[go: up one dir, main page]

WO2018130117A1 - Composite de polypropylène photochromique, son procédé de préparation et ses applications - Google Patents

Composite de polypropylène photochromique, son procédé de préparation et ses applications Download PDF

Info

Publication number
WO2018130117A1
WO2018130117A1 PCT/CN2018/071537 CN2018071537W WO2018130117A1 WO 2018130117 A1 WO2018130117 A1 WO 2018130117A1 CN 2018071537 W CN2018071537 W CN 2018071537W WO 2018130117 A1 WO2018130117 A1 WO 2018130117A1
Authority
WO
WIPO (PCT)
Prior art keywords
changing
photosensitive color
microcapsule
polypropylene composition
melamine
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2018/071537
Other languages
English (en)
Chinese (zh)
Inventor
雷亮
王大中
苏娟霞
林荣涛
孙刚
吴国峰
杨波
罗忠富
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Original Assignee
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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 Kingfa Science and Technology Co Ltd, Shanghai Kingfa Science and Technology Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Publication of WO2018130117A1 publication Critical patent/WO2018130117A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Definitions

  • the invention relates to the technical field of plastic modification, in particular to a photosensitive color changing polypropylene composition and a preparation method and application thereof.
  • CN 105111768 A and CN 103275509 A describe a color changing plastic process formulation which is a combination of a plastic body, a color changing agent, a photochromic material, an oxidizing agent and a stabilizer, said photochromic material being Spiropyrans.
  • a color changing plastic process formulation which is a combination of a plastic body, a color changing agent, a photochromic material, an oxidizing agent and a stabilizer, said photochromic material being Spiropyrans.
  • the CO bond in the colorless pyran structure is broken and opened to obtain a colored isoquinoline isomer.
  • the isoquinoline can absorb visible light and develop color.
  • the CO bond break in the spiropyran is completely reversible.
  • the open-loop body can return to the original spiro structure without coloration and become the original color, but photochemical side reactions occur during the reversible change, thereby affecting the number of cycles of the reversible color. And when subjected to strong light or strong heat, the spiropyran is susceptible to fatigue and loses its ability to change color, and thus fails to change color.
  • An object of the present invention is to provide a photosensitive color-changing polypropylene composition which can be subjected to long-term illumination by sunlight, stably reversible, and has long-term weather resistance.
  • Another object of the present invention is to provide a process for the preparation of the above polypropylene composition.
  • a photosensitive color-changing polypropylene composition comprising, by weight, the following components:
  • Photochromic microcapsules 0.5 to 2.5 parts
  • the core material of the photosensitive color microcapsule is a spiropyran compound
  • the wall material is a melamine formaldehyde resin
  • the melamine formaldehyde resin is polymerized by formaldehyde and melamine.
  • the microcapsule preparation process of the present invention comprises the steps of first adding an alkylation reaction of formaldehyde and melamine having a molar ratio of 2.5/1 to 3/1 at a pH of 7.5 to 8.5 to obtain a methylol melamine prepolymer, and then Dispersing the optically variable material spiropyran compound in an aqueous solution of sodium dodecyl sulfate having a concentration of 0.2 to 1.0 wt%, finally adding a methylol melamine prepolymer to the above solution, and adjusting the solution to a pH of 5.5. ⁇ 6.5 obtained microcapsule emulsion, reacted at 80-90 ° C for 3 h, washed, suction filtered, dried to obtain photochromic microcapsules.
  • the photosensitive color microcapsule has a particle diameter of 1 to 5 ⁇ m.
  • the particle size of the microcapsules is too large, the microcapsule emulsion is unstable and easy to be layered, the microcapsules are poorly coated, the discoloration is uneven, and the color difference before and after discoloration is large, and the number of times of the photochromic polypropylene composition can be changed back and forth.
  • the particle size of the microcapsules is too small, the amount of sodium dodecylsulfonate is too high, the residue is large, the smell is large, the cost is high, the processing is not easy to disperse, and the discoloration is uneven.
  • the particle diameter of the microcapsule is 1 to 5 um, the microcapsule has good coating property, the particle size is suitable, and the processing dispersibility is good.
  • the polypropylene resin is a random copolymer polypropylene resin, and the melt flow rate of the random copolymer polypropylene resin is 10 to 30 g/10 min under the load of 2.16 kg at 230 ° C according to ASTM D1238.
  • the photosensitive color-changing polypropylene composition further comprises 0.5-2 parts of an auxiliary agent selected from one or a mixture of an antioxidant, a light stabilizer, or a lubricant.
  • the antioxidant is a mixture of hindered phenols and phosphite antioxidants.
  • the light stabilizer is a hindered amine light stabilizer.
  • the lubricant is selected from one or a mixture of ethylene bis stearamide, erucamide, zinc stearate or silicone oil.
  • a photochromic polypropylene composition can be used in automotive dashboards, sub-dashboards, seats, door panels, bumpers or columns.
  • the present invention has the following beneficial effects:
  • the microcapsule wall material makes the core material photo-deformation material not be destroyed by the ultraviolet light in the sunlight, thereby effectively protecting the optically variable material from the long-term illumination of the sunlight.
  • the prepared polypropylene composition has fast discoloration and good long-term weather resistance.
