WO2024012475A1 - 净味环保聚丙烯再生塑料及其制备方法 - Google Patents

净味环保聚丙烯再生塑料及其制备方法 Download PDF

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WO2024012475A1
WO2024012475A1 PCT/CN2023/106900 CN2023106900W WO2024012475A1 WO 2024012475 A1 WO2024012475 A1 WO 2024012475A1 CN 2023106900 W CN2023106900 W CN 2023106900W WO 2024012475 A1 WO2024012475 A1 WO 2024012475A1
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odor
environmentally friendly
free
polypropylene
recycled plastic
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PCT/CN2023/106900
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English (en)
French (fr)
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许文殊
熊维
朱宽
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上海睿聚环保科技有限公司
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Publication of WO2024012475A1 publication Critical patent/WO2024012475A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/27—Cleaning; Purging; Avoiding contamination
    • B29C48/271—Cleaning; Purging; Avoiding contamination of feeding units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/27—Cleaning; Purging; Avoiding contamination
    • B29C48/2715—Cleaning; Purging; Avoiding contamination of plasticising units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/27—Cleaning; Purging; Avoiding contamination
    • B29C48/274—Cleaning; Purging; Avoiding contamination of the extruded articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]

Definitions

  • the invention relates to the technical field of recycled plastics, and in particular to a odor-free and environmentally friendly polypropylene recycled plastic and a preparation method thereof.
  • Plastic materials are difficult to degrade naturally in the environment. Recycling plastic materials to prepare recycled plastics can greatly alleviate environmental pollution, save resources and protect the environment. However, the smell of recycled plastics, especially recycled polypropylene, is very obvious, which will seriously affect people's experience of using recycled plastics and limit the scope of use of recycled plastics. All stages of manufacturing recycled plastics can cause odor, including recycling, polymerization and molding.
  • Chinese invention patent CN201611105231.4 discloses a low-odor recycled polypropylene composite material for automobile interior and exterior decoration.
  • the odor of the recycled polypropylene is reduced so that the recycled polypropylene material can It is used in automobile interior and exterior decoration, but it is only deodorized in the finished product step. It does not involve the deodorization of recycled polypropylene, and the proportion of recycled polypropylene is not high.
  • Chinese invention patent CN201911288711.2 discloses a long glass fiber reinforced polypropylene composite material.
  • the mechanical strength of the polypropylene material is enhanced by adding long glass fibers, and the odor generated by the material is improved by adding flavors. However, the odor is not eliminated. In later use, will still be released, affecting the use experience.
  • the object of the present invention is to propose a odor-free and environmentally friendly polypropylene recycled plastic and a preparation method thereof.
  • the present invention provides a odor-free and environmentally friendly polypropylene recycled plastic.
  • the preparation raw materials include: 90 to 100 parts of polypropylene base material, 0.1 to 1 part of antioxidant, and 1 to 2 toughening agents in parts by weight. 2 to 4 parts of deodorizing aid.
  • the antioxidant includes one or a combination of peroxide decomposing antioxidants, free radical scavenging antioxidants and metal deactivating antioxidants.
  • the peroxide decomposing antioxidant includes: one or a combination of organic molybdenum compounds, organic phosphorus compounds, organic sulfur compounds and alkylthiophosphate compounds;
  • the organophosphorus compounds include phosphite antioxidants, and the phosphite antioxidants include tris[2,4-di-tert-butylphenyl]phosphite, poly(dipropylene glycol)phenyl One or a combination of several of phosphite, dipropylene glycol bisphosphite, pentaerythritol diisodecyl diphosphite, tridecyl phosphite and trilaurate phosphite.
  • the free radical scavenging antioxidant includes one of a phenolic antioxidant or an amine antioxidant, wherein the phenolic antioxidant includes tetrakis[ ⁇ -(3,5-di tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, [3-(3,5-di-tert-butyl-4-hydroxyphenyl)isooctyl acrylate and thiobisphenol type antioxidants One or a combination of several.
  • the antioxidants include tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and tris[2,4-di-tert-butylphenyl]pyridine Phosphate ester, the tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester and the tris[2,4-di-tert-butylphenyl]phosphite
  • the mass ratio is 1:1-1:3, preferably, the mass ratio is 1:1.5.
