibilization and chain extension includes the following steps: mixing waste HIPS, waste PP, POE, alkylation reaction catalyst, and co-catalyst according to the above-mentioned dosage relationship to obtain a mixed material.
  • the main feeding device of the extruder adds the mixed material to melt, the screw speed is controlled to 80rpm, and the macromolecular chain extender is added from the fifth processing zone of the twin-screw extruder according to the above-mentioned dosage relationship, blended with the melted mixed material, and extruded Extraction, traction, cooling, pelletizing, that is, the recycled alloy material is obtained.
  • the temperature of the eight processing zones of the twin-screw extruder is set as follows: 180°C, 185°C, 185°C, 185°C, 225°C, 225°C, 235°C, 235°C.
  • Example 1 The preparation method and steps are the same as in Example 1, the material ratio is 50 parts of waste HIPS, 50 parts of waste PP, and does not contain POE, HIPS-based macromolecular chain extender, alkylation reaction catalyst and co-catalyst;
  • Example 2 The preparation method and steps are the same as in Example 1, and the material ratio is 50 parts of waste HIPS, 50 parts of waste PP, 5 parts of POE, and 6 parts of macromolecular chain extender, but does not contain alkylation reaction catalyst and co-catalyst;
  • Example 3 The preparation method and steps are the same as in Example 1, and the material ratio is 50 parts of waste HIPS, 50 parts of waste PP, 5 parts of POE, 0.4 parts of alkylation reaction catalyst, and 0.3 parts of co-catalyst, but does not contain macromolecular chain extender;
  • Example 5 The preparation method, steps and material ratio are the same as in Example 1, but the eight processing temperature zones are 230°C, 235°C, 235°C, 235°C, 235°C, 235°C, and 235°C.
  • Example 1 The difference between Example 1 and Comparative Example 1 lies in whether to generate a macromolecular compatibilizer through the alkylation reaction to compatibilize the blend system. It can be seen that after adding macromolecular chain extender, the impact and tensile strength of recycled alloys have been significantly improved, but the increase rate is lower than that of the components added with alkylation reaction catalyst. Therefore, it is proved that the grafting modification of the alkylation reaction is very meaningful, which is beneficial to improve the compatibility of the blend and thus improve the comprehensive performance of the recycled material.
  • Example 1 The difference between Example 1 and Comparative Example 2 lies in whether to add a HIPS-based macromolecular chain extender. It can be seen that if only the alkylation catalyst is added but no macromolecular chain extender is added, the overall performance of the recycled material is only slightly improved, which proves that the compatibility of the recycled alloy and the basic performance of each matrix are very important. Only by improving the compatibility of the recycled alloy, although the micro interface is improved, the overall performance is still low due to the short board of the comprehensive performance of each matrix. Under the combined effects of in situ compatibilization and in situ chain extension, the performance of the recycled alloy has been significantly improved.
  • Example 1 and Comparative Example 3 and Comparative Example 4 lies in the processing temperature.
  • the results prove that the active and rapid increase in the processing temperature of the fourth zone in the latter section is very effective in terms of the modification effect.
  • the processing temperature in the first four zones is about 180°C, which not only ensures the progress of the alkylation reaction, but also avoids the premature volatilization of aluminum chloride and the potential chain scission competition reaction at high temperature.
  • the processing temperature of the four zones in the latter section is about 230°C, which can quickly volatilize aluminum chloride and ensure the effective progress of the chain extension reaction.
  • the two-step reactive modification of the present invention that is, alkylation reaction modification and in-situ chain extension repair modification, can play a dual-effect modification role, thereby significantly improving the comprehensive performance of recycled materials. It is very beneficial to improve the environmental adaptability of recycled products and broaden their application scenarios.
  • the recycled alloy products with such comprehensive properties have a good market prospect.
  • the above examples are preferred embodiments of the present invention.
  • the POE, macromolecular chain extender HIPS-g-GMA, alkylation reaction catalyst AlCl 3 , and co-catalyst styrene selected in the examples are all obtained from commercially available ready-made products.
  • the embodiments of the present invention are not limited by the above examples.
  • the raw materials such as waste HIPS and waste PP selected in the above embodiments can also be commercially available ready-made products with similar performance, and there is no other material that does not deviate from the present invention. Changes, modifications, substitutions, combinations, and simplifications made under the spirit and principle should all be equivalent replacements, and all are included in the protection scope of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