  • Polypropylene resin random copolymer polypropylene resin, J-570S, Lotte Chemical Co., Ltd., tested at 230 ° C, 2.16 kg load according to ASTM D-1238 melt flow rate of 28g/10min;
  • Photochromic powder produced by Guangzhou Jingcai Pigment Technology Co., Ltd.;
  • Spiropyran compound N-hydroxyethyl-3,3-dimethyl-6-nitroporphyrin spiropyran, produced by Guangzhou Wengjiang Chemical Reagent Co., Ltd.; toluene diisocyanate, BASF;
  • Emulsifier Tween 80 Guangzhou Hao Chemical Co., Ltd.;
  • Antioxidants, light stabilizers, lubricants, melamine, formaldehyde, sodium dodecyl sulfonate are all commercially available.
  • the concentration of the above aqueous sodium dodecylsulfonate solution is 0.8% by weight, and the product is a photosensitive color-changing microcapsule A having a particle diameter of 0.5 um.
  • the concentration of the above aqueous sodium dodecylsulfonate solution is 0.7% by weight, and the product is a photosensitive color-changing microcapsule B having a particle diameter of 1 ⁇ m.
  • the concentration of the above aqueous sodium dodecyl sulfate solution is 0.6% by weight, and the product is a photosensitive color-changing microcapsule C having a particle diameter of 2.5 ⁇ m.
  • the concentration of the above aqueous sodium dodecylsulfonate solution is 0.5% by weight, and the product is a photosensitive color-changing microcapsule D having a particle diameter of 4 ⁇ m.
  • the concentration of the above aqueous sodium dodecyl sulfate is 0.4% by weight, and the product is a photosensitive color-changing microcapsule E having a particle size of 5 ⁇ m.
  • the above aqueous sodium dodecylsulfonate solution has a concentration of 0.3% by weight, and the product is a photosensitive color-changing microcapsule F having a particle diameter of 7 ⁇ m.
  • the spiropyran compound was added to a three-necked flask, and 20 ml of toluene diisocyanate (TDI), 10 ml of polypropylene glycol, 1.5 ml of emulsifier Tween 80, and 23 ml of acetone were slowly added dropwise, stirred at a low speed of 200 r/min for 10 min, and reacted at 46 ° C for 30 min.
  • TDI toluene diisocyanate
  • 10 ml of polypropylene glycol 1.5 ml of emulsifier Tween 80
  • 23 ml of acetone were slowly added dropwise, stirred at a low speed of 200 r/min for 10 min, and reacted at 46 ° C for 30 min.
  • DMPA Dimethylolpropionic acid
  • the polypropylene resin, the antioxidant, the light stabilizer, the lubricant and the photochromic microcapsules are mixed and added to a twin-screw extruder for melt-kneading, and the melt-kneading temperature is 170 to 190 ° C. Extrusion granulation gave the polypropylene composition, which was then injection molded into a color plate for testing its color change properties.
  • polypropylene resin, antioxidant, light stabilizer, lubricant and photosensitive color changing powder are mixed and added to a twin-screw extruder for melt-kneading, and the melt-kneading temperature is 170-190 ° C.
  • Granulation was carried out to obtain the polypropylene composition, and then the composition was injection molded into a color plate for testing its discoloration property.
  • the L, a, b and ⁇ E of the swatch before the sun illumination and after 30 days of sunlight are measured by a color difference meter of Color-Eye 7000a.
  • the Lab color model is composed of illuminance L and related colors a and b.
  • the polypropylene composition prepared in the example has a small color difference ⁇ E after 30 days of continuous sunlight illumination, and can be changed back to the original color when the light is removed.
  • the polypropylene composition of the photosensitive color-changing microcapsules which were not subjected to microcapsule coating or the photosensitive color-changing microcapsules which were made of micro-capsules in the comparative example had a large color difference ⁇ E after continuous illumination for 30 days, and could not be changed back to the original color when the light was removed, and was ineffective. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composite de polypropylène photochromique, comprenant les constituants suivants en termes de parties en poids : une résine de polypropylène en 96,5 à 98,5 parties et une microcapsule photochromique en 0,5 à 2,5 parties. Le matériau central de la microcapsule photochromique est un spiropyrane, le matériau de paroi est une résine de mélamine-formaldéhyde, le matériau de paroi est formé par polymérisation de formaldéhyde et de mélamine et le rapport molaire formaldéhyde/mélamine est de 2,5/1 à 3/1. Tout d'abord, la mélamine et le formaldéhyde subissent une réaction d'addition dans un environnement de pH 7,5 à 8,5 pour produire un prépolymère de mélamine d'hydroxyméthyle, puis un composé de spiropyrane de matériau photochromique est dispersé dans une solution aqueuse de sulfate de dodécyle de sodium d'une concentration de 0,2 % à 1,0 % en poids, puis le prépolymère de mélamine d'hydroxyméthyle est ajouté à la solution et la solution est régulée à un pH de 5,5 à 6,5 pour produire une émulsion de microcapsule, qui est mise à réagir entre 80 °C et 90 °C pendant 3 heures, rincé, filtré par aspiration et séché pour produire la microcapsule photochromique. Le composite de polypropylène photochromique est susceptible de résister à une exposition à long terme à la lumière du soleil, change de couleurs et reprend sa couleur d'origine de façon stable, présente une grande résistance aux conditions météorologiques à long terme et est largement applicable dans des accessoires décoratifs intérieurs et extérieurs pour un véhicule.
PCT/CN2018/071537 2017-01-12 2018-01-05 Composite de polypropylène photochromique, son procédé de préparation et ses applications Ceased WO2018130117A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710021332.1 2017-01-12
CN201710021332.1A CN107841048B (zh) 2017-01-12 2017-01-12 一种感光变色的聚丙烯组合物及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2018130117A1 true WO2018130117A1 (fr) 2018-07-19

