WO2022121329A1 - 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 - Google Patents

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 Download PDF

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WO2022121329A1
WO2022121329A1 PCT/CN2021/108824 CN2021108824W WO2022121329A1 WO 2022121329 A1 WO2022121329 A1 WO 2022121329A1 CN 2021108824 W CN2021108824 W CN 2021108824W WO 2022121329 A1 WO2022121329 A1 WO 2022121329A1
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hips
alloy material
physical
chemical
chain extender
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PCT/CN2021/108824
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French (fr)
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曹诺
符永高
胡嘉琦
王玲
万超
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中国电器科学研究院股份有限公司
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Priority to US17/794,622 priority Critical patent/US20230078328A1/en
Publication of WO2022121329A1 publication Critical patent/WO2022121329A1/zh

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    • 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
    • C08J3/005—Processes for mixing polymers
    • 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
    • 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
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • 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
    • C08J2325/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • 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
    • 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
    • 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 waste HIPS regeneration, in particular to a regenerated alloy material based on chemical and physical co-modification and a preparation method thereof.
  • HIPS high impact polystyrene
  • Polyphenylene ether has the advantages of high rigidity, high heat resistance, flame retardancy, high strength, and excellent electrical properties, but its fluidity is poor, and its viscosity is sensitive to temperature, so the molding temperature needs to be strictly controlled.
  • PPO is suitable for making heat-resistant parts, insulating parts, anti-wear and wear-resistant parts, transmission parts, medical and electronic parts, etc.
  • 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 scrap has a cost advantage, but it is necessary to effectively repair the properties of the scrap base material in order to prepare recycled alloy materials with market demand.
  • the aging degradation and changes in molecular structure and polarity of waste HIPS during use will negatively affect the compatibility of HIPS/PPO blends.
  • waste HIPS and PPO can be used to prepare polymer alloys, the active groups such as hydroxyl and carboxyl groups generated after waste HIPS aging can be fully utilized, and waste HIPS can be repaired by molecular chain extension and similar compatibility.
  • the compatibility of waste HIPS and PPO can effectively improve the compatibility of waste HIPS and PPO, and through the physical modification of compound toughening agents, give full play to the combined effect of chemical modification and physical modification, and will get A recycled alloy material with excellent comprehensive properties. Due to the extensive use of waste materials, this material has environmental protection properties while having cost-effectiveness advantages, and has wide application prospects.
  • the purpose of the present invention is to provide a regenerated alloy material based on chemical and physical co-modification.
  • the regenerated HIPS/PPO alloy material utilizes the in-situ chain extension of macromolecular chain extenders and the chemical modification of compatibilization to repair the molecules. Chain structure, improved phase interface, and increased compatibility; on the basis of the original improvement of the micro-properties and macro-mechanical properties of the waste, the physical modification effect introduced by compounding and adding elastomer tougheners can give full play to the The combined effect of chemical modification and physical modification was used to further improve the target performance, and finally a recycled plastic alloy material with excellent comprehensive performance was obtained, and the waste was fully utilized to achieve energy saving and emission reduction.
  • Another object of the present invention is to provide the above-mentioned preparation method of the regenerated alloy material based on the co-modification of chemical and physical.
  • a regenerated alloy material based on chemical and physical co-modification mainly consists of the following components in the proportions by mass:
  • HIPS-based macromolecular chain extender 2 to 8
  • Oxazoline chain extender 0.2 ⁇ 1
  • Chain extension catalyst 0.1 to 0.4.
  • the HIPS-based macromolecular chain extender is preferably high-impact polystyrene grafted maleic anhydride (HIPS-g-MAH).
  • the elastomer toughening agent is preferably styrene-ethylene-butylene-styrene block copolymer (SEBS).
  • the oxazoline chain extender is preferably 2,2'-(1,3-phenylene)-bisoxazoline (PBO).
  • the chain extension catalyst is preferably 4-dimethylaminopyridine (DMAP).
  • the waste HIPS is preferably a flake material obtained after the waste HIPS is crushed and homogenized.
  • Described PPO is polyphenylene ether.
  • the above-mentioned preparation method of the regenerated alloy material based on chemical and physical co-modification comprises the following steps: waste HIPS, PPO, HIPS-based macromolecular chain extender ,
  • the chain extension catalyst is mixed according to the above-mentioned dosage relationship to obtain the mixed material, and the mixed material is added from the main feeding device of the twin-screw extruder to melt, and the screw speed is controlled to be 60 to 90 rpm.