一种基于原位增容与扩链的再生材料，主要由以下质量份配比的原料制成：废HIPS：30～70；废PP：30～70；POE：2～6；烷基化反应催化剂：0.1～0.4；共催化剂：0.1～0.3；大分子扩链剂：2～8。该再生材料以废HIPS及废PP为原料，通过分段配合使用两类化学改性剂，分别通过接枝化和扩链反应，实现原位增容及扩链修复作用，从而对废HIPS及废PP直接进行原位改性制备出综合性能优良的再生材料，其在充分利用废物资源的前提下，也体现出高值化属性。还公开了上述基于原位增容与扩链的再生材料的制备方法。

Description

一种基于原位增容与扩链的再生材料及其制备方法 技术领域
本发明属于再生材料技术领域，具体涉及一种基于原位增容与扩链的再生材料及其制备方法。
背景技术
作为一种性价比优良且韧性得到明显提升的聚苯乙烯类材料，高抗冲聚苯乙烯(HIPS)被广泛应用于包括包装物、电子电器产品、汽车在内的各行业中。但其在长期服役后，会因为光热氧等作用，发生老化而降解，在造成分子链断链的同时，产生羟基、羧基等活性基团，并伴有微观相结构的改变。老化后的废HIPS性能较新料全面降低，若不经改性提升性能，其整体应用范围将严重受限。
另一方面，聚丙烯(PP)具有低密度、无毒、价格低、易加工等优势，但也存在刚性低、缺口敏感等不足。老化后的废PP同样会发生分子结构断裂或重排，生成羟基、羧基等基团，造成宏观性能的全面下降。
高分子材料的合金化，可综合各基体材料的较优性能，实现高值化应用，因此也是重要的研究及应用方向。以废料制备高分子合金具有成本优势，但需对废料基材的性能进行有效修复，且改善各基体间相容性，才能制备出性能平衡的有市场需求的再生合金材料。
结合上述现状，以废HIPS与废PP制备高分子合金，如果能充分利用废HIPS及废PP老化后生成的羟基和羧基等活性基团，通过原位扩链作用，修复这两种基体材料，全面提升其综合性能的同时，通过原位生成的增容剂有效地改善废HIPS与废PP的相容性，将得到一种综合性能优异的再生合金材料。由于大量使用了废料，使得这种材料在具有性价比优势的同时，还具有环保属性，应用前景广泛。
发明内容
本发明的目的在于提供一种基于原位增容与扩链的再生材料，该再生材料以废HIPS及废PP为原料，通过分段配合使用两类化学改性剂，分别通过接枝化和扩链反应，实现原位增容及扩链修复作用，从而对废HIPS及废PP直接进行原位改性制备出综合性能优良的再生HIPS/PP合金材料，其在充分利用废物资源的前提下，也体现出高值化属性。
本发明的目的还在于提供上述基于原位增容与扩链的再生材料的制备方法。
本发明上述第一个目的是通过如下技术方案来实现的：一种基于原位增容与扩链的再生材料，主要由以下质量份配比的原料制成：
废HIPS：30～70；
废PP：30～70；
POE：2～6；
烷基化反应催化剂：0.1～0.4；
共催化剂：0.1～0.3；
大分子扩链剂：2～8。
本发明中基于原位增容与扩链的再生材料的原料中，主要包括废HIPS及废PP这两个原本不相容的基体相，首先在共催化剂与烷基化反应催化剂的催化作用下通过Friedel-Crafts烷基化反应，生成HIPS-g-PP及HIPS-g-POE接枝物，该接枝物可对共混物中的废HIPS组分及废PP组分起到很好的增容作用；而后通过引入大分子扩链剂，使其与废HIPS及废PP老化链上生成的羟基等活性基团，在挤出条件下发生原位扩链反应，实现断链增长，同时通过大分子扩链剂中的HIPS主链与废HIPS主链结构大体相似的相似相容作用，进一步改善废HIPS老化后导致的微相界面力减弱问题；其中共催化剂配合烷基化反应催化剂，促进烷基化反应的发生，而POE的作用除了形成接枝物增加废HIPS及废PP两相的相容性之外，还可以起到改善废PP相的老化界面结构并显著提升废PP相因老化而恶化地最为明显的抗冲击性能，最终制备出综合性能优良的基于原位增容与扩链的再生HIPS/PP合金材料。
在上述基于原位增容与扩链的再生材料的各原料中：
优选的，所述废HIPS为废HIPS(废高抗冲聚苯乙烯)经过破碎均化后得到片状料。
优选的，所述废PP为废PP(废聚丙烯)经过破碎均化后得到片状料。
优选的，所述POE为乙烯-辛烯共聚弹性体新料。
优选的，所述烷基化反应催化剂为无水氯化铝。
优选的，所述共催化剂为苯乙烯。
优选的，所述大分子扩链剂为高抗冲聚苯乙烯接枝甲基丙烯酸缩水甘油酯 (HIPS-g-GMA)。
