WO2022134122A1 - Procédé de préparation d'un stabilisant thermique de pvc polymère - Google Patents

Procédé de préparation d'un stabilisant thermique de pvc polymère Download PDF

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Publication number
WO2022134122A1
WO2022134122A1 PCT/CN2020/139766 CN2020139766W WO2022134122A1 WO 2022134122 A1 WO2022134122 A1 WO 2022134122A1 CN 2020139766 W CN2020139766 W CN 2020139766W WO 2022134122 A1 WO2022134122 A1 WO 2022134122A1
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Prior art keywords
heat stabilizer
parts
polymer
preparation
reaction
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PCT/CN2020/139766
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English (en)
Chinese (zh)
Inventor
王金明
王琪宇
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王金明
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Priority to PCT/CN2020/139766 priority Critical patent/WO2022134122A1/fr
Publication of WO2022134122A1 publication Critical patent/WO2022134122A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention is in the field of preparation of plastic auxiliary agents, in particular to a preparation method of a polymer-type PVC heat stabilizer.
  • CN103450597B discloses an auxiliary heat stabilizer for PVC processing, which is a system in which organic carboxylic acid is used as a catalyst, and calcium oxide, zinc oxide and glycerin are added to react, and the obtained metal-organic complex is the stabilizer.
  • the specific reaction steps are as follows: take Equimolar calcium oxide, zinc oxide, and glycerin were heated to 180°C for 200 minutes in an organic carboxylic acid environment. When the reaction system became colorless and transparent, the temperature was lowered to 120°C, and the total addition amount was added dropwise at a rate of 1 ml per second.
  • 6-amino-2-mercapto-pyrimidin-4-ol in an equimolar amount with glycerol was added dropwise and kept at 80° C. for 60 minutes, filtered, dried and pulverized to obtain a stabilizer.
  • the invention combines the zinc components that improve the initial effect of thermal stability of PVC processing and the calcium components that inhibit "zinc burning", which not only solves the defect of the stabilizer with poor initial stability, but also can be used as a stabilizer alone Use directly.
  • CN104861393A discloses a composite heat stabilizer for PVC.
  • the composite heat stabilizer for PVC comprises: (1) aromatic 1,3,4 oxadiazole derivative or aromatic 1,3,4 oxadiazole derivative complex; (2) Ca/Zn heat stabilizer. Since it uses aromatic 1,3,4 oxadiazole derivatives or their complexes as the main stabilizer, it does not contain any heavy metals at all, is non-toxic and environmentally friendly, and can be widely used in food, medical and health care with high safety requirements. and toy products.
  • CN103540048A discloses a PVC thermal stabilizer with a long thermal stability time, which is used in PVC products requiring thermal stability time and excellent discoloration resistance.
  • the invention is modified with hydrotalcite, hydroxide and zeolite as the main body, and a special antioxidant is added. Solved the current thermal stability time is not long enough, and the phenomenon of poor discoloration. Using this product not only has excellent performance, but also is environmentally friendly, which has won the competitiveness of Chinese enterprises in the European and American markets.
  • the present invention provides a preparation method of a polymer-type PVC heat stabilizer.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • the imidazole hydrogen sulfate and 100-200 parts of N,N-dimethylformamide are mixed evenly, and the temperature is controlled at -5-5°C and stirred for 30-60min; the addition is completed at 20-60min, and then the temperature is raised to room temperature, The reaction is stirred for 10-18h, the material is precipitated in water after the reaction is completed, the filtrate is washed with ethanol after filtration, and the polymer-type PVC heat stabilizer can be obtained after drying.
  • the equation of the partial reaction is shown as:
  • Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
  • silica gel powder is activated at 300-400 ° C for 30-120 min, cooled to room temperature, and then added to 14-20 parts by mass of 5.4%-7.5% pentachloride Molybdenum aqueous solution, stirred at room temperature for 5-20h, filtered, dried at 80-120°C, put into a muffle furnace at 450-600°C for 3-6h calcination, cooled to room temperature after completion, and dispersed to 60-80 parts of In pure water, 0.5-3 parts of zirconium tetrachloride and 5-10 parts of ethanol are mixed uniformly and then slowly added to the reaction kettle, and the addition is controlled within 30-50 minutes, and then stirred and reacted for 1-5 hours and filtered. After washing with water and drying under vacuum at 100-120 DEG C, the metal-supported solid acid auxiliary can be obtained.
  • the particle size of the silica gel powder is 500-800 mesh.
  • the ethanol is absolute ethanol.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5-2:1.
  • the reducing agent is sodium thiosulfate or sodium sulfite or sodium bisulfite.