  • the processing temperature zone of the twin-screw extruder is preferably 225-255°C.
  • the temperature of the six processing zones of the twin-screw extruder is preferably: 225°C, 230°C, 230°C, 235°C, 255°C, 255°C.
  • the HIPS-based macromolecular chain extender added in the present invention can simultaneously play the following three key functions:
  • the active acid anhydride group on the molecular chain can react with the hydroxyl group generated on the aging chain of waste HIPS to undergo in-situ chain extension reaction under extrusion conditions to achieve chain scission growth of waste HIPS, thereby affecting the original molecular structure of waste. Repair, and then greatly improve the macro performance of HIPS substrates;
  • the HIPS main chain of the HIPS-based macromolecular chain extender is roughly similar in structure to the waste HIPS main chain, which is very beneficial to improve the microphase structure and the weakening of the interface force after the aging of waste HIPS, thereby promoting the HIPS phase and PPO phase. compatible;
  • the HIPS-based macromolecular chain extender contains a certain amount of PB (polybutadiene) components, and the addition of the HIPS-based macromolecular chain extender is also equivalent to increasing the overall rubber content of the recycled alloy material, and has a toughening effect .
  • PB polybutadiene
  • the chain extension catalyst in the present invention is very necessary, because the processing temperature of PPO is higher, and the stability of waste HIPS is lower than that of new material HIPS, so under the classical processing conditions of PPO, that is, under the higher processing temperature, the When processed over time, the spent HIPS components are likely to degrade, thereby affecting the overall properties of the recycled alloy. Therefore, in order to avoid waste degradation and ensure the effective progress of the chain extension reaction, the chain extension reaction is promoted by adding a chain extension catalyst to reduce the extrusion time and the extrusion temperature.
  • the oxazoline chain extender added in the present invention is a carboxyl-reactive chain extender under extrusion processing conditions.
  • the acid anhydride type HIPS-based macromolecular chain extender is firstly added from the main feeding device, which can react with the hydroxyl groups in the aging molecular chain of the mixed system, and supplement to generate new carboxyl groups, thereby increasing the follow-up
  • the chain extension potential of using oxazoline chain extender then add oxazoline chain extender at the feeding port in the middle of the barrel of the fourth zone, and realize step-by-step reaction by feeding separately, which can fully and effectively carry out in-situ chain extension repair,
  • the HIPS-based macromolecular chain extender and the oxazoline chain extender are directly blended, the direct reaction between the acid anhydride and the oxazoline group causes excessive consumption, which affects the main chain extension repair of waste HIPS.
  • the elastomer toughening agent SEBS added in the present invention belongs to the elastomer physical modifier with ultra-high toughness and low strength, and mainly neutralizes and improves the impact strength of the entire blending system through its own extremely high toughness.
  • the compatibility of PPO is good, and it does not contain unsaturated carbon-carbon double bonds that easily reduce the anti-aging performance of recycled products. It is a better choice of toughening agent for recycled HIPS/PPO alloys.
  • the most severely deteriorated performance of waste HIPS after aging is the impact strength (the retention value of tensile strength and flexural strength after aging is relatively high), while the other component of PPO itself has high rigidity and high strength.
  • the toughness is general, so the toughening of the recycled HIPS/PPO alloy is very beneficial to strengthen its short plate properties, thereby effectively broadening the application range.
  • the present invention has the following advantages:
  • the present invention uses two types of different chain extenders in combination, based on in-situ chain extension and compatibilization, the original source comprehensively improves the comprehensive performance of waste HIPS and improves the compatibility of the blend;
  • the present invention provides a brand-new solution for the high-value utilization of typical bulk waste plastics, and also drives the development of the recycled plastics industry. At the same time, the related products have strong market competitiveness and conform to the national energy conservation and emission reduction policies. , with good social and economic benefits.
  • Oxazoline chain extender 0.8
  • Chain extension catalyst 0.4.
  • the HIPS-based macromolecular chain extender is high-impact polystyrene grafted maleic anhydride (HIPS-g-MAH), and the elastomer toughening agent is styrene-ethylene-butylene-styrene block copolymer (SEBS).