本发明的上述第二个目的是通过如下技术方案来实现的：上述基于原位增容与扩链的再生材料的制备方法，包括以下步骤：将废HIPS、废PP、POE、烷基化反应催化剂、共催化剂按上述用量关系混合，得到混合物料，从双螺杆挤出机的主加料装置加入混合物料熔化，螺杆转速控制为40～80rpm，从双螺杆挤出机的加工中段的第五区按上述用量关系加入大分子扩链剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得基于原位增容与扩链的再生HIPS/PP合金材料。
在上述基于原位增容与扩链的再生材料的制备方法中：
优选的，所述双螺杆挤出机的加工温区为175～235℃。
进一步的，所述双螺杆挤出机的加工八区温度依次为：180℃，180℃，185℃，185℃，235℃，235℃，230℃，230℃。
本发明中，在挤出机的前四加工区，通过融熔状态下，利用Friedel-Crafts烷基化反应原位生成HIPS-g-PP及HIPS-g-POE接枝物，该接枝物可对共混物中的废HIPS组分及废PP组分起到很好的增容作用；在挤出机的后四加工区，则是通过引入大分子扩链剂，使其与废HIPS及废PP老化链上生成的羟基等活性基团，在挤出条件下发生原位扩链反应，实现断链增长，同时通过大分子扩链剂中的HIPS主链与废HIPS主链结构大体相似的相似相容作用，进一步改善废HIPS老化后导致的微相界面力减弱问题；POE的作用除了形成接枝物增加废HIPS及废PP两相的相容性之外，还可以起到改善废PP相的老化界面结构并显著提升废PP相因老化而恶化地最为明显的抗冲击性能，最终制备出综合性能优良的基于原位增容与扩链的再生HIPS/PP合金材料。
另一方面，本发明中后段四区与前段四区的加工温度有主动性提升，其主要目的有两点：首先是通过第五区加工温度的跃变提升，使烷基化反应催化剂得以快速挥发去除，避免高温下的断链竞争反应，以及后段引入大分子扩链剂后可能发生的其他副反应。另一方面，较高温度也有利于在有限的保留时间内有效发生扩链反应，实现扩链修复实效。通过大量试验证明，控制螺杆转速40～80rpm，后四段加工温区在230℃左右，可有效确保原位扩链效果。因此，通过前后段加工区的改变，既保证了烷基化反应的发生而生成增容剂，也不影响对废料基材的 扩链改性实效，使得制备出的再生合金性能得到优化。
本发明具有以下优点：
(1)本发明分段配合使用了两类化学改性剂，分别通过其接枝化和扩链反应，实现原位增容及扩链修复作用，从而对废HIPS及废PP直接进行原位改性制备再生HIPS/PP合金材料；
(2)本发明采用同基体型大分子扩链剂，可以扩链并改善废HIPS相老化结构，采用POE除了可以形成增容接枝物外，还可以改善废PP相的老化界面结构并显著提升废PP相因老化而恶化地最为明显的抗冲击性能，因此本发明制备的再生合金材料的两个基体相，虽然都是老化后的废料，但其各自的主链连续性及微观有序性都得到了修复，且两相间的相容性也得到了保障，因此再生合金的综合性能优良；
(3)本发明所用的加工设备无需特别改造，仅通过工艺条件及配方的优化，即可进行反应型挤出并实现原位增容和扩链改性，其应用推广的适应性较强；
(4)随着我国全面禁止废塑料进口，针对国内废塑料的回收利用技术，特别是高值化回收利用技术的应用潜力巨大，本发明为废塑料的高值化利用提供了一种全新的解决方案，有利于推进废塑料绿色再循环，助力实现碳中和目标，社会效益和经济效益良好。
具体实施方式
以下采用的原料中，如无特殊说明，均为市售。
实施例1
本实施例提供的基于原位增容与扩链的再生材料，主要由以下质量份配比的原料制成：
废HIPS：50
废PP：50
POE：5
烷基化反应催化剂：0.4
共催化剂：0.3
大分子扩链剂：6。
其中废HIPS为废HIPS(废高抗冲聚苯乙烯)经过破碎均化后得到片状料，废 PP为废PP(废聚丙烯)经过破碎均化后得到片状料，POE为乙烯-辛烯共聚弹性体新料，烷基化反应催化剂为无水氯化铝，共催化剂为苯乙烯，大分子扩链剂为高抗冲聚苯乙烯接枝甲基丙烯酸缩水甘油酯(HIPS-g-GMA)。
该基于原位增容与扩链的再生材料的制备方法，包括以下步骤：将废HIPS、废PP、POE、烷基化反应催化剂、共催化剂按上述用量关系混合，得到混合物料，从双螺杆挤出机的主加料装置加入混合物料熔化，螺杆转速控制为40rpm，从双螺杆挤出机的加工第五区按上述用量关系加入大分子扩链剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生合金材料。
双螺杆挤出机的加工八区温度依次为：180℃，180℃，185℃，185℃，235℃，235℃，230℃，230℃。
实施例2
本实施例提供的基于原位增容与扩链的再生材料，主要由以下质量份配比的原料制成：
废HIPS：30
废PP：70
POE：6
烷基化反应催化剂：0.4