  • the ultrasonic dispersion power is 1-5kW.
  • the polystyrene is firstly nitrated, and then the small molecular heat stabilizer is grafted onto the polystyrene molecular chain after reduction, which can effectively improve the compatibility between the organic heat stabilizer and the polyvinyl chloride, thereby improving the organic heat stabilizer.
  • the action efficiency of the stabilizer thereby improving the thermal stability performance of the organic thermal stabilizer.
  • a nitration reaction assistant is used, which can significantly improve the nitration rate of polystyrene, provide more grafting reaction sites, improve the graft rate of small molecular heat stabilizers, and obtain polymer PVC with better stabilization effect.
  • Heat stabilizers The thermal stability of the PVC of the invention does not contain heavy metal ions at all, and at the same time, it has good compatibility with the PVC resin. A very good PVC heat stabilizer.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
  • the particle size of the silica gel powder is 500 meshes.
  • the ethanol is absolute ethanol.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
  • the reducing agent is sodium thiosulfate.
  • the ultrasonic dispersion power is 1kW.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • Polystyrene was added to 650kg N,N-dimethylformamide, and then slowly added to the reaction kettle after stirring and mixing; 14kg of ammonium thiocyanate, 16.3kg of 1-carboxyethyl-3 -Methylimidazole hydrogen sulfate and 150kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled and stirred at 0°C for 40min; the addition was completed in 40min, then the temperature was raised to room temperature, and the reaction was stirred for 14h. After the reaction was completed, the material was placed in Precipitate in water, wash the filtrate with ethanol after filtration, and obtain the polymer-type PVC heat stabilizer after drying.
  • Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
  • the particle size of the silica gel powder is 600 meshes.
  • the ethanol is absolute ethanol.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.8:1.
  • the reducing agent is sodium sulfite.
  • the ultrasonic dispersion power is 3kW.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • Styrene was added to 800kg of N,N-dimethylformamide, and then slowly added to the reaction kettle after stirring and mixing; 16kg of ammonium thiocyanate, 20.3kg of 1-carboxyethyl-3- Methylimidazole hydrogen sulfate and 200kg N,N-dimethylformamide were mixed uniformly, and the temperature was controlled and stirred at 5°C for 60min; the addition was completed at 60min, then the temperature was raised to room temperature, and the reaction was stirred for 18h. After the reaction was completed, the material was placed in water After precipitation, the filtrate is washed with ethanol after filtration, and the polymer-type PVC heat stabilizer can be obtained after drying.
  • Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
  • the particle size of the silica gel powder is 800 meshes.
  • the ethanol is absolute ethanol.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 2:1.
  • the reducing agent is sodium bisulfite.
  • the ultrasonic dispersion power is 5kW.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
  • the reducing agent is sodium thiosulfate.
  • the ultrasonic dispersion power is 1kW.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
  • silica gel powder 10kg was activated at 300°C for 30min, cooled to room temperature, then added to 14kg of molybdenum pentachloride aqueous solution with a mass fraction of 5.4%, stirred at room temperature for 5h, filtered, dried at 80°C and put into 450°C.
  • the metal-supported solid acid auxiliary can be obtained by calcining in a muffle furnace at °C for 3-6 hours.
  • the particle size of the silica gel powder is 500 meshes.
  • the ethanol is absolute ethanol.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
  • the reducing agent is sodium thiosulfate.
  • the ultrasonic dispersion power is 1kW.
  • a kind of preparation method of polymer type PVC heat stabilizer, its concrete scheme is as follows:
  • Described nitration reaction assistant is a kind of metal-loaded solid acid assistant, and its preparation method is:
  • the particle size of the silica gel powder is 500 meshes.
  • the ethanol is absolute ethanol.
  • the volume ratio of concentrated sulfuric acid and concentrated nitric acid is 1.5:1.
  • the reducing agent is sodium thiosulfate.
  • the ultrasonic dispersion power is 1kW.
  • the stability effect test adopts the Congo red method: mix 5g of PVC dry powder and 0.1g of stabilizer evenly, pour it into a test tube, and then immerse the test tube in an oil bath at 180°C for heating. The upper surface of the sample is flush with the upper surface of the oil bath. At the same time, place a Congo red test paper above the sample, and the bottom end of the Congo red test paper is 2.5 cm from the upper surface of the sample.
  • the time when the sample is immersed in the oil bath until the Congo red test paper above turns blue is the thermal stabilization time of the sample; each sample is measured twice, and the average value is the stabilization time, accurate to half a minute.
  • the grafting rate of polystyrene material is calculated according to the weight gain rate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Procédé de préparation d'un stabilisant thermique de polychlorure de vinyle (PVC) polymère, consistant : d'abord, à réaliser la nitration du polystyrène, et à mettre en œuvre puis à greffer un stabilisant thermique à petite molécule sur une chaîne moléculaire de polystyrène. Le procédé peut améliorer efficacement la compatibilité d'un stabilisant thermique organique et de PVC, de telle sorte que l'efficacité d'action du stabilisant thermique organique est améliorée, ce qui permet d'améliorer la stabilité thermique du stabilisant thermique organique. Grâce à l'utilisation d'un promoteur de réaction de nitration, le taux de nitrification du polystyrène peut être remarquablement amélioré, et davantage de sites de réaction de greffage peuvent être obtenus, ce qui permet d'améliorer le taux de greffage du stabilisant thermique à petites molécules et d'obtenir un stabilisant thermique de PVC polymère ayant une meilleure stabilité thermique. Le stabilisant thermique de PVC ne contient pas d'ion de métal lourd, présente une bonne compatibilité avec une résine PVC, a un pouvoir lubrifiant sans affecter les propriétés rhéologiques d'un mélange, et n'affecte pas la plastification du PVC, et par conséquent est un excellent stabilisant thermique de PVC.
PCT/CN2020/139766 2020-12-26 2020-12-26 Procédé de préparation d'un stabilisant thermique de pvc polymère WO2022134122A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116789505A (zh) * 2023-03-29 2023-09-22 万载县建坤化工有限公司 一种烟花爆竹用颜色药剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1463792A (zh) * 2002-06-03 2003-12-31 北京石油化工学院材料与化工学院 一种新型的磷化钼加氢脱硫脱氮降烯烃催化剂及其制备方法
CN101857579A (zh) * 2010-06-10 2010-10-13 浙江工业大学 一种2-氨基-5,6-二氯苯并噻唑的合成方法
KR20160080555A (ko) * 2014-12-30 2016-07-08 주식회사 케이씨텍 연마 슬러리 조성물
CN105885043A (zh) * 2016-05-04 2016-08-24 江汉大学 具有核壳结构的聚苯胺纳米微球的制备方法
CN106589201A (zh) * 2015-10-15 2017-04-26 中国科学院过程工程研究所 一种聚苯乙烯类材料的亲水改性方法及其产品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1463792A (zh) * 2002-06-03 2003-12-31 北京石油化工学院材料与化工学院 一种新型的磷化钼加氢脱硫脱氮降烯烃催化剂及其制备方法
CN101857579A (zh) * 2010-06-10 2010-10-13 浙江工业大学 一种2-氨基-5,6-二氯苯并噻唑的合成方法
KR20160080555A (ko) * 2014-12-30 2016-07-08 주식회사 케이씨텍 연마 슬러리 조성물
CN106589201A (zh) * 2015-10-15 2017-04-26 中国科学院过程工程研究所 一种聚苯乙烯类材料的亲水改性方法及其产品
CN105885043A (zh) * 2016-05-04 2016-08-24 江汉大学 具有核壳结构的聚苯胺纳米微球的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LV CHAN-TING, ZHENG YU-BIN, LIU JIAN-PING: "Synthesis of a Novel Polymeric Organic Thermal Stabilizer for PVC", CHINESE JOURNAL OF SYNTHETIC CHEMISTRY, vol. 15, no. 6, 20 December 2007 (2007-12-20), CN , pages 768 - 770, XP055946633, ISSN: 1005-1511 *
LV DONG-WEI,XIAO LIN-FEI,SU DAN,LIU DAN,WU WEI(: "Immobilized BrФnsted ionic liquids:Heterogeneous catalyst for synthesis of cyclic carbonates from carbon dioxide and epoxides", MODERN CHEMICAL INDUSTRY, vol. 31, no. S1, 30 June 2011 (2011-06-30), pages 271 - 274+276, XP009537750, ISSN: 0253-4320, DOI: 10.16606/j.cnki.issn0253-4320.2011.s1.080 *
WU JINMING,TANG YANFENG,SHEN AIBAO: "Synthesis of 5-Nitrosalicylaldehyde Catalyzed by H6PMo9V3O40 Supported on Silica Gel", CHINESE JOURNAL OF APPLIED CHEMISTRY, vol. 29, no. 5, 10 May 2012 (2012-05-10), pages 545 - 550, XP055946634, ISSN: 1000-0518, DOI: 10.3724/SP.J.1095.2012.00263 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116789505A (zh) * 2023-03-29 2023-09-22 万载县建坤化工有限公司 一种烟花爆竹用颜色药剂及其制备方法

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