  • HIPS-g-MAH high-impact polystyrene grafted maleic anhydride
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • oxazoline chain extender is 2,2'-(1,3-phenylene)-bisoxazoline (PBO)
  • chain extension catalyst is 4-dimethylaminopyridine (DMAP)
  • waste HIPS waste HIPS is crushed and homogenized to obtain flakes
  • PPO polyphenylene ether.
  • the preparation method of the regenerated alloy material based on chemical and physical co-modification includes the following steps: mixing waste HIPS, PPO, HIPS-based macromolecular chain extender and chain extension catalyst according to the above-mentioned dosage relationship to obtain a mixed material,
  • the main feeding device of the extruder is added with the mixed material to melt, and the screw speed is controlled to 60 rpm.
  • the oxazoline chain extender and the elastomer toughening agent are added according to the above-mentioned dosage relationship, and the molten mixture is added.
  • the materials are blended, and the recycled HIPS/PPO alloy material is obtained by extrusion, traction, cooling and pelletizing.
  • the temperatures of the six processing zones of the twin-screw extruder were set as follows: 225°C, 230°C, 230°C, 235°C, 255°C, and 255°C.
  • Oxazoline chain extender 0.8
  • Chain extension catalyst 0.4.
  • Waste HIPS, PPO, HIPS-based macromolecular chain extender, elastomer toughening agent, oxazoline chain extender and chain extension catalyst are the same as in Example 1.
  • the preparation method of the regenerated alloy material based on chemical and physical co-modification includes the following steps: mixing waste HIPS, PPO, HIPS-based macromolecular chain extender and chain extension catalyst according to the above-mentioned dosage relationship to obtain a mixed material,
  • the main feeding device of the extruder is added with the mixed material to melt, and the screw speed is controlled to 60 rpm.
  • the oxazoline chain extender and the elastomer toughening agent are added according to the above-mentioned dosage relationship, and the molten mixture is added.
  • the materials are blended, and the recycled HIPS/PPO alloy material is obtained by extrusion, traction, cooling and pelletizing.
  • the temperatures of the six processing zones of the twin-screw extruder were set as follows: 225°C, 230°C, 230°C, 235°C, 255°C, and 255°C.
  • HIPS-based macromolecular chain extenders 4
  • Oxazoline chain extender 0.4
  • Chain extension catalyst 0.2.
  • Waste HIPS, PPO, HIPS-based macromolecular chain extender, elastomer toughening agent, oxazoline chain extender and chain extension catalyst are the same as in Example 1.
  • the preparation method of the regenerated alloy material based on chemical and physical co-modification includes the following steps: mixing waste HIPS, PPO, HIPS-based macromolecular chain extender and chain extension 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, and the screw speed is controlled to 90 rpm.
  • the oxazoline chain extender and the elastomer toughening agent are added according to the above-mentioned dosage relationship, and the molten mixture is added.
  • the materials are blended, and the recycled HIPS/PPO alloy material is obtained by extrusion, traction, cooling and pelletizing.
  • the temperatures of the six processing zones of the twin-screw extruder are set as follows: 225°C, 235°C, 235°C, 240°C, 255°C, and 250°C.
  • Example 1 The preparation method and steps are the same as those in Example 1, and the material ratio is 70 parts of waste HIPS and 30 parts of PPO, without HIPS-based macromolecular chain extender, elastomer toughening agent, oxazoline chain extender and chain extension catalyst;
  • Example 2 The preparation method and steps are the same as those in Example 1 and Example 2, and the material ratio is 70 parts of waste HIPS, 30 parts of PPO, 8 parts of HIPS-based macromolecular chain extender, 0.8 part of oxazoline chain extender, and 0.4 part of chain extension catalyst, Does not contain elastomer tougheners;
  • Example 3 The preparation method and steps are the same as in Example 3, and the material ratio is 60 parts of waste HIPS, 40 parts of PPO, 4 parts of HIPS-based macromolecular chain extenders, 0.4 parts of oxazoline chain extenders, and 0.2 parts of chain extension catalysts, without elastomers Toughening agent.
  • Example 1 The difference between Example 1 and Example 2 is that different amounts of elastomer toughening agents are added. According to Examples 1-2, it can be seen that when a relatively high amount of elastomer toughening agent is added, the strength of the alloy material can be greatly increased. Impact strength.