共催化剂：0.3
大分子扩链剂：4。
上述成分同实施例1。
该基于原位增容与扩链的再生材料的制备方法，包括以下步骤：将废HIPS、废PP、POE、烷基化反应催化剂、共催化剂按上述用量关系混合，得到混合物料，从双螺杆挤出机的主加料装置加入混合物料熔化，螺杆转速控制为60rpm，从双螺杆挤出机的加工第五区按上述用量关系加入大分子扩链剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生合金材料。
双螺杆挤出机加工八区温度依次设定为：175℃，175℃，180℃，185℃，225℃，225℃，225℃，230℃。
实施例3
本实施例提供的基于原位增容与扩链的再生材料，主要由以下质量份配比 的原料制成：
废HIPS：70
废PP：30
POE：2
烷基化反应催化剂：0.2
共催化剂：0.1
HIPS基大分子扩链剂：8。
上述成分同实施例1。
该基于原位增容与扩链的再生材料的制备方法，包括以下步骤：将废HIPS、废PP、POE、烷基化反应催化剂、共催化剂按上述用量关系混合，得到混合物料，从双螺杆挤出机的主加料装置加入混合物料熔化，螺杆转速控制为80rpm，从双螺杆挤出机的加工第五区按上述用量关系加入大分子扩链剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生合金材料。
双螺杆挤出机加工八区温度依次设定为：180℃，185℃，185℃，185℃，225℃，225℃，235℃，235℃。
实施例1-3制备的基于原位增容与扩链的再生材料的机械性能汇总如下表1。
表1实施例1-3制备的再生材料的机械性能汇总
Figure PCTCN2022133450-appb-000001
上述表1中：
①制备方法及步骤同实施例1，物料配比为废HIPS50份、废PP50份，不含POE、HIPS基大分子扩链剂、烷基化反应催化剂及共催化剂；
②制备方法及步骤同实施例1，物料配比为废HIPS50份、废PP50份、POE5份、大分子扩链剂6份，但不含烷基化反应催化剂及共催化剂；
③制备方法及步骤同实施例1，物料配比为废HIPS50份、废PP50份、POE5份、烷基化反应催化剂0.4份、共催化剂0.3份，但不含大分子扩链剂；
④制备方法、步骤及物料配比同实施例1，但八个加工温区分别为180℃，180℃，185℃，185℃，185℃，185℃，185℃，185℃；
⑤制备方法、步骤及物料配比同实施例1，但八个加工温区分别为230℃，235℃，235℃，235℃，235℃，235℃，235℃，235℃。
由以上具体实验数据可以看出，对比未改性的废HIPS/废PP，通过本发明制备的再生材料HIPS/PP合金，机械性能得到全面提升，改性效果显著。
实施例1及对比例1的差别在于是否通过烷基化反应生成大分子相容剂来增容共混体系。可以看出，加入大分子扩链剂后，再生合金的冲击及拉伸强度有了显著地提升，但其增幅较复配添加烷基化反应催化剂的组分而言偏低。因此证明烷基化反应接枝化改性非常有意义，有利于提升共混物相容性从而提升再生材料综合性能。
实施例1及对比例2的差别在于是否添加HIPS基大分子扩链剂。可以看出，若仅添加烷基化催化剂但不添加大分子扩链剂，再生材料的综合性能仅有小幅提升，证明再生合金的相容性及各基体的基础性能都非常重要。仅仅提升再生合金的相容性，虽然改善了微观界面，但还是因各基体综合性能的短板，导致整体性能偏低。在原位增容及原位扩链共同作用下，再生合金的性能得到了显著提升。
实施例1及对比例3与对比例4的差别在于加工温度的不同。结果证明后段四区加工温度较前段四区的主动快速提升，对改性效果而言是非常有效的。前段四区的加工温度在180℃左右，既保证了烷基化反应的进行，又避免了高温下氯化铝的过早挥发及潜在地断链竞争反应。后段四区的加工温度在230℃左右，可以快速挥发氯化铝，并保障扩链反应的有效进行。
综合而言，通过本发明的两步的反应型改性，即烷基化反应改性和原位扩链修复改性，可以起到双效改性作用，进而显著提升再生材料的综合性能。非常有 利于提升再生产品的环境适应性并拓宽其应用场景。具有这种综合性能的再生合金产品，市场前景良好。
上述实施例为本发明较佳的实施方式，实施例中选用的POE、大分子扩链剂HIPS-g-GMA、烷基化反应催化剂AlCl 3、共催化剂苯乙烯均由市售现成产品获得。
但本发明的实施方式并不受上述实施例的限制，上述实施方式中所选用的废HIPS、废PP等原料也可选用市售的类似性能的现成产品，没有其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围。