  • the deodorizing assistant includes a reactive deodorizing assistant and a devolatilizing deodorizing assistant, wherein the mass ratio of the reactive deodorizing assistant and the devolatilizing deodorizing assistant is 1: 3 ⁇ 1:4;
  • the devolatilization type deodorizing additive includes one or a combination of Hefei Innovation LDV 1035T, Hefei Innovation LDV 1040, BYKP4200 and BYK-MAX OR 4207;
  • the reactive deodorizing additives include BIORICHY104W, Evonik Degussa Sorb PY 88, Evonik One or a combination of Degussa Sorb PY 50PP, STRUKTOL RP17 and RP37.
  • the toughening agent includes one or a combination of polyethylene elastomer, polystyrene elastomer and polypropylene elastomer; the melt index of the polypropylene elastomer at 190°C is 3 ⁇ 20g/10min.
  • the invention also provides a method for preparing the odor-free and environmentally friendly polypropylene recycled plastic, which is used to prepare the odor-free and environmentally friendly polypropylene recycled plastic as described above, including:
  • the antioxidant is mixed in the premixer, it is added to the extruder, mixed and extruded to obtain recycled plastic particles;
  • the extruded recycled plastic particles are deodorized in a hot air circulation silo.
  • the extruder is equipped with three sets of vacuum systems, with a vacuum degree of -0.09 ⁇ -0.098MPa.
  • the operating conditions of the hot air circulation silo are: vacuuming and circulating hot air are performed alternately to gradually replace and extract volatile organic compounds.
  • the vacuum degree is -0.07 ⁇ -0.08MPa, and the drying parameters are 80°C ⁇ 120°C. Stay for 2 to 8 hours.
  • the extruder is a multi-screw extruder, and the equipment length-to-diameter ratio is (36 ⁇ 44):1.
  • the temperature control area of the extruder includes four sections, with temperatures of 155 ⁇ 165°C and 175 ⁇ 185°C, 185 ⁇ 195°C, 195 ⁇ 205°C.
  • the odor-free and environmentally friendly polypropylene recycled plastic generateds low-odor recycled polypropylene particles by deodorizing the polypropylene base material, and reprocesses the generated low-odor recycled polypropylene particles.
  • the deodorization treatment in the hot air circulation silo greatly improves the odor removal efficiency, solves the problem of residual odors at all stages, and greatly reduces the volatilization of TVOC.
  • the deodorization effect is good, no side reactions occur, and high efficiency
  • the cost is low, and the prepared odor-free and environmentally friendly polypropylene recycled plastic has a color close to the odor and color level of virgin resin, which expands the application scope of recycled plastics and improves the resource and environmental attributes of end products.
  • the embodiment of the present invention provides a odor-free and environmentally friendly polypropylene recycled plastic.
  • the raw materials for preparation include: 90 to 100 parts by weight of polypropylene base material, 0.1 to 1 part of antioxidant, and 1 to 2 parts of toughening agent. 2 to 4 parts of deodorizing aid.
  • the antioxidants include one or a combination of peroxide decomposition antioxidants, free radical scavenging antioxidants and metal deactivating antioxidants.
  • the peroxide-decomposing antioxidant includes one or a combination of organic molybdenum compounds, organic phosphorus compounds, organic sulfur compounds and alkylthiophosphate compounds.
  • the organophosphorus compounds include phosphite antioxidants, and the phosphite antioxidants include tris[2,4-di-tert-butylphenyl]phosphite, poly(dipropylene glycol)phenyl One or a combination of several of phosphite, dipropylene glycol bisphosphite, pentaerythritol diisodecyl diphosphite, tridecyl phosphite and trilaurate phosphite.
  • the free radical scavenging antioxidant includes one of a phenolic antioxidant or an amine antioxidant, wherein the phenolic antioxidant includes tetrakis[ ⁇ -(3,5-ditert. Butyl-4-hydroxyphenyl)pentaerythritol propionate,
  • the antioxidant includes tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and tris[2,4-di-tert-butyl phenyl]phosphite.
  • the mass ratio of tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and the tris[2,4-di-tert-butylphenyl]phosphite is 1: 1 ⁇ 1:3.
  • the mass ratio of tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and the tris[2,4-di-tert-butylphenyl]phosphite is 1:1.5.
  • regenerated polypropylene is more prone to oxidative degeneration than virgin polypropylene resin during the production and preparation process, causing the regenerated polypropylene to have lower whiteness and yellow color.
  • the use of antioxidants can reduce oxidative degeneration and further The combination of tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and tris[2,4-di-tert-butylphenyl]phosphite is suitable.
  • the weight ratio can better reduce oxidative degeneration during the preparation process of recycled polypropylene and achieve higher whiteness, so that the prepared odor-free and environmentally friendly polypropylene recycled plastic has a color close to the color grade of virgin resin.