  • Example 1 The difference between Examples 1-2 and Comparative Example 1 is that an elastomer toughening agent with ultra-high toughness and lower strength is added, and through chemical and physical co-modification, in Example 1, the impact strength is greatly increased by 65%, The flexural and tensile strengths are only slightly reduced by about 8% (the impact, flexural and tensile strengths are 253%, 6% and 12% higher than those of the unmodified waste HIPS/PPO, respectively), and the overall performance is very good.
  • Example 3 and Comparative Example 2 also have similar comparative effects. Because the most seriously deteriorated performance of waste HIPS after aging is the impact strength (the retention value of tensile and flexural strength after aging is relatively high), while the other component of PPO itself has the characteristics of high rigidity, high strength and general toughness , so the short-board property of the recycled HIPS/PPO alloy is the impact strength.
  • the present invention is based on the co-modification effect of chemistry and physics, by very limitedly reducing the non-short-board properties (strength properties) such as tensile and flexural strength, in exchange for a large improvement in short-board properties (toughness properties) such as impact strength, It is very beneficial to improve the environmental adaptability of recycled products and broaden their application scenarios. Recycled alloy products with such comprehensive properties have good market prospects.
  • stress properties such as tensile and flexural strength
  • the embodiments of the present invention are not limited by the above-mentioned examples.
  • the raw materials such as waste HIPS and PPO used in the above-mentioned embodiments can also be commercially available off-the-shelf products with similar properties. Changes, modifications, substitutions, combinations, and simplifications made under the substance and principle should all be equivalent substitution methods, and are all included in the protection scope of the present invention.

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  • 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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种基于化学与物理共同改性的再生HIPS/PPO合金材料，主要由以下质量份配比的成分组成：废HIPS 60～70、PPO 30～40、HIPS基大分子扩链剂2～8、弹性体增韧剂2～10、噁唑啉扩链剂0.2～1、扩链催化剂0.1～0.4。该合金材料利用大分子扩链剂的原位扩链及增容的化学改性作用，修复了分子链结构、改善了相界面、增加了相容性；通过复配添加弹性体增韧剂所引入的物理改性作用，发挥了化学改性与物理改性的共同作用，提升了目标性能，制得了综合性能优异的再生塑料合金材料，且充分进行了废物利用，实现了节能减排。还公开了上述合金材料的制备方法。

Description

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 技术领域
本发明属于废HIPS再生技术领域，具体涉及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。
背景技术
高抗冲聚苯乙烯(HIPS)因其优良的综合性能，广泛应用于制备空调机箱、电视机等电器塑料外壳中。HIPS主要优点包括抗冲击强度高、光泽度好、耐热性和流动性好等，但其在加工和使用过程中会发生老化降解，引起分子链断链、相结构的改变，导致废HIPS的性能远远差于HIPS新料的性能。
聚苯醚(PPO)具有刚性大、耐热性高、难燃、强度高、电性能优等优点，但其流动性差，粘度对温度比较敏感，需严格控制成型温度。PPO适于制作耐热件、绝缘件、减磨耐磨件、传动件、医疗及电子零件等，在汽车工业、电子电气、办公设备、精密器械、纺织器材等许多领域应用广泛。
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，才能制备出有市场需求的再生合金材料。将新料HIPS与PPO共混，由于两者之间相容很好，不仅提高了HIPS强度，还可以改善PPO的流动性。但是，废旧HIPS在使用过程中发生的老化降解及分子结构与极性的变化，则会对HIPS/PPO共混物相容性造成负面影响。
结合上述现状，若能将废HIPS与PPO制备高分子合金，充分利用废HIPS老化后生成的羟基和羧基等活性基团，通过分子扩链及相似相容作用，将废HIPS进行始源性修复，全面提升废HIPS基材综合性能的同时，有效改善废HIPS与PPO的相容性，并通过复配增韧剂的物理改性，充分发挥化学改性与物理改性的共同作用，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化学与物理共同改性的再生合金材料，该再生HIPS/PPO合金材料利用大分子扩链剂的原位扩链及增容的化学改性作用， 修复了分子链结构、改善了相界面、增加了相容性；在废料微观属性及宏观机械性能得到始源性改善的基础上，通过复配添加弹性体增韧剂所引入的物理改性作用，充分发挥了化学改性与物理改性的共同作用，进一步提升目标性能，最终制得了综合性能优异的再生塑料合金材料，且充分进行了废物利用，实现了节能减排。
本发明的目的还在于提供上述基于化学与物理共同改性的再生合金材料的制备方法。
本发明上述第一个技术问题是通过如下技术方案来实现的：一种基于化学与物理共同改性的再生合金材料，主要由以下质量份配比的成分组成：
废HIPS：60～70
PPO：30～40
HIPS基大分子扩链剂：2～8
弹性体增韧剂：2～10
噁唑啉扩链剂：0.2～1
扩链催化剂：0.1～0.4。
在上述基于化学与物理共同改性的再生合金材料的各成分中：
所述的HIPS基大分子扩链剂优选为高抗冲聚苯乙烯接枝马来酸酐(HIPS-g-MAH)。
所述的弹性体增韧剂优选为苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)。
所述的噁唑啉扩链剂优选为2,2'-(1,3-亚苯基)-二噁唑啉(PBO)。
所述的扩链催化剂优选为4-二甲氨基吡啶(DMAP)。
所述的废HIPS优选为废HIPS经过破碎均化后得到片状料。
所述的PPO为聚苯醚。
本发明的上述第二个目的是通过以下技术方案来实现的：上述基于化学与物理共同改性的再生合金材料的制备方法，包括以下步骤：将废HIPS、PPO、HIPS基大分子扩链剂、扩链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60～90rpm，从双螺杆挤出机的加工第四区按上述用量关系加入噁唑啉扩链剂及弹性体增韧剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生HIPS/PPO合金材料。
在该基于化学与物理共同改性的再生合金材料的制备方法中：
所述的双螺杆挤出机的加工温区优选为225～255℃。
进一步的，所述的双螺杆挤出机的加工六区温度依次优选为：225℃，230℃，230℃，235℃，255℃，255℃。
本发明中加入的HIPS基大分子扩链剂可同时起到以下三个关键作用：
(1)分子链上的活性酸酐基团可以与废HIPS老化链上生成的羟基，在挤出条件下发生原位扩链反应，实现废HIPS的断链增长，从而对废料始源性分子结构修复，进而大幅提升HIPS基材的宏观性能；
(2)HIPS基大分子扩链剂的HIPS主链，与废HIPS主链结构大体相似，十分有利于改善废HIPS老化后微相结构以及界面力减弱的问题，进而促进HIPS相与PPO相的相容；
(3)HIPS基大分子扩链剂含有一定量的PB(聚丁二烯)组分，加入HIPS基大分子扩链剂也相当于提高了再生合金材料的整体胶含量，起到增韧作用。
本发明中的扩链催化剂是非常必要的，由于PPO的加工温度较高，加之废HIPS较新料HIPS的稳定性有所降低，故在经典的PPO加工条件下，即较高加工温度下长时间加工时，废HIPS组分很有可能发生降解，从而影响再生合金的整体性能。因此，为了避免废料降解，并保证扩链反应的有效进行，通过加入扩链催化剂来促进扩链反应，以减少挤出时间和降低挤出温度来实现。
本发明中加入的噁唑啉扩链剂，在挤出加工条件下，是羧基反应型扩链剂。为了进一步提升扩链改性效果，首先从主加料装置加入酸酐型HIPS基大分子扩链剂，其可与混合体系老化分子链中的羟基发生反应，并补充生成新的羧基，从而增加了后续使用噁唑啉扩链剂的扩链潜力；继而在第四区机筒中部加料口加入噁唑啉扩链剂，通过分别投料实现分步反应，既能充分有效地进行原位扩链修复，同时避免了HIPS基大分子扩链剂及噁唑啉扩链剂直接共混时，酸酐与噁唑啉基团直接反应造成过度消耗，影响对废HIPS的主链扩链修复。
本发明中加入弹性体增韧剂SEBS属于超高韧性和较低强度的弹性体物理改性剂，主要通过其自身极高的韧性来中和提升整个共混体系的冲击强度，其与HIPS及PPO的相容性都较好，且不含易导致再生产品抗老化性能降低的不饱和碳碳双键，对再生HIPS/PPO合金是较好的增韧剂选择。另一方面，由于废HIPS老化 后恶化最严重的性能的正是冲击强度(老化后拉伸强度及弯曲强度的保留值相对较高)，而另一组分PPO本身就具有刚性大、强度大、韧性一般的特点，所以对再生HIPS/PPO合金进行增韧，非常有利于补强其短板属性，从而有效拓宽应用范围。
前述已经提及，温度及螺杆转速对再生合金的综合性能影响较大。较长的挤出保留时间和较高的温度有利于促进挤出时原位扩链反应的发生并使得共混更加均匀，但太长的加工时间及太高的温度又可能导致再生材料的分解。通过大量试验证明，基于扩链催化剂作用，控制螺杆转速60～90rpm，加工温区在225～255℃，可在不影响原位扩链效果的前提下，有效共混并避免再生材料发生分解。
与现有技术相比，本发明具有以下优点：
(1)本发明组合使用了两类不同扩链剂，基于原位扩链与增容，始源性全面提升废HIPS的综合性能并改善共混物的相容性；
(2)原位扩链始源性全面提升HIPS基材综合性能后，进一步引入SEBS弹性体物理改性剂，通过化学改性与物理改性的共同作用，进一步提升了再生HIPS/PPO合金的韧性，有效拓宽其应用范围；
(3)本发明整个加工过程使用的是常规的塑料加工设备，通过优选工艺及优化配方，进行反应型挤出，因此可以方便的进行推广应用；
(4)本发明为典型大宗废塑料的高值化利用提供一种全新的解决方案，也带动了再生塑料行业的发展，同时相关产品具有很强的市场竞争力，并且符合国家节能减排政策，具有很好的社会效益和经济效益。
具体实施方式
实施例1
本实施例提供的基于化学与物理共同改性的再生合金材料，主要由以下质量份配比的成分组成：
废HIPS：70
PPO：30
HIPS基大分子扩链剂：8
弹性体增韧剂：10
噁唑啉扩链剂：0.8
扩链催化剂：0.4。
其中HIPS基大分子扩链剂为高抗冲聚苯乙烯接枝马来酸酐(HIPS-g-MAH)，弹性体增韧剂为苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)，噁唑啉扩链剂为2,2'-(1,3-亚苯基)-二噁唑啉(PBO)，扩链催化剂为4-二甲氨基吡啶(DMAP)，废HIPS为废HIPS经过破碎均化后得到片状料，PPO为聚苯醚。
该基于化学与物理共同改性的再生合金材料的制备方法，包括以下步骤：将废HIPS、PPO、HIPS基大分子扩链剂、扩链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，从双螺杆挤出机加工第四区按上述用量关系加入噁唑啉扩链剂及弹性体增韧剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生HIPS/PPO合金材料。
双螺杆挤出机加工六区温度依次设定为：225℃，230℃，230℃，235℃，255℃，255℃。
实施例2
本实施例提供的基于化学与物理共同改性的再生合金材料，主要由以下质量份配比的成分组成：
废HIPS：70
PPO：30
HIPS基大分子扩链剂：8
弹性体增韧剂：2
噁唑啉扩链剂：0.8
扩链催化剂：0.4。
废HIPS、PPO、HIPS基大分子扩链剂、弹性体增韧剂、噁唑啉扩链剂及扩链催化剂同实施例1。
该基于化学与物理共同改性的再生合金材料的制备方法，包括以下步骤：将废HIPS、PPO、HIPS基大分子扩链剂、扩链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，从双螺杆挤出机加工第四区按上述用量关系加入噁唑啉扩链剂及弹性体增韧剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生HIPS/PPO合金材料。
双螺杆挤出机加工六区温度依次设定为：225℃，230℃，230℃，235℃，255℃，255℃。
实施例3
本实施例提供的基于化学与物理共同改性的再生合金材料，主要由以下质量份配比的成分组成：
废HIPS：60
PPO：40
HIPS基大分子扩链剂：4
弹性体增韧剂：4
噁唑啉扩链剂：0.4
扩链催化剂：0.2。
废HIPS、PPO、HIPS基大分子扩链剂、弹性体增韧剂、噁唑啉扩链剂及扩链催化剂同实施例1。
该基于化学与物理共同改性的再生合金材料的制备方法，包括以下步骤：将废HIPS、PPO、HIPS基大分子扩链剂、扩链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90rpm，从双螺杆挤出机加工第四区按上述用量关系加入噁唑啉扩链剂及弹性体增韧剂，与熔化的混合物料共混，经挤出、牵引、冷却、切粒，即制得再生HIPS/PPO合金材料。