Claims (10)

  1. 一种基于原位增容与扩链的再生材料，其特征是主要由以下质量份配比的原料制成：
    废HIPS：30～70；
    废PP：30～70；
    POE：2～6；
    烷基化反应催化剂：0.1～0.4；
    共催化剂：0.1～0.3；
    大分子扩链剂：2～8。
  2. 根据权利要求1所述的基于原位增容与扩链的再生材料，其特征是：所述废HIPS为废HIPS(废高抗冲聚苯乙烯)经过破碎均化后得到片状料。
  3. 根据权利要求1所述的基于原位增容与扩链的再生材料，其特征是：所述废PP为废PP(废聚丙烯)经过破碎均化后得到片状料。
  4. 根据权利要求1所述的基于原位增容与扩链的再生材料，其特征是：所述POE为乙烯-辛烯共聚弹性体新料。
  5. 根据权利要求1所述的基于原位增容与扩链的再生材料，其特征是：所述烷基化反应催化剂为无水氯化铝。
  6. 根据权利要求1所述的基于原位增容与扩链的再生材料，其特征是：所述共催化剂为苯乙烯。
  7. 根据权利要求1所述的基于原位增容与扩链的再生材料，其特征是：所述大分子扩链剂为高抗冲聚苯乙烯接枝甲基丙烯酸缩水甘油酯(HIPS-g-GMA)。
  8. 权利要求1-7任一项所述的基于原位增容与扩链的再生材料的制备方法，其特征是包括以下步骤：将废HIPS、废PP、POE、烷基化反应催化剂、共催化剂按上述用量关系混合，得到混合物料，从双螺杆挤出机的主加料装置加入混合物料熔化，螺杆转速控制为40～80rpm，从双螺杆挤出机的加工中段的第五区按上述用量关系加入大分子扩链剂，与熔化的混合物料共混，经挤出、牵引、 冷却、切粒，即制得基于原位增容与扩链的再生HIPS/PP合金材料。
  9. 根据权利要求8所述的基于原位增容与扩链的再生材料的制备方法，其特征是：所述双螺杆挤出机的加工温区为175～235℃。
  10. 根据权利要求9所述的基于原位增容与扩链的再生材料的制备方法，其特征是：所述双螺杆挤出机的加工八区温度依次为：180℃，180℃，185℃，185℃，235℃，235℃，230℃，230℃。
PCT/CN2022/133450 2021-11-26 2022-11-22 一种基于原位增容与扩链的再生材料及其制备方法 WO2023093705A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/274,467 US20240317986A1 (en) 2021-11-26 2022-11-22 Recycled material based on in-situ compatibilization and chain extension and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111422495.3A CN114276641B (zh) 2021-11-26 2021-11-26 一种基于原位增容与扩链的再生hips/pp合金材料及其制备方法
CN202111422495.3 2021-11-26