  • the deodorizing aids include reactive deodorizing aids and devolatilizing deodorizing aids.
  • the mass ratio of the reactive deodorizing assistant and the devolatilizing deodorizing assistant is 1:3 to 1:4.
  • the devolatilization deodorizing additive is selected from one or a combination of Hefei Innovation LDV 1035T, Hefei Innovation LDV 1040, BYK P4200 and BYK-MAX OR 4207.
  • the reactive deodorizing additive includes one or a combination of BIORICHY104W, Evonik Degussa Sorb PY 88, Evonik Degussa Sorb PY 50PP, STRUKTOL RP17 and RP37.
  • the toughening agent includes one or a combination of polyethylene elastomer, polystyrene elastomer and polypropylene elastomer.
  • the toughening agent is polypropylene elastomer
  • the melt index of the polypropylene elastomer at 190°C is 3 to 20 g/10 min.
  • the embodiment of the present invention also proposes a method for preparing the odor-free and environmentally friendly polypropylene recycled plastic, which is used to prepare the odor-free and environmentally friendly polypropylene recycled plastic as described above, which includes the following steps:
  • antioxidant is mixed in the premixer, it is then added to the extruder through the quantitative feeding control system, and mixed and extruded to obtain recycled plastic particles;
  • step S1 the extruder is equipped with three sets of vacuum systems, and the vacuum degree is -0.09 ⁇ -0.098MPa.
  • step S3 the operating conditions of the hot air circulation silo are: vacuuming and circulating hot air are carried out alternately to gradually replace and extract VOC (volatile organic compounds, volatile organic compounds) substances.
  • the air density is -0.07 ⁇ -0.08MPa
  • the drying parameters are 80°C ⁇ 120°C
  • the stay is 2 ⁇ 8h.
  • step S3 heating the polypropylene plastic particles to 80°C, circulating hot air to exchange air, and reacting for 3 hours can greatly increase the odor volatilization of the recycled polypropylene.
  • Volatile organic compounds in recycled polypropylene can dissociate from the polypropylene matrix at high temperatures above 80°C and volatilize quickly. Then through vacuuming and hot air circulation, most of the volatile components can be dissociated and volatilized. Remove and reduce the generation of odor from the source; and synergize with devolatilization additives to further improve the odor purification effect.
  • Reactive deodorizing additives and devolatilizing deodorizing additives work synergistically.
  • the reactive deodorizing additives react with VOC under high temperature to eliminate odors.
  • the water and VOC in the devolatilizing deodorizing additive are dissolved in the melt.
  • a large number of microbubbles are formed in the extruder to extract each other.
  • the bubbles mainly containing water also carry a certain amount of VOC. Then these microbubbles are extracted under the action of the vacuum negative pressure of the extruder, thereby purifying the odor.
  • the extruder is a multi-screw extruder, and the equipment length-to-diameter ratio is (36 ⁇ 44):1.
  • the temperature control area of the above-mentioned extruder includes four sections, with temperatures of 155 ⁇ 165°C and 175 ⁇ 185°C, 185 ⁇ 195°C and 195 ⁇ 205°C.
  • three sets of performance tests are also set for four groups of samples obtained by the preparation method provided by the invention. Unless otherwise specified, the raw materials used in the four groups of samples are all commercially available.
  • the preparation raw materials include, in parts by weight: 96 parts of polypropylene base material, 0.5 parts of antioxidant, 1.5 parts of toughening agent, and 3 parts of deodorizing additive.
  • the polypropylene substrate was purchased from Shanghai Ruiju Environmental Protection Technology Co., Ltd.
  • the antioxidant is a combination of tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol and tris[2,4-di-tert-butylphenyl]phosphite. , the weight ratio of the two is 1:1.5.
  • the deodorizing aid is a combination of a reactive deodorizing aid and a devolatilizing deodorizing aid, with a weight ratio of 1:3.6.
  • the devolatilization type deodorizing additive is Hefei Innovation LDV 1035T, purchased from Hefei Innovation Light Materials Co., Ltd.; the reaction type deodorizing additive is Evonik Degussa Sorb PY 88, purchased from Degussa, Germany.
  • the toughening agent is a polyolefin elastomer with a melt index of 33g/10min at 190°C. It is purchased from LG Chemical in South Korea with the brand name LC875.
  • the preparation method includes the following steps:
  • antioxidant is mixed in the premixer, it is then added to the extruder through the quantitative feeding control system, and mixed and extruded to obtain recycled plastic particles;
  • the extruder is equipped with three sets of vacuum systems, with a vacuum degree of -0.09MPa.
  • the operating conditions of the hot air circulation silo are: vacuuming and circulating hot air are carried out alternately, gradually replacing and extracting VOC substances, the vacuum degree is -0.07MPa, the drying parameter is 80°C, and the stay is 3 hours.
  • the extruder is a multi-screw extruder with an equipment length-to-diameter ratio of 40:1.
  • the temperature control area of the extruder includes four sections, with temperatures of 160°C, 180°C, 190°C, and 200°C.
  • Odor level test According to the Volkswagen standard PV-3900-2000-Automotive parts odor test, the odor level of the generated net-odor polypropylene recycled plastic is tested. The levels are divided into levels 1 to 6, with level 1 being the best and level 6 being the worst. Difference.
  • VOC release amount According to the Volkswagen standard PV3341 emission measurement of organic compounds of non-metallic materials in automobile interiors, the TVOC release amount of the generated clean-odor polypropylene recycled plastic was tested.
  • Yellow index According to the GB2409-1980 standard, the yellow index of the generated net-odor polypropylene recycled plastic is tested. The yellow index measured by this method, if it is a positive value, the material is yellow. The larger the value, the darker the color.
  • the preparation method of odor-free and environmentally friendly polypropylene recycled plastic provided in the solution of the present invention is adopted.
  • the odor and various volatile and semi-volatile substances in the processed and obtained recycled polypropylene plastics have been significantly reduced.
  • the obtained recycled polypropylene plastics can reach a higher whiteness, and the color is close to the color grade of the original resin; the overall recycling process
  • the process is simple, no side reactions occur, does not cause environmental pollution, is efficient and low-cost, expands the application scope of recycled plastics, and improves the resource and environmental attributes of end products.

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Abstract

一种净味环保聚丙烯再生塑料，制备原料以重量份计包括：聚丙烯基材90-100份，抗氧剂0.1-1份，增韧剂1-2份，除味助剂2-4份。通过对聚丙烯基材破碎料和再生聚丙烯颗粒进行除味处理，减少了各个阶段异味的生成，极大的降低了TVOC的挥发量，并且通过采用反应型除味助剂和脱挥型除味助剂的组合，极大的提升了气味的脱除效率，生成的聚丙烯再生塑料，气味色度接近原生树脂的气味色度等级，扩大了再生塑料的应用范围，提升终端产品的资源环境属性。

Description

一种净味环保聚丙烯再生塑料及其制备方法
相关申请的交叉引用
本申请要求于2022年07月13日申请的，申请号为202210828449.1，名称为“一种净味环保聚丙烯再生塑料及其制备方法”的中国专利申请的优先权。
技术领域
本发明涉及再生塑料技术领域，特别是涉及一种净味环保聚丙烯再生塑料及其制备方法。
背景技术
塑料材料在环境中难以自然降解，通过对塑料材料进行回收制备再生塑料可以极大地缓解环境污染，节约资源保护环境。但是再生塑料尤其是再生聚丙烯的气味非常明显，会严重影响人们对再生塑料的使用感受，限制了再生塑料的使用范围。制造再生塑料的各个阶段都会引起气味的产生，包括回收处理，聚合成型等阶段。
中国发明专利CN201611105231.4公开了一种用于汽车内外饰的低气味再生聚丙烯复合材料，通过聚丙烯与增强剂，除味剂复配，降低了再生聚丙烯的气味使再生聚丙烯材料可以应用于汽车内外饰，但是只在成品步骤进行除味，没有涉及再生聚丙烯的除味，再生聚丙烯的使用占比不高。
中国发明专利CN201911288711.2公开了一种长玻纤增强聚丙烯复合材料，通过加入长玻纤增强聚丙烯材料的力学强度，加入香精改善材料产生的异味，但是异味并没有消除，在后期的使用中还是会释放出来，影响使用感受。
发明内容
本发明的目的在于，提出一种净味环保聚丙烯再生塑料及其制备方法，通 过对聚丙烯基材进行除味处理生成低异味的再生聚丙烯颗粒以及对再生聚丙烯颗粒进行高温除味处理，解决聚丙烯再生塑料各个阶段异味处理问题。
为了达到上述目的，本发明提供了一种净味环保聚丙烯再生塑料，制备原料以重量份计包括：聚丙烯基材90～100份，抗氧剂0.1～1份，增韧剂1～2份，除味助剂2～4份。
可选的，所述抗氧剂包括过氧化物分解型抗氧剂、自由基清除型抗氧剂和金属减活型抗氧剂中的一种或几种的组合。
可选的，所述过氧化物分解型抗氧剂包括：有机钼化合物、有机磷化合物、有机硫类化合物和烷基硫代磷酸类化合物中的一种或几种的组合；
其中，所述有机磷化合物包括亚磷酸酯类抗氧剂，所述亚磷酸酯类抗氧剂包括三[2,4-二叔丁基苯基]亚磷酸酯、聚(二丙二醇)苯基亚磷酸酯、一缩二丙二醇双亚磷酸酯、二亚磷酸季戊四醇二异癸酯、亚磷酸三癸酯和亚磷酸三月桂酸酯中的一种或几种的组合。
可选的，所述自由基清除型抗氧剂包括酚型抗氧剂或胺型抗氧剂中的一种，其中，所述酚型抗氧剂包括四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、[3-(3,5-二叔丁基-4-羟基苯基)丙烯酸异辛酯和硫代双酚型抗氧剂中的一种或几种的组合。
可选的，所述抗氧剂包括四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯，所述四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和所述三[2,4-二叔丁基苯基]亚磷酸酯的质量比为1：1～1：3，优选的，质量比为1：1.5。
可选的，所述除味助剂包括反应型除味助剂和脱挥型除味助剂，其中，所述反应型除味助剂和脱挥型除味助剂的质量比为1：3～1：4；
其中，所述脱挥型除味助剂包括合肥创新LDV 1035T、合肥创新LDV 1040、BYKP4200和BYK-MAX OR 4207中的一种或几种的组合；
所述反应型除味助剂包括BIORICHY104W、赢创德固赛Sorb PY 88、赢创 德固赛Sorb PY 50PP、STRUKTOL RP17和RP37中的一种或几种的组合。
可选的，所述增韧剂包括聚乙烯弹性体、聚苯乙烯弹性体以及聚丙烯弹性体中的一种或几种的组合；所述聚丙烯弹性体在190℃的熔融指数为3～20g/10min。
本发明还提供了一种净味环保聚丙烯再生塑料的制备方法，用以制备如上所述的净味环保聚丙烯再生塑料，包括：
将配方中的聚丙烯基材、增韧剂和除味助剂，在预混机中混合后，加入挤出机；
将抗氧剂经过预混机混合后，加入挤出机中，混合挤出得到再生塑料颗粒；
将挤出后的再生塑料颗粒在热风循环料仓中进行除味处理。
可选的，所述挤出机配备三组抽真空系统，真空度为-0.09～-0.098MPa。
可选的，所述热风循环料仓的运行条件为：抽真空和循环热风交替进行，逐步置换抽提挥发性有机物，真空度为-0.07～-0.08MPa，干燥参数为80℃～120℃，停留2～8h。
可选的，所述挤出机为多螺杆挤出机，设备长径比为(36～44)：1，挤出机的温控区域包括四段，温度分别为155～165℃、175～185℃、185～195℃、195～205℃。
与现有技术相比，本发明提供的净味环保聚丙烯再生塑料，通过对聚丙烯基材进行除味处理生成低异味的再生聚丙烯颗粒，并对生成的低异味的再生聚丙烯颗粒再次在热风循环料仓中进行除味处理，极大地提升了气味的脱除效率，解决了各个阶段异味的残留，极大降低了TVOC的挥发量，除味效果好，无副反应的发生，高效且成本低，而且制备得到的净味环保聚丙烯再生塑料，色度接近原生树脂的气味色度等级，扩大了再生塑料的应用范围，提升终端产品的资源环境属性。
具体实施方式
下面将对本发明进行更详细的描述，其中表示了本发明的优选实施例，应 该理解本领域技术人员可以修改在此描述的本发明，而仍然实现本发明的有利效果。因此，下列描述应当被理解为对于本领域技术人员的广泛知道，而并不作为对本发明的限制。
在下列段落中以举例方式更具体地描述本发明。根据下面说明，本发明的优点和特征将更清楚。
本发明实施例中提供了一种净味环保聚丙烯再生塑料，制备原料以重量份计包括：聚丙烯基材90～100份，抗氧剂0.1～1份，增韧剂1～2份，除味助剂2～4份。
所述抗氧剂包括过氧化物分解型抗氧剂、自由基清除型抗氧剂和金属减活型抗氧剂中的一种或几种的组合。
优选的，所述过氧化物分解型抗氧剂包括：有机钼化合物、有机磷化合物、有机硫类化合物和烷基硫代磷酸类化合物中的一种或几种的组合。
其中，所述有机磷化合物包括亚磷酸酯类抗氧剂，所述亚磷酸酯类抗氧剂包括三[2,4-二叔丁基苯基]亚磷酸酯、聚(二丙二醇)苯基亚磷酸酯、一缩二丙二醇双亚磷酸酯、二亚磷酸季戊四醇二异癸酯、亚磷酸三癸酯和亚磷酸三月桂酸酯中的一种或几种的组合。
优选的，所述自由基清除型抗氧剂包括酚型抗氧剂或胺型抗氧剂中的一种，其中，所述酚型抗氧剂包括四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、
[3-(3,5-二叔丁基-4-羟基苯基)丙烯酸异辛酯和硫代双酚型抗氧剂中的一种或几种的组合。
在一些实施例中，优选的，所述抗氧剂包括四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯。
四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和所述三[2,4-二叔丁基苯基]亚磷酸酯的质量比为1：1～1：3。
进一步的，四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和所述三[2,4-二叔丁基苯基]亚磷酸酯的质量比为1：1.5。
申请人在实验过程中发现，再生聚丙烯在生产制备过程中比原生聚丙烯树脂更容易发生氧化变性，使再生聚丙烯的白度较低，颜色发黄，采用抗氧化剂可以减少氧化变性，进一步的，采用四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯的组合，配合适宜的重量比可以更好地减少再生聚丙烯制备过程中的氧化变性，达到较高的白度，使得制备得到的净味环保聚丙烯再生塑料，色度接近原生树脂的色度等级。
进一步的，所述除味助剂包括反应型除味助剂和脱挥型除味助剂。
其中，所述反应型除味助剂和脱挥型除味助剂的质量比为1：3～1：4。
所述脱挥型除味助剂选自合肥创新LDV 1035T、合肥创新LDV 1040、BYK P4200和BYK-MAX OR 4207中的一种或几种的组合。
所述反应型除味助剂包括BIORICHY104W、赢创德固赛Sorb PY 88、赢创德固赛Sorb PY 50PP、STRUKTOL RP17和RP37中的一种或几种的组合。
进一步的，所述增韧剂包括聚乙烯弹性体、聚苯乙烯弹性体以及聚丙烯弹性体中的一种或几种的组合。
优选的，所述增韧剂为聚丙烯弹性体，所述聚丙烯弹性体在190℃的熔融指数为3～20g/10min。
本发明实施例还提出了一种净味环保聚丙烯再生塑料的制备方法，用以制备如上所述的净味环保聚丙烯再生塑料，包括以下步骤：
S1、将上述配方中的聚丙烯基材，增韧剂和除味助剂，在预混机中混合，然后通过挤出机的主喂料斗加入挤出机；