双螺杆挤出机加工六区温度依次设定为：225℃，235℃，235℃，240℃，255℃，250℃。
实施例1-3制备的基于化学与物理共同改性的合金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HIPS/PPO合金材料的机械性能汇总
Figure PCTCN2021108824-appb-000001
Figure PCTCN2021108824-appb-000002
上述表1中：
①制备方法及步骤同实施例1，物料配比为废HIPS70份、PPO30份，不含HIPS基大分子扩链剂、弹性体增韧剂、噁唑啉扩链剂及扩链催化剂；
②制备方法及步骤同实施例1及实施例2，物料配比为废HIPS70份、PPO30份、HIPS基大分子扩链剂8份、噁唑啉扩链剂0.8份、扩链催化剂0.4份，不含弹性体增韧剂；
③制备方法及步骤同实施例3，物料配比为废HIPS60份、PPO40份、HIPS基大分子扩链剂4份、噁唑啉扩链剂0.4份、扩链催化剂0.2份，不含弹性体增韧剂。
由以上具体实验数据可以看出，对比未改性的废HIPS/PPO，通过本发明制备的再生HIPS/PPO合金，机械性能得到全面提升，特别是对主链分子量、分子链结构、相界面作用更为敏感的冲击强度的提升尤为明显。
实施例1与实施例2的差别在于添加了不同用量的弹性体增韧剂，根据实施例1-2可以看出，添加相对用量较高的弹性体增韧剂时，可以大大增加合金材料的冲击强度。
实施例1-2与对比例1的差别在于添加了超高韧性和较低强度的弹性体增韧剂，通过化学与物理共同改性作用，其中实施例1中使得冲击强度大幅提升65％，弯曲及拉伸强度仅小幅降低约8％(冲击、弯曲及拉伸强度较未改性的废HIPS/PPO则分别有253％、6％及12％的提升)，综合性能非常优良。
实施例3与对比例2也有类似的对比效果。由于废HIPS老化后恶化最严重的性能的正是冲击强度(老化后拉伸及弯曲强度的保留值相对较高)，而另一组分PPO本身就具有刚性大、强度大、韧性一般的特点，所以再生HIPS/PPO合金的短板属性就是冲击强度。
因此，本发明基于化学与物理的共同改性作用，通过非常有限地小幅降低拉伸及弯曲强度等非短板属性(强度属性)，换取冲击强度等短板属性(韧性属性)的大幅提升，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PPO、HIPS基大分子扩链剂HIPS-g-MAH、弹性体增韧剂SEBS、噁唑啉扩链剂PBO、扩链催化剂DMAP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、PPO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 (9)

  1. 一种基于化学与物理共同改性的再生合金材料，其特征是主要由以下质量份配比的成分组成：
    废HIPS：60～70
    PPO：30～40
    HIPS基大分子扩链剂：2～8
    弹性体增韧剂：2～10
    噁唑啉扩链剂：0.2～1
    扩链催化剂：0.1～0.4。
  2. 根据权利要求1所述的基于化学与物理共同改性的再生合金材料，其特征是：所述HIPS基大分子扩链剂为高抗冲聚苯乙烯接枝马来酸酐(HIPS-g-MAH)。
  3. 根据权利要求1所述的基于化学与物理共同改性的再生合金材料，其特征是：所述弹性体增韧剂为苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)。
  4. 根据权利要求1所述的基于化学与物理共同改性的再生合金材料，其特征是：所述噁唑啉扩链剂为2,2'-(1,3-亚苯基)-二噁唑啉(PBO)。
  5. 根据权利要求1所述的基于化学与物理共同改性的再生合金材料，其特征是：所述扩链催化剂为4-二甲氨基吡啶(DMAP)。
  6. 根据权利要求1所述的基于化学与物理共同改性的再生合金材料，其特征是：所述废HIPS为废HIPS经过破碎均化后得到片状料。
  7. 权利要求1-6任一项所述的基于化学与物理共同改性的再生合金材料的制备方法，其特征是包括以下步骤：将废HIPS、PPO、HIPS基大分子扩链剂、扩链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60～90rpm，从双螺杆挤出机的加工第四区按上述用量关系加入噁唑啉扩链剂及弹性体增韧剂，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。
  8. 根据权利要求7所述的基于化学与物理共同改性的再生合金材料的制备方法，其特征是：所述双螺杆挤出机的加工温区为225～255℃。
  9. 根据权利要求8所述的基于化学与物理共同改性的再生合金材料的制备方法，其特征是：所述双螺杆挤出机的加工六区温度依次为：225℃，230℃，230℃，235℃，255℃，255℃。
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CN114213852B (zh) * 2021-11-26 2023-04-07 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

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