Publications (1)

Publication Number Publication Date
WO2023093705A1 true WO2023093705A1 (zh) 2023-06-01

Family

ID=80870027

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/133450 WO2023093705A1 (zh) 2021-11-26 2022-11-22 一种基于原位增容与扩链的再生材料及其制备方法

Country Status (3)

Country Link
US (1) US20240317986A1 (zh)
CN (1) CN114276641B (zh)
WO (1) WO2023093705A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276641B (zh) * 2021-11-26 2023-06-06 中国电器科学研究院股份有限公司 一种基于原位增容与扩链的再生hips/pp合金材料及其制备方法
CN118165455A (zh) * 2024-03-13 2024-06-11 吉安市国亨科技有限公司 一种用于poss机的pcr hips材料及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102532734A (zh) * 2012-01-10 2012-07-04 常州大学 结构型耐候高抗冲聚苯乙烯制备方法
CN104327438A (zh) * 2014-11-26 2015-02-04 重庆可益荧新材料有限公司 一种废旧hips/pp复合材料及其制备方法
CN106166820A (zh) * 2016-07-04 2016-11-30 成都华麒顺新材料有限公司 再生聚苯乙烯管及其生产工艺和应用
CN106633455A (zh) * 2016-12-08 2017-05-10 上海锦湖日丽塑料有限公司 高光泽且耐油好的hips/pp合金塑料及制备方法
CN108641265A (zh) * 2018-05-24 2018-10-12 中北大学 弹性体接枝共聚物改性废旧hips/pp复合材料及制备方法
CN112724571A (zh) * 2020-12-08 2021-04-30 中国电器科学研究院股份有限公司 一种基于化学与物理共同改性的再生合金材料及其制备方法
CN112759876A (zh) * 2020-12-24 2021-05-07 金发科技股份有限公司 一种环保聚苯乙烯合金材料及其制备方法和应用
CN114213852A (zh) * 2021-11-26 2022-03-22 中国电器科学研究院股份有限公司 一种废hips基再生合金材料及其制备方法
CN114276641A (zh) * 2021-11-26 2022-04-05 中国电器科学研究院股份有限公司 一种基于原位增容与扩链的再生hips/pp合金材料及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101921438A (zh) * 2010-04-15 2010-12-22 浙江大学宁波理工学院 共催化增容改性的聚苯乙烯合金材料及其制备方法
WO2014085878A1 (pt) * 2012-12-04 2014-06-12 Braskem S.A. Método de compatibilização de blendas de polipropileno, blenda de polipropileno e seu uso, produto e agente iniciador de compatibilização de blenda de polipropileno
CN105623134B (zh) * 2014-11-21 2019-07-05 合肥杰事杰新材料股份有限公司 一种催化增容ps/poe复合材料