Family

ID=61682779

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/071537 Ceased WO2018130117A1 (fr) 2017-01-12 2018-01-05 Composite de polypropylène photochromique, son procédé de préparation et ses applications

Country Status (2)

Country Link
CN (1) CN107841048B (fr)
WO (1) WO2018130117A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110578258A (zh) * 2019-07-01 2019-12-17 绍兴墨织韵纺织科技有限公司 一种光致变色丙纶纱线织物的制备工艺
CN110885500A (zh) * 2019-12-03 2020-03-17 上海日之升科技有限公司 一种可光学变色的高透明聚丙烯树脂及其制备方法
CN112107089A (zh) * 2020-09-16 2020-12-22 浙江理工大学 一种基于离子液体水凝胶显示安全日晒时长的健康手环的制备方法
CN112358722A (zh) * 2020-12-11 2021-02-12 上海金发科技发展有限公司 一种聚酰胺复合材料及其制备方法和应用
CN114075371A (zh) * 2020-08-19 2022-02-22 中国石油化工股份有限公司 一种温感光感聚酯、薄膜及其制备方法
CN114316424A (zh) * 2021-11-22 2022-04-12 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法
CN116640382A (zh) * 2023-06-06 2023-08-25 成都金发科技新材料有限公司 一种免喷涂材料及其制备方法和应用
CN117568013A (zh) * 2023-09-06 2024-02-20 苏州宝丽迪材料科技股份有限公司 一种光致变色微胶囊、光致变色纤维及其制备方法
CN118772458A (zh) * 2024-07-22 2024-10-15 上海纳琳威科技股份有限公司 一种温度变色车膜及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101225296A (zh) * 2008-02-01 2008-07-23 北京服装学院 光致变色微胶囊的制备方法
WO2014057858A1 (fr) * 2012-10-12 2014-04-17 シーシーエス株式会社 Composition d'étanchéité pour pièces électriques et électroniques, matériau de revêtement pour pièces électriques et électroniques, et dispositif à led
CN105524399A (zh) * 2015-12-29 2016-04-27 银禧工程塑料（东莞）有限公司 一种3d打印的聚合物材料及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104059294A (zh) * 2014-06-24 2014-09-24 张剑升 一种紫外感光变色材料及其制品和用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101225296A (zh) * 2008-02-01 2008-07-23 北京服装学院 光致变色微胶囊的制备方法
WO2014057858A1 (fr) * 2012-10-12 2014-04-17 シーシーエス株式会社 Composition d'étanchéité pour pièces électriques et électroniques, matériau de revêtement pour pièces électriques et électroniques, et dispositif à led
CN105524399A (zh) * 2015-12-29 2016-04-27 银禧工程塑料（东莞）有限公司 一种3d打印的聚合物材料及其制备方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110578258A (zh) * 2019-07-01 2019-12-17 绍兴墨织韵纺织科技有限公司 一种光致变色丙纶纱线织物的制备工艺
CN110885500A (zh) * 2019-12-03 2020-03-17 上海日之升科技有限公司 一种可光学变色的高透明聚丙烯树脂及其制备方法
CN114075371A (zh) * 2020-08-19 2022-02-22 中国石油化工股份有限公司 一种温感光感聚酯、薄膜及其制备方法
CN112107089A (zh) * 2020-09-16 2020-12-22 浙江理工大学 一种基于离子液体水凝胶显示安全日晒时长的健康手环的制备方法
CN112107089B (zh) * 2020-09-16 2023-01-03 浙江理工大学 一种基于离子液体水凝胶显示安全日晒时长的健康手环的制备方法
CN112358722A (zh) * 2020-12-11 2021-02-12 上海金发科技发展有限公司 一种聚酰胺复合材料及其制备方法和应用
CN112358722B (zh) * 2020-12-11 2022-08-09 上海金发科技发展有限公司 一种聚酰胺复合材料及其制备方法和应用
CN114316424A (zh) * 2021-11-22 2022-04-12 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法
CN114316424B (zh) * 2021-11-22 2023-08-25 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法
CN116640382A (zh) * 2023-06-06 2023-08-25 成都金发科技新材料有限公司 一种免喷涂材料及其制备方法和应用
CN117568013A (zh) * 2023-09-06 2024-02-20 苏州宝丽迪材料科技股份有限公司 一种光致变色微胶囊、光致变色纤维及其制备方法
CN118772458A (zh) * 2024-07-22 2024-10-15 上海纳琳威科技股份有限公司 一种温度变色车膜及其制备方法

Also Published As

Publication number Publication date
CN107841048B (zh) 2019-11-26
CN107841048A (zh) 2018-03-27

Similar Documents

Publication Publication Date Title
WO2018130117A1 (fr) Composite de polypropylène photochromique, son procédé de préparation et ses applications
WO2018130120A1 (fr) Composite de polypropylène thermochromique, procédé de préparation de celui-ci et applications associées
EP1829923B1 (fr) Composition contenant additif microencapsulé pour caoutchouc
EP1216278B2 (fr) Liants modifies avec des nanoparticules, destines a des materiaux de revetement, et leur utilisation
WO2005049737A1 (fr) Compositions de pigments composees de pigment disazo jaune et de pigments organiques
EP1570006B1 (fr) Preparations de pigments solides, contenant des derives de pigment et des additifs tensioactifs
LU102280B1 (de) Verfahren zum Herstellen eines Nylonpulvers und dessen Verwendung
EP2933355B1 (fr) Procédé de fabrication d'un revêtement de protection anticorrosion foncé
DE102008020442A1 (de) Pigmentpräparationen
EP0218866B1 (fr) Procédé de préparation de résines à couler durcissables
DE2063948B2 (de) Verwendung von Harzen oder Harzgemischen zur Herstellung fluoreszierend« Pigmente
EP0011607B1 (fr) Compositions de pigments à base de chromates métalliques et procédé pour leur préparation
DE2536335A1 (de) 1,2,3-triazolverbindungen, verfahren zu ihrer herstellung und ihre verwendung als ultraviolettabsorber
EP1966342B1 (fr) Objet en plastique photochromique
WO2006040284A1 (fr) Pate de pigments a effet aqueuse, procede de fabrication et utilisation
DE69737004T2 (de) Kristallwachstumsmodifikatoren für Perylenpigmente
DE4235693C1 (de) Verfahren zur Flammschutzausrüstung von Polyolefin-Partikelschäumen
EP3039059B1 (fr) Mélange maître de pigments
EP2662134A1 (fr) Nouveaux revêtements transparents dotés de propriétés auto-cicatrisantes
EP1383839B1 (fr) Agent de recouvrement aqueux transparent contenant du verre pulverise
WO2005049738A1 (fr) Compositions de pigments composees de pigment jaune organique et de pigment de phtalocyanine
DE19754342B4 (de) Mikroverkapseltes Kautschukadditiv, dessen Herstellung und Verwendung
KR101083410B1 (ko) 투명성이 개선된 피톤치드 마이크로캡슐의 제조방법
DE2546118A1 (de) Verfahren zur herstellung von konzentraten, die tagesleuchtpigmente enthalten
DE102010044768A1 (de) Verfahren zur Herstellung von farbigen Pulvermaterialien,farbige Pulvermaterialien und deren Verwendung

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: 18739061

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18739061

Country of ref document: EP

Kind code of ref document: A1