S2、将抗氧剂经过预混机混合后，再通过定量喂料控制系统，加入挤出机中，混合挤出得再生塑料颗粒；
S3、将挤出后的再生塑料颗粒再次在热风循环料仓中进行除味处理。
在步骤S1中，所述挤出机配备三组抽真空系统，真空度为-0.09～-0.098MPa。
在步骤S3中，所述热风循环料仓的运行条件为：抽真空和循环热风交替进行，逐步置换抽提VOC(volatile organic compounds，挥发性有机物)物质，真 空度为-0.07～-0.08MPa，干燥参数为80℃～120℃，停留2～8h。
申请人在实验过程中发现，在聚丙烯的再生过程中，处理的回收聚丙烯具有较大的味道，在再生聚丙烯制备完成后还具有较高的异味，因此需要在多个步骤对聚丙烯进行除味，才能最终达到净味环保的效果。
进一步的，申请人发现：在步骤S3中，将聚丙烯塑料颗粒升温至80℃，热风循环交换空气，反应3h，可以很大程度上增加再生聚丙烯的异味挥发。
原因是：再生聚丙烯中的挥发性有机物在80℃以上的高温状态下可以与聚丙烯基体解离，快速挥发出来，再通过抽真空和热风循环，可以将大多数的挥发性成分解离挥发除去，从源头降低异味的产生；并且与脱挥型助剂协同作用，能够进一步提高净味的效果。
反应型除味助剂和脱挥型除味助剂协同作用，反应型除味助剂与VOC在高温作用下发生化学反应消除气味，脱挥型除味助剂中的水和VOC在熔体里形成大量的微气泡，相互萃取，以水为主的气泡也裹携了一定量的VOC，然后这些微气泡在挤出机真空负压的作用下被抽离，从而实现对气味的净化。
进一步的，所述挤出机为多螺杆挤出机，设备长径比为(36～44)：1，上述挤出机的温控区域包括四段，温度分别为155～165℃、175～185℃、185～195℃以及195～205℃。
本发明实施例中还对采用本发明所提供的制备方法得到的四组样品设置了三组性能测试，其中四组样品中除特别说明外，所用原料皆为市售得到的。
实验例一
制备原料以重量份计包括：聚丙烯基材96份，抗氧剂0.5份，增韧剂1.5份，除味助剂3份。
所述聚丙烯基材购自上海睿聚环保科技有限公司。
所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯的组合，两者的重量比为1：1.5。
所述除味助剂为反应型除味助剂和脱挥型除味助剂的组合，重量比为1：3.6。所述脱挥型除味助剂为合肥创新LDV 1035T，购自合肥创新轻质材料有限公司；所述反应型除味助剂为赢创德固赛Sorb PY 88，购自德国德固赛。
所述增韧剂为聚烯烃弹性体，在190℃的熔融指数为33g/10min，购自韩国LG化学，牌号为LC875。
制备方法包括以下步骤：
(1)将配方中的聚丙烯基材，增韧剂和除味助剂，在预混机中混合，然后通过挤出机的主喂料斗加入挤出机；
(2)将抗氧剂经过预混机混合后，再通过定量喂料控制系统，加入挤出机中，混合挤出得再生塑料颗粒；
(3)将挤出后的再生塑料颗粒再次在热风循环料仓中进行除味处理。
所述挤出机配备三组抽真空系统，真空度为-0.09MPa。
所述热风循环料仓的运行条件为：抽真空和循环热风交替进行，逐步置换抽提VOC物质，真空度为-0.07MPa，干燥参数为80℃，停留3h。
所述挤出机为多螺杆挤出机，设备长径比为40：1，挤出机的温控区域包括四段，温度分别为160℃、180℃、190℃、200℃。
对比例一
对比例一中的净味环保聚丙烯再生塑料及其制备方法，具体步骤同实验例一，不同点在于对比例一所采用的抗氧剂仅为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯。
对比例二
对比例二中的净味环保聚丙烯再生塑料及其制备方法，具体步骤同实验例一，不同点在于对比例二中的除味助剂仅为脱挥型除味助剂。
对比例三
对比例三中的净味环保聚丙烯再生塑料及其制备方法，具体步骤同实验例 一，不同点在于对比例三中所采用的增韧剂为聚烯烃弹性体，在190℃的熔融指数仅为13g/10min，购自美国陶氏，型号为ENGAGE TM 8137。
分别将四组样品进行如下三组性能测试：
1、气味等级测试：依据大众汽车标准PV-3900-2000-汽车部件气味检验，测试生成的净味聚丙烯再生塑料的气味等级，等级划分为1～6级，1级最佳，6级最差。
2、VOC释放量：依据大众汽车标准PV3341汽车内饰的非金属材料有机化合物的排放测定，测试生成的净味聚丙烯再生塑料的TVOC的释放量。
3、黄色指数：依据GB2409-1980标准，测试生成的净味聚丙烯再生塑料的黄色指数，本方法所测得的黄色指数，如是正值表示材料呈黄色，数值越大颜色越深。
测试结果见表1：
四组测试表明：实验例一中采用反应型除味助剂和脱挥型除味助剂的组合，采用的聚烯烃弹性体在190℃的熔融指数为33g/10min，并且选用了两种抗氧化剂的组合，由此制得的实验例一中的样品的气味，总挥发性有机化合物释放量以及黄色指数三方面的数据都较好，而且达到了聚丙烯再生塑料的回收再利用标准；而对比例一中只选用了一种抗氧化剂，抗氧化效果不佳；对比例二中除味助剂仅为脱挥型除味助剂，因此气味等级和挥发性有机化合物释放量对比实验例一都较差；对比例三中所选用的聚烯烃弹性体，在190℃的熔融指数为13g/10min，样品在样品气味，挥发性有机化合物释放量以及黄色指数三方面的表现比较稳定。
综上所述，采用本发明方案中提供的净味环保聚丙烯再生塑料的制备方法 处理并得到的聚丙烯再生塑料中气味、各种挥发和半挥发物质均有大幅下降，得到的聚丙烯再生塑料可以达到较高的白度，色度接近原生树脂的色度等级；整体回收处理流程简单，无副反应的发生，不会造成环境污染，高效且成本低，扩大了再生塑料的应用范围，提升终端产品的资源环境属性。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (11)

  1. 一种净味环保聚丙烯再生塑料，其特征在于，制备原料以重量份计包括：聚丙烯基材90～100份，抗氧剂0.1～1份，增韧剂1～2份，除味助剂2～4份。
  2. 根据权利要求1所述净味环保聚丙烯再生塑料，其特征在于，所述抗氧剂包括过氧化物分解型抗氧剂、自由基清除型抗氧剂和金属减活型抗氧剂中的一种或几种的组合。
  3. 根据权利要求2所述净味环保聚丙烯再生塑料，其特征在于，所述过氧化物分解型抗氧剂包括：有机钼化合物、有机磷化合物、有机硫类化合物和烷基硫代磷酸类化合物中的一种或几种的组合；
    其中，所述有机磷化合物包括亚磷酸酯类抗氧剂，所述亚磷酸酯类抗氧剂包括三[2,4-二叔丁基苯基]亚磷酸酯、聚(二丙二醇)苯基亚磷酸酯、一缩二丙二醇双亚磷酸酯、二亚磷酸季戊四醇二异癸酯、亚磷酸三癸酯和亚磷酸三月桂酸酯中的一种或几种的组合。
  4. 根据权利要求2所述净味环保聚丙烯再生塑料，其特征在于，所述自由基清除型抗氧剂包括酚型抗氧剂或胺型抗氧剂中的一种，其中，所述酚型抗氧剂包括四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、[3-(3,5-二叔丁基-4-羟基苯基)丙烯酸异辛酯和硫代双酚型抗氧剂中的一种或几种的组合。
  5. 根据权利要求2所述净味环保聚丙烯再生塑料，其特征在于，所述抗氧剂包括四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯，所述四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和所述三[2,4-二叔丁基苯基]亚磷酸酯的质量比为1：1～1：3，优选的，质量比为1：1.5。
  6. 根据权利要求1所述净味环保聚丙烯再生塑料，其特征在于，所述除味助剂包括反应型除味助剂和脱挥型除味助剂，其中，所述反应型除味助剂和脱挥型除味助剂的质量比为1：3～1：4；
    其中，所述脱挥型除味助剂包括合肥创新LDV 1035T、合肥创新LDV 1040、BYK P4200和BYK-MAX OR 4207中的一种或几种的组合；
    所述反应型除味助剂包括BIORICHY104W、赢创德固赛Sorb PY 88、赢创德固赛Sorb PY 50PP、STRUKTOL RP17和RP37中的一种或几种的组合。
  7. 根据权利要求1所述净味环保聚丙烯再生塑料，其特征在于，所述增韧剂包括聚乙烯弹性体、聚苯乙烯弹性体以及聚丙烯弹性体中的一种或几种的组合；所述聚丙烯弹性体在190℃的熔融指数为3～20g/10min。
  8. 一种净味环保聚丙烯再生塑料的制备方法，用以制备权利要求1-7中任意一项所述的净味环保聚丙烯再生塑料，其特征在于，包括：
    将配方中的聚丙烯基材、增韧剂和除味助剂，在预混机中混合后，加入挤出机；
    将抗氧剂经过预混机混合后，加入挤出机中，混合挤出得到再生塑料颗粒；
    将挤出后的再生塑料颗粒在热风循环料仓中进行除味处理。
  9. 根据权利要求8所述净味环保聚丙烯再生塑料的制备方法，其特征在于，所述挤出机配备三组抽真空系统，真空度为-0.09～-0.098MPa。
  10. 根据权利要求8所述净味环保聚丙烯再生塑料的制备方法，其特征在于，所述热风循环料仓的运行条件为：抽真空和循环热风交替进行，逐步置换抽提挥发性有机物，真空度为-0.07～-0.08MPa，干燥参数为80℃～120℃，停留2～8h。
  11. 根据权利要求8所述净味环保聚丙烯再生塑料的制备方法，其特征在于，所述挤出机为多螺杆挤出机，设备长径比为(36～44)：1，挤出机的温控区域包括四段，温度分别为155～165℃、175～185℃、185～195℃、195～205℃。
PCT/CN2023/106900 2022-07-13 2023-07-12 净味环保聚丙烯再生塑料及其制备方法 WO2024012475A1 (zh)

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