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102532734A (zh) * 2012-01-10 2012-07-04 常州大学 结构型耐候高抗冲聚苯乙烯制备方法
CN104327438A (zh) * 2014-11-26 2015-02-04 重庆可益荧新材料有限公司 一种废旧hips/pp复合材料及其制备方法
CN106166820A (zh) * 2016-07-04 2016-11-30 成都华麒顺新材料有限公司 再生聚苯乙烯管及其生产工艺和应用
CN106633455A (zh) * 2016-12-08 2017-05-10 上海锦湖日丽塑料有限公司 高光泽且耐油好的hips/pp合金塑料及制备方法
CN108641265A (zh) * 2018-05-24 2018-10-12 中北大学 弹性体接枝共聚物改性废旧hips/pp复合材料及制备方法
CN112724571A (zh) * 2020-12-08 2021-04-30 中国电器科学研究院股份有限公司 一种基于化学与物理共同改性的再生合金材料及其制备方法
CN112759876A (zh) * 2020-12-24 2021-05-07 金发科技股份有限公司 一种环保聚苯乙烯合金材料及其制备方法和应用
CN114213852A (zh) * 2021-11-26 2022-03-22 中国电器科学研究院股份有限公司 一种废hips基再生合金材料及其制备方法
CN114276641A (zh) * 2021-11-26 2022-04-05 中国电器科学研究院股份有限公司 一种基于原位增容与扩链的再生hips/pp合金材料及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DIAZ, M.F. BARBOSA, S.E. CAPIATI, N.J.: "Improvement of mechanical properties for PP/PS blends by in situ compatibilization", POLYMER, ELSEVIER, AMSTERDAM, NL, vol. 46, no. 16, 25 July 2005 (2005-07-25), AMSTERDAM, NL, pages 6096 - 6101, XP004971582, ISSN: 0032-3861, DOI: 10.1016/j.polymer.2005.04.098 *
DONG CAI: "Study on Polypropylene/Polystyrene Blends In-situ Compatibilized by AlCl3China Plastics", CHINA PLASTICS, vol. 21, no. 7, 1 July 2007 (2007-07-01), pages 44 - 47, XP093068375, DOI: 10.19491/j.issn.1001-9278.2007.07.010 *

Also Published As

Publication number Publication date
CN114276641B (zh) 2023-06-06
US20240317986A1 (en) 2024-09-26
CN114276641A (zh) 2022-04-05

Similar Documents

Publication Publication Date Title
WO2023093705A1 (zh) 一种基于原位增容与扩链的再生材料及其制备方法
CN112724571B (zh) 一种基于化学与物理共同改性的再生合金材料及其制备方法
CN101709125B (zh) 基于界面增容的聚苯乙烯/聚烯烃纳米复合材料及制备方法
CN108034138B (zh) 一种聚丙烯组合物及其制备方法与应用
CN103360732B (zh) 一种回收聚对苯二甲酸乙二醇酯/丙烯腈‑丁二烯‑苯乙烯共聚物合金及其制备方法
Triantou et al. Studies on morphology and thermomechanical performance of ABS/PC/Organoclay hybrids
CN106189126A (zh) 一种高热变形温度低成型周期阻燃增强pet材料及制备方法
CN114230986A (zh) 立构复合结晶增强的生物可降解材料
WO2023093706A1 (zh) 一种再生高分子合金材料及其制备方法
CN109486156B (zh) 一种阻燃挤出级pc/abs复合材料
CN108285598B (zh) 一种具有增韧功能的聚氯乙烯加工助剂母料及其制备方法
CN107936455B (zh) 一种基于原位扩链修复的再生abs/hips合金材料及其制备方法
CN112694702B (zh) 一种再生hips/ppo合金材料及其制备方法
CN105733231B (zh) 以硫酸钙晶须改性的聚碳酸酯合金材料及其制法
CN112694670B (zh) 一种玻纤增强废旧pp/pet膜复合材料及其制备方法
CN114479333A (zh) 一种低蠕变高韧性环烯烃共聚物复合材料及其制备方法
Bhattacharyya et al. Ionomer compatibilised PA6/EVA blends: mechanical properties and morphological characterisation
CN114031863A (zh) 一种高导电ps/hdpe复合材料及其制备方法
CN104910637A (zh) 一种sbs与pe改性的沥青材料
CN108129818B (zh) 一种利用大分子扩链剂始源性修复改性的再生pc/abs合金材料及其制备方法
CN108003549B (zh) 一种再生abs/pp合金材料及其制备方法
CN111234378B (zh) 一种具有核壳结构的pp/tpu复合材料及其制备方法
CN116376261A (zh) 一种超高韧性聚苯醚/聚苯乙烯合金制备方法
CN118271754A (zh) 一种高光泽高流动再生聚苯乙烯材料及其制备方法
CN113388206A (zh) 一种抗低温脆性ppr复合材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22897788

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18274467

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE